CN1350012A - Star-shaped butadiene, isopene and styrene block copolymer and its prepn - Google Patents
Star-shaped butadiene, isopene and styrene block copolymer and its prepn Download PDFInfo
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- CN1350012A CN1350012A CN 00130182 CN00130182A CN1350012A CN 1350012 A CN1350012 A CN 1350012A CN 00130182 CN00130182 CN 00130182 CN 00130182 A CN00130182 A CN 00130182A CN 1350012 A CN1350012 A CN 1350012A
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Abstract
The present invention relates to a butadiene-isoprene-styrene star-shaped block copolymer and its preparation method. Said copolymer possesses the folloiwng structure: (SBR-IBR)n-C, in which SBR is butadiene-styrene radom copolymer block, IBR is butadiene-isoprene random copolymer block, n is initiator functionality, n is greater than or equal to 3, the number-average molecular weight or the star-shaped block copolymer is 5X10 to the power 4-50X10 to the power 4, in the SBR block the styrene content is 10%-50%, butadiene content is 50%-90%, the ratio of SBR/IBR is 10/90-90/10, the ratio of I/B in IBR block is 10/90-90/10.
Description
The present invention relates to a class divinyl, isoprene, vinylbenzene star block copolymer and preparation method thereof, this class star block copolymer has following structure: (SBR-IBR) n-C, wherein: SBR is divinyl, styrene random copolymer block, IBR is divinyl, isoprene block of random copolymer, C is a polyfunctionality alkyl lithium initiator residue, n is the initiator functionality, and n is more than or equal to 3.
Usually based on divinyl, isoprene, three kinds of monomeric segmented copolymers of vinylbenzene SBS, SIS are arranged; SBS is a divinyl, (wherein: B is a polybutadiene block to styrene triblock copolymer; S is a polystyrene block); SIS is isoprene, styrene triblock copolymer (wherein: I is a polyisoprene blocks, and S is a polystyrene block).With the bifunctional lithium alkylide is initiator, change the order of addition(of ingredients) of divinyl, isoprene, styrene monomer, can obtain the segmented copolymer of different structure, this based block copolymer comprises following symmetrical structure: (1) S-I-B-I-S (divinyl, isoprene, vinylbenzene add in proper order); (2) S-B-I-B-S (isoprene, divinyl, vinylbenzene add in proper order); (3) S-I-BI-B-BI-I-S (divinyl and isoprene once add, vinylbenzene list add); (4) S-BS-B-I-B-BS-S (the isoprene list adds, divinyl and vinylbenzene add simultaneously); (5) S-IS-I-B-I-IS-S (the divinyl list adds, isoprene and vinylbenzene add simultaneously); (6) S-IS-I-BI-B-BI-I-IS-S (divinyl, isoprene and vinylbenzene add simultaneously); Wherein: S is a polystyrene block, B is a polybutadiene block, and I is a polyisoprene blocks, and BI is divinyl, the trapezoidal copolymer block of isoprene, BS is divinyl, the trapezoidal copolymer block of vinylbenzene, and IS is isoprene, the trapezoidal copolymer block of vinylbenzene.When divinyl and vinylbenzene add fashionable simultaneously, because divinyl is different with cinnamic reactivity ratio, can only obtain containing divinyl, five segmented copolymer S-BS-B-BS-S of the trapezoidal copolymer block of vinylbenzene, in order to change divinyl and cinnamic reactivity ratio, at divinyl, add polar additive in the time of styrene charge, make divinyl, cinnamic polymerization is carried out according to random mode, finally obtain random butylbenzene copolymer block SBR, the present invention is just from such polymer design, adopt the polyfunctionality alkyl lithium initiator, at first carry out the polymerization of divinyl/isoprene block of random copolymer IBR, carry out the polymerization of random butylbenzene copolymer block SBR again, prepared (SBR-IBR) n-C star block copolymer, from truly having realized the chemical composite of random styrene-butadiene rubber and divinyl/isoprene random copolymer rubber, and realize that the composite traditional method of rubber is various rubber to be carried out physical mixed on mill or Banbury mixer, obviously, composite method is simple for chemistry of the present invention, effect is better.
The object of the present invention is to provide a class based on divinyl, isoprene, three kinds of monomeric segmented copolymers of vinylbenzene, this based block copolymer is the broad-spectrum elastomer material of a class with the performance of SBR and IBR excellence.
Another object of the present invention is to provide a kind of method for preparing above-mentioned star block copolymer.
Technical characterictic of the present invention is general random butylbenzene copolymer rubber SBR and general divinyl/isoprene random copolymer rubber IBR in-situ accomplishes chemistry in polymerization reactor composite.
Prepared divinyl, isoprene and the vinylbenzene star block copolymer of the present invention has following structure: (SBR-IBR) n-C.The number-average molecular weight of star block copolymer (Mn) general range is 5 * 10
4-50 * 10
4, optimum range is 10 * 10
4-30 * 10
4Consisting of of divinyl and styrene random multipolymer SBR block: the general range of styrene content is 10%-50% (weight percent, below identical), and optimum range is 15%-35%; The general range of butadiene content is 50%-90% (weight percent, below identical), and optimum range is 65%-85%; 1.2-the polybutadiene content general range is 6%-80% (weight percent, below identical), optimum range is 10%-50%.The general range of divinyl, styrene random multipolymer SBR block and divinyl, isoprene random copolymers IBR block ratio SBR/IBR is 10/90-90/10 (weight ratio, below identical), and optimum range is 30/70-70/30.The general range of I and B ratio I/B is 10/90-90/10 (weight ratio, below identical) in divinyl, the isoprene random copolymers IBR block, and optimum range is 30/70-70/30.1.2-polybutadiene content general range is 6%-80% (weight percent, below identical) in divinyl, the isoprene random copolymers IBR block, and preferred range is 6%-55%, and optimum range is 6%-20%; 3.4-polyisoprene content general range is 6%-80% (weight percent, below identical), preferred range is 6%-55%, and optimum range is 6%-20%.C is a polyfunctionality alkyl lithium initiator residue, and n is the initiator functionality, and n is more than or equal to 3, and n is generally at 3-150, and preferred range is at 3-50, and optimum range is at 3-10.
Divinyl involved in the present invention, the preparation method of vinylbenzene star block copolymer (SBR-IBR) n-C is as follows: press monomer ratio with isoprene and first divinylic monomer in the non-polar hydrocarbon kind solvent, first polar additive joins in the reactor, add the polyfunctional group lithium initiator, the preparation divinyl, isoprene block of random copolymer IBR, after isoprene and the end of first divinylic monomer total overall reaction, press monomer ratio again with vinylbenzene and second batch of divinylic monomer, second batch of optional polar additive joins in the reactor, begin to prepare divinyl and styrene random copolymer block SBR, after divinyl and vinylbenzene total overall reaction are finished, stop polyreaction, obtain (SBR-IBR) n-C star block copolymer.
Divinyl involved in the present invention, isoprene and vinylbenzene star block copolymer preparation method's preferred version is as follows: press monomer ratio with isoprene and first divinylic monomer in the non-polar hydrocarbon kind solvent, first polar additive joins in the reactor, according to divinyl, the requirement of isoprene random copolymers IBR block microtexture and sequential structure adds an amount of polar additive, to guarantee that divinyl and isoprene carry out copolymerization by random mode in the IBR block, and the kind and the consumption of polar additive are looked divinyl, the design load of 1.2-polybutadiene content and 3.4-polyisoprene content in the isoprene random copolymers IBR block and deciding, the non-polar hydrocarbon kind solvent is selected from a kind of varsol in nonpolar aromatic hydrocarbons and the nonpolar fatty hydrocarbon or the mixture of several varsols, generally be selected from: benzene, toluene, ethylbenzene, dimethylbenzene, pentane, hexane, heptane, octane, hexanaphthene, Mixed XYLENE, raffinate oil, open stirring, after reaching kick off temperature, the initiation reaction temperature is 30 ℃-80 ℃, add the polyfunctional group lithium initiator, begin to prepare divinyl, isoprene block of random copolymer IBR, the consumption of polyfunctional group lithium initiator is decided according to the size of multipolymer number-average molecular weight, and the number-average molecular weight scope of star block copolymer of the present invention is generally 5 * 10
4-50 * 10
4After isoprene and the end of first divinylic monomer total overall reaction, press monomer ratio again with vinylbenzene and second batch of divinylic monomer, second batch of optional polar additive once joins in the reactor, begin to prepare divinyl and styrene random copolymer block SBR, the various monomeric total concn that each step of control is added is 10%-20% (weight percent), the purpose that adds polar additive is to change divinyl and cinnamic reactivity ratio, realize divinyl and cinnamic random copolymerization, obtain random butylbenzene copolymer block SBR, the polar additive consumption is relevant with the amount of the polar additive that adds for the first time, if the amount of the additive that adds is abundant for the first time, divinyl and vinylbenzene that the back is added carry out random copolymerization, then when adding vinylbenzene and divinyl, can not add second batch of polar additive; Otherwise, then need to add polar additive, to realize that divinyl and vinylbenzene carry out random copolymerization, second batch of polar additive that is added and first polar additive are identical or different, after divinyl and vinylbenzene total overall reaction are finished, add terminator, stop polyreaction, also can randomly add conventional additives, as anti-aging agent Irganox 1010 (trade(brand)name, Ciba-Geigy company is on sale) and Antigene BHT or 2.6.4 (trade(brand)name, SUMITOMO CHEMICAL KCC is on sale), adopt traditional method that the polymkeric substance glue is carried out aftertreatment, carry out analytical test behind the product drying, obtain (SBR-IBR) n-C star block copolymer.
Polar additive used in the present invention is selected from the mixture that contains oxygen, nitrogenous, sulfur-bearing, contains one or more compounds in Phosphorus polar compound and the alkoxide compound, as: (1) oxygenatedchemicals generally is selected from: ether, tetrahydrofuran (THF), R
1OCH
2CH
2OR
2(wherein: R
1, R
2Be that carbonatoms is the alkyl of 1-6, R
1, R
2Can be identical also can be different, with R
1, R
2Be not all good, as glycol dimethyl ether, ethylene glycol diethyl ether), R
1OCH
2CH
2OCH
2CH
2OR
2(wherein: R
1, R
2Be that carbonatoms is the alkyl of 1-6, R
1, R
2Can be identical also can be different, with R
1, R
2Be not all good, as diethylene glycol dimethyl ether, dibutyl ethylene glycol ether), crown ether; (2) nitrogenous compound generally is selected from: triethylamine, Tetramethyl Ethylene Diamine (TMEDA), two piperidines ethane (DPE), preferred TMEDA; (3) P contained compound is generally selected HMPA (HMPA) for use; (4) alkoxide compound generally is selected from ROM, and wherein: R is that carbonatoms is the alkyl of 1-6, and O is a Sauerstoffatom, and M is metal ion sodium Na or potassium K, preferably certainly: tert.-butoxy potassium, uncle's pentyloxy potassium.
Non-polar organic solvent used in the present invention is selected from a kind of varsol in nonpolar aromatic hydrocarbons and the nonpolar fatty hydrocarbon or the mixture of several varsols, generally be selected from: benzene, toluene, ethylbenzene, dimethylbenzene, pentane, hexane, heptane, octane, hexanaphthene, BTX aromatics (as: Mixed XYLENE), mixing-in fat hydrocarbon (as: raffinating oil), preferably from: hexane, hexanaphthene, raffinate oil.
Initiator used in the present invention is the disclosed any polyfunctional group lithium initiator of prior art, is selected from the mixture of a kind of polyfunctional group lithium initiator or several polyfunctional group lithium initiators, as: RLi
n, T (RLi) n, wherein: R is that carbonatoms is the alkyl of 4-20, R can be alkyl or aryl, T is an atoms metal, is generally metallic elements such as tin Sn, silicon Si, plumbous Pb, titanium Ti, germanium Ge, and n is the initiator functionality, n is more than or equal to 3, n is generally at 3-150, and preferred range is at 3-50, and optimum range is at 3-10.Polyfunctional group lithium initiator RLi
nCan be multi-chelate organolithium initiator, react the various multi-chelate organolithium initiators that obtain as Vinylstyrene (DVB) and the lithium alkylide of mentioning in the patents such as GB2124228A, US3280084, EP0573893A2, CN1197806A.The polyfunctional group lithium initiator also can be to contain above-mentioned metal species multifunctional group organic lithium initiator T (RLi) n, polyfunctional group lithium initiator T (RLi)
nGenerally be selected from stanniferous Sn class multifunctional group organic lithium initiator Sn (RLi)
n, as the stanniferous Sn class multifunctional group organic lithium initiator Sn (RLi) that mentions among the patent CN1148053A
4The polyfunctional group lithium initiator can also be that other functionality that can be used in initiation divinyl, isoprene equiconjugate diolefine and styrene monomer is not less than 3 polyfunctionality organic lithium initiator, as the various multifunctional group organic lithium initiators of mentioning among patent US5262213, the US5595951.
The consumption of initiator is decided according to the size of multipolymer number-average molecular weight, and the consumption of initiator makes that the number-average molecular weight of star block copolymer is 5 * 10 in the present invention
4-50 * 10
4
The used terminator of the present invention is the disclosed any terminator that can be used for anionic polymerisation of prior art, as water, methyl alcohol, ethanol or Virahol etc.
Further specify the present invention below in conjunction with embodiment, but and the scope of unrestricted claim protection of the present invention.
The used multifunctional group organic lithium initiator of following examples is a multi-chelate organolithium initiator; synthetic method is as follows: under the high pure nitrogen protection; by proportioning hexanaphthene 160 grams, 1; 3-divinyl 11 grams, tetrahydrofuran (THF) (THF) 80mmol, Vinylstyrene (DVB) 100mmol join in 500 milliliters of exsiccant saline bottles; after mixing; add n-Butyl Lithium 100mmol with syringe; after reacting 30 minutes under 70 ℃; generate scarlet homogeneous phase multi-chelate organolithium initiator solution, initiator concentration adopts two volumetrys to record.
Embodiment 1
In 5 liters of stainless steel cauldrons that have a stirring, add 3.5 liters of hexanaphthenes, 70 gram divinyl and 70 gram isoprene, add polar additive THF again, THF/Li (mol ratio) is 35, be warmed up to 50 ℃, add the polyfunctional group lithium initiator, making the multipolymer number-average molecular weight is 15 * 10
4Butadiene polymerization is all finished when polyreaction proceeds to 30 minutes, add 175 gram divinyl and 35 gram vinylbenzene again, continue reaction 60 minutes, after divinyl and styrene polymerization reaction are all finished, add terminator and finish reaction, add anti-aging agent (Irganox 1010 mixes with weight ratio with 2.6.4 at 1: 1) 3.5 grams, adopt traditional method to carry out the glue aftertreatment, classical way specimen structure and performance are adopted in dry back, and the result is as shown in table 1.
Embodiment 2-7
Polymerization process and processing condition are with embodiment 1, and just divinyl, isoprene, styrene monomer proportioning difference have prepared (SBR-IBR) n-C star block copolymer.Polymerization process condition, product structure transitivity test result are respectively shown in 2-7 in the table 1.
Table 1 polymerization process condition and product rerum natura
Annotate: S is the vinylbenzene consumption, B2 is a divinyl consumption among the SBR, B1 is a divinyl consumption among the IBR, I is an isoprene consumption among the IBR, SBR/IBR be SBR with the IBR block than (weight ratio), I/B1 is isoprene and a divinylic monomer proportioning (weight ratio) in the IBR block, S/B2 is vinylbenzene and a divinylic monomer proportioning (weight ratio) in the SBR block, 1.2-BR%+3.4-IR% is 1.2-polyhutadiene and 3.4-polyisoprene content sum, HI for the molecular weight distributing index that adopts gel permeation chromatography (GPC) to record (ratio of weight-average molecular weight and number-average molecular weight, Mw/Mn).
| Embodiment | ????1 | ????2 | ????3 | ????4 | ????5 | ????6 | ????7 |
| ????S(g) | ????35 | ????105 | ????105 | ????35 | ????70 | ????70 | ????70 |
| ????I(g) | ????70 | ????45 | ????35 | ????75 | ????35 | ????70 | ????60 |
| ????B1(g) | ????70 | ????60 | ????35 | ????30 | ????35 | ????70 | ????45 |
| ????I/B1 | ????1/1 | ????3/4 | ????1/1 | ????5/2 | ????1/1 | ????1/1 | ????4/3 |
| ????B2(g) | ????175 | ????140 | ????175 | ????210 | ????210 | ????140 | ????175 |
| ????S/B2 | ????17/83 | ????42/58 | ????37/53 | ????14/86 | ????25/75 | ????33/67 | ????28/72 |
| ????SBR/IBR | ????60/40 | ????70/30 | ????80/20 | ????70/30 | ????80/20 | ????60/40 | ????70/30 |
| ??1.2-BR％ ????+ ??3.4-IR％ | ????22.5 | ????19.?0 | ????21.8 | ????20.8 | ????22.7 | ????17.6 | ????19.3 |
| ????HI | ????1.33 | ????1.40 | ????1.41 | ????1.34 | ????1.36 | ????138 | ????1.38 |
Claims (30)
1. a class divinyl, isoprene, vinylbenzene star block copolymer, it is characterized in that this multipolymer has following structure: (SBR-IBR) n-C, wherein: SBR is divinyl, styrene random copolymer block, IBR is divinyl, isoprene block of random copolymer, C is a polyfunctional group lithium initiator residue, n is the initiator functionality, and n is more than or equal to 3, and the number-average molecular weight of star block copolymer is 5 * 10
4-50 * 10
4Styrene content is that 10%-50% (weight percent), butadiene content are 50%-90% (weight percent) in divinyl, the styrene random multipolymer SBR block, divinyl, styrene random multipolymer SBR block and divinyl, isoprene random copolymers IBR block ratio SBR/IBR are 10/90-90/10 (weight ratio), and the ratio I/B of I and B is 10/90-90/10 (weight ratio) in divinyl, the isoprene random copolymers IBR block.
2. star block copolymer according to claim 1, wherein the number-average molecular weight of star block copolymer is 10 * 10
4-30 * 10
4
3. star block copolymer according to claim 1, wherein styrene content is 15%-35% (weight percent) in divinyl and the styrene random multipolymer SBR block, butadiene content is 65%-85% (weight percent).
4. star block copolymer according to claim 1, wherein divinyl, styrene random multipolymer SBR block and divinyl, isoprene random copolymers IBR block ratio SBR/IBR are 30/70-70/30 (weight ratio).
5. star block copolymer according to claim 1, wherein the ratio I/B of I and B is 30/70-70/30 (weight ratio) in divinyl, the isoprene random copolymers IBR block.
6. star block copolymer according to claim 1, wherein the 1.2-polybutadiene content is 6%-80% (weight percent) in divinyl and the styrene random multipolymer SBR block.
7. star block copolymer according to claim 1, wherein the 1.2-polybutadiene content is 10%-50% (weight percent) in divinyl and the styrene random multipolymer SBR block.
8. star block copolymer according to claim 1, wherein the 1.2-polybutadiene content is 6%-80% (weight percent) in divinyl, the isoprene random copolymers IBR block.
9. star block copolymer according to claim 1, wherein the 1.2-polybutadiene content is 6%-55% (weight percent) in divinyl, the isoprene random copolymers IBR block.
10. star block copolymer according to claim 1, wherein the 1.2-polybutadiene content is 6%-20% (weight percent) in divinyl, the isoprene random copolymers IBR block.
11. star block copolymer according to claim 1, wherein 3.4-polyisoprene content is 6%-80% (weight percent) in divinyl, the isoprene random copolymers IBR block.
12. star block copolymer according to claim 1, wherein 3.4-polyisoprene content is 6%-55% (weight percent) in divinyl, the isoprene random copolymers IBR block.
13. star block copolymer according to claim 1, wherein 3.4-polyisoprene content is 6%-20% (weight percent) in divinyl, the isoprene random copolymers IBR block.
14. each described divinyl of claim 1-13, isoprene, the preparation method of vinylbenzene star block copolymer (SBR-IBR) n-C, it is characterized in that: in the non-polar hydrocarbon kind solvent, press monomer ratio isoprene and first divinylic monomer, first polar additive joins in the reactor, add the polyfunctional group lithium initiator, the preparation divinyl, isoprene block of random copolymer IBR, after isoprene and the end of first divinylic monomer total overall reaction, press monomer ratio again with vinylbenzene and second batch of divinylic monomer, second batch of optional polar additive joins in the reactor, begin to prepare divinyl and styrene random copolymer block SBR, after divinyl and vinylbenzene total overall reaction are finished, stop polyreaction, obtain (SBR-IBR) n-C star block copolymer.
15. method according to claim 14, wherein the polyfunctional group lithium initiator is selected from RLi
n, a kind of polyfunctional group lithium initiator among T (RLi) n or the mixture of several polyfunctional group lithium initiators, wherein: R is that carbonatoms is the alkyl of 4-20, T is tin Sn, silicon Si, plumbous Pb, titanium Ti, germanium Ge atoms metal, and n is the initiator functionality, and n is more than or equal to 3.
16. method according to claim 15, wherein polyfunctional group lithium initiator RLi
nBe selected from Vinylstyrene (DVB) and react the various multi-chelate organolithium initiators that obtain with lithium alkylide.
17. method according to claim 15, wherein polyfunctional group lithium initiator T (RLi)
nBe selected from stanniferous Sn class multifunctional group organic lithium initiator Sn (RLi)
n
18. method according to claim 17, wherein stanniferous Sn class multifunctional group organic lithium initiator Sn (RLi)
nBe selected from Sn (RLi)
4
19. method according to claim 14, wherein the non-polar hydrocarbon kind solvent is selected from: benzene, toluene, ethylbenzene, dimethylbenzene, pentane, hexane, heptane, octane, hexanaphthene, Mixed XYLENE, raffinate oil.
20. method according to claim 19, wherein the non-polar hydrocarbon kind solvent is selected from: hexane, hexanaphthene, raffinate oil.
21. method according to claim 14, wherein polar additive is selected from the mixture that contains oxygen, nitrogenous, sulfur-bearing, contains one or more compounds in Phosphorus polar compound and the alkoxide compound.
22. method according to claim 21 wherein contains the oxygen polar additive and is selected from: ether, tetrahydrofuran (THF), R
1OCH
2CH
2OR
2, R
1OCH
2CH
2OCH
2CH
2OR
2, wherein: R
1, R
2Be that carbonatoms is the alkyl of 1-6, R
1, R
2Identical or different.
23. method according to claim 22 wherein contains the oxygen polar additive and is selected from: glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, dibutyl ethylene glycol ether, crown ether.
24. method according to claim 21, wherein nitrogenous polar additive is selected from: triethylamine, Tetramethyl Ethylene Diamine (TMEDA), two piperidines ethane (DPE).
25. method according to claim 24, wherein nitrogenous polar additive is selected from: Tetramethyl Ethylene Diamine (TMEDA).
26. method according to claim 21, wherein phosphorous polar additive is selected HMPA (HMPA) for use.
27. method according to claim 21, wherein alkoxide compound is selected from ROM, and wherein: R is that carbonatoms is the alkyl of 1-6, and O is a Sauerstoffatom, and M is metal ion sodium Na or potassium K.
28. method according to claim 27, wherein alkoxide compound is selected from: tert.-butoxy potassium, uncle's pentyloxy potassium.
29. method according to claim 14, the various monomeric total concn that is wherein added are 10%-20% (weight percent).
30. method according to claim 14, wherein initiation reaction temperature are 30 ℃-80 ℃.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001301829A CN1133672C (en) | 2000-10-19 | 2000-10-19 | Star-shaped butadiene, isopene and styrene block copolymer and its prepn |
| US09/982,255 US6462137B2 (en) | 2000-10-19 | 2001-10-18 | Star-block interpolymers and preparation of the same |
| KR1020037005519A KR100806402B1 (en) | 2000-10-19 | 2001-10-19 | Star block copolymer and preparing method thereof |
| EP01273428A EP1333042B1 (en) | 2000-10-19 | 2001-10-19 | Star block copolymer and preparing method thereof |
| PCT/CN2001/001489 WO2002059174A1 (en) | 2000-10-19 | 2001-10-19 | Star block copolymer and preparing method thereof |
| JP2002559472A JP4213468B2 (en) | 2000-10-19 | 2001-10-19 | Star-block interpolymers and their manufacture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001301829A CN1133672C (en) | 2000-10-19 | 2000-10-19 | Star-shaped butadiene, isopene and styrene block copolymer and its prepn |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1350012A true CN1350012A (en) | 2002-05-22 |
| CN1133672C CN1133672C (en) | 2004-01-07 |
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ID=4594014
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|---|---|---|---|
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| CN101255223B (en) * | 2007-02-28 | 2010-12-01 | 中国石油化工股份有限公司 | Terpolymer rubber having low rolling resistance and high wet-sliding resistant performance, preparation and uses thereof |
| CN1922229B (en) * | 2004-02-19 | 2011-02-16 | 克雷顿聚合物研究公司 | Hot-melt adhesive composition for non-wovens |
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| CN110128607A (en) * | 2018-02-09 | 2019-08-16 | 中国石油化工股份有限公司 | Monovinylarene-conjugated diene block copolymer and block copolymer composition and vulcanized rubber and its application |
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-
2000
- 2000-10-19 CN CNB001301829A patent/CN1133672C/en not_active Expired - Lifetime
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1922229B (en) * | 2004-02-19 | 2011-02-16 | 克雷顿聚合物研究公司 | Hot-melt adhesive composition for non-wovens |
| CN101255223B (en) * | 2007-02-28 | 2010-12-01 | 中国石油化工股份有限公司 | Terpolymer rubber having low rolling resistance and high wet-sliding resistant performance, preparation and uses thereof |
| CN110128607A (en) * | 2018-02-09 | 2019-08-16 | 中国石油化工股份有限公司 | Monovinylarene-conjugated diene block copolymer and block copolymer composition and vulcanized rubber and its application |
| CN109181813A (en) * | 2018-07-31 | 2019-01-11 | 沈阳化工研究院有限公司 | A kind of star viscosity index improver and preparation method thereof for lubricating oil |
| CN109181813B (en) * | 2018-07-31 | 2021-07-06 | 沈阳化工研究院有限公司 | Star viscosity index improver for lubricating oil and preparation method thereof |
| CN113817112A (en) * | 2021-09-10 | 2021-12-21 | 大连理工大学 | Star block copolymer (SIBR-BR) n-C HIPS resin with ultrahigh impact strength and preparation method thereof |
| CN113817112B (en) * | 2021-09-10 | 2022-06-21 | 大连理工大学 | Star-shaped block copolymer (SIBR-BR) n-C HIPS resin with ultrahigh impact strength and preparation method thereof |
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|---|---|
| CN1133672C (en) | 2004-01-07 |
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