CN102391443B - Amphipathic block copolymer containing polyisobutylene and polyanion and preparation thereof - Google Patents
Amphipathic block copolymer containing polyisobutylene and polyanion and preparation thereof Download PDFInfo
- Publication number
- CN102391443B CN102391443B CN 201110247529 CN201110247529A CN102391443B CN 102391443 B CN102391443 B CN 102391443B CN 201110247529 CN201110247529 CN 201110247529 CN 201110247529 A CN201110247529 A CN 201110247529A CN 102391443 B CN102391443 B CN 102391443B
- Authority
- CN
- China
- Prior art keywords
- polyisobutene
- pib
- block
- diblock
- isoprene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229920002367 Polyisobutene Polymers 0.000 title claims abstract description 139
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 229920001400 block copolymer Polymers 0.000 title claims abstract description 23
- 229920000447 polyanionic polymer Polymers 0.000 title claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 229920001577 copolymer Polymers 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000000126 substance Substances 0.000 claims abstract description 12
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 6
- ROGIWVXWXZRRMZ-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1 ROGIWVXWXZRRMZ-UHFFFAOYSA-N 0.000 claims description 29
- 229920003051 synthetic elastomer Polymers 0.000 claims description 29
- 239000005061 synthetic rubber Substances 0.000 claims description 29
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 26
- -1 oxygen anion Chemical class 0.000 claims description 26
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 23
- 239000001301 oxygen Substances 0.000 claims description 23
- 229910052760 oxygen Inorganic materials 0.000 claims description 23
- 239000003795 chemical substances by application Substances 0.000 claims description 20
- 229920000642 polymer Polymers 0.000 claims description 20
- 238000006116 polymerization reaction Methods 0.000 claims description 20
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 17
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 16
- 230000000694 effects Effects 0.000 claims description 16
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 claims description 12
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 229920002845 Poly(methacrylic acid) Polymers 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- 150000001336 alkenes Chemical class 0.000 claims description 5
- 230000008021 deposition Effects 0.000 claims description 5
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 claims description 5
- 229910000105 potassium hydride Inorganic materials 0.000 claims description 5
- 238000000746 purification Methods 0.000 claims description 5
- 238000002390 rotary evaporation Methods 0.000 claims description 5
- 239000012279 sodium borohydride Substances 0.000 claims description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- 239000005457 ice water Substances 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 3
- 239000012044 organic layer Substances 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 238000007171 acid catalysis Methods 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 238000006197 hydroboration reaction Methods 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 238000010539 anionic addition polymerization reaction Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 229920000620 organic polymer Polymers 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 229920000469 amphiphilic block copolymer Polymers 0.000 abstract description 2
- 229910001414 potassium ion Inorganic materials 0.000 abstract 1
- 230000036632 reaction speed Effects 0.000 abstract 1
- 230000009257 reactivity Effects 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000005227 gel permeation chromatography Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- 230000002209 hydrophobic effect Effects 0.000 description 8
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 8
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 7
- 238000010828 elution Methods 0.000 description 7
- 239000003999 initiator Substances 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 6
- 239000004793 Polystyrene Substances 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 241000024287 Areas Species 0.000 description 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 101001012021 Homo sapiens Mammalian ependymin-related protein 1 Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 102100030031 Mammalian ependymin-related protein 1 Human genes 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000004523 agglutinating effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000002785 anti-thrombosis Effects 0.000 description 1
- 229960004676 antithrombotic agent Drugs 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 238000012711 chain transfer polymerization Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003747 fuel oil additive Substances 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910003471 inorganic composite material Inorganic materials 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- ODUCDPQEXGNKDN-UHFFFAOYSA-N nitroxyl Chemical compound O=N ODUCDPQEXGNKDN-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 208000016261 weight loss Diseases 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Images
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Graft Or Block Polymers (AREA)
Abstract
本发明属于有机高分子化合物领域，公开了一种含聚异丁烯和聚阴离子的两亲性嵌段共聚物及其制备方法，所述聚异丁烯嵌段共聚物的化学结构式为：
The invention belongs to the field of organic polymer compounds, and discloses an amphiphilic block copolymer containing polyisobutylene and polyanions and a preparation method thereof. The chemical structural formula of the polyisobutylene block copolymer is:
Description
Technical field
The invention belongs to the organic high molecular compound field, relate to a kind of amphipathic nature block polymer and preparation thereof that contains polyisobutene and polyanion.
Background technology
Polyolefine material comprises polyethylene (PE), polypropylene (PP), poly 1-butene, polyisobutene, poly(4-methyl-1-pentene), ethylene-propylene rubber(EPR) (EPR), EPDR (EPDM) etc., have P/C than high, mechanical property is good and thermal characteristics is stablized and the characteristics such as crystallinity modulation scope is large, processing characteristics is good, security and stability good, recycling capable of circulation.But the intrinsic nonpolar and inertia of polyolefine makes its printing and dyeing property, agglutinating value(of coal) and all relatively poor with the consistency of other materials.Dow chemical company has developed a kind of new olefin block copolymers (OBCs) by the breakthrough of catalysis technique, i.e. ethylene-octene segmented copolymer (Olefin Block Copolymers, OBCs).Because " hard (high rigidity) " and " soft (snappiness) " segment alternative arrangement in the molecular chain, and variable-length, thereby has the overall equilbrium performance of flexibility, thermotolerance, wear resistance, compression set performance and the processing characteristics etc. of uniqueness.Yet this class olefin block copolymers still is hydrophobic, can't be applied in the diphasic system of polar/non-polar.
In recent years, increasing to the demand of high-activity polyisobutene in the world.Polyisobutene (PIB) be iso-butylene through the product of cationoid polymerisation, roughly can be three grades of high, medium and low molecular weight by molecular size range.Colourless polyisobutene is tasteless, nontoxic, nonflammable, good, acidproof, alkaline-resisting, water-fast, cold-resistant, heat-resisting, ageing-resistant, the anti-ozone of chemical stability, oxytolerant, UV resistant, and its purposes is very extensive.And high-activity polyisobutene (HRPIB; Highly Reactive-Polyisobutylene) be polyisobutene α-terminal double link content greater than 85% low-molecular-weight polyisobutylene, its principal feature is to go out by the explained hereafter of environmental protection polyisobutene ashless dispersant (internal combustion engine lubrication oil additive), the all good and not halogen-containing products of this dispersing property and low-temperature performance just enjoy user's favor once coming out, almost be penetrated into low-molecular-weight polyisobutylene (LPIB) all Application Areass, especially lubricating oil additive and fuel oil additive industry.In addition, also be widely used in fields such as emulsion explosive, tensio-active agent, sanitising agent and rust-preventive agent, market outlook are wide.
High-activity polyisobutene can also prepare various grafting and segmented copolymer, many new purposes also develop gradually, such as multi-functional wetting agent polyisobutene acid glyceride, macromolecular material internal plasticizer etc., but these segmented copolymer overwhelming majority are hydrophobic, still can't be generalized in the nonhomogeneous system and use.Therefore, synthetic to have amphipathic polyisobutylene block copolymer imperative, and application potential is huge, has very large market outlook in the future.
In the prior art, mainly contain based on the research of synthesizing polyisobutylene segmented copolymer:
(1) the Matyjaszewski K. of U.S. Carnegie Mellon University seminar atom transfer radical polymerization (ATRP) method, take polyisobutene as precursor synthesis the ATRP macromole evocating agent, cause vinylbenzene (St) and methyl methacrylate (MMA) polymerization, form segmented copolymer PIB-b-PS and PIB-b-PMMA.(referring to: Jakubowski, W.; Tsarevsky, N.V.; Higashihara, T.; Faust, R.; Matyjaszewski, K.Macromolecules 2008,41,2318-2323);
(2) rubber performance of the uniqueness of polyisobutene and polyethylene ferrocene (PVFc) segmented copolymer (PIB-b-PVFc) has been studied by Faust R. seminar in Massachusetts, USA university Lu Weier branch school.(referring to: Higashihara, T.; Faust, R.Macromolecules 2007,40,7453-7463);
(3) the Storey seminar of American South University of Mississippi has synthesized the segmented copolymer (PAA of polyacrylic acid and polyisobutene and polystyrene with the method for cationoid polymerisation and atom transfer radical polymerization (ATRP) associating
2-PIB-b-PS).(referring to: Breland, L.K.; Storey, R.F.Polymer 2008,49,1154-1163);
(4) the Puskas J.E. of U.S.'s Akron university seminar adopts cationic polymerization process, prepare the organic/inorganic composite material (PIB-POSS) based on polyisobutene and multiaspect oligomeric silsesquioxanes (POSS), strengthened the mechanical property of material.(referring to: Soytas, S.H.; Lim, G.T.; Puskas, J.E.Macromol.Rapid Commun.2009,30,2112-2115);
(5) patent No. is invented for 200310116817.7 China and is provided a kind of for filling-modified coupling agent of organic polymer and preparation method thereof, this coupling agent is to utilize maleic anhydride and polyisobutene, under the effect of initiator or no initiator, carry out graft reaction and prepare maleic anhydride graft polyisobutene polymkeric substance, its percentage of grafting controlled range is 1～80%.Wherein polyisobutene is that molecular weight is common polyisobutene or the high-activity polyisobutene of 800～10000g/mol, 120～250 ℃ of graft reaction temperature, 30～240 minutes reaction times.The coupling agent of preparation can improve consistency and the bounding force of organic polymer and inorganic filler effectively, have pollution-free, percentage of grafting control accurately, applied range etc.;
(6) patent No. provides a kind of solvothermal preparation method of maleic anhydride graft polyisobutene co-polymer for China's invention of 200810038559.8: in autoclave, put into liquid polyisobutene, maleic anhydride, initiator and oxidation inhibitor, and put into when needed coordinative solvent, the control temperature of reaction makes system be in the postcritical state of class and carries out graft reaction and prepare the maleic anhydride graft polyisobutene.The maleic anhydride graft polyisobutene of preparation can be directly used in the toughner of polycarbonate, polyester, nylon, urethane, polyvinyl chloride isopolarity resin, can obtain preferably matrix material of over-all properties;
(7) patent No. provides a kind of preparation method of glycidyl methacrylate graft polyisobutene copolymer for China's invention of 200910048737.X, in autoclave, put into polyisobutene, glycidyl methacrylate, comonomer, initiator and stablizer, and put into when needed corresponding solvent, in control temperature of reaction and the reaction times, make system be in the postcritical state of class and carry out graft reaction and prepare glycidyl methacrylate graft polyisobutene copolymer.The glycidyl methacrylate graft polyisobutene copolymer of preparation can be directly used in the toughner of unsaturated polyester, Resins, epoxy, polycarbonate, saturated polyester, nylon, urethane polar materials, can obtain preferably matrix material of over-all properties.
Yet, according to our investigation, research report for the amphipathic nature block polymer that contains polyisobutene and polyanion and preparation thereof in the above-mentioned technology is very few, the polyisobutylene block copolymer overwhelming majority that contains of having reported is hydrophobic, do not have the amphipathic of hydrophilic-oleophylic, still can't be generalized in the nonhomogeneous system and use, thereby have certain limitation.
Amphipathic nature block polymer (amphiphilic block copolymer), in broad terms, two blocks that form the copolymer molecule chain are respectively wetting ability and hydrophobic chain segment.This analog copolymer when concentration reaches micelle-forming concentration (critical micelle concentration, cmc), can form the self-assembly aggregate in solvent.Amphipathic nature polyalcohol had both contained hydrophilic segment in same macromolecular chain, also contain the lipophilicity segment, thereby have unique surface property, can be used as antithrombotics, tensio-active agent and polymer blending material in emulsifying agent, dispersion agent, stablizer, the aqueous solution and the compatilizer of matrix material.
Usually the method for preparing amphipathic nature block polymer mainly contains: active anionic polymerization, group transfer polymerization (GTP), nitroxyl free radical polymerization (NMP), atom transfer radical polymerization (ATRP) and reversible addition-fracture chain transfer polymerization (RAFT) and oxygen anion initiated polymerization (OIP).These controlled/living polymerisation process are the strong technique means of preparation segmented copolymer.Wherein, the oxygen anion initiated polymerization has many advantages: reactive behavior is high, and speed is fast; By the change of initiator system structure, can design synthetic various novel, end with amphipathic multipolymer and the diversified Model Polymers of specific function group.Compare with active anionic polymerization, the method for oxygen anion initiated polymerization is easy, is easy to control, can at room temperature carry out.
Therefore, need a kind of get everything ready method of amphipathic polyisobutylene block copolymer of oxygen anion initiated polymerization legal system of utilizing of research and development, expand the range of application of polyisobutylene block copolymer.
Summary of the invention
Goal of the invention of the present invention provides a kind of amphipathic polyisobutylene block copolymer and preparation method thereof.
To achieve the above object of the invention, the technical solution used in the present invention is: a kind of polyisobutylene block copolymer, and the chemical structural formula of described polyisobutylene block copolymer is:
In the formula, x=18～60, y=10～120, M
+Represent K
+Or Na
+Ion.
In the technique scheme, the number-average molecular weight of described polyisobutylene block copolymer is 2000～14000g/mol.
Above-mentioned polyisobutylene block copolymer since simultaneously contain hydrophobic polyisobutene segment and hydrophilic polyanion segment (contain carboxyl-COOH or-COO
-Negatively charged ion), therefore, one section is hydrophilic chain, and another section is hydrophobic chain, belongs to typical amphipathic nature block polymer.
The preparation method of above-mentioned polyisobutylene block copolymer may further comprise the steps: at first utilize high-activity polyisobutene, by the hydroboration method for oxidation, prepare terminal hydroxyl (polyisobutene PIB-OH (HTPIB) OH); Then in the presence of potassium hydride KH (KH), the polyisobutene terminal hydroxyl is converted into oxygen anion PIB-O
-K
+, as macromole evocating agent, cause the Tert-butyl Methacrylate polymerization, obtain polyisobutene and polymethyl tert-butyl acrylate Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock PIB-b-PtBMA; Then under trifluoroacetic acid catalysis, the side group hydrolysis with the polymethyl tert-butyl acrylate segment obtains to contain polyisobutene and polymethyl acrylic acid Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock PIB-b-PMAA; Further, described segmented copolymer PIB-b-PMAA in alkaline medium, carboxyl formation-COO
-Negatively charged ion namely obtains containing the amphipathic nature block polymer of polyisobutene and polyanion;
Wherein, the structural formula of high-activity polyisobutene is:
Terminal hydroxyl (structural formula of polyisobutene PIB-OH OH) is:
The structural formula of polyisobutene oxygen anion macromole evocating agent is:
The structural formula of polyisobutene and polymethyl tert-butyl acrylate Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock PIB-b-PtBMA is:
The structural formula that contains polyisobutene and polymethyl acrylic acid Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock PIB-b-PMAA is:
The structural formula that contains the amphipathic nature block polymer of polyisobutene and polyanion is:
Say that strictly PIB-b-PMAA should be amphipathic multipolymer, only becomes at carboxyl-COOH-COO
-After, just can be called " segmented copolymer that contains polyanion ".Can form polyanion because it has been generally acknowledged that polymethyl acrylic acid, so two kinds of structures of general designation are polyanion in the application's book.
Particularly, the preparation method of above-mentioned polyisobutylene block copolymer may further comprise the steps:
(1) (polyisobutene PIB-OH (HTPIB) OH) :-5～0 ℃ under the ice-water bath condition, take anhydrous tetrahydro furan as solvent, with sodium borohydride (NaBH to prepare terminal hydroxyl
4) adding solvent, slowly the Eorontrifluoride etherate [(C of the amounts such as dropping and sodium borohydride
2H
5O)
2BF
3] solution, reacted 1～3 hour; Drip again high-activity polyisobutene (HRPIB) solution that is dissolved in anhydrous tetrahydro furan, reacted 15～20 hours; Then use sodium hydroxide solution regulation system pH to 10～about 12, slowly drip hydrogen peroxide (H
2O
2) solution, reacted 5～8 hours; Extraction, dry organic layer, desolventizing obtains terminal hydroxyl (polyisobutene PIB-OH (HTPIB) OH);
Above-mentioned reaction process is as follows:
Wherein, described high-activity polyisobutene (HRPIB) is commercial compound, and its number-average molecular weight is 1000～4000g/mol, and described high-activity polyisobutene (HRPIB) contains terminal double link, and its end alkene content is more than 85%; Preferably, described high-activity polyisobutene is selected from a kind of in the following commercialization high-activity polyisobutene: trade(brand)name and number-average molecular weight thereof
Be respectively JH-1000
JH-1300
JH-2300
Or JH-3300
(2) the terminal oxygen anion (PIB-O of polyisobutene
-K
+) preparation of macromole evocating agent: under the anhydrous and oxygen-free condition, under the atmosphere of inert gases, under 35～45 ℃, take anhydrous tetrahydro furan as solvent, make potassium hydride KH with etc. the hydroxyl reaction of polyisobutene PIB-OH end of amount, form the terminal oxygen anion (PIB-O of polyisobutene
-K
+), as the macromole evocating agent of oxygen anion initiated polymerization;
Above-mentioned reaction process is as follows:
(3) preparation of polyisobutene-b-polymethyl tert-butyl acrylate Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock: with the terminal oxygen anion (PIB-O of polyisobutene
-K
+) macromole evocating agent and monomer Tert-butyl Methacrylate (tBMA) polymerization, consist of polymerization system with mol ratio 1: 1～120, adopt oxygen anion polymerization polymerization 1～2 hour; Termination reaction is purified, and namely obtains polyisobutene-b-polymethyl tert-butyl acrylate Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock PIB-b-PtBMA;
Above-mentioned reaction process is as follows:
The structural formula of above-mentioned Tert-butyl Methacrylate is:
(4) preparation contains the amphipathic nature block polymer of polyisobutene and polyanion: take methylene dichloride as solvent, under the condition that trifluoroacetic acid exists, the tertiary butyl of polyisobutene-b-polymethyl tert-butyl acrylate Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock is hydrolyzed; React complete rear rotary evaporation desolventizing, carry out deposition and purification with cold acetone, be dried to constant weight, namely obtain required polyisobutene and the polymethyl acrylic acid Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock PIB-b-PMAA of containing;
Above-mentioned reaction process is as follows:
In the formula, x is 18～60; Y is 10～120.
In the further technical scheme, above-mentioned polyisobutene and polymethyl acrylic acid Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock PIB-b-PMAA, in alkaline medium, the carboxyl in the polymethyl acrylic acid segment-COOH formation-COO
-Negatively charged ion obtains the amphipathic nature block polymer that contains polyisobutene and polyanion shown in the following structural formula:
In the formula, x is 18～60; Y is 10～120; M
+Represent K
+Or Na
+Ion.
The present invention is polyisobutene PIB-OH (HTPIB) and the application in preparation dependency structure macromolecular material thereof of claimed above-mentioned end hydroxyl simultaneously.
The present invention is the polyisobutene (PIB-O of claimed above-mentioned end oxo-anions simultaneously
-K
+) and as the application of macromole evocating agent in preparation dependency structure macromolecular material.
The present invention is claimed above-mentioned polyisobutene and polymethyl tert-butyl acrylate segmented copolymer (PIB-b-PtBMA) and the application in preparation dependency structure macromolecular material thereof simultaneously.
The present invention is claimed above-mentioned polyisobutene and polymethyl acrylic acid segmented copolymer (PIB-b-PMAA) and the application in preparation dependency structure macromolecular material thereof simultaneously.
The present invention is the claimed above-mentioned amphipathic nature block polymer that contains polyisobutene and polyanion also
And the application in other Polymer materialspreparations.
When reality prepares, for guaranteeing the purity of product, can make with extra care raw material first, its method is to use the alkaline Al of activation before Tert-butyl Methacrylate (tBMA) uses
2O
3Post is processed, and then uses CaH
2More than the dry 12h, at high-purity N
2Carry out underpressure distillation under the protection; KH seals up for safekeeping in mineral oil for subsequent use; Solvents tetrahydrofurane (THF) was used potassium hydroxide dry three days, added benzophenone as indicator, carried out anaerobic with the sodium silk and refluxed, until be intense violet color, steamed before the use.
Because technique scheme is used, the present invention compared with prior art has following advantages:
1. the invention provides a kind of contain simultaneously hydrophobic polyisobutene segment and hydrophilic polyanion segment (contain carboxyl-COOH or-COO
-Negatively charged ion) amphipathic copolymer has overcome the deficiency that only has the segmented copolymer of Non-amphiphilic polyisobutene in the prior art, has expanded the range of application of the segmented copolymer that contains polyisobutene, makes it to be applied in the nonhomogeneous system; Owing to there is the polymethyl acrylic acid segment in final product, it has preferably wetting ability, thereby can obtain a kind of amphipathic nature block polymer that contains polyisobutene and polyanion; Can be applied to the fields such as the emulsifying agent of rubber modifier, blending additive, letex polymerization and fabric-treating agent.
The present invention utilize potassium hydride KH with etc. the terminal hydroxyl of amount (behind polyisobutene PIB-OH (HTPIB) stirring reaction OH), form the terminal oxygen anion (PIB-O of polyisobutene
-K
+), the polymerization process that utilizes oxygen anion to cause by the change of initiator system structure and the change of [monomer]/[primosome] proportioning, prepares the polymkeric substance of different chain length degree, different hydrophilic and hydrophobic, different blocks as required.
3. synthesis step of the present invention is simple, overcome the shortcoming that traditional anionic polymerisation need to carry out under the severe condition such as extremely low temperature, high vacuum, be easy to control, can at room temperature carry out, reactive behavior is high, and speed of response is fast, transformation efficiency convergence 100%, molecular weight is controlled, and product is pure, almost need not the aftertreatment sepn process.
4. gained amphipathic copolymer of the present invention can be applicable to rubber accelerator, papermaking and fabric auxiliary agent, emulsifier for emulsion polymerization and field of medical materials.
Description of drawings
Fig. 1 be (JH-3300) gel permeation chromatography (GPC) elution curve of the highly active polyisobutene of commercialization (HRPIB) among embodiment one and the embodiment two (standard specimen: polystyrene), actual test value:
Fig. 2 be the highly active polyisobutene of commercialization (HRPIB) among embodiment one and the embodiment two proton nmr spectra (
1H NMR) spectrogram, solvent are deuterochloroform (CDCl
3);
Fig. 3 be terminal hydroxyl among embodiment one and the embodiment two (proton nmr spectra of polyisobutene PIB-OH (HTPIB) OH) (
1H NMR) spectrogram, solvent are deuterochloroform (CDCl
3);
Fig. 4 is polyisobutene and polymethyl tert-butyl acrylate Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock (PIB-b-PtBMA among the embodiment one
53) proton nmr spectra (
1H NMR) spectrogram, solvent are deuterochloroform (CDCl
3);
Fig. 5 is HTPIB, PIB-b-PtBMA among the embodiment one
53And PIB-b-PtBMA among the embodiment two
36Gel permeation chromatography (GPC) elution curve figure (standard specimen: methyl methacrylate);
Fig. 6 is PIB-b-PtBMA among the embodiment one
53And PIB-b-PtBMA among the embodiment two
36Thermogravimetric analysis (TGA) curve;
Fig. 7 is polyisobutene and polymethyl acrylic acid Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock (PIB-b-PMAA among the embodiment one
53) proton nmr spectra (
1H NMR) spectrogram, solvent are deuterated dimethyl sulfoxide (DMSO-d
6).
Embodiment
The invention will be further described below in conjunction with drawings and Examples:
Embodiment one: PIB-b-PtBMA
53The preparation method
(1) the terminal hydroxyl (preparation of polyisobutene PIB-OH (HTPIB) OH): under-5～0 ℃ of ice-water bath condition, take anhydrous tetrahydro furan as solvent, add the sodium borohydride (NaBH of certain amount of substance in the three-necked flask
4).Slowly drip the Eorontrifluoride etherate [(C of Isoequivalent weight
2H
5O)
2BF
3] solution reaction 1.5 hours; Drip again highly active polyisobutene (HRPIB) solution that is dissolved in anhydrous tetrahydro furan, reacted 20 hours.Drip NaOH solution, about regulation system pH to 12, slowly drip 30% H
2O
2Solution reacted 7 hours.Obtain organic layer with extracted with diethyl ether, with anhydrous magnesium sulfate (MgSO
4) dry rear rotary evaporation, desolventizing, products therefrom drying under the vacuum drying oven room temperature namely obtained terminal hydroxyl (polyisobutene PIB-OH (HTPIB) OH) in 24 hours.
The molecular weight of the highly active polyisobutene of employed commercialization (HRPIB) and molecular weight distribution thereof are measured by gel permeation chromatography (GPC) in the present embodiment, as shown in Figure 1.The structure of HRPIB proton nmr spectra (
1H NMR) proves, as shown in Figure 2.
Reaction product in the present embodiment, namely the molecular structure of the polyisobutene PIB-OH (HTPIB) of terminal hydroxyl through proton nmr spectra (
1H NMR) checking, as shown in Figure 3, the chemical shift of terminal hydroxyl proton is at δ 2.18ppm.
(2) preparation of KH: the magnetic agitation rotor is put into the dry reaction flask with arm in advance, with turned welt soft rubber ball jam-pack.Then link to each other with vacuum pump with syringe needle, emulsion tube, be filled with high-purity argon gas while vacuumizing, remove oxygen and aqueous vapor in the bottle, so repeatable operation is three times.After moving into a certain amount of KH in the reaction flask, inject the anhydrous tetrahydrofuran (THF) of 5ml (THF) with the dry injection device, agitator treating staticly contains the THF of mineral oil with the syringe sucking-off afterwards, three times so repeatedly, dries up at last the THF solution of remnants with high-purity argon gas.(0.2～0.3g about 5.0～7.5mmol) to utilize the amount of KH in the decrement method accurate weighing reaction flask.
(3) preparation of macromole evocating agent: a certain amount of anhydrous THF is expelled in the polymerization bottle that KH is housed.Reaction flask is inserted (about 35～45 ℃) in the oil bath; magnetic agitation; ((HTPIB is dissolved in anhydrous THF to polyisobutene PIB-OH (HTPIB) OH) to the terminal hydroxyl of the amounts such as injection and KH in advance simultaneously; argon shield); reaction 10～12h fully reacts HTPIB and KH and generates polyisobutene oxygen anion (PIB-O
-K
+).
(4) polyreaction: then reaction flask is moved in 25 ℃ of constant temperature oil baths, syringe with drying adds monomer Tert-butyl Methacrylate (tBMA), with the mol ratio of macromole evocating agent be 55: 1, reaction 1～1.5h uses dry methyl alcohol termination reaction at last.Reacted polymkeric substance under 60～70 ℃ of conditions, revolves the steaming desolventizing, continues to carry out deposition and purification with cold methyl alcohol, and triplicate is dried to constant weight 40～50 ℃ of vacuum drying ovens at last.Obtain required product, record productive rate greater than 98%.
The structure of the polyisobutene that obtains and polymethyl tert-butyl acrylate (PIB-b-PtBMA) Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock proton nmr spectra (
1H NMR) detects, as shown in Figure 4.Figure 5 shows that the elution curve of gel permeation chromatography (GPC) of the polyisobutene (HTPIB) of PIB-b-PtBMA Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock and terminal hydroxyl, by relatively finding out, the elution time of PIB-b-PtBMA Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock shortens, illustrate that molecular weight of copolymer increases, and can prove to successfully synthesize PIB-b-PtBMA thus
53
By the thermogravimetric analysis curve, as shown in Figure 6, two heat decomposition temperatures are arranged in the curve, this be because: segmented copolymer is because the weight-loss curve in obvious two stages appears in formation polyisobutene and polymethyl tert-butyl acrylate microcell separately, thus, can prove equally and successfully synthesize Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock PIB-b-PtBMA.
(5) hydrolysis reaction: with gained PIB-b-PtBMA polymer dissolution in methylene dichloride, reaction flask is as in the ice-water bath, drip the trifluoroacetic acid of a certain amount of methylene dichloride dilution by constant pressure funnel, dropwised in 1～2 hour, the Water Under solution of room temperature two days, under 30～40 ℃ of conditions, the rotary evaporation desolventizing, carry out deposition and purification with cold acetone, triplicate is dried to constant weight 40～50 ℃ of vacuum drying ovens at last.Namely obtain required product P IB-b-PMAA, record productive rate greater than 90%.
The structure of the polyisobutene that obtains and polymethyl acrylic acid (PIB-b-PMAA) Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock proton nmr spectra (
1H NMR) detect, as shown in Figure 7, the chemical shift of carboxyl proton has obtained target product in δ 12.25ppm proof.
Embodiment two: PIB-b-PtBMA
36The preparation method
(1) the terminal hydroxyl (preparation of polyisobutene PIB-OH (HTPIB) OH): with embodiment one.
(2) preparation of KH: with embodiment one.
(3) preparation of macromole evocating agent: with embodiment one.
(4) polyreaction: then in the constant temperature oil bath with 25 ℃ of reaction flask immigrations, syringe with drying adds monomer Tert-butyl Methacrylate (tBMA), with the mol ratio of macromole evocating agent be 40: 1, reaction 1.0～1.5h uses dry methyl alcohol termination reaction at last.Reacted polymkeric substance, under 30～40 ℃ of conditions, the rotary evaporation desolventizing continues to carry out deposition and purification with cold methyl alcohol, and triplicate is dried to constant weight 40～50 ℃ of vacuum drying ovens at last.Obtain required product, record productive rate greater than 98%.
The molecular weight of the polyisobutene that obtains and polymethyl tert-butyl acrylate (PIB-b-PtBMA) Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock and molecular weight distribution are measured with gel permeation chromatography (GPC), and its GPC elution curve as shown in Figure 5.By with polyisobutene (HTPIB) and the PIB-b-PtBMA of terminal hydroxyl
53The GPC elution curve of Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock relatively can be found out the PIB-b-PtBMA that present embodiment synthesized
36The elution curve of Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock is between the said two devices curve.Proof adopts the oxygen anion initiated polymerization thus, by regulating the proportioning of [monomer]/[initiator], can control well structure and the molecular weight of multipolymer, obtains target product.
(5) hydrolysis reaction: with embodiment one.
Claims (5)
1. a polyisobutylene block copolymer is characterized in that, the chemical structural formula of described polyisobutylene block copolymer is:
Or
In the formula, x=18～60, y=10～120, M
+Represent K
+Or Na
+Ion; The number-average molecular weight of described polyisobutylene block copolymer is 2000～14000 g/mol.
2. the preparation method of the described polyisobutylene block copolymer of claim 1 is characterized in that, may further comprise the steps: at first utilize high-activity polyisobutene, by the hydroboration method for oxidation, prepare the polyisobutene PIB-OH of terminal hydroxyl; Then in the presence of potassium hydride KH, the polyisobutene terminal hydroxyl is converted into oxygen anion PIB-O
-K
+, as macromole evocating agent, cause the Tert-butyl Methacrylate polymerization, obtain polyisobutene and polymethyl tert-butyl acrylate Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock PIB-
b-P
tBMA; Then under trifluoroacetic acid catalysis, the side group hydrolysis with the polymethyl tert-butyl acrylate segment obtains to contain polyisobutene and polymethyl acrylic acid Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock PIB-
b-PMAA; Further, described Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock PIB-
b-PMAA in alkaline medium, the carboxyl in the polymethyl acrylic acid segment-COOH formation-COO
-Negatively charged ion namely obtains containing the amphipathic nature block polymer of polyisobutene and polyanion
In the formula, x=18～60, y=10～120, M
+Represent K
+Or Na
+Ion;
Wherein, the structural formula of high-activity polyisobutene is:
The structural formula of the polyisobutene PIB-OH of terminal hydroxyl is:
；
The structural formula of polyisobutene oxygen anion macromole evocating agent is:
；
Polyisobutene and polymethyl tert-butyl acrylate Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock PIB-
b-P
tThe structural formula of BMA is:
Contain polyisobutene and polymethyl acrylic acid Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock PIB-
bThe structural formula of-PMAA is:
In the formula, x=18～60, y=10～120.
3. the preparation method of the described polyisobutylene block copolymer of claim 2 is characterized in that, specifically may further comprise the steps:
(1) the polyisobutene PIB-OH of the terminal hydroxyl of preparation: under-5 ~ 0 ℃ of ice-water bath condition, take anhydrous tetrahydro furan as solvent, sodium borohydride is added solvent, slowly the Eorontrifluoride etherate solution of the amounts such as dropping and sodium borohydride reacted 1 ~ 3 hour; Drip again the high-activity polyisobutene solution that is dissolved in anhydrous tetrahydro furan, reacted 15 ~ 20 hours; Then use sodium hydroxide solution regulation system pH to 10 ~ about 12, slowly drip hydrogen peroxide H
2O
2Solution reacted 5 ~ 8 hours; Extraction, dry organic layer, desolventizing obtains the polyisobutene PIB-OH of terminal hydroxyl;
(2) the terminal oxygen anion PIB-O of polyisobutene
-K
+The preparation of macromole evocating agent: under the anhydrous and oxygen-free condition, under the atmosphere of inert gases, under 35 ~ 45 ℃, take anhydrous tetrahydro furan as solvent, make potassium hydride KH with etc. the hydroxyl reaction of PIB-OH end of amount, form the terminal oxygen anion PIB-O of polyisobutene
-K
+, as the macromole evocating agent of oxygen anion initiated polymerization;
(3) polyisobutene-
bThe preparation of-polymethyl tert-butyl acrylate Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock: with the terminal oxygen anion macromole evocating agent of polyisobutene and the polymerization of monomer Tert-butyl Methacrylate, consist of polymerization system with mol ratio 1: 1～120, adopt oxygen anion initiated polymerization method reaction 1～2 hour; Termination reaction is purified, namely obtain polyisobutene-
b-polymethyl tert-butyl acrylate Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock PIB-
b-P
tBMA;
(4) preparation contains the amphipathic nature block polymer of polyisobutene and polyanion: take methylene dichloride as solvent, in the presence of trifluoroacetic acid, to polyisobutene-
bThe tertiary butyl of-polymethyl tert-butyl acrylate Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock is hydrolyzed; React complete rear rotary evaporation desolventizing, carry out deposition and purification with cold acetone, be dried to constant weight, namely obtain required polyisobutene and the polymethyl acrylic acid Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock PIB-of containing
b-PMAA;
(5) above-mentioned polyisobutene and polymethyl acrylic acid Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock PIB-
b-PMAA, in alkaline medium, the carboxyl in the polymethyl acrylic acid segment-COOH formation-COO
-Negatively charged ion obtains the amphipathic nature block polymer that contains polyisobutene and polyanion shown in the following structural formula:
In the formula, x=18～60, y=10～120, M
+Represent K
+Or Na
+Ion.
4. the preparation method of the described polyisobutylene block copolymer of claim 3 is characterized in that, in the step (1), the end alkene content of described high-activity polyisobutene is more than 85%; The number-average molecular weight of described highly active polyisobutene is 1000～4000 g/mol.
5. a polyisobutene and polymethyl tert-butyl acrylate segmented copolymer is characterized in that the structural formula of described polyisobutene and polymethyl tert-butyl acrylate segmented copolymer is:
In the formula, x=18～60, y=10～120.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110247529 CN102391443B (en) | 2011-08-24 | 2011-08-24 | Amphipathic block copolymer containing polyisobutylene and polyanion and preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110247529 CN102391443B (en) | 2011-08-24 | 2011-08-24 | Amphipathic block copolymer containing polyisobutylene and polyanion and preparation thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102391443A CN102391443A (en) | 2012-03-28 |
| CN102391443B true CN102391443B (en) | 2013-04-17 |
Family
ID=45858840
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110247529 Expired - Fee Related CN102391443B (en) | 2011-08-24 | 2011-08-24 | Amphipathic block copolymer containing polyisobutylene and polyanion and preparation thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102391443B (en) |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7196142B2 (en) * | 2002-04-04 | 2007-03-27 | The University Of Akron | Polyisobutylene-based block anionomers and cationomers and synthesis thereof |
| DE10303275A1 (en) * | 2003-01-28 | 2004-07-29 | Basf Ag | Functionalization of isobutene polymers, useful for the production of polyurethanes, comprises reaction of at least one isobutene polymer having terminal unsaturation with a hydroboration agent |
| CN1271102C (en) * | 2003-06-12 | 2006-08-23 | 中国科学院化学研究所 | Method for preparation of functional polyolefin block copolymer |
| DE10338245A1 (en) * | 2003-08-20 | 2005-03-24 | Basf Ag | molding compound |
| US7135529B2 (en) * | 2004-08-09 | 2006-11-14 | Acushnet Company | Golf ball comprising saturated rubber/ionomer block copolymers |
-
2011
- 2011-08-24 CN CN 201110247529 patent/CN102391443B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN102391443A (en) | 2012-03-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104672403B (en) | A kind of environmentally friendly silicone acrylic emulsion and preparation method thereof | |
| Li et al. | Synthesis and self-assembly of poly (3-hexylthiophene)-block-poly (acrylic acid) | |
| CN102391444B (en) | Amphipathic block copolymer containing polyisobutylene and polycation and preparation thereof | |
| Lu et al. | Well‐defined amphiphilic polymethylene‐b‐poly (acrylic acid) diblock copolymers: New synthetic strategy and their self‐assembly | |
| CN100554291C (en) | The preparation method who contains the segmented copolymer of alpha-methyl styrol structural unit | |
| CN104211880B (en) | A kind of fire-retardant block copolymer of containing phosphorus silicon and preparation method thereof | |
| WO2007105898A1 (en) | Method for preparation of 1-alkene-acrylate based copolymer | |
| CN102432860A (en) | A kind of preparation method of hydroxyl-terminated polyethylene glycol-polytetrahydrofuran triblock copolyether | |
| CN104829795A (en) | Reactive flame-retardant block copolymer and preparing method thereof | |
| CN102911310B (en) | Method of preparing branched polyacrylate (methacrylate) polymer through emulsion polymerization | |
| CN110437426A (en) | A kind of scopiform copolymer and preparation method thereof | |
| CN102391443B (en) | Amphipathic block copolymer containing polyisobutylene and polyanion and preparation thereof | |
| CN107418125A (en) | A kind of method that multiphase polymer material is prepared using segmented copolymer latex | |
| Tsuchiya et al. | Synthesis of diblock copolymers consisting of POSS-containing random methacrylate copolymers and polystyrene and their cross-linked microphase-separated structure via fluoride ion-mediated cage scrambling | |
| Zhou et al. | Star polymerization of norbornene derivatives using a tri-functionalized Blechert's olefin metathesis catalyst | |
| CN108707213B (en) | A kind of preparation method and application of hyperbranched block polymer copolymer | |
| CN110437453A (en) | A kind of preparation method of low temperature self-healing polymer elastomer | |
| CN105367777A (en) | Two-block polyvinyl hyperbranched polymer and preparation method and application thereof | |
| CN107793542B (en) | Method for synthesizing hydrogenated styrene/isoprene block copolymer | |
| CN100469431C (en) | A kind of fluorine-containing cationic macromolecular emulsifier and preparation method thereof | |
| CN102304207A (en) | Method for preparing butylbenzene block copolymer core-shell emulsion through active radical miniemulsion polymerization | |
| JP2012500310A5 (en) | ||
| JP2014221868A (en) | Method for producing block copolymer and photonic material using the same | |
| CN100376614C (en) | A pH-responsive fluorine-containing block copolymer and its preparation method | |
| CN102167782A (en) | Method for grafting polymer in double bond position of natural rubber by adopting atom transfer radical polymerization (ATRP) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee | ||
| CP02 | Change in the address of a patent holder |
Address after: Suzhou City, Jiangsu province 215137 Xiangcheng District Ji Road No. 8 Patentee after: Soochow University Address before: 215123 Suzhou City, Suzhou Province Industrial Park, No. love road, No. 199 Patentee before: Soochow University |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130417 Termination date: 20160824 |