CN107428866B - 聚合物泡沫 - Google Patents
聚合物泡沫 Download PDFInfo
- Publication number
- CN107428866B CN107428866B CN201580077777.0A CN201580077777A CN107428866B CN 107428866 B CN107428866 B CN 107428866B CN 201580077777 A CN201580077777 A CN 201580077777A CN 107428866 B CN107428866 B CN 107428866B
- Authority
- CN
- China
- Prior art keywords
- polymer composition
- acid
- polymer
- zinc
- acid neutralizer
- 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 - Fee Related
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- 229920000642 polymer Polymers 0.000 title claims abstract description 130
- 239000006260 foam Substances 0.000 title claims abstract description 30
- 239000000203 mixture Substances 0.000 claims abstract description 83
- 239000002253 acid Substances 0.000 claims abstract description 43
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229920000098 polyolefin Polymers 0.000 claims abstract description 25
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims abstract description 16
- 239000004604 Blowing Agent Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 12
- -1 polypropylene Polymers 0.000 claims description 38
- 239000004743 Polypropylene Substances 0.000 claims description 24
- 229920001155 polypropylene Polymers 0.000 claims description 24
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 22
- 229910052751 metal Inorganic materials 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 22
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 20
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 18
- 239000011787 zinc oxide Substances 0.000 claims description 11
- 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 claims description 10
- 229960001545 hydrotalcite Drugs 0.000 claims description 10
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 10
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical group CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 claims description 6
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000159 acid neutralizing agent Substances 0.000 claims description 5
- 229940048053 acrylate Drugs 0.000 claims description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- 150000004706 metal oxides Chemical class 0.000 claims description 5
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 4
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical compound CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 claims description 4
- WGECXQBGLLYSFP-UHFFFAOYSA-N 2,3-dimethylpentane Chemical compound CCC(C)C(C)C WGECXQBGLLYSFP-UHFFFAOYSA-N 0.000 claims description 4
- GXDHCNNESPLIKD-UHFFFAOYSA-N 2-methylhexane Chemical compound CCCCC(C)C GXDHCNNESPLIKD-UHFFFAOYSA-N 0.000 claims description 4
- PFEOZHBOMNWTJB-UHFFFAOYSA-N 3-methylpentane Chemical compound CCC(C)CC PFEOZHBOMNWTJB-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 4
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 4
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000004386 diacrylate group Chemical group 0.000 claims description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 4
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 4
- XKMZOFXGLBYJLS-UHFFFAOYSA-L zinc;prop-2-enoate Chemical group [Zn+2].[O-]C(=O)C=C.[O-]C(=O)C=C XKMZOFXGLBYJLS-UHFFFAOYSA-L 0.000 claims description 4
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 claims description 3
- TUPMGGHTDIFOMI-UHFFFAOYSA-J 2-methylprop-2-enoate;zirconium(4+) Chemical compound [Zr+4].CC(=C)C([O-])=O.CC(=C)C([O-])=O.CC(=C)C([O-])=O.CC(=C)C([O-])=O TUPMGGHTDIFOMI-UHFFFAOYSA-J 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- MFPROKIABJECGK-UHFFFAOYSA-K aluminum;2-methylprop-2-enoate Chemical compound [Al+3].CC(=C)C([O-])=O.CC(=C)C([O-])=O.CC(=C)C([O-])=O MFPROKIABJECGK-UHFFFAOYSA-K 0.000 claims description 3
- LIQDVINWFSWENU-UHFFFAOYSA-K aluminum;prop-2-enoate Chemical compound [Al+3].[O-]C(=O)C=C.[O-]C(=O)C=C.[O-]C(=O)C=C LIQDVINWFSWENU-UHFFFAOYSA-K 0.000 claims description 3
- 239000008116 calcium stearate Substances 0.000 claims description 3
- 235000013539 calcium stearate Nutrition 0.000 claims description 3
- VZWHXRLOECMQDD-UHFFFAOYSA-L copper;2-methylprop-2-enoate Chemical compound [Cu+2].CC(=C)C([O-])=O.CC(=C)C([O-])=O VZWHXRLOECMQDD-UHFFFAOYSA-L 0.000 claims description 3
- XPLSDXJBKRIVFZ-UHFFFAOYSA-L copper;prop-2-enoate Chemical compound [Cu+2].[O-]C(=O)C=C.[O-]C(=O)C=C XPLSDXJBKRIVFZ-UHFFFAOYSA-L 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- BIXADNIHYBZLKU-UHFFFAOYSA-N prop-2-enoic acid;zirconium Chemical compound [Zr].OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C BIXADNIHYBZLKU-UHFFFAOYSA-N 0.000 claims description 3
- PQCHENNROHVIHO-UHFFFAOYSA-M silver;2-methylprop-2-enoate Chemical compound [Ag+].CC(=C)C([O-])=O PQCHENNROHVIHO-UHFFFAOYSA-M 0.000 claims description 3
- 229940047670 sodium acrylate Drugs 0.000 claims description 3
- SONHXMAHPHADTF-UHFFFAOYSA-M sodium;2-methylprop-2-enoate Chemical compound [Na+].CC(=C)C([O-])=O SONHXMAHPHADTF-UHFFFAOYSA-M 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 3
- PIMBTRGLTHJJRV-UHFFFAOYSA-L zinc;2-methylprop-2-enoate Chemical compound [Zn+2].CC(=C)C([O-])=O.CC(=C)C([O-])=O PIMBTRGLTHJJRV-UHFFFAOYSA-L 0.000 claims description 3
- BZHMBWZPUJHVEE-UHFFFAOYSA-N 2,3-dimethylpentane Natural products CC(C)CC(C)C BZHMBWZPUJHVEE-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 239000001282 iso-butane Substances 0.000 claims description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- CXOWYJMDMMMMJO-UHFFFAOYSA-N 2,2-dimethylpentane Chemical compound CCCC(C)(C)C CXOWYJMDMMMMJO-UHFFFAOYSA-N 0.000 claims 2
- 229920005672 polyolefin resin Polymers 0.000 claims 1
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- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 7
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- 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
- LLVWLCAZSOLOTF-UHFFFAOYSA-N 1-methyl-4-[1,4,4-tris(4-methylphenyl)buta-1,3-dienyl]benzene Chemical compound C1=CC(C)=CC=C1C(C=1C=CC(C)=CC=1)=CC=C(C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 LLVWLCAZSOLOTF-UHFFFAOYSA-N 0.000 description 1
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- ZACVGCNKGYYQHA-UHFFFAOYSA-N 2-ethylhexoxycarbonyloxy 2-ethylhexyl carbonate Chemical compound CCCCC(CC)COC(=O)OOC(=O)OCC(CC)CCCC ZACVGCNKGYYQHA-UHFFFAOYSA-N 0.000 description 1
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 description 1
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Abstract
一种聚合物组合物,可以包括聚烯烃或苯乙烯聚合物、金属丙烯酸盐和酸性中和剂。本发明还涉及一种方法,其包括:提供包括金属丙烯酸盐、酸性中和剂、以及聚烯烃或苯乙烯聚合物树脂的聚合物组合物;以及将上述聚合物组合物与发泡剂混合以形成聚合物泡沫。
Description
技术领域
本公开的实施方式一般涉及由聚合物制成的泡沫。
背景技术
聚合物可用于各种发泡应用,特别是用于需要轻量级能量管理或减震的应用。其例子包括汽车零部件、包装、衬垫、隔热和可能出现反复冲击的安全应用。
发明内容
本公开的一个实施方式包括一种聚合物组合物。该聚合物组合物包括聚烯烃或苯乙烯聚合物、金属丙烯酸盐、以及酸性中和剂。
本公开的另一个实施方式包括一种方法,该方法包括提供包括金属丙烯酸盐、酸性中和剂、以及聚烯烃或苯乙烯聚合物树脂的聚合物组合物,以及将所述聚合物组合物和发泡剂混合来形成聚合物泡沫。
附图说明
通过以下的详细说明,并结合附图,可以最好地了解本公开。
图1是描述根据实施例中的对照聚丙烯和样品1的、通过顶空GC/MS测定的在聚丙烯泡沫样品中发现的丙烯酸的量的曲线图。
图2是描述根据实施例中的样品1和样品2的、通过顶空GC/MS测定的在聚丙烯泡沫样品中发现的丙烯酸的量的曲线图。
图3是描述根据实施例中的样品1和样品3的、通过顶空GC/MS测定的在聚丙烯泡沫样品中发现的丙烯酸的量的曲线图。
图4是描述根据实施例中的样品1、样品4和样品5的、通过顶空GC/MS测定的在聚丙烯泡沫样品中发现的丙烯酸的量的曲线图。
具体实施方式
前言和定义
现在将提供详细描述。该描述包括特定的实施方式、版本和实施例,但本公开不限于这些实施方式、版本和实施例,通过包括这些信息,使本领域的普通技术人员能够将这些信息与现有的信息和技术结合而制造和使用本公开。
本文使用的各种术语如下所示。权利要求中使用的术语没有定义时,该术语应被给予最广泛的定义,该定义是相关领域的技术人员已经给予该术语的、反映在提交申请时的印刷出版物和已授权专利中的定义。而且,除非另有说明,本文描述的所有化合物是取代或未取代的,且列举的化合物包括其衍生物。
而且,各种范围和/或数值限制可在下文中明确说明。应当认识到,除非另有说明,否则端点是可互换的。此外,任何范围包括落在明确规定的范围或限定内的相近数量级的迭代范围。
聚合物
本公开中有用的聚合物包括苯乙烯聚合物和聚烯烃。
本公开中有用的苯乙烯单体包括单乙烯基芳香化合物,例如苯乙烯以及烷基化苯乙烯,其中该烷基化苯乙烯在核或侧链中被烷基化。α-甲基苯乙烯、叔丁基苯乙烯、对甲基苯乙烯、甲基丙烯酸和乙烯基甲苯是在形成本公开的聚合物中有用的单体。这些单体公开于Reimers等的美国专利号7,179,873中,其以引用的方式整体并入。苯乙烯聚合物可以是均聚物或可以可选地包括一种或多种共聚单体。本文使用的术语苯乙烯包括各种取代苯乙烯(如α-甲基苯乙烯)、环取代苯乙烯如对甲基苯乙烯、分布式苯乙烯(distributedstyrenes)如对叔丁基苯乙烯、以及未取代的苯乙烯及其组合。
单亚乙烯基芳香聚合物可以是通用目的聚苯乙烯或橡胶改性聚合物组合物,如高冲击强度聚苯乙烯,其中一定量的橡胶被分散在苯乙烯基质中。聚丁二烯或共轭1,3-二烯聚合物可以以按橡胶-苯乙烯溶液的重量计的0.1wt%到50wt%或更多、或者1%到30%的量被使用。
聚烯烃的例子包括但不限于聚乙烯、聚丙烯、聚烯烃弹性体及其组合。聚烯烃弹性体包括但不限于聚异戊二烯、聚丁二烯、氯丁二烯、丁基橡胶、苯乙烯丁二烯、丁腈橡胶、乙丙橡胶、表氯醇橡胶、聚丙烯酸酯橡胶、硅橡胶、氟硅橡胶、氟橡胶、全氟橡胶、聚醚嵌段酰胺、氯磺化聚乙烯和乙烯-乙酸乙烯酯。本公开中有用的聚烯烃的其它非限制性例子包括例如线性低密度聚乙烯、塑性体、高密度聚乙烯、低密度聚乙烯、中密度聚乙烯、聚丙烯和聚丙烯共聚物。该聚合物也可以包括上述官能化的版本,例如马来酸化的聚丙烯。
在一个或多个实施方式中,聚烯烃是基于丙烯的聚合物。本文使用的术语“丙烯基/基于丙烯的”可以与术语“丙烯聚合物”或“聚丙烯”互换使用,是指例如含有相对于聚合物总重量至少约50wt%、或至少约70wt%、或至少约75wt%、或至少约80wt%、或至少约85wt%、或至少约90wt%、或至少约95wt%的聚丙烯的聚合物。
在一些实施方式中,该聚丙烯可以是例如丙烯均聚物、丙烯无规共聚物、丙烯抗冲共聚物、间规聚丙烯、等规聚丙烯或无规聚丙烯。在其它实施方式中,基于丙烯的聚合物可以是“微-无规(mini-random)”聚丙烯。微-无规聚丙烯具有少于约1.0wt%的共聚单体。在某些实施方式中,该微-无规聚丙烯中的共聚单体是乙烯。基于丙烯的聚合物可以具有至少约100℃、或例如从约115℃到约175℃的熔点(Tm)(通过DSC测定)。基于丙烯的聚合物可以包括例如约15wt%或更少、或约12wt%或更少、或约10wt%或更少、或约6wt%或更少、或约5wt%或更少、或约4wt%或更少的二甲苯可溶物质(XS)(通过ASTM D5492-06测定)。在某些实施方式中,基于丙烯的聚合物可以具有例如从约2到约50、从约6到约30或大于等于8的分子量分布(Mw/Mn)(通过GPC测定)。这些基于丙烯的聚合物可具有从约0.01dg/分钟到约30dg/分钟、或从约10dg/分钟到约25dg/分钟、或少于25dg/分钟的熔体流动速率(MFR)(通过ASTM D-1238在190℃和2.16kg载荷的条件下测定)。
在一个或多个实施方式中,该聚合物包括基于乙烯的聚合物。本文使用的术语“基于乙烯的”可以与术语“乙烯聚合物”或“聚乙烯”互换使用,是指具有相对于聚合物总重量例如至少约50wt%、或至少约70wt%、或至少约75wt%、或至少约80wt%、或至少约85wt%、或至少约90wt%、或至少95wt%的聚乙烯的聚合物。
所述基于乙烯的聚合物的密度(通过ASTM D-792测定)可以是例如从约0.86g/cc到约0.98g/cc、或从约0.88g/cc到约0.965g/cc、或从约0.90g/cc到约0.965g/cc、或从约0.925g/cc到约0.97g/cc。
所述基于乙烯的聚合物的熔融指数(MI2)(通过ASTM D-1238在190℃和2.16kg载荷的条件下测定)可以是例如从约0.01dg/分钟到约1000dg/分钟、或从约0.01dg/分钟到约25dg/分钟、或从约0.03dg/分钟到约15dg/分钟或从约0.05dg/分钟到约10dg/分钟。
在一个或多个实施方式中,所述聚烯烃包括低密度聚乙烯。在一个或多个实施方式中,所述聚烯烃包括线性低密度聚乙烯。在一个或多个实施方式中,所述聚烯烃包括中密度聚乙烯。本文使用的术语“中密度聚乙烯”指的是具有密度为例如从约0.92g/cc到约0.94g/cc、或从约0.926g/cc到约0.94g/cc(通过ASTM D-792测定)的基于乙烯的聚合物。
在一个或多个实施方式中,所述聚烯烃包括高密度聚乙烯。本文使用的术语“高密度聚乙烯”指的是具有密度例如从约0.94g/cc到约0.97g/cc(通过ASTM D-792测定)的基于乙烯的聚合物。
在本公开的某些非限制性实施方式中,会使用一种或多种聚烯烃的混合物。
在本公开的某些实施方式中,聚烯烃或苯乙烯聚合物可以与一种或多种有机金属化合物结合来形成聚合物组合物。所述有机金属化合物可以包括例如官能化的有机金属化合物,例如具有丙烯酸盐官能团的有机金属盐,被称为“金属丙烯酸盐”。金属丙烯酸盐的非限制性例子是金属二丙烯酸盐,例如二丙烯酸锌、二甲基丙烯酸锌、二丙烯酸铜、二甲基丙烯酸铜及其组合。其它有机金属化合物包括二-乙烯基乙酸锌、二-乙基富马酸锌、二-乙烯基乙酸铜、二乙基富马酸铜、三丙烯酸铝、三甲基烯酸铝、三-乙烯基乙酸铝、三-乙基富马酸铝、四丙烯酸锆、四甲基丙烯酸锆、四-乙烯基乙酸锆、四-乙基富马酸锆、丙烯酸钠、甲基丙烯酸钠、甲基丙烯酸银及其组合。金属二丙烯酸盐的例子是9200产品(原SR732)或9201,二者都可以购自克雷威利特种化学品(Cray ValleySpecialty Chemicals)。9200可以以分子量约207g/mol的白色粉末形式获得。9201包括颗粒精料中的金属二丙烯酸盐。聚合物和有机金属化合物的聚合物组合物可以包括0.001wt%到8wt%的有机金属化合物、0.01wt%到6wt%的有机金属化合物、小于等于5wt%的有机金属化合物、或约2wt%的有机金属化合物。
在本公开的一些实施方式中,可以将添加剂与聚合物组合物组合。例如,添加剂可以是过氧二碳酸酯过氧化物。在这些实施方式中,过氧二碳酸酯过氧化物具有ROC(O)O-O(O)COR1的一般结构,其中R和R1代表烷基和/或芳基基团。过氧二碳酸酯过氧化物的非限制性例子包括但不限于双(4-叔-丁基环己基)过氧二碳酸酯、双十六烷基过氧二碳酸酯、双十四烷基过氧二碳酸酯、二异丙基过氧二碳酸酯、异丙基仲丁基过氧二碳酸酯、二仲丁基过氧二碳酸酯、双(2-乙基己基)过氧二碳酸酯及其混合物。该聚合物组合物可以包括0.001wt%到3wt%的过氧二碳酸酯过氧化物、0.01wt%到2.5wt%的过氧二碳酸酯过氧化物、或小于等于2wt%的过氧二碳酸酯过氧化物。
有机金属化合物与聚合物的混合可以通过使用中到高强度混合设备通过熔融混合来进行,该中到高强度混合设备包括单螺杆和双螺杆挤出机、混合器或辊磨机,前提是金属丙烯酸盐被充分分散。用于混合的温度可以比聚合物熔点高30℃。在特定的实施方式中,可以将聚合物组合物加热到高于200℃或在200-260℃之间。在本公开的某些实施方式中,例如当使用过氧二碳酸酯过氧化物时,有机金属化合物可以原位生成,即,可以在熔融混合过程中生成。例如,在一个实施方式中,有机金属化合物可以通过在与聚合物混合时将氧化锌与丙烯酸混合来形成。
在另一实施方式中,添加剂可以是极性聚合物,包括但不限于聚乳酸、聚己内酯、聚乙二醇或其混合物。在这些实施方式中,极性聚合物可以是聚合物组合物的0.001wt%到3wt%、聚合物组合物的0.01wt%到2.5wt%、或小于等于聚合物组合物的2wt%的量存在。在一些实施方式中,过氧二碳酸酯过氧化物和极性聚合物都可以存在于聚合物组合物中。
在又另一实施方式中,添加剂可以是非极性聚合物,例如与聚合物组合物中聚烯烃不同的那些聚烯烃。例子包括但不限于聚丙烯和聚乙烯。该非极性聚合物可以与聚合物组合物中的聚合物物理混合或一起化学生成,即,该非极性聚合物可以在一个或多个反应器中,在聚合物组合物中的聚合物的形成期间,与该聚合物组合物中的聚合物共同制造,或者,非极性聚合物可以物理混合,如通过单螺杆和双螺杆挤出机、混合器或辊磨机。
在本公开的某些实施方式中,可以在有机金属化合物不存在的情况下,将聚烯烃或苯乙烯聚合物与极性聚合物(如聚乳酸、聚己内酯、聚乙二醇或其混合物)混合来形成聚合物组合物。在这些实施方式中,极性聚合物可以以聚合物组合物的0.001wt%到3wt%、聚合物组合物的0.01wt%到2.5wt%、或小于等于聚合物组合物的2wt%的量存在。
在本公开的某些实施方式中,可以将聚烯烃或苯乙烯聚合物与酸性中和剂混合。非限制性酸性中和剂可以包括例如金属氧化物、金属碳酸盐、氢氧化物、金属硬脂酸盐、天然或合成水滑石中和剂。金属氧化物包括例如氧化锌、氧化镁、二氧化钛及其组合。金属碳酸盐包括例如碳酸钠、碳酸氢钠、碳酸钙、碳酸镁及其组合。氢氧化物包括例如氢氧化钠、氢氧化钾及其组合。金属硬脂酸盐的例子包括硬脂酸锌、硬脂酸钙及其组合。天然或合成水滑石中和剂的例子包括镁水滑石,例如 (全部可以从协和化学有限公司(Kyowa Chemical Co.)获得)、539和530(可以从J.M.胡贝尔公司(J.M.Huber Corporation)获得)、L-55RTM酸性中和剂(可以从Reheis Inc.公司获得),和锌水滑石,例如ZH4-ATM(可以从协和化学有限公司(Kyowa Chemical Co.)获得)。在某些实施方式中,可以将不同类型的酸性中和剂组合,例如金属氧化物和金属碳酸盐。
在某些实施方式中,一种或多种酸性中和剂可以与金属丙烯酸盐和聚烯烃或苯乙烯聚合物组合来形成聚合物组合物,该聚合物组合物中包括500ppm到10%的酸性中和剂、或0.1%到7.5%的酸性中和剂、或0.25%到4.0%间的酸性中和剂,全部以聚合物组合物总重量计。在其它实施方式中,可以形成“母料”或浓缩液。例如,聚烯烃或苯乙烯聚合物可以与酸性中和剂混合来形成混合物,该混合物包括按混合物重量计10%到90%、或30%到70%、或40%到60%、或约50%的酸性中和剂。这个母料可以随后与金属丙烯酸盐和聚烯烃或苯乙烯聚合物的混合物组合来得到聚合物组合物,该聚合物组合物中包括500ppm到10%的酸性中和剂、或0.1%到7.5%的酸性中和剂、或0.25%到4.0%酸性中和剂、或至少3%的酸性中和剂,全部以聚合物组合物总重量计。
已经发现,在聚合物组合物中含有酸性中和剂可以控制聚合物泡沫中酸的存在引起的气味,例如丙烯酸。在某些实施方式中,与含有金属丙烯酸盐但没有酸性中和剂的聚合物泡沫相比,酸性中和剂可以将丙烯酸的量减少约75%或更多、约95%或更多、或约100%。在其它实施方式中,与含有金属丙烯酸盐但没有酸性中和剂的聚合物泡沫相比,酸性中和剂可以将丙烯酸的量减少75%到95%。
在某些实施方式中,添加到聚合物组合物中的组分只有聚烯烃或苯乙烯聚合物、金属丙烯酸盐和酸性中和剂。在其它实施方式中,聚合物组合物可以包含添加剂,如抗氧化剂、光稳定剂、酸清除剂、润滑剂、抗静电添加剂、成核剂/澄清剂、着色剂或其组合。在一个实施方式中,添加剂存在的量为相对于聚合物组合物的重量的0.01wt%到5wt%、可选地为0.1wt%到3wt%、可选地为0.5wt%到2wt%。在一些实施方式中,可以将聚合物组合物制成颗粒。
在本公开的一些实施方式中,通过ASTM D-1238在190℃和2.16kg载荷的条件下测定的聚合物组合物的熔体流动速率可以为0.1g/10分钟到50g/10分钟、或1g/10分钟到10g/10分钟、或1.5g/10分钟到6g/10分钟。通过ASTM D-3835测定的聚合物组合物的离模膨胀可以为1到15、或3到10、或4到8。
产品的应用
聚合物组合物在聚合物发泡板材或膜中的发泡聚合物层(以下称为“聚合物泡沫”)的制造中有用。聚合物泡沫可以由聚合物组合物和发泡剂制备。在某些实施方式中,发泡之前,制成颗粒或未制成颗粒的聚合物组合物可以与添加剂(如抗氧化剂、光稳定剂、酸清除剂、润滑剂、抗静电添加剂、成核剂/澄清剂、着色剂或其组合)组合。聚合物组合物可以是本文之前描述过的类型。该发泡剂可以是与聚合物组合物的其它组分兼容的任何发泡剂,例如物理发泡剂、化学发泡剂等。物理发泡剂是通常是能够快速疏散聚合物组合物并在聚合物组合物中留下孔隙的气体。化学发泡剂是在高温下吸热分解的化学化合物。化学发泡剂的分解产生气体,该气体夹带在聚合物组合物中,因而导致在聚合物组合物中形成孔隙。本公开中适用的发泡剂的非限制性例子包括但不限于戊烷、异戊烷、二氧化碳、氮气、水蒸气、丙烷、正丁烷、异丁烷、正戊烷、2,3-二甲基丙烷、1-戊烯、环戊烯、正己烷、2-甲基戊烷、正己烷、3-甲基戊烷、2,3-二甲基丁烷、1-己烯、环己烷、正庚烷、2-甲基己烷、2,2-二甲基戊烷、2,3-二甲基戊烷和其组合。
在一个实施方式中,发泡聚合物组合物是通过将聚合物组合物与发泡剂接触、并通过例如复合或挤压使组分充分混合来制备。在一个实施方式中,该聚合物组合物通过在挤出机中被加热而增塑或熔化,并使其与发泡剂接触并充分混合。或者,可以在将混合物放入挤出机之前(例如通过主体混合)、将聚合物组合物放入挤出机期间或其组合将该聚合物组合物与发泡剂接触。
添加剂和泡沫制造方法的例子可以在贝里塑料公司(Berry PlasticsCorporation)于2012年6月18日申请的PCT/US2012/043018中找到,PCT/US2012/043018通过引用全部并入本文。
在本公开的某些实施方式中,聚合物泡沫显示开口小室含量低于80%、低于50%或低于30%。在某些实施方式中,聚合物泡沫中的小室不是开口小室是闭合的小室。在一些实施方式中,聚合物泡沫的密度低于0.50g/cc、低于0.25g/cc或低于0.20g/cc。在某些实施方式中,聚合物泡沫的密度是0.15g/cc到0.20g/cc,且开口小室的含量率在30%到40%。
实施例
在实施例中,比较了对照PP级(全部M3766可购自道达尔石化(TotalPetrochemicals)和炼油美国公司(Refining USA,Inc.))与五种聚合物组合物(表1所示的样品1到5)在加热后生成丙烯酸的含量。形成了一系列泡沫样品。样品1是从包括2wt%的二丙烯酸锌的聚丙烯组合物中挤出的泡沫(来自道达尔克雷威利(Total Cray Valley)的9200)。对于样品2到5,如上述所述形成氧化锌母料(50%氧化锌+50%聚丙烯)与碳酸钠母料(50%的碳酸钠和50%的聚丙烯),并与样品1中的聚合物组合物一起使用来形成表1中描述的泡沫样品。
表1
使用顶空气相色谱-质谱(GC-MS)法检测每个泡沫的丙烯酸的存在。GC-MS的条件示于表2。
表2
GC炉温 | 35℃(5分钟)-20℃/分钟-250℃-6℃/分钟-320℃(3分钟) |
GC入口温度 | 320℃ |
分离柱 | Ultra-ALLOY+-5 L=30m,i.d.=0.25mm,df=0.5μm |
柱流速 | 1mL/分钟He,分流比:1/50 |
样品大小 | 200uL |
检测器 | MS(m/z:35-800,2次扫描/秒) |
GC-MS法的结果示于图1-4。丙烯酸的降低通过样品2与样品3、4和5的对比进行计算。计算结果示于表3。
表3
酸性中和剂 | 酸性中和剂的量[%] | 丙烯酸的降低[%] | |
样品1 | - | - | - |
样品2 | 氧化锌 | 1% | 74.9 |
样品3 | 碳酸钠 | 1% | 94.6 |
样品4 | 氧化锌和碳酸钠 | 2% | 95.1 |
样品5 | 氧化锌和碳酸钠 | 3% | ~100 |
根据上下文,本文提及的所有“公开”在某些情况下仅指某些特定实施方式。在其它情况下,它可以指一个或多个中描述的、但不一定是全部权利要求中描述的客体。上述事项是针对本公开的实施方式、版本和实施例,通过包括这些信息,可以使本领域普通技术人员能够将本专利中的这些信息与可用的信息和技术结合而制造和使用本公开,但本公开不仅限于这些特定的实施方式,版本和实施例。在不偏离基本范围的情况下,可以设计本公开的其它和进一步的实施方式、版本和实施例,且其范围由所附权利要求决定。
Claims (20)
1.一种聚合物组合物,包括:
聚烯烃;
金属丙烯酸盐;以及
一种或多种酸性中和剂,
其中所述酸性中和剂包括碳酸钠,
其中所述聚合物组合物包括以所述聚合物组合物的重量计为500ppm到10wt%的酸性中和剂,以及
其中,与含有金属丙烯酸盐但没有酸性中和剂的聚合物组合物相比,所述酸性中和剂可以将丙烯酸的量减小75%或更多。
2.根据权利要求1所述的聚合物组合物,其中所述金属丙烯酸盐以0.01wt%到6wt%的量存在于所述聚合物组合物中。
3.根据权利要求2所述的聚合物组合物,其中所述金属丙烯酸盐以少于5wt%的量存在于所述聚合物组合物中。
4.根据权利要求2所述的聚合物组合物,其中所述金属丙烯酸盐是金属二丙烯酸盐。
5.根据权利要求2所述的聚合物组合物,其中所述金属丙烯酸盐是二丙烯酸锌、二甲基丙烯酸锌、二丙烯酸铜、二甲基丙烯酸铜、三丙烯酸铝、三甲基丙烯酸铝、四丙烯酸锆、四甲基丙烯酸锆、丙烯酸钠、甲基丙烯酸钠、甲基丙烯酸银或其组合。
6.根据权利要求1所述的聚合物组合物,其中所述酸性中和剂还包括金属氧化物、氢氧化物、金属硬脂酸盐、天然水滑石、合成水滑石或其组合。
7.根据权利要求6所述的聚合物组合物,其中所述酸性中和剂还包括氧化锌、氧化镁、二氧化钛、氢氧化钠、氢氧化钾、硬脂酸锌、硬脂酸钙、镁水滑石、锌水滑石或其组合。
8.根据权利要求7所述的聚合物组合物,其中所述酸性中和剂是氧化锌和碳酸钠的组合。
9.根据权利要求1所述的聚合物组合物,其中所述聚合物组合物包括0.25wt%到4.0wt%的酸性中和剂。
10.根据权利要求1-9中任一项所述的聚合物组合物,其中所述聚烯烃是聚丙烯或苯乙烯聚合物。
11.一种泡沫,包括权利要求1-10中任一项所述的聚合物组合物。
12.根据权利要求11所述的泡沫,其中所述泡沫中的丙烯酸的量比没有所述酸性中和剂且其他条件相同的泡沫中丙烯酸的量少95%。
13.一种方法,包括:
提供聚合物组合物,所述聚合物组合物包括金属丙烯酸盐、一种或多种酸性中和剂、以及聚烯烃树脂;以及
将所述聚合物组合物和发泡剂混合来形成聚合物泡沫,
其中所述酸性中和剂包括碳酸钠,
其中所述聚合物组合物包括以所述聚合物组合物的重量计为500ppm到10wt%的酸性中和剂,以及
其中,与含有金属丙烯酸盐但没有酸性中和剂的聚合物组合物相比,所述酸性中和剂可以将丙烯酸的量减小75%或更多。
14.根据权利要求13所述的方法,其中所述发泡剂是戊烷、异戊烷、二氧化碳、氮气、水蒸气、丙烷、正丁烷、异丁烷、正戊烷、2,3-二甲基丙烷、1-戊烯、环戊烯、正己烷、2-甲基戊烷、3-甲基戊烷、2,3-二甲基丁烷、1-己烯、环己烷、正庚烷,2-甲基己烷,2,2-二甲基戊烷、2,3-二甲基戊烷或其组合。
15.根据权利要求13所述的方法,其中所述金属丙烯酸盐是二丙烯酸锌、二甲基丙烯酸锌、二丙烯酸铜、二甲基丙烯酸铜、三丙烯酸铝、三甲基烯酸铝、四丙烯酸锆、四甲基丙烯酸锆、丙烯酸钠、甲基丙烯酸钠、甲基丙烯酸银或其组合。
16.根据权利要求13所述的方法,其中所述酸性中和剂还包括金属氧化物、氢氧化物、金属硬脂酸盐、天然水滑石、合成水滑石或其组合。
17.根据权利要求16所述的方法,其中所述酸性中和剂还包括氧化锌、氧化镁、二氧化钛、氢氧化钠、氢氧化钾、硬脂酸锌、硬脂酸钙、镁水滑石、锌水滑石或其组合。
18.根据权利要求17所述的方法,其中所述酸性中和剂是氧化锌和碳酸钠的组合。
19.根据权利要求13所述的方法,其中所述泡沫中的丙烯酸的量比没有所述酸性中和剂且其他条件相同的泡沫中丙烯酸的量少95%。
20.根据权利要求13-19中任一项所述的方法,其中所述聚烯烃是聚丙烯或苯乙烯聚合物。
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