CN1571805A - 可固化的氰酸酯组合物 - Google Patents
可固化的氰酸酯组合物 Download PDFInfo
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- CN1571805A CN1571805A CNA028207203A CN02820720A CN1571805A CN 1571805 A CN1571805 A CN 1571805A CN A028207203 A CNA028207203 A CN A028207203A CN 02820720 A CN02820720 A CN 02820720A CN 1571805 A CN1571805 A CN 1571805A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
- C08G73/065—Preparatory processes
- C08G73/0655—Preparatory processes from polycyanurates
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
- C08G73/065—Preparatory processes
- C08G73/0655—Preparatory processes from polycyanurates
- C08G73/0661—Preparatory processes from polycyanurates characterised by the catalyst used
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Abstract
本发明公开一种基于二或多官能芳族氰酸酯的可固化组合物,这种组合物至少包含:(a)按组分(a)和(b)的总量计,10-100重量%至少一种二或多官能芳族氰酸酯、含至少一种二或多官能芳族氰酸酯的预聚物或所述二或多官能芳族氰酸酯或其预聚物的混合物;(b)按组分(a)和(b)的总量计,0-90重量%至少一种一、二或多官能环氧树脂;(c)按组分(a)和(b)的总量计,0.5-30重量%至少一种一、二或多官能芳香胺;和(d)按组分(a)和(b)的总量计,0-5重量%至少一种选自过渡金属化合物和三卤化硼的催化剂。固化后,本发明的组合物提供热固性塑料。这种热固性塑料具有高的玻璃化转变温度,特别适用于制造电气设备或汽车和航空制造业中的耐高温模制件。
Description
本发明涉及含有芳族氰酸酯或芳族氰酸酯-环氧树脂混合物、芳香胺和任选催化剂的可固化混合物。这种可固化混合物可用于制造聚三嗪热固性塑料。本发明还涉及通过固化这种混合物得到的热固性塑料以及它在制造模制件上的应用。
由于具有优异的耐热性和良好的介电特性,由二或多官能芳族氰酸酯制得的聚三嗪以及由上述芳族氰酸酯和环氧树脂制得的热固性塑料是有用的材料。这里和下文中所述的多官能氰酸酯、环氧化物或胺可理解为一个分子中含有三个或更多个氰酸酯基、环氧基或氨基的化合物。
虽然只需加热就可以将上述原料固化,但一般也需加入催化有效量的过渡金属化合物,如乙酰乙酸钴或乙酰乙酸铜或辛酸锌。由于这些化合物具有毒性和/或环境危害性(特别是在清除用它们制造的材料时)以及可能对电磁性能产生的影响,所以它们不是理想的原料。
因此,本发明的任务是提供用于固化芳族氰酸酯和芳族氰酸酯-环氧化物混合物的另一些没有上述缺点的添加剂。
本发明的任务可以用权利要求1所述的可固化混合物加以解决。令人惊奇地发现,通过将芳香胺用作二或多官能芳族氰酸酯或它与环氧化物混合物的固化剂,不仅可以不使用含重金属的催化剂,而且在固化后可以获得性能优异的产物,特别是显著地提高玻璃化转变温度(Tg),而且固化的产物具有改进的耐冲击性。另外,可以改善完全固化性和固化过程,特别是固化时的潜伏期。
本发明的可固化混合物至少包含如下组分:
(a)按组分(a)和(b)的总量计,10-100重量%至少一种二或多官能芳族氰酸酯、含至少一种二或多官能芳族氰酸酯的预聚物或所述二或多官能芳族氰酸酯或其预聚物的混合物;
(b)按组分(a)和(b)的总量计,0-90重量%至少一种一、二或多官能环氧树脂;
(c)按组分(a)和(b)的总量计,0.5-30重量%至少一种一、二或多官能芳香胺;
(d)按组分(a)和(b)的总量计,0-5重量%至少一种选自过渡金属化合物和三卤化硼的催化剂。
过渡金属化合物既可以理解为它的盐也可以理解为配位化合物,其中过渡金属尤其是第一和第二族的过渡金属。例如是乙酰乙酸钴或乙酰乙酸铜之类的配位化合物或辛酸锌或硬脂酸锌之类的盐。
三卤化硼具体为三氟化硼和三氯化硼。
上述的二或多官能芳族氰酸酯较好使用选自用通式(I)、(II)和(III)表示的化合物和由一个或多个上述化合物形成的预聚物:
式中R1表示氢、甲基或溴,X选自-CH2-、-CH(CH3)-、-C(CH3)2-、-C(CF3)2-、-O-、-S-、-SO2-、-C(=O)-、-OC(=O)-、-OC(=O)O-,和
式中n是0-10的一个数,且R2是氢或甲基;和
式中n具有上述相同的含义。同样可以使用这些化合物的混合物、这些化合物的预聚物、这些化合物混合物的预聚物以及这些化合物预聚物的混合物。预聚物可以理解为通过部分三聚得到的低聚物。这种低聚物既含有通过三聚产生的三嗪基,也含有未反应的氰酸酯基。氰酸酯是已知的化合物,且大部分可以市售的。这些预聚物也是已知的,且部分是市售或易于由氰酸酯制得的。
上述的环氧树脂较好使用选自用通式(IV)、(V)和(VI)表示的化合物:
式中R1和X具有上述的含义,及其相应的低聚物,
式中n和R2具有上述的含义,和
式中n具有上述的含义。这些化合物也是已知的,而且可以从不同的制造商那里购得。
上述的芳香胺选自用通式(VII)和(VIII)表示的化合物:
式中R3、R4和R5分别表示氢、C1-4烷基或卤素,和
式中R6、R7和R8分别表示氢或C1-4烷基。这些化合物也是已知的,且大部分是市售的。例如,通式VII表示的化合物可用作聚氨酯的增链剂,通式VIII表示的化合物可用作聚脲的胺组分或制备异氰酸酯的原料。
在必要时加入填料和/或助剂的情况下通过热固化上述混合物得到的聚三嗪热固性塑料也是本发明的主题。上述的填料和助剂具体可理解为织物、纤维或颗粒状的增强材料、用于获得特定机械、光学、电学或磁性能或用于改善加工性能的颜料或其它添加剂。这些填料和助剂对于本领域中普通技术人员来说是己知的。
另外,上述得到的热固性材料在制造电子仪器、航空航天飞行器、公路、轨道和水上交通工具的模制件以及工业上的应用也是本发明的主题。
以下的实施例用于解释本发明,但不能看作对本发明的限制。
实施例1-8
制备氰酸酯(隆萨公司的PRIMASETPT 15,通式II,R2=H,80℃时的粘度为20-30Pa.s)、任选的环氧化物(Dow DER 330;通式IV,R1=H,X=-C(CH3)2-)和胺(隆萨公司的LONGZACUREDETDA,通式VIII,R6=R7=乙基,R8=甲基,异构体混合物)的混合物,然后进行热固化。通过热力学分析,确定固化试样的玻璃化转变温度(Tg)。混合比例、固化条件和玻璃化转变温度列于下表1中。
表1
实施例编号 | 环氧化物[克] | 氰酸酯[克] | 胺[克] | Tg[℃] | 固化温度[℃] | 固化时间[分钟] |
1 | - | 100 | 1.0 | 361 | 150 | 60 |
2 | - | 100 | 2.5 | 3611) | 150 | 60 |
3 | - | 100 | 5.0 | 368 | 150 | 60 |
4 | - | 100 | 10.0 | 377 | 150 | 60 |
5 | 75 | 25 | 2.5 | 375 | 150 | 60 |
6 | 75 | 25 | 5.0 | 367 | 150 | 60 |
7 | 75 | 25 | 10.0 | 351 | 150 | 60 |
8 | 75 | 25 | 10.0 | 378 | 150/200/250 | 180/180/180 |
1)完全固化后(2.测量周期)
实施例9-12
按上述实施例中所述的方法进行,所不同的是使用胺LONGZACUREM-CDEA(通式VII,R3=R4=乙基,R5=Cl)。结果列于表2中。
表2
实施例编号 | 环氧化物[克] | 氰酸酯[克] | 胺[克] | Tg[℃] | 固化温度[℃] | 固化时间[分钟] |
9 | - | 100 | 5.0 | 3841) | 150 | 60 |
10 | 75 | 25 | 2.5 | 366 | 150/200/250 | 180/180/180 |
11 | 75 | 25 | 5.0 | 362 | 150 | 60 |
12 | 75 | 25 | 10.0 | 370 | 150 | 60 |
1)完全固化后(2.测量周期)
实施例13-16
按实施例9-12中所述的方法进行,所不同的是用氰酸酯PRIMASETCT90(通式II,R2=甲基,软化温度>60℃)代替PRIMASETPT 15。结果列于表3中。
表3
实施例编号 | 环氧化物[克] | 氰酸酯[克] | 胺[克] | Tg[℃] | 固化温度[℃] | 固化时间[分钟] |
13 | 75 | 25 | 5.0 | 3691) | 150 | 60 |
14 | 75 | 25 | 5.0 | 376 | 150/200/250 | 180/180/180 |
15 | 75 | 25 | 10.0 | 372 | 150 | 60 |
16 | 75 | 25 | 10.0 | 373 | 150/200/250 | 180/180/180 |
1)完全固化后(2.测量周期)
Claims (6)
1.可固化混合物,至少包含:
(a)按组分(a)和(b)的总量计,10-100重量%至少一种二或多官能芳族氰酸酯、含至少一种二或多官能芳族氰酸酯的预聚物或所述二或多官能芳族氰酸酯或其预聚物的混合物;
(b)按组分(a)和(b)的总量计,0-90重量%至少一种一、二或多官能环氧树脂;
(c)按组分(a)和(b)的总量计,0.5-30重量%至少一种一、二或多官能芳香胺;
(d)按组分(a)和(b)的总量计,0-5重量%至少一种选自过渡金属化合物和三卤化硼的催化剂。
2.如权利要求1所述的可固化混合物,其特征在于所述的二或多官能芳族氰酸酯选自用通式(I)、(II)和(III)表示的化合物和由一个或多个上述化合物形成的预聚物:
式中R1表示氢、甲基或溴,X选自-CH2-、-CH(CH3)-、-C(CH3)2-、-C(CF3)2-、-O-、-S-、-SO2-、-C(=O)-、-OC(=O)-、-OC(=O)O-和
式中n是0-10的一个数,且R2是氢或甲基;和
式中n具有上述相同的含义。
5.聚三嗪热固性塑料,它在必要时加入填料和/或助剂的情况下通过热固化权利要求1-4中任一项所述的可固化混合物制得。
6.如权利要求5所述的热固性材料在制造电子仪器、航空航天飞行器、公路、轨道和水上交通工具的模制件以及工业上的应用。
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP01124967.9 | 2001-10-19 | ||
EP01124967 | 2001-10-19 | ||
US33042401P | 2001-10-22 | 2001-10-22 | |
US60/330,424 | 2001-10-22 |
Publications (2)
Publication Number | Publication Date |
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CN1571805A true CN1571805A (zh) | 2005-01-26 |
CN100478378C CN100478378C (zh) | 2009-04-15 |
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CNB028207203A Expired - Fee Related CN100478378C (zh) | 2001-10-19 | 2002-10-18 | 可固化的氰酸酯组合物 |
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Country | Link |
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EP (1) | EP1440111B1 (zh) |
JP (1) | JP2005506422A (zh) |
CN (1) | CN100478378C (zh) |
AT (1) | ATE388981T1 (zh) |
CA (1) | CA2464339C (zh) |
WO (1) | WO2003035718A1 (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN101177519B (zh) * | 2006-11-09 | 2010-11-24 | 莘茂复合材料股份有限公司 | 经改质的环氧树脂组成物 |
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Publication number | Priority date | Publication date | Assignee | Title |
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JP6116852B2 (ja) * | 2012-10-12 | 2017-04-19 | 株式会社日本触媒 | 液状硬化性樹脂組成物及びその用途 |
US9332637B2 (en) * | 2013-11-04 | 2016-05-03 | Novoset Llc | Ultra low loss dielectric thermosetting resin compositions and high performance laminates manufactured therefrom |
EP3077449B1 (en) * | 2013-12-04 | 2017-10-18 | Lonza Ltd | Method for preparing fiber-reinforced parts based on cyanate ester/epoxy blends |
JP6413915B2 (ja) | 2015-05-11 | 2018-10-31 | 信越化学工業株式会社 | 半導体封止用樹脂組成物及びその硬化物を備えた半導体装置 |
WO2017038603A1 (ja) | 2015-09-04 | 2017-03-09 | 株式会社Adeka | 繊維強化プラスチック用樹脂組成物、その硬化物、該硬化物を含有する繊維強化プラスチック、及び該繊維強化プラスチックの製造方法 |
CA3161938C (en) * | 2020-02-14 | 2024-02-06 | Gaetano La Delfa | Method for preparation of a moulded composite from a bulk moulding compound |
CN115698133A (zh) | 2020-06-24 | 2023-02-03 | 阿尔萨达股份公司 | 具有改善特性的新型组合物 |
CA3240964A1 (en) | 2021-12-14 | 2023-06-22 | Arxada Ag | Novel compositions with improved characteristics |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
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US4680378A (en) * | 1985-10-01 | 1987-07-14 | The Dow Chemical Company | Cyanate functional maleimide and polyamine copolymer |
JPS62252417A (ja) * | 1986-04-25 | 1987-11-04 | Toray Ind Inc | プリプレグ用樹脂組成物 |
US5003039A (en) * | 1988-11-18 | 1991-03-26 | The United States Of America As Represented By The Secretary Of The Navy | Amino phenyl containing curing agent for high performance phthalonitrile resin |
US5043411A (en) * | 1990-05-14 | 1991-08-27 | Nova Petrochemicals Inc. | Cyanate ester resin composition containing an epoxy/aromatic adduct |
AU3802793A (en) * | 1992-02-28 | 1993-09-13 | Johnson Matthey Inc. | Rapidly curing adhesive and method |
US5494981A (en) * | 1995-03-03 | 1996-02-27 | Minnesota Mining And Manufacturing Company | Epoxy-cyanate ester compositions that form interpenetrating networks via a Bronsted acid |
-
2002
- 2002-10-18 CN CNB028207203A patent/CN100478378C/zh not_active Expired - Fee Related
- 2002-10-18 WO PCT/EP2002/011662 patent/WO2003035718A1/de active IP Right Grant
- 2002-10-18 EP EP02782951A patent/EP1440111B1/de not_active Expired - Lifetime
- 2002-10-18 CA CA2464339A patent/CA2464339C/en not_active Expired - Lifetime
- 2002-10-18 AT AT02782951T patent/ATE388981T1/de active
- 2002-10-18 JP JP2003538230A patent/JP2005506422A/ja active Pending
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN101177519B (zh) * | 2006-11-09 | 2010-11-24 | 莘茂复合材料股份有限公司 | 经改质的环氧树脂组成物 |
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Publication number | Publication date |
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CN100478378C (zh) | 2009-04-15 |
WO2003035718A9 (de) | 2004-02-26 |
EP1440111A1 (de) | 2004-07-28 |
JP2005506422A (ja) | 2005-03-03 |
WO2003035718A1 (de) | 2003-05-01 |
EP1440111B1 (de) | 2008-03-12 |
CA2464339A1 (en) | 2003-05-01 |
ATE388981T1 (de) | 2008-03-15 |
CA2464339C (en) | 2010-09-21 |
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