CN106232881A - 聚合物泡沫 - Google Patents
聚合物泡沫 Download PDFInfo
- Publication number
- CN106232881A CN106232881A CN201580021990.XA CN201580021990A CN106232881A CN 106232881 A CN106232881 A CN 106232881A CN 201580021990 A CN201580021990 A CN 201580021990A CN 106232881 A CN106232881 A CN 106232881A
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- Prior art keywords
- polymer composition
- polymer
- astm
- foam
- acid
- Prior art date
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- Granted
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- 229920000642 polymer Polymers 0.000 title claims abstract description 136
- 239000006260 foam Substances 0.000 title claims abstract description 41
- 239000000203 mixture Substances 0.000 claims abstract description 106
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 19
- 230000008961 swelling Effects 0.000 claims abstract description 18
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims abstract description 13
- 229920000554 ionomer Polymers 0.000 claims abstract description 13
- 239000004088 foaming agent Substances 0.000 claims abstract description 12
- 229920006112 polar polymer Polymers 0.000 claims abstract description 12
- 229920000098 polyolefin Polymers 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 7
- 238000009826 distribution Methods 0.000 claims abstract description 6
- 238000005259 measurement Methods 0.000 claims abstract description 5
- -1 polypropylene Polymers 0.000 claims description 56
- 239000004743 Polypropylene Substances 0.000 claims description 34
- 229920001155 polypropylene Polymers 0.000 claims description 23
- 150000002978 peroxides Chemical class 0.000 claims description 14
- 239000000155 melt Substances 0.000 claims description 13
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- 150000002148 esters Chemical class 0.000 claims description 11
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical group CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 claims description 6
- 125000004386 diacrylate group Chemical group 0.000 claims description 5
- 229920006113 non-polar polymer Polymers 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
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 claims description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 4
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 4
- 239000004626 polylactic acid Substances 0.000 claims description 4
- 239000004925 Acrylic resin Substances 0.000 claims description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- DDEDHMQODQLHOG-UHFFFAOYSA-N [Zr].COC(C(=C(C)C)C)=O Chemical compound [Zr].COC(C(=C(C)C)C)=O DDEDHMQODQLHOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 3
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 claims description 2
- BZHMBWZPUJHVEE-UHFFFAOYSA-N 2,3-dimethylpentane Natural products CC(C)CC(C)C BZHMBWZPUJHVEE-UHFFFAOYSA-N 0.000 claims description 2
- NXOWKEPKGIKQAF-UHFFFAOYSA-N 2-methylprop-2-enoic acid;silver Chemical compound [Ag].CC(=C)C(O)=O NXOWKEPKGIKQAF-UHFFFAOYSA-N 0.000 claims description 2
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 claims description 2
- OZXICAOXXGATLZ-UHFFFAOYSA-N C(C)(=O)O.C(=C)[Zn]C=C Chemical compound C(C)(=O)O.C(=C)[Zn]C=C OZXICAOXXGATLZ-UHFFFAOYSA-N 0.000 claims description 2
- ZHUGDTCEPULRRK-YOTINIEPSA-N C(\C=C\C(=O)O)(=O)O.C(C)[Zn]CC Chemical compound C(\C=C\C(=O)O)(=O)O.C(C)[Zn]CC ZHUGDTCEPULRRK-YOTINIEPSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 2
- XHDYVSPJZQLWHB-IPZCTEOASA-N [Cu].C(C)\C(=C(/C(=O)O)\CC)\C(=O)O Chemical compound [Cu].C(C)\C(=C(/C(=O)O)\CC)\C(=O)O XHDYVSPJZQLWHB-IPZCTEOASA-N 0.000 claims description 2
- RDOPNMLBGTZQDB-RRABGKBLSA-N [Zr].C(C)OC(/C(=C(/C(=O)OCC)\CC)/CC)=O Chemical compound [Zr].C(C)OC(/C(=C(/C(=O)OCC)\CC)/CC)=O RDOPNMLBGTZQDB-RRABGKBLSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 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 2
- 150000001941 cyclopentenes Chemical class 0.000 claims description 2
- WCOATMADISNSBV-UHFFFAOYSA-K diacetyloxyalumanyl acetate Chemical compound [Al+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WCOATMADISNSBV-UHFFFAOYSA-K 0.000 claims description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
- 239000001282 iso-butane Substances 0.000 claims description 2
- 235000013847 iso-butane Nutrition 0.000 claims description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical group CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 2
- 229940047670 sodium acrylate Drugs 0.000 claims description 2
- PMLRVRLRXOMVHT-UHFFFAOYSA-N tetradecyl hydrogen carbonate Chemical compound CCCCCCCCCCCCCCOC(O)=O PMLRVRLRXOMVHT-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims 2
- BZJTUOGZUKFLQT-UHFFFAOYSA-N 1,3,5,7-tetramethylcyclooctane Chemical group CC1CC(C)CC(C)CC(C)C1 BZJTUOGZUKFLQT-UHFFFAOYSA-N 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- NSGQRLUGQNBHLD-UHFFFAOYSA-N butan-2-yl butan-2-yloxycarbonyloxy carbonate Chemical compound CCC(C)OC(=O)OOC(=O)OC(C)CC NSGQRLUGQNBHLD-UHFFFAOYSA-N 0.000 claims 1
- 229910001873 dinitrogen Inorganic materials 0.000 claims 1
- OQIOVJHINWLQCM-UHFFFAOYSA-J dizinc prop-2-enoate Chemical compound [Zn++].[Zn++].[O-]C(=O)C=C.[O-]C(=O)C=C.[O-]C(=O)C=C.[O-]C(=O)C=C OQIOVJHINWLQCM-UHFFFAOYSA-J 0.000 claims 1
- 150000002596 lactones Chemical class 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001294 propane Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 1
- 229910001868 water Inorganic materials 0.000 claims 1
- 229910052726 zirconium Inorganic materials 0.000 claims 1
- 239000000654 additive Substances 0.000 description 12
- 230000000996 additive effect Effects 0.000 description 11
- 150000001336 alkenes Chemical class 0.000 description 9
- 238000002156 mixing Methods 0.000 description 7
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 7
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 6
- 229920002554 vinyl polymer Polymers 0.000 description 6
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- 229920000573 polyethylene Polymers 0.000 description 5
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 5
- 238000005187 foaming Methods 0.000 description 4
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- 239000004700 high-density polyethylene Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 229920001684 low density polyethylene Polymers 0.000 description 3
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- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- CXOWYJMDMMMMJO-UHFFFAOYSA-N 2,2-dimethylpentane Chemical compound CCCC(C)(C)C CXOWYJMDMMMMJO-UHFFFAOYSA-N 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004604 Blowing Agent Substances 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
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- 125000000524 functional group Chemical group 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
- RZXDTJIXPSCHCI-UHFFFAOYSA-N hexa-1,5-diene-2,5-diol Chemical compound OC(=C)CCC(O)=C RZXDTJIXPSCHCI-UHFFFAOYSA-N 0.000 description 1
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- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
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Abstract
一种聚合物组合物可包含通过GPC测量的分子量分布大于或等于8的聚烯烃和金属丙烯酸盐。所述聚合物组合物可通过以下一个或多个性质表征:熔体流动速率为0.1‑10克/10分钟;熔体流动粘度为2,000‑6,000Pa.s;离模膨胀为2‑8;离模膨胀特性时间为0.3‑1.2秒。聚合物组合物可是泡沫形式。形成泡沫的方法可包括提供包含金属丙烯酸盐和聚烯烃树脂的聚合物组合物,并且将所述聚合物组合物与发泡剂混合。泡沫可包含含有聚烯烃和极性聚合物但不含有离聚物的聚合物组合物。所述泡沫可具有小于0.25克/立方厘米的泡沫密度。
Description
相关申请的交叉引用
本申请是2014年5月30提交的美国临时申请第62/005,613的非临时申请,并且是2014年5月2日提交的美国专利申请第14/268,826号的继续申请。
技术领域
本发明的实施方式通常涉及由聚合物制备的泡沫。
背景
聚合物可用于各种发泡应用,特别可用于需要轻量能量管理或缓冲的应用。例子包括汽车组件、包装、衬垫、绝热物以及可能发生重复撞击处的安全应用。
发明概述
本发明的一个实施方式包括聚合物组合物。所述聚合物组合物包含通过凝胶渗透色谱法(GPC)测量的分子量分布大于或等于8的聚烯烃和金属丙烯酸盐。所述聚合物组合物可通过以下一个或多个性质表征:通过ASTM D-1238测得的熔体流动速率为0.1-10克/10分钟;通过ASTM D-1238测得的熔体流动粘度为2,000-6,000Pa.s;通过ASTM D-3835测得的离模膨胀为2-8;离模膨胀特性时间为0.3-1.2秒。
本发明的另一个实施方式涉及泡沫。所述泡沫包含含有聚烯烃和极性聚合物的聚合物组合物。所述极性聚合物占所述聚合物组合物的0.001-3重量%。所述聚合物组合物不包含离聚物。所述泡沫具有小于0.25克/立方厘米的泡沫密度。
本发明的另一个实施方式包括一种方法。所述方法包括提供一种聚合物组合物,其包含通过GPC测量的分子量分布大于或等于8的聚烯烃树脂和金属丙烯酸盐。所述方法还包括将聚合物组合物和发泡剂混合以形成聚合物泡沫。所述聚合物组合物可通过以下一个或多个性质表征:通过ASTM D-1238测得的熔体流动速率为0.1-10克/10分钟;通过ASTM D-1238测得的熔体流动粘度为2,000-6,000Pa.s;通过ASTM D-3835测得的离模膨胀为2-8;离模膨胀特性时间为0.3-1.2秒。
发明详述
介绍和定义
现在给出详细说明。本发明包括具体实施方式、变化形式和实例,但公开的内容不限于这些实施方式、变化形式或实例,列举它们的目的是使本领域普通技术人员在将本专利的信息与可获得的其他信息和技术结合时能够实现和利用本发明。
本文使用的各种术语如下文所示。对于权利要求中使用但是下文中没有定义的术语,应给予在提交本申请时相关领域的人员按印刷出版物和公布的专利中的表述而赋予该术语的最宽泛的定义。此外,除非另有说明,否则,本文所述的所有化合物都可以是取代或未取代的,列出的化合物包括其衍生物。
此外,各种范围和/或数值限制可在下文中明确表示。应当认识到,除非另外指出,否则,端点是可以互换的。此外,任何范围包括落在该明确表示的范围或限值内的同样量级的迭代的范围。
聚合物
本发明中有用的聚合物包括苯乙烯类聚合物和聚烯烃。聚烯烃的例子包括但不限于:聚乙烯、聚丙烯、聚烯烃弹性体以及它们的组合。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、腈橡胶、乙烯丙烯橡胶、表氯醇橡胶、聚丙烯酸橡胶、硅橡胶、含氟硅橡胶、含氟弹性体、全氟弹性体、聚醚嵌段酰胺、氯磺化聚乙烯和乙烯-乙酸乙烯酯。其它用于本发明的聚烯烃的非限制性例子包括例如低密度聚乙烯、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。所述聚合物还可包括上述聚合物官能化的形式,例如马来酸化的聚丙烯。
苯乙烯类聚合物的例子包括苯乙烯均聚物、α-甲基苯乙烯、乙烯基甲苯、对-甲基苯乙烯、叔丁基苯乙烯、邻-氯苯乙烯、乙烯基吡啶和它们的任意组合。苯乙烯类聚合物可包含一种或多种共聚单体。这些共聚单体的非限制性例子包括:α-甲基苯乙烯;卤代苯乙烯;烷基化苯乙烯;丙烯腈;甲基丙烯酸与有1-8个碳原子的醇的酯;N-乙烯基化合物如乙烯基咔唑和马来酸酐;含两个可聚合双键的化合物,例如但不限于二乙烯基苯或二丙烯酸丁二醇酯;或者它们的组合。所述苯乙烯类聚合物可包括热塑性材料。热塑性材料的例子包括但不限于丙烯腈丁二烯苯乙烯、赛璐珞、醋酸纤维素、乙烯乙酸乙烯酯、乙烯乙烯基醇、氟塑料、离聚物、聚缩醛、聚丙烯酸酯、聚丙烯腈、聚酰胺、聚酰胺-酰亚胺、聚芳基醚酮、聚丁二烯、聚丁烯、聚对苯二甲酸丁二酯、聚氯三氟乙烯、聚对苯二甲酸乙二酯、聚对苯二甲酸环己二甲酯、聚碳酸酯、聚醚酰亚胺、聚醚砜、氯化聚乙烯(polyethylenechlorinate)、聚酰亚胺、聚乳酸、聚甲基戊烯、聚苯醚、聚苯硫醚、聚邻苯二甲酰胺、聚丙烯、聚砜、聚氯乙烯、聚偏二氯乙烯和它们的组合。所述苯乙烯类聚合物可包含包埋到聚合物基质中的弹性相。所述弹性相可包括偶联的二烯单体,例如1,3-丁二烯、2-甲基-1,3-丁二烯和2-氯-1,3-丁二烯或脂族偶联的二烯单体,例如C4至C9二烯如丁二烯单体。
在一个或多个实施方式中,所述聚烯烃是丙烯基聚合物。本文所用的术语“丙烯基”可以与术语“丙烯聚合物”或“聚丙烯”互换使用,表示一种聚合物中包含例如至少约50重量%,或者至少约70重量%,或者至少约75重量%,或者至少约80重量%,或者至少约85重量%,或者至少约90重量%,或至少95重量%的聚丙烯,所述含量是相对于聚合物的总重量的而言的。
在一些实施方式中,所述聚丙烯可以是例如丙烯均聚物、丙烯无规共聚物、丙烯抗冲击共聚物、间同立构聚丙烯、全同立构聚丙烯或无规立构聚丙烯。在其它实施方式中,所述丙烯基聚合物可以是“少量无规”聚丙烯。少量无规聚丙烯含有少于约1.0重量%的共聚单体。在某些实施方式中,在少量无规聚丙烯中的共聚单体是乙烯。所述丙烯基聚合物的熔点(Tm)(通过DSC测得)可以例如至少约为100℃,或者约为115℃-175℃。所述丙烯基聚合物可包括例如少于或等于约15重量%,或少于或等于约12重量%,或少于或等于约10重量%,或少于或等于约6重量%,或少于或等于约5重量%,或少于或等于约4重量%的可溶于二甲苯的材料(XS)(根据ASTM D5492-06测得)。在某些实施方式中,通过GPC测得,所述丙烯基聚合物可具有例如约2-50,约6-30或大于或等于8的分子量分布(Mw/Mn)。这些丙烯基聚合物的熔体流动速率(MFR)(根据ASTM D-1238,在190℃和2.16kg的负荷下测得)可例如约为0.01-20分克/分钟,或者约为0.01-10分克/分钟,或者小于10分克/分钟。
在一个或多个实施方式中,聚合物包括乙烯基聚合物。本文所用术语“乙烯基”可以与术语“乙烯聚合物”或“聚乙烯”互换使用,表示一种聚合物中包含例如至少约50重量%,或者至少约70重量%,或者至少约75重量%,或者至少约80重量%,或者至少约85重量%,或者至少约90重量%,或者至少约95重量%的聚乙烯,所述含量是相对于聚合物总重量的比例。
例如,乙烯基聚合物的密度(依据ASTM D-792测得)可以约为0.86-0.98克/立方厘米,或者约为0.88-0.965克/立方厘米,或者约为0.90-0.965克/立方厘米,或者约为0.925-0.97克/立方厘米。
乙烯基聚合物的熔体指数(MI2)(依据ASTM D-1238,在190℃和2.16kg负荷下测得)可以例如约为0.01-1000分克/分钟,或者约为0.01-25分克/分钟,或者约为0.03-15分克/分钟,或者约为0.05-10分克/分钟。
在一个或多个实施方式中,烯烃基聚合物包括低密度聚乙烯。在一个或多个实施方式中,烯烃基聚合物包括线型低密度聚乙烯。在一个或多个实施方式中,烯烃基聚合物包括中密度聚乙烯。本文所用术语“中密度聚乙烯”指的是密度是例如约为0.92-0.94克/立方厘米或约为0.926-0.94克/立方厘米的乙烯基聚合物,依据ASTM D-792测得。
在一个或多个实施方式中,烯烃基聚合物包括高密度聚乙烯。本文所用术语“高密度聚乙烯”指的是密度是例如约为0.94-0.97克/立方厘米的乙烯基聚合物,依据ASTM D-792测得。
在本发明某些非限制性实施方式中,可使用一种或多种烯烃基聚合物的混合物。
在本发明某些实施方式中,所述聚烯烃可与一种或多种离聚物组合以形成聚合物组合物。所述离聚物可包括官能化的有机金属化合物,例如具有丙烯酸根官能团的有机金属盐,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、二甲基丙烯酸铜和它们的组合。其它有机金属盐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、三甲基丙烯酸铝、三乙烯基乙酸铝、三乙基富马酸铝、四甲基丙烯酸锆、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、甲基丙烯酸银和它们的组合。金属二丙烯酸盐的例子是产品Dymalink 9200(之前称为SR732)或Dymalink 9201,两者都是购自克雷威利专业化学品公司(Cray Valley Specialty Chemicals)。Dymalink 9200以白色粉末状出售,并具有约207克/摩尔的分子量。Dymalink 9201包括粒状浓缩物形式的金属二丙烯酸盐。所述聚合物和离聚物的聚合物组合物可包含0.001-8重量%的离聚物,0.01-6重量%的离聚物,或小于或等于5重量%的离聚物。
在本发明的一些实施方式中,添加剂可与所述聚合物组合物混合。例如,所述添加剂可以是过氧二碳酸酯过氧化物。在这些实施方式中,所述过氧二碳酸酯过氧化物可具有通式ROC(O)O-O(O)COR1,其中R和R1表示烷基和/或芳基。过氧二碳酸酯过氧化物的非限制性例子包括但不限于过氧二碳酸二(4-叔丁基环己基)酯、过氧二碳酸二(十六烷基)酯、过氧二碳酸二肉豆蔻基酯、过氧二碳酸二异丙基酯、过氧二碳酸异丙基仲丁基酯、过氧二碳酸二仲丁基酯、过氧二碳酸二(2-乙基己基)酯以及它们的混合物。当存在过氧二碳酸酯过氧化物时,所述过氧二碳酸酯过氧化物可包含0.001-3重量%的过氧二碳酸酯过氧化物,0.01-2.5重量%的过氧二碳酸酯过氧化物,或小于或等于2重量%的过氧二碳酸酯过氧化物。
如果金属丙烯酸盐充分分散,可通过使用中等强度到高强度混合设备的熔融混合来进行离聚体与聚合物的混合,所述中等强度到高强度混合设备包括单螺杆和双螺杆挤出机、班伯里(Banbury)混合器、或辊研磨机。用于混合的温度可比聚合物的熔点高30℃。在具体实施方式中,可将所述聚合物/离聚体加热至高于200℃,或加热至200-260℃。在本发明的某些实施方式中,例如当使用过氧二碳酸酯过氧化物时,可原位形成离聚物,即可在熔融混合过程中形成。例如,在一个实施方式中,可通过在与聚合物混合的同时将氧化锌与丙烯酸混合来形成离聚物。
在其它实施方式中,所述添加剂可以是极性聚合物,包括但不限于聚乳酸、聚内酯、聚乙二醇或它们的混合物。在这些实施方式中,所述极性聚合物存在的量可为聚合物组合物的0.001-3重量%,聚合物组合物的0.01-2.5重量%,或小于或等于聚合物组合物的2重量%。在一些实施方式中,过氧二碳酸酯过氧化物和极性聚合物均可存在于聚合物组合物中。
在其它实施方式中,所述添加剂可以是非极性聚合物,例如不同于所述聚合物组合物的聚烯烃。例子包括但不限于聚丙烯和聚乙烯。可将非极性聚合物与聚合物组合物的聚合物物理掺混或化学混合,即可在一个或多个反应器中在聚合物组合物的聚合物形成过程中连同聚合物组合物的聚合物一起制备非极性聚合物,或者可例如通过单螺杆和双螺杆挤出机、班伯里混合器、或辊研磨机物理掺混所述非极性聚合物。
在本发明的某些实施方式中,可在不存在离聚物的情况下将烯烃基聚合物与极性聚合物混合以形成聚合物组合物,所述极性聚合物包括例如聚乳酸、聚己内酯、聚乙二醇或它们的混合物。在这些实施方式中,所述极性聚合物存在的量可为聚合物组合物的0.001-3重量%,聚合物组合物的0.01-2.5重量%,或小于或等于聚合物组合物的2重量%。
所述聚合物组合物可包含添加剂,例如抗氧化剂、光稳定剂、酸清除剂、润滑剂、抗静电添加剂、成核剂/澄清剂、着色剂或它们的组合。在一个实施方式中,添加剂存在的量相对于聚合物组合物的重量而言为0.01-5重量%,任选地为0.1-3重量%,任选地为0.5-2重量%。在一些实施方式中,所述聚合物组合物可以是粒状的。
在本发明的一些实施方式中,聚合物组合物的熔体流动速率可为0.1-10克/10分钟或1-3.5克/10分钟或1.5-3克/10分钟,根据ASTM D-1238,在190℃和2.16kg负荷下测得。在本发明的某些实施方式中,聚合物组合物的熔体流动粘度可为2,000-6,000Pa.s或2,700-5,200Pa.s,根据ASTM D-1238,在190℃和2.16kg负荷下测得。聚合物组合物的离模膨胀可为2-8,或3-5,根据ASTM D-3835测得。离模膨胀特性时间可为0.3-1.2秒,或0.4-1.1秒。在一个或多个实施方式中,所述聚合物组合物可通过以下一个或多个性质表征:熔体流动速率为0.1-10克/10分钟或1-3.5克/10分钟或1.5-3克/10分钟,根据ASTM D-1238,在190℃和2.16kg负荷下测得;熔体流动粘度可为2,000-6,000Pa.s或2,700-5,200Pa.s,根据ASTM D-1238,在190℃和2.16kg负荷下测得;离模膨胀可为2-8,或3-5,根据ASTM D-3835测得;离模膨胀特性时间可为0.3-1.2秒,或0.4-1.1秒。
产品应用
所述聚合物组合物掺混物用于制备聚合物发泡片或膜中发泡的聚合物层(下文中统称为“聚合物泡沫”)。聚合物泡沫可由聚合物组合物和发泡剂制备。在某些实施方式中,在发泡前,粒状或非粒状聚合物组合物可与添加剂混合,所述添加剂包括例如抗氧化剂、光稳定剂、酸清除剂、润滑剂、抗静电添加剂、成核剂/澄清剂、着色剂或它们的组合。聚合物组合物可以是本文前述的类型。发泡剂可是适用于聚合物组合物的其它组分的任何发泡剂,例如物理发泡剂、化学发泡剂等。物理发泡剂通常是能快速排出组合物并在组合物中留下空隙的不可燃气体。化学发泡剂是在升高的温度下吸热分解的化学化合物。化学发泡剂的分解产生了在聚合物组合物中形成夹带的气体,从而在聚合物组合物中形成空隙。适用于本发明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、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、2,3-二甲基戊烷和它们的组合。
在一个实施方式中,通过将聚合物组合物与发泡剂接触,并例如通过配混或挤出完全混合所述组分来制备发泡的聚合物组合物。在一个实施方式中,通过在挤出机中加热来塑化或熔融聚合物组合物并将其与发泡剂接触并完全混合。或者,在将混合物引入挤出机(如通过本体混合)之前,在将聚合物组合物引入挤出机期间,或者这两种情况的组合的条件下,将聚合物与发泡剂接触。
添加剂的例子和泡沫制造方法可在贝里塑料公司(Berry PlasticsCorporation)于2012年6月18日提交的PCT/US2012/043018中找到,该专利通过引用全文纳入本文。
在本发明的某些实施方式中,聚合物泡沫片具有1.0×104-5.0×104psi,1.5×104-3.5×104psi,或2.0×104-3.0×104psi的挠曲模量,依据ASTM-D-790测得。在本发明的一些实施方式中,聚合物泡沫片的挠曲强度为500-1400psi,600-1100psi,或700-1000psi,依据ASTM-D-790测得。在某些实施方式中,聚合物泡沫片具有小于80%,小于50%或小于30%的开孔率。在某些实施方式中,在聚合物泡沫中的未打开的孔是闭孔。在一些实施方式中,聚合物泡沫片的密度小于0.50克/立方厘米,小于0.25克/立方厘米或小于0.20克/立方厘米。在某些实施方式中,聚合物泡沫片具有0.15-0.20的密度,开孔率为30-40%。
实施例
实施例1-聚丙烯泡沫和相应的密度以及开孔率
将MWD为6的聚丙烯均聚物发泡。用聚丙烯聚合物制备三种聚丙烯组合物;所述聚丙烯组合物的熔体流动率、MWD、金属丙烯酸盐组成和添加剂列于表1。随后用CO2对这三种聚丙烯组合物进行发泡。测量相应的密度和开孔率百分数并列于表2。
表1
用ASTM-D-1238,在190℃和2.16kg的负荷下测量MFR。用GPC测量MWD。金属丙烯酸盐和添加剂组合物的百分数是重量百分数。
表2
实施例2
测量市售非支化的聚丙烯树脂(Total PP 3354、Total PP 3462、Total miPPM3282MZ、Total PP 3276、Total PP 3281、Total1471和Total1251)的熔体流动速率、熔体流动粘度、离模膨胀和离模膨胀特性时间。测量市售支化的聚丙烯树脂(Borealis DaployTMWB140HMS和Montell Pro-fax PF814)的熔体流动速率、熔体流动粘度、离模膨胀和离模膨胀特性时间。用聚丙烯均聚物制备六种聚丙烯组合物;所述聚丙烯组合物的熔体流动速率、熔体流动粘度、离模膨胀和离模膨胀特性时间以及组成列于表3。Perkadox24L是阿克苏诺贝尔公司(Akzo Nobel)生产的过氧二碳酸二(十六烷基)酯。TotalPP 3354、Total PP 3462、Total miPP M3282MZ、Total PP 3276、Total PP 3281、Total1471和Total1251是道达尔石油化学品公司(TotalPetrochemicals)生产的聚丙烯均聚物。SR351是巴斯夫公司(BASF)生产的2,2-二(丙-2-烯酰氧基甲基)丁基丙-2-烯酸酯(2,2-bis(prop-2-enoyloxymethyl)butyl prop-2-enoate)。
表3
用ASTM-D-1238,在190℃和2.16kg的负荷下测量熔体流动速率。用ASTM-D-1238,在190℃和2.16kg的负荷下测量熔体流动粘度。用ASTM D-3835测量聚合物组合物的离模膨胀。聚合物组合物中组分的百分数是重量百分数。
实施例3-聚丙烯泡沫的挠曲性能
测量由市售聚丙烯泡沫树脂和PP组合物2制备的泡沫的挠曲性能并列于表4。
表4
| 描述 | 市售PP泡沫树脂 | PP组合物2 |
| 挠曲模量,psi | 1.42X 104 | 2.46X 104 |
| 挠曲强度,psi | 547 | 829 |
用ASTM-D-790测量挠曲模量和挠曲强度。
实施例4
将表5中所列的实施例中的树脂和聚合物组合物用CO2作为发泡剂制成泡沫。泡沫的泡沫密度也列于表5。
表5
根据上下文,本文所有提到的“公开的内容”,在一些情况下都可以仅指某些具体的实施方式。在其他情况下,可能指在一个或多个但不必是所有权利要求中列出的主题。虽然前面的内容是就本发明的实施方式、形式和实例而言的,但列举它们的目的是使本领域的普通技术人员在将本专利的资料与可获得的其他资料和技术结合时能够实现和利用本发明,本发明不限于这些特定的实施方式、形式和实例。只要不偏离本发明的基本范围,可以设计本发明的其他和进一步的实施方式、形式和实例,本发明的范围由所附权利要求书确定。
Claims (25)
1.一种聚合物组合物,其包含:
通过GPC测量得到的分子量分布大于或等于8的聚烯烃;以及
金属丙烯酸盐;
其中所述聚合物组合物可通过以下一个或多个性质表征:
依据ASTM D-1238测得的熔体流动速率为0.1-10克/10分钟;
依据ASTM D-1238测得的熔体流动粘度为2,000-6,000Pa.s;
依据ASTM D-3835测得的离模膨胀为2-8;以及
离模膨胀特性时间为0.3-1.2秒。
2.如权利要求1所述的聚合物组合物,其特征在于,所述聚烯烃是聚丙烯。
3.如权利要求2所述的聚合物组合物,其特征在于,所述聚丙烯具有小于10分克/分钟的熔体流动速率,通过ASTM-D-1238测得。
4.如权利要求1所述的聚合物组合物,其特征在于,其还包含非极性聚合物。
5.如权利要求1所述的聚合物组合物,其特征在于,所述存在于所述聚合物组合物中的金属丙烯酸盐的量为0.01-6重量%。
6.如权利要求1所述的聚合物组合物,其特征在于,所述金属丙烯酸盐是金属二丙烯酸盐。
7.如权利要求1所述的聚合物组合物,其特征在于,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、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、三甲基丙烯酸铝、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、甲基丙烯酸银或它们的组合。
8.如权利要求1所述的聚合物组合物,其特征在于,所述聚合物组合物还包含过氧二碳酸酯过氧化物。
9.如权利要求8所述的聚合物组合物,其特征在于,所述过氧二碳酸酯过氧化物是过氧二碳酸二(4-叔丁基环己基)酯、过氧二碳酸二(十六烷基)酯、过氧二碳酸二肉豆蔻基酯、过氧二碳酸二异丙基酯、过氧二碳酸异丙基仲丁基酯、过氧二碳酸二仲丁基酯、过氧二碳酸二(2-乙基己基)酯或它们的混合物。
10.如权利要求8所述的聚合物组合物,其特征在于,存在于所述聚合物组合物中的所述过氧二碳酸酯过氧化物的量为0.01-2.5重量%。
11.如权利要求1所述的聚合物组合物,其特征在于,所述聚合物组合物还包含极性聚合物。
12.如权利要求11所述的聚合物组合物,其特征在于,所述极性聚合物是聚乳酸、聚己内酯、聚乙二醇或它们的混合物。
13.如权利要求11所述的聚合物组合物,其特征在于,存在于所述聚合物组合物中的所述极性聚合物的量为0.01-2.5重量%。
14.如权利要求1所述的聚合物组合物,其特征在于,所述聚合物组合物具有0.1-10克/10分钟的熔体流动速率,通过ASTM-D-1238测得。
15.如权利要求1所述的聚合物组合物,其特征在于,所述聚合物组合物的熔体流动粘度为2,000-6,000Pa.s,通过ASTM D-1238测得。
16.如权利要求1所述的聚合物组合物,其特征在于,所述聚合物组合物具有2-8的离模膨胀,通过ASTM D-3835测得。
17.如权利要求1所述的聚合物组合物,其特征在于,所述聚合物组合物具有0.3-1.2秒的离模膨胀特性时间。
18.一种泡沫,其包含如权利要求1所述的聚合物组合物。
19.如权利要求18所述的泡沫,其特征在于,通过ASTM-D-790测得,所述泡沫具有1.5×104-3.5×104psi的挠曲模量。
20.如权利要求18所述的泡沫,其特征在于,通过ASTM-D-790测得,所述聚烯烃泡沫具有600-1100psi的挠曲强度。
21.如权利要求18所述的泡沫,其特征在于,所述泡沫的密度小于0.50克/立方厘米。
22.如权利要求21所述的泡沫,其特征在于,所述泡沫的密度小于0.20克/立方厘米。
23.一种方法,其包括:
提供一种聚合物组合物,其包含金属丙烯酸盐、通过GPC测量得到的分子量分布大于或等于8的聚烯烃树脂;以及
将所述聚合物组合物和发泡剂混合以形成聚合物泡沫;
其中所述聚合物组合物可通过以下一个或多个性质表征:
依据ASTM D-1238测得的熔体流动速率为0.1-10克/10分钟;
依据ASTM D-1238测得的熔体流动粘度为2,000-6,000Pa.s;
依据ASTM D-3835测得的离模膨胀为2-8;以及
离模膨胀特性时间为0.3-1.2秒。
24.如权利要求23所述的方法,其特征在于,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、2,3-二甲基戊烷或它们的组合。
25.一种泡沫,其包含:
含有聚烯烃和极性聚合物的聚合物组合物,其中所述极性聚合物占所述聚合物组合物的0.001-3重量%,其中所述聚合物组合物不包含离聚物,并且其中所述泡沫具有小于0.25克/立方厘米的泡沫密度。
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| US201462005613P | 2014-05-30 | 2014-05-30 | |
| US62/005,613 | 2014-05-30 | ||
| US14/601,399 US9505906B1 (en) | 2014-05-02 | 2015-01-21 | Polymer foams |
| US14/601,399 | 2015-01-21 | ||
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| JP2020117719A (ja) | 2020-08-06 |
| BR112016025707B1 (pt) | 2021-11-09 |
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| CA2948140A1 (en) | 2015-11-05 |
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| MX2016014440A (es) | 2017-02-23 |
| CN106232881B (zh) | 2020-12-08 |
| KR102335730B1 (ko) | 2021-12-08 |
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