CN116375917A - High isotacticity high molecular weight polyvinyl alcohol and preparation method thereof - Google Patents
High isotacticity high molecular weight polyvinyl alcohol and preparation method thereof Download PDFInfo
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- CN116375917A CN116375917A CN202310499354.4A CN202310499354A CN116375917A CN 116375917 A CN116375917 A CN 116375917A CN 202310499354 A CN202310499354 A CN 202310499354A CN 116375917 A CN116375917 A CN 116375917A
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- lithium
- polyvinyl alcohol
- vinyl
- isotacticity
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- 239000004372 Polyvinyl alcohol Substances 0.000 title claims abstract description 62
- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000000178 monomer Substances 0.000 claims abstract description 41
- 229920001567 vinyl ester resin Polymers 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 21
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 18
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 18
- 238000010526 radical polymerization reaction Methods 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- -1 aldehyde compounds Chemical class 0.000 claims abstract description 10
- 230000003993 interaction Effects 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- 238000007259 addition reaction Methods 0.000 claims abstract description 5
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 5
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 43
- 239000003999 initiator Substances 0.000 claims description 29
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 27
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 25
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 229920001290 polyvinyl ester Polymers 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 12
- 238000001556 precipitation Methods 0.000 claims description 11
- 238000006136 alcoholysis reaction Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 8
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 150000002978 peroxides Chemical class 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 6
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 6
- 150000000180 1,2-diols Chemical class 0.000 claims description 5
- 238000009826 distribution Methods 0.000 claims description 5
- YCUBDDIKWLELPD-UHFFFAOYSA-N ethenyl 2,2-dimethylpropanoate Chemical compound CC(C)(C)C(=O)OC=C YCUBDDIKWLELPD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- VFXXTYGQYWRHJP-UHFFFAOYSA-N 4,4'-azobis(4-cyanopentanoic acid) Chemical compound OC(=O)CCC(C)(C#N)N=NC(C)(CCC(O)=O)C#N VFXXTYGQYWRHJP-UHFFFAOYSA-N 0.000 claims description 3
- RTANHMOFHGSZQO-UHFFFAOYSA-N 4-methoxy-2,4-dimethylpentanenitrile Chemical compound COC(C)(C)CC(C)C#N RTANHMOFHGSZQO-UHFFFAOYSA-N 0.000 claims description 3
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical group [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 3
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- ZBGRMWIREQJHPK-UHFFFAOYSA-N ethenyl 2,2,2-trifluoroacetate Chemical compound FC(F)(F)C(=O)OC=C ZBGRMWIREQJHPK-UHFFFAOYSA-N 0.000 claims description 3
- WNMORWGTPVWAIB-UHFFFAOYSA-N ethenyl 2-methylpropanoate Chemical compound CC(C)C(=O)OC=C WNMORWGTPVWAIB-UHFFFAOYSA-N 0.000 claims description 3
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 claims description 3
- GFJVXXWOPWLRNU-UHFFFAOYSA-N ethenyl formate Chemical compound C=COC=O GFJVXXWOPWLRNU-UHFFFAOYSA-N 0.000 claims description 3
- BLZSRIYYOIZLJL-UHFFFAOYSA-N ethenyl pentanoate Chemical compound CCCCC(=O)OC=C BLZSRIYYOIZLJL-UHFFFAOYSA-N 0.000 claims description 3
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- 239000004289 sodium hydrogen sulphite Substances 0.000 claims description 3
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 3
- NMOALOSNPWTWRH-UHFFFAOYSA-N tert-butyl 7,7-dimethyloctaneperoxoate Chemical compound CC(C)(C)CCCCCC(=O)OOC(C)(C)C NMOALOSNPWTWRH-UHFFFAOYSA-N 0.000 claims description 3
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 3
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 238000009776 industrial production Methods 0.000 abstract description 5
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 abstract description 3
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 abstract description 3
- 238000006011 modification reaction Methods 0.000 abstract description 3
- 229920002554 vinyl polymer Polymers 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 45
- 229920002689 polyvinyl acetate Polymers 0.000 description 12
- 239000011118 polyvinyl acetate Substances 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 11
- 229910013684 LiClO 4 Inorganic materials 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 238000005481 NMR spectroscopy Methods 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 230000007246 mechanism Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 230000004913 activation Effects 0.000 description 5
- 150000003254 radicals Chemical group 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- GRONZTPUWOOUFQ-UHFFFAOYSA-M sodium;methanol;hydroxide Chemical compound [OH-].[Na+].OC GRONZTPUWOOUFQ-UHFFFAOYSA-M 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- 241000255969 Pieris brassicae Species 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- HUZGVWOWOKGSDK-UHFFFAOYSA-N 1,2,2-trifluoroethenyl acetate Chemical compound CC(=O)OC(F)=C(F)F HUZGVWOWOKGSDK-UHFFFAOYSA-N 0.000 description 1
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 150000001723 carbon free-radicals Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- VILAVOFMIJHSJA-UHFFFAOYSA-N dicarbon monoxide Chemical group [C]=C=O VILAVOFMIJHSJA-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229920001580 isotactic polymer Polymers 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000012788 optical film Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 230000001902 propagating effect Effects 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 230000000707 stereoselective effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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Classifications
-
- 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
- C08F118/00—Homopolymers 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
- C08F118/02—Esters of monocarboxylic acids
- C08F118/04—Vinyl esters
- C08F118/08—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
- 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
- C08F8/00—Chemical modification by after-treatment
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to the field of polyvinyl alcohol materials, in particular to high-isotacticity high-molecular-weight polyvinyl alcohol and a preparation method thereof, wherein the preparation method comprises the following steps: in the free radical polymerization reaction of vinyl ester monomers, taking metal lithium salt as a control reagent, and performing ion-pi interaction with the vinyl ester monomers to enable the vinyl ester monomers to perform dominant orientation addition reaction in chain growth to generate high-isotacticity high-molecular-weight polyvinyl alcohol; wherein the number average molecular weight of the polyvinyl alcohol is not less than 80000g/mol, and the isotacticity is not less than 23% at the highest. The preparation method provided by the invention has the advantages of simple production process and easiness in realizing industrial production, and the polyvinyl alcohol with the characteristics of high molecular weight and high isotacticity can be prepared by the method, so that post-modification reaction is facilitated, and particularly, meso-acetal reaction is carried out with aldehyde compounds, thereby obtaining a high-quality polyvinyl acetal product, and the method is applied to the automobile and building industries.
Description
Technical Field
The invention relates to the field of polyvinyl alcohol materials, in particular to high-isotacticity high-molecular-weight polyvinyl alcohol and a preparation method thereof.
Background
Polyvinyl alcohol (PVA) is an important synthetic polymer material, has the characteristics of good solubility, degradability, biocompatibility, barrier property and the like, and has wide application in a plurality of fields such as packaging materials, medical supplies, textiles, food industry, construction, medicine, electronics and the like.
The conventional polyvinyl alcohol is a random polymer, and is produced by using vinyl acetate as a raw material, obtaining polyvinyl acetate through a free radical polymerization reaction, and removing acetic acid groups through an alcoholysis reaction to finally obtain the polyvinyl alcohol. However, in recent years, researchers have been focusing on synthesizing PVA having a stereoregular structure. This is because many physicochemical properties of PVA, such as heat resistance, hot water resistance, tensile strength and elastic modulus, are greatly affected by a fine change in the main chain stereospecificity.
At present, some methods have been reported in the literature to realize regulation and control on the stereoregularity of PVA, such as polymerization of monomer with larger volume, for example, trifluorovinyl acetate, vinyl pivalate and the like, and to obtain syndiotactic structured high-regularity PVA; the stereoregularity of PVA is controlled by introducing chiral auxiliary agents such as chiral ligands, chiral catalysts and the like and catalysts with special spatial structures. However, these methods have limitations in practical applications, such as the need to use expensive monomers or catalyst aids, severe operating conditions, and difficulty in large-scale application. Therefore, the method is more economical, efficient, simple and convenient, is favorable for realizing industrialization, synthesizes the PVA with high isotacticity and high molecular weight, and is very important for improving the performance of the PVA and expanding PVA products.
Disclosure of Invention
Based on the above, the invention provides a preparation method of high-isotacticity high-molecular-weight polyvinyl alcohol, which has the characteristics of high molecular weight and high isotacticity, and the preparation method has the advantages of simple production process and easy realization of industrial production.
According to a first aspect of the present invention, there is provided a process for the preparation of highly isotactic high molecular weight polyvinyl alcohol comprising:
in the free radical polymerization reaction of vinyl ester monomers, taking metal lithium salt as a control reagent, and performing ion-pi interaction with the vinyl ester monomers to enable the vinyl ester monomers to perform dominant orientation addition reaction in chain growth to generate the high-isotacticity high-molecular-weight polyvinyl alcohol;
wherein the number average molecular weight of the polyvinyl alcohol is not less than 80000g/mol, and the isotacticity is not less than 23% at most.
According to an embodiment of the present invention, the preparation method specifically includes:
vinyl ester monomers and metal lithium salts are subjected to the free radical polymerization reaction under the conditions of a solvent and an initiator to obtain a reaction solution containing polyvinyl ester;
the reaction liquid is subjected to precipitation treatment to obtain the polyvinyl ester;
and adding sodium hydroxide alcohol solution into the polyvinyl ester solution under the heating condition, and carrying out alcoholysis reaction to obtain the high-isotacticity high-molecular-weight polyvinyl alcohol.
According to an embodiment of the present invention, the vinyl ester monomer includes: vinyl acetate, vinyl trifluoroacetate, vinyl formate, vinyl propionate, vinyl valerate, vinyl butyrate, vinyl isobutyrate, and vinyl pivalate.
According to an embodiment of the present invention, the above-mentioned metallic lithium salt includes: one of lithium perchlorate, lithium chloride, lithium bromide, lithium acetate, lithium fluoride, lithium phosphate, lithium sulfate, lithium nitrate, lithium sulfate, lithium carbonate, lithium fluoroborate, and lithium hexafluorophosphate.
According to an embodiment of the present invention, the initiator is one or more of azo-type initiator and peroxide-type initiator.
According to an embodiment of the present invention, the azo-based initiator includes: 2,2 '-azobisisobutyronitrile, 2' -azobis (2, 4-dimethylvaleronitrile), 2 '-azobis (4-methoxy-2, 4-dimethylvaleronitrile) and 4,4' -azobis (4-cyanovaleric acid).
According to an embodiment of the present invention, the peroxide-based initiator includes: benzoyl peroxide, diisopropyl peroxydicarbonate, tert-butyl peroxyneodecanoate, potassium persulfate, ammonium persulfate and hydrogen peroxide.
According to an embodiment of the present invention, the initiator is a combination of the peroxide initiator and a reducing agent;
wherein the reducing agent is sodium bisulphite or sodium bicarbonate.
According to an embodiment of the present invention, the ratio of the amounts of the vinyl ester monomer, the initiator, and the metal lithium salt is 2:1.6X10 -3 -3.2×10 -3 :0.4-5。
According to an embodiment of the present invention, the step of obtaining polyvinyl ester by subjecting the reaction solution to precipitation treatment includes pouring the reaction solution into diethyl ether to precipitate, dissolving the precipitate in the solvent, repeating precipitation, and drying the precipitate to obtain the polyvinyl acetate.
According to a second aspect of the present invention, there is provided a highly isotactic high molecular weight polyvinyl alcohol produced by the above process, the polyvinyl alcohol having a number average molecular weight of not less than 80000g/mol, a molecular weight distribution of 1.9, an alcoholysis degree of more than 99.5%, an isotacticity of not less than 23%, and a 1, 2-diol content of not more than 1.7%.
From the technical scheme, the preparation method of the polyvinyl alcohol with high isotacticity and high molecular weight has the following beneficial effects:
the preparation method provided by the invention has the advantages of simple production process and easiness in realizing industrial production, and the polyvinyl alcohol with the characteristics of high molecular weight and high isotacticity can be prepared by the method. The polyvinyl alcohol prepared by the preparation method provided by the invention is favorable for post-modification reaction, particularly for meso-acetal reaction with aldehyde compounds, so that a high-quality polyvinyl acetal product is obtained, and the polyvinyl alcohol is applied to the automobile and building industries.
Drawings
FIG. 1 is a flow chart of the preparation of polyvinyl alcohol according to an embodiment of the invention;
FIG. 2 is a chart showing the nuclear magnetic resonance hydrogen spectrum and GPC spectrum of the polyvinyl alcohol synthesized in example 1 of the invention;
FIG. 3 is a chart showing the nuclear magnetic resonance hydrogen spectrum and GPC chart of the polyvinyl alcohol synthesized in example 2 of the invention.
FIG. 4 is a graph showing the dependence of the stereoregularity of vinyl acetate (VAc) free radical polymerization according to an embodiment of the present invention on temperature;
FIG. 5 shows LiClO according to an embodiment of the present invention 4 For carbonyl and double bonds of VAc 13 A graph of the change in CNMR chemical shift;
FIG. 6 shows LiClO according to an embodiment of the present invention 4 Carbonyl and double bond groups of VAc in the presence of 13 CNMR chemical shift change map;
FIG. 7 shows LiClO according to an embodiment of the present invention 4 Schematic of the mechanism of radical chain growth reaction regulating VAc.
Detailed Description
The present invention will be further described in detail below with reference to specific embodiments and with reference to the accompanying drawings, in order to make the objects, technical solutions and advantages of the present invention more apparent.
According to a first aspect of the present invention, there is provided a process for the preparation of highly isotactic high molecular weight polyvinyl alcohol comprising:
in the free radical polymerization reaction of vinyl ester monomers, taking metal lithium salt as a control reagent, and performing ion-pi interaction with the vinyl ester monomers to enable the vinyl ester monomers to perform dominant orientation addition reaction in chain growth to generate high-isotacticity high-molecular-weight polyvinyl alcohol;
wherein the number average molecular weight of the polyvinyl alcohol is not less than 80000g/mol, and the isotacticity is not less than 23% at the highest.
The invention prepares polyvinyl ester through free radical polymerization, and then prepares polyvinyl alcohol through alcoholysis reaction by taking sodium hydroxide as a base catalyst. Because the metal lithium salt can generate cation-pi interaction with vinyl ester monomers, the activity of the vinyl ester monomers is limited, and the vinyl ester monomers are oriented in the free radical polymerization reaction, so that the polyvinyl alcohol with higher isotacticity is synthesized. By adjusting the reaction temperature and the raw material proportion, the polyvinyl alcohol with the highest number average molecular weight of 80000 can be obtained. The method provided by the invention has the advantages of simple raw material composition, simple and convenient synthesis process and very strong industrialized prospect, and the obtained product has potential application value in the fields of optical films and automobiles.
In the radical polymerization of vinyl ester monomers, the growing chain ends with sp2 hybridized carbon radicals having a planar structure, which randomly attack the monomers in the chain growth radical reaction, are not azimuthally selective, and thus the conventional radical polymerization products are generally free of stereoregularity. In the invention, the metal lithium salt is adopted as a control reagent, and can generate ion-pi interaction with the vinyl ester monomer provided by the invention, so that the steric hindrance of the monomer is increased, the movement of the monomer is limited, the dominant orientation addition reaction is generated in the chain growth process, the polymerization reaction has certain stereoselectivity, and the isotacticity of the product polyvinyl alcohol is particularly improved.
The polyvinyl alcohol prepared by the invention has the characteristics of high molecular weight and high isotacticity, and has the advantages of simple production process and easy realization of industrial production.
FIG. 1 is a flow chart showing the preparation of polyvinyl alcohol according to an embodiment of the invention.
According to an embodiment of the present invention, as shown in fig. 1, it includes:
s1, carrying out free radical polymerization reaction on vinyl ester monomers and metal lithium salt under the conditions of a solvent and an initiator to obtain a reaction solution containing polyvinyl ester;
s2, carrying out precipitation treatment on the reaction solution to obtain polyvinyl ester;
and S3, adding sodium hydroxide alcohol solution into the polyvinyl ester solution under the heating condition, and carrying out alcoholysis reaction to generate the high-isotacticity high-molecular-weight polyvinyl alcohol.
According to an embodiment of the present invention, S1 is specifically: distilled vinyl ester monomer and metallic lithium salt (21.2-42.4 g,0.20-0.4 mol) are added into a three-neck flask protected by nitrogen under the conditions of solvent and initiator, and reacted for 5-10 hours at 50-70 ℃.
According to an embodiment of the present invention, in S1, the vinyl ester monomer includes: vinyl acetate, vinyl trifluoroacetate, vinyl formate, vinyl propionate, vinyl valerate, vinyl butyrate, vinyl isobutyrate, and vinyl pivalate.
According to an embodiment of the present invention, in S1, the metal lithium salt includes: one of lithium perchlorate, lithium chloride, lithium bromide, lithium acetate, lithium fluoride, lithium phosphate, lithium sulfate, lithium nitrate, lithium sulfate, lithium carbonate, lithium fluoroborate, and lithium hexafluorophosphate.
According to the embodiment of the invention, the metal lithium salt can effectively activate the polymerization process of vinyl ester monomers to obtain a macromolecular chain rich in isotactic structure.
Vinyl ester monomers may be activated by complexation of a lithium metal salt prior to polymerization of non-coordinating monomers. This results in the selective presence of metallic lithium salts around the omega end of the growing polymeric chain. Coordination of the lithium metal salt to the polar groups in the vicinity of the propagating polymer chain may control the stereochemical reaction of the polymer. After adding some vinyl ester monomers, the metal lithium salt is separated from the polymer chain, coordinates with the free monomer, and repeats the polymerization process to obtain the macromolecular chain rich in isotacticity.
According to an embodiment of the present invention, in S1, the initiator is one or more of azo-type initiator and peroxide-type initiator.
According to an embodiment of the present invention, the initiator may be an initiating system that generates living radicals and is soluble in the polymerization process system.
According to an embodiment of the present invention, wherein the azo-based initiator includes: 2,2 '-azobisisobutyronitrile, 2' -azobis (2, 4-dimethylvaleronitrile), 2 '-azobis (4-methoxy-2, 4-dimethylvaleronitrile) and 4,4' -azobis (4-cyanovaleric acid).
The peroxide initiator comprises: benzoyl peroxide, diisopropyl peroxydicarbonate, tert-butyl peroxyneodecanoate, potassium persulfate, ammonium persulfate and hydrogen peroxide.
According to an embodiment of the invention, the initiator is a combination of a peroxide-based initiator and a reducing agent;
wherein the reducing agent is sodium bisulphite or sodium bicarbonate.
According to an embodiment of the invention, in S1, the ratio of the amounts of vinyl ester monomer, initiator and lithium metal salt is 2:1.6X10 -3 -3.2×10 -3 :0.4-5。
In order to ensure a high molecular weight of the resulting polyvinyl alcohol, a solvent having a small chain transfer constant needs to be selected by a solution polymerization process. The method comprises the following steps: methanol, methyl acetate, ethyl acetate, benzene, toluene and the like are preferably used.
According to the embodiment of the invention, in S2, the reaction solution is subjected to precipitation treatment to obtain polyvinyl ester, wherein the reaction solution is poured into diethyl ether to precipitate, the precipitate is dissolved by a solvent, and the precipitate is dried after repeated precipitation to obtain polyvinyl acetate.
According to an embodiment of the present invention, S3 is specifically: adding the synthesized polyvinyl ester into a solvent to prepare a solution with the mass concentration of 10-15%, heating the solution in a water bath at the temperature of 40-50 ℃ for 10-30 minutes, adding the prepared sodium hydroxide methanol solution with the mass concentration of 40%, rapidly and uniformly stirring the solution, standing the solution for 20 minutes, separating out massive white solid, cutting the solid by a pulverizer, adding methanol for cleaning for 3 times, and placing the solution in a drying oven at the temperature of 50 ℃ for drying for 6 hours to obtain the high-isotacticity high-molecular-weight polyvinyl alcohol.
In S3, according to an embodiment of the present invention, sodium hydroxide: polyvinyl acetate=12:1 (mol).
According to a second aspect of the present invention, there is provided a highly isotactic high molecular weight polyvinyl alcohol produced by the process, the polyvinyl alcohol having a number average molecular weight of not less than 80000g/mol, a molecular weight distribution of 1.9, an alcoholysis degree of more than 99.5%, an isotacticity of not less than 23% at most, and a 1, 2-diol content of not more than 1.7%.
The preparation method provided by the invention has the advantages of simple production process and easiness in realizing industrial production, and the polyvinyl alcohol with the characteristics of high molecular weight and high isotacticity can be prepared by the method. The polyvinyl alcohol prepared by the preparation method provided by the invention is favorable for post-modification reaction, particularly for meso-acetal reaction with aldehyde compounds, so that a high-quality polyvinyl acetal product is obtained, and the polyvinyl alcohol is applied to the automobile and building industries.
The following detailed description of the present invention is given by way of example only, and not by way of limitation.
Example 1:
sample 1:
distilled vinyl acetate (VAc) (34.4 g,0.40 mol), methanol (40 mL,0.99 mol), ABVN (80.0 mg,0.32 mmol), and lithium perchlorate (LiClO) 4 ) (21.2 g,0.20 mol) was charged into a nitrogen-protected three-necked flask and reacted at 50℃for 5 hours, wherein the vinyl acetate: ABVN: lithium perchlorate=2:1.6X10 -3 1 (mol), the conversion rate of the vinyl acetate reaches 90.1 percent.
Then, the reaction solution is poured into a large amount of anhydrous diethyl ether for precipitation, then dissolved by methanol, and the anhydrous diethyl ether is precipitated for three times and dried to obtain the polyvinyl acetate.
Then, the synthesized polyvinyl acetate (10.0 g) is added into methanol to prepare a solution with the mass concentration of 10 percent, and the solution is placed in a water bath with the temperature of 40 ℃ for heating for 10 minutes, and 3.0mL of prepared sodium hydroxide methanol solution with the mass concentration of 40 percent is added, wherein the sodium hydroxide is prepared by the steps of: polyvinyl acetate=12:1 (mol), after rapid stirring, standing for 20 minutes, precipitating a large white solid, cutting by a pulverizer, adding methanol for cleaning 3 times, and placing in a drying oven at 50 ℃ for drying for 6 hours to obtain a sample 1.
Sample 2:
distilled vinyl acetate (VAc) (34.4 g,0.40 mol), methanol (50 mL,1.24 mol), AIBN (52.8 mg,0.32 mmol), and lithium perchlorate (LiClO) 4 ) (21.2 g,0.20 mol) was charged into a nitrogen-protected three-necked flask and reacted at 70℃for 3 hours, with a conversion of 88.7%. Subsequently, the reaction solution was poured into a large amount of diethyl ether to precipitateDissolving with methanol, precipitating with diethyl ether for three times, and drying to obtain polyvinyl acetate.
And adding 10.0g of the synthesized polyvinyl acetate into methanol to prepare a solution with the mass concentration of 10%, heating in a water bath at 40 ℃ for 10 minutes, adding 3.0mL of prepared sodium hydroxide methanol solution with the mass concentration of 40%, rapidly and uniformly stirring, standing for 20 minutes, separating out massive white solid, cutting by a pulverizer, adding methanol for cleaning for 3 times, and placing in a drying oven at 50 ℃ for 6 hours to obtain a sample 2.
Sample characterization
FIG. 2 shows the nuclear magnetic resonance hydrogen spectrum and GPC chart of the polyvinyl alcohol synthesized in example 1 of the invention.
FIG. 3 is a chart showing the nuclear magnetic resonance hydrogen spectrum and GPC chart of the polyvinyl alcohol synthesized in example 2 of the invention.
Taking a dried sample 1 and a dried sample 2, respectively dissolving in deuterated DMSO, and representing the result of the sample 1 by using a nuclear magnetic resonance technology, wherein the result of the sample 2 is shown in a graph 2, and the result of the sample 2 is shown in a graph 3, wherein the isotacticity (23.3%), the alcoholysis degree (99.7%) and the 1, 2-diol structural content (1.56%) of the sample 1;
the isotacticity (23.6%), alcoholysis (99.5%) and 1, 2-diol structural content (1.72%) of this sample 2. Taking a dried sample 1 and a dried sample 2, dissolving the dried sample 1 and the dried sample 2 in water added with sodium nitrate, detecting the molecular weight of the dried sample by using water phase GPC, and obtaining a number average molecular weight of the sample 1 of 86700g/mol and a distribution PDI of 1.9;
Example 2:
when LiClO is used as the metal lithium salt 4 In the case of vinyl acetate (VAc) as the vinyl ester monomer, it was used as the experimental group.
Distilled vinyl acetate (VAc), methanol, ABVN and lithium perchlorate (LiClO) 4 ) Is added into a three-neck flask protected by nitrogen gas to [ VAc ]]:[LiClO 4 ]Samples prepared with =1:1 conditions were reacted at 50 ℃ for 5 hours.
Then, the reaction solution is poured into a large amount of anhydrous diethyl ether for precipitation, then dissolved by methanol, and the anhydrous diethyl ether is precipitated for three times and dried to obtain the polyvinyl acetate.
And adding the synthesized polyvinyl acetate into methanol to prepare a solution with the mass concentration of 10%, heating in a water bath at 40 ℃ for 10 minutes, and adding 3.0mL of prepared sodium hydroxide methanol solution with the mass concentration of 40%, wherein sodium hydroxide is added: polyvinyl acetate=12:1 (mol), after rapid stirring, standing for 20 minutes, precipitating large white solid, cutting by a pulverizer, adding methanol for cleaning 3 times, and placing in a drying oven at 50 ℃ for drying for 6 hours to obtain a sample of an experimental group.
Comparative example:
samples prepared without adding lithium perchlorate were prepared as control samples according to the method of example 2.
Experimental example 2-1: the effect of lithium perchlorate on the polymerization activity of vinyl acetate was investigated.
(1) Influence of lithium perchlorate on the activation parameters of vinyl acetate radical polymerization
FIG. 4 is a graph showing the dependence of the stereoregularity of vinyl acetate (VAc) free radical polymerization according to the embodiment of the present invention on the temperature.
In order to understand the effect of lithium perchlorate on the stereoselectivity of vinyl acetate (VAc) free radical polymerization, we performed experiments to determine ΔH of polymerization in the presence or absence of lithium perchlorate i ≠ -ΔH s ≠ And DeltaS i ≠ -ΔS s ≠ Values.
Since the relationship of the tacticity with temperature is shown by the formula (1):
ln(P i /P s )＝(ΔS i ≠ -ΔS s ≠ )/R-(ΔH i ≠ -ΔH s ≠ )/RT (1)
wherein P is i And P s The probability or content in the isotactic direction and the syndiotactic direction, respectively, R is the gas constant, and T is the polymerization temperature (K).
Thus, by implementingExperimental group sample and control group sample in example 2, determination of lithium perchlorate vs. ΔH i ≠ -ΔH s ≠ And DeltaS i ≠ -ΔS s ≠ Influence of the value. The results are shown in Table 1.
TABLE 1 activation parameters for VAc radical polymerization
When lithium perchlorate is not added, ΔH in the case of VAc methanol solution polymerization i ≠ -ΔH s ≠ The positive value of (2) indicates that the enthalpy term in the solvent favors the syndiotactic growth, which is dominant at lower temperatures. In [ VAc ]]:[LiClO 4 ]Δh under the condition of=1:1 i ≠ -ΔH s ≠ The negative value of (2) indicates that the enthalpy term in the solvent favors an isotactic direction of growth. And DeltaS i ≠ -ΔS s ≠ The negative value of (2) indicates that the entropy term favors the growth of syndiotactic direction in the solvent.
FIG. 4 shows that, in [ VAc ]]:[LiClO 4 ]The enthalpy of activation of the isotactic and syndiotactic growth reactions (.DELTA.H) under the condition of =1:1 i ≠ -ΔH s ≠ ) And activation entropy (DeltaS) i ≠ -ΔS s ≠ ) The differences between-978.56 cal/mol and-3.71 cal/mol/K, respectively, whereas the values obtained without lithium perchlorate are-315.77 cal/mol and-0.58 cal/mol/K, respectively. It can be seen that the presence of lithium perchlorate can greatly affect the activation parameters of the polymerization reaction, making it more advantageous for the formation of isotactic polymers.
(2) Lithium perchlorate for vinyl acetate carbonyl and double bond 13 Influence of C NMR chemical shift
FIG. 5 shows LiClO according to an embodiment of the present invention 4 For carbonyl and double bonds of VAc 13 C NMR chemical shift diagram.
FIG. 6 shows LiClO according to an embodiment of the present invention 4 Carbonyl and double bond groups of VAc in the presence of 13 C NMR chemical shift diagram.
By passing through 13 C NMR test to detect interactions between lithium perchlorate and carbonyl and double bond groups in the monomer.
FIG. 5 shows the samples of the experimental group, i.e. in LiClO 4 In the presence of monomers CH 2 ＝CHOCOCH 3 Carbonyl groups and double bond groups of (C) 13 Variation of CNMR chemical shift. With increasing lithium perchlorate content, the chemical shift of the carbon atoms of VAc shifts to a lower field, indicating VAc and LiClO 4 There is an interaction between them. Wherein the chemical shift δ=168.7 to 167.8ppm represents a carbonyl carbon atom peak, and the chemical shift of the corresponding peak shifts from 168.2 to 168.6ppm as the lithium perchlorate content increases. Likewise, the chemical shift δ=96.9 to 96.4ppm represents the peak of the carbon atom of the double bond, and as the content of lithium perchlorate increases, the signal of the corresponding peak shifts to the lower field. The shift change of the carbon atom peak of carbonyl group was larger than that of double bond (as shown in FIG. 6), indicating LiClO 4 The effect on carbonyl groups is greater than on double bond groups.
Experimental example 2-2: lithium perchlorate regulates and controls stereoselective polymerization mechanism of vinyl acetate
(1) Exploration of mechanism of VAc free radical chain growth reaction in samples of experimental group and control group
FIG. 7 shows LiClO according to an embodiment of the present invention 4 Schematic of the mechanism of radical chain growth reaction regulating VAc.
FIG. 7 (a) is a schematic illustration of a free radical chain growth reaction mechanism of a conventional VAc;
FIG. 7 (b) is LiClO 4 In the presence of VAc, the mechanism of the free radical chain growth reaction is schematically shown.
As shown in FIG. 7, in LiClO 4 VAc can be coated with LiClO in the presence of 4 Is preferentially polymerized over non-coordinating monomers. This results in LiClO around the ω -end of the growing polymer chain 4 Optionally present. LiClO (LiClO) 4 Coordination with polar groups near the growing polymer chain can control the stereochemical reaction of the polymer to obtain a macromolecular chain rich in isotactic structure.
Example 3:
samples were prepared by the method of example 2, except,sample LiClO 4 The molar ratio of VAc is 0, 0.1, 0.2, 0.4, 1.0, 1.6 and 2.5 respectively.
Experimental example 3-1: investigation of the effect of lithium perchlorate on vinyl acetate polymerization in different molar ratios
By passing through 1 The H NMR spectrum, the ternary stereoregularity and the binary stereoregularity were characterized for the samples under the conditions of each molar ratio in example 3, the effect of the molar ratio on the polymer regularity was shown in table 2.
TABLE 2 LiClO 4 Effect of the VAc molar ratio on the stereoregularity of PVA
As is clear from Table 2, in the range of 0 to 2.5 in terms of molar ratio of lithium perchlorate to vinyl acetate, the triad isotacticity mm of polyvinyl alcohol gradually increases with increasing content of lithium perchlorate, the triad isotacticity rr gradually decreases, and the triad randomization mr content is substantially unchanged. And the corresponding two-unit isotacticity m gradually increases, while the two-unit isotacticity r gradually decreases).
The foregoing description of the embodiments has been provided for the purpose of illustrating the general principles of the invention, and is not meant to limit the invention thereto, but to limit the invention thereto, and any modifications, equivalents, improvements and equivalents thereof may be made without departing from the spirit and principles of the invention.
Claims (10)
1. A method for preparing high isotacticity high molecular weight polyvinyl alcohol, comprising:
in the free radical polymerization reaction of vinyl ester monomers, taking metal lithium salt as a control reagent, and performing ion-pi interaction with the vinyl ester monomers to enable the vinyl ester monomers to perform dominant orientation addition reaction in chain growth to generate the high-isotacticity high-molecular-weight polyvinyl alcohol;
wherein the number average molecular weight of the polyvinyl alcohol is not less than 80000g/mol, and the isotacticity is not less than 23% at most.
2. The preparation method according to claim 1, wherein the preparation method comprises:
carrying out the free radical polymerization reaction of vinyl ester monomers and metal lithium salt under the conditions of a solvent and an initiator to obtain a reaction solution containing polyvinyl ester;
the reaction liquid is subjected to precipitation treatment to obtain the polyvinyl ester;
and adding sodium hydroxide alcohol solution into the polyvinyl ester solution under the heating condition, and carrying out alcoholysis reaction to obtain the high-isotacticity high-molecular-weight polyvinyl alcohol.
3. The production method according to claim 1 or 2, wherein the vinyl ester monomer comprises: vinyl acetate, vinyl trifluoroacetate, vinyl formate, vinyl propionate, vinyl valerate, vinyl butyrate, vinyl isobutyrate, and vinyl pivalate.
4. The production method according to claim 1 or 2, wherein the metal lithium salt comprises: one of lithium perchlorate, lithium chloride, lithium bromide, lithium acetate, lithium fluoride, lithium phosphate, lithium sulfate, lithium nitrate, lithium sulfate, lithium carbonate, lithium fluoroborate, and lithium hexafluorophosphate.
5. The preparation method according to claim 2, wherein the initiator is one or more of azo initiator and peroxide initiator.
6. The preparation method according to claim 5, wherein,
the azo initiator includes: 2,2 '-azobisisobutyronitrile, 2' -azobis (2, 4-dimethylvaleronitrile), 2 '-azobis (4-methoxy-2, 4-dimethylvaleronitrile) and 4,4' -azobis (4-cyanovaleric acid);
the peroxide initiator comprises: benzoyl peroxide, diisopropyl peroxydicarbonate, tert-butyl peroxyneodecanoate, potassium persulfate, ammonium persulfate and hydrogen peroxide.
7. The method of claim 2, wherein the initiator is a combination of the peroxide-based initiator and a reducing agent;
wherein the reducing agent is sodium bisulphite or sodium bicarbonate.
8. The preparation method according to claim 2, wherein,
the ratio of the amounts of the vinyl ester monomer, the initiator and the lithium metal salt is 2:1.6X10 -3 -3.2×10 -3 :0.4-5。
9. The production method according to claim 2, wherein the step of subjecting the reaction solution to precipitation treatment to obtain the polyvinyl ester comprises pouring the reaction solution into diethyl ether to precipitate, dissolving the precipitate with the solvent, repeating the precipitation, and drying the precipitate to obtain the polyvinyl ester.
10. A highly isotactic high molecular weight polyvinyl alcohol produced by the process of claims 1-9, said polyvinyl alcohol having a number average molecular weight of not less than 80000g/mol, a molecular weight distribution of 1.9, an alcoholysis degree of greater than 99.5%, an isotacticity of not less than 23% at most, and a 1, 2-diol content of not more than 1.7%.
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