CN118515797A - Composite structure regulator and application thereof, styrene-butadiene polymer and preparation method and application thereof - Google Patents
Composite structure regulator and application thereof, styrene-butadiene polymer and preparation method and application thereof Download PDFInfo
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- CN118515797A CN118515797A CN202310132801.2A CN202310132801A CN118515797A CN 118515797 A CN118515797 A CN 118515797A CN 202310132801 A CN202310132801 A CN 202310132801A CN 118515797 A CN118515797 A CN 118515797A
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- Prior art keywords
- butadiene polymer
- liquid styrene
- styrene
- butadiene
- component
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- 229920000642 polymer Polymers 0.000 title claims abstract description 223
- 229920003048 styrene butadiene rubber Polymers 0.000 title claims abstract description 208
- 239000002174 Styrene-butadiene Substances 0.000 title claims abstract description 204
- 239000011115 styrene butadiene Substances 0.000 title claims abstract description 204
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 title claims abstract description 201
- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title description 12
- 239000007788 liquid Substances 0.000 claims abstract description 195
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 84
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000009826 distribution Methods 0.000 claims abstract description 19
- 239000000178 monomer Substances 0.000 claims abstract description 19
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 15
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims abstract description 14
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 14
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 52
- 238000000034 method Methods 0.000 claims description 46
- 229910052751 metal Inorganic materials 0.000 claims description 41
- 239000002184 metal Substances 0.000 claims description 34
- 239000003999 initiator Substances 0.000 claims description 29
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 26
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 claims description 24
- 239000007864 aqueous solution Substances 0.000 claims description 17
- 238000006116 polymerization reaction Methods 0.000 claims description 16
- 239000011734 sodium Substances 0.000 claims description 15
- 229910052708 sodium Inorganic materials 0.000 claims description 15
- 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 claims description 14
- 229910052700 potassium Inorganic materials 0.000 claims description 14
- 239000011591 potassium Substances 0.000 claims description 14
- -1 sodium alkoxide Chemical class 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 13
- 239000003963 antioxidant agent Substances 0.000 claims description 13
- 239000001569 carbon dioxide Substances 0.000 claims description 13
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 13
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 12
- 230000003078 antioxidant effect Effects 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 239000003607 modifier Substances 0.000 claims description 12
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims description 10
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 229940116411 terpineol Drugs 0.000 claims description 10
- 238000002834 transmittance Methods 0.000 claims description 10
- 238000010539 anionic addition polymerization reaction Methods 0.000 claims description 8
- 125000000129 anionic group Chemical group 0.000 claims description 8
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims description 8
- 239000004215 Carbon black (E152) Substances 0.000 claims description 7
- 229930195733 hydrocarbon Natural products 0.000 claims description 7
- 150000002430 hydrocarbons Chemical class 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 6
- 238000007639 printing Methods 0.000 claims description 6
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 6
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- NOOLISFMXDJSKH-UTLUCORTSA-N (+)-Neomenthol Chemical compound CC(C)[C@@H]1CC[C@@H](C)C[C@@H]1O NOOLISFMXDJSKH-UTLUCORTSA-N 0.000 claims description 4
- NOOLISFMXDJSKH-UHFFFAOYSA-N DL-menthol Natural products CC(C)C1CCC(C)CC1O NOOLISFMXDJSKH-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 4
- 230000009477 glass transition Effects 0.000 claims description 4
- 229940041616 menthol Drugs 0.000 claims description 4
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 4
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 3
- MYHTUEYPDSGYEE-UHFFFAOYSA-N CC(CCCC)O.[K] Chemical compound CC(CCCC)O.[K] MYHTUEYPDSGYEE-UHFFFAOYSA-N 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 2
- HSJXWMZKBLUOLQ-UHFFFAOYSA-M potassium;2-dodecylbenzenesulfonate Chemical compound [K+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HSJXWMZKBLUOLQ-UHFFFAOYSA-M 0.000 claims description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 claims 1
- 229940077388 benzenesulfonate Drugs 0.000 claims 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 abstract description 31
- 229920002554 vinyl polymer Polymers 0.000 abstract description 28
- 239000002861 polymer material Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 20
- 239000003153 chemical reaction reagent Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 229920001971 elastomer Polymers 0.000 description 9
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 8
- 239000000806 elastomer Substances 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000011260 aqueous acid Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 230000000977 initiatory effect Effects 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 101710171219 30S ribosomal protein S13 Proteins 0.000 description 3
- 101000722833 Geobacillus stearothermophilus 30S ribosomal protein S16 Proteins 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- DUEPRVBVGDRKAG-UHFFFAOYSA-N carbofuran Chemical compound CNC(=O)OC1=CC=CC2=C1OC(C)(C)C2 DUEPRVBVGDRKAG-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000008177 pharmaceutical agent Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 101100510299 Oryza sativa subsp. japonica KIN7A gene Proteins 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical group [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- VUFKMYLDDDNUJS-UHFFFAOYSA-N 2-(ethoxymethyl)oxolane Chemical compound CCOCC1CCCO1 VUFKMYLDDDNUJS-UHFFFAOYSA-N 0.000 description 1
- 101710171187 30S ribosomal protein S10 Proteins 0.000 description 1
- 101710171221 30S ribosomal protein S11 Proteins 0.000 description 1
- 101710171220 30S ribosomal protein S12 Proteins 0.000 description 1
- 101710192523 30S ribosomal protein S9 Proteins 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000004380 ashing Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical class OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- 239000012490 blank solution Substances 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 1
- SZAVVKVUMPLRRS-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].C[CH-]C SZAVVKVUMPLRRS-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- DOIRQSBPFJWKBE-UHFFFAOYSA-N phthalic acid di-n-butyl ester Natural products CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000008036 rubber plasticizer Substances 0.000 description 1
- 238000005464 sample preparation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to the technical field of high polymer materials, and discloses a composite structure regulator which is characterized by comprising a component A and a component B, wherein the molar ratio of the component A to the component B is 6-20:1, a step of; wherein the component A is tetrahydrofuran, and the component B is organic sodium salt and/or organic potassium salt. The composite structure regulator contains tetrahydrofuran and organic sodium salt and/or organic potassium salt in a specific proportion, can realize that when the liquid styrene-butadiene polymer is prepared, the vinyl content and the block styrene content in the liquid styrene-butadiene polymer can be simultaneously lower on the premise of realizing that the vinyl structure content and the monomer sequence distribution in the liquid styrene-butadiene polymer are highly controllable by using a small amount of the composite structure regulator.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a composite structure regulator and application thereof, a styrene-butadiene polymer and a preparation method and application thereof.
Background
The liquid styrene-butadiene polymer is a viscous polymer with the number average molecular weight below 20000 and certain fluidity at normal temperature, and is widely applied to the fields of 5G high-frequency communication, flexible printing, resin modification, rubber plasticizer, auxiliary crosslinking agent, photographic material, adhesive, water-based paint, electrophoretic paint and electric insulation material.
According to the content of the styrene structural units, the liquid styrene-butadiene polymer can be classified into a high-styrene-butadiene polymer (styrene content > 40 wt%), a medium-styrene-butadiene polymer (styrene content 20-40 wt%) and a low-styrene-butadiene polymer (styrene content < 20 wt%). Liquid styrene-butadiene polymers can be classified into high vinyl liquid styrene-butadiene polymers (vinyl content > 60 wt%), medium vinyl liquid styrene-butadiene polymers (vinyl content 30-60 wt%) and low vinyl liquid styrene-butadiene polymers (vinyl content < 30 wt%) according to vinyl content. The liquid styrene-butadiene polymer may be classified into a block liquid styrene-butadiene polymer (block styrene content > 4 wt%), a micro block liquid styrene-butadiene polymer (block styrene content 1-4 wt%) and a random liquid styrene-butadiene polymer (block styrene content < 1 wt%) according to the distribution of monomers in molecular chains.
The liquid styrene-butadiene polymer generally adopts an anionic solution polymerization process, the control of vinyl content and monomer sequence distribution is seriously dependent on the use level of a regulator, and as the use level of the regulator is increased, the vinyl content is increased, and butadiene and styrene monomers tend to be randomly distributed, so that the preparation difficulty of the styrene-butadiene polymer with low vinyl content and random distribution is extremely high. The liquid styrene-butadiene polymer has low molecular weight and large catalyst consumption, and the structure regulator has large consumption and higher control difficulty for realizing low vinyl content in order to realize the controllable distribution of monomer sequences.
CN113698536a discloses a liquid styrene-butadiene polymer, its preparation method and application, and composition, polymer coating, adhesive and cross-linking agent containing the liquid styrene-butadiene polymer, the liquid styrene-butadiene polymer has butadiene and styrene randomly distributed in molecular chain, but vinyl content is up to 80-90wt%.
CN104628951a discloses a structure regulator for anionic polymerization containing an alkyl silicon alkoxide compound and alkyl tetrahydrofurfuryl ether, and an anionic polymerization method using the structure regulator. The structure regulator of the invention can realize random distribution of various structural units on macromolecular chains when being used for solution copolymerization reaction of monovinylarene and conjugated diene. However, the structure regulator is used for preparing solid styrene-butadiene rubber, and the prepared polymer has higher vinyl content, and can not meet the requirement of controlling the content of block styrene when the vinyl content is within the range of the invention.
CN104059196a discloses a structure regulator for anionic polymerization of olefins, which contains a bis-tetrahydrofuran compound and alkylbenzene sulfonate, and the molar ratio of the bis-tetrahydrofuran compound to the alkylbenzene sulfonate is 1:0.0125-10. However, the structure regulator is used for preparing solid styrene-butadiene rubber, and the prepared polymer has higher vinyl content, and can not meet the requirement of controlling the content of block styrene when the vinyl content is within the range of the invention.
Disclosure of Invention
The invention aims to solve the problems that the vinyl content in the liquid styrene-butadiene polymer is higher or the preparation of styrene-butadiene rubber meeting the requirements of low vinyl content and low block styrene content can not be realized in the prior art, and provides a composite structure regulator and application thereof, the liquid styrene-butadiene polymer and a preparation method and application thereof, wherein the composite structure regulator contains tetrahydrofuran and organic sodium salt and/or organic potassium salt in a specific proportion, the preparation method can ensure that the vinyl content and the block styrene content in the liquid styrene-butadiene polymer are simultaneously lower on the premise of realizing the high controllability of the vinyl structure content and the monomer sequence distribution of the liquid styrene-butadiene polymer by using a small amount of the composite structure regulator, and is more favorable as the raw material of the photosensitive elastomer for the flexible resin plate.
In order to achieve the above object, a first aspect of the present invention provides a composite structure modifier, wherein the composite structure modifier comprises a component a and a component B, and the molar ratio of the component a to the component B is 6 to 20:1, a step of;
wherein the component A is tetrahydrofuran, and the component B is organic sodium salt and/or organic potassium salt.
In a second aspect, the invention provides the use of a composite structure modifier according to the first aspect of the invention in anionic solution polymerization.
The third aspect of the present invention provides a liquid styrene-butadiene polymer, wherein the content of block styrene in the liquid styrene-butadiene polymer is 0.1 to 1wt%, and the content of 1, 2-structure is 10 to 30wt% based on the content of butadiene structural units;
the number average molecular weight of the liquid styrene-butadiene polymer is 3000-5000.
In a fourth aspect, the present invention provides a method for preparing a liquid styrene-butadiene polymer, comprising the steps of: in a nonpolar hydrocarbon solvent, carrying out anionic polymerization on a polymerization monomer in the presence of a composite structure regulator and an initiator to obtain a styrene-butadiene polymer I;
wherein the composite structure modifier is the structure modifier of the first aspect of the invention.
In a fifth aspect, the present invention provides a liquid styrene-butadiene polymer, wherein the liquid styrene-butadiene polymer is produced by the method of the fourth aspect of the invention;
Wherein the liquid styrene-butadiene polymer comprises: at least one of liquid styrene-butadiene polymer I, liquid styrene-butadiene polymer II, liquid styrene-butadiene polymer III and liquid styrene-butadiene polymer IV.
In a sixth aspect, the present invention provides a use of the liquid styrene-butadiene polymer of the third or fifth aspect of the invention in the field of flexographic printing.
Through the technical scheme, the composite structure regulator and the application thereof, the liquid styrene-butadiene polymer and the preparation method and the application thereof provided by the invention have the following beneficial effects:
(1) The composite structure regulator contains tetrahydrofuran and organic sodium salt and/or organic potassium salt in a specific proportion, so that when the liquid styrene-butadiene polymer is prepared, the vinyl content and the block styrene content in the liquid styrene-butadiene polymer can be simultaneously lower on the premise of realizing high controllability of the vinyl structure content and the monomer sequence distribution of the liquid styrene-butadiene polymer by using a small amount of the composite structure regulator.
(2) The method for preparing the liquid styrene-butadiene polymer can realize that the metal stripping rate is not less than 99.5 weight percent, and the residual content of metal elements in the prepared liquid styrene-butadiene polymer is not more than 200ppm.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of the invention provides a composite structure regulator, which is characterized in that the composite structure regulator comprises a component A and a component B, and the molar ratio of the component A to the component B is 6-20:1, a step of;
wherein the component A is tetrahydrofuran, and the component B is organic sodium salt and/or organic potassium salt.
In the composite structure regulator, the component A has certain regulating capability on the vinyl content of butadiene, and can regulate the sequence distribution of butadiene structural units and styrene structural units in a molecular chain, and the component B in the structure regulator can effectively regulate the sequence distribution of butadiene structural units and styrene structural units in the molecular chain, and hardly influences the vinyl content of butadiene. The two-component composite structure regulator composed of the component A and the component B is particularly beneficial to preparing the styrene-butadiene polymer with low vinyl content and random distribution.
In the invention, the component A is tetrahydrofuran, the vinyl content adjusting capability of butadiene is weak, the upper adjusting limit exists, but the side reaction is less, the industrial is easy to obtain, and the industrialization is convenient.
In the invention, the component B is organic sodium salt and/or organic potassium salt, has stronger regulating capability on butadiene and styrene monomer sequence distribution, but the organic sodium salt and the organic potassium salt are both solid, have poor solubility in nonpolar solvents, and tetrahydrofuran has certain solubility on the organic sodium salt and/or the organic potassium salt, can form a composite structure regulator, and is simple and easy to operate.
Further, the content mole ratio of the component A to the component B is 8-18:1.
Still further, the molar ratio of the component A to the component B is 10 to 16:1.
According to the invention, component B is selected from organic sodium and/or potassium salts having 1 to 18 carbon atoms.
According to the invention, the component B is at least one selected from the group consisting of sodium organic alkoxides, potassium organic alkoxides and benzenesulfonates.
According to one embodiment of the present invention, the organic sodium salt is selected from at least one of sodium tert-butoxide, sodium tert-amyl alcohol, sodium 2-hexanol, sodium menthol, sodium terpineol and sodium dodecyl benzene sulfonate.
According to one embodiment of the invention, the organic potassium salt is at least one of potassium tert-butoxide, potassium tert-amyl alcohol, potassium 2-hexanol, potassium menthol, potassium terpineol and potassium dodecylbenzenesulfonate.
In the present invention, when the organic sodium salt and the organic potassium salt of the component are selected from the above-mentioned species, there is a stronger regulatory capability for the distribution of butadiene and styrene monomer sequences.
According to one embodiment of the invention, the sodium terpineol and the potassium terpineol are prepared in a laboratory, and the preparation method comprises the following steps of:
And adding excessive metal potassium into terpineol, and filtering metal potassium residues after the reaction is finished to obtain the terpineol potassium. Wherein, the mol ratio of terpineol to metal potassium is 1:1.1-1.2.
In the present invention, the filtration may be performed in a conventional manner in the art.
In a second aspect, the invention provides the use of a composite structure modifier according to the first aspect of the invention in anionic solution polymerization.
The third aspect of the present invention provides a liquid styrene-butadiene polymer, wherein the content of block styrene in the liquid styrene-butadiene polymer is 0.1 to 1wt%, and the content of 1, 2-structure is 10 to 30wt% based on the content of butadiene structural units;
the number average molecular weight of the liquid styrene-butadiene polymer is 3000-5000.
In the present invention, the term "1, 2-structure" means a structural unit in which 1, 3-butadiene is formed in a1, 2-polymerization manner, and the content of the 1, 2-structure may also be referred to as vinyl content.
In the invention, the number average molecular weight of the liquid styrene-butadiene polymer meets the range, so that the dynamic viscosity of the liquid styrene-butadiene polymer at 25 ℃ is suitable, and the liquid styrene-butadiene polymer has better processability.
In the invention, when the content of the block styrene and the 1, 2-structure content simultaneously meet the above ranges, the liquid styrene-butadiene polymer can be better applied to the field of high-end flexible printing.
Further, in the liquid styrene-butadiene polymer, the content of the block styrene is 0.2 to 0.9 weight percent, and the content of the 1, 2-structure is 15 to 25 weight percent based on the content of the butadiene structural unit.
Further, in the liquid styrene-butadiene polymer, the block styrene content is 0.2 to 0.7wt% and the 1, 2-structure content is 17 to 23wt% based on the content of the butadiene structural unit.
According to the present invention, the number average molecular weight of the liquid styrene-butadiene polymer is 3200 to 4800, preferably 3500 to 4500.
According to the present invention, the liquid styrene-butadiene polymer has a glass transition temperature of-68℃to-60℃and preferably-62℃to-66 ℃.
According to the present invention, in the liquid styrene-butadiene polymer, the content of the styrene structural unit is 15 to 35wt% and the content of the butadiene structural unit is 65 to 85wt%.
In the invention, the inventor discovers that the higher the content of the styrene structural unit in the liquid styrene-butadiene polymer, the better the mechanical property, but the too high content of the styrene structural unit can lead the liquid styrene-butadiene polymer to lose the rubber property and be unfavorable for crosslinking and curing, so that the content of the styrene structural unit is controlled within the range of 15-35wt percent, the liquid styrene-butadiene polymer can be easily crosslinked on the premise of having good mechanical property, and can be better applied to the required field.
Further, in the liquid styrene-butadiene polymer, the content of the styrene structural unit is 18-33wt%, and the content of the butadiene structural unit is 67-82wt%.
Further, in the liquid styrene-butadiene polymer, the styrene structural unit content is 20 to 30wt% and the butadiene structural unit content is 70 to 80wt%.
According to the invention, the dynamic viscosity of the liquid styrene-butadiene polymer at 25 ℃ is 100-250 poise.
In the invention, the dynamic viscosity of the liquid styrene-butadiene polymer at 25 ℃ meets the range, so that the liquid styrene-butadiene polymer has better processability.
Further, the dynamic viscosity of the liquid styrene-butadiene polymer at 25 ℃ is 120-220 poise, more preferably 140-200 poise.
According to the present invention, the molecular weight distribution index of the liquid styrene-butadiene polymer is 1 to 1.1, preferably 1 to 1.05, more preferably 1 to 1.04.
According to the invention, the metal content in the liquid styrene-butadiene polymer is less than or equal to 200ppm.
In the invention, the metal content in the liquid styrene-butadiene polymer is controlled to meet the range, which is beneficial to preparing a colorless and transparent liquid styrene-butadiene polymer product.
Further, the metal content in the liquid styrene-butadiene polymer is less than or equal to 50ppm, preferably less than or equal to 20ppm.
According to the invention, the light transmittance of the liquid styrene-butadiene polymer is not less than 85%, preferably not less than 90%, more preferably not less than 92%.
According to the present invention, the haze of the liquid styrene-butadiene polymer is 10% or less, preferably 5% or less, more preferably 3% or less.
According to the invention, the light transmittance and the haze of the liquid styrene-butadiene polymer are controlled, so that the light transmittance of the liquid styrene-butadiene polymer is improved, the haze is reduced, the haze of the photosensitive elastomer for the flexible resin plate is further reduced, the light transmittance is improved, and the liquid styrene-butadiene polymer is better applied to the field of flexible printing.
In a fourth aspect, the present invention provides a method for preparing a liquid styrene-butadiene polymer, comprising the steps of: in a nonpolar hydrocarbon solvent, carrying out anionic polymerization on a polymerization monomer in the presence of a composite structure regulator and an initiator to obtain a liquid styrene-butadiene polymer I;
Wherein the composite structure modifier is the composite structure modifier according to the first aspect of the present invention.
In the present invention, the anionic polymerization is preferably carried out in a protective atmosphere, such as N 2.
In the present invention, the type of the nonpolar hydrocarbon solvent is not particularly limited, and may be cyclohexane, for example.
According to the invention, the component B is used in an amount of 0.03 to 0.1 mol relative to 1mol of the initiator.
In the invention, the amount of the component B satisfies the above range, and stronger vinyl content and controllability of monomer sequence distribution adjustment can be realized.
Further, the component B is used in an amount of 0.04 to 0.1 relative to 1 mole of the initiator.
According to the invention, the initiator is used in an amount of 19 to 35 millimoles, preferably 21 to 31 millimoles, relative to 100 g of the polymerized monomer.
According to the invention, the polymeric monomers are 1, 3-butadiene and styrene.
According to the invention, the initiator is an alkyl lithium initiator.
In the present invention, the initiator may be illustratively selected from at least one of n-butyllithium, sec-butyllithium, and isopropyllithium.
According to the invention, the polymerization conditions include: the temperature is 40-100deg.C, preferably 45-95deg.C; the pressure is 0.1-1MPa, preferably 0.2-0.5MPa.
In the present invention, the reaction time is not particularly limited as long as the complete conversion of the two monomers is ensured.
In the invention, the inventor finds that in the initiation process, the initiation temperature has a certain influence on the structure of the final polymer, and the invention is beneficial to random distribution of the comonomer in the molecular chain when the initiation temperature is controlled to be 0-50 ℃.
In the present invention, the initiation temperature refers to the temperature of the polymerization system when the initiator is added.
According to one embodiment of the invention, the method comprises: under the protection of nitrogen, adding cyclohexane, a composite structure regulator and a polymerization monomer in required amounts into a reactor, controlling the temperature of the reactor to be not higher than 100 ℃, adding an initiator n-butyllithium, and carrying out polymerization reaction to obtain a polymer solution.
According to the invention, the method further comprises: and mixing the liquid styrene-butadiene polymer I with an aqueous solution of acid, and separating to obtain a liquid styrene-butadiene polymer II.
In the invention, the liquid styrene-butadiene polymer I is mixed with the aqueous solution of the acid, so that the metal exists in water in the form of ions, which is favorable for the removal of the metal, and further the metal content in the liquid styrene-butadiene polymer is reduced.
In the invention, the source of the metal is the metal in the initiator.
In the present invention, in order to more facilitate the removal of metals from the initiator, according to a specific embodiment of the present invention, the step of preparing the liquid styrene-butadiene polymer II comprises:
In a nonpolar hydrocarbon solvent, carrying out anionic solution polymerization on a1, 3-butadiene monomer and a styrene monomer in the presence of a composite structure regulator and an initiator to obtain a polymer solution containing a liquid styrene-butadiene polymer I; and mixing the polymer solution containing the liquid styrene-butadiene polymer I with an aqueous solution of acid, and separating to obtain the liquid styrene-butadiene polymer II.
In the present invention, the amount of water in the aqueous acid solution is not particularly limited, and may be any amount conventionally used in the art.
According to the invention, the molar ratio of acid to initiator, calculated as H +, is 1-1.5:1, preferably 1.1-1.3:1, in order to allow more thorough metal removal.
According to one embodiment of the invention, the acid is selected from at least one of sulfuric acid, nitric acid and hydrochloric acid.
According to one embodiment of the present invention, the step of separating the liquid styrene-butadiene polymer I after mixing with the aqueous acid solution comprises: mixing the liquid styrene-butadiene polymer I with an aqueous solution of acid, stirring, standing and layering, removing the aqueous solution of the acid in the solution, and distilling under reduced pressure to obtain the liquid styrene-butadiene polymer.
In the present invention, the conditions and modes of stirring, standing and reduced pressure distillation are not particularly limited, and those commonly used in the prior art can be employed.
According to the invention, the method further comprises: and mixing the liquid styrene-butadiene polymer II with an aqueous solution of carbon dioxide, and separating to obtain a liquid styrene-butadiene polymer III.
In order to further facilitate the removal of metals from the initiator in the present invention, the step of preparing the liquid styrene-butadiene polymer III according to a preferred embodiment of the present invention comprises: in a nonpolar hydrocarbon solvent, carrying out anionic solution polymerization on a1, 3-butadiene monomer and a styrene monomer in the presence of a composite structure regulator and an initiator to obtain a polymer solution containing a liquid styrene-butadiene polymer I; mixing the polymer solution containing the liquid styrene-butadiene polymer I with an aqueous solution of acid, and separating to obtain a liquid styrene-butadiene polymer II; and mixing the liquid styrene-butadiene polymer II with an aqueous solution of carbon dioxide, and separating to obtain a liquid styrene-butadiene polymer III.
In the present invention, the amount of water in the aqueous solution of carbon dioxide is not particularly limited, and may be any amount conventionally used in the art.
According to the invention, the molar ratio of carbon dioxide to the initiator in the aqueous solution of carbon dioxide is between 0.2 and 0.5:1, preferably between 0.2 and 0.4:1.
According to the invention, the method further comprises: combining the liquid styrene-butadiene polymer III with an antioxidant to obtain a liquid styrene-butadiene polymer IV.
According to the invention, the weight ratio of the liquid styrene-butadiene polymer III to the antioxidant is 100:0.02-0.1, preferably 100:0.02-0.08.
According to the invention, the antioxidant is a hindered phenol antioxidant.
According to the present invention, the antioxidant is at least one selected from the group consisting of antioxidant 264 (2, 6-di-t-butyl-4-methylphenol), antioxidant 168 (tris [2, 4-di-t-butylphenyl ] phosphite) and antioxidant 1076 (n-octadecanol β - (3, 5-di-t-butyl-4-hydroxyphenyl) propionate).
In a fifth aspect, the present invention provides a liquid styrene-butadiene polymer, wherein the liquid styrene-butadiene polymer is produced by the method of the fourth aspect of the invention;
Wherein the liquid styrene-butadiene polymer comprises: at least one of liquid styrene-butadiene polymer I, liquid styrene-butadiene polymer II, liquid styrene-butadiene polymer III and liquid styrene-butadiene polymer IV.
According to the invention, the metal content in the liquid styrene-butadiene polymer II, the liquid styrene-butadiene polymer III and the liquid styrene-butadiene polymer IV is respectively less than or equal to 200ppm independently; preferably less than or equal to 50ppm; more preferably 20ppm or less.
According to the invention, the light transmittance of the liquid styrene-butadiene polymer II, the liquid styrene-butadiene polymer III and the liquid styrene-butadiene polymer IV is more than or equal to 85%; preferably more than or equal to 90%; more preferably not less than 92%.
The haze of the liquid styrene-butadiene polymer II, the liquid styrene-butadiene polymer III and the liquid styrene-butadiene polymer IV is less than or equal to 10%; preferably less than or equal to 5%; more preferably 3% or less.
According to a particularly preferred embodiment of the present invention, the method of preparing a liquid styrene-butadiene polymer of the present invention comprises:
(1) In a nonpolar hydrocarbon solvent, carrying out anionic solution polymerization on a1, 3-butadiene monomer and a styrene monomer in the presence of a composite structure regulator and an initiator to obtain a polymer solution containing a liquid styrene-butadiene polymer I;
(2) Mixing the polymer solution containing the liquid styrene-butadiene polymer I with an aqueous solution of acid, and separating to obtain a liquid styrene-butadiene polymer II;
(3) Mixing the liquid styrene-butadiene polymer II obtained in the step (2) with an aqueous solution of carbon dioxide, and then separating to obtain a liquid styrene-butadiene polymer III;
(4) And (3) mixing the liquid styrene-butadiene polymer III obtained in the step (3) with an antioxidant to obtain a liquid styrene-butadiene polymer IV.
Under the preferable preparation method, the method for preparing the liquid styrene-butadiene polymer provided by the invention adopts a metal removal mode of combining carbon dioxide and acid, so that the metal removal rate is not less than 99.5wt%, the residual content of metal elements can be stabilized at 200ppm or below, and preferably at 20ppm or below.
In a sixth aspect, the present invention provides a use of the liquid styrene-butadiene polymer of the third or fifth aspect of the invention in the field of flexographic printing.
The invention will be described in detail below by way of examples. In the following examples, the various raw materials used were all commercially available products without any particular limitation.
Unless otherwise specified, both the room temperature and the room temperature represent 25.+ -. 3 ℃.
In the invention, the 1, 2-structure content, the styrene structure unit content and the monomer sequence distribution in the liquid styrene-butadiene polymer are tested by a Bruker AVANCE400 type superconducting nuclear magnetic resonance apparatus (1H-NMR), the solvent is deuterated chloroform CDCl 3, the sample concentration is 15% (W/V), the testing temperature is normal temperature, the scanning times are 16 times, and the chemical displacement of tetramethylsilane is 0ppm for calibration.
In the present invention, the number average molecular weight and the molecular weight distribution index of the liquid styrene-butadiene polymer are measured by using an HLC-8320 type gel permeation chromatograph of Tosoh Corp., japan, wherein the test conditions include: the chromatographic column is TSKgel SuperMultiporeHZ-N, the standard column is TSKgel SuperMultiporeHZ, the solvent is chromatographic pure THF, the calibration standard sample is polystyrene, the mass concentration of the sample is 1mg/mL, the sample injection amount is 10 mu L, the flow rate is 0.35mL/min, and the test temperature is 40 ℃.
In the invention, the glass transition temperature is measured by adopting a differential scanning calorimetry method, and the specific test method comprises the following steps: the temperature rise rate was 20℃per minute as measured by a TA-2980DSC differential scanning calorimeter according to the method specified in "GB/T29611-2013 raw rubber, glass transition temperature".
In the present invention, the dynamic viscosity is measured by referring to the capillary method specified in GBT10247-2008, wherein the dynamic viscosity is measured at 25℃using a Ubbelohde viscometer with a size number of 4B.
In the invention, the metal removal rate is calculated by the weight ratio of the residual metal content to the initiator addition.
In the present invention, the adhesion is measured by the following method: cutting the photoelastic plate material into a sample strip with the size of 20 cm by using a cutter, then exposing the sample strip for 5min by using a flexible plate making machine, simulating plate making and ageing, and finally testing the adhesion between the photoelastic body and a support (stainless steel plate) by using an electronic peeling tester on the sample strip at 180 degrees, wherein the specific test method is referred to the GB/T2790 standard.
In the invention, the method for preparing the photosensitive elastomer plate by the liquid styrene-butadiene polymer comprises the following steps: 30 parts by weight of a styrene thermoplastic elastomer (brand 1401), 50 parts by weight of a liquid styrene-butadiene polymer, 17 parts by weight of methyl methacrylate, 1 part of 1-hydroxycyclohexyl phenyl ketone, 0.5 part of 2, 6-di-tert-butyl-p-cresol and 1.5 parts of trimethylolpropane triacrylate are added into a twin-screw extruder, and the mixture is kneaded at 135 ℃ for 5 minutes to extrude a photosensitive elastomer layer with a thickness of 2.15mm, thereby obtaining a photosensitive elastomer plate.
In the present invention, hardness refers to shore hardness (shore a) of a plate material, which is measured by the following method: the photosensitive elastomer plate is cut into 5 cm-sized sample blocks, and the hardness of the plate is tested by a hardness tester.
In the invention, the content of metal elements in the polymer is measured by adopting a plasma method, and the specific test method comprises the following steps: an optical 8300 full-spectrum direct-reading ICP spectrometer of the American Perkin Elmer (PE) company is adopted, an echelle grating, a solid-state detector, an ultraviolet light region and a visible light region double-light-path double-solid-state detector are arranged, and a flat plasma technology is adopted; the instrument operating parameters were as follows: high-frequency power 1300W, plasma air flow 15L/min, atomization air flow 0.55L/min, auxiliary air flow 0.2L/min, peristaltic pump speed 1.50mL/min, integration time 10s, and plasma axial observation. The sample preparation method is as follows: accurately weighing 2g of a sample in a porcelain crucible, placing in a high-temperature resistance furnace, gradually heating to 500 ℃, taking out after ashing is completed, adding 5mL of 10 vol% dilute nitric acid, slowly heating on an electric plate until the sample is completely dissolved, steaming the solution to be completely dry, adding 1mL of concentrated nitric acid, transferring into a 50mL volumetric flask, and fixing the volume with water to prepare a reagent blank solution.
The haze and light transmittance of the liquid styrene-butadiene rubber were measured using a YH1810 haze meter manufactured by 3nh corporation.
Experimental device and process: the experiment is carried out in a 5L polymerization reactor, solvent, butadiene and styrene monomer are added from a polymerization pipeline, an initiator and a composite structure regulator are added from the top of the polymerization reactor by adopting an injector, after polymerization is completed, the structure regulator and metals in the initiator are subjected to removal treatment, and then an optional antioxidant is added, so that the liquid styrene-butadiene polymer is obtained.
The pressures described in this experiment are all gauge pressures.
Antioxidant 264, antioxidant 168, antioxidant 1076, all purchased from national pharmaceutical agents;
Cyclohexane (CYH) is purchased from national drug reagent company, the purity is more than 99.9%, and the water content is lower than 5ppm after the molecular sieve is soaked for 15 days;
styrene (St), polymeric grade, source of crape;
butadiene (Bd), polymeric grade, source of crape;
Butyl lithium (Li) was purchased from the Barling reagent company as 100mL specification, 1.6 mol.L-1 hexane solution;
component A:
tetrahydrofuran (THF) was purchased from enoKai reagent company, 500g gauge, analytically pure;
Component B:
sodium t-amyl alcohol (STA) was purchased from carbofuran reagent company with purity > 98wt%;
potassium tert-amyl alcohol (PTA) was purchased from the carbofuran reagent company with a purity of > 98wt%;
Potassium Terpineol (PTP) was purchased from Qingshi Hua Feng reagent company with a purity of > 98wt%;
Potassium 2-hexanolate (PHA) was purchased from Qingshi Hua Feng reagent company in a purity of > 98wt%;
sodium Dodecyl Benzene Sulfonate (SDBS), purchased from national pharmaceutical and chemical reagent company, purity > 98%;
Other structure modifiers:
Ditetrahydrofurfuryl propane (DTHFP) is available from Inoki reagent company in a purity of > 98wt%;
Tetrahydrofurfuryl ethyl ether (ETE), purchased from qingkai Hua Feng reagent company, purity > 98%;
Sodium dimethylbutyl Silanol (SA), purchased from national pharmaceutical and chemical reagent company, purity > 98%;
Sulfuric acid was purchased from carbofuran reagent company at a concentration of 98wt% and was formulated with water to a 20wt% solution;
Nitric acid was purchased from national reagent company at a concentration of 68wt% and was formulated as a 20wt% solution with water.
Unless otherwise indicated, the amounts used in the examples below are all in pure form.
The following examples illustrate the preparation of liquid styrene-butadiene polymer IV
Example 1
(1) Cyclohexane, a composite structure regulator, 1, 3-butadiene and styrene (the types and the amounts are shown in table 1, the amounts are all measured by pure compounds) are added into a 5L reactor under the protection of nitrogen, the temperature in the reactor is controlled to be the polymerization temperature shown in table 1, and a preset amount of n-butyllithium is added into the reactor (the specific amounts are shown in table 1, and the amounts are all measured by pure compounds); and carrying out anionic solution polymerization at the temperature and the pressure shown in Table 1 to obtain a polymer solution containing liquid styrene-butadiene polymer I.
(2) Adding an aqueous acid solution to the polymer solution containing the liquid styrene-butadiene polymer I obtained in the step (1), wherein the amount of water is 1800g (the specific amount and the type are listed in Table 2, the amounts are all calculated by the pure compounds in Table 2), stirring for 15 minutes, standing for delamination, separating an aqueous phase, and distilling the obtained oil phase under reduced pressure to obtain the liquid styrene-butadiene polymer II.
(3) Adding 1000g of water into the liquid styrene-butadiene polymer II obtained in the step (2), introducing carbon dioxide gas (the specific dosage of the carbon dioxide aqueous solution is shown in table 2) while stirring, standing for layering, separating out an aqueous phase, and performing reduced pressure distillation on the obtained oil phase to obtain a distillation residue containing the liquid styrene-butadiene polymer III; an antioxidant (specific amounts and types are shown in Table 2) was added to the distillation residue containing the liquid styrene-butadiene polymer III to obtain a liquid styrene-butadiene polymer IV, which was designated as BS1, wherein the structural property parameters of BS1 are shown in Table 3, and the residual amounts of metal elements and the metal removal rate in the polymer are shown in Table 4.
Examples 2 to 13
The procedure of example 1 was followed except that the anionic polymerization was conducted using the parameters shown in Table 1 and Table 1 (the subsequent tables), and the metal removal treatment from the initiator was conducted using the parameters shown in Table 2, thereby obtaining liquid styrene-butadiene polymers IV, which were designated as BS2-BS13, respectively, and the structural properties were as shown in Table 3, and the amounts of metal elements remaining in the polymers and the metal removal rates thereof were as shown in Table 4.
TABLE 1
Table 1 (subsequent table)
TABLE 2
Example 14
The procedure of example 1 was followed except that the liquid styrene-butadiene polymer I was subjected to metal removal treatment with an aqueous acid solution after completion of the polymerization, and the subsequent operation was not performed, to prepare a liquid styrene-butadiene polymer II, which was designated as BS14.
Among them, the structural property parameters of BS14 are listed in table 3, and the residual amounts of metal elements in the polymers thereof and the metal removal rates are listed in table 4.
Example 15
The procedure of example 1 was followed except that the liquid styrene-butadiene polymer I was subjected to metal removal treatment with an aqueous solution of carbon dioxide after completion of the polymerization, and the subsequent operation was not performed, to prepare a liquid styrene-butadiene polymer III, which was designated as BS15.
Among them, the structural property parameters of BS15 are listed in table 3, and the residual amounts of metal elements in the polymers thereof and the metal removal rates are listed in table 4.
Comparative example 1
According to the method of example 1, except that component A was ditetrahydrofuran propane, liquid styrene-butadiene polymer DBS1 was obtained, and the structure and properties were measured, the results are shown in Table 3 and Table 4.
Comparative example 2
The procedure of example 1 was followed except that only a single structure-controlling agent, tetrahydrofuran, was used, and sodium t-amyl alcohol was not added to give liquid styrene-butadiene polymer DBS2, and the structure and properties were determined, the results of which are shown in Table 3 and Table 4.
Comparative example 3
The procedure of example 1 was followed except that only a single structure-controlling agent, sodium t-amyl alcohol, was used, and tetrahydrofuran was not added to give liquid styrene-butadiene polymer DBS3, and the structure and properties were determined, the results of which are shown in Table 3 and Table 4.
Comparative example 4
The process according to example 1, except that tetrahydrofuran is added in an amount of 8g, so that component A, component B, is 25:1, a liquid styrene-butadiene polymer DBS4 was obtained, and the structure and properties were measured, and the results are shown in Table 3 and Table 4.
Comparative example 5
The procedure of example 1 was followed except that sodium tert-amyl alcohol was added in an amount of 1.5mmol, such that component A, component B, was 37:1, a liquid styrene-butadiene polymer DBS5 was obtained, and the structure and properties were measured, and the results are shown in Table 3 and Table 4.
Comparative example 6
The procedure of example 1 is followed except that sodium tert-amyl alcohol is added in an amount of 15mmol, so that component A, component B, is 3.7:1, a liquid styrene-butadiene polymer DBS6 was obtained, and the structure and properties were measured, and the results are shown in Table 3 and Table 4.
Comparative example 7
According to the procedure of example 1, except that 4mmol of ETE (as component A) and 0.08mmol of SA (as component B) were added, the molar ratio of component A to component B was ensured to be 50:1, to obtain liquid styrene-butadiene polymer DBS7, and the results of the structure and property measurements are shown in Table 3 and Table 4.
Comparative example 8
The procedure of example 1 was followed except that 4mmol of ETE (as component A) and 0.8mmol of SA (as component B) were added to ensure that the molar ratio of component A to component B was 5:1 to give liquid styrene-butadiene polymer DBS8, and structure and property measurements were made, and the results are shown in tables 3 and 4.
Comparative example 9
According to the procedure of example 1, except that 3mmol DTHFP (as component A) and 0.0375mmol SDBS (as component B) were added to ensure a molar ratio of component A to component B of 80:1, liquid styrene-butadiene polymer DBS9 was obtained, and structure and property measurements were made, the results of which are shown in tables 3 and 4.
Comparative example 10
According to the procedure of example 1, except that 3mmol DTHFP (as component A) and 30mol SDBS (as component B) were added to ensure a molar ratio of component A to component B of 1:10, a liquid styrene-butadiene polymer DBS10 was obtained, and structural and performance measurements were made, the results of which are shown in tables 3 and 4.
TABLE 3 Table 3
TABLE 4 Table 4
| Name of the name | Hardness of | Adhesive force, N/2 cm | Transmittance of light,% | Haze, percent | Residual amount of metal element, ppm | Metal stripping rate, percent |
| BS1 | 63 | 35.6 | 93.1 | 2.4 | 7 | 99.6 |
| BS2 | 61 | 35.2 | 92.7 | 2.9 | 10 | 99.5 |
| BS3 | 63 | 35.8 | 91.9 | 3.4 | 9 | 99.4 |
| BS4 | 58 | 36.3 | 92.1 | 3.5 | 11 | 99.4 |
| BS5 | 66 | 31.7 | 91.6 | 3.8 | 12 | 99.3 |
| BS6 | 63 | 33.8 | 90.8 | 4.8 | 9 | 99.4 |
| BS7 | 60 | 32.4 | 91.4 | 4.2 | 8 | 99.5 |
| BS8 | 58 | 33.7 | 92.1 | 3.4 | 11 | 99.5 |
| BS9 | 62 | 34.2 | 90.3 | 5.2 | 14 | 99.1 |
| BS10 | 56 | 33.5 | 90.2 | 6.9 | 18 | 99.2 |
| BS11 | 64 | 31.8 | 91.7 | 5.4 | 12 | 99.2 |
| BS12 | 55 | 36.1 | 89.5 | 7.4 | 15 | 99.1 |
| BS13 | 66 | 28.6 | 87.8 | 8.6 | 26 | 98.5 |
| BS14 | 63 | 35.4 | 86.2 | 9.6 | 126 | 92.8 |
| BS15 | 63 | 35.3 | 85.3 | 9.9 | 174 | 90.1 |
| DBS1 | 50 | 38.4 | 90.8 | 5.4 | 17 | 99 |
| DBS2 | 61 | 22.6 | 80.3 | 12.7 | 54 | 96.9 |
| DBS3 | 62 | 24.8 | 84.5 | 10.6 | 22 | 98.7 |
| DBS4 | 52 | 36.7 | 91.8 | 3.3 | 12 | 99.3 |
| DBS5 | 61 | 25.8 | 89.7 | 5.8 | 18 | 98.9 |
| DBS6 | 54 | 21.7 | 90.8 | 4.7 | 14 | 99.2 |
| DBS7 | 53 | 18.4 | 76.9 | 14.8 | 86 | 95.1 |
| DBS8 | 52 | 21.9 | 80.4 | 13.2 | 64 | 96.3 |
| DBS9 | 62 | 13.6 | 71.5 | 22.8 | 184 | 89.5 |
| DBS10 | 51 | 34.6 | 87.6 | 11.3 | 37 | 97.9 |
As can be seen from the results of tables 3 and 4, the present invention can prepare a liquid styrene-butadiene polymer having a low vinyl content and having butadiene and styrene randomly distributed in the molecular chain, and when the metal in the liquid styrene-butadiene polymer is subjected to a removal treatment by a specific method, the metal content in the product is low, so that the light transmittance is good, the haze is low, and the present invention is more suitable as a raw material of a photosensitive elastomer for a flexographic resin plate.
It should be further noted that in table 3, taking BS1 and BS2 as examples, there is a small error in the content of the styrene structural unit, which is caused by a slight error in the raw materials at the time of feeding, and the content of the styrene structural unit is acceptable within the error range of 0.5%.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (19)
1. The composite structure regulator is characterized by comprising a component A and a component B, wherein the molar ratio of the component A to the component B is 6-20:1, a step of;
wherein the component A is tetrahydrofuran, and the component B is organic sodium salt and/or organic potassium salt.
2. The composite structure modifier according to claim 1, wherein the content molar ratio of the component a and the component B is 8 to 18:1, a step of;
Preferably, the molar ratio of the component A to the component B content is 10-16:1, a step of;
Preferably, the component B is selected from organic sodium salt and/or organic potassium salt with 1-18 carbon atoms;
Preferably, the component B is at least one selected from organic sodium alkoxide, organic potassium alkoxide and benzene sulfonate;
Preferably, the organic sodium salt is selected from at least one of sodium tert-butoxide, sodium tert-amyl alcohol, sodium 2-hexanol, sodium menthol, sodium terpineol and sodium dodecyl benzene sulfonate;
Preferably, the organic potassium salt is at least one of potassium tert-butoxide, potassium tert-amyl alcohol, potassium 2-hexanol, potassium menthol, potassium terpineol and potassium dodecylbenzenesulfonate.
3. Use of a composite structure modifier according to claim 1 or 2 in anionic solution polymerization.
4. A liquid styrene-butadiene polymer, characterized in that the content of block styrene in the liquid styrene-butadiene polymer is 0.1-1wt%, and the 1, 2-structure content is 10-30wt% based on the total content of butadiene structural units;
the number average molecular weight of the liquid styrene-butadiene polymer is 3000-5000.
5. The liquid styrene-butadiene polymer of claim 4, wherein the liquid styrene-butadiene polymer has a block styrene content of 0.2-0.9wt%, preferably 0.2-0.7wt%, and a 1, 2-structure content of 15-25wt%, preferably 17-23wt%, based on the total content of butadiene structural units;
Preferably, the liquid styrene-butadiene polymer has a number average molecular weight of 3200 to 4800, preferably 3500 to 4500;
Preferably, the glass transition temperature of the styrene-butadiene polymer is-68 ℃ to-60 ℃, preferably-62 ℃ to-66 ℃.
6. The liquid styrene-butadiene polymer of claim 4 or 5, wherein the content of styrene structural units in the liquid styrene-butadiene polymer is 15-35wt%, preferably 18-33wt%, more preferably 20-30wt%; the butadiene structural unit content is 65 to 85wt%, preferably 67 to 82wt%, more preferably 70 to 80wt%.
7. The liquid styrene-butadiene polymer of any one of claims 4-6, wherein the liquid styrene-butadiene polymer has a dynamic viscosity of 100-250 poise, preferably 120-220 poise, more preferably 140-200 poise at 25 ℃;
preferably, the molecular weight distribution index of the liquid styrene-butadiene polymer is 1 to 1.1, preferably 1 to 1.05, more preferably 1 to 1.04.
8. The liquid styrene-butadiene polymer of any one of claims 4-6, wherein the metal content of the liquid styrene-butadiene polymer is each independently less than or equal to 200ppm; preferably less than or equal to 50ppm; more preferably 20ppm or less;
Preferably, the transmittance of the liquid styrene-butadiene polymer is more than or equal to 85%; preferably more than or equal to 90%; more preferably not less than 92%;
preferably, the haze of the liquid styrene-butadiene polymer is less than or equal to 10%; preferably less than or equal to 5%; more preferably 3% or less.
9. A method of preparing a liquid styrene-butadiene polymer, the method comprising the steps of: in a nonpolar hydrocarbon solvent, carrying out anionic polymerization on a polymerization monomer in the presence of a composite structure regulator and an initiator to obtain a liquid styrene-butadiene polymer I;
Wherein the composite structure modulator is the composite structure modulator of claim 1 or 2.
10. The method according to claim 9, wherein the composite structure modifier is used in an amount of 6 to 20 parts by weight, preferably 8 to 18 parts by weight, more preferably 10 to 16 parts by weight, relative to 1000 parts by weight of the polymerized monomer;
preferably, the component B is used in an amount of 0.03 to 0.1 mole, preferably 0.04 to 0.1 mole, relative to 1 mole of the initiator;
preferably, the initiator is used in an amount of 19 to 35 millimoles, preferably 21 to 31 millimoles, relative to 100 grams of the polymerized monomer.
11. The method of claim 9 or 10, wherein the polymerized monomers are 1, 3-butadiene and styrene;
preferably, the initiator is an alkyl lithium initiator;
Preferably, the polymerization conditions include: the temperature is 40-100deg.C, preferably 45-95deg.C; the pressure is 0.1-1MPa, preferably 0.2-0.5MPa.
12. The method according to any one of claims 9-11, wherein the method further comprises: mixing the liquid styrene-butadiene polymer I with an aqueous solution of acid, and then separating to obtain a liquid styrene-butadiene polymer II;
Preferably, the molar ratio of acid to the initiator, calculated as H +, is 1-1.5:1, preferably 1.1-1.3:1, a step of;
Preferably, the acid is selected from at least one of sulfuric acid, nitric acid and hydrochloric acid.
13. The method of claim 12, wherein the method further comprises: mixing the liquid styrene-butadiene polymer II with an aqueous solution of carbon dioxide, and separating to obtain a liquid styrene-butadiene polymer III;
Preferably, the molar ratio of carbon dioxide to the initiator in the aqueous solution of carbon dioxide is 0.2-0.5:1.
14. The process of claim 13, further comprising combining liquid styrene-butadiene polymer III with an antioxidant to provide liquid styrene-butadiene polymer IV;
preferably, the weight ratio of the liquid styrene-butadiene polymer III to the antioxidant is 100:0.02-0.1;
preferably, the antioxidant is at least one of hindered phenol antioxidants;
preferably, the antioxidant is selected from at least one of antioxidant 264, antioxidant 168 and antioxidant 1076.
15. A liquid styrene-butadiene polymer, characterized in that it is produced by the process of any one of claims 8-13;
Wherein the liquid styrene-butadiene polymer comprises: at least one of liquid styrene-butadiene polymer I, liquid styrene-butadiene polymer II, liquid styrene-butadiene polymer III and liquid styrene-butadiene polymer IV.
16. The liquid styrene-butadiene polymer of claim 15, wherein the metal content in the liquid styrene-butadiene polymer II, the liquid styrene-butadiene polymer III, and the liquid styrene-butadiene polymer IV are each independently less than or equal to 200ppm; preferably less than or equal to 50ppm; more preferably 20ppm or less.
17. The liquid styrene-butadiene polymer of claim 15 or 16, wherein the light transmittance of the liquid styrene-butadiene polymer II, the liquid styrene-butadiene polymer III, and the liquid styrene-butadiene polymer IV is greater than or equal to 85%; preferably more than or equal to 90%; more preferably not less than 92%.
18. The liquid styrene-butadiene polymer of any one of claims 15-17, wherein the haze of the liquid styrene-butadiene polymer II, the liquid styrene-butadiene polymer III, and the liquid styrene-butadiene polymer IV is less than or equal to 10%; preferably less than or equal to 5%; more preferably 3% or less.
19. Use of the liquid styrene-butadiene polymer of any one of claims 4-8 or 15-18 in the field of flexographic printing.
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