CN117683341A - 聚醚嵌段酰胺-聚(甲基)丙烯酸系物泡沫 - Google Patents
聚醚嵌段酰胺-聚(甲基)丙烯酸系物泡沫 Download PDFInfo
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Abstract
本发明涉及聚醚嵌段酰胺‑聚(甲基)丙烯酸系物泡沫,尤其涉及包含至少一种聚醚嵌段酰胺(PEBA)和至少一种聚(甲基)丙烯酸系物的混合物,所述聚(甲基)丙烯酸系物选自聚(甲基)丙烯酰亚胺、聚(甲基)丙烯酸烷基酯和它们的混合物。PEBA与聚(甲基)丙烯酸系物的质量比例为95:5至60:40。所述聚(甲基)丙烯酸烷基酯含有基于聚(甲基)丙烯酸烷基酯的总重量计80重量%至99重量%的甲基丙烯酸甲酯(MMA)单元和1重量%至20重量%的丙烯酸C1‑C10‑烷基酯单元。所述混合物可被加工成经发泡的模制品。所述模制品可用于鞋底、鞋钉材料、绝缘材料、隔绝材料、减震组件、轻质组件或用于夹芯结构中。
Description
本分案申请是基于申请号为201980068004.4、申请日为2019年10月16日、发明名称为“聚醚嵌段酰胺-聚(甲基)丙烯酸系物泡沫”的中国专利申请的分案申请。
技术领域
本发明涉及由聚醚嵌段酰胺和聚(甲基)丙烯酸系物形成的混合物,涉及这些混合物的经发泡的模制品,涉及制备这些模制品的方法,并涉及它们的用途。
背景技术
聚合物泡沫在工业上被大规模使用。聚醚嵌段酰胺(PEBA)作为泡沫材料中的成分是已知的。然而,如果在没有添加物的情况下将PEBA发泡,则不会获得稳定的泡沫:经发泡的模制品会坍塌。
聚醚嵌段酰胺(PEBA)是通过使(低)聚酰胺,特别是经酸调节的聚酰胺,与醇封端的或氨基封端的聚醚进行缩聚获得的嵌段共聚物。经酸调节的聚酰胺具有过量的羧酸端基。本领域技术人员认为所述聚酰胺嵌段是硬嵌段和所述聚酯嵌段是软嵌段。
WO 2017/167197公开了含有20%至99%的热塑性塑料和1-80%的聚(甲基)丙烯酰亚胺泡沫粒子的聚合物混合物。DE 102014216992描述了由聚酰胺(例如PEBA)制备膨胀的聚合物粒料的方法,所述聚酰胺可例如用于制备运动服用减震元件。
发明内容
就此方面,本发明要解决的技术问题是,找到合适的基于PEBA的混合物,其具有稳定的和轻质的泡沫。密度应当足够低以至于可实现在组件中重量的显著降低。另外,要获得表现出特定柔韧性以及反弹或回弹特性的软质泡沫。获得的经发泡的模制品要具有高的机械负荷能力和高的泡沫稳定性。所述泡沫要具有均匀的泡孔分布和均一的泡孔尺寸。
该技术问题通过包含PEBA和至少一种聚(甲基)丙烯酸系物(Poly(meth)acrylat)的混合物得以解决,其中PEBA与聚(甲基)丙烯酸系物的质量比例为95:5至60:40。所述聚(甲基)丙烯酸系物选自聚(甲基)丙烯酰亚胺、聚(甲基)丙烯酸烷基酯和它们的混合物。
PEBA可例如得自聚酰胺与聚醚的反应,所述聚醚例如聚醚二醇或聚醚二胺。PEBA的制备例如描述在EP-A-1518901(US 2005/014842)中。
合适的聚酰胺(PA)例如是PA6、PA11、PA12、PA613、PA1012、PA612、PA109、PA1013、PA1010和PA69。它们可由内酰胺或ω-氨基羧酸制备或由二胺与二羧酸的反应制备。
合适的聚醚二醇例如是1,4-丁二醇、1,3-丁二醇、1,3-丙二醇、乙二醇或聚四氢呋喃。还可以使用混合的聚醚二醇嵌段,其具有无规或嵌段状的分布。它们通常具有约230至4000g/mol的数均摩尔质量。
合适的聚醚二胺可通过将相应的聚醚二醇通过还原性胺化或偶联至丙烯腈并随后进行氢化而进行转化获得(例如EP-A-0434244;EP-A-0296852)。它们通常具有约230至4000g/mol的数均摩尔质量。衍生自丙二醇的可商购聚醚二胺可作为JEFFAMIN D类型商购自Huntsman公司。
在所述PEBA中的聚醚的比例优选为10重量%至50重量%,更优选20重量%至40重量%,在每种情况下基于PEBA的总重量计。
合适的PEBA是本领域技术人员已知的,并且可例如以产品名称商购自Evonik Resource Efficiency GmbH,Marl公司。
合适的PEBA可例如具有30至70,优选35至65的肖氏D硬度。肖氏D硬度是根据ISO868在23℃±2℃下测量的。
在根据本发明优选的一个实施方案中,所述PEBA是经氨基调节的。其因此具有相对于羧基端基而言摩尔过量的氨基端基。在本专利申请中,术语“经氨基调节的”和“氨基封端的”是同义使用的。所述经氨基调节的PEBA优选具有每kg PEBA 20至60mmol过量的氨基端基,优选30至50mmol/kg。
在另一个优选的实施方案中,根据本发明使用的PEBA是经羧基调节的。这因此具有相对于氨基端基而言摩尔过量的羧基端基。在本专利申请中,术语“经羧基调节的”和“羧基封端的”是同义使用的。所述经羧基调节的PEBA优选具有每kg PEBA 20至60mmol过量的羧基端基,优选30至50mmol/kg。
除了PEBA外,根据本发明的混合物还包含聚(甲基)丙烯酸系物,其包括聚(甲基)丙烯酰亚胺、聚(甲基)丙烯酸烷基酯或它们的混合物。此处术语“(甲基)丙烯酸系物”意思指甲基丙烯酸系物和丙烯酸系物二者以及它们的混合物,所述甲基丙烯酸系物例如甲基丙烯酸甲酯、甲基丙烯酸乙酯等,所述丙烯酸系物例如丙烯酸甲酯、丙烯酸乙酯等。另外,术语“(甲基)丙烯酸系物”广义上包括丙烯酸的衍生物和甲基丙烯酸的衍生物,例如酰亚胺和酰胺。
根据本发明优选使用的聚(甲基)丙烯酰亚胺优选具有可由式(IV)表示的重复单元
其中R1和R2是相同或不同的,并且是氢或甲基基团,和R3是氢、具有1至20个碳原子的烷基或具有2至20个,优选4至15个,更优选5至12个,最优选6至10个碳原子的芳基。优选其中三个基团R1、R2和R3各自是甲基基团的化合物(IV)。
优选的聚(甲基)丙烯酰亚胺包含以下基团:a)式(IV)的N-烷基丙烯酰亚胺,b)(甲基)丙烯酸,c)(甲基)丙烯酸酐,d)(甲基)丙烯酸酯,其中基团a)-d)各自存在的量为基于聚(甲基)丙烯酰亚胺的总重量计的至少1重量%。优选地,所述聚(甲基)丙烯酰亚胺含有10-95重量%,优选20-70重量%和更优选25-40重量%的式(IV)的N-烷基丙烯酰亚胺。基团b)和c)的总和优选在5-20重量%范围内,更优选在8-17重量%范围内,和尤其优选在10-15重量%范围内。所述聚(甲基)丙烯酰亚胺可含有e)其它单体。其比例通常为<10重量%。所述比例基于聚(甲基)丙烯酰亚胺的总重量。它们可借助于NMR或IR光谱法测定。
所述聚(甲基)丙烯酰亚胺的典型分子量Mw在50000-150000g/mol范围内,和优选在90000-110000g/mol范围内(通过GPC相对于PMMA标准品测定的)。
合适的优选聚(甲基)丙烯酰亚胺是聚(N-甲基)甲基丙烯酰亚胺(PMMI)。在本发明的一个特别优选的实施方案中,聚(甲基)丙烯酰亚胺包含25-35重量%的其中所述三个基团R1、R2和R3各自是甲基基团的式(IV)的N-烷基丙烯酰亚胺,1-5重量%的甲基丙烯酸基团,5-20重量%的甲基丙烯酸酐基团和40-65重量%的甲基丙烯酸甲酯基团。
聚(甲基)丙烯酰亚胺的制备本身是已知的,并且例如公开在以下文献中:英国专利1 078 425、英国专利1 045 229、德国专利1 817 156(=美国专利3 627 711)或德国专利27 26 259(=美国专利4 139 685)或DE-A-10 2008 001 695(=US2011/015317A1)。
此外,这些聚合物可含有例如由以下物质形成的其它单体单元:丙烯酸或甲基丙烯酸的酯,尤其是与具有1-4个碳原子的低级醇形成的酯,苯乙烯,马来酸或其酸酐,衣康酸或其酸酐,乙烯基吡咯烷酮,氯乙烯或偏二氯乙烯。不能环化或仅能很困难地环化的共聚单体的比例基于所述单体的重量计不应超过30重量%,优选20重量%,和更优选10重量%。
所述聚(甲基)丙烯酸烷基酯可单独使用或者以多种不同聚(甲基)丙烯酸烷基酯的混合物的形式使用。此外,所述聚(甲基)丙烯酸烷基酯也可以是共聚物的形式。
在本发明的情况下,特别优选的是以下物质的均聚物和共聚物:(甲基)丙烯酸C1-C18-烷基酯,合适的是(甲基)丙烯酸C1-C10-烷基酯,尤其是(甲基)丙烯酸C1-C4-烷基酯聚合物,其可任选还含有与其不同的单体单元。
根据本发明使用的聚(甲基)丙烯酸烷基酯含有基于聚(甲基)丙烯酸烷基酯的总重量计80重量%至99重量%的甲基丙烯酸甲酯(MMA)单元和1重量%至20重量%,优选1重量%至5重量%的丙烯酸C1-C10-烷基酯单元。特别优选的丙烯酸C1-C10-烷基酯单元是丙烯酸甲酯、丙烯酸乙酯和丙烯酸丁酯单元,以及它们的混合物。
所述产物和它们的制备是已知的(Hans R.Kricheldorf,Handbook of PolymerSynthesis,A部分,Verlag Marcel Dekker Inc.New York-Basel-Hongkong,第223页和后续页;H.G.Elias,Makromoleküle,Hüthig und Wepf Verlag Basel-Heidelberg-NewYork;US2 146 209,US 4 246 374)。
已经发现非常特别有用的是使用以下共聚物,该共聚物含有基于共聚物的总重量计70重量%至99重量%,尤其是70重量%至90重量%的甲基丙烯酸C1-C10烷基酯。优选的甲基丙烯酸C1-C10-烷基酯包括甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丙酯、甲基丙烯酸异丙酯、甲基丙烯酸正丁酯、甲基丙烯酸异丁酯、甲基丙烯酸叔丁酯、甲基丙烯酸戊酯、甲基丙烯酸己酯、甲基丙烯酸庚酯、甲基丙烯酸辛酯、甲基丙烯酸异辛酯和甲基丙烯酸乙基己酯、甲基丙烯酸壬酯、甲基丙烯酸癸酯,和甲基丙烯酸环烷基酯,例如甲基丙烯酸环己酯、甲基丙烯酸异冰片酯或甲基丙烯酸乙基环己酯。
非常特别优选的共聚物包括基于共聚物的总重量计70重量%至99重量%的甲基丙烯酸甲酯(MMA)单元和1重量%至20重量%,优选1重量%至5重量%的丙烯酸C1-C10-烷基酯单元,尤其是丙烯酸甲酯、丙烯酸乙酯和/或丙烯酸丁酯单元。进一步优选的共聚单体是苯乙烯。
聚甲基丙烯酸甲酯(PMMA)是特别优选的聚(甲基)丙烯酸烷基酯。
已经发现可用的聚甲基丙烯酸甲酯含有1重量%至18重量%的丙烯酸甲酯和82重量%至99重量%的甲基丙烯酸甲酯,更优选2重量%至10重量%的丙烯酸甲酯和90重量%至98重量%的甲基丙烯酸甲酯,和最优选3重量%至6重量%的丙烯酸甲酯和94重量至97重量%的甲基丙烯酸甲酯,在每种情况下基于丙烯酸甲酯和甲基丙烯酸甲酯的总重量计。分子量Mw优选为70000g/mol至240000g/mol,更优选80000g/mol至220000g/mol和最优选90000g/mol至200000g/mol。此外,这些聚合物可含有例如由以下物质形成的其它单体单元:丙烯酸或甲基丙烯酸的酯,尤其是与具有1-4个碳原子的低级醇形成的酯,马来酸或其酸酐,衣康酸或其酸酐,乙烯基吡咯烷酮,氯乙烯或偏二氯乙烯。不能环化或仅能很困难地环化的共聚单体的比例基于所述单体的重量计不应超过30重量%,优选20重量%,和更优选10质量%。可环化单体要被理解为意指α-、β-不饱和的官能化体系,其在乙烯基类基团上带有在文献中被描述为EWG(=吸电子基团)的官能团。具有EWG官能团的体系的实例可包括具有腈基团或羧酸及其酯的分子。这些不包括不能环化的但能乙烯基聚合的单体;这些的实例可包括α-甲基苯乙烯、苯乙烯、乙酸乙烯酯、乙烯基吡咯烷酮、乙烯、丙烯、氯乙烯、偏二氯乙烯、异戊二烯、丁二烯、乙烯基醚或异丁烯。
同样可以使用抗冲改性的聚合物。优选的抗冲改性的聚合物具有核/壳结构或核/壳/壳结构。特别优选的是接枝有一个或两个壳的基于聚丁二烯的核。所述壳可选自甲基丙烯酸甲酯、丙烯酸甲酯、(甲基)丙烯酸乙酯、苯乙烯、丙烯腈和它们的混合物。这些聚合物例如描述在WO 2002/062890A1中。
所述聚(甲基)丙烯酸烷基酯可通过本身已知的聚合方法制备,其中特别优选的是自由基聚合方法,尤其是本体、溶液、悬浮和乳液聚合方法。特别适合于这些目的的引发剂尤其包括偶氮化合物,例如2,2'-偶氮双(异丁腈)或2,2'-偶氮双(2,4-二甲基戊腈),氧化还原体系,例如以下物质的组合:叔胺与过氧化物或焦亚硫酸钠和过硫酸钾、过硫酸钠或过硫酸铵或优选过氧化物(为此参见例如H.Rauch-Puntigam,Th.“Acryl-undMethacrylverbindungen”,Springer,Heidelberg,1967,或Kirk-Othmer,Encyclopedia ofChemical Technology,第1卷,第386页及后续页,J.Wiley,New York,1978)。特别合适的过氧化物聚合引发剂的实例是过氧化二月桂酰、过辛酸叔丁酯、过异壬酸叔丁酯、过氧二碳酸二环己酯、过氧化二苯甲酰和2,2-双(叔丁基过氧)丁烷。为了在聚合过程中以及在不同的聚合温度下保持自由基流恒定,还可以优选使用具有不同半衰期的不同聚合引发剂(例如过氧化二月桂酰和2,2-双(叔丁基过氧)丁烷)的混合物进行所述聚合。使用的聚合引发剂的量通常为基于所述单体混合物计的0.01重量%至2重量%。
所述聚合可连续或分批进行。在聚合后,经由常规的离析和分离步骤,例如过滤、凝聚、喷雾干燥或排气挤出获得所述聚合物。在板式聚合产物(本体)的情况下,通常不进行上述意义上的进一步的后处理。
可通过在分子量调节剂的存在下聚合所述单体或单体混合物来调节所述聚合产物或共聚产物的链长,所述分子量调节剂例如特别是已知用于该目的的硫醇,例如正丁基硫醇、正十二烷基硫醇、2-巯基乙醇或硫代乙醇酸2-乙基己酯、季戊四醇四硫代乙醇酸酯,其中所述分子量调节剂的用量通常为基于所述单体或单体混合物计的0.05重量%至5重量%,优选0.1重量%至2重量%,和更优选基于所述单体或单体混合物计的0.2重量%至1重量%(参见例如H.Rauch-Puntigam,Th.“Acryl-undMethacrylverbindungen”,Springer,Heidelberg,1967;Houben-Weyl,Methoden derorganischen Chemie,第XIV/1卷,第66页,Georg Thieme,Heidelberg,1961或Kirk-Othmer,Encyclopedia of Chemical Technology,第1卷,第296页及后续页,J.Wiley,NewYork,1978)。特别优选的是使用正十二烷基硫醇作为分子量调节剂。
根据本发明的混合物优选含有至少一种式(I)化合物作为相转移试剂
其中
R彼此独立地是具有1至11个,优选1至4个碳原子的烷基,优选甲基,
R1彼此独立地是R或聚酯残基,
R2彼此独立地是R或具有12至36个碳原子,优选14至30个碳原子,优选16至26个碳原子的烃残基,
n、m和p彼此独立地是0至58,
条件是
N=n+m+p+2,为10至100,优选15至60,
和
当所有R2是R时,所有R1不是R,和当所有R1是R时,至少一个R2不是R
和/或
当m和p是零时,所有基团R1不是R,和当所有基团R1是R时,m或p,优选m,不是0。
这些是聚酯硅氧烷或烷基硅氧烷。
在所述式中使用的指数应被认为是统计平均值(数均值)。
优选存在那些其中p=0的式(I)化合物。
如果所述R1基团是聚酯残基,则这些优选是由3至30个,更优选8至25个,和尤其优选15至22个酯单元构成的。作为起始醇,所述聚酯残基可包括那些衍生自不饱和伯醇的醇残基(参见制备方法)。所述聚酯残基优选具有式(II)的结构:
-Rq-(Rr)zH (II)
其中
Rq=-(CH2)x-O-,
Rr=C(O)-(CH2)y-O-
x=2至10,优选3至7,尤其是6,和
y=2至10,优选3至8,和更优选4或5。
Z=3至30,优选8至25,和尤其优选15至22。
符号“q”和“r”仅用于区分所述基团与其它“R”基团,并且不代表与任何数值相关的指数。
所述聚酯残基可由相同或不同的起始分子形成。所述聚酯残基优选是由相同的起始分子形成的。优选的聚酯残基是优选通过内酯的开环(聚)酯化获得的那些。特别优选的聚酯残基是通过己内酯或戊内酯的(聚)酯化获得的那些,所述己内酯或戊内酯尤其是ε-己内酯、3,5,5-三甲基己内酯或δ-戊内酯,并且尤其优选ε-己内酯。优选的其中R1是聚酯残基的式(I)化合物是其中所述聚酯残基是由3至30个,优选8至25个和尤其优选15至22个ε-己内酯单元形成的那些。所述R1基团优选是相同的聚酯残基。
当所述R1基团全都是R时,其中R优选是甲基,则R2优选是具有12至36个碳原子,优选14至30个碳原子,更优选16至26个碳原子的烃残基,N优选不小于30,优选40至50。在提及的情况下,p优选是0,和m优选是30至48。
当所述R1基团中的一个或多个是聚酯残基时,则N优选是10至45,优选18至35,和尤其优选20至30。
合适的式(I)化合物例如是可得自Evonik的H-Si6440P和TEGOPREN 6846。
式(I)化合物可通过已知的方法通过以下过程获得:相应的氢硅氧烷与不饱和烃或不饱和醇的反应和随后的(聚)酯化;或者不饱和聚酯与氢硅氧烷的直接反应。所述反应可如在EP 1 640 418中描述的那样,通过氢化硅烷化或者通过脱氢的氢化硅烷化进行。包含聚酯残基的聚硅氧烷的制备可在例如EP 0 208 734中找到。
所述至少一种式(I)化合物优选存在的比例为基于所述均匀混合物(包括所述至少一种式(I)化合物和所述至少一种式(II)化合物)的总重量计的0.1至10重量%。聚酯硅氧烷的比例优选在0.5至8重量%范围内,尤其优选在0.9至5重量%范围内。烷基硅氧烷的比例优选在0.4至9重量%范围内,尤其优选在0.9至6重量%范围内。
根据本发明的混合物中优选进一步包括至少一种式(III)化合物作为相转移试剂
R3O(SO)a(EO)b(PO)c(BO)dR4 (III)
其中
R3=具有2至30个碳原子的直链的或支化的或脂环族的基团,
R4=氢,酰基、烷基或羧酸残基,它们在每种情况下具有1至8个碳原子,
SO=苯基环氧乙烷,
EO=环氧乙烷,
PO=环氧丙烷,
BO=环氧丁烷,和
a=1至5,
b=3至50,
c=0至10,
d=0至10,
其中a、c或d不是0,b>=a+c+d。
这些是苯基环氧乙烷聚醚。
通过各种不同的环氧烷单体及其在整个聚合物中的比例可以特定控制疏水/亲水平衡。特别优选的是嵌段状排布,其具有末端的相对较疏水的基团,例如环氧丙烷,或者特别是环氧丁烷。
如公知的那样,脂肪醇聚二醇醚是在工业规模上,特别是在根据现有技术的酸性或碱性催化剂的存在下,优选在压力和在升高的温度下,通过环氧乙烷和/或环氧丙烷的加成反应制备的物质。取决于使用的催化剂的性质,产物可能具有或多或少窄化的同系物分布。
然而,因此形成的羟基封端的聚环氧烷也可用羧酸和/或其酸酐进行酯化以实现OH基团的封端。所述酯化反应可用具有2至18个碳原子的脂族或芳族羧酸进行。所述酯化在此可以自身已知的方式在酸性催化下进行。还可以选择醚化替代酯化作为端基封端反应。为此目的,使所述化合物根据现有技术与芳族或脂族的直链的或支化的烷基卤化物在Williamschen醚合成条件下反应。与氯甲烷的反应是特别优选的。所述羟基端基可以此方式被部分或全部醚化。
所述至少一种式(III)化合物优选存在的比例为基于所述均匀混合物(包括所述至少一种式(I)化合物和所述至少一种式(III)化合物)的总重量计的0.1至20重量%。苯基环氧乙烷聚醚的比例优选在0.9至15重量%范围内,更优选在2至12重量%范围内。
根据本发明的混合物可含有至少一种式(I)化合物和至少一种式(III)化合物二者。
根据本发明的混合物优选含有添加剂,例如着色剂,例如颜料或染料,特别是有机染料。另外,根据本发明的混合物可含有光稳定剂、UV稳定剂、UV吸收剂、IR吸收剂、抗微生物活性剂、阻燃剂、热稳定剂、抗氧化剂、交联性聚合物、有机或无机类型的纤维增强性添加剂、抗冲改性剂和它们的混合物。根据本发明的混合物中优选含有不超过10重量%,更优选不超过5重量%和尤其不超过2重量%的助剂和填料,在每种情况下基于混合物和添加剂的总重量计。
本发明进一步提供可由根据本发明的混合物获得的经发泡的模制品。所述模制品优选具有不超过350kg/m3,优选不超过130kg/m3的密度。
制备本发明的经发泡的模制品的方法1包括以下步骤:
a.熔融根据本发明的混合物,
b.将所熔融的混合物挤出以获得粒料,
c.注射模塑所述粒料以获得模制品或挤出片材,和
d.将所述模制品或所述挤出片材引入到高压釜中并用物理发泡剂处理以获得经发泡的模制品。
所述方法1可例如如下进行:将由PEBA和聚(甲基)丙烯酸系物形成的粒料作为干燥的预混物或者单独地经由重量或体积计量天平计量加入到预热到适当温度的配混机中(例如双螺杆配混机,其得自Coperion或Berstorff公司,或单螺杆配混机,其得自Buss公司,或其它常用型号)。在相应的螺杆中,在适当的转速下,将所述粒料加热以形成熔体。在所述配混机中,将所述混合物在合适的螺杆转速下加热以形成熔体。将所述熔体挤压穿过模头板以形成熔体线料。可使这些熔体线料在水浴中冷却下来,例如达到室温。将已冷却和硬化的线料在线料粒化机中切成粒料。或者,它们可借助于水下造粒(可得自例如Econ,BKG,Gala公司)被切成粒料并冷却下来。使所形成的粒料在风干干燥机中在例如50至95℃下干燥数小时以得到例如0.001%至0.1%的降低的水含量。将经干燥的粒料例如在多区段螺杆注塑机上在150至300℃的料筒温度下加工成片材。然后将注塑模具冷却。可从得到的注塑片材锯下立方体形状的测试样品。然后可用CO2将所述测试样品在标准高压釜中在100至400巴的压力下和80至180℃,优选145至180℃,更优选150至170℃的温度下用CO2饱和化数小时的时间。
已经发现,令人惊奇地,包含经氨基调节的PEBA的混合物可在比包含经羧基调节的PEBA的混合物稍微更低的温度下发泡。这导致较低的能量消耗,并允许加工相对热敏感的组件。因此优选用CO2将包含经氨基调节的PEBA的混合物在高压釜中在100至400巴的压力下和80至180℃,优选130至180℃,更优选140至170℃的温度下用CO2饱和化。
相反,在具有经羧基调节的PEBA的混合物情况下,有利的是,用CO2在高压釜中在100至400巴的压力下和在100至180℃,优选145至180℃,更优选150至190℃的温度下用CO2进行所述饱和化。
在泡沫挤出过程中,饱和化温度还可以更高,因为必须将所述聚合物粒料熔融。
然后利用自发卸压进行所述发泡。
根据本发明的另一种方法2包括如下步骤:
a.熔融根据本发明的混合物,和
b.将所熔融的混合物用物理发泡剂进行处理,并将所熔融的混合物借助于孔板或合适的模头挤出以获得经发泡的模制品。
所述方法2可例如如下进行:将由PEBA和聚(甲基)丙烯酸系物形成的粒料作为干燥的预混物或者单独地经由重量或体积计量天平计量加入到预热到适当温度的配混机中(例如双螺杆配混机,其得自Coperion或Berstorff公司,或单螺杆配混机,其得自Buss公司,或其它常用型号)。在相应的螺杆中,在适当的转速下,将所述粒料加热以形成熔体。将发泡剂,例如CO2,添加到所述熔体中并在其中分散。在第二螺杆中,将所述熔体冷却下来,尤其是因为所述发泡剂具有粘度降低作用。此处选择的模头板例如是宽缝模头,其在厚度和宽度方面对应于希望的几何形状。在该模头处,所述熔体将在离开时自发膨胀(发泡)并冷却下来以形成经发泡的挤出物。根据希望的几何形状,可将所述经发泡的挤出物要么借助于压延机作为片材拉出,要么借助于其它连续拉拔设备(由型材挤出已知的那些)拉出,并冷却。在有效冷却过程后,将经发泡的挤出物切割到相应希望的长度。
所述方法2是连续方法,并且因此优于方法1。
所述经发泡的组件可被用作鞋底、鞋钉材料、绝缘材料(Isoliermaterial)、隔绝材料减震组件、轻质组件或用于夹芯结构中。
具体地,本发明提供以下技术方案:
项目1.混合物,其包含:
a.至少一种聚醚嵌段酰胺(PEBA),
b.至少一种聚(甲基)丙烯酸系物,其选自聚(甲基)丙烯酰亚胺、聚(甲基)丙烯酸烷基酯和它们的混合物,
其中PEBA与聚(甲基)丙烯酸系物的质量比例为95:5至60:40,和其中所述聚(甲基)丙烯酸烷基酯含有基于聚(甲基)丙烯酸烷基酯的总重量计80重量%至99重量%的甲基丙烯酸甲酯(MMA)单元和1重量%至20重量%的丙烯酸C1-C10-烷基酯单元。
项目2.根据项目1的混合物,其特征在于所述PEBA是经氨基调节的PEBA。
项目3.根据项目1的混合物,其特征在于所述PEBA是经羧基调节的PEBA。
项目4.根据前述项目中任一项的混合物,其特征在于所述PEBA含有20至60mmol/kg的氨基端基,优选30至50mmol/kg的氨基端基。
项目5.根据前述项目中任一项的混合物,其特征在于在所述PEBA中聚醚的含量为基于PEBA的总重量计的10重量%至50重量%。
项目6.根据前述项目中任一项的混合物,其特征在于所述聚(甲基)丙烯酰亚胺包含以下基团:
a.式(IV)的N-烷基丙烯酰亚胺
其中R1和R2是相同或不同的,并且是氢或甲基基团,和R3是氢、具有1至20个碳原子的烷基或具有2至20个碳原子的芳基,
b.(甲基)丙烯酸,
c.(甲基)丙烯酸酐,和
d.(甲基)丙烯酸酯,
其中基团a.至d.各自的存在量为基于聚(甲基)丙烯酰亚胺的总重量计的至少1重量%。
项目7.根据项目6的混合物,其特征在于所述聚(甲基)丙烯酰亚胺含有10-95重量%,优选20-70重量%和更优选25-40重量%的式(IV)的单元。
项目8.根据前述项目中任一项的混合物,其特征在于所述聚(甲基)丙烯酰亚胺的分子量Mw在50000至150000g/mol范围内,所述分子量是通过GPC相对于PMMA标准品测定的。
项目9.根据前述项目中任一项的混合物,其特征在于聚(甲基)丙烯酸烷基酯含有作为共聚单体的苯乙烯。
项目10.根据前述项目中任一项的混合物,其特征在于所述聚(甲基)丙烯酸烷基酯是抗冲改性的聚合物。
项目11.根据前述项目中任一项的混合物,其特征在于所述混合物含有至少一种选自以下的组分:着色剂,特别是颜料和染料,更优选有机染料,光稳定剂,UV稳定剂,UV吸收剂,IR吸收剂,抗微生物活性剂,阻燃剂,热稳定剂,抗氧化剂,交联性聚合物,有机或无机类型的纤维增强性添加剂,抗冲改性剂和它们的混合物。
项目12.可由根据项目1至11中任一项的混合物获得的经发泡的模制品。
项目13.制备经发泡的模制品的方法,该方法包括以下步骤:
a.将根据项目1至11中任一项的混合物熔融,
b.将所熔融的混合物挤出以获得粒料,
c.注射模塑所述粒料以获得模制品或挤出片材,和
d.将所述模制品或所述挤出片材引入到高压釜中并用物理发泡剂处理以获得经发泡的模制品。
项目14.制备经发泡的模制品的方法,该方法包括以下步骤:
a.将根据项目1至11中任一项的混合物熔融,和
b.将所熔融的混合物用物理发泡剂进行处理,并将所熔融的混合物借助于孔板或模头挤出以获得经发泡的模制品。
项目15.根据项目11的经发泡的模制品用作鞋底、鞋钉材料、绝缘材料、隔绝材料、减震组件、轻质组件或用于夹芯结构中的用途。
附图说明
图1至9显示得自实施例1至9的显微照片。
具体实施方式
实施例
由粒料制备含有PEBA和聚(甲基)丙烯酸系物的干燥的预混物。将这些混合物借助于重力计量天平计量加入到预热到240℃的具有20kg/h的生产能力的Coperion ZSK25WLE双螺杆配混机中。所使用的螺杆构型是标准螺杆,例如是用于制备聚酰胺配混物的标准螺杆。在所述双螺杆配混机中,在250rpm的螺杆转速下加热所述混合物以得到熔体。将所述熔体挤压穿过各自具有4mm直径的3-孔洞模头板以得到熔体线料。使这些熔体线料在室温下的水浴中冷却下来。将已冷却和硬化的线料在标准线料粒化机中切成粒料。将所得粒料在风干干燥机中在80℃下干燥12小时至水含量<0.02%。将经干燥的粒料在标准注塑机(Engel Victory 650/200)上用标准3-区段螺杆在240℃的料筒温度下加工以获得片材。将注塑模具冷却到40℃。从所得注塑片材上锯下具有可选地边缘长度为30×10×5mm或边缘长度为40×30×10mm的立方体形状的测试样品。用CO2将所述测试样品在标准高压釜中在4.5小时(小测试样品)或95小时(大测试样品)的时间内在300巴的压力和140℃的温度下用CO2饱和化。在自发卸压情况下进行所述发泡。
使用以下物质:
PEBA 1:含有30重量%聚醚嵌段的氨基封端的PEBA(E58-S4)
PEBA 2:含有20重量%聚醚嵌段的羧基封端的PEBA(E62-S3)
(甲基)丙烯酸系物1:聚甲基甲基丙烯酰亚胺,如在EP 1 755 890B1中描述的,其具有100000g/mol的分子量(通过GPC相对于PMMA标准品测定的),由以下单元组成:30重量%的式IV单元,其中R1、R2和R3各自是甲基基团,57重量%的甲基丙烯酸甲酯(MMA)单元,10重量%的甲基丙烯酸酐(MSA)单元和3重量%的甲基丙烯酸(MAS)单元(通过IR光谱法测定的)。
(甲基)丙烯酸系物2:抗冲改性的聚(甲基)丙烯酸系物,其具有200000g/mol的分子量(通过GPC相对于PMMA标准品测定的),由以下单元组成:55重量%的甲基丙烯酸甲酯(MMA)单元,20重量%的苯乙烯单元,2重量%的丙烯酸乙酯(EA)单元和23重量%的橡胶。所述橡胶是聚丁二烯,其接枝有由MMA单元和苯乙烯单元构成的壳,并且具有的用于抗冲击性的有效直径(对应于平均附聚物直径)为300nm(其是通过透射电子显微镜测定的)。
(甲基)丙烯酸系物3:抗冲改性的聚(甲基)丙烯酸系物,如(甲基)丙烯酸系物2那样,此处具有140000g/mol的分子量(通过GPC相对于PMMA标准品测定的)。
PA12:羧基封端的聚酰胺-12(L1901)/>
表1:使用的组合物#1至#9
*非根据本发明的
之后,将已发泡的组合物在扫描电子显微镜下目测检测,并确定或计算以下性能:
d泡孔:以μm为单位的泡孔的平均直径
t泡孔:以μm为单位的泡孔壁的平均厚度
N泡孔:每cm3的泡孔的数量
ρ:以kg/cm3为单位的经发泡材料的密度
Δρ:与未发泡材料相比密度的变化
泡沫品质:通过在不同分辨率下的显微照片目测评价所述泡沫。在图1至9中再现了得自实施例1至9的显微照片。
1:非均匀泡孔分布,不均一的泡孔
2:均匀泡孔分布,均一的泡孔尺寸
表2:组合物#1至#9的物理测量数据
T,℃ | d泡孔 | t泡孔 | N泡孔 | ρ | Δρ | 泡沫品质 | |
#1* | 140 | 6 | 0.5 | 48·109 | 460 | 55% | 1 |
#2 | 140 | 25 | 0.9 | 0.11·109 | 110 | 89% | 2 |
#3 | 140 | 24 | 0.9 | 0.14·109 | 110 | 90% | 2 |
#4 | 140 | 23 | 1.2 | 0.14·109 | 260 | 76% | 2 |
#5 | 155 | 22 | 1 | 0.14·109 | 150 | 86% | 2 |
#6* | 140 | *** | *** | *** | 900 | 15% | 1 |
#7 | 140 | 20 | 0.7 | 0.24·109 | 110 | 90% | 2 |
#8 | 140 | 23 | <0.5 | 0.12·109 | 90 | 91% | 2 |
#9* | 140 | ** | ** | ** | ** | ** | 1 |
*非根据本发明的
**泡沫坍塌
***未测定,因为密度过高
与现有技术组合物相比,本发明组合物#2至5和#7和#8的泡沫,显示出21至25μm的高的泡孔直径d泡孔和降低的每立方厘米的泡孔数量N泡孔。密度在90至260kg/cm3范围内,并且与起始材料相比降低了76%至91%。此外,根据本发明的组合物的泡沫显示出均匀的泡孔分布,其具有近似相等尺寸的泡孔(参见图2至5、7和8)。
在现有技术材料的情况下,记录到15%至55%的密度的显著更低的降低率(#1、#6);泡孔的平均直径同样低于本发明组合物的值(#1)。混合物#6显示出高的密度以至于泡孔的直径和数量不能被测定。混合物#9的泡沫坍塌。泡沫结构具有非均匀泡孔分布以及不同尺寸的泡孔(参见图1、6和9)。
非本发明的组合物#1(PEBA含量为99重量%)、#6(聚酰胺12代替PEBA)和#9(PEBA,没有丙烯酸系物)经证实是不合适的泡沫材料。由具有与混合物#1相比更高聚(甲基)丙烯酸系物含量的氨基封端的和羧基封端的PEBA组成的本发明的混合物#2至#4和#5和#7显示出均匀的、规则的泡孔。
Claims (13)
1.混合物,其包含:
a.至少一种经羧基调节的聚醚嵌段酰胺(PEBA),
b.至少一种聚(甲基)丙烯酸系物,其选自聚(甲基)丙烯酰亚胺、聚(甲基)丙烯酸烷基酯和它们的混合物,
其中PEBA与聚(甲基)丙烯酸系物的质量比例为95:5至60:40,和其中所述聚(甲基)丙烯酸烷基酯含有基于聚(甲基)丙烯酸烷基酯的总重量计80重量%至99重量%的甲基丙烯酸甲酯(MMA)单元和1重量%至20重量%的丙烯酸C1-C10-烷基酯单元。
2.根据权利要求1的混合物,其特征在于所述PEBA含有20至60mmol/kg的氨基端基,优选30至50mmol/kg的氨基端基。
3.根据权利要求1或2的混合物,其特征在于在所述PEBA中聚醚的含量为基于PEBA的总重量计的10重量%至50重量%。
4.根据权利要求1-3中任一项的混合物,其特征在于所述聚(甲基)丙烯酰亚胺包含以下基团:
a.式(IV)的N-烷基丙烯酰亚胺
其中R1和R2是相同或不同的,并且是氢或甲基基团,和R3是氢、具有1至20个碳原子的烷基或具有2至20个碳原子的芳基,
b.(甲基)丙烯酸,
c.(甲基)丙烯酸酐,和
d.(甲基)丙烯酸酯,
其中基团a.至d.各自的存在量为基于聚(甲基)丙烯酰亚胺的总重量计的至少1重量%。
5.根据权利要求4的混合物,其特征在于所述聚(甲基)丙烯酰亚胺含有10-95重量%,优选20-70重量%和更优选25-40重量%的式(IV)的单元。
6.根据权利要求1-5中任一项的混合物,其特征在于所述聚(甲基)丙烯酰亚胺的分子量Mw在50000至150000g/mol范围内,所述分子量是通过GPC相对于PMMA标准品测定的。
7.根据权利要求1-6中任一项的混合物,其特征在于聚(甲基)丙烯酸烷基酯含有作为共聚单体的苯乙烯。
8.根据权利要求1-7中任一项的混合物,其特征在于所述聚(甲基)丙烯酸烷基酯是抗冲改性的聚合物。
9.根据权利要求1-8中任一项的混合物,其特征在于所述混合物含有至少一种选自以下的组分:着色剂,特别是颜料和染料,更优选有机染料,光稳定剂,UV稳定剂,UV吸收剂,IR吸收剂,抗微生物活性剂,阻燃剂,热稳定剂,抗氧化剂,交联性聚合物,有机或无机类型的纤维增强性添加剂,抗冲改性剂和它们的混合物。
10.可由根据权利要求1至9中任一项的混合物获得的经发泡的模制品。
11.制备经发泡的模制品的方法,该方法包括以下步骤:
a.将根据权利要求1至9中任一项的混合物熔融,
b.将所熔融的混合物挤出以获得粒料,
c.注射模塑所述粒料以获得模制品或挤出片材,和
d.将所述模制品或所述挤出片材引入到高压釜中并用物理发泡剂处理以获得经发泡的模制品。
12.制备经发泡的模制品的方法,该方法包括以下步骤:
a.将根据权利要求1至9中任一项的混合物熔融,和
b.将所熔融的混合物用物理发泡剂进行处理,并将所熔融的混合物借助于孔板或模头挤出以获得经发泡的模制品。
13.根据权利要求9的经发泡的模制品用作鞋底、鞋钉材料、绝缘材料、隔绝材料、减震组件、轻质组件或用于夹芯结构中的用途。
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EP18200738.5 | 2018-10-16 | ||
EP18200738.5A EP3640287A1 (de) | 2018-10-16 | 2018-10-16 | Polyetherblockamid-poly(meth)acrylat-schäume |
CN201980068004.4A CN112867755B (zh) | 2018-10-16 | 2019-10-16 | 聚醚嵌段酰胺-聚(甲基)丙烯酸系物泡沫 |
PCT/EP2019/078086 WO2020079081A1 (de) | 2018-10-16 | 2019-10-16 | Polyetherblockamid-poly(meth)acrylat-schäume |
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WO2023082250A1 (en) * | 2021-11-15 | 2023-05-19 | Evonik Operations Gmbh | Foamed article and method for preparing the same |
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WO2023139195A1 (en) | 2022-01-24 | 2023-07-27 | Röhm Gmbh | Polymer foams based on poly(meth)acrylimide |
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JP7431818B2 (ja) | 2024-02-15 |
EP3688080B1 (de) | 2020-11-18 |
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US20210371651A1 (en) | 2021-12-02 |
WO2020079081A1 (de) | 2020-04-23 |
KR20210076950A (ko) | 2021-06-24 |
JP2022502555A (ja) | 2022-01-11 |
KR20210076083A (ko) | 2021-06-23 |
MX2021004066A (es) | 2021-06-04 |
EP3867304A1 (de) | 2021-08-25 |
JP2022505089A (ja) | 2022-01-14 |
US20220363901A1 (en) | 2022-11-17 |
CN112867755A (zh) | 2021-05-28 |
CN113330059A (zh) | 2021-08-31 |
EP3688080A1 (de) | 2020-08-05 |
EP3640287A1 (de) | 2020-04-22 |
WO2020078856A1 (de) | 2020-04-23 |
KR102541676B1 (ko) | 2023-06-13 |
JP7438206B2 (ja) | 2024-02-26 |
KR102606397B1 (ko) | 2023-11-27 |
MX2021004072A (es) | 2021-06-04 |
CN113330059B (zh) | 2022-11-08 |
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