Patent Application
20150247069
The invention relates to a polyolefin adhesive composition used in woodworking applications.
Adhesive composition components such as base polymers, tackifiers, waxes, functionalized polyolefins and oils are customarily provided as separate components for formulation into hot melt adhesive (HMA) compositions. HMA compositions for woodworking applications are used to construct woodworking products, e.g., adhering wood boards, and to prepare final wood-based products, e.g., adhering various substrates to a woodworking product. Woodworking applications can include furniture, toys, musical instruments, window frames and sills, doors, flooring, fencing, tools, ladders, sporting goods, dog houses, gazebos/decks, picnic tables, playground structures, planters, scaffolding planks, kitchen utensils, coffins, church pews/altars, and canes. In woodworking applications, HMA compositions are sought that provide a desired combination of physical properties such as stable adhesion over time indicative of broad application temperature ranges, and a long open time. Open time is a term well known in the art to refer to the working time to make a bond. An adhesive formulation having a long open time can improve the efficiency of the process to prepare woodworking applications, as the structure of the desired woodworking application can be adjusted during the time it takes to form the bond. A short open time of an adhesive formulation in a woodworking application can result in a woodworking product that has a compromised structure as a result of the limited time available to place the product in a desired structure before the bond forms and strengthens. HMAs having stable and consistent adhesion over broad application temperatures is also generally sought to construct woodworking products and to prepare final wood-based products.
Exemplary base polymer compositions and methods of making polymer compositions for HMA applications are disclosed in U.S. Pat. Nos. 7,294,681 and 7,524,910. Various polymers described in these patents and/or produced by the methods disclosed in these patents have been sold by ExxonMobil Chemical Company as LINXAR™ polymers.
WO Publication No. 2013/134038 discloses a method for producing a polymer blend having at least two different propylene-based polymers produced in parallel reactors. The multi-modal polymer blend has a Mw of about 10,000 g/mol to about 150,000 g/mol. When subjected to Temperature Rising Elution Fractionation, the polymer blend exhibits a first fraction that is soluble at −15° C. in xylene, the first fraction having an isotactic (mm) triad tacticity of about 70 mol % to about 90 mol %; and a second fraction that is insoluble or less soluble than the first fraction at −15° C. in xylene, the second fraction having an isotactic (mm) triad tacticity of about 85 mol % to about 98 mol %.
Although many different types of polymers are known and have been used in HMA formulations, there remains a need for an adhesive formulation that has high loading of the new base polymers to achieve equivalent or better adhesive performance attributes including stable adhesion over time indicative of broad application temperature ranges, and a long open time, as compared to HMA formulations that are currently available.
The foregoing and/or other challenges are addressed by the methods and products disclosed herein.
In one aspect, a polymer blend is provided for use in an adhesive composition. The polymer blend includes a first propylene-based polymer, wherein the first propylene-based polymer is a homopolymer of propylene or a copolymer of propylene and ethylene or a C4 to C10 alpha-olefin; and a second propylene-based polymer, wherein the second propylene-based polymer is a homopolymer of propylene or a copolymer of propylene and ethylene or a C4 to C10 alpha-olefin; wherein the second propylene-based polymer is different than the first propylene-based polymer. The polymer blend has a melt temperature of about 75 to about 125° C. When subjected to Temperature Rising Elution Fractionation, the polymer blend exhibits: a first fraction that is soluble at −15° C. in xylene, the first fraction having an isotactic (mm) triad tacticity of about 70 mol % to about 90 mol %; and a second fraction that is insoluble at −15° C. in xylene, the second fraction having an isotactic (mm) triad tacticity of about 85 mol % to about 98 mol %. The polymer blend is present in the amount of about 75 to about 90 wt % of the adhesive composition.
In another aspect, a polymer blend is provided for use in an adhesive composition. The polymer blend includes a first propylene-based polymer, wherein the first propylene-based polymer is a homopolymer of propylene or a copolymer of propylene and ethylene or a C4 to C10 alpha-olefin; and a second propylene-based polymer, wherein the second propylene-based polymer is a homopolymer of propylene or a copolymer of propylene and ethylene or a C4 to C10 alpha-olefin; wherein the second propylene-based polymer is different than the first propylene-based polymer. The polymer blend has a melt viscosity of about 6,000 cP to about 14,000 cP. When subjected to Temperature Rising Elution Fractionation, the polymer blend exhibits: a first fraction that is soluble at −15° C. in xylene, the first fraction having an isotactic (mm) triad tacticity of about 70 mol % to about 90 mol %; and a second fraction that is insoluble at −15° C. in xylene, the second fraction having an isotactic (mm) triad tacticity of about 85 mol % to about 98 mol %. The polymer blend is present in the amount of about 75 to about 90 wt % of the adhesive composition.
These and other aspects of the present inventions are described in the following detailed description and are illustrated in the accompanying figures and tables.
Various specific embodiments of the invention will now be described, including preferred embodiments and definitions that are adopted herein for purposes of understanding the claimed invention. While the illustrative embodiments have been described with particularity, it will be understood that various other modifications will be apparent to and can be readily made by those skilled in the art without departing from the spirit and scope of the invention. For determining infringement, the scope of the “invention” will refer to any one or more of the appended claims, including their equivalents and elements or limitations that are equivalent to those that are recited.
The inventors have discovered that high loading polymer blends to form adhesive compositions for use in woodworking applications results in advantageous properties for the adhesive compositions including stable adhesion over time, which is indicative of broad application temperature ranges, and a long open time, equivalent to or better than commercially available adhesives. The adhesive compositions described can be used to construct woodworking products and to prepare final wood-based products alike. The inventive adhesives may be produced using a new process platform that is more robust and lacks many of the limitations and difficulties associated with the processes employed to make LINXAR™ polymers and those disclosed in U.S. Pat. Nos. 7,294,681 and 7,524,910.
A solution polymerization process for preparing a polyolefin adhesive component is generally performed by a system that includes a first reactor, a second reactor in parallel with the first reactor, a liquid-phase separator, a devolatilizing vessel, and a pelletizer. The first reactor and second reactor may be, for example, continuous stirred-tank reactors.
The first reactor may receive a first monomer feed, a second monomer feed, and a catalyst feed. The first reactor may also receive feeds of a solvent and an activator. The solvent and/or the activator feed may be combined with any of the first monomer feed, the second monomer feed, or catalyst feed or the solvent and activator may be supplied to the reactor in separate feed streams. A first polymer is produced in the first reactor and is evacuated from the first reactor via a first product stream. The first product stream comprises the first polymer, solvent, and any unreacted monomer. In an embodiment, hydrogen may be added to one or more reactors to adjust the molecular weight of the polymer blend.
In any embodiment, the first monomer in the first monomer feed may be propylene and the second monomer in the second monomer feed may be ethylene or a C4 to C10 olefin. In any embodiment, the second monomer may be ethylene, butene, hexene, and octene. Generally, the choice of monomers and relative amounts of chosen monomers employed in the process depends on the desired properties of the first polymer and final polymer blend. For adhesive compositions, ethylene and hexene are particularly preferred comonomers for copolymerization with propylene. In any embodiment, the relative amounts of propylene and comonomer supplied to the first reactor may be designed to produce a polymer that is predominantly propylene, i.e., a polymer that is more than 50 mol % propylene. In another embodiment, the first reactor may produce a homopolymer of propylene.
The second reactor may receive a third monomer feed of a third monomer, a fourth monomer feed of a fourth monomer, and a catalyst feed of a second catalyst. The second reactor may also receive feeds of a solvent and activator. The solvent and/or the activator feed may be combined with any of the third monomer feed, the fourth monomer feed, or second catalyst feed, or the solvent and activator may be supplied to the reactor in separate feed streams. A second polymer is produced in the second reactor and is evacuated from the second reactor via a second product stream. The second product stream comprises the second polymer, solvent, and any unreacted monomer.
In any embodiment, the third monomer may be propylene and the fourth monomer may be ethylene or a C4 to C10 olefin. In any embodiment, the fourth monomer may be ethylene, butene, hexene, and octene. In any embodiment, the relative amounts of propylene and comonomer supplied to the second reactor may be designed to produce a polymer that is predominantly propylene, i.e., a polymer that is more than 50 mol % propylene. In another embodiment, the second reactor may produce a homopolymer of propylene.
Preferably, the second polymer is different than the first polymer. The difference may be measured, for example, by the comonomer content, heat of fusion, crystallinity, branching index, weight average molecular weight, and/or polydispersity of the two polymers. In any embodiment, the second polymer may comprise a different comonomer than the first polymer or one polymer may be a homopolymer of propylene and the other polymer may comprise a copolymer of propylene and ethylene or a C4 to C10 olefin. For example, the first polymer may comprise a propylene-ethylene copolymer and the second polymer may comprise a propylene-hexene copolymer. In any embodiment, the second polymer may have a different weight average molecular weight (Mw) than the first polymer and/or a different melt viscosity than the first polymer. Furthermore, in any embodiment, the second polymer may have a different crystallinity and/or heat of fusion than the first polymer. Specific examples of the types of polymers that may be combined to produce advantageous blends are described in greater detail herein.
It should be appreciated that any number of additional reactors may be employed to produce other polymers that may be integrated with (e.g., grafted) or blended with the first and second polymers. In any embodiment, a third reactor may produce a third polymer. The third reactor may be in parallel with the first reactor and second reactor or the third reactor may be in series with one of the first reactor and second reactor. It should be appreciated that the one or more reactors may be configured in series.
Further description of exemplary methods for polymerizing the polymers described herein may be found in U.S. Pat. No. 6,881,800, which is incorporated by reference herein.
The first product stream and second product stream may be combined to produce a blend stream. For example, the first product stream and second product stream may supply the first and second polymer to a mixing vessel, such as a mixing tank with an agitator.
The blend stream may be fed to a liquid-phase separation vessel to produce a polymer rich phase and a polymer lean phase. The polymer lean phase may comprise the solvent and be substantially free of polymer. At least a portion of the polymer lean phase may be evacuated from the liquid-phase separation vessel via a solvent recirculation stream. The solvent recirculation stream may further include unreacted monomer. At least a portion of the polymer rich phase may be evacuated from the liquid-phase separation vessel via a polymer rich stream.
In any embodiment, the liquid-phase separation vessel may operate on the principle of Lower Critical Solution Temperature (LCST) phase separation. This technique uses the thermodynamic principle of spinodal decomposition to generate two liquid phases; one substantially free of polymer and the other containing the dissolved polymer at a higher concentration than the single liquid feed to the liquid-phase separation vessel.
Employing a liquid-phase separation vessel that utilizes spinodal decomposition to achieve the formation of two liquid phases may be an effective method for separating solvent from multi-modal polymer blends, particularly in cases in which one of the polymers of the blend has a weight average molecular weight less than 100,000 g/mol, and even more particularly between 10,000 g/mol and 60,000 g/mol. The concentration of polymer in the polymer lean phase may be further reduced by catalyst selection. Catalysts of Formula I (described below), particularly dimethylsilyl bis(2-methyl-4-phenylindenyl) zirconium dichloride, dimethylsilyl bis(2-methyl-5-phenylindenyl) hafnium dichloride, dimethylsilyl bis(2-methyl-4-phenylindenyl) zirconium dimethyl, and dimethylsilyl bis(2-methyl-4-phenylindenyl) hafnium dimethyl were found to be a particularly effective catalysts for minimizing the concentration of polymer in the lean phase. Accordingly, in any embodiment, one, both, or all polymers may be produced using a catalyst of Formula I, particularly dimethylsilyl bis(2-methyl-4-phenylindenyl) zirconium dichloride, dimethylsilyl bis(2-methyl-4-phenylindenyl) hafnium dichloride, dimethylsilyl bis(2-methyl-4-phenylindenyl) zirconium dimethyl, and dimethylsilyl bis(2-methyl-4-phenylindenyl) hafnium dimethyl.
Upon exiting the liquid-phase separation vessel, the polymer rich stream may then be fed to a devolatilizing vessel for further polymer recovery. In any embodiment, the polymer rich stream may also be fed to a low pressure separator before being fed to the inlet of the devolatilizing vessel. While in the vessel, the polymer composition may be subjected to a vacuum in the vessel such that at least a portion of the solvent is removed from the polymer composition and the temperature of the polymer composition is reduced, thereby forming a second polymer composition comprising the multi-modal polymer blend and having a lower solvent content and a lower temperature than the polymer composition as the polymer composition is introduced into the vessel. The polymer composition may then be discharged from the outlet of the vessel via a discharge stream.
The cooled discharge stream may then be fed to a pelletizer where the multi-modal polymer blend is then discharged through a pelletization die as formed pellets. Pelletization of the polymer may be performed by an underwater, hot face, strand, water ring, or other similar pelletizer. Preferably an underwater pelletizer is used, but other equivalent pelletizing units known to those skilled in the art may also be used. General techniques for underwater pelletizing are known to those of ordinary skill in the art. Anti-agglomeration aids, such as dusting powder, may be added during or after pelletization for specific polymers to prevent pellets from agglomerating during storage.
WO Publication No. 2013/134038 generally describes the method of preparing polyolefin adhesive components and compositions. The contents of WO Publication No. 2013/134038 is incorporated herein in its entirety.
Preferred polymers are semi-crystalline propylene-based polymers. In any embodiment, the polymers may have a relatively low molecular weight, preferably about 150,000 g/mol or less. In any embodiment, the polymer may comprise a comonomer selected from the group consisting of ethylene and linear or branched C4 to C20 olefins and diolefins. In any embodiment, the comonomer may be ethylene or a C4 to C10 olefin.
The term “polymer” as used herein includes, but is not limited to, homopolymers, copolymers, interpolymers, terpolymers, etc. and alloys and blends thereof. Further, as used herein, the term “copolymer” is meant to include polymers having two or more monomers, optionally with other monomers, and may refer to interpolymers, terpolymers, etc. The term “polymer” as used herein also includes impact, block, graft, random and alternating copolymers. The term “polymer” shall further include all possible geometrical configurations unless otherwise specifically stated. Such configurations may include isotactic, syndiotactic and random symmetries. The term “polymer blend” as used herein includes, but is not limited to a blend of one or more polymers prepared in solution or by physical blending, such as melt blending. Generally, the polymer blend is present in the adhesive composition in amount of about 75 to 95 wt %. Preferably, the polymer blend is present in the adhesive composition within the range of about 80 wt % or 85 wt % or 90 wt % to less than about 95 wt %.
“Propylene-based” or “predominantly propylene-based” as used herein, is meant to include any polymer comprising propylene, either alone or in combination with one or more comonomers, in which propylene is the major component (i.e., greater than 50 mol % propylene).
In any embodiment, one or more polymers of the blend may comprise one or more propylene-based polymers, which comprise propylene and from about 2 mol % to about 30 mol % of one or more comonomers selected from C2 and C4-C10 α-olefins. In any embodiment, the α-olefin comonomer units may derive from ethylene, butene, pentene, hexene, 4-methyl-1-pentene, octene, or decene. The embodiments described below are discussed with reference to ethylene and hexene as the α-olefin comonomer, but the embodiments are equally applicable to other copolymers with other α-olefin comonomers. In this regard, the copolymers may simply be referred to as propylene-based polymers with reference to ethylene or hexene as the α-olefin.
In any embodiment, the one or more propylene-based polymers of the polymer blend may include at least about 5 mol %, at least about 6 mol %, at least about 7 mol %, or at least about 8 mol %, or at least about 10 mol %, or at least about 12 mol % ethylene-derived or hexene-derived units. In those or other embodiments, the copolymers of the propylene-based polymer may include up to about 30 mol %, or up to about 25 mol %, or up to about 22 mol %, or up to about 20 mol %, or up to about 19 mol %, or up to about 18 mol %, or up to about 17 mol % ethylene-derived or hexene-derived units, where the percentage by mole is based upon the total moles of the propylene-derived and α-olefin derived units. Stated another way, the propylene-based polymer may include at least about 70 mol %, or at least about 75 mol %, or at least about 80 mol %, or at least about 81 mol % propylene-derived units, or at least about 82 mol % propylene-derived units, or at least about 83 mol % propylene-derived units; and in these or other embodiments, the copolymers of the propylene-based polymer may include up to about 95 mol %, or up to about 94 mol %, or up to about 93 mol %, or up to about 92 mol %, or up to about 90 mol %, or up to about 88 mol % propylene-derived units, where the percentage by mole is based upon the total moles of the propylene-derived and alpha-olefin derived units. In any embodiment, the propylene-based polymer may comprise from about 5 mol % to about 25 mol % ethylene-derived or hexene-derived units, or from about 8 mol % to about 20 mol % ethylene-derived or hexene-derived units, or from about 12 mol % to about 18 mol % ethylene-derived or hexene-derived units.
The one or more polymers of the blend of one or more embodiments are characterized by a melting point (Tm), which can be determined by differential scanning calorimetry (DSC). For purposes herein, the maximum of the highest temperature peak is considered to be the melting point of the polymer. A “peak” in this context is defined as a change in the general slope of the DSC curve (heat flow versus temperature) from positive to negative, forming a maximum without a shift in the baseline where the DSC curve is plotted so that an endothermic reaction would be shown with a positive peak.
In any embodiment, the Tm of the one or more polymers of the blend (as determined by DSC) may be less than about 130° C., or less than about 125° C., less than about 120° C., or less than about 115° C., or less than about 110° C., or less than about 100° C., or less than about 90° C., and greater than about 70° C., or greater than about 75° C., or greater than about 80° C., or greater than about 85° C. In any embodiment, the Tm of the one or more polymers of the blend may be greater than about 25° C., or greater than about 30° C., or greater than about 35° C., or greater than about 40° C. Tm of the polymer blend can be determined by taking 5 to 10 mg of a sample of the polymer blend, equilibrating a DSC Standard Cell FC at −90° C., ramping the temperature at a rate of 10° C. per minute up to 200° C., maintaining the temperature for 5 minutes, lowering the temperature at a rate of 10° C. per minute to −90° C., ramping the temperature at a rate of 10° C. per minute up to 200° C., maintaining the temperature for 5 minutes, and recording the temperature as Tm.
In one or more embodiments, the crystallization temperature (Tc) of the polymer blend (as determined by DSC) is less than about 110° C., or less than about 90° C., or less than about 80° C., or less than about 70° C., or less than about 60° C., or less than about 50° C., or less than about 40° C., or less than about 30° C., or less than about 20° C., or less than about 10° C. In the same or other embodiments, the Tc of the polymer is greater than about 0° C., or greater than about 5° C., or greater than about 10° C., or greater than about 15° C., or greater than about 20° C. In any embodiment, the Tc lower limit of the polymer may be 0° C., 5° C., 10° C., 20° C., 30° C., 40° C., 50° C., 60° C., and 70° C.; and the Tc upper limit temperature may be 100° C., 90° C., 80° C., 70° C., 60° C., 50° C., 40° C., 30° C., 25° C., and 20° C. with ranges from any lower limit to any upper limit being contemplated. Tc of the polymer blend can be determined by taking 5 to 10 mg of a sample of the polymer blend, equilibrating a DSC Standard Cell FC at −90° C., ramping the temperature at a rate of 5-10° C. per minute up to 200° C., maintaining the temperature for 5 minutes, lowering the temperature at a rate of 5-10° C. per minute to −90° C., and recording the temperature as Tc.
The polymers suitable for use herein are said to be “semi-crystalline”, meaning that in general they have a relatively low crystallinity. The term “crystalline” as used herein broadly characterizes those polymers that possess a high degree of both inter and intra molecular order, and which preferably melt higher than 110° C., more preferably higher than 115° C., and most preferably above 130° C. A polymer possessing a high inter and intra molecular order is said to have a “high” level of crystallinity, while a polymer possessing a low inter and intra molecular order is said to have a “low” level of crystallinity. Crystallinity of a polymer can be expressed quantitatively, e.g., in terms of percent crystallinity, usually with respect to some reference or benchmark crystallinity. As used herein, crystallinity is measured with respect to isotactic polypropylene homopolymer. Preferably, heat of fusion is used to determine crystallinity. Thus, for example, assuming the heat of fusion for a highly crystalline polypropylene homopolymer is 190 J/g, a semi-crystalline propylene copolymer having a heat of fusion of 95 J/g will have a crystallinity of 50%. The term “crystallizable” as used herein refers to those polymers which can crystallize upon stretching or annealing. Thus, in certain specific embodiments, the semi-crystalline polymer may be crystallizable. The semi-crystalline polymers used in specific embodiments of this invention preferably have a crystallinity of from 2% to 65% of the crystallinity of isotatic polypropylene. In further embodiments, the semi-crystalline polymers may have a crystallinity of from about 3% to about 40%, or from about 4% to about 30%, or from about 5% to about 25% of the crystallinity of isotactic polypropylene.
The semi-crystalline polymer can have a level of isotacticity expressed as percentage of isotactic triads (three consecutive propylene units), as measured by 13C NMR, of 75 mol % or greater, 80 mol % or greater, 85 mol % or greater, 90 mol % or greater, 92 mol % or greater, 95 mol % or greater, or 97 mol % or greater. In one or more embodiments, the triad tacticity may range from about 75 mol % to about 99 mol %, or from about 80 mol % to about 99 mol %, or from about 85 mol % to about 99 mol %, or from about 90 mol % to about 99 mol %, or from about 90 mol % to about 97 mol %, or from about 80 mol % to about 97 mol %. Triad tacticity is determined by the methods described in U.S. Pat. No. 7,232,871.
The semi-crystalline polymer may have a tacticity index m/r ranging from a lower limit of 4, or 6 to an upper limit of 10, or 20, or 25. The tacticity index, expressed herein as “m/r”, is determined by 13C nuclear magnetic resonance (“NMR”). The tacticity index m/r is calculated as defined by H. N. Cheng in 17 M
In one or more embodiments, the semi-crystalline polymer may have a density of from about 0.85 g/cm3 to about 0.92 g/cm3, or from about 0.86 g/cm3 to about 0.90 g/cm3, or from about 0.86 g/cm3 to about 0.89 g/cm3 at room temperature and determined according to ASTM D-792.
In one or more embodiments, the semi-crystalline polymer can have a weight average molecular weight (Mw) of from about 5,000 to about 500,000 g/mol, or from about 7,500 to about 300,000 g/mol, or from about 10,000 to about 200,000 g/mol, or from about 25,000 to about 175,000 g/mol.
Weight-average molecular weight, Mw, molecular weight distribution (MWD) or Mw/Mn where Mn is the number-average molecular weight, and the branching index, g′(vis), are characterized using a High Temperature Size Exclusion Chromatograph (SEC), equipped with a differential refractive index detector (DRI), an online light scattering detector (LS), and a viscometer. Experimental details not shown below, including how the detectors are calibrated, are described in: T. Sun, P. Brant, R. R. Chance, and W. W. Graessley, Macromolecules, Volume 34, Number 19, pp. 6812-6820, 2001.
Solvent for the SEC experiment is prepared by dissolving 6 g of butylated hydroxy toluene as an antioxidant in 4 L of Aldrich reagent grade 1,2,4 trichlorobenzene (TCB). The TCB mixture is then filtered through a 0.7 μm glass pre-filter and subsequently through a 0.1 μm Teflon filter. The TCB is then degassed with an online degasser before entering the SEC. Polymer solutions are prepared by placing the dry polymer in a glass container, adding the desired amount of TCB, then heating the mixture at 160° C. with continuous agitation for about 2 hr. All quantities are measured gravimetrically. The TCB densities used to express the polymer concentration in mass/volume units are 1.463 g/mL at room temperature and 1.324 g/mL at 135° C. The injection concentration ranges from 1.0 to 2.0 mg/mL, with lower concentrations being used for higher molecular weight samples. Prior to running each sample the DRI detector and the injector are purged. Flow rate in the apparatus is then increased to 0.5 mL/min, and the DRI was allowed to stabilize for 8-9 hr before injecting the first sample. The LS laser is turned on 1 to 1.5 hr before running samples.
The concentration, c, at each point in the chromatogram is calculated from the baseline-subtracted DRI signal, IDRI, using the following equation:
c=K
DRI
I
DRI/(dn/dc)
where KDRI is a constant determined by calibrating the DRI, and dn/dc is the same as described below for the LS analysis. Units on parameters throughout this description of the SEC method are such that concentration is expressed in g/cm3, molecular weight is expressed in kg/mol, and intrinsic viscosity is expressed in dL/g.
The light scattering detector used is a Wyatt Technology High Temperature mini-DAWN. The polymer molecular weight, M, at each point in the chromatogram is determined by analyzing the LS output using the Zimm model for static light scattering (M. B. Huglin, L
[Koc/ΔR(θ,c)]=[1/MP(θ)]+2A2c
where ΔR(θ) is the measured excess Rayleigh scattering intensity at scattering angle θ, c is the polymer concentration determined from the DRI analysis, A2 is the second virial coefficient, P(θ) is the form factor for a monodisperse random coil (described in the above reference), and Ko is the optical constant for the system:
in which NA is the Avogadro's number, and dn/dc is the refractive index increment for the system. The refractive index, n=1.500 for TCB at 135° C. and λ=690 nm. In addition, A2=0.0015 and dn/dc=0.104 for ethylene polymers, whereas A2=0.0006 and dn/dc=0.104 for propylene polymers.
The molecular weight averages are usually defined by considering the discontinuous nature of the distribution in which the macromolecules exist in discrete fractions i containing Ni molecules of molecular weight Mi. The weight-average molecular weight, Mw, is defined as the sum of the products of the molecular weight Mi of each fraction multiplied by its weight fraction wi:
M
w
≡Σw
i
M
i=(ΣNiMi2/ΣNiMi)
since the weight fraction wi is defined as the weight of molecules of molecular weight Mi divided by the total weight of all the molecules present:
w
i
=N
i
M
i
/ΣN
i
M
i
The number-average molecular weight, Mn, is defined as the sum of the products of the molecular weight Mi of each fraction multiplied by its mole fraction xi:
M
n
Σx
i
M
i
≡ΣN
i
M
i
/ΣN
i
since the mole fraction xi is defined as Ni divided by the total number of molecules
x
i
=N
i
/ΣN
i
In the SEC, a high temperature Viscotek Corporation viscometer is used, which has four capillaries arranged in a Wheatstone bridge configuration with two pressure transducers. One transducer measures the total pressure drop across the detector, and the other, positioned between the two sides of the bridge, measures a differential pressure. The specific viscosity, ηs, for the solution flowing through the viscometer is calculated from their outputs. The intrinsic viscosity, [η], at each point in the chromatogram is calculated from the following equation:
ηs=c[η]+0.3(c[η])2
where c was determined from the DRI output.
The branching index (g′, also referred to as g′(vis)) is calculated using the output of the SEC-DRI-LS-VIS method as follows. The average intrinsic viscosity, [η]avg, of the sample is calculated by:
where the summations are over the chromatographic slices, i, between the integration limits.
The branching index g′ is defined as:
where k=0.000579 and α=0.695 for ethylene polymers; k=0.0002288 and α=0.705 for propylene polymers; and k=0.00018 and α=0.7 for butene polymers.
Mv is the viscosity-average molecular weight based on molecular weights determined by the LS analysis:
M
v≡(ΣciMiα/Σci)1/α
In one or more embodiments, the semi-crystalline polymer may have a viscosity (also referred to a Brookfield viscosity or melt viscosity), measured at 190° C. and determined according to ASTM D-3236 from about 100 cP to about 500,000 cP, or from about 100 to about 100,000 cP, or from about 100 to about 50,000 cP, or from about 100 to about 25,000 cP, or from about 100 to about 15,000 cP, or from about 100 to about 10,000 cP, or from about 100 to about 5,000 cP, or from about 500 to about 15,000 cP, or from about 500 to about 10,000 cP, or from about 500 to about 5,000 cP, or from about 1,000 to about 10,000 cP, wherein 1 cP=1 mPa·sec.
In one or more embodiments, the semi-crystalline polymer may be characterized by its viscosity at 190° C. In one or more embodiments, the semi-crystalline polymer may have a viscosity that is at least about 100 cP (centipoise), or at least about 500 cP, or at least about 1,000 cP, or at least about 1,500 cP, or at least about 2,000 cP, or at least about 3,000 cP, or at least about 4,000 cP, or at least about 5,000 cP. In these or other embodiments, the semi-crystalline polymer may be characterized by a viscosity at 190° C. of less than about 100,000 cP, or less than about 75,000 cP, or less than about 50,000 cP, or less than about 25,000 cP, or less than about 20,000 cP, or less than about 15,000 cP, or less than about 10,000 cP, or less than about 5,000 cP with ranges from any lower limit to any upper limit being contemplated.
The polymers that may be used in the adhesive compositions disclosed herein generally include any of the polymers according to the process disclosed in WO Publication No. 2013/134038. The triad tacticity and tacticity index of a polymer may be controlled by the catalyst, which influences the stereoregularity of propylene placement, the polymerization temperature, according to which stereoregularity can be reduced by increasing the temperature, and by the type and amount of a comonomer, which tends to reduce the length of crystalline propylene derived sequences. Such polymers made in accordance with WO Publication No. 2013/134038, when subjected to Temperature Rising Elution Fractionation, exhibit: a first fraction that is soluble at −15° C. in xylene, the first fraction having an isotactic (mm) triad tacticity of about 70 mol % to about 90 mol %; and a second fraction that is insoluble at −15° C. in xylene, the second fraction having an isotactic (mm) triad tacticity of about 85 mol % to about 98 mol %. The contents of WO Publication No. 2013/134038 is incorporated herein in its entirety.
Polymers and blended polymer products are also provided. In any embodiment, one or more of the polymers described herein may be blended with another polymer, such as another polymer described herein, to produce a physical blend of polymers.
The polymers described herein may be prepared using one or more catalyst systems. As used herein, a “catalyst system” comprises at least a transition metal compound, also referred to as catalyst precursor, and an activator. Contacting the transition metal compound (catalyst precursor) and the activator in solution upstream of the polymerization reactor or in the polymerization reactor of the process described above yields the catalytically active component (catalyst) of the catalyst system. Any given transition metal compound or catalyst precursor can yield a catalytically active component (catalyst) with various activators, affording a wide array of catalysts deployable in the processes of the present invention. Catalyst systems of the present invention comprise at least one transition metal compound and at least one activator. However, catalyst systems of the current disclosure may also comprise more than one transition metal compound in combination with one or more activators. Such catalyst systems may optionally include impurity scavengers. Each of these components is described in further detail below.
The triad tacticity and tacticity index of the polymer may be controlled by the catalyst, which influences the stereoregularity of propylene placement, the polymerization temperature, according to which stereoregularity can be reduced by increasing the temperature, and by the type and amount of a comonomer, which tends to reduce the length of crystalline propylene derived sequences.
In any embodiment, the catalyst systems used for producing semi-crystalline polymers may comprise a metallocene compound. In any embodiment, the metallocene compound may be a bridged bisindenyl metallocene having the general formula (In1)Y(In2)MX2, where In1 and In2 are identical substituted or unsubstituted indenyl groups bound to M and bridged by Y, Y is a bridging group in which the number of atoms in the direct chain connecting In1 with In2 is from 1 to 8 and the direct chain comprises C, Si, or Ge; M is a Group 3, 4, 5, or 6 transition metal; and X2 are leaving groups. In1 and In2 may be substituted or unsubstituted. If In1 and In2 are substituted by one or more substituents, the substituents are selected from the group consisting of a halogen atom, Ci to C10 alkyl, C5 to C15 aryl, C6 to C25 alkylaryl, and Si-, N- or P-containing alkyl or aryl. Each leaving group X may be an alkyl, preferably methyl, or a halide ion, preferably chloride or fluoride. Exemplary metallocene compounds of this type include, but are not limited to, μ-dimethylsilylbis(indenyl) hafnium dimethyl and μ-dimethylsilylbis(indenyl) zirconium dimethyl.
In any embodiment, the metallocene compound may be a bridged bisindenyl metallocene having the general formula (In1)Y(In2)MX2, where In1 and In2 are identical 2,4-substituted indenyl groups bound to M and bridged by Y, Y is a bridging group in which the number of atoms in the direct chain connecting Inl with In2 is from 1 to 8 and the direct chain comprises C, Si, or Ge, M is a Group 3, 4, 5, or 6 transition metal, and X2 are leaving groups. Inl and In2 are substituted in the 2 position by a C1 to C10 alkyl, preferably a methyl group and in the 4 position by a substituent selected from the group consisting of C5 to C15 aryl, C6 to C25 alkylaryl, and Si-, N- or P-containing alkyl or aryl. Each leaving group X may be an alkyl, preferably methyl, or a halide ion, preferably chloride or fluoride. Exemplary metallocene compounds of this type include, but are not limited to, (dimethylsilyl)bis(2-methyl-4-(3,′5′-di-tert-butylphenyl)indenyl) zirconium dimethyl, (dimethylsilyl)bis(2-methyl-4-(3,′5′-di-tert-butylphenyl)indenyl) hafnium dimethyl, (dimethylsilyl)bis(2-methyl-4-naphthylindenyl) zirconium dimethyl, (dimethylsilyl)bis(2-methyl-4-naphthylindenyl) hafnium dimethyl, (dimethylsilyl)bis(2-methyl-4-(N-carbazyl)indenyl) zirconium dimethyl, and (dimethylsilyl)bis(2-methyl-4-(N-carbazyl)indenyl) hafnium dimethyl.
Alternatively, in any embodiment, the metallocene compound may correspond to one or more of the formulas disclosed in U.S. Pat. No. 7,601,666. Such metallocene compounds include, but are not limited to, dimethylsilyl bis(2-(methyl)-5,5,8,8-tetramethyl-5,6,7,8-tetrahydrobenz(f)indenyl) hafnium dimethyl, diphenylsilyl bis(2-(methyl)-5,5,8,8-tetramethyl-5,6,7,8-tetrahydrobenz(f)indenyl) hafnium dimethyl, diphenylsilyl bis(5,5,8,8-tetramethyl-5,6,7,8-tetrahydrobenz(f)indenyl) hafnium dimethyl, diphenylsilyl bis(2-(methyl)-5,5,8,8-tetramethyl-5,6,7,8-tetrahydrobenz(f)indenyl) zirconium dichloride, and cyclo-propylsilyl bis(2-(methyl)-5,5,8,8-tetramethyl-5,6,7,8-tetrahydrobenz(f)indenyl)hafnium dimethyl.
In any embodiment, the activators of the catalyst systems used to produce semi-crystalline polymers may comprise a cationic component. In any embodiment, the cationic component may have the formula [R1R2R3AH]+, where A is nitrogen, R1 and R2 are together a —(CH2)a— group, where a is 3, 4, 5, or 6 and form, together with the nitrogen atom, a 4-, 5-, 6-, or 7-membered non-aromatic ring to which, via adjacent ring carbon atoms, optionally one or more aromatic or heteroaromatic rings may be fused, and R3 is C1, C2, C3, C4, or C5 alkyl, or N-methylpyrrolidinium or N-methylpiperidinium. Alternatively, in any embodiment, the cationic component has the formula [RnAH4-n]+, where A is nitrogen, n is 2 or 3, and all R are identical and are Ci to C3 alkyl groups, such as for example trimethylammonium, trimethylanilinium, triethylammonium, dimethylanilinium, or dimethylammonium.
A particularly advantageous catalyst that may be employed in any embodiment is illustrated in Formula I.
In any embodiment, M is a Group IV transition metal atom, preferably a Group IVB transition metal, more preferably hafnium or zirconium, and X are each an alkyl, preferably methyl, or a halide ion, preferably chloride or fluoride. Methyl or chloride leaving groups are most preferred. In any embodiment, R1 and R2 may be independently selected from the group consisting of hydrogen, phenyl, and naphthyl. R1 is preferably the same as R2. Particularly advantageous species of Formula I are dimethylsilyl bis(2-methyl-4-phenylindenyl) zirconium dichloride, dimethylsilyl bis(2-methyl-4-phenylindenyl) zirconium dimethyl, dimethylsilyl bis(2-methyl-4-phenylindenyl) hafnium dichloride, and dimethylsilyl bis(2-methyl-4-phenylindenyl) hafnium dimethyl.
Any catalyst system resulting from any combination of a metallocene compound, a cationic activator component, and an anionic activator component mentioned in this disclosure shall be considered to be explicitly disclosed herein and may be used in accordance with the present invention in the polymerization of one or more olefin monomers. Also, combinations of two different activators can be used with the same or different metallocene(s).
In any embodiment, the activators of the catalyst systems used to produce the semi-crystalline polymers may comprise an anionic component, [Y]−. In any embodiment, the anionic component may be a non-coordinating anion (NCA), having the formula [B(R4)4]−, where R4 is an aryl group or a substituted aryl group, of which the one or more substituents are identical or different and are selected from the group consisting of alkyl, aryl, a halogen atom, halogenated aryl, and haloalkylaryl groups. The substituents may be perhalogenated aryl groups, or perfluorinated aryl groups, including, but not limited to, perfluorophenyl, perfluoronaphthyl and perfluorobiphenyl.
Together, the cationic and anionic components of the catalysts systems described herein form an activator compound. In any embodiment, the activator may be N,N-dimethylanilinium-tetra(perfluorophenyl)borate, N,N-dimethylanilinium-tetra(perfluoronaphthyl)borate, N,N-dimethylanilinium-tetrakis(perfluorobiphenyl)borate, N,N-dimethylanilinium-tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbenium-tetra(perfluorophenyl)borate, triphenylcarbenium-tetra(perfluoronaphthyl)borate, triphenylcarbenium-tetrakis(perfluorobiphenyl)borate, or triphenylcarbenium-tetrakis(3,5-bis(trifluoromethyl)phenyl)borate.
A non-coordinating anion activator may be employed with the catalyst. A particularly advantageous activator is dimethylaniliniumtetrakis(heptafluoronaphthyl)borate.
Suitable activators for the processes of the present invention also include aluminoxanes (or alumoxanes) and aluminum alkyls. Without being bound by theory, an alumoxane is typically believed to be an oligomeric aluminum compound represented by the general formula (Rx—Al—O)n, which is a cyclic compound, or Rx (Rx—Al—O)nAlRx2, which is a linear compound. Most commonly, alumoxane is believed to be a mixture of the cyclic and linear compounds. In the general alumoxane formula, Rx is independently a C1-C20 alkyl radical, for example, methyl, ethyl, propyl, butyl, pentyl, isomers thereof, and the like, and n is an integer from 1-50. In any embodiment, Rx may be methyl and n may be at least 4. Methyl alumoxane (MAO), as well as modified MAO containing some higher alkyl groups to improve solubility, ethyl alumoxane, iso-butyl alumoxane, and the like are useful for the processes disclosed herein.
Further, the catalyst systems suitable for use in the present invention may contain, in addition to the transition metal compound and the activator described above, additional activators (co-activators), and/or scavengers. A co-activator is a compound capable of reacting with the transition metal complex, such that when used in combination with an activator, an active catalyst is formed. Co-activators include alumoxanes and aluminum alkyls.
In any embodiment, scavengers may be used to “clean” the reaction of any poisons that would otherwise react with the catalyst and deactivate it. Typical aluminum or boron alkyl components useful as scavengers are represented by the general formula RxJZ2 where J is aluminum or boron, Rx is a C1-C20 alkyl radical, for example, methyl, ethyl, propyl, butyl, pentyl, and isomers thereof, and each Z is independently Rx or a different univalent anionic ligand such as halogen (Cl, Br, I), alkoxide (ORx), and the like. Exemplary aluminum alkyls include triethylaluminum, diethylaluminum chloride, ethylaluminium dichloride, tri-iso-butylaluminum, tri-n-octylaluminum, tri-n-hexylaluminum, trimethylaluminum, and combinations thereof. Exemplary boron alkyls include triethylboron. Scavenging compounds may also be alumoxanes and modified alumoxanes including methylalumoxane and modified methylalumoxane.
The solvent used in the reaction system of the present invention may be any non-polymeric species capable of being removed from the polymer composition by heating to a temperature below the decomposition temperature of the polymer and/or reducing the pressure of the solvent/polymer mixture. In any embodiment, the solvent may be an aliphatic or aromatic hydrocarbon fluid.
Examples of suitable, preferably inert, hydrocarbon fluids are readily volatile liquid hydrocarbons, which include, for example, hydrocarbons containing from 1 to 30, preferably 3 to 20, carbon atoms. Preferred examples include propane, n-butane, isobutane, mixed butanes, n-pentane, isopentane, neopentane, n-hexane, cyclohexane, isohexane, octane, other saturated C6 to C8 hydrocarbons, toluene, benzene, ethylbenzene, chlorobenzene, xylene, desulphurized light virgin naphtha, and any other hydrocarbon solvent recognized by those skilled in the art to be suitable for the purposes of this invention. Particularly preferred solvents for use in the processes disclosed herein are n-hexane and toluene.
The optimal amount of solvent present in combination with the polymer at the inlet to the devolatilizer will generally be dependent upon the desired temperature change of the polymer melt within the devolatilizer, and can be readily determined by persons of skill in the art. For example, the polymer composition may comprise, at the inlet of the devolatilizer, from about 1 wt % to about 50 wt % solvent, or from about 5 wt % to about 45 wt % solvent, or from about 10 wt % to about 40 wt % solvent, or from about 10 wt % to about 35 wt % solvent.
WO Publication No. 2013/134038 generally describes the catalysts, activators, and solvents used to prepare the polymer blend used in the adhesive compositions. The contents of WO Publication No. 2013/134038 is incorporated herein in its entirety.
The term “tackifier” is used herein to refer to an agent that allows the polymer of the composition to be more adhesive by improving wetting during the application. Tackifiers may be produced from petroleum-derived hydrocarbons and monomers of feedstock including tall oil and other polyterpene or resin sources. Tackifying agents are added to give tack to the adhesive and also to modify viscosity. Tack is required in most adhesive formulations to allow for proper joining of articles prior to the HMA solidifying. Useful commercial available tackifiers include the Escorez™ series, available from ExxonMobil Chemical, such as Escorez™ 5415.
Although the exemplary formulations disclosed herein focus on formulations in which one or more tackifiers are blended with one or more polymer blends, adhesive formulations having no tackifier or substantially no tackifier are also contemplated. In embodiments, other tackifiers may be used with the polymer blends of the invention including, but not limited to, alkylphenolic, coumarone indene, other hydrogenated or non-hydrogenated hydrocarbon resins, hydroxylated polyester resin, phenolic, pure monomer styrene, resin dispersion, rosin ester, rosin, and terpene tackifiers. Generally, the tackifier of the HMA ranges from about 5 wt % to about 25 wt % of the adhesive composition. Preferably, the tackifier is present in the HMA within the range of about 5 wt % or 10 wt % or 15 wt % or 20 wt % to less than about 25 wt % of the adhesive composition.
The HMA composition can include other additives, e.g., plasticizers, waxes, antioxidants, fillers, rheology improvers and combinations thereof either alone or in combination with one or more tackifiers disclosed herein. The HMA composition can also include one or more polymer additives, either alone or in combination with one or more tackifiers, plasticizers, waxes, antioxidants, or functionalized polyolefins, and combinations thereof as disclosed herein. In an embodiment, it is also appreciated that one or more additives, including but not limited to antioxidants, may be added during the process to prepare the polymer blends described herein.
The term “plasticizer” is used herein to refer to a substance that improves the fluidity of a material. Useful commercial available plasticizers include Primol™ 352, a white oil available from ExxonMobil Chemical.
The term “antioxidant” is used herein to refer to high molecular weight hindered phenols and multifunctional phenols. A useful commercially available antioxidant is Irganox™ 1010. Irganox 1010 is a hindered phenolic antioxidant available from BASF SE Corporation located in Ludwigshafen, Germany. The invention is not limited to Irganox 1010 as the antioxidant. In embodiments, other antioxidants that may be used with the polymer blends of the invention, including, but are not limited to amines, hydroquinones, phenolics, phosphites, and thioester antioxidants.
The term “wax” is used herein to refer to a substance that tweaks the overall viscosity of the adhesive composition. The primary function of wax is to control the set time and cohesion of the adhesive system. Adhesive compositions of the present invention may comprise paraffin (petroleum) waxes and microcrystalline waxes. In embodiments, the adhesive compositions of the present invention may comprise no wax. In embodiments, waxes may be used with the polymer blends of the invention including, but not limited to, Castor Oil derivatives (HCO-waxes), ethylene co-terpolymers, Fisher-Tropsch waxes, microcrystalline, paraffin, polyolefin modified, and polyolefin.
The term “functionalized polyolefin” is used herein to refer to maleic anhydride-modified polypropylene and maleic anhydride-modified polypropylene wax. A useful commercially available functionalized polyolefin is Honeywell AC™-596. AC-596 is polypropylene-maleic anhydride copolymer from Honeywell. Generally, the functionalized polymer is present in the adhesive composition in the amount of less than or equal to about 5 wt %.
The HMA composition can include additives known in the art as “fillers” and/or “rheology improvers” to reduce sagging in the final woodworking application. The use of fillers and/or rheology improvers can also serve to reduce costs associated with preparing HMA formulations as the polymer blend loading of such formulations can be lowered. Preferred fillers include silicates, ceramics, glass, quartz, mica, titanium dioxide, graphite, talcum, calcium carbonates, barium sulfate, silica, glass beads, mineral aggregates, clays, or carbon black. Suitable rheology improvers imparting thixotropy or sag resistance are, for example, organically modified clays, pyrogenic (fumed) silicas, urea derivatives and fibrillated or pulp chopped fibers. The polymer blend of the HMA of the present invention is present in the amount of about 75 to about 95 wt % of the adhesive composition, wherein the adhesive composition does not contain any filler and/or rheology improver. In an embodiment of the present invention, one or more fillers and/or rheology improvers may be added. In such an embodiment, the polymer blend of the HMA will be present in the amount of about 50 to about 95 wt % of the adhesive composition. Preferably, the polymer blend will be present in the HMA, wherein the HMA contains one or more fillers and/or rheology improvers, within the range of about 50 wt % or 55 wt % or 60 wt % or 65 wt % or 70 wt % or 75 wt % or 80 wt % or 85 wt % to less than about 90 wt % or 95 wt % of the adhesive composition.
The HMA composition of the present invention can optionally include one or more amorphous poly-alpha-olefins or “APAO.” Useful commercially available APAOs include REXtac® available from Hunstman and Vestoplast® available from Degussa. In an embodiment, the HMA composition of the present invention can include one or more crystalline polypropylenes. A useful commercially available crystalline polypropylene is Achieve™ available from ExxonMobil Chemical.
The adhesive formulations disclosed herein can be used in various woodworking applications including, but not limited to furniture, toys, musical instruments, window frames and sills, doors, flooring, fencing, tools, ladders, sporting goods, dog houses, gazebos/decks, picnic tables, playground structures, planters, scaffolding planks, kitchen utensils, coffins, church pews/altars, and canes. The adhesive formulations described herein, having a high polymer load, provide a desired combination of physical properties such as stable adhesion over time, indicative of broad application temperature ranges, and a long open time and therefore can be used in a variety of woodworking applications disclosed herein. It should be appreciated that the adhesive formulations of the present disclosure, while being well suited for use in woodworking products, may also find utility in other applications as well.
In a particular embodiment, a woodworking process to prepare the woodworking application involves forming a woodworking article by applying an adhesive composition to at least a portion of a structural element. The structural element can include a variety of materials, which include, but are not limited to wood or plywood, or plastic or veneer. For example, the structural element can also include lumber, wood, fiberboard, plasterboard, gypsum, wallboard, plywood, PVC, melamine, polyester, impregnated paper and sheetrock. A woodworking process can be used to form indoor furniture, outdoor furniture, trim, molding, doors, sashes, windows, millwork and cabinetry, for example.
“Peel” or is a measure of the amount of a substrate that remains bonded to the HMA after the substrate is manual peeled from the HMA. Peel is measured in %. In the present invention, Peel was measured by the following method. A 3 cm×7 cm portion of the substrate Alkorcell #5 was cut. Alkorcell is pattern foil used for facing chipboards for furniture production, edging, user electronics, ceiling panels, elements for interior doors. 0.3 g of molten HMA composition was placed on a 5 cm×13 cm wooden plate. The substrate was bonded to the wooden plate via the molten HMA. To ensure good adhesion, a 2 kg weight was placed on the bonded area for 1 minute. The bonded samples were stored at room temperature for 24 hours and manually peeled by hand. Another set of samples were stored at 6° C. for 24 hours and manually peeled by hand. The amount of substrate that remains bonded to the HMA after the substrate is manual peeled from the HMA was recorded as the Peel at Room Temperature and as the Peel at 6° C., respectively. As used herein, the term “Room Temperature” is used to refer to the temperature range of about 20° C. to about 23.5° C. A Peel of 100% means that all of the substrate remained bonded to the HMA, indicating a strong adhesive bond. Peel was also measured at various intervals: after 5 seconds, after 10 seconds, after 15 seconds, and after 20 seconds of bonding in order to assess the open time. For the open time evaluation, a 100 g weight was placed on the bonded area for 1 minute.
“Shear Adhesion Failure Temperature” or “SAFT” is defined as the temperature at which the adhesive bond of the composition fails when the bond is subjected to a stepwise temperature increase under a constant force that pulls the bond in the shear mode. In the present invention, SAFT was measured by the following method. A 12 g sample of HMA was place in a square mold (15 cm×15 cm) 200-micron thick and put between two silicon papers in a press operated at 160° C. The press can be operated by the following procedure: a 7 minute preheating step, a 7 minute degassing step, a 30 second pressurizing step at 100 kN, and a cooling step using plates operated at room temperature for 30 seconds at 100 kN pressure. As used herein, the term “Room Temperature” is used to refer to the temperature range of about 20° C. to about 23.5° C. A 2 cm×2 cm area of HMA cut from the HMA preparation plate was placed on a 2.5 cm×8 cm wood sample in an oven for 5 minutes at 190° C. A 2.2 cm×7 cm strip of wood laminate substrate was placed on top of the molten HMA. To ensure a good adhesion, a 2 kg weight was placed on the bonded area for 1 minute. After a conditioning for 24 hours at 23° C. and 50% Relative Humidity, the test specimens were suspended vertically in an oven at 50° C. with a 1 kg load attached to the bottom and were held for 1 hour. The temperature of the oven was increased by 10° C. during 5-minute intervals, after which the specimen was held for 55 minutes at this temperature. The temperature was gradually increased until the bond failed, at which point the temperature and time were recorded. Adhesives possessing high failure temperature are essential for the assembly of woodworking goods that are often subjected to very high temperatures when exposed to sunlight, e.g., furniture positioned next to a window. Generally, the SAFT of the HMA of the present invention ranges from about 70° C. to about 120° C. Preferably, the SAFT is within the range of about 80° C. or 90° C. or 100° C. or 110° C. to less than about 120° C.
“Peel Adhesion Failure Temperature” or “PAFT” is defined as the temperature at which the HMA bond fails, when it is submitted to increased heat and constant stress. In the present invention, PAFT was measured by the following method. A 2 cm×2 cm area of HMA was placed on a 2.5 cm×8 cm wood sample and placed in an oven for 5 minutes at 190° C. A 2.2 cm×7 cm strip of substrate, Alkorcell #5, was placed on top of the molten HMA. To ensure good adhesion, a 2 kg weight was placed on the bonded area for 1 minute. The test specimen had a 100 g load attached by a hook to the Alkorcell #5 substrate and was placed horizontally in an oven at 50° C. and were held for 1 hour. The temperature of the oven was increased by 10° C. over a 5 minute interval, after which the specimen was held for 55 minutes. The temperature of the oven was gradually increased until the bond failed, at which point the temperature was recorded. Generally, the PAFT of the HMA of the present invention ranges from about 50° C. to about 100° C. Preferably, the PAFT is within the range of about 60° C. or 70° C. or 80° C. or 90° C. to less than about 100° C.
The tensile properties measured in the present invention include “Tensile Elongation at Break” and “Tensile Strength.” To measure the tensile properties, samples of the HMA were prepared according to ASTM D 638. The sample was fixed between 2 clamps, positioned 80 mm apart. A 0.5N load was applied to the sample and measurements were taken as the sample extends, yields, further extends, and breaks. The Tensile Elongation at Break is a measure of the increase in distance between the clamps initially and at the break point, measured in %. Generally, the Tensile Elongation at Break of the HMA ranges from about 200% to about 2000%. Preferably, the Tensile Elongation at Break is within the range of about 200% or 300% or 400% or 500% or 600% or 700% or 800% or 900% or 1000% or 1100% or 1200% or 1300% or 1400% or 1500% or 1600% to less than about 1700% or 1800% or 1900% or 2000%. Tensile Strength is the maximum stress that a material can withstand before breaking, measured in MPa. Generally, the Tensile Strength of the HMA ranges from about 1 MPa to about 10 MPa. Preferably, the Tensile Strength is within the range of about 1.5 MPa or 2 MPa or 3 MPa or 4 MPa or 5 MPa or 6 MPa or 7 MPa to less than about 8 MPa or 9 MPa or 10 MPa.
“Agglomeration” of the pellets of the HMA compositions was measured to evaluate the stability of the composition during storage and/or transportation. 35 g of HMA pellet samples and optionally dusting powder (as an anti-agglomeration agent) was placed inside a glass container having a diameter of about 40 mm. The container was placed inside an air-ventilated oven and a weight was placed on top of the pellets to compress the pellets. To replicate a 1 ton supersack or a 1 ton pallet build from a 25 kg bag, the mass of the weight used was 1160 g. The temperature of the oven can be adjusted at a specified temperature, from room temperature up to 55° C. The samples were removed from the glass container, subjected to a tensile machine and tested between 2 compression plates to determine the force required to separate the pellets. Qualitative observations of the pellets were recorded, such as “No Separation” (i.e., there is no separation in the pellets), “Block Break” (i.e., the agglomerated block breaks up in large lumps), “Good Separation” (i.e., the agglomerated block breaks up in small lumps and some pellets separate), or “Full Separation” (i.e., the majority of the pellets separate). In the present invention, Polymer Blend A and Polymer Blend B displayed favorable agglomeration when subjected to the above-mentioned test. Specifically, both samples showed Full Separation of the pellets and there was no evidence of sticky pellets upon visually observing the samples. Accordingly, the inventive formulations display favorable storage and/or transportation stability.
“Thermal Stability” of the HMA compositions was measured by placing a sample of HMA in an oven for 8 hours at 190° C., to simulate aging in warehouse conditions. Following the aging test, the samples were observed for yellowing/discoloration, indicating a decrease in stability of the sample. 4 inventive formulations (Polymer Blends D, E, G, and I) and Comparative were evaluated. All 4 inventive formulations displayed noticeably less yellowing/discoloration as compared to the Comparative formulation.
“Melt Viscosity” of the polymer blend and the HMA composition was measured with a Brookfield™ rotoviscometer, according to ASTM D-3236-88. Generally, the melt viscosity of the polymer blend ranges from about 1,000 cP to about 20,000 cP. Preferably, the melt viscosity is within the range of about 1,000 cP or 2,000 cP or 3,000 cP or 4,000 cP or 5,000 cP or 6,000 cP or 7,000 cP or 8,000 cP or 9,000 cP or 10,000 cP or 11,000 cP or 12,000 cP or 13,000 cP or 14,000 cP to less than about 15,000 cP or 16,000 cP or 17,000 cP or 18,000 cP or 19,000 cP or 20,000 cP.
In a pilot plant, propylene-ethylene copolymers are produced by reacting a feed stream of propylene with a feed stream of ethylene in the presence of a metallocene catalyst. The polymer blends used in the Examples of the present invention were produced in accordance with the method disclosed above and by the method generally described for preparing polyolefin adhesive components and compositions in WO Publication No. 2013/134038. Table 1 shows properties of the polymer blends used in the Examples.
The adhesive blends presented in the Tables below are prepared by the method described herein. The polymer blend was mixed with antioxidant in a Z Blade mixer. Tackifier was added when the polymer became molten. After 10 minutes, the functionalized polyolefin was added. After 60 minutes, a tray of release paper was positioned underneath the mixer. The mixer was stopped and the blend was poured on to the tray.
The comparative example (referred to herein as Comparative) is the commercially available premium grade of hot melt adhesives used for woodworking applications by ExxonMobil Chemical: Linxar™ 205.
Table 1 lists the polymer blends used in the examples of the invention. The invention is not limited to the polymer blends disclosed in Table 1.
Table 2 shows viscosity, SAFT, PAFT, Tensile Strength, Tensile Elongation and Break, Peel at Room Temperature and at 6° C. of 5 adhesive formulations and the Comparative formulation 6A. All formulations, including the Comparative 6A, displayed favorable Peel values at both Room Temperature and at 6° C., indicating stable adhesion. However, Comparative 6A displayed a significantly lower Tensile Strength value compared to all of the inventive formulations 1A to 5A. Likewise, Comparative 6A also displayed a lower Tensile Elongation at Break compared to inventive formulations 2A to 5A, indicating a lower cohesiveness strength of the bond required during the manufacturing process of woodworking applications. While the tensile properties—Tensile Strength and Tensile Elongation at Break—did not correlate directly with the polymer blend melting temperature, the Tensile Strength did correlate with the formulation viscosity: higher formulation viscosities generally resulted in higher Tensile Strength.
The SAFT and PAFT values of Comparative 6A were also unfavorable. Generally, SAFT and PAFT temperatures of the inventive formulations correlate with the respective polymer blend melting temperature. SAFT and PAFT of 6A was lower than those of formulations 2A and 3A, despite that the polymer blend melting temperatures of 2A and 3A were similar to that of the Comparative 6A. The adhesive formulations of Table 2 can be used in construction/finalized woodworking applications given their display of stable adhesion over a broad application temperature without compromising tensile/shear properties.
Table 3 shows Peel after different open times of 5 seconds, 10 seconds, 15 seconds, and 20 seconds for 7 adhesive formulations and the Comparative formulation 8B. Inventive formulations 1B to 4B generally displayed satisfactory Peel values at all-time intervals. While the Comparative 8B also displayed stable Peel values, the Comparative did not display stable adhesion over a wide temperature range (by way of SAFT and PAFT measurements as indicated in Table 2). Formulations 5B and 7B did not maintain the high Peel after 10 seconds, 15 seconds, or after 20 seconds. Formulation 6B did not display high Peel at any time interval. However, as Table 2 indicates, these formulations (by way of formulation 4A and 5A) maintain stable adhesion over broad temperatures and sufficient tensile properties. Table 3 generally indicates that at higher polymer blend melt temperatures, the open time of the adhesive composition is compromised.
Accordingly, depending on the desired property of the adhesive bond for the respective woodworking application—whether a long open time and a stable adhesion temperature or a stable adhesion temperature without a long open time is desired—the appropriate formulation can be chosen from the disclosed inventive HMA formulations. The inventive polymers described herein are designed to enable an appropriate balance between the high crystallinity/high melting temperature and open time depending on the desired application.
The invention may also be understood with relation to the following specific embodiments:
Paragraph A: An adhesive composition comprising (i) a polymer blend comprising (a) a first propylene-based polymer, wherein the first propylene-based polymer is a homopolymer of propylene or a copolymer of propylene and ethylene or a C4 to C10 alpha-olefin; and (b) a second propylene-based polymer, wherein the second propylene-based polymer is a homopolymer of propylene or a copolymer of propylene and ethylene or a C4 to C10 alpha-olefin; wherein the second propylene-based polymer is different than the first propylene-based polymer; wherein the polymer blend has a melt temperature of about 75 to about 125° C.; and wherein the polymer blend is present in the amount of about 75 to about 95 wt % of the adhesive composition; and (ii) a tackifier present in the amount of less than or equal to about 25 wt % of the adhesive composition.
Paragraph B: The adhesive composition of Paragraph A, further comprising an additive selected from the group consisting of antioxidants, plasticizers, fillers, rheology improvers, and mixtures thereof.
Paragraph C: The adhesive composition of Paragraph A or B, further comprising a wax present in the amount of less than or equal to about 5 wt % of the adhesive composition.
Paragraph D: The adhesive composition of Paragraph A and optionally Paragraph B and/or C, further comprising a functionalized polyolefin selected from the group consisting of a maleic anhydride-modified polypropylene and a maleic anhydride-modified polypropylene wax, wherein the polyolefin is present in the amount of less than or equal to about 5 wt % of the adhesive composition.
Paragraph E: The adhesive composition of Paragraph A and optionally any one or any combination of Paragraphs B to D, wherein the adhesive composition has a SAFT of about 70° C. to about 120° C.
Paragraph F: The adhesive composition of Paragraph A and optionally any one or any combination of Paragraphs B to E, wherein the adhesive composition has a PAFT of about 50° C. to about 100° C.
Paragraph G: The adhesive composition of Paragraph A and optionally any one or any combination of Paragraphs B to F, wherein the adhesive composition has an Elongation at Break of about 200% to about 2000%.
Paragraph H: The adhesive composition of Paragraph A and optionally any one or any combination of Paragraphs B to G, wherein the adhesive composition has a Tensile Strength of about 1 MPa to about 10 MPa.
Paragraph I: An article comprising the adhesive composition of Paragraph A and optionally any one or any combination of Paragraphs B to H.
Paragraph J: An article of Paragraph I, wherein the adhesive composition adheres one or more substrates, and wherein at least one of the one or more substrates comprises paper, cardboard, plastic, nonwoven, metal, wood, other natural fiber based material, or combinations thereof.
Paragraph K: An adhesive composition comprising a polymer blend comprising (a) a first propylene-based polymer, wherein the first propylene-based polymer is a homopolymer of propylene or a copolymer of propylene and ethylene or a C4 to C10 alpha-olefin; and (b) a second propylene-based polymer, wherein the second propylene-based polymer is a homopolymer of propylene or a copolymer of propylene and ethylene or a C4 to C10 alpha-olefin; wherein the second propylene-based polymer is different than the first propylene-based polymer; wherein the polymer blend has a melt viscosity of about 1,000 cP to about 20,000 cP.
Paragraph L: The adhesive composition of Paragraph K, wherein the polymer blend is present in the amount of about 75 to about 95 wt % of the adhesive composition; and wherein the adhesive composition further comprises a tackifier, wherein the tackifier is present in the amount of less than or equal to about 25 wt % of the adhesive composition.
Paragraph M: The adhesive composition of Paragraph K or L, further comprising an additive selected from the group consisting of antioxidants, plasticizers, fillers, rheology improvers, and mixtures thereof.
Paragraph N: The adhesive composition of Paragraph K and optionally Paragraph L and/or M, further comprising a wax present in the amount of less than or equal to about 5 wt % of the adhesive composition.
Paragraph O: The adhesive composition of Paragraph K and optionally any one or any combination of Paragraphs L to N, further comprising a functionalized polyolefin selected from the group consisting of a maleic anhydride-modified polypropylene and a maleic anhydride-modified polypropylene wax, wherein the functionalized polyolefin is present in the amount of less than or equal to about 5 wt % of the adhesive composition.
Paragraph P: The adhesive composition of Paragraph K and optionally any one or any combination of Paragraphs L to 0, wherein the adhesive composition has a SAFT of about 70° C. to about 120° C.
Paragraph Q: The adhesive composition of Paragraph K and optionally any one or any combination of Paragraphs L to P, wherein the adhesive composition has a PAFT of about 50° C. to about 100° C.
Paragraph R: The adhesive composition of Paragraph K and optionally any one or any combination of Paragraphs L to Q, wherein the adhesive composition has an Elongation at Break of about 200% to about 2000%.
Paragraph S: The adhesive composition of Paragraph K and optionally any one or any combination of Paragraphs L to R, wherein the adhesive composition has a Tensile Strength of about 1 MPa to about 10 MPa.
Paragraph T: An article comprising the adhesive composition of Paragraph K and optionally any one or any combination of Paragraphs L to S.
Paragraph U: An article of Paragraph T, wherein the adhesive composition adheres one or more substrates, and wherein at least one of the one or more substrates comprises paper, cardboard, plastic, nonwoven, metal, wood, other natural fiber based material, or combinations thereof.
Paragraph V: The adhesive composition of Paragraph K and optionally any one of any combination of Paragraphs L to S, wherein the adhesive further comprises an amorphous poly-alpha-olefin.
Paragraph W: A process to prepare an adhesive composition, comprising blending (a) a polymer blend, comprising a first propylene-based polymer, wherein the first propylene-based polymer is a homopolymer of propylene or a copolymer of propylene and ethylene or a C4 to C10 alpha-olefin; and a second propylene-based polymer, wherein the second propylene-based polymer is a homopolymer of propylene or a copolymer of propylene and ethylene or a C4 to C10 alpha-olefin; wherein the second propylene-based polymer is different than the first propylene-based polymer; wherein the polymer blend is present in the amount of about 75 to about 95 wt % of the adhesive composition; and (b) a tackifier, wherein the tackifier is present in the amount of less than or equal to about 25 wt % of the adhesive composition.
Paragraph X: The process of Paragraph W, wherein the polymer blend has a melt temperature of about 75 to about 125° C.
Paragraph Y: The process of Paragraph W, wherein the polymer blend has a melt viscosity of about 1,000 cP to about 20,000 cP.
Certain embodiments and features have been described using a set of numerical upper limits and a set of numerical lower limits. It should be appreciated that ranges from any lower limit to any upper limit are contemplated unless otherwise indicated. Certain lower limits, upper limits, and ranges appear in one or more claims below. All numerical values are “about” or “approximately” the indicated value, and take into account experimental error and variations that would be expected by a person having ordinary skill in the art.
To the extent a term used in a claim is not defined above, it should be given the broadest definition persons in the pertinent art have given that term as reflected in at least one printed publication or issued patent. Furthermore, all patents, test procedures, and other documents cited in this application are fully incorporated by reference to the extent such disclosure is not inconsistent with this application and for all jurisdictions in which such incorporation is permitted.
While the foregoing is directed to embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.
This application claims the benefit of priority to U.S. Provisional Application No. 61/946,084 filed Feb. 28, 2014, the disclosure of which is fully incorporated herein by its reference.
| Number | Date | Country | |
|---|---|---|---|
| 61946084 | Feb 2014 | US |
