CN101781391B - Preparation method of controllable modified SEBS rubber - Google Patents
Preparation method of controllable modified SEBS rubber Download PDFInfo
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- CN101781391B CN101781391B CN2010101001501A CN201010100150A CN101781391B CN 101781391 B CN101781391 B CN 101781391B CN 2010101001501 A CN2010101001501 A CN 2010101001501A CN 201010100150 A CN201010100150 A CN 201010100150A CN 101781391 B CN101781391 B CN 101781391B
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Abstract
The invention discloses a preparation method of modified SEBS rubber, which comprises the following steps: (1) chloromethylating SEBS rubber to prepare the chloromethylated SEBS as an initiator; (2) and constituting a polymerization system through monomer, the initiator, catalyst, complexant and reducer, and carrying out the AGET ATRP reaction, wherein the mol ratio of monomer to initiator is 100-1000:1. Since the invention firstly designs SEBS with different degrees of chloromethylation as the initiator and then the AGET ATRP method is adopted, the polar SEBS with controllable grafting density, molecular weight and distribution can be finally obtained by regulating the reaction time and selecting different reaction monomers. Since the invention adopts molysites with good biocompatibility and low toxicity as the catalyst, the synthesized SEBS graft polymer has no or little toxicity. In addition, since the chemical reagents are stable in the air and the reaction can be operated in the air atmosphere, the invention is convenient for industrial production.
Description
Technical field
The present invention relates to a kind of preparation method of modified SEBS rubber; Be specifically related to the method for a kind of use AGETATRP (ATRP using Activators Generated by Electron Transfer is through the ATRP of transfer transport generation catalyzer) modified SEBS rubber.
Background technology
SEBS is a kind of multiduty novel thermoplastic elastomer, has the people it to be referred to as " the 4th generation rubber " in scientific and technological circle.It is the new modified elastomerics that rubber segments polyhutadiene unsaturated double-bond makes through selecting hydrogenation in thermoplastic polystyrene-polyhutadiene-polystyrene triblock copolymer (SBS) molecule.The middle polybutadiene block of SBS behind the hydrogenation is with regard to the random copolymerization section that changed into ethene and 1-butylene and become SEBS.
SEBS belongs to non-polar material, and is relatively poor with the polar material consistency, therefore limited the use range of SEBS, need carry out modification to it.
In order to improve this shortcoming, improve the polarity of SEBS, patent EP0743330 adopts dilithium initiator; Carrying out selective hydrogenation at SBS makes and contains polarity segmental SEBS; It has adopted and in the production process of SEBS, has directly carried out polar-modifiedly, but his polarity main officer of Tibet property condition is harsh, and polymer concentration is low; Suitability for industrialized production yields poorly, and production cost is high; In addition, the post-modification method that extensively adopts is the toxilic acid anhydridization of sulfonation, acetylize, carboxylation, chloromethylation, methylolation and EB section in the PS section, the esterification of esters of acrylic acid etc.; Carry out radical initiation grafting modification by copolymerization.Like (" SCIs " 1997 such as Jiang Ming; 18 (2), 309-312) be employed on the phenyl ring of SEBS and carry out sulfonation modifying, (" SCI " 1995 such as Shen Chong; 20 (5), 827-829) studied chloromethylation and hydroxymethylation on the SEBS phenyl ring; Guo Yan etc. (88-91) studied and utilize Banbury mixer to carry out SEBS grafted maleic anhydride reaction by " polymer material science and engineering " 2003,19 (6); (" polymer science and engineering " 2003 such as Liu Chengmei; 19 (5); 54-56) studied with solution graft copolymerization vinylformic acid and carried out the polar modification; Wang Xiaolan etc. (51-55) studied with twin screw reaction extrusion molding SY-Monomer G (GMA) be grafted to SEBS by " synthetic resins and plastics " 2003,20 (4); This post-modification method exists monomer conversion low, and product is prone to crosslinked, complex process, shortcomings such as cost height.The patent No. is that the invention of China of 200410046769.3 provides SEBS of a kind of polar and preparation method thereof; Product structure can be represented with SEBS-P; Wherein S represents polystyrene block; EB represents the hydrogenated diblock of polyhutadiene, and P represents polar block, and polar block is obtained by vinyl pyridine class, the polymerization of methyl acrylic ester polar monomer; The preparation method is initiator with the butyllithium, and THF is an acvator, and hexanaphthene is a solvent, prepares SBS-P four block polymers earlier and carries out the SEBS that selective hydration obtains polar then.The polar SEBS of preparation has obvious polarity, has more superior performance than common SEBS, can widen Application Areas greatly.
AGET ATRP (ATRP using Activators Generated by Electron Transfer; Generate the ATRP of catalyzer through transfer transport) be 2005 by (the Jakubowski W. of Matyjaszewski seminar; Matyjaszewski K.Macromolecules; 2005,38,4139-4146.) a kind of a kind of brand-new polymerization method that integrates the advantage of conventional ATRP and reverse ATRP and grow up has been proposed.In this reaction system, still adopt Organohalogen compounds used among the conventional ATRP as initiator, but the transition metal salt that adopts employed high oxidation state in the reverse ATRP is (like CuCl
2) be catalyzer.The transition metal salt (like CuCl) that is used for producing the low-oxidation-state that increases radical among the conventional ATRP is then reacted and the original position generation with reductive agent by the transition metal salt of the high oxidation state of adding system.Reductive agent is generally polyose organic cpds (like glucose), and xitix and stannous octoate etc. is easy to get and nontoxic or low toxicity compounds.Simultaneously owing to produce in position in the reaction of transition metal salt (like CuCl) of low-oxidation-state, reductive agent only and the transition metal salt of high oxidation state (like CuCl
2) reaction and not with system in Organohalogen compounds and monomer react, produce so in position in the process of transition metal salt of low-oxidation-state with regard to the reaction between the transition metal salt that can not have influence on Organohalogen compounds and low-oxidation-state.The particularly important is: (1) is because the oxygen that the existence of reductive agent exists in can also the consumption reaction system; So before carrying out the ATRP polymerization, then needn't will carry out deoxygenation in advance as conventional and reverse ATRP as long as add the whole polymerization system of an amount of reductive agent (removing the amount of consume oxygen); (2) transition metal salt catalyst owing to low-oxidation-state produces in position; Then the amount of needed catalyzer can descend greatly in the system; Can be reduced to 5ppm even lower; Be significantly less than the level of the required hundreds of of conventional ATRP～several thousand ppm, the residual quantity of the transition metal salt in the polymerisate that obtains like this is very low, even product even need not carry out aftertreatment.These 2 then mean a great concerning commercial run.
The catalyzer that in the AGET ATRP that reports at present, relates to basically only is confined to the mantoquita catalystsystem.Although mantoquita catalystsystem catalytic efficiency (is higher because its inherent bio-toxicity; Make its synthetic going up that is applied to bio-medical material bring material with bigger toxic problem with regard to existing; And molysite is owing to have better biocompatibility and less toxicity, makes it aspect the catalysis ATRP synthesising biological material and have a special advantages.
The contriver belongs to seminar and has taken the lead in carrying out the AGET ATRP of the oil-soluble monomer TEB 3K under the molysite catalysis in air atmosphere in the world, finds that molysite has preferably catalytic performance equally and existing 4 pieces of papers are delivered (Bai L., Zhang L. on international polymer periodical; Zhu J., Cheng Z., Zhu X.Journal of Polymer Science; Part A:Polymer Chemistry; 2009,47,2002-2008; Zhang L., Cheng Z., L ü Y., Zhu X.Macromolecular RapidCommunications, 2009,30,543-547; Zhang L., Cheng Z., Shi S., Li Q., ZhuX.Polymer, 2008,49,3054-3059; Zhang L., Cheng Z., Tang F., Li Q., Zhu X.Macromolecular Chemistry Physics, 2008,209,1705-1713.).Simultaneously Sen seminar (Luo, the R. of the Pennsylvania State University of the U.S.; Sen, A.Macromolecules, 2008,41,4514-4518) also reported the AGET ATRP of the catalytic oil soluble styrene monomer of molysite system.
But do not see any relevant open source literature report that adopts good biocompatibility and the less catalytic AGET ATRP of the molysite method of toxicity to be used for the SEBS modification at present both at home and abroad as yet.
Summary of the invention
The object of the invention provides a kind of preparation method of modified SEBS rubber.
For achieving the above object, the technical scheme that the present invention adopts is: a kind of preparation method of modified SEBS rubber comprises following concrete steps:
(1) phenyl ring in the SEBS rubber is carried out chloromethylation and prepare chloromethylation SEBS, as initiator;
(2) in molar ratio, monomer: initiator=100～1000: 1, monomer, initiator, catalyzer, coordination agent and reductive agent are formed polymerization system, carry out generating ATRP (AGET ATRP) reaction of catalyzer through transfer transport;
Said monomer is selected from:
Methylacrylic acid-N, one or both in TMSDMA N dimethylamine base ethyl ester or the vinyl cyanide, in the formula, R
1Be selected from hydrogen, R
2Be selected from a kind of in hydrogen or the methyl, R
3Be selected from the saturated alkyl of C1～C4;
SEBS itself can't be as the initiator of living polymerization, and still because contain phenyl ring among the SEBS, and phenyl ring carries out can becoming initiator behind the chloromethylation, and Cholromethylation method belongs to prior art; Can be with reference to pertinent literature (Shen Chong, Zhang Yan etc., SCI; 1999,20,827-829.); Phenyl ring can be by chloromethylation among the SEBS, and the chloromethylation degree can be through changing the length in reaction times, and the consumption that changes reagent is regulated.
Said catalyzer is selected from: a kind of in high iron(ic)chloride of six hydrations or the iron bromide;
Said coordination agent is selected from: three (3,6-dioxy heptyl) amine (TDA-1), triphenylphosphine (PPh
3), a kind of in imido oxalic acid (IDA) or the m-phthalic acid;
Said reductive agent is selected from: xitix (VC) or glucose.
In the technique scheme, the temperature of reaction of AGET ATRP reaction is generally 50～120 ℃; At least 30 minutes reaction times, and can adjust the molecular weight of polymkeric substance the reaction times through adjustment.
In the technique scheme, according to mol ratio, the mol ratio of the consumption of said initiator, catalyzer, coordination agent, reductive agent is 1: 1～3: 1～3: 1～4.
Ultimate principle of the present invention is: utilize AGET ATRP method to have activity/controlled polymerization characteristics; Can design and obtain having different molecular weight; Different grafting densities; The pectination grafting homopolymerization or the segmented copolymer of different grafted monomer, grafting opposed polarity high molecular polymer on SEBS can be regulated SEBS polarity according to monomeric kind.
Because the technique scheme utilization, the present invention compared with prior art has advantage:
Since the present invention at first design different chloromethylation degree SEBS as initiator; Then through adopting AGET ATRP method; Can select the differential responses monomer through the adjustment reaction times, obtain grafting density, molecular weight at last and distribute all controlled opposed polarity SEBS that has.
2. be catalyzer owing to the present invention adopts good biocompatibility and the little molysite of toxicity, the SEBS graftomer that synthesizes is nontoxic or toxicity is very little; And used chemical reagent is stable in the air and this reaction can be operated under air atmosphere, is convenient to suitability for industrialized production.
Description of drawings
Among accompanying drawing 1 embodiment one before and after the SEBS chloromethylation
1H NMR figure is (a) before the chloromethylation; (b) behind the chloromethylation.
Embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is further described
1, used chemical reagent:
SEBS (YH-501), the massfraction of vinylbenzene section are 30%, the Ba Ling of assets management Management Co., Ltd petrochemical industry branch office of SINOPEC.Trimethylchlorosilane, CP, 98% Chemical Reagent Co., Ltd., Sinopharm Group.Tin tetrachloride, 98%; Trioxymethylene, molecular weight are 90.08g/mol, CP, Chemical Reagent Co., Ltd., Sinopharm Group.THF (THF), molecular weight are 72.11g/mol, 99%, and Jiangsu Qiangsheng Chemical Co., Ltd..Trichloromethane, molecular weight are 119.38g/mol, analytical pure, Changshu City Yang Yuan chemical industry ltd.Vinylbenzene, molecular weight are 104.15g/mol, CP, 99%.Methymethacrylate (MMA), molecular weight are 100.12g/mol, CP, 98%.Methylacrylic acid-N, TMSDMA N dimethylamine base ethyl ester (DMAEMA), 99%, Aldrich company.Vinyl cyanide (AN), 99%, Aldrich company.Vinylbenzene (St), 99%, China Medicine (Group) Shanghai Chemical Reagent Co..High iron(ic)chloride (the FeCl of six hydrations
3.6H
2O) and xitix (VC), analytical pure, China Medicine (Group) Shanghai Chemical Reagent Co..Three-(3,6-dioxy heptyl) amine (TDA-1), 97%, Linhai Xinhua chemical plant.Methyl alcohol, analytical pure, Changshu City Yang Yuan chemical reagent ltd.
2, testing tool and condition
Gel permeation chromatograph: the 1515 type GPC of U.S. Waters (Waters).
Condition determination: HR1, HR3 and the series connection of HR4 three posts are used, the differential detector, moving phase is THF (1ml/min), 30 ℃ of column temperatures are done correction with polystyrene standards.
Embodiment one: SEBS macromole evocating agent SEBSCH
2Cl's is synthetic
The SEBS of 5g (YH501) and 5.4g trioxymethylene are added in the chloroform of 250ml.After the dissolving, in ice-water bath, add the trimethylchlorosilane of 22.8ml and the tin tetrachloride of 2～3ml fully, stir 30min.Remove ice-water bath, at room temperature continue to stir for some time.With a large amount of methanol extractions, suction filtration.Purify last vacuum-drying then through twice dissolution/precipitation circulation.The material that obtains is SEBSCH
2Cl.
The nuclear magnetic spectrogram of Fig. 1 has proved that the success of chloromethylation carries out.
Table 1 is the chloromethylation SEBS of different grafting densities
Embodiment two: with SEBSCH
2Cl is that initiator prepares SEBS-g-PSt.
Press proportioning n (St): n (SEBSCH
2Cl): n (FeCl
3.6H
2O): n (TDA-1): n (VC)=100: 1: 0.5: 1: 1, add FeCl successively
3.6H
2O, SEBSCH
2Cl, vinylbenzene (St), TDA-1, VC in the ampoule of 5mL under air atmosphere direct tube sealing.Place the oil bath under the steady temperature (100 ℃) to react (2-20h) ampoule behind the tube sealing by preset time.After reaction finishes, take out tube sealing, with the cold water cooling, open tube sealing immediately, with an amount of THF dissolving, then with a large amount of methanol extractions, suction filtration.Vacuum-drying.Can obtain SEBS-g-PSt.
Adopt SEBSCH
2Cl is a macromole evocating agent, through changing the graftomer that the reaction times can obtain different molecular weight.Data are as shown in table 2.Can find out that by data in the table molecular weight size of polymkeric substance can be through changing the reaction times better controlled, thus the length of control grafting section.
Table 2. is used SEBSCH
2The SEBS-g-PSt molecular weight size and the time relation of Cl preparation
Polymerizing condition: St=1.0mL; [St]
0/ [SEBSCH
2Cl]
0/ [FeCl
3.6H
2O]
0/ [TDA-1]
0/ [VC]
0=100/1/0.5/1/1; T=100 ℃.
Embodiment three: with SEBSCH
2Cl is that initiator prepares SEBS-g-PMMA
Press proportioning n (MMA): n (SEBSCH
2Cl): n (FeCl
3.6H
2O): n (TDA-1): n (VC)=100: 1: 0.5: 1: 1, add FeCl successively
3.6H
2O, SEBSCH
2Cl, TEB 3K (MMA), TDA-1, VC in the ampoule of 5mL under air atmosphere direct tube sealing.Place the oil bath under the steady temperature (90 ℃) to react (2-20h) ampoule behind the tube sealing by preset time.After reaction finishes, take out tube sealing, with the cold water cooling, open tube sealing immediately, with an amount of THF dissolving, then with a large amount of methanol extractions, suction filtration.Vacuum-drying.Can obtain SEBS-g-PMMA.
Adopt SEBSCH
2Cl is a macromole evocating agent, through changing the graftomer that the reaction times can obtain different molecular weight.Data are as shown in table 3.Can find out that by data in the table molecular weight size of polymkeric substance can be through changing the reaction times better controlled, thus the length of control grafting section.
Table 3. is used SEBSCH
2The SEBS-g-PMMA molecular weight size and the time relation of Cl preparation
Polymerizing condition: MMA=1.0mL; [MMA]
0/ [SEBSCH
2Cl]
0/ [FeCl
3.6H
2O]
0/ [TDA-1]
0/ [VC]
0=100/1/0.5/1/1; T=90 ℃.
Embodiment four: be that macromole evocating agent prepares SEBS-g-(PMMA-b-PDMAEMA) with SEBS-g-PMMA
Press proportioning n (DMAEMA): n (SEBS-g-PMMA): n (FeCl
3.6H
2O): n (TDA-1): n (VC)=200: 1: 0.5: 1: 1, add FeCl successively
3.6H
2O, SEBS-g-PMMA, methylacrylic acid-N, TMSDMA N dimethylamine base ethyl ester (DMAEMA), TDA-1, VC in the ampoule of 5mL under air atmosphere direct tube sealing.Place the oil bath under the steady temperature (90 ℃) to react 6h the ampoule behind the tube sealing by preset time.After reaction finishes, take out tube sealing, with the cold water cooling, open tube sealing immediately, with an amount of THF dissolving, then with a large amount of methanol extractions, suction filtration.Vacuum-drying.Can obtain the amphipathic graft block copolymer SEBS-g-(PMMA-b-PDMAEMA) after the SEBS modification, the molecular weight of polymkeric substance is 132000g/mol.
Embodiment five: with SEBSCH
2Cl is that macromole evocating agent prepares SEBS-g-PAN by proportioning n (AN): n (SEBSCH
2Cl): n (FeCl
3.6H
2O): n (IDA): n (VC)=1000: 1: 0.5: 1: 1, add FeCl successively
3.6H
2O, SEBSCH
2Cl, vinyl cyanide (AN), IDA, VC in the ampoule of 5mL under air atmosphere direct tube sealing.Place the oil bath under the steady temperature (60 ℃) to react 20h the ampoule behind the tube sealing by preset time.After reaction finishes, take out tube sealing, with the cold water cooling, open tube sealing immediately, with an amount of THF dissolving, then with a large amount of methanol extractions, suction filtration.Vacuum-drying.Can obtain to obtain SEBS-g-PAN.The molecular weight of polymkeric substance is 156000g/mol.
Claims (2)
1. the preparation method of a controllable modified SEBS rubber is characterized in that, comprises following concrete steps:
(1) phenyl ring in the SEBS rubber is carried out chloromethylation and prepare chloromethylation SEBS, as initiator;
(2) in molar ratio, monomer: initiator=100～1000: 1, monomer, initiator, catalyzer, coordination agent and reductive agent are formed polymerization system, carry out generating the atom transition free radical polymerization reaction of catalyzer through transfer transport;
Said monomer is selected from:
Methylacrylic acid-N, one or both in TMSDMA N dimethylamine base ethyl ester or the vinyl cyanide, in the formula, R
1Be selected from hydrogen, R
2Be selected from a kind of in hydrogen or the methyl, R
3Be selected from the saturated alkyl of C1～C4;
Said catalyzer is selected from: a kind of in high iron(ic)chloride of six hydrations or the iron bromide;
Said coordination agent is selected from: a kind of in three (3,6-dioxy heptyl) amine, triphenylphosphine, imido oxalic acid or the m-phthalic acid;
Said reductive agent is selected from: xitix or glucose;
The mol ratio of the consumption of said initiator, catalyzer, coordination agent, reductive agent is 1: 1～3: 1～3: 1～4;
Temperature of reaction is 50～120 ℃.
2. preparation method according to claim 1 is characterized in that the reaction times is at least 30 minutes.
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| US9074023B2 (en) * | 2010-12-27 | 2015-07-07 | Sumitomo Rubber Industries, Ltd. | Surface modification method, surface-modified elastic body, gasket for injector, injector, and tire |
| CN106632747B (en) * | 2016-12-28 | 2020-03-06 | 四川大学 | Bromomethylated styrene thermoplastic elastomer and preparation method and application thereof |
| CN107082858B (en) * | 2017-06-06 | 2020-03-03 | 浙江众立合成材料科技股份有限公司 | Polarized styrene thermoplastic elastomer and preparation method and application thereof |
| CN111560165B (en) * | 2020-04-29 | 2022-06-21 | 宁波泰甬汽车零部件有限公司 | TPE (thermoplastic elastomer) encapsulating material and preparation method thereof |
| CN111909329B (en) * | 2020-08-13 | 2021-06-01 | 吉林大学 | SEBS rubber grafted poly (p-chloromethyl styrene) and controllable modification synthesis method thereof |
| CN114197266B (en) * | 2021-10-30 | 2023-02-28 | 山东高速工程建设集团有限公司 | Rapid construction process of road bed |
Citations (1)
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|---|---|---|---|---|
| CN1749290A (en) * | 2004-09-14 | 2006-03-22 | 中国石化集团巴陵石油化工有限责任公司 | Polarized SEBS and its preparing mthod |
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| CN1749290A (en) * | 2004-09-14 | 2006-03-22 | 中国石化集团巴陵石油化工有限责任公司 | Polarized SEBS and its preparing mthod |
Non-Patent Citations (2)
| Title |
|---|
| JP特开平8－311134A 1996.11.26 |
| 胡孝勇等.SEBS接枝MAH及SEBS复合材料的制备.《现代塑料加工应用》.2008,第20卷(第5期),16－18. * |
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