CN108164751A - 一种适用于tpv的反应型无卤阻燃剂及其制备方法和应用 - Google Patents
一种适用于tpv的反应型无卤阻燃剂及其制备方法和应用 Download PDFInfo
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- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 claims abstract description 12
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- 238000005580 one pot reaction Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
- C07F9/657172—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and one oxygen atom being part of a (thio)phosphinic acid ester: (X = O, S)
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Abstract
本发明公开了一种适用于TPV的反应型无卤阻燃剂及其制备方法和应用,其中无卤阻燃剂的结构式为:R代表酰亚胺基团的残基,为:本发明将含酚羟基的酰亚胺引入9,10‑二氢‑9‑氧杂‑10‑磷杂菲‑10‑氧化物(DOPO)阻燃剂结构中,酰亚胺结构赋予该阻燃剂具有很好的耐热性和力学性能,保留的酚羟基的活性基团可以增加与TPV的相容性,同时阻燃剂中含有氮磷元素可以达到协调阻燃效果,阻燃剂为粉末状易于弹性体共混加工。利用本发明阻燃剂制备的阻燃TPV材料,阻燃剂的添加份数少,同时具有很好的阻燃效果,扩宽了TPV在阻燃特殊材料应用范围。
Description
技术领域
本发明涉及一种适用于TPV的反应型无卤阻燃剂及其制备方法和应用,属于无卤氮磷反应型阻燃剂技术领域。
背景技术
阻燃剂市场主要分为卤素阻燃剂和无卤阻燃剂,卤素阻燃剂其阻燃性能好、用量少、对基材树脂性能影响小,在市场上仍然占据主要市场,但是其因环保问题受欧盟条例的限制,未来其逐渐被无卤阻燃剂替代,但是无卤阻燃相容性差、耐热性差、对基材树脂性能影响较大等一系列问题,成为研发改善的重点。反应型无卤阻燃剂参与了树脂基材的反应相容性好,对聚合物性能影响较小,阻燃的持久性好。
动态硫化橡胶(TPV)是热塑性弹性体(TPE)中特殊的一类,是经三元乙丙橡胶(EPDM)与聚丙烯(PP)动态硫化后配合防老化体系经物理及化学改性而成的一种高档全硫化弹性体。材料可挤出、注塑成型,且制品表面档次高,并且具有良好的耐老化、耐化学等特性,材料环保,可回收利用。目前,热塑性弹性体广泛被应用于汽车、建筑、电线电缆等众多行业。但是热塑性弹性体含有大量的软化油,缺点是易燃烧,限制该材料的应用领域。
CN 103694434A公开了一种用于聚氨酯泡沫的无卤反应型阻燃剂及其制备方法和应用,合成的阻燃剂增加泡沫的强度和阻燃持久性,氧指数达到23-28%,在建筑、保温及一些特殊场合有广泛的应用前景。CN 106675007A利用DOPO基反应型磷系阻燃剂与而冤案之间反应得到阻燃剂盐,然后阻燃改性聚酰胺6,可用于齿轮、轴承及汽车部件等产品。反应型无卤阻燃剂在工程塑料和弹性体都有所应用,但是目前,无卤反应型阻燃剂应用在TPV材料方面国内尚未报道。
发明内容
传统的添加型无卤阻燃剂与TPV的相容性差,阻燃剂容易析出,制品表面差,并大大降低了TPV的耐热性。为了解决以上技术问题,本发明旨在提供一种适用于TPV的反应型无卤阻燃剂及其制备方法和应用。本发明阻燃剂结构中活性酚羟基可以和TPV中未交联的EPDM发生部分化学反应,改善与TPV的相容性,同时通过降冰片烯和马来酸酐封端的烯酰亚胺结构赋予TPV很高的耐热性和力学性能。
本发明适用于TPV的反应型无卤阻燃剂,其结构式为:
其中R代表酰亚胺基团的残基,为:
本发明适用于TPV的反应型无卤阻燃剂的制备方法,包括如下步骤:
向反应器中加入二酸酐和100-200ml有机溶剂,搅拌溶解后加入对氨基苯酚,室温搅拌2h,制得封端的酰胺酸;随后向反应液中加入DOPO,升温至120℃回流反应6h,反应结束后冷却至室温,用5wt%的NaHCO3溶液清洗得到大量沉淀,用大量去离子水洗涤并过滤干燥,得到粉末状目标产物。
所述二酸酐选自顺丁烯二酸酐或降冰片烯二酸酐。
所述有机溶剂选自冰醋酸、DMAC或DMF。
DOPO、对氨基苯酚和二酸酐的摩尔比为1:1:1.2。
反应过程如下:
二酸酐过量保证反应条件为酸性,催化酰胺化反应和DOPO的加成反应,并吸收酰亚胺反应中产生的水分,使得酰亚胺反应更加彻底,提高目标产物的产率。
以本发明无卤阻燃剂作为改性剂制备阻燃TPV,包括如下步骤:
将无卤阻燃剂15-30质量份和TPV 70-85质量份混合均匀,在双螺杆挤出机中挤出造粒,即得到阻燃TPV。双螺杆挤出机的加工温度为180℃-230℃。
所述TPV为市售产品,其硬度为60-80A,在230℃/5kg负荷融熔指数为10-30g/10min。
本发明提供一种反应型无卤阻燃剂及制备方法,先添加对氨基苯酚和二酸酐反应生成酰胺酸,高温反应然后加入DOPO,酰亚胺脱水缩合成酰亚胺和DOPO的双键加成反应同时发生,采用一锅煮法,优化制备工艺,易于实现工业化生产。
目前,多官能型无卤阻燃适用于TPV材料方面在国内尚未报道。
与已有技术相比,本发明的有益效果体现在:
1、本发明阻燃剂成功将新型DOPO中引入带酚羟基的封端酰亚胺结构,提高了阻燃TPV的相容性、耐热性和力学性能。
2、本发明无卤反应型阻燃剂为氮磷型,氮磷可以达到协调阻燃效果,阻燃剂为粉末,易于TPV分散加工。
3、本发明阻燃剂制备工艺采用一锅煮发,制备工艺简单,溶剂可多种选择,易于实现工业化生产,收率超过70%。
附图说明
图1是本发明阻燃剂的红外谱图。从图中可以看出,3380cm-1是酚羟基的吸收峰,1770、1710、1380cm-1为降冰片烯酰亚胺的特征峰,1770cm-1为酰亚胺的C=O非对称伸缩振动的吸收峰,1710cm-1为酰亚胺的C=O对称伸缩振动的吸收峰,1380cm-1为酰亚胺的C-N伸缩振动吸收峰;2900-3000cm-1为降冰片烯的CH2的伸缩振动吸收峰;1614cm-1与1518cm-1为苯环C=C特征吸收峰;1190cm-1为DOPO的P=O特征吸收峰;1460cm-1为DOPO的P-C特征峰。综上可知,得到了目标产物。
具体实施方法
以下结合具体的实施例对本发明的技术方案进行详细说明,但本发明不局限于以下实施例。
实施例1:
1、反应型无卤阻燃剂的制备
向反应器中加入0.12mol顺丁烯二酸酐和100ml冰醋酸,搅拌溶解后加入0.1mol对氨基苯酚,室温搅拌2h,制得封端的酰胺酸;向反应液加入0.1molDOPO,升温120℃回流反应6h,反应结束后降溶液冷却到室温,用5%的NaHCO3溶液清洗得到大量沉淀,后加入大量去离子水反复洗涤过滤干燥,即得到粉末状目标产物阻燃剂。测试其红外数据见图1。
2、阻燃TPV的制备
将质量份数阻燃剂15份和TPV85份混合均匀,在双螺杆挤出机中挤出造粒,加工温度为190℃,得到阻燃TPV产品。
实施例2:
1、反应型无卤阻燃剂的制备
向反应器中加入0.12mol顺丁烯二酸酐和120mlDMAC,搅拌溶解后加入0.1mol对氨基苯酚,室温搅拌2h,制得封端的酰胺酸;向反应液加入0.1molDOPO,升温120℃回流反应6h,反应结束后降溶液冷却到室温,用5%的NaHCO3溶液清洗得到大量沉淀,后加入大量去离子水反复洗涤过滤干燥,即得到粉末状目标产物阻燃剂。
2、阻燃TPV的制备
将质量份数阻燃剂20份和TPV80份混合均匀,在双螺杆挤出机中挤出造粒,加工温度为190℃,得到阻燃TPV产品。
实施例3:
1、反应型无卤阻燃剂的制备
向反应器中加入0.12mol顺丁烯二酸酐和200mlDMF,搅拌溶解后加入0.1mol对氨基苯酚,室温搅拌2h,制得封端的酰胺酸;向反应液加入0.1molDOPO,升温120℃回流反应6h,反应结束后降溶液冷却到室温,用5%的NaHCO3溶液清洗得到大量沉淀,后加入大量去离子水反复洗涤过滤干燥,即得到粉末状目标产物阻燃剂。
2、阻燃TPV的制备
将质量份数阻燃剂25份和TPV85份混合均匀,在双螺杆挤出机中挤出造粒,加工温度为200℃,得到阻燃TPV产品。
实施例4:
向反应器中加入0.12mol降冰片烯二酸酐和100ml冰醋酸,搅拌溶解后加入0.1mol对氨基苯酚,室温搅拌2h,制得封端的酰胺酸;向反应液加入0.1molDOPO,升温120℃回流反应6h,反应结束后降溶液冷却到室温,用5%的NaHCO3溶液清洗得到大量沉淀,后加入大量去离子水反复洗涤过滤干燥,即得到粉末状目标产物阻燃剂。
2、阻燃TPV的制备
将质量份数阻燃剂20份和TPV80份混合均匀,在双螺杆挤出机中挤出造粒,加工温度为200℃,得到阻燃TPV产品。
实施例5:
向反应器中加入0.12mol降冰片烯二酸酐和120mlDMAC,搅拌溶解后加入0.1mol对氨基苯酚,室温搅拌2h,制得封端的酰胺酸;向反应液加入0.1molDOPO,升温120℃回流反应6h,反应结束后降溶液冷却到室温,用5%的NaHCO3溶液清洗得到大量沉淀,后加入大量去离子水反复洗涤过滤干燥,即得到粉末状目标产物阻燃剂。
2、阻燃TPV的制备
将质量份数阻燃剂25份和TPV75份混合均匀,在双螺杆挤出机中挤出造粒,加工温度为200℃,得到阻燃TPV产品。
下表1为本发明实施例制备的阻燃TPV产品对比物性表。
表1阻燃TPV产品对比物性表
由表1可见,本发明的无卤阻燃耐改性TPV材料经测试常规物性:随着阻燃剂的量的增加硬度升高,其拉伸强度也有显著的改善,其阻燃等级和氧指数都有很高的改善。主要是反应型阻燃剂的加入增加了TPV的交联密度,使得橡胶硫化更加彻底,其拉伸强度有显著的提高,同时该阻燃剂与TPV的相容性好,同等阻燃效果,阻燃剂的添加份数少,阻燃效果明显。
以上所述仅为本发明的实施例,并非因此限制本发明的专利范围,凡是利用本发明说明书内容所作的等效结构或等效流程变换,或直接或间接运用在其他相关的技术领域,均同理包括在本发明的专利保护范围内。
Claims (9)
1.一种适用于TPV的反应型无卤阻燃剂,其特征在于其结构式为:
其中R代表酰亚胺基团的残基,为:
2.一种权利要求1所述的适用于TPV的反应型无卤阻燃剂的制备方法,其特征在于包括如下步骤:
向反应器中加入二酸酐和有机溶剂,搅拌溶解后加入对氨基苯酚,室温搅拌2h,制得封端的酰胺酸;随后向反应液中加入DOPO,升温至120℃回流反应6h,反应结束后冷却至室温,用5wt%的NaHCO3溶液清洗得到大量沉淀,用大量去离子水洗涤并过滤干燥,得到粉末状目标产物。
3.根据权利要求2所述的制备方法,其特征在于:
所述二酸酐选自顺丁烯二酸酐或降冰片烯二酸酐。
4.根据权利要求2所述的制备方法,其特征在于:
所述有机溶剂选自冰醋酸、DMAC或DMF。
5.根据权利要求2所述的制备方法,其特征在于:
DOPO、对氨基苯酚和二酸酐的摩尔比为1:1:1.2。
6.一种权利要求1所述的适用于TPV的反应型无卤阻燃剂的应用,其特征在于:
是以所述无卤阻燃剂作为改性剂制备阻燃TPV。
7.根据权利要求6所述的应用,其特征在于包括如下步骤:
将无卤阻燃剂15-30质量份和TPV 70-85质量份混合均匀,在双螺杆挤出机中挤出造粒,即得到阻燃TPV。
8.根据权利要求7所述的应用,其特征在于:
双螺杆挤出机的加工温度为180℃-230℃。
9.根据权利要求6或7所述的应用,其特征在于:
所述TPV硬度为60-80A,在230℃/5kg负荷融熔指数为10-30g/10min。
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109897219A (zh) * | 2017-12-11 | 2019-06-18 | 广东广山新材料股份有限公司 | 一种反应性阻燃剂及其制备方法和应用 |
CN112442073A (zh) * | 2019-08-28 | 2021-03-05 | 广东广山新材料股份有限公司 | 一种含磷的反应型阻燃剂及其制备方法和应用 |
CN112442080A (zh) * | 2019-08-28 | 2021-03-05 | 广东广山新材料股份有限公司 | 一种带有酚羟基的反应型阻燃剂及其制备方法和应用 |
CN114316215A (zh) * | 2022-01-27 | 2022-04-12 | 安徽建筑大学 | 一种自交联成炭本征阻燃聚双环戊二烯工程材料及其制备方法 |
CN114685901A (zh) * | 2021-12-28 | 2022-07-01 | 道恩高材(北京)科技有限公司 | 一种交联反应型无卤阻燃tpv材料 |
CN118344686A (zh) * | 2024-06-17 | 2024-07-16 | 山东振曦新材料科技有限公司 | 含阻燃增塑剂的pvc材料及其制备方法 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20050014873A1 (en) * | 2003-07-18 | 2005-01-20 | Chung Yuan Christian University | Phosphorus-containing compound for use as flame retardant and flame retardant resin |
CN102127289A (zh) * | 2010-12-23 | 2011-07-20 | 广东生益科技股份有限公司 | 无卤阻燃环氧树脂组合物及使用其制作的胶膜与覆铜板 |
CN104987664A (zh) * | 2015-06-26 | 2015-10-21 | 四川东材科技集团股份有限公司 | 一种特高压直流输变电用绝缘层、模压结构件及其制备方法 |
CN106632487A (zh) * | 2015-10-28 | 2017-05-10 | 广东生益科技股份有限公司 | 含酰亚胺结构的环三磷腈无卤阻燃剂、制备方法及用途 |
CN106700475A (zh) * | 2016-12-28 | 2017-05-24 | 广东生益科技股份有限公司 | 一种阻燃的聚苯醚树脂组合物 |
-
2017
- 2017-12-27 CN CN201711444459.0A patent/CN108164751B/zh active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20050014873A1 (en) * | 2003-07-18 | 2005-01-20 | Chung Yuan Christian University | Phosphorus-containing compound for use as flame retardant and flame retardant resin |
CN102127289A (zh) * | 2010-12-23 | 2011-07-20 | 广东生益科技股份有限公司 | 无卤阻燃环氧树脂组合物及使用其制作的胶膜与覆铜板 |
CN104987664A (zh) * | 2015-06-26 | 2015-10-21 | 四川东材科技集团股份有限公司 | 一种特高压直流输变电用绝缘层、模压结构件及其制备方法 |
CN106632487A (zh) * | 2015-10-28 | 2017-05-10 | 广东生益科技股份有限公司 | 含酰亚胺结构的环三磷腈无卤阻燃剂、制备方法及用途 |
CN106700475A (zh) * | 2016-12-28 | 2017-05-24 | 广东生益科技股份有限公司 | 一种阻燃的聚苯醚树脂组合物 |
Non-Patent Citations (1)
Title |
---|
SHUANG YANG: "Preparation and flame retardancy of an intumescent flame-retardant epoxy resin system constructed by multiple flame-retardant compositions containing phosphorus and nitrogen heterocycle", 《POLYMER DEGRADATION AND STABILITY》 * |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109897219A (zh) * | 2017-12-11 | 2019-06-18 | 广东广山新材料股份有限公司 | 一种反应性阻燃剂及其制备方法和应用 |
CN112442073A (zh) * | 2019-08-28 | 2021-03-05 | 广东广山新材料股份有限公司 | 一种含磷的反应型阻燃剂及其制备方法和应用 |
CN112442080A (zh) * | 2019-08-28 | 2021-03-05 | 广东广山新材料股份有限公司 | 一种带有酚羟基的反应型阻燃剂及其制备方法和应用 |
CN114685901A (zh) * | 2021-12-28 | 2022-07-01 | 道恩高材(北京)科技有限公司 | 一种交联反应型无卤阻燃tpv材料 |
CN114316215A (zh) * | 2022-01-27 | 2022-04-12 | 安徽建筑大学 | 一种自交联成炭本征阻燃聚双环戊二烯工程材料及其制备方法 |
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