CN101602826B - Polyvinyl alcohol with 1,2-diol bond on side chain - Google Patents
Polyvinyl alcohol with 1,2-diol bond on side chain Download PDFInfo
- Publication number
- CN101602826B CN101602826B CN2009101599442A CN200910159944A CN101602826B CN 101602826 B CN101602826 B CN 101602826B CN 2009101599442 A CN2009101599442 A CN 2009101599442A CN 200910159944 A CN200910159944 A CN 200910159944A CN 101602826 B CN101602826 B CN 101602826B
- Authority
- CN
- China
- Prior art keywords
- polyvinyl alcohol
- saponification
- moles
- agent
- vinyl acetate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000004372 Polyvinyl alcohol Substances 0.000 title claims abstract description 104
- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 104
- 150000001875 compounds Chemical class 0.000 claims abstract description 23
- 239000000178 monomer Substances 0.000 claims abstract description 22
- 229920001567 vinyl ester resin Polymers 0.000 claims abstract description 14
- 238000007127 saponification reaction Methods 0.000 claims description 79
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 238000007334 copolymerization reaction Methods 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 125000001118 alkylidene group Chemical group 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 118
- 238000000034 method Methods 0.000 abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 17
- 239000007788 liquid Substances 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 9
- 239000002699 waste material Substances 0.000 abstract description 6
- 229920001577 copolymer Polymers 0.000 abstract description 5
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 description 39
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 36
- 229920003023 plastic Polymers 0.000 description 28
- 239000004033 plastic Substances 0.000 description 28
- 238000006116 polymerization reaction Methods 0.000 description 27
- 238000011156 evaluation Methods 0.000 description 24
- -1 methacrylonitrile Chemical compound 0.000 description 24
- 230000008676 import Effects 0.000 description 22
- 239000000243 solution Substances 0.000 description 19
- 239000007864 aqueous solution Substances 0.000 description 18
- 239000002904 solvent Substances 0.000 description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000000126 substance Substances 0.000 description 13
- 238000005160 1H NMR spectroscopy Methods 0.000 description 12
- 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 description 12
- 239000011248 coating agent Substances 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 239000003513 alkali Substances 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 10
- 230000007062 hydrolysis Effects 0.000 description 10
- 238000006460 hydrolysis reaction Methods 0.000 description 10
- 229920005989 resin Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 239000000123 paper Substances 0.000 description 7
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 6
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 239000003995 emulsifying agent Substances 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000012856 packing Methods 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 230000008961 swelling Effects 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- MPNXSZJPSVBLHP-UHFFFAOYSA-N 2-chloro-n-phenylpyridine-3-carboxamide Chemical compound ClC1=NC=CC=C1C(=O)NC1=CC=CC=C1 MPNXSZJPSVBLHP-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 3
- 125000004423 acyloxy group Chemical group 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000004513 sizing Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000375 suspending agent Substances 0.000 description 3
- 230000008719 thickening Effects 0.000 description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- YRIZYWQGELRKNT-UHFFFAOYSA-N 1,3,5-trichloro-1,3,5-triazinane-2,4,6-trione Chemical compound ClN1C(=O)N(Cl)C(=O)N(Cl)C1=O YRIZYWQGELRKNT-UHFFFAOYSA-N 0.000 description 2
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 235000018185 Betula X alpestris Nutrition 0.000 description 2
- 235000018212 Betula X uliginosa Nutrition 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 239000004902 Softening Agent Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical class CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000004931 aggregating effect Effects 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- HNPDNOZNULJJDL-UHFFFAOYSA-N ethyl n-ethenylcarbamate Chemical compound CCOC(=O)NC=C HNPDNOZNULJJDL-UHFFFAOYSA-N 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000005911 methyl carbonate group Chemical class 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N methyl pentane Natural products CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 239000011118 polyvinyl acetate Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- WDCYWAQPCXBPJA-UHFFFAOYSA-N 1,3-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC([N+]([O-])=O)=C1 WDCYWAQPCXBPJA-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- BQCXFGVWPFXMKD-UHFFFAOYSA-N 2,2-dimethylpropanoic acid;ethenyl acetate Chemical compound CC(=O)OC=C.CC(C)(C)C(O)=O BQCXFGVWPFXMKD-UHFFFAOYSA-N 0.000 description 1
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 1
- XEEYSDHEOQHCDA-UHFFFAOYSA-N 2-methylprop-2-ene-1-sulfonic acid Chemical compound CC(=C)CS(O)(=O)=O XEEYSDHEOQHCDA-UHFFFAOYSA-N 0.000 description 1
- KMPBSNWACXDMII-UHFFFAOYSA-N 3-methylpent-4-ene-1,2-diol Chemical compound C=CC(C)C(O)CO KMPBSNWACXDMII-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- XMLPUMZEMHWAGV-UHFFFAOYSA-N 5-methylidene-1,6-diphenylcyclohexa-1,3-diene Chemical compound C1(=CC=CC=C1)C=1C(C(C=CC1)=C)C1=CC=CC=C1 XMLPUMZEMHWAGV-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical class C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- QDOSSOAEQAJPAH-UHFFFAOYSA-N C(C)(=O)OC=C.OC(=O)CCCCCCCCC Chemical compound C(C)(=O)OC=C.OC(=O)CCCCCCCCC QDOSSOAEQAJPAH-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- ZAQJHHRNXZUBTE-NQXXGFSBSA-N D-ribulose Chemical compound OC[C@@H](O)[C@@H](O)C(=O)CO ZAQJHHRNXZUBTE-NQXXGFSBSA-N 0.000 description 1
- ZAQJHHRNXZUBTE-UHFFFAOYSA-N D-threo-2-Pentulose Natural products OCC(O)C(O)C(=O)CO ZAQJHHRNXZUBTE-UHFFFAOYSA-N 0.000 description 1
- 101150027068 DEGS1 gene Proteins 0.000 description 1
- 229920003656 Daiamid® Polymers 0.000 description 1
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical group O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- FSNCEEGOMTYXKY-JTQLQIEISA-N Lycoperodine 1 Natural products N1C2=CC=CC=C2C2=C1CN[C@H](C(=O)O)C2 FSNCEEGOMTYXKY-JTQLQIEISA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- QORUGOXNWQUALA-UHFFFAOYSA-N N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 Chemical compound N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 QORUGOXNWQUALA-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- MBHRHUJRKGNOKX-UHFFFAOYSA-N [(4,6-diamino-1,3,5-triazin-2-yl)amino]methanol Chemical compound NC1=NC(N)=NC(NCO)=N1 MBHRHUJRKGNOKX-UHFFFAOYSA-N 0.000 description 1
- VZWLZRVVPWDRJR-UHFFFAOYSA-M [Cl-].C[N+](OC)(OC)OC.C(C=C)(=O)N Chemical compound [Cl-].C[N+](OC)(OC)OC.C(C=C)(=O)N VZWLZRVVPWDRJR-UHFFFAOYSA-M 0.000 description 1
- LDBBENZEOFGRAS-UHFFFAOYSA-N [Cl-].OC(C(=O)OOCCC[N+](C)(C)C)=CC Chemical compound [Cl-].OC(C(=O)OOCCC[N+](C)(C)C)=CC LDBBENZEOFGRAS-UHFFFAOYSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 125000002339 acetoacetyl group Chemical group O=C([*])C([H])([H])C(=O)C([H])([H])[H] 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- SRBFZHDQGSBBOR-LECHCGJUSA-N alpha-D-xylose Chemical compound O[C@@H]1CO[C@H](O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-LECHCGJUSA-N 0.000 description 1
- SRBFZHDQGSBBOR-QMKXCQHVSA-N alpha-L-arabinopyranose Chemical compound O[C@H]1CO[C@@H](O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-QMKXCQHVSA-N 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
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- 238000004458 analytical method Methods 0.000 description 1
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- 239000007767 bonding agent Substances 0.000 description 1
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- IOMDIVZAGXCCAC-UHFFFAOYSA-M diethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](CC)(CC)CC=C IOMDIVZAGXCCAC-UHFFFAOYSA-M 0.000 description 1
- GKJMOBYTOXEHKJ-UHFFFAOYSA-N dihydroxymethylurea Chemical compound NC(=O)NC(O)O GKJMOBYTOXEHKJ-UHFFFAOYSA-N 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000012674 dispersion polymerization Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
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- 239000000975 dye Substances 0.000 description 1
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- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- HLMAOUJZLUOWAH-UHFFFAOYSA-N ethenyl acetate 2-methylpropanoic acid Chemical compound C(=C)OC(C)=O.C(C(C)C)(=O)O HLMAOUJZLUOWAH-UHFFFAOYSA-N 0.000 description 1
- VVXDXPYRHUQGRL-UHFFFAOYSA-N ethenyl acetate pentanoic acid Chemical compound C(=C)OC(C)=O.C(CCCC)(=O)O VVXDXPYRHUQGRL-UHFFFAOYSA-N 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- GLVVKKSPKXTQRB-UHFFFAOYSA-N ethenyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC=C GLVVKKSPKXTQRB-UHFFFAOYSA-N 0.000 description 1
- GFJVXXWOPWLRNU-UHFFFAOYSA-N ethenyl formate Chemical compound C=COC=O GFJVXXWOPWLRNU-UHFFFAOYSA-N 0.000 description 1
- AFSIMBWBBOJPJG-UHFFFAOYSA-N ethenyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC=C AFSIMBWBBOJPJG-UHFFFAOYSA-N 0.000 description 1
- 235000021050 feed intake Nutrition 0.000 description 1
- 239000011094 fiberboard Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 150000002314 glycerols Chemical class 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- WGTGQGJDNAGBCC-UHFFFAOYSA-N hex-5-ene-1,2-diol Chemical compound OCC(O)CCC=C WGTGQGJDNAGBCC-UHFFFAOYSA-N 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 239000003906 humectant Substances 0.000 description 1
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- 239000004434 industrial solvent Substances 0.000 description 1
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- 239000003014 ion exchange membrane Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 1
- JILPJDVXYVTZDQ-UHFFFAOYSA-N lithium methoxide Chemical compound [Li+].[O-]C JILPJDVXYVTZDQ-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical class CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical group CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 229940059574 pentaerithrityl Drugs 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001290 polyvinyl ester Polymers 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- 125000001844 prenyl group Chemical group [H]C([*])([H])C([H])=C(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 239000011122 softwood Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000012453 solvate Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229950009390 symclosene Drugs 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229960003487 xylose Drugs 0.000 description 1
- 125000006839 xylylene group Chemical group 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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Abstract
The invention provides polyvinyl alcohol with a 1,2-diol bond on a side chain, which is characterized in that when the polyvinyl alcohol is prepared, dimethyl carbonate and the like are not produced, so a process for removing the dimethyl carbonate is not needed in a process of reclaiming waste liquid after reclaiming and saponifying, in addition, even if the introducing amount of the 1,2-diol bond is increased, the dissolubility of the saponified solution (methanol) is not destroyed by a copolymer (paste) before saponifying, and the water solubility is not reduced even heating. The polyvinyl alcohol with the 1,2-diol bond on the side chain is prepared by saponifying a vinyl ester monomer and the copolymer of compounds represented by formula (1).
Description
The application be that August 18, application number in 2004 are 200480043815.2 the applying date, denomination of invention divides an application for the application of " side chain has 1, the polyvinyl alcohol of 2-diol bond and manufacture method thereof ".
Technical field
The present invention relates to a kind of side chain and have 1, the polyvinyl alcohol of 2-diol bond and manufacture method thereof.
Background technology
Traditionally, polyvinyl alcohol utilizes its system membrane property (film-forming properties, oil-proofness, intensity etc.), water-soluble etc., is widely used as emulsifying agent, suspension agent, tensio-active agent, fiber processing agent, various tackiness agent, paper conversion agent, caking agent, film etc.And, except Special Circumstances, make the aqueous solution usually and use.
Can use the polyvinyl alcohol of various saponification degs according to application target, but using under the situation of saponification deg than higher polyvinyl alcohol, when it is water-soluble when making the aqueous solution, in water temperature low winter etc., this viscosity in aqueous solution rises in time, and flowability degenerates, under extreme case, the aqueous solution is understood gelation and is lost flowability fully, becomes very big problem.
In order to solve such problem, propose a kind of side chain and had 1, the scheme of the polyvinyl alcohol of 2-diol bond (opening the 2002-241433 communique) with reference to the Japanese Patent spy, this polyvinyl alcohol by the multipolymer to vinyl ester monomers and vinylethylene carbonate carry out saponification, decarbonate makes.This polyvinyl alcohol has good high-speed coating and adhesiveproperties etc.
Yet, though this polyvinyl alcohol is excellence aspect above-mentioned all rerum naturas, but this polyvinyl alcohol uses vinylethylene carbonate (for example to import high modification amount, 7 moles more than the %) 1, the 2-diol bond, in this case, when the polyvinyl acetate (PVA) that imports vinylethylene carbonate is carried out saponification or from the polymerization paste of the polyvinyl acetate (PVA) that imports vinylethylene carbonate, removing in the operation of unreacted Vinyl Acetate Monomer, this resin has the tendency of reduction to the solvability of methyl alcohol equal solvent, and in manufacturing processes such as saponification, be subjected to the restriction of modification amount based on the industrial solvent that is used usually.In addition, also there is following problem: when deriving to glycol, must handle to the by products such as methylcarbonate of sneaking into the solvent recuperation system when utilizing the basic hydrolysis vinylethylene carbonate.
Summary of the invention
Above-mentioned problem is furtherd investigate, found that carrying out the side chain that saponification makes by the multipolymer to compound shown in vinyl ester monomers and the following formula (1) has 1, the polyvinyl alcohol of 2-diol bond can solve above-mentioned problem, and then, possess the feature of the water-soluble and package stability that can significantly improve polyvinyl alcohol, thereby finished the present invention.
[changing 1]
(in the formula, R
1Be hydrogen or alkyl, R
2The carbonatoms that maybe can have an alkyl for singly-bound is 1～3 alkylidene group, R
3And R
4Be hydrogen or R independently of one another
5-CO-(in the formula, R
5Be alkyl))
In addition, the present invention also has following feature: by using at the compound shown in the above-mentioned formula (1), can solve the existing thawless problem that takes place of polyvinyl alcohol (partly-hydrolysed thing) of 99.0 moles of % of saponification deg less than when its process thermal history.
That is, the present invention relates to a kind of side chain and have 1, the polyvinyl alcohol of 2-diol bond, it carries out saponification by the multipolymer to compound shown in vinyl ester monomers and the formula (1) and makes.
In addition, the invention still further relates to a kind of side chain and have 1, the manufacture method of the polyvinyl alcohol of 2-diol bond is characterized in that, this polyvinyl alcohol carries out saponification by the multipolymer to compound shown in vinyl ester monomers and the formula (1) and makes.
Preferably saponification deg is more than 99.0 moles of % or less than 99.0 moles of %.
More preferably the copolymerization ratio of compound shown in the formula (1) is 0.1～40 mole of %.
Description of drawings
Fig. 1 is for the polyvinyl alcohol (I) that makes in embodiment 1
1H-NMR figure.
Fig. 2 is for the polyvinyl alcohol (II) that makes in embodiment 1
1H-NMR figure.
Fig. 3 is for the polyvinyl alcohol (I) that makes in embodiment 3
1H-NMR figure.
Embodiment
The present invention relates to a kind of side chain and have 1, the polyvinyl alcohol of 2-diol bond.
Polyvinyl alcohol of the present invention is to carry out saponification by the multipolymer to compound shown in vinyl ester monomers and the following formula (1) to make.
[changing 2]
(in the formula, R
1Be hydrogen or alkyl, be preferably methyl, ethyl or butyl; R
2The carbonatoms that maybe can have alkyl preferable methyl, ethyl or a butyl for singly-bound is 1～3 alkylidene group; R
3And R
4Be hydrogen or R independently of one another
5-CO-(in the formula, R
5Be alkyl, be preferably methyl, propyl group, butyl, hexyl or octyl group))
As compound shown in the formula (1), can list 3,4-dihydroxyl-1-butylene, 3,4-two acyloxy-1-butylene, 3-acyloxy-4-hydroxyl-1-butylene, 4-acyloxy-3-hydroxyl-1-butylene, 3,4-two acyloxy-2-methyl-1-butene alkene, 4,5-dihydroxyl-1-amylene, 4,5-two acyloxy-1-amylene, 4,5-dihydroxyl-3-Methyl-1-pentene, 4,5-two acyloxy-3-Methyl-1-pentene, 5,6-dihydroxyl-1-hexene, 5,6-two acyloxy-1-hexene etc.Wherein, consider, be preferably 3 from the good aspect of copolyreaction and industrial treatment, 4-two acyloxy-1-butylene, and 3, in 4-two acyloxy-1-butylene, more preferably 3,4-diacetoxy-1-butylene.
In addition, 3,4-two acyloxy-1-butylene can be bought the product of EastmanChemical company or the manufacturing of Acro ' s company from market.
As vinyl ester monomers, can list vinyl formate, vinyl acetate, propionate, valeric acid vinyl acetate, vinyl butyrate, isopropylformic acid vinyl acetate, trimethylacetic acid vinyl acetate, capric acid vinyl acetate, vinyl laurate, stearic acid vinyl ester, vinyl benzoate and tertiary ethylene carbonate etc.Wherein, from the viewpoint of economy, preferably use vinyl acetate.
In addition, among the present invention, except aforementioned copolymer composition, can also be in the scope that does not hinder the object of the invention, for example with 0.5～10 mole of other monomer of % left and right sides copolymerization.
As other monomer, for example can list, ethene, propylene, iso-butylene, α-octene, α-laurylene, olefines such as α-octadecylene, vinylformic acid, methacrylic acid, Ba Dousuan, toxilic acid, maleic anhydride, unsaturated acids such as methylene-succinic acid or its salt, list or dialkyl etc., vinyl cyanide, nitriles such as methacrylonitrile, diacetone-acryloamide(DAA), acrylamide, amines such as Methacrylamide, ethylene-sulfonic acid, allyl sulphonic acid, olefinic sulfonic acid or its salt such as methallyl sulfonic acid, the alkyl vinyl ethers, dimethyl-allyl vinyl ketone, the N-vinyl pyrrolidone, vinylchlorid, vinylidene chloride, polyoxyethylene (first generation) allyl ethers, polyoxyalkylene (first generation) allyl etherss such as polyoxypropylene (first generation) allyl ethers, polyoxyethylene (methyl) acrylate, polyoxyalkylene (methyl) acrylate such as polyoxypropylene (methyl) acrylate, polyoxyethylene (methyl) acrylamide, polyoxyalkylene (methyl) acrylamides such as polyoxypropylene (methyl) acrylamide, polyoxyethylene (1-(methyl) acrylamide-1, the 1-dimethyl propylene) ester, the polyoxyethylene vinyl ether, the polyoxypropylene vinyl ether, the polyoxyethylene allylamine, the polyoxypropylene allylamine, the polyoxyethylene vinyl-amine, polyoxypropylene vinyl-amine etc.
In addition, can also list N acrylamide methyl trimethoxy ammonium chloride; the N acrylamide ethyl-trimethyl salmiac; N acrylamide oxypropyl trimethyl ammonium chloride; 2-acryloxy ethyl-trimethyl salmiac; 2-methacryloxyethyl trimethyl ammonium chloride; 2-hydroxy-3-methyl acryloxy oxypropyl trimethyl ammonium chloride; the allyl group trimethyl ammonium chloride; the methylallyl trimethyl ammonium chloride; 3-butylene trimethyl ammonium chloride; dimethyl diallyl ammonium chloride; diethyl diallyl ammonium chloride etc. contains the monomer of cation radical; contain the monomer of acetoacetyl etc.
As (in addition with compound shown in vinyl ester monomers and the formula (1), also have other monomer) polymerization process when carrying out copolymerization, be not particularly limited, can adopt known method such as mass polymerization, solution polymerization, suspension polymerization, dispersion polymerization or letex polymerization, but adopt solution polymerization usually.
The feeding method of the monomer component during as copolymerization is not particularly limited, can adopt disposablely feed intake, any means such as fed batch, continuous dosing.From compound shown in the formula (1) is distributed in the molecular chain of polyvinyl esters polymer equably, the reactivity of raising and linking agent, the rerum natura aspects such as fusing point that reduce polyvinyl alcohol consider, preferably drips polymerization, is preferably based on the polymerization process of HANNA method especially.
As employed solvent in the copolymerization, can list lower alcohols such as methyl alcohol, ethanol, Virahol, propyl alcohol, butanols usually, and ketone such as acetone, methylethylketone etc.Wherein, industrial particular methanol.
The usage quantity of solvent needs only the polymerization degree that cooperates the target multipolymer and considers the suitably selection of chain transfer constant of solvent, for example, when solvent is methyl alcohol, S (solvent)/M (monomer)=0.01～10 (weight ratio), preferably the scope from about 0.05～3 (weight ratio) is selected.
Use polymerizing catalyst during copolymerization, as this polymerizing catalyst, for example can list, known catalysts for radical polymerization such as azobis isobutyronitrile, acetyl peroxide, benzoyl peroxide, lauroyl peroxide, low temperature active catalysts for radical polymerization such as the two methyl pentane nitriles of azo, azo bi-methoxy methyl pentane nitrile etc.
The usage quantity of polymerizing catalyst is different because of the kind of catalyzer, cannot treat different things as the same, and but, can select arbitrarily according to polymerization velocity.For example, under the situation of using azobis isobutyronitrile or acetyl peroxide, be preferably 0.01～0.2 mole of %, be preferably 0.02～0.15 mole of % especially with respect to vinyl ester monomers.
In addition, according to employed solvent and pressure, the temperature of reaction of copolyreaction is preferably about 40 ℃～boiling point.
Among the present invention, the copolymerization ratio of compound is not particularly limited shown in the formula (1), as long as cooperate followingly 1, the import volume decision copolymerization ratio of 2-diol bond gets final product.
Prepared multipolymer, is dissolved in prepared multipolymer in alcohol or the aqueous alcohol when this saponification next by saponification, uses basic catalyst or an acidic catalyst to carry out.As alcohol, can list methyl alcohol, ethanol, propyl alcohol, the trimethyl carbinol etc.Wherein, special particular methanol.Though can suitably select the concentration of the multipolymer in the alcohol according to the viscosity of system, select from the scope of 10～60 weight % usually.As employed catalyzer in the saponification, can list alkali-metal oxyhydroxide or the such basic catalysts of alkoxide such as sodium hydroxide, potassium hydroxide, sodium methylate, sodium ethylate, potassium methylate, lithium methoxide, an acidic catalysts such as sulfuric acid, hydrochloric acid, nitric acid, methylsulfonic acid, zeolite, Zeo-karb.
The usage quantity of this saponification catalyzer can suitably be selected according to method for saponification, target saponification deg etc., but under the situation of using basic catalyst, usually, with respect to 1 mole of the total amount of compound shown in vinyl ester monomers and the formula (1), the usage quantity of saponification catalyzer is 0.1～30 mmole, be preferably 2～17 mmoles.
In addition, though the temperature of reaction of saponification reaction is not particularly limited, be preferably 10～60 ℃, more preferably 20～50 ℃.
Polyvinyl alcohol of the present invention, it is by when saponification, convert the acyloxy part of compound shown in the ester moiety of vinyl ester monomers and the formula (1) to hydroxyl simultaneously and make, therefore, possesses following feature: the by products such as methylcarbonate of the shortcoming in the time of can not producing as the use vinylethylene carbonate.
In the present invention, the mean polymerisation degree of this polyvinyl alcohol (measuring according to JIS K6726) is preferably 150～4000 (more preferably 300～2600, particularly preferred is 500～2200).When mean polymerisation degree less than 150 the time, the worry that when being used for film purposes etc., exists physical strength to descend; When mean polymerisation degree surpasses 4000, be difficult to a large amount of importings 1 sometimes, the 2-diol bond.
In addition, the saponification deg of polyvinyl alcohol is preferably 60 moles more than the %, more preferably 70 moles more than the %, more preferably 80 moles more than the %, is preferably 90 moles especially more than the %.Under the situation of saponification deg less than 60 moles of %, there is the tendency of water-soluble decline.
In addition, saponification deg among the present invention be with the total amount of the acyloxy of compound shown in the ester moiety of vinyl ester monomers and the formula (1) part convert that the velocity of variation (mole %) of hydroxyl represents to (in saponification reaction, when saponification deg is 70～80 moles of % when above, the part of the acyloxy of compound shown in the formula (1) is almost completely by saponification).
The upper limit for saponification deg, according to purposes certain change is arranged, when its application target for the aqueous vinyl urethane with caking agent, paper conversion agent (sizing agent), ink-jet during with various silica tackiness agent such as the black receiving layer of paper or gloss layer, the upper limit of preferred saponification deg is less than 99.0 moles of %, when being applied to the acid or alkaline wrapping material of agricultural chemicals or washing composition etc., from the viewpoint of water-soluble so peculiar action effect that changes in time hardly of showing membrane, preferred saponification deg is 99.0 moles more than the %.
In addition, import to 1 in the polyvinyl alcohol, 2-diol bond amount is not particularly limited, but is preferably 0.1～40 mole of %, more preferably 0.5～25 mole of %, more preferably 1～20 mole of %.Under the situation of this import volume less than 0.1 mole of %, exist and during with linking agent etc. with the reactive low of linking agent and the tendency of viscosity stability reduction when making the aqueous solution, and the tendency that exists its coating also to reduce when this aqueous solution is used for the high-speed coating purposes.If this import volume surpasses 40 moles of %, the polymerization degree that then has a polyvinyl alcohol is the tendency of step-down too.
Especially in the present invention, importing 7 moles of a large amount of 1 more than % as mentioned above like that, under the situation of 2-diol bond, industrial enforcement there is not any obstacle yet, can easily make, and, the polyvinyl alcohol that import volume is high has following feature: its crystallinity further reduces, water-soluble becoming easily, in addition, the aqueous stability of polyvinyl alcohol is also good especially, polyvinyl alcohol water solution is a low foaming, even and the film that makes by this polyvinyl alcohol under alkaline environment, place for a long time, water-solublely can not reduce yet, therefore, the water soluble package material applications that can be used for alkalis packing etc.On the other hand, because 1, the 2-diol bond has primary hydroxyl and can significantly increase its import volume, thereby is being used under the situation of aqueous vinyl urethane adhesive purposes etc., can significantly improve bonding strength, can be used for the caking agent purposes of bonding wood, particularly softwood tree glued board etc.In addition, also high with the interaction of silicon-dioxide such as colloidal silica, pyrogenic silica, the gloss layer of using applicable to ink-jet also.
In addition, polyvinyl alcohol of the present invention, even its saponification deg is the high saponification deg about 99 moles of %, fusing point is also low, thereby when being blended in the ethylene-vinyl acetate copolymer ethylene series resins such as (content of vinyl acetate between to for plastic are about 1～40 weight %) with compatilizer (the various ethylene series resins that maleic anhydride etc. are anhydride modified etc.), melt blending easily, for example by to ethylene-vinyl acetate copolymer blending 20 weight % left and right sides polyvinyl alcohol of the present invention, possess and to make the heat retaining property availabilities such as film for agricultural use identical with vinyl chloride film.
Side chain has 1, the polyvinyl alcohol of the present invention of 2-diol bond, even saponification deg height, it also is low-crystalline, thereby it is fast to the dissolution rate of water, also demonstrating very good effect aspect the package stability of the aqueous solution, because hydroxyl exists as primary alconol, thereby polyvinyl alcohol of the present invention and isocyanic ester based compound, daiamid epoxy chloropropane, oxalic dialdehyde, melamine is that the reactivity of linking agents such as resin, methylol melamine, methylolation bisphenol S, dihydroxymethyl urea is also high in addition.As the isocyanic ester based compound, can use the compound that has 2 above isocyanate group in the molecule, for example can list, tolylene diisocyanate (TDI), hydrogenation TDI, TriMethylolPropane(TMP)-TDI adducts (for example " the Desmodur L " of Bayer company manufacturing), triphenylmethane triisocyanate, methylene-bis phenylbenzene isocyanic ester (MDI), hydrogenation MDI, polymeric MDI, hexamethylene diisocyanate, xylylene vulcabond, 4,4-dicyclohexyl methane diisocyanate, isophorone diisocyanate etc.In addition, can also list the prepolymer that terminal group that the polyisocyanates with surplus obtains the pre-dimerization of polyvalent alcohol has isocyanic ester.As the cooperation ratio of isocyanic ester based compound, the mol ratio of isocyanate group and hydroxyl (NCO/OH) is preferably 0.1～2.In addition, even under the high-shear when high-speed coating, can thickening yet, have good coating.In addition, even when butyralization or acetal, still can obtain and also high butyral resin of the reactive height of aldehydes and flexibility etc.
Polyvinyl alcohol of the present invention can be used for various uses, the part purposes as mentioned above, below, can list following example as concrete example.
(1) caking agent is relevant
The caking agent of timber, paper, aluminium foil, plastics etc., tackiness agent, again humectant, non-woven fabrics with various building materials such as tackiness agent, plasterboard and fiberboard with tackiness agent, various powder granulation with tackiness agent, cement or mortar with the tackiness agent of additive, hot-melting type caking agent, pressure sensitive caking agent, anionic property coating etc.
(2) moulded product is relevant
Fiber, film (particularly the water processable film used with the article packing of additive, sterilant, dyestuff, pigment etc. of agricultural chemicals, washing composition, washing clothes class, building: the saponification deg of polyvinyl alcohol is preferably 65 moles more than the %), polaroid raw sheet (preferred 1,2-diol bond amount is 0.2～2 mole of %, and the polymerization degree is more than 2000), sheet material, pipeline, pipe, leakproof film, interim tunicle, chemical lace be with water soluble fibre etc.
(3) coating agent is relevant
The Clear coating agent of paper, paper pigment coated dose, the sizing agent of paper, fiber product are with sizing agent, warp thread paste, fiber processing agent, hide finishes, coating, antifogging agent, anticorrosive metal agent, zinc-plated with gloss-imparting agent, antistatic agent, conductive agent, interim coating etc.
(4) emulsifying agent is relevant
The back emulsifying agent of hydrophobic resins such as the emulsifier for emulsion polymerization of alefinically unsaturated compounds, butadiene compounds, various acrylic monomers, polyolefine, vibrin, Resins, epoxy, paraffin, pitch etc. etc.
(5) suspension agent is relevant
The dispersion stabilizer for suspension polymerization of various vinyl compounds such as the colo(u)rant dispersion stablizer of coating, prepared Chinese ink, watercolors, caking agent etc., vinylchlorid, vinylidene chloride, vinylbenzene, (methyl) acrylate, vinyl acetate between to for plastic etc.
(6) hydrophobic resin is relevant with dopant
The antistatic agent of hydrophobic resin and wetting ability imparting agent, conjugated fibre, film (aspect the film for agricultural use purposes, can give heat retaining property especially), other moulded product are with additive etc.
(7) thickening material is relevant
The thickening material of the various aqueous solution and latex etc.
(8) aggregating agent prepared therefrom is relevant
Drainage agent of the aggregating agent prepared therefrom of suspended substance and solute, paper pulp, mud etc. in the water.
(9) soil improvement agent is relevant
(10) relevant, the photosensitivity resin against corrosion of quick dose of sensitizer, electricity, etc.
(11) and ion exchange resin, ion-exchange membrane are relevant, chelate exchange resin etc.
In above-mentioned, expect its practicality of performance in the purposes of (1)～(5) especially.
In addition, when being applicable to various uses, preferably add softening agent as required, as this softening agent, can list 3～6 yuan polyvalent alcohol (glycerine, TriMethylolPropane(TMP), Glycerol dimer, tetramethylolmethane, wood sugar, pectinose, ribulose, Sorbitol Powder etc.), various oxirane (the mixing adducts of oxyethane, propylene oxide, oxyethane and propylene oxide etc.).
Embodiment
Below, enumerate embodiment and specifically describe the present invention.Yet the present invention is not limited to following embodiment.
In addition, only otherwise do special explanation, " part " and " % " means weight basis.
Embodiment 1
With 1300g vinyl acetate between to for plastic, 650g methyl alcohol, 78.1g (3 moles of %) 3,4-diacetoxy-1-butylene be fed into be furnished with reflux exchanger, in the retort of dropping funnel and agitator, drop into 0.06 mole of % (with respect to input vinyl acetate between to for plastic) azobis isobutyronitrile again, temperature is risen, carry out polymerization.
Then, when the percent polymerization of vinyl acetate between to for plastic reaches 87.5%, drop into the Meta-dinitrobenzene of 50ppm (with respect to input vinyl acetate between to for plastic), stop polyreaction as stopper.Then, adopt the method that is blown into methanol vapor, unreacted Vinyl Acetate Monomer is removed to system, make the methanol solution of multipolymer.
Then, dilute this solution with methyl alcohol, being adjusted to concentration is 40%, again it is put in the kneader, the limit remains on 40 ℃ with solution temperature, the limit is with respect to the vinyl acetate between to for plastic in the multipolymer and 3, and the total amount of 4-diacetoxy-1-butylene is that 2% methanol solution that the ratio of 8 mmole % adds sodium hydroxide carries out saponification.Saponified deposition when saponification is carried out when it becomes particulate state, is carried out filtering separation, and is dry in hot air dryer behind methanol cleaning, makes polyvinyl alcohol.
In the manufacturing of described polyvinyl alcohol, use GC-MS (" 597N GC/MSD " system that Agilent company makes), whether the waste liquid after stopping according to following condition analysis saponification exists by product.
[column condition]
Post: HP-WAX (crosslinked polyoxyethylene glycol) capillary column
Column temperature: heat up 240 ℃ * placed 10 minutes after 40 ℃ * constant five minutes with 10 ℃/min
Inlet temperature: 240 ℃
Carrier gas: He
Post flow: 1.0ml/min
[MS portion condition]
Use machine: " 5973MSD " system that Agilent company makes
Mass range: 10-600
Threshold value: 20
Scanning/second: 2.54
Its result does not detect methylcarbonate.In addition, except sodium acetate, do not detect other salt.
According to residual vinyl acetate between to for plastic and residual 3, the quantity of alkali consumption that the hydrolysis of 4-diacetoxy-1-butylene is required, saponification deg to gained polyvinyl alcohol (I) is analyzed, this saponification deg is 9.5 moles of % as a result, analyze according to 6726 pairs of mean polymerisation degree of JIS K, this mean polymerisation degree is 870 as a result.In addition, 4% viscosity in aqueous solution of this polyvinyl alcohol of having used the hopper viscometer determining, this viscosity is 8.6mPas (20 ℃) as a result, uses
1H-NMR (internal standard substance: tetramethylsilane, solvent: d6-DMSO) measure and calculate 1, the import volume of 2-diol bond, this import volume is 3.1 moles of % as a result.In addition, in NMR measures, " the AVANCE DPX400 " that has used Japanese Bruker company to make.
[
1H-NMR] (with reference to Fig. 1)
1.2～1.5ppm: methene proton
1.8ppm: methine protons (result from modification kind)
3.5ppm: the methene proton of uncle's methylol
3.82～3.84ppm: methine protons
4.13～4.6ppm: hydroxyl
4.25ppm: glycol hydroxyl
In addition, draw samples in the saponification process obtains polyvinyl alcohol (II) [partly-hydrolysed thing (84.2 moles of % of saponification deg)] thus.This polyvinyl alcohol (II)
1(solvent: d6-DMS0) figure is as follows for H-NMR.
[
1H-NMR] (with reference to Fig. 2)
1.36～1.8ppm: methene proton
1.93～1.95ppm: methyl proton
3.5ppm: the methene proton of uncle's methylol
3.8ppm: methine protons
4.15～4.57ppm: hydroxyl
4.3ppm: the hydroxyl of glycol
4.7～5.2ppm: methine protons
For polyvinyl alcohol that makes (I) and polyvinyl alcohol (II), carried out following evaluation.
(solvability)
Prepared polyvinyl alcohol carries out 3 hours drying under 150 ℃, after the aqueous solution of modulation 10%, use 400 these aqueous solution of purpose metal mesh filter, measures and filters residual content, carries out following evaluation.Evaluation result is as shown in table 1.
Zero: filter residual content less than 0.005%
△: filtering residual content is 0.005%～0.01%
*: filter residual content and surpass 0.01%
With 1300g vinyl acetate between to for plastic, 190g methyl alcohol, 60.5g (2.28 moles of %) 3,4-diacetoxy-1-butylene (B) be fed into be furnished with reflux exchanger, in the retort of dropping funnel and agitator, drop into 0.06 mole of % (with respect to input vinyl acetate between to for plastic) azobis isobutyronitrile, temperature is risen, under 67 ℃, begin polymerization, simultaneously, drip equably and drop into 3,5.4% methanol solution of 4-diacetoxy-1-butylene reaches 85.3% until percent polymerization and has dropped into 116 milliliters.
When the percent polymerization of vinyl acetate between to for plastic is 85.3%, polymerization is stopped, then, adopt the method that is blown into methanol vapor, unreacted Vinyl Acetate Monomer is removed to system, make the methanol solution of multipolymer.
Then, dilute this solution with methyl alcohol, being adjusted to concentration is 40%, again it is put in the kneader, the limit remains on 40 ℃ with solution temperature, the limit is with respect to the vinyl acetate between to for plastic in the multipolymer and 3, and the total amount of 4-diacetoxy-1-butylene is that 2% methanol solution that the ratio of 9 mmole % adds sodium hydroxide carries out saponification.When saponification was carried out, saponified deposition when it becomes particulate state, was carried out filtering separation, and is dry in hot air dryer behind methanol cleaning, makes polyvinyl alcohol.
In the manufacturing of described polyvinyl alcohol, the waste liquid after stopping by the methods analyst saponification identical with embodiment 1, the result does not detect methylcarbonate.
According to residual vinyl acetate between to for plastic and 3, the quantity of alkali consumption that the hydrolysis of 4-diacetoxy-1-butylene is required, saponification deg to gained polyvinyl alcohol (I) is analyzed, this saponification deg is 99.6 moles of % as a result, analyze according to 6726 pairs of mean polymerisation degree of JIS K, this mean polymerisation degree is 1320 as a result.In addition, with the hopper viscometer determining 4% viscosity in aqueous solution of this polyvinyl alcohol, this viscosity is 18.7mPas (20 ℃) as a result.With
1H-NMR (internal standard substance: tetramethylsilane, solvent: d6-DMSO) measure and calculate 1, the import volume of 2-diol bond, this import volume is 3.2 moles of % as a result.In addition, draw samples in the saponification process obtains polyvinyl alcohol (II) [partly-hydrolysed thing (95.0 moles of % of saponification deg)] thus.Gained polyvinyl alcohol (I) and (II) have been carried out the evaluation identical with embodiment 1.Evaluation result is as shown in table 1.
With 1000g vinyl acetate between to for plastic (A), 50g methyl alcohol, 3,4-diacetoxy-1-butylene (6 moles of %) be fed into be furnished with reflux exchanger, in the retort of dropping funnel and agitator, drop into 0.03 mole of % (with respect to input Vinyl Acetate Monomer) azobis isobutyronitrile, temperature is risen, carry out polymerization.When the percent polymerization of vinyl acetate between to for plastic is 72%, drop into stopper, polymerization is stopped.Then, adopt the method that is blown into methanol vapor, unreacted Vinyl Acetate Monomer is removed to system, make the methanol solution of multipolymer.
Then, dilute this solution with methyl alcohol, being adjusted to concentration is 40%, again it is put in the kneader, the limit remains on 40 ℃ with solution temperature, the limit is with respect to the vinyl acetate between to for plastic in the multipolymer and 3, and the total amount of 4-diacetoxy-1-butylene is that 2% methanol solution that the ratio of 8 mmole % adds sodium hydroxide carries out saponification.When saponification was carried out, saponified deposition finally became particulate state.With the polyvinyl alcohol filtering separation that is generated, use methanol cleaning, dry in hot air dryer, make polyvinyl alcohol.
According to residual vinyl acetate between to for plastic and 3, the quantity of alkali consumption that the hydrolysis of 4-diacetoxy-1-butylene is required, saponification deg to gained polyvinyl alcohol (I) is analyzed, this saponification deg is 99.5 moles of % as a result, analyze according to 6726 pairs of mean polymerisation degree of JIS K, this mean polymerisation degree is 1450 as a result.In addition, 4% viscosity in aqueous solution of this polyvinyl alcohol of having used the hopper viscometer determining, this viscosity is 18.6mPas (20 ℃) as a result, uses
1H-NMR (internal standard substance: tetramethylsilane, solvent: d6-DMSO) measure and calculate 1, the import volume of 2-diol bond (with reference to Fig. 3), this import volume is 6.2 moles of % as a result.In addition, draw samples in the saponification process obtains polyvinyl alcohol (II) [partly-hydrolysed thing (87.8 moles of % of saponification deg)] thus.The polyvinyl alcohol (I) that makes and polyvinyl alcohol (II) have been carried out the evaluation identical with embodiment 1.Evaluation result is as shown in table 1.
Embodiment 4
With 1000g vinyl acetate between to for plastic, 50g methyl alcohol, 3,4-diacetoxy-1-butylene (15 moles of %) be dosed to be furnished with reflux exchanger, in the retort of dropping funnel and agitator, drop into 0.06 mole of % (with respect to input Vinyl Acetate Monomer) azobis isobutyronitrile, temperature is risen, carry out polymerization.When the percent polymerization of vinyl acetate between to for plastic is 70%, drop into stopper, polymerization is stopped.Then, adopt the method that is blown into methanol vapor, unreacted Vinyl Acetate Monomer is removed to system, make the methanol solution of multipolymer.
Then, dilute this solution with methyl alcohol, being adjusted to concentration is 40%, again it is put in the kneader, the limit remains on 40 ℃ with solution temperature, the limit is with respect to the vinyl acetate between to for plastic in the multipolymer and 3, and the total amount of 4-diacetoxy-1-butylene is that 2% methanol solution that the ratio of 11 mmole % adds sodium hydroxide carries out saponification.When saponification was carried out, saponified deposition finally became particulate state.With the polyvinyl alcohol filtering separation that is generated, use methanol cleaning, dry in hot air dryer, make polyvinyl alcohol.
According to residual vinyl acetate between to for plastic and 3, the quantity of alkali consumption that the hydrolysis of 4-diacetoxy-1-butylene is required, saponification deg to the polyvinyl alcohol (I) that makes is analyzed, this saponification deg is 99.2 moles of % as a result, analyze according to 6726 pairs of mean polymerisation degree of JIS K, this mean polymerisation degree is 900 as a result.In addition, 4% viscosity in aqueous solution of this polyvinyl alcohol of having used the hopper viscometer determining, this viscosity is 9.5mPas (20 ℃) as a result, uses
1H-NMR (internal standard substance: tetramethylsilane, solvent: d6-DMSO) measure and calculate 1, the import volume of 2-diol bond, this import volume is 14.9 moles of % as a result.In addition, draw samples in the saponification process obtains polyvinyl alcohol (II) [partly-hydrolysed thing (87.8 moles of % of saponification deg)] thus.The polyvinyl alcohol (I) that makes and (II) have been carried out the evaluation identical with embodiment 1.Evaluation result is as shown in table 1.
Comparative example 1
Use the vinylethylene carbonate shown in the following formula (2) to replace 3,4-diacetoxy-1-butylene, in addition identical with embodiment 1, make side chain and have 1, the polyvinyl alcohol of 2-diol bond, and it is estimated.
In addition, use the method identical with embodiment 1, analyzed the waste liquid after the saponification termination, the result detects a large amount of methylcarbonates, in the operation of solvent recuperation, needs the operation of hydrolysis methylcarbonate.
[changing 3]
According to the required quantity of alkali consumption of the unitary hydrolysis of residual vinyl acetate between to for plastic, saponification deg to gained polyvinyl alcohol (I) is analyzed, this saponification deg is 99.5 moles of % as a result, analyzes according to 6726 pairs of mean polymerisation degree of JIS K, and this mean polymerisation degree is 1220 as a result.In addition, with the hopper viscometer determining 4% viscosity in aqueous solution of this polyvinyl alcohol, this viscosity is 15.1mPas (20 ℃) as a result.With
1H-NMR (internal standard substance: tetramethylsilane, solvent: d6-DMSO) measure and calculate 1, the import volume of 2-diol bond, this import volume is 2.8 moles of % as a result.In addition, draw samples in the saponification process obtains polyvinyl alcohol (II) [partly-hydrolysed thing (81.9 moles of % of saponification deg)] thus.The polyvinyl alcohol (I) that makes and (II) have been carried out the evaluation identical with embodiment 1.Evaluation result is as shown in table 1.
Comparative example 2
Satisfy S/M=0.05[S: methyl alcohol (50g), M: vinyl acetate between to for plastic (1000g), percent polymerization are 70%] relation, and drop into 205g (15.5 moles of %) vinylethylene carbonate, in addition operate equally with comparative example 1, attempt making side chain and have 15 moles of %1, the polyvinyl alcohol of 2-diol bond.
Though made multipolymer, when residual unreacted vinyl acetate between to for plastic is removed on input methyl alcohol limit, polymerization termination back, polymkeric substance sedimentary problem in methyl alcohol occurred.
In addition, when saponified copolymer, this polymer deposition can't be avoided inhomogeneous saponification in methanol solvate.In addition, by the method identical with embodiment 1, analyze the waste liquid after saponification stops, the result detects a large amount of methylcarbonates, in the operation of solvent recuperation, needs the operation of hydrolysis methylcarbonate.
According to the required quantity of alkali consumption of the unitary hydrolysis of residual vinyl acetate between to for plastic, saponification deg to gained polyvinyl alcohol (I) is analyzed, this saponification deg is 99.5 moles of % as a result, analyzes according to 6726 pairs of mean polymerisation degree of JIS K, and this mean polymerisation degree is 720 as a result.In addition, with the hopper viscometer determining 4% viscosity in aqueous solution of this polyvinyl alcohol, this viscosity is 7.5mPas (20 ℃) as a result, uses
1H-NMR (internal standard substance: tetramethylsilane, solvent: d6-DMSO) measure and calculate 1, the import volume of 2-diol bond, this import volume is 15 moles of % as a result.In addition, draw samples in the saponification process obtains polyvinyl alcohol (II) [partly-hydrolysed thing (85.1 moles of % of saponification deg)] thus.To polyvinyl alcohol (I) and the polyvinyl alcohol (II) that makes, carried out the evaluation identical with embodiment 1.Evaluation result is as shown in table 1.
[table 1]
Table 1
Embodiment 5
Polyvinyl alcohol that use makes in embodiment 1 (I) and polyvinyl alcohol (II) according to following main points, modulate the binary liquid shape caking agent.
[modulation of binary liquid shape caking agent]
Modulate following host [solids component is 43.5% aqueous emulsion] and solidifying agent [multicomponent isocyanate compound].
(host)
40 parts of 15% aqueous solution of polyvinyl alcohol (I) or polyvinyl alcohol (II)
Solids component is 50% styrene-butadiene copolymer
35 parts of (company of Asahi Chemical Industry's (strain) makes " DL612 ") emulsions
20 parts in lime carbonate
5 parts in water
(solidifying agent)
(content of NCO base is 6.71 * 10 to MDI
-3Mol/g) 9.72 parts
Then, mix and stir above-mentioned synthetic binary liquid shape caking agent, carried out following evaluation.Evaluation result is as shown in table 2.
(normality bonding strength)
At two birch material straight burr planks (on the single face of 10mm * 25mm * 30mm), by 100 ± 10g/m
2Be coated with above-mentioned tackiness agent, coated face is mutually bonding and with 8kg/cm
2Pressurizeed bonding 12 hours, and measured the bonding strength of this moment according to JIS K 6852.
(initial bond strenght)
With the two sides of aforementioned (normality bonding strength) similarly bonding birch material, with 8kg/cm
2Pressurizeed bonding 5 minutes or 10 minutes, and measured the bonding strength of this moment according to JIS K 6852.
(durable bonding strength)
Similarly make bonding sample with aforementioned (normality bonding strength), after 25 ℃ of following slakings 6 days, dipping is 5 hours in ebullient water, 60 ℃ air dryings 24 hours, then, in boiling water, flooded 4 hours again, after this in the water of room temperature, be placed to cooling, measure the bonding strength of just from water, taking out back (wetting state) according to JIS K 6852.
Embodiment 6～8
Polyvinyl alcohol (I) and polyvinyl alcohol (II) that use makes in embodiment 2 (embodiment 6)～embodiment 4 (embodiment 8) carry out evaluation similarly to Example 5, and evaluation result is as shown in table 2.
Comparative example 3
Vinyl acetate between to for plastic (1000g)) and carry out saponification do not use 3,4-diacetoxy-1-butylene, a polymerization vinyl acetate between to for plastic (S/M=0.5, S: methyl alcohol (500g), M:, in addition, make two kinds of polyvinyl alcohol in the same manner with embodiment 1.
According to the required quantity of alkali consumption of the unitary hydrolysis of residual acetic acid, saponification deg to the gained polyvinyl alcohol is analyzed, its saponification deg is 99.1 moles of %[polyvinyl alcohol (I) as a result] and 88.2 moles of %[polyvinyl alcohol (II)], analyze according to 6726 pairs of polymerization degree of JIS K, this polymerization degree is 1200 as a result.
The polyvinyl alcohol that use makes has carried out the evaluation identical with embodiment 5.Evaluation result is as shown in table 2.
[table 2]
Table 2
Embodiment 9
The polyvinyl alcohol that use makes in embodiment 1 (I) is made film according to following main points, and then estimates cold water-soluble, alkali resistance and the chemical proofing of gained film according to following main points.Evaluation result is as shown in table 2.
(making of film)
15% aqueous solution of modulation polyvinyl alcohol (I) adds 15 parts of glycerine with respect to 100 parts of polyvinyl alcohol (I), and curtain coating on 70 ℃ hot-rolling makes the film that thickness is 50 μ m.
(cold water-soluble)
(the 3cm * 3cm), measure and stir down of the above-mentioned film of dipping in the water of 10 ℃ of 1000ml until the consoluet time.
(alkali resistance)
In the sack of the 10cm * 15cm that will make sealing above-mentioned film, the yellow soda ash of packing into after placing half a year under the condition of 40 ℃ * 85%RH, is gathered the diaphragm of 3cm * 3cm from sack, in the water of 15 ℃ of 1000ml, flood, measure and stir down until the consoluet time.
(chemical proofing)
Use TCCA (Trichloroisocyanuric acid) to replace yellow soda ash, in addition, carry out and above-mentioned (alkali resistance) same evaluation.
Embodiment 10～12, comparative example 4
The polyvinyl alcohol (I) that use makes in embodiment 2 (embodiment 10)～embodiment 4 (embodiment 12) and comparative example 3 (comparative example 4) has carried out the evaluation identical with embodiment 9.Evaluation result is as shown in table 3.
In addition, comparative example 4 all is the film swelling in arbitrary evaluation, does not dissolve.
[table 3]
Table 3
| Cold water-soluble (second) | Alkali resistance (second) | Chemical proofing (second) | |
| Embodiment 9 | 30 | 39 | 35 |
| Embodiment 10 | 27 | 31 | 33 |
| Embodiment 11 | 20 | 21 | 24 |
| Embodiment 12 | 12 | 16 | 18 |
| Comparative example 4 | Swelling only | Swelling only | Swelling only |
Industrial applicability
Side chain of the present invention has 1, the polyvinyl alcohol of 2-diol bond makes by making compound shown in the formula (1) and vinyl ester monomers carry out combined polymerization, therefore when making this polyvinyl alcohol, can not produce dimethyl carbonate etc., the operation of removing of need to be after not reclaiming saponification not carrying out dimethyl carbonate in the recovery liquid operation of waste liquid, in addition, even increase by 1, the import volume of 2-diol bond can not destroy the front copolymer (paste) of saponification to the dissolubility of saponification solution (methyl alcohol) yet, therefore can adopt industrial very useful method manufacturing, and then, also possesses gained polyvinyl alcohol (particularly partly-hydrolysed thing) even also can not produce the feature of water insoluble matter through thermal history, the various uses that can be used for existing polyvinyl alcohol from the aspect of operability and product quality, particularly relevant at bonding agent, mechanograph is relevant, coating agent is relevant, emulsifying agent is relevant, useful in the purposes such as suspending agent is relevant, particularly at water soluble package material applications or bonding woods such as alkaline detergent packings, especially useful in the adhesive applications of coniferous tree glued board etc.
Claims (4)
1. a side chain has 1, the polyvinyl alcohol of 2-diol bond, and it carries out saponification by the multipolymer to compound shown in vinyl ester monomers and the following formula (1) and makes,
In the formula, R
1Be hydrogen or alkyl, R
2For singly-bound or optional carbonatoms with alkyl are 1～3 alkylidene group, R
3And R
4Be R independently of one another
5-CO-, in the formula, R
5Be alkyl.
2. polyvinyl alcohol according to claim 1, wherein saponification deg is 99.0 moles more than the %.
3. polyvinyl alcohol according to claim 1, wherein saponification deg is more than 60 moles of % and less than 99.0 moles of %.
4. polyvinyl alcohol according to claim 1, the copolymerization ratio of compound shown in its Chinese style (1) is 0.1～40 mole of %.
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