CN112812508A - 一种汽车电缆用阻燃tpee材料及其制备方法 - Google Patents
一种汽车电缆用阻燃tpee材料及其制备方法 Download PDFInfo
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 156
- 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 155
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- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 2
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 2
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- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
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Abstract
本发明公开了一种汽车电缆用阻燃TPEE材料,包括以下重量份的原料:TPEE 70‑80份、阻燃母粒10‑30份、OP蜡0.5‑1份、内润滑剂0.5‑3份、抗氧化剂0.5‑1份、抗滴落剂0.5‑1份,抗臭氧剂0.1‑0.5份。本发明提供的一种汽车电缆用阻燃TPEE材料的制备方法。本发明通过添加阻燃母粒,增加了阻燃剂与TPEE之间的相容性;加入润滑剂OP蜡,降低阻燃剂的析出,减少挤出过程中材料的降解,提高材料体系中各组分的均匀性;加入内润滑剂,改善因加入阻燃剂后,材料表面不光滑的现状,同时,降低TPEE的粘度,提高TPEE材料的流动性;阻燃母粒和OP蜡、内润滑剂协同作用,大幅提高阻燃效果的均匀性,更好的适用于汽车电缆。
Description
技术领域
本发明涉及TPEE复合材料技术领域,具体涉及一种汽车电缆用阻燃TPEE材料及其制备方法。
背景技术
聚氯乙烯(PVC),因其具有较好的机械性能,抗张强度、冲击强度和优异的介电性能,而被广泛用做电线电缆的绝缘物料。但是,现有的电缆在使用过程中,由于电阻导致产生大量热量易发生自燃现象,在燃烧过程中火焰无法快速熄灭,使得电缆受损严重,且随着电缆的长时间的阳光曝晒,PVC的耐热变形和耐老化性能差等问题,会使得PVC分解,引起变色,物理机械性能也迅速下降。在实际应用中多会采用添加耐高温稳定剂、阻燃剂之类的添加剂,以稳定和提高对光热的稳定性和阻燃效果;但是,较多助剂的添加,随着使用时间的正常,添加剂或阻燃物质析出,进而导致电缆的阻燃效果的丧失,阻燃效果不均匀,因此,亟需一种耐高低温,阻燃性能稳定,且材料成本较低的用于电缆的复合材料。
发明内容
本发明的目的在于,克服现有技术中存在的缺陷,提供一种耐高低温性能优越,降低阻燃剂的析出,阻燃性能稳定的汽车电缆用阻燃TPEE材料。
本发明的另一目的在于,提供一种汽车电缆用阻燃TPEE材料的制备方法。
为实现上述目的,本发明的技术方案是设计一种汽车电缆用阻燃TPEE材料,包括以下重量份的原料:TPEE 70-80份、阻燃母粒10-30份、OP蜡0.5-1份、内润滑剂0.5-3份、抗氧化剂0.5-1份、抗滴落剂0.5-1份,抗臭氧剂0.1-0.5份。TPEE(热塑性聚酯弹性体)是一种嵌段式共聚物,由无定型脂肪族聚酯或聚醚类软段和芳香族聚酯类硬段交替排列构成,成两相结构,硬链段结晶起物理交联作用,稳定制品尺寸,软链段无定形赋予聚合物高回弹性。TPEE同时具有橡胶的柔软性、弹性,以及热塑性塑料的刚性、易加工性。然而TPEE极容易燃烧,其极限氧指数(LOI)仅在19%左右,且在燃烧时会产生滴落,在发生火灾时,滴落会带来火焰的蔓延或者烫伤等危险,因此,需要另外添加阻燃剂;如若直接添加阻燃剂,在加工制造的过程中,阻燃剂混合不均匀,阻燃剂易析出,造成阻燃效果不佳。本发明通过添加阻燃母粒,增加了阻燃剂与TPEE之间的相容性;加入润滑剂OP蜡,降低阻燃剂的析出,减少挤出过程中材料的降解,提高材料体系中各组分的均匀性;加入内润滑剂,改善因加入阻燃剂后,材料表面不光滑的现状,同时,降低TPEE的粘度,提高TPEE材料的流动性;但是,OP蜡和内润滑剂的添加量并不是越多越好,OP蜡加入TPEE体系中,对阻燃母粒的分散有利;但加入OP蜡的同时又降低了TPEE体系的粘度,使得加工过程中能够传递到阻燃母粒表面的剪切力大大降低,于阻燃剂的分散不利。因此,阻燃母粒与OP蜡、内润滑剂在整个TPEE体系中的比例是根据多次试验获得的;阻燃母粒和OP蜡、内润滑剂协同作用,大幅提高阻燃效果的均匀性。
优选的技术方案为,所述阻燃母粒按照质量百分比计包括5%-10%的TPEE、40%-45%的聚乳酸、40%-50%的主阻燃剂和5%-10%的协效阻燃剂。在阻燃母粒中,通过添加少量的TPEE、具有优异的相容性的聚乳酸和主阻燃剂、协效阻燃剂一起共混造粒,显著提高了主阻燃剂和协效阻燃剂在TPEE材料体系中的分散性和相容性,进一步提高了主阻燃剂和协效阻燃剂在后续使用过程中的阻燃均匀性和减少阻燃剂的析出作用。
为了进一步提高阻燃效果的均匀性且减少阻燃剂的析出,进一步优选的技术方案为,所述TPEE的粘度为1.25-1.3,硬度为50-72D。选用合适粘度和硬度的TPEE,能够与添加的OP蜡、内润滑剂、阻燃母粒之间既能形成较佳的稳定的均衡的阻燃效果,又不会过渡降低TPEE体系的粘度,使其达到平衡,另外,选用合适粘度和硬度的TPEE还可以增加材料的耐高低温性能。
进一步优选的技术方案为,所述内润滑剂为脂类内润滑剂;所述抗臭氧剂为3,9-二-3-环己烯-1-基-2,4,8,10-四氧螺[5.5]十一烷。脂类内润滑剂具有熔点低、粘度低的特点,可以快速的润湿颗粒表面,提高颗粒物的分散性。
进一步优选的技术方案为,所述主阻燃剂为三聚氰胺磷酸酯和/或三聚氰胺多聚磷酸酯,所述协效阻燃剂为硼酸锌、磷酸锆、有机蒙脱土中的一种或几种。
进一步优选的技术方案为,所述抗氧化剂包括抗氧剂1010、抗氧剂168、抗氧剂1076、抗氧剂164中的一种或者几种;所述抗滴落剂是分子量为400万-500万之间的聚四氟乙烯。
本发明提供的一种汽车电缆用阻燃TPEE材料的制备方法,包括以下步骤:
S1:制备阻燃母粒:首先按照阻燃母粒配方的质量百分比称量TPEE、PLA、主阻燃剂和协效阻燃剂,接着将TPEE、PLA在45℃真空干燥箱中干燥12h,然后将TPEE、PLA、主阻燃剂和协效阻燃剂按质量百分比置于密炼机中进行共混,将均混好的材料从双螺杆挤出机的加料口加入,挤出造粒,获得阻燃母粒;
S2:基材干燥:将阻燃TPEE材料中所需的TPEE称量,加入反应釜中,120℃烘干1h,反应釜的转速为3.5-4rpm/min;
S3:辅料混合:称量步骤S1获得的阻燃母粒,称量OP蜡、内润滑剂、抗氧化剂、抗滴落剂、抗臭氧剂,将上述物料加入高速混合机120~150℃混合0.5-1h;
S4:将步骤S2和步骤S3获得的混合物依次放入失重秤,经双螺杆挤出机主喂料***送入螺杆挤出机共混、熔融、造粒,获得汽车用阻燃TPEE材料,成品冷却、包装。
本发明的优点和有益效果在于:本发明通过添加阻燃母粒,增加了阻燃剂与TPEE之间的相容性;加入润滑剂OP蜡,降低阻燃剂的析出,减少挤出过程中材料的降解,提高材料体系中各组分的均匀性;加入内润滑剂,改善因加入阻燃剂后,材料表面不光滑的现状,同时,降低TPEE的粘度,提高TPEE材料的流动性;但是,OP蜡和内润滑剂的添加量并不是越多越好,OP蜡加入TPEE体系中,对阻燃母粒的分散有利;但加入OP蜡的同时又降低了TPEE体系的粘度,使得加工过程中能够传递到阻燃母粒表面的剪切力大大降低,于阻燃剂的分散不利。因此,阻燃母粒与OP蜡、内润滑剂在整个TPEE体系中的比例是根据多次试验获得的;阻燃母粒和OP蜡、内润滑剂协同作用,大幅提高阻燃效果的均匀性;选用合适粘度和硬度的TPEE,能够与添加的OP蜡、内润滑剂、阻燃母粒之间既能形成较佳的稳定的均衡的阻燃效果,又不会过渡降低TPEE体系的粘度,使其达到平衡,另外,选用合适粘度和硬度的TPEE还可以增加材料的耐高低温性能;本发明提供的汽车电缆用阻燃TPEE材料具有耐高低温性能优越,降低阻燃剂的析出,阻燃性能稳定的优点,上述TPEE材料的阻燃等级达到UL-94VO等级,可以更好的适用于汽车电缆。
具体实施方式
下面结合实施例,对本发明的具体实施方式作进一步描述。以下实施例仅用于更加清楚地说明本发明的技术方案,而不能以此来限制本发明的保护范围。
实施例1
本发明是一种汽车电缆用阻燃TPEE材料,包括以下重量份的原料:粘度为1.25-1.3,硬度为50-72D的TPEE 75份、阻燃母粒20份、OP蜡0.75份、内润滑剂1.8份、抗氧化剂0.75份、分子量为400万-500万之间的聚四氟乙烯0.75份,抗臭氧剂0.3份。
所述内润滑剂为脂类内润滑剂lubde;所述抗臭氧剂为3,9-二-3-环己烯-1-基-2,4,8,10-四氧螺[5.5]十一烷。
一种汽车电缆用阻燃TPEE材料的制备方法,包括以下步骤:
S1:制备阻燃母粒:首先按照阻燃母粒的配方质量百分比称取7.5份的TPEE、42.5份的PLA、45份的主阻燃剂和5份的协效阻燃剂,接着将称量的TPEE、PLA在45℃真空干燥箱中干燥12h,然后将TPEE、PLA、主阻燃剂和协效阻燃剂按质量百分比置于密炼机中进行共混,将均混好的材料从双螺杆挤出机的加料口加入,挤出造粒,获得阻燃母粒;
S2:基材干燥:称量阻燃TPEE材料中所需的75份的TPEE,加入反应釜中,120℃烘干1h,反应釜的转速为3.5-4rpm/min;
S3:辅料混合:将步骤S1获得的阻燃母粒20份,OP蜡0.75份、内润滑剂1.8份、抗氧化剂0.75份、抗滴落剂0.75份、抗臭氧剂0.3份加入高速混合机120-150℃混合0.5-1h;
S4:将步骤S2和步骤S3获得的混合物依次放入失重秤,经双螺杆挤出机主喂料***送入螺杆挤出机共混、熔融、造粒,获得汽车用阻燃TPEE材料,成品冷却、包装。
所述主阻燃剂为三聚氰胺磷酸酯和三聚氰胺多聚磷酸酯,重量比为1:1,所述协效阻燃剂为硼酸锌。
实施例2
本发明是一种汽车电缆用阻燃TPEE材料,包括以下重量份的原料:粘度为1.25-1.3,硬度为50-72D的TPEE 75份、阻燃母粒20份、OP蜡0.75份、lubde内润滑剂1.8份、抗氧化剂0.75份、分子量为400万-500万之间的聚四氟乙烯0.75份,抗臭氧剂0.3份。
所述内润滑剂为脂类内润滑剂lubde;所述抗臭氧剂为3,9-二-3-环己烯-1-基-2,4,8,10-四氧螺[5.5]十一烷。
一种汽车电缆用阻燃TPEE材料的制备方法,包括以下步骤:
S1:制备阻燃母粒:首先按照阻燃母粒的配方质量百分比称取10份的TPEE、45份的PLA、40份的主阻燃剂和5份的协效阻燃剂,接着将称量的TPEE、PLA在45℃真空干燥箱中干燥12h,然后将TPEE、PLA、主阻燃剂和协效阻燃剂按质量百分比置于密炼机中进行共混,将均混好的材料从双螺杆挤出机的加料口加入,挤出造粒,获得阻燃母粒;
S2:基材干燥:称量阻燃TPEE材料中所需的75份的TPEE,加入反应釜中,120℃烘干1h,反应釜的转速为3.5-4rpm/min;
S3:辅料混合:将步骤S1获得的阻燃母粒20份,OP蜡0.75份、内润滑剂1.8份、抗氧化剂0.75份、抗滴落剂0.75份、抗臭氧剂0.3份加入高速混合机120-150℃混合0.5-1h;
S4:将步骤S2和步骤S3获得的混合物依次放入失重秤,经双螺杆挤出机主喂料***送入螺杆挤出机共混、熔融、造粒,获得汽车用阻燃TPEE材料,成品冷却、包装。
所述主阻燃剂为三聚氰胺磷酸酯和三聚氰胺多聚磷酸酯,重量比为1:1,所述协效阻燃剂为磷酸锆。
实施例3
本发明是一种汽车电缆用阻燃TPEE材料,包括以下重量份的原料:粘度为1.25-1.3,硬度为50-72D的TPEE 75份、阻燃母粒20份、OP蜡0.75份、lubde内润滑剂1.8份、抗氧化剂0.75份、分子量为400万-500万之间的聚四氟乙烯0.75份,抗臭氧剂0.3份。
所述内润滑剂为脂类内润滑剂lubde;所述抗臭氧剂为3,9-二-3-环己烯-1-基-2,4,8,10-四氧螺[5.5]十一烷。
一种汽车电缆用阻燃TPEE材料的制备方法,包括以下步骤:
S1:制备阻燃母粒:首先按照阻燃母粒的配方质量百分比称取5份的TPEE、40份的PLA、50份的主阻燃剂和5份的协效阻燃剂,接着将称量的TPEE、PLA在45℃真空干燥箱中干燥12h,然后将TPEE、PLA、主阻燃剂和协效阻燃剂按质量百分比置于密炼机中进行共混,将均混好的材料从双螺杆挤出机的加料口加入,挤出造粒,获得阻燃母粒;
S2:基材干燥:称量阻燃TPEE材料中所需的75份的TPEE,加入反应釜中,120℃烘干1h,反应釜的转速为3.5-4rpm/min;
S3:辅料混合:将步骤S1获得的阻燃母粒20份,OP蜡0.75份、内润滑剂1.8份、抗氧化剂0.75份、抗滴落剂0.75份、抗臭氧剂0.3份加入高速混合机120-150℃混合0.5-1h;
S4:将步骤S2和步骤S3获得的混合物依次放入失重秤,经双螺杆挤出机主喂料***送入螺杆挤出机共混、熔融、造粒,获得汽车用阻燃TPEE材料,成品冷却、包装。
所述主阻燃剂为三聚氰胺磷酸酯和三聚氰胺多聚磷酸酯,重量比为1:1,所述协效阻燃剂为有机蒙脱土。
实施例4
实施例4与实施例3的区别在于,一种汽车电缆用阻燃TPEE材料,包括以下重量份的原料:粘度为1.25-1.3,硬度为50-72D的TPEE 70份、阻燃母粒10份、OP蜡0.5份、lubde内润滑剂0.5份、抗氧化剂0.5份、分子量为400万-500万之间的聚四氟乙烯0.5份。
实施例5
实施例5与实施例3的区别在于,一种汽车电缆用阻燃TPEE材料,包括以下重量份的原料:粘度为1.25-1.3,硬度为50-72D的TPEE 80份、阻燃母粒30份、OP蜡1份、lubde内润滑剂3份、抗氧化剂1份、抗滴落剂1份。
上述实施例1-5的电缆TPEE材料的拉伸强度大于30Mpa,氧指数大于30%,阻燃达到UL-94V0等级,没有滴落物出现。
以上所述仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明技术原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。
Claims (7)
1.一种汽车电缆用阻燃TPEE材料,其特征在于,包括以下重量份的原料:TPEE 70-80份、阻燃母粒10-30份、OP蜡0.5-1份、内润滑剂0.5-3份、抗氧化剂0.5-1份、抗滴落剂0.5-1份,抗臭氧剂0.1-0.5份。
2.根据权利要求1所述的汽车电缆用阻燃TPEE材料,其特征在于,所述阻燃母粒按照质量百分比计包括5%-10%的TPEE、40%-45%的聚乳酸、40%-50%的主阻燃剂和5%-10%的协效阻燃剂。
3.根据权利要求2所述的汽车电缆用阻燃TPEE材料,其特征在于,所述TPEE的粘度为1.25-1.3,硬度为50-72D。
4.根据权利要求3所述的汽车电缆用阻燃TPEE材料,其特征在于,所述内润滑剂为脂类内润滑剂;所述抗臭氧剂为3,9-二-3-环己烯-1-基-2,4,8,10-四氧螺[5.5]十一烷。
5.根据权利要求4所述的汽车电缆用阻燃TPEE材料,其特征在于,所述主阻燃剂为三聚氰胺磷酸酯和/或三聚氰胺多聚磷酸酯,所述协效阻燃剂为硼酸锌、磷酸锆、有机蒙脱土中的一种或几种。
6.根据权利要求5所述的汽车电缆用阻燃TPEE材料,其特征在于,所述抗氧化剂包括抗氧剂1010、抗氧剂168、抗氧剂1076、抗氧剂164中的一种或者几种;所述抗滴落剂是分子量为400万-500万之间的聚四氟乙烯。
7.一种如权利要求1-6任一项所述的汽车电缆用阻燃TPEE材料的制备方法,其特征在于,包括以下步骤:
S1:制备阻燃母粒:首先按照阻燃母粒配方的质量百分比称量TPEE、PLA、主阻燃剂和协效阻燃剂,接着将TPEE、PLA在45℃真空干燥箱中干燥12h,然后将TPEE、PLA、主阻燃剂和协效阻燃剂按质量百分比置于密炼机中进行共混,将均混好的材料从双螺杆挤出机的加料口加入,挤出造粒,获得阻燃母粒;
S2:基材干燥:将阻燃TPEE材料中所需的TPEE称量,加入反应釜中,120℃烘干1h,反应釜的转速为3.5-4rpm/min;
S3:辅料混合:称量步骤S1获得的阻燃母粒,称量OP蜡、内润滑剂、抗氧化剂、抗滴落剂、抗臭氧剂,将上述物料加入高速混合机120~150℃混合0.5-1h;
S4:将步骤S2和步骤S3获得的混合物依次放入失重秤,经双螺杆挤出机主喂料***送入螺杆挤出机共混、熔融、造粒,获得汽车用阻燃TPEE材料,成品冷却、包装。
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CN106398128A (zh) * | 2016-08-31 | 2017-02-15 | 贵州国塑科技管业有限责任公司 | 无卤阻燃长玻纤增强tpee复合材料及其制备方法 |
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JPH1025401A (ja) * | 1996-07-12 | 1998-01-27 | Toyobo Co Ltd | 難燃性ポリエステルエラストマー組成物 |
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