CN113773596A - 一种高机械性能高阻燃耐泥浆电缆护套料及其制备方法 - Google Patents
一种高机械性能高阻燃耐泥浆电缆护套料及其制备方法 Download PDFInfo
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- CN113773596A CN113773596A CN202111031643.9A CN202111031643A CN113773596A CN 113773596 A CN113773596 A CN 113773596A CN 202111031643 A CN202111031643 A CN 202111031643A CN 113773596 A CN113773596 A CN 113773596A
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- C08L31/02—Homopolymers or copolymers of esters of monocarboxylic acids
- C08L31/04—Homopolymers or copolymers of vinyl acetate
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- 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
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L75/04—Polyurethanes
- C08L75/06—Polyurethanes from polyesters
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- H01B3/448—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from other vinyl compounds
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- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2203/20—Applications use in electrical or conductive gadgets
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- C—CHEMISTRY; METALLURGY
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- C08L2207/04—Thermoplastic elastomer
Abstract
本发明公开了一种高机械性能高阻燃耐泥浆电缆护套料及其制备方法，该电缆护套料由以下组分按重量份制备而成：乙烯共聚物40～70份，热塑性聚氨酯弹性体30～60份，相容剂10～20份，阻燃剂30～180份，交联剂1～10份，其他助剂1～20份。该电缆护套料可通过辐照交联、硅烷交联、紫外光交联等工艺进行交联硫化，性能满足NEK TS 606与IEC 60092等标准要求，同时兼容EN50264/EN 50306等机车线缆护套耐油性能要求，具备高拉伸强度、高阻燃、耐高低温、耐油、耐泥浆等特性。
Description
技术领域
本发明属于高分子改性材料技术领域，特别涉及一种高机械性能高阻燃耐泥浆电缆护套料及其制备方法。
背景技术
海上油气开采、海上风电、海洋科学探测等海洋工程技术及设备其作业环境的特殊性，对与之配套的电缆提出了很高的技术要求。通常，海洋工程用电缆(以下称为海工电缆)需要具备耐油、耐盐雾、耐海水、耐泥浆、耐光照、耐高低温、高机械强度、低烟、无卤、阻燃等性能。传统的低烟无卤阻燃聚烯烃材料虽能满足低烟、无卤、阻燃等性能要求，但其耐油、耐海水、耐泥浆、耐高低温性能不能很好的满足海工装备线缆要求，因此需要针对海工装备线缆相关要求开发高阻燃耐泥浆电缆护套材料及其制备方法。
公开的耐泥浆电缆护套里，公开号为CN104927176B的专利公开了采用乙烯醋酸乙烯共聚物(VA含量33％)，乙烯-醋酸乙烯-一氧化碳共聚物、聚乙烯及马来酸酐接枝聚乙烯为基材的辐照交联聚烯烃护套料，具有低烟无卤阻燃等特性，通过该专利发明内容可以发现，其树脂基材极性基团含量较低，在测试液作用下拉伸强度变化率与体积膨胀率均超过了20％。公开号为CN103030874B的专利公开了采用乙烯-丙烯酸丁酯与高密度聚乙烯为基材的辐照交联耐泥浆电缆料，其中，乙烯-丙烯酸丁酯共聚物的极性基团——丙烯酸丁酯含量为10％～30％，树脂基体内极性基团比例仍不高，耐IRM902、IRM903等非极性测试液性能一般，力学性能较低。
发明内容
针对现有技术的不足，本发明的目的是提供一种高机械性能高阻燃耐泥浆电缆护套料及其制备方法，该电缆护套料具备耐高低温、耐油、耐泥浆、耐海水等性能，同时满足低烟、无卤、高阻燃特性，可长期应用于海工装备线缆等场合。
本发明的目的是通过以下技术方案来实现的：
一种高机械性能高阻燃耐泥浆电缆护套料，由以下组分按重量份制备而成：乙烯共聚物40～70份，热塑性聚氨酯弹性体(TPU)30～60份，相容剂10～20份，阻燃剂30～180份，交联剂1～10份，其他助剂1～20份。
优选的，所述乙烯共聚物为乙烯-醋酸乙烯酯共聚物(EVA，其VA含量 28％～80％)、乙烯-丙烯酸甲酯共聚物(EMA，其MA含量30％～70％)、乙烯-丙烯酸丁酯共聚物(EBA，其BA含量21％～40％)、乙烯-乙烯醇共聚物(EVOH，其VOH含量30％～50％)、热塑性乙烯基弹性体中的至少一种。
优选的，所述热塑性聚氨酯弹性体为聚醚型TPU、聚酯型TPU、脂肪族TPU、聚己内酯TPU、聚碳酸酯TPU中的一种。
优选的，所述相容剂为POE-MAH、EVA-MAH、SEBS-MAH、LLDPE-MAH、 EPDM-MAH、E-GMA-MAH中的至少一种。
优选的，所述阻燃剂为三氧化二锑、五氧化二锑、氢氧化铝、氢氧化镁、硼酸锌、氧化锌、聚磷酸铵、聚磷酸三聚氰胺、六苯氧基环三磷腈、次磷酸盐、磷酸酯、焦磷酸哌嗪、有机改性膨润土、有机改性海泡石、三嗪类阻燃剂、笼型倍半硅氧烷中的至少一种。所述有机改性海泡石是采用改性试剂对海泡石进行改性处理所得；改性试剂可选择氨基硅烷、氨基或乙烯基硅烷等材料，其中优选为氨基硅烷，采用氨基硅烷改性海泡石所得的材料记为氨基硅烷表面改性海泡石。
优选的，所述交联剂为三烯丙基异氰脲酸酯(TAIC)、三聚氰酸三烯丙酯 (TAC)、三聚氰酸三烯丙酯(TGIC)、三聚硫氰酸(TMT)、三甲代烯丙基异氰酸酯(TMAIC)、三羟甲基丙烷三丙烯酸酯(TMPTA)、三羟甲基丙烷三甲基丙烯酸酯(TMPTMA)、过氧化二异丙苯、2,5-二甲基-2,5-双己烷(双25)、双叔丁基过氧异丙基苯(BIPB)中的至少一种。
优选的，所述其他助剂包括氰酸酯类助剂、醇类助剂、硅酮、抗氧化剂、紫外光吸收剂、光稳定剂、紫外光引发剂、硅烷、有机锡催化剂、抗水解剂中的至少一种。
优选的，所述氰酸酯类助剂为二苯基甲烷-4,4'-二异氰酸酯(MDI)或甲苯二异氰酸酯(TDI)；所述醇类助剂为乙二醇、丙二醇、丁二醇、聚四氢呋喃二醇、丙三醇、三羟甲基丙烷、丁四纯、季戊四醇、聚四氢呋喃多元醇中的一种；所述抗氧化剂为亚磷酸酯类抗氧剂、受阻酚类抗氧剂、硫代酯类抗氧剂、苯胺类抗氧剂中的至少一种。
本发明还公开了上述所述的高机械性能高阻燃耐泥浆电缆护套料的制备方法，包括以下步骤：按配比称取各个组分后，将其混合均匀得到混合物料；混合物料经挤出后得到最终产品。进一步优选的，所述挤出是利用密炼机进行挤出或利用密炼机与螺杆挤出机进行组合使用的方式进行挤出；所述挤出的温度为 100℃～200℃。
与现有技术相比，本发明有益效果体现在：
本发明提供了一种高机械性能高阻燃耐泥浆电缆护套料，该电缆护套料以乙烯共聚物、热塑性聚氨酯弹性体等极性材料为基体材料，由于一般燃油、齿轮油等是以非极性脂肪烃为主体的材料，基于相似相容原理，本发明制得的材料具有良好的耐油、耐泥性能；本发明通过在材料中添加热塑性聚氨酯弹性体，使产品具有高拉伸强度，表现出优异的机械性能；本发明通过在材料中添加阻燃剂及相关助剂，使产品具有优异的阻燃性能。该电缆护套料可通过辐照交联、硅烷交联、紫外光交联等工艺进行交联硫化，性能满足NEK TS 606与IEC 60092等标准要求，同时兼容EN 50264/EN 50306等机车线缆护套耐油性能要求，具备高拉伸强度、高阻燃、耐高低温、耐油、耐泥浆等特性。
具体实施方式
下面结合实施例对本发明作更进一步的说明。显然，所描述的实施例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作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。
下列实施例中所用试剂的型号以及供应商如下：
聚醚型TPU为BASF 1190A(硬度90A)、1185A(硬度85A)，脂肪族型TPU 为科思创聚合物(中国)有限公司的DP 85085A；有机蒙脱土为浙江丰虹新材料股份有限公司DK4；聚酯型TPU为华峰集团有限公司3090(90A)；有机次磷酸铝为OP1230；紫外光敏化剂为二苯甲酮；受阻酚类抗氧剂为抗氧剂1010；硫代酯类抗氧剂为抗氧剂DLTP；硅酮选自浙江佳华的GT-500；硅烷为硅烷偶联剂 A171；有机锡催化剂为二辛基锡。
上述试剂只是为了说明本发明实验时所采用的试剂来源和成分，以便充分公开，并不表示采用其他同类试剂或其他供应商提供的试剂就不能实现本发明。
实施例1
(1)按照重量份数，称取EVA(VA含量70％)为50份，聚醚型TPU1190 (硬度90A)40份，EVA-MAH为10份，TAIC为3份，季戊四醇为0.5份，氢氧化铝160份，氨基硅烷表面改性海泡石10份，受阻酚类抗氧剂0.5份，硫代酯类抗氧剂0.5份，硅酮5份；其中：氨基硅烷表面改性海泡石的制备方法为：将氨基硅烷分散在90％的乙醇溶液中得到分散液，然后将海泡石加入至分散液中混合搅拌30min后，经过分离、水洗、干燥后制备所得；氨基硅烷的用量是海泡石质量的0.8％。氨基硅烷具有两种功能团，即氨基和乙氧基，其中三个可水解的乙氧基在反应中先水解生成硅醇，由于硅醇不稳定，极易与海泡石表面的羟基结合脱水，从而与海泡石结合起来；氨基上带有两个活泼氢可以和有机聚合物发生反应，从而通过化学键将两种性质完全不同的材料紧密的结合起来。
(2)采用双螺杆挤出机混炼挤出，挤出温度为160℃左右，挤出后造粒形成耐温等级125℃的辐照交联高阻燃耐泥浆电缆护套料。
实施例2
(1)按照重量份数，称取EMA(MA含量40％)为70份，脂肪族型TPU (硬度85A)为30份，SEBS-MAH为10份，TMPTA为4份，氢氧化镁为160 份，有机蒙脱土为10份，受阻酚类抗氧剂0.5份，硫代酯类抗氧剂0.5份，硅酮 5份；
(2)采用密炼混炼，密炼温度为160℃左右，单螺杆挤出后造粒形成耐温等级105℃的辐照交联高阻燃耐泥浆电缆护套料。
实施例3
(1)按照重量份数，称取EBA(BA含量为35％)为30份，EVOH(VOH 含量44％)为10份，聚酯型TPU(硬度90A)为60份，E-GMA-MAH为15份，有机次磷酸铝OP1230为40份，间苯二酚四苯基二磷酸酯为8份，氧化锌为2 份，紫外光敏化剂BP为3份，TAIC为4份，受阻酚类抗氧剂0.5份，亚磷酸酯类抗氧剂为1份；
(2)采用双螺杆挤出机混炼挤出，挤出温度为190℃左右，挤出后造粒，形成耐温等级125℃的紫外光交联高阻燃耐泥浆电缆护套料；
实施例4
(1)按照重量份数，称取EVA(VA含量50％)为30份，聚醚型TPU(硬度85A)60份，LLDPE-MAH为10份，氢氧化镁160份，有机海泡石为10份，硅烷为3份，BIPB为0.5份，有机锡催化剂为0.2份，MDI为1份，受阻酚类抗氧剂0.5份，硫代酯类抗氧剂0.5份，硅酮5份；
(2)先将EVA、TPU、LLDPE-MAH、氢氧化镁、有机海泡石干燥后，用双螺杆挤出机混炼挤出，挤出温度为160℃左右，挤出后造粒形成耐温等级125℃的硅烷可交联高阻燃耐泥浆电缆护套料。
对比例1
与实施例1相比，对比例1的区别在于不添加“聚醚型TPU(硬度90A)40 份”，其他工艺均与实施例1相同。
对比例2
与实施例1相比，对比例1的区别在于不添加“氨基硅烷表面改性海泡石10 份”，其他工艺均与实施例1相同。
对上述各实施例和对比例制得的产品进行性能检测，结果如下表1所示：
表1实施例及对比例的高机械性能高阻燃耐泥浆电缆护套料性能检测结果
通过表1可以发现，实施例制得的材料的性能明显优于对比例中产品的性能，本发明通过对材料的配方进行改进，制得的电缆护套料具有优异机械性能、高阻燃性能和耐油耐泥浆性能。
Claims (10)
1.一种高机械性能高阻燃耐泥浆电缆护套料，其特征在于：由以下组分按重量份制备而成：乙烯共聚物40～70份，热塑性聚氨酯弹性体30～60份，相容剂10～20份，阻燃剂30～180份，交联剂1～10份，其他助剂1～20份。
2.根据权利要求1所述的高机械性能高阻燃耐泥浆电缆护套料，其特征在于：所述乙烯共聚物为乙烯-醋酸乙烯酯共聚物、乙烯-丙烯酸甲酯共聚物、乙烯-丙烯酸丁酯共聚物、乙烯-乙烯醇共聚物、热塑性乙烯基弹性体中的至少一种。
3.根据权利要求1所述的高机械性能高阻燃耐泥浆电缆护套料，其特征在于：所述热塑性聚氨酯弹性体为聚醚型TPU、聚酯型TPU、脂肪族TPU、聚己内酯TPU、聚碳酸酯TPU中的一种。
4.根据权利要求1所述的高机械性能高阻燃耐泥浆电缆护套料，其特征在于：所述相容剂为POE-MAH、EVA-MAH、SEBS-MAH、LLDPE-MAH、EPDM-MAH、E-GMA-MAH中的至少一种。
5.根据权利要求1所述的高机械性能高阻燃耐泥浆电缆护套料，其特征在于：所述阻燃剂为三氧化二锑、五氧化二锑、氢氧化铝、氢氧化镁、硼酸锌、氧化锌、聚磷酸铵、聚磷酸三聚氰胺、六苯氧基环三磷腈、次磷酸盐、磷酸酯、焦磷酸哌嗪、有机改性膨润土、有机改性海泡石、三嗪类阻燃剂、笼型倍半硅氧烷中的至少一种。
6.根据权利要求1所述的高机械性能高阻燃耐泥浆电缆护套料，其特征在于：所述交联剂为三烯丙基异氰脲酸酯、三聚氰酸三烯丙酯、三聚氰酸三烯丙酯、三聚硫氰酸、三甲代烯丙基异氰酸酯、三羟甲基丙烷三丙烯酸酯、三羟甲基丙烷三甲基丙烯酸酯、过氧化二异丙苯、2,5-二甲基-2,5-双己烷(双25)、双叔丁基过氧异丙基苯中的至少一种。
7.根据权利要求1所述的高机械性能高阻燃耐泥浆电缆护套料，其特征在于：所述其他助剂包括氰酸酯类助剂、醇类助剂、硅酮、抗氧化剂、紫外光吸收剂、光稳定剂、紫外光引发剂、硅烷、有机锡催化剂、抗水解剂中的至少一种。
8.根据权利要求7所述的高机械性能高阻燃耐泥浆电缆护套料，其特征在于：所述氰酸酯类助剂为二苯基甲烷-4,4'-二异氰酸酯(MDI)或甲苯二异氰酸酯(TDI)；所述醇类助剂为乙二醇、丙二醇、丁二醇、聚四氢呋喃二醇、丙三醇、三羟甲基丙烷、丁四纯、季戊四醇、聚四氢呋喃多元醇中的一种；所述抗氧化剂为亚磷酸酯类抗氧剂、受阻酚类抗氧剂、硫代酯类抗氧剂、苯胺类抗氧剂中的至少一种。
9.如权利要求1-8任一项所述的高机械性能高阻燃耐泥浆电缆护套料的制备方法，其特征在于：包括以下步骤：按配比称取各个组分后，将其混合均匀得到混合物料；混合物料经挤出后得到最终产品。
10.根据权利要求9所述的高机械性能高阻燃耐泥浆电缆护套料的制备方法，其特征在于：所述挤出是利用密炼机进行挤出或利用密炼机与螺杆挤出机进行组合使用的方式进行挤出；所述挤出的温度为100℃～200℃。
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| CN115612200A (zh) * | 2022-10-31 | 2023-01-17 | 常州八益电缆股份有限公司 | 海面漂浮光伏系统耐盐雾耐弯折电缆的制备方法 |
| CN115627068A (zh) * | 2022-11-15 | 2023-01-20 | 广东安拓普聚合物科技有限公司 | 耐高温防焊渣电缆护套料 |
| CN117447788A (zh) * | 2023-12-23 | 2024-01-26 | 河北尚华新材料股份有限公司 | 一种光伏电缆用低烟无卤阻燃电缆料及其制备方法 |
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| CN114292487A (zh) * | 2021-12-28 | 2022-04-08 | 会通新材料(上海)有限公司 | 一种高粘结强度热塑性弹性体包胶材料及其制备方法 |
| CN115260746A (zh) * | 2022-08-31 | 2022-11-01 | 广东安拓普聚合物科技有限公司 | 一种耐腐蚀耐油岸电电缆护套材料及其制备方法 |
| CN115612200A (zh) * | 2022-10-31 | 2023-01-17 | 常州八益电缆股份有限公司 | 海面漂浮光伏系统耐盐雾耐弯折电缆的制备方法 |
| CN115612200B (zh) * | 2022-10-31 | 2023-08-25 | 常州八益电缆股份有限公司 | 海面漂浮光伏系统耐盐雾耐弯折电缆的制备方法 |
| CN115627068A (zh) * | 2022-11-15 | 2023-01-20 | 广东安拓普聚合物科技有限公司 | 耐高温防焊渣电缆护套料 |
| CN117447788A (zh) * | 2023-12-23 | 2024-01-26 | 河北尚华新材料股份有限公司 | 一种光伏电缆用低烟无卤阻燃电缆料及其制备方法 |
| CN117447788B (zh) * | 2023-12-23 | 2024-04-12 | 河北尚华新材料股份有限公司 | 一种光伏电缆用低烟无卤阻燃电缆料及其制备方法 |
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