CN105764958B - 固化自由基可固化树脂的方法 - Google Patents

固化自由基可固化树脂的方法 Download PDF

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CN105764958B
CN105764958B CN201480064268.XA CN201480064268A CN105764958B CN 105764958 B CN105764958 B CN 105764958B CN 201480064268 A CN201480064268 A CN 201480064268A CN 105764958 B CN105764958 B CN 105764958B
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登 贝格 M·范
A·G·塔耶马
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Abstract

本发明涉及一种固化自由基可固化树脂的方法，其通过向该树脂添加有机过氧化物及带金属聚合物进行，该带金属聚合物包含与选自由Cu、Mn、Fe及V组成的群的金属配位且与该金属及络合剂一起形成配合物的官能基。

Description

固化自由基可固化树脂的方法
本发明涉及一种加速用有机过氧化物经氧化还原体系固化自由基可固化树脂的方法。
常规氧化还原体系包含氧化剂(例如过氧化物)及作为加速剂的可溶性过渡金属离子。加速剂用于提高氧化剂在较低温下的活性，且因此加速固化。
加速剂体系可添加至欲以不同方式固化的树脂。一种方法涉及在添加过氧化物之前将个别加速剂成分添加至树脂。这可在即将添加过氧化物之前进行或在添加过氧化物前几天或几周进行。在后一情况下，涉及预加速的树脂组合物，其包含树脂及加速剂成分且可储存直至进一步使用及用过氧化物固化。另一方法涉及预先制备含有加速剂成分的加速剂溶液，该溶液可储存直至进一步使用及添加至树脂。经预加速的树脂可通过将加速剂体系的个别成分添加至树脂或通过添加呈加速剂溶液形式的这些成分的混合物来制备。
典型加速剂体系包含过渡金属盐或配合物。用于此目的的最常用过渡金属为钴。然而，鉴于钴的毒性，法规要求减少钴的量。
因此，需要提供无Co的加速剂。公开此类无Co的加速剂体系的文献实例为WO2008/003492、WO 2008/003793及WO 2008/003500。根据这些文献，用于加速剂体系的金属为Mn、Cu、Fe及Ti而非Co。所公开的加速剂体系以经预加速的树脂形式存在于不饱和聚酯或乙烯基酯树脂中。据称此经预加速的树脂每公斤树脂含有小于0.01mmol Co。
这些申请中所公开的金属化合物为金属羧酸盐、乙酰乙酸盐及氯化物。虽然比许多钴盐及配合物害处小，但这些金属化合物中有许多也存在毒性及环境问题。因此，需要甚至较少健康及/或环境问题的加速剂体系。
本发明提供此类体系。本发明涉及一种固化自由基可固化树脂的方法，通过向该树脂添加有机过氧化物及带金属聚合物而进行，该带金属聚合物包含与选自由Cu、Mn、Fe及V组成的群的金属配位且与该金属及络合剂一起形成配合物的官能基。
术语“配位”及“络合”在本说明书中涉及金属与有机化合物之间任何形式的相互作用，以离子键或金属-配体相互作用形式。
本发明也关于一种适用于与过氧化物形成氧化还原对且包含带金属聚合物及溶剂的加速剂溶液。
本发明也关于一种包含用该带金属聚合物预加速的树脂及有机过氧化物的双组分组合物。
应注意带Mn聚合物已公开于WO 2012/000934中。此聚合物在醇酸树脂基油漆及油墨中用作干燥剂。然而，此醇酸树脂固化涉及风干方法；非类似本发明方法使用过氧化物的自由基方法。
带金属聚合物可为任何类型聚合物，包括均聚物、无规共聚物及嵌段共聚物。适合聚合物的实例为聚苯乙烯、苯乙烯-马来酸酐共聚物、聚丙烯酸酯或聚甲基丙烯酸酯、饱和或不饱和聚酯、聚酰胺及聚酰亚胺。聚酯为最优选的。甚至更优选为不饱和聚酯。
聚合物优选为极性的。这例如与醇酸树脂形成对比，后者因其脂肪酸链而极具非极性。
聚合物的重量平均分子量优选在500g/mol至50,000g/mol，更优选1,000g/mol至20,000g/mol，且最优选5,000g/mol至10,000g/mol范围内。此分子量使用聚苯乙烯标准物，通过高效尺寸排阻层析法(HP-SEC)来测定。
存在于聚合物上的官能基的实例为胺、羧酸酯、膦酸酯、膦酸、膦、1,3-二酮、具有结构R-C(＝O)-CH2-C(＝NR)-R的亚胺及例如双吡酮(bispidon)配体(例如，2,4-二(2-吡啶基)-3-甲基-7-(吡啶-2-基甲基)-3,7-二氮-双环[3.3.1]壬-9-酮-1,5-二甲酸二甲酯三甲基-1,4,7-三氮杂环壬烷)、冠醚、氮杂-冠醚、苯并-冠醚、卟啉(porphirine)及离子载体(ionophore)的配体。
最优选为胺、羧酸酯、1,3-二酮及双吡酮配体。
这些官能基可例如以描述于A.G.Talma等人,Synthesis 1986,680-683中的方式，在制备聚合物期间通过共聚合具有所需官能基的单体引入聚合物。配体官能化单体可通过首先用可与适合单体(例如，羟基及氨基)反应的基团官能化该配体，之后使该官能化配体与单体反应来制备。
也有可能例如经由加成化学或缩合反应(例如，酰胺化或酯化)将配体或官能基引入现有聚合物。
金属可添加至官能化聚合物，或可在制备该官能化聚合物期间已存在。
带金属聚合物的金属含量优选在以带金属聚合物重量计0.01wt％至15wt％，更优选0.1wt％至10wt％，且最优选1wt％至5wt％范围内。此金属含量可易于通过ICP测定。
金属选自由Cu、Mn、Fe及V组成的群。优选金属为Cu、Fe及V。
金属由该聚合物中的官能基且由络合剂两者络合。此络合剂可选自带羧酸酯化合物、1,3-二酮、卤素原子、胺、膦酸酯、膦酸、膦、具有结构R-C(＝O)-CH2-C(＝NR)-R的亚胺及例如冠醚、氮杂-冠醚、苯并-冠醚、卟啉及离子载体的配体。
适合带羧酸酯化合物的实例为2-乙基己酸酯、辛酸酯、壬酸酯、庚酸酯、新癸酸酯、环烷酸酯及如上文所描述的带羧酸酯聚合物。
1,3-二酮的实例为乙酰基丙酮、苯甲酰基丙酮及二苯甲酰基甲烷，及乙酰乙酸酯例如二乙基乙酰乙酰胺、二甲基乙酰乙酰胺、二丙基乙酰乙酰胺、二丁基乙酰乙酰胺、乙酰乙酸甲酯、乙酰乙酸乙酯、乙酰乙酸丙酯及乙酰乙酸丁酯。
优选卤素原子为Cl。
带金属聚合物可用于加速不饱和树脂的自由基固化。带金属聚合物可按原样或以除带金属聚合物外含有溶剂及任选地存在的其他化合物的所谓加速剂溶液形式添加至树脂中。
带金属聚合物可在即将添加过氧化物之前或在添加过氧化物之前几天或几周添加至树脂(按原样或以加速剂溶液形式)。在后一情况下，涉及经预加速的树脂。
适合溶剂的实例为磷化合物及羟基官能性溶剂。优选地，加速剂溶液含有至少一种选自以下的溶剂：具有式P(R)3、P(R)3＝O及HO-(-CH2-C(R1)2-(CH2)m-O-)n-R2的化合物，其中各R独立地选自氢、具有1至10个碳原子的烷基及具有1至10个碳原子的烷氧基，各R1独立地选自由氢、具有1至10个碳原子的烷基及具有1至10个碳原子的羟基烷基组成的群，n＝1至10，m＝0或1，且R2为氢或具有1至10个碳原子的烷基。
优选地，在具有式P(R)3及P(R)3＝O的磷化合物中，至少两个R基团选自烷基或烷氧基。适合含磷化合物的特定实例为磷酸二乙酯、磷酸二丁酯、磷酸三丁酯、磷酸三乙酯(TEP)、亚磷酸二丁酯及磷酸三乙酯。
在式HO-(-CH2-C(R1)2-(CH2)m-O-)n-R2中，各R1优选独立选自H、CH3及CH2OH。此类溶剂的实例为二醇，如二甘醇单丁醚、乙二醇、二甘醇、二丙二醇及聚乙二醇、甘油及季戊四醇。
另外，加速剂溶液可包含额外有机化合物，例如脂族烃溶剂(例如石油溶剂、石蜡或无味矿油精(OMS))；芳族烃溶剂(例如萘或萘混合物)；醛；酮(例如1,2-二酮，如丁二酮或乙二醛)；醚；酯(例如马来酸二丁酯、琥珀酸二丁酯、乙酸乙酯、乙酸丁酯、酮戊二酸的单酯及二酯、丙酮酸酯、抗坏血酸酯(例如抗坏血酸棕榈酸酯、丙二酸二乙酯或琥珀酸酯)；醇类(例如异丁醇、戊醇、苯甲醇或脂肪醇)；磷酸盐；酰胺；羧酸；1,2-二肟；N-甲基吡咯烷酮；N-乙基吡咯烷酮；二甲基甲酰胺(DMF)；二甲亚砜(DMSO)；及2,2,4-三甲基戊二醇二异丁酸酯(TXIB)；
加速剂溶液及经预加速的树脂可任选地含有一或多种促进剂、碱、水、抑制剂、添加剂及/或填料。
适合促进剂为铵、碱金属或碱土金属的羧酸盐。铵、碱金属及碱土金属的适合金属羰酸盐的实例为2-乙基己酸盐(也即辛酸盐)、壬酸盐、庚酸盐、新癸酸盐及萘酸盐。优选碱金属为K。盐可按原样添加至加速剂溶液或树脂中，或其可当场形成。举例而言，碱金属2-乙基己酸盐可在将碱金属氢氧化物及2-乙基己酸添加至溶液之后在加速剂溶液中当场制备。
若一或多种促进剂存在于加速剂溶液中，则其量优选为至少0.01wt％，更优选至少0.1wt％，甚至更优选至少1wt％，更优选至少10wt％，且最优选至少20wt％；优选不超过90wt％，更优选不超过80wt％，且最优选不超过70wt％，均以加速剂溶液的总重量计。
待存在于加速剂溶液及经预加速的树脂中的适合含氮碱为伯胺、仲胺及叔胺，例如三乙胺、二甲基苯胺、二乙基苯胺或N,N-二甲基-对-甲苯胺(DMPT)；多元胺，例如1,2-(二甲基胺)乙烷；仲胺，例如二乙胺；乙氧基化胺，例如三乙醇胺、二甲氨基乙醇、二乙醇胺或单乙醇胺；及芳族胺，例如吡啶或联吡啶。含氮碱优选以5wt％至50wt％的量存在于加速剂溶液中。其优选以0.5g/kg树脂至10g/kg树脂的量存在于经预加速的树脂中。
加速剂溶液可任选地包含水。若存在，则溶液的水含量优选为至少0.01wt％且更优选至少0.1wt％。水含量优选不超过50wt％，更优选不超过40wt％，更优选不超过20wt％，甚至更优选不超过10wt％，且最优选不超过5wt％，均以加速剂溶液的总重量计。
加速剂溶液可通过简单地混合各成分，任选地伴以中间加热及/或混合步骤来制备。
经预加速的树脂可以不同方式制备：通过混合个别成分与树脂，或通过混合包括任选单体的树脂与根据本发明的加速剂溶液。优选后一方法。
待根据本发明方法固化的适合树脂包括醇酸树脂、不饱和聚酯(UP)树脂、乙烯基酯树脂、(甲基)丙烯酸酯树脂、聚氨酯、环氧树脂及其混合物。优选树脂为(甲基)丙烯酸酯树脂、UP树脂及乙烯基酯树脂。
在本申请的上下文中，术语“不饱和聚酯树脂”及“UP树脂”是指不饱和聚酯树脂与烯属不饱和单体化合物的组合。术语乙烯基酯树脂是指通过环氧树脂与不饱和单羧酸酯化产生，且溶解于烯属不饱和单体化合物(例如苯乙烯)中的树脂。如上文所定义的UP树脂及乙烯基酯树脂为惯例且市场有售。
待通过本发明的方法固化的适合UP树脂为所谓邻位型树脂、间位型树脂、间位-npg型树脂及二环戊二烯(DCPD)树脂。此类树脂的实例为马来酸、富马酸、烯丙基、乙烯属及环氧型树脂、双酚A树脂、对苯二甲酸树脂及杂化树脂。
不含额外烯属不饱和单体化合物(如苯乙烯)的丙烯酸酯及甲基丙烯酸脂树脂在本申请中称为(甲基)丙烯酸酯树脂。
烯属不饱和单体化合物的实例包括苯乙烯及苯乙烯衍生物，如α-甲苯苯乙烯、乙烯基甲苯、茚、二乙烯基苯、乙烯基吡咯烷酮、乙烯基硅氧烷、乙烯基己内酰胺、茋，以及邻苯二甲酸二烯丙酯、二亚苄基丙酮、烯丙基苯、甲基丙烯酸甲酯、丙烯酸甲酯、(甲基)丙烯酸、二丙烯酸酯、二甲基丙烯酸酯、丙烯酰胺；乙酸乙烯酯、氰脲酸三烯丙酯、异氰脲酸三烯丙酯、用于光学应用的烯丙基化合物(例如(二)乙二醇二烯丙基碳酸酯)、氯苯乙烯、叔丁基苯乙烯、丙烯酸叔丁酯、丁二醇二甲基丙烯酸酯及其混合物。(甲基)丙烯酸酯反应性稀释剂的适合实例为PEG200二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,3-丁二醇二(甲基)丙烯酸酯、2,3-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯及其异构体；二甘醇二(甲基)丙烯酸酯、三甘醇二(甲基)丙烯酸酯、甘油二(甲基)丙烯酸酯、三羟甲基丙烷二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、二丙二醇二(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯、PPG250二(甲基)丙烯酸酯、三环癸烷二羟甲基二(甲基)丙烯酸酯、1,10-癸二醇二(甲基)丙烯酸酯、四甘醇二(甲基)丙烯酸酯、三羟甲基丙烷三(甲基)丙烯酸酯、(甲基)丙烯酸缩水甘油酯、(双)马来酰亚胺、(双)柠康酰亚胺、(双)衣康酰亚胺及其混合物。
烯属不饱和单体在经预加速的树脂中的量优选为以树脂重量计的至少0.1wt％，更优选至少1wt％，且最优选至少5wt％。烯属不饱和单体的量优选为不超过50wt％，更优选不超过40wt％，且最优选不超过35wt％。
若加速剂溶液用于固化树脂或用于制备经预加速的树脂，则加速剂溶液一般以树脂的重量计至少0.01wt％，优选至少0.1wt％，且优选不超过5wt％，更优选不超过3wt％加速剂溶液的量使用。
适用于固化树脂且适用于存在于双组分组合物的第二组分中的过氧化物包括无机过氧化物及有机过氧化物，例如常规使用的酮过氧化物、过氧酯、二芳基过氧化物、二烷基过氧化物及过氧二碳酸酯；以及过氧碳酸酯、过氧缩酮、氢过氧化物、二酰基过氧化物及过氧化氢。优选过氧化物为有机氢过氧化物、酮过氧化物、过氧酯及过氧碳酸酯。甚至更优选为氢过氧化物及酮过氧化物。优选氢过氧化物包括枯基氢过氧化物、1,1,3,3-四甲基丁基氢过氧化物、叔丁基氢过氧化物、异丙基枯基氢过氧化物、叔戊基氢过氧化物、2,5-二甲基己基-2,5-二氢过氧化物、蒎烷氢过氧化物、对-薄荷烷-氢过氧化物、萜类-氢过氧化物及蒎烯氢过氧化物。优选酮过氧化物包括甲基乙基酮过氧化物、甲基异丙基酮过氧化物、甲基异丁基酮过氧化物、环己酮过氧化物及乙酰丙酮过氧化物。
当然，也可使用两种或更多种过氧化物的混合物；例如氢过氧化物或酮过氧化物与过氧酯的组合。
尤其优选的过氧化物为甲基乙基酮过氧化物。本领域熟练技术人员应理解这些过氧化物可与常规添加剂(例如填料、颜料及减敏剂(phlegmatiser))组合。减敏剂的实例为亲水性酯及烃溶剂。待用于固化树脂的过氧化物的量优选为每100份树脂至少0.1(phr)，更优选至少0.5phr，且最优选至少1phr。过氧化物的量优选不超过8phr，更优选不超过5phr，最优选不超过2phr。
固化一般通过将根据本发明的加速剂溶液及引发剂(过氧化物)添加至树脂中，或通过将过氧化物添加至经预加速的树脂开始。换言之，过氧化物可添加至经预加速的树脂，添加至树脂与加速剂溶液的预混物，或在添加加速剂溶液之前添加至树脂。
混合且分散所得混合物。取决于引发剂体系、加速剂体系、调适固化速率的化合物及待固化的树脂组合物，固化工艺可在-15℃至250℃的任何温度下进行。优选地，其在例如手工涂布、喷布、长丝卷绕、树脂转移模制、涂布(例如凝胶涂布及标准涂布)、按钮制造、离心铸造、波纹薄片或扁平面板、换衬体系、倾倒化合物的厨房水槽等应用中常用的环境温度下进行。然而，其也可用于SMC、BMC、拉挤成形技术等，上述技术使用高达180℃，更优选高达150℃，最优选高达100℃的温度。
例如填料、纤维、颜料、抑制剂、辅剂及促进剂的其他任选地选用的添加剂可用于固化工艺。
纤维的实例为玻璃纤维、碳纤维、芳族聚酰胺纤维(例如)、天然纤维(例如黄麻、洋麻、工业大麻、亚麻(亚麻布)、苎麻等)。
填料的实例为石英、沙石、氢氧化铝、氢氧化镁、白垩、氢氧化钙、黏土及石灰。
固化树脂可经受固化后处理以进一步使硬度优化。此类固化后处理一般在40℃至180℃温度范围内进行30分钟至15小时。
固化树脂可用于不同应用，包括海事应用、化学锚定、屋面、建筑、换衬、管道及贮槽、地板、风车叶片、层压制品等。

Claims (7)

1.一种固化自由基可固化树脂的方法，其通过向该树脂添加有机过氧化物及带金属聚合物进行，其中该树脂选自不饱和聚酯树脂和乙烯基酯树脂，该带金属聚合物包含与选自由Cu、Mn、Fe及V组成的群的金属配位且与该金属及络合剂一起形成配合物的官能基。
2.根据权利要求1的方法，其中该金属选自由Cu、Fe及V组成的群。
3.一种双组分组合物，其包含第一组分及第二组分，该第一组分包含自由基可固化树脂及带金属聚合物，其中该树脂选自不饱和聚酯树脂和乙烯基酯树脂，该带金属聚合物包含与选自由Cu、Mn、Fe及V组成的群的金属配位且与该金属及络合剂一起形成配合物的官能基；该第二组分包含有机过氧化物。
4.根据权利要求3的双组分组合物，其中该过氧化物选自由有机氢过氧化物、酮过氧化物、过氧碳酸酯及过氧酯组成的群。
5.根据权利要求3或4的双组分组合物，其中该金属选自由Cu、Fe及V组成的群。
6.根据权利要求1或2的方法，其中以加速剂溶液形式将该带金属聚合物添加至该树脂中，该加速剂溶液适用于与过氧化物形成氧化还原对，其包含：
-至少一种选自具有式P(R)3、P(R)3＝O及HO-(-CH2-C(R1)2-(CH2)m-O-)n-R2的化合物的溶剂，其中各R独立选自氢、具有1至10个碳原子的烷基及具有1至10个碳原子的烷氧基，各R1独立选自由氢、具有1至10个碳原子的烷基及具有1至10个碳原子的羟基烷基组成的群，n＝1至10，m＝0或1，且R2为氢或具有1至10个碳原子的烷基，及
-带金属聚合物，该带金属聚合物包含与选自由Cu、Mn、Fe及V组成的群的金属配位且与该金属及络合剂一起形成配合物的官能基。
7.根据权利要求1或2的方法，其包括如下步骤：提供双组分组合物，该双组分组合物包含第一组分及第二组分，该第一组分包含自由基可固化树脂及带金属聚合物，其中该树脂选自不饱和聚酯树脂和乙烯基酯树脂，该带金属聚合物包含与选自由Cu、Mn、Fe及V组成的群的金属配位且与该金属及络合剂一起形成配合物的官能基，该第二组分包含有机过氧化物，及混合该第一组分与该第二组分。
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3282909A (en) * 1965-05-18 1966-11-01 Exxon Research Engineering Co Metallo-organic polymers, their preparation and utility
US5212210A (en) * 1992-03-18 1993-05-18 Minnesota Mining And Manufacturing Company Energy curable compositions having improved cure speeds

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3476532A (en) 1964-11-25 1969-11-04 Allied Chem Metal-containing complexes of oxidized polyethylene
JPH04504873A (ja) * 1989-04-26 1992-08-27 アクゾ　ナムローゼ　フェンノートシャップ チオール系化合物重合触媒
US5419954A (en) * 1993-02-04 1995-05-30 The Alpha Corporation Composition including a catalytic metal-polymer complex and a method of manufacturing a laminate preform or a laminate which is catalytically effective for subsequent electroless metallization thereof
US6063637A (en) 1995-12-13 2000-05-16 California Institute Of Technology Sensors for sugars and other metal binding analytes
US8268189B2 (en) * 2005-05-31 2012-09-18 Akzo Nobel N.V. Storage-stable accelerator solution
ES1063481Y (es) 2006-07-03 2007-03-01 Saez Rosanna Pastor Protector para pies
EP2038338B1 (en) * 2006-07-06 2017-10-04 Akzo Nobel Chemicals International B.V. Unsaturated polyester resin or vinyl ester resin compositions
DK2038311T3 (en) 2006-07-06 2014-03-24 Dsm Ip Assets Bv UNSATURED POLYESTER RESIST OR VINYL RESIST COMPOSITIONS
US20100041836A1 (en) 2006-07-06 2010-02-18 Johan Franz Gradus Antonius Jansen Unsaturated polyester resin compositions
MX2009010657A (es) * 2007-04-02 2009-12-16 Akzo Nobel Nv Solucion aceleradora.
EP2014729A1 (en) 2007-07-09 2009-01-14 Sicpa Holding S.A. Vanadium-drier intaglio ink
JP5561454B2 (ja) * 2008-05-23 2014-07-30 スリーボンドファインケミカル株式会社 硬化型樹脂組成物
WO2011057673A1 (en) * 2009-11-13 2011-05-19 Felicitas Grauer Animal tracking and surveillance system
MY160959A (en) 2010-06-16 2017-03-31 Akzo Nobel Chemicals Int Bv Accelerator solution and process for curing curable resins
WO2012000934A1 (en) 2010-06-29 2012-01-05 Umicore Manganese based catalytic dryer for polymer coatings

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3282909A (en) * 1965-05-18 1966-11-01 Exxon Research Engineering Co Metallo-organic polymers, their preparation and utility
US5212210A (en) * 1992-03-18 1993-05-18 Minnesota Mining And Manufacturing Company Energy curable compositions having improved cure speeds

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