CN112029239A - 一种可降解阻燃环氧smc树脂组合物 - Google Patents
一种可降解阻燃环氧smc树脂组合物 Download PDFInfo
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- CN112029239A CN112029239A CN202010721809.9A CN202010721809A CN112029239A CN 112029239 A CN112029239 A CN 112029239A CN 202010721809 A CN202010721809 A CN 202010721809A CN 112029239 A CN112029239 A CN 112029239A
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- Prior art keywords
- degradable
- epoxy
- agent
- epoxy resin
- smc
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000004593 Epoxy Substances 0.000 title claims abstract description 72
- 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 54
- 239000003063 flame retardant Substances 0.000 title claims abstract description 50
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- 230000015556 catabolic process Effects 0.000 claims description 22
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- 239000007787 solid Substances 0.000 claims description 19
- -1 alkyl phosphinate Chemical compound 0.000 claims description 18
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 15
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 9
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- 239000003733 fiber-reinforced composite Substances 0.000 claims description 7
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- 125000002723 alicyclic group Chemical group 0.000 claims description 5
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 claims description 5
- 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
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
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- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 4
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- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 3
- PISLZQACAJMAIO-UHFFFAOYSA-N 2,4-diethyl-6-methylbenzene-1,3-diamine Chemical compound CCC1=CC(C)=C(N)C(CC)=C1N PISLZQACAJMAIO-UHFFFAOYSA-N 0.000 claims description 3
- NWYDEWXSKCTWMJ-UHFFFAOYSA-N 2-methylcyclohexane-1,1-diamine Chemical compound CC1CCCCC1(N)N NWYDEWXSKCTWMJ-UHFFFAOYSA-N 0.000 claims description 3
- BKFWZZRDUKASOU-UHFFFAOYSA-N 2-n-cyclohexylpropane-1,2-diamine Chemical compound NCC(C)NC1CCCCC1 BKFWZZRDUKASOU-UHFFFAOYSA-N 0.000 claims description 3
- KOGSPLLRMRSADR-UHFFFAOYSA-N 4-(2-aminopropan-2-yl)-1-methylcyclohexan-1-amine Chemical compound CC(C)(N)C1CCC(C)(N)CC1 KOGSPLLRMRSADR-UHFFFAOYSA-N 0.000 claims description 3
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- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 claims description 3
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 claims description 3
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 claims description 3
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 3
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- GKQPCPXONLDCMU-CCEZHUSRSA-N lacidipine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C1=CC=CC=C1\C=C\C(=O)OC(C)(C)C GKQPCPXONLDCMU-CCEZHUSRSA-N 0.000 claims description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 3
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- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 claims description 2
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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 20
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
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- 229920001187 thermosetting polymer Polymers 0.000 description 3
- 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
- 229920000877 Melamine resin Polymers 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 229920000388 Polyphosphate Polymers 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 239000001205 polyphosphate Substances 0.000 description 2
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- 229960001124 trientine Drugs 0.000 description 2
- 229920006337 unsaturated polyester resin Polymers 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
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- GZDFHIJNHHMENY-UHFFFAOYSA-N Dimethyl dicarbonate Chemical compound COC(=O)OC(=O)OC GZDFHIJNHHMENY-UHFFFAOYSA-N 0.000 description 1
- 239000011157 advanced composite material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- ITZGNPZZAICLKA-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) 7-oxabicyclo[4.1.0]heptane-3,4-dicarboxylate Chemical compound C1C2OC2CC(C(=O)OCC2OC2)C1C(=O)OCC1CO1 ITZGNPZZAICLKA-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
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- 239000000047 product Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
Classifications
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- C08G59/50—Amines
- C08G59/5033—Amines aromatic
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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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)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Epoxy Resins (AREA)
- Reinforced Plastic Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
本发明公开了一种可降解阻燃环氧SMC树脂组合物，涉及一种适用于SMC成型的可降解阻燃环氧树脂组合物，该环氧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，具有高阻燃性，可降解等特点，阻燃等级可到UL94‑VO,极限氧指数可到32％以上，制备的复合材料部件可以实现回收再利用。
Description
技术领域
本发明涉及环氧SMC树脂领域，特别涉及一种可降解阻燃环氧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，无法满足轨道交通、汽车等领域对SMC材料的高阻燃、低烟、低毒等要求。
发明内容
本发明所要解决的技术问题：提供一种可降解阻燃环氧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：
一种可降解阻燃环氧SMC树脂组合物，由如下重量份的组分制备而成：
环氧树脂90-100质量份、稀释剂0-10质量份、助剂1-15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、氢氧化镁中的一种或几种；
所述固化剂为双氰胺、芳香胺、改性胺至少一种与可降解有机芳香胺类和有机芳香铵盐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，所述增稠剂的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。
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、内脱模剂至少一种。
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，所述增稠剂为具有一个或多个伯氨基和仲氨基基团的单胺或多元胺至少一种，其中包括如乙二胺、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。
一种纤维增强复合材料的降解工艺，具体步骤如下：
(1)纤维增强复合材料采用上述可降解环氧SMC树脂组合物制备而成，将纤维增强复合材料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，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。
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、100g氢氧化铝混合均匀，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，最后加入增稠剂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35℃烘房熟化20小时后即得环氧片状模塑料。
所述可降解芳香胺固化剂固体粉末粒径≤15um，化学结构如下：
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62MPa，拉伸模量为3.2GPa，弯曲强度为108MPa，弯曲模量为3.4GPa；按照GB/T1447测试片状模塑料拉伸强度为148MPa，拉伸模量为11.3GPa；按照GB/T1449测试片状模塑料弯曲强度为288MPa，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114KJ/㎡；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％。
实施例2
将78g双酚A缩水甘油醚型液体环氧树脂NPEL-128、5g脂环族缩水甘油脂环氧树脂TDE-85、6g内脱模剂、0.75g浸润剂、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，最后加入增稠剂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。
所述固化剂为芳香胺与可降解芳香胺固化剂质量比1:1混合制备，其中可降解固化剂固体粉末粒径≤15um，化学结构同实施例1。
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68MPa，拉伸模量为3.0GPa，弯曲强度为113MPa，弯曲模量为3.2GPa；按照GB/T1447测试片状模塑料拉伸强度为153MPa，拉伸模量为11.8GPa；按照GB/T1449测试片状模塑料弯曲强度为281MPa，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121KJ/㎡；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％。
实施例3
将81g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、6g内脱模剂、0.75g消泡剂、0.75g浸润剂、60g聚磷酸铵阻燃剂混合均匀，接着加入由17g双酚A缩水甘油醚型液体环氧树脂NPEL-128、8g固化剂、1.5g有机脲组成的混合研磨料，搅拌均匀，最后加入增稠剂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。
所述固化剂为改性胺与可降解芳香胺固化剂质量比1:1混合制备，其中可降解固化剂固体粉末粒径≤15um，化学结构同实施例1。
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138MPa，拉伸模量为10.4GPa；按照GB/T1449测试片状模塑料弯曲强度为262MPa，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121KJ/㎡；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％。
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、150g氢氧化镁混合均匀，接着加入由20g双酚A缩水甘油醚型液体环氧树脂NPEL-128、8.5g固化剂、1.5g有机脲组成的混合研磨料，搅拌均匀，最后加入增稠剂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。
所述固化剂为双氰胺和芳香胺与可降解芳香胺固化剂按质量比2：1：3混合制备，其中可降解固化剂固体粉末粒径≤15um，化学结构同实施例1。
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59MPa，拉伸模量为3.4GPa，弯曲强度为104MPa，弯曲模量为3.3GPa；按照GB/T1447测试片状模塑料拉伸强度为118MPa，拉伸模量为11.8GPa；按照GB/T1449测试片状模塑料弯曲强度为241MPa，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107KJ/㎡；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％。
实施例5
将82g双酚A缩水甘油醚型液体环氧树脂NPEL-128、6g内脱模剂、0.75g消泡剂、0.75g浸润剂、150g六苯氧基环三磷腈均匀，接着加入由18g双酚A缩水甘油醚型液体环氧树脂NPEL-128、7g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。
所述固化剂为芳香胺、改性胺与可降解芳香胺固化剂质量比1：1：5混合制备，其中可降解固化剂固体粉末粒径≤15um，化学结构同实施例1。
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58MPa，拉伸模量为3.1GPa，弯曲强度为108MPa，弯曲模量为3.0GPa；按照GB/T1447测试片状模塑料拉伸强度为114MPa，拉伸模量为10.4GPa；按照GB/T1449测试片状模塑料弯曲强度为258MPa，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110KJ/㎡；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％。
实施例6
将82g双酚A缩水甘油醚型液体环氧树脂NPEL-128、150g碳酸钙、80g三聚氰胺氰尿酸盐、18g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、10g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。
所述固化剂为双氰胺、改性胺与可降解芳香胺固化剂质量比3:1:6混合制备，其中可降解固化剂固体粉末粒径≤15um，化学结构同实施例1。
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60MPa，拉伸模量为3.5GPa，弯曲强度为101MPa，弯曲模量为3.4GPa；按照GB/T1447测试片状模塑料拉伸强度为135MPa，拉伸模量为10.8GPa；按照GB/T1449测试片状模塑料弯曲强度为239MPa，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103KJ/㎡；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％。
实施例7
将65g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、100g三聚氰胺聚磷酸盐混合均匀，接着加入由30g双酚A缩水甘油醚型液体环氧树脂NPEL-128、8g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。
所述固化剂为双氰胺、芳香胺、改性胺与可降解芳香胺固化剂按质量比1：1：1：7混合制备，其中可降解固化剂固体粉末粒径≤15um，化学结构同实施例1。
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141MPa，拉伸模量为10.5GPa；按照GB/T1449测试片状模塑料弯曲强度为253MPa，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118KJ/㎡；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％。
实施例8
将80g双酚A缩水甘油醚型液体环氧树脂NPEL-128、6g内脱模剂、0.5g消泡剂、0.5g浸润剂、100g三聚氰胺聚磷酸盐、50g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、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8g改性脂环胺，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。
可降解固化剂固体粉末粒径≤15um，化学结构同实施例1。
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58MPa，拉伸模量为3.2GPa，弯曲强度为98MPa，弯曲模量为3.3GPa；按照GB/T1447测试片状模塑料拉伸强度为128MPa，拉伸模量为11.3GPa；按照GB/T1449测试片状模塑料弯曲强度为253MPa，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104KJ/㎡；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45％。
实施例9
将82g双酚A缩水甘油醚型液体环氧树脂NPEL-128、6g内脱模剂、0.5g消泡剂、0.5g浸润剂、100g烷基次膦酸盐混合均匀，接着加入由18g双酚A缩水甘油醚型液体环氧树脂NPEL-128、6g芳香胺、2g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5g芳香胺，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。
可降解固化剂固体粉末粒径≤15um，化学结构同实施例1。
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56MPa，拉伸模量为3.2GPa，弯曲强度为98MPa，弯曲模量为3.3GPa；按照GB/T1447测试片状模塑料拉伸强度为131MPa，拉伸模量为11.4GPa；按照GB/T1449测试片状模塑料弯曲强度为244MPa，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100KJ/㎡；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39％。
实施例10
将63g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、15gCTBN改性环氧树脂预聚体861340，6g内脱模剂、0.5g消泡剂、0.5g浸润剂、60g磷氮阻燃剂、50g六苯氧基环三磷腈混合均匀，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芳香胺，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50℃烘房熟化10小时后即得环氧片状模塑料。
可降解固化剂固体粉末粒径≤15um，化学结构同实施例1。
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2.8GPa，弯曲强度为110MPa，弯曲模量为3.0GPa；按照GB/T1447测试片状模塑料拉伸强度为141MPa，拉伸模量为10.2GPa；按照GB/T1449测试片状模塑料弯曲强度为251MPa，弯曲模量为11.4GPa；按照GB/T1451测试片状模塑料无缺口冲击强度为126KJ/㎡；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％。
上述实施例中的HTDA、DMDC、异氟尔酮二胺作为增稠剂可等同替换为具有一个或多个伯氨基和仲氨基基团的单胺或多元胺，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。
实施例11
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(采用实施例1中制备的可降解阻燃环氧SMC树脂制备而成)，10ml浓盐酸和90ml乙二醇，搅拌加热到15℃，保温600小时后过滤，降解溶液用浓度0.01wt％氢氧化钠溶液中和，调节降解溶液pH值时保持温度为200℃，调节降解溶液pH值，最终pH值8.5；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12
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(采用实施例4中制备的可降解阻燃环氧SMC树脂制备而成)，5ml浓盐酸和95ml辛醇，搅拌加热到155℃，4小时后冷却至100℃，趁热过滤，降解溶液用浓度45wt％氢氧化钠溶液中和，调节降解溶液pH值时保持温度为0℃，调节降解溶液pH值，最终pH值10.0；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％。
实施例13
在250ml三口烧瓶中，加入5g实施例10制备的SMC复合材料板材样品(采用实施例10中制备的可降解阻燃环氧SMC树脂制备而成)，20ml浓盐酸和80ml丙醇，搅拌加热到400℃，保温1小时后冷却至100℃，趁热过滤，降解溶液用纯度99％氢氧化钠固体中和，调节降解溶液pH值时保持温度为100℃，调节降解溶液pH值，最终pH值7.5；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4.5g，质量回收率90％。
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 (8)
1.一种可降解阻燃环氧SMC树脂组合物，其特征在于，由如下重量份的组分制备而成：
环氧树脂90-100质量份、稀释剂0-10质量份、助剂1-15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、氢氧化镁中的一种或几种；
所述固化剂为双氰胺、芳香胺、改性胺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：
2.根据权利要求1所述的一种可降解阻燃环氧SMC树脂组合物，其特征在于：所述增稠剂的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。
3.根据权利要求1所述的一种可降解阻燃环氧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。
4.根据权利要求1所述的一种可降解阻燃环氧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、内脱模剂至少一种。
6.根据权利要求1所述的一种可降解阻燃环氧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。
7.根据权利要求1所述的一种可降解阻燃环氧SMC树脂组合物，其特征在于：所述增稠剂为具有一个或多个伯氨基和仲氨基基团的单胺或多元胺至少一种，其中包括如乙二胺、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。
8.一种纤维增强复合材料的降解工艺，具体步骤如下：
(1)纤维增强复合材料采用权利要求1～7中任一项所述可降解环氧SMC树脂组合物制备而成，将纤维增强复合材料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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Application publication date: 20201204 |