CN101589096A - 包含共聚醚酯弹性体的组合物 - Google Patents
包含共聚醚酯弹性体的组合物 Download PDFInfo
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- CN101589096A CN101589096A CNA2007800487561A CN200780048756A CN101589096A CN 101589096 A CN101589096 A CN 101589096A CN A2007800487561 A CNA2007800487561 A CN A2007800487561A CN 200780048756 A CN200780048756 A CN 200780048756A CN 101589096 A CN101589096 A CN 101589096A
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- ethylene
- thermoplastic elastomer
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- 239000000203 mixture Substances 0.000 title claims abstract description 50
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- 239000005038 ethylene vinyl acetate Substances 0.000 claims abstract description 20
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- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 8
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- MWRWFPQBGSZWNV-UHFFFAOYSA-N Dinitrosopentamethylenetetramine Chemical compound C1N2CN(N=O)CN1CN(N=O)C2 MWRWFPQBGSZWNV-UHFFFAOYSA-N 0.000 claims 1
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- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
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- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
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- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
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- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- CGPRUXZTHGTMKW-UHFFFAOYSA-N ethene;ethyl prop-2-enoate Chemical compound C=C.CCOC(=O)C=C CGPRUXZTHGTMKW-UHFFFAOYSA-N 0.000 description 1
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- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
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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
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0869—Acids or derivatives thereof
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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
- C08J2201/00—Foams characterised by the foaming process
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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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- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
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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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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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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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- C—CHEMISTRY; METALLURGY
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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
本发明公开了组合物,所述组合物包含下列物质、基本上由下列物质组成、或由下列物质组成:乙烯聚合物、热塑性弹性体、交联剂、以及任选地发泡剂,其中所述乙烯聚合物包括乙烯乙酸乙烯酯共聚物、聚乙烯、乙烯酸性共聚物、酸性共聚物的离聚物、乙烯烷基(甲基)丙烯酸酯共聚物、或它们中的两种或更多种的组合;所述热塑性弹性体可包括共聚醚酯、共聚醚酰胺、弹性体聚烯烃、苯乙烯二烯嵌段共聚物、热塑性聚氨酯、或它们的两种或更多种的组合;并且所述交联剂包括一种或多种有机过氧化物、辐射、或它们的组合。本发明还公开了由所述组合物制成的产品,例如用于鞋类应用的泡沫。
Description
本发明涉及一种包含共聚醚酯弹性体的组合物及其产品。
发明背景
十多年前研发出了注模发泡方法(IP)来用于克服劳动密集型压模的缺点。由于缺乏超过在持续几天的生产周期中从一批到一批复制完全相同尺寸所需的高质量化合物,这种方法尚未被广泛接受。在此类方法中,可能难以获得密度与特性性能(例如,压缩形变)之间的平衡。
多年来,乙烯乙酸乙烯酯(EVA)的共聚物已成为鞋类泡沫应用的优选材料。与化学发泡剂一起膨胀的交联EVA泡沫提供了鞋底应用所需的弹性、耐久性和其它物理特性之间的良好平衡。这些性质可在低密度(对于较轻的重量而言是可取的)和较低的成本下获得。然而,EVA在获得柔软性如表面柔软性、低压缩形变和高弹性方面具有局限性。随着发泡方法向一步式注模方法发展,使得获得具有平衡性能,即具有高弹性、低压缩形变和高剖层撕裂强度的EVA泡沫更加困难。
注模的EVA泡沫牺牲了常规压模(CM)EVA泡沫的一些特性。与CM-EVA泡沫相比,IP-EVA泡沫通常弹性较小,其表面趋于较硬,并且其压缩形变较高。似乎IP方法比CM方法得到具有平衡性能的EVA泡沫更困难,因为泡沫由IP方法一步制成,而它是由两步法制成。
发明概述
组合物,所述组合物包含下列物质或由下列物质制备:乙烯聚合物、热塑性弹性体、以及任选地交联剂、发泡剂或它们的组合,其中
所述乙烯聚合物包括乙烯乙酸乙烯酯共聚物、聚乙烯、乙烯酸性共聚物、酸性共聚物的离聚物、乙烯烷基(甲基)丙烯酸酯共聚物、或它们中的两种或更多种的组合;
所述热塑性弹性体可包括共聚醚酯、共聚醚酰胺、弹性体聚烯烃、苯乙烯二烯嵌段共聚物、热塑性聚氨酯、或它们中的两种或更多种的组合;并且
所述交联剂可包括一种或多种有机过氧化物、辐射、或它们的组合。
发明详述
乙烯/乙酸乙烯酯(EVA)共聚物是本领域的技术人员熟知的聚合物。掺入EVA中的乙酸乙烯酯共聚单体的相对量可为所述总共聚物的0.1%重量最多至高达40%重量或更高。例如,EVA可具有按重量计2至50%、10至40%、或按重量计6至30%的乙酸乙烯酯含量。EVA可用本领域熟知的方法进行改性,包括用例如不饱和的羧酸或其衍生物如马来酸酐或马来酸改性。EVA可具有0.1至60g/10分钟、或0.3至30g/10分钟的熔融流动速率(ASTM D-1238)。
聚乙烯(PE)可包括PE均聚物和共聚物,例如高密度聚乙烯、低密度聚乙烯、线性低密度聚乙烯、非常低密度聚乙烯、超低密度聚乙烯、茂金属催化的聚乙烯、乙烯丙烯共聚物、乙烯/丙烯/二烯单体(EPDM)三元共聚物、衍生自乙烯和CO的乙烯共聚物、这些聚合物中的一种与马来酸(或马来酸酐或马来酸单酯)的接枝组合物、或它们中的两种或更多种的组合。商业PE包括乙烯和1-丁烯的共聚物,其包含12.6重量%的1-丁烯,具有3.5的熔融指数,以商品名得自ExxonMobil,以及乙烯和1-辛烯的共聚物,其含有12重量%的辛烯,具有3.5的熔融指数,以商品名得自DuPont Performance Elastomers。
包含乙烯的聚合物也可包括一种或多种由乙烯与至少一种极性单体共聚所得到的乙烯共聚物,如乙烯/乙酸乙烯酯共聚物、乙烯/丙烯酸酯共聚物、乙烯/异丁烯酸酯共聚物、乙烯/乙酸乙烯酯/CO共聚物、乙烯/丙烯酸酯/CO共聚物、和/或任何这些共聚物的混合物。
乙烯酸性共聚物可包含重复单元,所述重复单元衍生自乙烯和不饱和羧酸或其衍生物,例如(甲基)丙烯酸、马来酸、富马酸、衣康酸、马来酸酐、富马酸酐、包括C1至C4醇(如,甲醇、乙醇、正丙醇、异丙醇和正-丁醇)的酯的马来酸(马来酸的半酯)、或它们中的一种或多种的组合。酸性共聚物的实例可描述成E/X/Y共聚物,其中E为乙烯,X可为上述的至少一个不饱和羧酸,Y为软化共聚单体,如丙烯酸烷基酯、烷基甲基丙烯酸酯或它们的组合。X的含量可以E/X/Y共聚物的约3至约30,4至25,或5至20重量%的量存在,而Y以E/X/Y共聚物的0至约35,0.1至35,或5至30重量%的量存在。
酸性共聚物的实例包括乙烯/(甲基)丙烯酸共聚物、乙烯/(甲基)丙烯酸/正丁基(甲基)丙烯酸酯共聚物、乙烯/(甲基)丙烯酸/异丁基(甲基)丙烯酸酯共聚物、乙烯/(甲基)丙烯酸/叔丁基(甲基)丙烯酸酯共聚物、乙烯/(甲基)丙烯酸/甲基(甲基)丙烯酸酯共聚物、乙烯/(甲基)丙烯酸/乙基(甲基)丙烯酸酯共聚物、乙烯/马来酸和乙烯/马来酸单酯共聚物、乙烯/马来酸单酯/正丁基(甲基)丙烯酸酯共聚物、乙烯/马来酸单酯/甲基(甲基)丙烯酸酯共聚物、乙烯/马来酸单酯/乙基(甲基)丙烯酸酯共聚物、或它们中的两种或更多种的组合,例如可从E.I.Du Pont du Pont de Nemours and Company,Wilmington,Delaware(杜邦)商购获得。
离聚物可由酸性共聚物用能够中和共聚物中酸性部分的碱性化合物处理来制备。酸性基团标称可用碱土金属离子、碱金属离子或过渡金属离子中和至约0.1至约90%,约15至约80%,或约40至约75%的任何水平。当与有机酸混合时,离聚物也可制备成具有比上述70%更高的标称中和水平。
用于制造酸性共聚物和离聚物的方法是本领域的技术人员所熟知的。为了简洁起见,本文省略了对它的描述。
乙烯烷基(甲基)丙烯酸酯共聚物包含重复单元,其衍生自乙烯和丙烯酸烷基酯、烷基甲基丙烯酸酯、或它们的组合,其中所述烷基部分包含1至8个碳原子。烷基的实例包括甲基、乙基、丙基、丁基、或它们中的两种或更多种的组合。烷基(甲基)丙烯酸酯共聚单体可掺入乙烯/(甲基)丙烯酸烷基酯共聚物中,其含量为总共聚物的0.1重量%至最多45重量%或甚至更高。烷基可包含1至约8个碳。例如,烷基(甲基)丙烯酸酯共聚单体可能以5至45、10至35、或10至28的重量%的量存在于所述共聚物中。乙烯烷基(甲基)丙烯酸酯共聚物可利用本领域熟知的方法使用高压釜或管状反应器来制造。例如,参见美国专利5,028,674、2,897,183、3,404,134、5,028,674、6,500,888和6,518,365。由于所述方法是熟知的,为了简洁起见,本文省略了对它的描述。乙烯烷基(甲基)丙烯酸酯共聚物的实例包括乙烯/丙烯酸甲酯、乙烯/丙烯酸乙酯、乙烯/丙烯酸丁酯、或它们中的两种或更多种的组合,如可从DuPont商购获得的可使用两种或更多种不同乙烯烷基(甲基)丙烯酸酯共聚物的混合物。
热塑性弹性体可包括共聚醚酯、共聚醚酰胺、弹性体聚烯烃、苯乙烯二烯嵌段共聚物、热塑性聚氨酯、或它们中的两种或更多种的组合,其是本领域熟知的聚合物。
共聚醚酯包括一种或多种共聚物,所述共聚物具有大量通过酯联接而头尾相连的循环长链酯单元和短链酯单元循环。长链酯单元包含-OGO-C(O)RC(O)-重复单元,而短链酯单元包含-OGO-C(O)RC(O)-重复单元。G是具有约400至约6000,或优选约400至约3000的数均分子量的聚(烯化氧)二醇上除去末端羟基后余下的二价基团。R是从二羧酸中去除羧基后余下的二价基团,其具有小于约300的分子量;D是从二醇中除去羟基后余下的二价基团,其具有小于约250的分子量。
所述共聚醚酯优选包含约15至约99重量%的短链酯单元和约1至约85重量%的长链酯单元,或约25至约90重量%的短链酯单元和约10至约75重量%的长链酯单元。
共聚醚酰胺也是本领域熟知的,如US 4331786中所公开。它们包含一条刚性聚酰胺片段和柔韧聚醚片段的直正链,如化学式HO-[C(O)PAC(O)OPEO]n-H所示,其中PA为直链饱和脂族聚酰胺序列,其由具有包含4至14个碳原子的烃链的内酰胺或氨基酸或由脂族C6-C9二胺在有具有4至20个碳原子的链限制脂族羧基二元酸存在的情况下形成。聚酰胺具有300至15,000的平均分子量。PE为聚氧化烯序列,其由一种或多种直链或支链的脂族聚氧化烯二元醇或由所述聚氧化烯二元醇衍生的具有小于或等于6000分子量的共聚醚形成。下标n表示使得所述聚醚酰胺共聚物具有约0.8至约2.05的特性粘度的重复单元数。由于制造聚醚酰胺的方法是熟知的(例如,参见US6815480),因此为了简洁起见,本文省略了制造聚醚酰胺的方法。
弹性体聚烯烃包含乙烯的重复单元和高级伯烯烃如丙烯、己烯、辛烯或它们中的两种或更多种的组合、以及任选1,4-己二烯、亚乙基降冰片烯、降冰片二烯、或它们中的两种或更多种的组合。弹性体聚烯烃可通过用酸性酸酐如马来酸酐接枝来官能化。由于弹性体聚烯烃是熟知的,因此为了简洁起见,本文省略了它的制备方法。
嵌段苯乙烯二烯共聚物包含重复单元,所述重复单元衍生自聚苯乙烯单元和聚二烯单元。聚二烯单元衍生自聚丁二烯、聚异戊二烯单元或这两者的共聚物。所述共聚物可氢化以生产饱和的橡胶主链片段,通常称作SBS、SIS或SEBS热塑性弹性体。它们也可通过用酸性酸酐如马来酸酐接枝来官能化。由于苯乙烯二烯共聚物是熟知的,因此为了简洁起见,本文省略了它的制备方法。
热塑性聚氨酯为由硬嵌段和软弹性体嵌段组成的直链或稍微支链化的聚合物。它们可通过使软羟基封端的弹性体聚醚或聚酯与二异氰酸酯如亚甲基二异氰酸酯或甲苯二异氰酸酯反应来生产。这些聚合物可为以二醇、二胺、二元酸或氨基醇延伸的链状。异氰酸酯与醇的反应产物为尿烷,这些嵌段相对较硬且是高熔融的。这些硬的高熔点嵌段是形成聚氨酯热塑性特性的原因。
常用的交联剂可包括一种或多种有机过氧化物,包括二烷基过氧化物、过氧化酯、过氧化二碳酸酯、过氧缩酮、二酰基过氧化物,或它们中的两种或更多种的组合。过氧化物的实例包括过氧化二异丙苯、二(3,3,5-三甲基己酰基)过氧化物、叔丁基过氧化新戊酸酯、叔丁基过氧新癸酸酯、二(仲-丁基)过氧化二碳酸酯、叔戊基过氧新癸酸酯、1,1-二-叔丁基过氧-3,3,5-三甲基环己烷、叔丁基-异丙苯基过氧化物、2,5-二甲基-2,5-二(叔丁基过氧)己烷、1,3-双(叔丁基过氧异丙基)苯,或它们中的两种或更多种的组合。这些和其它过氧化物可以购自Arkema或以得自Akzo Nobel。
发泡剂,也称为鼓泡剂,包括化学发泡剂或物理发泡剂。化学发泡剂包括偶氮二酰胺、二亚硝基-1,5-亚戊基-四胺、对-甲苯甲磺酰肼、p,p′-氧基-双(苯磺酰肼)、或它们中的两种或更多种的组合,并且任选一种或多种有机或无机发泡剂。物理发泡剂为卤烷、挥发性有机化合物、或非易燃的惰性气氛气体、或它们中的两种或更多种的组合。为了定制膨胀-分解温度和发泡方法,发泡剂也可为发泡剂或发泡剂与活化剂的混合物。
所述组合物可包含按(所述组合物的)重量计约0.1至约10%或约1至5%的活化剂(用于发泡剂)以降低发泡剂的分解温度/特征。活化剂可为一种或多种金属氧化物、金属盐、或有机金属络合物、或它们中的两种或更多种的组合。实例包括ZnO、硬脂酸锌、MgO、或它们中的两种或更多种的组合。
其它添加剂,其在所述组合物中的含量按所述组合物的重量计为约0.1至约20%或约2至约12%,可包括颜料(TiO2和其它相容的彩色颜料)、粘附促进剂(以提高膨胀的泡沫与其它材料的粘附力)、填料(如,碳酸钙、硫酸钡和/或氧化硅)、成核剂(纯态或浓缩态,如CaCO3、ZnO、SiO2,或它们中的两种或更多种的组合)、橡胶(以改善橡胶状的弹性,如天然橡胶、SBR、聚丁二烯、和/或乙烯丙烯三元共聚物)、稳定剂(如抗氢化剂、紫外线吸收剂、和/或阻燃剂)、和加工助剂(如台湾Octene Co.制造的Octene R-130)。抗氧化剂(改善感官刺激性如减小气味或味道)可包括苯酚抗氧化剂,如得自Ciba Geigy Inc.(Tarrytown,New York)的IRGANOX。
所述组合物可包含约50至约98重量%或约70至约90重量%的乙烯聚合物。如果存在EVA和乙烯共聚物,EVA的含量可为乙烯聚合物总重量的约60至约90%。热塑性弹性体在所述组合物中含量可为所述组合物的约0.1至约20重量%或约1至约10重量%。其它组分包括约0.01%或0.1至约2%的交联剂,约0.5至约10%的发泡剂,约0.1至10%的活化剂和约0.0001至约10%的一种或多种其它添加剂,所有组分均按所述组合物的重量计。
所述组合物可由多种方法生产,如压模、注模、或挤出与模制混合。例如,一种方法可包括在加热的情况下混合聚合物和交联剂以形成熔融物,同时加入发泡剂和其它添加剂,得到均匀的化合物。可用本领域已知的任何方法来混合和共混所述成分,如利用班伯里密炼机、增强搅拌器、双辊开炼机和挤出机。可调节时间、温度、剪切速率以确保最佳分散,而无过早交联或发泡。混合的高温可能因过氧化物和发泡剂的分解而导致过早交联和发泡。需要适当的温度以确保聚合物的良好混合以及其它成分的混合或分散。当在约60℃至约150℃、或约80℃至约150℃、或约70℃至约120℃或约80℃至约130℃的温度下共混时,聚合物可形成均匀的共混物。安全操作的温度上限可取决于所用过氧化物和发泡剂的开始分解温度。聚合物在与其它成分配混之前可熔融共混。
任选地,聚合物可在最高约250℃的温度下在挤出机中熔融共混以保证潜在的良好混合。然后所得混合物可与上文公开的成分配混。
混合后,可进行成型。通常使用压片辊或压光辊来制成用于发泡的适当尺寸的片。可使用挤出机来将所述组合物成型为小丸。
发泡可在压缩模具中一定温度和时间下进行,以完成过氧化物和发泡剂的分解。可控制压力、模制温度和加热时间。发泡可在注模装置中使用小丸状的发泡组合物进行。所得泡沫可使用本领域已知的任何方法如通过热成形和压模进一步成型为成品的尺寸。
由所述组合物生产制得的泡沫可基本上为闭孔的,并且可用于多种制品,包括鞋类应用(如,鞋底夹层或鞋内底)、汽车座椅和内饰、家具扶手、轨下垫板、和其它工业泡沫材料应用。
可用以下的实施例对本发明进行举例说明,但这些实施例不应理解为是对本发明范围的限制。
实施例
比较实施例2。EMA(乙烯丙烯酸甲酯共聚物,DuPontAC1224)600g,EVA(DuPont2288)1400g,DCP 20.3g,发泡剂(AZ-H)64.4g,TiO2 180g,和ZnO 80g。
实施例1。EMA(DuPontAC 1224;275g),EVA(DuPont2288;1600g),共聚醚-酯嵌段共聚物(DuPont4056;125g),TiO2(180g),ZnO(80g),DCP(20.3g),和AZ-H(66.67g)。
实施例2。EMA(DuPontAC 1224;300g),EVA(DuPont2288;1500g),共聚醚-酯嵌段共聚物(DuPont4056;100g),TiO2(180g),ZnO(80g),DCP(19.4g),和AZ-H(62.64g)。
下表显示用共聚醚-酯嵌段共聚物改性的EVA泡沫具有较低的压缩形变。发泡在165℃下进行10分钟。
压缩测试进行如下。使用约10mm厚度的模制正方形板。从板上切下两个或三个2.54cm直径的圆环。标出测量(用于确定厚度)的确切位置。
将圆环加载到金属压缩板设备上,并将圆环压缩至原始厚度的50%。将圆环与置于其侧面的压缩板一起放入预热至50℃的烘箱中6小时。在时限结束时,从烘箱中取出设备,并立即取出样本。在室温(22+/-2℃)下冷却30分钟后,记录下最后样本的厚度,然后如下计算每个样本的压缩形变百分比(%):永久变形率=((初始厚度-最终厚度)/(初始厚度-50%压缩厚度))×100。
剖层撕裂强度测试按照ASTM D3574进行。
测试结果示于下表中。
泡沫密度(g/cc) | 硬度 | 压缩形变(%) | 剖层撕裂强度(N/mm) | |
比较1 | 0.22 | 53.5 | 63 | 1.64 |
比较1 | 0.22 | 62.3 | 54 | 2.01 |
实施例1 | 0.21 | 60 | 45 | 2.2 |
实施例2 | 0.22 | 59 | 42 | 2.52 |
Claims (11)
1.一种组合物,所述组合物包含下列物质或由下列物质制备:乙烯聚合物、热塑性弹性体、以及任选地交联剂、发泡剂、或它们的组合,其中
所述乙烯聚合物包括乙烯乙酸乙烯酯共聚物、聚乙烯、乙烯酸性共聚物、所述酸性共聚物的离聚物、乙烯烷基(甲基)丙烯酸酯共聚物、或它们中的两种或更多种的组合;
所述热塑性弹性体包括共聚醚酯、共聚醚酰胺、弹性体聚烯烃、苯乙烯二烯嵌段共聚物、热塑性聚氨酯、或它们中的两种或更多种的组合;
所述交联剂包括一种或多种有机过氧化物、辐射、或它们的组合;
并且
所述发泡剂包括偶氮二酰胺、二亚硝基-1,5-亚戊基-四胺、对-甲苯甲磺酰肼、p,p′-氧基-双(苯磺酰肼)、或它们中的两种或更多种的组合。
2.权利要求1的组合物,其中所述乙烯共聚物包括乙烯乙酸乙烯酯共聚物、乙烯烷基(甲基)丙烯酸酯共聚物、或它们的组合。
3.权利要求1或2的组合物,其中所述组合物包含下列物质或由下列物质制备:乙烯聚合物、热塑性弹性体、和交联剂;所述交联剂包括过氧化二异丙苯、二(3,3,5-三甲基己酰基)过氧化物、叔丁基过氧化新戊酸酯、叔丁基过氧化新癸酸酯、二(仲-丁基)过氧化二碳酸酯、叔戊基过氧化新癸酸酯、1,1-二-叔丁基过氧-3,3,5-三甲基环己烷、叔丁基异丙苯基过氧化物、2,5-二甲基-2,5-二(叔丁基过氧)己烷、1,3-双(叔丁基过氧异丙基)苯、或它们中的两种或更多种的组合;并且所述乙烯共聚物包括所述乙烯乙酸乙烯酯共聚物和所述乙烯丙烯酸甲酯共聚物。
4.权利要求1、2或3的组合物,其中所述热塑性弹性体包括共聚醚酯。
5.权利要求3或4的组合物,其中所述交联剂包括过氧化二异丙苯。
6.权利要求1、2、3、4或5的组合物,其中所述组合物包含下列物质或由下列物质制备:乙烯聚合物、热塑性弹性体、交联剂、以及发泡剂。
7.权利要求6的组合物,其中所述发泡剂包括偶氮二酰胺、对甲苯磺酰肼、以及任选地一种或多种有机或无机发泡剂的共混物。
8.权利要求6或7的组合物,其中所述发泡剂还包含活化剂,所述活化剂包括一种或多种金属氧化物、金属盐、有机金属络合物、或它们中的两种或更多种的组合。
9.权利要求8的组合物,其中所述活化剂包括ZnO、硬脂酸锌、MgO、或它们中的两种或更多种的组合。
10.一种制品,所述制品包含组合物或由组合物制备,其中
所述制品包括鞋类的鞋底夹层或鞋内底、汽车座椅和内饰、家具扶手、轨下垫板、或它们中的两种或更多种的组合;并且
所述组合物如权利要求1至9中任一项所定义。
11.权利要求10的制品,其中所述制品包括鞋类的鞋底夹层或鞋内底。
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