CN104650523A - Block copolymer composition - Google Patents
Block copolymer composition Download PDFInfo
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- CN104650523A CN104650523A CN201410092379.3A CN201410092379A CN104650523A CN 104650523 A CN104650523 A CN 104650523A CN 201410092379 A CN201410092379 A CN 201410092379A CN 104650523 A CN104650523 A CN 104650523A
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- block copolymer
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- copolymer composition
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- 239000000203 mixture Substances 0.000 title claims abstract description 49
- 229920001400 block copolymer Polymers 0.000 title claims abstract description 40
- 229920000642 polymer Polymers 0.000 claims abstract description 59
- -1 vinyl aromatic hydrocarbon Chemical class 0.000 claims abstract description 42
- 229920000359 diblock copolymer Polymers 0.000 claims abstract description 40
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 37
- 150000001993 dienes Chemical class 0.000 claims abstract description 35
- 108700015862 A-B-A triblock copolymer Proteins 0.000 claims abstract description 26
- 230000015572 biosynthetic process Effects 0.000 description 50
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 47
- 239000003795 chemical substances by application Substances 0.000 description 37
- 238000003786 synthesis reaction Methods 0.000 description 35
- 239000002904 solvent Substances 0.000 description 26
- 238000011010 flushing procedure Methods 0.000 description 24
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 21
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 20
- 239000000243 solution Substances 0.000 description 19
- 239000000178 monomer Substances 0.000 description 18
- 239000000126 substance Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 16
- 230000004044 response Effects 0.000 description 12
- 229920000428 triblock copolymer Polymers 0.000 description 11
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 10
- 238000009826 distribution Methods 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 239000007858 starting material Substances 0.000 description 8
- 230000000937 inactivator Effects 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 238000005227 gel permeation chromatography Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 3
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 2
- ROGIWVXWXZRRMZ-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1 ROGIWVXWXZRRMZ-UHFFFAOYSA-N 0.000 description 2
- VSKJLJHPAFKHBX-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 VSKJLJHPAFKHBX-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- 150000001339 alkali metal compounds Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- OSXYHAQZDCICNX-UHFFFAOYSA-N dichloro(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](Cl)(Cl)C1=CC=CC=C1 OSXYHAQZDCICNX-UHFFFAOYSA-N 0.000 description 2
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- GKESIQQTGWVOLH-UHFFFAOYSA-N (1,2-dibromo-2-phenylethyl)benzene Chemical compound C=1C=CC=CC=1C(Br)C(Br)C1=CC=CC=C1 GKESIQQTGWVOLH-UHFFFAOYSA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- OQOGEOLRYAOSKO-UHFFFAOYSA-N 1,1-dichloro-1-nitroethane Chemical compound CC(Cl)(Cl)[N+]([O-])=O OQOGEOLRYAOSKO-UHFFFAOYSA-N 0.000 description 1
- LHDZNHIBJAIMAQ-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C LHDZNHIBJAIMAQ-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- GDXHBFHOEYVPED-UHFFFAOYSA-N 1-(2-butoxyethoxy)butane Chemical compound CCCCOCCOCCCC GDXHBFHOEYVPED-UHFFFAOYSA-N 0.000 description 1
- GSWSUDFFJVJMLG-UHFFFAOYSA-N 2,2-dibromo-1,3-diphenylpropane-1,3-dione Chemical compound C=1C=CC=CC=1C(=O)C(Br)(Br)C(=O)C1=CC=CC=C1 GSWSUDFFJVJMLG-UHFFFAOYSA-N 0.000 description 1
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical class CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 1
- RCJMVGJKROQDCB-UHFFFAOYSA-N 2-methylpenta-1,3-diene Chemical compound CC=CC(C)=C RCJMVGJKROQDCB-UHFFFAOYSA-N 0.000 description 1
- IGLWCQMNTGCUBB-UHFFFAOYSA-N 3-methylidenepent-1-ene Chemical compound CCC(=C)C=C IGLWCQMNTGCUBB-UHFFFAOYSA-N 0.000 description 1
- CJSBUWDGPXGFGA-UHFFFAOYSA-N 4-methylpenta-1,3-diene Chemical compound CC(C)=CC=C CJSBUWDGPXGFGA-UHFFFAOYSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- WXZIKFXSSPSWSR-UHFFFAOYSA-N [Li]CCCCC Chemical compound [Li]CCCCC WXZIKFXSSPSWSR-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- KGQLBLGDIQNGSB-UHFFFAOYSA-N benzene-1,4-diol;methoxymethane Chemical compound COC.OC1=CC=C(O)C=C1 KGQLBLGDIQNGSB-UHFFFAOYSA-N 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- FUGIIBWTNARRSF-UHFFFAOYSA-N decane-5,6-diol Chemical compound CCCCC(O)C(O)CCCC FUGIIBWTNARRSF-UHFFFAOYSA-N 0.000 description 1
- YUYHCACQLHNZLS-UHFFFAOYSA-N dichloro-cyclohexyl-methylsilane Chemical compound C[Si](Cl)(Cl)C1CCCCC1 YUYHCACQLHNZLS-UHFFFAOYSA-N 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- APPOKADJQUIAHP-UHFFFAOYSA-N hexa-2,4-diene Chemical class CC=CC=CC APPOKADJQUIAHP-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- SZAVVKVUMPLRRS-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].C[CH-]C SZAVVKVUMPLRRS-UHFFFAOYSA-N 0.000 description 1
- XBEREOHJDYAKDA-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].CC[CH2-] XBEREOHJDYAKDA-UHFFFAOYSA-N 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 230000007170 pathology Effects 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- YGSFNCRAZOCNDJ-UHFFFAOYSA-N propan-2-one Chemical compound CC(C)=O.CC(C)=O YGSFNCRAZOCNDJ-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- SBYHFKPVCBCYGV-UHFFFAOYSA-N quinuclidine Chemical compound C1CC2CCN1CC2 SBYHFKPVCBCYGV-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229920006132 styrene block copolymer Polymers 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- MHNHYTDAOYJUEZ-UHFFFAOYSA-N triphenylphosphane Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 MHNHYTDAOYJUEZ-UHFFFAOYSA-N 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- ABDKAPXRBAPSQN-UHFFFAOYSA-N veratrole Chemical compound COC1=CC=CC=C1OC ABDKAPXRBAPSQN-UHFFFAOYSA-N 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Graft Or Block Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a block copolymer composition, which comprises an A-B diblock copolymer and an A-B-A triblock copolymer, wherein A is a vinyl aromatic hydrocarbon polymer , and B is a conjugated diene polymer (conjugated diene polymer). The A-B diblock copolymer has a first peak molecular weight and a second peak molecular weight, wherein the first peak molecular weight is from 8 to 13 ten thousand and the second peak molecular weight is from 17 to 27 ten thousand.
Description
Technical field
The present invention relates to a kind of copolymer compositions, and in particular to a kind of block copolymer composition (block copolymer composition).
Background technology
In industry with people's livelihood articles for use, usually come as adhesion agent composition with styrenic block copolymer.These compositions such as can be applicable to industrial gummed tape, label and as disposable type article such as diaper, female pathology articles for use and surgical operation covertures.
Generally speaking, adhesion agent composition must have good tackiness (adhesiveness), processibility (processing property) and mechanical property (mechanical property).In addition, different adhesion agent compositions can form the tackiness agent of different qualities, to be applicable to different application.Specifically, the character such as tackiness, thermostability (heat stability) and viscosity (viscosity) is extremely important for the application of tackiness agent.At present, all circles are devoted to provide a kind of adhesion agent composition that can be used for preparing the tackiness agent with good adhesion one after another.But, although developed many adhesion agent compositions forming the tackiness agent with good adhesion at present, but the tackiness of described tackiness agent and separability (stripping property) are difficult to have concurrently, and then have influence on the scope of application of tackiness agent.
Therefore, how to prepare the adhesion agent composition with tackiness and separability, become the problem that industry carries out studying in a hurry.
Summary of the invention
In view of this, the invention provides a kind of block copolymer composition, wherein when this block copolymer composition is applied to tackiness agent, described tackiness agent shows good tackiness and separability.
The invention provides a kind of block copolymer composition, it comprises A-B diblock copolymer (diblockcopolymer) and A-B-A triblock copolymer (triblock copolymer), wherein A is vinyl aromatic hydrocarbon polymer (vinyl aromatic hydrocarbon polymer), and B is conjugated diolefin polymer (conjugated diene polymer).A-B diblock copolymer has the first peak molecular weight (peak molecular weight) and the second peak molecular weight, and wherein the first peak molecular weight is 8-13 ten thousand, and the second peak molecular weight is 17-27 ten thousand.
The present invention separately provides a kind of block copolymer composition, and it comprises A-B diblock copolymer and A-B-A triblock copolymer, and wherein A is vinyl aromatic hydrocarbon polymer, and B is conjugated diolefin polymer.A-B-A triblock copolymer has the 4th peak molecular weight, and the 4th peak molecular weight be 28-40 ten thousand and content for being more than or equal to 1wt%.
Based on above-mentioned, the present invention by the A-B diblock copolymer with specified molecular weight distribution with there is A-B-A triblock copolymer that specified molecular weight distributes to form block copolymer composition.Again, when this block copolymer composition is applied to tackiness agent, described tackiness agent is easy to peel off and thus shows good tackiness and separability.
For above-mentioned feature and advantage of the present invention can be become apparent, special embodiment below is described in detail below.
Embodiment
The invention provides a kind of block copolymer composition, it comprises A-B diblock copolymer and A-B-A triblock copolymer, and wherein " A " is vinyl aromatic hydrocarbon polymer, and " B " is conjugated diolefin polymer.Below describe A-B diblock copolymer and A-B-A triblock copolymer in detail.
A-B diblock copolymer
A-B diblock copolymer is the segmented copolymer of " vinyl aromatic hydrocarbon polymer (A)-conjugated diolefin polymer (B) ".Specifically, A-B diblock copolymer is the segmented copolymer be made up of the block of the block of vinyl aromatic hydrocarbon polymer (A) and conjugated diolefin polymer (B).
The preparation method of A-B diblock copolymer first forms vinyl aromatic hydrocarbon polymer (A), then add the monomer for the formation of conjugated diolefin polymer (B) again, prepare to form conjugated diolefin polymer (B) on vinyl aromatic hydrocarbon polymer (A).Or, the method preparing A-B diblock copolymer also can be first form conjugated diolefin polymer (B), then the monomer for the formation of vinyl aromatic hydrocarbon polymer (A) is added again, to prepare at upper vinyl aromatic hydrocarbon polymer (A) that formed of conjugated diolefin polymer (B).
The molecular weight distribution of above-mentioned A-B diblock copolymer comprises the first peak molecular weight, the second peak molecular weight and the 3rd peak molecular weight.First peak molecular weight is 8-13 ten thousand.Second peak molecular weight is 17-27 ten thousand.3rd peak molecular weight is more than 400,000.In the weight of A-B diblock copolymer for 100wt%, the content with the polymkeric substance of the first peak molecular weight is 25-50wt%, is preferably 30-50wt%; The content with the polymkeric substance of the second peak molecular weight is 50-75wt%, is preferably 50-70wt%; And there is the content of the polymkeric substance of the 3rd peak molecular weight for being less than 1wt%.When the content of the polymkeric substance with the 3rd peak molecular weight is less than 1wt%, the tackiness agent prepared with the block copolymer composition formed by A-B diblock copolymer has tackiness and separability concurrently.
Be 100 parts by weight with the weight of block copolymer composition, the content of A-B diblock copolymer can be 20-80 weight part.
Below the formation method of above-mentioned vinyl aromatic hydrocarbon polymer (A) and the formation method of above-mentioned conjugated diolefin polymer (B) is described respectively.
Vinyl aromatic hydrocarbon polymer (A) under the existence of polymerization starter, carries out polyreaction by vinyl aromatic hydrocarbon monomer and formed.Vinyl aromatic hydrocarbon monomer can be vinylbenzene, alpha-methyl styrene, Vinylstyrene (Divinylbenzene) or its combination.Polymerization starter can be organic alkali metal compound, such as lithium ethide, n-propyl lithium, isopropyl lithium, n-Butyl Lithium (n-butyllithium, n-BL), n-pentyl lithium, phenyl lithium, tolyl lithium or its combination.Above-mentioned polymerization starter can be used alone, or mixes the use of two or more polymerization starter.The usage quantity of polymerization starter, can select according to the actual requirements.
Conjugated diolefin polymer (B) under the existence of polymerization starter, carries out polyreaction by conjugate diene monomer and formed.Conjugate diene monomer can be 1,3-butadiene, isoprene, 1,3-pentadiene, 2-ethyl-1,3-butadiene, 2,3-dimethylbutadienes, 2-methylpentadiene, 4-methylpentadiene, 2,4-hexadienes or its combination.Polymerization starter as formed vinyl aromatic hydrocarbon polymer (A) the organic alkali metal compound that uses.
Generally speaking, be 100 parts by weight with the total amount of vinyl aromatic hydrocarbon monomer and conjugate diene monomer, the consumption of polymerization starter is 0.0001 weight part to 0.1 weight part.
Above-mentioned formation vinyl aromatic hydrocarbon polymer (A) can be carried out in the presence of the solvent with the polyreaction of conjugated diolefin polymer (B).Solvent can comprise non-polar solvent, the aliphatic hydrocarbons such as such as (but being not limited to) pentane, normal hexane, heptane; The clicyclic hydrocarbons such as pentamethylene, hexanaphthene, methylcyclopentane, methylcyclohexane; The mixture of the aromatic hydrocarbonss such as benzene,toluene,xylene or aforementioned solvents.Above-mentioned solvent can be used alone, or mixes the use of two or more solvent.The usage quantity of solvent, can select according to the actual requirements.Generally speaking, be 100 parts by weight with the total amount of vinyl aromatic hydrocarbon monomer and conjugate diene monomer, the consumption of solvent is 300 weight part to 900 weight parts.Above-mentioned formation vinyl aromatic hydrocarbon polymer (A) can be carried out with the polyreaction of conjugated diolefin polymer (B) under the existence of microstructure adjusting agent.Microstructure adjusting agent includes, but is not limited to the ethers such as tetrahydrofuran (THF), diethyl ether, dioxan, glycol dimethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, dibutyl ethylene glycol ether, dimethoxy benzene, 2,2-two (2-tetrahydrofuran base) propane; The tertiary amine compounds such as Tetramethyl Ethylene Diamine, dipiperidinoethane, Trimethylamine 99, triethylamine, pyridine, rubane (quinuclidine); The alkali metal alkanolates compounds such as tertiary amyl alcohol potassium, potassium tert.-butoxide, sodium tert-butoxide, sodium tert-amyl alcohol; The phosphine compounds such as triphenylphosphine (triphenyl phosphine); Alkylsulphonic acid compound or aryl sulfonic acid compound etc.Above-mentioned microstructure adjusting agent can be used alone, or mixes the use of two or more microstructure adjusting agent.The usage quantity of microstructure adjusting agent, can select according to the actual requirements.Generally speaking, be 100 parts by weight with the total amount of vinyl aromatic hydrocarbon monomer and conjugate diene monomer, the consumption of microstructure adjusting agent is preferably 0.01 weight part to 0.1 weight part.Above-mentioned formation vinyl aromatic hydrocarbon polymer (A) can be carried out with the polyreaction of conjugated diolefin polymer (B) under the existence of coupler (coupling agent).Coupler includes, but is not limited to diphenyl dichlorosilane (diphenyldichlorosilane, DPDCS), methyl dichloro cyclohexyl silane (methylcyclohexyldiclorosilane), 1,3-phenylbenzene-2,2-bis-bromo-1,3-propanedione (2,2-dibromo-1,3-diphenyl-1,3-propanedione), 1,2-bis-bromo-1, the dihalide such as 2-diphenylethane (1,2-dibromo-1,2-diphenylethane).Above-mentioned coupler can be used alone, or mixes the use of two or more coupler.The usage quantity of coupler, can select according to the actual requirements.Generally speaking, be 100 parts by weight with the total amount of vinyl aromatic hydrocarbon monomer and conjugate diene monomer, the consumption of coupler is 0.1 weight part to 0.5 weight part.
Above-mentioned formation vinyl aromatic hydrocarbon polymer (A) can use inactivator (inactivator) to carry out termination reaction, to obtain polymkeric substance with the polyreaction of conjugated diolefin polymer (B).Inactivator includes, but is not limited to the ethers such as alcohols such as ketone, methyl alcohol (methanol) such as the aldehydes such as propionic aldehyde (propylaldehyde), butyraldehyde (butylaldehyde), acetone (acetone) etc., MEHQ (Mono Methyl Ether Hydroquinone, MEHQ).Above-mentioned inactivator can be used alone, or mixes the use of two or more inactivator.The usage quantity of inactivator, can select according to the actual requirements.Generally speaking, be 100 parts by weight with the total amount of vinyl aromatic hydrocarbon monomer and conjugate diene monomer, the consumption of inactivator is 0.05 weight part to 0.5 weight part.
A-B-A triblock copolymer
A-B-A triblock copolymer is the segmented copolymer of " vinyl aromatic hydrocarbon polymer (A)-conjugated diolefin polymer (B)-vinyl aromatic hydrocarbon polymer (A) ".Specifically, the segmented copolymer that A-B-A triblock copolymer is made up of the block of two vinyl aromatic hydrocarbon polymers (A) and the block of a conjugated diolefin polymer (B), wherein the block of conjugated diolefin polymer (B) is positioned between two vinyl aromatic hydrocarbon polymers (A).
The preparation method of A-B-A triblock copolymer first forms vinyl aromatic hydrocarbon polymer (A); Add the monomer for the formation of conjugated diolefin polymer (B) again, to form conjugated diolefin polymer (B) on vinyl aromatic hydrocarbon polymer (A); Then add the monomer for the formation of vinyl aromatic hydrocarbon polymer (A), prepare to add at conjugated diolefin polymer (B) upper formation vinyl aromatic hydrocarbon polymer (A).
The formation method of vinyl aromatic hydrocarbon polymer (A) and the formation method of conjugated diolefin polymer (B) are identical with the formation method of conjugated diolefin polymer (B) with the formation method of the vinyl aromatic hydrocarbon polymer (A) in above-mentioned A-B diblock copolymer respectively, do not repeat separately at this.
The molecular weight distribution of above-mentioned A-B-A triblock copolymer comprises the 4th peak molecular weight.4th peak molecular weight is 28-40 ten thousand.In the weight of A-B-A triblock copolymer for 100wt%, the content with the polymkeric substance of the 4th peak molecular weight can be and is more than or equal to 1wt%, and is preferably 6-20wt%.When the 4th peak molecular weight is more than or equal to 1wt%, the tackiness agent prepared with the block copolymer composition formed by A-B-A triblock copolymer has tackiness and separability concurrently.
With the weight of block copolymer composition for total amount, the content of A-B-A triblock copolymer can be 20-80wt%.
Synthesis example
Synthesis example 1
First, sequentially normal hexane 54.1 kilograms, 6wt% tetrahydrofuran solution (solvent is for normal hexane) 164.4 grams (afterwards again with 2 kilograms of normal hexane flushing pipelines), vinylbenzene 2.4 kilograms (afterwards again with 2 kilograms of normal hexane flushing pipelines) and 8.08wt% n-butyllithium solution (solvent is for normal hexane) 204 grams (afterwards again with 2 kilograms of normal hexane flushing pipelines) are added also fully stirring in reactor with pipeline.After question response device reaches the highest temperature, add 40wt% isoprene solution (solvent is normal hexane) 31.5 kilograms (afterwards again with 2 kilograms of normal hexane flushing pipelines).When question response reaches the highest temperature once again, then add 10wt% coupler hexichol dichlorosilane (DPDCS) solution (solvent is normal hexane) 317 grams (afterwards again with 2 kilograms of normal hexane flushing pipelines).After question response reaches the highest temperature again, wait for 10 minutes, and add 20wt% acetone soln (solvent is normal hexane) 60 grams (afterwards again with 2 kilograms of normal hexane flushing pipelines), to stop polyreaction.So just can obtain the diblock copolymer of the styrene-isoprene of synthesis example 4.
Synthesis example 2
Synthesis example 2 is only with the difference of synthesis example 1: the addition of the initiator (n-butyllithium solution) used is not identical, and its detailed addition is as shown in table 1.
Synthesis example 3
First, sequentially normal hexane 54.1 kilograms, 6wt% tetrahydrofuran solution (solvent is for normal hexane) 164.4 grams (afterwards again with 2 kilograms of normal hexane flushing pipelines), vinylbenzene 2.4 kilograms (afterwards again with 2 kilograms of normal hexane flushing pipelines) and 8.08wt% n-butyllithium solution (solvent is for normal hexane) 215 grams (afterwards again with 2 kilograms of normal hexane flushing pipelines) are added also fully stirring in reactor with pipeline.After question response device reaches the highest temperature, add 40wt% isoprene solution (solvent is normal hexane) 31.5 kilograms (afterwards again with 2 kilograms of normal hexane flushing pipelines).When question response reaches the highest temperature once again, then add 10wt% coupler hexichol dichlorosilane (DPDCS) solution (solvent is normal hexane) 242 grams (afterwards again with 2 kilograms of normal hexane flushing pipelines).After question response reaches the highest temperature again, wait for 10 minutes, and add 20wt% acetone soln (solvent is normal hexane) 60 grams (afterwards again with 2 kilograms of normal hexane flushing pipelines), to stop polyreaction.So just can obtain the diblock copolymer of the styrene-isoprene of synthesis example 3.
Synthesis example 4 ~ 5
Synthesis example 4 ~ 5 is only with the difference of synthesis example 3: the addition of the initiator (n-butyllithium solution) used is not identical, and its detailed addition is as shown in table 1.
Synthesis example 6
First, sequentially normal hexane 51 kilograms, 6wt% tetrahydrofuran solution (solvent is for normal hexane) 32 milliliters (afterwards again with 2 kilograms of normal hexane flushing pipelines), vinylbenzene 2.25 kilograms (afterwards again with 2 kilograms of normal hexane flushing pipelines) and 8.08wt% n-butyllithium solution (solvent is for normal hexane) 223 grams (afterwards again with 2 kilograms of normal hexane flushing pipelines) are added also fully stirring in reactor with pipeline.After question response device reaches the highest temperature, add 40wt% isoprene solution (solvent is normal hexane) 26.3 kilograms (afterwards again with 2 kilograms of normal hexane flushing pipelines).When question response reaches the highest temperature once again, then add vinylbenzene 2.25 kilograms (afterwards again with 2 kilograms of normal hexane flushing pipelines).After question response reaches the highest temperature again, wait for 10 minutes, then add 20wt% acetone soln (solvent is normal hexane) 63 grams (afterwards again with 2 kilograms of normal hexane flushing pipelines), to stop polyreaction.So just can obtain the triblock copolymer of the styrene-isoprene-phenylethene of synthesis example 6.
Synthesis example 7
Synthesis example 7 is only with the difference of synthesis example 6: the addition of the initiator (n-butyllithium solution) used is not identical, and its detailed addition is as shown in table 2.
Synthesis example 8
First, sequentially normal hexane 48.3 kilograms, 6wt% tetrahydrofuran solution (solvent is for normal hexane) 32.9 milliliters (afterwards again with 2 kilograms of normal hexane flushing pipelines), vinylbenzene 1.35 kilograms (afterwards again with 2 kilograms of normal hexane flushing pipelines) and 8.08wt% n-butyllithium solution (solvent is for normal hexane) 126 grams (afterwards again with 2 kilograms of normal hexane flushing pipelines) are added also fully stirring in reactor with pipeline.After question response device reaches the highest temperature, add 40wt% isoprene solution (solvent is normal hexane) 30.8 kilograms (afterwards again with 2 kilograms of normal hexane flushing pipelines).When question response reaches the highest temperature once again, then add vinylbenzene 1.35 kilograms (afterwards again with 2 kilograms of normal hexane flushing pipelines).After question response reaches the highest temperature again, wait for 10 minutes, and add 20wt% acetone soln (solvent is normal hexane) 34 grams (afterwards again with 2 kilograms of normal hexane flushing pipelines), to stop polyreaction.So just can obtain the triblock copolymer of the styrene-isoprene-phenylethene of synthesis example 8.
Synthesis example 9
Synthesis example 9 is only with the difference of synthesis example 8: the addition of the initiator (n-butyllithium solution) used is not identical, and its detailed addition is as shown in table 2.
Molecular weight distribution determination
Utilize gel permeation chromatography (Gel Permeation Chromatography, GPC) method to measure the molecular weight distribution of above-mentioned polymkeric substance.Specifically, utilize tetrahydrofuran (THF) that the polymer dilution of synthesis example 1 to synthesis example 9 is become the solution that concentration is about 0.15wt%, then, tubing string PLgel7.5 × the 300mm using HEWLETT PACKARD company to manufacture using tetrahydrofuran (THF) as developping agent, measure by gel permeation chromatography (GPC) instrument (model SERIES1100 is manufactured by HEWLETT PACKARD company).
According to obtained graph of molecular weight distribution, the weight percent (wt%) (in the total amount of polymkeric substance for 100wt%) corresponding to the peak value of the graph of molecular weight distribution of the polymkeric substance of synthesis example 1 to synthesis example 9 and each peak value is listed in table 1 and table 2.In Table 1, descending according to the molecular weight of polymkeric substance, define the first peak molecular weight, the second peak molecular weight and the 3rd peak molecular weight respectively.First peak molecular weight (A-B-MW1) of diblock copolymer, the second peak molecular weight (A-B-MW2) and the 3rd peak molecular weight (A-B-MW3) are sequentially defined as more than 8-13 ten thousand, 17-27 ten thousand and 400,000.In addition, as shown in table 2, the molecular weight distribution of triblock copolymer is defined as the first peak molecular weight (A-B-A-MW1) that molecular weight is 10-17 ten thousand, and molecular weight is second peak molecular weight (A-B-A-MW2) of 28-40 ten thousand.
It should be noted that in the polymkeric substance of synthesis example 1 ~ 5, its 3rd peak molecular weight (AB-MW3) i.e. molecular weight is that the content of the polymkeric substance of more than 400,000 is less than 1wt%.Again, in the polymkeric substance of synthesis example 6 ~ 9, its second peak molecular weight (A-B-A-MW2) i.e. molecular weight is the content of the polymkeric substance of 28-40 ten thousand is 6-20wt%.
In addition, compare with TSRC1307 (diblock copolymer), the TSRC1308 (diblock copolymer) of Tai Xiang Co., Ltd's manufacture, TSRC2411 (triblock copolymer) and TSRC2311 (triblock copolymer).Again, measure the molecular weight distribution of above-mentioned TSRC1307, TSRC1308, TSRC2411 and TSRC2311 according to the identical measuring method of above-mentioned synthesis example 1 to synthesis example 4, and define the peak molecular weight of above-mentioned diblock copolymer and triblock copolymer in the mode identical with synthesis example 1 to synthesis example 4.
Respectively in the weight of diblock copolymer and triblock copolymer for 100wt%, the weight percent corresponding to the peak molecular weight of the polymkeric substance of comparative example and each peak molecular weight is listed in table 2.It should be noted that in TSRC1307 (diblock copolymer) and TSRC1308 (diblock copolymer), the content with the polymkeric substance of the 3rd peak molecular weight (more than 400,000) is greater than 3wt%.Again in triblock copolymer (TSRC2411, TSRC2311), the content with the polymkeric substance of the second peak molecular weight (i.e. 28-40 ten thousand) is less than 1wt%.
Table 1
Table 2
Table 3
Embodiment
Embodiment 1
Be that the triblock copolymer of the diblock copolymer of synthesis example 2 with synthesis example 8 mixes by 20:80 with weight ratio, after gas stripping process removes solvent, namely form the block copolymer composition (tackiness agent) of embodiment 1.
Embodiment 2 to embodiment 8 and comparative example 1 to comparative example 4
The block copolymer composition (tackiness agent) of embodiment 2 to embodiment 8 and comparative example 1 to comparative example 4 prepares with the step identical with embodiment 1.Only, difference is: the kind of feed change and usage quantity thereof.The raw material type that embodiment 2 to embodiment 8 and comparative example 1 to comparative example 4 use and usage quantity thereof are as table 4.
Embodiment 9 to embodiment 16
The block copolymer composition (tackiness agent) of embodiment 9 to embodiment 16 prepares with the step identical with embodiment 3, and the weight ratio of namely fixing diblock copolymer and triblock copolymer is 50:50.Only, difference is: the kind of feed change.The raw material type that embodiment 9 to embodiment 16 uses and usage quantity thereof are as table 5.
Tackiness and separability evaluation
Tackiness agent embodiment 1 to embodiment 16 and comparative example 1 to comparative example 4 formed is with spreader (board: ZFR20404-sided applicator, purchased from Zehntner) be coated on the PET film (trade(brand)name: CH295Y of 2.5cm × 20cm, purchased from Nanya Plastic Cement Industry Co., Ltd, thickness is 100 μm) on, to make the adhesive tape of test tackiness.The test adhesive tape each embodiment and comparative example obtained is attached on different stainless steel plates (trade(brand)name: SUS304#800) respectively, use adherence force tester (board: TCD-200, purchased from Chatillon) test 180 degree of stripping strengths (peel strength), wherein 180 degree of larger expressions of stripping strength are more not easily peeled off, and namely tackiness is better.Again with cull situation on visual inspection stainless steel plate.Separability is not good to have cull namely to represent.
Evaluation result
Referring to table 4 and table 5, embodiment 1 to embodiment 16 is the block copolymer compositions (tackiness agent) using synthesis example 1 to synthesis example 9 to prepare.Comparative example 1 to comparative example 4 is block copolymer composition (tackiness agent) prepared by TSRC1307, TSRC1308, TSRC2411 and TSRC2311 polymkeric substance using Tai Xiang Co., Ltd to manufacture.From the numerical value of 180 ° of stripping strengths of table 4 and table 5, the tackiness of embodiment 1 to embodiment 16 is obviously better than comparative example 1 to comparative example 4.This result shows the tackiness agent that the block copolymer composition that distributed by specified molecular weight formed can represent good tackiness.In addition, because the block copolymer composition (tackiness agent) of embodiment 1 to embodiment 16 and comparative example 1 to comparative example 4 all residues on stainless steel plate without cull, good separability is all shown.
In addition, according to the test result of embodiment 1 to the embodiment 16 of table 4 and table 5, when the content of the A-B diblock copolymer in block copolymer composition is 20-80 weight part and the content of A-B-A triblock copolymer is 20-80 weight part, tackiness agent shows excellent tackiness and separability.
Table 4
Table 4 (Continued)
Table 5
In sum, the present invention proposes a kind of by having A-B diblock copolymer that specified molecular weight distributes and the block copolymer composition having A-B-A triblock copolymer that specified molecular weight distributes and form.When this block copolymer composition is applied to tackiness agent, described tackiness agent shows good tackiness and separability.In addition, when mixing above-mentioned A-B diblock copolymer and A-B-A triblock copolymer to prepare block copolymer composition with specified proportion, tackiness agent shows more excellent tackiness and separability.
Although the present invention discloses as above with embodiment; so itself and be not used to limit the present invention; have in any art and usually know the knowledgeable; without departing from the spirit and scope of the present invention; when doing a little change and retouching, therefore protection scope of the present invention is when being as the criterion depending on the appending claims person of defining.
Claims (10)
1. a block copolymer composition, is characterized in that, comprising:
A-B diblock copolymer; And
A-B-A triblock copolymer,
Wherein A is vinyl aromatic hydrocarbon polymer, B is conjugated diolefin polymer, described A-B diblock copolymer has the first peak molecular weight, the second peak molecular weight and the 3rd peak molecular weight, described first peak molecular weight is 8-13 ten thousand, described second peak molecular weight is 17-27 ten thousand, described 3rd peak molecular weight be more than 400,000 and content for being less than 1wt%.
2. block copolymer composition according to claim 1, is characterized in that, in the content of described A-B diblock copolymer for 100wt%, described 3rd peak molecular weight content is for being less than 1wt%.
3. block copolymer composition according to claim 1, is characterized in that, in the content of described block copolymer composition for 100wt%, described 3rd peak molecular weight content is for being less than 1wt%.
4. block copolymer composition according to claim 1, is characterized in that, described A-B-A triblock copolymer has the 4th peak molecular weight, described 4th peak molecular weight be 28-40 more than ten thousand and content for being more than or equal to 1wt%.
5. block copolymer composition according to claim 4, is characterized in that, the content of described 4th peak molecular weight accounts for the 6-20wt% of A-B-A triblock copolymer.
6. block copolymer composition according to claim 1, it is characterized in that, be 100 parts by weight with the total amount of described block copolymer composition, the content of described A-B diblock copolymer is 20-80 weight part, and the content of described A-B-A triblock copolymer is 20-80 weight part.
7. a block copolymer composition, is characterized in that, comprising:
A-B diblock copolymer; And
A-B-A triblock copolymer,
Wherein A is vinyl aromatic hydrocarbon polymer, and B is conjugated diolefin polymer, and described A-B-A triblock copolymer has the 4th peak molecular weight, described 4th peak molecular weight be 28-40 more than ten thousand and content for being more than or equal to 1wt%.
8. block copolymer composition according to claim 7, is characterized in that, the content of described 4th peak molecular weight accounts for the 6-20wt% of A-B-A triblock copolymer.
9. block copolymer composition according to claim 7, it is characterized in that, described A-B diblock copolymer has the first peak molecular weight and the second peak molecular weight, and described first peak molecular weight is 8-13 ten thousand, and described second peak molecular weight is 17-27 ten thousand.
10. block copolymer composition according to claim 7, it is characterized in that, be 100 parts by weight with the total amount of described block copolymer composition, the content of described A-B diblock copolymer is 20-80 weight part, and the content of described A-B-A triblock copolymer is 20-80 weight part.
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| WO2005054320A1 (en) * | 2003-12-04 | 2005-06-16 | Korea Kumho Petrochemical Co., Ltd. | Hetero-branched radial polystyrene-polyisoprene block copolymer composition and preparation method thereof |
| CN102146191A (en) * | 2010-02-05 | 2011-08-10 | 台橡股份有限公司 | Mixture of conjugated diene-vinyl aromatic hydrocarbon copolymers and adhesive composite containing same |
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| US20110319549A1 (en) * | 2009-03-31 | 2011-12-29 | Ryouji Oda | Adhesive composition for labels |
| CN102146191A (en) * | 2010-02-05 | 2011-08-10 | 台橡股份有限公司 | Mixture of conjugated diene-vinyl aromatic hydrocarbon copolymers and adhesive composite containing same |
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