CN116080210B - 一种酚醛树脂基覆铜板及其制备方法 - Google Patents
一种酚醛树脂基覆铜板及其制备方法 Download PDFInfo
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- phenolic resin
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- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 67
- 239000005011 phenolic resin Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000003063 flame retardant Substances 0.000 claims abstract description 40
- 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 claims abstract description 39
- HIVGXUNKSAJJDN-UHFFFAOYSA-N [Si].[P] Chemical compound [Si].[P] HIVGXUNKSAJJDN-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 34
- 239000010703 silicon Substances 0.000 claims abstract description 34
- 239000011256 inorganic filler Substances 0.000 claims abstract description 27
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 27
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 21
- 239000011574 phosphorus Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 65
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- 238000007731 hot pressing Methods 0.000 claims description 48
- 238000010438 heat treatment Methods 0.000 claims description 34
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 28
- -1 silicon modified phenolic resin Chemical class 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 25
- 238000010992 reflux Methods 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 239000003292 glue Substances 0.000 claims description 21
- 239000003365 glass fiber Substances 0.000 claims description 19
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 claims description 19
- 239000004744 fabric Substances 0.000 claims description 18
- 238000005470 impregnation Methods 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 238000001914 filtration Methods 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 16
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 16
- 238000002390 rotary evaporation Methods 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- 239000003822 epoxy resin Substances 0.000 claims description 15
- 229920000647 polyepoxide Polymers 0.000 claims description 15
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- LXJXRIRHZLFYRP-VKHMYHEASA-N D-glyceraldehyde 3-phosphate Chemical compound O=C[C@H](O)COP(O)(O)=O LXJXRIRHZLFYRP-VKHMYHEASA-N 0.000 claims description 12
- LJDGKIUMGVMSGI-UHFFFAOYSA-N [hydroxymethyl(phenyl)phosphanyl]methanol Chemical compound OCP(CO)C1=CC=CC=C1 LJDGKIUMGVMSGI-UHFFFAOYSA-N 0.000 claims description 12
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 claims description 11
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 claims description 11
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 claims description 11
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 claims description 11
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 claims description 11
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 claims description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 9
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical group [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 9
- 239000007795 chemical reaction product Substances 0.000 claims description 9
- 239000011889 copper foil Substances 0.000 claims description 9
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 9
- 238000003825 pressing Methods 0.000 claims description 9
- 238000010008 shearing Methods 0.000 claims description 9
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 9
- 229950005499 carbon tetrachloride Drugs 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 2
- 238000004945 emulsification Methods 0.000 claims 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 6
- 230000004048 modification Effects 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 4
- 229920005989 resin Polymers 0.000 abstract description 4
- 239000011347 resin Substances 0.000 abstract description 4
- 238000010276 construction Methods 0.000 abstract description 2
- 230000001804 emulsifying effect Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000002485 combustion reaction Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
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Abstract
本发明涉及覆铜板技术领域,具体为一种酚醛树脂基覆铜板及其制备方法;本发明首先制备了硅改性在酚醛树脂体系中引入含有高键能的硅氧键,提升酚醛树脂的热体积稳定性,拓宽覆铜板的可适用工作温度范围;之后为了增加酚醛树脂施工过程中的流动性,提升无机填料的分散度,本发明进一步地制备了具有超支化结构的超支化磷硅阻燃剂,利用其类球形的空间结构增加酚醛树脂流动性,同时引入大量的磷元素,增加树脂体系的阻燃能力,减少火灾安全隐患。
Description
技术领域
本发明涉及覆铜板技术领域,具体为一种酚醛树脂基覆铜板及其制备方法。
背景技术
酚醛树脂是一种具有优异性能的树脂,具有良好的机械性能与化学稳定性,耐氧化能力强,成本低廉,常用作电子信息领域的覆铜板原料。覆铜板作为电子元器件原料之一,对其阻燃性往往具有较高的要求,以避免在面临短路等情况时出现火灾隐患;因此酚醛树脂常与阻燃剂联用,以提高其阻燃性能。
发明内容
本发明的目的在于提供一种酚醛树脂基覆铜板及其制备方法,以解决上述背景技术中提出的问题。
为了解决上述技术问题,本发明提供如下技术方案:一种酚醛树脂基覆铜板,具有以下特征:所述酚醛树脂基覆铜板由改性酚醛树脂基板与其两侧的铜层构成;
其中,所述改性酚醛树脂基板由6-10张浸渍有改性酚醛树脂胶液的玻璃纤维布烘干后,热压制得。
进一步的,按重量份数计,所述改性酚醛树脂胶液,包括以下组分:45-64份硅改性酚醛树脂、24-35份无机填料、5-10份环氧树脂,5-9份超支化磷硅阻燃剂、0.1-0.2份二甲基咪唑。
进一步的,所述无机填料为氢氧化铝,粒径为0.05-02μm;所述环氧树脂为双酚A型环氧树脂。
一种酚醛树脂基覆铜板的制备方法,包括以下步骤:
S1.制备硅改性酚醛树脂;
S11.将8mol腰果酚、10mol甲醛混合,加入氢氧化钠溶液调节pH至10,升温至70℃,氮气氛围下回流反应1h,旋蒸去除多余溶剂,得到酚醛树脂预聚体;
S12.将3.5mol苯基三乙氧基硅烷溶于10mol无水乙醇,缓慢滴加至酚醛树脂预聚体中,滴加时间为2h,之后滴加盐酸调节pH至1,升温至回流温度,回流反应1.5h,滴加氢氧化钠,调节pH至11,过滤,使用去离子水洗涤沉淀至中性,真空60℃干燥至恒重,得到硅改性酚醛树脂;
S2.制备超支化磷硅阻燃剂;
S21.氮气氛围保护,将磷酸甘油醛溶于二氯甲烷中,冰水浴处理,加入三乙胺,搅拌混合后,缓慢滴加溶有3-氨基丙基三乙氧基硅烷的四氯甲烷溶液,滴加结束后,升温至20-25℃,搅拌反应12-24h后,旋蒸反应产物,并使用无水乙醇洗涤,真空干燥,得到含磷硅氧烷;
S22.将步骤S21制备得到的含磷硅氧烷溶于二氯甲烷中,滴加溶有双(羟基甲基)苯基磷的二氯甲烷溶液,滴加结束后,升温至85-95℃,回流反应12-18h后,旋蒸去除多余溶剂,真空干燥,得到超支化磷硅阻燃剂;
S3.将无机填料浸没在硅烷偶联剂中,超声分散1-3h后,过滤,干燥后得到表面改性无机填料;
S4.将硅改性酚醛树脂、无机填料、环氧树脂、超支化磷硅阻燃剂、二甲基咪唑混合均匀,高速剪切乳化2-3h后,得到改性酚醛树脂胶液;
S5.对玻璃纤维布使用改性酚醛树脂胶液双重浸渍,浸渍结束后,190-210℃干燥,制得半干燥片;
S6.将多张半干燥片堆叠,并在堆叠的半干燥片相册覆盖铜箔,热压,制得酚醛树脂基覆铜板。
进一步的,步骤S1中,按摩尔份数计,所述腰果酚、甲醛、苯基三乙氧基硅烷的摩尔比为(8-10):(10-12):(3.5-4)。
进一步的,步骤S2中,按摩尔份数计,磷酸甘油醛、三乙胺、3-氨基丙基三乙氧基硅烷、双(羟基甲基)苯基磷的摩尔比为(8-10):(7-10):(10-12):(5-8)。
进一步的,步骤S4中,高速剪切速率为1100-1400rpm。
进一步的,步骤S6中,热压时,热压温度为210-240℃,热压压力为2.4-3MPa,热压时长为1.5-2h;热压结束后,停止加热,继续以1.0-1.5MPa的压力冷压0.5-1h。
本发明为提高酚醛树脂的阻燃性能,首先制备了硅改性酚醛树脂,首先利用腰果酚与甲醛合成酚醛树脂预聚体,之后将其与苯基三乙氧基硅烷混合反应,从而在酚醛树脂体系中引入硅元素,在酚醛树脂体系中引入含高键能的硅氧键,提升耐高温能力,增加其高温下的体积稳定性,增加覆铜板的使用温度范围,同时,将硅元素引入酚醛树脂体系中,在燃烧时,这些硅元素会加速含硅炭层的产生,从而生成隔热层,阻碍燃烧的蔓延。
但是在酚醛树脂中引入硅氧键后,会造成酚醛树脂体系内硬段物质增加,流动性降低,从而造成无机填料等物质添加量下降;为避免此问题,本发明进一步制备了具有超支化结构的超支化磷硅阻燃剂,使用含有氨基的3-氨基丙基三乙氧基硅烷作为支化核心,首先将其与磷酸甘油醛混合反应,使得氨基与醛基反应,从而在3-氨基丙基三乙氧基硅烷接枝带有磷元素的磷酸甘油醛,之后又将其与带有端羟基的双(羟基甲基)苯基磷混合,从而生成具有支化结构的超支化磷硅阻燃剂,利用其类球形的空间结构,提高树脂体系的流动性;同时本发明所制备的超支化磷硅阻燃剂中含有大量的磷元素,在燃烧时,磷元素会生成自由基PO·,与燃烧反应所产生的H·反应,阻止燃烧反应的进行,从而进一步的提高覆铜板的阻燃性。
与现有技术相比,本发明所达到的有益效果是:本发明首先制备了硅改性在酚醛树脂体系中引入含有高键能的硅氧键,提升酚醛树脂的热体积稳定性,拓宽覆铜板的可适用工作温度范围;之后为了增加酚醛树脂施工过程中的流动性,提升无机填料的分散度,本发明进一步地制备了具有超支化结构的超支化磷硅阻燃剂,利用其类球形的空间结构增加酚醛树脂流动性,同时引入大量的磷元素,增加树脂体系的阻燃能力,减少火灾安全隐患。
具体实施方式
下面将对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
实施例1.
一种酚醛树脂基覆铜板的制备,包括以下步骤:
S1.制备硅改性酚醛树脂;
S11.将8mol腰果酚、10mol甲醛混合,加入氢氧化钠溶液调节pH至10,升温至70℃,氮气氛围下反应1h后,旋蒸去除多余溶剂,得到酚醛树脂预聚体;
S12.将3.5mol苯基三乙氧基硅烷溶于10mol无水乙醇,缓慢滴加至酚醛树脂预聚体中,滴加盐酸调节pH至1,升温至回流温度,回流反应1.5h后,滴加氢氧化钠,调节pH至11,过滤,使用去离子水洗涤至中性,真空60℃干燥至恒重,得到硅改性酚醛树脂;
S2.制备超支化磷硅阻燃剂;
S21.氮气氛围保护,将8mol磷酸甘油醛溶于二氯甲烷中,冰水浴处理,加入7mol三乙胺,搅拌混合后,缓慢滴加溶有10mol3-氨基丙基三乙氧基硅烷的四氯甲烷溶液,滴加结束后,升温至20℃,搅拌反应12h,旋蒸反应产物,并使用无水乙醇洗涤,真空60℃干燥8h,得到含磷硅氧烷;
S22.将步骤S21制备得到的含磷硅氧烷溶于二氯甲烷中,滴加溶有5mol双(羟基甲基)苯基磷的二氯甲烷溶液,滴加结束后,升温至85℃,回流反应12h后,旋蒸去除多余溶剂,真空60℃干燥12h,得到超支化磷硅阻燃剂;
S3.将氢氧化铝浸没在硅烷偶联剂KH-560中,超声分散1h后,过滤,干燥后得到表面改性无机填料;
S4.将4.5kg硅改性酚醛树脂、2.4kg改性无机填料、0.5kg环氧树脂、0.5kg超支化磷硅阻燃剂、0.01kg二甲基咪唑混合均匀,以1100rpm的速率高速剪切乳化2h后,得到改性酚醛树脂胶液;
S5.对玻璃纤维布使用改性酚醛树脂胶液双重浸渍,浸渍结束后,190℃干燥3min,制得半干燥片;
S6.将6张半干燥片堆叠,并在堆叠的半干燥片相册覆盖铜箔,热压,制得酚醛树脂基覆铜板;
其中热压温度为210℃,热压压力为2.4MPa,热压时长为1.5h;热压结束后,停止加热,继续以1MPa的压力冷压0.5h。
实施例2.
与实施例1相比,本实施例增加了步骤苯基三乙氧基硅烷的添加量;
一种酚醛树脂基覆铜板的制备,包括以下步骤:
S1.制备硅改性酚醛树脂;
S11.将8mol腰果酚、10mol甲醛混合,加入氢氧化钠溶液调节pH至10,升温至70℃,氮气氛围下反应1h后,旋蒸去除多余溶剂,得到酚醛树脂预聚体;
S12.将4mol苯基三乙氧基硅烷溶于10mol无水乙醇,缓慢滴加至酚醛树脂预聚体中,滴加盐酸调节pH至1,升温至回流温度,回流反应1.5h后,滴加氢氧化钠,调节pH至11,过滤,使用去离子水洗涤至中性,真空60℃干燥至恒重,得到硅改性酚醛树脂;
S2.制备超支化磷硅阻燃剂;
S21.氮气氛围保护,将8mol磷酸甘油醛溶于二氯甲烷中,冰水浴处理,加入7mol三乙胺,搅拌混合后,缓慢滴加溶有10mol3-氨基丙基三乙氧基硅烷的四氯甲烷溶液,滴加结束后,升温至20℃,搅拌反应12h,旋蒸反应产物,并使用无水乙醇洗涤,真空60℃干燥8h,得到含磷硅氧烷;
S22.将步骤S21制备得到的含磷硅氧烷溶于二氯甲烷中,滴加溶有5mol双(羟基甲基)苯基磷的二氯甲烷溶液,滴加结束后,升温至85℃,回流反应12h后,旋蒸去除多余溶剂,真空60℃干燥12h,得到超支化磷硅阻燃剂;
S3.将氢氧化铝浸没在硅烷偶联剂KH-560中,超声分散1h后,过滤,干燥后得到表面改性无机填料;
S4.将4.5kg硅改性酚醛树脂、2.4kg改性无机填料、0.5kg环氧树脂、0.5kg超支化磷硅阻燃剂、0.01kg二甲基咪唑混合均匀,以1100rpm的速率高速剪切乳化2h后,得到改性酚醛树脂胶液;
S5.对玻璃纤维布使用改性酚醛树脂胶液双重浸渍,浸渍结束后,190℃干燥3min,制得半干燥片;
S6.将6张半干燥片堆叠,并在堆叠的半干燥片相册覆盖铜箔,热压,制得酚醛树脂基覆铜板;
其中热压温度为210℃,热压压力为2.4MPa,热压时长为1.5h;热压结束后,停止加热,继续以1MPa的压力冷压0.5h。
实施例3.
与实施例1相比,本实施例增加了步骤S22中双(羟基甲基)苯基磷的添加量;
一种酚醛树脂基覆铜板的制备,包括以下步骤:
S1.制备硅改性酚醛树脂;
S11.将8mol腰果酚、10mol甲醛混合,加入氢氧化钠溶液调节pH至10,升温至70℃,氮气氛围下反应1h后,旋蒸去除多余溶剂,得到酚醛树脂预聚体;
S12.将3.5mol苯基三乙氧基硅烷溶于10mol无水乙醇,缓慢滴加至酚醛树脂预聚体中,滴加盐酸调节pH至1,升温至回流温度,回流反应1.5h后,滴加氢氧化钠,调节pH至11,过滤,使用去离子水洗涤至中性,真空60℃干燥至恒重,得到硅改性酚醛树脂;
S2.制备超支化磷硅阻燃剂;
S21.氮气氛围保护,将8mol磷酸甘油醛溶于二氯甲烷中,冰水浴处理,加入7mol三乙胺,搅拌混合后,缓慢滴加溶有10mol3-氨基丙基三乙氧基硅烷的四氯甲烷溶液,滴加结束后,升温至20℃,搅拌反应12h,旋蒸反应产物,并使用无水乙醇洗涤,真空60℃干燥8h,得到含磷硅氧烷;
S22.将步骤S21制备得到的含磷硅氧烷溶于二氯甲烷中,滴加溶有8mol双(羟基甲基)苯基磷的二氯甲烷溶液,滴加结束后,升温至85℃,回流反应12h后,旋蒸去除多余溶剂,真空60℃干燥12h,得到超支化磷硅阻燃剂;
S3.将氢氧化铝浸没在硅烷偶联剂KH-560中,超声分散1h后,过滤,干燥后得到表面改性无机填料;
S4.将4.5kg硅改性酚醛树脂、2.4kg改性无机填料、0.5kg环氧树脂、0.5kg超支化磷硅阻燃剂、0.01kg二甲基咪唑混合均匀,以1100rpm的速率高速剪切乳化2h后,得到改性酚醛树脂胶液;
S5.对玻璃纤维布使用改性酚醛树脂胶液双重浸渍,浸渍结束后,190℃干燥3min,制得半干燥片;
S6.将6张半干燥片堆叠,并在堆叠的半干燥片相册覆盖铜箔,热压,制得酚醛树脂基覆铜板;
其中热压温度为210℃,热压压力为2.4MPa,热压时长为1.5h;热压结束后,停止加热,继续以1MPa的压力冷压0.5h。
实施例4.
与实施例1相比,本实施例增加了步骤S4中超支化磷硅阻燃剂的添加量;
一种酚醛树脂基覆铜板的制备,包括以下步骤:
S1.制备硅改性酚醛树脂;
S11.将8mol腰果酚、10mol甲醛混合,加入氢氧化钠溶液调节pH至10,升温至70℃,氮气氛围下反应1h后,旋蒸去除多余溶剂,得到酚醛树脂预聚体;
S12.将3.5mol苯基三乙氧基硅烷溶于10mol无水乙醇,缓慢滴加至酚醛树脂预聚体中,滴加盐酸调节pH至1,升温至回流温度,回流反应1.5h后,滴加氢氧化钠,调节pH至11,过滤,使用去离子水洗涤至中性,真空60℃干燥至恒重,得到硅改性酚醛树脂;
S2.制备超支化磷硅阻燃剂;
S21.氮气氛围保护,将8mol磷酸甘油醛溶于二氯甲烷中,冰水浴处理,加入7mol三乙胺,搅拌混合后,缓慢滴加溶有10mol3-氨基丙基三乙氧基硅烷的四氯甲烷溶液,滴加结束后,升温至20℃,搅拌反应12h,旋蒸反应产物,并使用无水乙醇洗涤,真空60℃干燥8h,得到含磷硅氧烷;
S22.将步骤S21制备得到的含磷硅氧烷溶于二氯甲烷中,滴加溶有5mol双(羟基甲基)苯基磷的二氯甲烷溶液,滴加结束后,升温至85℃,回流反应12h后,旋蒸去除多余溶剂,真空60℃干燥12h,得到超支化磷硅阻燃剂;
S3.将氢氧化铝浸没在硅烷偶联剂KH-560中,超声分散1h后,过滤,干燥后得到表面改性无机填料;
S4.将4.5kg硅改性酚醛树脂、2.4kg改性无机填料、0.5kg环氧树脂、0.9kg超支化磷硅阻燃剂、0.01kg二甲基咪唑混合均匀,以1100rpm的速率高速剪切乳化2h后,得到改性酚醛树脂胶液;
S5.对玻璃纤维布使用改性酚醛树脂胶液双重浸渍,浸渍结束后,190℃干燥3min,制得半干燥片;
S6.将6张半干燥片堆叠,并在堆叠的半干燥片相册覆盖铜箔,热压,制得酚醛树脂基覆铜板;
其中热压温度为210℃,热压压力为2.4MPa,热压时长为1.5h;热压结束后,停止加热,继续以1MPa的压力冷压0.5h。
实施例5.
一种酚醛树脂基覆铜板的制备,包括以下步骤:
S1.制备硅改性酚醛树脂;
S11.将10mol腰果酚、12mol甲醛混合,加入氢氧化钠溶液调节pH至12,升温至75℃,氮气氛围下反应2h后,旋蒸去除多余溶剂,得到酚醛树脂预聚体;
S12.将4mol苯基三乙氧基硅烷溶于10mol无水乙醇,缓慢滴加至酚醛树脂预聚体中,滴加盐酸调节pH至2,升温至回流温度,回流反应3h后,滴加氢氧化钠,调节pH至12,过滤,使用去离子水洗涤至中性,真空60℃干燥至恒重,得到硅改性酚醛树脂;
S2.制备超支化磷硅阻燃剂;
S21.氮气氛围保护,将10mol磷酸甘油醛溶于二氯甲烷中,冰水浴处理,加入10mol三乙胺,搅拌混合后,缓慢滴加溶有12mol3-氨基丙基三乙氧基硅烷的四氯甲烷溶液,滴加结束后,升温至25℃,搅拌反应24h,旋蒸反应产物,并使用无水乙醇洗涤,真空60℃干燥8h,得到含磷硅氧烷;
S22.将步骤S21制备得到的含磷硅氧烷溶于二氯甲烷中,滴加溶有8mol双(羟基甲基)苯基磷的二氯甲烷溶液,滴加结束后,升温至95℃,回流反应18h后,旋蒸去除多余溶剂,真空60℃干燥12h,得到超支化磷硅阻燃剂;
S3.将氢氧化铝浸没在硅烷偶联剂KH-560中,超声分散3h后,过滤,干燥后得到表面改性无机填料;
S4.将6.4kg硅改性酚醛树脂、3.5kg改性无机填料、1kg环氧树脂、0.9kg超支化磷硅阻燃剂、0.02kg二甲基咪唑混合均匀,以1400rpm的速率高速剪切乳化3h后,得到改性酚醛树脂胶液;
S5.对玻璃纤维布使用改性酚醛树脂胶液双重浸渍,浸渍结束后,210℃干燥3min,制得半干燥片;
S6.将6张半干燥片堆叠,并在堆叠的半干燥片相册覆盖铜箔,热压,制得酚醛树脂基覆铜板;
其中热压温度为240℃,热压压力为3MPa,热压时长为2h;热压结束后,停止加热,继续以1.5MPa的压力冷压1h。
对比例1.
与实施例1相比,本对比例未制备硅改性酚醛树脂;仅以普通酚醛树脂等量替代;
一种酚醛树脂基覆铜板的制备,包括以下步骤:
S1.制备超支化磷硅阻燃剂;
S11.氮气氛围保护,将8mol磷酸甘油醛溶于二氯甲烷中,冰水浴处理,加入7mol三乙胺,搅拌混合后,缓慢滴加溶有10mol3-氨基丙基三乙氧基硅烷的四氯甲烷溶液,滴加结束后,升温至20℃,搅拌反应12h,旋蒸反应产物,并使用无水乙醇洗涤,真空60℃干燥8h,得到含磷硅氧烷;
S12.将步骤S11制备得到的含磷硅氧烷溶于二氯甲烷中,滴加溶有5mol双(羟基甲基)苯基磷的二氯甲烷溶液,滴加结束后,升温至85℃,回流反应12h后,旋蒸去除多余溶剂,真空60℃干燥12h,得到超支化磷硅阻燃剂;
S2.将氢氧化铝浸没在硅烷偶联剂KH-560中,超声分散1h后,过滤,干燥后得到表面改性无机填料;
S3.将4.5kg酚醛树脂、2.4kg改性无机填料、0.5kg环氧树脂、0.5kg超支化磷硅阻燃剂、0.01kg二甲基咪唑混合均匀,以1100rpm的速率高速剪切乳化2h后,得到改性酚醛树脂胶液;
S4.对玻璃纤维布使用改性酚醛树脂胶液双重浸渍,浸渍结束后,190℃干燥3min,制得半干燥片;
S5.将6张半干燥片堆叠,并在堆叠的半干燥片相册覆盖铜箔,热压,制得酚醛树脂基覆铜板;
其中热压温度为210℃,热压压力为2.4MPa,热压时长为1.5h;热压结束后,停止加热,继续以1MPa的压力冷压0.5h。
对比例2.
与实施例1相比,本对比例未制备超支化磷硅阻燃剂;
一种酚醛树脂基覆铜板的制备,包括以下步骤:
S1.制备硅改性酚醛树脂;
S11.将8mol腰果酚、10mol甲醛混合,加入氢氧化钠溶液调节pH至10,升温至70℃,氮气氛围下反应1h后,旋蒸去除多余溶剂,得到酚醛树脂预聚体;
S12.将3.5mol苯基三乙氧基硅烷溶于10mol无水乙醇,缓慢滴加至酚醛树脂预聚体中,滴加盐酸调节pH至1,升温至回流温度,回流反应1.5h后,滴加氢氧化钠,调节pH至11,过滤,使用去离子水洗涤至中性,真空60℃干燥至恒重,得到硅改性酚醛树脂;
S2.将氢氧化铝浸没在硅烷偶联剂KH-560中,超声分散1h后,过滤,干燥后得到表面改性无机填料;
S3.将4.5kg硅改性酚醛树脂、2.4kg改性无机填料、0.5kg环氧树脂、0.01kg二甲基咪唑混合均匀,以1100rpm的速率高速剪切乳化2h后,得到改性酚醛树脂胶液;
S4.对玻璃纤维布使用改性酚醛树脂胶液双重浸渍,浸渍结束后,190℃干燥3min,制得半干燥片;
S5.将6张半干燥片堆叠,并在堆叠的半干燥片相册覆盖铜箔,热压,制得酚醛树脂基覆铜板;
其中热压温度为210℃,热压压力为2.4MPa,热压时长为1.5h;热压结束后,停止加热,继续以1MPa的压力冷压0.5h。
检测:根据IPC-TM-650检测实施例1-5与对比例1-2所制备覆铜板的阻燃性能与剥离强度;检测结果见下表:
UL94级别 | 有效燃烧总时间(s) | 剥离强度(N/mm) | |
实施例1 | UL94-V0 | 39 | 1.67 |
实施例2 | UL94-V0 | 36 | 1.67 |
实施例3 | UL94-V0 | 34 | 1.68 |
实施例4 | UL94-V0 | 30 | 1.7 |
实施例5 | UL94-V0 | 32 | 1.68 |
对比例1 | UL94-V0 | 35 | 1.72 |
对比例2 | UL94-V1 | 52 | 1.65 |
最后应说明的是:以上所述仅为本发明的优选实施例而已,并不用于限制本发明,尽管参照前述实施例对本发明进行了详细的说明,对于本领域的技术人员来说,其依然可以对前述各实施例所记载的技术方案进行修改,或者对其中部分技术特征进行等同替换。凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (7)
1.一种酚醛树脂基覆铜板的制备方法,其特征在于,包括以下步骤:
S1. 制备硅改性酚醛树脂;
S11.将腰果酚、甲醛混合,加入氢氧化钠溶液调节pH至10-12,升温至70-75℃,氮气氛围下反应1-2h后,旋蒸去除多余溶剂,得到酚醛树脂预聚体;
S12. 将苯基三乙氧基硅烷溶于无水乙醇,缓慢滴加至酚醛树脂预聚体中,滴加盐酸调节pH至1-2,升温至回流温度,回流反应1.5-3h后,滴加氢氧化钠,调节pH至11-12,过滤,使用去离子水洗涤至中性,真空干燥至恒重,得到硅改性酚醛树脂;
S2. 制备超支化磷硅阻燃剂;
S21. 氮气氛围保护,将磷酸甘油醛溶于二氯甲烷中,冰水浴处理,加入三乙胺,搅拌混合后,缓慢滴加溶有3-氨基丙基三乙氧基硅烷的四氯甲烷溶液,滴加结束后,升温至20-25℃,搅拌反应12-24h后,旋蒸反应产物,并使用无水乙醇洗涤,真空干燥,得到含磷硅氧烷;
S22. 将步骤S21制备得到的含磷硅氧烷溶于二氯甲烷中,滴加溶有双(羟基甲基)苯基磷的二氯甲烷溶液,滴加结束后,升温至85-95℃,回流反应12-18h后,旋蒸去除多余溶剂,真空干燥,得到超支化磷硅阻燃剂;
S3. 将无机填料浸没在硅烷偶联剂中,超声分散1-3h后,过滤,干燥后得到表面改性无机填料;
S4. 将硅改性酚醛树脂、表面改性无机填料、环氧树脂、超支化磷硅阻燃剂、二甲基咪唑混合均匀,高速剪切乳化2-3h后,得到改性酚醛树脂胶液;
S5. 对玻璃纤维布使用改性酚醛树脂胶液双重浸渍,浸渍结束后,190-210℃干燥,制得半干燥片;
S6. 将6-10张半干燥片堆叠,并在堆叠的半干燥片两侧覆盖铜箔,热压,制得酚醛树脂基覆铜板。
2.根据权利要求1所述的一种酚醛树脂基覆铜板的制备方法,其特征在于:步骤S1中,按摩尔份数计,所述腰果酚、甲醛、苯基三乙氧基硅烷的摩尔比为(8-10):(10-12):(3.5-4)。
3.根据权利要求1所述的一种酚醛树脂基覆铜板的制备方法,其特征在于:步骤S2中,按摩尔份数计,磷酸甘油醛、三乙胺、3-氨基丙基三乙氧基硅烷、双(羟基甲基)苯基磷的摩尔比为(8-10):(7-10):(10-12):(5-8)。
4.根据权利要求1所述的一种酚醛树脂基覆铜板的制备方法,其特征在于:所述无机填料为氢氧化铝,粒径为0.05-02μm;所述环氧树脂为双酚A型环氧树脂。
5.根据权利要求1所述的一种酚醛树脂基覆铜板的制备方法,其特征在于:步骤S4中,按重量份数计,所述改性酚醛树脂胶液,包括以下组分:45-64份硅改性酚醛树脂、24-35份表面改性无机填料、5-10份环氧树脂,5-9份超支化磷硅阻燃剂、0.1-0.2份二甲基咪唑。
6.根据权利要求1所述的一种酚醛树脂基覆铜板的制备方法,其特征在于:步骤S4中,高速剪切速率为1100-1400rpm。
7.根据权利要求1所述的一种酚醛树脂基覆铜板的制备方法,其特征在于:步骤S6中,热压时,热压温度为210-240℃,热压压力为2.4-3MPa,热压时长为1.5-2h;热压结束后,停止加热,继续以1.0-1.5MPa的压力冷压0.5-1h。
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