CN102146191B - 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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- CN102146191B CN102146191B CN201010114006.3A CN201010114006A CN102146191B CN 102146191 B CN102146191 B CN 102146191B CN 201010114006 A CN201010114006 A CN 201010114006A CN 102146191 B CN102146191 B CN 102146191B
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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 a kind of mixture of conjugated diolefine-vinyl aromatic hydrocarbon copolymer and the sticking agent composition that comprises this mixture, relate in particular to one and there is the mixture that improves the conjugated diolefine-vinyl aromatic hydrocarbon copolymer that extends (elongation) character, and a kind of for the preparation of thering is the sticking agent composition that improves initial viscosity (initialtack), stripping strength (peel strength) and shear the sticking agent of stamina (holding power).
Background technology
The industrial often main material using conjugated diolefine (conjugated diene)-vinylaromatic hydrocarbon (vinyl aromatichydrocarbon) block polymer as sticking agent composition, and these sticking agent compositions can be applicable in such as adhesive tape, label and object as soft in disposable types such as diaper, female pathology articles for use and surgical operation covertures for the use of sticking together.
U.S. Patent number 5,089,550 disclose a kind of block copolymer composition, vinylaromatic hydrocarbon-conjugated diolefine-vinylaromatic hydrocarbon triblock copolymer of conjugated diolefine-vinylaromatic hydrocarbon di-block copolymer that it comprises 50～85wt% and 15～50wt%.This block copolymer composition can be used in sticking agent composition.
U.S. Patent number 5,112,889 disclose a kind of pressure sensitive adhesive (pressure-sensitive adhesive), it comprises A-B-A block polymer, or the AB segmented copolymer of the geometrical shape of for example tapered block copolymer (tapered block copolymer) or radial pattern (radial) segmented copolymer, wherein A block obtains from vinylbenzene or alpha-methyl styrene, and 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 first with at least one vinylaromatic hydrocarbon of anionoid polymerization and at least one conjugated diolefine to form an activity (living) segmented copolymer, then add a coupler (coupling agent) with by the in addition coupling of above-mentioned reactive block copolymers, and then in the mode of heating by 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 vinylaromatic hydrocarbon polymer blocks, B is mainly conjugated diolefin polymer block, C represents to comprise the alternation block of the vinylaromatic hydrocarbon occurring in the conjugated diolefine that occurs in B block and D block, and wherein the vinylaromatic hydrocarbon in C block increases gradually in the direction of D block.This line-type block polymer can use in sticking agent composition.
U.S. Patent number 5,719,226 open one have hot melt adhesive sticking agent (hotmelt adhesive) composition of low-viscosity (viscosity), and it comprises the adulterant that a vinylbenzene-diene triblock copolymer by not hydrogenation or hydrogenation and unhydrided styrene-isoprene di-block copolymer form.
Above-mentioned United States Patent (USP) case discloses the segmented copolymer of some different compositions and the sticking agent composition that comprises this segmented copolymer, and different sticking agent compositions is by forming the sticking agent of different qualities, to be suitable for different application.Generally speaking, the 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 the sticking agent composition that preparation has a sticking agent that improves initial viscosity, stripping strength and shearing stamina and be necessary.
Summary of the invention
One of object of the present invention is for a kind of mixture with the conjugated diolefine-vinyl aromatic hydrocarbon copolymer that improves extended nature is provided, 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 for the preparation of having the sticking agent that improves initial viscosity, stripping strength and shearing stamina, it can effectively improve the value added of conjugated diolefine-vinylaromatic hydrocarbon copolymer product, significantly expands the Application Areas of conjugated diolefine-vinyl aromatic hydrocarbon copolymer simultaneously.
For reaching above-mentioned and other objects, one embodiment of the invention provides a kind of mixture of conjugated diolefine-vinyl aromatic hydrocarbon copolymer, its conjugated diolefine-vinylaromatic hydrocarbon di-block copolymer (di-block copolymer) that comprises about 10～45wt%, approximately conjugated diolefine-vinylaromatic hydrocarbon alternation di-block copolymer (tapered block copolymer) and the about conjugated diolefine-vinylaromatic hydrocarbon segmented copolymer (multi-block copolymer) of 10～80wt% of 10～45wt%.
Another embodiment of the present invention provides a kind of sticking agent composition, the mixture of its above-mentioned conjugated diolefine-vinyl aromatic hydrocarbon copolymer that comprises 100 weight parts, and the viscosity increaser of 1～700 weight part.
For above and other object of the present invention, feature and advantage can be become apparent, cited below particularly go out preferred embodiment using as detailed description.
Embodiment
" one " of the present invention or " one " are not for the restriction as on actual quantity, unless otherwise.
One embodiment of the invention mainly provides a kind of mixture with the conjugated diolefine-vinyl aromatic hydrocarbon copolymer that improves extended nature, and it can be used for the characteristic of plastic cement upgrading or improvement sticking agent.
The mixture of conjugated diolefine-vinyl aromatic hydrocarbon copolymer that the present embodiment provides, comprises:
Conjugated diolefine-vinylaromatic hydrocarbon di-block copolymer of 10～45wt%;
Conjugated diolefine-vinylaromatic hydrocarbon alternation di-block copolymer of 10～45wt%; And
Conjugated diolefine-vinylaromatic hydrocarbon segmented copolymer of 10～80wt%.
The weight percent of above-mentioned each segmented copolymer is take the weight of the mixture of conjugated diolefine-vinyl aromatic hydrocarbon copolymer as benchmark.And in some cases, in the mixture of conjugated diolefine-vinyl aromatic hydrocarbon copolymer, also can comprise appropriate additive to improve its character, for example add a small amount 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-butadiene (1,3-butadiene), 2,3-dimethyl-1,3-butadiene (2,3-dimethyl-1,3-butadiene), 3-butyl-1,3-octadiene (3-butyl-1,3-octadiene), isoprene (isoprene), m-pentadiene (trans-1,3-pentadiene), in the group that 2-phenyl-1,3-butadiene (2-phenyl-1,3-butadiene) and above-mentioned composition form, 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), in the group that vinylnaphthalene (vinyl naphthalene) and above-mentioned composition form, choose, however the present invention also visual actual needs use other conjugate diene monomers and vinyl aromatic hydrocarbon monomer.In one embodiment, conjugated diolefine-vinyl aromatic hydrocarbon block copolymer is preferably the butadiene/styrene copolymers or the isoprene/styrol copolymer that have industrial value.
Conjugated diolefine-vinylaromatic hydrocarbon di-block copolymer is made up of a conjugated diolefin polymer block (polymerblock) and a vinylaromatic hydrocarbon polymer blocks, wherein above-mentioned conjugated diolefin polymer block is polymerized by conjugate diene monomer, and 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) approximately 2 × 10
4～10 × 10
4g/mol, better approximately 4 × 10
4～8 × 10
4g/mol, better approximately 5 × 10
4～7.5 × 10
4g/mol; Conjugated diolefine-vinylaromatic hydrocarbon bi-block copolymer can have approximately 25～50wt% of vinyl aromatic hydrocarbon content, better approximately 30～45wt%, better approximately 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 end of the alternation section of conjugated diolefine-vinylaromatic hydrocarbon alternation di-block copolymer is better is mainly polymerized by vinyl aromatic hydrocarbon monomer.In one embodiment, conjugated diolefine-vinylaromatic hydrocarbon alternation di-block copolymer can have weight average molecular weight approximately 2 × 10
4～10 × 10
4g/mol, better approximately 4 × 10
4～8 × 10
4g/mol, better approximately 5 × 10
4～7.5 × 10
4g/mol; Conjugated diolefine-vinylaromatic hydrocarbon alternation di-block copolymer can have approximately 25～55wt% of vinyl aromatic hydrocarbon content, better approximately 30～50wt%, better approximately 35～45wt%.
Three blocks or three the more than block multipolymers of conjugated diolefine-vinylaromatic hydrocarbon segmented copolymer for being formed 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 approximately 5 × 10
4～20 × 10
4g/mol, better approximately 8 × 10
4～17 × 10
4g/mol, better approximately 10 × 10
4～15 × 10
4g/mol; Conjugated diolefine-vinylaromatic hydrocarbon segmented copolymer can have approximately 25～50wt% of vinyl aromatic hydrocarbon content, better approximately 30～45wt%, better approximately 35～40wt%.
The mixture of the conjugated diolefine-vinyl aromatic hydrocarbon copolymer providing according to one embodiment of the invention can have weight average molecular weight between 2 × 10
4～20 × 10
4between 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 of polymkeric substance is dissolved in the tetrahydrofuran (THF) (THF) of 10 milliliters (ml) to prepare a solution, and (μ l) this solution is injected into the weight average molecular weight of measuring to obtain polymkeric substance in gel permeation chromatograph (GPC) by 70 microlitres.And the gross weight that above-mentioned " vinyl aromatic hydrocarbon content " is the vinyl aromatic hydrocarbon monomer in order to form conjugated diolefine-vinylaromatic hydrocarbon block polymer accounts for the total weight percent of all monomers of formation conjugated diolefine-vinyl aromatic hydrocarbon block copolymer.
Between each conjugated diolefin polymer block in above-mentioned conjugated diolefine-vinyl aromatic hydrocarbon block copolymer that the present embodiment provides, can be formed by identical or different conjugate diene monomer, and also can be made up 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 use respectively knockdown conjugate diene monomer or vinyl aromatic hydrocarbon monomer to carry out copolymerization according to the demand of Industrial products characteristic 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, first utilize polyreaction to form the polymers soln of each different conjugated diolefine-vinyl aromatic hydrocarbon copolymer, then the polymers soln of above-mentioned conjugated diolefine-vinyl aromatic hydrocarbon copolymer is mixed to form a mixed with polymers solution in varing proportions.Then by this mixed with polymers solution removal solvent and dry, 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 such as aromatic hydrocarbon, straight or branched hydrocarbon polymer, cycloalkanes ether and alicyclic hydrocarbon type etc.Aromatic hydrocarbon can comprise the organic solvents such as such as benzene (benzene), toluene (toulene), dimethylbenzene (xylene) and ethylbenzene (ethyl benzene); 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 can comprise such as pentamethylene (cyclopentane), hexanaphthene (cyclohexane), methylcyclopentane (methyl cyclopentane), suberane (cycloheptane) and methyl suberane (methyl cycloheptane) etc.Wherein hexanaphthene, normal hexane, normal heptane are example preferably.
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 catalyst initiator, to obtain reactive polymer, it has anion active base at molecule chain end, thereby after monomer, can carry out polymerization again and molecular chain is grown up adding.Organolithium compound can comprise for example n-propyl lithium (n-propyl lithium), isopropyl 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, two lithium-bis-the diphenylphosphino ethanes (1 of 2-, 2-dilithium-diphenylethane), 1, two lithium-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 of 4-, 4-di (1-lithium-3-methylpentyl) benzene).The consumption of organolithium compound generally with wish obtain the molecular weight of polymkeric substance and determined, be generally monomer usage quantity 0.05 to 5wt%, take whole monomer consumptions as benchmark.
The temperature of reaction of carrying out anionoid polymerization can be greatly in the temperature range of 0 ℃ to 150 ℃.If temperature of reaction is lower than 0 ℃, organic solvent can condense and separative phenomenon.And if temperature of reaction is higher than 150 ℃, may has and cause polymer unwinds, and then reduce polymkeric substance physical property.Therefore, preferably polymeric reaction temperature approximately between 25 ℃ to 120 ℃.
In embodiments of the present invention, in the polymers soln of conjugated diolefine-vinyl aromatic hydrocarbon copolymer, can add a small amount of antioxidant, be beneficial to preserve in the situation that not affecting multipolymer physical property.Applicable antioxidant 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 mixed with polymers solution also can or be removed via direct heating by stirring in hot water, 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, first, prepare respectively conjugated diolefine-vinyl aromatic hydrocarbon copolymer of different solid-state or meltings, mixingly in plastic cement or rubber tooling carry out melting blending.Then, carry out extrusion granulation, obtain the mixture of granular conjugated diolefine-vinyl aromatic hydrocarbon copolymer.
Blending temperature is reducible between 100 to 250 ℃, and can adjust according to the softening temperature of block polymer.The for example blending temperature of polystyrene-poly divinyl-polystyrene triblock polymer is reducible between 100 to 230 ℃, better approximately 130 to 200 ℃.
The mixture of the conjugated diolefine-vinyl aromatic hydrocarbon copolymer obtaining through the above embodiment of the present invention is thermoplastic elastomer (the thermoplastic elastomer with high value; TPE), it can be used for the characteristic of for example plastic cement upgrading or improvement sticking agent.
Another embodiment of the present invention provides a kind of sticking agent composition of the mixture that comprises above-mentioned conjugated diolefine-vinyl aromatic hydrocarbon copolymer, and the sticking agent composition providing can be used for preparation and has the sticking agent that improves initial viscosity, stripping strength and shearing stamina.In one embodiment, sticking agent composition can comprise the mixture of 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 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 poly-terpene (polyterpene), poly-firpene terpine resin (Poly (pinene terpene resin)), rosin ester (rosinesters), rosin derivative or its combination etc. of C9 hydrocarbon resin, perhydro-or the part hydrogenation of 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 part hydrogenation.
In another embodiment, sticking agent composition can comprise the viscosity increaser good with vinylaromatic hydrocarbon block polymer consistency, and also comprises in the lump the viscosity increaser good with conjugated diene block polymer phase capacitive.
In addition, the sticking agent composition that the embodiment of the present invention provides 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, for improving viscosity and the processibility of sticking agent.In one embodiment, treated oil can for example comprise the or derivatives thereofs such as naphthenic oil (naphthenic oil), fatty hydrocarbon ils (paraffinic oil), hydrocarbon oil (aromatic oil), natural oil (natural oil), but the present invention is not as limit.
Sticking agent composition also visual actual demand also comprises the additive of other kinds, such as fluidizer (plasticizer) etc.
Below will be by several embodiment to illustrate further method of the present invention, feature and advantage, but the content of embodiment is not used for limiting the scope of the invention.
Comparative example 1: coupling process is prepared the polymer A of polystyrene-poly butadiene block copolymer
1860 grams of (gram) hexanaphthenes (containing 120ppm THF) solvent is placed in to the reactor (autoclave) of 5 liters and is heated to 55 ℃.Sequentially add the n-Butyl Lithium of the styrene monomer of 100 grams and 9.74 grams of 5wt% to start to carry out polyreaction.Almost after complete reaction, add the divinylic monomer of 210 grams to proceed polyreaction, until almost complete reaction of divinylic monomer until styrene monomer.Add the dimethyldichlorosilane(DMCS) (dimethyldichlorosilane) of 5.0 grams of 8.74wt% to carry out extremely almost complete reaction of coupled reaction (coupling reaction), and form a polymers soln.The antioxidant (Irgafos 126 of Phosphite series mixes antioxidant with the Irganox 1076 of Phenolic series) that adds afterwards 0.7phr (part per hundred rubber) is so far in polymers soln, and stirred and make to mix.
Above-mentioned polymers soln is slowly added in the hot boiling water of stirring, to remove solvent, and obtain the aqueous solution containing solid polymer particles (crumb).This polymer beads is leached, via 100 ℃ of hot-air dries, to obtain the micelle of polymer A of polystyrene-poly butadiene block copolymer.The polymer A of polystyrene-poly butadiene block copolymer has coupling rate approximately 85%, weight average molecular weight approximately 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 of polymkeric substance is dissolved in the tetrahydrofuran (THF) (THF) of 10 milliliters (ml) to prepare a solution, and (μ l) this solution is injected into gel permeation chromatograph (Waters Pump 515 by 70 microlitres, RI Detector-2414, Shodex Column) in to measure.
Comparative example 2: continuous polymerization is prepared the polymer B of polystyrene-poly butadiene block copolymer
Prepare the polymers soln of polystyrene-poly divinyl-polystyrene block copolymer 2a.1885 grams of hexanaphthenes (containing 120ppm THF) solvent is placed in to the reactor of 5 liters and is heated to 58 ℃.Sequentially add the n-Butyl Lithium of the styrene monomer of 44.5 grams and 2.85 grams of 15wt% to start to carry out polyreaction.Almost after complete reaction, add the divinylic monomer of 218 grams to proceed polyreaction, until almost complete reaction of divinylic monomer until styrene monomer.Then, add the styrene monomer of 44.5 grams to react extremely almost complete reaction, add afterwards the water of 1.27 grams with termination reaction.Add 0.7phr antioxidant (Irgafos 126 of Phosphite series mixes antioxidant with the Irganox 1076 of Phenolic series) uniform stirring in addition, to obtain the polymers soln of polystyrene-poly divinyl-polystyrene block copolymer 2a.
Prepare the polymers soln of polystyrene-poly butadiene block copolymer 2b.1885 grams of hexanaphthenes (containing 120ppm THF) solvent is placed in to the autoclave of 5 liters and is heated to 58 ℃.Sequentially add the styrene monomer of 89.0 grams and the n-Butyl Lithium of 4.2 grams of 15wt% to start to carry out polyreaction.Almost after complete reaction, add the divinylic monomer of 218 grams to proceed polyreaction, until almost complete reaction of divinylic monomer until styrene monomer.Add afterwards the water of 1.27 grams with termination reaction.Add 0.7phr antioxidant (Irgafos 126 of Phosphite series mixes antioxidant with the Irganox 1076 of Phenolic series) uniform stirring in addition, to obtain the polymers soln of polystyrene-poly butadiene block copolymer 2b.
The polymers soln of above-mentioned segmented copolymer 2a and 2b is mixed take solid substance (total solid) weight ratio as the ratio of 82.3/17.7, then the polymers soln of mixing is slowly added in the hot boiling water in stirring, to remove solvent, and obtain the aqueous solution containing solid polymer particles.This polymer beads is leached, via 100 ℃ of hot-air dries, to obtain the micelle of polymer B of polystyrene-poly butadiene block copolymer.The polymer B of polystyrene-poly butadiene block copolymer has weight average molecular weight approximately 11.3 × 10
4g/mol, and the about 29wt% of polystyrene content.
Anionic polymerization is prepared 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
Prepare the polymers soln of polystyrene-poly butadiene amphiphilic block copolymer SB-1.1885 grams of hexanaphthenes (containing 120ppm THF) solvent is placed in to the reactor of 5 liters and is heated to 55 ℃.Sequentially add the n-Butyl Lithium of the styrene monomer of 116.7 grams and 3.2 grams of 15wt% to start to carry out polyreaction.Almost after complete reaction, add the divinylic monomer of 190 grams to proceed polyreaction, until almost complete reaction of divinylic monomer until styrene monomer.Add afterwards the water of 1.7 grams with termination reaction.When stirring after 20 minutes, add 0.7phr antioxidant (Irgafos 126 of Phosphite series mixes antioxidant with the Irganox 1076 of Phenolic series) also to be 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%.
Prepare the polymers soln of polystyrene-poly divinyl tapered block copolymer SB-2.1885 grams of hexanaphthenes (containing 120ppm THF) solvent is placed in to the reactor of 5 liters and is heated to 55 ℃.Sequentially add the n-Butyl Lithium of the styrene monomer of 91.2 grams and 4.0 grams of 15wt% to start to carry out polyreaction.Almost after complete reaction, add the divinylic monomer of 181.1 grams to proceed polyreaction until styrene monomer, when temperature of reaction arrives 65～70 ℃, add the styrene monomer of 33.8 grams to proceed reaction.After reaction completes, add the water of 2.0 grams with termination reaction.When stirring after 20 minutes, add 0.7phr antioxidant (Irgafos 126 of Phosphite series mixes antioxidant with the Irganox 1076 of Phenolic series) also to be 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%.
Prepare the polymers soln of polystyrene-poly divinyl-polystyrene triblock copolymer SBS.1885 grams of hexanaphthenes (containing 120ppm THF) solvent is placed in to the reactor of 5 liters and is heated to 55 ℃.Sequentially add the n-Butyl Lithium of the styrene monomer of 50.7 grams and 2.59 grams of 15wt% to start to carry out polyreaction.Almost after complete reaction, add the divinylic monomer of 205.7 grams to proceed polyreaction until styrene monomer, when temperature of reaction reach the highest after continuation reaction 10 minutes, make almost complete reaction of divinylic monomer.Add 50.7 grams of styrene monomers, treat almost complete reaction of styrene monomer.Add afterwards the water of 1.3 grams with termination reaction.When stirring after 20 minutes, add 0.7phr antioxidant (Irgafos 126 of Phosphite series mixes antioxidant with the Irganox 1076 of Phenolic series) and 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 for preparing polystyrene-poly butadiene block copolymer
The polymers soln of above-mentioned polystyrene-poly butadiene amphiphilic block copolymer SB-1 and polystyrene-poly divinyl-polystyrene triblock copolymer SBS is mixed take solid substance weight ratio as 65/35 ratio, to obtain a uniform mixed with polymers solution.This mixed with polymers solution is slowly added in the hot boiling water in stirring to remove solvent, and obtains the aqueous solution containing solid polymer particles.This polymer beads is leached, via 100 ℃ of hot-air dries, to obtain the micelle of polymkeric substance C of vinylbenzene-butadiene block copolymer.
Comparative example 4: the polymkeric substance D for preparing polystyrene-poly butadiene block copolymer
Ratio by the polymers soln of prepared polystyrene-poly divinyl tapered block copolymer SB-2 and polystyrene-poly divinyl-polystyrene triblock copolymer SBS take solid substance weight ratio as 65/35 uniform stirring 60 minutes under room temperature, to obtain a uniform mixed with polymers solution.This mixed with polymers solution is slowly added in the hot boiling water in stirring to remove solvent, and obtains the aqueous solution containing solid polymer particles.This polymer beads is leached, via 100 ℃ of hot-air dries, to obtain the micelle of polymkeric substance D of vinylbenzene-butadiene block copolymer.
Embodiment 1: the polymkeric substance E for preparing polystyrene-poly butadiene block copolymer
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 is mixed take solid substance weight ratio as 35/28/37 ratio, stir 60 minutes, to obtain a uniform mixed with polymers solution.This mixed with polymers solution is slowly added in the hot boiling water in stirring to remove solvent, and obtains the aqueous solution containing solid polymer particles.This polymer beads is leached, via 100 ℃ of hot-air dries, to obtain the micelle of polymkeric substance E of vinylbenzene-butadiene block copolymer.
Embodiment 2: the polymkeric substance F for preparing 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 mixed take solid substance weight ratio as 40/23/37 ratio 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.
Embodiment 3: the polymkeric substance G for preparing 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 mixed take solid substance weight ratio as 30/33/37 ratio 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.
Embodiment 4: the polymkeric substance H for preparing polystyrene-poly butadiene block copolymer
Anionic polymerization is prepared 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)
Prepare the polymers soln of polystyrene-poly butadiene amphiphilic block copolymer SB-1 (H).1885 grams of (gram) hexanaphthenes (containing 120ppm THF) solvent is placed in to the reactor of 5 liters and is heated to 55 ℃.Sequentially add the n-Butyl Lithium of the styrene monomer of 92.1 grams and 7.2 grams of 15wt% to start to carry out polyreaction.Almost after complete reaction, add the divinylic monomer of 215 grams to proceed polyreaction, until almost complete reaction of divinylic monomer until styrene monomer.Add afterwards the water of 1.7 grams with termination reaction.When stirring after 20 minutes, add 0.7phr antioxidant (Irgafos 126 of Phosphite series mixes antioxidant with the Irganox 1076 of Phenolic series) and 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%.
Prepare the polymers soln of polystyrene-poly divinyl tapered block copolymer SB-2 (H).The reactor that 1885 grams of (gram) hexanaphthenes (containing 120ppm THF) solvent is placed in to 5 liters is heated to 55 ℃.Sequentially add the n-Butyl Lithium of the styrene monomer of 67.2 grams and 7.2 grams of 15wt% to start to carry out polyreaction.Almost after complete reaction, add the divinylic monomer of 215 grams to proceed polyreaction until styrene monomer, when temperature of reaction arrives 65～70 ℃, add the styrene monomer of 24.9 grams to proceed polyreaction.After polyreaction completes, add the water of 2.0 grams with termination reaction.When stirring after 20 minutes, add the 0.7phr antioxidant Irganox1076 mixing antioxidant of Phenolic series (Irgafos 126 of Phosphite series with) and 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%.
Prepare the polymers soln of polystyrene-poly divinyl-polystyrene triblock copolymer SBS (H).The reactor that 1885 grams of (gram) hexanaphthenes (containing 120ppm THF) solvent is placed in to 5 liters is heated to 55 ℃.Sequentially add the n-Butyl Lithium of the styrene monomer of 46.1 grams and 3.5 grams of 15wt% to start to carry out polyreaction.Almost after complete reaction, add the divinylic monomer of 218 grams to proceed polyreaction until styrene monomer, when temperature of reaction reach the highest after continuation reaction 10 minutes, make almost complete reaction of divinylic monomer.Add 46.1 grams of styrene monomers, treat almost complete reaction of styrene monomer.Add afterwards the water of 1.3 grams with termination reaction.When stirring after 20 minutes, add 0.7phr antioxidant (Irgafos 126 of Phosphite series mixes antioxidant with the Irganox 1076 of Phenolic series) and 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%.
In 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), all there is the about 30wt% of polystyrene content.The polymers soln of prepared 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) is stirred to 60 minutes evenly to mix under 10/10/80 ratio take solid substance weight ratio, and then obtained a uniform mixed with polymers solution.This mixed with polymers solution is slowly added in the hot boiling water in stirring to remove solvent, and obtains the aqueous solution containing solid polymer particles.This polymer beads is leached, via 100 ℃ of hot-air dries, to obtain the micelle of polymkeric substance H of 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 to pressure at the roller having heated, is compression molded into the test piece of 2mm thickness, then be cut into after dumbbell shape test piece with the #3 cutting unit of dumbbell shape, under the relative humidity of the temperature of 25 ℃ and 65%, carry out the test of the basic physical properties of unit elongation with Instron tension testing machine according to ASTM D 412 methods (drawing high speed: 500mm/min.), the measured table 1 that the results are shown in.
Prepare the characteristic test of sticking agent composition and sticking agent with polymer A～H
By the dry micelle of above-mentioned vinylbenzene-butadiene block copolymer A～H of 100 grams, (P100 belongs to perhydro-polyterpene resin series, S-125 belongs to poly-firpene terpine resin series with the P100 of 120 grams, the S-125 viscosity increaser of 60 grams respectively, purchased from Chu Guang petroleum chemistry company), the Semi-paraffinicoil (purchased from S-Oil company of Korea S) of 85 grams and the antioxidant Irganox-1076 (purchased from Ciba Geigy company) of 1 gram mix, to obtain sticking agent composition.Each sticking agent composition rotating speed with 150rpm at 180 ℃ of temperature is stirred 2 hours, to be prepared into hot melt adhesive sticking agent.
Prepared hot melt adhesive is utilized to Hot Melt Coater Cheminstruments-HLCL 1000 type coating machines, at 280 °F of temperature, hot melt adhesive is coated with at 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 initial viscosity test according to PSTC-16 method on this adhesive tape, utilize Instron 4464 type peel strength testers to carry out peel strength test according to PSTC-101 method, and utilize Cheminstruments RT-10 type to carry out 60 ℃ of detections of shearing stamina according to 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, F, G and the H that comprises 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 has the elongation property of improvement, is suitable for the upgrading of plastic cement.
In addition, as shown in table 1, the initial viscosity of the sticking agent that comprises the prepared polymer A of coupling process is not good.And comprise be mixed with polystyrene-poly divinyl-polystyrene block copolymer 2a and polystyrene-poly butadiene block copolymer 2b polymer B, comprise and be mixed with the polymkeric substance C of polystyrene-poly butadiene amphiphilic block copolymer SB-1 and polystyrene-poly divinyl-polystyrene triblock copolymer SBS or comprise that to be mixed with the initial viscosity of the sticking agent that the polymkeric substance D of polystyrene-poly divinyl tapered block copolymer SB-2 and polystyrene-poly divinyl-polystyrene triblock copolymer SBS forms not good yet.
Table 1 shows that the sticking agent that comprises fusion polystyrene-poly butadiene amphiphilic block copolymer SB-1, polystyrene-poly divinyl tapered block copolymer SB-2 in varing proportions and prepared polymkeric substance E, the F of polystyrene-poly divinyl-polystyrene triblock copolymer SBS and G and form has the initial viscosity of improvement.And, although the blending ratio of the weight average molecular weight that the polystyrene-poly butadiene amphiphilic block copolymer SB-1 (H) comprising in polymkeric substance H, polystyrene-poly divinyl tapered block copolymer SB-2 (H) and polystyrene-poly divinyl-polystyrene triblock copolymer SBS (H) have 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, but the sticking agent that comprises polymkeric substance H also has the initial viscosity of improvement.
Therefore, according to table 1, polymkeric substance E, F, G, the H that the embodiment of the present invention is provided blends in sticking agent composition, and can effectively promote initial viscosity, the stripping strength of sticking agent and shear stamina, and then the scope of application of promoting sticking agent.
Finally it should be noted that: above embodiment only, in order to technical scheme of the present invention to be described, is not intended to limit; Although the present invention is had been described in detail with reference to previous embodiment, those of ordinary skill in the art is to be understood that: its technical scheme that still can record aforementioned each embodiment is modified, or part technical characterictic is wherein equal to replacement; And these modifications or replacement do not make the essence of appropriate technical solution depart from the spirit and scope of various embodiments of the present invention technical scheme.
Claims (9)
1. a mixture for conjugated diolefine-vinyl aromatic hydrocarbon copolymer, comprises:
A 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;
An 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
A segmented copolymer of 10～80wt%, this segmented copolymer is polymerized by a triple conjugation diene monomers and a trivinyl aromatic hydrocarbon monomer;
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, in the group that 3-octadiene, isoprene, m-pentadiene, 2-phenyl-1,3-butadiene and above-mentioned composition form, choose;
This first vinyl aromatic hydrocarbon monomer, this second vinyl aromatic hydrocarbon monomer and this trivinyl aromatic hydrocarbon monomer are chosen respectively from vinylbenzene, alpha-methyl styrene, a group that ethyl styrene, phenylcyclohexane ethene, p-methylstyrene, o-methyl styrene, a vinyl toluene, 1-vinyl-5-hexyl naphthalene, vinylnaphthalene and above-mentioned composition are formed;
It is 2 × 10 that this di-block copolymer has a weight average molecular weight
4～10 × 10
4g/mol, it is 2 × 10 that this alternation di-block copolymer has a weight average molecular weight
4～10 × 10
4g/mol, it is 5 × 10 that this segmented copolymer has a weight average molecular weight
4～20 × 10
4g/mol;
It is 25～50wt% that this di-block copolymer has a vinyl aromatic hydrocarbon content, and it is 25～55wt% that this alternation di-block copolymer has a vinyl aromatic hydrocarbon content, and it is 25～50wt% that this segmented copolymer has a vinyl aromatic hydrocarbon content.
2. the mixture of conjugated diolefine-vinyl aromatic hydrocarbon copolymer according to claim 1, 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.
3. the mixture of conjugated diolefine-vinyl aromatic hydrocarbon copolymer according to claim 1, wherein an end of this alternation di-block copolymer is mainly polymerized by this second vinyl aromatic hydrocarbon monomer.
4. the mixture of conjugated diolefine-vinyl aromatic hydrocarbon copolymer according to claim 1, also comprises an antioxidant.
5. a sticking agent composition, comprises:
The mixture of 100 weight part conjugated diolefine-vinyl aromatic claimed in claim 1 hydrocarbon copolymer; And
One viscosity increaser of 1～700 weight part.
6. sticking agent composition according to claim 5, 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.
7. sticking agent composition according to claim 5, wherein this viscosity increaser comprises following arbitrary material or its combination: poly-terpene, poly-firpene terpine resin and the rosin derivative of C9 hydrocarbon resin, perhydro-or the part hydrogenation of C5 hydrocarbon resin, hydrogenation C5 hydrocarbon resin, polystyrene C9 resin, C5/C9 resin, polystyrene terpene resin, perhydro-or part hydrogenation.
8. sticking agent composition according to claim 7, also comprises a treated oil of 1～500 weight part.
9. sticking agent composition according to claim 8, wherein this treated oil comprises following arbitrary material or its combination: naphthenic oil and derivative thereof, fatty hydrocarbon ils and derivative, hydrocarbon oil and derivative thereof and natural oil and derivative thereof.
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|---|---|---|---|---|
| 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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