CN101365731A - 弹性甲基丙烯酸酯组合物 - Google Patents
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Abstract
显示出改进的弹性的双组分粘合剂组合物,其包含一种或多种丙烯酸酯或甲基丙烯酸酯单体,含硫化合物、优选为磺酰氯,胺促进剂,优选为胺醛反应产物和热塑性嵌段共聚物组分,该热塑性嵌段共聚物组分选自:a.线性苯乙烯-丁二烯-苯乙烯共聚物,b.带增塑剂的径向苯乙烯-丁二烯-苯乙烯嵌段共聚物,c.线性或径向苯乙烯-异戌二烯-苯乙烯嵌段共聚物,和d.线性或径向的苯乙烯-丁二烯-异戌二烯-苯乙烯嵌段共聚物,以及它们的混合物。
Description
技术领域
本发明涉及一种液体和糊状组合物,其包含聚合物和丙烯酸或甲基丙烯酸酯单体的混合物,其通过自由基聚合而硬化来形成高强度的、增韧的材料。该硬化的组合物通常可用作粘合剂、填料和修复材料、涂料等等。
背景技术
在此以前,商用的和现有技术的能以1:1比率混合、且还具有实用的保存期或储存期限的甲基丙烯酸酯粘合剂组合物的弹性和可延展性与具有普通的但较不实用的10:1混合比率的粘合剂的弹性和可延展性不一样。在粘合剂随着时间在高温下的老化时,这问题尤其明显。后者的组合物通常使用过氧化苯甲酰作为主要引发物质。最早和最广泛使用的催化剂组合包含过氧化苯甲酰和叔芳族胺。通常将该胺掺入到聚合物和单体混合物中,而在使用时分别将过氧化苯甲酰提供和添加到单体组合物中。单体组合物和过氧化物的混合比率典型地从100:1,如果使用纯BPO,到10:1或更低,如果为了更方便混合而用增塑剂稀释。因为在过氧化物组分中的惰性增塑剂和其它成分对固化的组合物性能有副作用,因此单体组合物和过氧化物组分的最小实用比率是4:1。当和甲基丙烯酸酯单体混合时,过氧化苯甲酰是不稳定的。在以典型的1:1混合比率配制剂中对于安全和在使用之前的实用储存而言,过氧化物催化剂物质在与甲基丙烯酸酯混合物的混合中的稳定性是必需的。因此,过氧化苯甲酰不是本发明组合物的优选实施方案中的催化剂组分。
商业的和现有技术的具有1:1混合比率的甲基丙烯酸酯粘合剂典型地使用包括磺酰氯引发物质、氢过氧化物或其它稳定的非BPO共引发物的引发剂体系和胺-醛活化剂。该引发物质包含在粘合剂部分或粘合剂的组分A中,醛-胺活化剂包含在活化剂部分或粘合剂的组分B中。磺酰氯的常见来源是duPont商业上作为Hypalon销售的氯磺化聚乙烯。优选的醛-胺活化剂是Reillcat ASY-2,丁醛和苯胺的反应产物,在活性二氢吡啶组分中富集,一般被称为DHP。
虽然氢过氧化物/磺酰氯/DHP固化体系提供了一种制造具有方便的和非-决定性的1:1混合比率的粘合剂的方法,但得到的配制剂对于最需要的结构粘合剂应用来说并不是优选的。这是因为相对于用BPO和叔胺固化的组合物,这些配制剂通常较硬,而且随着老化可变脆。因此,公认需要一种具有方便的1:1混合比率和高度的挠度以及在老化后保留挠度的粘合剂。现在已经发现可以使用特定的苯乙烯、丁二烯和异戌二烯的嵌段共聚物,通过使用提供方便的1:1混合比率的组分来配制具有这些所期望特性的粘合剂组合物。进一步地,在优选实施方案中,这些组合物可以不使用过氧化苯甲酰来配制。
Charnock的美国专利4,574,142公开了增韧的基于双组分丙烯酸单体的粘合剂组合物,其使用苯乙烯-丁二烯(SBS)嵌段共聚物橡胶。仅仅公开了苯乙烯和丁二烯的嵌段共聚物,没有公开对丁二烯或苯乙烯的相对比率的优选,也没有公开聚合物结构。使用醛-胺组分作为固化催化剂体系的一部分。然而,指出的是该组合物包括不含有机磺酰氯的自由基催化剂体系。磺酰氯和含有磺酰氯的聚合物、例如氯磺化聚乙烯,它们是现有技术粘合剂的优选促进剂,但它们是从组合物中特别排除的。还公开聚氯丁二烯、即在现有技术组合物中所使用的另一氯化聚合物,具有不期望的效果。因此,Charnock或者排除或者教导远离在组合物中的任何含氯物质,尤其是磺酰氯。
美国专利5,206,288公开了在低温挠曲的粘接性能改进的组合物,该组合物结合具有低玻璃化转变温度Tg的弹性体和核壳冲击改性剂。在一个以大约1:1混合比率混合的配制剂中使用Kraton的实施方案中,催化剂体系在单体组分中包含BPO糊剂作为在聚合物中的添加剂,和在另一中的叔胺,N,N-二甲基-对甲苯胺。BPO不是该优选实施方案组合物的优选组分。
美国专利6,989,416公开基于苯乙烯和丁二烯嵌段共聚物的具有改进的挠度的甲基丙烯酸酯粘合剂。该粘合剂含有过氧化物和叔胺引发剂但不含有磺酰氯或任何其它含硫的组分或DHP组分。进一步地,它们优选以10:1的混合比率使用糊过氧化苯甲酰作为催化剂组分。
本发明优选实施方案的概述
本发明的优选实施方案提供双组分结构粘合剂组合物,其显示出改进的弹性和弹性保持性。该粘合剂组合物是丙烯酸酯或甲基丙烯酸酯单体和聚合物的混合物,其包含:
A、一种或多种乙烯基单体,优选丙烯酸酯或甲基丙烯酸酯单体,
B、含硫化合物,优选磺酰氯,
C、胺促进剂,优选胺醛反应产品,
D、热塑性嵌段共聚物组分,选自
a、线性苯乙烯-丁二烯-苯乙烯共聚物,
b、附加增塑剂的径向苯乙烯-丁二烯-苯乙烯嵌段共聚物,
c、线性或径向苯乙烯-异戌二烯-苯乙烯嵌段共聚物,和
d、线性或径向苯乙烯-丁二烯-异戌二烯-苯乙烯嵌段共聚物,以及
E、任选的粘合促进聚合物,优选氯化聚合物。
该组合物特别适合配制具有方便的1:1混合比率的室温固化粘合剂。虽然对这些组合物而言不要求以1:1混合比率混合来受益于本发明的优点,但对于商业产品而言,这是高度优选和实用的特点。进一步地,这些实施方案不要求过氧化苯甲酰的存在。
本发明的详细说明
现在已经发现在能够以更方便的1:1比率混合的配制剂中,对改进的和永久的弹性有用的重要成分是与某些自由基引发体系组合使用的热塑性嵌段共聚物组分。优选的热塑性嵌段共聚物组分选自:
a、20~45%苯乙烯含量的线性苯乙烯-丁二烯-苯乙烯共聚物,
b、20~45%苯乙烯含量附加增塑剂的径向苯乙烯-丁二烯-苯乙烯嵌段共聚物,
c、10~45%苯乙烯含量的线性或径向苯乙烯-异戌二烯-苯乙烯嵌段共聚物,和
d、10~45%苯乙烯含量的线性或径向苯乙烯-丁二烯-异戌二烯-苯乙烯嵌段共聚物。
可接受的热塑性嵌段共聚物的例子是Kraton Polymers,Inc.以商品名KratonTM销售的那些,Dexco Polymers以商品名VectorTM销售的那些,以及其它。优选的自由基引发体系包括与二氢吡啶组合的含硫化合物,优选磺酰氯或硫酰亚胺。
当将本发明组合物配制作为粘合剂时,优选使用粘合促进聚合物来改进固化的组合物对各种塑料、金属、陶瓷、木材或其它材料或材料组合的粘结强度。粘合促进聚合物的选择依赖于要粘结的材料的性质和固化的粘合剂组合物所要求的物理性能。
优选的粘合促进聚合物是在甲基丙烯酸酯单体中可溶或可分散的热塑性树脂和弹性体。用于该目的的优选聚合物公开在美国专利4,182,644中,它在此被引入作为参考。更优选的粘合-促进聚合物是氯化的聚合物,且最优选的聚合物是氯化的弹性体,包括氯磺化聚乙烯、氯化聚乙烯和聚氯丁二烯聚合物。可以有利地使用任何或所有优选聚合物的混合物。
在本发明配制剂中,可以有利使用的其它聚合物是冲击改性剂,优选核壳冲击改性剂。除了提供对一些材料的改进粘合性,这类聚合物还可以提供流变性或处理性能的额外好处,并进一步改善固化的组合物的延展性或韧性。冲击改性剂,特别是核壳冲击改性剂的好处,公开在US专利4,536,546中,它在此被引入作为参考。
用于本发明配制剂的优选实施方案的丙烯酸酯和甲基丙烯酸酯单体是本领域技术人员所熟知的,并公开在上面引用的′644专利中。最优选的单体是甲基丙烯酸甲基酯单体和更高分子量的单体,其中该单体的醇部分基于C6或更高级烃的部分。后一类的最优选单体是甲基丙烯酸月桂酯。如果需要提供特定的好处例如控制固化速率,可以使用非甲基丙烯酸酯的不饱和或乙烯基单体,例如苯乙烯、乙烯基甲苯、α-甲基苯乙烯等等。
本发明组合物的优选实施方案的引发物质包括含硫化合物和过氧化物。本发明优选实施方案的活化剂包括叔芳香族胺、胺-醛活化剂和活性金属物质。优选的含硫化合物包括磺酰氯或氯磺化聚合物,例如氯磺化聚乙烯,和硫酰亚胺,包括邻磺酰苯酰亚胺或糖精。优选的过氧化物包括氢过氧化物,例如氢过氧化枯烯和过氧化甲基乙基酮,苯甲酸酯类,包括过苯甲酸叔丁酯,和其它本领域熟知的过氧物质。过氧化苯甲酰不是优选的。
优选的活化剂是丁醛和苯胺的加合物,包括在市场上以ReillcatASY-2销售的富集在活性二氢吡啶(DHP)组分中的产品。组合物还可以含有能够增加粘合剂反应性和固化速度的有机金属物质。优选的活性金属物质是过渡金属化合物,最优选长链羧酸的衍生物,例如环烷酸铜、辛酸铜或本领域技术人员所熟知的类似的有机金属化合物。
本发明优选实施方案重要特征是提供相比现有技术组合物,在完全固化时显示出非凡的机械性能改进的组合物,其能够配制为1:1混合比率的粘合剂产品。当根据ASTM方法D638测试块状(bulk)机械性能时,现有技术的完全固化甲基丙烯酸酯粘合剂组合物显示出宽的和混合范围的热塑性、粘弹性和弹性。这些现象描述在美国专利申请公开US 2005/0004303 A1中,它在此被引入作为参考。出于讨论的目的,在本发明优选实施方案的优选组合物中的显著改进由高拉伸强度和破坏伸长率的结合组成,加上高度线性弹性、在屈服之前的可恢复变形性,和优选的在破坏前显著的应变硬化。从工程的观点考虑,对于结构粘合剂,这些是非常期望的特点。
除了上面列举的聚合物组分,可以使用许多本领域技术人员熟知的任何数量的附加组分来配制本发明优选实施方案的粘合剂组合物。所述的附加组分包括非聚合物粘合促进剂,例如可聚合的羧酸和丙烯酸酯化或甲基丙烯酸酯化磷酸酯、腐蚀抑制剂,包括锌和钼酸盐化合物、环氧树脂、填料、增塑剂、蒸气屏蔽蜡等等。它们还可以包括聚酯树脂和炔属醇。
优选的组合物包含(A)20~90%甲基丙烯酸酯单体,(B)0.02~30%含硫化合物或氯磺化聚合物,(C)0.05~10%胺促进剂,优选二氢吡啶和(D)5~50%热塑性嵌段共聚物组分。如需要,可以添加另外的促进剂,特别是粘合促进剂。使用过氧化苯甲酰是不优选的。
根据下列实施例的描述,可以进一步理解优选实施方案。然而,不管怎样,这些实施例并不打算限制本发明的范围。
实验步骤
甲基丙烯酸酯溶液的制备
在1加仑玻璃罐中,通过使用罐辊(jar roller)在甲基丙烯酸甲酯中溶解足够量的聚合物而提供30-45%浓度范围的溶液来制备热塑性嵌段共聚物的储备溶液。对于单独的实施例,在添加另外的配制成分之后,通过添加另外的MMA来调节最终粘度。就在制造试样前,添加DHP组分或BPO组分作为最终的添加剂来引发聚合反应。
试样的制备
根据ASTM检测方法D638测量粘合剂的体积应力-应变性能。通过混合足够量的粘合剂来制备直径约为6~7英寸和约0.125英寸厚的粘合剂的均匀平面薄膜来制备试样。粘合剂组分在烧杯中通过简单的手工搅拌以特定的比率混合。在彻底混合粘合剂后,将烧杯放置于真空室中,并间歇地施加真空来去除空气,直到最后一次或两次真空的施加不产生另外的发泡或膨胀。然后将粘合剂转移到直径约为12英寸的两个玻璃或塑料盘的一个上,在其顶部具有类似大小的聚酯薄膜(Mylar)隔离膜(release film)。将粘合剂放置于膜的中心,将配套(mating)聚酯薄膜和盘放置在粘合剂上且均匀地下压来使薄膜扩算。沿着盘周边放置金属垫片以形成所期望的膜厚度。
在膜固化后,将盘除去。按照测试方法的规定,从膜上剪下哑铃形试样(test dumbbell),注意要从膜的最无空隙区段切割试样。在切割哑铃形试样前,将膜在室温下固化过夜,然后在82℃下进行热后固化1小时。每个测试数值是5个单独测试试样的平均值。
实施例1-5比较了优选配制剂(2-4)和现有技术配制剂(5)。当热塑性嵌段共聚物是径向SBS嵌段共聚物时,实施例1和2的对比说明了添加的增塑剂提供所期望的性能的效果。
实施例 1 2 3 4 5
组分
MMA单体 63.81 53.85 58.50 59.25 61.50
甲基丙烯酸 5.00 5.00 5.00 5.00 5.00
Kraton D 1116 27.35 27.40
Kraton D 1101 31.50
Kraton D 1111 31.90 33.00
DOP 10.00
p-TSC1 3.00 3.00 3.00 3.00
CHP 0.75 0.75 0.50 0.75
DHP 2.50 2.50 2.40 2.50
HET 0.5
CuAcAc溶液 0.10 0.10 0.10 0.10
Benox B55 2.5
在82℃/1hr下后固化后
ASTM D638的拉伸性能
拉伸应力(psi) 1190 905 1545 1295 1467
伸长率,% 91.8 407 342 534 100
应变硬化 Y/N 没有 有 有 有 没有
嵌段共聚物
类型 SBS SBS SBS SIS SIS
线性/径向 径向 径向 线性 线性 线性
增塑剂 Y/N 没有 有 没有 没有 没有
其它组分
MMA 单体 甲基丙烯酸甲酯单体 Lucite
Kraton 热塑性嵌段共聚物 Kraton Polymers
DOP 邻苯二甲酸二辛酯增塑剂 Aldrich
p-TSC1 对甲苯磺酰氯 Aldrich
CHP 氢过氧化枯烯 Hercules
DHP 富集的二氢吡啶(DHP) Reilly Industries
HET N,N-双羟乙基甲苯胺 Bayer
CuAcAc溶液 在MMA单体中0.5%乙酰基丙酮合铜溶液 实验室制备/Aldrich
Benox B55 55%过氧化苯甲酰/苯甲酸酯增塑剂 Norac
特别优选的组合物如实施例2、3和4所示。
Claims (8)
1.能以1:1比率混合形成弹性或可延展的粘合剂的双组分粘合剂组合物,其包含:
一种或多种丙烯酸酯或甲基丙烯酸酯单体、优选选自甲基丙烯酸甲酯单体,和更高分子量的丙烯酸酯和甲基丙烯酸酯单体,其中单体的醇部分基于C6或更高级烃的部分,及其混合物,更优选甲基丙烯酸月桂酯;含硫化合物,优选磺酰氯;胺促进剂,优选胺醛反应产物或二氢吡啶;以及选自以下的热塑性嵌段共聚物组分:
a、线性苯乙烯-丁二烯-苯乙烯共聚物,
b、具有增塑剂的径向苯乙烯-丁二烯-苯乙烯嵌段共聚物,
c、线性或径向苯乙烯-异戌二烯-苯乙烯嵌段共聚物,
d、线性或径向苯乙烯-丁二烯-异戌二烯-苯乙烯嵌段共聚物,及其混合物。
2.权利要求1的双组分粘合剂,其进一步包含粘合促进聚合物,优选氯化聚合物,且更优选选自氯磺化聚乙烯、氯化聚乙烯、聚氯丁二烯聚合物及其混合物的氯化聚合物。
3.权利要求1的双组分粘合剂,其进一步包含冲击改性剂,优选核壳冲击改性剂。
4.权利要求1的双组分粘合剂组合物,其进一步包含选自含硫化合物、过氧化物及其混合物的引发剂,其中该过氧化物优选选自氢过氧化枯烯、过氧化甲基乙基酮、包括过苯甲酸叔丁酯的苯甲酸酯类,及其混合物,且更优选其中该引发剂不包括苯甲酰氯。
5.权利要求1的双组分粘合剂组合物,其进一步包含活化剂,该活化剂包括丁醛和苯胺的加合物。
6.能以1:1比率混合形成弹性或可延展的粘合剂的双组分粘合剂组合物,其包含:
20~90%重量的一种或多种丙烯酸酯或甲基丙烯酸酯单体,优选选自甲基丙烯酸甲酯单体和更高分子量的丙烯酸酯和甲基丙烯酸酯单体,其中该单体的醇部分基于C6或更高级烃的部分,及其混合物,更优选为甲基丙烯酸月桂酯;0.02~30%重量含硫化合物,优选为磺酰氯;0.05~10%重量胺促进剂,优选为胺醛反应产品或二氢吡啶;粘合促进剂,和5~50%重量热塑性嵌段共聚物组分,其选自:
a.线性苯乙烯-丁二烯-苯乙烯共聚物,
b、具有增塑剂的径向苯乙烯-丁二烯-苯乙烯嵌段共聚物,
c、线性或径向苯乙烯-异戌二烯-苯乙烯嵌段共聚物,
d、线性或径向苯乙烯-丁二烯-异戌二烯-苯乙烯嵌段共聚物,以及它们的混合物,但没有使用过氧化苯甲酰。
7.形成具有1:1比率的粘合剂的方法,包括
制备组分A,其包含一种或多种甲基丙烯酸酯或丙烯酸酯单体和含硫化合物,
制备组分B,其包含一种或多种丙烯酸酯或甲基丙烯酸酯单体和胺促进剂或活化剂,
其中组分A或组分B或两者都进一步包含选自以下的热塑性嵌段共聚物组分:
a、线性苯乙烯-丁二烯-苯乙烯共聚物,
b、具有增塑剂的径向苯乙烯-丁二烯-苯乙烯嵌段共聚物,
c、线性或径向苯乙烯-异戌二烯-苯乙烯嵌段共聚物,
d、线性或径向苯乙烯-丁二烯-异戌二烯-苯乙烯嵌段共聚物,及其混合物,
其中组分A与组分B的比率是1:1,
将组分A和组分B混合形成粘合剂组合物;而且
优选过氧化苯甲酰既不和组分A也不和组分B一起使用。
8.权利要求7的方法,进一步包括往组分A或B或两者中添加粘合促进剂。
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CN114213778B (zh) * | 2021-11-30 | 2024-03-19 | 上海金发科技发展有限公司 | 一种高抗冲高光泽hips材料及其制备方法与应用 |
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ES2389090T3 (es) | 2012-10-23 |
EP1979388B1 (en) | 2012-08-01 |
ES2471465T3 (es) | 2014-06-26 |
JP2009521573A (ja) | 2009-06-04 |
JP5343563B2 (ja) | 2013-11-13 |
CA2633719C (en) | 2013-09-10 |
DK1979388T3 (da) | 2012-08-27 |
EP2289957A1 (en) | 2011-03-02 |
CN101365731B (zh) | 2015-06-17 |
EP1979388A1 (en) | 2008-10-15 |
AU2006331622B2 (en) | 2013-03-07 |
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