CN102146191A - Mixture of conjugated diene-vinyl aromatic hydrocarbon copolymers and adhesive composite containing same - Google Patents
Mixture of conjugated diene-vinyl aromatic hydrocarbon copolymers and adhesive composite containing same Download PDFInfo
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- CN102146191A CN102146191A CN2010101140063A CN201010114006A CN102146191A CN 102146191 A CN102146191 A CN 102146191A CN 2010101140063 A CN2010101140063 A CN 2010101140063A CN 201010114006 A CN201010114006 A CN 201010114006A CN 102146191 A CN102146191 A CN 102146191A
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Abstract
The invention provides a mixture of conjugated diene-vinyl aromatic hydrocarbon copolymers and an adhesive composite containing same. The mixture of conjugated diene-vinyl aromatic hydrocarbon copolymers comprises the following components by weight percent: 10-45% of conjugated diene-vinyl aromatic hydrocarbon diblock copolymer, 10-45% of conjugated diene-vinyl aromatic hydrocarbon tapered diblock copolymer and 10-80% of conjugated diene-vinyl aromatic hydrocarbon multiblock copolymer.
Description
Technical field
The present invention relates to the mixture of a kind of conjugated diolefine-vinyl aromatic hydrocarbon copolymer and comprise the sticking agent composition of this mixture, relate in particular to a kind of mixture, and a kind ofly be used for the sticking agent composition that preparation has the sticking agent that improves initial viscosity (initialtack), stripping strength (peel strength) and shearing stamina (holding power) with the conjugated diolefine-vinyl aromatic hydrocarbon copolymer that improve to extend (elongation) character.
Background technology
Industrial often with the main material of conjugated diolefine (conjugated diene)-vinylaromatic hydrocarbon (vinyl aromatichydrocarbon) block polymer as the sticking agent composition, and these sticking agent compositions for example can be applicable to adhesive tape, label and as diaper, female pathology articles for use and surgical operation with in the soft object of disposable types such as coverture for the usefulness of sticking together.
U.S. Patent number 5,089,550 disclose a kind of block copolymer composition, and it comprises conjugated diolefine-vinylaromatic hydrocarbon di-block copolymer of 50～85wt% and vinylaromatic hydrocarbon-conjugated diolefine-vinylaromatic hydrocarbon triblock copolymer of 15～50wt%.This block copolymer composition can be used in the sticking agent composition.
U.S. Patent number 5,112,889 disclose a kind of pressure sensitive adhesive (pressure-sensitive adhesive), it comprises the A-B-A block polymer, the perhaps AB segmented copolymer of the geometrical shape of tapered block copolymer (tapered block copolymer) or radial pattern (radial) segmented copolymer for example, wherein the A block obtains from vinylbenzene or alpha-methyl styrene, and the B block obtains from isoprene, divinyl or its hydrogenation state.
U.S. Patent number 5,420,203 disclose a kind of method that forms segmented copolymer, its earlier with at least a vinylaromatic hydrocarbon of anionoid polymerization and at least a conjugated diolefine to form an activity (living) segmented copolymer, then add a coupler (coupling agent) with the in addition coupling of above-mentioned reactive block copolymers, and then in the mode of heating with coupling segmented copolymer decoupling.
U.S. Patent number 5,510,423 disclose a kind of line-type block polymer A-B-C-D of conjugated diolefine-vinylaromatic hydrocarbon, wherein A and D are mainly the vinylaromatic hydrocarbon polymer blocks, B is mainly the conjugated diolefin polymer block, C represents to comprise the alternation block of the vinylaromatic hydrocarbon that is occurred in the conjugated diolefine that occurred in the B block and the D block, and wherein the vinylaromatic hydrocarbon in the C block increases on the direction of D block gradually.This line-type block polymer can use in the sticking agent composition.
U.S. Patent number 5,719,226 disclose a kind of hot melt adhesive sticking agent (hotmelt adhesive) composition with low-viscosity (viscosity), and it comprises an adulterant that is made of not hydrogenation or hydrogenant vinylbenzene-diene triblock copolymer and unhydrided styrene-isoprene di-block copolymer.
Above-mentioned United States Patent (USP) case discloses some different segmented copolymers of forming and has comprised the sticking agent composition of this segmented copolymer, and different sticking agent compositions will form the sticking agent of different qualities, to be suitable for different application.Generally speaking, character such as initial viscosity, stripping strength and shearing stamina are extremely important for the application of sticking agent, in order to promote the scope of application of sticking agent, therefore provide a kind of and can be used for preparing sticking agent composition and be necessary with the sticking agent that improves initial viscosity, stripping strength and shearing stamina.
Summary of the invention
One of purpose of the present invention is for providing a kind of mixture that improves the conjugated diolefine-vinyl aromatic hydrocarbon copolymer that extends character that has, and it can be used for the characteristic of plastic cement upgrading or improvement sticking agent.
Another object of the present invention is for providing a kind of sticking agent composition with the sticking agent that improves initial viscosity, stripping strength and shearing stamina that is used to prepare, it can effectively improve the value added of conjugated diolefine-vinylaromatic hydrocarbon copolymer product, significantly enlarges the Application Areas of conjugated diolefine-vinyl aromatic hydrocarbon copolymer simultaneously.
For reaching above-mentioned and other purposes, one embodiment of the invention provides the mixture of a kind of conjugated diolefine-vinyl aromatic hydrocarbon copolymer, and it comprises conjugated diolefine-vinylaromatic hydrocarbon alternation di-block copolymer (tapered block copolymer) of conjugated diolefine-vinylaromatic hydrocarbon di-block copolymer (di-block copolymer) of about 10～45wt%, about 10～45wt% and conjugated diolefine-vinylaromatic hydrocarbon segmented copolymer (multi-block copolymer) of about 10～80wt%.
Another embodiment of the present invention provides a kind of sticking agent composition, and it comprises the mixture of the above-mentioned conjugated diolefine-vinyl aromatic hydrocarbon copolymer of 100 weight parts, and the viscosity increaser of 1～700 weight part.
For above-mentioned and other purposes, feature and advantage of the present invention can be become apparent, cited below particularlyly go out preferred embodiment with as detailed description.
Embodiment
" one " of the present invention or " a kind of " are not the restriction that is used for as on the actual quantity, unless otherwise.
One embodiment of the invention mainly provides a kind of mixture that improves the conjugated diolefine-vinyl aromatic hydrocarbon copolymer that extends character that has, and it can be used for the characteristic of plastic cement upgrading or improvement sticking agent.
The mixture of the conjugated diolefine that present embodiment provided-vinyl aromatic hydrocarbon copolymer comprises:
The conjugated diolefine of 10～45wt%-vinylaromatic hydrocarbon di-block copolymer;
The conjugated diolefine of 10～45wt%-vinylaromatic hydrocarbon alternation di-block copolymer; And
The conjugated diolefine of 10～80wt%-vinylaromatic hydrocarbon segmented copolymer.
The weight percent of above-mentioned each segmented copolymer is a benchmark with the weight of the mixture of conjugated diolefine-vinyl aromatic hydrocarbon copolymer.And in some cases, also can comprise an amount of additive in the mixture of conjugated diolefine-vinyl aromatic hydrocarbon copolymer to improve its character, for example add a spot of antioxidant and be beneficial to preserve.
Above-mentioned di-block copolymer, alternation di-block copolymer and segmented copolymer are polymerized by conjugate diene monomer and vinyl aromatic hydrocarbon monomer respectively.In the present embodiment, conjugate diene monomer (monomer) can be for example from 1,3-divinyl (1,3-butadiene), 2,3-dimethyl-1,3-divinyl (2,3-dimethyl-1,3-butadiene), 3-butyl-1,3-octadiene (3-butyl-1,3-octadiene), isoprene (isoprene), m-pentadiene (trans-1,3-pentadiene), 2-phenyl-1,3-divinyl (2-phenyl-1,3-butadiene) and in the group that forms of above-mentioned composition choose, vinyl aromatic hydrocarbon monomer can be for example from vinylbenzene (styrene), alpha-methyl styrene (α-methyl styrene), to ethyl styrene (p-ethyl styrene), phenylcyclohexane ethene (cyclohexyl styrene), p-methylstyrene (p-methylstyrene), o-methyl styrene (o-methyl styrene), between vinyl toluene (m-methyl styrene), 1-vinyl-5-hexyl naphthalene (1-vinyl-5-hexyl naphthalene), choose in the group that vinylnaphthalene (vinyl naphthalene) and above-mentioned composition are formed, yet the also visual actual needs of the present invention uses other conjugate diene monomers and vinyl aromatic hydrocarbon monomer.In one embodiment, conjugated diolefine-vinyl aromatic hydrocarbon block copolymer is preferably butadiene/styrene copolymers or the isoprene/styrol copolymer that has industrial value.
Conjugated diolefine-vinylaromatic hydrocarbon di-block copolymer is made of a conjugation diene polymer block (polymerblock) and a vinylaromatic hydrocarbon polymer blocks, wherein above-mentioned conjugated diolefin polymer block is polymerized by conjugate diene monomer, and the vinylaromatic hydrocarbon polymer blocks is polymerized by vinyl aromatic hydrocarbon monomer.In one embodiment, conjugated diolefine-vinylaromatic hydrocarbon di-block copolymer can have weight average molecular weight (weight-average molecular weight; Mw) about 2 * 10
4～10 * 10
4G/mol, preferable about 4 * 10
4～8 * 10
4G/mol, better about 5 * 10
4～7.5 * 10
4G/mol; Conjugated diolefine-vinylaromatic hydrocarbon bi-block copolymer can have the about 25～50wt% of vinyl aromatic hydrocarbon content, preferable about 30～45wt%, better about 35～40wt%.
Conjugated diolefine-vinylaromatic hydrocarbon alternation di-block copolymer mainly comprises a polymer blocks and an alternation section (tapered segment).In one embodiment, the polymer blocks of conjugated diolefine-vinylaromatic hydrocarbon alternation di-block copolymer is polymerized by vinyl aromatic hydrocarbon monomer, and alternation Duan Ze is polymerized jointly by conjugate diene monomer and vinyl aromatic hydrocarbon monomer.In another embodiment, the terminal preferable of alternation section of conjugated diolefine-vinylaromatic hydrocarbon alternation di-block copolymer mainly is polymerized by vinyl aromatic hydrocarbon monomer.In one embodiment, conjugated diolefine-vinylaromatic hydrocarbon alternation di-block copolymer can have weight average molecular weight about 2 * 10
4～10 * 10
4G/mol, preferable about 4 * 10
4～8 * 10
4G/mol, better about 5 * 10
4～7.5 * 10
4G/mol; Conjugated diolefine-vinylaromatic hydrocarbon alternation di-block copolymer can have the about 25～55wt% of vinyl aromatic hydrocarbon content, preferable about 30～50wt%, better about 35～45wt%.
Conjugated diolefine-vinylaromatic hydrocarbon segmented copolymer three blocks or three multipolymers more than the block for being constituted by conjugated diolefin polymer block and vinylaromatic hydrocarbon polymer blocks.In one embodiment, conjugated diolefine-vinylaromatic hydrocarbon segmented copolymer can have weight average molecular weight about 5 * 10
4～20 * 10
4G/mol, preferable about 8 * 10
4～17 * 10
4G/mol, better about 10 * 10
4～15 * 10
4G/mol; Conjugated diolefine-vinylaromatic hydrocarbon segmented copolymer can have the about 25～50wt% of vinyl aromatic hydrocarbon content, preferable about 30～45wt%, better about 35～40wt%.
Mixture according to conjugated diolefine-vinyl aromatic hydrocarbon copolymer that one embodiment of the invention provided can have weight average molecular weight between 2 * 10
4～20 * 10
4Between the g/mol.
In embodiments of the present invention, above-mentioned weight average molecular weight utilizes Waters Pump 515 gel permeation chromatographs (GPC) collocation RI Detector-2414 detector and Shodex Column tubing string to measure.The dry micelle of 0.02 gram polymkeric substance is dissolved in the tetrahydrofuran (THF) (THF) of 10 milliliters (ml) preparing a solution, and this solution of 70 microlitres (μ l) is injected in the gel permeation chromatograph (GPC) measures to obtain the weight average molecular weight of polymkeric substance.And above-mentioned " vinyl aromatic hydrocarbon content " accounts for all monomeric total weight percent of formation conjugated diolefine-vinyl aromatic hydrocarbon block copolymer for the gross weight in order to the vinyl aromatic hydrocarbon monomer that forms conjugated diolefine-vinylaromatic hydrocarbon block polymer.
Can constitute by identical or different conjugate diene monomer between each conjugated diolefin polymer block in above-mentioned conjugated diolefine-vinyl aromatic hydrocarbon block copolymer that present embodiment provided, and also can be made of identical or different vinyl aromatic hydrocarbon monomer between each vinylaromatic hydrocarbon polymer blocks, and each conjugated diolefin polymer block and vinylaromatic hydrocarbon polymer blocks also can be according to the demands of Industrial products characteristic and use knockdown conjugate diene monomer or vinyl aromatic hydrocarbon monomer to carry out copolymerization respectively to form.
In one embodiment, the mixture of conjugated diolefine-vinyl aromatic hydrocarbon copolymer can utilize a kind of solution blending means and form.In this solution blending means, at first utilize polyreaction to form the polymers soln of each different conjugated diolefines-vinyl aromatic hydrocarbon copolymer, the polymers soln with above-mentioned conjugated diolefine-vinyl aromatic hydrocarbon copolymer is mixed in varing proportions to form a mixed with polymers solution then.Then with this mixed with polymers solution removal solvent and drying, to obtain the mixture of solid-state conjugated diolefine-vinyl aromatic hydrocarbon copolymer.
The solvent that is used for carrying out polyreaction is preferably inert organic solvents, and it can comprise for example aromatic hydrocarbon, straight or branched hydrocarbon polymer, cycloalkanes ether and alicyclic hydrocarbon type etc.Aromatic hydrocarbon can comprise for example benzene (benzene), toluene (toulene), dimethylbenzene (xylene) and ethylbenzene organic solvents such as (ethyl benzene); The straight or branched hydrocarbon polymer can comprise for example Skellysolve A (n-pentane), normal hexane (n-hexane), normal heptane (n-Heptane), octane (n-octane) and other analogue; Cycloalkanes ether can comprise for example tetrahydrofuran (THF) (tetrahydrofuran; THF) etc.; Alicyclic hydrocarbon type then can comprise for example pentamethylene (cyclopentane), hexanaphthene (cyclohexane), methylcyclopentane (methyl cyclopentane), suberane (cycloheptane) and methyl suberane (methyl cycloheptane) etc.Wherein hexanaphthene, normal hexane, normal heptane are preferable example.
Conjugated diolefine-vinylaromatic hydrocarbon di-block copolymer, conjugated diolefine-vinylaromatic hydrocarbon alternation di-block copolymer and conjugated diolefine-vinylaromatic hydrocarbon segmented copolymer can for example use anionic polymerization (anion polymerization) and form, use organolithium compound as the catalyst initiator, to obtain reactive polymer, it has the anion active base at molecule chain end, thereby can carry out polymerization again and molecular chain is grown up after adding monomer.Organolithium compound just for example can comprise-propyl lithium (n-propyl lithium), sec.-propyl lithium (isopropyl lithium), n-Butyl Lithium (n-butyl lithium), s-butyl lithium (sec-butyllithium), tert-butyl lithium (tert-butyl lithium), n-pentyl lithium (n-pentyl lithium), phenyl lithium (phenyl lithium), the hydrocarbon polymer of tolyl lithium (tolyl lithium) and two lithiums etc., and wherein the hydrocarbon polymer of two lithiums can for example comprise 1, two lithium-the normal butanes (1 of 4-, 4-dilithium n-butane), 1, two lithium-the pentanes (1 of 5-, 5-dilithiumpentane), 1, the two lithiums of 2--two diphenylphosphino ethanes (1,2-dilithium-diphenylethane), 1, the two lithiums-1 of 4-, 1,4,4-tetraphenyl butane (1,4-dilithium-1,1,4,4-tetraphenyl butane), 1, two (1-lithium-3 methyl amyl) benzene (1 of 3-, 3-di (1-lithium-3methylpentyl) benzene) or 1, two (1-lithium-3 methyl amyl) benzene (1,4-di (1-lithium-3-methylpentyl) benzene) of 4-.The consumption of organolithium compound is generally determined with the molecular weight of institute's desire acquisition polymkeric substance, is generally in 0.05 to the 5wt% scope of monomer usage quantity, and be benchmark with whole monomer consumptions.
The temperature of reaction of carrying out anionoid polymerization can be greatly in 0 ℃ to 150 ℃ temperature range.Temperature of reaction is if be lower than 0 ℃, and organic solvent can condense and separative phenomenon.And if temperature of reaction is higher than 150 ℃, then may has and cause polymer unwinds, and then reduce the polymkeric substance rerum natura.Therefore, preferable polymeric reaction temperature is approximately between 25 ℃ to 120 ℃.
In embodiments of the present invention, in the polymers soln of conjugated diolefine-vinyl aromatic hydrocarbon copolymer, can add small amount of antioxidant, be beneficial under the situation that does not influence the multipolymer rerum natura, preserve.The antioxidant that is suitable for can for example comprise Hinered phenols (hindered phenolic) antioxidant and derivative, phosphorous acid esters (phosphite) antioxidant and derivative thereof or its combination etc.
The polymers soln of each segmented copolymer of above-mentioned conjugated diolefine-vinyl aromatic hydrocarbon block copolymer or mixed with polymers solution can make polymkeric substance condense out by adding a kind of polar solvent, this polar solvent can be the poor solvent of conjugated diolefine-vinyl aromatic hydrocarbon block copolymer, for example methyl alcohol or acetone.In addition, the solvent in the polymers soln of segmented copolymer or the mixed with polymers solution also can be removed by stirring in hot water or via direct heating, and then isolates polymkeric substance.
In another embodiment, the mixture of conjugated diolefine-vinyl aromatic hydrocarbon copolymer can utilize a kind of solid-state blending means and form.In this solid-state blending means, at first, prepare different solid-state or fused conjugated diolefine-vinyl aromatic hydrocarbon copolymers respectively, mixingly in plastic cement or rubber tooling carry out the fusion blending.Then, carry out the extrusion granulation, obtain the mixture of granulous conjugated diolefine-vinyl aromatic hydrocarbon copolymer.
The blending temperature is reducible between 100 to 250 ℃, and can adjust according to the softening temperature of block polymer.For example the blending temperature of polystyrene-poly divinyl-polystyrene triblock polymer is reducible between 100 to 230 ℃, preferable about 130 to 200 ℃.
Mixture through the resulting conjugated diolefine of the above embodiment of the present invention-vinyl aromatic hydrocarbon copolymer is thermoplastic elastomer (the thermoplastic elastomer with high value; TPE), it can be used for the characteristic of plastic cement upgrading for example or improvement sticking agent.
Another embodiment of the present invention provides a kind of sticking agent composition that comprises the mixture of above-mentioned conjugated diolefine-vinyl aromatic hydrocarbon copolymer, and the sticking agent composition that is provided can be used for preparing and has the sticking agent that improves initial viscosity, stripping strength and shearing stamina.In one embodiment, the sticking agent composition can comprise the mixture of the above-mentioned conjugated diolefine-vinyl aromatic hydrocarbon copolymer of 100 weight parts, and the viscosity increaser of 1～700 weight part (tackifier) (corresponding to the mixture of the conjugated diolefine-vinyl aromatic hydrocarbon copolymer of 100 weight parts).
In one embodiment, viscosity increaser can for example comprise the coumarone indene resin good with vinylaromatic hydrocarbon block polymer consistency (Coumarone-indene resin), inden resin (poly-indene resin), polystyrene resin (polystyrene resin), poly-methyl-indene resin (poly (methyl indene) resin), alpha-methyl styrene resin (alpha-methylstyrene resin), Vinyl toluene-alpha-methyl styrene resin (vinyltoluene-alphamethylstyrene resin), poly-phenylene ether (polyphenylene ether) or its combination etc.
In another embodiment, viscosity increaser can for example comprise the C5 hydrocarbon resin good with conjugated diene block polymer phase capacitive, hydrogenation C5 hydrocarbon resin, polystyrene C9 resin, C5/C9 resin, polystyrene terpene resin, perhydro-or partly hydrogenant C9 hydrocarbon resin, perhydro-or the partly poly-terpene (polyterpene) of hydrogenant, poly-firpene terpine resin (Poly (pinene terpene resin)), rosin ester (rosinesters), rosin derivative or its combination etc.
In another embodiment, the sticking agent composition can comprise and the good viscosity increaser of vinylaromatic hydrocarbon block polymer consistency, and also comprises in the lump and the good viscosity increaser of conjugated diene block polymer phase capacitive.
In addition, the sticking agent composition that the embodiment of the invention provided can also comprise the treated oil (process oil) (corresponding to 100 parts by weight of conjugated diene-vinyl aromatic hydrocarbon copolymer) of 1～500 weight part, to be used to improve the viscosity and the processibility of sticking agent.In one embodiment, treated oil can for example comprise naphthenic oil (naphthenic oil), fatty hydrocarbon ils (paraffinic oil), fragrant hydrocarbon ils (aromatic oil), natural oil or derivatives thereofs such as (natural oil), yet the present invention is not as limit.
The also visual actual demand of sticking agent composition also comprises the additive of other kinds, for example fluidizer (plasticizer) etc.
Below will be by several embodiment illustrating further method of the present invention, feature and advantage, however the content of embodiment is not to be used for limiting the scope of the invention.
Comparative example 1: coupling process prepares the polymer A of polystyrene-poly butadiene block copolymer
1860 gram (gram) hexanaphthene (containing 120ppm THF) solvents are placed 5 liters reactor (autoclave) and are heated to 55 ℃.The styrene monomer and 9.74 that adds 100 grams in regular turn restrains the n-Butyl Lithium of 5wt% to begin to carry out polyreaction.After treating that styrene monomer almost completely reacts, the divinylic monomer that adds 210 grams almost completely reacts until divinylic monomer to proceed polyreaction.The dimethyldichlorosilane(DMCS) (dimethyldichlorosilane) that adds 5.0 gram 8.74wt% carries out coupled reaction (coupling reaction) to almost completely reaction, and forms a polymers soln.The antioxidant (Irgafos 126 of Phosphite series mixes antioxidant with the Irganox 1076 of Phenolic series) that adds 0.7phr (part per hundred rubber) afterwards is so far in the polymers soln, and stirred to make and mix.
Above-mentioned polymers soln is slowly added in the hot boiling water of stirring, removing solvent, and obtain an aqueous solution that contains solid polymer particles (crumb).This polymer beads is leached, via 100 ℃ of hot-air dries, with the micelle of the polymer A that obtains the polystyrene-poly butadiene block copolymer.It is about 85% that the polymer A of polystyrene-poly butadiene block copolymer has the coupling rate, weight average molecular weight about 11.8 * 10
4G/mol, and the about 29wt% of polystyrene content.
In embodiments of the present invention, weight average molecular weight is measured in the following manner: the dry micelle of 0.02 gram polymkeric substance is dissolved in the tetrahydrofuran (THF) (THF) of 10 milliliters (ml) to prepare a solution, and this solution of 70 microlitres (μ l) is injected into gel permeation chromatograph (Waters Pump 515, RI Detector-2414, Shodex Column) in to measure.
Comparative example 2: continuous polymerization prepares the polymer B of polystyrene-poly butadiene block copolymer
The polymers soln of preparation polystyrene-poly divinyl-polystyrene block copolymer 2a.1885 gram hexanaphthene (containing 120ppm THF) solvents are placed 5 liters reactor and are heated to 58 ℃.The styrene monomer and 2.85 that adds 44.5 grams in regular turn restrains the n-Butyl Lithium of 15wt% to begin to carry out polyreaction.After treating that styrene monomer almost completely reacts, the divinylic monomer that adds 218 grams almost completely reacts until divinylic monomer to proceed polyreaction.Then, the styrene monomer that adds 44.5 grams reacts to almost completely reaction, and the water that adds 1.27 grams afterwards is with termination reaction.Add 0.7phr antioxidant (Irgafos 126 of Phosphite series mixes antioxidant with the Irganox 1076 of Phenolic series) and also evenly stir, to obtain the polymers soln of polystyrene-poly divinyl-polystyrene block copolymer 2a.
The polymers soln of preparation polystyrene-poly butadiene block copolymer 2b.1885 gram hexanaphthene (containing 120ppm THF) solvents are placed 5 liters autoclave and are heated to 58 ℃.Add the styrene monomer of 89.0 grams and the n-Butyl Lithium of 4.2 gram 15wt% in regular turn and begin to carry out polyreaction.After treating that styrene monomer almost completely reacts, the divinylic monomer that adds 218 grams almost completely reacts until divinylic monomer to proceed polyreaction.The water that adds 1.27 grams afterwards is with termination reaction.Add 0.7phr antioxidant (Irgafos 126 of Phosphite series mixes antioxidant with the Irganox 1076 of Phenolic series) and also evenly stir, to obtain the polymers soln of polystyrene-poly butadiene block copolymer 2b.
Is that the ratio of 82.3/17.7 is mixed with the polymers soln of above-mentioned segmented copolymer 2a and 2b with solid substance (total solid) weight ratio, then the blended polymers soln is slowly added in the hot boiling water in the stirring, removing solvent, and obtain an aqueous solution that contains solid polymer particles.This polymer beads is leached, via 100 ℃ of hot-air dries, with the micelle of the polymer B that obtains the polystyrene-poly butadiene block copolymer.The polymer B of polystyrene-poly butadiene block copolymer has weight average molecular weight about 11.3 * 10
4G/mol, and the about 29wt% of polystyrene content.
Anionic polymerization prepares the polymers soln of polystyrene-poly butadiene amphiphilic block copolymer SB-1, polystyrene-poly divinyl tapered block copolymer SB-2 and polystyrene-poly divinyl-polystyrene triblock copolymer SBS
The polymers soln of preparation polystyrene-poly butadiene amphiphilic block copolymer SB-1.1885 gram hexanaphthene (containing 120ppm THF) solvents are placed 5 liters reactor and are heated to 55 ℃.The styrene monomer and 3.2 that adds 116.7 grams in regular turn restrains the n-Butyl Lithium of 15wt% to begin to carry out polyreaction.After treating that styrene monomer almost completely reacts, the divinylic monomer that adds 190 grams almost completely reacts until divinylic monomer to proceed polyreaction.The water that adds 1.7 grams afterwards is with termination reaction.After stirring 20 minutes, add 0.7phr antioxidant (Irgafos 126 of Phosphite series mixes antioxidant with the Irganox 1076 of Phenolic series) and also stirred to obtain the polymers soln of polystyrene-poly butadiene amphiphilic block copolymer SB-1.The weight average molecular weight of polystyrene-poly butadiene amphiphilic block copolymer SB-1 is about 68000g/mol, and polystyrene content is about 37.5wt%.
The polymers soln of preparation polystyrene-poly divinyl tapered block copolymer SB-2.1885 gram hexanaphthene (containing 120ppm THF) solvents are placed 5 liters reactor and are heated to 55 ℃.The styrene monomer and 4.0 that adds 91.2 grams in regular turn restrains the n-Butyl Lithium of 15wt% to begin to carry out polyreaction.After treating that styrene monomer almost completely reacts, the divinylic monomer that adds 181.1 grams when temperature of reaction arrives 65～70 ℃, adds 33.8 styrene monomers that restrain to proceed reaction to proceed polyreaction.After reaction was finished, the water that adds 2.0 grams was with termination reaction.After stirring 20 minutes, add 0.7phr antioxidant (Irgafos 126 of Phosphite series mixes antioxidant with the Irganox 1076 of Phenolic series) and also stirred to obtain the polymers soln of polystyrene-poly divinyl tapered block copolymer SB-2.The weight average molecular weight of polystyrene-poly divinyl tapered block copolymer SB-2 is about 68000g/mol, and polystyrene content is about 40.5wt%.
The polymers soln of preparation polystyrene-poly divinyl-polystyrene triblock copolymer SBS.1885 gram hexanaphthene (containing 120ppm THF) solvents are placed 5 liters reactor and are heated to 55 ℃.The styrene monomer and 2.59 that adds 50.7 grams in regular turn restrains the n-Butyl Lithium of 15wt% to begin to carry out polyreaction.After treating that styrene monomer almost completely reacts, the divinylic monomers that add 205.7 grams continue to react 10 minutes when temperature of reaction reaches the highest back to proceed polyreaction, and divinylic monomer is almost completely reacted.Add 50.7 gram styrene monomers, treat that styrene monomer almost completely reacts.The water that adds 1.3 grams afterwards is with termination reaction.After stirring 20 minutes, add 0.7phr antioxidant (Irgafos 126 of Phosphite series mixes antioxidant with the Irganox 1076 of Phenolic series) and also stirred, to obtain the polymers soln of polystyrene-poly divinyl-polystyrene triblock copolymer SBS.The weight average molecular weight of polystyrene-poly divinyl-polystyrene triblock copolymer SBS is about 127000g/mol, and polystyrene content is about 37.5wt%.
Comparative example 3: the polymkeric substance C of preparation polystyrene-poly butadiene block copolymer
Is that 65/35 ratio is mixed with the polymers soln of above-mentioned polystyrene-poly butadiene amphiphilic block copolymer SB-1 and polystyrene-poly divinyl-polystyrene triblock copolymer SBS with the solid substance weight ratio, to obtain a homogeneous polymer mixing solutions.This mixed with polymers solution slowly is added in the hot boiling water in the stirring removing solvent, and obtains an aqueous solution that contains solid polymer particles.This polymer beads is leached, via 100 ℃ of hot-air dries, with the micelle of the polymkeric substance C that obtains vinylbenzene-butadiene block copolymer.
Comparative example 4: the polymkeric substance D of preparation polystyrene-poly butadiene block copolymer
Is that 65/35 ratio evenly stirred 60 minutes under room temperature with the polymers soln of prepared polystyrene-poly divinyl tapered block copolymer SB-2 and polystyrene-poly divinyl-polystyrene triblock copolymer SBS with the solid substance weight ratio, to obtain a homogeneous polymer mixing solutions.This mixed with polymers solution slowly is added in the hot boiling water in the stirring removing solvent, and obtains an aqueous solution that contains solid polymer particles.This polymer beads is leached, via 100 ℃ of hot-air dries, with the micelle of the polymkeric substance D that obtains vinylbenzene-butadiene block copolymer.
Embodiment 1: the polymkeric substance E of preparation polystyrene-poly butadiene block copolymer
S' 35/28/37 mixed with the polymers soln of prepared polystyrene-poly butadiene amphiphilic block copolymer SB-1, polystyrene-poly divinyl tapered block copolymer SB-2 and polystyrene-poly divinyl-polystyrene triblock copolymer SBS with the solid substance weight ratio, stirred 60 minutes, to obtain a homogeneous polymer mixing solutions.This mixed with polymers solution slowly is added in the hot boiling water in the stirring removing solvent, and obtains an aqueous solution that contains solid polymer particles.This polymer beads is leached, via 100 ℃ of hot-air dries, with the micelle of the polymkeric substance E that obtains vinylbenzene-butadiene block copolymer.
Embodiment 2: the polymkeric substance F of preparation polystyrene-poly butadiene block copolymer
The preparation method of the polymkeric substance F of polystyrene-poly butadiene block copolymer is identical with the polymkeric substance E of vinylbenzene-butadiene block copolymer, except its mixed with polymers solution is that 40/23/37 ratio is mixed by the polymers soln of polystyrene-poly butadiene amphiphilic block copolymer SB-1, polystyrene-poly divinyl tapered block copolymer SB-2 and polystyrene-poly divinyl-polystyrene triblock copolymer SBS with the solid substance weight ratio.
Embodiment 3: the polymkeric substance G of preparation polystyrene-poly butadiene block copolymer
The preparation method of the polymkeric substance G of polystyrene-poly butadiene block copolymer is identical with the polymkeric substance E of vinylbenzene-butadiene block copolymer, except its mixed with polymers solution is that 30/33/37 ratio is mixed by polystyrene-poly butadiene amphiphilic block copolymer SB-1, polystyrene-poly divinyl tapered block copolymer SB-2 and polystyrene-poly divinyl-polystyrene triblock copolymer SBS polymers soln with the solid substance weight ratio.
Embodiment 4: the polymkeric substance H of preparation polystyrene-poly butadiene block copolymer
Anionic polymerization prepares the polymers soln of polystyrene-poly butadiene amphiphilic block copolymer SB-1 (H), polystyrene-poly divinyl tapered block copolymer SB-2 (H) and polystyrene-poly divinyl-polystyrene triblock copolymer SBS (H)
The polymers soln of preparation polystyrene-poly butadiene amphiphilic block copolymer SB-1 (H).1885 gram (gram) hexanaphthene (containing 120ppm THF) solvents are placed 5 liters reactor and are heated to 55 ℃.The styrene monomer and 7.2 that adds 92.1 grams in regular turn restrains the n-Butyl Lithium of 15wt% to begin to carry out polyreaction.After treating that styrene monomer almost completely reacts, the divinylic monomer that adds 215 grams almost completely reacts until divinylic monomer to proceed polyreaction.The water that adds 1.7 grams afterwards is with termination reaction.After stirring 20 minutes, add 0.7phr antioxidant (Irgafos 126 of Phosphite series mixes antioxidant with the Irganox 1076 of Phenolic series) and also stirred, to obtain the polymers soln of polystyrene-poly butadiene amphiphilic block copolymer SB-1 (H).The weight average molecular weight of polystyrene-poly butadiene amphiphilic block copolymer SB-1 (H) is about 30000g/mol, and polystyrene content is about 30wt%.
The polymers soln of preparation polystyrene-poly divinyl tapered block copolymer SB-2 (H).Place 5 liters reactor to be heated to 55 ℃ 1885 gram (gram) hexanaphthene (containing 120ppm THF) solvents.The styrene monomer and 7.2 that adds 67.2 grams in regular turn restrains the n-Butyl Lithium of 15wt% to begin to carry out polyreaction.After treating that styrene monomer almost completely reacts, the divinylic monomer that adds 215 grams when temperature of reaction arrives 65～70 ℃, adds 24.9 styrene monomers that restrain to proceed polyreaction to proceed polyreaction.After polyreaction was finished, the water that adds 2.0 grams was with termination reaction.After stirring 20 minutes, add the 0.7phr antioxidant Irganox1076 mixing antioxidant of Phenolic series (Irgafos 126 of Phosphite series with) and also stirred, to obtain the polymers soln of polystyrene-poly divinyl tapered block copolymer SB-2 (H).The weight average molecular weight of polystyrene-poly divinyl tapered block copolymer SB-2 (H) is about 30000g/mol, and polystyrene content is about 30wt%.
The polymers soln of preparation polystyrene-poly divinyl-polystyrene triblock copolymer SBS (H).Place 5 liters reactor to be heated to 55 ℃ 1885 gram (gram) hexanaphthene (containing 120ppm THF) solvents.The styrene monomer and 3.5 that adds 46.1 grams in regular turn restrains the n-Butyl Lithium of 15wt% to begin to carry out polyreaction.After treating that styrene monomer almost completely reacts, the divinylic monomers that add 218 grams continue to react 10 minutes when temperature of reaction reaches the highest back to proceed polyreaction, and divinylic monomer is almost completely reacted.Add 46.1 gram styrene monomers, treat that styrene monomer almost completely reacts.The water that adds 1.3 grams afterwards is with termination reaction.After stirring 20 minutes, add 0.7phr antioxidant (Irgafos 126 of Phosphite series mixes antioxidant with the Irganox 1076 of Phenolic series) and also stirred, to obtain the polymers soln of polystyrene-poly divinyl-polystyrene triblock copolymer SBS (H).The weight average molecular weight of polystyrene-poly divinyl-polystyrene triblock copolymer SBS (H) is about 60000g/mol, and polystyrene content is about 30wt%.
All has the about 30wt% of polystyrene content among above-mentioned polystyrene-poly butadiene amphiphilic block copolymer SB-1 (H), polystyrene-poly divinyl tapered block copolymer SB-2 (H) and polystyrene-poly divinyl-polystyrene triblock copolymer SBS (H).Stirred 60 minutes with uniform mixing under 10/10/80 the ratio, and then obtained a homogeneous polymer mixing solutions.This mixed with polymers solution slowly is added in the hot boiling water in the stirring removing solvent, and obtains an aqueous solution that contains solid polymer particles.This polymer beads is leached, via 100 ℃ of hot-air dries, with the micelle of the polymkeric substance H that obtains vinylbenzene-butadiene block copolymer.
The test of the basic physical properties of polymer A～H
The dry micelle of the polymer A～H of above-mentioned prepared vinylbenzene-butadiene block copolymer is prolonged pressure at the roller that has heated, is compression molded into the test piece of 2mm thickness, after being cut into the dumbbell shape test piece with the #3 cutting unit of dumbbell shape then, under the relative humidity of 25 ℃ temperature and 65%, (draw high speed: 500mm/min.) carry out the test of the basic physical properties of unit elongation, the measured table 1 that the results are shown in according to ASTM D 412 methods with the Instron tension testing machine.
The characteristic test for preparing sticking agent composition and sticking agent with polymer A～H
(P100 belongs to perhydro-polyterpene resin series, S-125 and belongs to poly-firpene terpine resin series with the P100 of 120 grams, the S-125 viscosity increasers of 60 grams respectively with the dry micelle of the above-mentioned vinylbenzene-butadiene block copolymer A～H of 100 grams, available from first light petroleum chemistry company), the Semi-paraffinicoil (available from Korea S S-Oil company) of 85 grams and the antioxidant Irganox-1076 (available from Ciba Geigy company) of 1 gram mix, to obtain the sticking agent composition.Each sticking agent composition rotating speed with 150rpm under 180 ℃ of temperature was stirred 2 hours, to be prepared into the hot melt adhesive sticking agent.
Prepared hot melt adhesive is utilized Hot Melt Coater Cheminstruments-HLCL 1000 type coating machines, under 280 temperature, hot melt adhesive is coated on OPP film (gap of coating machine roller is 0.208mm) to make an adhesive tape, utilize Chatillon DFM 10 type initial viscosity testers to carry out the initial viscosity test on this adhesive tape according to the PSTC-16 method, utilize Instron 4464 type peel strength testers to carry out peel strength test according to the PSTC-101 method, and utilizing Cheminstruments RT-10 type to carry out 60 ℃ of detections of shearing stamina according to the PSTC-107 method, it the results are shown in table 1.
Table 1
| Polymkeric substance | A | B | C | D | E | F | G | H |
| SB-1: SB-2: SBS (solid substance weight ratio) | ? | ? | ? | ? | 35∶28∶37 | 40∶23∶37 | 30∶33∶37 | ? |
| SB-1 (H): SB-2 (H): SBS (H) (solid substance weight ratio) | ? | ? | ? | ? | ? | ? | ? | 10∶10∶80 |
| Unit elongation (%) | 962 | 1075 | 770 | 966 | 1150 | 1113 | 1114 | 1050 |
| Sticking agent | ? | ? | ? | ? | ? | ? | ? | ? |
| Initial viscosity (Newton) | 3.7 | 5.4 | 8.1 | 7.2 | 13.5 | 12.8 | 13.7 | 10.2 |
| Stripping strength (Kgf/2.54cm) | 0.52 | 0.59 | 1.8 | 0.7 | 2.4 | 2.5 | 2.1 | 2.1 |
| Shear stamina (min.) for 60 ℃ | 1.0 | 6.5 | 5.9 | 5.1 | 8.6 | 9.8 | 7.5 | 11.5 |
With reference to table 1, polymkeric substance E, the F, G and the H that comprise polystyrene-poly butadiene amphiphilic block copolymer SB-1/SB-1 (H), polystyrene-poly divinyl tapered block copolymer SB-2/SB-2 (H) and polystyrene-poly divinyl-polystyrene triblock copolymer SBS/SBS (H) all have the elongation property of improvement, are suitable for the upgrading of plastic cement.
In addition, as shown in table 1, the initial viscosity of sticking agent that comprises the prepared polymer A of coupling process is not good. and comprise the polymer B that is mixed with polystyrene-poly butadiene-polystyrene block copolymer 2a and polystyrene-poly butadiene block copolymer 2b, comprise the polymer C that is mixed with polystyrene-poly butadiene amphiphilic block copolymer SB-1 and polystyrene-poly butadiene-polystyrene triblock copolymer SBS or comprise the initial viscosity of the formed adhesive agent of polymer D that is mixed with polystyrene-poly butadiene tapered block copolymer SB-2 and polystyrene-poly butadiene-polystyrene triblock copolymer SBS also not good.
Table 1 shows that the sticking agent comprise fusion polystyrene-poly butadiene amphiphilic block copolymer SB-1, polystyrene-poly divinyl tapered block copolymer SB-2 in varing proportions and polystyrene-poly divinyl-polystyrene triblock copolymer SBS prepared polymkeric substance E, F and G and to form has the initial viscosity of improvement.And, although the blending ratio of the polystyrene-poly butadiene amphiphilic block copolymer SB-1 (H) that is comprised among the polymkeric substance H, polystyrene-poly divinyl tapered block copolymer SB-2 (H) and the polystyrene-poly divinyl-weight average molecular weight that polystyrene triblock copolymer SBS (H) has respectively and the content ratio of vinylaromatic hydrocarbon and multipolymer SB-1 (H), SB-2 (H) and SBS (H) is different from polymkeric substance E, F and G, yet the sticking agent that comprises polymkeric substance H also has the initial viscosity of improvement.
Therefore,, polymkeric substance E, F, G, H that the embodiment of the invention provided are blended in the sticking agent composition, can effectively promote initial viscosity, the stripping strength of sticking agent and shear stamina according to table 1, and then the scope of application of promoting sticking agent.
It should be noted that at last: above embodiment only in order to technical scheme of the present invention to be described, is not intended to limit; Although with reference to previous embodiment the present invention is had been described in detail, those of ordinary skill in the art is to be understood that: it still can be made amendment to the technical scheme that aforementioned each embodiment put down in writing, and perhaps part technical characterictic wherein is equal to replacement; And these modifications or replacement do not make the essence of appropriate technical solution break away from the spirit and scope of various embodiments of the present invention technical scheme.
Claims (20)
1. the mixture of conjugated diolefine-vinyl aromatic hydrocarbon copolymer comprises:
The di-block copolymer of 10～45wt%, this di-block copolymer is polymerized by one first conjugate diene monomer and one first vinyl aromatic hydrocarbon monomer;
The alternation di-block copolymer of 10～45wt%, this alternation di-block copolymer is polymerized by one second conjugate diene monomer and one second vinyl aromatic hydrocarbon monomer; And
The segmented copolymer of 10～80wt%, this segmented copolymer is polymerized by a triple conjugation diene monomers and a trivinyl aromatic hydrocarbon monomer.
2. the mixture of conjugated diolefine according to claim 1-vinyl aromatic hydrocarbon copolymer, wherein this first conjugate diene monomer, this second conjugate diene monomer and this triple conjugation diene monomers are respectively from 1,3-divinyl, 2,3-dimethyl-1,3-divinyl, 3-butyl-1, choose in the group that 3-octadiene, isoprene, m-pentadiene, 2-phenyl-1,3-butadiene and above-mentioned composition are formed.
3. the mixture of conjugated diolefine according to claim 1-vinyl aromatic hydrocarbon copolymer is wherein chosen the group that this first vinyl aromatic hydrocarbon monomer, this second vinyl aromatic hydrocarbon monomer and this trivinyl aromatic hydrocarbon monomer are formed from vinylbenzene, alpha-methyl styrene, to ethyl styrene, phenylcyclohexane ethene, p-methylstyrene, o-methyl styrene, a vinyl toluene, 1-vinyl-5-hexyl naphthalene, vinylnaphthalene and above-mentioned composition respectively.
4. the mixture of conjugated diolefine according to claim 1-vinyl aromatic hydrocarbon copolymer, wherein to have a weight average molecular weight be 2 * 10 to the mixture of this conjugated diolefine-vinyl aromatic hydrocarbon copolymer
4～20 * 10
4G/mol.
5. the mixture of conjugated diolefine according to claim 1-vinyl aromatic hydrocarbon copolymer, wherein to have a weight average molecular weight be 2 * 10 to this di-block copolymer
4～10 * 10
4G/mol.
6. the mixture of conjugated diolefine according to claim 1-vinyl aromatic hydrocarbon copolymer, wherein to have a weight average molecular weight be 2 * 10 to this alternation di-block copolymer
4～10 * 10
4G/mol.
7. the mixture of conjugated diolefine according to claim 1-vinyl aromatic hydrocarbon copolymer, wherein to have a weight average molecular weight be 5 * 10 to this segmented copolymer
4～20 * 10
4G/mol.
8. the mixture of conjugated diolefine according to claim 1-vinyl aromatic hydrocarbon copolymer, wherein to have a weight average molecular weight be 2 * 10 to this di-block copolymer
4～10 * 10
4G/mol, it is 2 * 10 that this alternation di-block copolymer has a weight average molecular weight
4～10 * 10
4It is 5 * 10 that g/mol, this segmented copolymer have a weight average molecular weight
4～20 * 10
4G/mol.
9. the mixture of conjugated diolefine according to claim 1-vinyl aromatic hydrocarbon copolymer, wherein to have a vinyl aromatic hydrocarbon content be 25～50wt% to this di-block copolymer.
10. the mixture of conjugated diolefine according to claim 1-vinyl aromatic hydrocarbon copolymer, wherein to have a vinyl aromatic hydrocarbon content be 25～55wt% to this tapered block copolymer.
11. the mixture of conjugated diolefine according to claim 1-vinyl aromatic hydrocarbon copolymer, wherein to have a vinyl aromatic hydrocarbon content be 25～50wt% to this segmented copolymer.
12. the mixture of conjugated diolefine according to claim 1-vinyl aromatic hydrocarbon copolymer, wherein to have a vinyl aromatic hydrocarbon content be 25～50wt% to this di-block copolymer, it is 25～55wt% that this tapered block copolymer has a vinyl aromatic hydrocarbon content, and it is 25～50wt% that this segmented copolymer has a vinyl aromatic hydrocarbon content.
13. the mixture of conjugated diolefine according to claim 8-vinyl aromatic hydrocarbon copolymer, wherein to have a vinyl aromatic hydrocarbon content be 25～50wt% to this di-block copolymer, it is 25～55wt% that this tapered block copolymer has a vinyl aromatic hydrocarbon content, and it is 25～50wt% that this segmented copolymer has a vinyl aromatic hydrocarbon content.
14. the mixture of conjugated diolefine according to claim 1-vinyl aromatic hydrocarbon copolymer, wherein an end of this alternation di-block copolymer mainly is polymerized by this second vinyl aromatic hydrocarbon monomer.
15. the mixture of conjugated diolefine according to claim 1-vinyl aromatic hydrocarbon copolymer also comprises an antioxidant.
16. a sticking agent composition comprises:
The mixture of the described conjugated diolefine of 100 weight part claims 1-vinyl aromatic hydrocarbon copolymer; And
One viscosity increaser of 1～700 weight part.
17. sticking agent composition according to claim 16, wherein this viscosity increaser comprises following arbitrary material or its combination: coumarone indene resin, inden resin, polystyrene resin, poly-methyl-indene resin, alpha-methyl styrene resin, Vinyl toluene-alpha-methyl styrene resin and poly-phenylene ether.
18. sticking agent composition according to claim 16, wherein this viscosity increaser comprises following arbitrary material or its combination: C5 hydrocarbon resin, hydrogenation C5 hydrocarbon resin, polystyrene C9 resin, C5/C9 resin, polystyrene terpene resin, perhydro-or part hydrogenant C9 hydrocarbon resin, perhydro-or the poly-terpene of part hydrogenant, poly-firpene terpine resin, rosin ester and rosin derivative.
19. sticking agent composition according to claim 18 also comprises a treated oil of 1～500 weight part.
20. sticking agent composition according to claim 19, wherein this treated oil comprises following arbitrary material or its combination: naphthenic oil and derivative thereof, fatty hydrocarbon ils and derivative thereof, fragrant hydrocarbon ils and derivative thereof and natural oil and derivative thereof.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104650523A (en) * | 2013-11-19 | 2015-05-27 | 奇美实业股份有限公司 | Block copolymer composition |
| CN111410924A (en) * | 2019-01-04 | 2020-07-14 | 台橡股份有限公司 | Pressure sensitive adhesive composition and protective film comprising the same |
| CN115216105A (en) * | 2021-12-30 | 2022-10-21 | 台橡（上海）实业有限公司 | Polymer composition for preparing transparent material, transparent material and shoe pad |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6025071A (en) * | 1997-10-23 | 2000-02-15 | H.B.Fuller Licensing & Financing Inc. | Removable grade hot melt pressure sensitive adhesive |
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2010
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6025071A (en) * | 1997-10-23 | 2000-02-15 | H.B.Fuller Licensing & Financing Inc. | Removable grade hot melt pressure sensitive adhesive |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104650523A (en) * | 2013-11-19 | 2015-05-27 | 奇美实业股份有限公司 | Block copolymer composition |
| CN104650523B (en) * | 2013-11-19 | 2018-03-13 | 奇美实业股份有限公司 | Block copolymer composition |
| CN111410924A (en) * | 2019-01-04 | 2020-07-14 | 台橡股份有限公司 | Pressure sensitive adhesive composition and protective film comprising the same |
| CN111410924B (en) * | 2019-01-04 | 2022-11-08 | 台橡股份有限公司 | Pressure sensitive adhesive composition and protective film comprising the same |
| CN115216105A (en) * | 2021-12-30 | 2022-10-21 | 台橡（上海）实业有限公司 | Polymer composition for preparing transparent material, transparent material and shoe pad |
| CN115216105B (en) * | 2021-12-30 | 2023-09-05 | 台橡（上海）实业有限公司 | Polymer composition for manufacturing transparent material, transparent material and insole |
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