CN102477139B - 无卤无磷树脂制剂及无卤无磷低介电耐燃复合材料 - Google Patents
无卤无磷树脂制剂及无卤无磷低介电耐燃复合材料 Download PDFInfo
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- 239000011347 resin Substances 0.000 title claims abstract description 40
- 239000002131 composite material Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title abstract description 29
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title abstract description 4
- 239000003063 flame retardant Substances 0.000 title abstract description 4
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- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000009472 formulation Methods 0.000 claims abstract description 31
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims abstract description 8
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 57
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 41
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- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
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- KCWDJXPPZHMEIK-UHFFFAOYSA-N isocyanic acid;toluene Chemical compound N=C=O.N=C=O.CC1=CC=CC=C1 KCWDJXPPZHMEIK-UHFFFAOYSA-N 0.000 claims description 4
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
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- UJMDYLWCYJJYMO-UHFFFAOYSA-N benzenetricarboxylic Acid Natural products OC(=O)C1=CC=CC(C(O)=O)=C1C(O)=O UJMDYLWCYJJYMO-UHFFFAOYSA-N 0.000 description 10
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- 239000000463 material Substances 0.000 description 10
- KSOCVFUBQIXVDC-FMQUCBEESA-N p-azophenyltrimethylammonium Chemical compound C1=CC([N+](C)(C)C)=CC=C1\N=N\C1=CC=C([N+](C)(C)C)C=C1 KSOCVFUBQIXVDC-FMQUCBEESA-N 0.000 description 10
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 10
- 238000002485 combustion reaction Methods 0.000 description 6
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 5
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 5
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- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 3
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
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- 239000002994 raw material Substances 0.000 description 2
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- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
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- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- HLJDOURGTRAFHE-UHFFFAOYSA-N isocyanic acid;3,5,5-trimethylcyclohex-2-en-1-one Chemical compound N=C=O.N=C=O.CC1=CC(=O)CC(C)(C)C1 HLJDOURGTRAFHE-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- NHDHVHZZCFYRSB-UHFFFAOYSA-N pyriproxyfen Chemical compound C=1C=CC=NC=1OC(C)COC(C=C1)=CC=C1OC1=CC=CC=C1 NHDHVHZZCFYRSB-UHFFFAOYSA-N 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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- C—CHEMISTRY; METALLURGY
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/343—Polycarboxylic acids having at least three carboxylic acid groups
- C08G18/345—Polycarboxylic acids having at least three carboxylic acid groups having three carboxylic acid groups
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L35/02—Homopolymers or copolymers of esters
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- 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
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
- Y10T442/2631—Coating or impregnation provides heat or fire protection
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- 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
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
- Y10T442/2631—Coating or impregnation provides heat or fire protection
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Abstract
本发明提供一种无卤无磷树脂制剂,系由下列方法所制备:混合羧酸酐衍生物、二异氰酸酯、苯乙烯马来酸酐共聚衍生物与溶剂,以形成混合物;以及加热该混合物,以形成一树脂制剂。本发明亦提供一种由该树脂制剂制备之无卤无磷低介电耐燃复合材料。
Description
技术领域
本发明系有关于一种树脂制剂,特别是有关于一种无卤无磷树脂制剂及由该树脂制剂制备之无卤无磷低介电耐燃复合材料。
背景技术
在无卤材料制剂组成中,一般以选择磷化物当作耐燃剂,取代现有卤素化合物,但由于含磷量不可偏高,致造成耐热性不足。因此,选择适当含磷量制剂组成,搭配氢氧化铝来达成UL-94 V0耐燃需求。目前,即使无卤无磷型高耐热制剂组成亦使用氢氧化铝来达成UL-94 V0耐燃需求,例如US 2006/0084787A1“Novelcyanate ester compound,flame-retardant resin composition,andcured product thereof”以及US 2008/02621397A1“Flame retardantcrosslink agent and epoxy resin compositions free of halogen andphosphorous”。在有机高耐热基板材料的选择上,除了BT(Bismaleimide Triazine)树脂外,目前,以环氧树脂为主要的耐热性材料,以TMA测量所得到的Tg皆在180℃左右。
发明内容
本发明之一实施例,提供一种无卤无磷树脂制剂(halogen-freeand pho sphorus-free resin formulation),系由下列方法所制备:混合羧酸酐(carboxy anhydride)衍生物、二异氰酸酯、苯乙烯马来酸酐(styrene maleic anhydride,SMA)共聚衍生物与溶剂,以形成混合物;以及加热该混合物,以形成一树脂制剂。
本发明之一实施例,提供一种无卤无磷低介电耐燃复合材料,系由下列方法所制备:提供上述之无卤无磷树脂制剂;以及将该树脂制剂含浸纤维并加热硬化,以制备一无卤无磷低介电耐燃复合材料。
本发明复合材料为一种环保型(无卤无磷)高耐热低介电材料,主要由羧酸酐(carboxy anhydride)衍生物、例如二异氰酸二苯甲烷(methylene diphenyl diisocyanate,MDI)、二异氰酸甲苯(toluenediisocyanate,TDI)或二异氰酸异佛尔酮(isophorone diisocyanate,IPDI)的二异氰酸酯与苯乙烯马来酸酐(styrene maleic anhydride,SMA)共聚衍生物等原料所构成,其Tg超过180℃,且不须额外添加例如氢氧化铝的填充剂(filler)即可达到UL-94 V0耐燃需求,对未来高耐热及高频基板材料的开发有相当助益。
本发明主要将高氮含量之二异氰酸酯单体(例如MDI、TDI或IPDI)、羧酸酐单体(例如TMA)与树脂(例如SMA)混合搅拌进行反应,并控制适当的反应物比例及温度,以合成此无卤无磷低介电耐燃复合材料。
为让本发明之上述目的、特征及优点能更明显易懂,下文特举一较佳实施例,作详细说明如下:
具体实施方式
本发明之一实施例,提供一种无卤无磷树脂制剂,其由下列方法所制备。首先,混合羧酸酐(carboxy anhydride)衍生物、二异氰酸酯、苯乙烯马来酸酐(styrene maleic anhydride,SMA)共聚衍生物与溶剂,以形成混合物。之后,加热混合物,以形成一树脂制剂。
上述羧酸酐衍生物具有下列化学式:
化学式中,A可为苯环或环己烷,R可为H、CH3或COOH,n可为0~8。本发明羧酸酐衍生物较佳为苯三甲酸酐(trimelliticanhydride,TMA)。
上述二异氰酸酯可包括二异氰酸二苯甲烷(methylene diphenyldiisocyanate,MDI)、二异氰酸甲苯(toluene diisocyanate,TDI)或二异氰酸异佛尔酮(isophorone diisocyanate,IPDI),较佳为二异氰酸二苯甲烷(MDI)。
上述苯乙烯马来酸酐共聚衍生物具有下列化学式:
化学式中,m可为1~7,较佳为2~3,n可为2~15。
上述溶剂可包括二甲基甲酰胺(DMF)、甲基吡咯烷酮(NMP)或二甲基亚砜(DMSO)。
上述混合物中,羧酸酐衍生物在混合物固含量(solid content)中之重量百分比大体介于10~30%,二异氰酸酯在混合物固含量中之重量百分比大体介于10~35%,苯乙烯马来酸酐共聚衍生物在混合物固含量中之重量百分比大体介于35~80%。上述溶剂在混合物中之重量百分比大体介于20~60%。
上述加热混合物之温度大体介于摄氏80~140度,较佳介于摄氏95~110度。
本发明之一实施例,提供一种无卤无磷低介电耐燃复合材料,其由下列方法所制备。首先,提供上述之无卤无磷树脂制剂,之后,将树脂制剂含浸纤维并加热硬化,即可得到无卤无磷低介电耐燃复合材料。
上述纤维可包括玻璃纤维布或聚酰胺纤维。
本发明复合材料为一种环保型(无卤无磷)高耐热低介电材料,主要由羧酸酐(carboxy anhydride)衍生物、例如二异氰酸二苯甲烷(methylene diphenyl diisocyanate,MDI)、二异氰酸甲苯(toluenediisocyanate,TDI)或二异氰酸异佛尔酮(isophorone diisocyanate,IPDI)的二异氰酸酯与苯乙烯马来酸酐(styrene maleic anhydride,SMA)共聚衍生物等原料所构成,其Tg超过180℃,且不须额外添加例如氢氧化铝的填充剂(filler)即可达到UL-94 V0耐燃需求,对未来高耐热及高频基板材料的开发有相当助益。
本发明主要将高氮含量之二异氰酸酯单体(例如MDI、TDI或IPDI)、羧酸酐单体(例如TMA)与树脂(例如SMA)混合搅拌进行反应,并控制适当的反应物比例及温度,以合成此无卤无磷低介电耐燃复合材料。
实施例
【实施例1】
本发明无卤无磷低介电耐燃复合材料之制备(1)
使用500毫升,3口之玻璃反应器,2片叶轮的搅拌棒,加入100g苯三甲酸酐(trimellitic anhydride,TMA,Fu-Pao ChemicalCo.)、25g苯乙烯马来酸酐(styrene maleic anhydride,SMA3000F,Cray Valley Co.)、137.5g二异氰酸二苯甲烷(methylene diphenyldiisocyanate,MDI,Fu-Pao Chemical Co.)及262.5g二甲基甲酰胺(dimethylformamide,DMF,C-ECHO Co.)于80~140℃下搅拌反应均匀后,待温度降至室温,即得到无卤无磷树脂制剂。将该制剂含浸玻璃纤维布后,此预浸片(pre-preg)经叠层于200℃下加热、加压3小时,则可得到无卤无磷低介电耐燃复合材料。
【实施例2】
本发明无卤无磷低介电耐燃复合材料之制备(2)
使用500毫升,3口之玻璃反应器,2片叶轮的搅拌棒,加入100g苯三甲酸酐(trimellitic anhydride,TMA,Fu-Pao ChemicalCo.)、100g苯乙烯马来酸酐(styrene maleic anhydride,SMA3000F,Cray Valley Co.)、155.4g二异氰酸二苯甲烷(methylene diphenyldiisocyanate,MDI,Fu-Pao Chemical Co.)及355.4g二甲基甲酰胺(dimethylformamide,DMF,C-ECHO Co.)于80~140℃下搅拌反应均匀后,待温度降至室温,即得到无卤无磷树脂制剂。将该制剂含浸玻璃纤维布后,此预浸片(pre-preg)经叠层于200℃下加热、加压3小时,则可得到无卤无磷低介电耐燃复合材料。
【实施例3】
本发明无卤无磷低介电耐燃复合材料之制备(3)
使用500毫升,3口之玻璃反应器,2片叶轮的搅拌棒,加入100g苯三甲酸酐(trimellitic anhydride,TMA,Fu-Pao ChemicalCo.)、25g苯乙烯马来酸酐(styrene maleic anhydride,SMA3000F,Cray Valley Co.)、375g二异氰酸二苯甲烷(methylene diphenyldiisocyanate,MDI,Fu-Pao Chemical Co.)及499.3g二甲基甲酰胺(dimethylformamide,DMF,C-ECHO Co.)于80~140℃下搅拌反应均匀后,待温度降至室温,即得到无卤无磷树脂制剂。将该制剂含浸玻璃纤维布后,此预浸片(pre-preg)经叠层于200℃下加热、加压3小时,则可得到无卤无磷低介电耐燃复合材料。
【实施例4】
本发明无卤无磷低介电耐燃复合材料之制备(4)
使用500毫升,3口之玻璃反应器,2片叶轮的搅拌棒,加入100g苯三甲酸酐(trimellitic anhydride,TMA,Fu-Pao ChemicalCo.)、25g苯乙烯马来酸酐(styrene maleic anhydride,SMA3000F,Cray Valley Co.)、83.3g二异氰酸二苯甲烷(methylene diphenyldiisocyanate,MDI,Fu-Pao Chemical Co.)及208g二甲基甲酰胺(dimethylformamide,DMF,C-ECHO Co.)于80~140℃下搅拌反应均匀后,待温度降至室温,即得到无卤无磷树脂制剂。将该制剂含浸玻璃纤维布后,此预浸片(pre-preg)经叠层于200℃下加热、加压3小时,则可得到无卤无磷低介电耐燃复合材料。
【实施例5】
本发明无卤无磷低介电耐燃复合材料之制备(5)
使用500毫升,3口之玻璃反应器,2片叶轮的搅拌棒,加入100g苯三甲酸酐(trimellitic anhydride,TMA,Fu-Pao ChemicalCo.)、12.5g苯乙烯马来酸酐(styrene maleic anhydride,SMA3000F,Cray Valley Co.)、134.5g二异氰酸二苯甲烷(methylene diphenyldiisocyanate,MDI,Fu-Pao Chemical Co.)及247g二甲基甲酰胺(dimethylformamide,DMF,C-ECHO Co.)于80~140℃下搅拌反应均匀后,待温度降至室温,即得到无卤无磷树脂制剂。将该制剂含浸玻璃纤维布后,此预浸片(pre-preg)经叠层于200℃下加热、加压3小时,则可得到无卤无磷低介电耐燃复合材料。
【实施例6】
本发明无卤无磷低介电耐燃复合材料之制备(6)
使用500毫升,3口之玻璃反应器,2片叶轮的搅拌棒,加入30g苯三甲酸酐(trimellitic anhydride,TMA,Fu-Pao Chemical Co.)、240g苯乙烯马来酸酐(styrene maleic anhydride,SMA3000F,CrayValley Co.)、30g二异氰酸二苯甲烷(methylene diphenyldiisocyanate,MDI,Fu-Pao Chemical Co.)及300g二甲基甲酰胺(dimethylformamide,DMF,C-ECHO Co.)于80~140℃下搅拌反应均匀后,待温度降至室温,即得到无卤无磷树脂制剂。将该制剂含浸玻璃纤维布后,此预浸片(pre-preg)经叠层于200℃下加热、加压3小时,则可得到无卤无磷低介电耐燃复合材料。
【实施例7】
本发明无卤无磷低介电耐燃复合材料之制备(7)
使用500毫升,3口之玻璃反应器,2片叶轮的搅拌棒,加入60g苯三甲酸酐(trimellitic anhydride,TMA,Fu-Pao Chemical Co.)、75g苯乙烯马来酸酐(styrene maleic anhydride,SMA3000F,CrayValley Co.)、75g二异氰酸二苯甲烷(methylene diphenyldiisocyanate,MDI,Fu-Pao Chemical Co.)及210g二甲基甲酰胺(dimethylformamide,DMF,C-ECHO Co.)于80~140℃下搅拌反应均匀后,待温度降至室温,即得到无卤无磷树脂制剂。将该制剂含浸玻璃纤维布后,此预浸片(pre-preg)经叠层于200℃下加热、加压3小时,则可得到无卤无磷低介电耐燃复合材料。
【实施例8】
本发明无卤无磷低介电耐燃复合材料之制备(8)
使用500毫升,3口之玻璃反应器,2片叶轮的搅拌棒,加入20g苯三甲酸酐(trimellitic anhydride,TMA,Fu-Pao Chemical Co.)、110g苯乙烯马来酸酐(styrene maleic anhydride,SMA3000F,CrayValley Co.)、70g二异氰酸二苯甲烷(methylene diphenyldiisocyanate,MDI,Fu-Pao Chemical Co.)及200g二甲基甲酰胺(dimethylformamide,DMF,C-ECHO Co.)于80~140℃下搅拌反应均匀后,待温度降至室温,即得到无卤无磷树脂制剂。将该制剂含浸玻璃纤维布后,此预浸片(pre-preg)经叠层于200℃下加热、加压3小时,则可得到无卤无磷低介电耐燃复合材料。
【实施例9】
本发明无卤无磷低介电耐燃复合材料之制备(9)
使用500毫升,3口之玻璃反应器,2片叶轮的搅拌棒,加入100g环己烷-1,2,4-三羧酸-1,2-酐(cyclohexane-1,2,4-tricarboxylicacid-1,2-anhydride,c-TMA,Fu-Pao Chemical Co.)、100g苯乙烯马来酸酐(styrene maleic anhydride,SMA3000F,Cray Valley Co.)、155.4g二异氰酸二苯甲烷(methylene diphenyl diisocyanate,MDI,Fu-Pao Chemical Co.)及355.4g二甲基甲酰胺(dimethylformamide,DMF,C-ECHO Co.)于80~140℃下搅拌反应均匀后,待温度降至室温,即得到无卤无磷树脂制剂。将该制剂含浸玻璃纤维布后,此预浸片(pre-preg)经叠层于200℃下加热、加压3小时,则可得到无卤无磷低介电耐燃复合材料。
【实施例10】
本发明无卤无磷低介电耐燃复合材料之制备(10)
使用500毫升,3口之玻璃反应器,2片叶轮的搅拌棒,加入100g苯三甲酸酐(trimellitic anhydride,TMA,Fu-Pao ChemicalCo.)、110g苯乙烯马来酸酐(styrene maleic anhydride,SMA3000F,Cray Valley Co.)、155.4g二异氰酸异佛尔酮(isophoronediisocyanate,IPDI,Fu-Pao Chemical Co.)及355.4g二甲基甲酰胺(dimethylformamide,DMF,C-ECHO Co.)于80~140℃下搅拌反应均匀后,待温度降至室温,即得到无卤无磷树脂制剂。将该制剂含浸玻璃纤维布后,此预浸片(pre-preg)经叠层于200℃下加热、加压3小时,则可得到无卤无磷低介电耐燃复合材料。
【比较例1】
常规无卤无磷低介电耐燃材料之制备
使用500毫升,3口之玻璃反应器,2片叶轮的搅拌棒,加入110g酰胺酰亚胺树脂(AIN,Fu-Pao Chemical Co.)、67.3g环氧树脂(828EL,Shell Chemical Co.)及13.3g二甲基甲酰胺(dimethylformamide,DMF,C-ECHO Co.)于120℃下搅拌反应均匀后,待温度降至室温,将13.3g 4,4′-二胺基二苯基砜(4,4-diaminodiphenyl sulfone,DDS,Ciba Chemical Co.)加入上述溶液于反应器中搅拌,即得到无卤无磷树脂制剂。将该制剂含浸玻璃纤维布后,此预浸片(pre-preg)经叠层于200℃下加热、加压3小时,则可得到无卤无磷低介电耐燃材料。
【比较例2】
常规无卤无磷耐燃材料之制备
使用500毫升,3口之玻璃反应器,2片叶轮的搅拌棒,加入110g酰胺酰亚胺树脂(AIN,Fu-Pao Chemical Co.)、67.3g环氧树脂(828EL,Shell Chemical Co.)及13.3g二甲基甲酰胺(dimethylformamide,DMF,C-ECHO Co.)于120℃下搅拌反应均匀后,待温度降至室温,将13.3g 4,4′-二胺基二苯基砜(4,4-diaminodiphenyl sulfone,DDS,Ciba Chemical Co.)及114g氢氧化铝(Al(OH)3,Showa Denko Co.)加入上述溶液于反应器中搅拌,即得到耐燃无卤无磷树脂制剂。将该制剂含浸玻璃纤维布后,此预浸片(pre-preg)经叠层于200℃下加热、加压3小时,则可得到无卤无磷低介电耐燃材料。
(以下之DK、Tg等数据均是以含浸玻璃纤维布之树脂材料所得之结果)
表一
Dk:介电常数(dielectric constant)
Tg:玻璃转移温度(glass transition temperature)
CTE:热膨胀系数(coefficient of thermal expansion)
玻璃纤维布使用7628
将实施例1~10与比较例1~2之物理特性列于上表,由表一可知实施例1~10皆具有良好耐燃特性,明显优于比较例。另实施例2及实施例6亦兼具低介电特性。
虽然本发明已以较佳实施例揭露如上,然其并非用以限定本发明,任何熟习此项技艺者,在不脱离本发明之精神和范围内,当可作更动与润饰,因此本发明之保护范围当视后附之申请专利范围所界定者为准。
Claims (4)
1.一种无卤无磷树脂制剂,其由下列方法所制备:
混合羧酸酐衍生物、二异氰酸酯、苯乙烯马来酸酐共聚衍生物与溶剂,以形成混合物,其中该羧酸酐衍生物于该混合物固含量中之重量百分比介于10~30%,该二异氰酸酯于该混合物固含量中之重量百分比介于10~35%,以及该苯乙烯马来酸酐共聚衍生物于该混合物固含量中之重量百分比介于35~80%,其中该羧酸酐衍生物具有化学式其中A为苯环或环己烷,R为H、CH3或COOH,n为0~8;该二异氰酸酯包括二异氰酸二苯甲烷、二异氰酸甲苯或二异氰酸异佛尔酮;该苯乙烯马来酸酐共聚衍生物具有化学式其中m为1~7,n为2~15;该溶剂包括二甲基甲酰胺、甲基吡咯烷酮或二甲基亚砜;以及
加热该混合物,以形成一树脂制剂。
2.如权利要求1所述之无卤无磷树脂制剂,其中加热该混合物之温度介于摄氏80~140度。
3.一种无卤无磷低介电耐燃复合材料,其由下列方法所制备:
提供如权利要求1所述之无卤无磷树脂制剂;以及
将该树脂制剂含浸纤维并加热硬化,以制备一无卤无磷低介电耐燃复合材料。
4.如权利要求3所述之无卤无磷低介电耐燃复合材料,其中该纤维包括玻璃纤维布或聚酰胺纤维。
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