CN102666595A - 用于结构粘合剂的组合物 - Google Patents
用于结构粘合剂的组合物 Download PDFInfo
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- CN102666595A CN102666595A CN2010800410631A CN201080041063A CN102666595A CN 102666595 A CN102666595 A CN 102666595A CN 2010800410631 A CN2010800410631 A CN 2010800410631A CN 201080041063 A CN201080041063 A CN 201080041063A CN 102666595 A CN102666595 A CN 102666595A
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- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
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- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- 239000002512 suppressor factor Substances 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical group 0.000 description 1
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
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Abstract
本发明涉及用于丙烯酸类粘合剂的聚合引发剂,所述聚合引发剂含有环氧化的硅烷。
Description
本发明涉及结构粘合剂领域,特别是丙烯酸类结构粘合剂(基于丙烯酸酯或基于甲基丙烯酸酯),并涉及它们的应用。
结构粘合剂是用于将两种材料(如金属或塑料)结合在一起的其他机械技术的良好替代方式。这是因为相比于使用替代技术(如铆接或焊接)时,通过粘合剂结合的力分布更好。此外,粘合剂结合的使用常常使得更快操作成为可能,且也显示出提供比机械技术更好的对外界因素(灰尘、湿气)的绝缘的优点。
因此结构粘合剂在许多工业领域中使用,包括用于复合材料的粘合剂结合。
结构粘合剂由两个要素组成,即,催化要素和另一要素(包含单体的树脂),其中催化要素用于进行另一要素(包含单体的树脂)的聚合。因此,取决于存在于树脂中的单体的性质,存在三种类型的双组分粘合剂(环氧类、聚氨酯类和丙烯酸类)。
丙烯酸类粘合剂是特别有利的,特别是在聚合属性(de profil de polymérisation)方面以及在非预先准备的表面上使用的可能性的方面。
然而,可证实使用这些粘合剂的复合材料的粘合剂结合结果显示出比使用环氧化物粘合剂所获得的那些性能更差的性能,特别是对于在闭式模具中制得的复合材料。因此可提及RTM(树脂传递模塑)、SMC(片材模塑化合物,基于片材的预浸渍体)或拉挤成型体(les pultrudés)(聚酯/玻璃纤维复合材料)。
通过模塑法,通过将聚酯树脂注入玻璃纤维的簇(其为密封闭式模具)而获得RTM复合材料。施加真空以使树脂更好地流动,并因此抑制缺陷,如气泡或间隙。
已提供一些解决方法用于改进丙烯酸类粘合剂((甲基)丙烯酸酯基粘合剂)的粘合剂结合性质。因此可提及用于准备表面的步骤,如US3 838 093中所描述。因此,可证实必要的是使用异丙醇磨蚀一些RTM的表面并将其脱脂,以去除能够通过迁移至表面而造成主要的附着缺 陷的可能的试剂。
也可提及WO 03/040248的教导,其提供了对困难的极合理的重述,所述困难在于难以产生(甲基)丙烯酸酯基粘合剂对复合材料(如RTM)的粘合,特别是由于增塑剂(如邻苯二甲酸二丁酯和/或邻苯二甲酸二异丁酯和/或邻苯二甲酸二苄酯)在催化组合物(包含聚合引发剂)中的存在。因此,增塑剂可迁移至待粘合结合的材料中,或可从材料中提取某些化合物(如抑制剂或脱模剂),所述化合物渗透至粘合剂界面中。因此粘合性可大大降低。
WO 03/040248提出了通过特定的(甲基)丙烯酸酯树脂的配方来解决所述问题。
专利申请WO 2008/080913和WO 2008/125521也提供了将组分加入(甲基)丙烯酸酯树脂,从而有可能获得对复合材料的更好粘合。
本申请人现在已开发了催化剂的配方,其有可能相当大地改进(甲基)丙烯酸酯粘合剂在复合材料基材上的机械性能。因此,对至复合材料的粘合,且特别是至在闭式模具中制得的所有复合材料的粘合的剪切强度得以改进。
在复合材料上的粘合剂结合的问题在于,在发生机械应力时不能获得粘合破坏。因此其反而涉及获得至少两个部分之一的破坏。
可通过基于标准ISO 4587的测试,使用两个RTM测试试样确定对该拉伸剪切强度的粘合剂的性质。目的是基于该测试,找到2MPa以上,优选2.5MPa以上且更优选3MPa以上的拉伸剪切强度。
实际上,粘合破坏显示了结构粘合剂在RTM上的附着缺陷,所述附着缺陷存在引发由水的渗透、热冲击、振动等导致的脱附的风险。许多机动车身工件被制造为RTM,并必须被结构粘合剂结合而无任何附着缺陷。
所述催化剂包含自由基聚合引发剂,并被加入至包含单体试剂的树脂中以引发其聚合,由此提供两个材料的内聚结合。
因此,本发明涉及一种可用于结构粘合剂中的组合物,其包含自由基聚合引发剂和环氧化的硅烷。
环氧化的硅烷是本领域公知的。因此申请WO 02/051899引用了一系列环氧化的硅烷。因此,在根据本发明的组合物的情况中,可使用 选自如下的环氧化的硅烷:β-(3,4-环氧环己基)乙基三甲氧基硅烷、β-(3,4-环氧环己基)乙基三乙氧基硅烷、γ-环氧丙氧基丙基三甲氧基硅烷、γ-环氧丙氧基丙基甲基二甲氧基硅烷、γ-环氧丙氧基丙基甲基二乙氧基硅烷、γ-环氧丙氧基丙基甲基三乙氧基硅烷、3-缩水甘油基氧丙基三乙氧基硅烷(GLYEO)和3-缩水甘油基氧丙基三甲氧基硅烷(GLYMO)。
特别地以名称Coatosil 1770(Momentive Performance Materials,Wilton,CT,United States)销售的β-(3,4-环氧环己基)乙基三乙氧基硅烷特别适合用于根据本发明的组合物中。
也可使用官能环氧硅烷低聚物,如CoatOsil MP 200交联剂(Momentive Performance Materials)。
环氧化的硅烷通常为组合物的1至30%之间,优选5至20%之间(以重量计)。
在根据本发明的组合物中环氧化的硅烷(环氧硅烷)的使用使得有可能显著降低增塑剂在组合物中的存在。
实际上,由此有可能获得包含20%以下的增塑剂的组合物。在一些实施方案中,根据本发明的组合物包含15%以下,实际上甚至12%以下或10%以下(以重量计)的增塑剂。术语“xxx%以下”应理解为包括上限,并表示包括“至多xxx%”。
自由基聚合引发剂是本领域技术人员公知的。因此,是氧化剂与存在于树脂中的还原化合物(胺)反应。因此该试剂可为过氧化物(如过氧化苯甲酰和任何其他二酰基过氧化物)、氢过氧化物(如氢过氧化枯烯)、过酸酯(如过氧化苯甲酸P-丁酯(le P-butylperoxybenzoate)或过氧化苯甲酸叔丁酯),或酮氢过氧化物(如甲乙酮氢过氧化物)。其也可为有机过渡金属盐(如环烷酸钴),或包含不稳定氯的化合物(如磺酰氯)。
通常,所述组合物包含0.5至50%之间(以重量计),或优选5至40重量%之间,且最优选10至20重量%之间的所述聚合引发剂。在一个优选的实施方案中,所述组合物包含大约20重量%的聚合引发剂。优选试剂为过氧化苯甲酰。如果希望减慢聚合速率以增加施用粘合剂的持续时间,可使用10重量%量级的聚合引发剂。根据本发明的组合 物也可包含填料,特别是无机填料,如二氧化硅、碳酸钙或氧化钛。
根据本发明的组合物也可包含稳定剂、增稠剂、消泡剂或着色剂。
在一个特定实施方案中,所述组合物另外包含环氧化物树脂(或环氧树脂)。这种试剂在本领域中描述,特别是在WO 2003/097756中描述。该环氧树脂以10至60%之间(以重量计),优选15至45%之间且更优选20至30%之间的量存在于组合物中。
术语“环氧树脂”涵盖多种化合物,特别是环氧十八烷、甲基丙烯酸缩水甘油酯、双酚A二缩水甘油醚、二氧化乙烯基环己烯、3,4-环氧环己烷羧酸3,4-环氧环己基甲基酯、环氧甲酚酚醛清漆、环氧苯酚酚醛清漆,或基于双酚A的环氧树脂。可用于本发明的组合物中的其他化合物在WO 2003/097756中提及。
优选使用相对较便宜的基于双酚A的液体环氧树脂,特别是双酚A二缩水甘油醚。
根据本发明的组合物用于引发(甲基)丙烯酸类树脂的聚合,所述(甲基)丙烯酸类树脂即基于丙烯酸酯单体或甲基丙烯酸酯单体(其可通过醇和甲基丙烯酸或丙烯酸的酯化而获得)的树脂。根据本发明的组合物通常以相对于所述树脂1∶1至1∶30,优选1∶5至1∶30,还更优选大约1∶10(1份根据本发明的组合物与10份所述树脂混合)的比例(以体积计)使用。
在一个优选的实施方案中,使用包括含有可聚合树脂的隔室和含有根据本发明的组合物的另一隔室的药筒。在使用之时混合所述两个部分以引发聚合。因此经由喷嘴中的静态混合器制得所述混合物。该体系有可能在施用过程中计量粘合剂的量,这对于大规模应用是有利的。因此,在混合两个产品之后,用所述粘合剂体系涂布待组装表面之一或两个表面,并将表面彼此接触放置。
用于(甲基)丙烯酸类粘合剂的提供和使用的这种体系是本领域公知的。其特别描述于WO 03/097756(其涉及与根据本发明的组合物具有相同的聚合引发作用的组合物的组分B,并涉及(甲基)丙烯酸类树脂的组分A)中。
因此,树脂包含(甲基)丙烯酸类单体。在一个优选的实施方案中,其为甲基丙烯酸酯单体。优选地,选择其中醇部分显示出短线性链(即 具有一个或两个碳原子的链)的甲基丙烯酸酯单体。因此,优选的单体为甲基丙烯酸甲酯和甲基丙烯酸乙酯。
在另一实施方案中,所述醇部分显示出至少一个环,所述环可为取代的或未取代的。因此,在该实施方案中,所述单体可特别地选自甲基丙烯酸四氢糠基酯、甲基丙烯酸苯氧基乙酯、甲基丙烯酸异冰片酯、甲基丙烯酸缩水甘油醚、甲基丙烯酸苄酯、甲基丙烯酸环己酯或甲基丙烯酸三甲基环己酯。
也可使用这些酯的混合物。(甲基)丙烯酸酯单体在树脂中的重量百分比优选为20至80%之间,更优选为30至65%之间,还更优选为42至58%之间,即大约在50%附近。
在一个具体实施方案中,所述树脂也包含至少一种丙烯酸酯单体,其中醇部分显示出具有至少6个碳原子的线性链(长链)。因此,优选使用甲基丙烯酸十二烷基酯、甲基丙烯酸2-乙基己酯、丙烯酸2-乙基己酯、基于聚乙二醇的酯,或这些酯的混合物。树脂优选包含至多10重量%,更优选至多8重量%,实际上甚至至多5重量%的这些长链丙烯酸类单体的总量。在一个具体实施方案中,所述树脂包含两种长链丙烯酸酯单体的混合物。优选地,当所述树脂仅包含单个丙烯酸酯单体时,所述丙烯酸酯单体优选以小于或等于8重量%的量存在,而当所述树脂包含这些酯的混合物时,可接受的是其含量为8至10%之间。在此情况中,每一个酯优选以至多5%存在。
所述树脂也可包含其他单体,如丙烯腈、甲基丙烯腈或苯乙烯。
所述树脂也可包括包含苯乙烯的弹性体嵌段共聚物(特别是包含苯乙烯和异戊二烯的弹性体嵌段共聚物或包含苯乙烯和丁二烯或乙烯的弹性体嵌段共聚物)或不同的嵌段共聚物的掺合物。
因此,所述树脂可包含苯乙烯/异戊二烯/苯乙烯(SIS)嵌段共聚物、苯乙烯/丁二烯/苯乙烯(SBS)共聚物、苯乙烯/异戊二烯/丁二烯/苯乙烯(SIBS)共聚物或苯乙烯/乙烯/丁烯/苯乙烯(SEBS)共聚物。其也可包含这些化合物的掺合物,特别是SIS/SBS、SIS/SIBS和SIS/SBS/SIBS掺合物。
优选地,根据本发明的组合物包含5至30重量%之间,优选12至25重量%之间,且更优选15至25重量%之间的弹性体嵌段共聚物。
所述树脂也可包含弹性体。如果需要,其可为官能化的(在其末端显示出双键,特别是甲基丙烯酸酯官能团,以改进与单体的结合)。在一些情况中,选择液体弹性体。优选使用至少一种官能化弹性体,所述至少一种官能化弹性体单独使用或作为与至少一种非官能化弹性体的混合物使用。
当所述树脂包含一种或多种弹性体嵌段共聚物时(参见下文),选择弹性体,使得该弹性体与所用的嵌段共聚物在溶液中可相容。特别地,选择弹性体,使得该弹性体的Hildebrand溶解度参数与所用的嵌段共聚物的Hildebrand溶解度参数可相容。特别地,选择弹性体,使得该弹性体的值与所用的嵌段共聚物的Hildebrand溶解度参数的平均值的差异不大于10%。Hildebrand溶解度参数是公知的,并通过化合物的内聚能密度的平方根计算得到。Hildebrand溶解度参数与色散力(范德华力)直接相关,所述色散力在化学物质分子之间产生。因此,优选使用聚丁二烯均聚物(则其优选选择为液体和官能化的)、聚异戊二烯均聚物或聚氯丁二烯均聚物型的弹性体。也可使用丁二烯/丙烯腈共聚物弹性体,其特别为官能化的。官能团由端链携带,且可使用的官能团为羧基(COOH)、胺基(NH或NH2)、甲基丙烯酸乙烯酯或环氧基团。因此,可使用官能化的聚丁二烯,如HyproTMVTB 2000x168(乙烯基末端)(单独使用或作为与聚氯丁二烯的掺合物使用),或者使用非官能化的聚丁二烯,如HyproTMCTB 2000x162(羧基末端)(Emerald Performance Materials(EPM),Cuyahoga Falls,Ohio,USA)。也可使用分别具有羧基和乙烯基官能团的HyproTM VTBNX或CTBNX(丁二烯/丙烯腈共聚物),更特别地使用HyproTMVTBNX 1300x43或1300x33。
该弹性体有利地以4至30重量%之间,优选6至15重量%之间且更优选8至12重量%之间的量存在于根据本发明的组合物中。当组合物包含一种或多种嵌段共聚物时,使用少量弹性体。
如果树脂包含一种或多种嵌段共聚物,则在组合物中嵌段共聚物∶弹性体混合物的相对比例以重量计为4∶1至0.5∶1之间,优选为大约2∶1。然而,也有可能具有大约0.5∶1量级的相对比例。
根据本发明的组合物也可包含弹性体聚合物粒子,所述弹性体聚合物粒子称为核-壳粒子,是本领域技术人员公知的(特别地描述于US 3 985 703,US 4 304 709,US 6 433 091,EP 1 256 615或US 6 869 497中),并由“硬”热塑性壳和弹性体芯组成,所述“硬”热塑性壳优选基于聚甲基丙烯酸甲酯(PMMA),所述弹性体芯通常基于常与苯乙烯共聚的丁二烯或基于丙烯酸类。
在本发明的实施中,可特别提及丙烯腈/丁二烯/苯乙烯(ABS)、甲基丙烯酸酯/丁二烯/苯乙烯(MBS)、甲基丙烯酸酯/丙烯腈/丁二烯/苯乙烯(MABS)或甲基丙烯酸酯/丙烯腈聚合物和这些聚合物的掺合物。
特别优选冲击改性粒子,尤其是冲击改性MBS(MBS冲击改性剂)。在一个优选实施方案中,这些MBS显示形成芯的聚合物的低交联。此外,这些MBS除了其冲击强度之外,也优选显示出对由冲击引起的碎裂的抗性。
因此,特别地使用来自Arkema(Paris,France)的ClearstrengthC301、C303H、C223、C350、C351、E920或C859型或者DurastrengthD300或D340型粒子,优选MBS C301和C303H。也可使用由Rohm and Haas(Philadelphia,PA,United States)开发的MBS,特别是ParaloidTMBTA 753。
这些粒子可单独使用或作为混合物使用。因此,在本发明的一个具体实施方案中,使用MBS粒子(特别是C303H或C301)和显示出PMMA壳和丙烯腈芯的粒子(特别是D340粒子)的混合物。
优选地,这些粒子以组合物的2至20重量%之间,优选5至15重量%之间的量存在于组合物中。
所述树脂也可包含酸单体,如可通过本领域已知的自由基进行聚合的不饱和羧酸型的酸单体,马来酸、巴豆酸、间苯二甲酸、富马酸,且优选甲基丙烯酸。
也有可能加入丙烯酸异冰片酯(IBXA)、甲基丙烯酸2-羟基乙酯(HEMA)、甲基丙烯酸2-羟基丙酯(HPMA)、丙烯酸2-(全氟辛基)乙酯(POA)、丙烯酸四氢糠基酯(THFA)或异丁氧基甲基丙烯酰胺(IBMA)。可加入这些化合物的混合物,特别是HEMA和HPMA的混合物。
优选地,所述树脂包含甲基丙烯酸、丙烯酸和/或HEMA。加入2 至10%之间,优选3至7%之间的这些化合物的每一种。
根据本发明的树脂也可包含至少一种另外的化合物,如流变剂、聚合加速剂和粘合增进剂。
流变剂用于保证根据本发明的组合物的良好粘性,以使所述组合物能够被容易地施用至待粘合剂结合的表面。可使用聚酰胺,如Disparlon 6500(Kusumoto Chemicals Ltd,Japan),或二氧化硅基粉状要素或等同物(未处理的火成二氧化硅或热解法二氧化硅)。
当加入催化剂时,聚合加速剂用于促进聚合和粘合剂的固化。聚合加速剂为叔胺,优选为芳族叔胺,如二甲基对甲苯胺,和/或2,2’-(对甲苯基亚氨基)二乙醇。也可使用Leuco Crystal Violet(LCV)。
粘合增进剂特别地为甲基丙烯酸酯化的磷酸酯,如甲基丙烯酸2-羟乙酯磷酸酯(来自Rahn AG,Zurich,Switzerland的Genorad 40)。
也可将其他要素加入树脂,所述其他要素如无机填料(TiO2、CaCO3、Al2O3或磷酸锌)、耐紫外辐射的试剂(如来自Ciba-Geigy的2-羟基苯基三嗪或Tinuvin 400)或石蜡。也可加入少量的自由基聚合抑制剂以增加树脂寿命,所述自由基聚合抑制剂如BHT或苯醌,如萘醌、氢醌或乙基氢醌。
所述树脂也可包含硅烷。选择显示出乙烯基、甲基丙烯酸酯/丙烯酸酯或胺基官能团的硅烷(乙烯基硅烷、丙烯酰基氧基硅烷或氨基硅烷)。
可用于本发明的情况中的树脂以及它们的应用详细描述于申请WO 2008/080913和WO 2008/125521中。
根据本发明的组合物与丙烯酸类树脂一起使用,以促进基材彼此之间的粘合,并且当根据本发明的组合物适用于将材料粘合剂结合至复合材料时,其是特别有利的。
因此,有可能进行金属、塑料或复合材料对复合材料的粘合剂结合。因此,应用特别是在筒仓、风力涡轮机、船只或货车挂车的构建领域。本发明描述的体系也可用于机动车辆工业领域或铁路领域。
因此,根据本发明的体系的树脂/组合物有可能将一种材料粘合至另一材料,所述一种材料或另一材料特别为金属、塑料、木材或复合材料。因此,组合物可用于如下应用中的一种或其他种:金属/金属粘 合、金属/复合材料粘合、金属/塑料粘合、金属/木材粘合、木材/塑料粘合、木材/复合材料粘合、木材/木材粘合、塑料/复合材料粘合、塑料/塑料粘合或复合材料/复合材料粘合。
根据本发明的体系特别用于促进部件对在闭式模具中获得的复合材料,特别是RTM(树脂传递模塑)复合材料的粘合。
为了改进粘合剂性能,可在粘合之前处理这些复合材料。所述处理由砂磨阶段和/或清洁阶段组成,以为了去除易于妨碍聚合,并存在于复合材料(如RTM复合材料)的表面上的要素(特别是脱模剂)。清洁可使用异丙醇进行。
实施例
根据衍生自标准ISO 4587的方案测量拉伸剪切强度(SS)。简言之,使用尺寸为100×25×1.6mm(l×w×t)的复合材料的测试试样。将两个测试试样彼此粘合剂结合,重叠面积为25×12mm(300mm2),粘合剂密封的厚度为大约200至400μm。随后测量通过拉引两个测试试样而破坏粘合所需的力。寻找两个测试试样之一的接触表面的撕裂。
根据特别地由标准ISO 527描述的方法观察断裂伸长,粘合剂的牵伸速率恒定,并为50mm/min。
制备包含自由基聚合引发剂的两种组合物。
组合物I:
组合物II:
Epon 828(液体环氧树脂) | 20% |
环氧化的硅烷(Coatosil 1770) | 5% |
氧化钛 | 20% |
[0073]
消泡剂(Byk 088) | 1% |
二氧化硅(惰性和Cab-O-Sil M5) | 14% |
作为糊剂的50%过氧化苯甲酰 | 40% |
所用的作为糊剂的过氧化苯甲酰包含大约50%的过氧化苯甲酰、大约25%的增塑剂和大约25%的填料、稳定剂和流变剂。
因此,所述两种组合物包含大约20%的过氧化物。
组合物I包含大约22%的增塑剂,而组合物II仅包含10%的增塑剂(源自过氧化物源)。
在组合物II中,增塑剂被惰性填料(二氧化硅)和环氧化的硅烷代替。
这些聚合引发剂与树脂一起使用:
树脂和聚合引发剂(组合物I或组合物II)以比例10∶1(以体积计)混合,即10份树脂/1份过氧化物基试剂。
测量树脂的剪切强度SS和断裂伸长。
通过用颗粒80砂磨,并用异丙醇清洗来制备RTM测试试样。
因此,当催化组合物包含环氧化的硅烷时,观察到更好的剪切强度,而同时保持粘合剂的伸长性质。
权利要求书(按照条约第19条的修改)
1.一种聚合催化剂,其可用于结构粘合剂中,并旨在将其加入包含单体试剂的树脂中以引发所述树脂的聚合,所述聚合催化剂包含自由基聚合引发剂和环氧化的硅烷。
2.根据权利要求1所述的催化剂,其特征在于所述催化剂不包含增塑剂,或特征在于所述催化剂包含至多20%(以重量计)的增塑剂。
3.根据权利要求1和2中任一项所述的催化剂,其特征在于所述自由基聚合引发剂为过氧化物。
4.根据权利要求3所述的催化剂,其特征在于所述过氧化物为过氧化苯甲酰。
5.根据权利要求1至4中之一所述的催化剂,其特征在于所述催化剂包含5至40重量%之间的聚合引发剂。
6.根据权利要求1至5中之一所述的催化剂,其特征在于所述催化剂包含10至20重量%之间的聚合引发剂。
7.根据权利要求1至6中之一所述的催化剂,其特征在于所述催化剂另外包含环氧树脂。
8.根据权利要求1至7中之一所述的催化剂,其特征在于所述催化剂另外包含无机填料。
9.根据权利要求1至8中之一所述的催化剂用于引发(甲基)丙烯酸类树脂的聚合的用途。
10.根据权利要求9所述的用途,其特征在于所述催化剂以相对于所述树脂1∶1至1∶30(以体积计)的比例使用。
11.根据权利要求10所述的用途,其特征在于所述催化剂以1∶10的以体积计的比例(1份组合物/10份树脂)使用。
12.根据权利要求9至11中之一所述的用途,其特征在于所述树脂另外包含至少一种其他要素,所述其他要素选自包含苯乙烯和异戊二烯的弹性体嵌段共聚物、包含苯乙烯和丁二烯或乙烯的弹性体嵌段共聚物、弹性体、其中醇部分显示出至少一个具有至少6个碳原子的线性链的丙烯酸酯单体、聚合加速剂、流变剂、粘合增进剂、酸单体、由热塑性壳和弹性体芯形成的粒子(丙烯腈/丁二烯/苯乙烯、甲基丙烯酸酯/丁二烯/苯乙烯、甲基丙烯酸酯/丙烯腈/丁二烯/苯乙烯或甲基丙烯酸酯/丙烯腈粒子和这些的混合物)。
13.根据权利要求9至12中之一所述的用于促进部件对复合材料,特别是RTM(树脂传递模塑)复合材料的粘合的用途。
Claims (13)
1.一种可用于结构粘合剂中的组合物,其包含自由基聚合引发剂和环氧化的硅烷。
2.根据权利要求1所述的组合物,其特征在于所述组合物不包含增塑剂,或特征在于所述组合物包含至多20%(以重量计)的增塑剂。
3.根据权利要求1和2中任一项所述的组合物,其特征在于所述自由基聚合引发剂为过氧化物。
4.根据权利要求3所述的组合物,其特征在于所述过氧化物为过氧化苯甲酰。
5.根据权利要求1至4中之一所述的组合物,其特征在于所述组合物包含5至40重量%之间的聚合引发剂。
6.根据权利要求1至5中之一所述的组合物,其特征在于所述组合物包含10至20重量%之间的聚合引发剂。
7.根据权利要求1至6中之一所述的组合物,其特征在于所述组合物另外包含环氧树脂。
8.根据权利要求1至7中之一所述的组合物,其特征在于所述组合物另外包含无机填料。
9.根据权利要求1至8中之一所述的组合物用于引发(甲基)丙烯酸类树脂的聚合的用途。
10.根据权利要求9所述的用途,其特征在于所述组合物以相对于所述树脂1∶1至1∶30(以体积计)的比例使用。
11.根据权利要求10所述的用途,其特征在于所述组合物以1∶10的以体积计的比例(1份组合物/10份树脂)使用。
12.根据权利要求9至11中之一所述的用途,其特征在于所述树脂另外包含至少一种其他要素,所述其他要素选自包含苯乙烯和异戊二烯的弹性体嵌段共聚物、包含苯乙烯和丁二烯或乙烯的弹性体嵌段共聚物、弹性体、其中醇部分显示出至少一个具有至少6个碳原子的线性链的丙烯酸酯单体、聚合加速剂、流变剂、粘合增进剂、酸单体、由热塑性壳和弹性体芯形成的粒子(丙烯腈/丁二烯/苯乙烯、甲基丙烯酸酯/丁二烯/苯乙烯、甲基丙烯酸酯/丙烯腈/丁二烯/苯乙烯或甲基丙烯酸酯/丙烯腈粒子和这些的混合物)。
13.根据权利要求9至12中之一所述的用于促进部件对复合材料,特别是RTM(树脂传递模塑)复合材料的粘合的用途。
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2010
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- 2010-09-15 SG SG2012019097A patent/SG179210A1/en unknown
- 2010-09-15 PL PL15162106T patent/PL2944655T3/pl unknown
- 2010-09-15 PT PT151621067T patent/PT2944655T/pt unknown
- 2010-09-15 LT LTEP15162106.7T patent/LT2944655T/lt unknown
- 2010-09-15 JP JP2012529263A patent/JP5946408B2/ja active Active
- 2010-09-15 CA CA2774025A patent/CA2774025C/fr active Active
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- 2010-09-15 EP EP15162106.7A patent/EP2944655B1/fr active Active
- 2010-09-15 WO PCT/EP2010/063580 patent/WO2011033002A1/fr active Application Filing
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Publication number | Priority date | Publication date | Assignee | Title |
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CN110769799A (zh) * | 2017-06-23 | 2020-02-07 | 皮埃尔·罗兰多牙科用品有限公司 | 牙用粘合剂 |
AU2018287701B2 (en) * | 2017-06-23 | 2023-11-02 | Produits Dentaires Pierre Rolland | A dental adhesive |
CN109054709A (zh) * | 2018-06-29 | 2018-12-21 | 安徽尼古拉电子科技有限公司 | 一种微电子产品用耐腐蚀封装胶及其制备方法 |
Also Published As
Publication number | Publication date |
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IN2012DN02991A (zh) | 2015-07-31 |
JP5946408B2 (ja) | 2016-07-06 |
DK2944655T3 (en) | 2017-04-03 |
CN102666595B (zh) | 2015-08-19 |
EP2478017B1 (fr) | 2015-04-01 |
SG179210A1 (en) | 2012-05-30 |
CA2774025C (fr) | 2017-12-05 |
CA2774025A1 (fr) | 2011-03-24 |
PT2944655T (pt) | 2017-03-17 |
KR101771751B1 (ko) | 2017-08-25 |
EP2944655A1 (fr) | 2015-11-18 |
LT2944655T (lt) | 2017-04-10 |
MX2012003187A (es) | 2012-05-08 |
ES2620464T3 (es) | 2017-06-28 |
FR2950059B1 (fr) | 2016-09-16 |
FR2950059A1 (fr) | 2011-03-18 |
BR112012005858A2 (pt) | 2020-11-03 |
US9540456B2 (en) | 2017-01-10 |
KR20120073277A (ko) | 2012-07-04 |
WO2011033002A1 (fr) | 2011-03-24 |
JP2013504677A (ja) | 2013-02-07 |
ES2541359T3 (es) | 2015-07-17 |
HK1175487A1 (zh) | 2013-07-05 |
BR112012005858B1 (pt) | 2021-05-18 |
US20120252978A1 (en) | 2012-10-04 |
DK2478017T3 (en) | 2015-07-13 |
PL2944655T3 (pl) | 2017-06-30 |
PL2478017T3 (pl) | 2015-08-31 |
EP2478017A1 (fr) | 2012-07-25 |
EP2944655B1 (fr) | 2016-12-28 |
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