CN101528818B - 包含基于乙烯-丙烯酸酯的共聚物的隔氧膜和容器 - Google Patents
包含基于乙烯-丙烯酸酯的共聚物的隔氧膜和容器 Download PDFInfo
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- CN101528818B CN101528818B CN2007800388049A CN200780038804A CN101528818B CN 101528818 B CN101528818 B CN 101528818B CN 2007800388049 A CN2007800388049 A CN 2007800388049A CN 200780038804 A CN200780038804 A CN 200780038804A CN 101528818 B CN101528818 B CN 101528818B
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 239000001301 oxygen Substances 0.000 title claims abstract description 44
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 44
- 230000004888 barrier function Effects 0.000 title claims abstract description 39
- 229920006228 ethylene acrylate copolymer Polymers 0.000 title abstract description 7
- 239000000178 monomer Substances 0.000 claims abstract description 42
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 31
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 16
- 229920002554 vinyl polymer Polymers 0.000 claims description 16
- -1 alkyl methacrylate Chemical compound 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 235000013305 food Nutrition 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 5
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 5
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 4
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- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims 4
- JGRXEBOFWPLEAV-UHFFFAOYSA-N 2-ethylbutyl prop-2-enoate Chemical compound CCC(CC)COC(=O)C=C JGRXEBOFWPLEAV-UHFFFAOYSA-N 0.000 claims 2
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 claims 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims 2
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 claims 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 8
- 230000009477 glass transition Effects 0.000 abstract description 5
- 239000005977 Ethylene Substances 0.000 abstract description 4
- 229920001577 copolymer Polymers 0.000 abstract description 4
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 27
- 238000000034 method Methods 0.000 description 17
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- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 13
- 229920001897 terpolymer Polymers 0.000 description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
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- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 6
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- 229920006225 ethylene-methyl acrylate Polymers 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
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- 150000001875 compounds Chemical class 0.000 description 3
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- 239000000126 substance Substances 0.000 description 3
- 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
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
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- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010559 graft polymerization reaction Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
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- 229920000642 polymer Polymers 0.000 description 2
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- 239000007858 starting material Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-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
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- JFZHPFOXAAIUMB-UHFFFAOYSA-N Phenylethylmalonamide Chemical compound CCC(C(N)=O)(C(N)=O)C1=CC=CC=C1 JFZHPFOXAAIUMB-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- PROZFBRPPCAADD-UHFFFAOYSA-N ethenyl but-3-enoate Chemical compound C=CCC(=O)OC=C PROZFBRPPCAADD-UHFFFAOYSA-N 0.000 description 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000003475 lamination Methods 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
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
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- 239000002244 precipitate Substances 0.000 description 1
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- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
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- 230000001105 regulatory effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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Abstract
本发明涉及一种包含乙烯-丙烯酸酯共聚物的隔氧膜和容器,更具体而言,涉及一种包含基于乙烯-丙烯酸酯的共聚物的隔氧膜和容器,所述基于乙烯-丙烯酸酯的共聚物由10-50mol%的乙烯单体和50-90mol%的基于丙烯酸酯的单体组成且重均分子量为至少30,000g/mol。本发明提供了一种隔氧膜和容器,它们具有优异的包括挠性、拉伸性、玻璃化转变温度、抗吸收性和洛氏硬度的机械性能以及例如氧气阻隔性和透明性的其它特性。
Description
技术领域
本发明涉及一种包含基于乙烯-丙烯酸酯的共聚物的隔氧膜和容器,更确切地,涉及一种隔氧膜和容器,它们除了具有优异的氧气阻隔性和透明性之外,还具有优异的例如挠性、拉伸性、玻璃化转变温度、抗吸收性和洛氏硬度的机械性能。
背景技术
通常,例如聚乙烯(PE)和聚丙烯(PP)的基于聚烯烃的树脂具有优异的易成型性和机械性能以及隔潮性,因此这些树脂已经广泛用于多种领域。但是,由于基于聚烯烃的树脂的高透气性,特别是氧气透过性,该树脂还不能用于食品包装。为了克服这一缺点,存在通过将纳米复合物与基于聚烯烃的树脂化合而提高氧气阻隔性的尝试。然而,这种尝试在改善阻隔性能方面是不成功的,并且甚至降低了机械性能。因此,为了用于食品包装膜、片材和容器,通过与具有极好的氧气阻隔性的乙烯-乙烯醇共聚物(EVOH)、尼龙和聚偏1,1-二氯乙烯进行共挤压或者层压,将基于聚烯烃的树脂制备成多层膜。
乙烯-乙烯醇共聚物是一种具有优异的气体阻隔性和透明性的聚合材料,因而其已经用于食物或者化学产品的包装。但是,由于高价格和相对较低的例如挠性及拉伸性的机械性能,乙烯-乙烯醇共聚物的使用受到限制。
为了克服基于聚烯烃的树脂的较差的氧气阻隔性以及乙烯-乙烯醇共聚物的较差的挠性和拉伸性,尝试将基于聚烯烃的树脂和乙烯-乙烯醇共聚物混合。但是,由于两者之间不令人满意的相容性,它们仅制备降低膜或片材产品的机械性能的无规混合物。因此,通过选择适当的用于混合的增容剂来提高混合物的规整性是一项重要的任务。
欧洲专利No.0,015,556(公开于1980年9月17日)和No.0.210,725(公开于1987年2月4日)以及美国专利No.4,971,864(登记于1990年11月20日)描述了通过使用由具有极性基团的化合物与聚乙烯的接枝聚合制备的增容剂来提高基于聚烯烃的树脂和乙烯-乙烯醇共聚物的混合物的规整性,从而制备具有改善的氧气阻隔性和机械性能的膜。美国专利No.5,310,788描述了通过使用由聚酰胺(或聚酰胺低聚物)和作为增容剂的聚烯烃反应生成的反应产物来改善基于聚烯烃树脂和乙烯-乙烯醇共聚物的混合物的拉伸性和挠性的方法,所述的聚烯烃由具有极性基团的化合物与聚乙烯进行接枝聚合而制备。
但是,由于为改善相容性加入了大量的增容剂,由上述方法制备的膜被证实具有较低的氧气阻隔性和较差的熔化易成型性,并且如果加入少量的增容剂,膜产品的透明性和其它机械性能将成为问题。
美国专利No.5,356,990(登记于1994年10月18日)描述了一种方法,其中,首先将乙烯-乙烯醇共聚物(EVOH)熔化,而后加入乙烯共聚物以改善机械性能和产品外观。但是,为了实施这一方法,需要特别设计的挤出机或者模塑设备。
韩国专利中请No.1996-001657描述了一种多层膜,其通过如下步骤制备:将部分皂化的乙烯-乙烯基乙酸酯共聚物树脂作为增容剂分别加入到基于聚烯烃的树脂和乙烯-乙烯醇共聚物中;和用所述基于聚烯烃的树脂涂覆乙烯-乙烯醇共聚物膜的两侧。但是,根据这一方法,基于聚烯烃的树脂和乙烯-乙烯醇共聚物之间的相容性仍然受到限制并且该多层膜的制备过程是麻烦的。
研究人员也已论述了直接将极性基团插入基于聚烯烃的树脂用以改善隔氧膜的规整性。但是,例如高温高压法和催化法的常规方法存在生产过程困难和极性基团的引入率低的问题。
因此,需要开发一种新型隔氧膜和容器,它们具有源于聚烯烃树脂的优异的机械性能以及例如透明性和氧气阻隔性的其它特性,所述聚烯烃树脂没有无规性的问题并且具有足够的引入的极性基团。
发明内容
技术问题
本发明的一个目的是为了克服常规方法的问题,提供一种隔氧膜和容器,它们不但具有优异的机械性能而且具有优异的透明性和氧气阻隔性能,而不会导致树脂内部的无规性。
技术方案
本发明的上述目的可以通过本发明的以下实施方案来实现。
在下文中,将详细描述本发明。
为了实现上述目的,本发明提供了一种包含乙烯-丙烯酸酯共聚物的隔氧膜和容器,所述乙烯-丙烯酸酯共聚物由10-50mol%的乙烯单体和50-90mol%的丙烯酸酯单体组成且重均分子量为至少30,000g/mol。
本发明人通过如下方法设法实现上述目的并且完成了这一发明:通过使用一种具有新型组成的共聚物来制备具有优异透明性和氧气阻隔性以及高玻璃化转变温度和洛氏硬度的膜和容器,该共聚物不同于在常规方法中作为主要成分使用的常规乙烯-乙烯醇共聚物(EVOH)。
本发明的隔氧膜和容器的特征在于,包含基于乙烯-丙烯酸酯的共聚物,该基于乙烯-丙烯酸酯的共聚物由10-50mol%的乙烯单体和50-90mol%的基于丙烯酸酯的单体组成且重均分子量为至少30,000g/mol。
通过使用自由基聚合引发剂,在金属氧化物或者路易斯酸的存在下,乙烯单体和基于丙烯酸酯的单体的聚合反应来制备基于乙烯-丙烯酸酯的共聚物。
乙烯单体的优选含量为10-50mol%,并且更优选为15-40mol%。如果乙烯单体的含量小于10mol%,则最终产物的挠性和拉伸性可能不令人满意,从而导致生成不适当的膜产品。另一方面,如果乙烯单体的含量大于50mol%,则将对机械性能有利但是对透明性和乙烯反应性不利,与丙烯酸酯反应性相比,乙烯反应性可能会显著降低,这意味着其在技术上不可能实施。因此,15-40mol%的乙烯单体的含量是实施该技术的最佳含量,并且由此制备具有改善的机械强度的膜和容器。
基于丙烯酸酯的单体可以为丙烯酸烷基酯、甲基丙烯酸烷基酯或者它们的混合物。丙烯酸烷基酯或者甲基丙烯酸烷基酯可以为碳数为1-12个的直链或支链醇的丙烯酸或者甲基丙烯酸酯,并且更优选碳数为1-8个的直链或支链醇的丙烯酸或者甲基丙烯酸酯,并且最优选(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸异丁酯、(甲基)丙烯酸叔丁酯、(甲基)丙烯酸正己酯、(甲基)丙烯酸2-乙基丁酯、(甲基)丙烯酸2-乙基己酯或者碳数为5-12个的醇的新异构体的丙烯酸酯。
基于丙烯酸酯的单体的含量是决定氧气阻隔性和透明性的非常重要的因素。因此,通过调节影响机械性能的基于丙烯酸酯的单体的含量和乙烯单体的含量可以制备具有优异的透明性、氧气阻隔性和其它机械性能的基于乙烯-丙烯酸酯的共聚物。用于本发明隔氧膜和容器的基于丙烯酸酯的单体的优选含量为50-90mol%,并且更优选含量为60-85mol%。
乙烯单体和基于丙烯酸酯的单体可以另外包含第三单体。这里所述第三单体选自例如乙酸乙烯酯的乙烯基酯和例如丙烯酸、甲基丙烯酸或马来酸及一氧化碳的偏酯单体中。相对于100重量份的乙烯单体和基于丙烯酸酯的单体的混合物,所述第三单体的优选含量为5-80重量份。
基于乙烯-丙烯酸酯的共聚物的分子量优选为至少30,000g/mol(重均分子量),并且更优选为至少70,000g/mol,并且不设定上限,但是考虑到常规技术优选最高至300,000g/mol。基于乙烯-丙烯酸酯的共聚物的重均分子量低于30,000g/mol会导致膜的机械强度减小,而重均分子量超过70,000g/mol会导致包括拉伸强度的机械强度增大。
隔氧膜为薄隔膜的泛称,其包括片材和包装材料等。所述隔氧膜的优选厚度为5-1000μm。
这里,隔氧容器指由塑料制成的容器,其实例为食品容器、包装容器和化妆品容器。由于其高玻璃化转变温度和低吸湿率,这种容器也可以用作用于加热箱的容器。
所述金属氧化物可以是碱土金属、过渡金属、13族和14族金属的氧化物等,其特征在于,因其可物理回收从而能够重复用于聚合反应。相对于1mol基于丙烯酸酯的单体,所述金属氧化物的优选用量为0.1-10mol,并且更优选用量为0.5-3mol。
所述路易斯酸为金属盐,优选金属卤化物,更优选金属氯化物,并且最优选氯化铝(III)、氯化锌、氯化铁(II)或者氯化铁(III),但不一定限制于此。相对于1mol基于丙烯酸酯的单体,路易斯酸的优选用量为0.01-1mol。
加入金属氧化物或者路易斯酸可以克服常规高温高压法和催化法的问题,例如生产过程困难和极性基团的添加有限。
可以使用本领域已知的任何聚合引发剂,但是优选过氧化物或者偶氮化合物引发剂,并且更优选偶氮化合物引发剂。相对于1mol基于丙烯酰基的共聚单体,聚合引发剂的优选用量为0.001-1.0mol,并且更优选用量为0.01-0.1mol。
所述基于乙烯-丙烯酸酯的单体的聚合反应可以在溶剂存在下进行,并且此时可以使用本领域技术人员公知的常规溶剂,其优选为选自甲苯、氯苯、正己烷、正庚烷、四氢呋喃、氯仿和二氯甲烷中的一种或者多种溶剂。相对于基于丙烯酸酯的单体的总体积,可以加入0.5-5.0,优选1.5-3.5份聚合溶剂。
优选在30-150℃于常压200ap下,并且更优选在50-120℃于5-50ap下,进行乙烯单体和基于丙烯酸酯的单体的聚合反应。
与需要高温高压的常规方法不同,本发明的基于乙烯-丙烯酸酯的共聚物的制备方法需要中等反应条件,例如最高至100℃的温度和最高至200ap的压力,这意味着生产程序简单,并且容易调节共聚物的性能。通过本发明的方法制备的基于乙烯-丙烯酸酯的共聚物的特征在于,其为乙烯单体和基于丙烯酸酯的单体的无规共聚物,与常规方法的产物相比,该共聚物具有显著较高的极性基团含量,所以不会导致乙烯结晶,这意味着因其在加工为其它产品后仍然保持透明,所以该共聚物可用作光学材料。
具体实施方式
如以下实施例所示,举例说明了本发明的实践和目前优选实施方案。
但是,应理解,考虑到本公开内容,本领域技术人员可以在本发明的实质和范围内进行修改和改进。
[实施例]
实施例1-11和比较实施例1-4
对125ml高压反应器进行抽真空,而后充满氮气。向其中加入30ml甲苯。将反应器放入适当的烘箱中,按表1所示的量加入氯化铝(III)。向反应器中加入6ml MMA(甲基丙烯酸甲酯)或者MA(甲基丙烯酸酯),静置30分钟直至反应温度稳定。以表1所示的浓度将AIBN(偶氮二异丁腈)溶解在5ml氯苯中,将其注入到反应器内。以35bar将乙烯充入反应器,并将反应温度升高至70℃,随后聚合2小时。当聚合反应完成时,将反应温度降低到室温,加入乙醇以使制得的聚合物以固体形式沉淀(当加入例如Al2O3的金属氧化物代替上述氯化铝(III)时,在注入乙醇之前需要过滤和回收)。将固体物质沉淀并除去上层清液。向其中加入乙醇以洗涤固体物质。再次除去上层清液并向残留的固体物质中加入水,随后搅拌。过滤混合物以仅收集聚合物。在60℃真空烘箱中,将所得到的共聚物干燥一天。
实施例1-11和比较实施例1-4的反应条件和结果示于表1中。
表1
单体 | MMA∶AlCl3 | AIBN∶MMA | 乙烯含量(mol%) | 分子量(g/mol) | |
实施例1 | MMA | 1∶0.700 | 1.0∶1000 | 25.3 | 153,000 |
实施例2 | MMA | 1∶0.500 | 1.0∶1000 | 19.4 | 161,000 |
实施例3 | MMA | 1∶0.300 | 1.0∶1000 | 12.3 | 149,000 |
实施例4 | MMA | 1∶0.300 | 1.5∶1000 | 12.5 | 96,600 |
实施例5 | MMA | 1∶0.300 | 2.0∶1000 | 11.6 | 61,000 |
实施例6 | MMA | 1∶0.500 | 1.5∶1000 | 20.0 | 98,000 |
实施例7 | MA | 1∶0.700 | 1.5∶1000 | 34.5 | 129,000 |
实施例8 | MA | 1∶0.350 | 1.0∶1000 | 21.4 | 135,000 |
实施例9 | MA | 1∶0.300 | 1.0∶1000 | 17.1 | 130,000 |
实施例10 | MA | 1∶0.300 | 2.0∶1000 | 17.9 | 61,000 |
实施例11 | MMA | 1∶0.500 | 2.0∶1000 | 20.0 | 89,000 |
比较实施例1 | MMA | 1∶0.150 | 1.5∶1000 | 5.9 | 97,000 |
比较实施例2 | MMA | 1∶0.300 | 10∶1000 | 12.7 | 15,000 |
比较实施例3 | MA | 1∶0.100 | 1.5∶1000 | 7.4 | 114,000 |
比较实施例4 | MA | 1∶0.300 | 10∶1000 | 18.4 | 18000 |
比较实施例5
用包含44mol%的乙烯、重均分子量为100,000g/mol且密度为1.14g/cm2的乙烯-乙烯醇共聚物(EVOH,AT4403,Nippon Goshei)进行实验,该材料是现在在市场上用作食品、食品包装和化妆品等的容器的材料。
实验实施例1
*玻璃化转变温度:在20-150℃下,用TA仪器(TA Instrument)的DSCQ100测试由实施例6-7和比较实施例5得到共聚物的玻璃化转变温度,并将结果示于表2中。
*吸湿率:将由实施例1、2、11、12和比较实施例5得到的共聚物加工成圆片(直径50mm x厚度3mm),随后在50℃烘箱中干燥24小时。在干燥器中于室温下冷却该圆片,并且测定各圆片的重量(m1)。在23℃蒸馏水中浸泡经干燥的圆片24小时,然后取出。除去表面的水分,并再次测定各圆片的重量(m2)。通过以下数学式1计算吸湿率,并将结果示于表3中。
数学式1
吸湿率(%)=(m2-m1)/mlx100
*洛氏硬度:将由实施例2、3、4和比较实施例5得到的共聚物制备成30mmx3mm的矩形样品,随后用Wilson Rockwell series 2000(Instron)测定洛氏硬度。结果示于表4中。
表2
玻璃化转变温度(℃) | |
实施例6 | 98.0 |
实施例7 | 82.1 |
比较实施例5(EVOH) | 55.5 |
如表2中所示,与常规乙烯-乙烯醇共聚物(比较实施例5)相比,本发明的乙烯-丙烯酸酯共聚物具有显著较高的玻璃化转变温度。
表3
吸湿率(%) | |
实施例1 | 0.29 |
实施例2 | 0.30 |
实施例9 | 0.35 |
实施例10 | 0.37 |
比较实施例5(EVOH) | 5.09 |
如表3中所示,与常规乙烯-乙烯醇共聚物(比较实施例5)相比,本发明的乙烯-丙烯酸酯共聚物几乎不吸收湿气。
表4
洛氏硬度(R级) | |
实施例2 | 113.9 |
实施例3 | 119.6 |
实施例4 | 118.4 |
比较实施例5(EVOH) | 90.3 |
如表4中所示,与乙烯-乙烯醇共聚物(比较实施例5)相比,本发明的乙烯-丙烯酸酯共聚物具有优异的硬度。
实施例12
将10g实施例1中制备的乙烯-甲基丙烯酸甲酯共聚物粉末与20g四氢呋喃混合,并将这一混合物均匀且线性地分布在玻璃盘中。将调节器的桨叶与底部间的距离设定为150μm,并在通风厨中干燥玻璃盘中均匀调节的混合物。从玻璃盘中取出干燥的膜,并在60℃烘箱中干燥24小时以得到25μm厚的膜。
实施例13
除了使用实施例2中制得的乙烯-甲基丙烯酸甲酯共聚物粉末得到23μm厚的膜以外,以与实施例12中所述的相同方式进行实验。
实施例14
除了使用实施例3中制得的乙烯-甲基丙烯酸甲酯共聚物粉末得到12μm厚的膜以外,以与实施例12中所述的相同方式进行实验。
实施例15
除了使用实施例4中制得的乙烯-甲基丙烯酸甲酯共聚物粉末得到20μm厚的膜以外,以与实施例12中所述的相同方式进行实验。
实施例16
除了使用实施例5中制得的乙烯-甲基丙烯酸甲酯共聚物粉末得到20μm厚的膜以外,以与实施例12中所述的相同方式进行实验。
实施例17
除了使用实施例7中制得的乙烯-甲基丙烯酸酯共聚物粉末得到24μm厚的膜以外,以与实施例12中所述的相同方式进行实验。
实施例18
除了使用实施例8中制得的乙烯-甲基丙烯酸酯共聚物粉末得到25μm厚的膜以外,以与实施例12中所述的相同方式进行实验。
实施例19
除了使用实施例9中制得的乙烯-甲基丙烯酸酯共聚物粉末得到25μm厚的膜以外,以与实施例12中所述的相同方式进行实验。
实施例20
除了使用实施例10中制得的乙烯-甲基丙烯酸酯共聚物粉末得到25μm厚的膜以外,以与实施例12中所述的相同方式进行实验。
实施例21
除了使用实施例11中制得的乙烯-甲基丙烯酸甲酯共聚物粉末并将调节器的桨叶与底部间的距离调节至100μm得到15μm厚的膜以外,以与实施例12中所述的相同方式进行实验。
实施例22
除了将调节器的桨叶与底部间的距离调节至200μm得到30μm厚的膜以外,以与实施例21中所述的相同方式进行实验。
实施例23
除了将调节器的桨叶与底部间的距离调节至450μm得到70μm厚的膜以外,以与实施例21中所述的相同方式进行实验。
实施例24
除了将调节器的桨叶与底部间的距离调节至2,000μm得到400μm厚的膜以外,以与实施例21中所述的相同方式进行实验。
实施例25
除了将调节器的桨叶与底部间的距离调节至6,000μm得到1,200μm厚的膜以外,以与实施例21中所述的相同方式进行实验。
比较实施例7
除了使用比较实施例1中制得的乙烯-甲基丙烯酸甲酯共聚物粉末以外,以与实施例12中所述的相同方式进行实验。结果,由于破裂,未能制备成膜。
比较实施例8
除了使用比较实施例2中制得的乙烯-甲基丙烯酸甲酯共聚物粉末得到20μm厚的膜以外,以与实施例12中所述的相同方式进行实验。
比较实施例9
除了使用实施例6中制得的乙烯-甲基丙烯酸甲酯共聚物粉末得到4μm厚的膜以外,以与实施例12中所述的相同方式进行实验。
比较实施例10
除了使用比较实施例3中制得的乙烯-甲基丙烯酸甲酯共聚物粉末以外,以与实施例12中所述的相同方式进行实验。结果,由于破裂,未能制备成膜。
比较实施例11
除了使用比较实施例4中制得的乙烯-甲基丙烯酸甲酯共聚物粉末得到24μm厚的膜以外,以与实施例12中所述的相同方式进行实验。
比较实施例12
除了使用比较实施例5中制得的乙烯-乙烯醇共聚物并使用DMSO(二甲亚砜)代替四氢呋喃得到20μm厚的膜以外,以与实施例12中所述的相同方式进行实验。
实验实施例2
*氧气渗透性:将实施例12-20和比较实施例7-12中制得的乙烯-甲基丙烯酸甲酯共聚物膜(PEMMA)、乙烯-甲基丙烯酸酯共聚物膜(PEMA)和乙烯-乙烯醇共聚物膜(EVOH)制备成10cmx10cm的样品,在相对湿度为0%、所供氧气纯度为99.9%且所供压力为0.5bar下,用Mocon Oxtran在至少12小时内每隔1小时测定氧气渗透性。结果示于表5中。
表5
如表5中所示,本发明的隔氧膜(实施例12-20)的氧气渗透性非常低,为0.1-0.4。特别是,分子量为至少70,000g/mol的氧气渗透性更低,为0.1-0.3,这意味着这些膜具有优异的氧气阻隔性。
当乙烯的含量小于10mol%时,例如在比较实施例7和10中,未能制备成膜。当膜的重均分子量小于30,000g/mol(比较实施例8和11)以及当膜太薄(4μm)(比较实施例9)时,氧气渗透性增大得很高。
常规乙烯-乙烯醇共聚物(EVOH)膜(比较实施例12)的氧气阻隔性比比较实施例7和11的膜高,而比本发明的膜(实施例12-20)低。
实验实施例3
*根据膜厚度的透明度:将在实施例21-25中制得的乙烯-甲基丙烯酸甲酯共聚物膜制成2cmx2cm的样品。然后,用UV测光仪在200~1000nm下测定样品的透明度。结果示于表6中。
表6
膜厚度(μm) | 透明度(%) | |
实施例21 | 15 | 92.5 |
实施例22 | 30 | 91.4 |
实施例23 | 70 | 91.2 |
实施例24 | 400 | 80.4 |
实施例25 | 1,200 | 75.3 |
如表6中所示,直至厚度最高至1,200μm,本发明的隔氧膜的透明度仍未减小很多,这意味着只要其厚度在5-1000μm的范围内,这种膜就适合作为工业透明材料。
工业实用性
由于作为膜其优异的机械性能和优异的氧气阻隔性和透明性,同时克服了常规树脂的无规性问题,由基于乙烯-丙烯酸酯的共聚物制备的本发明的隔氧膜能够用于多种工业领域。
并且,由基于乙烯-丙烯酸酯的共聚物制得的本发明的隔氧容器具有高玻璃化转变温度、低吸湿率和优异的洛氏硬度,因此本发明的容器可以用作食品容器、包装容器、化妆品容器和用于加热箱的容器。
本领域技术人员应理解,前述说明书中公开的构思和具体实施方案可以容易地用作修改或设计用于实施与本发明目的相同的其它实施方案的基础。本领域技术人员也将理解,这种等效实施方案不偏离所附权利要求书中所阐明的本发明的实质和范围。
Claims (15)
1.一种隔氧膜,其包含基于乙烯-丙烯酸酯的共聚物,该基于乙烯-丙烯酸酯的共聚物由10-50mol%的乙烯单体和50-90mol%的基于丙烯酸酯的单体组成,且重均分子量为至少30,000g/mol。
2.根据权利要求1所述的隔氧膜,其中,所述乙烯单体的含量为15-40mol%,且所述基于丙烯酸酯的单体的含量为60-85mol%。
3.根据权利要求1所述的隔氧膜,其中,所述基于乙烯-丙烯酸酯的共聚物的重均分子量为至少70,000g/mol。
4.根据权利要求1所述的隔氧膜,其中,所述基于丙烯酸酯的单体为选自丙烯酸烷基酯和甲基丙烯酸烷基酯中的一种或者多种单体。
5.根据权利要求1所述的隔氧膜,其中,所述基于丙烯酸酯的单体为选自碳数为1-12个的直链或支链醇的丙烯酸酯和甲基丙烯酸酯中的一种或者多种单体。
6.根据权利要求1所述的隔氧膜,其中,所述基于丙烯酸酯的单体为选自丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯、丙烯酸异丁酯、丙烯酸叔丁酯、丙烯酸正己酯、丙烯酸-2-乙基丁酯、丙烯酸-2-乙基己酯和碳数为5-12个的醇的新异构体的丙烯酸酯中的一种或者多种单体。
7.根据权利要求1至权利要求6中任一项所述的隔氧膜,其中,该膜的厚度为5-1,000μm。
8.一种隔氧容器,其包含基于乙烯-丙烯酸酯的共聚物,该基于乙烯-丙烯酸酯的共聚物由10-50mol%的乙烯单体和50-90mol%的基于丙烯酸酯的单体组成,且重均分子量为至少30,000g/mol。
9.根据权利要求8所述的隔氧容器,其中,所述乙烯单体的含量为15-40mol%,且所述基于丙烯酸酯的单体的含量为60-85mol%。
10.根据权利要求8所述的隔氧容器,其中,所述基于乙烯-丙烯酸酯的共聚物的重均分子量为至少70,000g/mol。
11.根据权利要求8所述的隔氧容器,其中,所述基于丙烯酸酯的单体为选自丙烯酸烷基酯和甲基丙烯酸烷基酯中的一种或者多种单体。
12.根据权利要求8所述的隔氧容器,其中,所述基于丙烯酸酯的单体为选自碳数为1-12个的直链或支链醇的丙烯酸酯和甲基丙烯酸酯中的一种或者多种单体。
13.根据权利要求8所述的隔氧容器,其中,所述基于丙烯酸酯的单体为选自丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯、丙烯酸异丁酯、丙烯酸叔丁酯、丙烯酸正己酯、丙烯酸-2-乙基丁酯、丙烯酸-2-乙基己酯和碳数为5-12个的醇的新异构体的丙烯酸酯中的一种或者多种单体。
14.根据权利要求8至权利要求13中任一项所述的隔氧容器,其中,该容器为包装容器或者用于加热箱的容器。
15.根据权利要求14所述的隔氧容器,其中,所述包装容器为食品容器或者化妆品容器。
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