CN1118498C - Star-shaped isoprene, butadiene and styrene block copolymer and its prepn - Google Patents
Star-shaped isoprene, butadiene and styrene block copolymer and its prepn Download PDFInfo
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- CN1118498C CN1118498C CN 00130185 CN00130185A CN1118498C CN 1118498 C CN1118498 C CN 1118498C CN 00130185 CN00130185 CN 00130185 CN 00130185 A CN00130185 A CN 00130185A CN 1118498 C CN1118498 C CN 1118498C
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Abstract
The present invention relates to a star-shaped block copolymer of isoprene, butadiene and styrene, and a preparation method thereof. The present invention is characterized in that the copolymer has the following structure; (SBR-IR)n-C; in the structure, SBR is the random copolymer block of butadiene and styrene; IR is an isoprene homopolymer block; C is a polyfunctionality alkyllithium initiator residue; n is large than or equal to 3; the number average molecular weight of the star-shaped block copolymer is from 5*10<4> to 35*10<4>; in the SBR block, the styrene content is from 10% to 50%, and the butadiene content is from 50% to 90%; the proportion SBR/IR of an SBR block to an IR block is from 10:90 to 90:10.
Description
The present invention relates to an isoprenoid, divinyl, vinylbenzene star block copolymer and preparation method thereof, this class star block copolymer has following structure: (SBR-IR) n-C, wherein: SBR is divinyl, styrene random copolymer block, IR is the isoprene homopolymer block, 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 polyfunctional group lithium initiator, at first carry out the polymerization of isoprene homopolymer block IR, carry out the polymerization of random butylbenzene copolymer block SBR again, prepared (SBR-IR) n-C star block copolymer, from truly having realized the chemical composite of random styrene-butadiene rubber and polyisoprene 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 isoprene, divinyl, vinylbenzene star block copolymer, this class star block copolymer is the broad-spectrum elastomer material of a class with the performance of SBR and IR 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 polyisoprene rubber IR in-situ accomplishes chemistry in polymerization reactor composite.
Prepared isoprene, divinyl, the vinylbenzene star block copolymer of the present invention has following structure: (SBR-IR) 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 and styrene random multipolymer SBR block and polyisoprene IR block ratio SBR/IR is 10/90-90/10 (weight ratio, below identical), and optimum range is 30/70-70/30.3.4-polyisoprene content general range is 6%-80% (weight percent, below identical) in the polyisoprene IR block, and 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-IR) n-C is as follows: press monomer ratio with isoprene monomer in the non-polar hydrocarbon kind solvent, optional polar additive joins in the reactor, add the polyfunctional group lithium initiator, preparation isoprene homopolymerization block IR, after the isoprene total overall reaction finishes, the vinylbenzene and the divinylic monomer that will contain polar additive by monomer ratio once joins in the reactor again, begin to prepare divinyl and styrene random copolymer block SBR, after divinyl and vinylbenzene total overall reaction are finished, termination reaction obtains (SBR-IR) n-C star block copolymer.
Isoprene involved in the present invention, divinyl, vinylbenzene star block copolymer preparation method's preferred version is as follows: press monomer ratio with isoprene monomer in the non-polar hydrocarbon kind solvent, optional polar additive joins in the reactor, look the polyisoprene microtexture and require to determine whether to use polar additive, and the kind of polar additive and consumption are decided on the design load of 3.4-polyisoprene content in the polyisoprene blocks, 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 isoprene homopolymer block IR, 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 the isoprene total overall reaction finishes, the vinylbenzene and the divinylic monomer that will contain polar additive by monomer ratio once joins in the reactor again, 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 SBR, the polar additive consumption is to realize that divinyl and vinylbenzene carry out random copolymerization and is as the criterion, kind on polar compound is decided, 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)names, 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-IR) 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, 140 gram isoprene, be warmed up to 50 ℃, add the polyfunctional group lithium, the multipolymer number-average molecular weight is 15 * 10
4The isoprene polymerization reaction is all finished when polyreaction proceeds to 30 minutes, add the 175 gram divinyl and the 35 gram vinylbenzene that contain polar additive THF again, THF/Li (mol ratio) is 35, continue reaction 60 minutes, after the reaction of divinyl and styrene polymerization is 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, styrene monomer proportioning difference have prepared (SBR-IR) n-C star block copolymer, and 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, B is the divinyl consumption, I is the isoprene consumption, SBR/IR be SBR with the IR block than (weight ratio), S/B 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) | 140 | 105 | 70 | 105 | 70 | 140 | 105 |
| B(g) | 175 | 140 | 175 | 210 | 210 | 140 | 175 |
| SBR/IR | 60/40 | 70/30 | 80/20 | 70/30 | 80/20 | 60/40 | 70/30 |
| S/B | 17/83 | 42/58 | 37/53 | 14/86 | 25/75 | 33/67 | 28/72 |
| 1.2-BR％ + 3.4-IR％ | 19.5 | 18.0 | 17.8 | 21.5 | 19.7 | 17.6 | 16.8 |
| HI | 1.37 | 1.42 | 1.38 | 1.35 | 1.31 | 1.40 | 1.36 |
Claims (25)
1. an isoprenoid, divinyl, vinylbenzene star block copolymer, it is characterized in that this multipolymer has following structure: (SBR-IR) n-C, wherein: SBR is divinyl, styrene random copolymer block, IR is the isoprene homopolymer block, C is a polyfunctionality alkyl lithium initiator residue, n is the initiator functionality, and n is 3-150, 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 and the styrene random multipolymer SBR block, and divinyl and styrene random multipolymer SBR block and polyisoprene IR block SBR/IR are 10/90-90/10 (weight ratio).
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 and styrene random multipolymer SBR block and polyisoprene IR block SBR/IR are 30/70-70/30 (weight ratio).
5. 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.
6. 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.
7. star block copolymer according to claim 1, wherein 3.4-polyisoprene content is 6%-80% (weight percent) in the polyisoprene IR block.
8. star block copolymer according to claim 1, wherein 3.4-polyisoprene content is 6%-55% (weight percent) in the polyisoprene IR block.
9. star block copolymer according to claim 1, wherein 3.4-polyisoprene content is 6%-20% (weight percent) in the polyisoprene IR block.
10. each described isoprene of claim 1-9, divinyl, the preparation method of vinylbenzene star block copolymer (SBR-IR) n-C, it is characterized in that: in the non-polar hydrocarbon kind solvent, press monomer ratio isoprene monomer, optional polar additive joins in the reactor, when the initiation reaction temperature reaches 30 ℃-80 ℃, add the polyfunctional group lithium initiator, preparation isoprene homopolymerization block IR, after the isoprene total overall reaction finishes, the vinylbenzene and the divinylic monomer that will contain polar additive by monomer ratio once joins in the reactor again, begin to prepare divinyl and styrene random copolymer block SBR, after divinyl and vinylbenzene total overall reaction are finished, termination reaction obtains (SBR-IR) n-C star block copolymer.
11. method according to claim 10, 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 3-150.
12. method according to claim 11, wherein polyfunctional group lithium initiator RLi
nBe selected from the various multi-chelate organolithium initiators that the reaction of Vinylstyrene and lithium alkylide obtains.
13. method according to claim 11, wherein polyfunctional group lithium initiator T (RLi)
nBe selected from stanniferous Sn class multifunctional group organic lithium initiator Sn (RLi)
n
14. method according to claim 13, wherein stanniferous Sn class multifunctional group organic lithium initiator Sn (RLi)
nBe selected from Sn (RLi)
4
15. method according to claim 10, wherein the non-polar hydrocarbon kind solvent is selected from: benzene, toluene, ethylbenzene, dimethylbenzene, pentane, hexane, heptane, octane, hexanaphthene, Mixed XYLENE, raffinate oil.
16. method according to claim 15, wherein the non-polar hydrocarbon kind solvent is selected from: hexane, hexanaphthene, raffinate oil.
17. method according to claim 10, 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.
18. method according to claim 17 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.
19. method according to claim 18 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.
20. method according to claim 17, wherein nitrogenous polar additive is selected from: triethylamine, Tetramethyl Ethylene Diamine, two piperidines ethane.
21. method according to claim 20, wherein nitrogenous polar additive is selected from: Tetramethyl Ethylene Diamine.
22. method according to claim 17, wherein phosphorous polar additive is selected HMPA for use.
23. method according to claim 17, 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.
24. method according to claim 23, wherein alkoxide compound is selected from: tert.-butoxy potassium, uncle's pentyloxy potassium.
25. method according to claim 10, the various monomeric total concn that is wherein added are 10%-20% (weight percent).
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00130185 CN1118498C (en) | 2000-10-19 | 2000-10-19 | Star-shaped isoprene, butadiene 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 |
| PCT/CN2001/001489 WO2002059174A1 (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 |
| JP2002559472A JP4213468B2 (en) | 2000-10-19 | 2001-10-19 | Star-block interpolymers and their manufacture |
| KR1020037005519A KR100806402B1 (en) | 2000-10-19 | 2001-10-19 | Star block copolymer and preparing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00130185 CN1118498C (en) | 2000-10-19 | 2000-10-19 | Star-shaped isoprene, butadiene and styrene block copolymer and its prepn |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1350015A CN1350015A (en) | 2002-05-22 |
| CN1118498C true CN1118498C (en) | 2003-08-20 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 00130185 Expired - Lifetime CN1118498C (en) | 2000-10-19 | 2000-10-19 | Star-shaped isoprene, butadiene and styrene block copolymer and its prepn |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4480675B2 (en) * | 2003-12-04 | 2010-06-16 | コリア クムホ ペトロケミカル カンパニー，リミテッド | Radial polystyrene-polyisoprene block copolymer having hetero branches and method for producing the same |
| CN100513446C (en) * | 2007-05-21 | 2009-07-15 | 北京化工大学 | Method for synthesizing star amphiphilic rubber |
| CN101817911B (en) * | 2009-02-26 | 2013-09-25 | 中国石油化工股份有限公司 | Star block copolymer prepared from isoprene, butadiene and styrene, and preparation method and application thereof |
| CN103382241B (en) * | 2012-05-04 | 2016-06-08 | 中国石油天然气股份有限公司 | Star isoprene-b-butadiene styrene terpolymer and its preparation method |
| CN110885412B (en) * | 2019-12-17 | 2023-01-06 | 广东众和高新科技有限公司 | Preparation method of SBS glue solution, star-shaped SBS prepared by preparation method and application of star-shaped SBS |
| CN113717336A (en) * | 2021-09-10 | 2021-11-30 | 大连理工大学 | Star block copolymer (SIBR-BR) n-C and preparation method thereof |
| CN113801277A (en) * | 2021-09-10 | 2021-12-17 | 大连理工大学 | Star block copolymer (SBR-BR) n-C HIPS resin with ultrahigh impact strength and preparation method thereof |
| CN113980214B (en) * | 2021-11-15 | 2023-04-28 | 大连理工大学 | ABS resin containing DPE derivative, butadiene and styrene star copolymer block and preparation method thereof |
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2000
- 2000-10-19 CN CN 00130185 patent/CN1118498C/en not_active Expired - Lifetime
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