Patent Application
20130324755
This invention concerns novel silanes. It further concerns novel polyorganosiloxanes and their use.
It is known to use polyorganosiloxanes for treating textile fabrics. Textiles can thereby be endowed with desired properties such as, for example, a soft hand and water-repellent properties.
It is further known to use monomeric silanes for preparing polyorganosiloxanes. Polysiloxanes containing acrylato groups are also known, for example from DE-A 102 19 734, EP-A 564 253, U.S. Pat. No. 4,528,081 and EP-A 373 659 and U.S. Pat. No. 6,211,322 B1. The references cited above also reveal that it is known to cure silicon compounds which contain acrylate units by free-radical polymerization. This free-radical polymerization may be effected by UV irradiation for example.
According to the prior art, polyorganosiloxanes having functional groups, for example acrylate groups, in side chains are obtainable by condensation or equilibration reactions. In these reactions, polyorganosiloxanes are reacted with monomeric silanes bearing reactive groups, the starting compounds used in the case of condensation reactions being polysiloxanes having terminal OH groups.
The silanes known from the prior art and the polyorganosiloxanes prepared from these prior art silanes have disadvantages, for example with regard to properties of the textiles finished therewith and the durability of these properties, as well as advantages. Furthermore, some known silanes and some known polysiloxanes are costly and inconvenient to prepare because of the choice of desired substituents.
It is an object of the present invention to provide silanes useful for incorporation into a given polyorganosiloxane chain and also polyorganosiloxanes useful in the treatment of textile fabrics composed of fiber materials in that they endow the fiber materials in the treatment with advantageous properties coupled with high durability to laundering operations.
We have found that this object is achieved for the first part by monomeric silanes of the general structural formula (XXXV)
wherein all R radicals independently represent phenyl or a branched or unbranched alkyl radical of 1 to 18 carbon atoms, preferably represent —CH3 or —CH2—CH3, wherein R1 represents R or OR or
wherein R20 represents a radical of one of the formulae (XXXVI) to (XLI) or one of the formulae (XLI a) to (XLI h)
wherein each of the R21 radicals either has the abovementioned meaning or represents a radical of the formula
or wherein R22 represents a radical of formula
wherein R23 represents a linear or branched alkyl radical of 8 to 18 carbon atoms,
where, in the formula (XXXVIII), R23 either has the abovementioned meaning or represents H or —CH3,
wherein one of the R3 radicals represents H and the other represents CH3, k and I are each from 1 to 31, preferably from 1 to 22, and the sum total of k+I is in the range from 3 to 45, preferably from 3 to 25, and where the individual units
may be distributed across the chain in any desired manner,
wherein each of the two R24 radicals independently represents a linear or branched alkyl radical of 1 to 6 carbon atoms,
where, in the formula (XL), R21 either has the abovementioned meaning or represents a divalent radical of the formula
wherein x is from 0 to 1500,
where the silane of the formula (XXXV) may also be a product formed by reaction of a silane of the formula
with a polyether amine or a product T, in which case the polyether amine is preferably a product of the formula
or of the formula
or of the formula
or of the formula
H2N—CH(CH3)—CH2—O—CH(CH3)—CH2—w—O—CH2—C[—CH2—OCH2—CH(CH3)—Ow—CH2—CH(CH3)—NH2]3
where w is from 2 to 8,
or where the product T is a 3-(2-aminoethyl)aminopropylmethylsilsesquioxane with terminal —OCH3 group.
The stated object is further achieved by providing polyorganosiloxanes obtainable by reaction of a polyorganosiloxane of the formula (VIII) or of a mixture of polyorganosiloxanes of the formula (VIII)
where R6 represents R or a radical of the formula (IX)
where x is from 0 to 1500, preferably from 10 to 1500,
wherein R, R20 and R1 have the meanings mentioned in claim 1 and where R2 represents vinyl or a linear or branched alkyl radical of 1 to 18 carbon atoms which may be substituted by one or more, optionally quaternized, amino groups, amido groups, mercapto groups, epoxy groups, phosphono groups, hydroxyl groups or fluorine atoms,
wherein both the R5 radicals represent
or one of the R5 radicals represents H and the other represents
where p is 0, 1 or 2,
where, in the formulae (Ill), (IV) and (V), R4 in each occurrence represents a divalent linear or branched hydrocarbyl radical of 1 to 4 carbon atoms,
wherein R8 represents H or CH3 or C2H5 or —CH2CH2—OH and R9 represents H or —COOR8
or wherein R2 represents a radical of one of the formulae (XI), (XIa) or (XII) to (XX) or of the formula (XVIIIa) or of the formula (XXa) or of the formula (XXb) or of the formula (XXc),
where p represents 0, 1 or 2,
wherein A represents a direct bond or a divalent radical of the formula
where, in the case of the formula (XVII), the values of u, v and s are so chosen that the equivalent weight of this R2 radical is in the range from 100 to 5000, where one or two of u, v and s may also assume the value of 0 and where the individual units
can be distributed across the chain in any desired manner,
where M is selected from
wherein RF represents a perfluoroalkyl radical of 5 to 23 carbon atoms,
wherein R13 represents H or —CH(CH3)2 or —CH2—CH(CH3)2,
wherein K represents a linear or branched alkylene radical of 2 to 18 carbon atoms,
wherein f represents 0 or 1,
—CH2—d—
wherein d is from 1 to 6,
wherein z is from 8 to 500, preferably from 8 to 20,
The silanes of the formula (XXXV) according to the present invention make it possible to prepare novel polyorganosiloxanes which have specific, hitherto unknown structures. By selecting the silanes in an appropriate manner it is thereby possible to obtain polyorganosiloxanes having specific structural units, including polyorganosiloxanes in which polymer units are bonded together intramolecularly that would not be miscible with each other as intermolecular polymers. On the other hand, the poiyorganosiloxanes obtainable by reaction of polyorganosiloxanes of the formula (VIII) with silanes of the formula (I) also have advantageous properties when used in the treatment of textile fabrics composed of fiber materials.
The polyorganosiloxanes according to the present invention are very useful in the treatment of fiber materials irrespectively of whether they were prepared using silanes of the formula (I) or of the formula (XXXV) or a mixture of such silanes. They are also useful for coating operations, for example coating of textile fabrics. Similarly, glass fiber fabrics can be treated with these novel polysiloxanes. The dimeric/oligomeric silanes according to the present invention or the novel polysiloxanes according to the present invention can be applied to the textile fabrics or to the glass fiber fabrics by following known methods, for example by coating or padding (bath impregnation).
The novel polyorganosiloxanes according to the present invention which are obtainable by reacting the silanes of the formula (XXXV) according to the present invention or the silanes of the formula (I) with polyorganosiloxanes of the formula (VIII) are useful, inter alia, in the treatment of textile fabrics composed of fiber materials. Useful fiber materials include wovens, knits or nonwovens composed of natural or synthetic fibers, as for example of cotton, polyester, polypropylene or polyamide or mixtures thereof. In the case of polypropylene a plasma pretreatment can be carried out first. Application can be for example by means of padder processes or spraying. Application takes the form of a coating, if appropriate. The novel polyorganosiloxanes according to the present invention are also useful for the curtain-coating methods known to a person skilled in the art. When the R2 radical in the silane of the formula (I) or the R20 radical in the silane of the formula (XXXV) includes (meth)acrylate units, the curtain-coating operation may be followed by a curing operation in which the acrylate units are polymerized. This can be effected in a known manner by means of electron beams or UV radiation. Known photoinitiators such as products of the IRGACURE® range (Ciba Spezialitätenchemie, Basel, Switzerland) can be used for this, or products as mentioned in U.S. Pat. No. 6,211,308 B1 (column 10).
The novel polysiloxanes according to the present invention are also useful for finishing precursor fibers, for example acrylic fibers, in the manufacture of carbon fibers. They can further be used for modifying epoxy resins for a variety of applications.
The reaction of the silanes of the formula (I) or of the formula (XXXV) or of mixtures of these silanes with organosiloxanes of the formula (VIII) leads to novel polyorganosiloxanes. It was found that, surprisingly, these novel polyorganosiloxanes can have excellent reactivity, particularly in curing operations, and also can bring about improved effects on the part of fiber materials treated therewith, for example an enhanced oil-repellent effect. Advantages also result particularly when the functional groups present in the silanes (R2 and R20 respectively) contain acrylate radicals, see for example the formulae (III), (IV), (V) and (XVI). These acrylate radicals are then also present in the products obtained after reaction with organosiloxanes, and can be cured/polymerized, by UV radiation for example. This renders these novel polysiloxanes useful for the coating of textiles.
To prepare the polyorganosiloxanes according to the present invention, a silane of the formula (I) or of the formula (XXXV) or a mixture of such silanes is reacted with a polyorganosiloxane of the formula (VIII) or a mixture of such polyorganosiloxanes.
The polyorganosiloxane of the formula (VIII) may contain substituents in that, for example, R7 may represent R or OH or OR, in which case R has the meaning mentioned above and in claim 1, and R6 may represent R or a radical of the formula (IX).
Preferably, however, an unsubstituted polydialkylsiloxane, in particular a polydimethylsiloxane, is used for the reaction with silane (mixture).
The compounds of the formula (VIII) are hereinafter referred to as “polyorganosiloxanes” for simplicity, even though they are oligoorganosiloxanes when x has low values.
In formula (VIII)
The polyorganosiloxanes of the formula (VIII) which are used for this reaction contain at least two R7 radicals at the ends of the polysiloxane chain. Each R7 radical represents an R radical of the abovementioned meaning or represents a hydroxyl group or an —OR group, where R has the abovementioned meaning.
The polyorganosiloxanes used for this reaction may contain further functional groups in side chains, for example amino groups, even though this possibility is not reflected in the formula (VIII). In the event of such a possibility, one or more of the R6 radicals present represent(s) a radical comprising such a functional group.
Furthermore, low molecular weight oligodialkylsiloxanes, for example, can be used as further organosiloxanes in addition to polyorganosiloxanes of the formula (VIII).
When the silanes are reacted with polyorganosiloxanes of the formula (VIII) in which none of the R7 radicals represents OH, the reaction is carried out under the conditions of equilibration which are known from silicone chemistry and the silane structure becomes incorporated into the polysiloxane chain.
When, however, one or more of the R7 radicals present is an OH group, condensation reactions can take place between these OH groups and OR groups of the silane to eliminate alcohol ROH.
The conditions required for the equilibration and condensation reactions are known from the silicone literature. The reactions leading to the novel polyorganosiloxanes are preferably carried out in the presence of a catalyst or catalyst mixture and at a temperature in the range from 80 to 130° C. Lewis acids or dilute mineral acids may make suitable catalysts, where appropriate. However, preference is given to basic catalysts such as alkali metal hydroxides or alkoxides, or to the catalysts mentioned hereinbelow.
As already mentioned, polyorganosiloxanes of the formula (VIII) can be used in which two of the R7 radicals present each represent an OH group.
The hydroxyl-containing polyorganosiloxanes mentioned, hereinafter referred to as “α,ω-dihydroxypolyorganosiloxanes” can thus be reacted with silanes of the formula (XXXV) according to the present invention or with silanes of the formula (I). This reaction, as will be more particularly described hereinbelow, can be carried out such that either an equilibration takes place, in which case structural units of the silanes are incorporated into the chain of the α,ω-dihydroxypolyorganosiloxane, or that condensation reactions take place between terminal OH groups on the polysiloxane and the silanes. The second version, i.e., condensation, is preferable in this case if only because it can be carried out under more gentle conditions, i.e., at lower temperature, than the equilibration reaction. The reactions mentioned give rise to polyorganosiloxanes which contain the R2 or R20 units from the silanes.
Preferably, however, unsubstituted polydimethylsiloxanes are used and not OH-containing polysiloxanes of the formula (VIII).
There are in principle 2 conceivable forms of reaction mechanisms, namely one which leads to equilibration reactions and one which leads to condensation reactions. The condensation reaction takes place at lower temperatures. In the condensation reaction, OR groups on the silanes react with terminal OH groups on the α,ω-dihydroxypolysiloxane via elimination of alcohol ROH and chain extension.
The reaction can be carried out as condensation at a temperature in the range from 80 to 105° C. during 3 to 4 hours, preferably under reduced pressure, for example at a pressure in the region of 100 mbar. Details of condensation reactions are known from silicone chemistry. The polysiloxane used has to have hydroxyl groups at two or more chain ends for a condensation reaction to be able to take place at all.
Equilibration reactions are likewise well known from the literature of silicone chemistry. An equilibration reaction involves the insertion of silane units into the polysiloxane chain. Equilibration thus requires that Si—O—Si bonds in the chain be scissioned. This explains why higher temperatures are needed for equilibration than for condensation. The reaction to form polysiloxanes according to the present invention is carried out at a temperature in the range from 110 to 135° C. during a time of 3 to 4 hours when equilibration is desired. When the polyorganosiloxane of the formula (VIII) does not contain any OH groups, the equilibration reaction is preferably carried out in the presence of water in order that OR groups may be hydrolyzed to OH groups.
The reaction which leads to novel polyorganosiloxanes according to the present invention is preferably carried out in the presence of a catalyst or a mixture of catalysts, both when the reaction takes the form of a condensation and when the reaction takes the form of an equilibration.
Suitable catalysts are known from the literature of the silicone field. Acidic catalysts can be used in some cases, examples being Lewis acids or dilute mineral acids; normally, however, basic catalysts are more suitable and therefore preferable. Alkali metal hydroxides such as NaOH, KOH or LiOH and particularly metal alkoxides are particularly suitable basic catalysts. Alkali metal alkoxides of the formula M(OR) are particularly highly suitable. These metal alkoxides can be used for example as a 20% to 30% solution in the underlying alcohol. In the formula, M represents Na or K and R represents alkyl of 1 to 4 carbon atoms.
Useful catalysts further include 4-dimethylaminopyridine and bicyclic compounds which contain one or more nitrogen atoms as ring members. Examples are 1,5-diazabicyclo[2.2.2]octane, 1,5-diazabicyclo[4.3.0]non-5-ene and 1,8-diazabicyclo[5.4.0]undec-7-ene.
The silanes of the formula (XXXV) according to the present invention contain two or three —OR groups.
Here, all R radicals independently represent phenyl or a branched or unbranched alkyl radical of 1 to 18 carbon atoms. Preferably, all R radicals represent methyl or ethyl.
The R1 radical in the formula (XXXV) represents R or —OR or
The R20 radical in the silanes of the formula (XXXV) does not react with the polyorganosiloxane and reappears intact in the resulting new polyorganosiloxane, while the —OR radicals do react with the polyorganosiloxane, either by condensation or by equilibration.
The R20 radical represents a radical of one of the formulae (XXXVI) to (XLI) or of one of the formulae (XLI a) to (XLI h)
In these formulae:
In this formula, each of the R21 radicals has the abovementioned meaning or represents
—R23 represents a linear or branched alkyl radical of 8 to 18 carbon atoms.
In the formula (XXXVIII), the R23 radical either has the abovementioned meaning or represents H or —CH3.
In the formula (XXXVIII), each
unit has one of the R3 radicals representing H and the other representing CH3. k and I are each from 1 to 31, preferably from 1 to 22, and the sum total of k+I is from 3 to 45, preferably from 3 to 25. Furthermore, the individual units
can be distributed across the chain in any desired manner.
In the formula (XXXIX), each of the two R24 radicals independently represents a linear or branched alkyl radical of 1 to 6 carbon atoms.
In the formula (XL), each R21 radical either has the abovementioned meaning or represents a radical of the formula
where x is from 0 to 1500.
The silane of the formula (XXXV) can also be a product formed by reaction of a silane of the formula
with a polyether amine or a product T, in which case the polyether amine is preferably a product of the formula
or of the formula
or of the formula
or of the formula
H2N—CH(CH3)—CH2—O—CH(CH3)—CH2—w—O—CH2—C[—CH2—OCH2—CH(CH3)—Ow—CH2—CH(CH3)—NH2]3
where w is from 2 to 8,
or where the product T is a 3-(2-aminoethyl)aminopropylmethylsilsesquioxane with terminal —OCH3.
The novel polyorganosiloxanes according to the present invention are obtainable by reacting a polyorganosiloxane of the formula (VIII)
with either an above-described silane of the formula (XXXV) according to the present invention or with a silane of the formula (I)
The silanes of the formula (I) were described above in connection with the statements about the achievement of the object.
It is also possible to use two or more silanes of the formula (I) or two or more silanes of the formula (XXXV) for the reaction with polyorganosiloxane, or else mixtures containing both one or more silanes of the formula (I) and one or more silanes of the formula (XXXV).
When silanes of the formula (I) are used, it is particularly preferable to use silanes or silane mixtures of the formula (I) which contain at least one silane of the formula (I) wherein R2 is a radical of the formula (V)
It was also found that it is often advantageous when silanes with acrylate radicals are used wherein the R3 radical is a methyl group, i.e., methacryloyl compounds.
The silanes of the formula (I) and of the formula (XXXV) are commercially available or they are obtainable by following methods which are known to a chemist. Possible syntheses are the reaction of a silane which contains an Si—H bond and 2 or 3 Si-attached chlorine atoms with allyl compounds, for example with allyl chloride, and subsequent further reaction with ammonia or an amine (in which case the terminal chlorine atom of the original allyl group is replaced by the corresponding nitrogenous radical) and also subsequent replacement of the Si-attached chlorine atoms by OR through reaction with alcohol. Furthermore, phosphorus-containing silanes of the formula (I) are obtainable by addition of (CH3O)2P(O)—H onto bisalkoxy- or trisalkoxysilanes which contain substituents having C═C double bonds, for example onto
The preparation of certain fluorine-containing silanes of the formula (I) can be effected by reacting
Si(OR)2(R1)CH2—t—NH2
with fluoroalkyl-containing epoxides (see JP-2000-53950 A2 and JP-2000-53686 A2).
Silanes of the formula (I) in which the R2 radical is a radical of the formula (V) are obtainable by reacting (RO)2Si(R1)—R4—Cl with
Such silanes are also obtainable from ABCR in Germany.
Silanes of the formula (I) in which the R2 radical is a radical of the formula (VI) are obtainable by reacting (Cl)2Si(R)—H with
(the last-mentioned compound is obtainable by reacting one of the 3 OH groups of 1,1,1-trismethylolpropane with (meth)allyl chloride),
Silanes of the formula (I) in which the R2 radical is a radical of the formula (III) or of the formula (IV) are obtainable by addition of a lactone, for example γ-butyrolactone, onto an aminoalkyl-dialkoxysilane and subsequent reaction with (meth)acrylic acid or derivatives thereof.
Silane of the formula (I) in which the R2 radical is a radical of the formula (VII) are obtainable by addition of (meth)acrylic esters onto aminoalkyldialkoxysilane.
In preferred silanes of the formula (I), the R2 radical contains acrylate units or methacrylate units. Such silanes are commercially available, for example from ABCR GmbH & Co., Karlsruhe, Germany. Furthermore, such silanes are obtainable by following the teaching of DE-A 102 19 734.
Silanes of the formula (I) in which the R2 radical is a radical of the formula (XI) and R10 is a radical of the formula (XXIII) are obtainable by reacting an amino-functional silane (formula (I) where R1═R and R2═—R4—NH2) with an alkylene diacrylate.
Silanes in which the R10 radical is a radical of one of the formulae (XVII), (XVIII) or (XX) are obtainable by reacting appropriate epoxides with appropriate amines.
Silanes of the formula (XII) where R14=alkyl are obtainable by reacting
with an acrylic ester.
Silanes of the formula (I) in which the R2 radical contains acrylate units or methacrylate units are commercially available, for example from ABCR GmbH & Co., Karlsruhe, Germany. Such silanes, for example of the formula (XVI), are also obtainable by reacting
with an alkylene carbonate and then with acrylic acid (ester).
The silanes of the formula (XXXV) according to the present invention are likewise obtainable by following conventional methods, for example by reacting a commercially available silane of the formula
or of the formula
with acrylates (in the form of a Michael addition) or with cyclic carbonates such as ethylene carbonate or with mono- or polyamines (in which case the epoxy group of the silane reacts with an amino group by ring opening). Silanes of the formula (XXXV) are also obtainable by reacting the amino- or epoxysilanes mentioned with acrylates or with
with diisocyanates and diols. The products are acrylates which contain urethane units.
The examples which follow illustrate the invention.
51.0 g of Si(CH3)(OCH3)2(CH2CH2CH2NHCH2CH2NH2)
and
This gave a clear, beige-colored and viscous addition product =silane of formula (I) where R═CH3, R1═CH3 and R2=radical of formula (XII) where R4=
—CH2—3—.
p=1, R3═H, R14=alkyl.
The acrylic ester used was a mixture of decyl acrylate and octyl acrylate.
After a further 3 hours, the vacuum was relieved and the oil cooled down.
The product formed was a thin, slightly cloudy oil.
37.16 g of CH2CH(CO)O(CH2CH2CH2CH2CH2CH2)O(CO)CHCH2
and
62.84 g of Si(OCH2CH3)2(CH3)(CH2CH2CH2NH2)
were placed together in the initial charge and heated without solvent to 60° C. with stirring. The mixture was maintained at 60° C. for 5 hours.
A slightly brownish cloudy liquid was obtained.
41.7 g of α,ω-dihydroxypolydimethylsiloxane (about 100 mPa·s)
99.3 g of α,ω-dihydroxypolydimethylsiloxane (about 600 mPa·s)
and
8.7 g of the abovementioned silane
were placed together in the initial charge and heated to 90° C. with stirring. On attainment of the temperature the catalyst (0.3 g of sodium methoxide, 6% in methanol) was added, stirring was continued at the stated temperature for 15 minutes and subsequently a vacuum of 200 mbar was applied. After 7 hours, the vacuum was relieved and the oil cooled down.
A thin cloudy oil was obtained.
were placed in the initial charge together with 11.42 g of a catalyst mixture based on triethanolamine and heated to 70° C. with stirring. This temperature was maintained for 6 hours.
A slightly yellowish liquid was obtained.
A thick cloudy oil was obtained.
| Number | Date | Country | Kind |
|---|---|---|---|
| 08005246.7 | Mar 2008 | EP | regional |
This application is a divisional of U.S. patent application Ser. No. 12/933,212, pending, which is the National Phase of International Application PCT/EP2009/001819 filed Mar. 13, 2009 which designated the U.S. and which claims priority to European Patent Application (EP) 08005246.7 filed Mar. 20, 2008. The noted applications are incorporated herein by reference.
| Number | Date | Country | |
|---|---|---|---|
| Parent | 12933212 | Sep 2010 | US |
| Child | 13963315 | US |
