CN108026370B - 交联性聚芳硫醚组合物 - Google Patents
交联性聚芳硫醚组合物 Download PDFInfo
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- CN108026370B CN108026370B CN201680030895.0A CN201680030895A CN108026370B CN 108026370 B CN108026370 B CN 108026370B CN 201680030895 A CN201680030895 A CN 201680030895A CN 108026370 B CN108026370 B CN 108026370B
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- polymer composition
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- shaped product
- polyarylene sulfide
- impact modifier
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- 239000004609 Impact Modifier Substances 0.000 claims abstract description 51
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- 238000002156 mixing Methods 0.000 claims description 12
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Abstract
提供可以在各种不同条件下展示出优异的强度和柔性的聚合物组合物。更特别地,聚合物组合物包含聚芳硫醚、环氧官能聚合冲击改性剂和包括金属羧酸盐的交联体系。在某些情况下,交联体系也可以使用交联剂,所述交联剂是“多官能的”达到这种程度以致其包含至少两个反应性官能团。
Description
相关申请
本申请要求于2015年12月11日提交的美国临时申请序列号62/266,210的优先权,其全部内容通过引用并入本文。
背景技术
聚苯硫醚(“PPS”)是具有出色的耐机械、热和化学性质的高性能热塑性树脂。不幸的是,PPS趋向于相对较脆,这会限制其在要求高水平的冲击强度的应用中的使用。为了帮助补偿其脆性,PPS通常与冲击改性剂如弹性体共混。然而,冲击改性剂与PPS固有地不相容,这会使得难以实现具有良好性质的共混物。虽然已经将相容剂用于帮助改进这些性质,但是它们在需要高温或低温的应用中通常不起作用。因此,目前需要在宽范围的不同温度具有改进的性质的PPS组合物。
发明内容
根据本发明的一个实施方案,公开了交联性聚合物组合物,所述组合物包含聚芳硫醚,每100份的聚芳硫醚约0.5至约50份的冲击改性剂,和每100份的聚芳硫醚约0.1至约15份的交联体系。冲击改性剂包括环氧官能聚合物和交联体系包括金属羧酸盐。
根据另一个本发明实施方案,公开了用于形成聚合物产物的方法,其包括熔融共混聚合物组合物,所述组合物包含聚芳硫醚、冲击改性剂和交联体系。交联体系包括金属羧酸盐和冲击改性剂包括环氧官能聚合物。
下文更详细地阐述本发明的其它特征和方面。
附图的简要说明
参考以下附图可更好地理解本公开:
图1是形成片材的方法的侧视图,所述片材可包含本发明的聚合物组合物;
图2是可用于本发明的一个实施例的热成形方法的侧视图;
图3是食物托盘形式的可由本发明的聚合物组合物形成的成型零件的一个实施方案的透视图;
图4是如本文所公开的用于形成聚合物组合物的方法的示意图;
图5是实施例2的样品6的SEM图;
图6是实施例2的样品8的SEM图;和
图7是实施例2的样品11的SEM图。
详细说明
本领域普通技术人员将理解的是,本讨论仅是对示例性实施方案的描述,而并非旨在限制本公开的更广泛的方面。
一般而言,本发明涉及在各种不同条件下能够展示出优异的强度和柔性的交联聚合物产物。更特别地,交联产物由含有聚芳硫醚、环氧官能聚合物冲击改性剂和包括金属羧酸盐的交联体系的交联性聚合物组合物形成。不受理论限制,据信羧酸盐中的金属原子可以充当接受来自位于冲击改性剂的环氧官能团中的氧原子的电子的路易斯酸。一旦与羧酸盐反应,环氧官能团变得活化,并且可以经由亲核取代容易地在三元环中的任一个碳原子上受到攻击。这导致冲击改性剂的链之间的交联。在某些情况下,交联体系还可以使用另外的交联剂,所述交联剂是“多官能的”达到这种程度以致其包含至少两个反应性官能团。这种多官能交联剂可用作弱亲核试剂,其可以与冲击改性剂上的活化环氧官能团反应。这种分子的多官能性质使其能够桥接两个环氧基团,有效地起到固化剂的作用。
通过使用这种独特的交联体系,本发明人已经发现聚芳硫醚和冲击改性剂的相容性和分布可以得到显著提高。例如,冲击改性剂能够以纳米级尺寸的离散域的形式分散在聚合物组合物内。例如,域可具有约1至约1000纳米,在一些实施方案中约5至约800纳米,在一些实施方案中约10至约500纳米的平均横截面尺寸。该域可具有各种不同的形状,例如椭圆形,球形,圆柱形,板状,管状等。这种改进的分散体可以导致更好的机械性质,或者允许在更低量的冲击改性剂下实现等价的机械性质。例如,交联的聚合物产物可以展示出约10kJ/m2或更高,在一些实施方案中约20至约150kJ/m2,并且在一些实施方案中约30至约100kJ/m2的缺口却贝冲击强度,根据ISO测试号179-1:2010(技术上等同于ASTM D256,方法B),在23℃的温度测定。有利地,聚合物产物具有高程度的耐热性,因此可以在高温和低温均展示出良好的性质。例如,聚合物产物可以展示出约2kJ/m2或更高,在一些实施方案中约5至约100kJ/m2,并且在一些实施方案中约8至约50kJ/m2的缺口却贝冲击强度,根据ISO测试号179-1:2010(技术上等同于ASTM D256,方法B)在-30℃的温度测定。
交联的聚合物产物还可展示出非常好的拉伸特性。例如,聚合物组合物可以展示出约40%或更多,在一些实施方案中约50%或更多,并且在一些实施方案中约60%至约100%的断裂拉伸应变;约3,000MPa或更低,在一些实施方案中约2,500MPa或更低,并且在一些实施方案中约100至约2,000MPa的拉伸模量;和/或约25MPa或更多,在一些实施方案中约30MPa或更多,并且在一些实施方案中约35至约100MPa的拉伸断裂应力。这种拉伸性质可根据ISO测试号527-1,2:2012以5mm/min的测试速度(技术上等同于ASTM D638),在23℃的温度下测定。
现在将更详细地讨论本发明的各种实施例。
I.交联性聚合物组合物
A.聚芳硫醚
聚芳硫醚通常构成聚合物组合物的约40wt.%至约95wt.%,在一些实施方案中约50wt.%至约90wt.%,并且在一些实施方案中约60wt.%至约80wt.%。该组合物中使用的一种或多种聚芳硫醚通常具有以下式的重复单元:
-[(Ar1)n-X]m-[(Ar2)i-Y]j-[(Ar3)k-Z]l-[(Ar4)o-W]p-
其中,
Ar1、Ar2、Ar3和Ar4独立地为6至18个碳原子的亚芳基单元;
W,X,Y和Z独立地为选自以下的二价连接基团:–SO2–,–S–,–SO–,–CO–,–O–,–C(O)O–或1-6个碳原子的亚烷基或烷叉基,其中至少一个连接基团为-S-;和
n,m,i,j,k,l,o和p独立地为0、1、2、3或4,条件是它们的总和不小于2。
亚芳基单元Ar1、Ar2、Ar3和Ar4可以被选择性地取代或未取代。有利的亚芳基单元是亚苯基,亚联苯基,亚萘基,蒽和菲。聚芳硫醚通常包含大于约30摩尔%,大于约50摩尔%或大于约70摩尔%的亚芳基硫醚(-S-)单元。例如,聚芳硫醚可包含至少85摩尔%的直接连接到两个芳环上的硫醚键。在一个具体的实施方案中,聚芳硫醚是聚苯硫醚,在本文中定义为含有亚苯硫醚结构-(C6H4-S)n-(其中n是1或更多的整数)作为其组分。
可以用于制造聚芳硫醚的合成技术通常在本领域中是已知的。举例来说,用于生产聚芳硫醚的方法可以包括使提供氢硫离子的材料(例如碱金属硫化物)与二卤代芳族化合物在有机酰胺溶剂中反应。碱金属硫化物可以是例如硫化锂,硫化钠,硫化钾,硫化铷,硫化铯或其混合物。当碱金属硫化物是水合物或含水混合物时,碱金属硫化物可以在聚合反应之前根据脱水操作进行处理。碱金属硫化物也可以原位生成。另外,可以在反应中包含少量的碱金属氢氧化物以除去或反应杂质(例如,将这些杂质变成无害的材料),例如碱金属多硫化物或碱金属硫代硫酸盐,其可以与碱金属硫化物以非常少的量存在。
二卤代芳族化合物可以是但不限于邻二卤苯,间二卤苯,对二卤苯,二卤甲苯,二卤萘,甲氧基二卤苯,二卤联苯,二卤苯甲酸,二卤二苯基醚,二卤二苯基砜,二卤二苯基亚砜或二卤二苯基酮。二卤代芳族化合物可以单独使用或以其任何组合使用。具体的示例性二卤代芳族化合物可以包括但不限于对二氯苯;间二氯苯;邻二氯苯;2,5-二氯甲苯;1,4-二溴苯;1,4-二氯萘;1-甲氧基-2,5-二氯苯;4,4'-二氯联苯;3,5-二氯苯甲酸;4,4'-二氯二苯基醚;4,4'-二氯二苯基砜;4,4'-二氯二苯基亚砜;和4,4'-二氯二苯基酮。卤素原子可以是氟,氯,溴或碘,同一种二卤代芳族化合物中的两个卤素原子彼此可以相同或不同。在一个实施方案中,将邻二氯苯、间二氯苯、对二氯苯或其两种或更多种化合物的混合物用作二卤代芳族化合物。如本领域已知的,还可能将单卤代化合物(不需要是芳族化合物)与二卤代芳族化合物组合,从而形成聚芳硫醚的端基或调节聚合反应和/或聚芳硫醚的分子量。
一种或多种聚芳硫醚可以是均聚物或共聚物。例如,二卤代芳族化合物的选择性组合可以导致含有不少于两个不同单元的聚芳硫醚共聚物。例如,当对二氯苯与间二氯苯或4,4'-二氯二苯基砜组合使用时,可以形成含有以下的聚芳硫醚共聚物:
具有下式的结构的链段:
和具有下式的结构的链段:
或具有下式的结构的链段:
一种或多种聚芳硫醚可以是线型的,半线型的,支化的或交联的。线型聚芳硫醚通常含有80mol%或更多的重复单元-(Ar-S)-。这样的线型聚合物还可以包括少量的支化单元或交联单元,但支化或交联单元的量通常小于聚芳硫醚的全部单体单元的约1mol%。线型聚芳硫醚聚合物可以是含有上述重复单元的无规共聚物或嵌段共聚物。半线型聚芳硫醚同样可具有交联结构或分支结构,其将少量的一种或多种具有三个或更多个反应性官能团的单体引入聚合物中。举例来说,用于形成半线型聚芳硫醚的单体组分可以包括一定量的每分子具有两个或更多个卤素取代基的多卤代芳族化合物,其可以用于制备支化聚合物。这样的单体可以由式R'Xn表示,其中每个X选自氯、溴和碘,n是3至6的整数,并且R'是化合价n的多价芳族基团,其可以具有至多约4个甲基取代基,R'中的碳原子总数在6至约16的范围内。可以用于形成半线型聚芳硫醚的每个分子具有多于两个卤素取代的一些多卤代芳族化合物的实例包括1,2,3-三氯苯,1,2,4-三氯苯,1,3-二氯-5-溴苯,1,2,4-三碘苯,1,2,3,5-四溴苯,六氯苯,1,3,5-三氯-2,4,6-三甲基苯,2,2',4,4'-四氯联苯,2,2',5,5'-四碘联苯,2,2',6,6'-四溴-3,3',5,5'-四甲基联苯,1,2,3,4-四氯萘,1,2,4-三溴-6-甲基萘等及其混合物。
如果需要,聚芳硫醚可以是官能化的。例如,可以使含有反应性官能团(例如羧基,羟基,胺等)的二硫化物化合物与聚芳硫醚反应。聚芳硫醚的官能化可以进一步提供用于冲击改性剂和聚芳硫醚之间键合的位点,其可以改进冲击改性剂在整个聚芳硫醚中的分布并防止相分离。二硫化物化合物可在熔融加工期间与聚芳硫醚发生断链反应以降低其总熔体粘度。当使用时,二硫化物化合物通常构成聚合物组合物的约0.01wt.%至约3wt.%,在一些实施方案中约0.02wt.%至约1wt.%,并且在一些实施方案中约0.05wt.%至约0.5wt.%。聚芳硫醚的量与二硫化物化合物的量的比例同样可为约1000:1至约10:1,约500:1至约20:1,或约400:1至约30:1。合适的二硫化物化合物通常是具有下式的那些:
R3–S–S–R4
其中R3和R4可相同或不同,并且是独立地包含1至约20个碳的烃基。例如,R3和R4可以是烷基,环烷基,芳基或杂环基。在某些实施方案中,R3和R4通常是非反应性官能团,例如苯基,萘基,乙基,甲基,丙基等。这种化合物的实例包括二苯基二硫醚,萘基二硫醚,二甲基二硫醚,二乙基二硫醚和二丙基二硫醚。R3和R4还可包括在二硫化物化合物的一个或多个末端处的反应性官能团。例如,R3和R4中的至少一个可包括末端羧基,羟基,取代或未取代的氨基,硝基等。化合物的实例可以包括但不限于2,2'-二氨基二苯基硫醚,3,3'-二氨基二苯基硫醚,4,4'-二氨基二苯基硫醚,二苄基硫醚,二硫代水杨酸(或2,2'-二硫代苯甲酸),二硫代甘醇酸,α,α'-二硫代二乳酸,β,β'-二硫代二乳酸,3,3'-二硫代二吡啶,4,4'-二硫代吗啉,2,2'-二硫代双(苯并噻唑),2,2'-二硫代双(苯并咪唑),2,2'-二硫代双(苯并恶唑),2-(4'-吗啉基二硫代)苯并噻唑等,及其混合物。
在一个实施方案中,聚芳硫醚可以是未经处理的聚芳硫醚。在另一个实施方案中,聚芳硫醚可以是经处理的聚芳硫醚。例如,聚芳硫醚可在氧气氛中和/或在交联剂如过氧化物存在下加热。通过使用经处理的聚芳硫醚聚合物,可以获得聚芳硫醚聚合物组合物的颜色变化。例如,可以通过调整未经处理的聚芳硫醚与经处理的聚芳硫醚的比例来改变组合物的颜色。颜色变化也可以通过代替经处理的聚芳硫醚或除了经处理的聚芳硫醚之外使用固化或支化的聚芳硫醚来实现。
B.冲击改性剂
冲击改性剂通常构成每100份的聚芳硫醚5至约50份,在一些实施方案中约10至约45份,并且在一些实施方案中约20至约40份。例如,冲击改性剂可构成聚合物组合物的约1wt.%至约40wt.%,在一些实施方案中约5wt.%至约35wt.%,并且在一些实施方案中约15wt.%至约30wt.%。
如上所述,冲击改性剂包括环氧官能聚合物。通常,这种聚合物被认为是“聚环氧化物”达到这种程度以致其包含每个分子含有至少两个环氧乙烷环。聚环氧化物可以是含有末端环氧基、骨架环氧乙烷单元和/或侧基环氧基的线型或支化的均聚物或共聚物(例如无规,接枝,嵌段等)。用于形成这种聚环氧化物的单体可以变化。在一个具体的实施方案中,例如,冲击改性剂含有至少一种环氧官能的(甲基)丙烯酸系单体组分。术语“(甲基)丙烯酸系”包括丙烯酸和甲基丙烯酸单体,以及其盐或酯,如丙烯酸酯和甲基丙烯酸酯单体。合适的环氧官能的(甲基)丙烯酸系单体可包括但不限于含1,2-环氧基团的那些,如丙烯酸缩水甘油酯和甲基丙烯酸缩水甘油酯。其它合适的环氧官能单体包括烯丙基缩水甘油醚,乙基丙烯酸缩水甘油酯和衣康酸缩水甘油酯。
当然,该共聚物也可含有本领域已知的其它单体单元。例如,另一种合适的单体可包括不是环氧官能的(甲基)丙烯酸系单体。这种(甲基)丙烯酸系单体的实例可包括丙烯酸甲酯,丙烯酸乙酯,丙烯酸正丙酯,丙烯酸异丙酯,丙烯酸正丁酯,丙烯酸仲丁酯,丙烯酸异丁酯,丙烯酸叔丁酯,丙烯酸正戊酯丙烯酸异戊酯,丙烯酸异冰片酯,丙烯酸正己酯,丙烯酸2-乙基丁酯,丙烯酸2-乙基己酯,丙烯酸正辛酯,丙烯酸正癸酯,丙烯酸甲基环己酯,丙烯酸环戊酯,丙烯酸环己酯,甲基丙烯酸甲酯,甲基丙烯酸乙酯,甲基丙烯酸2-羟乙酯,甲基丙烯酸正丙酯,甲基丙烯酸正丁酯,甲基丙烯酸异丙酯,甲基丙烯酸异丁酯,甲基丙烯酸正戊酯,甲基丙烯酸正己酯,甲基丙烯酸异戊酯,甲基丙烯酸仲丁酯,甲基丙烯酸叔丁酯,甲基丙烯酸2-乙基丁酯,甲基丙烯酸甲基环己酯,甲基丙烯酸肉桂酯,甲基丙烯酸巴豆基酯,甲基丙烯酸环己酯,甲基丙烯酸环戊酯,甲基丙烯酸2-乙氧基乙酯,甲基丙烯酸异冰片酯等以及它们的组合。在一个具体的实施方案中,例如,该共聚物可为由环氧官能的(甲基)丙烯酸系单体组分、α-烯烃单体组分和非环氧官能的(甲基)丙烯酸系单体组分形成的三元共聚物。该共聚物可以是例如具有以下结构的聚(乙烯-共-丙烯酸丁酯-共-甲基丙烯酸缩水甘油酯):
其中,x、y和z为1或更大。
可选择一种或多种单体组分的相对部分以实现环氧反应性和熔体流速之间的平衡。更具体地,高的环氧单体含量可以导致与基质聚合物的良好反应性,但是太高的含量可降低熔体流速,使得共聚物不利地影响聚合物共混物的熔体强度。因此,在大多数实施方案中,一种或多种环氧官能的(甲基)丙烯酸单体构成共聚物的约1wt.%至约20wt.%,在一些实施方案中约2wt.%至约15wt.%,一些实施方案约3wt.%至约10wt.%。(一种或多种)α-烯烃单体同样可构成共聚物的约55wt.%至约95wt.%,在一些实施方案中约60wt.%至约90wt.%,并且在一些实施方案中约65wt.%至约85wt.%。当使用时,其它单体组分(例如非环氧官能的(甲基)丙烯酸系单体)可构成共聚物的约5wt.%至约35wt.%,在一些实施方案中约8wt.%至约30wt.%,并且在一些实施方案中约10wt.%至约25wt.%。结果熔体流速通常为约1至约30克/10分钟(“g/10min”),在一些实施方案中约2至约20g/10min,并且在一些实施方案中约3至约15g/10min,根据ASTM D1238-13在2.16kg的负荷和190℃的温度下测定。
可用于本发明的合适的环氧官能化共聚物的一个实例可从Arkema以商品名AX8840商购获得。例如,AX8840具有5g/10min的熔体流速,并且是乙烯和甲基丙烯酸缩水甘油酯(单体含量为8wt.%)的无规共聚物。另一种合适的共聚物可从DuPont以商品名PTW商购获得,其是乙烯、丙烯酸丁酯和甲基丙烯酸缩水甘油酯的三元共聚物,其熔体流速为12g/10min,甲基丙烯酸缩水甘油酯单体含量为4wt.%至5wt.%。
如果需要,还可以将另外的冲击改性剂与环氧官能的冲击改性剂组合使用。例如,另外的冲击改性剂可包括嵌段共聚物,其中至少一个相由在室温下是硬的但在加热时是流体的材料制成,而另一个相是在室温下为橡胶状的较软的材料。例如,嵌段共聚物可具有A-B或A-B-A嵌段共聚物重复结构,其中A代表硬链段,B代表软链段。具有A-B重复结构的冲击改性剂的非限制性实例包括聚酰胺/聚醚,聚砜/聚二甲基硅氧烷,聚氨酯/聚酯,聚氨酯/聚醚,聚酯/聚醚,聚碳酸酯/聚二甲基硅氧烷和聚碳酸酯/聚醚。三嵌段共聚物同样可包含作为硬链段的聚苯乙烯和作为软链段的聚丁二烯、聚异戊二烯或聚乙烯-共-丁烯。类似地,可使用苯乙烯丁二烯重复共聚物以及聚苯乙烯/聚异戊二烯重复聚合物。在一个具体的实施方案中,嵌段共聚物可具有聚酰胺和聚醚的交替嵌段。这样的材料是可商购的,例如以商品名PEBAXTM从Atofina商购获得。聚酰胺嵌段可来源于二酸组分和二胺组分的共聚物,或可通过环状内酰胺的均聚来制备。聚醚嵌段可来源于环醚如环氧乙烷、环氧丙烷和四氢呋喃的均聚物或共聚物。
C.交联体系
可包含金属羧酸盐和其它任选交联剂的交联体系通常构成每100份的聚芳硫醚约0.1至约15份,在一些实施方案中约0.2至约10份,并且在一些实施方案中约0.5至约5份。例如,交联体系构成聚合物组合物的约0.05wt.%至约15wt.%,在一些实施方案中约0.1wt.%至约10wt.%,并且在一些实施方案中约0.2wt.%至约5wt.%。
i.金属羧酸盐
如上所述,交联体系包括金属羧酸盐。不受理论限制,据信羧酸盐中的金属原子可以充当接受来自位于冲击改性剂的环氧官能团中的氧原子的电子的路易斯酸。一旦与羧酸盐反应,环氧官能团变得活化,并且可以经由亲核取代容易地在三元环中的任一个碳原子上受到攻击,由此导致冲击改性剂链之间的交联。
金属羧酸盐通常是脂肪酸的金属盐。盐中使用的金属阳离子可以变化,但通常是二价金属,如钙,镁,铅,钡,锶,锌,铁,镉,镍,铜,锡等及其混合物。锌是特别适合的。脂肪酸通常可为碳链长度为约8至22个碳原子且在一些实施方案中约10至约18个碳原子的任何饱和或不饱和的酸。如果需要,酸可被取代。合适的脂肪酸可包括例如月桂酸,肉豆蔻酸,山酸,油酸,棕榈酸,硬脂酸,蓖麻油酸,癸酸,新癸酸,氢化牛油脂肪酸,羟基硬脂酸,氢化蓖麻油的脂肪酸,芥酸,椰子油脂肪酸等,以及它们的混合物。金属羧酸盐通常构成聚合物组合物的约0.05wt.%至约5wt.%,在一些实施方案中约0.1wt.%至约2wt.%,并且在一些实施方案中约0.2wt.%至约1wt.%。
ii.多官能交联剂
虽然不是必需要求,但交联体系还可使用交联剂,所述交联剂是“多官能的”达到这种程度以致其包含至少两个反应性官能团。这种多官能交联剂可作为弱亲核试剂,其可以与冲击改性剂上的活化环氧官能团反应。当使用时,这样的多官能交联剂通常构成交联体系的约50wt.%至约95wt.%,在一些实施方案中约60wt.%至约90wt.%,并且在一些实施方案中约70wt.%约85wt.%,而金属羧酸盐典型地构成交联体系的约5wt.%至约50wt.%,在一些实施方案中约10wt.%至约40wt.%,并且在一些实施方案约15wt.%至约30wt.%。例如,多官能交联剂可构成聚合物组合物的约0.1wt.%至约10wt.%,在一些实施方案中约0.2wt.%至约5wt.%,并且在一些实施方案中约0.5wt.%至约3wt.%。当然,在某些实施方案中,组合物通常可不含这样的多官能交联剂,使得交联体系完全由金属羧酸盐形成。
多官能交联剂通常包括通过键或非聚合(非重复)连接组分连接的两个或更多个反应性官能末端结构部分。作为举例,交联剂可以包括二环氧化物,多官能环氧化物,二异氰酸酯,多异氰酸酯,多元醇,水溶性碳二亚胺,二胺,二醇,二氨基烷烃,多官能羧酸,二酸卤等。多官能羧酸和胺是特别合适的。多官能羧酸交联剂的具体实例可包括但不限于间苯二甲酸,对苯二甲酸,邻苯二甲酸,1,2-二(对羧基苯基)乙烷,4,4'-二羧基二苯基醚,4,4'-二苯甲酸,1,4-或1,5-萘二甲酸,十氢萘二甲酸,降冰片烯二甲酸,二环辛烷二甲酸,1,4-环己烷二甲酸(顺式和反式两者),1,4-亚己基二甲酸,己二酸,壬二酸,二羧基十二碳酸,琥珀酸,马来酸,戊二酸,辛二酸,壬二酸和癸二酸。也可以使用相应的二羧酸衍生物,例如在醇基团中具有1至4个碳原子的羧酸二酯,羧酸酐或羧酸卤化物。在某些实施方案中,芳族二羧酸是特别合适的,例如间苯二甲酸或对苯二甲酸。
D.其它组分
组合物还可以包括本领域通常已知的一种或多种添加剂,例如填料(例如粒状填料,纤维等),着色剂(例如无机颜料),阻燃剂,成核剂,偶合剂,稳定剂(例如UV稳定剂,UV吸收剂,热稳定剂等),润滑剂,抗氧化剂,流动促进剂等以提高性质和/或可加工性。在一个实施方案中,例如,聚合物组合物可含有热稳定剂。举例来说,热稳定剂可以是亚磷酸酯稳定剂,如有机亚磷酸酯。例如,合适的亚磷酸酯稳定剂包括单亚磷酸酯和二亚磷酸酯,其中二亚磷酸酯具有抑制水分吸收和/或具有相对高的螺异构体含量的分子构型。例如,可选择具有大于90%,例如大于95%,例如大于98%的螺异构体含量的二亚磷酸酯稳定剂。这种二亚磷酸酯稳定剂的具体实例包括例如双(2,4-二枯基苯基)季戊四醇二亚磷酸酯,双(2,4-二叔丁基苯基)季戊四醇二亚磷酸酯,二硬脂基季戊四醇二亚磷酸酯,其混合物等。当使用时,热稳定剂通常构成组合物的约0.1wt.%至约3wt.%,并且在一些实施方案中约0.2wt.%至约2wt.%。
在其它实施方案中,也可使用无机填料(例如纤维填料,粒状填料等),例如量为组合物的约0.5wt.%至约50wt.%,在一些实施方案中约1wt.%至约45wt.%,并且在一些实施方案中约5wt.%至约40wt.%。合适的纤维填料可包括例如玻璃纤维。纤维直径可以取决于使用的纤维而变化,并且可以以短切或连续形式获得。例如,纤维可以具有小于约100μm,例如小于约50μm的直径。无机粒状填料也可以单独使用或与纤维填料组合使用。粒状填料的实例可包括例如含硼化合物(例如氮化硼,四硼酸钠,四硼酸钾,四硼酸钙等),碱土金属碳酸盐(例如碳酸钙镁),氧化物(例如氧化钛,氧化铝,氧化镁,氧化锌,三氧化锑等),硅酸盐(例如滑石,硅酸钠铝,硅酸钙,硅酸镁等),碱土金属的盐(例如碳酸钙,硫酸钙等)等。
粘土矿物可为特别合适的。这种粘土矿物的实例包括例如滑石(Mg3Si4O10(OH)2),埃洛石(Al2Si2O5(OH)4),高岭石(Al2Si2O5(OH)4),伊利石((K,H3O)(Al,Mg,Fe)2(Si,Al)4O10[(OH)2,(H2O)]),蒙脱石(Na,Ca)0.33(Al,Mg)2Si4O10(OH)2·nH2O),蛭石((MgFe,Al)3(Al,Si)4O10(OH)2·4H2O),坡缕石((Mg,Al)2Si4O10(OH)·4(H2O)),叶蜡石(Al2Si4O10(OH)2)等以及它们的组合。代替或除了粘土矿物之外,还可以使用仍然其它矿物填料。例如,也可使用其它合适的硅酸盐填料,如硅酸钙,硅酸铝,云母,硅藻土,硅灰石等。例如,云母可为用于本发明的特别合适的矿物。如本文所用,术语“云母”意指一般地包括这些物质中的任一种,例如白云母(KAl2(AlSi3)O10(OH)2),黑云母(K(Mg,Fe)3(AlSi3)O10(OH)2),金云母(KMg3(AlSi3)O10(OH)2),锂云母(K(Li,Al)2-3(AlSi3)O10(OH)2),海绿石(K,Na)(Al,Mg,Fe)2(Si,Al)4O10(OH)2)等,以及它们的组合。
II.交联反应
在本发明中可使用各种不同的技术来使聚芳硫醚和冲击改性剂在交联体系存在下反应。在一个实施方案中,例如,交联聚合物产物通过在足以引发所需反应的温度下熔融加工聚芳硫醚、冲击改性剂和交联体系而形成。例如,熔融加工可在约50℃至约500℃,在一些实施方案中约100℃至约400℃,在一些实施方案中约150℃至约350℃的温度下进行。
可将材料同时或依次提供至分散共混材料的熔融加工装置。可使用间歇和/或连续熔融加工技术。例如,可以使用混合机/捏合机、班伯里混合机、法雷尔连续混合机、单螺杆挤出机、双螺杆挤出机、辊磨机等来共混和熔融加工材料。一种特别合适的熔融加工装置是同向旋转双螺杆挤出机(例如Leistritz同向旋转完全啮合双螺杆挤出机)。这种挤出机可包括进料口和排出口,并提供高强度分布式和分散式混合。例如,可将组分进料至双螺杆挤出机的相同或不同的进料口并熔融共混以形成基本均匀的熔融混合物。在高剪切力/压力下可发生熔融共混以确保充分分散。例如,在熔融加工期间的表观剪切速率可在约100秒-1至约10,000秒-1,并且在一些实施方案中在约500秒-1至约1,500秒-1的范围内。当然,也可控制其它变量,例如与生产率成反比例的熔融加工期间的停留时间,以达到所需的均匀性程度。
如果需要,可以在熔融加工单元的混合区段内使用一个或多个分布式和/或分散式混合元件。合适的分布式混合器可包括例如Saxon,Dulmage,Cavity Transfer混合器等。同样,合适的分散式混合器可包括泡罩环,Leroy/Maddock,CRD混合器等。如本领域所公知的,可通过在桶中使用产生聚合物熔体的折叠和重新取向的销钉以在腐蚀性方面进一步提高混合,例如在Buss捏合机挤出机、腔穴传递式混合器和涡旋啮合销式混合机中使用的那些。还可控制螺杆的速度以改进组合物的特性。例如,在一个实施例中,螺杆速度可以是约400rpm或更低,例如在约200rpm和约350rpm之间,或者在约225rpm和约325rpm之间。在一个实施方案中,可以平衡配混条件以提供展示出改进的冲击和拉伸性质的聚合物组合物。例如,配混条件可以包括螺杆设计以提供温和、中等或腐蚀性的螺杆条件。例如,系统可以具有温和腐蚀性螺杆设计,其中螺杆在螺杆的下游半部上具有一个单一的熔融区段,目的在于缓和熔融和分布式熔体均化。中等腐蚀性螺杆设计可以在填料进料筒上游具有更强的熔融区段,其更多地集中在更强的分散式元件以实现均匀熔融。另外,它可以在下游具有另一个温和的混合区段来混合填料。该区段虽然比较弱,但仍然可以增加螺杆的剪切强度,以使其整体比温和腐蚀性设计更强。高度腐蚀性螺杆设计可以具有三者中最强的剪切强度。主要的熔融区段可以由长列的高度分散式捏合块组成。下游混合区段可以利用分布式和密集分散式元件的混合来实现所有类型填料的均匀分散。高度腐蚀性螺杆设计的剪切强度可以明显高于其它两种设计。在一个实施例中,系统可以包括具有相对缓和的螺杆速度(例如,在约200rpm和约300rpm之间)的中等至腐蚀性螺杆设计。
图4示意性地示出了可以用于形成聚合物组合物的方法。如图所示,组合物的组分可在熔融加工单元例如挤出机100中熔融捏合。在所示的实施方案中,挤出机100包括沿挤出机100的长度编号为21-30的十(10)个桶,如图所示。每个筒21-30可以包括可以独立操作的进料管线14、16,排出12,温度控制器等。可以使用通用螺杆设计来熔融加工聚合物组合物。举例来说,可使用双螺杆挤出机(例如Coperion同向旋转完全啮合双螺杆挤出机)将组合物熔融混合。如果需要,可将聚芳硫醚在主进料喉14处进料至挤出机100。以这种方式,当聚芳硫醚通过挤出机100时,聚芳硫醚可以与组合物中的其它组分熔融并混合。也可在主进料喉14或主进料喉下游添加冲击改性剂、金属羧酸盐和任选的多官能交联剂,如果需要的话。在某些实施方案中,例如,在主进料喉14处加入冲击改性剂和金属羧酸盐,并且在混合其它组分之后加入多官能交联剂。例如,在所示的实施例中,筒26处的第二进料管线16可以用于添加交联剂。在将所有组分添加至混合器中之后,将聚合物组合物在挤出机的一个或多个其余区段中彻底混合,并通过模头挤出。可以根据需要将最终的挤出物造粒或以其它方式成型。
不管将它们组合在一起的方式,本发明人已经发现聚合物组合物可具有相对较低的熔体粘度,这允许其在生产零件的过程中容易地流入模腔。例如,组合物可以具有约1,500Pa·s或更低,在一些实施方案中约1,000Pa·s或更低,并且在一些实施方案中约100至约800泊的熔体粘度,通过毛细管流变仪在约310℃的温度和1200秒-1的剪切速率来测定。然而,当交联时,所得聚合物产物通常将具有高的复数粘度,例如约1,000Pa·s或更高,在一些实施方案中约1,500Pa·s或更高,并且在一些实施方案中约2,000至约10,000Pa,通过平行板流变仪在0.1弧度/秒的角频率、310℃的温度和3%的恒定应变幅度来测定。
另外,可改变聚芳硫醚组合物(和由其形成的成型零件)的颜色而不改变任何着色剂或其它添加剂的浓度。例如,这可以通过使用经处理的聚芳硫醚与未经处理的聚芳硫醚的组合来实现。颜色测量可以通过根据称为“CIELAB”的标准测试方法利用光学读取器测量吸光度来量化,所述标准测试方法描述于F Cost,Delmar Publishers,Albany,NY的数字印刷袖珍指南ISBN 0-8273-7592-1第144和145页和“Photoelectric color differencemeter”,美国光学学会杂志,第48卷,第985-995页,S.Hunter,(1958),这两篇以全文通过引入并入本文。更具体地,CIELAB测试方法定义了三个“Hunter”刻度值L*、a*和b*,它们对应于基于色彩感知的对立理论的感知颜色的三个特征,并定义如下:L=亮度(或光度),范围从0到100,其中0=暗,100=亮;a*=红色/绿色轴,范围从-100到100;正值偏红,负值偏绿;和b*=黄/蓝轴,范围从-100到100;正值偏黄,负值偏蓝。然后可以确定色度以提供颜色品质的指示。
III.成型零件
可使用各种技术,例如挤出,注射模制,吹塑模制,热成形,发泡,压缩模制,热冲压,纤维纺丝,拉挤成型等,将聚合物组合物用于各种不同类型的成型零件中等。在某些实施方案中,例如,成型零件可以通过模制技术成形,例如注射模制,压缩模制,纳米成型,包覆模制,吹塑模制等。例如,如本领域已知的,注射模制可以发生在两个主要阶段-即注射阶段和保持阶段。在注射阶段期间,模腔完全填充有熔融的聚合物组合物。保持阶段在完成注射阶段之后开始,在该阶段中控制保持压力以将另外的材料包装到空腔中并且补偿在冷却期间发生的体积收缩。注射形成后,然后可以将其冷却。一旦冷却完成,当模具打开并且将零件排出,例如在模具内的顶出销的辅助下时,模制周期完成。
各种装置可使用包含本发明的聚合物组合物的模制零件。例如,聚合物组合物可用于部件,例如轴承,电传感器,线圈(例如铅笔,点火器等),夹具(例如软管夹),阀,开关,打印机零件,泵(例如齿轮泵,泵叶轮,泵壳体等),仪表板,管道,软管(例如,用于车辆排气系统),管,油气流送管(例如,井下扶正器)。例如,在一个实施例中,可以形成具有中空内部以允许流体(例如,油,燃料,水,废气等)通过的细长构件。细长构件可具有各种形状,例如管状或其它复杂的形状。细长构件可在单个方向或多个方向上延伸,使得其包括多个角位移。在另一个实施例中,细长构件可为井下扶正器,其包括装配有铰接环管的弓形元件。如本领域已知的,这种扶正器通常用于将套管或衬套保持在井眼的中心,以确保在套管柱周围有效地放置鞘(例如水泥)。
在又一个实施方案中,成型零件可以用于形成包覆模制结构件。这可以通过将聚合物组合物“包覆模制”到金属组件的一部分或整个表面上以使形成附着于其的树脂组分来实现。金属组件可包含各种不同的金属中的任一种,例如铝,不锈钢,镁,镍,铬,铜,钛及其合金。镁铝合金特别适用于金属组件。这样的合金通常含有0.5wt.%至15wt.%的铝和85wt.%至99.5wt.%的镁。金属组件可以使用已知的技术例如铸造、锻造等来成型,并且可具有任何期望的形状或尺寸,这取决于复合结构件的预期用途。聚合物组合物通常在包覆模制期间通过在金属组件的表面压痕或孔隙内和/或周围流动而附着到金属组件。为了提高附着性,可以任选地预处理金属组件以增加表面压痕和表面积的程度。这可使用机械技术(例如,喷砂,研磨,扩口,冲压,模制等)和/或化学技术(例如蚀刻,阳极氧化等)来实现。例如,Lee等人的美国专利第7,989,079号更详细地描述了用于阳极氧化金属表面的技术。除了预处理表面之外,还可在接近但低于聚合物组合物的熔融温度的温度预热金属组件。这可以使用各种技术来实现,例如接触加热,辐射气体加热,红外加热,对流或强制对流空气加热,感应加热,微波加热或其组合。无论如何,通常将聚合物组合物注射到含有任选经预热的金属组件的模具中。一旦形成所需的形状,使复合结构件冷却,使得树脂组分牢固地附着到金属组件上。
当然,可以使用用于形成成型零件的其它技术。在一个实施方案中,例如,可以将聚合物组合物熔融挤出成可用于形成膜、纤维、热成形制品等的片材。合适的熔融挤出技术可包括例如管状捕集气泡膜方法,平坦或管流延膜方法,狭缝平模流延膜方法等。参考图1,例如,更详细地示出熔融挤出方法的一个实施方案。如图所示,可将聚合物组合物的组分首先添加至挤出机110中,该挤出机将组合物加热到足以使其流动的温度。在一个实施方案中,将聚合物组合物加热至处于聚合物组合物的熔融温度的温度或在高于或低于聚合物组合物的熔融温度约20℃的温度。挤出机110产生前体片材112。在有机会固化之前,可任选地将前体片材112进料至压延装置114的辊隙中以形成具有更均匀厚度的聚合物片材。压延装置114可包括例如形成辊隙的一对压延辊。一旦压延,可以使用切割装置116将得到的聚合物片材任选地切割成单独的片材118。
在某些实施方案中,所得的熔融挤出片材可通过以下来用于热成形方法:将其加热至一定温度以使其变得可流动,在模具内使片材成型,然后任选地修整成型制品以形成所需的制品。例如,可将片材夹在热成形机内并加热(例如,用红外加热器)至处于或接近聚合物基质的熔融温度熔融温度的温度,例如加热至约250℃或更高,在一些实施方案中约270℃或更高,在一些实施方案中约280℃至约350℃的温度。取决于所使用的机器的类型,可以将片材转移到成形台,或者可移动底部加热元件以使成形工具能够形成片材。如果需要的话,片材也可以在热成形之前干燥以帮助从组合物中除去水分。例如,干燥可在约60℃至约200℃,在一些实施方案中约100℃至约160℃的温度进行。可以成功使用不同的热成形技术,例如真空成形,柱塞辅助真空成形,压力成形,反向拉伸,双片热成形和其它。一旦成形步骤完成,可以修整零件。
参照图2,例如,更详细地示出热成形方法的一个特定实施方案。如所示,首先将聚合物片材118进料至加热装置120,加热装置120将其加热到足以引起聚合物变形或拉伸的温度。通常,可使用任何合适的加热装置,例如对流烘箱,电阻加热器,红外线加热器等。一旦加热,将聚合物片材118进料至模制装置122,其中它被模制成制品。可在热成形方法中使用各种模制装置中的任一种,例如真空模具(例如多孔模具)。无论如何,通常相对于片材设置力(例如吸力)以使其与模具的轮廓相符。例如,在轮廓处,拉伸比可为大于1:1至约5:1。聚合物片材118的模制通常在片材基本固化和/或结晶之前发生。因此,聚合物的性质不仅在聚合物片材118的生产过程中是重要的,而且在随后的模制过程中也是重要的。如果聚合物片材118过快固化和/或结晶,聚合物可在模制过程中在最终制品中撕裂、破裂、起泡或以其它方式形成缺陷。
不管所使用的方法,可将熔融挤出组合物成型为各种尺寸,并且可以用于广泛的不同应用中。例如,由于其热稳定性、耐化学性和良好的机械性质的独特组合,熔融挤出组合物可用作金属或用作热屏蔽或化学屏蔽的涂覆金属的替代品。这种应用的实例包括例如热交换器(例如烟气换热器),汽车零件,器具(例如烤箱或微波炉),建筑设备,铁路,包装,容器,托盘(例如用于食物制品或在电子应用中),反应器,氢气发生器,电子零件(例如外壳,连接器,电路板等),炊具,烤盘等。在这种应用中制品的典型用途包括例如壳体,防护物,框架,覆盖物等。
参照图3,在一个实施方案中,例如,食物托盘2可以部分或完全由本发明的熔融挤出聚合物组合物成形。在所示的实施方案中,例如,食物托盘2的形状通常为矩形,并且包含从托盘2的下壁向上延伸以限定用于一种或多种食物产品的贮器5的侧壁6。侧壁和/或底壁可以由本发明的聚合物组合物成形。可以由本发明的聚合物组合物成形的凸缘10也从侧壁6突出并围绕托盘2的周边延伸。如果需要,盖子(未示出)可以覆盖托盘2,使得它定位在凸缘10的上表面11附近。如果需要,盖子也可以由本发明的聚合物组合物成形。
测试方法
缺口却贝冲击强度:可根据ISO测试号179-1:2010(技术上等同于ASTM D256,方法B)测定缺口却贝性质。该测试可以使用A型缺口(0.25mm基部半径)和1型试样尺寸(长度80mm,宽度10mm,厚度4mm)进行。使用单齿铣床从多用途棒的中心切割试样。测试温度可为23℃或-30℃。
拉伸性质:拉伸模量、断裂强度、断裂伸长率等可以根据ISO测试号527-1,2:2012(技术上等同于ASTM D638)来测定。在长度为80mm、厚度为10mm和宽度为4mm的测试条样品上进行测量。测试温度为23℃,测试速度为5mm/min。
熔体粘度:可使用Dynisco 7001毛细管流变仪根据ISO测试号11443:2005在310℃和1200s-1的剪切速率下测定熔体粘度(Pa·s)。流变仪孔口(模口)的直径为1mm,长度为20mm,L/D比为20.1,入射角为180°。筒的直径为9.55mm±0.005mm,杆的长度为233.4mm。
复数粘度:复数粘度在本文中用作对低频下聚合物组合物的“低剪切”粘度的估计。复数粘度是频率依赖性粘度,在0.1和500弧度/秒的角频率下剪切应力的强制谐波振荡期间测定。测量可使用具有平行板构型(25mm板直径)的ARES-G2流变仪(TA Instruments)在310℃的恒定温度和3%的恒定应变幅度下测定。粒料样品的间隙距离可以保持在1.5mm。在频率扫描之前可对样品进行动态应变扫描以找到LVE状态和优化的测试条件。应变扫描可以6.28rad/s的频率从0.1%至100%来完成。
颜色测量:利用积分球使用DataColor650分光光度计进行颜色测量,其中使用包括镜面模式进行测量。色坐标同样可以使用CIELAB单元(L*,a*,b*)根据ASTM D2244-11在光源D65/10°,A/10°或F2/10°观察者下计算。还报告了通过以下等式计算的C*值(色度):C*=(a*2+B*2)1/2,其中,a*是试样颜色的红/绿轴值,b*是试样颜色的黄/蓝轴值。
使用的材料
在实施方案中使用以下材料:
交联剂1:对苯二甲酸;
交联剂3:单硬脂酸铝;
交联剂4:来自Sigma的新癸酸锌;
玻璃纤维:来自Owens Corning的10微米玻璃纤维;
着色剂:无机颜料。
实施例1
使用具有十个温度控制区(包括在模口处的一个)的32mm Coperion同向旋转完全啮合双螺杆挤出机将各种样品熔融混合。将聚芳硫醚、冲击改性剂、热稳定剂、交联剂2和润滑剂通过重力进料器进料至第一桶中的主进料喉。在上述成分熔融和混合之后,使用重量进料器在料筒6处进料交联剂1。将材料进一步混合,然后通过线材模口挤出。将该线材在浴中水淬以固化并在造粒机中造粒。所得组合物在下表中更详细地阐述。
样品1 | 样品2 | 样品3 | 样品4 | 样品5 | |
PPS片 | 73.45 | 73.15 | 72.95 | 72.65 | 72.90 |
冲击改性剂1 | 25 | 25 | 25 | 25 | 25 |
交联剂1 | 1.25 | 1.25 | 1.25 | 1.25 | 1 |
交联剂2 | 0 | 0.3 | 0.5 | 0.8 | 0.5 |
润滑剂 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 |
热稳定剂 | 0 | 0 | 0 | 0 | 0.3 |
成形之后,测试样品的各种物理特性。结果如下所述。
如所指出,与样品1相比,样品2中的硬脂酸锌(交联剂2)的使用将熔体粘度提高了约15%。此外,通过增加样品3和4中硬脂酸锌的量,高剪切和低剪切熔体粘度呈线性关系增加。23℃和-30℃的冲击强度也同样增加。还对样品1和5进行了测试以评估滴料(drool)积聚。更特别地,使用包含具有20/60/20网筛组件、20mm模口/8mm心轴和20mm校准套筒的能量传递螺杆的挤出机。挤出条件总结在下表中。
观察到,由于模口流涎积聚显著小于样品1,因此样品5也更耐受挤出中的工艺变化。
实施例2
使用具有十个温度控制区(包括在模口处的一个)的32mm Coperion同向旋转完全啮合双螺杆挤出机将各种样品熔融混合。将聚芳硫醚、冲击改性剂、热稳定剂、交联剂2、3或4以及润滑剂通过重力进料器进料至第一桶中的主进料喉。在上述成分熔融和混合之后,使用重量进料器在筒6处进料交联剂1。将材料进一步混合,然后通过线材模口挤出。将该线材在浴中水淬以固化并在造粒机中造粒。所得组合物在下表中更详细地阐述。
样品 | 6 | 7 | 8 | 9 | 10 | 11 | 12 | 13 | 14 |
PPS 1 | 84.70 | 83.70 | 84.40 | 84.40 | 84.40 | 74.20 | 71.70 | - | - |
PPS 2 | - | - | - | - | - | - | - | 57.5 | 57.4 |
冲击改性剂1 | 15.00 | 15.00 | 15.00 | 15.00 | 15.00 | 25.00 | 25.00 | 10.00 | 10.00 |
交联剂1 | - | 1.00 | 0.2 | 0.2 | 0.2 | 0.40 | 0.40 | - | - |
交联剂2 | - | - | 0.10 | - | - | 0.10 | 0.10 | - | 0.10 |
交联剂3 | - | - | - | 0.10 | - | - | - | - | - |
交联剂4 | - | - | - | - | 0.10 | - | - | - | - |
玻璃纤维 | 30 | 30 | |||||||
热稳定剂 | - | - | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | - | - |
润滑剂 | 0.30 | 0.30 | - | - | - | - | - | - | - |
黑颜色 | - | - | - | - | - | - | 2.50 | 2.50 | 2.50 |
成形之后,测试样品的各种物理特性。结果如下所述。
如所述,使用对苯二甲酸和硬脂酸锌(样品8,交联剂1和2)的组合提高了材料的柔性和耐冲击性。还对样品6和8在165℃进行加速热老化测试2000小时。当两种样品保持拉伸强度时,样品8的断裂伸长保持率是样品6的保持率3倍。还对样品1、6、7、8和11进行溶胀测试。如所指,更高的冲击改性剂含量导致暴露后更高的体积变化和拉伸强度变化。
还拍摄了样品6、8和11的SEM图。结果示于图5-7中。对于样品6(图5),冲击改性剂存在于平均尺寸为约1微米的域中。然而,对于样品8和11(分别为图6和7),冲击改性剂几乎不可见,因此具有远低于1微米的平均尺寸。
实施例3
经下表1中列出的组分在具有25mm直径的Werner Pfleiderer ZSK 25同向旋转啮合双螺杆挤出机中混合。
表1
成分 | 重量% |
黑浓缩物 | 2.5 |
玻璃纤维 | 30.0 |
交联剂2 | 0.1 |
冲击改性剂2 | 6.0 |
PPS 2 | 61.4 |
还将粒料在Mannesmann Demag D100NCIII注射模制机上注射模制并测试某些物理特性,如下表2中所提供。
表2
性质 | 值 |
熔体粘度(Pa·s) | 2,600 |
拉伸模量(MPa) | 9,857 |
拉伸应力(MPa) | 140 |
拉伸断裂伸长率(%) | 2.03 |
却贝缺口冲击强度(kJ/m2) | 9.7 |
DTUL(℃) | 261 |
实施例4
将下表3中列出的组分在具有25mm直径的Werner Pfleiderer ZSK 25同向旋转啮合双螺杆挤出机中混合。
表3
样品 | A-1 | A-2 | A-3 | A-4 | A-5 |
PPS 1 | 91.15 | 68.36 | 45.575 | 22.79 | - |
PPS 3 | - | 22.79 | 45.575 | 68.36 | 91.15 |
冲击改性剂1 | 7.5 | 7.5 | 7.5 | 7.5 | 7.5 |
润滑剂 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 |
着色剂 | 1.05 | 1.05 | 1.05 | 1.05 | 1.05 |
然后将粒料模制成板以获得颜色测量,其汇总于下表4中。
表4
样品 | A-1 | A-2 | A-3 | A-4 | A-5 |
L* | 79.23 | 71.05 | 64.56 | 57.32 | 50.12 |
a* | 4.7 | 5.09 | 5.47 | 5.09 | 4.93 |
b* | 26.36 | 20.22 | 17.73 | 14.28 | 12.35 |
C* | 26.78 | 20.85 | 18.55 | 15.16 | 13.36 |
如数据所证实,特别是色度值,可以通过改变PPS 1和PPS 3(经处理的PPS)的比例来实现颜色变化,而不需要调节着色剂或任何其它添加剂的浓度。
在不脱离本公开的精神和范围的情况下,本领域普通技术人员可实践对本公开的这些和其它修改和变型。此外,应该理解,各种实施方案的各方面可以全部或部分互换。此外,本领域普通技术人员将会理解,前面的描述仅仅是作为示例,并不意图限制本公开。
Claims (19)
1.成型产物,其通过熔融加工聚合物组合物和在经熔融加工的聚合物组合物可流动时将其成型来形成,所述聚合物组合物包含:
聚芳硫醚;
每100份的聚芳硫醚0.5至50份的冲击改性剂,其中冲击改性剂包括包含环氧官能(甲基)丙烯酸系单体组分的环氧官能聚合物,且所述环氧官能(甲基)丙烯酸系单体组分由丙烯酸缩水甘油酯、甲基丙烯酸缩水甘油酯或其组合形成;和
每100份的聚芳硫醚0.1至15份的交联体系,其中交联体系包括占所述聚合物组合物0.05wt.%至0.2wt.%的量的硬脂酸锌和占所述聚合物组合物0.20wt.%至0.40wt.%的量的间苯二甲酸或对苯二甲酸;
其中,在所述熔融加工时,所述冲击改性剂的聚合物链通过所述交联体系交联,
其中,所述经熔融加工的聚合物组合物根据ASTM D638在23℃温度下测定时显示的拉伸断裂应力为42MPa或以上。
2.根据权利要求1所述的成型产物,其特征在于,聚芳硫醚构成所述组合物的40wt.%至95wt.%。
3.根据权利要求1所述的成型产物,其特征在于,所述聚芳硫醚是聚苯硫醚。
4.根据权利要求1所述的成型产物,其特征在于,所述聚芳硫醚是官能化的。
5.根据权利要求1所述的成型产物,其特征在于,所述冲击改性剂进一步包含α-烯烃单体组分。
6.根据权利要求1所述的成型产物,其特征在于,所述硬脂酸锌构成所述聚合物组合物的0.05wt.%至0.1wt.%。
7.根据权利要求1所述的成型产物,其特征在于,进一步包含热稳定剂。
8.根据权利要求1所述的成型产物,其特征在于,所述冲击改性剂以平均尺寸为5至800纳米的离散域的形式分散在所述经熔融加工的聚合物组合物内。
9.根据权利要求1所述的成型产物,其特征在于,所述聚合物组合物进一步包含所述组合物的0.5wt.%至50wt.%的量的无机填料。
10.根据权利要求1所述的成型产物,其特征在于,所述经熔融加工的聚合物组合物展示出1,000Pa·s或更多的复数粘度,通过平行板流变仪在0.1弧度/秒的角频率,310℃的温度,和3%的恒定应变幅度来测定。
11.根据权利要求1所述的成型产物,其特征在于,所述经熔融加工的聚合物组合物展示出10kJ/m2或更多的缺口却贝冲击强度,根据ISO测试号179-1:2010在23℃温度来测定。
12.根据权利要求11所述的成型产物,其特征在于,所述经熔融加工的聚合物组合物展示出2kJ/m2或更多的缺口却贝冲击强度,根据ISO测试号179-1:2010在-30℃的温度来测定。
13.根据权利要求1所述的成型产物,其特征在于,所述成型产物包括熔融挤出片材,所述熔融挤出片材包含所述经熔融加工的聚合物组合物。
14.根据权利要求1所述的成型产物,其特征在于,所述成型产物包括食物托盘,所述食物托盘包含所述经熔融加工的聚合物组合物。
15.根据权利要求14所述的成型产物,其特征在于,所述托盘包含从下壁向上延伸以限定用于一种或多种食物产品的贮器的侧壁,其中侧壁、下壁或其组合包含所述经熔融加工的聚合物组合物。
16.根据权利要求1所述的成型产物,其特征在于,所述成型产物包括包覆模制结构件,所述包覆模制结构件包含所述经熔融加工的聚合物组合物和金属组件。
17.用于形成成型产物的方法,所述方法包括熔融共混聚合物组合物,所述组合物包含聚芳硫醚、每100份的聚芳硫醚0.5至50份的冲击改性剂,和每100份的聚芳硫醚0.1至15份的交联体系,其中所述交联体系包括占所述聚合物组合物0.05wt.%至0.2wt.%的量的硬脂酸锌和占所述聚合物组合物0.20wt.%至0.40wt.%的量的间苯二甲酸或对苯二甲酸,并且其中所述冲击改性剂包括包含环氧官能(甲基)丙烯酸系单体组分的环氧官能聚合物,且所述环氧官能(甲基)丙烯酸系单体组分由丙烯酸缩水甘油酯、甲基丙烯酸缩水甘油酯或其组合形成;其中,在所述熔融加工时,所述冲击改性剂的聚合物链通过所述交联体系交联,所述方法包括在经熔融加工的聚合物组合物可流动时将其成型以形成成型产物,其中,所述经熔融加工的聚合物组合物根据ASTM D638在23℃温度下测定时显示的拉伸断裂应力为42MPa或以上。
18.根据权利要求17所述的方法,其特征在于,熔融共混发生在100℃至400℃的温度。
19.根据权利要求17所述的方法,其特征在于,所述交联体系包括占所述聚合物组合物0.05wt.%至0.1wt.%的量的硬脂酸锌。
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