CN103755899B - A kind of thermoplastic elastomer and preparation method - Google Patents
A kind of thermoplastic elastomer and preparation method Download PDFInfo
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- CN103755899B CN103755899B CN201310752003.6A CN201310752003A CN103755899B CN 103755899 B CN103755899 B CN 103755899B CN 201310752003 A CN201310752003 A CN 201310752003A CN 103755899 B CN103755899 B CN 103755899B
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- 229920002725 thermoplastic elastomer Polymers 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims description 15
- 239000000178 monomer Substances 0.000 claims abstract description 85
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- 239000000839 emulsion Substances 0.000 claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229920001577 copolymer Polymers 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 27
- 230000015556 catabolic process Effects 0.000 claims abstract description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 26
- 239000000047 product Substances 0.000 claims description 22
- 239000000126 substance Substances 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000008346 aqueous phase Substances 0.000 claims description 14
- -1 dodecyl trithio Chemical group 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 125000004185 ester group Chemical group 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- WTXXSZUATXIAJO-OWBHPGMISA-N (Z)-14-methylpentadec-2-enoic acid Chemical compound CC(CCCCCCCCCC\C=C/C(=O)O)C WTXXSZUATXIAJO-OWBHPGMISA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000012065 filter cake Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000012071 phase Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 7
- KYLUHLJIAMFYKW-UHFFFAOYSA-N 5-methyl-3-methylideneoxolan-2-one Chemical compound CC1CC(=C)C(=O)O1 KYLUHLJIAMFYKW-UHFFFAOYSA-N 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 6
- 125000004414 alkyl thio group Chemical group 0.000 claims description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- 239000007858 starting material Substances 0.000 claims description 5
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 4
- 239000004159 Potassium persulphate Substances 0.000 claims description 4
- 229960003328 benzoyl peroxide Drugs 0.000 claims description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 4
- 235000019394 potassium persulphate Nutrition 0.000 claims description 4
- 229920005604 random copolymer Polymers 0.000 claims description 4
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 3
- XRUKRHLZDVJJSX-UHFFFAOYSA-N 4-cyanopentanoic acid Chemical compound N#CC(C)CCC(O)=O XRUKRHLZDVJJSX-UHFFFAOYSA-N 0.000 claims description 3
- 239000004160 Ammonium persulphate Substances 0.000 claims description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 3
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- 239000012988 Dithioester Substances 0.000 claims description 2
- 239000004471 Glycine Substances 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 239000003643 water by type Substances 0.000 claims 1
- 230000007704 transition Effects 0.000 abstract description 16
- 239000004816 latex Substances 0.000 abstract description 13
- 229920000126 latex Polymers 0.000 abstract description 13
- 238000010526 radical polymerization reaction Methods 0.000 abstract description 11
- 238000012546 transfer Methods 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 239000000693 micelle Substances 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 238000004581 coalescence Methods 0.000 abstract description 3
- 238000011049 filling Methods 0.000 abstract description 3
- 238000010900 secondary nucleation Methods 0.000 abstract description 3
- 239000002612 dispersion medium Substances 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract description 2
- 230000002708 enhancing effect Effects 0.000 abstract description 2
- 230000004044 response Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 23
- 238000013461 design Methods 0.000 description 15
- 238000006116 polymerization reaction Methods 0.000 description 15
- 239000003153 chemical reaction reagent Substances 0.000 description 14
- 238000009826 distribution Methods 0.000 description 14
- 239000002245 particle Substances 0.000 description 14
- 239000004793 Polystyrene Substances 0.000 description 9
- 229920002223 polystyrene Polymers 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000000523 sample Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 230000009466 transformation Effects 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- GSLDEZOOOSBFGP-UHFFFAOYSA-N alpha-methylene-gamma-butyrolactone Natural products C=C1CCOC1=O GSLDEZOOOSBFGP-UHFFFAOYSA-N 0.000 description 6
- 229920006132 styrene block copolymer Polymers 0.000 description 6
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 5
- 229920001400 block copolymer Polymers 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000007720 emulsion polymerization reaction Methods 0.000 description 5
- 238000005227 gel permeation chromatography Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 206010036711 Primary mediastinal large B-cell lymphomas Diseases 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000003995 emulsifying agent Substances 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 101710141544 Allatotropin-related peptide Proteins 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 239000010985 leather Substances 0.000 description 3
- 239000000123 paper Substances 0.000 description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 3
- 239000004926 polymethyl methacrylate Substances 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229920001169 thermoplastic Polymers 0.000 description 3
- 239000004416 thermosoftening plastic Substances 0.000 description 3
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical group CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000013013 elastic material Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000013467 fragmentation Methods 0.000 description 2
- 238000006062 fragmentation reaction Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 238000012705 nitroxide-mediated radical polymerization Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229920000428 triblock copolymer Polymers 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 1
- 239000008364 bulk solution Substances 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- ODUCDPQEXGNKDN-UHFFFAOYSA-N nitroxyl Chemical compound O=N ODUCDPQEXGNKDN-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 230000001902 propagating effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 230000003019 stabilising effect Effects 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
Landscapes
- Graft Or Block Polymers (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention discloses a kind of thermoplastic elastomer, the structural formula of described thermoplastic elastomer is: AA
n1-b-St
n2-b-(MeMBL-co-St)
n3-b-nBA
n4-b-(MeMBL-co-St)
n5-R; The present invention utilizes emulsion system, in conjunction with RAFT living radical polymerization technique, obtain that molecular weight is controlled, colloidal stability is high, hard section second-order transition temperature higher than the segmented copolymer latex of 100 DEG C, can thermoplastic elastomer product be obtained after breakdown of emulsion drying; The present invention is dispersion medium with water, is beneficial to heat transfer, Environmental Safety, and latex viscosity is low, is convenient to Cemented filling and continuous seepage; Speed of response is fast, each section of monomer conversion is high, is conducive to enhancing productivity, and there is not micelle coalescence and secondary nucleation phenomenon, under room temperature and hot conditions, all there is good mechanical property, have broad application prospects in high heat resistance thermoplastic elastomer field.
Description
(1) technical field
The present invention relates to a kind of thermoplastic elastomer, particularly a kind of reversible addition fragmentation chain emulsion polymerization preparation is containing the method for second-order transition temperature higher than the thermoplastic elastomer of 100 DEG C of blocks.
(2) background technology
Thermoplastic elastomer (thermolplasticelastomers, TPEs) as under a class room temperature, there is caoutchouc elasticity, again can the polymer materials of plasticizing forming under high temperature, its market requirement increases fast, wherein especially with styrenic block copolymer (styrenicblockcopolymers, SBCs) demand is maximum, and its market requirement has accounted for the over half of thermoplastic elastomer aggregate demand.Polystyrene-b-polyhutadiene-b-polystyrene (poly (styrene)-b-poly (butidiene)-b-poly (styrene), SBS) and polystyrene-b-polyisoprene-b-polystyrene (poly (styrene)-b-poly (isoprene)-b-poly (styrene), SIS) be two most widely used class SBCs products.Its prior synthesizing method mainly contains anionoid polymerization and cationoid polymerisation.But these two kinds of polymerization process purity requirements to reaction raw materials are higher, and reaction process needs high vacuum condition and generally will carry out at low temperatures; On the other hand, the research of ionic copolymerization is less, and its practical application is limited to more carries out modification with a small amount of second comonomer, and directly prepare segmented copolymer by vinyl monomer remains great challenge for anionoid polymerization or cationoid polymerisation.Therefore, compared with radical polymerization, anionoid polymerization and cationoid polymerisation no matter in energy-conserving and environment-protective, or all also exist huge inferior position in polymerization implementation condition.In addition, this two series products also also exists two large inherent defects: one, and because polydiolefin mid-block exists unsaturated double-bond, material is easily oxidized, UV degradation occurs, and therefore carrying out alternative PB, PI section with more stable diblock rubber becomes the research emphasis improving its material property; Its two, due to the second-order transition temperature of PS end-blocks lower (being about 100 DEG C), because which limit the SC service ceiling temperature of material, between 60 ~ 70 DEG C, the strength degradation of SBS thermoplastic elastomer is very serious usually.In sum, how to use the polymerization means of more environmental protection and energy saving to synthesize and there is more stabilising rubber block and Geng Gao T
gthe segmented copolymer of plastics block is the key widening SBCs class materials application field.
In controllable/active free radical polymerization (controlled/livingradicalpolymerization, the C/LRP) technology that twentieth century just grows up the nineties, become academic research focus and be subject to the extensive concern of industry member.Ripe and the most most widely used C/LRP technology of Developing mainly contains three kinds: nitroxyl free radical polymerization (nitroxidemediatedpolymerization, NMP), atom transfer radical polymerization (atomtransferradicalpolymerization, and RAFT (reversibleaddition-fragmentationchaintransfer, RAFT) radical polymerization ATRP).Wherein, RAFT radical polymerization is with its monomer scope of application and gentle reaction conditions and be considered to the living radical polymerization technique having industrial prospect now most widely.RAFT technology effectively can control the polymerization of monomer by the reversible transfer of degrading of Propagating Radical, realizes the controllable adjustment of polymer micro-structural (as synthetic segmented copolymer etc.) and the polymerization degree.It can be applicable to homopolymerization and the copolymerization system of various of monomer, almost all applicable to all vinyl monomers, and reaction conditions is polymerized with conventional free radical and is as good as, and is applicable to the multiple reaction systems such as mass polymerization, solution polymerization, letex polymerization, suspension polymerization.Wherein, adopt emulsion polymerization systems in industrial radical polymerization process, because emulsion system has many advantages, as being medium with water, be beneficial to heat transfer, Environmental Safety, latex viscosity is low, is convenient to Cemented filling and continuous seepage more; Molecular chain increases and carries out in the isolation mutually of micella or micelle, and therefore radical life is long, has the feature of high speed and high-polymerization degree concurrently; The latex be obtained by reacting can directly use, such as, as water emulsion, binding agent, paper, leather, fabric-treating agent etc.Amphiphilic macromolecular RAFT reagent is obtained with hydrophilic monomer and lipophilicity monomer polymerization successively by small molecules RAFT reagent, amphipathic due to self, macromole RAFT reagent not only can serve as chain transfer agents but also can serve as emulsifying agent, be applied to the use can avoiding conventional emulsifier in emulsion polymerization systems, thus prevent the generation of foam in production process and reduce costs.Therefore, if RAFT technology can be combined with emulsion system, be just expected to provide an environmental protection, product controlled for preparing styremic based block copolymer, there is the polymerisation routes of good industrial applications prospect.In recent years, the people such as Luo Yingwu utilize the polyacrylic acid-b-polystyrene macromolecular RAFT reagent with longer hydrophilic segment, in RAFT mini-emulsion polymerization system, successfully prepare SBS triblock copolymer, but it fails to solve the two large inherent defects of SBS, SIS mentioned above.In addition, the people such as Luo Yingwu also successfully prepare a series of structure-controllable by RAFT emulsion polymerisation process, the positive butyl ester of polystyrene-b-polyacrylic acid-b-polystyrene (poly (styrene)-b-poly (the n-butylacrylate)-b-poly (styrene) of excellent in mechanical performance, S-nBA-S) triblock copolymer, it is easily oxidized that the introducing of polyacrylic acid positive butyl ester block can solve material, there is the problem of UV degradation, but be limited to the Vitrification Occurred of the hard section of PS, it still fails to solve the SC service ceiling temperature problem of material.But, the research work of the people such as Luo Yingwu imply that RAFT(is thin) letex polymerization is in the great potential of synthesis commercialization block copolymer material.
On the other hand, (methyl) acrylic polymer has good antioxygen, uvioresistant stability, and its T
gcoverage very wide (from-50 DEG C to 200 DEG C).Therefore, take polyacrylic ester as rubber segments, polymethacrylate is the two large inherent defects that the full ester class TPEs of plastics section is expected to solve SBS, SIS mentioned above.The people such as Tong are 10 ~ 15MPa by the PMMA-PnBA-PMMA breaking tenacity that active anionic polymerization obtains, and elongation at break is 700%.Controllable/active free radical polymerization can replace active anionic polymerization synthetic segmented copolymer effectively, but also there is a lot of problem in practical study.The people such as Moineau, the people such as Tong utilize ATRP bulk-solution two step synthesis PMMA-PnBA-PMMA, and that comprehensive mechanical property (solution film forming) is best is tensile strength 5.0MPa, elongation at break 385% and tensile strength 4.2MPa, elongation at break 410%.The people such as Matyjaszewski have used ATRP solution techniques to synthesize, and poly-(the n-butyl acrylate)-b-of poly-(alpha-methylene-gamma-butyrolactone)-b-gathers (alpha-methylene-gamma-butyrolactone) (poly (α-methylene-γ-butyrolactone)-b-poly (nBA)-b-poly (α-methylene-γ-butyrolactone), PMBL-PnBA-PMBL), PMMA-PnBA-PMMA tri-block, the tensile strength of material is respectively 0.7MPa, 2.2MPa, elongation at break is respectively 100%, 550%, wherein the second-order transition temperature of the hard section of PMBL-PnBA-PMBL is up to 195 DEG C.Up to now, the mechanical property of all acrylic ester based block copolymer prepared by C/LRP homogeneous system still can not be satisfactory, and the use of a large amount of organic solvent is also unfavorable for that its large-scale industrialization is promoted.
For solve above-mentioned SBCs Material Field three large problems, the present invention is on the basis adopting the positive butyl ester of RAFT letex polymerization route synthetic polystyrene-b-polyacrylic acid-b-polystyrene block copolymer, γ-methyl-alpha-methylene-gamma-butyrolactone (γ-methyl-α-methylene-γ-butyrolactone is introduced in the hard section of PS, MeMBL) monomer (second-order transition temperature of this monomer homopolymer is up to more than 200 DEG C), by the accuracy controlling of each block molecule amount, synthesize a series of thermoplastic elastomer at high temperature still with excellent mechanical performance, at high heat resistance thermoplastic elastomer, coating electric wire layer, hot air duct, the fields such as motor car engine liner and sealing-ring have huge market outlook.
(3) summary of the invention
The object of the invention is to provide a kind of second-order transition temperature higher than the thermoplastic elastomer of 100 DEG C of blocks and preparation method, by the accuracy controlling of each block molecule amount, synthesize a series of thermoplastic elastomer at high temperature still with excellent mechanical performance, have huge market outlook in fields such as high heat resistance thermoplastic elastomer, coating electric wire layer, hot air duct, motor car engine liner and sealing-rings.
The technical solution used in the present invention is:
The invention provides a kind of containing the thermoplastic elastomer of second-order transition temperature higher than 100 DEG C of blocks, the structural formula of described thermoplastic elastomer is: AA
n1-b-St
n2-b-(MeMBL-co-St)
n3-b-nBA
n4-b-(MeMBL-co-St)
n5-R(letter b represents block);
Wherein, AA
n1in, AA is methacrylic acid monomer units or acrylic monomer units, n
1for the mean polymerisation degree of AA, n
1=20 ~ 60;
St
n2in, St is styrenic monomer units, n
2for the mean polymerisation degree of St, n
2=3 ~ 10;
(MeMBL-co-St)
n3in, MeMBL-co-St is the random copolymers of MeMBL and St, and MeMBL is γ-methyl-alpha-methylene-gamma-butyrolactone monomeric unit, and St is styrenic monomer units, and the ratio of the unit number of MeMBL and St is 1:2, n
3for the mean polymerisation degree of MeMBL-co-St multipolymer, n
3=120 ~ 600;
NBA
n4in, nBA is n-butyl acrylate monomer unit, n
4for the mean polymerisation degree of nBA, n
4=200 ~ 1450;
(MeMBL-co-St)
n5in, MeMBL-co-St is the random copolymers of MeMBL and St, and MeMBL is γ-methyl-alpha-methylene-gamma-butyrolactone monomeric unit, and St is styrenic monomer units, and the ratio of the unit number of MeMBL and St is 1:2, n
5for the mean polymerisation degree of MeMBL-co-St multipolymer, n
5=120 ~ 600;
R is C4 ~ C12 alkyl dithioesters group or C4 ~ C12 alkyl trithio ester group, preferred molybdenum didodecyl dithiophosphate ester group or dodecyl trithio ester group.
Further, preferred described AA
n1in, AA is acrylic monomer units, n
1for the mean polymerisation degree of AA, n
1=20 ~ 40.
Further, preferred described St
n2in, n
2=3 ~ 8.
Further, preferably described (MeMBL-co-St)
n3in, n
3=145 ~ 525.
Further, preferred described nBA
n4in, n
4=235 ~ 1200.
Further, preferably described (MeMBL-co-St)
n5in, n
5=145 ~ 525.
Further, preferred described thermoplastic elastomer is one of following: (1) AA is acrylic monomer units, n
1=20, n
2=5, n
3=145, n
4=235, n
5=145, R is dodecyl trithio ester group; (2) AA is acrylic monomer units, n
1=20, n
2=5, n
3=145, n
4=275, n
5=145, R is dodecyl trithio ester group; (3) AA is acrylic monomer units, n
1=32, n
2=5, n
3=145, n
4=350, n
5=145, R is dodecyl trithio ester group; (4) AA is acrylic monomer units, n
1=32, n
2=5, n
3=435, n
4=703, n
5=435, R is dodecyl trithio ester group; (5) AA is acrylic monomer units, n
1=32, n
2=5, n
3=290, n
4=1094, n
5=290, R is dodecyl trithio ester group.
The present invention also provides described in a kind of preparation containing the method for second-order transition temperature higher than the thermoplastic elastomer of 100 DEG C of blocks, described method for: oligopolymer shown in the formula I of 1 weight part (i.e. amphiphilic macromolecular RAFT reagent) is dissolved in 29.73 ~ 83.16 weight parts (preferably 29.73 ~ 39.31 weight parts by (1), more preferably 29.73 ~ 53.35 weight parts) water in form aqueous phase, again will by 3.18 ~ 11.59 weight parts (preferably 3.18 ~ 4.22 weight parts, more preferably 3.18 ~ 9.55 weight parts) St and 1.70 ~ 6.52 weight parts (preferably 1.70 ~ 2.37 weight parts, more preferably 1.70 ~ 5.09 weight parts) oil phase of MeMBL composition pours in aqueous phase and is uniformly mixed, be warming up to 50 ~ 80 DEG C, insulated and stirred, letting nitrogen in and deoxidizing more than 5 minutes, add the water soluble starter of 0.016 ~ 0.021 weight part, 50 ~ 80 DEG C are reacted 40 ~ 150 minutes, obtain AA
n1-b-St
n2-b-(MeMBL-co-St)
n3-R polymkeric substance, described water soluble starter is Potassium Persulphate, 4,4'-azos two (4-cyanopentanoic acid), ammonium persulphate or Sodium Persulfate,
In formula I, Z is the alkylthio of C4 ~ C12, the alkyl of C4 ~ C12, phenyl or benzyl, St is styrenic monomer units, AA is methacrylic acid monomer units or acrylic monomer units, and X is isopropyl acidic group, acetoxyl, 2-itrile group acetoxyl or 2-glycine base; n
6for the mean polymerisation degree of styrenic monomer units, n
6=3 ~ 10, n
7for the mean polymerisation degree of methacrylic acid monomer units or acrylic monomer units, n
7=20 ~ 60;
(2) after step (1) reaction terminates, 7.21 ~ 62.66 weight parts (preferably 7.21 ~ 16.02 weight parts are added in step (1) product, more preferably 7.21 ~ 60.30 weight parts) water and 12.64 ~ 58.88 weight parts (preferably 12.64 ~ 14.75 weight parts, more preferably 12.64 ~ 44.42 weight parts) nBA monomer after, 50 ~ 80 DEG C are continued reaction 60 ~ 120 minutes, obtain AA
n1-b-St
n2-b-(MeMBL-co-St)
n3-b-nBA
n4-R segmented copolymer;
(3) after step (2) reaction terminates, 5.21 ~ 21.95 weight parts (preferably 5.21 ~ 7.06 weight parts are added in step (2) product, more preferably 5.21 ~ 11.17 weight parts) water and 3.14 ~ 13.41 weight parts (preferably 3.14 ~ 4.22 amount parts, more preferably 3.14 ~ 9.59 weight parts) St and 1.69 ~ 6.81 weight parts (preferably 1.69 ~ 2.27 weight parts, more preferably 1.69 ~ 5.14 weight parts) M
eafter the mix monomer of MBL, 50 ~ 80 DEG C are continued reaction 90 ~ 180 minutes, obtain polymer emulsion, i.e. AA
n1-b-St
n2-b-(MeMBL-co-St)
n3-b-nBA
n4-b-(MeMBL-co-St)
n5-R segmented copolymer;
(4) after step (3) reaction terminates, the polymer emulsion that step (3) obtains is joined in solvent and stirs breakdown of emulsion, suction filtration dewaters, filter cake vacuum-drying (preferably 130 DEG C of vacuum-drying 24h), namely obtains described containing the thermoplastic elastomer product of second-order transition temperature higher than 100 DEG C of blocks; Described solvent is anhydrous methanol, the sodium chloride aqueous solution of mass concentration 10 ~ 20% or the aqueous hydrochloric acid of mass concentration 5 ~ 10%, and the consumption of usual preferred solvent is 0.2 ~ 0.5mL solvent/g emulsion.
Further, oligopolymer shown in preferred described formula I is one of following: 1. Z is the alkylthio of C12, and St is styrenic monomer units, and AA is acrylic monomer units, and X is isopropyl acidic group; n
6for the mean polymerisation degree of styrenic monomer units, n
6=5, n
7for the mean polymerisation degree of acrylic monomer units, n
7=20; 2. Z is the alkylthio of C12, and St is styrenic monomer units, and AA is acrylic monomer units, and X is isopropyl acidic group; n
6for the mean polymerisation degree of styrenic monomer units, n
6=5, n
7for the mean polymerisation degree of acrylic monomer units, n
7=32.
Thermoplastic elastomer of the present invention can be used for the fields such as high heat resistance thermoplastic elastomer, coating electric wire layer, hot air duct, motor car engine liner and sealing-ring.
Beneficial effect of the present invention is mainly reflected in: the present invention utilizes emulsion system, in conjunction with RAFT living radical polymerization technique, obtain that molecular weight is controlled, colloidal stability is high, hard section second-order transition temperature is higher than the segmented copolymer latex of 100 DEG C (about about 135 DEG C); Can thermoplastic elastomer product be obtained after breakdown of emulsion drying, there is following feature:
(1) be dispersion medium with water, be beneficial to heat transfer, Environmental Safety, latex viscosity is low, is convenient to Cemented filling and continuous seepage;
(2) the amphiphilic macromolecular RAFT reagent that the inventive method adopts has the dual-use function of chain transfer agents and emulsifying agent concurrently, has both achieved the good control to monomer polymerization, and turn avoid the use of conventional emulsifier;
(3) speed of response of the present invention is fast, and each section of monomer conversion is high, is conducive to enhancing productivity;
(4) micelle increases stable, and population keeps constant and size distribution is narrower, there is not micelle coalescence and secondary nucleation phenomenon;
(5) growth of building-up process polymericular weight is controlled, and actual measurement molecular weight is substantially identical with design molecular weight, molecular weight distribution relative narrower;
(6) the hard section second-order transition temperature of multipolymer that the inventive method is obtained is higher than 100 DEG C (about about 135 DEG C), material all has good mechanical property under room temperature (20 DEG C) and hot conditions (80 DEG C), has broad application prospects in high heat resistance thermoplastic elastomer field;
(7) latex (before breakdown of emulsion) be obtained by reacting can directly as water emulsion, binding agent, the uses such as paper, leather, fabric-treating agent.
(4) accompanying drawing explanation
Fig. 1 is the GPC graphic representation of the polymkeric substance that the embodiment of the present invention 1 step (1) ~ step (3) obtains;
Fig. 2 is the DSC graphic representation of the segmented copolymer (i.e. thermoplastic elastomer) that the embodiment of the present invention 1 ~ 3 obtains;
Fig. 3 is segmented copolymer (i.e. thermoplastic elastomer) stress-strain curve at 20 DEG C that the embodiment of the present invention 1 ~ 3 obtains;
Fig. 4 is segmented copolymer (i.e. thermoplastic elastomer) stress-strain curve at 80 DEG C that the embodiment of the present invention 1 ~ 3 obtains.
(5) embodiment
Below in conjunction with specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in this:
The chemical structural formula of amphiphilic macromolecular RAFT reagent used in the embodiment of the present invention is:
Or
In thermoplastic elastomer building-up process, the monomer conversion of each step is recorded by weighting method.
The particle diameter of emulsion particle and size distribution test are carried out on MalvernZETASIZER3000HAS particle size analyzer, and probe temperature is 25 DEG C.Emulsion particle subnumber is calculated by formula (1):
N
p=(6m
0x)/π d
v 3ρ P formula (1)
In formula (1), N
pfor emulsion particle subnumber, m
0for initial monomer concentration (g/g
latex), x is monomer conversion, d
vfor the volume mean diameter of emulsion particle, ρ
pfor the density of polymkeric substance, calculated by formula (2):
Formula (2)
ρ
P=ρ
Poly(St)W
st+ρ
Poly(MeMBL)W
MeMBL+ρ
Poly(nBA)W
nBA
In formula (2), the density p of poly (St)
poly (St), the density p of poly (MeMBL)
poly (MeMBL), the density p of poly (nBA)
poly (nBA)be respectively 1.05g/mL, 1.4g/mL and 1.08g/mL, the massfraction W of monomer
st, W
meMBL, W
nBAcalculated by monomer feed amount and transformation efficiency.Size distribution coefficient is the ratio (d of volume average particle size and number average particle size
v/ d
n).
Design molecular weight is calculated by formula (3):
M
n, th=(mx)/[RAFT]+M
n, RAFTformula (3)
In formula (3), M
n, ththe design load of polymericular weight in emulsion at the end of referring to the reaction of each step, m walks the total mass of the added monomer of reaction for this reason, and x is transformation efficiency, and [RAFT] be the amount of substance of the amphipathic RAFT reagent added by before reaction starts, M
n, RAFTfor the molecular weight of amphipathic RAFT reagent.
The molecular weight characterization of polymkeric substance carries out on gel permeation chromatography Waters1525-2414-717GPC instrument, and elutriant is tetrahydrofuran (THF), corrects with Narrow distribution polystyrene standard specimen.Polymkeric substance actual measurement molecular weight is number-average molecular weight, and molecular weight distribution is the ratio of weight-average molecular weight and number-average molecular weight.
The characteristic group of segmented copolymer is characterized by Nicolet5700 infrared spectrometer and obtains.
The T of segmented copolymer
gbe determined on TAQ200 instrument and carry out, use nitrogen atmosphere, be heated to 200 DEG C with the temperature rise rate of 10 DEG C/min from-80 DEG C.
Be naturally volatilize 5 days under room temperature by pouring in glass culture dish after polymkeric substance is dissolved completely in tetrahydrofuran (THF) for the tensile bars of Mechanics Performance Testing, then at 150 DEG C, vacuum-drying, to constant weight, finally cuts with standard cutter again and obtains.
Mechanics Performance Testing under tensile bars room temperature is carried out on Zwick/RoellZ020 instrument, and testing method is undertaken by GB16421-1996, and probe temperature is 20 DEG C, and Elongation test speed is 50mm/min, and each sample at least repeats four times.
Mechanics Performance Testing under tensile bars high temperature is carried out on Inston3367 instrument, and testing method is undertaken by GB6037-85.Probe temperature is 80 DEG C, and rate of extension is 50mm/min.Each sample at least repeats four times.
Embodiment 1 (MeMBL-co-St)
n3-b-nBA
n4-b-(MeMBL-co-St)
n5, three blocks each section of mean polymerisation degree is n
3=145, n
4=235, n
5=145, namely three block design molecular weight are 17K-30K-15K
The first step: the amphiphilic macromolecular RAFT reagent (1) of 1.43 grams is dissolved in the water of 55.85 grams and forms aqueous phase, again the oil phase be made up of 5.99 grams of St, 3.39 grams of MeMBL is poured in aqueous phase and be uniformly mixed, be warming up to 70 DEG C, insulated and stirred, letting nitrogen in and deoxidizing 30 minutes, add the Potassium Persulphate of 0.03 gram, react 50 minutes, obtain AA
n1-b-St
n2-b-(MeMBL-co-St)
n3-R polymkeric substance.
Second step: after the first step reaction terminates, add the water of 10.31 grams in the first step product, and after the nBA monomer of 18.07 grams 70 DEG C continue reaction 60 minutes, obtain AA
n1-b-St
n2-b-(MeMBL-co-St)
n3-b-nBA
n4-R segmented copolymer.
3rd step: after second step reaction terminates, add the mix monomer of the water of 10.10 grams and 6.02 grams of St and 3.23 gram MeMBL in second step product after, 70 DEG C are continued reaction 90 minutes, obtain emulsion 114g, i.e. AA
n1-b-St
n2-b-(MeMBL-co-St)
n3-b-nBA
n4-b-(MeMBL-co-St)
n5-R segmented copolymer.
4th step: after three-step reaction terminates, the emulsion that the 3rd step obtains joined in 50mL anhydrous methanol and stir breakdown of emulsion, suction filtration dewaters, and namely obtains thermoplastic elastomer product after filter cake 130 DEG C of vacuum-drying 24h.
The reaction times that the first step respectively walks to the 3rd step, transformation efficiency, latex particle size, population and size distribution are as shown in table 1, the design molecular weight of each step resulting polymers, actual measurement molecular weight and molecular weight distribution are as shown in table 2, and end product mechanical property is at different temperatures as shown in table 3.The first step respectively walks the GPC graphic representation of polymkeric substance as shown in Figure 1 to the 3rd step, the DSC graphic representation of end product thermoplastic elastomer as shown in Figure 2, as shown in Figure 3, the stress-strain curve of thermoplastic elastomer at 80 DEG C as shown in Figure 4 for the stress-strain curve of thermoplastic elastomer at 20 DEG C.
As shown in embodiment in table 11 data, the reaction times of each step is shorter and transformation efficiency is very high, along with the carrying out of reaction, the particle diameter of emulsion particle is in continuous increase, population maintenance is simultaneously constant and size distribution is very narrow, and identity system is stablized, and there is not micelle coalescence and secondary nucleation phenomenon.From embodiment in table 21 data, the measured value of each step resulting polymers molecular weight meets design load, and the molecular weight of multipolymer is progressively increasing, and final molecular weight distribution relative narrower, show that method controls the polymerization of monomer well; As shown in Figure 1, the molecular weight of each block presents unimodal and is progressively increasing, and proves to obtain segmented copolymer.In Fig. 2, the DSC curve of 17K-30K-15K has obvious glass transition endotherm(ic)peak near-55 DEG C with near 135 DEG C, and also demonstrate the structure that product is design, its hard section second-order transition temperature is 133 DEG C.From embodiment in table 31 data, the Young's modulus of thermoplastic elastic material at 20 DEG C is 212MPa, and yield strength and tensile strength are respectively 7.1MPa and 10.8MPa, and elongation at break is 350%, demonstrates good elasticity body performance.As shown in Figure 3, at 20 DEG C, there is obvious yield-point in 17K-30K-15K material in drawing process, and after having there is yield-point, along with strain increases, stress significantly declines, and occurs strain softening phenomenon; When straining continuation and increasing, stress value is substantially constant, occurs cold drawn phenomenon; Finally along with the increase of strain, stress continues rising and occurs strain hardening phenomenon, until Materials Fracture destroys, demonstrates typical thermoplastic elastomer mechanical behavior.From embodiment in table 31 data, when probe temperature rises to 80 DEG C, the Young's modulus of material drops to 105MPa, and yield strength and tensile strength drop to 3.2MP respectively
aand 4.7MP
a, and elongation at break is increased to 370%, still demonstrates good thermoplastic elastomer mechanical property.The stress-strain curve of thermoplastic elastic material at 80 DEG C as shown in Figure 4, similar at its mechanical behavior and 20 DEG C.
Embodiment 2((MeMBL-co-St)
n3-b-nBA
n4-b-(MeMBL-co-St)
n5, three blocks each section of mean polymerisation degree is n
3=145, n
4=275, n
5=145, namely three block design molecular weight are 16K-35K-15K):
The first step: the amphiphilic macromolecular RAFT reagent (1) of 1.43 grams is dissolved in the water of 56.21 grams and forms aqueous phase, again the oil phase be made up of 6.03 grams of St and 3.32 gram MeMBL is poured in aqueous phase and be uniformly mixed, be warming up to 70 DEG C, insulated and stirred, letting nitrogen in and deoxidizing 40 minutes, adds 4, the 4'-azos two (4-cyanopentanoic acid) of 0.03 gram, react 50 minutes, obtain AA
n1-b-St
n2-b-(MeMBL-co-St)
n3-R polymkeric substance.
Second step: after the first step reaction terminates, add the water of 15.17 grams, and after the nBA monomer of 21.09 grams 70 DEG C continue reaction 70 minutes, obtain AA
n1-b-St
n2-b-(MeMBL-co-St)
n3-b-nBA
n4-R segmented copolymer.
3rd step: after second step reaction terminates, after adding the mix monomer of the water of 10.02 grams and 6.03 grams of St and 3.25 gram MeMBL, 70 DEG C are continued reaction 90 minutes, obtain emulsion 122g, i.e. AA
n1-b-St
n2-b-(MeMBL-co-St)
n3-b-nBA
n4-b-(MeMBL-co-St)
n5-R segmented copolymer.
4th step: after three-step reaction terminates, emulsion droplets be added in 50mL mass concentration 20% sodium chloride aqueous solution and stir breakdown of emulsion, suction filtration dewaters, and namely obtains thermoplastic elastomer product after filter cake 130 DEG C of vacuum-drying 24h.
The first step respectively walks the GPC graphic representation of polymkeric substance as shown in Figure 1 to the 3rd step, the DSC graphic representation of end product thermoplastic elastomer as shown in Figure 2, as shown in Figure 3, the stress-strain curve of thermoplastic elastomer at 80 DEG C as shown in Figure 4 for the stress-strain curve of thermoplastic elastomer at 20 DEG C.Reaction times of each step, transformation efficiency, latex particle size, population and size distribution are as shown in table 1.The design molecular weight of each step resulting polymers, actual measurement molecular weight and molecular weight distribution are as shown in table 2.In Fig. 2, the DSC curve of 16K-35K-15K has obvious glass transition endotherm(ic)peak near-55 DEG C with near 135 DEG C, and also demonstrate the structure that product is design, its hard section second-order transition temperature is 133 DEG C.Material mechanical property at different temperatures, as shown in table 3 embodiment 2 data, demonstrates the thermoplastic elastomer mechanical property that material is good.Material stress-strain curve at different temperatures, as shown in 16K-35K-15K curve in Fig. 3, Fig. 4, follows typical thermoplastic elastomer mechanical behavior equally.
Embodiment 3((MeMBL-co-St)
n3-b-nBA
n4-b-(MeMBL-co-St)
n5, three blocks each section of mean polymerisation degree is n
3=145, n
4=350, n
5=145, namely three block design molecular weight are 17K-45K-15K):
The first step: the amphiphilic macromolecular RAFT reagent (2) of 1.91 grams is dissolved in the water of 56.78 grams and forms aqueous phase, again the oil phase be made up of 6.08 grams of St and 3.24 gram MeMBL is poured in aqueous phase and be uniformly mixed, be warming up to 70 DEG C, insulated and stirred, letting nitrogen in and deoxidizing 10 minutes, add the ammonium persulphate of 0.03 gram, 70 DEG C are reacted 40 minutes, obtain AA
n1-b-St
n2-b-(MeMBL-co-St)
n3-R polymkeric substance.
Second step: after the first step reaction terminates, add the water of 30.60 grams, and after the nBA monomer of 27.03 grams 70 DEG C continue reaction 80 minutes, obtain AA
n1-b-St
n2-b-(MeMBL-co-St)
n3-b-nBA
n4-R segmented copolymer.
3rd step: after second step reaction terminates, after adding the mix monomer of the water of 9.96 grams and 5.99 grams of St and 3.23 gram MeMBL, 70 DEG C are continued reaction 90 minutes, obtain emulsion 144g, i.e. AA
n1-b-St
n2-b-(MeMBL-co-St)
n3-b-nBA
n4-b-(MeMBL-co-St)
n5-R segmented copolymer.
4th step: after three-step reaction terminates, emulsion droplets be added in the aqueous hydrochloric acid of 50mL mass concentration 10% and stir breakdown of emulsion, suction filtration dewaters, and namely obtains thermoplastic elastomer product after filter cake 130 DEG C of vacuum-drying 24h.
The first step respectively walks the GPC graphic representation of polymkeric substance as shown in Figure 1 to the 3rd step, the DSC graphic representation of end product thermoplastic elastomer as shown in Figure 2, as shown in Figure 3, the stress-strain curve of thermoplastic elastomer at 80 DEG C as shown in Figure 4 for the stress-strain curve of thermoplastic elastomer at 20 DEG C.Reaction times of each step, transformation efficiency, latex particle size, population and size distribution are as shown in table 1.The design molecular weight of each step resulting polymers, actual measurement molecular weight and molecular weight distribution are as shown in table 2.
In Fig. 2, the DSC curve of 17K-45K-15K has obvious glass transition endotherm(ic)peak near-54 DEG C with near 135 DEG C, and also demonstrate the structure that product is design, its hard section second-order transition temperature is 135 DEG C.Material mechanical property at different temperatures as shown in table 3 embodiment 3 data, wherein material at 80 DEG C elongation at break up to 540%, tensile strength is 3.6MPa, demonstrate the thermoplastic elastomer performance that material is excellent in the case of a high temperature.Material stress-strain curve is at different temperatures as shown in 17K-45K-15K curve in Fig. 3, Fig. 4.
Embodiment 4((MeMBL-co-St)
n3-b-nBA
n4-b-(MeMBL-co-St)
n5, three blocks each section of mean polymerisation degree is n
3=435, n
4=703, n
5=435, namely three block design molecular weight are 45K-90K-45K):
The first step: the amphiphilic macromolecular RAFT reagent (2) of 1.91 grams is dissolved in the water of 84.78 grams and forms aqueous phase, again the oil phase be made up of 18.24 grams of St and 9.73 gram MeMBL is poured in aqueous phase and be uniformly mixed, be warming up to 50 DEG C, insulated and stirred, letting nitrogen in and deoxidizing 30 minutes, add the Potassium Persulphate of 0.03 gram, react 150 minutes, obtain AA
n1-b-St
n2-b-(MeMBL-co-St)
n3-R polymkeric substance.
Second step: after the first step reaction terminates, add the water of 40.27 grams, and after the nBA monomer of 54.07 grams 50 DEG C continue reaction 120 minutes, obtain AA
n1-b-St
n2-b-(MeMBL-co-St)
n3-b-nBA
n4-R segmented copolymer.
3rd step: after second step reaction terminates, after adding the mix monomer of the water of 21.34 grams and 18.32 grams of St and 9.81 gram MeMBL, 50 DEG C are continued reaction 180 minutes, obtain emulsion 258g, i.e. AA
n1-b-St
n2-b-(MeMBL-co-St)
n3-b-nBA
n4-b-(MeMBL-co-St)
n5-R segmented copolymer.
4th step: after three-step reaction terminates, emulsion droplets being added to 50mL mass concentration is stir breakdown of emulsion in the aqueous hydrochloric acid of 5%, and suction filtration dewaters, and namely obtains thermoplastic elastomer product after filter cake 130 DEG C of vacuum-drying 24h.
The Young's modulus of product at 20 DEG C is 243MPa, and yield strength is 7.5MPa, and tensile strength is 11.2MP
a, elongation at break is 380%.
Embodiment 5((MeMBL-co-St)
n3-b-nBA
n4-b-(MeMBL-co-St)
n5, three blocks each section of mean polymerisation degree is n
3=290, n
4=1904, n
5=290, namely three block design molecular weight are 30K-140K-30K):
The first step: the amphiphilic macromolecular RAFT reagent (2) of 0.97 gram is dissolved in the water of 51.75 grams and forms aqueous phase, again the oil phase be made up of 5.62 grams of St and 3.16 gram MeMBL is poured in aqueous phase and be uniformly mixed, be warming up to 80 DEG C, insulated and stirred, letting nitrogen in and deoxidizing 30 minutes, add the Sodium Persulfate of 0.02 gram, 80 DEG C are reacted 40 minutes, obtain AA
n1-b-St
n2-b-(MeMBL-co-St)
n3-R polymkeric substance.
Second step: after the first step reaction terminates, add the water of 58.49 grams, and after the nBA monomer of 43.09 grams 80 DEG C continue reaction 100 minutes, obtain AA
n1-b-St
n2-b-(MeMBL-co-St)
n3-b-nBA
n4-R segmented copolymer.
3rd step: after second step reaction terminates, continue reaction 120 minutes after adding the mix monomer of the water of 10.39 grams and 5.95 grams of St and 3.22 gram MeMBL, obtain emulsion 182g, i.e. AA
n1-b-St
n2-b-(MeMBL-co-St)
n3-b-nBA
n4-b-(MeMBL-co-St)
n5-R segmented copolymer.
4th step: after three-step reaction terminates, emulsion droplets be added in 50mL mass concentration 10% sodium chloride aqueous solution and stir breakdown of emulsion, suction filtration dewaters, and namely obtains thermoplastic elastomer product after filter cake 130 DEG C of vacuum-drying 24h.
The Young's modulus of product at 20 DEG C is 0.23MPa, and tensile strength is 3.68MPa, and elongation at break is 595%.(note: yield-point does not appear in this sample, therefore does not have yield strength).
Embodiment 1 ~ 5 shows no matter prepare material water soluble starter used is persulfuric acid salt initiator or azo-initiator, and breakdown of emulsion process uses anhydrous methanol, sodium chloride aqueous solution or aqueous hydrochloric acid all not to affect the performance of material.
Table 1: the transformation efficiency that segmented copolymer latex preparation process respectively walks and latex particle develop situation
Table 2: segmented copolymer building-up process respectively walks the differentiation situation of molecular weight
Table 3: thermoplastic elastomer mechanical property situation at different temperatures
Experiment proves, the hard section second-order transition temperature of block co-polymer thermoplastic's elastomerics that reversible addition fragmentation chain emulsion polymerization of the present invention preparation is prepared higher than the method for the thermoplastic elastomer of 100 DEG C of blocks containing second-order transition temperature is higher than 100 DEG C (about about 135 DEG C), material all has good mechanical property under room temperature (20 DEG C) and hot conditions (80 DEG C), has broad application prospects in high heat resistance thermoplastic elastomer field; Emulsion system after reaction terminates can directly as water emulsion, binding agent, the uses such as paper, leather, fabric-treating agent.
Above-described embodiment is used for explaining and the present invention is described, instead of limits the invention, and in the protection domain of spirit of the present invention and claim, any amendment make the present invention and change, all fall into protection scope of the present invention.
Claims (8)
1. a process for preparation of thermoplastic elastomer, it is characterized in that described method for: oligopolymer shown in the formula I of 1 weight part to be dissolved in the water of 29.73 ~ 83.16 weight parts and to form aqueous phase by (1), again the oil phase be made up of 3.18 ~ 11.59 weight part St and 1.70 ~ 6.52 weight part MeMBL is poured in aqueous phase and be uniformly mixed, be warming up to 50 ~ 80 DEG C, insulated and stirred, letting nitrogen in and deoxidizing more than 5 minutes, add the water soluble starter of 0.016 ~ 0.021 weight part, 50 ~ 80 DEG C are reacted 40 ~ 150 minutes, obtain AA
n1-b-St
n2-b-(MeMBL-co-St)
n3-R polymkeric substance; Described water soluble starter is Potassium Persulphate, 4,4'-azos two (4-cyanopentanoic acid), ammonium persulphate or Sodium Persulfate;
In formula I, Z is the alkylthio of C4 ~ C12, the alkyl of C4 ~ C12, phenyl or benzyl, St is styrenic monomer units, AA is methacrylic acid monomer units or acrylic monomer units, and X is isopropyl acidic group, acetoxyl, 2-itrile group acetoxyl or 2-glycine base; n
6for the mean polymerisation degree of styrenic monomer units, n
6=3 ~ 10, n
7for the mean polymerisation degree of methacrylic acid monomer units or acrylic monomer units, n
7=20 ~ 60;
(2), after step (1) reaction terminates, add the water of 7.21 ~ 62.66 weight parts and the nBA monomer of 12.64 ~ 58.88 weight parts in step (1) product after, 50 ~ 80 DEG C are continued reaction 60 ~ 120 minutes, obtain AA
n1-b-St
n2-b-(MeMBL-co-St)
n3-b-nBA
n4-R segmented copolymer;
(3) after step (2) reaction terminates, add the mix monomer of 5.21 ~ 21.95 weight parts waters and 3.14 ~ 13.41 weight part St and 1.69 ~ 6.81 weight part MeMBL in step (2) product after, 50 ~ 80 DEG C are continued reaction 90 ~ 180 minutes, obtain polymer emulsion, i.e. AA
n1-b-St
n2-b-(MeMBL-co-St)
n3-b-nBA
n4-b-(MeMBL-co-St)
n5-R segmented copolymer;
(4), after step (3) reaction terminates, joined in solvent by the polymer emulsion that step (3) obtains and stir breakdown of emulsion, suction filtration dewaters, filter cake vacuum-drying, namely obtains described thermoplastic elastomer product; Described solvent is anhydrous methanol, the sodium chloride aqueous solution of mass concentration 10 ~ 20% or the aqueous hydrochloric acid of mass concentration 5 ~ 10%;
The structural formula of described thermoplastic elastomer is:
AA
n1-b-St
n2-b-(MeMBL-co-St)
n3-b-nBA
n4-b-(MeMBL-co-St)
n5-R；
Wherein, AA
n1in, AA is methacrylic acid monomer units or acrylic monomer units, n
1for the mean polymerisation degree of AA, n
1=20 ~ 60;
St
n2in, St is styrenic monomer units, n
2for the mean polymerisation degree of St, n
2=3 ~ 10;
(MeMBL-co-St)
n3in, MeMBL-co-St is the random copolymers of MeMBL and St, and MeMBL is γ-methyl-alpha-methylene-gamma-butyrolactone monomeric unit, and St is styrenic monomer units, and the ratio of the unit number of MeMBL and St is 1:2, n
3for the mean polymerisation degree of MeMBL-co-St multipolymer, n
3=120 ~ 600;
NBA
n4in, nBA is n-butyl acrylate monomer unit, n
4for the mean polymerisation degree of nBA, n
4=200 ~ 1450;
(MeMBL-co-St)
n5in, MeMBL-co-St is the random copolymers of MeMBL and St, and MeMBL is γ-methyl-alpha-methylene-gamma-butyrolactone monomeric unit, and St is styrenic monomer units, and the ratio of the unit number of MeMBL and St is 1:2, n
5for the mean polymerisation degree of MeMBL-co-St multipolymer, n
5=120 ~ 600;
R is C4 ~ C12 alkyl dithioesters group or C4 ~ C12 alkyl trithio ester group.
2. process for preparation of thermoplastic elastomer as claimed in claim 1, is characterized in that described AA
n1in, AA is acrylic monomer units, n
1=20 ~ 40.
3. process for preparation of thermoplastic elastomer as claimed in claim 1, is characterized in that described St
n2in, n
2=3 ~ 8.
4. process for preparation of thermoplastic elastomer as claimed in claim 1, is characterized in that described (MeMBL-co-St)
n3in, n
3=145 ~ 525.
5. process for preparation of thermoplastic elastomer as claimed in claim 1, is characterized in that described nBA
n4in, n
4=235 ~ 1200.
6. process for preparation of thermoplastic elastomer as claimed in claim 1, is characterized in that described (MeMBL-co-St)
n5in, n
5=145 ~ 525.
7. process for preparation of thermoplastic elastomer as claimed in claim 1, is characterized in that described thermoplastic elastomer is one of following: (1) AA is acrylic monomer units, n
1=20, n
2=5, n
3=145, n
4=235, n
5=145, R is dodecyl trithio ester group; (2) AA is acrylic monomer units, n
1=20, n
2=5, n
3=145, n
4=275, n
5=145, R is dodecyl trithio ester group; (3) AA is acrylic monomer units, n
1=32, n
2=5, n
3=145, n
4=350, n
5=145, R is dodecyl trithio ester group; (4) AA is acrylic monomer units, n
1=32, n
2=5, n
3=435, n
4=703, n
5=435, R is dodecyl trithio ester group; (5) AA is acrylic monomer units, n
1=32, n
2=5, n
3=290, n
4=1094, n
5=290, R is dodecyl trithio ester group.
8. process for preparation of thermoplastic elastomer as claimed in claim 1, is characterized in that oligopolymer shown in described formula I is one of following: 1. Z is the alkylthio of C12, and St is styrenic monomer units, and AA is acrylic monomer units, and X is isopropyl acidic group; n
6for the mean polymerisation degree of styrenic monomer units, n
6=5, n
7for the mean polymerisation degree of acrylic monomer units, n
7=20; 2. Z is the alkylthio of C12, and St is styrenic monomer units, and AA is acrylic monomer units, and X is isopropyl acidic group; n
6for the mean polymerisation degree of styrenic monomer units, n
6=5, n
7for the mean polymerisation degree of acrylic monomer units, n
7=32.
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