Patent Application
20230169947
The invention relates to acoustic products for sound insulation and absorption. In particular the invention relates to methods of making such acoustic products and systems comprising such acoustic products.
It is well known to provide acoustic products for sound absorption and insulation. A common form for such products is an acoustic element in the form of a panel and having a facing adhered to a major surface of the panel.
It is important that the adhesive used to adhere the facing to the panel has appropriate properties. In particular it is important that the adhesion strength (usually defined in terms of peel-off strength) is adequate.
It is common to use phenol-formaldehyde resin as an adhesive for the facing. This is particularly useful in the context of acoustic panels which are formed of a matrix of man-made vitreous fibres (MMVF) bonded by a binder, because phenol-formaldehyde resins are commonly used as binder for such products already. Phenol-formaldehyde adhesive gives good results and is commonly used in commercial practice.
Phenol-formaldehyde resins can be economically produced and can be extended with urea prior to use as a binder. However, the existing and proposed legislation directed to the lowering or elimination of formaldehyde emissions have led to the development of formaldehyde-free binders such as, for instance, the binder compositions based on polycarboxy polymers and polyols or polyamines, such as disclosed in EP-A-583086, EP-A-990727, EP-A-1741726, U.S. Pat. No. 5,318,990 and US-A-2007/0173588.
Another group of non-phenol-formaldehyde binders are the addition/-elimination reaction products of aliphatic and/or aromatic anhydrides with alkanolamines, e.g., as disclosed in WO 99/36368, WO 01/05725, WO 01/96460, WO 02/06178, WO 2004/007615 and WO 2006/061249. These binder compositions are water soluble and exhibit excellent binding properties in terms of curing speed and curing density.
WO 2008/023032 discloses urea-modified binders of that type which provide mineral wool products having reduced moisture take-up.
These could in principle be used as adhesives for the facing on an acoustic element. However, since some of the starting materials used in the production of these binders are rather expensive chemicals, there is an ongoing need to provide formaldehyde-free adhesives which are economically produced.
A further effect in connection with previously known aqueous adhesive compositions for mineral fibres is that at least the majority of the starting materials used for the productions of these binders stem from fossil fuels. There is an ongoing trend of consumers to prefer products that are fully or at least partly produced from renewable materials and there is therefore a need to provide binders for mineral wool which are, at least partly, produced from renewable materials.
A further effect in connection with previously known aqueous adhesive compositions for mineral fibres is that they involve components which are corrosive and/or harmful. This requires protective measures for the machinery involved in the production of mineral wool products to prevent corrosion and also requires safety measures for the persons handling this machinery. This leads to increased costs and health issues and there is therefore a need to provide adhesive compositions with a reduced content of corrosive and/or harmful materials.
In the meantime, a number of binders for mineral fibres have been provided, which are to a large extent based on renewable starting materials. In many cases these binders based to a large extent on renewable resources are also formaldehyde-free.
However, many of these binders are still comparatively expensive because they are based on comparatively expensive basic materials and so their use as adhesives for bonding a facing to an acoustic element would be uneconomical.
Accordingly, it is an object of the present invention to provide an adhesive composition which is particularly suitable for bonding a facing to an acoustic element, uses renewable materials as starting materials, reduces or eliminates corrosive and/or harmful materials, and is comparatively inexpensive to produce.
A further object of the present invention is to provide an acoustic product formed of an acoustic element having bonded to it a facing, wherein the adhesion properties are good, and in particular as good as those provided by phenol-formaldehyde binder, but which minimises the disadvantages of phenol-formaldehyde binder.
According to a first aspect of the invention we provide a method of making an acoustic product, the method comprising:
providing an acoustic element comprising first and second major surfaces;
providing a first facing;
fixing the first facing to the first major surface of the acoustic element by the use of an adhesive; and
curing the adhesive, wherein the adhesive is an aqueous composition which comprises
In the invention we use as an adhesive a composition as defined above. This has the advantage that it gives adhesion properties which are commercially acceptable, and indeed as good as those of phenol-formaldehyde resin, but without the attendant disadvantages.
According to a second aspect of the invention we provide an acoustic product obtained by the method of the first aspect of the invention.
According to a third aspect of the invention we provide an acoustic product comprising an acoustic element comprising first and second major surfaces and a first facing, wherein the first facing is fixed to the first major surface of the acoustic element by an adhesive, wherein the adhesive before curing is an aqueous adhesive composition which comprises
A preferred method of making the acoustic products comprises applying a second facing to the second major surface of the acoustic element prior to curing, and, after curing, cutting the acoustic element into two halves in the plane parallel to the major faces. Each half has a cut face which becomes the front face of the acoustic product. Each acoustic element has front and rear major faces which extend in the XY plane and side edges which extend in the Z direction between the front and rear faces. The front face is the face which is to face towards the room or other space which is to benefit from the sound absorption properties.
Each front face is abraded to make it as flat as possible, and a further facing is usually then bonded to it. The first and second facings are thus on the back faces of the two acoustic products that have been made.
The acoustic products that have been formed according to the method of the first aspect of the invention or that are according to the second and third aspects of the invention can be formed into a suspended ceiling system comprising a plurality of acoustic products suspended in a grid. It is also useful to provide a wall system comprising a plurality of acoustic products as defined according to the second or third aspect of the invention suspended on a wall.
The method of the invention comprises providing an acoustic element. This can be an acoustic insulation element but is more commonly an acoustic absorption element. Thus more commonly it is capable of absorbing soundwaves which reach its surface.
The acoustic element can be formed of any material known for provision of acoustic elements but preferably it is formed of MMVF. The acoustic element can be made by casting wet or fluid materials (for instance they can be made from wet-laid mineral fibres) but it is preferred to form acoustic elements of air-laid mineral fibres, usually bonded in a matrix with a binder.
The binder can be any of the binders known for use in bonding MMVF.
Preferably the binder is an organic binder such as phenol formaldehyde binder, urea formaldehyde binder, phenol urea formaldehyde binder or melamine formaldehyde binder. Conventionally-used phenol-formaldehyde or phenol-urea-formaldehyde (PUF) based resol binders optionally contain a sugar component. For these binders, without sugar component, reference is for example made to EP 0148050 and EP 0996653. For these binders, with sugar component, reference is made to WO 2012/076462.
It can be a formaldehyde-free binder such as, for instance, the binder compositions based on polycarboxy polymers and polyols or polyamines, such as disclosed in EP-A-583086, EP-A-990727, EP-A-1741726, U.S. Pat. No. 5,318,990 and US-A-2007/0173588.
Another group of non-phenol-formaldehyde binders that can be used in the MMVF matrix are the addition/-elimination reaction products of aliphatic and/or aromatic anhydrides with alkanolamines, e.g., as disclosed in WO 99/36368, WO 01/05725, WO 01/96460, WO 02/06178, WO 2004/007615 and WO 2006/061249. These binder compositions are water soluble and exhibit excellent binding properties in terms of curing speed and curing density. WO 2008/023032 discloses urea-modified binders of that type which provide mineral wool products having reduced moisture take-up.
Preferably the binder for the MMVF is an aqueous adhesive composition which comprises
Further preferred features of the binder are described below in the context of the material used as the adhesive. All of the same preferred features are applicable, independently of the features of the adhesive, when a material in this class is used as binder for MMVF in the acoustic element.
The density of the acoustic element is preferably in the range of 40 to 180 kg/m3, preferably 80 to 160 kg/m3, preferably 100 to 140 kg/m3. More preferably it is at least 100 kg/m3. In particular it is often not more than 150 kg/m3.
When the acoustic element is formed of MMVF, the loss on ignition (LOI) of the batt of man-made vitreous fibres bonded by the binder is generally within the range of 0.5 to 8 wt %, preferably 2 to 5 wt %. The LOI is taken as the binder content, in conventional manner. Binder will normally include minor amounts of oil and other organic binder additives in addition to the main bonding components.
When the acoustic element is formed of MMVF, they generally have average fibre diameter in the range 3 to 8 microns.
Man-made vitreous fibres (MMVF) used in the invention can have any suitable oxide composition. The fibres can be glass fibres, ceramic fibres, basalt fibres, slag fibres or rock or stone fibres. The fibres are preferably of the types generally known as rock, stone or slag fibres, most preferably stone fibres.
Stone fibres commonly comprise the following oxides, in percent by weight:
SiO2: 30 to 51
CaO: 8 to 30
MgO: 2 to 25
FeO (including Fe2O3): 2 to 15
Na2O+K2O: not more than 10
CaO+MgO: 10 to 30
In preferred embodiments the MMVF have the following levels of elements, calculated as oxides in wt %:
SiO2: at least 30, 32, 35 or 37; not more than 51, 48, 45 or 43
Al2O3: at least 12, 16 or 17; not more than 30, 27 or 25
CaO: at least 8 or 10; not more than 30, 25 or 20
MgO: at least 2 or 5; not more than 25, 20 or 15
FeO (including Fe2O3): at least 4 or 5; not more than 15, 12 or 10
FeO+MgO: at least 10, 12 or 15; not more than 30, 25 or 20
Na2O+K2O: zero or at least 1; not more than 10
CaO+MgO: at least 10 or 15; not more than 30 or 25
TiO2: zero or at least 1; not more than 6, 4 or 2
TiO2+FeO: at least 4 or 6; not more than 18 or 12
B2O3: zero or at least 1; not more than 5 or 3
P2O5: zero or at least 1; not more than 8 or 5
Others: zero or at least 1; not more than 8 or 5
The MMVF used in the invention preferably have the composition in wt %:
Another preferred composition for the MMVF is as follows in wt %:
SiO2 39-55% preferably 39-52%
Al2O3 16-27% preferably 16-26%
CaO 6-20% preferably 8-18%
MgO 1-5% preferably 1-4.9%
Na2O 0-15% preferably 2-12%
K2O 0-15% preferably 2-12%
R2O (Na2O+K2O) 10-14.7% preferably 10-13.5%
P2O5 0-3% preferably 0-2%
Fe2O3 (iron total) 3-15% preferably 3.2-8%
B2O3 0-2% preferably 0-1%
TiO2 0-2% preferably 0.4-1%
Others 0-2.0%
Glass fibres commonly comprise the following oxides, in percent by weight:
SiO2: 50 to 70
Al2O3: 10 to 30
CaO: not more than 27
MgO: not more than 12
Glass fibres can also contain the following oxides, in percent by weight:
Na2O+K2O: 8 to 18, in particular Na2O+K2O greater than CaO+MgO
B2O3: 3 to 12
Al2O3: less than 2%. The acoustic element is usually in the form of a panel. The element has first and second major faces which are essentially parallel (and extend in the XY direction). These are connected by minor faces, which are usually perpendicular to the major faces (and so extend in the Z direction).
The acoustic element, when formed of MMVF, is formed by a standard process for production of an MMVF panel.
MMV fibres can be made from a mineral melt. A mineral melt is provided in a conventional manner by providing mineral materials and melting them in a furnace. This furnace can be any of the types of furnace known for production of mineral melts for MMVF, for instance a shaft furnace such as a cupola furnace, a tank furnace, or a cyclone furnace.
Any suitable method may be employed to form MMVF from the mineral melt by fiberization. The fiberization can be by a spinning cup process in which melt is centrifugally extruded through orifices in the walls of a rotating cup (spinning cup, also known as internal centrifugation). Alternatively the fiberization can be by centrifugal fiberization by projecting the melt onto and spinning off the outer surface of one fiberizing rotor, or off a cascade of a plurality of fiberizing rotors, which rotate about a substantially horizontal axis (cascade spinner).
Binder for the fibres is applied as they are formed and entrained in air. The fibres can initially be collected on the collector as a primary web and this primary web is then cross-lapped in conventional manner to form a secondary web.
The first facing is preferably applied to the first major face before the step of curing the binder for the MMVF. This is also the case for a second facing if used. This means that the adhesive for the facing(s) can also be cured in the same curing step as the binder. However, it is also possible to apply the facing(s) after the binder for the matrix of MMVF has been cured, and then conduct a step of curing the adhesive.
When a second facing is applied, preferably the adhesive for the second facing is of the same chemical type as the adhesive for the first facing.
Curing of the adhesive is preferably carried out at temperatures from 100 to 300° C., such as 170 to 270° C., such as 180 to 250° C., such as 190 to 230° C.
In a preferred embodiment, the curing of the adhesive takes place in a conventional curing oven for mineral wool production, preferably operating at a temperature of from 150 to 300° C., such as 170 to 270° C., such as 180 to 250° C., such as 190 to 230° C.
In one embodiment, the curing takes place for a time of 30 seconds to 20 minutes, such as 1 to 15 minutes, such as 2 to 10 minutes.
In a typical embodiment, curing takes place at a temperature of 150 to 250° C. for a time of 30 seconds to 20 minutes.
Where the acoustic product is a bonded web of MMVF, the web also includes a binder. This also has to be cured. The curing process for the binder may commence immediately after application of the binder to the fibres.
The curing of adhesive and/or binder is defined as a process whereby the adhesive/binder composition undergoes a physical and/or chemical reaction which in case of a chemical reaction usually increases the molecular weight of the compounds in the adhesive/binder composition and thereby increases the viscosity of the adhesive/binder composition, usually until the adhesive/binder composition reaches a solid state. The cured binder composition binds the fibres to form a structurally coherent matrix of fibres. The cured adhesive composition bonds the facing(s) to the acoustic element.
In a one embodiment, the curing of the adhesive/binder takes place in a heat press. The curing of a binder in contact with mineral fibres in a heat press has the particular advantage that it enables the production of high-density products.
In one embodiment the curing process comprises drying by pressure. The pressure may be applied by blowing air or gas through/over the product to be cured.
Two products can be made by forming a cured batt of fibres with first and second facings bonded to the first and second major faces respectively and then cutting the batt into two halves in the plane parallel to the major faces. Each half has a cut face which becomes the front face of the acoustic product. Each front face is abraded to make it as flat as possible.
In the method it is also possible to apply a further facing on the front face. This is preferably applied using dry binder rather than adhesive according to the invention.
Preferably the method of the invention is according to WO 2005/095727. According to this method the acoustic products are made by a process comprising
collecting MMVF entrained in air on a travelling collector and vertically compressing the collected fibres, optionally after cross-lapping, to form a web,
reorienting the fibres to provide an unbonded batt having a density of 70 to 200 kg/m3 and an increased fibre orientation in the Z direction,
curing the binder to form a cured batt,
cutting the cured batt in the XY plane into two cut batts at a position in the Z dimension wherein the fibres have the increased orientation in the Z direction,
and smoothing each cut surface by abrasion to produce a flat smooth face.
Preferably, the first and preferably second facings are applied to the first and second major faces of the batt before the curing step.
The method can also comprise the routine steps of forming elements having the desired XY dimensions by sub-dividing the cured batt before it is cut into the two cut batts and/or by subdividing the cut batts before or after abrasion, to form elements having the desired XY dimensions.
The cutting of the bonded batt can be conducted in conventional manner, for instance using a band saw or rotary saw having a suitably small tooth size, for instance resembling a conventional fine wood saw. The abrasion or grinding can be by abrasive belt or any other abrasive or grinding element. The abrasive particles on the belt can be relatively coarse and thus the abrasion can be similar to a conventional coarse wood abrader or grinder.
Other details of preferred production methods can be found in WO 2005/095727.
The acoustic product has a thickness which is the perpendicular distance between the major faces of the product. This is usually in the range of 12 to 100 mm, such as 15 to 50 mm.
The acoustic product has a length which is preferably in the range 550 to 650 mm or in the range 1100 to 1300 mm. Preferred lengths are around 600 mm and around 1200 mm. For special products the length could be up to 3000 mm, which however gives rise to practical problems with handling and installation, so can be less preferred.
The acoustic product has a width in the range 550 to 650 mm. A preferred width is about 600 mm. For special products the length could be as low as 150 mm, which however increases installation time, but can be preferred for design reasons, or to utilize parts of products that would otherwise be scrapped.
The first and second and further facings may independently be any of the materials known for use as a facing for an acoustic product. Preferably the or each facing is a fibre veil, in particular a glass fibre veil. Glass fibre veils can be themselves bonded with a binder, for instance any of the conventional binders known for bonding a matrix of MMVF. Binder content of the veil can be in the range 10 to 25%, for instance 12 to 23%.
An example of such a glass veil is Owens Corning I50U. Another example is Evalith Glass Fibre Veil DH50/20. Another suitable glass veil is Saint-Gobain Adfors Glass Veil U 50 D75.
A facing, for example glass fibre veil, may have an area weight in the range 20 to 80 g/m2, preferably in the range 40 to 60 g/m2.
In the method the adhesive is usually applied to the first facing, and the second facing if used, before the facing is brought into contact with the respective major face of the acoustic element. It is however possible to apply the adhesive directly to the major face of the element to which the facing is to be adhered.
Application weight is preferably in the range 5 to 12 g/m2, preferably 7 to 10 g/m2. Application weight is dry solids content per m2.
Preferably the adhesive is applied by passing the facing through a coating bath containing adhesive. Another method of application is by spraying.
Any of the facings can be provided with a paint coating. Paint can be applied to a facing prior to adhering it to the acoustic element, or after it has been applied.
The product is an acoustic product and therefore preferably has good acoustic absorption properties. For instance the sound absorption coefficient aw is preferably at least 0.7, more preferably at least 0.8, more preferably at least 0.85 and even more preferably at least 0.9 or 0.95. Sound absorption coefficient aw is determined at the front face.
The acoustic product made according to the method of the invention, and the acoustic product of the third aspect of the invention, can be used in any of the applications known for acoustic products.
For instance it may be a ceiling tile or form part of a suspended ceiling, or be used as a wall tile or as a baffle. Acoustic products can be bonded direct to a wall or ceiling, but usually they are mounted on a grid, and in particular it is desirable to provide ceiling tiles that are suspended from a grid.
The adhesive used according to the present invention is in the form of an aqueous composition. Preferred features are discussed below. When the acoustic product is formed of MMVF bonded with a binder, the binder may also be of the type discussed below, and all the same preferred features apply.
The aqueous adhesive and/or binder comprises
In a preferred embodiment, the adhesives and/or binders used according to the present invention are formaldehyde free.
For the purpose of the present application, the term “formaldehyde free” is defined to characterize a mineral wool product where the emission is below 5 μg/m2/h of formaldehyde from the mineral wool product, preferably below 3 μg/m2/h. Preferably, the test is carried out in accordance with ISO 16000 for testing aldehyde emissions.
Component (i)
Component (i) is in form of one or more oxidized lignins.
Lignin, cellulose and hemicellulose are the three main organic compounds in a plant cell wall. Lignin can be thought of as the glue, that holds the cellulose fibres together. Lignin contains both hydrophilic and hydrophobic groups. It is the second most abundant natural polymer in the world, second only to cellulose, and is estimated to represent as much as 20-30% of the total carbon contained in the biomass, which is more than 1 billion tons globally.
There are at least four groups of technical lignins available in the market. These four groups are shown in
A summary of the properties of these technical lignins is shown in
Lignosulfonate from the sulfite pulping process remains the largest commercial available source of lignin, with capacity of 1.4 million tonnes. But taking these aside, the kraft process is currently the most used pulping process and is gradually replacing the sulfite process. An estimated 78 million tonnes per year of lignin are globally generated by kraft pulp production but most of it is burned for steam and energy. Current capacity for kraft recovery is estimated at 160,000 tonnes, but sources indicate that current recovery is only about 75,000 tonnes. Kraft lignin is developed from black liquour, the spent liquor from the sulfate or kraft process. At the moment, 3 well-known processes are used to produce the kraft lignin: LignoBoost, LignoForce and SLRP. These 3 processes are similar in that they involve the addition of CO2 to reduce the pH to 9-10, followed by acidification to reduce pH further to approximately 2. The final step involves some combination of washing, leaching and filtration to remove ash and other contaminants. The three processes are in various stages of commercialization globally.
The kraft process introduces thiol groups, stilbene while some carbohydrates remain. Sodium sulphate is also present as an impurity due to precipitation of lignin from liquor with sulphuric acid but can potentially be avoided by altering the way lignin is isolated. The kraft process leads to high amount of phenolic hydroxyl groups and this lignin is soluble in water when these groups are ionized (above pH-10).
Commercial kraft lignin is generally higher in purity than lignosulfonates. The molecular weight are 1000-3000 g/mol·s
Soda lignin originates from sodium hydroxide pulping processes, which are mainly used for wheat straw, bagasse and flax. Soda lignin properties are similar to kraft lignins one in terms of solubility and Tg. This process does not utilize sulphur and there is no covalently bound sulphur. The ash level is very low. Soda lignin has a low solubility in neutral and acid media but is completely soluble at pH 12 and higher.
The lignosulfonate process introduces large amount of sulphonate groups making the lignin soluble in water but also in acidic water solutions. Lignosulfonates has up to 8% sulfur as sulphonate, whereas kraft lignin has 1-2% sulfur, mostly bonded to the lignin. The molecular weight of lignosulfonate is 15.000-50.000 g/mol. This lignin contains more leftover carbohydrates compared to other types and has a higher average molecular weight. The typical hydrophobic core of lignin together with large number of ionized sulphonate groups make this lignin attractive as a surfactant and it often finds application in dispersing cement etc.
A further group of lignins becoming available is lignins resulting from biorefining processes in which the carbohydrates are separated from the lignin by chemical or biochemical processes to produce a carbohydrate rich fraction. This remaining lignin is referred to as biorefinery lignin. Biorefineries focus on producing energy, and producing substitutes for products obtained from fossil fuels and petrochemicals as well as lignin. The lignin from this process is in general considered a low value product or even a waste product mainly used for thermal combustion or used as low grade fodder or otherwise disposed of.
Organosolv lignin availability is still considered on the pilot scale. The process involves extraction of lignin by using water together with various organic solvents (most often ethanol) and some organic acids. An advantage of this process is the higher purity of the obtained lignin but at a much higher cost compared to other technical lignins and with the solubility in organic solvents and not in water.
Previous attempts to use lignin as a basic compound for adhesive and/or binder compositions for mineral fibres failed because it proved difficult to find suitable cross-linkers which would achieve desirable mechanical properties of the cured mineral wool product and at the same time avoid harmful and/or corrosive components. Presently lignin is used to replace oil derived chemicals, such as phenol in phenolic resins in adhesive and/or binder applications or in bitumen. It is also used as cement and concrete additives and in some aspects as dispersants.
The cross-linking of a polymer in general should provide improved properties like mechanical, chemical and thermal resistance etc. Lignin is especially abundant in phenolic and aliphatic hydroxyl groups that can be reacted leading to cross-linked structure of lignin. Different lignins will also have other functional groups available that can potentially be used. The existence of these other groups is largely dependent on the way lignin was separated from cellulose and hemicellulose (thiols in kraft lignin, sulfonates in lignosulfonate etc.) depending on the source.
It has been found that by using oxidized lignins, adhesive and/or binder compositions can be prepared which allow excellent properties of the mineral fibre product produced.
In one embodiment, the component (i) is in form of one or more oxidized kraft lignins.
In one embodiment, the component (i) is in form of one or more oxidized soda lignins.
In one embodiment, the component (i) is in form of one or more ammonia-oxidized lignins. For the purpose of the present invention, the term “ammonia-oxidized lignins” is to be understood as a lignin that has been oxidized by an oxidation agent in the presence of ammonia. The term “ammonia-oxidized lignin” is abbreviated as AOL.
In an alternative embodiment, the ammonia is partially or fully replaced by an alkali metal hydroxide, in particular sodium hydroxide and/or potassium hydroxide.
A typical oxidation agent used for preparing the oxidized lignins is hydrogen peroxide.
In one embodiment, the ammonia-oxidized lignin comprises one or more of the compounds selected from the group of ammonia, amines, hydroxides or any salts thereof.
In one embodiment, the component (i) is having a carboxylic acid group content of 0.05 to 10 mmol/g, such as 0.1 to 5 mmol/g, such as 0.20 to 1.5 mmol/g, such as 0.40 to 1.2 mmol/g, such as 0.45 to 1.0 mmol/g, based on the dry weight of component (i).
In one embodiment, the component (i) is having an average carboxylic acid group content of more than 1.5 groups per macromolecule of component (i), such as more than 2 groups, such as more than 2.5 groups.
It is believed that the carboxylic acid group content of the oxidized lignins plays an important role in the surprising advantages of the aqueous adhesive and/or binder compositions for mineral fibres according to the present invention. In particular, it is believed that the carboxylic acid group of the oxidized lignins improve the cross-linking properties and therefore allow better mechanical properties of the cured mineral fibre products.
Component (ii)
Component (ii) is in form of one or more cross-linkers.
In one embodiment, the component (ii) comprises in one embodiment one or more cross-linkers selected from p-hydroxyalkylamide-cross-linkers and/or oxazoline-cross-linkers.
β-hydroxyalkylamide-cross-linkers is a curing agent for the acid-functional macromolecules. It provides a hard, durable, corrosion resistant and solvent resistant cross-linked polymer network. It is believed the β-hydroxyalkylamide cross-linkers cure through esterification reaction to form multiple ester linkages. The hydroxy functionality of the β-hydroxyalkylamide-cross-linkers should be an average of at least 2, preferably greater than 2 and more preferably 2-4 in order to obtain optimum curing response.
Oxazoline group containing cross-linkers are polymers containing one of more oxazoline groups in each molecule and generally, oxazoline containing crosslinkers can easily be obtained by polymerizing an oxazoline derivative. The U.S. Pat. No. 6,818,699 B2 provides a disclosure for such a process.
In one embodiment, the component (ii) is an epoxidised oil based on fatty acid triglyceride.
It is noted that epoxidised oils based on fatty acid triglycerides are not considered hazardous and therefore the use of these compounds in the adhesive and/or binder compositions according to the present invention do not render these compositions unsafe to handle.
In one embodiment, the component (ii) is a molecule having 3 or more epoxy groups.
In one embodiment, the component (ii) is one or more flexible oligomer or polymer, such as a low Tg acrylic based polymer, such as a low Tg vinyl based polymer, such as low Tg polyether, which contains reactive functional groups such as carbodiimide groups, such as anhydride groups, such as oxazoline groups, such as amino groups, such as epoxy groups.
In one embodiment, component (ii) is selected from the group consisting of cross-linkers taking part in a curing reaction, such as hydroxyalkylamide, alkanolamine, a reaction product of an alkanolamine and a polycarboxylic acid. The reaction product of an alkanolamine and a polycarboxylic acid can be found in U.S. Pat. No. 6,706,853B1.
Without wanting to be bound by any particular theory, it is believed that the very advantageous properties of the aqueous adhesive and binder compositions according to the present invention are due to the interaction of the oxidized lignins used as component (i) and the cross-linkers mentioned above. It is believed that the presence of carboxylic acid groups in the oxidized lignins enable the very effective cross-linking of the oxidized lignins.
In one embodiment, the component (ii) is one or more cross-linkers selected from the group consisting of multifunctional organic amines such as an alkanolamine, diamines, such as hexamethyldiamine, triamines.
In one embodiment, the component (ii) is one or more cross-linkers selected from the group consisting of polyethylene imine, polyvinyl amine, fatty amines.
In one embodiment, the component (ii) is one or more fatty amides.
In one embodiment, the component (ii) is one or more cross-linkers selected from the group consisting of dimethoxyethanal, glycolaldehyde, glyoxalic acid.
In one embodiment, the component (ii) is one or more cross-linkers selected from polyester polyols, such as polycaprolactone.
In one embodiment, the component (ii) is one or more cross-linkers selected from the group consisting of starch, modified starch, CMC.
In one embodiment, the component (ii) is one or more cross-linkers in form of aliphatic multifunctional carbodiimides.
In one embodiment, the component (ii) is one or more cross-linkers selected from melamine based cross-linkers, such as a hexakis(methylmethoxy)melamine (HMMM) based cross-linkers.
Examples of such compounds are Picassian XL 701, 702, 725 (Stahl Polymers), such as ZOLDINE® XL-29SE (Angus Chemical Company), such as CX300 (DSM), such as Carbodilite V-02-L2 (Nisshinbo Chemical Inc.).
Component (ii) can also be any mixture of the above mentioned compounds.
In one embodiment, the adhesive and/or binder composition according to the present invention comprises component (ii) in an amount of 1 to 40 wt.-%, such as 4 to 20 wt.-%, such as 6 to 12 wt.-%, based on the dry weight of component (i).
Component (iii)
Component (iii) is in form of one or more plasticizers.
In one embodiment, component (iii) is in form of one or more plasticizers selected from the group consisting of polyols, such as carbohydrates, hydrogenated sugars, such as sorbitol, erythriol, glycerol, monoethylene glycol, polyethylene glycols, polyethylene glycol ethers, polyethers, phthalates and/or acids, such as adipic acid, vanillic acid, lactic acid and/or ferullic acid, acrylic polymers, polyvinyl alcohol, polyurethane dispersions, ethylene carbonate, propylene carbonate, lactones, lactams, lactides, acrylic based polymers with free carboxy groups and/or polyurethane dispersions with free carboxy groups, polyamides, amides such as carbamide/urea, or any mixtures thereof.
In one embodiment, component (iii) is in form of one or more plasticizers selected from the group consisting of carbonates, such as ethylene carbonate, propylene carbonate, lactones, lactams, lactides, compounds with a structure similar to lignin like vanillin, acetosyringone, solvents used as coalescing agents like alcohol ethers, polyvinyl alcohol.
In one embodiment, component (iii) is in form of one or more non-reactive plasticizer selected from the group consisting of polyethylene glycols, polyethylene glycol ethers, polyethers, hydrogenated sugars, phthalates and/or other esters, solvents used as coalescing agents like alcohol ethers, acrylic polymers, polyvinyl alcohol.
In one embodiment, component (iii) is one or more reactive plasticizers selected from the group consisting of carbonates, such as ethylene carbonate, propylene carbonate, lactones, lactams, lactides, di- or tricarboxylic acids, such as adipic acid, or lactic acid, and/or vanillic acid and/or ferullic acid, polyurethane dispersions, acrylic based polymers with free carboxy groups, compounds with a structure similar to lignin like vanillin, acetosyringone.
In one embodiment, component (iii) is in form of one or more plasticizers selected from the group consisting of fatty alcohols, monohydroxy alcohols such as pentanol, stearyl alcohol.
In one embodiment, component (iii) comprises one or more plasticizers selected from the group consisting of polyethylene glycols, polyethylene glycol ethers.
Another particular surprising aspect of the present invention is that the use of plasticizers having a boiling point of more than 100° C., in particular 140 to 250° C., strongly improves the mechanical properties of the mineral fibre products according to the present invention although, in view of their boiling point, it is likely that these plasticizers will at least in part evaporate during the curing of the aqueous adhesive and/or binders in contact with the mineral fibres.
In one embodiment, component (iii) comprises one or more plasticizers having a boiling point of more than 100° C., such as 110 to 280° C., more preferred 120 to 260° C., more preferred 140 to 250° C.
It is believed that the effectiveness of these plasticizers in the aqueous adhesive and/or binder composition according to the present invention is associated with the effect of increasing the mobility of the oxidized lignins during the curing process. It is believed that the increased mobility of the lignins or oxidized lignins during the curing process facilitates the effective cross-linking.
In one embodiment, component (iii) comprises one or more polyethylene glycols having an average molecular weight of 150 to 50000 g/mol, in particular 150 to 4000 g/mol, more particular 150 to 1000 g/mol, preferably 150 to 500 g/mol, more preferably 200 to 400 g/mol.
In one embodiment, component (iii) comprises one or more polyethylene glycols having an average molecular weight of 4000 to 25000 g/mol, in particular 4000 to 15000 g/mol, more particular 8000 to 12000 g/mol.
In one embodiment component (iii) is capable of forming covalent bonds with component (i) and/or component (ii) during the curing process. Such a component would not evaporate and remain as part of the composition but will be effectively altered to not introduce unwanted side effects e.g. water absorption in the cured product. Non-limiting examples of such a component are caprolactone and acrylic based polymers with free carboxyl groups.
In one embodiment, component (iii) is selected from the group consisting of fatty alcohols, monohydroxy alcohols, such as pentanol, stearyl alcohol.
In one embodiment, component (iii) is selected from one or more plasticizers selected from the group consisting of alkoxylates such as ethoxylates such as butanol ethoxylates, such as butoxytriglycol.
In one embodiment, component (iii) is selected from one or more propylene glycols.
In one embodiment, component (iii) is selected from one or more glycol esters.
In one embodiment, component (iii) is selected from one or more plasticizers selected from the group consisting of adipates, acetates, benzoates, cyclobenzoates, citrates, stearates, sorbates, sebacates, azelates, butyrates, valerates.
In one embodiment, component (iii) is selected from one or more plasticizers selected from the group consisting of phenol derivatives such as alkyl or aryl substituted phenols.
In one embodiment, component (iii) is selected from one or more plasticizers selected from the group consisting of silanols, siloxanes.
In one embodiment, component (iii) is selected from one or more plasticizers selected from the group consisting of sulfates such as alkyl sulfates, sulfonates such as alkyl aryl sulfonates such as alkyl sulfonates, phosphates such as tripolyphosphates; such as tributylphosphates.
In one embodiment, component (iii) is selected from one or more hydroxy acids.
In one embodiment, component (iii) is selected from one or more plasticizers selected from the group consisting of monomeric amides such as acetamides, benzamide, fatty acid amides such as tall oil amides.
In one embodiment, component (iii) is selected from one or more plasticizers selected from the group consisting of quaternary ammonium compounds such as trimethylglycine, distearyldimethylammoniumchloride.
In one embodiment, component (iii) is selected from one or more plasticizers selected from the group consisting of vegetable oils such as castor oil, palm oil, linseed oil, tall oil, soybean oil.
In one embodiment, component (iii) is selected from one or more plasticizers selected from the group consisting of hydrogenated oils, acetylated oils.
In one embodiment, component (iii) is selected from one or more fatty acid methyl esters.
In one embodiment, component (iii) is selected from one or more plasticizers selected from the group consisting of alkyl polyglucosides, gluconamides, aminoglucoseamides, sucrose esters, sorbitan esters.
It has surprisingly been found that the inclusion of plasticizers in the aqueous adhesive and/or binder compositions according to the present invention strongly improves the mechanical properties of the mineral fibre products according to the present invention.
The term plasticizer refers to a substance that is added to a material in order to make the material softer, more flexible (by decreasing the glass-transition temperature Tg) and easier to process.
Component (iii) can also be any mixture of the above mentioned compounds.
In one embodiment, component (iii) is present in an amount of 0.5 to 50, preferably 2.5 to 25, more preferably 3 to 15 wt.-%, based on the dry weight of component (i).
Aqueous adhesive and/or binder composition for mineral fibers comprising components (i) and (iia)
In one embodiment the aqueous adhesive and/or binder composition for mineral fibers comprises:
The present inventors have found that the excellent binder properties can also be achieved by a two-component system which comprises component (i) in form of one or more oxidized lignins and a component (iia) in form of one or more modifiers, and optionally any of the other components mentioned above and below.
In one embodiment, component (iia) is a modifier in form of one or more compounds selected from the group consisting of epoxidised oils based on fatty acid triglycerides.
In one embodiment, component (iia) is a modifier in form of one or more compounds selected from molecules having 3 or more epoxy groups.
In one embodiment, component (iia) is a modifier in form of one or more flexible oligomer or polymer, such as a low Tg acrylic based polymer, such as a low Tg vinyl based polymer, such as low Tg polyether, which contains reactive functional groups such as carbodiimide groups, such as anhydride groups, such as oxazoline groups, such as amino groups, such as epoxy groups.
In one embodiment, component (iia) is one or more modifiers selected from the group consisting of polyethylene imine, polyvinyl amine, fatty amines.
In one embodiment, the component (iia) is one or more modifiers selected from aliphatic multifunctional carbodiimides.
Component (iia) can also be any mixture of the above mentioned compounds.
Without wanting to be bound by any particular theory, it is believed that the excellent binder properties achieved by the adhesive and/or binder composition for mineral fibers comprising components (i) and (iia), and optional further components, are at least partly due to the effect that the modifiers used as components (iia) at least partly serve the function of a plasticizer and a crosslinker.
In one embodiment, the aqueous adhesive and/or binder composition comprises component (iia) in an amount of 1 to 40 wt.-%, such as 4 to 20 wt.-%, such as 6 to 12 wt.-%, based on the dry weight of the component (i).
Further Components
In some embodiments, the aqueous adhesive and/or binder composition used in the present invention comprises further components.
In one embodiment, the aqueous adhesive and/or binder composition used in the present invention comprises a catalyst selected from inorganic acids, such as sulfuric acid, sulfamic acid, nitric acid, boric acid, hypophosphorous acid, and/or phosphoric acid, and/or any salts thereof such as sodium hypophosphite, and/or ammonium salts, such as ammonium salts of sulfuric acid, sulfamic acid, nitric acid, boric acid, hypophosphorous acid, and/or phosphoric acid. The presence of such a catalyst can improve the curing properties of the aqueous adhesive and/or binder compositions according to the present invention.
In one embodiment, the aqueous adhesive and/or binder composition used in the present invention comprises a catalyst selected from Lewis acids, which can accept an electron pair from a donor compound forming a Lewis adduct, such as ZnCl2, Mg (ClO4)2, Sn [N(SO2-n-C8F17)2]4.
In one embodiment, the aqueous adhesive and/or binder composition used in the present invention comprises a catalyst selected from metal chlorides, such as KCl, MgCl2, ZnCl2, FeCl3 and SnCl2.
In one embodiment, the aqueous adhesive and/or binder composition used in the present invention comprises a catalyst selected from organometallic compounds, such as titanate-based catalysts and stannum based catalysts.
In one embodiment, the aqueous adhesive and/or binder composition used in the present invention comprises a catalyst selected from chelating agents, such as transition metals, such as iron ions, chromium ions, manganese ions, copper ions.
In one embodiment, the aqueous adhesive and/or binder composition used in the present invention further comprises a further component (iv) in form of one or more silanes.
In one embodiment, the aqueous adhesive and/or binder composition used in the present invention comprises a further component (iv) in form of one or more coupling agents, such as organofunctional silanes.
In one embodiment, component (iv) is selected from group consisting of organofunctional silanes, such as primary or secondary amino functionalized silanes, epoxy functionalized silanes, such as polymeric or oligomeric epoxy functionalized silanes, methacrylate functionalized silanes, alkyl and aryl functionalized silanes, urea funtionalised silanes or vinyl functionalized silanes.
In one embodiment, the aqueous adhesive and/or binder composition used in the present invention further comprises a component (v) in form of one or more components selected from the group of ammonia, amines or any salts thereof.
It has been found that the inclusion of ammonia, amines or any salts thereof as a further component can in particular be useful when oxidized lignins are used in component (i), which oxidised lignin have not been oxidized in the presence of ammonia.
In one embodiment, the aqueous adhesive and/or binder composition used in the present invention further comprises a further component in form of urea, in particular in an amount of 5 to 40 wt.-%, such as 10 to 30 wt.-%, 15 to 25 wt.-%, based on the dry weight of component (i).
In one embodiment, the aqueous adhesive and/or binder composition used in the present invention further comprises a further component in form of one or more carbohydrates selected from the group consisting of sucrose, reducing sugars, in particular dextrose, polycarbohydrates, and mixtures thereof, preferably dextrins and maltodextrins, more preferably glucose syrups, and more preferably glucose syrups with a dextrose equivalent value of DE=30 to less than 100, such as
DE=60 to less than 100, such as DE=60-99, such as DE=85-99, such as DE=95-99.
In one embodiment, the aqueous adhesive and/or binder composition used in the present invention further comprises a further component in form of one or more carbohydrates selected from the group consisting of sucrose and reducing sugars in an amount of 5 to 50 wt.-%, such as 5 to less than 50 wt.-%, such as 10 to 40 wt.-%, such as 15 to 30 wt.-% based on the dry weight of component (i).
In the context of the present invention, an adhesive or binder composition having a sugar content of 50 wt.-% or more, based on the total dry weight of the adhesive or binder components, is considered to be a sugar based adhesive or binder. In the context of the present invention, an adhesive or binder composition having a sugar content of less than 50 wt.-%, based on the total dry weight of the adhesive or binder components, is considered a non-sugar based adhesive or binder.
In one embodiment, the aqueous adhesive and/or binder composition used in the present invention further comprises a further component in form of one or more surface active agents that are in the form of non-ionic and/or ionic emulsifiers such as polyoxyethylenes (4) lauryl ether, such as soy lecithin, such as sodium dodecyl sulfate.
In one embodiment, the aqueous adhesive and/or binder composition used in the present invention comprises
In one embodiment, the aqueous adhesive and/or binder composition used in the present invention comprises
In one embodiment, the aqueous adhesive and/or binder composition used in the present invention comprises
In one embodiment, the aqueous adhesive and/or binder composition used in the present invention comprises
In one embodiment, the aqueous adhesive and/or binder composition used in the present invention consists essentially of
In one embodiment, the aqueous adhesive and/or binder composition used in the present invention consists essentially of
Oxidised Lignins which can be Used as Component in the Aqueous Binder and/or Adhesive Composition for Mineral Fibres According to the Present Invention and Method for Preparing Such Oxidised Lignins
In the following, we describe oxidised lignins which can be used as component of the binder and/or adhesive compositions and their preparation.
Method I to Prepare Oxidised Lignins
Oxidised lignins, which can be used as component for the binders and/or adhesives used in the present invention can be prepared by a method comprising bringing into contact
Component (a)
Component (a) comprises one or more lignins.
In one embodiment of the method, component (a) comprises one or more kraft lignins, one or more soda lignins, one or more lignosulfonate lignins, one or more organosolv lignins, one or more lignins from biorefining processes of lignocellulosic feedstocks, or any mixture thereof.
In one embodiment, component (a) comprises one or more kraft lignins.
Component (b)
In one embodiment according to the present invention, component (b) comprises ammonia, one or more amino components, and/or any salts thereof. Without wanting to be bound by any particular theory, it is believed that replacement of the alkali hydroxides used in previously known oxidation processes of lignin by ammonia, one or more amino components, and/or any salts thereof, plays an important role in the improved properties of the oxidised lignins prepared according to the present invention.
It has surprisingly been found that the lignins oxidised by an oxidation agent in the presence of ammonia or amines contain significant amounts of nitrogen as a part of the structure of the oxidised lignins. Without wanting to be bound to any particular theory, it is believed that the improved fire resistance properties of the oxidised lignins when used in products where they are comprised in a binder and/or adhesive composition, said oxidised lignins prepared according to the present invention, are at least partly due to the nitrogen content of the structure of the oxidised lignins.
In one embodiment, component (b) comprises ammonia and/or any salt thereof.
Without wanting to be bound by any particular theory, it is believed that the improved stability properties of the derivatized lignins prepared according to the present invention are at least partly due to the fact that ammonia is a volatile compound and therefore evaporates from the final product or can be easily removed and reused. In contrast to that, it has proven difficult to remove residual amounts of the alkali hydroxides used in the previously known oxidation process.
Nevertheless, it can be advantageous in the present invention that component (b), besides ammonia, one or more amino components, and/or any salts thereof, also comprises a comparably small amount of an alkali and/or earth alkali metal hydroxide, such as sodium hydroxide and/or potassium hydroxide.
In the embodiments, in which component (b) comprises alkali and/or earth alkali metal hydroxides, such as sodium hydroxide and/or potassium hydroxide, as a component in addition to the ammonia, one or more amino components, and/or any salts thereof, the amount of the alkali and/or earth alkali metal hydroxides is usually small, such as 5 to 70 weight parts, such as 10 to 20 weight parts alkali and/or earth alkali metal hydroxide, based on ammonia.
Component (c)
In the present invention, component (c) comprises one or more oxidation agents.
In one embodiment, component (c) comprises one or more oxidation agents in form of hydrogen peroxide, organic or inorganic peroxides, molecular oxygen, ozone, air, halogen containing oxidation agents, or any mixture thereof.
In the initial steps of the oxidation, active radicals from the oxidant will typically abstract the proton from the phenolic group as that bond has the lowest dissociation energy in lignin. Due to lignin's potential to stabilize radicals through mesomerism multiple pathways open up to continue (but also terminate) the reaction and various intermediate and final products are obtained. The average molecular weight can both increase and decrease due to this complexity (and chosen conditions) and in their experiments, the inventors have typically seen moderate increase of average molecular weight of around 30%.
In one embodiment, component (c) comprises hydrogen peroxide.
Hydrogen peroxide is perhaps the most commonly employed oxidant due to combination of low price, good efficiency and relatively low environmental impact. When hydrogen peroxide is used without the presence of catalysts, alkaline conditions and temperature are important due to the following reactions leading to radical formation:
H2O2+OH−⇄HOO−+H2O
H2O2+OOH−⇄.OH+H2O+.O2−
It has been found that the derivatized lignins prepared with the method according to the present invention contain increased amounts of carboxylic acid groups as a result of the oxidation process. Without wanting to be bound by any particular theory, it is believed that the carboxylic acid group content of the oxidised lignins prepared in the process according to the present invention plays an important role in the desirable reactivity properties of the derivatized lignins prepared by the method according to the present invention.
Another advantage of the oxidation process is that the oxidised lignin is more hydrophilic. Higher hydrophilicity can enhance solubility in water and facilitate the adhesion to polar substrates such as mineral fibers.
Further Components
In one embodiment, the method according to the present invention comprises an adhesive and/or binder composition that comprises further components, in particular a component (d) in form of an oxidation catalyst, such as one or more transition metal catalyst, such as iron sulfate, such as manganese, palladium, selenium, tungsten containing catalysts.
Such oxidation catalysts can increase the rate of the reaction, thereby improving the properties of the oxidised lignins prepared by the method according to the present invention.
Mass Ratios of the Components
The person skilled in the art will use the components (a), (b) and (c) in relative amounts that the desired degree of oxidation of the lignins is achieved.
In one embodiment,
wherein the mass ratios of lignin, ammonia and hydrogen peroxide are such that the amount of ammonia is 0.01 to 0.5 weight parts, such as 0.1 to 0.3, such as 0.15 to 0.25 weight parts ammonia, based on the dry weight of lignin, and wherein the amount of hydrogen peroxide is 0.025 to 1.0 weight parts, such as 0.05 to 0.2 weight parts, such as 0.075 to 0.125 weight parts hydrogen peroxide, based on the dry weight of lignin.
Process
There is more than one possibility to bring the components (a), (b) and (c) in contact to achieve the desired oxidation reaction.
In one embodiment, the method comprises the steps of:
In one embodiment, the pH adjusting step is carried so that the resulting aqueous solution and/or dispersion is having a pH ≥9, such as ≥10, such as ≥10.5.
In one embodiment, the pH adjusting step is carried out so that the resulting aqueous solution and/or dispersion is having a pH in the range of 10.5 to 12.
In one embodiment, the pH adjusting step is carried out so that the temperature is allowed to raise to ≥25° C. and then controlled in the range of 25-50° C., such as 30-45° C., such as 35-40° C.
In one embodiment, during the oxidation step, the temperature is allowed to raise ≥35° C. and is then controlled in the range of 35-150° C., such as 40-90° C., such as 45-80° C.
In one embodiment, the oxidation step is carried out for a time of 1 second to 48 hours, such as 10 seconds to 36 hours, such as 1 minute to 24 hours such as 2-5 hours.
Method II to Prepare Oxidised Lignins
Oxidised lignins, which can be used as component for the binders and/or adhesives used in the present invention can be prepared by a method comprising bringing into contact
Component (a)
Component (a) comprises one or more lignins.
In one embodiment of the method, component (a) comprises one or more kraft lignins, one or more soda lignins, one or more lignosulfonate lignins, one or more organosolv lignins, one or more lignins from biorefining processess of lignocellulosic feedstocks, or any mixture thereof.
In one embodiment, component (a) comprises one or more kraft lignins.
Component (b)
In one embodiment, component (b) comprises ammonia, one or more amino components, and/or any salts thereof and/or an alkali and/or earth alkali metal hydroxide, such as sodium hydroxide and/or potassium hydroxide.
“Ammonia-oxidized lignins” is to be understood as a lignin that has been oxidized by an oxidation agent in the presence of ammonia. The term “ammonia-oxidized lignin” is abbreviated as AOL.
In one embodiment, component (b) comprises ammonia and/or any salt thereof.
Without wanting to be bound by any particular theory, it is believed that the improved stability properties of the derivatized lignins prepared according to the present invention with component (b) being ammonia and/or any salt thereof are at least partly due to the fact that ammonia is a volatile compound and therefore evaporates from the final product or can be easily removed and reused.
Nevertheless, it can be advantageous in this embodiment of the method that component (b), besides ammonia, one or more amino components, and/or any salts thereof, also comprises a comparably small amount of an alkali and/or earth alkali metal hydroxide, such as sodium hydroxide and/or potassium hydroxide.
In the embodiments, in which component (b) comprises alkali and/or earth alkali metal hydroxides, such as sodium hydroxide and/or potassium hydroxide, as a component in addition to the ammonia, one or more amino components, and/or any salts thereof, the amount of the alkali and/or earth alkali metal hydroxides is usually small, such as 5 to 70 weight parts, such as 10 to 20 weight parts alkali and/or earth alkali metal hydroxide, based on ammonia.
Component (c)
In the method according to the present invention, component (c) comprises one or more oxidation agents.
In one embodiment, component (c) comprises one or more oxidation agents in form of hydrogen peroxide, organic or inorganic peroxides, molecular oxygen, ozone, air, halogen containing oxidation agents, or any mixture thereof.
In the initial steps of the oxidation, active radicals from the oxidant will typically abstract the proton from the phenolic group as that bond has the lowest dissociation energy in lignin. Due to lignin's potential to stabilize radicals through mesomerism, multiple pathways open up to continue (but also terminate) the reaction and various intermediate and final products are obtained. The average molecular weight can both increase and decrease due to this complexity (and chosen conditions) and in their experiments, we have typically seen moderate increase of average molecular weight of around 30%.
In one embodiment, component (c) comprises hydrogen peroxide.
Hydrogen peroxide is perhaps the most commonly employed oxidant due to combination of low price, good efficiency and relatively low environmental impact. When hydrogen peroxide is used without the presence of catalysts, alkaline conditions and temperature are important due to the following reactions leading to radical formation:
H2O2+OH−⇄HOO−+H2O
H2O2+OOH−⇄.OH+H2O+.O2−
It has been found that the derivatized lignins prepared with the method according to the present invention contain increased amounts of carboxylic acid groups as a result of the oxidation process. Without wanting to be bound by any particular theory, it is believed that the carboxylic acid group content of the oxidized lignins prepared in the process plays an important role in the desirable reactivity properties of the derivatized lignins prepared by the method.
Another advantage of the oxidation process is that the oxidized lignin is more hydrophilic. Higher hydrophilicity can enhance solubility in water and facilitate the adhesion to polar substrates such as mineral fibres.
Component (d)
Component (d) comprises one or more plasticizers.
In one embodiment, component (d) comprises one or more plasticizers in form of polyols, such as carbohydrates, hydrogenated sugars, such as sorbitol, erythriol, glycerol, monoethylene glycol, polyethylene glycols, polyethylene glycol ethers, polyethers, phthalates and/or acids, such as adipic acid, vanillic acid, lactic acid and/or ferullic acid, acrylic polymers, polyvinyl alcohol, polyurethane dispersions, ethylene carbonate, propylene carbonate, lactones, lactams, lactides, acrylic based polymers with free carboxy groups and/or polyurethane dispersions with free carboxy groups, polyamides, amides such as carbamide/urea, or any mixtures thereof.
It has been found that the inclusion of component (d) in form of one or more plasticizers provides a decrease of the viscosity of the reaction mixture which allows a very efficient method to produce oxidised lignins.
In one embodiment, component (d) comprises one or more plasticizers in form of polyols, such as carbohydrates, hydrogenated sugars, such as sorbitol, erythriol, glycerol, monoethylene glycol, polyethylene glycols, polyvinyl alcohol, acrylic based polymers with free carboxy groups and/or polyurethane dispersions with free carboxy groups, polyamides, amides such as carbamide/urea, or any mixtures thereof.
In one embodiment, component (d) comprises one or more plasticizers selected from the group of polyethylene glycols, polyvinyl alcohol, urea or any mixtures thereof.
Further Components
In one embodiment, the method comprises further components, in particular a component (v) in form of an oxidation catalyst, such as one or more transition metal catalyst, such as iron sulfate, such as manganese, palladium, selenium, tungsten containing catalysts.
Such oxidation catalysts can increase the rate of the reaction, thereby improving the properties of the oxidized lignins prepared by the method.
Mass Ratios of the Components
The person skilled in the art will use the components (a), (b), (c), and (d) in relative amounts that the desired degree of oxidation of the lignins is achieved.
In one embodiment, the method is carried out such that the method comprises
For the purpose of the present invention, the “dry weight of lignin” is preferably defined as the weight of the lignin in the supplied form.
Process
There is more than one possibility to bring the components (a), (b), (c), and (d) in contact to achieve the desired oxidation reaction.
In one embodiment, the method comprises the steps of:
In one embodiment, the pH adjusting step is carried so that the resulting aqueous solution and/or dispersion is having a pH ≥9, such as ≥10, such as ≥10.5.
In one embodiment, the pH adjusting step is carried out so that the resulting aqueous solution and/or dispersion is having a pH in the range of 9.5 to 12.
In one embodiment, the pH adjusting step is carried out so that the temperature is allowed to raise to ≥25° C. and then controlled in the range of 25-50° C., such as 30-45° C., such as 35-40° C.
In one embodiment, during the oxidation step, the temperature is allowed to raise to ≥35° C. and is then controlled in the range of 35-150° C., such as 40-90° C., such as 45-80° C.
In one embodiment, the oxidation step is carried out for a time of 1 seconds to 24 hours, such as 1 minutes to 12 hours, such as 10 minutes to 8 hours, such as 5 minutes to 1 hour.
It has been found that the process allows to produce a high dry matter content of the reaction mixture and therefore a high throughput is possible in the process which allows the reaction product in form of the oxidised lignins to be used as a component in industrial mass production products such as mineral fibre products.
In one embodiment, the method is carried out such that the dry matter content of the reaction mixture is 20 to 80 wt. %, such as 40 to 70 wt. %.
In one embodiment, the method is carried out such that the viscosity of the oxidised lignin has a value of 100 cP to 100.000 cP, such as a value of 500 cP to 50.000 cP, such as a value of 1.000 cP to 25.000 cP.
For the purpose of the present invention, viscosity is dynamic viscosity and is defined as the resistance of the liquid/paste to a change in shape, or movement of neighbouring portions relative to one another. The viscosity is measured in centipoise (cP), which is the equivalent of 1 mPa s (milipascal second). Viscosity is measured at 20° C. using a viscometer. For the purpose of the present invention, the dynamic viscosity can be measured at 20° C. by a Cone Plate Wells Brookfield Viscometer.
In one embodiment, the method is carried out such that the method comprises a rotator-stator device.
In one embodiment, the method is carried out such that the method is performed as a continuous or semi-continuous process.
Apparatus for Performing the Method
The present disclosure also includes an apparatus for performing the method described above.
In one embodiment, the apparatus for performing the method comprises:
In one embodiment, the apparatus is constructed in such a way that the inlets for the premix of the components (a), (b) and (d) are to the rotor-stator device and the apparatus furthermore comprises a chamber,
said chamber having an inlet for component (c) and
said chamber having an outlet for an oxidised lignin.
A rotator-stator device is a device for processing materials comprising a stator configured as an inner cone provided with gear rings. The stator cooperates with a rotor having arms projecting from a hub. Each of these arms bears teeth meshing with the teeth of the gear rings of the stator. With each turn of the rotor, the material to be processed is transported farther outward by one stage, while being subjected to an intensive shear effect, mixing and redistribution. The rotor arm and the subjacent container chamber of the upright device allow for a permanent rearrangement of the material from the inside to the outside and provide for a multiple processing of dry and/or highly viscous matter so that the device is of excellent utility for the intensive mixing, kneading, fibrillating, disintegrating and similar processes important in industrial production. The upright arrangement of the housing facilitates the material's falling back from the periphery toward the center of the device.
In one embodiment, the rotator-stator device used in the method comprises a stator with gear rings and a rotor with teeth meshing with the teeth of the stator. In this embodiment, the rotator-stator device has the following features: Between arms of the rotor protrudes a guiding funnel that concentrates the material flow coming in from above to the central area of the container. The outer surface of the guiding funnel defines an annular gap throttling the material flow. At the rotor, a feed screw is provided that feeds towards the working region of the device. The guiding funnel retains the product in the active region of the device and the feed screw generates an increased material pressure in the center.
For more details of the rotator-stator device to be used in one embodiment of the method, reference is made to US 2003/0042344 A1, which is incorporated by reference.
In one embodiment, the method is carried out such that the method uses one rotator-stator device. In this embodiment, the mixing of the components and the reaction of the components is carried out in the same rotator-stator device.
In one embodiment, the method is carried out such that the method uses two or more rotator-stator devices, wherein at least one rotator-stator device is used for the mixing of the components and at least one rotator-stator device is used for reacting the components.
This process can be divided into two steps:
Typically, two different types of rotor-/stator machines are used:
In the open rotor-/stator system the highly concentrated (45 to 50 wt-%) mass of Lignin/water is prepared. The lignin powder is added slowly to the warm water (30 to 60 deg. C.) in which the correct amount of watery ammonia and/or alkali base have been added. This can be done in batch mode, or the materials are added intermittently/continuously creating a continuous flow of mass to the next step.
The created mass should be kept at a temperature of about 60 deg. to keep the viscosity as low as possible and hence the material pumpable. The hot mass of lignin/water at a pH of 9 to 12 is then transferred using a suitable pump, e.g. progressive cavity pump or another volumetric pump, to the oxidation step.
In on embodiment the oxidation is done in a closed rotor-/stator system in a continuous inline reaction. A watery solution of ammonia and/or alkali base is dosed with a dosing pump into the rotor-/stator chamber at the point of highest turbulence/shear. This ensures a rapid oxidation reaction. The oxidized material (AOL) leaves the inline-reactor and is collected in suitable tanks.
Reaction Product
It has surprisingly been found, that the oxidized lignins prepared have very desirable reactivity properties and at the same time display improved fire resistance properties when used in products where they are comprised in a binder and/or adhesive composition, and improved long term stability over previously known oxidized lignins.
The oxidised lignin also displays improved hydrophilicity.
An important parameter for the reactivity of the oxidized lignins prepared is the carboxylic acid group content of the oxidized lignins.
In one embodiment, the oxidized lignin prepared has a carboxylic acid group content of 0.05 to 10 mmol/g, such as 0.1 to 5 mmol/g, such as 0.20 to 2.0 mmol/g, such as 0.40 to 1.5 mmol/g, such as 0.45 to 1.0 mmol/g, based on the dry weight of component (a).
Another way to describe the carboxylic acid group content is by using average carboxylic acid group content per lignin macromolecule according to the following formula:
In one embodiment, the oxidized lignin prepared has an average carboxylic acid group content of more than 1.5 groups per macromolecule of component (a), such as more than 2 groups, such as more than 2.5 groups.
Method III to prepare oxidised lignins
Oxidised lignins, which can be used as a component for the binder and/or adhesive used in the present invention can be prepared by a method comprising bringing into contact
and allowing a mixing/oxidation step, wherein an oxidised mixture is produced, followed by an oxidation step, wherein the oxidised mixture is allowed to continue to react for a dwell time of dwell time of 1 second to 10 hours, such as 10 seconds to 6 hours, such as 30 seconds to 2 hours.
Components (a), (b), (c) and (d) are as defined above under Method II to prepare oxidised lignins.
In one embodiment of the invention, the process comprises a premixing step in which components are brought into contact with each other.
In the premixing step the following components can be brought into contact with each other:
In an embodiment of the invention, it is possible that the premixing step is carried out as a separate step and the mixing/oxidation step is carried out subsequently to the premixing step. In such an embodiment of the invention it is particularly advantageous to bring component (a) and component (b) and optionally component (d) into contact with each other in a premixing step. In a subsequent mixing/oxidation step, component (c) is then added to the premixture produced in the premixing step.
In another example of the invention, it is possible that the premixing step corresponds to the mixing/oxidation step. In this embodiment of the invention, the components, for example component (a), component (b) and component (c) are mixed and an oxidation process is started at the same time. It is possible that the subsequent dwell time is performed in the same device as that used to perform the mixing/oxidation step. Such an implementation of the invention is particularly advantageous if component (c) is air.
It has been found out that by allowing a mixing/oxidation step followed by an oxidation step, in which the reaction mixture is preferably not continued to be mixed, the oxidation rate can be controlled in a very efficient manner. At the same time, the costs for performing the method are reduced because the oxidation step subsequent to the mixing/oxidation step requires less complex equipment.
Another advantage is that oxidized lignin, which is produced is particularly stable. Another surprising advantage is that the oxidized lignin produced is very well adjustable in terms of viscosity. Another surprising advantage is that the concentration of the oxidized lignin can be very high.
In one embodiment, the dwell time is so chosen that the oxidation reaction is brought to the desired degree of completion, preferably to full completion.
System I for Performing the Method III
In one embodiment, the system for performing the method comprises:
In one embodiment, the system comprises one or more inlets for component (c) and/or component (d).
In one embodiment, the system comprises a premixing device.
The premixing device can comprise one or more inlets for water and/or component (a) and/or component (b) and/or component (c) and/or component (d).
In one embodiment, the premixing device comprises inlets for water and component (a) and component (b).
It is possible that, in a premixing step, component (c) is also mixed with the three mentioned ingredients (water, component (a) and component (b)). It is then possible that the premixing device has a further inlet for component (c). If component (c) is air, it is possible that the premixing device is formed by an open mixing vessel, so that in this case component (c) is already brought into contact with the other components (water, component (a) and component (b)) through the opening of the vessel. Also in this embodiment of the invention, it is possible that the premixing device optionally comprises an inlet for component (d).
In one embodiment, the system is constructed in such a way that
the inlets for components (a), (b) and (d) are inlets of a premixing device, in particular of an open rotor-stator device,
whereby the system furthermore comprises an additional rotor-stator device,
said additional rotor-stator device having an inlet for component (c) and said additional rotor-stator device having an outlet for an oxidized lignin.
It is possible that the premixing step and the mixing/oxidizing step are carried out simultaneously. In this case, the premixing device and the mixing/oxidizing device are a single device, i. e. a rotor-stator device.
In one embodiment, one rotator-stator device used in the method according to the present invention comprises a stator with gear rings and a rotor with teeth meshing with the teeth of the stator. In this embodiment, the rotator-stator device has the following features: Between arms of the rotor protrudes a guiding funnel that concentrates the material flow coming in from above to the central area of the container. The outer surface of the guiding funnel defines an annular gap throttling the material flow. At the rotor, a feed screw is provided that feeds towards the working region of the device. The guiding funnel retains the product in the active region of the device and the feed screw generates an increased material pressure in the center.
System II for Performing the Method III
In one embodiment, the system for performing the method comprises:
In one embodiment, the system comprises additional one or more inlets for component (c) and/or component (d).
In one embodiment, the system comprises a premixing device.
The premixing device can comprise one or more inlets for water and/or component (a) and/or component (b) and/or component (c) and/or component (d).
In one embodiment, the premixing device comprises inlets for water and component (a) and component (b).
It is possible that, in a premixing step, component (c) is also mixed with the three mentioned ingredients (water, component (a) and component (b)). It is then possible that the premixing device has a further inlet for component (c). If component (c) is air, it is possible that the premixing device is formed by an open mixing vessel, so that in this case component (c) is already brought into contact with the other components (water, component (a) and component (b)) through the opening of the vessel. Also in this embodiment of the invention, it is possible that the premixing device optionally comprises an inlet for component (d).
In one embodiment, the system is constructed in such a way that the inlets for components (a), (b) and (d) are inlets of an open rotor-stator device,
whereby the system furthermore comprises a mixer/heat-exchanger, having an inlet for component (c) and an outlet for an oxidized lignin.
It is possible that the premixing step and the mixing/oxidizing step are carried out simultaneously. In this case, the premixing device and the mixing/oxidizing device are a single device.
In one embodiment, one rotator-stator device used in the method according to the present invention comprises a stator with gear rings and a rotor with teeth meshing with the teeth of the stator. In this embodiment, the rotator-stator device has the following features: Between arms of the rotor protrudes a guiding funnel that concentrates the material flow coming in from above to the central area of the container. The outer surface of the guiding funnel defines an annular gap throttling the material flow. At the rotor, a feed screw is provided that feeds towards the working region of the device. The guiding funnel retains the product in the active region of the device and the feed screw generates an increased material pressure in the center.
Of course other devices can also be used as premixing devices. Furthermore, it is possible that the premixing step is carried out in the mixing and oxidizing apparatus.
In one embodiment, the mixing and oxidizing apparatus is a static mixer. A static mixer is a device for the continuous mixing of fluid materials, without moving components. One design of static mixer is the plate-type mixer and another common device type consists of mixer elements contained in a cylindrical (tube) or squared housing.
In one embodiment, the mixer/heat-exchanger is constructed as multitube heat exchanger with mixing elements. The mixing element are preferably fixed installations through which the mixture has to flow, whereby mixing is carried out as a result of the flowing through. The mixer/heat-exchanger can be constructed as a plug flow reactor.
The amounts of ingredients used according to the example IA are provided in table IA 1.1 and IA 1.2.
Although kraft lignin is soluble in water at relatively high pH, it is known that at certain weight percentage the viscosity of the solution will strongly increase. It is typically believed that the reason for the viscosity increase lies in a combination of strong hydrogen bonding and interactions of π-electrons of numerous aromatic rings present in lignin. For kraft lignin an abrupt increase in viscosity around 21-22 wt.-% in water was observed and 19 wt.-% of kraft lignin were used in the example presented.
Ammonia aqueous solution was used as base in the pH adjusting step. The amount was fixed at 4 wt.-% based on the total reaction weight. The pH after the pH adjusting step and at the beginning of oxidation was 10.7.
Table IA2 shows the results of CHNS elemental analysis before and after oxidation of kraft lignin. Before the analysis, the samples were heat treated at 160° C. to remove adsorbed ammonia. The analysis showed that a certain amount of nitrogen became a part of the structure of the oxidised lignin during the oxidation process.
During testing in batch experiments, it was determined that it is beneficial for the oxidation to add the entire amount of hydrogen peroxide during small time interval contrary to adding the peroxide in small portions over prolonged time period. In the present example 2.0 wt.-% of H2O2 based on the total reaction weight was used.
The oxidation is an exothermic reaction and increase in temperature is noted upon addition of peroxide. In this example, temperature was kept at 60° C. during three hours of reaction.
After the oxidation, the amount of lignin functional groups per gram of sample increased as determined by 31P NMR and aqueous titration. Sample preparation for 31P NMR was performed by using 2-chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane (TMDP) as phosphitylation reagent and cholesterol as internal standard. NMR spectra of kraft lignin before and after oxidation were made and the results are summarized in table IA3.
The change in COOH groups was determined by aqueous titration and utilization of the following formula:
Where V2s and V1s are endpoint volumes of a sample while V2b and Vib are the volume for the blank. Cacid is 0.1M HCl in this case and ms is the weight of the sample. The values obtained from aqueous titration before and after oxidation are shown in table IA4.
The average COOH functionality can also be quantified by a saponification value which represents the number of mg of KOH required to saponify 1 g lignin. Such a method can be found in AOCS Official Method Cd 3-25.
Average molecular weight was also determined before and after oxidation with a PSS PolarSil column (9:1 (v/v) dimethyl sulphoxide/water eluent with 0.05 M LiBr) and UV detector at 280 nm. Combination of COOH concentration and average molecular weight also allowed calculating average carboxylic acid group content per lignin macromolecule and these results are shown in table IA5.
Lignin oxidation with hydrogen peroxide is an exothermic process and even in lab-scale significant temperature increases were seen upon addition of peroxide. This is a natural concern when scaling up chemical processes since the amount of heat produced is related to dimensions in the 3rd power (volume) whereas cooling normally only increase with dimension squared (area). In addition, due to the high viscosity of the adhesive intermediates process equipment has to be carefully selected or designed. Thus, the scale up was carefully engineered and performed in several steps.
The first scale up step was done from 1 L (lab scale) to 9 L using a professional mixer in stainless steel with very efficient mechanical mixing The scale-up resulted only in a slightly higher end temperature than obtained in lab scale, which was attributed to efficient air cooling of the reactor and slow addition of hydrogen peroxide
The next scale up step was done in a closed 200 L reactor with efficient water jacket and an efficient propeller stirrer. The scale was this time 180 L and hydrogen peroxide was added in two steps with appr. 30 minute separation. This up-scaling went relatively well, though quite some foaming was an issue partly due to the high degree reactor filling. To control the foaming a small amount of food grade defoamer was sprayed on to the foam. Most importantly the temperature controllable and end temperatures below 70° C. were obtained using external water-cooling.
The pilot scale reactions were performed in an 800 L reactor with a water cooling jacket and a twin blade propeller stirring. 158 kg of lignin (UPM LignoBoost™ BioPiva 100) with a dry-matter content of 67 wt.-% was de-lumped and suspended in 224 kg of water and stirred to form a homogenous suspension. With continued stirring 103 kg of 25% ammonia in water was pumped into the reactor and stirred another 2 hours to from a dark viscous solution of lignin.
To the stirred lignin solution 140 kg of 7.5 wt.-% at 20-25° C. hydrogen peroxide was added over 15 minutes. Temperature and foam level was carefully monitored during and after the addition of hydrogen peroxide and cooling water was added to the cooling jacket in order to maintain an acceptable foam level and a temperature rise less than 4° C. per minute as well as a final temperature below 70° C. After the temperature increase had stopped, cooling was turned off and the product mixture was stirred for another 2 hours before transferring to transport container.
Based on the scale up runs it could be concluded that even though the reactions are exothermic a large part of the reaction heat is actually balanced out by the heat capacity of the water going from room temperature to about 60° C., and only the last part has to be removed by cooling. It should be noted that due to this and due to the short reaction time this process would be ideal for a scale up and process intensification using continuous reactors such as in-line mixers, tubular reactors or CSTR type reactors. This would ensure good temperature control and a more well-defined reaction process.
Tests of the scale up batches indicated the produced oxidised lignin had properties in accordance to the batches produced in the lab.
In the following examples, several oxidised lignins were prepared.
The following properties were determined for the oxidised lignins:
Component Solids Content:
The content of each of the components in a given oxidised lignin solution is based on the anhydrous mass of the components or as stated below.
Kraft lignin was supplier by UPM as BioPiva100™ as dry powder. NH4OH 25% was supplied by Sigma-Aldrich and used in supplied form. H2O2, 30% (Cas no 7722-84-1) was supplied by Sigma-Aldrich and used in supplied form or by dilution with water. PEG 200 was supplied by Sigma-Aldrich and were assumed anhydrous for simplicity and used as such. PVA (Mw 89.000-98.000, Mw 85.000-124.000, Mw 130.000, Mw 146.000-186.000) (Cas no 9002-89-5) were supplied by Sigma-Aldrich and were assumed anhydrous for simplicity and used as such. Urea (Cas no 57-13-6) was supplied by Sigma-Aldrich and used in supplied form or diluted with water. Glycerol (Cas no 56-81-5) was supplied by Sigma-Aldrich and was assumed anhydrous for simplicity and used as such.
Oxidised Lignin Solids
The content of the oxidised lignin after heating to 200° C. for 1 h is termed “Dry solid matter” and stated as a percentage of remaining weight after the heating.
Disc-shaped stone wool samples (diameter: 5 cm; height 1 cm) were cut out of stone wool and heat-treated at 580° C. for at least 30 minutes to remove all organics. The solids of the binder mixture were measured by distributing a sample of the binder mixture (approx. 2 g) onto a heat treated stone wool disc in a tin foil container. The weight of the tin foil container containing the stone wool disc was weighed before and directly after addition of the binder mixture. Two such binder mixture loaded stone wool discs in tin foil containers were produced and they were then heated at 200° C. for 1 hour. After cooling and storing at room temperature for 10 minutes, the samples were weighed and the dry solids matter was calculated as an average of the two results.
COOH Group Content
The change in COOH group content was also determined by aqueous titration and utilization of the following formula:
Where V2s and V1s are endpoint volumes of a sample while V2b and V1b are the volume for a blank sample. Cacid is 0.1M HCl in this case and ms,g is the weight of the sample.
Method of producing an oxidised lignin:
Oxidised Lignin Compositions
In the following, the entry numbers of the oxidised lignin example correspond to the entry numbers used in Table II.
71.0 g lignin UPM Biopiva 100 was dissolved in 149.0 g water at 20° C. and added 13.3 g 25% NH4OH and stirred for 1 h by magnetic stirrer, where after 16.8 g H2O2 30% was added slowly during agitation. The temperature was increased to 60° C. in the water bath. After 1 h of oxidation, the water bath was cooled and hence the reaction was stopped. The resulting material was analysed for COOH, dry solid matter, pH, viscosity and density.
71.0 g lignin UPM Biopiva 100 was dissolved in 88.8 g water at 20° C. and added 13.3 g 25% NH4OH and stirred for 1 h by magnetic stirrer. PEG 200, 22.8 g was added and stirred for 10 min, where after 16.7 g H2O2 30% was added slowly during agitation. The temperature was increased to 60° C. in the water bath. After 1 h of oxidation, the water bath was cooled and hence the reaction was stopped. The resulting material was analysed for COOH, dry solid matter, pH, viscosity and density.
71.0 g lignin UPM Biopiva 100 was dissolved in 57.1 g water at 20° C. and added 13.3 g 25% NH4OH and stirred for 1 h by mechanical stirrer, where after 16.6 g H2O2 30% was added slowly during agitation. The temperature was increased to 60° C. in the water bath. After 1 h of oxidation, the water bath was cooled and hence the reaction was stopped. The resulting material was analysed for COOH, dry solid matter, pH, viscosity and density.
71.0 g lignin UPM Biopiva 100 was dissolved in 57.1 water at 20° C. and added 13.3 g 25% NH4OH and stirred for 1 h by mechanical stirrer. PEG 200, 19.0 g was added and stirred for 10 min, where after 16.6 g H2O2 30% was added slowly during agitation. The temperature was increased to 60° C. in the water bath. After 1 h of oxidation, the water bath was cooled and hence the reaction was stopped. The resulting material was analysed for COOH, dry solid matter, pH, viscosity and density.
8.5 l hot water (50° C.) and 1.9 l NH4OH (24.7%) was mixed, where after 9.0 kg lignin (UPM biopiva 100) was added slowly over 10 minutes at high agitation (660 rpm, 44 Hz).
The temperature increased by high shear forces. After 30 minutes, 4 l of hot water was added, and the material was stirred for another 15 minutes before adding the remaining portion of hot water (5 l). Samples were taken out for analyses of un-dissolved lignin by use of a Hegman Scale and pH measurements.
This premix was then transferred to a rotor-stator device and a reaction device where the oxidation was made by use of H2O2 (17.5 vol %). The reaction device used in this case has at least partially a reaction tube and a reaction vessel. Dosage of the premixture was 150 l/h and the H2O2 was dosed at 18 l/h.
In the present case, a Cavitron CD1000 rotor-stator device was used to carry out the mixing/oxidation step. The rotor-stator device was run at 250 Hz (55 m/s circumferential speed) with a counter pressure at 2 bar. The dwell time in the reaction tube was 3.2 minutes and in the reaction vessel 2 hours.
Temperature of the premixture was 62° C., and the oxidation step increased the temperature to 70° C.
The final product was analysed for the COOH group content, dry solid matter, pH, viscosity and remaining H2O2.
484 l hot water (70° C.) and 47.0 l NH4OH (24.7%) was mixed, where after 224.0 kg lignin (UPM biopiva 100) was added slowly over 15 minutes at high agitation.
Samples were taken out for analyses of un-dissolved lignin by use of a Hegman Scale and pH measurements.
This premixture was then transferred to a static mixer and a mixer/heat-exchanger, where the oxidation was made by use of H2O2 (35 vol %). Dosage of the premixture was 600 l/h and the H2O2 was dosed at 17.2 l/h. The dwell time in the mixer/heat-exchanger was 20 minutes.
The temperature of the mixture increased during the oxidation step up to 95° C.
The final product was analysed for the COOH group content, dry solid matter, pH, viscosity and remaining H2O2.
A binder was made based on this AOL: 49.3 g AOL (19.0% solids), 0.8 g primid XL552 (100% solids) and 2.4 g PEG200 (100% solids) were mixed with 0.8 g water to yield 19% solids; and then used for test of mechanical properties in bar tests.
Primid XL 552 has the structure:
Bar Tests
The mechanical strength of the binders was tested in a bar test. For each binder, 16 bars were manufactured from a mixture of the binder and stone wool shots from the stone wool spinning production.
A sample of this binder solution having 15% dry solid matter (16.0 g) was mixed well with shots (80.0 g). The resulting mixture was then filled into four slots in a heat resistant silicone form for making small bars (4×5 slots per form; slot top dimension: length=5.6 cm, width=2.5 cm; slot bottom dimension: length=5.3 cm, width=2.2 cm; slot height=1.1 cm). The mixtures placed in the slots were then pressed with a suitably sized flat metal bar to generate even bar surfaces. 16 bars from each binder were made in this fashion. The resulting bars were then cured at 200° C. The curing time was 1 h. After cooling to room temperature, the bars were carefully taken out of the containers. Five of the bars were aged in a water bath at 80° C. for 3 h.
After drying for 1-2 days, the aged bars as well as five unaged bars were broken in a 3 point bending test (test speed: 10.0 mm/min, rupture level: 50%; nominal strength: 30 N/mm2; support distance: 40 mm; max deflection 20 mm; nominal e-module 10000 N/mm2) on a Bent Tram machine to investigate their mechanical strengths. The bars were placed with the “top face” up (i.e. the face with the dimensions length=5.6 cm, width=2.5 cm) in the machine.
The acoustic product 1 of
As shown in
The secondary web 15A is led by conveyor 14 to a pair of conveyors 16 for applying vertical compression to the secondary web from its natural depth, at point A, to its compressed depth at point B. The secondary web at point A has a weight per unit area of W.
The compressed secondary web 15B is transferred from point C to point D by conveyors 17. Conveyors 16 and 17 usually all travel at substantially the same speed so as to establish a constant speed of travel of the secondary web from the vertical compression stage AB to point D.
The web is then transported between a pair of conveyors 18 which extend between points E and F. Conveyors 18 travel much more slowly than conveyors 16 and 17 so that longitudinal compression is applied between points D and F.
Although items 14, 16, 17 and 18 are shown for clarity as conveyor belts spaced apart from one another in the X direction, in practice they are normally very close to one another in the X direction.
Points D and E are preferably sufficiently close to one another or are interconnected by bands, to prevent the secondary web escaping from the desired line of travel. As a result, substantial longitudinal compression has occurred when the web emerges at point F. Restraining guides can be provided, if necessary, between D and E to prevent break out of the web if D and E are not close together.
The resultant longitudinally compressed batt 15C is then carried along conveyor 19 between points G and H at a higher speed than by the conveyors 18. This applies some longitudinal decompression or extension to the longitudinally compressed web and prevents the web breaking out from the desired line of travel and, for instance, buckling upwards due to internal forces within the web. If desired or necessary, a conveyor or other guide (not shown) may rest on the upper surface of the batt (above conveyor 19) so as to ensure that there is no breakout.
When vertical compression is to be applied to the longitudinally compressed web, this is done by passing the web, after it leaves point H, between conveyors 20, which converge so as to compress the web vertically as it travels between the conveyors and points I and J.
The resultant uncured batt 15D has first and second major faces 3A and 3B. A glass fibre veil 22 from rolls 23 is then contacted with faces 3A and 3B. The glass veil 22 has been provided with adhesive as required by the invention, to bond the veil to the batt. The resultant assembly then passes through a curing oven 25 where just sufficient pressure is applied by conveyors 24 to hold the sandwich of two layers of veil 22 and the batt 15D together while curing of the binder for the MMVF and the adhesive occurs.
The bonded batt 15E emerges from the curing oven and is sliced centrally by a band saw 26 or other suitable saw into two cut batts 27 each having an outer face 3 carrying the veil 22 and an inner cut face 2. Each cut batt 27 is supported on a conveyor 28 and travels beneath an abrading belt 29 where it is abraded or ground to a flat configuration, and a further facing 22 is applied from roll 30 and bonded to the abraded surface 2. The abraded or ground cut batt 27 is then divided by appropriate cutters 31 into individual batts 1 which are carried away on conveyor 32.
Paint may be applied to either or both faces.
Throughout this description, conveyor bands or belts are illustrated but any or all of the conveyors can be replaced by any suitable means of causing the relevant transport with acceleration, deceleration or vertical compression as required. For instance roller trains may be used instead of belts.
Testing was undertaken to determine the peel strength of a glass veil that had been applied to an MMVF acoustic element using an adhesive as required by claim 1. The acoustic element had the properties defined in Table 1 below:
Determination of LOI (binder content) is performed according to DS/EN13820:2003 Determination of organic content, where the binder content is defined as the quantity of organic material burnt away at a given temperature, here using (590±20° C.) for at least 10 min or more until constant mass. Determination of ignition loss consists of at least 10 g wool corresponding to 8-20 cut-outs (minimum 8 cut-outs) performed evenly distributed over the test specimen using a cork borer ensuring to comprise an entire product thickness.
Peel strength is determined as follows:
Veil adhesion measurement is made using a 5 cm wide metal punch and a small manual weight with a hook [g].
Measuring Method:
Place the product on an even flat surface,
Using a cutter, cut the surface of the veil for a length of approx. 50 cm,
Attach the torn end to the grip of a dynamometer and pull.
At the same time the maximum and minimum scale deflection should be read.
Results
It is generally considered that a peel strength at least 100 g is necessary for commercial production. It can be seen that the products of the invention comfortably meet that standard.
Details of Binder Composition:
3267 kg of water is charged in 6000 l reactor followed by 287 kg of ammonia water (24.7%). Then 1531 kg of Lignin UPM BioPiva 100 is slowly added over a period of 30 min to 45 min. The mixture is heated to 40° C. and kept at that temperature for 1 hour. After 1 hour a check is made on insolubilized lignin. This can be made by checking the solution on a glass plate or a Hegman gauge. Insolubilized lignin is seen as small particles in the brown binder. During the dissolution step the lignin solution will change color from brown to shiny black.
After the lignin is completely dissolved, 1 liter of a foam dampening agent (Skumdmper 11-10 from NCA-Verodan) is added. Temperature of the batch is maintained at 40° C.
Then addition of 307.5 kg 35% hydrogen peroxide is started. The hydrogen peroxide is dosed at a rate of 200-300 liter/hour. First half of the hydrogen peroxide is added at a rate of 200 l/h where after the dosage rate is increased to 300 liter/hour.
During the addition of hydrogen peroxide the temperature in the reaction mixture is controlled by heating or cooling in such a way that a final reaction temperature of 65° C. is reached.
After 15 min reaction at 65° C. the reaction mixture is cooled to a temperature below 50° C. Hereby a resin is obtained having a COOH value of 1.2 mmol/g solids.
From this ammonia oxidized lignin (AOL) resin, a binder was formulated by addition of 270 kg polyethylene glycol 200 and 281 kg of a 31% solution of a 3-hydroxyalkylamide (Primid XL-552) in water.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2020/059645 | 4/3/2020 | WO |
