CN104072747A - Polarized isoprene/styrol copolymer containing polyethylene oxide block and preparation method of polarized isoprene/styrol copolymer - Google Patents
Polarized isoprene/styrol copolymer containing polyethylene oxide block and preparation method of polarized isoprene/styrol copolymer Download PDFInfo
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- CN104072747A CN104072747A CN201410328723.4A CN201410328723A CN104072747A CN 104072747 A CN104072747 A CN 104072747A CN 201410328723 A CN201410328723 A CN 201410328723A CN 104072747 A CN104072747 A CN 104072747A
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Abstract
The invention belongs to the technical field of high polymer materials, and relates to a polarized isoprene/styrol copolymer containing a polyethylene oxide block. The polarized isoprene/styrol copolymer is a linear diblock copolymer which sequentially comprises a first segment of isoprene/styrene random copolymer and a second segment of polyethylene oxide. The polarized isoprene/styrol copolymer is characterized by comprising following components according to total mass of the copolymer of 100%: 5-50% of styrene, 35-90% of isoprene, and 1-30% of ethylene oxide, wherein the number-average molecular weight of the copolymer is 5*10<3>-100*10<4>. The polarized isoprene/styrol copolymer has the beneficial effect of containing the polyethylene oxide block, can be well bonded with a polarized material and a metal material, and has a good application prospect in fields like high performance tyre manufacture, and special function rubber products.
Description
Technical field
The invention belongs to technical field of polymer materials, relate to a class polar elastomeric material, refer to the polar isoprene/styrol copolymer that contains poly-ethylene oxide block.
Background technology
Isoprene/styrol copolymer is a kind of tartan, can be used for the mechanicalss such as sebific duct, adhesive tape, offset plate, also can be used for the tread rubber of doughnut.Isoprene/styrol copolymer is polymerized by nonpolar isoprene and styrene monomer, and oil-proofness is poor, bonding bad to polar material.By improving the polarity of isoprene/styrol copolymer, can improve its oil-proofness, with the cementability of polar material etc., in fields such as high-performance tire manufacture, features rubber items, there is good application prospect.The polar modification of isoprene/styrol copolymer can be undertaken by series of chemical such as chlorination, epoxidation, grafting and sulfonation on the aromatic ring of combined styrene, chlorosulphonation, chloromethylations, but complex technical process, reaction conversion ratio is lower.
Isoprene and styrene monomer be by adopting living anion polymerization technology can prepare its multipolymer, and in polymerization process, introducing polar monomer, to carry out block copolymerization be a kind of method that realizes production polar isoprene/styrol copolymer.
Document (Polymer, 2010,51 (24): 5674-5679) disclose a kind of di-block copolymer that contains poly-ethylene oxide block, i.e. polystyrene polyethylene oxide segmented copolymer and polyisoprene-polyethylene oxide block copolymer.Polar isoprene/the styrol copolymer of the poly-ethylene oxide block that does not occur containing polarity in its disclosed method.
Summary of the invention
The invention provides a class containing polar isoprene/styrol copolymer and the preparation method of poly-ethylene oxide block, after the first copolymerization isoprene of living anion polymerization technology and two kinds of monomers of vinylbenzene, repolymerization oxirane monomers just can be prepared the polar isoprene/styrol copolymer that contains poly-ethylene oxide block.This class polar isoprene/styrol copolymer and polar material and metallic substance have good cementability, in fields such as high-performance tire manufacture, features rubber items, have good application prospect.
Polar isoprene/styrol copolymer containing poly-ethylene oxide block involved in the present invention is a kind of Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock, the line style block structure being comprised of first paragraph isoprene/styrene random multipolymer and the combination of second segment polyethylene oxide order; In total polymer mass 100%, combined styrene content mass percent general range is 5%-50%, and optimum range is 10%-45%; In conjunction with isoprene content mass percent general range, be 35%-90%, optimum range is 40%-85%; In conjunction with ethylene oxide content mass percent general range, be 1%-30%, optimum range is 2%-20%; The number-average molecular weight general range of polymkeric substance is 5 * 10
3-100 * 10
4, optimum range is 1 * 10
4-80 * 10
4; In in multipolymer in conjunction with isoprene total mass 100%, Isosorbide-5-Nitrae-structural content mass percent general range is 20%-95%, optimum range is 40%-80%.
The preparation method of the polar isoprene/styrol copolymer containing poly-ethylene oxide block involved in the present invention is as follows:
Use anionic polymerization method synthetic copolymer, its detailed process is in non-polar hydrocarbon kind solvent, polar activator and first paragraph isoprene and three kinds of monomers of vinylbenzene to be joined in reactor; Open stirring, add lithium alkylide class initiator, start to prepare isoprene/styrene random copolymer block, the consumption of lithium alkylide class initiator is determined according to the total number-average molecular weight size of block polymer, after first paragraph polyreaction is complete; Alkylaluminium cpd is joined in reactor, and the molar ratio of alkylaluminium cpd and alkyls lithium initiator is between 2/1-20/1; After 1-10 minute; Second segment oxirane monomers is joined in reactor, after second segment ethylene oxide polymerization has reacted; After termination reaction is dry by polymkeric substance separation, obtain the polar isoprene/styrol copolymer containing poly-ethylene oxide block; The total mass of isoprene used, vinylbenzene and three kinds of monomers of oxyethane is 1/4-1/12 with non-polar hydrocarbon solvent quality ratio; Polymeric reaction temperature is controlled between 20-120 ℃; Polyreaction total time was controlled between 30-300 minute.
Non-polar hydrocarbon kind solvent used in the present invention is selected from pentane, hexane, heptane, octane, hexanaphthene, benzene, toluene, ethylbenzene, dimethylbenzene.
Polar activator used in the present invention is selected from ether, tetrahydrofuran (THF), glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, dibutyl ethylene glycol ether, triethylamine, N, N, N ', N '-Tetramethyl Ethylene Diamine, dipiperidinoethane.
Alkyls lithium initiator used in the present invention is selected from the mixture of one or more the simple function group alkyl lithium initiators in RLi, and R is that carbonatoms is the alkyl of 1-10, and Li is lithium atom.
Alkylaluminium cpd used in the present invention is selected from: trimethyl aluminium, triethyl aluminum, tri-n-n-propyl aluminum, triisopropylaluminiuand, three n-butylaluminum, triisobutyl aluminium, three tertiary butyl aluminium.
Effect of the present invention and benefit have been to provide a kind of polar isoprene/styrol copolymer that contains poly-ethylene oxide block.This class polar isoprene/styrol copolymer and polar material and metallic substance have good cementability, in fields such as high-performance tire manufacture, features rubber items, have good application prospect.
Embodiment
The present invention proposes following examples as further instruction, but and the scope of unrestricted the claims in the present invention protection.
Embodiment 1
In 2 liters of stainless steel cauldrons with stirring, add 1.2 liters of hexanaphthenes, 1 milliliter, 70 grams isoprene of tetrahydrofuran (THF), 20 grams of vinylbenzene, open stirring, be warmed up to 50 ℃, with syringe, inject the cyclohexane solution of n-Butyl Lithium, butyllithium consumption is 1 * 10
-3mole, polymerization adds the cyclohexane solution of triisobutyl aluminium after 90 minutes, the consumption of triisobutyl aluminium is to be 10:1 with n-Butyl Lithium mol ratio, after 5 minutes, add 10 grams of oxyethane, polymerization adds water termination reaction after 40 minutes, by polymkeric substance dehydrated alcohol sedimentation, be dried to constant weight, obtain the polar isoprene/styrol copolymer containing poly-ethylene oxide block.
Employing nuclear magnetic resonance spectrometer (
1h-NMR) composition of multipolymer being carried out to analytical test, is 69.1% in conjunction with isoprene content mass percent, and combined styrene content mass percent is 21.1%, in conjunction with ethylene oxide content mass percent, is 9.8%; Adopt infrared spectrometer to the test of multipolymer microstructure analysis, in multipolymer, in conjunction with the Isosorbide-5-Nitrae-structural content of isoprene, be 80% (mass percent, in multipolymer in conjunction with isoprene total mass 100%); Adopt gel permeation chromatograph to carry out analytical test to the molecular weight of multipolymer and distribution, the number-average molecular weight of multipolymer is 10.3 * 10
4, molecular weight distributing index is 1.15.
Embodiment 2
In 2 liters of stainless steel cauldrons with stirring, add 1.2 liters of hexanaphthenes, N, N, N ', 1 milliliter, 60 grams isoprene of N '-Tetramethyl Ethylene Diamine, 35 grams of vinylbenzene, open stirring, be warmed up to 50 ℃, inject the cyclohexane solution of n-Butyl Lithium with syringe, butyllithium consumption is 0.67 * 10
-3mole, polymerization adds the cyclohexane solution of triisobutyl aluminium after 90 minutes, the consumption of triisobutyl aluminium is to be 12:1 with n-Butyl Lithium mol ratio, after 5 minutes, add 5 grams of oxyethane, polymerization adds water termination reaction after 40 minutes, by polymkeric substance dehydrated alcohol sedimentation, be dried to constant weight, obtain the polar isoprene/styrol copolymer containing poly-ethylene oxide block.
Employing nuclear magnetic resonance spectrometer (
1h-NMR) composition of multipolymer being carried out to analytical test, is 59.3% in conjunction with isoprene content mass percent, and combined styrene content mass percent is 35.8%, in conjunction with ethylene oxide content mass percent, is 4.9%; Adopt infrared spectrometer to the test of multipolymer microstructure analysis, in multipolymer, in conjunction with the Isosorbide-5-Nitrae-structural content of isoprene, be 60% (mass percent, in multipolymer in conjunction with isoprene total mass 100%); Adopt gel permeation chromatograph to carry out analytical test to the molecular weight of multipolymer and distribution, the number-average molecular weight of multipolymer is 15.6 * 10
4, molecular weight distributing index is 1.18.
Embodiment 3
In 2 liters of stainless steel cauldrons with stirring, add 1.2 liters of hexanaphthenes, 1 milliliter, 65 grams isoprene of diethylene glycol dimethyl ether, 31 grams of vinylbenzene, open stirring, be warmed up to 50 ℃, the cyclohexane solution that injects n-Butyl Lithium with syringe, butyllithium consumption is 0.4 * 10
-3mole, polymerization adds the cyclohexane solution of triisobutyl aluminium after 90 minutes, the consumption of triisobutyl aluminium is to be 8:1 with n-Butyl Lithium mol ratio, after 5 minutes, add 4 grams of oxyethane, polymerization adds water termination reaction after 40 minutes, by polymkeric substance dehydrated alcohol sedimentation, be dried to constant weight, obtain the polar isoprene/styrol copolymer containing poly-ethylene oxide block.
Employing nuclear magnetic resonance spectrometer (
1h-NMR) composition of multipolymer being carried out to analytical test, is 65.1% in conjunction with isoprene content mass percent, and combined styrene content mass percent is 31.1%, in conjunction with ethylene oxide content mass percent, is 3.8%; Adopt infrared spectrometer to the test of multipolymer microstructure analysis, in multipolymer, in conjunction with the Isosorbide-5-Nitrae-structural content of isoprene, be 55% (mass percent, in multipolymer in conjunction with isoprene total mass 100%); Adopt gel permeation chromatograph to carry out analytical test to the molecular weight of multipolymer and distribution, the number-average molecular weight of multipolymer is 24.6 * 10
4, molecular weight distributing index is 1.21.
Claims (10)
1. the polar isoprene/styrol copolymer containing poly-ethylene oxide block, it is characterized in that: this polar isoprene/styrol copolymer is a kind of Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock the line style block structure being formed by first paragraph isoprene/styrene random multipolymer and the combination of second segment polyethylene oxide order; In multipolymer total mass 100%, combined styrene content mass percent is 5%-50%, in conjunction with isoprene content mass percent, is 35%-90%, in conjunction with ethylene oxide content mass percent, is 1%-30%; The number-average molecular weight of multipolymer is 5 * 10
3-100 * 10
4.
2. the polar isoprene/styrol copolymer containing poly-ethylene oxide block according to claim 1, it is characterized in that: in multipolymer total mass 100%, combined styrene content mass percent is 10%-45%, in conjunction with isoprene content mass percent, being 40%-85%, is 2%-20% in conjunction with ethylene oxide content mass percent; The number-average molecular weight of multipolymer is 1 * 10
4-80 * 10
4.
3. the polar isoprene/styrol copolymer containing poly-ethylene oxide block according to claim 1 and 2, is characterized in that: in multipolymer in conjunction with isoprene total mass 100%, Isosorbide-5-Nitrae-structural content mass percent is 20%-95%.
4. the polar isoprene/styrol copolymer containing poly-ethylene oxide block according to claim 3, is characterized in that: in multipolymer in conjunction with isoprene total mass 100%, Isosorbide-5-Nitrae-structural content mass percent is 40%-80%.
5. described in claim 1-4, contain the preparation method of the polar isoprene/styrol copolymer of poly-ethylene oxide block, use anionic polymerization method synthetic segmented copolymer, it is characterized in that: in non-polar hydrocarbon kind solvent, polar activator and first paragraph isoprene and two kinds of monomers of vinylbenzene are joined in reactor; Open stirring, add lithium alkylide class initiator, start to prepare isoprene/styrene random copolymer block, the consumption of lithium alkylide class initiator is determined according to the total number-average molecular weight size of block polymer, after first paragraph polyreaction is complete; Alkylaluminium cpd is joined in reactor, and the molar ratio of alkylaluminium cpd and alkyls lithium initiator is between 2/1-20/1; After 1-10 minute, second segment oxirane monomers is joined in reactor, after second segment ethylene oxide polymerization has reacted; After termination reaction is dry by polymkeric substance separation, obtain the polar isoprene/styrol copolymer containing poly-ethylene oxide block; The total mass of isoprene used, vinylbenzene and three kinds of monomers of oxyethane is 1/4-1/12 with non-polar hydrocarbon solvent quality ratio; Polymeric reaction temperature is controlled between 20-120 ℃; Polyreaction total time was controlled between 30-300 minute.
6. preparation method according to claim 5, is characterized in that, wherein non-polar hydrocarbon kind solvent is selected from pentane, hexane, heptane, octane, hexanaphthene, benzene, toluene, ethylbenzene, dimethylbenzene.
7. according to the preparation method described in claim 5 or 6, it is characterized in that, wherein polar activator is selected from ether, tetrahydrofuran (THF), glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, dibutyl ethylene glycol ether, triethylamine, N, N, N ', N '-Tetramethyl Ethylene Diamine, dipiperidinoethane.
8. according to the preparation method described in claim 5 or 6, it is characterized in that, wherein alkyls lithium initiator is selected from the mixture of one or more simple function group alkyl lithium initiators in RLi, and R is that carbonatoms is the alkyl of 1-10, and Li is lithium atom.
9. preparation method according to claim 5, is characterized in that, wherein alkylaluminium cpd is selected from trimethyl aluminium, triethyl aluminum, tri-n-n-propyl aluminum, triisopropylaluminiuand, three n-butylaluminum, triisobutyl aluminium, three tertiary butyl aluminium.
10. preparation method according to claim 8, is characterized in that, wherein alkylaluminium cpd is selected from trimethyl aluminium, triethyl aluminum, tri-n-n-propyl aluminum, triisopropylaluminiuand, three n-butylaluminum, triisobutyl aluminium, three tertiary butyl aluminium.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104436200A (en) * | 2014-11-05 | 2015-03-25 | 大连理工大学 | Hot-melt pressure-sensitive adhesive for transdermal drug delivery patch and preparation method of hot-melt pressure-sensitive adhesive |
| CN112981581A (en) * | 2021-01-13 | 2021-06-18 | 盐城优和博新材料有限公司 | Preparation method of high-quality high-strength high-modulus polyethylene fiber |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3867295A (en) * | 1973-08-13 | 1975-02-18 | Mobil Oil Corp | Block copolymers and lubricant compositions containing the same |
| CN103483475A (en) * | 2013-09-30 | 2014-01-01 | 北京化工大学 | Method for preparing terminal carboxyl group polymer through active anionic polymer termination |
-
2014
- 2014-07-10 CN CN201410328723.4A patent/CN104072747A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3867295A (en) * | 1973-08-13 | 1975-02-18 | Mobil Oil Corp | Block copolymers and lubricant compositions containing the same |
| CN103483475A (en) * | 2013-09-30 | 2014-01-01 | 北京化工大学 | Method for preparing terminal carboxyl group polymer through active anionic polymer termination |
Non-Patent Citations (4)
| Title |
|---|
| VIRGINIE REJSEK ET AL.: "Polymerization of ethylene oxide initiated by lithium derivatives via the monomer-activated approach: Application to the direct synthesis of PS-b-PEO and PI-b-PEO diblock copolymers", 《POLYMER》 * |
| 冯华东等: ""异戊二烯-苯乙烯无规共聚物微观结构影响因素的研究"", 《2005年全国高分子学术论文报告会》 * |
| 古山种俊等: "《生物高分子 第2卷 类聚异戊二烯》", 31 October 2004, 化学工业出版社 * |
| 陈闯等: "环氧化液体丁二烯-苯乙烯共聚物的制备", 《合成树脂及塑料》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104436200A (en) * | 2014-11-05 | 2015-03-25 | 大连理工大学 | Hot-melt pressure-sensitive adhesive for transdermal drug delivery patch and preparation method of hot-melt pressure-sensitive adhesive |
| CN112981581A (en) * | 2021-01-13 | 2021-06-18 | 盐城优和博新材料有限公司 | Preparation method of high-quality high-strength high-modulus polyethylene fiber |
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Application publication date: 20141001 |