CN1035980A - 聚烯烃和尼龙/聚乙烯醇共混物的层状制品 - Google Patents
聚烯烃和尼龙/聚乙烯醇共混物的层状制品 Download PDFInfo
- Publication number
- CN1035980A CN1035980A CN89101562A CN89101562A CN1035980A CN 1035980 A CN1035980 A CN 1035980A CN 89101562 A CN89101562 A CN 89101562A CN 89101562 A CN89101562 A CN 89101562A CN 1035980 A CN1035980 A CN 1035980A
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- Prior art keywords
- polyolefin
- weight
- goods
- polyvinyl alcohol
- copolymer
- 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
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- 239000000203 mixture Substances 0.000 title claims abstract description 97
- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 71
- 239000004372 Polyvinyl alcohol Substances 0.000 title claims abstract description 68
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- 229920001778 nylon Polymers 0.000 title abstract description 48
- 239000004677 Nylon Substances 0.000 title abstract description 47
- 239000000463 material Substances 0.000 claims abstract description 54
- 239000000155 melt Substances 0.000 claims abstract description 22
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- -1 polyethylene Polymers 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 25
- 239000002245 particle Substances 0.000 claims description 19
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- 229920002647 polyamide Polymers 0.000 claims description 15
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 13
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 12
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 12
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 11
- 229930195733 hydrocarbon Natural products 0.000 claims description 11
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- 239000002828 fuel tank Substances 0.000 claims description 5
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- 239000004711 α-olefin Substances 0.000 claims description 5
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 229940117958 vinyl acetate Drugs 0.000 claims description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 3
- 125000005907 alkyl ester group Chemical group 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
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- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims 1
- 150000001408 amides Chemical class 0.000 claims 1
- 230000007062 hydrolysis Effects 0.000 claims 1
- 238000006460 hydrolysis reaction Methods 0.000 claims 1
- 125000005395 methacrylic acid group Chemical group 0.000 claims 1
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- 230000004888 barrier function Effects 0.000 abstract description 31
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 11
- 239000002904 solvent Substances 0.000 abstract description 2
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- 239000010410 layer Substances 0.000 description 43
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- 239000012046 mixed solvent Substances 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
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- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
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- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 2
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- 239000006057 Non-nutritive feed additive Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
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- 230000005540 biological transmission Effects 0.000 description 2
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- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
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- 239000011877 solvent mixture Substances 0.000 description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 2
- GUOSQNAUYHMCRU-UHFFFAOYSA-N 11-Aminoundecanoic acid Chemical compound NCCCCCCCCCCC(O)=O GUOSQNAUYHMCRU-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
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Natural products CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 description 1
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- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 1
- 235000008534 Capsicum annuum var annuum Nutrition 0.000 description 1
- 240000008384 Capsicum annuum var. annuum Species 0.000 description 1
- 241001529572 Chaceon affinis Species 0.000 description 1
- 241000498255 Enterobius vermicularis Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
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- 241000361919 Metaphire sieboldi Species 0.000 description 1
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- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 208000034189 Sclerosis Diseases 0.000 description 1
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- 229920006125 amorphous polymer Polymers 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- NIDNOXCRFUCAKQ-UHFFFAOYSA-N bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2C(O)=O NIDNOXCRFUCAKQ-UHFFFAOYSA-N 0.000 description 1
- PVEOYINWKBTPIZ-UHFFFAOYSA-N but-3-enoic acid Chemical compound OC(=O)CC=C PVEOYINWKBTPIZ-UHFFFAOYSA-N 0.000 description 1
- UTOVMEACOLCUCK-PLNGDYQASA-N butyl maleate Chemical compound CCCCOC(=O)\C=C/C(O)=O UTOVMEACOLCUCK-PLNGDYQASA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
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- 150000001470 diamides Chemical class 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000005066 dodecenyl group Chemical group C(=CCCCCCCCCCC)* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
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- DPUXQWOMYBMHRN-UHFFFAOYSA-N hexa-2,3-diene Chemical compound CCC=C=CC DPUXQWOMYBMHRN-UHFFFAOYSA-N 0.000 description 1
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- 229910052739 hydrogen Inorganic materials 0.000 description 1
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- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- FGTVYMTUTYLLQR-UHFFFAOYSA-N n-ethyl-1-phenylmethanesulfonamide Chemical class CCNS(=O)(=O)CC1=CC=CC=C1 FGTVYMTUTYLLQR-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
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- 238000006068 polycondensation reaction Methods 0.000 description 1
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- 239000004800 polyvinyl chloride Substances 0.000 description 1
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- 238000010008 shearing Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
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- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L2203/10—Applications used for bottles
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
- C08L23/0861—Saponified vinylacetate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
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Abstract
一种对含氧溶剂和烃化合物具有良好阻隔性的
层状制品,它是将一种聚烯烃与约2-39%尼龙/聚
乙烯醇组分的熔融共混物共混而制备的,共混时用烷
羧基取代的聚烯烃作相容剂。
Description
美国专利4,410,482公开了一些聚烯烃和缩聚物的层状制品。具体讲,业已发现由聚烯烃和尼龙得到的层状制品适于用作液体烃的容器,包括汽车燃料箱。近来汽油加工技术的变化趋向于向市售的烃燃料中添加越来越多的氧化化合物,如甲醇。当用具有聚烯烃和尼龙层状结构的容器盛装时,由于透过器壁扩散而造成的氧化化合物和烃类的燃料混合物的损失量一般是很大的,从环境保护的角度讲这是不能接受的。
欧洲专利申请0015556公开类似的层状制品,不同之处是其中用聚乙烯醇或乙烯/乙烯醇共聚物代替了尼龙阻隔树脂。这些层状结构也不具备对含氧化化合物的烃类足够的阻隔性。
因此需要改进用于贮装烃和氧化化合物的混合物的容器,如汽油箱和汽油罐。
本发明提供了一种对氧化化合物和烃的混合物具有改进的阻隔性的层状制品,例如容器。
具体讲,本发明提供了一种含有下列组合成分的层状制品:
(a)聚烯烃;
(b)聚酰胺和聚乙烯醇组分熔融共混物;
(c)烷羧基取代的聚烯烃;
其中共混物(b)以大量彼此平行相互重迭的二维薄层的形式存在于聚烯烃(a)中。
共混物(b)是由10-60%(重量)至少一种尼龙和40-90%(重量)聚乙烯醇组分构成的混合物的熔融共混物。所述聚乙烯醇组分含有50-100%(重量)选自:(a)聚乙烯醇、(b)含有可达10%(重量)丙烯酸低级烷基酯或甲基丙烯酸低级烷基酯的乙烯基乙酸脂皂化共聚物和(c)它们的混合物,以及0-50%(重量)含有可达50%(重量)乙烯单元的乙烯一乙烯醇共聚物。
盛装氧化化合物/烃混合物时,根据本发明制造的层状结构容器与用聚烯烃、相容剂和尼龙或聚乙烯醇(后两者没有同时使用)制造的层状容器相比,所盛装材料的损失量少得多。
本发明另一个实施例涉及一种层合板,其中第一层材料具有由聚烯烃、相容剂和尼龙/乙烯醇共聚物的熔融共混物得到的层状结构,第二层为聚烯烃占该层合板总厚度的10-90%,所述两层被熔融粘结在一起,第二层的聚烯烃最好与第一层中的聚烯烃相同。
制备本发明的层状制品所用的聚烯烃(a)包括聚乙烯、聚丙烯、聚丁烯、相应的共聚物等。聚乙烯是优选的,可为高、中或低密度。聚烯烃的优选用量为约60-97%(重量),最好约80-96%(重量)。
组分(b)是一种或多种尼龙与聚乙烯醇或其共聚物的熔融共混物。组分(b)的优选用量为约2-39%(重量),最好约2-15%(重量)。
适用的尼龙(聚酰胺)包括半结晶的和无定形的聚合物。本发明所用的聚酰胺包括那些分子量至少为5000通常称为尼龙的半结晶和无定形聚合物。适用的聚酰胺包括美国专利2071250、2071251、2130523、2130948、2241322、2312966、2512606、3393210和4369305、中所公开的那些。上述聚酰胺树脂可通过含4-12个碳原子的二元饱和羧酸与等摩尔的含4-14个碳原子的二胺缩聚而制备。聚酰胺的例子包括聚亚己基己二酰胺(尼龙66)、聚亚己基壬二酰胺(尼龙69)、聚亚己基癸二酰胺、聚亚己基十二烷二酰胺(尼龙612)、聚-11-氨基十一酸和双(对-氨基环己基)甲烷十二烷酰胺,以及由内酰胺开环制备的聚酰胺,如聚己内酰胺、聚月桂内酰胺。本发明的组合物中还可以使用由两种上述聚合物的共聚合或三种上述聚合物或其单体组分(如己二酸、间苯二酸、己二胺共聚物)的三元聚合制备的聚酰胺。聚己酰胺和己二酸、己二胺与己内酰胺的共聚酰胺是优选的。
组成(b)中所用的另一种材料是聚乙烯醇或其相应的共聚物或混合物。所有这些聚合物都是按常规方法制备的,即:将乙烯基乙酸酯单独聚合,或将其与其它单体共聚,然后进行皂化,得到相应的聚乙烯醇均聚物或共聚物。为适用于本发明,皂化程度应大于95%,最好至少为99%。这些聚合物的数均分子量一般约为20,000-80,000,但它们的分子量对本发明并不重要。
制备组分(b)时,可以单独使用聚乙烯醇(这是优选的),或者使用可含有约达10%(重量)丙烯酸甲酯或甲基丙烯酸甲酯或其它(甲基)丙烯酸低级烷基酯的共聚物。也可以使用两种或多种上述聚合物的共混物。含有可达50%(摩尔)乙烯单元的乙烯/乙烯醇共聚物可与上述聚乙烯醇或其(甲基)丙烯酸酯共聚物混用。没考虑单独使用乙烯/乙烯醇共聚物(即不使用聚乙烯醇),因为这种共聚物本身不能提供足够的燃料混合物阻隔性。该乙烯/乙烯醇共聚物可与聚乙烯醇或其(甲基)丙烯酸酯共聚物一起使用,其量可达50%(重量)。
组分(b)的熔融共混物优选含有约10-60%(重量)至少一种尼龙和约40-90%(重量)聚乙烯醇或其适当的共聚物;最好含有约20-35%(重量)至少一种尼龙和约65-80%(重量)聚乙烯醇或其适当的共聚物。在制备上述熔融共混物时,最好混入少量与所述聚乙烯醇相容的增塑剂,以改善该共混物的加工性。还可以添加其它加工助剂和抗氧剂。
组分(b)的熔融共混物可按常规方法制备,即:在挤塑机中,在高于混合物中最难熔组分熔点的温度,将尼龙与聚乙烯醇或其共聚物的干共混物混合。从挤塑机挤出的物料最好呈细条状,冷却并切成粒状,粒料特别适于用来制造本发明的制品。
组分(c)是一种烷羧基取代的聚烯烃,它起着相容剂的作用将相邻的聚烯烃层和尼龙/聚乙烯醇熔融共混物层粘结在一起。使用此相容剂是重要的,因为若不用相容剂构成本发明层状制品的聚合物层就不能彼此粘结,从而该制品不具备适于实用的机械性质。组分(c)的优选用量为约0.25-12%(重量),最好约2-5%(重量)。
上述烷羧基取代的聚烯烃相容剂是一种或者在聚烯烃主链上或者在其侧链上连有羧基部分的聚烯烃。所谓“羧基部分”是指选自酸、酯、酐和盐的羧基。羧酸盐是被中和的羧酸,而含有羧酸盐作为羧基部分的相容剂也包括该盐的羧酸。这种相容剂称为离聚物。
相容剂可通过直接合成或接枝而制备。直接合成的例子是将一种α一烯烃与一种含有羧基部分的烯烃单体聚合。接枝的例子是将含有羧基部分的单体接到一种聚烯烃的骨架上。在由接枝法制备的相容剂中,聚烯烃是聚乙烯或乙烯与至少一种C3-8α-烯烃(如聚丙烯)等的共聚物或含有至少一种C3-8α-烯烃和一种非共轭二烯(如1,4-己二烯)等的共聚物。将上述聚烯烃与不饱羧酸、酸酐、或酯单体反应,得到接枝聚合物。典型的羧酸、酸酐和酯包括甲基丙烯酸、丙烯酸、乙基丙烯酸、甲基丙烯酸甘油酯、丙烯酸2-羟乙酯、甲基丙烯2-羟乙酯、马来酸二乙酯、马来酸单乙酯、马来酸二正丁酯、马来酸酐、马来酸、富马酸、依康酸、这些二元酸的单酯、十二碳烯基琥珀酐、5-降冰片烯-2,3-酸酐、nadic酸酐(3,6-桥亚甲基-1,2,3,6-四氢苯二酸酐)等。一般讲,该接枝聚合物含有约0.01-20%,较好约0.1-10%,最好约0.2-5%(重量)的接枝单体。最优选的接枝聚合物是约0.25-2%(重量)马来酸酐部分接枝到聚乙烯骨架上形成的接枝聚合物。关于接枝聚合物更详细的情况,请参见美国专利4,026,967和3,953,655。
在由直接合成法制备的相容剂中,聚合材料是一种C2-10α-烯烃和带有1个或2个羧基部分的α、β烯属不饱和羧酸、酯、酐或盐的共聚物。上述直接合成的相容剂由至少75%(摩尔)的烯烃组分和约0.2-25%(摩尔)的羧基组分。
离聚物相容剂最好是直接合成的相容剂,并且最好含有约90-99%(摩尔)烯烃和约1-10%(摩尔)含有羧基部分的α、β烯属不饱和单体,其中羧基部分被视为酸等价物,并且当该羧酸等价物为单羧基时用1-3价的金属离子中和,当该羧酸等价物为双羧基时用1价的金属离子中和。为控制中和程度,金属离子的用量要足以中和至少10%的羧基部分。典型的α-烯烃和不饱和羧酸、酸酐和酯单体本文在前面部分已叙及。在美国专利3,264,272中对离聚物有更详细的介绍。
在制备本发明成型制品时,构成该层状制品连续相的聚烯烃的用量为60-97%(重量)。与该聚烯烃不相容并构成不连续相的尼龙/聚乙烯醇聚合物熔融共混物的用量为2-40%(重量)。相容剂的用量为0.25-12%(重量)。尼龙/聚乙烯醇聚合物的熔融共混物的优选用量为2-15%(重量),与2-5%的相容剂混谩?
本发明的制品基本上是按美国专利4,410,482所述方法制造的,此专利收录于此作为参考。最好按下述方式制造该层合制品,将聚烯烃粒料、预制的尼龙/聚乙烯醇熔融共混物粒料和相容剂的粒料混合在一起,加热此混合物得到一种多相熔体材料,将此熔体以下述方式成型,即:拉伸该熔体,产生一种拉伸的不连续聚合物相,此相由尼龙/聚乙烯醇聚合物的共混物组成。
在一个实施例中,将非熔融态的聚合物颗粒(组分(a)、(b)和(c)充分混合,以便提供一种统计均匀的分散体。在将聚合物加热为熔体之后,必需十分小心,避免进一步的剧烈混合。在另一个实施例中,可以在软化或熔融状态混合聚合物颗粒,只要能保持非均相特性即可。这种共混物也可以通过将熔融的聚烯烃与尼龙/聚乙烯醇共混物和相容剂的固体颗粒相混合,然后将其加热而得到。本发明的成功归因于得到了一种不相容聚合物的非均相熔融共混物。因此,当拉伸该熔体时(如用挤压力),一种聚合物以连续基质相的形式存在,而另一种聚合物以不连续分散的形式存在。构成不连续相的聚合物以大量彼此平行相互重迭的基本为二维薄层的形式包埋在连续相中。
如前所述,实施本发明时所用的尼龙/聚乙烯醇熔融共混物,最好为颗粒形式,上述聚烯烃和熔融共混物最好以颗粒的形式相混合,当然并不要求一定如此。作为一般性原则,上述颗粒应该具有这样的粒度,使得该不相容聚合物的熔融共混物在引入某一熔体拉伸装置(如挤出口模唇口)时显示出实施本发明所必需的不均匀性。当上述颗粒,特别是熔融共混物颗粒的粒度过小时,既使没有过度混合,该熔融共混物也趋向于具有均匀组合物的功能,因为构成不连续聚合物相的材料的单元区域是如此之小。当上述颗粒特别是熔融共混物颗粒的粒度过大时,该熔融共混物倾向于形成一种大理石状结构而不是层状结构的成型制品,因为构成不连续相的材料的大单元区域会延伸到成型制品的背面,从而破坏构成连续相的聚烯烃。发现粒度为约1-5mm,最好约3mm的颗粒特别适用。颗粒的形状最好为规整的,如立方体或圆柱体等。当然,这些颗粒也可以是不规整的,而且其一维尺寸可以远远大于另一维尺寸,例如,使用薄片材料时就是这种情况。
当每种不相容聚合物均以单独颗粒的形式存在时,这些颗粒一般具有大约相同的粒度,然而并不要求一定如此。相容剂本身可以颗粒的形式使用,也可混入或涂到上述一种或两种不相容聚合物上,或以其它的方式与上述不相容聚合物相结合。
不连续相中材料层的厚度是颗粒粒度及成型步骤中的拉伸程度的函数。构成不连续相的熔融共混物的颗粒粒度一般是这样选择的,使得拉伸后可以得到许多相互重迭的层,这些层的厚度为约0.5-50或可能稍厚些。
对聚合物颗粒进行干混可按任何已知的方法进行,如用V型干混机、桶混机,较大规模时可采用双锥体掺合机。可用任何已知方法对上述颗粒进行连续混合。当然,也可用于手工进行混合,对混合的唯一要求是,给定量的两个该混合物的统计样品应该具有基本相同的组成。不相容聚合物的混合可这样进行,将熔融温度较高的聚合物的颗粒添加到熔融温度较低的聚合物的熔体中,该熔体温度保持在前者的熔点以下。在上述条件下搅拌此熔体,得到一充分混合的混合物,此混合物已可用于加热步骤。
经混合后,将不相容聚合物加热到其中具有最高熔融温度的聚合物组分的熔点温度以上。应注意,加热进行到可以拉伸软化或熔融的共混物即可。当不相聚合物没有很明确的熔融温度时,则上文所用的“熔融温度”一词是指这样的温度,此温度足以使该聚合物软化到成型时对其进行拉伸所需的程度。上述加热可导致一种不同材料的软化或熔融的非均相共混物,加热必须以能够避免对该不相容聚合物混合体产生附加过份混合的方式进行,因为这种混合可以导致均化;产生基本均匀的未层化的熔体和成型制品。加热可按任何已知的方法进行,通常是在挤塑机中进行的。发现在加热和成型步骤之间采用设计用于物料传输而不是用于物料混合的这类单螺杆挤塑机,不会造成两相不相容的聚合物组分发生均化。通常用于聚氯乙烯、聚丙烯腈或聚偏二氯乙烯的那类低剪切低混合挤塑机也可用于本发明,当然要以适当的方式使用,即主要是熔融和传输物料并最大限度地降低对物料的混合作用。一般不应使用常用于尼龙和聚乙烯的那类高剪切高混合挤塑机。由这些挤塑机制成的组合物可保持很大程度的非均匀性,因为可以实现本发明的优点。
在成型步骤要对熔融的共混物进行拉伸,然后将其淙础@焓墙昧较嗳厶謇ぃ沟貌涣嘀锌帕5某叽绶⑸艽蟮母谋洹@炜砂慈舾煞椒ń小@纾赏ü诠鲎又浠蛱ò逯浣屑费梗蛲?过口模唇口挤出而将该熔体拉伸。模塑法如吹塑也可造成拉伸。在制造成型制品(如容器)过程中,拉伸是与挤塑过程相结合的,首先挤塑非均相熔体共混物,得到容器型坯,然后将该型坯吹塑为容器成品。
拉伸可在单方向进行,也可在相互垂直的双向进行。无论单向或双向拉伸,在至少一个方向上应该具有约100-500%或甚至大于1000%的伸长率,优选的伸长率为约100-300%。这里所给出的上限并不重要,而下限是很重要的,因为不充分拉伸就不能得到作为本发明特征的对液体透过的阻隔性。避免过份拉伸只是因为熔体过份伸长可能会削弱或破坏制品。
拉伸以后,将温度降至最低熔点组分的熔点温度以下,以便使成型制品硬化,冷却可以按任何需要的方式以任何方便的降温速度进行。在吹塑拉伸的情况下,经常是冷却模具,从而将制品冷却;在挤出膜的情况下,可暴露于冷却空气或通过与骤冷滚接触而进行冷却。
正如前面所指出的,另一个实施例包括一种具有上述层状结构而且其上粘结有一层或两层均匀聚烯烃熔体的层合制品,这类层合制品的例子包括层合膜,该膜的第一层含有一种层状结构材料,此层状材料是通过拉伸聚烯烃和尼龙/乙烯醇聚合物及相容剂的不相容混合物的熔体而得到,第一层粘结在由纯聚烯烃组成的第二层上;吹塑容器,其外部为由聚烯烃和尼龙/乙烯醇聚合物及相容剂的混合物的熔体得到的层状结构阻隔层,此阻隔层粘结在一个聚烯烃内层上。组成第二层的聚烯烃最好与在层状共混物中用作组分(a)的聚烯烃相同。在这些条件下,不同的层无需使用粘结层即可粘结在一起。美国专利4,416,942中介绍了类似的层合制品的制造方法,其中用来形成不连续重迭阻隔层的聚合物与本发明不同。
在本发明又一个实施例中,可以通过将一层上述非均相混合物与至少一层聚烯烃共挤塑而制造层合结构。非均相混合物是在上述第一个挤塑机中形成的,同时将聚烯烃通过第二个适于聚烯烃的挤塑机熔融挤出。当这两种组分在各自的挤塑机中分别被熔融后,将它们通过供料头传输到口模,此两种组分在这里作为共挤塑层而从口模狭缝挤出。调整供料头使聚烯烃层占该层合制品总厚度的10-90%,最好50-90%。容器如瓶子可这样制造,将两层或多层共挤塑,形成多层型坯,在适当的模具中吹胀上述型坯,形成所需的制品。
与具有相同量尼龙/乙烯醇聚合物不连续相、同样厚度层状材料层的单层层合制品相比,本发明的层合制品显示出改进的对含氧化溶剂的烃类的流体阻隔性。因此,将这种层合制品制成厚壁容器,如燃料箱和55加仑油罐,可以最大限度地发挥上述尼龙/乙烯醇阻隔树脂的作用。同时,吹塑箱和罐的冲击性能得到改善,因为壁厚的主要部分是由均聚乙烯构成的。
本发明的共混物和层合制品可用于制造盛装烃和含氧液体的容器,也可用来制造板、膜、管材等,尤其是用于汽车燃料箱。
对比例1
将聚烯烃、尼龙和相容剂的颗粒在聚乙烯袋中进行混合,然后加工成共混物。所用尼龙是一种共聚酰胺,是将己二胺、己二酸和己内酰胺缩合而得到的一种含约80%(重量)聚亚己基己二酰胺和20%(重量)聚己内酰胺的共聚物。所用聚乙烯是线型聚乙烯,密度为0.953克/立方厘米,按ASTM D-1238(条件下)测定熔体指料为10克/10分钟。
相容剂是通过将富马酸熔融接枝到密度为0.958克/立方厘米熔体指数约为10(按ASTM D-1238标准测定)的聚烯烃上而得到的。按美国专利4,026,967的做法使接枝到聚乙烯上的富马酸的量约为0.9%(重量)(以聚合物总重为基准)。
使用了下列组分:
共聚酰胺,7%(重量);相容剂,3.5%(重量);聚乙烯,89.5%(重量)。将此混合物喂入配备有不带混合尖梢、压缩比为2∶1的螺杆(直径38.1mm)的挤坯吹塑机(型号:Rocheleau Model 7A)。于大约225-230℃的挤出温度吹塑容量为约100ml的瓶子。瓶重约62克。侧壁约1mm厚,显示出具有层状分布的阻隔树脂,即共聚酰胺。
用10%(体积)甲醇/二甲苯和3%(体积)甲醇/二甲苯混合物充满试验容器,于室温放置几周后测定失重量,以确定阻隔效率。对每种溶剂混合物,重复试验三次,定期称量瓶子的重量,将它们的失重量对时间作图,记录下每组试验的平均稳定态失重量。根据容器的重量和几何形状可计算出(ASTM-2684标准)其表面积和平均厚度。计算透过值(P)。结果如下:
混合物 (体积) P;克.毫米/天.米2
10% 甲醇/二甲苯 14.3
3% 甲醇/二甲苯 11.2
对比例2
在另一个操作中,采用相同的材料由10.8%(重量)共聚酰胺、5.7%(重量)相容剂和83.5%(重量)聚乙烯制成层状结构的瓶子,得到如下结果:
混合物(体积) P;克.毫米/天.米2
10%甲醇/二甲苯 12.3
可以看到增加尼龙含量对阻隔性几乎没有什么改善。此外,当混合物中甲醇含量从10%降至3%如对比例1所示)时,阻隔性稍有改善。
实例1
此例中所用的阻隔材料是对比1中所用共聚酰胺与聚乙烯醇(PVOH)的熔融共混物。用甲醇洗涤数均分子量约为30.000皂化程度为99+%的聚乙烯醇,以降低乙酸钠含量。干燥后将此PVOH与作为增塑剂的邻和对N-乙基甲苯氨磺酰的10%(重量)异构体混合物(·“Santicizer 8”Monsanto出售)、2000ppm辛酸加工助剂和1000ppm,1,3,5-三甲基-2,4,6-三(3,5-二叔丁基-4-氢苄基)苯抗氧剂在双螺杆挤塑机中于大约230℃的熔融温度进行共混。然后,在单螺杆挤塑机中于大约230℃的熔融温度,将100份重上述混合好的PVOH和50份重共聚酰胺熔融共混,得到一种尼龙/PVOH熔融共混物。将从挤塑机挤出的物料造粒。按对比例1的方法,用10%(重量)上述尼龙/PVOH共混物、3.5%(重量)对比例1的相容剂和86.5%(重量)对比例1的聚烯烃剂制备层状结构的瓶。阻隔效率如下所示:
混合物(体积) P;克.毫米/天.米2
10%甲醇/二甲苯 2.3
3%甲醇/二甲苯 2.3
很明显,对烃和含氧溶剂混合物的阻隔性有显著的提高。
实例2
将实例1所用经洗涤的PVOH在双螺杆挤塑机中于约230℃的熔融温度与10%(重量)的三甘醇增塑剂混合。将26.5份重对比例1所用的共聚酰胺与73.5份重上述增塑的PVOH组分熔融混合,得到尼龙/PVOH共混物。按对比例1的方法,再7%(重量)上述尼龙/PVOH共混物、3.6%(重量)对比例1所用的相容剂和89.4%(重量)对比例1所用的聚乙烯制备层状结构的瓶子。阻隔效率在下面给出:
混合物(体积) P;克.毫米/天.米2
5%甲醇/二甲苯 1.5
很明显本发明的层状结构瓶子优于对比例1的层状结构瓶。
实例3
在此实例中采用了与实例2所用相同的尼龙/PVOH,用7%(重量)尼龙/PVOH、4%(重量)相容剂,和聚乙烯制备1升容积的瓶子。然而,制造此1升容积瓶时,使用的是带有储料缸式机头的吹塑机(型号:Hayssen Model Econo Blow;储料缺容量454克;螺杆直径50.8毫米,不带混合尖梢)。侧壁具有层状结构。阻隔性如下所示:
混合物(体积) P;克.毫米/天.米2
15%甲醇/不加铅汽油 1.7
可以看到,在带有储料罐式机头的吹塑机中加工该组合物时,对含甲醇混合溶剂的阻隔性也有显著提高。
实例4
采用与实例3相同的设备和配方。然而用不同的模具制造3.8升(1加仑)层状结构容器(220克)。得到如下阻隔性:
混合物(体积) P;克.毫米/天.米2
15%甲醇/二甲苯 2.2
因此,较大的容器对混合溶剂的阻隔性也有显著提高。
实例5
将100份重实例1所用的经混合的PVOH与50份重无定形尼龙熔融共混,制得阻隔材料。所述尼龙是按美国专利4,369,303实例1中所述的方法,由70%(摩尔)间苯二酸、30%(摩尔)邻苯二酸、94%(摩尔)己二胺和6%(摩尔)双(对氨基环己基)甲烷制备的。在实例1所述的Rocheleau机上用10%(重量)尼龙/PVOH、3.5%(重量)对比例1所用的相容剂和86.5%(重量)对比例1所用的聚乙烯的混合物制造1升容积的层状结构容器。阻隔性能如下所示:
混合物(体积) P;克.毫米/天.米2
10%甲醇/二甲苯 3.2
因此,用无定形尼龙以及半结晶尼龙可以获得改进的阻隔性。
实例6
将74份重实例2所用的经混合的PVOH与26份重聚己内酰胺(尼龙6)熔融共混,制得一种阻隔材料。在实例1所述的Rocheleau机上,由4,2%(重量)尼龙/PVOH共混物、2.8%(重量)对比例1所用的相容剂和93%(重量)对比例1所用的聚乙烯组成的混合物制造1升容积层状结构瓶。于40℃及60%的填充量条件下测定阻隔性,并以40℃时的透过量除以4外推至室温。结果如下:
混合物(体积) P;克.毫米/天.米2
15%甲醇/二甲苯 3.9
当尼龙/PVOH熔融共混物中采用己内酰胺均聚物时,也获得了改进的阻隔性。
实例7
按实例1的方法,用26份重对比例1所用的尼龙和74份重聚乙烯醇共聚物制得一种熔融共混物。所述聚乙烯醇共聚物是含5.5%(重量)甲基丙烯酸甲酯数均分子量为34.000的乙烯基乙酸酯共聚物的皂化产物。在实例1所述的Rocheleau机上制得1升容积的瓶子。所用的聚合物混合物含4.2%(重量)尼龙/PVOH共聚物的共混物、2.8%(重量)对比例1所用的相容剂和93%(重量)对比例1所用的聚乙烯。按实例6计算,得到如下结果;
混合物(体积) P;克.毫米/天.米2
15%甲醇/二甲苯 3.9
甲基丙烯酸甲酯共聚物也能提供改进的的阻隔性。
实例8
重复实例7的过程,不同之处是用等重量的另一种聚乙烯醇共聚物代替甲基丙烯酸甲酯/共聚物,即含有9%(重量)丙烯酸甲酯数均匀分子量为30.000的乙烯基乙酸酯的皂化产物。按实例6方法计算,得到如下结果:
混合物(体积) P;克.毫米/天.米2
15%甲醇/二甲苯 6.2
两种PVOH共聚物对混合溶剂的阻隔性结果差不多。实例9
由37份重实例1所述经混合的PVOH、37份重含有30%(摩尔)乙烯单元的乙烯-乙烯醇共聚物(熔体指数3)和26份重对比例1所用的共聚酰胺组成的混合物制得一种熔融共混物。在Rocheleau吹塑机上,用由3.8%(重量)上述三元熔融共煳铮?.85%(重量)对比例1的相容剂的92.35%(重量)对比例1所用的聚乙烯组成的混合物制造1升容积的层状结构瓶。按实例6的方法计算,得到如下结果:
混合物(体积) P;克.毫米/天.米2
15%甲醇/二甲苯 6.2
当一半PVOH被乙烯/乙烯醇共聚物所代替时仍可保持改进的阻隔特性。
实例10
在此实例中,将90份重实例1所用但未经洗涤的PVOH与10份重三甘醇增塑剂混合。然后将74份重经混合的PVOH与26份重对比例1所用的共聚酰胺熔融共混。按对比例1的方法,在Rocheleau机上用由4.2%(重量)上述尼龙/PVOH熔融共混物、3.8%(重量)对比例1所用的相容剂和92%(重量)对比例1所用的聚乙烯组成的混合物制造层状结构的瓶。按实例6方法计算,得到如下结果:
混合物(体积) P;克.毫米/天.米2
15%甲醇/二甲苯 2.0
使含有大量乙酸钠的未经洗的市售PVOH得到了优异的阻隔性。
实例11
用74份重实例所用的但未经洗涤的PVOH和26份重对比例1所用的共聚酰胺制得一种熔融共混物。不向PVOH中添加增塑剂。按对比1的方法,在Rocheleau机上用由4.2%(重量)上述尼龙/PVOH熔融共混物、3.8%(重量)对比例1所用的相容剂和92%(重量)对比例1所用的聚乙烯组成的混合物制造层将结构的瓶。按实例6方法计算,得到如下结果:
混合物(体积) P;克.毫米/天.米2
15%甲醇/二甲苯 4.3
使用未经增塑的商售PVOH得到了改进的对混合溶剂的阻隔性。
Claims (31)
1、一种具有层状结构的制品,包括下列各成分的组合:
(a)一种聚烯烃
(b)一种聚酰胺和聚乙烯醇组分的熔融共混物;
(c)一种烷酸基取代的聚烯烃;其中共混物(b)以大量彼此平行相互重迭且基本为二维的薄层的形式存在于聚烯烃(a)中。
2、按权利要求1的制品,其中聚烯烃(a)含量为约60-97%(重量),聚酰胺和聚乙烯醇组分的共混物(b)的含量为约2-39%(重量),烷羧基取代的聚烯烃(c)的含量为约0.25-12%(重量)。
3、按权利要求2的制品,其中烷羧基取代的聚烯烃至少要有一部分位于共混物(b)层和聚烯烃(a)层之间。
4、按权利要求2的制品,其聚烯烃是聚乙烯。
5、按权利要求2的制品,其中共混物(b)含有约10-60%的聚酰胺和约40-90%的聚乙烯醇组分。
6、按权利要求5的制品,其中共混合物(b)含有约20-35%的酰胺和约80-65%的聚乙烯醇组分。
7、按权利要求2的制品,其中所述聚乙烯醇组分含有约50-100%(重量)选自(ⅰ)聚乙烯醇、(ⅱ)含有可达约10%(重量)丙烯酸低级烷基酯或甲基丙烯酸低级烷基酯的乙烯基乙酸酯的皂化共聚物、(ⅲ)它们的混合物的一种聚合物,以及约0-50%(重量)含有可达约50%(重量)含有可达约50%(重量)乙烯单元的乙烯-乙烯醇共聚物。
8、按权利要求7的制品,其中聚乙烯醇组分的皂化度至少为约95%。
9、按权利要求8的制品,其中聚乙烯醇组分的皂化度至少为约99%。
10、按权利要求8的制品,其中聚乙烯醇组分是聚乙烯。
11、按权利要求2的制品,其中聚酰胺选自聚己酰胺和己二酸与己二胺及己内酰胺的共聚物。
12、按权利要求11的制品,其中聚酰胺是己二酸与己二胺及己内酰胺的共聚物。
13、按权利要求6的制品,其中共混物(b)的含量为约2-15%(重量),烷羧基取代的聚烯烃(c)的含量为约2-5%(重量)。
14、按权利要求2的制品,其中烷羧基取代的聚烯烃是直接合成的共聚物。
15、按权利要求14的制品,其中所述直接合成的共聚物是含有约0.25-25%(摩尔)带1或2个羧基部分的α,β-烯属不饱和羧酸、酯、酐或盐的C2-10α烯烃共聚物。
16、按权利要求15的制品,其中所述直接合成的共聚物是乙烯和甲基丙烯酸的共聚物。
17、按权利要求16的制品,其中共聚物含有约1-10%(摩尔)的甲基丙烯酸单元,并且其中约0-90%至少被一种1-3价的金属离子所中和。
18、按权利要求2的制品,其中烷羧基取代的聚烯烃是接枝共聚物。
19、按权利要求14的制品,其中所述接枝共聚物是约0.25-2.0%(重量)马来酸酐接枝到聚烯烃骨架上所构成的接枝共聚物。
20、按权利要求1的制品,其中:
(a)聚烯烃是聚乙烯,其含量为约80-96%(重量);
(b)熔融共混物含有约20-35%(重量)己二酸与己二胺及己内酰胺的共聚物和约80-65%(重量)水解度至少为99%的聚乙烯醇,此共混物含量为约2-15%(重量);
(c)烷羧基取代的聚烯烃是约0.25-2.0%(重量)马来酸酐接枝到聚乙烯骨架上所构成的接枝共聚物,此取代聚烯烃的含量为约2-5%(重量)。
21、一种制造聚合材料层制品的方法,包括如下步骤:
(a)制备聚酰胺和聚乙烯醇组分的熔融共混物;
(b)于足以熔融所有所述组分的温度将上述熔融共混物与聚烯烃和烷羧基取代的聚烯烃相混合,形成一种熔融的非均相混合物;
(c)通过(ⅰ)拉伸上述混合体、(ⅱ)将经拉伸的混合体冷却到最低熔点聚合物组分的熔点温度以下,从而将该熔融的非均相混合物成型。
22、按权利要求20的方法,其中将聚酰胺和聚乙烯醇组分的熔融共混物造粒,然后与聚烯烃颗粒和烷羧基取代的聚烯烃的颗粒相混合,接着加热形成一种熔融的非均相混合物。
23、按权利要求22的方法,其中共混物粒料和聚烯烃颗粒的粒度为约1-5毫米。
24、按权利要求23的方法,其中拉伸使得该混合体的伸长率至少在一个方向上至少为100%。
25、按权利要求2的制品,它是容器。
26、按权利要求25的制品,其中所述容器是汽车燃料箱。
27、一种层合结构,含有至少一个第一层权利要求2的层状制品层和至少一个第二层聚烯烃层。
28、按权利要求27的层合结构,其中第二层的聚烯烃与第一层中的聚烯烃相同。
29、按权利要求28的层合结构,其中聚烯烃是聚乙烯。
30、按权利要求29的层合结构,其具体形式是容器。
31、按权利要求30的层合结构,其中所述容器是汽车燃料箱。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US07/181,119 US4950513A (en) | 1988-03-17 | 1988-03-17 | Laminar articles of a polyolefin and a nylon/polyvinyl alcohol blend |
US181,119 | 1988-03-17 |
Publications (2)
Publication Number | Publication Date |
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CN1035980A true CN1035980A (zh) | 1989-10-04 |
CN1016496B CN1016496B (zh) | 1992-05-06 |
Family
ID=22662981
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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CN89101562A Expired CN1016496B (zh) | 1988-03-17 | 1989-03-17 | 聚烯烃和尼龙/聚乙烯醇共混物的层状制品 |
Country Status (15)
Country | Link |
---|---|
US (2) | US4950513A (zh) |
EP (1) | EP0333471B1 (zh) |
JP (1) | JPH0639152B2 (zh) |
KR (1) | KR960008304B1 (zh) |
CN (1) | CN1016496B (zh) |
AT (1) | ATE82995T1 (zh) |
AU (1) | AU609953B2 (zh) |
BR (1) | BR8901163A (zh) |
CA (1) | CA1313934C (zh) |
DE (1) | DE68903656T2 (zh) |
DK (1) | DK172174B1 (zh) |
ES (1) | ES2052903T3 (zh) |
FI (1) | FI891246A (zh) |
MX (1) | MX166938B (zh) |
WO (1) | WO1989008548A1 (zh) |
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-
1988
- 1988-03-17 US US07/181,119 patent/US4950513A/en not_active Expired - Lifetime
-
1989
- 1989-03-01 WO PCT/US1989/000758 patent/WO1989008548A1/en unknown
- 1989-03-13 BR BR898901163A patent/BR8901163A/pt not_active IP Right Cessation
- 1989-03-15 AU AU31299/89A patent/AU609953B2/en not_active Expired
- 1989-03-15 CA CA000593844A patent/CA1313934C/en not_active Expired - Lifetime
- 1989-03-16 AT AT89302596T patent/ATE82995T1/de not_active IP Right Cessation
- 1989-03-16 JP JP1062332A patent/JPH0639152B2/ja not_active Expired - Lifetime
- 1989-03-16 ES ES89302596T patent/ES2052903T3/es not_active Expired - Lifetime
- 1989-03-16 EP EP89302596A patent/EP0333471B1/en not_active Expired - Lifetime
- 1989-03-16 DE DE8989302596T patent/DE68903656T2/de not_active Expired - Lifetime
- 1989-03-16 KR KR1019890003302A patent/KR960008304B1/ko not_active IP Right Cessation
- 1989-03-16 FI FI891246A patent/FI891246A/fi not_active Application Discontinuation
- 1989-03-16 MX MX015301A patent/MX166938B/es unknown
- 1989-03-17 CN CN89101562A patent/CN1016496B/zh not_active Expired
-
1990
- 1990-09-11 DK DK217290A patent/DK172174B1/da not_active IP Right Cessation
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN101171294B (zh) * | 2005-05-09 | 2012-05-30 | 托塔尔石油化学产品研究弗吕公司 | 由包含聚乙烯的共混物制备的单层旋转模塑制品 |
Also Published As
Publication number | Publication date |
---|---|
MX166938B (es) | 1993-02-15 |
JPH0639152B2 (ja) | 1994-05-25 |
EP0333471B1 (en) | 1992-12-02 |
FI891246A (fi) | 1989-09-18 |
US4950513A (en) | 1990-08-21 |
WO1989008548A1 (en) | 1989-09-21 |
KR890014261A (ko) | 1989-10-23 |
JPH01275137A (ja) | 1989-11-02 |
AU3129989A (en) | 1989-09-21 |
DK172174B1 (da) | 1997-12-15 |
ES2052903T3 (es) | 1994-07-16 |
DE68903656D1 (de) | 1993-01-14 |
CN1016496B (zh) | 1992-05-06 |
FI891246A0 (fi) | 1989-03-16 |
AU609953B2 (en) | 1991-05-09 |
DE68903656T2 (de) | 1993-05-13 |
BR8901163A (pt) | 1989-10-31 |
DK217290A (da) | 1990-09-11 |
KR960008304B1 (ko) | 1996-06-24 |
DK217290D0 (da) | 1990-09-11 |
EP0333471A3 (en) | 1990-08-08 |
ATE82995T1 (de) | 1992-12-15 |
EP0333471A2 (en) | 1989-09-20 |
CA1313934C (en) | 1993-03-02 |
US5330696A (en) | 1994-07-19 |
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C15 | Extension of patent right duration from 15 to 20 years for appl. with date before 31.12.1992 and still valid on 11.12.2001 (patent law change 1993) | ||
OR01 | Other related matters | ||
C17 | Cessation of patent right | ||
CX01 | Expiry of patent term |