CN107446081A - The preparation method of block copolymer - Google Patents
The preparation method of block copolymer Download PDFInfo
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- CN107446081A CN107446081A CN201710658365.7A CN201710658365A CN107446081A CN 107446081 A CN107446081 A CN 107446081A CN 201710658365 A CN201710658365 A CN 201710658365A CN 107446081 A CN107446081 A CN 107446081A
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- Prior art keywords
- block copolymer
- preparation
- xanthate
- copolymer according
- acrylate
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- 229920001400 block copolymer Polymers 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229940117958 vinyl acetate Drugs 0.000 claims abstract description 35
- 239000012991 xanthate Substances 0.000 claims abstract description 30
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 claims abstract description 22
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 12
- 238000005286 illumination Methods 0.000 claims abstract description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 10
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- -1 alkene ester Chemical class 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 238000012546 transfer Methods 0.000 claims description 6
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 5
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims description 5
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 5
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- 230000002441 reversible effect Effects 0.000 claims description 4
- 159000000000 sodium salts Chemical class 0.000 claims description 4
- LXXNWCFBZHKFPT-UHFFFAOYSA-N Ethyl 2-mercaptopropionate Chemical compound CCOC(=O)C(C)S LXXNWCFBZHKFPT-UHFFFAOYSA-N 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000013467 fragmentation Methods 0.000 claims description 3
- 238000006062 fragmentation reaction Methods 0.000 claims description 3
- ARFLASKVLJTEJD-UHFFFAOYSA-N ethyl 2-bromopropanoate Chemical compound CCOC(=O)C(C)Br ARFLASKVLJTEJD-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims 2
- XQJYPXKBAKQPOH-UHFFFAOYSA-N [S].ClC1=CC=C(C=C1)F Chemical compound [S].ClC1=CC=C(C=C1)F XQJYPXKBAKQPOH-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 239000000178 monomer Substances 0.000 abstract description 20
- 238000000034 method Methods 0.000 abstract description 13
- 238000012712 reversible addition−fragmentation chain-transfer polymerization Methods 0.000 abstract description 10
- 230000009257 reactivity Effects 0.000 abstract description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical group CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 26
- 229920000642 polymer Polymers 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 239000003153 chemical reaction reagent Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 150000003254 radicals Chemical class 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229920002689 polyvinyl acetate Polymers 0.000 description 3
- 239000011118 polyvinyl acetate Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 150000007970 thio esters Chemical class 0.000 description 2
- 238000011426 transformation method Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- AISZNMCRXZWVAT-UHFFFAOYSA-N 2-ethylsulfanylcarbothioylsulfanyl-2-methylpropanenitrile Chemical compound CCSC(=S)SC(C)(C)C#N AISZNMCRXZWVAT-UHFFFAOYSA-N 0.000 description 1
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000012988 Dithioester Substances 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000012987 RAFT agent Substances 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- PVEOYINWKBTPIZ-UHFFFAOYSA-N but-3-enoic acid Chemical compound OC(=O)CC=C PVEOYINWKBTPIZ-UHFFFAOYSA-N 0.000 description 1
- FXBZWPXBAZFWIY-UHFFFAOYSA-N butyl prop-2-enoate;ethenyl acetate Chemical compound CC(=O)OC=C.CCCCOC(=O)C=C FXBZWPXBAZFWIY-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000012711 chain transfer polymerization Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N deuterated chloroform Substances [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- 125000005022 dithioester group Chemical group 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000005909 ethyl alcohol group Chemical group 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000007539 photo-oxidation reaction Methods 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000004936 stimulating effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/02—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C329/00—Thiocarbonic acids; Halides, esters or anhydrides thereof
- C07C329/12—Dithiocarbonic acids; Derivatives thereof
- C07C329/14—Esters of dithiocarbonic acids
- C07C329/16—Esters of dithiocarbonic acids having sulfur atoms of dithiocarbonic groups bound to acyclic carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F218/02—Esters of monocarboxylic acids
- C08F218/04—Vinyl esters
- C08F218/08—Vinyl acetate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2438/00—Living radical polymerisation
- C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
Abstract
The present invention relates to a kind of preparation method of block copolymer, comprise the following steps：By acrylate and vinylacetate in the presence of xanthate, Invertible ideal is carried out under light illumination, obtains block copolymer.The method of the present invention, using the difference of the reactivity ratio of polymerized monomer, prepare that molecular weight is controllable using light-initiated RAFT polymerization one kettle ways, the narrower block copolymer of molecular weight distribution.
Description
Technical field
The present invention relates to field of macromolecule polymerization, more particularly to a kind of preparation method of block copolymer.
Background technology
Reversible addion-fragmentation chain transfer (Reversible Addition-Fragmentation Chain Transfer,
RAFT) polymerization is one of method maximally efficient in controllable free-radical polymerisation, and what this method can realize most monomers can
Control polymerization.Compared with traditional thermal initiation RAFT polymerizations, light-initiated RAFT polymerizations are gentle with reaction condition, and side reaction is few, ring
The advantages that border close friend.At present, light-initiated RAFT polymerizations mainly pass through additional photochemical catalyst (including light trigger or photooxidation
Change reducing agent) trigger polymerization-filling, or the photodestruciton generation free radical initiation polymerization-filling of RAFT reagents is utilized, and the latter
Without extra catalyst light-initiated RAFT polymerization have it is easy to operate, without expensive catalyst, prepare resulting polymers
End group functionality it is high, many advantages, such as system is free of metal, thus this method have possess good prospects for commercial application and
Researching value.
Traditional system that free radical is produced using the photodestruciton of RAFT reagents is carried out generally under conditions of ultraviolet radiation,
But there is this method light source to be not easy to obtain, the shortcomings of RAFT reagents are perishable to ultraviolet-sensitive.
Vinylacetate (VAc) is a kind of common free yl polymerizating monomer, both can with autohemagglutination can also and other monomers
Copolymerization, so as to prepare many high polymer materials with property.The good, adhesive force of polyvinyl acetate (PVAc) elasticity
By force, it is widely used in the industries such as coating, adhesive, paper, leather.In addition, the poly-vinegar of some or all of hydrolysis
Product-polyvinyl alcohol (PVA) of vinyl acetate is even more a kind of environment-friendly, water-soluble, nontoxic and poly- with biocompatibility
Compound material.But the double bond of vinylacetate (VAc) is connected with electron-donating group, make its abnormal free radical active, in polymerization
Chain tra nsfer and chain termination reaction easily occurs, so, realizing VAc controllable polymerization just becomes the difficulty of macromolecule worker
Topic.
Up to the present, in several " activity "/controllable free radical polymerization process, RAFT polymerizations are to realize vinylacetate
(VAc) polymerization maximally efficient in controllable polymerization.In conventional RAFT reagents, double thioester compounds
(dithioester) it is chain-transferring agent the most frequently used in RAFT polymerization systems, but uses it for Polymerization of Vac
When but inhibited completely.This is due to the energy of its stable addition free radical when the Z group in double thioesters is phenyl or alkyl
Power is stronger, only advantageously forms the addition free radical of no growing ability, but brings it about and is broken and discharges becoming for R free radicals
Potential drop is low.
Block copolymer is in chemistry, physics, material science, plays the role of in biology and medicine and pharmacology important.Especially
Be in drug delivery, surface modification, solar cell, be even more in terms of nano-reactor and stimulating responsive material have it is many
Using.Generally preparing the method for block copolymer includes sequence charging method, mechanism transformation method and polymer coupling method etc..Sequence
Charging method refers to add second of monomer after first paragraph polymerized monomer completely polymerization, after second segment polymer is formed, led to
Cross isolated block copolymer.Mechanism transformation method is embedding so as to prepare by two kinds of different mechanisms of polymerization progress polymerisations
Section copolymer.Coupling method is to carry out coupling reaction by the functional group between two sections of polymer residences so as to prepare block copolymer.
Therefore, sequence charging method or coupling can only be passed through for two kinds of monomers of mechanism of polymerization identical, the preparation of its block copolymer
Prepared by method, and both approaches are required for first carrying out the preparation of single polymers, then could prepare block copolymer.
The content of the invention
In order to solve the above technical problems, it is an object of the invention to provide a kind of preparation method of block copolymer, using poly-
The difference of the reactivity ratio of monomer is closed, prepares that molecular weight is controllable, and molecular weight distribution is narrower using light-initiated RAFT polymerization one kettle ways
Block copolymer.
The invention provides a kind of preparation method of block copolymer, comprise the following steps：
By acrylate and vinylacetate (VAc) in the presence of xanthate, carried out under the irradiation of light source reversible
Addition-fracture chain transfer polymerization, obtains the block copolymer.
Further, acrylate is n-butyl acrylate (BA), tert-butyl acrylate (t-BA), ethyl acrylate
(EA), the one or more in methyl acrylate (MA) and N-isopropylacrylamide (NiPAM).
Further, xanthate be oxygen-(ethyl)-sulphur-(2- ethyl propionates base) two thio-xanthates (EXEP),
Oxygen-(methyl)-sulphur-(2- ethyl propionates base) two thio-xanthates (MXEP), oxygen-(phenyl)-sulphur-(2- ethyl propionates base)
In two thio-xanthates (PXEP) and oxygen-(4- fluorophenyls)-sulphur-(2- ethyl propionates base) two thio-xanthates (FPXEP)
One or more.The Z group of xanthate is alkoxy or aryl.
Further, the structural formula of xanthate is
Further, the mol ratio of acrylate, vinylacetate and xanthate is 200:100-400:1.Preferably,
The mol ratio of acrylate, vinylacetate and xanthate is 200:100:1,200:200:1 or 200:400:1.
Further, wavelength is used to carry out illumination for 256-420nm light source.
Further, it is polymerize at 0-100 DEG C.Reaction does not need solvent above.
Further, polymerization time 5-420min.Preferably, polymerization time 20-420min.
Further, comprise the following steps for the xanthate that Z group is alkoxy, its preparation method：
Sodium salt is prepared using alcohol and sodium hydroxide, carbon disulfide and 2 bromopropionic acid ethyl ester are then sequentially added, after reaction
Obtain xanthate.
Further, alcohol is methanol or ethanol.
Further, comprise the following steps for the xanthate that Z group is aryl, its preparation method：
First with mercaptopropionic acid ethyl ester and sodium hydroxide generation sodium salt, phenylchloride thiocarboxylic or 4- fluorophenyls are added
Chlorine thiocarboxylic is reacted, and obtains xanthate.
The present invention uses xanthate in RAFT polymerizations, plays a part of initiator and chain-transferring agent, double with others
The difference of thioesters class chain transfer agents is：The Z group of xanthate and carbon atom in carbon sulphur double bond be joined directly together for oxygen it is former
Son, this change add xanthate free radical center charge density, so that the breakdown rate of addition free radical is accelerated, oxygen
The carbon sulphur double bond of atom and product after fracture is conjugated, and adds the stability of cleavage product, can be used for regulating and controlling acetic acid second
The RAFT polymerizations of the low activity class monomer such as alkene ester.However, this activated carbon sulphur double bond, relative to more inactive acrylic acid
For esters free radical, its chain transfer ability is weaker, it is meant that xanthate is poor to acrylic ester monomer control, less
Chain transfer reaction the chain propagation reaction of acrylate is increased, improve rate of polymerization.Therefore, using vinylacetate with
The bigger difference of the reactivity ratio of acrylate, it means that when two kinds of monomers by it is free-radical polymerized when, acrylate will be quick
Run out of, so as to prepare the block copolymer of vinylacetate and acrylate using one kettle way.
By such scheme, the present invention at least has advantages below：
It is one under the irradiation of visible ray using monomer reactivity ratio difference by RAFT reagents (effect of xanthate)
Pot prepares molecular weight and the controllable vinylacetate butyl acrylate blocks copolymer of molecular weight distribution provides a kind of having for row
The method of effect.
Described above is only the general introduction of technical solution of the present invention, in order to better understand the technological means of the present invention,
And can be practiced according to the content of specification, below with presently preferred embodiments of the present invention and coordinate accompanying drawing describe in detail as after.
Brief description of the drawings
Fig. 1 is in the embodiment of the present invention 1, and RAFT reagent Es XEP nucleus magnetic hydrogen spectrum characterizes；
Fig. 2 be the embodiment of the present invention 2 in, [BA]0:[VAc]0:[EXEP]0=200:100:Under the conditions of 1 monomer conversion with
The change curve of time；
Fig. 3 be the embodiment of the present invention 2 in, [BA]0:[VAc]0:[EXEP]0=200:100:Dynamics under the conditions of 1 is bent
Line；
Fig. 4 be the embodiment of the present invention 2 in, [BA]0:[VAc]0:[EXEP]0=200:200:Under the conditions of 1 monomer conversion with
The change curve of time；
Fig. 5 be the embodiment of the present invention 2 in, [BA]0:[VAc]0:[EXEP]0=200:200:Dynamics under the conditions of 1 is bent
Line；
Fig. 6 be the embodiment of the present invention 2 in, [BA]0:[VAc]0:[EXEP]0=200:400:Under the conditions of 1 monomer conversion with
The change curve of time；
Fig. 7 be the embodiment of the present invention 2 in, [BA]0:[VAc]0:[EXEP]0=200:400:Dynamics under the conditions of 1 is bent
Line.
Embodiment
With reference to the accompanying drawings and examples, the embodiment of the present invention is described in further detail.Implement below
Example is used to illustrate the present invention, but is not limited to the scope of the present invention.
In following examples, method of testing is as follows：
(1) nucleus magnetic hydrogen spectrum (1H NMR) it is by Bruker 300MHz nuclear magnetic resonance spectrometers, by sample to be tested with CDCl3For solvent,
Tetramethylsilane (TMS) is to be tested after internal standard dissolves；
(2) the molecular weight and molecualr weight distribution index test of polymer：Use Agilent PL-50 gel permeation chrommatographs
(GPC) determine, using differential refraction detector PL mixed gel columns D (5 μm of beads size), the molecular weight ranges of pillar are
200-4×105G/mol, using THF as mobile phase, flow velocity 1.0mLmin-1, with PL-AS RT automatic sampler sample introductions, 40
DEG C measure, molecular weight with polymethyl methacrylate standard specimen calculate.
The xanthate EXEP of embodiment 1 synthesis
40mL absolute ethyl alcohols, sodium hydroxide (4g, 0.1mol), stirring are added into the 150mL round-bottomed flasks equipped with magneton
It is completely dissolved to solid, carbon disulfide (20mL, 0.33mmol) is added dropwise, continues stirring 30 minutes, then 2- bromines are added dropwise
Ethyl propionate (15g, 0.08mmol), reaction 30 minutes is stirred at room temperature.Solvent is spin-dried for after the completion of reaction, adds 100mL water
Dilution, extracted with 100mL ethyl acetate.Organic phase is dried with anhydrous magnesium sulfate.Yellow liquid product must be obtained after removing solvent, i.e.,
For EXEP, product is kept in dark place standby in refrigerator.Fig. 1 is RAFT reagent Es XEP nucleus magnetic hydrogen spectrum in the embodiment of the present invention 1
Characterization result, group also marks in figure corresponding to each peak, illustrates that the present embodiment has successfully obtained EXEP.
The route of reaction is as follows above：
Embodiment 2
Monomer BA and VAc are added in 25mL Schlenk pipes by different proportion, while use EXEP to be tried as RAFT
Agent, wherein, BA, VAc and EXEP initial molar ratio ([BA]0:[VAc]0:[EXEP]0) it is respectively 200:100:1,200:
200:1,200:400:1, be 5mL as standard using monomer BA).Through liquid nitrogen frozen-vacuumize-nitrogen charging circulate 3 times, then in vacuum
Tube sealing under state.Schlenk pipes are put under the purple LED for setting temperature (25 DEG C) in advance and reacted.By different reactions
After time, block copolymer is obtained, a large amount of n-hexanes are added dropwise to after resulting polymers are dissolved in tetrahydrofuran and are precipitated,
Pure polymer is obtained after products therefrom drying will be filtered.Product is tested, as a result as shown in table 1-3.Wherein, table 1-3
Respectively [BA]0:[VAc]0:[EXEP]0=200:100:1、200:200:1、200:400:Under conditions of 1, different polymerization times
Polymerization result.In above reaction system, the reactivity ratio r of vinylacetate1=0.018, the reactivity ratio r of acrylic acid2=
3.48。
Polymerization temperature is changed to 100 DEG C, [BA]0:[VAc]0:[EXEP]0=200:200:1,4 are the results are shown in Table, therefrom can be with
Find out under the conditions of its polymerization behavior and 25 DEG C slightly difference, but remain to form block copolymer.
Table 1 [BA]0:[VAc]0:[EXEP]0=200:100:Polymerization result under the conditions of 1
Table 2 [BA]0:[VAc]0:[EXEP]0=200:200:Polymerization result under the conditions of 1
Table 3 [BA]0:[VAc]0:[EXEP]0=200:400:Polymerization result under the conditions of 1
Table 4 [BA]0:[VAc]0:[EXEP]0=200:200:Polymerization result under the conditions of 1,100 DEG C
In table, Conversion% represents conversion ratio (%), and Time represents reaction time, Mn,thRepresentation theory molecular weight,
Mn,GPCGPC test molecule amounts are represented,Represent molecular weight distribution.It can be seen that from result above, butyl acrylate is in the short period
Interior to can reach larger conversion ratio, after butyl acrylate reacts completely completely, vinylacetate is only a small amount of to participate in reaction,
Subsequent vinylacetate continues to polymerize, and second segment polyvinyl acetate is formed, so as to form block copolymer.Survey molecular weight with
There is certain gap in theoretical molecular, this is due to that standard specimen has certain error with sample used in test.In addition, can from form
To find out that the final gained block copolymer amount for preparing is distributed in 1.30 or so, illustrate that this method successfully prepares molecular weight distribution
Controllable block copolymer.
Can more intuitively it find out from Fig. 2-7, butyl acrylate speed is far longer than Polymerization of Vac speed, makes
One kettle way prepares block copolymer and is possibly realized.
Embodiment 3
10mL water is added into the 25mL round-bottomed flasks equipped with magneton, sodium hydroxide (0.4g, 10mmol), is stirred to solid
It is completely dissolved, adds ethyl 2-mercaptopropionate (0.83g, 6.2mmoL), stir half an hour, adds phenylchloride thiocarboxylic
(0.86g, 5mmoL), continue stirring three hours.Reaction adds the dilution of 50mL water after terminating, extracted with 100mL ethyl acetate, does
Revolving removes solvent after dry, and crude product is with petroleum ether:Ethyl acetate=20:1 is that solvent carries out column chromatography for separation, and product is Huang
Color oily liquids, as PXEP.
The route of reaction is as follows above：
Monomer BA and VA are added in 25mL Schlenk pipes, while use PXEP as RAFT reagents, wherein, BA,
VAc and PXEP initial molar ratio ([BA]0:[VAc]0:[PXEP]0) it is 200:100:1, be 5mL as standard using monomer BA).
Through liquid nitrogen frozen-vacuumize-nitrogen charging circulates 3 times, then tube sealing under vacuum conditions.Schlenk pipes are put into and set temperature in advance
Spend under the ultraviolet light or visible ray (wavelength 256-420nm) of (25 DEG C) and react, after reacting 7h, block copolymer is obtained, by institute
Polymer dissolve in tetrahydrofuran after be added dropwise to a large amount of n-hexanes and precipitated, will filter obtained after products therefrom is dried it is pure
Polymer.
More than react in, BA polymerized monomers can also be replaced with tert-butyl acrylate (t-BA), ethyl acrylate (EA),
One or more in methyl acrylate (MA) and N-isopropylacrylamide (NiPAM), are reacted as stated above.Reaction
Time can continue to extend.
Described above is only the preferred embodiment of the present invention, is not intended to limit the invention, it is noted that for this skill
For the those of ordinary skill in art field, without departing from the technical principles of the invention, can also make it is some improvement and
Modification, these improvement and modification also should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of block copolymer, it is characterised in that comprise the following steps：
By acrylate and vinylacetate in the presence of xanthate, reversible addion-fragmentation chain transfer is carried out under light illumination
Polymerization, obtains the block copolymer.
2. the preparation method of block copolymer according to claim 1, it is characterised in that：The acrylate is acrylic acid
One or more in N-butyl, tert-butyl acrylate, ethyl acrylate, methyl acrylate and N-isopropylacrylamide.
3. the preparation method of block copolymer according to claim 1, it is characterised in that：The xanthate is oxygen-(second
Base)-sulphur-(2- ethyl propionates base) two thio-xanthates, oxygen-(methyl)-sulphur-(2- ethyl propionates base) two Thioxanthates
Ester, oxygen-(phenyl)-sulphur-(2- ethyl propionates base) two thio-xanthates and oxygen-(4- fluorophenyls)-sulphur-(2- ethyl propionates base)
One or more in two thio-xanthates.
4. the preparation method of block copolymer according to claim 1, it is characterised in that：The acrylate, acetic acid second
The mol ratio of alkene ester and xanthate is 200:100-400:1.
5. the preparation method of block copolymer according to claim 1, it is characterised in that：Wavelength is used as 256-420nm
Light source carry out illumination.
6. the preparation method of block copolymer according to claim 1, it is characterised in that：It is polymerize at 0-100 DEG C.
7. the preparation method of block copolymer according to claim 1, it is characterised in that：Polymerization time is 5-420min.
8. the preparation method of block copolymer according to claim 1, it is characterised in that be alkoxy for Z group
Xanthate, its preparation method comprise the following steps：
Sodium salt is prepared using alcohol and sodium hydroxide, carbon disulfide and 2 bromopropionic acid ethyl ester is then sequentially added, is obtained after reaction
The xanthate.
9. the preparation method of block copolymer according to claim 8, it is characterised in that：The alcohol is methanol or ethanol.
10. the preparation method of block copolymer according to claim 1, it is characterised in that for the Huang that Z group is aryl
Ortho esters, its preparation method comprise the following steps：
First with mercaptopropionic acid ethyl ester and sodium hydroxide generation sodium salt, phenylchloride thiocarboxylic or 4- fluorophenyl chlorine sulphur are added
Subtituted acid ester is reacted, and obtains the xanthate.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109651575A (en) * | 2018-12-17 | 2019-04-19 | 南京邮电大学 | A kind of multiple tooth sulfydryl Amphipathilic block polymer and preparation method thereof |
| CN110028638A (en) * | 2019-04-29 | 2019-07-19 | 苏州大学 | Illumination RAFT polymerization prepares the block copolymer of different activities monomer |
| CN111138578A (en) * | 2019-12-31 | 2020-05-12 | 苏州雄鹰笔墨新材料有限公司 | Hyperbranched polyvinyl acetate and high-stability writing ink based on same |
| CN111285983A (en) * | 2020-03-10 | 2020-06-16 | 苏州大学 | High/low activity monomer block copolymer and preparation method thereof |
| CN111303326A (en) * | 2020-04-09 | 2020-06-19 | 中国科学技术大学 | Polyolefin material with controllable degradation units and high monomer utilization rate and preparation method thereof |
| CN111732683A (en) * | 2020-07-20 | 2020-10-02 | 南昌师范学院 | Method for preparing water-soluble PVA resin by photoinduction-reversible addition fragmentation chain transfer polymerization |
| CN113831561A (en) * | 2021-09-08 | 2021-12-24 | 长春工业大学 | Preparation method of hydrophilic controllable polylactic acid film |
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| CN109651575A (en) * | 2018-12-17 | 2019-04-19 | 南京邮电大学 | A kind of multiple tooth sulfydryl Amphipathilic block polymer and preparation method thereof |
| CN109651575B (en) * | 2018-12-17 | 2021-05-11 | 南京邮电大学 | Multidentate sulfhydryl amphiphilic block polymer and preparation method thereof |
| CN110028638A (en) * | 2019-04-29 | 2019-07-19 | 苏州大学 | Illumination RAFT polymerization prepares the block copolymer of different activities monomer |
| CN110028638B (en) * | 2019-04-29 | 2021-07-20 | 苏州大学 | Preparation of block copolymer of different active monomers by using illumination RAFT polymerization method |
| CN111138578A (en) * | 2019-12-31 | 2020-05-12 | 苏州雄鹰笔墨新材料有限公司 | Hyperbranched polyvinyl acetate and high-stability writing ink based on same |
| CN111138578B (en) * | 2019-12-31 | 2022-06-28 | 苏州雄鹰笔墨新材料有限公司 | Hyperbranched polyvinyl acetate and high-stability writing ink based on same |
| CN111285983A (en) * | 2020-03-10 | 2020-06-16 | 苏州大学 | High/low activity monomer block copolymer and preparation method thereof |
| CN111285983B (en) * | 2020-03-10 | 2023-01-17 | 苏州大学 | High/low activity monomer block copolymer and preparation method thereof |
| CN111303326A (en) * | 2020-04-09 | 2020-06-19 | 中国科学技术大学 | Polyolefin material with controllable degradation units and high monomer utilization rate and preparation method thereof |
| CN111732683A (en) * | 2020-07-20 | 2020-10-02 | 南昌师范学院 | Method for preparing water-soluble PVA resin by photoinduction-reversible addition fragmentation chain transfer polymerization |
| CN113831561A (en) * | 2021-09-08 | 2021-12-24 | 长春工业大学 | Preparation method of hydrophilic controllable polylactic acid film |
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