CN102947087A - 耐长期户外暴露的聚酯复合结构及其制备方法 - Google Patents
耐长期户外暴露的聚酯复合结构及其制备方法 Download PDFInfo
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- WYXIGTJNYDDFFH-UHFFFAOYSA-Q triazanium;borate Chemical compound [NH4+].[NH4+].[NH4+].[O-]B([O-])[O-] WYXIGTJNYDDFFH-UHFFFAOYSA-Q 0.000 description 1
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Classifications
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- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
- B32B5/024—Woven fabric
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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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract
本发明涉及紫外线稳定的热塑性聚酯复合结构及其制备方法的领域。所公开的复合结构具有表面并包含纤维材料,所述表面的至少一部分由表面树脂组合物制成,所述纤维材料选自非织造结构、纺织品、纤维絮以及它们的组合,所述纤维材料用基质树脂组合物浸渍,其中所述表面树脂组合物选自聚酯组合物,所述聚酯组合物包含a)一种或多种聚酯树脂,和b)至少三种紫外线稳定剂。
Description
发明领域
本发明涉及紫外光稳定的热塑性聚酯复合结构及其制备方法的领域。
发明背景
为了替换金属部件以减轻重量和降低成本并同时保持相当的或优异的机械性能,开发了基于复合材料的结构,所述复合材料具有包含纤维材料的聚合物基质。随着对此领域关注度的日益增长,已设计了纤维增强的塑性复合结构,原因在于其具有由纤维材料和聚合物基质的组合而产生的优异物理特性,并且这些纤维增强的塑性复合结构已用于多种最终应用中。已开发了多种制造技术来改善聚合物基质对纤维材料的浸渍,从而优化复合结构的特性。
在要求很高的应用中,例如机动车和航空航天应用中的结构部件,由于复合材料具有重量轻、高强度和耐温性的独特组合,因此是为人们所期望的。
可使用热固性树脂或热塑性树脂作为聚合物基质来获得高性能复合结构。基于热塑性的复合结构相对于基于热固性的复合结构表现出若干优点,例如以下事实:它们可通过施加热和压力被后成型或再加工,由于不需要固化步骤而减少了制造复合结构所需的时间;并且增加了回收利用的可能性。实际上,在热塑性塑料的加工过程中,不需要热固性树脂耗时的化学交联(固化)反应。
由于热塑性聚酯的良好耐热性、机械强度、电特性、良好可加工性以及其它特性,其用于广泛范围的应用中,包括机动车应用;娱乐和体育设施部件;家用电器、电气/电子部件;动力设备;以及建筑或机械装置。
基于热塑性聚酯的复合结构实例公开于美国专利4,549,920和美国专利6,369,157中。
美国专利4,549,920公开了由热塑性聚酯例如聚对苯二甲酸乙二醇酯(PET)树脂制得并增强包封于所述树脂中的长丝的纤维增强复合结构。
美国专利6,369,157公开了热塑性聚酯复合结构。通过用就地快速聚合的聚酯低聚物浸渍纤维材料形成所述复合结构,制得所公开的复合结构。
美国专利申请公布2007/0182047公开了制备热塑性聚酯复合结构的方法。所公开的方法包括以下步骤:用聚酯低聚物(尤其是PBT的环状低聚物)浸渍纤维材料,并且涂覆在一面或两面上,使外层包含聚合的聚酯。聚酯低聚物在复合结构制备期间快速聚合。
美国专利5,011,523公开了由混合的纤维材料制得的热塑性复合材料,所述混合的纤维材料由混合的热塑性聚酯纤维和玻璃纤维形成。通过热和压力,用存在于混合纤维材料中的热塑性聚酯浸渍纤维材料即玻璃纤维。
使用聚酯的许多应用是用于户外的,并且要求由聚酯制得的复合材料在正常使用期间暴露于风化条件下。如果用于户外应用,包含聚酯树脂组合物的复合结构因风化条件如高温、湿度、暴露于紫外线(UV)和其它类型辐射而经历快速并且严重的降解/劣化。对紫外线辐射和高温源的此类暴露减弱了正常使用期间的制品特性。在长期风化条件下,包含聚酯树脂组合物的复合结构可能降解,从而造成物理/机械特性丧失,并且美观外观减弱,例如变色和/或表面开裂。
遗憾的是,常规聚酯复合结构在长期风化暴露后以及长期高温暴露后,它们的机械特性和美观外观可能遭受不可接受的劣化。由于这个原因,现有技术不满足要求很高的应用。
因此,需要有效保护聚酯复合结构,抵抗因风化暴露而致的劣化,具体地讲为光引发的降解和热引发的热氧化。
发明概述
本文描述了具有表面并包含纤维材料的复合结构,所述表面的至少一部分由表面树脂组合物制成,并且所述纤维选自非织造结构、纺织品、纤维絮以及它们的组合,所述纤维材料用基质树脂组合物浸渍,并且其中所述表面树脂组合物选自聚酯组合物,所述聚酯组合物包含a)一种或多种聚酯树脂,和b)0.3重量%或约0.3重量%至3重量%或约3重量%的至少三种紫外线稳定剂;其中所述至少三种紫外线稳定剂中的一种为b1),另一种为b2),并且另一种为b3),所述重量百分比是基于所述聚酯组合物的总重量计的。
本文还描述了用于制备上述复合结构的方法。制备上述复合结构的方法包括以下步骤:i)用基质树脂组合物浸渍纤维材料,其中复合结构表面的至少一部分由表面树脂组合物制成。
发明详述
在本说明书中引用了若干专利和出版物。所有这些专利和出版物的全部公开内容均以引用方式并入本文。
如本文所用,术语“一个”是指一个以及至少一个,并且不是必定限制其指示名称为单数的冠词。
如本文所用,术语“约”和“为或为约”旨在表示所述量或数值可为指定值或与指定值接近的某个其它值。所述短语旨在表达根据本发明的类似的值产生了相同的结果或效果。
本发明涉及复合结构及其制备方法。根据本发明的复合结构包含用基质树脂组合物浸渍的纤维材料。复合结构表面的至少一部分由表面树脂组合物制成。基质树脂组合物和表面树脂组合物可相同或不同。
如本文所用,术语“用基质树脂组合物浸渍的纤维材料”是指基质树脂组合物包封并嵌入所述纤维材料,以便形成基本上被基质树脂组合物围绕的纤维材料的互穿网状物。出于本文的目的,术语“纤维”是指宏观上均匀的主体,所述主体在垂直于长度方向的横截面上具有较高长宽比。纤维横截面可为任何形状,但通常为圆形。纤维材料可为本领域中技术人员已知的任何合适形式,并且优选地选自非织造结构、纺织品、纤维絮以及它们的组合。非织造结构可选自无规纤维取向的或对齐的纤维结构。无规纤维取向的实例无限制地包括短切和连续的材料,其可为垫、针刺垫或毡的形式。对齐的纤维结构的实例无限制地包括单向纤维股线、双向股线、多向股线、多轴向纺织品。纺织品可选自织造形式、针织品、编织品以及它们的组合。纤维材料可为连续或不连续的形式。根据复合结构的最终应用以及所需的机械特性,可使用多于一种的纤维材料,具体方式为采用若干相同的纤维材料或不同纤维材料的组合,即根据本发明的复合结构可包含一种或多种纤维材料。不同纤维材料的组合的实例是这样的组合,其包含布置成中间层的非织造结构例如平面无规垫,和布置成外层的一种或多种织造的连续纤维材料。此组合可改善复合结构的加工及其同质性,从而得到改善的机械特性。纤维材料可由任何合适的材料或材料混合物制成,前提条件是材料或材料混合物能够经受在基质树脂组合物和表面树脂组合物浸渍期间所用的加工条件。
优选地,纤维材料包含玻璃纤维、碳纤维、芳族聚酰胺纤维、石墨纤维、金属纤维、陶瓷纤维、天然纤维或它们的混合物;更优选地,纤维材料包含玻璃纤维、碳纤维、芳族聚酰胺纤维、天然纤维或它们的混合物;并且还更优选地,纤维材料包含玻璃纤维、碳纤维和芳族聚酰胺纤维或它们的混合物。所谓天然纤维是指任何植物源或动物源的材料。当使用时,天然纤维优选地衍生自植物源,例如衍生自种子纤维(如,棉花)、茎杆植物(如大麻、亚麻、竹子;韧皮纤维和芯纤维均可)、叶子植物(如剑麻和马尼拉麻)、农作物纤维(如谷类稿秆、玉米棒、稻壳和椰子纤维)或木质纤维质的纤维(如木料、木料纤维、木粉、纸材和与木料相关的材料)。如上文提及的,可使用一种以上的纤维材料。可使用由不同纤维制成的纤维材料的组合,例如这样的复合结构,其包括由玻璃纤维或天然纤维制成的一个或多个中间层,以及由碳纤维或玻璃纤维制成的一个或多个表面层。优选地,所述纤维材料选自织造结构、非织造结构或它们的组合,其中所述结构由玻璃纤维制成,并且其中所述玻璃纤维为E-玻璃长丝,其具有介于6和30微米之间的直径,并且优选具有介于10至24微米之间的直径。
纤维材料还可包含热塑性材料与上述材料,例如纤维材料可为混纤纱或混编纱的形式或用适合随后加工成织造或非织造形式的热塑性材料制成的粉末浸渍的纤维材料,或用作单向材料的混合物,或用浸渍期间就地聚合的低聚物浸渍的纤维材料。
优选地,复合结构中介于纤维材料和聚合物材料之间的比率(即,与基质树脂组合物和表面树脂组合物结合的纤维材料)为至少30%的纤维材料,并且更优选介于40%和60%之间的纤维材料,所述百分比是基于所述复合结构的总体积计的体积百分比。
基质树脂组合物由包含热塑性树脂的组合物制成,所述热塑性树脂与表面树脂组合物相容;优选地,所述基质树脂组合物由包含一种或多种聚酯树脂的组合物制成,或选自聚酯组合物,所述聚酯组合物包含a)一种或多种聚酯树脂,和b)至少三种紫外线稳定剂,如表面树脂组合物中所述。这是指基质树脂组合物和表面树脂组合物可相同或不同。当基质树脂组合物选自聚酯组合物,所述聚酯组合物包含一种或多种聚酯树脂,和b)至少三种紫外线稳定剂时,它可相同或不同于表面树脂组合物。当表面树脂组合物和基质树脂组合物不同时,这是指表面树脂组合物和基质树脂组合物中,组分a)即一种或多种聚酯树脂和/或组分b)即至少三种紫外线稳定剂不相同,和/或组分a)和b)的量不同。
一种或多种聚酯树脂选自衍生自一种或多种二羧酸和一种或多种二醇的热塑性聚酯。热塑性聚酯通常衍生自一种或多种二羧酸(其中本文中的术语“二羧酸”也指二羧酸衍生物,例如酯)和一种或多种二醇。在优选的热塑性聚酯中,二羧酸包括对苯二甲酸、间苯二甲酸和2,6-萘二羧酸中的一种或多种,并且二醇组分包括HO(CH2)nOH(I);1,4-环己烷二甲醇;HO(CH2CH2O)mCH2CH2OH(II);和HO(CH2CH2CH2CH2O)zCH2CH2CH2CH2OH(III)中的一种或多种,其中n为2至10的整数,m平均为1至4,并且z平均为约7至约40。应注意(II)和(III)可为化合物的混合物,其中m和z可各自不同,并且因为m和z为平均值,所以它们不一定为整数。可用于形成热塑性聚酯的其他二甲酸包括癸二酸和己二酸。羟基羧酸,例如羟基苯甲酸可用作共聚单体。优选地,包含于本文所述聚酯组合物中的一种或多种聚酯树脂独立地选自聚(对苯二甲酸乙二醇酯)(PET)、聚(对苯二甲酸丙二醇酯)(PTT)、聚(对苯二甲酸1,4-丁二醇酯)(PBT)、聚(2,6-萘二甲酸乙二醇酯)(PEN)和聚(对苯二甲酸1,4-环己基二甲醇酯)(PCT)以及它们的共聚物和共混物。更优选地,包含于本文所述聚酯组合物中的一种或多种热塑性聚酯独立地选自聚(对苯二甲酸乙二醇酯)(PET)、聚(对苯二甲酸1,4-丁二醇酯)(PBT)、聚(对苯二甲酸1,4-环己基二甲醇酯)(PCT)以及它们的共聚物和共混物。
本文所述的聚酯组合物优选地包含0.3重量%或约0.3重量%至3重量%或约3重量%的至少三种紫外线稳定剂,其中所述至少三种紫外线稳定剂中的一种为b1),另一种为b2),并且另一种为b3),所述重量百分比是基于所述聚酯组合物的总重量计的。
优选地,所述至少三种紫外线稳定剂选自b1)一种或多种苯并三唑衍生物,b2)一种或多种三嗪衍生物和/或嘧啶衍生物;和b3)一种或多种受阻胺衍生物(也被称为受阻胺型光稳定剂(HALS))。
优选地,所述一种或多种苯并三唑衍生物b1)以0.01重量%或约0.01重量%至2.98重量%或约2.98重量%的量存在,所述一种或多种三嗪衍生物和/或嘧啶衍生物b2)以0.01重量%或约0.01重量%至2.98重量%或约2.98重量%的量存在,并且所述一种或多种受阻胺衍生物b3)以0.01重量%至2.98重量%或约2.98重量%的量存在,前提条件是b1)+b2)+b3)之和介于0.3重量%或约0.3重量%和3重量%或约3重量%之间,所述重量百分比是基于所述聚酯组合物的总重量计的。
优选地,三种紫外线稳定剂中的一种为具有以下通式(A)的一种或多种苯并三唑衍生物b1)以及它们的组合:
其中R1为C1-C12烷基;C1-C5烷氧基;C1-C5烷氧羰基;C5-C7环烷基;C6-C10芳基;或芳烷基;
R3为氢;C1-C5烷基;C1-C5烷氧基;卤素,优选氯;或羟基;
m为1或2;
当m=1时,R2为氢;未取代或苯基取代的C1-C12烷基;或C6-C10芳基;
当m=2时,R2为介于苯基之间的直接键;或-(CH2)p-;并且p为1至3。
所谓“它们的组合”一般理解为,当所述聚酯组合物中存在例如一种或多种苯并三唑衍生物b1)中的多于一种的稳定剂,不同的稳定剂b1)可具有不同的结构,并且可独立地选自通式(A),所有这些稳定剂均具有通式(A)。
更优选地,一种或多种苯并三唑衍生物b1)具有以下通式(B)以及
它们的组合:
其中R1为C1-C12烷基。
还更优选地,一种或多种苯并三唑衍生物b1)具有以下通式(C):
其中苯并三唑衍生物为2,2′-亚甲基二(6-(2H-苯并三唑-2-基)-4-1,1,3,3-四甲基丁基)-苯酚((CAS号:103597-45-1;也被称为2,2′-亚甲基二(6-(苯并三唑-2-基)-4-叔辛基苯酚))。
优选地,一种或多种苯并三唑衍生物b1)以0.01重量%或约0.01重量%至2.98重量%或约2.98重量%,更优选0.05重量%或约0.05重量%至2重量%或约2重量%,并且还更优选0.1重量%或约0.1重量%至1重量%或约1重量%的量存在,前提条件是b1)+b2)+b3)之和介于0.3重量和3重量%之间,所述重量百分比是基于所述聚酯组合物的总重量计的。
优选地,所述三种紫外线稳定剂中的一种为具有以下通式(D)的一种或多种三嗪衍生物和/或嘧啶衍生物b2)以及它们的组合:
其中Y为N(三嗪衍生物)或CH(嘧啶衍生物);并且其中R4、R5、R6、R7、R8、R9、R10和R11各自独立地选自氢、烷基、环烷基、卤素、卤代烷基、烷氧基、亚烷基、芳基、烷基-芳基、或它们的组合。
更优选地,所述一种或多种三嗪衍生物和/或嘧啶衍生物b2)为下式(E)的三嗪衍生物,即Y为N(氮),以及它们的组合:
其中R4、R5、R6、R7、R8、R9、R10和R11各自独立地选自氢、烷基、环烷基、卤素、卤代烷基、烷氧基、亚烷基、芳基、烷基-芳基、或它们的组合。
还更优选地,一种或多种三嗪衍生物和/或嘧啶衍生物b2)为以下通式(F)的化合物:
其中三嗪衍生物和/或嘧啶衍生物为2-(4,6-二苯基-1,3,5-三嗪-2-基)-5-己氧基-苯酚(CAS Nb 147315-50-2)。
优选地,一种或多种三嗪衍生物和/或嘧啶衍生物b2)以0.01重量%或约0.01重量%至2.98重量%或约2.98重量%,更优选0.05重量%或约0.05重量%至2重量%或约2重量%,并且还更优选0.1重量%或约0.1重量%至1重量%或约1重量%的量存在,前提条件是b1)+b2)+b3)之和介于0.3重量%和3重量%之间,所述重量百分比是基于所述聚酯组合物的总重量计的。
优选地,三种紫外线稳定剂中的一种为具有以下通式(G)的一种或多种受阻胺衍生物b3)以及它们的组合:
其中R12、R13、R14、R15和R16各自独立地选自氢、醚基、酯基、胺基、酰胺基、烷基、烯基、炔基、芳烷基、环烷基、芳基或它们的组合;其中取代基继而可包含官能团;所述官能团的实例是醇、酮、酸酐、亚胺、硅氧烷、醚、羧基、醛、酯、酰胺、酰亚胺、胺、腈、醚、尿烷、以及它们的任何组合。一种或多种受阻胺衍生物还可形成聚合物或低聚物的一部分。
更优选地,一种或多种受阻胺衍生物b3)为衍生自取代的哌啶化合物的化合物,具体地讲为衍生自烷基取代的哌啶基、哌啶基或哌嗪酮化合物以及取代的烷氧基哌啶基化合物的任何化合物。还更优选地,一种或多种受阻胺衍生物b3)为N-(2-羟乙基)-2,2,6,6-四甲基-4-哌啶醇和琥珀酸的低聚物,其低聚物具有3100-4000的分子量Mn。(CAS号:65447-77-0)。
优选地,一种或多种受阻胺衍生物b3)以0.01重量%或约0.01重量%至2.98重量%或约2.98重量%,更优选0.05重量%或约0.05重量%至2重量%或约2重量%,并且还更优选0.1重量%或约0.1重量%至1重量%或约1重量%的量存在,前提条件是b1)+b2)+b3)之和介于0.3重量%和3重量%之间,所述重量百分比是基于所述聚酯组合物的总重量计的。
根据优选的实施方案,所述至少三种紫外线稳定剂为:
具有上述通式(A)的b1),
具有上述通式(D)的b2),和
具有上述通式(G)的b3)。
根据更优选的实施方案,所述至少三种紫外线稳定剂为:
为2,2′-亚甲基二(6-(2H-苯并三唑-2-基)-4-1,1,3,3-四甲基丁基)-苯酚的b1),为2-(4,6-二苯基-1,3,5-三嗪-2-基)-5-己氧基-苯酚的b2),和
为N-(2-羟乙基)-2,2,6,6-四甲基-4-哌啶醇与琥珀酸的低聚物的b3)。
本文所述的表面树脂组合物和/或基质树脂组合物还可包含一种或多种增韧剂、一种或多种热稳定剂、一种或多种增强剂、一种或多种阻燃剂或它们的混合物。
表面树脂组合物和/或基质树脂组合物还可包含一种或多种增韧剂。所述增韧剂通常为弹性体,所述弹性体具有较低的熔点,一般低于200℃,优选低于150℃,并且为官能化聚合物,以与一种或多种聚酯(以及任选存在的其它聚合物)中的羧基和/或羟基反应。所谓“官能化聚合物”是指聚合物与有机官能团进行接枝和/或共聚,该聚合物可为均聚物、共聚物或三元共聚物。适宜的有机官能团为环氧基、羧酸酐、羟基(醇)、羧基和异氰酸酯官能团。作为接枝的一个实例,可采用自由基接枝技术将马来酸酐接枝到烃橡胶上。其中有机官能团共聚形成聚合物的增韧剂的实例为乙烯与包含适宜官能团的(甲基)丙烯酸酯单体以及可共聚形成此类聚合物的任选其它单体的共聚物,所述包含适宜官能团的(甲基)丙烯酸酯单体如(甲基)丙烯酸、(甲基)丙烯酸2-羟基乙酯、(甲基)丙烯酸缩水甘油酯(GMA)和(甲基)丙烯酸2-异氰酸根合乙酯,所述任选其它单体如乙酸乙烯酯、未官能化(甲基)丙烯酸酯,如(甲基)丙烯酸乙酯、(甲基)丙烯酸正丁酯和(甲基)丙烯酸环己酯。尤其优选的增韧剂为乙烯、丙烯酸烷基酯和甲基丙烯酸缩水甘油酯的共聚物如EBAGMA,以及乙烯/丙烯酸甲酯共聚物。所述一种或多种增韧剂还可为离聚物。离聚物为除了包含聚合物的有机主链外还包含金属离子的热塑性树脂。离聚物为由烯烃如乙烯与α-β-不饱和C3-C8羧酸如丙烯酸(AA)、甲基丙烯酸(MAA)或马来酸单乙酯(MAME)形成的离子共聚物,其中所述共聚物中的至少一部分羧酸部分(优选10至99.9%)被中和剂(例如碱金属如锂、钠或钾,或过渡金属如锰或锌)中和形成相应的羧酸盐。聚合物增韧剂还可为非乙烯共聚物的热塑性丙烯酸聚合物。所述热塑性丙烯酸聚合物可通过聚合以下物质制得:丙烯酸、丙烯酸酯(如丙烯酸甲酯、丙烯酸正丙酯、丙烯酸异丙酯、丙烯酸正丁酯、丙烯酸正己酯、和丙烯酸正辛酯)、甲基丙烯酸和甲基丙烯酸酯(如甲基丙烯酸甲酯、甲基丙烯酸正丙酯、甲基丙烯酸异丙酯、甲基丙烯酸正丁酯(BA)、甲基丙烯酸异丁酯、甲基丙烯酸正戊酯、甲基丙烯酸正辛酯、甲基丙烯酸缩水甘油酯(GMA)等)。还可使用衍生自两种或更多种上述类型单体的共聚物,以及通过一种或多种上述类型单体与苯乙烯、丙烯腈、丁二烯、异戊二烯等的聚合反应制备的共聚物。这些共聚物中的部分或所有组分应优选具有不高于0℃的玻璃化转变温度。用于制备热塑性丙烯酸类聚合物增韧剂的优选单体为丙烯酸甲酯、丙烯酸正丙酯、丙烯酸异丙酯、丙烯酸正丁酯、丙烯酸正己酯和丙烯酸正辛酯。热塑性丙烯酸类聚合物增韧剂优选具有芯-壳结构。所述芯-壳结构是其中芯部分优选具有0℃或更低的玻璃化转变温度,而壳部分优选具有比所述芯部分的玻璃化转变温度更高的玻璃化转变温度的结构。可用硅氧烷接枝所述芯部分。可用低表面能基质如硅氧烷、氟等接枝所述壳部分。具有芯-壳结构的丙烯酸类聚合物将在与本发明组合物中的热塑性聚酯和其它组分混合期间或之后与其自身附聚,并且易于均匀分散在所述组合物中,所述芯-壳结构具有接枝在所述表面上的低表面能基质。当一种或多种增韧剂存在时,其优选包含0.5重量%或约0.5重量%至30重量%或约30重量%,或更优选1重量%或约1重量%至20重量%或约20重量%的量,所述重量百分比是根据具体情况基于所述表面树脂组合物或所述基质树脂组合物的总重量计的。
表面树脂组合物和/或基质树脂组合物还可包含采用高温应用情况下阻碍热引发聚合物氧化的一种或多种热稳定剂(也被称为抗氧化剂或氧化稳定剂)。优选地,所述一种或多种氧化稳定剂选自基于苯酚的稳定剂、基于磷的稳定剂、受阻胺稳定剂、芳胺稳定剂、硫酯以及它们的混合物,以在采用高温应用情况下阻碍热引发聚酯氧化。更优选地,所述一种或多种氧化稳定剂选自基于苯酚的稳定剂、基于磷的稳定剂、以及它们的混合物。基于苯酚的抗氧化剂的优选实例为位阻酚。基于磷的抗氧化剂的优选实例为亚磷酸盐稳定剂、次磷酸盐稳定剂和亚膦酸盐稳定剂,并且更优选二亚磷酸酯稳定剂。当一种或多种氧化稳定剂存在时,其包含0.1重量%或约0.1重量%至3重量%或约3重量%,或优选0.1重量%或约0.1重量%至1重量%或约1重量%,或更优选0.1重量%或约0.1重量%至0.8重量%或约0.8重量%的量,所述重量百分比是根据具体情况基于所述表面树脂组合物或所述基质树脂组合物的总重量计的。一种或多种热稳定剂的添加改善复合结构在其制备期间的热稳定性(即减少分子量降低)以及其随着使用和时间流逝的热稳定性。一种或多种热稳定剂的存在除了改善热稳定性外,还可允许在复合结构的浸渍期间升高所用的温度,从而降低本文所述的基质树脂和/或表面树脂组合物的熔融粘度。由于基质树脂和/或表面树脂组合物熔融粘度降低的结果,浸渍速率可提高。
本文所述的表面树脂组合物和/或基质树脂组合物还可包含一种或多种增强剂如非圆形横截面的纤维玻璃填料;具有圆形横截面的玻璃纤维、玻璃片、碳纤维、碳纳米管、云母、钙硅石、碳酸钙、滑石、煅烧粘土、高岭土、硫酸镁、硅酸镁、氮化硼、硫酸钡、二氧化钛、碳酸钠铝、钡铁氧体和钛酸钾。当存在一种或多种增强剂时,其以1重量%或约1重量%至60重量%或约60重量%,优选1重量%或约1重量%至40重量%或约40重量%,或更优选1重量%或约1重量%至35重量%或约35重量%的量存在,所述重量百分比是根据具体情况基于表面树脂组合物或基质树脂组合物的总重量计的。
本文所述表面树脂组合物和/或基质树脂组合物还可包含附加的紫外线稳定剂。优选地,所述附加的紫外线稳定剂选自受阻胺光稳定剂(HALS)、炭黑、取代的间苯二酚、水杨酸盐、苯并三唑、三嗪、二苯甲酮以及它们的混合物。当附加的紫外线稳定剂存在时,其以0.1重量%或约0.1重量%至5重量%或约5重量%,优选0.2重量%或约0.2重量%至3重量%或约3重量%的量存在,所述重量百分比是根据具体情况基于所述表面树脂组合物或所述基质树脂组合物的总重量计的。
本文所述表面树脂组合物和/或基质树脂组合物还可包含一种或多种阻燃剂(本领域中还称为耐火剂)。所述阻燃剂用于热塑性组合物中,以通过所述组合物或基于所述组合物的制品抑制、降低、延缓或改变火焰的蔓延。一种或多种阻燃剂可为卤化的阻燃剂、无机阻燃剂、含磷化合物、含氮化合物或它们的组合。
卤化的有机阻燃剂无限制地包括含氯和溴的化合物。适宜含氯化合物的实例无限制地包括氯化烃、氯化脂环族化合物、氯化烷基磷酸盐、氯化磷酸酯、氯化多磷酸盐、氯化有机膦酸酯、氯烷基磷酸盐、多氯化联苯和氯化石蜡。适宜含溴化合物的实例无限制地包括四溴双酚A、二(三溴苯氧基)烷烃、多溴二苯醚、溴化磷酸酯、三溴苯酚、四溴二苯硫醚、聚丙烯酸五溴苄酯、溴化苯氧树脂、基于四溴双酚A的溴化聚碳酸酯聚合物添加剂、基于四溴双酚A的溴化环氧化物聚合物添加剂和溴化聚苯乙烯。
无机阻燃剂无限制地包括金属氢氧化物、金属氧化物、锑化合物、钼化合物和硼化合物。适宜金属氢氧化物的实例无限制地包括氢氧化镁、氢氧化铝、三水氧化铝、以及其它金属氢氧化物。适宜金属氧化物的实例无限制地包括锌和镁的氧化物。适宜锑化合物的实例无限制地包括三氧化锑、锑酸钠和五氧化锑。适宜钼化合物的实例无限制地包括三氧化钼和八钼酸铵(AOM)。适宜硼化合物的实例无限制地包括硼酸锌、硼砂(硼酸钠)、硼酸铵和硼酸钙。
适宜含磷化合物的实例无限制地包括红磷;卤化磷酸盐;磷酸三苯酯;低聚和聚合的磷酸盐;膦酸盐、次膦酸盐、双次膦酸盐和/或它们的聚合物。
适宜含氮化合物的实例无限制地包括三嗪或其衍生物、胍或其衍生物、氰尿酸或其衍生物以及异氰脲酸酯或其衍生物。
当一种或多种阻燃剂存在时,其包含5重量%或约5重量%至30重量%或约30重量%,或优选10重量%或约10重量%至25重量%或约25重量%的量,所述重量百分比是根据具体情况基于所述表面树脂组合物或所述基质树脂组合物的总重量计的。
如上所述,基质树脂组合物和表面树脂组合物可相同或不同。为了提高纤维材料的浸渍速率,可降低组合物的熔融粘度,尤其是基质树脂组合物的熔融粘度。为了改善复合结构的制造并使纤维材料的浸渍更容易、更快并且均匀,已经开发了多个方法以降低聚合物基质的熔融粘度。通过使熔融粘度尽可能的低,聚合物组合物流动更快,并且使得纤维材料的浸渍更快更好。通过降低聚合物基质的熔融粘度,可缩短达到浸渍程度所需的有限浸渍时间,从而提高总体制造速度,从而致使所述结构的制造产量提高以及与较短循环时间相关联的能耗降低,这对环境保护也是有益的。除了改善生产能力外,提高浸渍速率还最大程度地降低了基质组合物的热降解。为了降低基质树脂组合物的熔融粘度,本文所述基质树脂组合物还可包含一种或多种流变改性剂,所述流变改性剂选自超支化聚合物(也被称为为超支化聚合物、树枝状或高度支化的聚合物、树枝状高分子、或树状聚合物)、多元醇、多酚和LCP嵌段共聚物。超支化聚合物为具有枝状结构的三维的高度支化分子。超支化聚合物是包含一个或多个支化共聚单体单元的大分子。支化单位包括支化层和任选地一个核(也称为芯)、一个或多个空间层和/或一层链终止分子。支化层的连续复制导致层的多样性提高、支链密度提高、以及末端官能团的数目比其他分子增加。优选的超支化聚合物包括超支化聚酯。超支化聚合物的优选实例是美国专利5,418,301、美国专利申请公布2007/0173617中所述的那些。此类超支化聚合物在热塑性树脂中的用途公开于美国专利6,225,404、美国专利6,497,959、美国专利6,663,966、世界专利申请公布WO 2003/004546、欧洲专利申请1424360和世界专利申请公布WO 2004/111126中。当一种或多种超支化聚合物存在时,其包含0.05重量%或约0.05重量%至10重量%或约10重量%,或更优选0.1重量%或约0.1重量%至5重量%或约5重量%的量,所述重量百分比是基于所述基质树脂组合物的总重量计的。
根据本发明所述复合结构的最终应用和此类应用所需的耐水解性,本文所述表面树脂组合物和/或基质树脂组合物还可包含一种或多种含环氧基化合物。适宜的含环氧基化合物的实例无限制地包括含环氧基的聚烯烃、多酚的缩水甘油醚、双酚环氧树脂和酚醛环氧树脂。含环氧基的聚烯烃为用环氧基官能化的聚烯烃,优选聚乙烯;所谓“官能化”是指基团被有机官能团接枝和/或共聚。用于官能化聚烯烃的环氧化物的实例为包含四至十一个碳原子的不饱和环氧化物,例如(甲基)丙烯酸缩水甘油酯、烯丙基缩水甘油醚、乙烯基缩水甘油醚和衣康酸缩水甘油酯,尤其优选(甲基)丙烯酸缩水甘油酯(GMA)。乙烯/(甲基)丙烯酸缩水甘油酯共聚物还可包含具有一至六个碳原子的(甲基)丙烯酸烷基酯与具有1-8个碳原子的α-烯烃的共聚单元。代表性的(甲基)丙烯酸烷基酯包括(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸异丁酯、(甲基)丙烯酸己酯或它们中的两种或更多种的组合。值得注意的是丙烯酸乙酯和丙烯酸丁酯。双酚环氧树脂为具有环氧官能团和双酚部分的缩合产物。实例无限制地包括双酚A与环氧氯丙烷缩合获得的产物,和双酚F与环氧氯丙烷缩合获得的产物。酚醛环氧树脂为醛如甲醛与含芳族羟基的化合物如苯酚或甲酚的缩合产物。当存在时,一种或多种含环氧基化合物以根据具体情况足以提供3或约3至300或约300毫当量的总环氧基官能团每千克包含于表面树脂组合物中的一种或多种热塑性聚酯,或每千克包含于基质树脂组合物中的一种或多种热塑性聚酯的量存在;优选5或约5至300或约300毫当量的总环氧基官能团每千克聚酯。
本文所述表面树脂组合物和/或基质树脂组合物还可包含调节剂和其它成分,无限制地包括润滑剂、防静电剂、着色剂(包括染料、颜料、炭黑等)、成核剂、结晶促进剂、以及聚合物配混领域已知的其它加工助剂。
上述填料、改性剂和其他成分可以本领域熟知的量和形式存在,包括所谓的纳米材料形式,其中颗粒的至少一个尺寸在1nm至1000nm的范围内。
优选地,表面树脂组合物和基质树脂组合物为熔融混合的共混物,其中所有聚合物组分都均匀分散在彼此中,并且所有非聚合物成分都均匀分散在聚合物基质中并通过聚合物基质粘结,使得共混物形成一个统一整体。可使用任何熔融混合方法来混合本发明的聚合物组分和非聚合物成分。例如,可将聚合物组分和非聚合物成分加入熔融搅拌器中,例如单螺杆或双螺杆挤出机、共混机、单螺杆或双螺杆捏合机或班伯里密炼机,可通过单步骤添加方式一次性全部加入,也可以分步方式加入,然后进行熔融混合。当以分步方式加入聚合物组分和非聚合物成分时,首先加入部分聚合物组分和/或非聚合物成分并进行熔融混合,随后再加入剩余的聚合物组分和非聚合物成分,并进一步进行熔融混合,直至获得混合充分的组合物。
根据最终应用,根据本发明的复合结构可具有任何形状。在一个优选的实施方案中,根据本发明所述的复合结构为片材结构的形式。复合结构可为柔性的,在此情况下可将其卷起。
在另一方面,本发明涉及制备上述复合结构的方法以及由该方法获得的复合结构。制备具有表面的复合结构的方法包括以下步骤:i)用基质树脂组合物浸渍纤维材料,其中复合结构表面的至少一部分由表面树脂组合物制成。本文还描述了制备本文所述复合结构的方法,其中所述方法包括将表面树脂组合物施加到所述纤维材料表面的至少一部分的步骤,所述纤维材料用本文所述基质树脂组合物浸渍。优选地,通过热压法用基质树脂浸渍纤维材料。在热压过程中,纤维材料、基质树脂组合物和表面树脂组合物受到热和压力的作用,从而使树脂复合物熔融并渗入纤维材料中,从而浸渍所述纤维材料。
通常,热压法在以下条件下进行:压力介于2和100巴之间,并且更优选地介于10和40巴之间,和温度高于基质树脂组合物和表面树脂组合物的熔点,优选地高于熔点至少约20℃,从而能够适当的浸渍。加热可通过多种方式完成,包括接触加热、辐射气体加热、红外线加热、对流或强制对流空气加热、感应加热、微波加热或它们的组合。
可通过静态方法或连续方法(也称为动态方法)来施加浸渍压,出于速度原因,连续方法是优选的。浸渍方法的实例无限制地包括真空模塑、模内涂覆、横向模挤出、拉挤、线材涂覆型方法、层压、烫印、隔膜成型或加压模塑,层压是优选的。在层压过程中,通过加热区中相对的受压辊或带,将热和压力施加到纤维材料、基质树脂组合物和表面树脂组合物,然后优选地通过加压装置在冷却区连续施加压力,以完成固结并将浸渍的纤维材料冷却。层压技术的实例包括但不限于压延、平台层压和双带压力机层压。当将层压用作浸渍方法时,优选使用双带压力机进行层压。
可采用常规方法将基质树脂组合物和表面树脂组合物施用到纤维材料,这些方法例如有粉末涂覆、膜层压、挤出涂覆或其两种或更多种方法的组合,前提条件是表面树脂组合物施用到复合结构表面的至少一部分,所述表面暴露于复合结构的环境。
在粉末涂覆过程中,将通过常规碾磨方法获得的聚合物粉末施用到纤维材料。可通过散射、喷洒、喷涂、热喷涂或火焰喷涂、或流化床涂覆方法将粉末施用到纤维材料上。任选地,粉末涂覆方法还可包括对纤维材料上的粉末进行后烧结的步骤。将基质树脂组合物和表面树脂组合物施用到纤维材料,使得复合结构表面的至少一部分由表面树脂组合物制成。随后,在粉末涂覆的纤维材料上进行热压,并可任选地在加压区之外的粉末涂覆的纤维材料进行预热。
在膜层压过程中,将一个或多个由基质树脂组合物制成的膜和一个或多个由表面树脂组合物制成的膜通过层叠施用到纤维材料,这些膜事先通过本领域已知的常规挤出方法获得,例如吹塑膜挤出、流延膜挤出和流延片材挤出。随后,对组件进行热压操作,所述组件包含一个或多个由基质树脂组合物制成的膜和一个或多个由表面树脂组合物制成的膜和一种或多种纤维材料。在所得复合结构中,膜熔化并渗入整个纤维材料中,在纤维材料周围形成连续的聚合物统一体。
在挤出涂覆过程中,将由基质树脂组合物制成的粒料和/或颗粒以及由表面树脂组合物制成的粒料和/或颗粒通过一个或多个平模熔融并挤出,以便形成一个或多个熔帘,随后通过铺放所述一个或多个熔帘而将熔帘施用到纤维材料上。随后,在包含基质树脂组合物、表面树脂组合物和一种或多种纤维材料的组件上进行热压。
根据最终应用,通过步骤i)获得的复合结构可成型为期望的几何形状或构型,或以片材形式使用。制备根据本发明的复合结构的方法还可包括使复合结构成型的步骤ii),所述步骤在浸渍步骤i)之后发生。使通过步骤i)获得的复合结构成型的步骤可通过压塑、烫印、或者利用热和/或压力的任何技术来完成。优选地,使用液压式压型机来施加压力。在压塑或烫印过程中,将复合结构预热到表面树脂组合物的熔融温度之上的温度,然后转移到形成或成型装置例如模塑压机中,其包括具有腔体的模具,而腔体具有最终期望的几何结构的形状,借此将第一组件成型为期望的构型,然后在冷却到表面聚酰胺树脂组合物的熔融温度之下的温度并优选地冷却到基质树脂组合物的熔融温度之下后从压机或模具中取出。
根据本发明所述的复合结构提供抵抗长期风化暴露的不利效应的良好稳定性和高温暴露下的良好机械特性保持性,因此可用于多种应用中,如用作机动车组件、卡车组件、商用飞机组件、航空航天器组件、轨道组件、家用电器组件、计算机硬件组件、手持式装置组件、娱乐和体育设施组件、机器结构组件,建筑结构组件、光电设备结构组件、风能结构组件(例如桨叶)或机械装置结构组件。
机动车应用的实例无限制地包括座椅组件和座椅框架、引擎盖支架、引擎架、悬吊臂和架、备胎支架、底盘加强件、车身底板、前端模块、转向管柱框架、仪表板、车门系统、车身板件(例如水平车身板件和门板件)、后挡板、硬顶轿车框架结构、敞篷车顶框架结构、顶板结构、引擎盖、传动装置和传能组件的外壳、油底壳、气囊外壳罐、机动车内部撞击结构、引擎支架、交叉车横梁、缓冲梁、行人安全横梁、隔火墙、后置物板、交叉车舱壁、压力容器(例如制冷剂瓶和灭火器以及卡车压缩空气制动系统容器)、混合内燃机/电动车电池托架、机动车悬吊横臂和控制臂、悬吊平衡杆接杆、叶片弹簧、车轮、休旅车和摩托车摆臂、挡泥板、车顶框架以及油箱盖板。
家用电器的实例无限制地包括洗衣机、烘干机、冰箱、空调、暖气和便携式电力发电机外壳。娱乐和体育设施的实例无限制地包括单线滚轴溜冰鞋组件、棒球棒、曲棍球棍、雪橇和滑雪板固定器、背包背衬和框架以及自行车架。机器结构组件的实例包括电气/电子部件,例如手持式电子装置外壳、计算机外壳。
实施例
以下材料用于制备根据本发明的和比较实施例的复合结构。
材料
以下材料构成实施例和比较实施例中所用的组合物。
聚酯1:以商品名PET 1101由Invista(Kansas,USA)提供的聚(对苯二甲酸乙二醇酯)。
聚酯2:熔体流动速率(MFR)为42.5至53.6g/0min(根据ISO1133测得,250℃,2.16kg)的聚(对苯二甲酸1,4-丁二醇酯)。此类产品可以商品名从E.I.DuPont de Nemours and Company(Wilmington,Delaware,USA)商购获得。
紫外线稳定剂b1:以商品名360由Ciba Specialty Chemicals(Tarrytown,New York,USA)提供的2,2′-亚甲基二(6-(2H-苯并三唑-2-基)-4-1,1,3,3-四甲基丁基)-苯酚(CAS Nb 103597-45-1)。
紫外线稳定剂b2:以商品名1577由Ciba Specialty Chemicals(Tarrytown,New York,USA)提供的2-(4,6-二苯基-1,3,5-三嗪-2-基)-5-己氧基-苯酚(CAS Nb 147315-50-2)。
紫外线稳定剂b3:以商品名622由Ciba Specialty Chemicals(Tarrytown,New York,USA)提供的N-(2-羟乙基)-2,2,6,6-四甲基-4-哌啶醇与琥珀酸的低聚物,所述低聚物具有3100-4000的分子量Mn(CAS号:65447-77-0)。
表1中所列的所有组合物1-8包含其它添加剂:0.4重量%的基于二亚磷酸酯的抗氧化剂,0.4重量%的基于酚醛树脂的抗氧化剂,0.8重量%的环氧树脂,和0.4重量%的磷酸酯盐,其中所述添加剂为:
基于二亚磷酸酯的抗氧化剂:以商品名626由G.E SpecialtyChemicals(Parkersburg,West Virginia,USA)提供的双(2.4-二叔丁基苯基)季戊四醇二亚磷酸酯。
基于酚醛树脂的抗氧化剂:以商品名1010由Ciba SpecialtyChemicals(Tarrytown,New York,USA)提供。
环氧树脂:以商品名EponTM 1009由Hexion Speciality Chemicals(Columbus,Ohio,USA)提供的环氧氯丙烷/四酚基乙烷环氧树脂,其具有4348-5128mmol/kg的环氧基含量(ASTM D1652)。
磷酸盐:以商品名N 13-50由Budenheim(Germany)提供的磷酸钠。
组合物的制备。通过如下制备表1中所列的组合物:在约260℃下运转的40mm双螺杆捏合机中,采用约300rpm的螺杆转速,显示约267℃的熔融温度,且手动测定约281℃的熔融温度,熔融共混表1中所示的成分。从挤出机中出料后,将组合物冷却并粒化。通过微粉化研磨如此获得的粒料以致形成粉末组合物,将所述粉末组合物筛分至D90值小于200μm的颗粒。
复合结构的制备。将表1中所列的粉末组合物手动分散到3层织造连续玻璃纤维片上(E-玻璃纤维,其具有17微米直径,0.4%的基于硅烷的胶料,和1200g/km的标称粗纱特克斯,所述玻璃纤维已被织造成2/2斜纹(平衡编织)具有600g/m的面积重量),以形成组件,所述组件包含6.4g粉末组合物/尺寸为16cm×16cm的玻璃纤维片/6.4g粉末组合物/尺寸为16cm×16cm的玻璃纤维片/6.4g粉末组合物/尺寸为16cm×16cm的玻璃纤维片/6.4g粉末组合物。根据下列条件,经由压塑(Dr.Collin压机),由如此获得的组件制备表2中所列的复合结构C1-C7和E1:1)将组合件在315℃和110巴下预热25秒,2)将这些条件再保持40秒时间,3)在110巴和40℃下冷却组合件60秒,以及4)打开压机以便回收如此获得的复合结构。表2中所列的复合结构具有约1.5mm的总体厚度。
Claims (15)
1.复合结构,其具有表面并包含纤维材料,所述表面的至少一部分由表面树脂组合物制成,所述纤维材料选自非织造结构、纺织品、纤维絮以及它们的组合,所述纤维材料用基质树脂组合物浸渍,其中所述表面树脂组合物选自聚酯组合物,所述聚酯组合物包含:
a)一种或多种聚酯树脂,和
b)0.3重量%或约0.3重量%至3重量%或约3重量%的至少三种紫外线稳定剂;其中所述至少三种紫外线稳定剂中的一种为
b1),另一种为b2),并且另一种为b3),所述重量百分比是基于所述聚酯组合物的总重量计的。
2.根据权利要求1所述的复合结构,其中所述基质树脂组合物与所述表面树脂组合物相同或不同并且独立地选自聚酯组合物,所述聚酯组合物包含:a)一种或多种聚酯树脂,和b)0.3重量%或约0.3重量%至3重量%或约3重量%的至少三种紫外线稳定剂;其中所述至少三种紫外线稳定剂中的一种为b1),另一种为b2),并且另一种为b3),所述重量百分比是基于所述聚酯组合物的总重量计的。
3.根据前述权利要求中任一项所述的复合结构,其中所述纤维材料由玻璃纤维、碳纤维、芳族聚酰胺纤维、天然纤维或它们的混合物组成。
4.根据前述权利要求中任一项所述的复合结构,其中所述一种或多种聚酯树脂独立地选自聚(对苯二甲酸乙二醇酯)(PET)、聚(对苯二甲酸丙二醇酯)(PTT)、聚(对苯二甲酸1,4-丁二醇酯)(PBT)、聚(2,6-萘二甲酸乙二醇酯)(PEN)和聚(对苯二甲酸1,4-环己基二甲醇酯)(PCT)以及它们的共聚物和共混物。
5.根据前述权利要求中任一项所述的复合结构,其中所述至少三种紫外线稳定剂选自b1)一种或多种苯并三唑衍生物;b2)一种或多种三嗪衍生物和/或嘧啶衍生物;和b3)一种或多种受阻胺衍生物。
6.根据前述权利要求中任一项所述的复合结构,其中b1)为以0.01重量%或约0.01重量%至2.98重量%或约2.98重量%的量存在的一种或多种苯并三唑衍生物,b2)为以0.01重量%或约0.01重量%至2.98重量%或约2.98重量%的量存在的一种或多种三嗪衍生物和/或嘧啶衍生物,并且b3)为以0.01重量%至2.98重量%或约2.98重量%的量存在的一种或多种受阻胺衍生物,
前提条件是b1)+b2)+b3)之和介于0.3重量%或约0.3重量%和3重量%或约3重量%之间,
所述重量百分比是基于所述聚酯组合物的总重量计的。
9.根据前述权利要求中任一项所述的复合结构,其中b2)为具有下式(D)的一种或多种三嗪衍生物和/或嘧啶衍生物以及它们的组合:
其中Y为N(三嗪衍生物)或CH(嘧啶衍生物);并且其中R4、R5、R6、R7、R8、R9、R10和R11各自独立地选自氢、烷基、环烷基、卤素、卤代烷基、烷氧基、亚烷基、芳基、烷基-芳基、或它们的组合。
10.根据权利要求9所述的复合结构,其中b2)为2-(4,6-二苯基-1,3,5-三嗪-2-基)-5-己氧基-苯酚或具有下式(F):
12.根据权利要求11所述的复合结构,其中b3)为N-(2-羟乙基)-2,2,6,6-四甲基-4-哌啶醇与琥珀酸的低聚物。
14.根据前述权利要求中任一项所述的复合结构,其形式为机动车组件、卡车组件、商用飞机组件、航空航天器组件、轨道组件、家用电器组件、计算机硬件组件、手持式装置组件、娱乐和体育设施组件、机器结构组件、建筑结构组件、光电设备结构组件、风能结构组件。
15.制备具有表面的复合结构的方法,所述方法包括以下步骤:
用权利要求1、权利要求2或权利要求4至13中任一项所述的基质树脂组合物浸渍权利要求1或3中所述的纤维材料,其中所述复合结构表面的至少一部分由权利要求1、权利要求2或权利要求4至13中任一项所述的表面树脂组合物制成。
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- 2011-03-11 CA CA2799308A patent/CA2799308A1/en not_active Abandoned
- 2011-03-11 JP JP2013515331A patent/JP2013534875A/ja not_active Withdrawn
- 2011-03-11 WO PCT/US2011/028091 patent/WO2011159377A1/en active Application Filing
- 2011-03-11 BR BR112012031848A patent/BR112012031848A2/pt not_active IP Right Cessation
- 2011-03-11 KR KR1020137000793A patent/KR20130100954A/ko not_active Application Discontinuation
- 2011-03-11 EP EP11712717.5A patent/EP2580053A1/en not_active Withdrawn
- 2011-03-18 US US13/051,263 patent/US20110306257A1/en not_active Abandoned
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CN104302706A (zh) * | 2011-12-26 | 2015-01-21 | 株式会社日立制作所 | 复合材料 |
CN104302706B (zh) * | 2011-12-26 | 2017-02-15 | 株式会社日立制作所 | 复合材料 |
CN113201085A (zh) * | 2016-06-15 | 2021-08-03 | 住友化学株式会社 | 聚合物、成型体、发泡体、树脂组合物及聚合物的制造方法 |
US11773266B2 (en) | 2016-06-15 | 2023-10-03 | Sumitomo Chemical Company, Limited | Polymer, molded body, foam, resin composition, and production method for polymer |
WO2022111007A1 (zh) * | 2020-11-30 | 2022-06-02 | 金发科技股份有限公司 | 一种聚碳酸酯/pct聚酯组合物及其制备方法和应用 |
Also Published As
Publication number | Publication date |
---|---|
JP2013534875A (ja) | 2013-09-09 |
WO2011159377A1 (en) | 2011-12-22 |
KR20130100954A (ko) | 2013-09-12 |
US20110306257A1 (en) | 2011-12-15 |
CA2799308A1 (en) | 2011-12-22 |
EP2580053A1 (en) | 2013-04-17 |
BR112012031848A2 (pt) | 2017-07-04 |
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