CN104650523B - Block copolymer composition - Google Patents
Block copolymer composition Download PDFInfo
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- CN104650523B CN104650523B CN201410092379.3A CN201410092379A CN104650523B CN 104650523 B CN104650523 B CN 104650523B CN 201410092379 A CN201410092379 A CN 201410092379A CN 104650523 B CN104650523 B CN 104650523B
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- 239000000203 mixture Substances 0.000 title claims abstract description 42
- 229920001400 block copolymer Polymers 0.000 title claims abstract description 35
- 229920000642 polymer Polymers 0.000 claims abstract description 74
- -1 vinyl aromatic hydrocarbon Chemical class 0.000 claims abstract description 40
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 35
- 150000001993 dienes Chemical class 0.000 claims abstract description 32
- 229920000359 diblock copolymer Polymers 0.000 claims abstract description 31
- 108700015862 A-B-A triblock copolymer Proteins 0.000 claims abstract 2
- 229920000428 triblock copolymer Polymers 0.000 claims description 29
- 229920001577 copolymer Polymers 0.000 claims description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 94
- 230000015572 biosynthetic process Effects 0.000 description 40
- 238000003786 synthesis reaction Methods 0.000 description 35
- 239000002904 solvent Substances 0.000 description 27
- 238000011010 flushing procedure Methods 0.000 description 24
- 239000000243 solution Substances 0.000 description 21
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 19
- 239000000178 monomer Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 16
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 12
- 230000004044 response Effects 0.000 description 12
- 238000009826 distribution Methods 0.000 description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 11
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 10
- 239000007822 coupling agent Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 239000003505 polymerization initiator Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- 230000000937 inactivator Effects 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000005227 gel permeation chromatography Methods 0.000 description 5
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000012360 testing method 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
- 239000002585 base Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 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
- 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
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- KOEHAANXCGOZBS-UHFFFAOYSA-N benzene dichlorosilane Chemical compound Cl[SiH2]Cl.C1=CC=CC=C1 KOEHAANXCGOZBS-UHFFFAOYSA-N 0.000 description 2
- 238000012661 block copolymerization Methods 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
- 150000002170 ethers Chemical class 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 150000002240 furans Chemical class 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- SBYHFKPVCBCYGV-UHFFFAOYSA-N quinuclidine Chemical compound C1CC2CCN1CC2 SBYHFKPVCBCYGV-UHFFFAOYSA-N 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
- TWPKIBFRKXFXRJ-UHFFFAOYSA-N (1-bromo-2-phenylethyl)benzene Chemical class C=1C=CC=CC=1C(Br)CC1=CC=CC=C1 TWPKIBFRKXFXRJ-UHFFFAOYSA-N 0.000 description 1
- VKJWJILXLWFQEU-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene Chemical compound C=CC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C VKJWJILXLWFQEU-UHFFFAOYSA-N 0.000 description 1
- BSZXAFXFTLXUFV-UHFFFAOYSA-N 1-phenylethylbenzene Chemical compound C=1C=CC=CC=1C(C)C1=CC=CC=C1 BSZXAFXFTLXUFV-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
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- RCJMVGJKROQDCB-UHFFFAOYSA-N 2-methylpenta-1,3-diene Chemical class 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
- BPBQIKALCXYXID-UHFFFAOYSA-N 3-oxopropanoyl bromide Chemical compound BrC(=O)CC=O BPBQIKALCXYXID-UHFFFAOYSA-N 0.000 description 1
- CJSBUWDGPXGFGA-UHFFFAOYSA-N 4-methylpenta-1,3-diene Chemical class CC(C)=CC=C CJSBUWDGPXGFGA-UHFFFAOYSA-N 0.000 description 1
- 229920002799 BoPET Polymers 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
- 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
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- WXZIKFXSSPSWSR-UHFFFAOYSA-N [Li]CCCCC Chemical compound [Li]CCCCC WXZIKFXSSPSWSR-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes 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
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000003556 assay Methods 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
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 230000021615 conjugation Effects 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
- 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
- 150000002012 dioxanes Chemical class 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- BLHLJVCOVBYQQS-UHFFFAOYSA-N ethyllithium Chemical compound [Li]CC BLHLJVCOVBYQQS-UHFFFAOYSA-N 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- APPOKADJQUIAHP-UHFFFAOYSA-N hexa-2,4-diene Chemical class CC=CC=CC APPOKADJQUIAHP-UHFFFAOYSA-N 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 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
- COTNUBDHGSIOTA-UHFFFAOYSA-N meoh methanol Chemical compound OC.OC COTNUBDHGSIOTA-UHFFFAOYSA-N 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 1
- VIKNJXKGJWUCNN-XGXHKTLJSA-N norethisterone Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 VIKNJXKGJWUCNN-XGXHKTLJSA-N 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N penta-1,3-diene Chemical class CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 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
- 229920003023 plastic Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 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
- 238000012545 processing Methods 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
- 238000011160 research Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- CMXPERZAMAQXSF-UHFFFAOYSA-M sodium;1,4-bis(2-ethylhexoxy)-1,4-dioxobutane-2-sulfonate;1,8-dihydroxyanthracene-9,10-dione Chemical compound [Na+].O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=CC=C2O.CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC CMXPERZAMAQXSF-UHFFFAOYSA-M 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
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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 (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 more particularly to a kind of block copolymer composition (block
copolymer composition)。
Background technology
In industry with people's livelihood articles for use, generally being come with SBC as adhesion agent composition.These groups
Compound is such as can be applied to industrial gummed tape, label and can be abandoned as diaper, female physical care products and surgical operation covering
Formula article.
In general, adhesion agent composition must have good adherence (adhesiveness), processability
(processing property) and mechanical performance (mechanical property).In addition, different sticker combination
Thing can form the sticker of different qualities, with suitable for different applications.Specifically, adherence, heat endurance (heat
Stability) and the application of the property for sticker such as viscosity (viscosity) is extremely important.At present, all circles endeavour one after another
It is a kind of available for the adhesion agent composition for preparing the sticker with good adhesion in providing.Although however, develop at present
Many adhesion agent compositions for forming the sticker with good adhesion, but the adherence and fissility of the sticker
(stripping property) is difficult to have concurrently, and then has influence on the scope of application of sticker.
Therefore, the adhesion agent composition with adherence and fissility how is prepared, it has also become industry is carried out in a hurry
The problem of research.
The content of the invention
In view of this, the present invention provides a kind of block copolymer composition, wherein when this block copolymer composition application
When sticker, the sticker shows good adherence and fissility.
The present invention provides a kind of block copolymer composition, and it includes A-B diblock copolymers (diblock
Copolymer) and A-B-A triblock copolymers (triblock copolymer), wherein A are vinyl aromatic hydrocarbon polymer
(vinyl aromatic hydrocarbon polymer), and B is conjugated diolefin polymer (conjugated diene
polymer).A-B diblock copolymers have the first peak molecular weight (peak molecular weight) and the second peak value
Molecular weight, 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 includes A-B diblock copolymers and A-B-A three blocks
Copolymer, wherein A are vinyl aromatic hydrocarbon polymer, and B is conjugated diolefin polymer.A-B-A triblock copolymers have the
Four peak molecular weights, and the 4th peak molecular weight is 28-40 ten thousand, and using the weight of the A-B-A triblock copolymers as
100wt% is counted, and the 4th peak molecular weight content is more than or equal to 1wt%.
Based on above-mentioned, the present invention by the A-B diblock copolymers being distributed with specified molecular weight with specified molecular weight
The A-B-A triblock copolymers of distribution form block copolymer composition.Also, this block copolymer composition is applied to viscous
When agent, the sticker is easily peeled off thus shows good adherence and fissility.
For features described above of the invention and advantage can be become apparent, special embodiment below is described in detail below.
Embodiment
The present invention provides a kind of block copolymer composition, and it includes A-B diblock copolymers and A-B-A three blocks are total to
Polymers, wherein " A " is vinyl aromatic hydrocarbon polymer, and " B " is conjugated diolefin polymer.A-B described further below is double embedding
Section copolymer and A-B-A triblock copolymers.
A-B diblock copolymers
A-B diblock copolymers are the block copolymerizations of " vinyl aromatic hydrocarbon polymer (A)-conjugated diolefin polymer (B) "
Thing.Specifically, A-B diblock copolymers are the block and conjugated diolefin polymer (B) by vinyl aromatic hydrocarbon polymer (A)
The block copolymer that is formed of block.
The preparation method of A-B diblock copolymers can be initially formed vinyl aromatic hydrocarbon polymer (A), be added followed by
For forming conjugated diolefin polymer (B) monomer, to form conjugated diolefin polymer on vinyl aromatic hydrocarbon polymer (A)
(B) prepare.Or it can also be initially formed conjugated diolefin polymer (B) to prepare the methods of A-B diblock copolymers, then
The monomer for forming vinyl aromatic hydrocarbon polymer (A) is added, to form vinyl aromatic (co) on conjugated diolefin polymer (B)
It is prepared by fragrant hydrocarbon polymer (A).
The molecular weight distribution of above-mentioned A-B diblock copolymers include the first peak molecular weight, the second peak molecular weight and
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
For more than 400,000.Counted using the weight of A-B diblock copolymers as 100wt%, the polymer with the first peak molecular weight contains
Measure as 25-50wt%, preferably 30-50wt%；The content of polymer with the second peak molecular weight is 50-75wt%, compared with
Good is 50-70wt%；And the content of the polymer with the 3rd peak molecular weight is less than 1wt%.With block copolymer group
The content of compound is counted for 100wt%, and the 3rd peak molecular weight content is less than 1wt%.When poly- with the 3rd peak molecular weight
When the content of compound is less than 1wt%, with the block copolymer composition formed by A-B diblock copolymers come the adhesion for preparing
Agent has adherence and fissility concurrently.
Counted by 100 parts by weight of the weight of block copolymer composition, the content of A-B diblock copolymers can be 20-80
Parts by weight.
The forming method of above-mentioned vinyl aromatic hydrocarbon polymer (A) and above-mentioned conjugated diolefin polymer are described individually below
(B) forming method.
Vinyl aromatic hydrocarbon polymer (A) is to be polymerize by vinyl aromatic hydrocarbon monomer in the presence of polymerization initiator
React and formed.Vinyl aromatic hydrocarbon monomer can be styrene, α-methylstyrene, divinylbenzene (Divinylbenzene)
Or its combination.Polymerization initiator can be organic alkali metal compound, such as ethyl-lithium, n-propyl lithium, isopropyl lithium, n-BuLi
(n-butyllithium, n-BL), n-pentyl lithium, phenyl lithium, tolyl lithium or its combination.Above-mentioned polymerization initiator can individually make
With, or mix the use of two or more polymerization initiator.The usage amount of polymerization initiator, it can be selected according to the actual requirements
Select.
Conjugated diolefin polymer (B) be polymerisation is carried out in the presence of polymerization initiator by conjugate diene monomer and shape
Into.Conjugate diene monomer can be 1,3- butadiene, isoprene, 1,3- pentadienes, 2- ethyl -1,3- butadiene, 2,3- diformazans
Base butadiene, 2- methylpentadienes, 4- methylpentadienes, 2,4- hexadienes or its combination.Polymerization initiator such as forms vinyl
Organic alkali metal compound used in fragrant hydrocarbon polymer (A).
In general, being counted by 100 parts by weight of the total amount of vinyl aromatic hydrocarbon monomer and conjugate diene monomer, polymerization triggers
The dosage of agent is 0.0001 parts by weight to 0.1 parts by weight.
The polymerisation of above-mentioned formation vinyl aromatic hydrocarbon polymer (A) and conjugated diolefin polymer (B) can be in solvent
In the presence of carry out.Solvent may include non-polar solven, the such as (but not limited to) aliphatic hydrocarbon such as pentane, n-hexane, heptane；Ring penta
The clicyclic hydrocarbons such as alkane, hexamethylene, methyl cyclopentane, hexahydrotoluene；The aromatic hydrocarbons such as benzene,toluene,xylene or aforementioned solvents
Mixture.Above-mentioned solvent can be used alone, or mix the use of two or more solvent.The usage amount of solvent, can basis
Actual demand is selected.In general, using the total amount of vinyl aromatic hydrocarbon monomer and conjugate diene monomer as 100 parts by weight
Meter, the dosage of solvent is 300 parts by weight to 900 parts by weight.Above-mentioned formation vinyl aromatic hydrocarbon polymer (A) and conjugated-diolefin (co) polymer
The polymerisation of compound (B) can be carried out in the presence of micro-structural regulator.Micro-structural regulator includes but is not limited to tetrahydrochysene
Furans, diethyl ether, dioxanes, glycol dimethyl ether, butyl cellosolve, diethylene glycol dimethyl ether, dibutyl ethylene glycol ether, two
The ethers such as double (2- tetrahydrofuran bases) propane of methoxybenzene, 2,2-；Tetramethylethylenediamine, dipiperidinoethane, trimethylamine, three second
The tertiary amine compounds such as amine, pyridine, quinuclidine (quinuclidine)；Tert-pentyl alcohol potassium, potassium tert-butoxide, sodium tert-butoxide, tert-pentyl alcohol
The alkali metal alkanolates compound such as sodium；The phosphine compounds such as triphenylphosphine (triphenyl phosphine)；Alkyl sulfonic acid compound
Or aryl sulfonic acid compound etc..Above-mentioned micro-structural regulator can be used alone, or mix the adjustment of two or more micro-structural
Agent uses.The usage amount of micro-structural regulator, it can be selected according to the actual requirements.In general, with vinylaromatic hydrocarbon list
The total amount of body and conjugate diene monomer is 100 parts by weight meters, and the dosage of micro-structural regulator is preferably 0.01 parts by weight to 0.1 weight
Measure part.The polymerisation of above-mentioned formation vinyl aromatic hydrocarbon polymer (A) and conjugated diolefin polymer (B) can be in coupling agent
Carried out in the presence of (coupling agent).Coupling agent includes but is not limited to diphenyl dichlorosilane
(diphenyldichlorosilane, DPDCS), methyl dichloro hexamethylene base silane
(methylcyclohexyldiclorosilane), the bromo- 1,3- propanedione of 1,3- diphenyl -2,2- two (2,2-dibromo-1,
3-diphenyl-1,3-propanedione), the bromo- 1,2- diphenylethanes (1,2-dibromo-1,2- of 1,2- bis-
The dihalide such as diphenylethane).Above-mentioned coupling agent can be used alone, or mixes two or more coupling agent and make
With.The usage amount of coupling agent, it can be selected according to the actual requirements.In general, with vinyl aromatic hydrocarbon monomer and conjugation two
The total amount of alkene monomer is 100 parts by weight meters, and the dosage of coupling agent is 0.1 parts by weight to 0.5 parts by weight.
Inactivation can be used in above-mentioned formation vinyl aromatic hydrocarbon polymer (A) and the polymerisation of conjugated diolefin polymer (B)
Agent (inactivator) carrys out terminating reaction, to obtain polymer.Inactivator includes but is not limited to propionic aldehyde
(propylaldehyde), the ketone such as the aldehydes such as butyraldehyde (butylaldehyde), acetone (acetone), methanol (methanol)
Deng ethers such as alcohols etc., MEHQs (Mono Methyl Ether Hydroquinone, MEHQ).Above-mentioned inactivator can
It is used alone, or mixes the use of two or more inactivator.The usage amount of inactivator, it can be selected according to the actual requirements
Select.In general, counted by 100 parts by weight of the total amount of vinyl aromatic hydrocarbon monomer and conjugate diene monomer, the dosage of inactivator
For 0.05 parts by weight to 0.5 parts by weight.
A-B-A triblock copolymers
A-B-A triblock copolymers are " vinyl aromatic hydrocarbon polymers (A)-conjugated diolefin polymer (B)-vinyl aromatic (co)
The block copolymer of fragrant hydrocarbon polymer (A) ".Specifically, A-B-A triblock copolymers are by two vinyl aromatic hydrocarbon polymers
(A) block copolymer that block and the block of a conjugated diolefin polymer (B) is formed, wherein conjugated diolefin polymer
(B) block is between two vinyl aromatic hydrocarbon polymers (A).
The preparation method of A-B-A triblock copolymers can be initially formed vinyl aromatic hydrocarbon polymer (A)；Add use
In the monomer for forming conjugated diolefin polymer (B), to form conjugated diolefin polymer on vinyl aromatic hydrocarbon polymer (A)
(B)；The monomer for forming vinyl aromatic hydrocarbon polymer (A) is subsequently added into, to form second on conjugated diolefin polymer (B)
Alkenyl aroma hydrocarbon polymer (A) is added to prepare.
The forming method of the forming method of vinyl aromatic hydrocarbon polymer (A) and conjugated diolefin polymer (B) respectively with it is upper
State the forming method of the vinyl aromatic hydrocarbon polymer (A) in A-B diblock copolymers and the formation of conjugated diolefin polymer (B)
Method is identical, does not repeat separately herein.
The molecular weight distribution of above-mentioned A-B-A triblock copolymers includes the 4th peak molecular weight.4th peak molecular weight
For 28-40 ten thousand.Counted using the weight of A-B-A triblock copolymers as 100wt%, the polymer with the 4th peak molecular weight contains
Amount is greater than or equal to 1wt%, and preferably 6-20wt%.When the 4th peak molecular weight is more than or equal to 1wt%, with by
The block copolymer composition that A-B-A triblock copolymers are formed has adherence and fissility concurrently come the sticker prepared.
Counted using the weight of block copolymer composition as total amount, the content of A-B-A triblock copolymers can be 20-
80wt%.
Synthesis example
Synthesis example 1
First, using pipeline sequentially by 54.1 kilograms of n-hexane, 6wt% tetrahydrofuran solutions (solvent is n-hexane) 164.4
Gram (afterwards again with 2 kilograms of n-hexane flushing lines), 2.4 kilograms of styrene (afterwards again with 2 kilograms of n-hexane flushing lines) and
204 grams of 8.08wt% n-butyllithium solutions (solvent is n-hexane) (afterwards again with 2 kilograms of n-hexane flushing lines) add reaction
In device and it is sufficiently stirred.After question response device reaches the highest temperature, 40wt% isoprene solutions (solvent is n-hexane) 31.5 are added
Kilogram (afterwards again with 2 kilograms of n-hexane flushing lines).When question response reaches the highest temperature once again, 10wt% coupling agents two are added
317 grams of benzene dichlorosilane (DPDCS) solution (solvent is n-hexane) (afterwards again with 2 kilograms of n-hexane flushing lines).Question response
After reaching the highest temperature again, wait 10 minutes, and add 60 grams of 20wt% acetone solns (solvent is n-hexane) (afterwards again with 2,000
Gram n-hexane flushing line), to terminate polymerisation.Double blocks of the styrene-isoprene of synthesis example 4 can so be obtained
Copolymer.
Synthesis example 2
The difference of synthesis example 2 and synthesis example 1 is only that：The addition of used initiator (n-butyllithium solution) not phase
Together, its detailed addition is as shown in table 1.
Synthesis example 3
First, using pipeline sequentially by 54.1 kilograms of n-hexane, 6wt% tetrahydrofuran solutions (solvent is n-hexane) 164.4
Gram (afterwards again with 2 kilograms of n-hexane flushing lines), 2.4 kilograms of styrene (afterwards again with 2 kilograms of n-hexane flushing lines) and
215 grams of 8.08wt% n-butyllithium solutions (solvent is n-hexane) (afterwards again with 2 kilograms of n-hexane flushing lines) add reaction
In device and it is sufficiently stirred.After question response device reaches the highest temperature, 40wt% isoprene solutions (solvent is n-hexane) 31.5 are added
Kilogram (afterwards again with 2 kilograms of n-hexane flushing lines).When question response reaches the highest temperature once again, 10wt% coupling agents two are added
242 grams of benzene dichlorosilane (DPDCS) solution (solvent is n-hexane) (afterwards again with 2 kilograms of n-hexane flushing lines).Question response
After reaching the highest temperature again, wait 10 minutes, and add 60 grams of 20wt% acetone solns (solvent is n-hexane) (afterwards again with 2,000
Gram n-hexane flushing line), to terminate polymerisation.Double blocks of the styrene-isoprene of synthesis example 3 can so be obtained
Copolymer.
Synthesis example 4~5
The difference of synthesis example 4~5 and synthesis example 3 is only that：The addition of used initiator (n-butyllithium solution)
Differ, its detailed addition is as shown in table 1.
Synthesis example 6
First, using pipeline sequentially by 51 kilograms of n-hexane, 32 milliliters of 6wt% tetrahydrofuran solutions (solvent is n-hexane)
(afterwards again with 2 kilograms of n-hexane flushing lines), 2.25 kilograms of styrene (afterwards again with 2 kilograms of n-hexane flushing lines) and
223 grams of 8.08wt% n-butyllithium solutions (solvent is n-hexane) (afterwards again with 2 kilograms of n-hexane flushing lines) add reaction
In device and it is sufficiently stirred.After question response device reaches the highest temperature, 40wt% isoprene solutions (solvent is n-hexane) 26.3 are added
Kilogram (afterwards again with 2 kilograms of n-hexane flushing lines).When question response reaches the highest temperature once again, 2.25 kilograms of styrene is added
(afterwards again with 2 kilograms of n-hexane flushing lines).After question response reaches the highest temperature again, wait 10 minutes, add 20wt% third
63 grams of ketone solution (solvent is n-hexane) (afterwards again with 2 kilograms of n-hexane flushing lines), to terminate polymerisation.So
Obtain the triblock copolymer of the styrene-isoprene-phenylethene of synthesis example 6.
Synthesis example 7
The difference of synthesis example 7 and synthesis example 6 is only that：The addition of used initiator (n-butyllithium solution) not phase
Together, its detailed addition is as shown in table 2.
Synthesis example 8
First, using pipeline sequentially by 48.3 kilograms of n-hexane, the milli of 6wt% tetrahydrofuran solutions (solvent is n-hexane) 32.9
Rise (afterwards again with 2 kilograms of n-hexane flushing lines), 1.35 kilograms of styrene (afterwards again with 2 kilograms of n-hexane flushing lines) and
126 grams of 8.08wt% n-butyllithium solutions (solvent is n-hexane) (afterwards again with 2 kilograms of n-hexane flushing lines) add reaction
In device and it is sufficiently stirred.After question response device reaches the highest temperature, 40wt% isoprene solutions (solvent is n-hexane) 30.8 are added
Kilogram (afterwards again with 2 kilograms of n-hexane flushing lines).When question response reaches the highest temperature once again, 1.35 kilograms of styrene is added
(afterwards again with 2 kilograms of n-hexane flushing lines).After question response reaches the highest temperature again, wait 10 minutes, and add 20wt% third
34 grams of ketone solution (solvent is n-hexane) (afterwards again with 2 kilograms of n-hexane flushing lines), to terminate polymerisation.So
Obtain the triblock copolymer of the styrene-isoprene-phenylethene of synthesis example 8.
Synthesis example 9
The difference of synthesis example 9 and synthesis example 8 is only that：The addition of used initiator (n-butyllithium solution) not phase
Together, its detailed addition is as shown in table 2.
Molecular weight distribution determination
Above-mentioned polymer is determined using gel permeation chromatography (Gel Permeation Chromatography, GPC) method
Molecular weight distribution.Specifically, the polymer dilution of synthesis example 1 to synthesis example 9 is turned into concentration about using tetrahydrofuran
0.15wt% solution, then, using HEWLETT PACKARD companies manufacture 7.5 × 300mm of tubing string PLgel and with tetrahydrochysene
Furans is as solvent, by gel permeation chromatography (GPC) instrument (model SERIES 1100, by HEWLETT PACKARD companies
Manufacture) it is measured.
According to the graph of molecular weight distribution obtained, by synthesis example 1 to the peak of the graph of molecular weight distribution of the polymer of synthesis example 9
Percentage by weight (wt%) (being counted using the total amount of polymer as 100wt%) corresponding to value and each peak value is listed in table 1 and table 2.
It is descending according to the molecular weight of polymer in table 1, define respectively the first peak molecular weight, the second peak molecular weight with
And the 3rd peak molecular weight.The first peak molecular weight (A-B-MW1), the second peak molecular weight (A-B- of diblock copolymer
MW2) and the 3rd peak molecular weight (A-B-MW3) is sequentially defined as 8-13 ten thousand, 17-27 ten thousand and more than 400,000.In addition, such as table
Shown in 2, the molecular weight distribution of triblock copolymer is defined as the first peak molecular weight (A-B-A- that molecular weight is 10-17 ten thousand
MW1), and, molecular weight is 28-40 ten thousand the second peak molecular weight (A-B-A-MW2).
It is worth noting that, in the polymer of synthesis example 1~5, its 3rd peak molecular weight (AB-MW3) is that molecular weight is
The content of more than 400000 polymer is less than 1wt%.Also, in the polymer of synthesis example 6~9, its second peak molecular weight (A-B-
A-MW2 it is) that the content of the polymer that molecular weight is 28-40 ten thousand is 6-20wt%.
In addition, with the TSRC 1307 (diblock copolymer) of Tai Xiang Co., Ltd's manufacture, TSRC1308 (double blocks
Copolymer), TSRC 2411 (triblock copolymer) and TSRC 2311 (triblock copolymer) be compared.Also, according to
Above-mentioned synthesis example 1 determined to the identical assay method of synthesis example 4 above-mentioned TSRC 1307, TSRC 1308, TSRC 2411 with
And TSRC 2311 molecular weight distribution, and define above-mentioned double block copolymerizations in a manner of with synthesis example 1 to the identical of synthesis example 4
The peak molecular weight of thing and triblock copolymer.
Counted respectively using the weight of diblock copolymer and triblock copolymer as 100wt%, by the polymer of comparative example
Percentage by weight corresponding to peak molecular weight and each peak molecular weight is listed in table 3.It is worth noting that, TSRC 1307
In (diblock copolymer) and TSRC 1308 (diblock copolymer), there is the poly- of the 3rd peak molecular weight (more than 400,000)
The content of compound is more than 3wt%.Again in triblock copolymer (TSRC 2411, TSRC 2311), there is the second peak value molecule
The content for measuring the polymer of (i.e. 28-40 ten thousand) is less than 1wt%.
Table 1
Table 2
Table 3
Embodiment
Embodiment 1
Using weight ratio as 20：80 are mixed the diblock copolymer of synthesis example 2 and the triblock copolymer of synthesis example 8
Close, after gas stripping process removes solvent, that is, form the block copolymer composition (sticker) of embodiment 1.
Embodiment 2 is to embodiment 8 and comparative example 1 to comparative example 4
Embodiment 2 to embodiment 8 and comparative example 1 to the block copolymer composition (sticker) of comparative example 4 be with
It is prepared by embodiment 1 identical step.Only, difference is：The species and its usage amount of feed change.Embodiment 2 is to reality
Apply raw material type used in example 8 and comparative example 1 to comparative example 4 and its usage amount such as table 4.
Embodiment 9 is to embodiment 16
The block copolymer composition (sticker) of embodiment 9 to embodiment 16 is come with step same as Example 3
Prepare, i.e., the weight ratio of fixed diblock copolymer and triblock copolymer is 50:50.Only, difference is：Feed change
Species.Raw material type used in embodiment 9 to embodiment 16 and its usage amount such as table 5.
Adherence and fissility evaluation
The sticker that embodiment 1 to embodiment 16 and comparative example 1 are formed to comparative example 4 is with spreader (board：ZFR
20404-sided applicator, purchased from Zehntner) it is coated on 2.5cm × 20cm PET film (trade name：CH295Y, purchase
From Nanya Plastic Cement Industry Co., Ltd, thickness is 100 μm) on, so that the adhesive tape of test adherence is made.By each embodiment
And test made from comparative example is attached to different stainless steel plate (trade names with adhesive tape respectively：SUS304#800 on), adhesion is used
Force tester (board：TCD-200, purchased from Chatillon) test 180 degree peel strength (peel strength), wherein
The bigger expression of 180 degree peel strength is more not easily stripped, i.e., adherence is better.Again to visually observe cull situation on stainless steel plate.
There is cull to represent that fissility is bad.
Evaluation result
Referring to table 4 and table 5, embodiment 1 to embodiment 16 is embedding come what is prepared using synthesis example 1 to synthesis example 9
Section copolymer compositions (sticker).Comparative example 1 to comparative example 4 then be using Tai Xiang Co., Ltd manufacture TSRC
1307th, TSRC 1308, TSRC 2411 and the polymer of TSRC 2311 are come the block copolymer composition (sticker) for preparing.
From the point of view of table 4 and the numerical value of 180 ° of peel strengths of table 5, the adherence of embodiment 1 to embodiment 16 be clearly superior to comparative example 1 to
Comparative example 4.It is good that this result shows that the sticker formed by the block copolymer composition of specified molecular weight distribution can show
Good adherence.In addition, because the block copolymer composition of embodiment 1 to embodiment 16 and comparative example 1 to comparative example 4 (is adhered
Agent) all residued in without cull on stainless steel plate, all show good fissility.
In addition, according to the test result of the embodiment 1 of table 4 and table 5 to embodiment 16, when in block copolymer composition
The content of A-B diblock copolymers is the content of 20-80 parts by weight and A-B-A triblock copolymers when being 20-80 parts by weight, glues
Agent and show excellent adherence and fissility.
Table 4
The (Continued) of table 4
Table 5
In summary, the present invention proposes a kind of A-B diblock copolymers by being distributed with specified molecular weight and with spy
Determine the block copolymer composition that the A-B-A triblock copolymers of molecular weight distribution are formed.When by this block copolymer combinations
When thing is applied to sticker, the sticker shows good adherence and fissility.In addition, mix above-mentioned A- with special ratios
When B diblock copolymers and A-B-A triblock copolymers are to prepare block copolymer composition, sticker shows more excellent
Adherence and fissility.
Although the present invention is disclosed above with embodiment, so it is not limited to the present invention, any art
Middle tool usually intellectual, without departing from the spirit and scope of the present invention, when a little change and retouching can be made, thus it is of the invention
Protection domain when being defined depending on appended claims institute defender.
Claims (3)
- A kind of 1. block copolymer composition, it is characterised in that including：A-B diblock copolymers；AndA-B-A triblock copolymers, wherein A are vinyl aromatic hydrocarbon polymer, and B is conjugated diolefin polymer, and the A-B is double embedding Section copolymer has the first peak molecular weight, the second peak molecular weight and the 3rd peak molecular weight, the first peak value molecule It is 17-27 ten thousand to measure as 8-13 ten thousand, second peak molecular weight, and the 3rd peak molecular weight is more than 400,000, and with described The weight of A-B diblock copolymers is counted for 100wt%, and the 3rd peak molecular weight content is less than 1wt%, the A-B-A Triblock copolymer has the 4th peak molecular weight, and the 4th peak molecular weight is 28-40 ten thousand, and embedding with the A-B-A tri- The weight of section copolymer is counted for 100wt%, and the 4th peak molecular weight content is 6-20wt%.
- 2. block copolymer composition according to claim 1, it is characterised in that with the block copolymer composition Content is counted for 100wt%, and the 3rd peak molecular weight content is less than 1wt%.
- 3. block copolymer composition according to claim 1, it is characterised in that with the block copolymer composition Total amount is 100 parts by weight meters, and the contents of the A-B diblock copolymers is 20-80 parts by weight, the A-B-A triblock copolymers The content of thing is 20-80 parts by weight.
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