CN112029233A - 一种可降解低密度阻燃环氧smc树脂组合物 - Google Patents
一种可降解低密度阻燃环氧smc树脂组合物 Download PDFInfo
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- CN112029233A CN112029233A CN202010708879.0A CN202010708879A CN112029233A CN 112029233 A CN112029233 A CN 112029233A CN 202010708879 A CN202010708879 A CN 202010708879A CN 112029233 A CN112029233 A CN 112029233A
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- 239000004593 Epoxy Substances 0.000 title claims abstract description 61
- 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 claims abstract description 49
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- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 9
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- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 claims description 4
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- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 4
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- NWYDEWXSKCTWMJ-UHFFFAOYSA-N 2-methylcyclohexane-1,1-diamine Chemical compound CC1CCCCC1(N)N NWYDEWXSKCTWMJ-UHFFFAOYSA-N 0.000 claims description 2
- BKFWZZRDUKASOU-UHFFFAOYSA-N 2-n-cyclohexylpropane-1,2-diamine Chemical compound NCC(C)NC1CCCCC1 BKFWZZRDUKASOU-UHFFFAOYSA-N 0.000 claims description 2
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- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 claims description 2
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 claims description 2
- 239000004844 aliphatic epoxy resin Substances 0.000 claims description 2
- HZVVJJIYJKGMFL-UHFFFAOYSA-N almasilate Chemical compound O.[Mg+2].[Al+3].[Al+3].O[Si](O)=O.O[Si](O)=O HZVVJJIYJKGMFL-UHFFFAOYSA-N 0.000 claims description 2
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 claims description 2
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- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
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- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 claims description 2
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 claims description 2
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- HUAUNKAZQWMVFY-UHFFFAOYSA-M sodium;oxocalcium;hydroxide Chemical compound [OH-].[Na+].[Ca]=O HUAUNKAZQWMVFY-UHFFFAOYSA-M 0.000 claims description 2
- 239000012745 toughening agent Substances 0.000 claims description 2
- 230000000593 degrading effect Effects 0.000 claims 1
- 239000003677 Sheet moulding compound Substances 0.000 abstract description 105
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 10
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- DGUJJOYLOCXENZ-UHFFFAOYSA-N 4-[2-[4-(oxiran-2-ylmethoxy)phenyl]propan-2-yl]phenol Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C1=CC=C(O)C=C1 DGUJJOYLOCXENZ-UHFFFAOYSA-N 0.000 description 14
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- 238000003825 pressing Methods 0.000 description 7
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- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
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- 229920001187 thermosetting polymer Polymers 0.000 description 4
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- 238000000465 moulding Methods 0.000 description 3
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- 229920006337 unsaturated polyester resin Polymers 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 229940098779 methanesulfonic acid Drugs 0.000 description 2
- 239000000047 product Substances 0.000 description 2
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- 238000005516 engineering process Methods 0.000 description 1
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- 239000011159 matrix material Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
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Abstract
本发明公开了一种可降解低密度阻燃环氧SMC树脂组合物,该组合物采用含氨基基团的多元胺化合物对环氧树脂体系进行改性增稠,熟化后粘度大幅增加,满足片状模塑料模压成型工艺。该环氧组合物不含溶剂等无易挥发物质,满足汽车部件材料低VOC环保要求,并且具有140~160℃*3~10min快速成型等特性,成型后机械强度高,具有低密度,高阻燃性,可降解等特点,阻燃等级可到UL94‑V0,极限氧指数可到32%以上,密度为1.1g/cm3左右,制备的复合材料部件可以实现回收再利用。
Description
技术领域
本发明涉及SMC树脂组合物领域,特别涉及一种可降解低密度阻燃环氧SMC树脂组合物。
背景技术
SMC模压工艺是一种先进的复合材料成型方法,SMC片状模塑料价格低廉,使用方便,能够快速成型用来压制不同规格大小型状的产品,越来越得到市场的认可。目前SMC主要以不饱和聚酯树脂、乙烯基树脂为基体,然而这种不饱和聚酯树脂、乙烯基树脂SMC存在如耐温性、耐热性差,结构强度和模量都较低等缺点,由于这种不饱和聚酯树脂、乙烯基树脂粘度较大,在体系中会加入大量的稀释剂苯乙烯,成型时稀释剂苯乙烯挥发出大量的刺激性气味,不仅长期接触会影响人体的身体健康,而且对环境也有较大的污染,随着环氧基纤维复合材料在汽车部件轻量化设计产品的广泛应用,所产生的热固性树脂复合材料废弃物与日俱增,一方面给周围环境带来污染,另一方面复合材料在制造过程中产生的边角料无法回收利用会带来不小的经济损失。传统的SMC树脂是不具备阻燃性的,且密度在2.0g/cm3左右,无法满足轨道交通、汽车等领域对SMC材料的高阻燃、低密度等轻量化应用要求。
发明内容
本发明所要解决的技术问题:本发明的目的在于提供一种可降解低密度阻燃环氧SMC树脂组合物,以解决背景技术中提出的问题。
为解决上述技术问题,本发明提供以下的技术方案:
一种可降解低密度阻燃环氧SMC树脂组合物,组合物包括的重量组分如下:
环氧树脂90-95质量份、稀释剂5-10质量份、助剂1-15质量份、轻质填料5-30质量份、阻燃剂40-250质量份、固化剂2-20质量份、促进剂1-8质量份、增稠剂2-15质量份;
所述增稠剂为单胺和/或多元胺,所述单胺、多元胺具有一个或多个伯氨基和/或仲氨基基团;所述增稠剂伯氨基和仲氨基总量与环氧树脂的环氧基摩尔比大于0.01小于0.4;
所述稀释剂是由含有一个、两个及以上环氧官能团的反应活性稀释剂中一种或一种以上组成;
所述轻质填料为酚醛微球、中空玻璃微珠、铝硅酸镁其中一种,优选主要成分为碱石灰硼硅酸盐、抗压强度大于20MPa的中空玻璃微珠。
优选地,所述环氧树脂为缩水甘油醚型环氧树脂、缩水甘油脂型环氧树脂、缩水甘油胺型环氧树脂、脂肪族环氧树脂、脂环族环氧树脂、特种环氧树脂、改性环氧树脂中的至少一种。
优选地,所述阻燃剂为磷氮混合阻燃剂、聚磷酸铵阻燃剂、三聚氰胺氰尿酸盐、六苯氧基环三磷腈、烷基次膦酸盐、氢氧化铝、氢氧化镁等无卤环保阻燃剂一种或几种。
优选地,所述稀释剂为缩水甘油醚和/或缩水甘油酯类。
优选地,所述助剂为偶联剂、降粘剂、润湿剂、分散剂、消泡剂、流平剂、增韧剂、浸润剂、防沉降剂、内脱模剂中的至少一种。
优选地,所述固化剂为双氰胺、芳香胺、改性胺中的至少一种与可降解有机芳香胺类潜伏型环氧树脂固化剂混合制备,其中,可降解固化剂固体粉末粒径≤15um,可降解固化剂氨基量与混合固化剂氨基总量摩尔比应大于0.05小于0.6,化学结构如下:
优选地,所述促进剂为有机脲、改性有机脲、咪唑、改性咪唑促进剂至少一种。
优选地,所述增稠剂包括如乙二胺、二丙撑三胺、二乙烯三胺、三乙烯四胺、间苯二甲胺、1,3-环己二甲胺、N-氨乙基哌嗪、异佛尔酮二胺、甲基环己二胺、环已基丙二胺、1,2-环己二胺、3,3'-二甲基-4,4-二氨基二环己基甲烷、孟烷二胺、聚醚胺、二乙基甲苯二胺等脂肪胺、脂环胺以及芳香胺中的一种或多种。
一种可降解低密度环氧SMC树脂组合物降解工艺,具体步骤如下:
(1).利用可降解低密度阻燃环氧SMC树脂制备的纤维增强复合材料零部件浸泡在包含酸和溶剂的降解体系中经过1-600小时后获得降解混合物,降解体系温度为15-400℃,酸在降解体系中的质量浓度为0.01-100%;
(2).步骤(1)中的利用可降解环氧树脂制备的纤维增强复合材料完全降解后,通过分离、洗涤、干燥后回收纤维;
(3).使用碱溶液调节步骤(1)和(2)所得降解溶液的pH值;所述碱溶液的质量浓度为0.01-99%,调节降解溶液pH值时保持温度为0-200℃,调节降解溶液pH值,最终pH值大于6;
(4).将步骤(3)中经过调节pH值在降解溶液中产生的沉淀物进行物理分离、清洗和干燥。
本发明获得的有益效果:
该可降解低密度阻燃环氧SMC树脂组合物无易挥发物质,满足汽车部件材料低VOC环保要求,具有140~150℃快速固化特性,能够将环氧复合材料部件成型周期缩短到5~10min,且具有可降解性,密度低,阻燃等级可到UL94-V0,极限氧指数可到32%以上,固化后机械强度高。
具体实施方式
下面通过对实施例的描述,对本发明的具体实施方式作进一步详细的说明,以帮助本领域的技术人员对本发明的发明构思、技术方案有更完整、准确和深入的理解。
实施例1:
将73g双酚A缩水甘油醚型液体环氧树脂NPEL-128、10g三羟甲基丙烷三缩水甘油醚XY-636、6g内脱模剂、0.75g浸润剂、10g玻璃微珠、50g磷氮阻燃剂混合均匀,接着加入由17g双酚A缩水甘油醚型液体环氧树脂NPEL-128、6g双氰胺、2g可降解固化剂、1.5g有机脲组成的混合研磨料,搅拌均匀,最后加入4.4g异氟尔酮二胺,搅拌均匀,即得环氧SMC树脂糊;将制得的环氧SMC树脂糊浸渍25mm无序短切玻璃纤维,经SMC片料机辊压后,送入35℃烘房熟化20小时后即得环氧片状模塑料。
浇筑可降解低密度阻燃环氧SMC树脂试样条及环氧阻燃片状模塑料压板测试:
按照GB/T2567-2008测试树脂拉伸、弯曲试样条,拉伸强度为58MPa,拉伸模量为3.2GPa,弯曲强度为93MPa,弯曲模量为3.4GPa;按照GB/T1447测试片状模塑料拉伸强度为108MPa,拉伸模量为11.3GPa;按照GB/T1449测试片状模塑料弯曲强度为228MPa,弯曲模量为10.4GPa;按照GB/T1451测试片状模塑料无缺口冲击强度为84KJ/㎡;按照GB/T4609测试片状模塑料燃烧等级为UL94-V0;按照GB/T8924测试片状模塑料极限氧指数为36%;按照GB/T1033测试片状模塑料密度为1.382g/cm3。
实施例2
将78g双酚A缩水甘油醚型液体环氧树脂NPEL-128、5g三羟甲基丙烷三缩水甘油醚XY-636、6g内脱模剂、0.75g浸润剂、10g玻璃微珠、60g磷氮阻燃剂混合均匀,接着加入由17g双酚A缩水甘油醚型液体环氧树脂NPEL-128、6g双氰胺、2g可降解固化剂、1.5g有机脲固化剂组成的混合研磨料,搅拌均匀,最后加入5g异氟尔酮二胺,搅拌均匀,即得环氧SMC树脂糊;将制得的环氧SMC树脂糊浸渍25mm无序短切玻璃纤维,经SMC片料机辊压后,送入35℃烘房熟化20小时后即得环氧片状模塑料。
浇筑可降解阻燃环氧SMC树脂试样条及环氧阻燃片状模塑料压板测试:
按照GB/T2567-2008测试树脂拉伸、弯曲试样条,拉伸强度为54MPa,拉伸模量为3.0GPa,弯曲强度为96MPa,弯曲模量为3.2GPa;按照GB/T1447测试片状模塑料拉伸强度为103MPa,拉伸模量为11.8GPa;按照GB/T1449测试片状模塑料弯曲强度为221MPa,弯曲模量为10.9GPa;按照GB/T1451测试片状模塑料无缺口冲击强度为81KJ/㎡;按照GB/T4609测试片状模塑料燃烧等级为UL94-V0;按照GB/T8924测试片状模塑料极限氧指数为36%;按照GB/T1033测试片状模塑料密度为1.388g/cm3。
实施例3
将76g双酚A缩水甘油醚型液体环氧树脂NPEL-128、2g脂环族环氧树脂TTA-21、5g三羟甲基丙烷三缩水甘油醚XY-636、6g内脱模剂、0.75g消泡剂、0.75g浸润剂、10g玻璃微珠、60g磷氮阻燃剂混合均匀,接着加入由17g双酚A缩水甘油醚型液体环氧树脂NPEL-128、6g双氰胺、2g可降解固化剂、1.5g有机脲组成的混合研磨料,搅拌均匀,最后加入5g脂环胺,搅拌均匀,即得环氧SMC树脂糊;将制得的环氧SMC树脂糊浸渍25mm无序短切玻璃纤维,经SMC片料机辊压后,送入35℃烘房熟化20小时后即得环氧片状模塑料。
浇筑可降解阻燃环氧SMC树脂试样条及环氧阻燃片状模塑料压板测试:
按照GB/T2567-2008测试树脂拉伸、弯曲试样条,拉伸强度为65MPa,拉伸模量为3.0GPa,弯曲强度为114MPa,弯曲模量为3.0GPa;按照GB/T1447测试片状模塑料拉伸强度为118MPa,拉伸模量为10.4GPa;按照GB/T1449测试片状模塑料弯曲强度为222MPa,弯曲模量为10.5GPa;按照GB/T1451测试片状模塑料无缺口冲击强度为81KJ/㎡;按照GB/T4609测试片状模塑料燃烧等级为UL94-V0;按照GB/T8924测试片状模塑料极限氧指数为35%;按照GB/T1033测试片状模塑料密度为1.396g/cm3。
实施例4
将75g双酚A缩水甘油醚型液体环氧树脂NPEL-128、5g三羟甲基丙烷三缩水甘油醚XY-636、6g内脱模剂、0.75g消泡剂、0.75g浸润剂、30g玻璃微珠、150g氢氧化铝混合均匀,接着加入由20g双酚A缩水甘油醚型液体环氧树脂NPEL-128、6.5g双氰胺、2g可降解固化剂、1.5g有机脲、组成的混合研磨料,搅拌均匀,最后加入5g脂环胺,搅拌均匀,即得环氧SMC树脂糊;将制得的环氧SMC树脂糊浸渍25mm无序短切玻璃纤维,经SMC片料机辊压后,送入40℃烘房熟化15小时后即得环氧片状模塑料。
浇筑可降解阻燃环氧SMC树脂试样条及环氧阻燃片状模塑料压板测试:
按照GB/T2567-2008测试树脂拉伸、弯曲试样条,拉伸强度为50MPa,拉伸模量为3.4GPa,弯曲强度为88MPa,弯曲模量为3.3GPa;按照GB/T1447测试片状模塑料拉伸强度为85MPa,拉伸模量为11.8GPa;按照GB/T1449测试片状模塑料弯曲强度为201MPa,弯曲模量为12.6GPa;按照GB/T1451测试片状模塑料无缺口冲击强度为73KJ/㎡;按照GB/T4609测试片状模塑料燃烧等级为UL94-V0;按照GB/T8924测试片状模塑料极限氧指数为40%;按照GB/T1033测试片状模塑料密度为1.425g/cm3。
实施例5
将72g双酚A缩水甘油醚型液体环氧树脂NPEL-128、10g三羟甲基丙烷三缩水甘油醚XY-636、6g内脱模剂、0.75g消泡剂、0.75g浸润剂、30g玻璃微珠、150g氢氧化铝混合均匀,接着加入由18g双酚A缩水甘油醚型液体环氧树脂NPEL-128、6g双氰胺、2g可降解固化剂、2g有机脲、1g咪唑组成的混合研磨料,搅拌均匀,最后加入3g脂环胺、4g聚醚胺,搅拌均匀,即得环氧SMC树脂糊;将制得的环氧SMC树脂糊浸渍25mm无序短切玻璃纤维,经SMC片料机辊压后,送入35℃烘房熟化20小时后即得环氧片状模塑料。
浇筑可降解阻燃环氧SMC树脂试样条及环氧阻燃片状模塑料压板测试:
按照GB/T2567-2008测试树脂拉伸、弯曲试样条,拉伸强度为49MPa,拉伸模量为3.1GPa,弯曲强度为88MPa,弯曲模量为3.0GPa;按照GB/T1447测试片状模塑料拉伸强度为84MPa,拉伸模量为10.4GPa;按照GB/T1449测试片状模塑料弯曲强度为208MPa,弯曲模量为12.0GPa;按照GB/T1451测试片状模塑料无缺口冲击强度为70KJ/㎡;按照GB/T4609测试片状模塑料燃烧等级为UL94-V0;按照GB/T8924测试片状模塑料极限氧指数为40%;按照GB/T1033测试片状模塑料密度为1.423g/cm3。
实施例6
将72g双酚A缩水甘油醚型液体环氧树脂NPEL-128、10g三羟甲基丙烷三缩水甘油醚XY-636、30g玻璃微珠、150g碳酸钙、80g磷氮阻燃剂、8g内脱模剂、0.75g消泡剂、0.75g浸润剂、1.5g降粘剂混合均匀,接着加入由18g双酚A缩水甘油醚型液体环氧树脂NPEL-128、6g双氰胺、2g可降解固化剂、2g有机脲、1g咪唑组成的混合研磨料,搅拌均匀,最后加入6g脂环胺,搅拌均匀,即得环氧SMC树脂糊;将制得的环氧SMC树脂糊浸渍25mm无序短切玻璃纤维,经SMC片料机辊压后,送入35℃烘房熟化20小时后即得环氧片状模塑料。
浇筑可降解阻燃环氧SMC树脂试样条及环氧阻燃片状模塑料压板测试:
按照GB/T2567-2008测试树脂拉伸、弯曲试样条,拉伸强度为42MPa,拉伸模量为3.5GPa,弯曲强度为81MPa,弯曲模量为3.4GPa;按照GB/T1447测试片状模塑料拉伸强度为85MPa,拉伸模量为10.8GPa;按照GB/T1449测试片状模塑料弯曲强度为189MPa,弯曲模量为12.8GPa;按照GB/T1451测试片状模塑料无缺口冲击强度为68KJ/㎡;按照GB/T4609测试片状模塑料燃烧等级为UL94-V0;按照GB/T8924测试片状模塑料极限氧指数为37%;按照GB/T1033测试片状模塑料密度为1.43g/cm3。
实施例7
将75g双酚A缩水甘油醚型液体环氧树脂NPEL-128、5g三羟甲基丙烷三缩水甘油醚XY-636、6g内脱模剂、0.5g浸润剂、10g玻璃微珠;100g三聚氰胺聚磷酸盐混合均匀,接着加入由20g双酚A缩水甘油醚型液体环氧树脂NPEL-128、5g双氰胺、3g可降解固化剂、2g有机脲组成的混合研磨料,搅拌均匀,最后加入4.4g脂环胺,搅拌均匀,即得环氧SMC树脂糊;将制得的环氧SMC树脂糊浸渍25mm无序短切玻璃纤维,经SMC片料机辊压后,送入40℃烘房熟化15小时后即得环氧片状模塑料。
浇筑可降解阻燃环氧SMC树脂试样条及环氧阻燃片状模塑料压板测试:
按照GB/T2567-2008测试树脂拉伸、弯曲试样条,拉伸强度为65MPa,拉伸模量为3.0GPa,弯曲强度为105MPa,弯曲模量为3.1GPa;按照GB/T1447测试片状模塑料拉伸强度为101MPa,拉伸模量为10.5GPa;按照GB/T1449测试片状模塑料弯曲强度为213MPa,弯曲模量为12.2GPa;按照GB/T1451测试片状模塑料无缺口冲击强度为78KJ/㎡;按照GB/T4609测试片状模塑料燃烧等级为UL94-V0;按照GB/T8924测试片状模塑料极限氧指数为38%;按照GB/T1033测试片状模塑料密度为1.39g/cm3。
实施例8
在250ml三口烧瓶中,加入5g实施例1制备的SMC复合材料板材样品,5ml浓盐酸和95ml乙二醇,搅拌加热到160℃,6小时后冷却至100℃,趁热过滤,降解溶液用5%氢氧化钠溶液中和,析出固体,过滤,并用水洗涤固体,干燥后得到热固性环氧树脂降解产物和玻璃纤维4.75g,质量回收率95%。
实施例9
在250ml三口烧瓶中,加入5g实施例1制备的SMC复合材料板材样品,5ml甲磺酸和80ml已醇,搅拌加热到160℃,6小时后冷却至100℃,趁热过滤,降解溶液用5%氢氧化钠溶液中和,析出固体,过滤,并用水洗涤固体,干燥后得到热固性环氧树脂降解产物和玻璃纤维4.75g,质量回收率95%。
实施例10
在250ml三口烧瓶中,加入5g实施例4制备的SMC复合材料板材样品,5ml甲磺酸和90ml辛醇,搅拌加热到155℃,4小时后冷却至100℃,趁热过滤,降解溶液用5%氢氧化钠溶液中和,析出固体,过滤,并用水洗涤固体,干燥后得到热固性环氧树脂降解产物和玻璃纤维4.8g,质量回收率96%。
综上所述,该可降解低密度阻燃环氧SMC树脂组合物无易挥发物质,满足汽车部件材料低VOC环保要求,具有140~150℃快速固化特性,能够将环氧复合材料部件成型周期缩短到5~10min,且具有可降解性,密度低,阻燃等级可到UL94-VO,极限氧指数可到32%以上,固化后机械强度高。
以上实施例仅为说明本发明的技术思想,不能以此限定本发明的保护范围,凡是按照本发明提出的技术思想,在技术方案基础上所做的任何改动,均落入本发明保护范围之内;本发明未涉及的技术均可通过现有技术加以实现。
Claims (9)
1.一种可降解低密度阻燃环氧SMC树脂组合物,其特征在于,组合物包括的重量组分如下:
环氧树脂90-95质量份、稀释剂5-10质量份、助剂1-15质量份、轻质填料5-30质量份、阻燃剂40-250质量份、固化剂2-20质量份、促进剂1-8质量份、增稠剂2-15质量份;
所述增稠剂为单胺和/或多元胺,所述单胺、多元胺具有一个或多个伯氨基和/或仲氨基基团;所述增稠剂伯氨基和仲氨基总量与环氧树脂的环氧基摩尔比大于0.01小于0.4;
所述稀释剂是由含有一个、两个及以上环氧官能团的反应活性稀释剂中一种或一种以上组成;
所述轻质填料为酚醛微球、中空玻璃微珠、铝硅酸镁其中一种,优选主要成分为碱石灰硼硅酸盐、抗压强度大于20MPa的中空玻璃微珠。
2.根据权利要求1所述的一种可降解低密度阻燃环氧SMC树脂组合物,其特征在于:所述环氧树脂为缩水甘油醚型环氧树脂、缩水甘油脂型环氧树脂、缩水甘油胺型环氧树脂、脂肪族环氧树脂、脂环族环氧树脂、特种环氧树脂、改性环氧树脂中的至少一种。
3.根据权利要求1所述的一种可降解低密度阻燃环氧SMC树脂组合物,其特征在于:所述阻燃剂为磷氮混合阻燃剂、聚磷酸铵阻燃剂、三聚氰胺氰尿酸盐、六苯氧基环三磷腈、烷基次膦酸盐、氢氧化铝、氢氧化镁等无卤环保阻燃剂一种或几种。
4.根据权利要求1所述的一种可降解低密度阻燃环氧SMC树脂组合物,其特征在于:所述稀释剂为缩水甘油醚和/或缩水甘油酯类。
5.根据权利要求1所述的一种可降解低密度阻燃环氧SMC树脂组合物,其特征在于:所述助剂为偶联剂、降粘剂、润湿剂、分散剂、消泡剂、流平剂、增韧剂、浸润剂、防沉降剂、内脱模剂中的至少一种。
7.根据权利要求1所述的一种可降解低密度阻燃环氧SMC树脂组合物,其特征在于:所述促进剂为有机脲、改性有机脲、咪唑、改性咪唑促进剂至少一种。
8.根据权利要求1所述的一种可降解低密度阻燃环氧SMC树脂组合物,其特征在于:所述增稠剂包括如乙二胺、二丙撑三胺、二乙烯三胺、三乙烯四胺、间苯二甲胺、1,3-环己二甲胺、N-氨乙基哌嗪、异佛尔酮二胺、甲基环己二胺、环已基丙二胺、1,2-环己二胺、3,3'-二甲基-4,4-二氨基二环己基甲烷、孟烷二胺、聚醚胺、二乙基甲苯二胺等脂肪胺、脂环胺以及芳香胺中的一种或多种。
9.根据权利要求1中所述的一种可降解低密度环氧SMC树脂组合物降解工艺,其特征在于,具体步骤如下:
(1).利用可降解低密度阻燃环氧SMC树脂制备的纤维增强复合材料零部件浸泡在包含酸和溶剂的降解体系中经过1-600小时后获得降解混合物,降解体系温度为15-400℃,酸在降解体系中的质量浓度为0.01-100%;
(2).步骤(1)中的利用可降解环氧树脂制备的纤维增强复合材料完全降解后,通过分离、洗涤、干燥后回收纤维;
(3).使用碱溶液调节步骤(1)和(2)所得降解溶液的pH值;所述碱溶液的质量浓度为0.01-99%,调节降解溶液pH值时保持温度为0-200℃,调节降解溶液pH值,最终pH值大于6;
(4).将步骤(3)中经过调节pH值在降解溶液中产生的沉淀物进行物理分离、清洗和干燥。
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