JP4451935B2 - Process for producing saponified ethylene-vinyl acetate copolymer film - Google Patents
Process for producing saponified ethylene-vinyl acetate copolymer film Download PDFInfo
- Publication number
- JP4451935B2 JP4451935B2 JP01330598A JP1330598A JP4451935B2 JP 4451935 B2 JP4451935 B2 JP 4451935B2 JP 01330598 A JP01330598 A JP 01330598A JP 1330598 A JP1330598 A JP 1330598A JP 4451935 B2 JP4451935 B2 JP 4451935B2
- Authority
- JP
- Japan
- Prior art keywords
- vinyl acetate
- ethylene
- acid
- acetate copolymer
- polymerization
- 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
- 239000005038 ethylene vinyl acetate Substances 0.000 title claims description 37
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 title claims description 37
- 238000000034 method Methods 0.000 title description 20
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 27
- 239000003054 catalyst Substances 0.000 claims description 24
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 23
- 239000005977 Ethylene Substances 0.000 claims description 23
- -1 azo compound Chemical class 0.000 claims description 21
- 239000002738 chelating agent Substances 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 238000000465 moulding Methods 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 10
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 7
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- RBNPOMFGQQGHHO-UHFFFAOYSA-N -2,3-Dihydroxypropanoic acid Natural products OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 claims description 3
- RBNPOMFGQQGHHO-UWTATZPHSA-N D-glyceric acid Chemical compound OC[C@@H](O)C(O)=O RBNPOMFGQQGHHO-UWTATZPHSA-N 0.000 claims description 3
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 3
- 150000002978 peroxides Chemical group 0.000 claims description 2
- 229920006026 co-polymeric resin Polymers 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 45
- 238000006116 polymerization reaction Methods 0.000 description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 241000251468 Actinopterygii Species 0.000 description 9
- 238000007127 saponification reaction Methods 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 239000008188 pellet Substances 0.000 description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 5
- 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 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 4
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- 229920001451 polypropylene glycol Polymers 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 2
- 235000011054 acetic acid Nutrition 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000001112 coagulating effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
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- 239000004753 textile Substances 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 1
- QBYIENPQHBMVBV-HFEGYEGKSA-N (2R)-2-hydroxy-2-phenylacetic acid Chemical compound O[C@@H](C(O)=O)c1ccccc1.O[C@@H](C(O)=O)c1ccccc1 QBYIENPQHBMVBV-HFEGYEGKSA-N 0.000 description 1
- NOBYOEQUFMGXBP-UHFFFAOYSA-N (4-tert-butylcyclohexyl) (4-tert-butylcyclohexyl)oxycarbonyloxy carbonate Chemical compound C1CC(C(C)(C)C)CCC1OC(=O)OOC(=O)OC1CCC(C(C)(C)C)CC1 NOBYOEQUFMGXBP-UHFFFAOYSA-N 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- UOFGSWVZMUXXIY-UHFFFAOYSA-N 1,5-Diphenyl-3-thiocarbazone Chemical compound C=1C=CC=CC=1N=NC(=S)NNC1=CC=CC=C1 UOFGSWVZMUXXIY-UHFFFAOYSA-N 0.000 description 1
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- MFLLXRJTHGPGEB-UHFFFAOYSA-N 1-propylperoxypropane Chemical compound CCCOOCCC MFLLXRJTHGPGEB-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- 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 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- GYAZFWRAWZSHCP-UHFFFAOYSA-N 2-[(2-cyano-4,4-dimethylpentan-2-yl)diazenyl]-2,4,4-trimethylpentanenitrile Chemical compound CC(C)(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)(C)C GYAZFWRAWZSHCP-UHFFFAOYSA-N 0.000 description 1
- PFHOSZAOXCYAGJ-UHFFFAOYSA-N 2-[(2-cyano-4-methoxy-4-methylpentan-2-yl)diazenyl]-4-methoxy-2,4-dimethylpentanenitrile Chemical compound COC(C)(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)(C)OC PFHOSZAOXCYAGJ-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- UPZFLZYXYGBAPL-UHFFFAOYSA-N 2-ethyl-2-methyl-1,3-dioxolane Chemical compound CCC1(C)OCCO1 UPZFLZYXYGBAPL-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
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- FCKYPQBAHLOOJQ-UHFFFAOYSA-N Cyclohexane-1,2-diaminetetraacetic acid Chemical compound OC(=O)CN(CC(O)=O)C1CCCCC1N(CC(O)=O)CC(O)=O FCKYPQBAHLOOJQ-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 1
- JYXGIOKAKDAARW-UHFFFAOYSA-N N-(2-hydroxyethyl)iminodiacetic acid Chemical compound OCCN(CC(O)=O)CC(O)=O JYXGIOKAKDAARW-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
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- IWYDHOAUDWTVEP-UHFFFAOYSA-N R-2-phenyl-2-hydroxyacetic acid Natural products OC(=O)C(O)C1=CC=CC=C1 IWYDHOAUDWTVEP-UHFFFAOYSA-N 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-N Salicylic acid Natural products OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
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- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
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- XJOBOFWTZOKMOH-UHFFFAOYSA-N decanoyl decaneperoxoate Chemical compound CCCCCCCCCC(=O)OOC(=O)CCCCCCCCC XJOBOFWTZOKMOH-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
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- 239000002274 desiccant Substances 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
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- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
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- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
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- NMOALOSNPWTWRH-UHFFFAOYSA-N tert-butyl 7,7-dimethyloctaneperoxoate Chemical compound CC(C)(C)CCCCCC(=O)OOC(C)(C)C NMOALOSNPWTWRH-UHFFFAOYSA-N 0.000 description 1
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- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- TZYULTYGSBAILI-UHFFFAOYSA-M trimethyl(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC=C TZYULTYGSBAILI-UHFFFAOYSA-M 0.000 description 1
- ZQYKGADTDCTWSZ-UHFFFAOYSA-N trimethyl-[(prop-2-enoylamino)methyl]azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CNC(=O)C=C ZQYKGADTDCTWSZ-UHFFFAOYSA-N 0.000 description 1
- 229920006163 vinyl copolymer Polymers 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
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- Chemical Kinetics & Catalysis (AREA)
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- Organic Chemistry (AREA)
- Polymerisation Methods In General (AREA)
- Polymerization Catalysts (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、エチレン−酢酸ビニル共重合体ケン化物の溶融成形フィルムの製造方法に関し、着色が少なく、かつフィッシュアイの少ないフィルムの製造方法に関する。
【０００２】
【従来の技術】
エチレン−酢酸ビニル共重合体ケン化物はガスバリアー性、機械的強度等の諸性質に優れていることから、フィルム、シート、容器、繊維等の各種用途に多用されている。
該ケン化物はエチレンと酢酸ビニルを溶媒中で共重合し、次いでケン化することによって製造されるが、該エチレン−酢酸ビニル共重合体の重合は、通常、メタノール等のアルコール溶媒中で、原料であるエチレン及び酢酸ビニルを導入してパーオキシド類、アゾ化合物等の触媒の共存下で行われる。
【０００３】
【発明が解決しようとする課題】
しかしながら、上記の如き公知の触媒のみの存在下でエチレン−酢酸ビニル共重合体の重合を行った場合、該重合体のケン化物をフィルムにした時、フィッシュアイが多発し、品質の低下を招く場合もあり、更なる改善が望まれるところである。
【０００４】
【課題を解決するための手段】
そこで、本発明者は上記の問題を解決するため鋭意研究を重ねた結果、キレート化剤および触媒の共存下に溶媒中でエチレンと酢酸ビニルを共重合させると、エチレン含有量が１５〜６０モル％のエチレン−酢酸ビニル共重合体より得られたケン化物は着色が少なく、該ケン化物を溶融成形によりフィルムにした時、フィッシュアイも少ないことを見出し本発明を完成するに到った。
【０００５】
【発明の実施の形態】
以下に本発明を詳細に説明する。
エチレンと酢酸ビニルの共重合は溶媒中での重合、すなわち溶液重合法が実施される。
エチレンと酢酸ビニルの溶液重合法は、溶媒中で触媒の存在下に行われ、連続式、回分式のいずれであっても良く、重合法に応じて適宜条件が設定される。
溶媒としては炭素数４以下のアルコール又は炭素数４以下のアルコールを主とする混合溶媒が用いられ、該アルコールとしては、メタノール、エタノール、プロパノール等が挙げられるが、好ましくはメタノールが用いられ、溶媒量としては酢酸ビニル１００重量部に対して、１〜６０重量部が好ましい。
【０００６】
触媒としては、ラジカル開始剤であれば特に制限なく用いられるが、好ましくは２，２′−アゾビス−（２，４−ジメチルバレロニトリル）、２，２′−アゾビス−（２，４，４−トリメチルバレロニトリル）、２，２′−アゾビスイソブチロニトリル、２，２′−アゾビス−（４−メトキシ−２，４−ジメチルバレロニトリル）、２，２′−アゾビス−（２−メチルイソブチラート）などのアゾ化合物、ｔ−ブチルパーオキシネオデカノエート、ｔ−ブチルパーピバレート、ｔ−ブチルパーオキシ−２−エチルヘキノエートなどのアルキルパーエステル類、ビス−（４−ｔ−ブチルシクロヘキシル）パーオキシ−ジ−カーボネート、ジ−シクロヘキシルパーオキシ−ジ−カーボネート、ビス（２−エチルヘキシル）ジ−ｓｅｃ−ブチルパーオキシ−ジ−カーボネート、ジ−イソプロピルパーオキシ−ジ−カーボネートなどのパーオキシ−ジ−カーボネート類、アセチルパーオキシド、ベンゾイルパーオキシド、ラウロイルパーオキシド、ジ−ラウロイルパーオキシド、ジ−デカノイルパーオキシド、ジ−オクタノイルパーオキシド、ジ−プロピルパーオキシドなどのパーオキシド類などが挙げられる。
【０００７】
触媒の使用量は、回分式の場合、酢酸ビニル１００重量部に対して、０．００２〜０．１重量部が好ましく、０．００２重量部未満では、触媒効率が悪く重合時間が長くなったり、重合が進まない場合があり、０．１重量部を越えると、重合の制御が困難となったり、重合終了後も触媒が残存して後重合を起こすことがあり好ましくない。連続式の場合、酢酸ビニル１００重量部に対して、０．００２〜０．０６重量部が好ましく、０．００２重量部未満では、触媒効率が悪く重合時間が長くなったり、重合が進まない場合があり、０．０６重量部を越えると、重合の制御が困難となったり、重合終了後も触媒が残存して後重合を起こすことがあり好ましくない。
【０００８】
本発明では、エチレン−酢酸ビニル共重合体を重合するに当たり、上記触媒とともにキレート化剤を共存させることを最大の特徴とするのもので、該キレート化剤としては、エチレンジアミンモノ酢酸、エチレンジアミン二酢酸、エチレンジアミン四酢酸（以下ＥＤＴＡと略記する）、ニトリロ三酢酸、１、２−シクロヒキサンジアミン四酢酸、ジエチレントリアミン五酢酸、、３，６−ジオキサ−１，８−オクタンジアミン四酢酸、２−ヒドロキシエチルエチレンジアミン三酢酸、２−ヒドロキシエチルイミノ二酢酸、イミノ酢酸、トリエチレンテトラミン六酢酸などのポリアミノカルボン酸類、クエン酸、グリコール酸、グリセリン酸、乳酸、リンゴ酸、酒石酸、マンデル酸、サリチル酸などのオキシカルボン酸類、縮合リン酸塩、ジメチルグリオキシム、オキシン、ジチゾン等が挙げられ、好ましくは、ＥＤＴＡ、ニトリロ三酢酸、クエン酸、グリコール酸、グリセリン酸である。
【０００９】
共存させるキレート化剤の量は回分式の反応、連続式いずれの場合でも、酢酸ビニル１００重量部に対して０．００１〜０．０１重量部が好ましく、更には０．００２〜０．００６重量部である。０．００１重量部未満あるいは０．０１重量部を越えると、共重合させたエチレン−酢酸ビニル共重合体をケン化してケン化物とした時、著しく着色したり、溶融成形した場合にフィッシュアイが発生することがあるので好ましくない。
【００１０】
上記のキレート化剤と触媒を重合反応系に仕込むにあたっては、▲１▼酢酸ビニル、キレート化剤、触媒を別々に、あるいはキレート化剤含有量を予めコントロールした酢酸ビニルをアルコール溶媒に溶解し、触媒を添加し、更にエチレンを高圧下に仕込む方法、▲２▼酢酸ビニルをアルコール溶媒に溶解し、触媒及びキレート化剤を添加し、更にエチレンを高圧下に仕込む方法等が実施される。
【００１１】
重合温度として好ましくは４０〜８０℃、更には５５〜７０℃である。該重合温度が４０℃未満では重合に長時間を要し、重合時間を短縮しようとすると触媒が多量に必要となり、８０℃を越えると重合制御が困難となり好ましくない。 重合時間は、回分式の場合、好ましくは４〜１０時間、更には６〜９時間である。該重合時間が４時間未満では重合温度を高くしたり、触媒量を多く設定しなければならず、重合制御が困難となり、１０時間を越えると生産性の面で問題があり好ましくない。連続式の場合、重合缶内での平均滞留時間は２〜８時間が好ましく、更には２〜６時間である。該滞留時間が２時間未満では重合温度を高くしたり、触媒量を多く設定しなければならず、重合制御が困難となり、８時間を越えると生産性の面で問題があり好ましくない。
【００１２】
重合率（酢酸ビニル）は生産性の面から重合制御が可能な範囲で出来るだけ高く設定され、回分式の場合、好ましくは２０〜９０％に設定される。該重合率が２０％未満では工業的に生産性が悪く、未重合の酢酸ビニルが多量に残存するという問題があり、９０％を越えると重合制御が困難となり好ましくない。
連続式の場合、重合率は、好ましくは２０〜６０％に設定される。該重合率が２０％未満では工業的に生産性が悪く、未重合の酢酸ビニルが多量に残存するという問題があり、６０％を越えると重合制御が困難となり好ましくない。
【００１３】
また、エチレン−酢酸ビニル共重合体中のエチレン含有量は、重合缶内のエチレン圧等によりコントロールすることができ、かかる含有量は１５〜６０モル％であり、好ましくは２５〜５５モル％である。該エチレン含有量が１５モル％未満では、エチレン−酢酸ビニル共重合体をケン化して得られたケン化物を溶融成形する場合、溶融成形性が低下すると共に、溶融成形物の高湿時のガスバリヤー性が大きく低下し、６０モル％を越えると、該ケン化物を溶融成形した場合、成形物の機械的強度及びガスバリアー性が充分でなく好ましくない。この時のエチレン圧としては１．４７〜７．３５ＭＰａに設定される。
【００１４】
又、本発明において、エチレン−酢酸ビニル共重合体の重合法はエチレン、酢酸ビニル以外に、これらと共重合可能なエチレン性不飽和単量体を共重合成分として含有しても差し支えない。該単量体としては、例えばプロピレン、イソブチレン、α−オクテン、α−ドデセン、α−オクタデセン等のオレフィン類、アクリル酸、メタクリル酸、クロトン酸、マレイン酸、無水マレイン酸、イタコン酸等の不飽和酸類あるいはその塩あるいはモノ又はジアルキルエステル等、アクリロニトリル、メタアクリロニトリル等のニトリル類、アクリルアミド、メタクリルアミド等のアミド類、エチレンスルホン酸、アリルスルホン酸、メタアリルスルホン酸等のオレフィンスルホン酸あるいはその塩、アルキルビニルエーテル類、Ｎ−アクリルアミドメチルトリメチルアンモニウムクロライド、アリルトリメチルアンモニウムクロライド、ジメチルアリルビニルケトン、Ｎ−ビニルピロリドン、塩化ビニル、塩化ビニリデン、ポリオキシエチレン（メタ）アリルエーテル、ポリオキシプロピレン（メタ）アリルエーテルなどのポリオキシアルキレン（メタ）アリルエーテル、ポリオキシエチレン（メタ）アクリレート、ポリオキシプロピレン（メタ）アクリレート等のポリオキシアルキレン（メタ）アクリレート、ポリオキシエチレン（メタ）アクリルアミド、ポリオキシプロピレン（メタ）アクリルアミド等のポリオキシアルキレン（メタ）アクリルアミド、ポリオキシエチレン（１−（メタ）アクリルアミド−１，１−ジメチルプロピル）エステル、ポリオキシエチレンビニルエーテル、ポリオキシプロピレンビニルエーテル、ポリオキシエチレンアリルアミン、ポリオキシプロピレンアリルアミン、ポリオキシエチレンビニルアミン、ポリオキシプロピレンビニルアミン等が挙げられる。
【００１５】
かくして本発明の重合法でエチレン−酢酸ビニル共重合体が得られるわけであるが、かかるエチレン−酢酸ビニル共重合体は、接着剤、粘着剤、塗料、繊維・織物の加工剤、紙・皮革の加工剤、各種材料のバインダー、セメント・モルタルの混和液等に利用される。
【００１６】
上記の重合法で得られたエチレン−酢酸ビニル共重合体は更にケン化され、エチレン−酢酸ビニル共重合体ケン化物として用途拡大が可能であり、かかるケン化反応は、通常、アルカリ触媒の共存下に実施される。
ケン化に当たっては、上記エチレン−酢酸ビニル共重合体を、アルコール（通常メタノールが用いられる）又はアルコール含有媒体中に通常２０〜６０重量％程度の濃度になる如く溶解し、アルカリ触媒（通常水酸化ナトリウム、水酸化カリウムなどのアルカリ金属水酸化物が用いられる）を添加して４０〜１４０℃の温度で反応せしめる。
【００１７】
かかるケン化により得られるエチレン−酢酸ビニル共重合体ケン化物の酢酸ビニル成分のケン化度は８０〜１００モル％とすることが好ましく、更にはケン化度９０〜１００モル％、特に９５〜１００モル％とするのが有利である。ケン化度が８０モル％未満の場合、該エチレン−酢酸ビニル共重合体ケン化物を溶融成形する場合の熱安定性が悪くなると共に、得られた成形物も機械的強度やガスバリアー性が大きく低下して好ましくない。
【００１８】
次に上記で得られたエチレン−酢酸ビニル共重合体ケン化物のアルコール溶液はそのままでもよいが、好ましくは、水を加えるだけか、水を加えて、更に該ケン化物溶液を適宜濃度調整して、アルコール／水溶液としてストランド製造用の溶液とする。
【００１９】
次いで、エチレン−酢酸ビニル共重合体ケン化物のアルコール／水溶液は、水又は水／アルコール（混合）溶液等の凝固液中にストランド状に押し出して析出させるのである。
【００２０】
析出させたストランドは次に切断されてペレット状となり、次いで水洗される。
水洗したペレットは酸及び／又はそれらの塩類等の薬剤の水溶液で浸漬させる等の方法で化学処理を行なうことが好ましく、かかる薬剤としては、ギ酸、酢酸、アジピン酸、リン酸、ホウ酸あるいはそれらの塩類等が挙げられ、より好ましくは酢酸、リン酸、ホウ酸あるいはそれらの塩類が用いられる。
【００２１】
上記で得られたペレットは溶融成形されて所望する成形物に成形されるのであるが、溶融成形に際しての温度条件としては１６０〜２６０℃程度とするのが望ましい。成形に際しては必要に応じガラス繊維、炭素繊維などの補強材、フィラー、着色剤、ハイドロタルサイトなどの安定剤、発泡剤、乾燥剤などの公知の添加剤を適当量配合することもある。又、エチレン−酢酸ビニル共重合体ケン化物には改質用の熱可塑性樹脂を適当量配合することもできる。
【００２２】
溶融成形法としては射出成形法、圧縮成形法、押出成形法など任意の成形法が採用できる。このうち押出成形法としてはＴ−ダイ法、中空成形法、パイプ押出法、線条押出法、異形ダイ押出法、インフレーション法などが挙げられるが、エチレン−酢酸ビニル共重合体ケン化物単独の成形物（フィルム、シート、テープ、ボトル、パイプ、フィラメント、異型断面押出物など）のみならず、エチレン−酢酸ビニル共重合体ケン化物層と他の熱可塑性樹脂層との共押出成形も可能である。
【００２３】
【実施例】
以下、実施例を挙げて本発明を具体的に説明する。尚、実施例中、「部」、「％」とあるのは、特に断りのない限り重量基準である。
実施例１
内容量１０ｌの重合缶を用いて以下の条件でエチレン−酢酸ビニル共重合体を連続重合した。
酢酸ビニル供給量 １２９０ｇ／ｈｒ
メタノール供給量 ２００ｇ／ｈｒ
ベンゾイルパーオキサイド供給量 ２５０ｍｇ／ｈｒ
ＥＤＴＡ供給量 ５２ｍｇ／ｈｒ
（酢酸ビニル１００重量部に対して０．００４重量部となる）
重合温度 ６７℃
エチレン圧 ３．９２ＭＰａ
平均滞留時間 ４ｈｒ
この時得られたエチレン−酢酸ビニル共重合体のエチレン含有量は３２モル％で、酢酸ビニルの重合率は３８％であった。
得られたエチレン−酢酸ビニル共重合体を以下の様にエチレン−酢酸ビニル共重合体ケン化物として、ペレットの色相や製膜時のフィッシュアイについて評価した。
【００２４】
上記エチレン−酢酸ビニル共重合体を５０％含むメタノール溶液１００部に、該共重合体中の酢酸ビニル基に対して０．０１７当量の水酸化ナトリウムを含有するメタノール溶液１５０部を供給し、１２０〜１３０℃、圧力０．３９ＭＰａで、３０分間ケン化反応を行った。得られたエチレン−酢酸ビニル共重合体ケン化物（ケン化度９９．８モル％）のメタノール溶液の樹脂分濃度は３０％であった。
【００２５】
次に含水率６２．５％のメタノール水溶液６０部を、該エチレン−酢酸ビニル共重合体ケン化物のメタノール溶液に共沸下で供給し、１００〜１１０℃、圧力０．２９ＭＰａで、エチレン−酢酸ビニル共重合体ケン化物のメタノール／水溶液中の樹脂分濃度が４０％になるまでメタノールを留出させ、完全透明なメタノール／水均一溶液を得た。
続いて得られたエチレン−酢酸ビニル共重合体ケン化物のメタノール／水溶液を、水／メタノール溶液（重量比９５／５）よりなる凝固液槽に、ストランド状に押し出してカッターで切断し、エチレン−酢酸ビニル共重合体ケン化物のペレットを得た。
【００２６】
（１）ペレットの色相
○・・・着色なし
△・・・目視でやや黄色に着色
×・・・目視で黄色に着色
次に上記で得られたケン化物を以下の条件で製膜し、得られたフィルムのフィッシュアイを以下の様に評価した。
（２）フィッシュアイ
フィルム１００ｃｍ２当たりのフィッシュアイの数を測定した。
○・・・５個未満
△・・・５〜１０個未満
×・・・１０個以上
結果を表１に示した。
【００２８】
実施例２
実施例１において触媒を２，２’−アゾビスイソブチロニトリルとした以外は同様に実施し、エチレン含有量３２モル％、酢酸ビニルの重合率４２％のエチレン−酢酸ビニル共重合体を得た後、実施例１と同様にしてケン化物として、実施例１と同様に評価した。
【００２９】
実施例３
実施例１において、ＥＤＴＡの替わりに、クエン酸を用いた以外は同様に実施して、エチレン含有量３２モル％、酢酸ビニルの重合率３８％のエチレン−酢酸ビニル共重合体を得た後、実施例１と同様にしてケン化物として、実施例１と同様に評価した。
【００３０】
比較例１
実施例１において、ＥＤＴＡを用いなかった以外は同様に実施してエチレン含量３２モル％、酢酸ビニルの重合率３８％のエチレン−酢酸ビニル共重合体を得た後、実施例１と同様にしてケン化物として、実施例１と同様に評価した。
実施例および比較例の評価を表１に示した。
【００３１】
【表１】
【発明の効果】
本発明では、キレート化剤および触媒の共存下にエチレンと酢酸ビニルを溶媒中で共重合させるので、得られた、エチレン含有量が１５〜６０モル％のエチレン−酢酸ビニル共重合体から製造されるエチレン−酢酸ビニル共重合体ケン化物は着色が少なく、またかかるケン化物から溶融成形により得られたフィルムはフィッシュアイが少ない。[0001]
BACKGROUND OF THE INVENTION
The present invention is an ethylene - relates to a method for producing a melt-molded film of vinyl acetate copolymer saponified, little discoloration, and a method of manufacturing a small fill arm of fish eyes.
[0002]
[Prior art]
Saponified ethylene-vinyl acetate copolymer is widely used in various applications such as films, sheets, containers, and fibers because of its excellent properties such as gas barrier properties and mechanical strength.
The saponified product is produced by copolymerizing ethylene and vinyl acetate in a solvent and then saponifying, but the polymerization of the ethylene-vinyl acetate copolymer is usually performed in a raw material in an alcohol solvent such as methanol. This is carried out in the presence of catalysts such as peroxides and azo compounds by introducing ethylene and vinyl acetate.
[0003]
[Problems to be solved by the invention]
However, when an ethylene-vinyl acetate copolymer is polymerized in the presence of only a known catalyst as described above, when a saponified product of the polymer is formed into a film, fish eyes frequently occur and the quality is deteriorated. In some cases, further improvements are desired.
[0004]
[Means for Solving the Problems]
Therefore, as a result of intensive studies to solve the above problems, the present inventors have found that when ethylene and vinyl acetate are copolymerized in a solvent in the presence of a chelating agent and a catalyst , the ethylene content is 15 to 60 mol. % Of the saponified product obtained from the ethylene-vinyl acetate copolymer was found to be less colored, and when the saponified product was formed into a film by melt molding , the fish eye was also found to be completed, and the present invention was completed.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
The present invention is described in detail below.
Copolymerization of ethylene and vinyl acetate is carried out in a solvent, that is, a solution polymerization method.
The solution polymerization method of ethylene and vinyl acetate is performed in the presence of a catalyst in a solvent, and may be either a continuous type or a batch type, and conditions are appropriately set according to the polymerization method.
As the solvent, an alcohol having 4 or less carbon atoms or a mixed solvent mainly containing an alcohol having 4 or less carbon atoms is used, and examples of the alcohol include methanol, ethanol, propanol, etc., preferably methanol is used, The amount is preferably 1 to 60 parts by weight with respect to 100 parts by weight of vinyl acetate.
[0006]
The catalyst is not particularly limited as long as it is a radical initiator, but preferably 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobis- (2,4,4- Trimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 2,2'-azobis- (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis- (2-methyliso) Azo compounds such as butyrate), alkyl peresters such as t-butylperoxyneodecanoate, t-butylperpivalate, t-butylperoxy-2-ethylhexanoate, bis- (4-t -Butylcyclohexyl) peroxy-dicarbonate, di-cyclohexylperoxy-dicarbonate, bis (2-ethylhexyl) di-sec-butylper Peroxy-di-carbonates such as x-di-carbonate, di-isopropyl peroxy-di-carbonate, acetyl peroxide, benzoyl peroxide, lauroyl peroxide, di-lauroyl peroxide, di-decanoyl peroxide, di -Peroxides such as octanoyl peroxide and di-propyl peroxide.
[0007]
In the case of a batch system, the amount of catalyst used is preferably 0.002 to 0.1 parts by weight with respect to 100 parts by weight of vinyl acetate, and if it is less than 0.002 parts by weight, the catalyst efficiency is poor and the polymerization time is prolonged. In some cases, the polymerization does not proceed. If the amount exceeds 0.1 parts by weight, it is difficult to control the polymerization, or the catalyst may remain after the polymerization is completed, which is not preferable. In the case of continuous type, 0.002 to 0.06 parts by weight is preferable with respect to 100 parts by weight of vinyl acetate, and if it is less than 0.002 parts by weight, the catalyst efficiency is poor and the polymerization time is prolonged or the polymerization does not proceed. If the amount exceeds 0.06 parts by weight, it is difficult to control the polymerization, or the catalyst may remain after the completion of the polymerization and cause post-polymerization.
[0008]
In the present invention, in the polymerization of the ethylene-vinyl acetate copolymer, the greatest feature is that a chelating agent is allowed to coexist with the above catalyst. Examples of the chelating agent include ethylenediamine monoacetic acid, ethylenediaminediacetic acid. , Ethylenediaminetetraacetic acid (hereinafter abbreviated as EDTA), nitrilotriacetic acid, 1,2-cyclohexanediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 3,6-dioxa-1,8-octanediaminetetraacetic acid, 2-hydroxy Polyaminocarboxylic acids such as ethylethylenediaminetriacetic acid, 2-hydroxyethyliminodiacetic acid, iminoacetic acid, triethylenetetraminehexaacetic acid, oxyacids such as citric acid, glycolic acid, glyceric acid, lactic acid, malic acid, tartaric acid, mandelic acid, salicylic acid Carboxylic acids, condensed phosphates, dimethyl Caprylyl oxime, oxine, dithizone and the like, preferably, EDTA, nitrilotriacetic acid, citric acid, glycolic acid, glyceric acid.
[0009]
The amount of the chelating agent to be coexisted is preferably 0.001 to 0.01 parts by weight, more preferably 0.002 to 0.006 parts by weight with respect to 100 parts by weight of vinyl acetate in both batch reaction and continuous reaction. Part. If it is less than 0.001 part by weight or more than 0.01 part by weight, when the copolymerized ethylene-vinyl acetate copolymer is saponified to form a saponified product, fish eyes may be noticeably colored or melt-formed. It is not preferable because it may occur.
[0010]
In charging the above-mentioned chelating agent and catalyst into the polymerization reaction system, (1) vinyl acetate, the chelating agent and the catalyst are separately added, or vinyl acetate whose content of the chelating agent is controlled in advance is dissolved in an alcohol solvent, A method of adding a catalyst and further charging ethylene under high pressure, and (2) a method of dissolving vinyl acetate in an alcohol solvent, adding a catalyst and a chelating agent, and further charging ethylene under high pressure, etc.
[0011]
The polymerization temperature is preferably 40 to 80 ° C, more preferably 55 to 70 ° C. If the polymerization temperature is less than 40 ° C., it takes a long time for the polymerization. If the polymerization time is to be shortened, a large amount of catalyst is required, and if it exceeds 80 ° C., it is difficult to control the polymerization. In the case of a batch system, the polymerization time is preferably 4 to 10 hours, and further 6 to 9 hours. If the polymerization time is less than 4 hours, the polymerization temperature must be increased or the amount of catalyst must be set large, and polymerization control becomes difficult, and if it exceeds 10 hours, there is a problem in terms of productivity, which is not preferred. In the case of the continuous type, the average residence time in the polymerization can is preferably 2 to 8 hours, more preferably 2 to 6 hours. If the residence time is less than 2 hours, the polymerization temperature must be increased or the amount of catalyst must be set large, and the polymerization control becomes difficult, and if it exceeds 8 hours, there is a problem in productivity and this is not preferred.
[0012]
The polymerization rate (vinyl acetate) is set as high as possible in the range in which polymerization can be controlled from the viewpoint of productivity, and in the case of a batch system, it is preferably set to 20 to 90%. If the polymerization rate is less than 20%, the industrial productivity is poor and there is a problem that a large amount of unpolymerized vinyl acetate remains, and if it exceeds 90%, polymerization control becomes difficult, which is not preferable.
In the case of the continuous type, the polymerization rate is preferably set to 20 to 60%. If the polymerization rate is less than 20%, the industrial productivity is poor, and there is a problem that a large amount of unpolymerized vinyl acetate remains. If it exceeds 60%, polymerization control becomes difficult, which is not preferable.
[0013]
In addition, the ethylene content in the ethylene-vinyl acetate copolymer can be controlled by the ethylene pressure in the polymerization can, and the content is 15 to 60 mol% , preferably 25 to 55 mol%. is there. When the ethylene content is less than 15 mol%, when melt-molding a saponified product obtained by saponifying an ethylene-vinyl acetate copolymer, the melt moldability deteriorates and the gas at high humidity of the melt-molded product is reduced. When the barrier property is greatly lowered and exceeds 60 mol%, when the saponified product is melt-molded, the mechanical strength and gas barrier property of the molded product are not sufficient, which is not preferable. The ethylene pressure at this time is set to 1.47 to 7.35 MPa.
[0014]
In the present invention, the ethylene-vinyl acetate copolymer polymerization method may contain, as a copolymerization component, an ethylenically unsaturated monomer copolymerizable therewith in addition to ethylene and vinyl acetate. Examples of the monomer include olefins such as propylene, isobutylene, α-octene, α-dodecene, α-octadecene, and unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, maleic anhydride, and itaconic acid. Acids or salts thereof or mono- or dialkyl esters, nitriles such as acrylonitrile and methacrylonitrile, amides such as acrylamide and methacrylamide, olefin sulfonic acids such as ethylene sulfonic acid, allyl sulfonic acid, methallyl sulfonic acid or salts thereof, Alkyl vinyl ethers, N-acrylamidomethyltrimethylammonium chloride, allyltrimethylammonium chloride, dimethylallyl vinyl ketone, N-vinylpyrrolidone, vinyl chloride, vinylidene chloride, polyoxyethylene (Meth) allyl ether, polyoxyalkylene (meth) allyl ether such as polyoxypropylene (meth) allyl ether, polyoxyalkylene (meth) acrylate such as polyoxyethylene (meth) acrylate and polyoxypropylene (meth) acrylate , Polyoxyethylene (meth) acrylamide, polyoxyalkylene (meth) acrylamide such as polyoxypropylene (meth) acrylamide, polyoxyethylene (1- (meth) acrylamide-1,1-dimethylpropyl) ester, polyoxyethylene vinyl ether , Polyoxypropylene vinyl ether, polyoxyethylene allylamine, polyoxypropylene allylamine, polyoxyethylene vinylamine, polyoxypropylene vinylamine, etc. It is below.
[0015]
Thus, an ethylene-vinyl acetate copolymer can be obtained by the polymerization method of the present invention. Such an ethylene-vinyl acetate copolymer can be used for adhesives, pressure-sensitive adhesives, paints, textile / textile processing agents, paper / leather. It is used in various processing agents, binders of various materials, cement and mortar admixtures.
[0016]
The ethylene-vinyl acetate copolymer obtained by the above-described polymerization method is further saponified, and its application can be expanded as a saponified ethylene-vinyl acetate copolymer. Such a saponification reaction is usually performed in the presence of an alkali catalyst. Implemented below.
In the saponification, the above ethylene-vinyl acetate copolymer is dissolved in an alcohol (usually methanol is used) or an alcohol-containing medium to a concentration of usually about 20 to 60% by weight, and an alkali catalyst (usually hydroxylated) is used. An alkali metal hydroxide such as sodium or potassium hydroxide is used) and the reaction is carried out at a temperature of 40 to 140 ° C.
[0017]
The saponification degree of the vinyl acetate component of the saponified ethylene-vinyl acetate copolymer obtained by such saponification is preferably 80 to 100 mol%, more preferably 90 to 100 mol%, particularly 95 to 100 mol%. The mol% is advantageous. When the saponification degree is less than 80 mol%, the thermal stability when melt-molding the ethylene-vinyl acetate copolymer saponified product is deteriorated, and the obtained molded product also has high mechanical strength and gas barrier properties. Decreasing and not preferable.
[0018]
Next, the alcohol solution of the ethylene-vinyl acetate copolymer saponified product obtained above may be used as it is, but preferably only water is added or water is added, and the concentration of the saponified solution is adjusted appropriately. A solution for producing a strand is used as an alcohol / water solution.
[0019]
Next, the alcohol / water solution of the saponified ethylene-vinyl acetate copolymer is extruded into a coagulating liquid such as water or a water / alcohol (mixed) solution and precipitated.
[0020]
The precipitated strand is then cut into pellets and then washed with water.
The pellets washed with water are preferably subjected to chemical treatment by a method such as immersion in an aqueous solution of a chemical such as acid and / or their salts. Examples of such chemicals include formic acid, acetic acid, adipic acid, phosphoric acid, boric acid, or the like. More preferably, acetic acid, phosphoric acid, boric acid or salts thereof are used.
[0021]
The pellets obtained as described above are melt-molded and formed into a desired molded product. The temperature condition during melt-molding is preferably about 160 to 260 ° C. In molding, an appropriate amount of a known additive such as a reinforcing material such as glass fiber or carbon fiber, a filler, a colorant, a stabilizer such as hydrotalcite, a foaming agent or a drying agent may be blended as necessary. Further, an appropriate amount of a thermoplastic resin for modification can be blended in the saponified ethylene-vinyl acetate copolymer.
[0022]
As the melt molding method, any molding method such as an injection molding method, a compression molding method, and an extrusion molding method can be employed. Among these, the extrusion molding method includes a T-die method, a hollow molding method, a pipe extrusion method, a linear extrusion method, a deformed die extrusion method, an inflation method, etc., but molding of an ethylene-vinyl acetate copolymer saponified product alone. Coextrusion of not only products (films, sheets, tapes, bottles, pipes, filaments, profile cross-section extrudates, etc.) but also saponified ethylene-vinyl acetate copolymer layers and other thermoplastic resin layers is possible. .
[0023]
【Example】
Hereinafter, the present invention will be specifically described with reference to examples. In the examples, “parts” and “%” are based on weight unless otherwise specified.
Example 1
An ethylene-vinyl acetate copolymer was continuously polymerized using a polymerization vessel having an internal volume of 10 l under the following conditions.
Vinyl acetate supply 1290 g / hr
Methanol supply rate 200g / hr
Benzoyl peroxide supply amount 250mg / hr
EDTA supply amount 52mg / hr
(0.004 parts by weight with respect to 100 parts by weight of vinyl acetate)
Polymerization temperature 67 ° C
Ethylene pressure 3.92 MPa
Average residence time 4 hr
The ethylene content of the ethylene-vinyl acetate copolymer obtained at this time was 32 mol%, and the polymerization rate of vinyl acetate was 38%.
The obtained ethylene-vinyl acetate copolymer was evaluated as the ethylene-vinyl acetate copolymer saponified product as follows in terms of the hue of the pellet and the fish eye during film formation.
[0024]
To 100 parts of a methanol solution containing 50% of the ethylene-vinyl acetate copolymer, 150 parts of a methanol solution containing 0.017 equivalents of sodium hydroxide with respect to the vinyl acetate group in the copolymer is supplied. The saponification reaction was performed at ˜130 ° C. and a pressure of 0.39 MPa for 30 minutes. The resin concentration of the methanol solution of the obtained ethylene-vinyl acetate copolymer saponified product (saponification degree: 99.8 mol%) was 30%.
[0025]
Next, 60 parts of an aqueous methanol solution having a water content of 62.5% was supplied azeotropically to the methanol solution of the ethylene-vinyl acetate copolymer saponified product, and the ethylene-acetic acid was added at 100 to 110 ° C. and a pressure of 0.29 MPa. Methanol was distilled off until the resin concentration in the methanol / water solution of the vinyl copolymer saponified product reached 40% to obtain a completely transparent homogeneous methanol / water solution.
Subsequently, the methanol / water solution of the saponified ethylene-vinyl acetate copolymer obtained was extruded into a coagulating liquid tank composed of a water / methanol solution (weight ratio 95/5) and cut with a cutter. A pellet of a saponified vinyl acetate copolymer was obtained.
[0026]
(1) Hue of pellet ○: No coloring Δ: Colored slightly yellow visually Visual color: Yellow colored visually Next, a saponified product obtained as described above was formed into a film under the following conditions. The fish eyes of the obtained films were evaluated as follows.
(2) The number of fish eyes per 100 cm 2 of fish eye film was measured.
○: Less than 5 Δ: Less than 5-10 ×× 10 or more The results are shown in Table 1.
[0028]
Example 2
The same procedure as in Example 1 was carried out except that the catalyst was 2,2′-azobisisobutyronitrile, to obtain an ethylene-vinyl acetate copolymer having an ethylene content of 32 mol% and a vinyl acetate polymerization rate of 42%. Thereafter, the saponified product was evaluated in the same manner as in Example 1 in the same manner as in Example 1.
[0029]
Example 3
In Example 1, instead of EDTA, citric acid was used in the same manner to obtain an ethylene-vinyl acetate copolymer having an ethylene content of 32 mol% and a vinyl acetate polymerization rate of 38%. The saponified product was evaluated in the same manner as in Example 1 in the same manner as in Example 1.
[0030]
Comparative Example 1
The same procedure as in Example 1 was conducted except that EDTA was not used in Example 1 to obtain an ethylene-vinyl acetate copolymer having an ethylene content of 32 mol% and a vinyl acetate polymerization rate of 38%. The saponification product was evaluated in the same manner as in Example 1.
The evaluation of Examples and Comparative Examples is shown in Table 1.
[0031]
[Table 1]
【The invention's effect】
In the present invention, since ethylene and vinyl acetate are copolymerized in a solvent in the presence of a chelating agent and a catalyst, the ethylene-vinyl acetate copolymer having an ethylene content of 15 to 60 mol% is obtained. The saponified ethylene-vinyl acetate copolymer is less colored, and the film obtained from such a saponified product by melt molding has less fish eyes.
Claims (4)
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|---|---|---|---|
| JP01330598A JP4451935B2 (en) | 1998-01-07 | 1998-01-07 | Process for producing saponified ethylene-vinyl acetate copolymer film |
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|---|---|---|---|
| JP01330598A JP4451935B2 (en) | 1998-01-07 | 1998-01-07 | Process for producing saponified ethylene-vinyl acetate copolymer film |
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| JPH11199607A JPH11199607A (en) | 1999-07-27 |
| JP4451935B2 true JP4451935B2 (en) | 2010-04-14 |
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| JP4607285B2 (en) * | 2000-06-01 | 2011-01-05 | 株式会社クラレ | Method for producing vinyl alcohol polymer |
| JP5051955B2 (en) * | 2001-09-19 | 2012-10-17 | 日本合成化学工業株式会社 | Production method of vinyl acetate polymer and saponified product thereof |
| JP5051956B2 (en) * | 2001-09-19 | 2012-10-17 | 日本合成化学工業株式会社 | Production method of vinyl acetate polymer and saponified product thereof |
| KR100842114B1 (en) | 2007-02-12 | 2008-06-30 | 주식회사 제닉 | (nitrilotriacetic acid)-end-functionalized polymer, synthesis method thereof and analyzing, separating or purifing method of protein using the same |
| KR102405288B1 (en) | 2019-01-22 | 2022-06-07 | 주식회사 엘지화학 | Vinyl alcohol based copolymer, method for preparing the same and gas barrier film comprising the same |
| CN114920864B (en) * | 2021-07-14 | 2023-06-06 | 江苏斯尔邦石化有限公司 | Ethylene-vinyl acetate copolymer and preparation method and application thereof |
| CN115215955B (en) * | 2021-08-11 | 2023-06-02 | 江苏斯尔邦石化有限公司 | Ethylene-vinyl acetate copolymer and preparation method and application thereof |
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