CN1127005A - 环氧树脂和环氧化聚二烯的相容共混物 - Google Patents
环氧树脂和环氧化聚二烯的相容共混物 Download PDFInfo
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Abstract
一种相容聚合物共混物含有可固化芳香环氧树脂、环氧化聚二烯聚合物，和酐或多羧酸固化剂。此外本发明涉及含有所述固化相容聚合物共混物的结构粘合剂组合物。
Description
本发明涉及环氧树脂和环氧化聚二烯聚合物的相容共混物。更具体地讲，本发明涉及环氧树脂和环氧化聚二烯相容并用酐固化剂固化的共混物。
诸如缩水甘油醚的环氧树脂由表氯醇和一种至少含有一个羟基的化合物在碱性反应条件下进行反应来制备，已知可用于粘合剂中，并且特别用于结构粘合剂。在美国专利5,169,910中介绍了这类环氧树脂。结构粘合剂是用于在粘合体间形成永久承重连接的粘合剂并通常应有强度高、粘合性好和耐环境的特性。含有这类环氧树脂的结构粘合剂的缺点是呈刚性和耐冲击性差。
此外已知低粘度环氧化聚二烯聚合物可用于粘合剂中。在美国专利5,229,464中介绍了这类聚合物。这类聚合物相对来说柔度较高和耐冲击性好。
把环氧树脂和聚二烯共混以得到具有两种聚合物共同特性即高强度以及柔韧性和耐冲击性好的共混物。这看起来是很有利的。然而，已发现这种类型的环氧树脂与聚二烯不相容。这将在下面的实施例中详细讨论。因此，很明显，能制成一种环氧树脂和环氧化聚二烯的相容共混物是很有利的。本发明提供一种这两种聚合物相容并通过引入酐固化剂而固化的共混物。
因此本发明涉及一种聚合物共混物，有足够的相容性以形成一种均匀混合物，其中含有可固化芳香环氧树脂、环氧化聚二烯聚合物和一种酐或多羧酸固化剂。优选一种加速剂加到共混物中而使共混物固化。借助固化剂的存在，该共混物可通过在93—178℃的烘箱中焙烤而固化。
优选环氧树脂是通过表氯醇和一种至少含有一个羟基的芳香化合物在碱性反应条件下进行反应而制备的缩水甘油醚。优选的环氧化聚二烯聚合物是低分子量、低粘度并且环氧化作用相对较低的聚合物。适宜的酐固化剂是选自邻苯二甲酸酐、取代邻苯二甲酸酐和氢化邻苯二甲酸酐。优选的酐固化剂是十二碳烯基琥珀酐和六氢化邻苯二甲酸酐。
根据本发明的组合物包含环氧树脂。组合物的环氧树脂组分可以是任何可固化树脂，平均每个分子有一个以上的邻位环氧基团和至少有一个芳香基团，并且可以带有不会严重影响固化反应的取代基。
适宜的环氧树脂包括通过表氯醇和一种至少含有一个羟基的芳香化合物在碱性反应条件下进行反应而制备的缩水甘油醚。当含羟基的化合物是双酚—A时得到的环氧树脂产物以下面的结构式表示，其中n是0或大于0的数，通常在范围0—10之间，优选0—2之间，R是H或烷基，优选甲基或乙基。
其它适宜的环氧树脂可通过表氯醇与诸如间苯二酚和间苯三酚之类的单环二或三羟基酚化合物、诸如双(对—羟苯基)甲烷和4，4—二羟基联苯之类的特定多元环多羟基酚化合物，或诸如1，4—丁二醇和丙三醇之类的脂族多元醇反应而制备。
适用于本发明组合物的环氧树脂的分子量通常在范围86—10000，优选200—1500之间。市场上的环氧树脂EPON，树脂828是一种表氯醇和2，2—双(4—羟苯基丙烷)(双酚—A)的反应产物，分子量为400，环氧当量为185—192(ASTM D—1652)和n值(由上式)为0.2，目前是优选环氧树脂，因为其粘度低并且市场上可买到。
含有烯不饱和度的聚合物可通过把一种或多种烯烃，尤其是二烯，自身共聚合或与一种或多种链烯基芳香烃单体共聚合而制备。该共聚物当然可以是无规的、锥形的、嵌段的或这些的组合体，也可以是线形、星形或放射形。
含有烯不饱和度的聚合物或既含有芳香不饱和度又含有烯不饱和度的聚合物可以使用阴离子引发剂或聚合催化剂制备。可使用本体、溶液或乳液技术制备这类聚合物。总之，至少含烯不饱和度的聚合物通常可作为诸如碎屑、粉末、片材或类似物的固体回收，而且也可以作为液体回收，诸如在本发明中。含烯不饱和度的聚合物和既含芳香不饱和度又含烯不饱和度的聚合物皆可从市场上买到。
通常，当使用溶液阴离子技术时，共轭二烯和链烯基芳香烃的共聚物可通过把待聚合单体同时或先后地与诸如第IA族金属，其烷基化物、酰胺化物、硅烷醇化物、萘基化物、联苯化物或蒽衍生物之类的阴离子聚合引发剂接触而制备。优选在适宜的溶剂中使用有机碱金属(例如钠或钾)，温度范围是—150—300℃，优选0—100℃。特别有效的阴离子聚合引发剂是有以下通式的有机锂化合物：
RLin其中R是有1—20个碳原子的脂族的、环脂族的、芳香的或烷基取代芳香烃基团，n是1—4中的整数。
可阴离子聚合的共轭二烯包括含有4—24个碳原子诸如1，3—丁二烯、异戊二烯、戊间二烯、甲基戊二烯、苯基丁二烯、3，4—二甲基—1，3—己二烯、4，5—二乙基—1，3—辛二烯及类似物的那些共轭二烯。异戊二烯和丁二烯是用于本发明的优选共轭二烯单体，因为其价格低和易买到。可共聚的链烯基芳香烃包括诸如苯乙烯、各种烷基取代的苯乙烯、烷氧基取代的苯乙烯、乙烯基萘、烷基取代的乙烯基萘及类似物之类的乙烯基芳基化合物。
无论是否氢化，这些聚合物都可环氧化，并且优选环氧化作用仅进行到每克聚合物0.1—3毫当量环氧化物(0.1—3Meq环氧化物/g)的程度。因此优选的环氧化聚合物的环氧当量重量是10000—333。
优选环氧化聚二烯的式子如下：
(A—B—Ap)n—Yr—(Aq—B)m其中Y是偶合剂或偶合单体或引发剂，A和B是聚合物嵌段，可以是共轭二烯单体的均聚物嵌段、共轭二烯单体的共聚物嵌段、二烯单体和单链烯基芳香烃单体的共聚物嵌段或单链烯基芳烃单体的均聚物嵌段；A嵌段的分子量为100—3000，B嵌段的分子量为1000—15000；并且n大于0，r是0或1，m大于或等于0，n＋m是在1—100之间。p和q可是0或1。
这些聚合物在美国专利5,229,464中作了详细介绍并引入以供参考。通常，优选A嵌段的较多取代的脂族双键的浓度高于B嵌段。
适宜的无规环氧化星形聚合物以至少一种共轭二烯单体为基，有4个以上的臂，其中每个臂的分子量为1500—15000。星形聚合物含有二、三、或四取代的烯烃环氧化物(1，1—二取代、1，2—二取代、1，1，2—三取代和1，1，2，2—四取代烯烃环氧化物)，浓度为每克聚合物0.05—5毫当量环氧化物。
正如在下面的实施例中详细描述的，上述的环氧树脂和环氧化聚合物的共混物是不相容的。对本发明来说，进行相容意味着能形成至少一种分散良好的外观均匀的两相混合物。已发现把酐固化剂加到共混物中而使这类共混物相容是有可能的。这类酐固化剂通常描述作任何含有一个或多个酐官能团的化合物。最常用的酐有芳香或环脂族结构。这样的例子包括邻苯二甲酸酐、四氢化邻苯二甲酸酐、内—顺—双环(2，2，1)—5—庚烯—2，3—二甲酸甲基酐(nadic methyl anhydride)、六氢化邻苯二甲酸酐、1，2，4，5—苯四酸酐和十二碳烯基琥珀酐。此外多官能羧酸也有相似的性质。优选的酐固化剂有脂族特征以提高与环氧化聚二烯的相容性。已发现十二碳烯基琥珀酐和六氢化邻苯二甲酸酐在环氧树脂和环氧化聚二烯的相容共混物中的效果很好。
相容剂也是用于共混物材料的固化剂，这特别有利。这就可以不用额外的材料并且也可以使相容和固化在一步中进行。为了使该共混物固化，须加入固化加速剂。适宜的固化加速剂包括三烷基胺、含羟基的化合物和咪唑。已发现苯甲基二甲胺在使本发明的共混物固化时效果很好。
本发明共混物的实际固化在下面条件下进行：固化温度93—232℃，有足够的时间以得到固化良好的材料，通常是20分钟到4小时。
本发明的固化共混物可用于结构粘合剂组合物中。已知环氧树脂在这类组合物中的实用性。当用于结构粘合剂中时本发明的共混物应比单使用环氧树脂的结构粘合剂有更好的柔韧性和高耐冲击性能。
结构粘合剂组成中可包括各种类型的填料。可使用广泛的填料，适宜的填料包括碳酸钙、粘土、滑石粉、氧化锌、二氧化钛及类似物。填料的用量通常是0—65％重量(以该组成的溶剂自由部分为基计)，取决于所用填料的类型和粘合剂的用途。特别优选的填料是二氧化钛。
现有技术中已知的稳定剂也可引入到粘合剂组合物中。可在例如抗氧、抗臭氧和抗紫外线辐射的物品的寿命中起保护作用。
实施例1
204是线形异戊二烯—苯乙烯/丁二烯—异戊二烯分子，含有38.7％苯乙烯。已部分氢化并接着环氧化到1.0meq/g的程度。205是已和6％的二乙烯基苯(DVB)偶合的异戊二烯—丁二烯星形聚合物。也已部分氢化并接着环氧化到0.8meq/g的程度。103是已用四氯化硅偶合并环氧化的放射形异戊二烯—丁二烯聚合物。已制成了两种103：103A环氧化到0.4meq/g的程度，103B环氧化到1.0meq/g的程度。
上述环氧化聚二烯聚合物与EPON 828树脂和EPON 825树脂共混(EPON是商标)。前者介绍如上，825是高度纯化类型的828。制成含有90％、75％、50％、25％和10％的环氧化聚二烯聚合物的共混物。结果见下表1。
表1
相容性结果
| 组分1 | |||
| 组分2 | 103A | 204 | 205 |
| EPON 828EPON 825 | 90，75，50，25，10％不溶混90，75，50，25，10％不溶混 | 90，75，50，25，10％不溶混90，75，50，25，10％不溶混 | 90，75，50，25，10％不溶混90，75，50，25，10％不溶混 |
表2
| 项目 | 重量％ | 重量％ | 重量％ | 重量％ | 重量％ | 重量％ |
| EPON 828聚合物103AHHPA外观 | 100082极好清晰 | 802067极好浑浊 | 604053良好浑浊 | 406039差浑浊 | 208024不能混合 | 010010极好清晰 |
称为“极好”的那些共混物是均质的，没有明显的大量相分离。称为“良好”的共混物有点胶粘、表面有少量的相分离物质。称为“差”的共混物很明显相分离。
可看出，环氧化聚二烯聚合物直到60％时该共混物可相容和固化，达到80％聚合物103A时共混物不能混合。实施例3
以80％重量环氧树脂/20％重量环氧化聚二烯树脂的比率制成实施例1所述的EPON 828树脂和环氧化聚二烯聚合物的共混物。加入化学计算量的十二碳烯基琥珀酐作为相容剂和固化剂。百分之一份苯甲基二甲胺用作加速剂(催化剂)。用与实施例2中所说的同样的步骤进行固化反应。测定胶凝体的甲苯不可溶的百分率，假定所有的甲苯可溶物质是环氧化二烯。因此，就得到了引入到环氧网中的环氧化二烯的百分率。结果见下表。
可看出，含有103A环氧化聚二烯聚合物的共混物固化得不够好，但其它的相容充分并且固化很好。103A固化不好，是因为分子上有少量的环氧基团。
表3
| 环氧化聚二烯聚合物环氧化聚二烯在凝胶体中的百分率(％重量) | 20469 | 103A(0.4Meq/g环氧树脂)25 | 20584 | 103B(1.0Meq/g环氧树脂)87 |
实施例4
以80％重量环氧树脂/20％重量环氧化聚二烯树脂的比率制成实施例1中所述的EPON 828树脂和环氧化聚二烯聚合物的共混物。加入化学计算量的六氢化邻苯二甲酸酐作为相容剂和固化剂。百分之一份苯甲基二甲胺用作加速剂(催化剂)，使用与实施例2中同样的步骤进行固化反应。结果见下表。可看出，线形聚合物(204)固化得不够好，而其它三种聚合物相容充分并且固化很好。
表4
| 环氧化聚二烯聚合物环氧化聚二烯在凝胶体中百分率(％重量) | 20422 | 103A(0.4Meq/g环氧树脂)68 | 20566 | 103B(1.0Meq/g环氧树脂)75 |
Claims (8)
1.一种有足够的相容性而形成均匀混合物的聚合物共混物，含有可固化芳香环氧树脂、环氧化聚二烯聚合物和酐或多羧酸固化剂。
2.根据权利要求1的聚合物共混物，其中加入加速剂并且共混物固化。
3.根据权利要求2的聚合物共混物，其中芳香环氧树脂是通过表氯醇和至少含有一个羟基的芳香化合物在碱性反应条件下进行反应而制备的缩水甘油醚。
4.根据权利要求2的聚合物共混物，其中环氧化聚二烯式子如下：
(A—B—Ap)n—Yr—(Aq—B)m其中Y是偶合剂或偶合单体或引发剂，A和B是聚合物嵌段，可以是共轭二烯单体的均聚物嵌段、共轭二烯单体的共聚物嵌段、二烯单体和单链烯基芳香烃单体的共聚物嵌段或单链烯基芳香烃单体的均聚物嵌段；A嵌段的分子量为100—3000，B嵌段的分子量为1000—15000；并且n大于0，r是0或1，m大于或等于0，n＋m是在1—100之间。p和q可是0或1。
5.根据权利要求2的聚合物共混物，其中环氧化聚二烯聚合物是无规环氧化星形聚合物，含有至少一种共轭二烯烃单体和有4个以上的臂，其中每个臂的分子量为1500—15000。
6.根据权利要求2的聚合物共混物，其中酐固化剂选自邻苯二甲酸酐、取代邻苯二甲酸酐和氢化邻苯二甲酸酐。
7.根据权利要求2的聚合物共混物，其中酐选自十二碳烯基琥珀酐和六氢化邻苯二甲酸酐。
8.把权利要求2的聚合物共混物用于结构粘合剂。
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| US5478885A (en) * | 1994-04-15 | 1995-12-26 | Shell Oil Company | Composition of epoxy resin, epoxidized block polydiene and curing agent |
| US5459200A (en) * | 1994-10-11 | 1995-10-17 | Shell Oil Company | Polyurethane coatings and adhesives containing monohydroxylated diene polymers and epoxidized derivatives thereof |
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| TW346498B (en) * | 1994-10-11 | 1998-12-01 | Shell Int Research | Epoxidized monohydroxylated rubber toughening modifiers for epoxy resins |
| US5576388A (en) * | 1994-10-11 | 1996-11-19 | Shell Oil Company | Telechelic polymers and heterotelechelic polydiene block polymers with dual cure systems |
| US5500481A (en) * | 1995-05-17 | 1996-03-19 | Shell Oil Company | Compositions containing epoxidized monohydroxylated diene polymers, amino resins, and reactive reinforcement agents |
| US5461112A (en) * | 1994-10-11 | 1995-10-24 | Shell Oil Company | Epoxidized monohydroxylated block polymer, epoxy resin, curing agent and epoxy diluent |
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| US5721316A (en) * | 1995-07-12 | 1998-02-24 | Shell Oil Company | Process for incorporation of expoxidized polydienes into epoxy resins |
| KR100454366B1 (ko) * | 1995-11-16 | 2005-04-28 | 셀 인터나쵸나아레 레사아치 마아츠샤피 비이부이 | 가교결합성하이드록시작용성폴리디엔중합체코팅조성물및이의제조방법 |
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| US5922467A (en) * | 1996-10-15 | 1999-07-13 | Shell Oil Company | Method for coating crosslinkable epoxidized monohydroxylated diene polymer coating compositions on primed substrates |
| US6043316A (en) * | 1996-11-13 | 2000-03-28 | Shell Oil Company | Crosslinkable hydroxy terminated polydiene polymer coating compositions for use on substrates and a process for preparing them |
| JPH10279881A (ja) * | 1997-04-03 | 1998-10-20 | Yuka Shell Epoxy Kk | 粉体塗料用エポキシ樹脂組成物 |
| DE19916109A1 (de) | 1999-04-09 | 2000-10-12 | Basf Ag | Als Separatoren in elektrochemischen Zellen geeignete Verbundkörper |
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- 1994-07-11 AT AT94921644T patent/ATE160153T1/de not_active IP Right Cessation
- 1994-07-11 CN CN94192756A patent/CN1048270C/zh not_active Expired - Fee Related
- 1994-07-11 BR BR9406883A patent/BR9406883A/pt not_active IP Right Cessation
- 1994-07-11 ES ES94921644T patent/ES2109711T3/es not_active Expired - Lifetime
- 1994-07-11 KR KR1019960700130A patent/KR100306560B1/ko not_active IP Right Cessation
-
1996
- 1996-01-10 FI FI960115A patent/FI960115A/fi unknown
- 1996-01-10 NO NO960117A patent/NO960117L/no unknown
-
1997
- 1997-12-23 GR GR970403401T patent/GR3025751T3/el unknown
Also Published As
| Publication number | Publication date |
|---|---|
| NO960117L (no) | 1996-03-08 |
| ATE160153T1 (de) | 1997-11-15 |
| NO960117D0 (no) | 1996-01-10 |
| DE69406791T2 (de) | 1998-03-19 |
| TW295595B (zh) | 1997-01-11 |
| DK0708791T3 (da) | 1997-12-22 |
| MX9405227A (es) | 1995-01-31 |
| CN1048270C (zh) | 2000-01-12 |
| FI960115A0 (fi) | 1996-01-10 |
| KR100306560B1 (ko) | 2001-11-30 |
| CA2166969A1 (en) | 1995-01-26 |
| WO1995002622A1 (en) | 1995-01-26 |
| DE69406791D1 (de) | 1997-12-18 |
| GR3025751T3 (en) | 1998-03-31 |
| JPH08512354A (ja) | 1996-12-24 |
| FI960115A (fi) | 1996-01-10 |
| AU686202B2 (en) | 1998-02-05 |
| US5332783A (en) | 1994-07-26 |
| ES2109711T3 (es) | 1998-01-16 |
| BR9406883A (pt) | 1996-04-02 |
| AU7228694A (en) | 1995-02-13 |
| JP3589463B2 (ja) | 2004-11-17 |
| EP0708791A1 (en) | 1996-05-01 |
| EP0708791B1 (en) | 1997-11-12 |
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