CN116601223A - 乙烯-乙烯醇共聚物组合物及其制备方法 - Google Patents
乙烯-乙烯醇共聚物组合物及其制备方法 Download PDFInfo
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- CN116601223A CN116601223A CN202180069366.2A CN202180069366A CN116601223A CN 116601223 A CN116601223 A CN 116601223A CN 202180069366 A CN202180069366 A CN 202180069366A CN 116601223 A CN116601223 A CN 116601223A
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- Prior art keywords
- acid
- ethylene
- potassium
- vinyl alcohol
- alcohol copolymer
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- 229920000219 Ethylene vinyl alcohol Polymers 0.000 title claims abstract description 71
- 239000000203 mixture Substances 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 19
- 125000002252 acyl group Chemical group 0.000 claims abstract description 33
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 29
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000011591 potassium Substances 0.000 claims abstract description 28
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 28
- 239000011734 sodium Substances 0.000 claims abstract description 26
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 25
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 24
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 16
- 239000011574 phosphorus Substances 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims description 18
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 18
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 claims description 18
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 18
- 239000003999 initiator Substances 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 15
- 229910052796 boron Inorganic materials 0.000 claims description 15
- 238000006116 polymerization reaction Methods 0.000 claims description 14
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 12
- 238000006136 alcoholysis reaction Methods 0.000 claims description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 9
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 claims description 8
- 239000004327 boric acid Substances 0.000 claims description 7
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- 235000011181 potassium carbonates Nutrition 0.000 claims description 6
- 235000011054 acetic acid Nutrition 0.000 claims description 5
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 5
- 239000011736 potassium bicarbonate Substances 0.000 claims description 5
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 5
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 5
- 159000000001 potassium salts Chemical class 0.000 claims description 5
- WDJHALXBUFZDSR-UHFFFAOYSA-N Acetoacetic acid Natural products CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 claims description 4
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 4
- WOWBFOBYOAGEEA-UHFFFAOYSA-N diafenthiuron Chemical compound CC(C)C1=C(NC(=S)NC(C)(C)C)C(C(C)C)=CC(OC=2C=CC=CC=2)=C1 WOWBFOBYOAGEEA-UHFFFAOYSA-N 0.000 claims description 4
- 229940040102 levulinic acid Drugs 0.000 claims description 4
- QDAWXRKTSATEOP-UHFFFAOYSA-N 2-acetylbenzoic acid Chemical compound CC(=O)C1=CC=CC=C1C(O)=O QDAWXRKTSATEOP-UHFFFAOYSA-N 0.000 claims description 3
- YIXSKDRXJTZCHT-UHFFFAOYSA-N 2-acetylbutanedioic acid Chemical compound CC(=O)C(C(O)=O)CC(O)=O YIXSKDRXJTZCHT-UHFFFAOYSA-N 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- BSYNRYMUTXBXSQ-FOQJRBATSA-N 59096-14-9 Chemical compound CC(=O)OC1=CC=CC=C1[14C](O)=O BSYNRYMUTXBXSQ-FOQJRBATSA-N 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims 1
- UFRKOOWSQGXVKV-UHFFFAOYSA-N ethene;ethenol Chemical compound C=C.OC=C UFRKOOWSQGXVKV-UHFFFAOYSA-N 0.000 abstract description 34
- 239000004715 ethylene vinyl alcohol Substances 0.000 abstract description 33
- 239000011342 resin composition Substances 0.000 abstract description 22
- 238000000354 decomposition reaction Methods 0.000 abstract description 11
- -1 phosphorus compound Chemical class 0.000 abstract description 9
- 238000004383 yellowing Methods 0.000 abstract description 8
- 150000001639 boron compounds Chemical class 0.000 abstract description 5
- 238000010438 heat treatment Methods 0.000 abstract description 5
- 238000012545 processing Methods 0.000 abstract description 5
- 229920005989 resin Polymers 0.000 abstract description 5
- 239000011347 resin Substances 0.000 abstract description 5
- 229960003975 potassium Drugs 0.000 description 17
- 239000000243 solution Substances 0.000 description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 5
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 3
- 229910001414 potassium ion Inorganic materials 0.000 description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 3
- GRONZTPUWOOUFQ-UHFFFAOYSA-M sodium;methanol;hydroxide Chemical compound [OH-].[Na+].OC GRONZTPUWOOUFQ-UHFFFAOYSA-M 0.000 description 3
- YQTCQNIPQMJNTI-UHFFFAOYSA-N 2,2-dimethylpropan-1-one Chemical group CC(C)(C)[C]=O YQTCQNIPQMJNTI-UHFFFAOYSA-N 0.000 description 2
- 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 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 238000004380 ashing Methods 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 150000001642 boronic acid derivatives Chemical class 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
- 235000019797 dipotassium phosphate Nutrition 0.000 description 2
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- 238000004255 ion exchange chromatography Methods 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000010128 melt processing Methods 0.000 description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 2
- 235000019799 monosodium phosphate Nutrition 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 description 2
- 235000011009 potassium phosphates Nutrition 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 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
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- MTLWTRLYHAQCAM-UHFFFAOYSA-N 2-[(1-cyano-2-methylpropyl)diazenyl]-3-methylbutanenitrile Chemical compound CC(C)C(C#N)N=NC(C#N)C(C)C MTLWTRLYHAQCAM-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- RPBWMJBZQXCSFW-UHFFFAOYSA-N 2-methylpropanoyl 2-methylpropaneperoxoate Chemical compound CC(C)C(=O)OOC(=O)C(C)C RPBWMJBZQXCSFW-UHFFFAOYSA-N 0.000 description 1
- 239000004254 Ammonium phosphate Substances 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
- VRHVJSKHTCZHDV-UHFFFAOYSA-N C(CCCCCC(C)(C)C)(=O)OOCC(C)(C)C Chemical compound C(CCCCCC(C)(C)C)(=O)OOCC(C)(C)C VRHVJSKHTCZHDV-UHFFFAOYSA-N 0.000 description 1
- 239000005696 Diammonium phosphate Substances 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 238000001636 atomic emission spectroscopy Methods 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- ZGPBOPXFOJBLIV-UHFFFAOYSA-N butoxycarbonyloxy butyl carbonate Chemical compound CCCCOC(=O)OOC(=O)OCCCC ZGPBOPXFOJBLIV-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004434 industrial solvent Substances 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000006012 monoammonium phosphate Substances 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- WFIZEGIEIOHZCP-UHFFFAOYSA-M potassium formate Chemical compound [K+].[O-]C=O WFIZEGIEIOHZCP-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
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- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
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Abstract
本发明提供一种乙烯‑乙烯醇共聚物组合物及其制备方法，该组合物含有乙烯‑乙烯醇共聚物、钾元素和钠元素，其特征在于，钠元素与钾元素的质量比为0.1:1‑1:1优选为0.2：1‑0.8：1更优选0.3:1‑0.5:1。本发明通过控制EVOH树脂组合物中钠元素与钾元素的含量在特定比例范围内，使得所得EVOH树脂组合物的耐热性能大幅提高，起始分解温度可提高至370‑400℃，最大分解温度可提高至400‑440℃，使EVOH树脂能够适应更高加工温度的工艺需要。而且，通过进一步加入含酰基的羧酸以及含磷化合物/含硼化合物，能够提高EVOH树脂组合物的耐热黄变性能，150℃热处理5小时后的黄变指数YI的增加值可以达到不超过15。
Description
相关申请的交叉引用
本申请要求2020年10月15日提交的中国专利申请CN202011103182.7和CN202011104215.X的权益，上述申请的内容通过引用被合并于本文。
本发明涉及一种乙烯-乙烯醇共聚物组合物及其制备方法。
EVOH树脂具有极好的气味阻隔性、透明性和光泽性，且耐油脂、耐化学药品、耐紫外线及其他射线，而且机械性能、强度和拉伸模量好，用作肉类、油脂、工业溶剂、农药等复合包装膜，发泡处理、中空容器和阻隔层。此外，EVOH树脂还可以与其他材料复合，构成耐火、抗菌、抗氧化材料等。
然而，EVOH树脂的耐热性能较差，在加工(通常为熔融加工)过程中，易造成产品高温黄变，并产生热分解产物，影响产品质量。
目前，主要通过加入添加剂来解决这一问题，例如CN105623163A通过在含乙烯及乙烯醇结构单元的共聚物中添加其质量0.1-4.0％的组分B(酸，选自无机酸或有机羧酸中的一种或其混合物，有机羧酸选自碳数为2-20的多元羧酸)、0.01-1.8％的组分C(有机酚类或胺类化合物)和0.1-4.0％的组分D(碱金属或碱土金属盐)来提高其热稳定性。其中声称所制备组合物在氮气和空气气氛下初始分解温度(T0)分别为264℃和236℃，分解温度(Td)分别为326℃和311℃。然而，该方案对于热稳定性的提高程度有限，无法满足更高加工温度的应用要求。
WO0020211A1则通过添加硼化合物如硼酸、硼酸酯、硼酸盐等来提高EVOH树脂组合物的稳定性，可以使初始分解温度提高40-50℃。然而，该方法获得的EVOH组合物存在熔融加工过程中熔体粘度增大从而导致加工不便的问题。
发明内容
本发明的目的是为了克服现有技术的EVOH树脂组合物存在热稳定差的缺 陷，从而提供一种具有较高热稳定性的EVOH树脂组合物及其制备方法。
本发明第一方面提供一种乙烯-乙烯醇共聚物组合物，该组合物含有乙烯-乙烯醇共聚物、钾元素和钠元素，其特征在于，钠元素与钾元素的质量比为0.1:1-1:1优选为0.2：1-0.8：1更优选0.3:1-0.5:1。
本发明第二方面提供一种乙烯-乙烯醇共聚物组合物的制备方法，其特征在于，该方法包括将聚合反应得到的乙烯-醋酸乙烯酯共聚物醇解后成型造粒，然后进行清洗，以除去大部分钠元素，之后加入钾源，钾源的加入量使得钠元素与钾元素的质量比为0.1:1-1:1优选为0.2：1-0.8：1更优选0.3:1-0.5:1。
本发明通过控制EVOH树脂组合物中钠元素与钾元素的含量在特定比例范围内，使得所得EVOH树脂组合物的耐热性能大幅提高，起始分解温度可提高至370-400℃，最大分解温度可提高至400-440℃，使EVOH树脂能够适应更高加工温度的工艺需要。而且，通过进一步加入含酰基的羧酸以及含磷化合物/含硼化合物，能够提高EVOH树脂组合物的耐热黄变性能，150℃热处理5小时后的黄变指数YI的增加值可以达到不超过15。
本发明提供的EVOH树脂组合物方法简单，易于操作，有利于实现工业化生产。
乙烯-乙烯醇共聚物组合物中，乙烯-乙烯醇共聚物为主要成分，通过乙烯-醋酸乙烯共聚合后醇解得到，钠元素是在乙烯-醋酸乙烯共聚物醇解过程中产生的副产物带来的，通常通过后续清洗来降低钠元素的含量。通常认为钠元素的含量需控制在尽量低的范围内，以获得性能较好的乙烯-乙烯醇共聚物组合物。
本发明的发明人意外的发现，通过在醇解和清洗后加入钾元素，并控制钠元素与钾元素的质量比在0.1:1-1:1优选为0.2：1-0.8：1特定范更优选0.3:1-0.5:1围内，能够使所得EVOH树脂组合物的耐热性能大幅提高。
控制钠元素的含量在一定范围内，能够获得更好的效果。优选地，相对于乙烯-乙烯醇共聚物的质量，钾元素和钠元素的总量为100-3000ppm优选为200-2000ppm更优选500-1000ppm。
优选地，所述钾元素以离子形式存在，更优选以钾盐形式存在，进一步优选所述钾盐为碳酸钾和/或碳酸氢钾。相对于硝酸钾、磷酸钾、磷酸钾、磷酸二氢 钾、磷酸氢二钾、硫酸钾、氯化钾等无机钾盐以及醋酸钾、甲酸钾等有机钾盐，碳酸钾和碳酸氢钾能够取得更优的效果。
为了防止EVOH树脂组合物熔融成型着色，根据本发明的一种优选实施方式，所述EVOH树脂组合物还含有一元羧酸，所述一元羧酸可以是各种能够获得上述功效的含有一个COOH且不含酰基的羧酸，优选所述一元羧酸的结构式为R
1COOH，R
1为碳原子数为1-8更优选1-5的烷基如甲基、乙基、丙基、异丙基、丁基、异丁基、叔丁基，进一步优选甲酸、醋酸、丙酸、丁酸中的一种或多种。
优选地，相对于乙烯-乙烯醇共聚物的质量，所述一元羧酸的含量为100-3000ppm优选为150-2000ppm更优选300-1000ppm。
本发明的发明人意外的发现，通过使EVOH树脂组合物中含有一定量的含酰基的羧酸，能够使得树脂组合物的耐热黄变性进一步提高。因此，优选地，该组合物还含有含酰基的羧酸。优选地，相对于乙烯-乙烯醇共聚物的质量，所述含酰基的羧酸的含量为50-1000ppm优选为100-500ppm更优选200-350ppm。
当本发明的组合物同时含有一元羧酸和含酰基的羧酸时，优选地，相对于乙烯-乙烯醇共聚物的质量，所述含酰基的羧酸的含量为50-1000ppm优选为100-500ppm，所述一元羧酸的含量为100-3000ppm优选为150-2000ppm更优选200-1500ppm。
所述含酰基的羧酸可以为各种分子内同时含有酰基-C(＝O)-和羧基-COOH的物质，酰基和羧基的个数可以为一个或多个，酰基和羧基之间可以相隔一个或多个碳原子，所述酰基优选为乙酰基CH
3-C(＝O)-。所述含酰基的羧酸可以含有一个或多个芳环。所述含酰基的羧酸的碳原子数可以为3-10。优选地，所述含酰基的羧酸为乙酰乙酸、乙酰丙酸、乙酰丁酸、乙酰水杨酸、乙酰丙酸、乙酰基丁二酸和乙酰基苯甲酸中的一种或多种。
本发明优选所述含酰基的羧酸的结构式为R
2COR
3COOH，其中R
2为碳原子数为1-5的烷基如甲基、乙基、丙基、异丙基、丁基、异丁基、叔丁基，进一步优选甲基即所述含酰基的羧酸为含乙酰基的羧酸，R
3为碳原子数为1-5的直链或支链亚烷基如亚甲基、亚乙基、亚丙基等，进一步优选R
3与R
1的碳原子数相同。本发明的发明人发现，通过使含酰基的羧酸满足R
3与R
1的碳原子数相同，可以使所得EVOH组合物的耐热稳定性和耐热黄变性均大幅提高。
本发明组合物中还可以含有硼元素和/或磷元素。优选地，相对于乙烯-乙烯醇共聚物的质量，以硼酸H
3BO
3计，硼元素的含量为50-1000ppm优选为50-500ppm，以H
3PO
4计磷元素的含量为50-1000ppm优选100-500ppm。硼元素可以以各种含硼化合物的形式存在，该含硼化合物可以为硼酸、硼酸酯或硼酸盐等。该含磷化合物可以为磷酸及其盐，作为磷酸盐没有特别限制，优选为磷酸的碱金属盐。具体的，可以为磷酸钾、磷酸钠、磷酸铵、磷酸氢二铵、磷酸二氢铵、磷酸氢二钾、磷酸氢二钠、磷酸二氢钾、磷酸二氢钠等中的一种或多种。需要说明的是，当所述磷化合物为磷酸的各种钾盐时，其中的钾的量计入组合物中钾元素含量内。
本发明中，钾元素和钠元素的含量通过ICP-0ES来测得。一元羧酸、含酰基的羧酸和磷化合物的含量通过离子色谱方法来测得。硼化合物的含量通过样品灰化后用原子发射光谱测得。
本发明中，所述乙烯-醋酸乙烯酯共聚物可以是各种规格、方法得到的EVOH共聚物，优选地，所述乙烯-醋酸乙烯酯共聚物的熔融指数(190℃、2160g)为0.5-10g/10分钟。
根据本发明的一种优选实施方式，所述EVOH树脂组合物含有乙烯-乙烯醇共聚物、醋酸、钾盐和钠盐，所述醋酸的含量为相对于乙烯-乙烯醇共聚物质量的100-3000ppm，钾盐和钠盐的用量为钠盐中含有的钠离子与钾盐中含有的钾离子的总量相对于乙烯-乙烯醇共聚物质量的100-3000ppm，且钠盐中含有的钠离子与钾盐中含有的钾离子的质量比为0.1:1-1:1。
可以为各种通过现有方法制备得到的乙烯-醋酸乙烯酯共聚物，例如可以通过聚合反应制得，聚合反应采用的溶剂优选为醇类溶剂，聚合反应所采用的引发剂优选为偶氮类引发剂或过氧化物类引发剂。
本发明第二方面提供了乙烯-乙烯醇共聚物组合物的制备方法，该方法包括将聚合反应得到的乙烯-醋酸乙烯酯共聚物醇解后成型造粒，然后进行清洗，以除去大部分钠元素，之后加入钾源，钾源的加入量使得钠元素与钾元素的质量比为0.1:1-1:1优选为0.2：1-0.8：1更优选0.3:1-0.5:1。
优选地，所述钾源为钾盐，进一步优选所述钾盐为碳酸钾和/或碳酸氢钾。
优选地，所述清洗使得钠元素的含量降低至50-2000ppm，再加入钾盐，控制钠离子与钾盐中含有的钾离子的总量在所需范围内。
所述清洗一般包括水洗和酸洗。
本发明中，优选使用一元羧酸和含酰基的羧酸进行所述酸洗。
优选地，一元羧酸与乙烯-乙烯醇共聚物的质量比可以为0.0001：1-0.1：1优选0.001:1-0.05:1更优选0.015:1-0.05:1。
进一步优选情况下，含酰基的羧酸与一元羧酸的质量比为0.1：1-1:1优选0.2：1-0.8：1更优选0.2:1-0.5:1。
所述一元羧酸和所述含酰基的羧酸的种类如上文所述。
进一步优选地，该方法还包括向酸洗后的乙烯-醋酸乙烯酯共聚物中加入含磷化合物和/或含硼化合物。
优选地，相对于1重量份的乙烯-醋酸乙烯酯共聚物，所述含磷化合物的加入量为0.0002-0.001重量份。
优选地，相对于1重量份的乙烯-醋酸乙烯酯共聚物，所述含硼化合物的加入量为0.0001-0.001重量份。
可以在加入钾盐时，加入含硼化合物和含磷化合物，也可以各自单独加入。
加入钾盐、含硼化合物和含磷化合物的方式没有特别限制，优先采用将上述化合物用水溶解后，将溶液加入到乙烯-乙烯醇共聚物中并混合均匀。溶液的浓度没有特别限定，可以是各种浓度，只要能将钾盐、含硼化合物、含磷化合物负载到乙烯-乙烯醇共聚物中即可。由于乙烯-乙烯醇共聚物具有一定的孔结构，因此可以采用饱和浸渍的方法将钾盐、含硼化合物、含磷化合物负载到乙烯-乙烯醇共聚物中，然后干燥除去溶剂，即得乙烯-乙烯醇共聚物组合物。
聚合反应制备乙烯-醋酸乙烯酯共聚物的方式可以采用现有的各种方式，可以采用溶液聚合、乳液聚合或悬浮聚合等方法。优选溶液聚合法，聚合反应采用的溶剂优选为醇类溶剂。所述醇类溶剂可以包括碳原子数1-4的醇类，如甲醇、乙醇、丙醇、乙二醇、正丁醇和叔丁醇等，也可以是上述两种醇类的混合溶剂，或者以上述醇类作为主要成份而含有其他少量成份。
聚合反应所采用的引发剂可以为偶氮类引发剂或过氧化物类引发剂。
进一步，偶氮类引发剂包括油溶性引发剂如偶氮二异丁腈、偶氮二异戊腈、偶氮异丁氰基甲酰胺、偶氮二环已基甲腈、偶氮二异丁酸二甲酯等。
进一步，过氧化物类引发剂包括有机过氧化物(如过氧化苯甲酰、过氧化苯甲酰叔丁酯、过氧化甲乙酮、过氧化二异丁酰、过氧化新癸酸特戊酯、过氧化二 碳酸双(4-特丁基环己酯)、过氧化特戊酸特戊酯、过氧化醋酸特丁酯、过氧化二碳酸双丁酯等)或无机过氧化物(如过氧化氢、过硫酸铵、过硫酸钾等)
进一步，所述引发剂包括有机过氧类引发剂。
进一步，以质量份计，配比关系为：溶剂10-40份，醋酸乙烯酯单体60-200份、引发剂0.01-0.3份和乙烯单体5-60份。
进一步，以质量份计，配比关系为：溶剂10-35份，醋酸乙烯酯单体80-150份、引发剂0.03-0.2份和乙烯单体20-40份。
所述醇解和成型造粒的方法已为本领域技术人员所公知，在此不再赘述。
本发明中，除非另有说明，所述份均指质量份、重量份。
下面将通过实施例对本发明进行进一步的说明。实施例中，初始分解温度和最高分解温度的检测方法为：采用热失重分析仪，氮气氛围下，升温速率10℃/min，温度从室温升至800℃，当样品分解5％(w)时的温度即为初始分解温度T
0(℃)，当样品分解50％(w)时的温度即为最高分解温度T
1(℃)。
黄度指数YI的检测方法为：称取10-15g样品，用色度仪测试样品初始黄度指数YI和150℃热处理5小时后的黄度指数YI。YI值越小代表着色度越低。
钠和钾离子含量的检测方法为：将EVOH样品粉碎过100目筛，称10g样品与50ml离子交换水，在95℃水浴中搅拌回流提取10小时。将提取液用离子交换水稀释5倍，采用电感耦合等离子体原子发射光谱仪(ICP-0ES)测试。
一元羧酸、磷酸和含酰基羧酸含量的检测方法为：将EVOH样品粉碎过筛，称10g样品与50ml去离子水，在95℃水浴中搅拌回流提取10小时。将提取液用去离子水稀释5倍(体积)，采用离子色谱进行测试，色谱柱为Metrosep A Supp/250,4，流动相为Na
2CO
3和NaHCO
3混合溶液，校正液为乙酸钠水溶液。
硼酸测试方法为称取样品100克，通过马弗炉灰化后将灰分溶解于0.01当量的硝酸水溶液200ml中通过原子吸收光谱分析硼元素含量，再换算为硼酸的重量，得到硼化合物的含量。
实施例1
A.聚合：在带有搅拌器的聚合釜中加入甲醇25份、醋酸乙烯酯190份、过氧化新癸酸特戊酯0.05份，通入乙烯使聚合釜内压力保持在3.7MPa，温度60℃，反应5h，得到乙烯-醋酸乙烯共聚物溶液，经减压和精馏除去乙烯和醋酸乙烯单 体，得到乙烯-醋酸乙烯共聚物溶液；
B.醇解：将步骤A得到的乙烯-醋酸乙烯共聚物溶液调整质量分数为40％，然后加入浓度为40g/L的氢氧化钠-甲醇溶液(氢氧化钠为溶质)进行醇解，氢氧化钠-甲醇溶液的用量为氢氧化钠-甲醇溶液中的氢氧化钠与乙烯-醋酸乙烯酯共聚物中含有的醋酸乙烯酯基团的摩尔比为0.05:1，反应4h直至醇解完全；
C.造粒：将乙烯-醋酸乙烯酯共聚物醇解后，将醇解得到的乙烯-乙烯醇共聚物溶液通过带有孔板的挤出设备挤出到5℃的水溶液中，析出成条状后，采用通用的切断方式切割成颗粒；
D.水洗：随后通过带有搅拌装置的釜式容器加入颗粒5倍质量的水清洗乙烯-乙烯醇共聚物颗粒，每次洗涤2小时，反复洗涤2次；
E.酸洗：在带有搅拌装置的釜式容器加入颗粒5倍质量的水清洗乙烯-乙烯醇共聚物颗粒，在水洗液中加入相对于EVOH(以质量为1份计)质量0.015份的醋酸和0.007份的乙酰乙酸，进行酸洗2小时，酸洗完成后离心脱水；
F.调质：然后在离心脱水后的EVOH颗粒加入相对于EVOH(以质量为1份计)质量0.0013份的碳酸钾和0.0001份硼酸和0.0006份磷酸二氢钠的水溶液，充分混合均匀进行饱和浸渍，接着在115℃下烘干处理24小时，即得EVOH树脂组合物。
实施例2-实施例12
按照实施例1的方法制备EVOH树脂组合物，不同的是步骤E中一元羧酸、含酰基的羧酸和钾源的种类和用量如表1所示，所得EVOH树脂组合物的性能如表2所示。
对比例1
按照实施例1的方法制备EVOH树脂组合物，不同的是步骤E中一元羧酸、含酰基的羧酸和F步骤中钾源的种类和用量如表1所示，所得EVOH树脂组合物的性能如表2所示。
表1
表2
从上表2的数据可以看出，采用本发明提供的方法，能够获得具有提高的耐热性和耐热黄变性的EVOH树脂组合物。
此外，应当理解，虽然本说明书按照实施方式加以描述，但并非每个实施方式仅包含一个独立的技术方案，说明书的这种叙述方式仅仅是为清楚起见，本领域技术人员应当将说明书作为一个整体，各实施例中的技术方案也可以经适当组合，形成本领域技术人员可以理解的其他实施方式。
Claims (16)
- 乙烯-乙烯醇共聚物组合物，该组合物含有乙烯-乙烯醇共聚物、钾元素和钠元素，其特征在于，钠元素与钾元素的质量比为0.1:1-1:1优选为0.2：1-0.8：1更优选0.3:1-0.5:1。
- 根据权利要求1所述的组合物，其中，相对于乙烯-乙烯醇共聚物的质量，钾元素和钠元素的总量为100-3000ppm优选为200-2000ppm更优选500-1000ppm。
- 根据权利要求1或2所述的组合物，其中，所述钾元素以离子形式存在，优选以钾盐形式存在，优选的，所述钾盐为碳酸钾和/或碳酸氢钾。
- 根据权利要求1-3任一项所述的组合物，其中，该组合物还含有一元羧酸R 1COOH，R 1为碳原子数为1-5的烷基，优选甲酸、醋酸、丙酸、丁酸中的一种或多种；优选地，相对于乙烯-乙烯醇共聚物的质量，所述一元羧酸的含量为100-3000ppm优选为150-2000ppm更优选300-1000ppm。
- 根据权利要求4所述的组合物，其中，该组合物还含有含酰基的羧酸；优选地，所述含酰基的羧酸为乙酰乙酸、乙酰水杨酸、乙酰丙酸、乙酰丁酸、乙酰基丁二酸和乙酰基苯甲酸中的一种或多种。
- 根据权利要求5所述的组合物，其中，所述含酰基的羧酸的结构式为R 2COR 3COOH，R 2为碳原子数为1-5的烷基，R 3为碳原子数为1-5的亚烷基，进一步优选R 3与R 1的碳原子数相同。
- 根据权利要求5或6所述的组合物，其中，相对于乙烯-乙烯醇共聚物的质量，所述含酰基的羧酸的含量为50-1000ppm优选为100-500ppm更优选200-350ppm。
- 根据权利要求1-7中任意一项所述的组合物，其中，该组合物还含有硼元素和/或磷元素，相对于乙烯-乙烯醇共聚物的质量，以硼酸H 3BO 3计，硼元素的含量为50-1000ppm优选为50-500ppm，以H 3PO 4计磷元素的含量为50-1000ppm优选100-500ppm。
- 乙烯-乙烯醇共聚物组合物的制备方法，其特征在于，该方法包括将聚合反应得到的乙烯-醋酸乙烯酯共聚物醇解后成型造粒，然后进行清洗，以除去大部分钠元素，之后加入钾源，钾源的加入量使得钠元素与钾元素的质量比为0.1:1-1:1优选为0.2：1-0.8：1更优选0.3:1-0.5:1。
- 根据权利要求9所述的制备方法，其中，所述钾源为钾盐，优选地，所述钾盐为碳酸钾和/或碳酸氢钾。
- 根据权利要求9或10所述的制备方法，其中，所述清洗使得相对于乙烯-乙烯醇共聚物的质量，钾元素和钠元素的总量为100-3000ppm优选为200-2000ppm更优选1000-2000ppm。
- 根据权利要求9-11中任意一项所述的制备方法，其中，所述清洗包括水洗和酸洗，使用一元羧酸R 1COOH和含酰基的羧酸进行所述酸洗，其中R 1为碳原子数为1-5的烷基，一元羧酸与乙烯-乙烯醇共聚物的质量比为0.0001：1-0.1：1优选0.001:1-0.05:1更优选0.015:1-0.05:1；含酰基的羧酸与一元羧酸的质量比为0.1：1-1:1优选0.2：1-0.8：1更优选0.2:1-0.5:1。
- 根据权利要求12所述的制备方法，其中，所述一元羧酸为甲酸、醋酸、丙酸中的一种或多种，所述含酰基的羧酸为乙酰乙酸、乙酰水杨酸、乙酰丙酸、乙酰基丁二酸和乙酰基苯甲酸中的一种或多种。
- 根据权利要求12所述的制备方法，其中，所述含酰基的羧酸的结构式为R 2COR 3COOH，R 2为碳原子数为1-5的烷基，R 3为碳原子数为1-5的亚烷基，优选R 3与R 1的碳原子数相同。
- 根据权利要求12-14中任意一项所述的制备方法，其中，该方法还包括向酸洗后的乙烯-醋酸乙烯酯共聚物中加入含磷化合物和/或含硼化合物；优选地，相对于1重量份的乙烯-醋酸乙烯酯共聚物，所述含磷化合物的加入量为0.0002-0.001重量份，所述含硼化合物的加入量为0.0001-0.001重量份。
- 根据权利要求9-15中任意一项所述的制备方法，其中，聚合反应采用的溶剂为醇类溶剂，聚合反应所采用的引发剂为偶氮类引发剂或过氧化物类引发剂。
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| JPS6469652A (en) * | 1987-09-09 | 1989-03-15 | Kuraray Co | Ethylene/vinyl alcohol copolymer composition |
| CN1290209A (zh) * | 1998-10-07 | 2001-04-04 | 可乐丽股份有限公司 | 多层结构体及其制法 |
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