CN1942515A - 低放热和低发烟的增强纤维-环氧复合材料 - Google Patents
低放热和低发烟的增强纤维-环氧复合材料 Download PDFInfo
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- CN1942515A CN1942515A CNA2005800119912A CN200580011991A CN1942515A CN 1942515 A CN1942515 A CN 1942515A CN A2005800119912 A CNA2005800119912 A CN A2005800119912A CN 200580011991 A CN200580011991 A CN 200580011991A CN 1942515 A CN1942515 A CN 1942515A
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- fire retardant
- epoxy
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- 239000002131 composite material Substances 0.000 title abstract description 9
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- 239000000779 smoke Substances 0.000 title description 3
- 229920005989 resin Polymers 0.000 claims abstract description 27
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- 239000000203 mixture Substances 0.000 claims abstract description 20
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims abstract description 15
- 239000003063 flame retardant Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
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- 239000000835 fiber Substances 0.000 claims description 28
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- 239000010439 graphite Substances 0.000 claims description 10
- 229910002804 graphite Inorganic materials 0.000 claims description 10
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- 239000010456 wollastonite Substances 0.000 claims description 3
- 229910052882 wollastonite Inorganic materials 0.000 claims description 3
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 2
- 238000006424 Flood reaction Methods 0.000 claims 1
- 239000003822 epoxy resin Substances 0.000 abstract description 14
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- FUOZJYASZOSONT-UHFFFAOYSA-N 2-propan-2-yl-1h-imidazole Chemical compound CC(C)C1=NC=CN1 FUOZJYASZOSONT-UHFFFAOYSA-N 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
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- 150000004693 imidazolium salts Chemical class 0.000 description 2
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- 238000010030 laminating Methods 0.000 description 2
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 229960000969 phenyl salicylate Drugs 0.000 description 2
- 238000010010 raising Methods 0.000 description 2
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- 230000001988 toxicity Effects 0.000 description 2
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- 125000001989 1,3-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([H])C([*:2])=C1[H] 0.000 description 1
- URJFKQPLLWGDEI-UHFFFAOYSA-N 1-benzyl-2-methylimidazole Chemical compound CC1=NC=[C]N1CC1=CC=CC=C1 URJFKQPLLWGDEI-UHFFFAOYSA-N 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- LLEASVZEQBICSN-UHFFFAOYSA-N 2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=CN1 LLEASVZEQBICSN-UHFFFAOYSA-N 0.000 description 1
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical compound C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 description 1
- CPHGOBGXZQKCKI-UHFFFAOYSA-N 4,5-diphenyl-1h-imidazole Chemical compound N1C=NC(C=2C=CC=CC=2)=C1C1=CC=CC=C1 CPHGOBGXZQKCKI-UHFFFAOYSA-N 0.000 description 1
- TYOXIFXYEIILLY-UHFFFAOYSA-N 5-methyl-2-phenyl-1h-imidazole Chemical compound N1C(C)=CN=C1C1=CC=CC=C1 TYOXIFXYEIILLY-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
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- 239000004114 Ammonium polyphosphate Substances 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
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- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical compound C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
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- 150000004678 hydrides Chemical class 0.000 description 1
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- KSSNXJHPEFVKHY-UHFFFAOYSA-N phenol;hydrate Chemical group O.OC1=CC=CC=C1 KSSNXJHPEFVKHY-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 229960001553 phloroglucinol Drugs 0.000 description 1
- 150000003008 phosphonic acid esters Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
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- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
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- 150000003839 salts Chemical class 0.000 description 1
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- 150000003512 tertiary amines Chemical class 0.000 description 1
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- JIVZKJJQOZQXQB-UHFFFAOYSA-N tolazoline Chemical compound C=1C=CC=CC=1CC1=NCCN1 JIVZKJJQOZQXQB-UHFFFAOYSA-N 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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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
- C08L85/00—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers
- C08L85/02—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers containing phosphorus
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Reinforced Plastic Materials (AREA)
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- Adhesives Or Adhesive Processes (AREA)
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
本发明提供包括增强纤维和粘合剂组合物的复合材料,所述粘合剂组合物包括环氧树脂、任选的树脂固化剂、固化催化剂和活性膦酸酯阻燃剂,以及复合材料的制备方法。
Description
相关申请的交叉引用
本申请要求2004年4月1日提交的序列号为60/558452的临时美国专利申请的优先权,其全部内容在此引入作为参考。
发明背景
本发明涉及具有高耐火性和低发烟性的轻质复合材料,尤其涉及由树脂组合物、更特别地是环氧树脂组合物和增强纤维形成的结构复合材料。这种复合材料掺入了某些添加剂以大量提高其耐火性。它们尤其可用作飞机中的装饰性、半结构性和结构性部件。
航空工业所关注的事情已涉及降低航空设备内侧壁、储存箱、天花板和隔壁中所用复合材料的可燃性和着火性。从放火安全的角度看,侧壁板是尤其受关注的,因为它们具有大的表面积,可能潜在地被卷入客舱着火之中。
用于航空工业的纤维复合材料通常包括各种粘合剂环氧组合物,该环氧组合物已用来浸渍纤维的增强体系。这种增强纤维的浸渍体系表现出良好的粘着性,从而它们可容易地附着到复合材料的核心物质上。但是,当这种含氧树脂暴露于火焰下时,它们会燃烧并产生冒烟情况,由于明显的安全原因,这是不期望的。在非阻燃环氧树脂的情况下,例如石墨/环氧复合材料由于着火而引起的降解,以及因此分解石墨纤维并使这些纤维散布到电类设备中,这会引起严重的问题。因此,开发含这些导电短纤维并防止其散布的任何方法将有重大价值。
影响乘客生存性的航线客舱着火危害包括:材料的可燃性和放热性;此类材料的发烟性;以及产生的烟导致的毒性。这些危害中每个的相对重要性取决于任何特定着火事件周围的环境。对于失事后的客舱着火,大量燃料着火是最主要类型的着火源。已经确定,“轰燃(flashover)”对乘客生存性的关系最大,所述轰燃是火从着火源的周围区域突然和快速地不受控制地扩大至客舱内部的其余区域。在轰燃开始之前,热、烟和毒气的水平是明显可容忍的;在轰燃开始之后,危害迅速增加到使得极不可能生存的水平。因此,对于强烈的失事后着火,使由于客舱材料燃烧引起的危害最小化的最有效和直接的方法是延迟轰燃的开始。相比于烟和毒性因素,可燃性因素直接影响轰燃的发生。
因此,使用增强纤维/树脂复合材料不仅取决于因存在增强纤维而致的复合材料强度,而且取决于树脂的耐火性。有许多加入到树脂中时起阻燃剂作用的添加剂。一些添加剂如三水合氧化铝、多磷酸铵和硼酸锌是提供优良耐火性的固体,但是它们引起层压材料厚度增加,由此导致强度降低,从而有害地影响层压材料的机械性能。
一些含卤素的化合物可用于这些应用,通常将其与作为增效剂的三氧化锑结合。这些优良阻燃性化合物的问题是,它们也具有一些非常令人讨厌的性质,例如,当对芳族溴化合物进行热分解时,其由于溴自由基和溴化氢而具有高度腐蚀性。而且,溴对于降低树脂燃烧时所产生烟的水平没有一点作用。实际上,溴化环氧树脂可导致发烟水平的增加。
发明简述
因此,本发明的目的是提供具有高耐火性和低发烟特性的增强纤维/树脂复合材料。另一目的是提供上述类型的复合材料,其能够承受高温而不分裂和散布增强纤维。另一目的是提供粘合剂环氧树脂组合物,以及由其制造的复合材料,该复合材料包含充分提高树脂耐火性、且不会有害地影响复合材料的物理和机械性能的物质,并且该物质在高温下起到使树脂或树脂烧焦物稳定,同时保持复合材料的结构完整性。
因此,本发明提供复合材料,其包括增强纤维和粘合剂组合物,该粘合剂组合物包括环氧树脂、任选的树脂固化剂、固化催化剂和活性膦酸酯阻燃剂。本发明也提供制备该复合材料的方法,该方法包括用上述粘合剂组合物浸渍增强纤维。
发明详述
在下面的段落中将详细描述本发明的某些优选实施方案。
环氧树脂占粘合剂配方总重量的约40~约80重量%。代表性的树脂包括:双酚A型环氧树脂;双酚F型环氧树脂;双酚S型环氧树脂;4,4’-双酚型环氧树脂;苯酚酚醛清漆型环氧树脂;甲酚酚醛清漆型环氧树脂;双酚A酚醛清漆型环氧树脂;双酚F酚醛清漆型环氧树脂;苯酚水杨酸酯醛酚醛清漆(phenol salicylate aldehyde novolac)型环氧树脂;脂环族环氧树脂;脂肪链环氧树脂;缩水甘油醚型环氧树脂;以及其它化合物如双官能酚基团缩水甘油醚化合物;双官能醇缩水甘油醚化合物;多酚基团缩水甘油醚化合物;和多酚缩水甘油醚化合物及其氢化物。也可使用这些树脂的混合物。
与依靠改变前述组分的组合的现有技术方法相比,形成本发明新颖和必需添加剂的活性膦酸酯阻燃剂,占粘合剂配方总重量的约5~约60重量%,优选约10~约30重量%。PCT国际申请公布WO 03/029258号和PCT国际公布WO/2004/113411号(其全部内容在此引入作为参考)中所述的这种阻燃剂是包括(-OP(O)(R)-O-亚芳基-)n重复单元的低聚膦酸酯,其中“n”可为约2~约30,该阻燃剂的磷含量大于约12重量%。R基团可为低级烷基,如C1~C6。R优选为甲基。可用于本发明实践的这些低聚膦酸酯可包含或可不包含-OH端基。包含-OH端基的各个膦酸酯类可为单羟基或二羟基取代的。端基可连接到亚芳基部分或磷部分上,它们可与加入了阻燃剂的组合物中的环氧官能团反应。以潜在地可能带有-OH端基的末端(“链端”)总数为基准,连接到磷上的-OH端基的浓度为约20%~约100%,优选约50%~约100%。
“亚芳基”是指在非邻接的位置应具有两个羟基基团的任何二元酚的基团。这种二元酚的例子包括间苯二酚;对苯二酚;和双酚,如双酚A、双酚F和4,4’-双酚、酚酞、4,4’-硫代双酚或4,4’-磺酰基双酚。可包括少量具有三个或更多羟基基团的多酚,如酚醛清漆或间苯三酚,以增加组合物的分子量。“亚芳基”基团可为1,3-亚苯基、1,4-亚苯基或双酚双自由基单元,但是它优选为1,3-亚苯基。
本发明的环氧树脂组合物的这种组分可由下述几种路线中任一种制备:(1)通式为RPOCl2的化合物与HO-芳基-OH或其盐的反应,其中R为低级烷基,优选为甲基;(2)烷基膦酸二苯酯,优选甲基膦酸二苯酯,与HO-亚芳基-OH在酯交换条件下的反应;(3)具有-OP(OR’)-O-亚芳基-重复单元结构的低聚亚磷酸酯与Arbuzov重排催化剂的反应,其中R’为低级烷基,优选为甲基;或(4)具有-OP(O-Ph)-O-亚芳基重复单元结构的低聚亚磷酸酯与亚磷酸三甲酯和Arbuzov催化剂,或者与甲基膦酸二甲酯、任选地与Arbuzov催化剂的反应。如要将-OH端基连接到亚芳基上,可通过在反应介质中具有控制性摩尔过量的HO-亚芳基-OH来制备。-OH端基如果是酸类型(P-OH),可由水解反应形成。低聚物的端基优选主要是-亚芳基-OH类型。膦酸酯低聚物的分子量可例如通过调节初始试剂,例如甲基膦酸二苯酯和间苯二酚(上述反应方案(2))之间的比例来控制。以接近1∶1的摩尔比获得最高的分子量。任何上述试剂过量都导致较低的分子量。分子量也可通过调节反应时间来控制。越长的反应时间产生越高分子量的产物。
任选地,在粘合剂配方中可包括固化剂,如多官能酚,其量例如为粘合剂配方总重量的约5%~约10重量%。这种固化剂包括例如双酚F;双酚A;双酚S;聚乙烯基酚;和酚醛清漆树脂,其通过酚基团如苯酚、甲酚、烷基酚、儿茶酚、双酚F、双酚A和双酚S与醛基团的加成缩合而获得。任何这些化合物的分子量没有特别限制,并且可使用这些物质的混合物。
固化催化剂在粘合剂配方中的用量为粘合剂配方总重量的约0.05~约1.0重量%,固化催化剂可为起到促进环氧基团与酚水合物基团化学反应的作用的任何化合物。代表性的催化剂包括碱金属化合物、碱土金属化合物、咪唑化合物、有机磷化合物、仲胺、叔胺、季铵盐等。
可用于本发明的咪唑化合物包括咪唑、2-乙基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑、2-十一烷基咪唑、1-苄基-2-甲基咪唑、2-十七烷基咪唑、4,5-二苯基咪唑、2-甲基咪唑啉、2-苯基咪唑啉、2-十一烷基咪唑啉、2-十七烷基咪唑、2-异丙基咪唑、2,4-二甲基咪唑、2-苯基-4-甲基咪唑、2-乙基咪唑啉、2-异丙基咪唑啉、2,4-二甲基咪唑啉、2-苯基-4-甲基咪唑啉等。这些固化催化剂可彼此结合使用。
通常,在本发明的实践中,粘合剂配方占复合材料总重量的约20~约60重量%。
可用于本发明实践的增强纤维包括例如石墨纤维、玻璃纤维和其它矿物纤维,如硅灰石。其中优选由石墨纤维制造的复合材料。石墨纤维可描述为可由中间相或非中间相石油沥青、碳纤维的加工获得的碳纤维,或可由煤焦油沥青或类似含碳物质获得的碳纤维。而且,也可使用由PAN、丙烯酸或人造丝前体制备的碳纤维。本发明中有用的碳纤维形式由纸、毡或垫(织造或非织造)结构组成。
通常,在本发明的实践中,增强纤维占复合材料总重量的约50~约90重量%。
在本发明的优选实施方案中,通常用如上所述的环氧树脂粘合剂配方的溶液浸渍石墨纤维垫,对于树脂用溶剂例如有丙酮或甲基乙基酮。浸渍方法包括浸泡、刷涂、喷洒等。使由此浸渍的垫干燥,从而形成预浸料坯(包含约20%~约40重量%含量的粘合剂),然后可通过在高压釜中真空装袋而使固化,或通过在约150℃~约225℃下热压固化约1~约2小时而使固化,以制备适合于商业飞机内部的层压材料。
在以下代表性实施例中进一步说明本发明。
实施例1
在60℃下使11g苯酚-甲醛树脂(来自Schenectady International的HRJ 2210牌)溶于30ml 2-丁酮溶剂中,然后加入63.5g环氧酚醛清漆树脂(来自Bakelite AG的RUETAPOX 300牌)和25g反应性聚(甲基膦酸间亚苯酯),其中“n”为约14(如下所述合成),从而使其在60℃下也溶解到溶剂中。然后,加入0.5重量%2-甲基咪唑(来自Air Products的AMI-2牌)。将所得的热清漆施涂到平织石墨纤维(来自Fibre Glast的No.530)上。所得的预浸料坯在室温下干燥过夜,然后在90℃下干燥30分钟。然后,将十六堆预浸料坯(4×4英寸)堆叠在一起,在130℃和8MPa压力下预固化30分钟,然后在171℃和30MPa压力下固化70分钟。
制备聚(甲基膦酸间亚苯酯)
在230℃下于反应烧瓶中加热和搅拌124g(0.5mol)甲基膦酸二苯酯、113g(1.03mol)间苯二酚和0.54g甲醇钠。反应烧瓶设置有约40厘米高的Vigreux柱,该柱包有电热带和保温层,以保持苯酚和任何挥发的间苯二酚不在柱中固化。使真空从625mmHg逐渐下降至5mmHg。4小时后反应停止。在反应过程中蒸馏出苯酚,在冷阱中收集到93g馏出物(如果以苯酚计算,约1mol),并且反应烧瓶中保存有241g聚(甲基膦酸间亚苯酯)产物。馏出物似乎是几乎纯的苯酚。
(对比)实施例2
在本实施例中,在60℃下使15g苯酚-甲醛树脂(来自SchenectadyInternational的HRJ 2210牌)溶于30ml 2-丁酮中,然后加入84.5g环氧酚醛清漆树脂(来自Bakelite AG的RUETAPOX 300牌),从而使其在60℃下也溶解到溶剂中。然后,加入0.5重量%2-甲基咪唑(来自AirProducts的AMI-2牌)。预浸料坯和复合材料的进一步制造与实施例1所述类似。
(对比)实施例3
在本实施例中,在60℃下使15g苯酚-甲醛树脂(来自SchenectadyInternational的HRJ 2210牌)溶于含84.5g溴化双酚A环氧树脂(来自Dow Chemicals的D.E.R.530-A80牌)的100g丙酮溶液中。然后,加入0.5重量%2-甲基咪唑(来自Air Products的AMI-2牌)。预浸料坯和复合材料的进一步制造与实施例1所述类似。
实施例4
然后根据ISO/DP 5660标准,用锥形量热计在75kw/m2的热流下评价实施例1~3中分别制造的复合材料的可燃性。该可燃性试验的结果在下表中提供:
参数 | 实施例1 | 实施例2 | 实施例3 |
至着火的时间(秒) | 44 | 13 | 18 |
质量损失(重量%) | 37 | 43 | 49 |
平均放热速率(kW/m2) | 73 | 110 | 85 |
总放热量(MJ/m2) | 60 | 81 | 59 |
总发烟量(arb.Units) | 2750 | 3220 | 5180 |
上述实施例仅仅说明本发明的某些实施方案,因此不应被认为是限制性的。请求保护的范围在以下权利要求中提出。
Claims (15)
1.复合材料,其包括增强纤维和粘合剂组合物,
所述粘合剂组合物包括环氧树脂、任选的树脂固化剂、固化催化剂和活性膦酸酯阻燃剂。
2.权利要求1的复合材料,其中增强纤维占复合材料总重量的约50~约90重量%。
3.权利要求1的复合材料,其中粘合剂组合物占复合材料总重量的约20~约60重量%。
4.权利要求1的复合材料,其中环氧树脂占粘合剂组合物总重量的约40~约80重量%。
5.权利要求1的复合材料,其中活性膦酸酯阻燃剂占粘合剂组合物总重量的5~60重量%。
6.权利要求1的复合材料,其中固化催化剂占粘合剂组合物总重量的0.05~1.0重量%。
7.权利要求1的复合材料,其中任选的树脂固化剂占粘合剂组合物总重量的5~约10重量%。
8.权利要求1的复合材料,其中增强纤维选自石墨、玻璃和硅灰石。
9.权利要求1的复合材料,其中活性膦酸酯阻燃剂是包括(-OP(O)(R)-O-亚芳基-)n重复单元的低聚膦酸酯,其中“n”为约2~约30。
10.权利要求8的复合材料,其中增强纤维是石墨。
11.权利要求9的复合材料,其中活性膦酸酯阻燃剂是聚(甲基膦酸间亚苯酯)。
12.制备复合材料的方法,所述方法包括用粘合剂组合物浸渍增强纤维,所述粘合剂组合物包括环氧树脂、任选的树脂固化剂、固化催化剂和活性膦酸酯阻燃剂。
13.权利要求12的方法,其中增强纤维选自石墨、玻璃和硅灰石。
14.权利要求12的方法,其中活性膦酸酯阻燃剂是包括(-OP(O)(R)-O-亚芳基-)n重复单元的低聚膦酸酯,其中“n”为约2~约30。
15.权利要求14的方法,其中活性膦酸酯阻燃剂是聚(甲基膦酸间亚苯酯)。
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CN104024338A (zh) * | 2011-06-03 | 2014-09-03 | Frx聚合物股份有限公司 | 阻燃性树脂组合物、使用所述树脂组合物的挠性印刷线路板用金属箔基层压板、覆盖层、挠性印刷线路板用粘合片、以及挠性印刷线路板 |
CN112105703A (zh) * | 2018-05-17 | 2020-12-18 | 株式会社T&K东华 | 固化性环氧化物组合物 |
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JP2010530017A (ja) * | 2007-06-14 | 2010-09-02 | ビーエーエスエフ ソシエタス・ヨーロピア | 難燃剤組成物 |
US8058363B2 (en) * | 2009-04-09 | 2011-11-15 | Iteq Corporation | Varnish and prepreg, and substrates thereof |
CN103602300B (zh) * | 2013-11-08 | 2014-12-31 | 福州大学 | 一种高阻隔阻燃抗静电环氧树脂胶粘剂及其制备方法 |
KR101665680B1 (ko) | 2014-12-26 | 2016-10-12 | 연세대학교 산학협력단 | 표면에 인이 도핑된 산화 그래핀을 포함하는 난연제 및 이의 제조방법 |
GB2580283B (en) * | 2018-08-03 | 2022-02-23 | Gurit Uk Ltd | Fire-retardant epoxide resins and use thereof |
RU2751337C1 (ru) * | 2020-11-27 | 2021-07-13 | Акционерное общество "Научно-исследовательский институт конструкционных материалов на основе графита "НИИграфит" | Антифрикционная композиция и способ её получения |
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US223411A (en) * | 1880-01-06 | Saddle-loop | ||
US4940740A (en) * | 1989-04-21 | 1990-07-10 | Basf Aktiengesellschaft | Single phase toughened heat-curable resin systems exhibiting high strength after impact |
EP0425424A3 (en) * | 1989-08-31 | 1991-09-11 | United Technologies Corporation | Method for fabricating graphite fiber epoxy composites |
US6605354B1 (en) * | 2001-08-28 | 2003-08-12 | Borden Chemical, Inc. | High nitrogen containing triazine-phenol-aldehyde condensate |
JP4518538B2 (ja) * | 2001-10-04 | 2010-08-04 | サプレスタ エルエルシー | ヒドロキシ末端化されたオリゴマー状ホスホネートを含む熱硬化性樹脂組成物 |
DE10300462A1 (de) * | 2003-01-07 | 2004-07-15 | Bakelite Ag | Phosphormodifiziertes Epoxidharz |
-
2005
- 2005-03-23 US US11/547,107 patent/US20080057314A1/en not_active Abandoned
- 2005-03-23 WO PCT/US2005/009634 patent/WO2005118276A2/en active Application Filing
- 2005-03-23 JP JP2007506245A patent/JP4975610B2/ja active Active
- 2005-03-23 CA CA 2561582 patent/CA2561582A1/en not_active Abandoned
- 2005-03-23 EP EP20050804752 patent/EP1751222A2/en not_active Withdrawn
- 2005-03-23 KR KR1020067022858A patent/KR101323751B1/ko active IP Right Grant
- 2005-03-25 CN CNB2005800119912A patent/CN100528949C/zh active Active
- 2005-03-25 RU RU2006138503/04A patent/RU2006138503A/ru not_active Application Discontinuation
- 2005-03-29 TW TW94109822A patent/TWI383029B/zh not_active IP Right Cessation
Cited By (5)
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CN103249775A (zh) * | 2010-07-30 | 2013-08-14 | 陶氏环球技术有限责任公司 | 可固化组合物 |
CN104024338A (zh) * | 2011-06-03 | 2014-09-03 | Frx聚合物股份有限公司 | 阻燃性树脂组合物、使用所述树脂组合物的挠性印刷线路板用金属箔基层压板、覆盖层、挠性印刷线路板用粘合片、以及挠性印刷线路板 |
CN112105703A (zh) * | 2018-05-17 | 2020-12-18 | 株式会社T&K东华 | 固化性环氧化物组合物 |
US11084960B2 (en) | 2018-05-17 | 2021-08-10 | T&K Toka Co., Ltd. | Curable epoxide composition |
CN112105703B (zh) * | 2018-05-17 | 2022-01-04 | 株式会社T&K东华 | 固化性环氧化物组合物 |
Also Published As
Publication number | Publication date |
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JP4975610B2 (ja) | 2012-07-11 |
CN100528949C (zh) | 2009-08-19 |
US20080057314A1 (en) | 2008-03-06 |
KR101323751B1 (ko) | 2013-11-21 |
RU2006138503A (ru) | 2008-05-10 |
TWI383029B (zh) | 2013-01-21 |
EP1751222A2 (en) | 2007-02-14 |
CA2561582A1 (en) | 2005-12-15 |
WO2005118276A2 (en) | 2005-12-15 |
TW200604306A (en) | 2006-02-01 |
WO2005118276A3 (en) | 2006-03-16 |
JP2007530769A (ja) | 2007-11-01 |
KR20070011428A (ko) | 2007-01-24 |
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