CN115260584B - 一种新能源充电电缆用环保稳定剂 - Google Patents
一种新能源充电电缆用环保稳定剂 Download PDFInfo
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- CN115260584B CN115260584B CN202210971738.7A CN202210971738A CN115260584B CN 115260584 B CN115260584 B CN 115260584B CN 202210971738 A CN202210971738 A CN 202210971738A CN 115260584 B CN115260584 B CN 115260584B
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- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 27
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- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K5/05—Alcohols; Metal alcoholates
- C08K5/053—Polyhydroxylic alcohols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/057—Metal alcoholates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/07—Aldehydes; Ketones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
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Abstract
本发明公开了一种新能源充电电缆用环保稳定剂,该新能源充电电缆用环保稳定剂包括以下重量份数的原料制成:主稳定剂A 15~35份、主稳定剂B15~35份、辅稳定剂5~10份、水滑石10~20份、抗氧剂2~8份、改质剂1~5份、表面活性剂1~5份、增韧剂1~5份、光稳定剂1~5份。相对于现有技术,使用本发明提供的新能源充电电缆用环保稳定剂,所得制品具有优秀的耐高温性能,优异的电绝缘性能;而且,使用该稳定剂制得的耐高温聚氯乙烯材料,可通用到电缆绝缘层和护套层,所制电缆具有耐磨性好、柔韧性高、抗撕裂、抗老化的优势。
Description
技术领域
本发明属于热稳定剂技术领域,尤其涉及一种新能源充电电缆用环保稳定剂。
背景技术
塑料工业多年的改进和发展,已经和人们的生活有着千丝万缕的联系。近年来,随着人民生活水平提高,乘用车数量激增,家电以及汽车用电线电缆领域蓬勃发展。与此同时,国家及时出台并更新相应的材料使用标准。比如,电器用线材方面我们有GB/T8815-2008《电线电缆用软聚氯乙烯塑料》,在乘用车充电线材方面,我们有CQC1103~1105-2015《电动汽车传导充电***用电缆技术规范》系列标准。
中国的国家新标准GB/T 33594-2017《电动汽车充电用电缆》2017年5月发布,并于2017年12月1日正式实施。将电动汽车充电用电缆纳入一个标准的体系中来,既能够让生产制造企业有一个统一的标准作为参考,也可以为质量安全保驾护航。
电动汽车充电电缆作为电动汽车充电设施的基本组成部分,其性能对整个充电过程有着重要的影响。电动汽车充电需要充电电缆来连接汽车与电源,电缆是充电***中比较关键的一部分,直接影响电动汽车充电的安全性。
目前市面上销售的充电电缆料一般分为:耐低温-40℃至高温125℃和耐低温-40℃至耐高温105℃两种等级。据市场调研,耐温125℃料几乎是TPE弹性体,进料渠道多为海外引入,进料周期较长,且价格昂贵。耐温105℃料主要是PVC,根据充电电缆新国标要求,一时是无法达到绝缘等性能要求。
根据充电电缆标准要求,耐高温125℃弹性体TPE料,125℃试验环境下持久3000小时,150℃试验环境下持久240小时,热过载试验温度175℃,要求材料无明显褪变色,抗撕裂性能优良(6N/mm以上,按照橡胶电缆实验方法),该要求极高。如果TPE制品长期受外界或环境因素主要是光、氧、热、水汽、机械应力、高能辐射、电、工业气体(如二氧化碳、硫化氢)等作用,可能会发生老化,使得TPE材料很快丧失其使用性能。
通常为了延长材料使用周期,所选基材会通过化学交联技术或者辐照交联技术来实现大分子的交联反应,使线性聚合物变成具有三围空间网络结构的聚合物。结合交联技术和阻燃技术,所制得的线缆材料才具有更高耐热性、优秀的阻燃性、绝缘性能和机械物理性能。众所周知,辐照交联技术的设备投入成本是高昂的,且环境污染较大。化学交联技术工艺复杂,产品品质有一定的不确定性。通过阻燃技术,也加大了TPE弹性体充电电缆的成本投入。
另外,市售的多数TPE阻燃材料由于含有苯醚成分,耐应力开裂性与耐缺口增长性都很差,而这方面的要求对于电线材料至关重要,抗撕裂性能差可能会造成电线短路,导致严重后果。在耐油性方面遇到的问题也很严重,由于目前充电站大多与加油站配套建设,因此需要电缆耐各种油,可能会面临受油污染后失效的风险。与此同时,TPE电缆不耐磨,易刮花,也是众所周知。
鉴于此,有必要开发一种在新能源充电电缆用聚氯乙烯改性过程中,使其耐热性好、电绝缘性能优良,且韧性高、抗老化的环保稳定剂。
发明内容
本发明的目的在于:针对现有技术的不足,而提供一种耐热性能好、电绝缘性能优良、柔韧性高、抗撕裂、抗老化的新能源充电电缆用环保稳定剂。
为了实现上述目的,本发明采用以下技术方案:
一种新能源充电电缆用环保稳定剂,包括以下重量份数的原料制成:
所述主稳定剂A为硬脂酸铈;
所述主稳定剂B为2-氨基对苯二甲酸镧;
所述辅稳定剂为环氧基封端的聚硅氧烷;
所述水滑石为锌铝镧水滑石和钙铝镧水滑石按重量比1:1形成的混合物;
所述改质剂为甲基丙烯酸甲酯-苯乙烯-有机硅聚合物,所述改质剂具有核壳结构,其核为交联的苯乙烯和有机硅,壳为接枝的聚甲基丙烯酸甲酯,所述有机硅甲基苯基硅油;
所述增韧剂为乙酰柠檬酸三丁酯和聚氧丙烯甘油醚按重量比2:1形成的混合物。
优选的,还包括重量份数为5~10份的硅烷封端聚醚,所述硅烷封端聚醚为端基为三甲氧基硅烷、分子量30000~50000的硅烷封端聚醚。其中,硅烷封端聚醚树脂其主链为聚醚,端基为可水解的硅烷,固化时不起泡,同时其弹性好,具有优良的复原性,可吸收和补偿动态载荷,均匀传递受力,防止材料过早疲劳,而且,在湿气存在下,硅氧烷基水解,得到不稳定的硅醇,该不稳定的硅醇通过分子间脱水缩合或与基材表面羟基脱水缩合生成稳定的聚醚硅-氧-硅交联网状结构,而且由于Si-O键的键能比C-C键的键能高,因而加入硅烷封端聚醚后可以进一步提高PVC材料的耐热性和耐候性。
优选的,还包括重量份数为1~5份的1,3-二甲基-6-氨基尿嘧啶。1,3-二甲基-6-氨基尿嘧啶能吸收PVC生产过程中产生的HCl,还能取代不稳定氯原子,防止“锌烧”,大大增强PVC制品的长期稳定性。
优选的,还包括重量份数为1~5份的甘油锌和1~5份的季戊四醇。将其与主稳定剂A硬脂酸铈复配能够起协同作用,进一步提高热稳定性能。
优选的,还包括重量份数为1~4份的硬脂酰苯甲酰甲烷和2~8份的季戊四醇。将其与主稳定剂B 2-氨基对苯二甲酸镧复配能够起协同作用,进一步提高热稳定性能。
优选的,还包括重量份数为1~5份的丙烯酸酯类加工助剂,所述丙烯酸酯类加工助剂为甲基丙烯酸甲酯和丙烯酸甲酯按重量比1:1形成的混合物。加入混合丙烯酸酯类加工助剂,塑化加工性能优越,不黄变,透光率高;同时可改善压延PVC制品表面水波纹现象,提高表面光滑及平整度;还克服了PVC制品加工性能较差、塑化不佳的缺陷。
优选的,所述表面活性剂为平均分子量为800~1200的聚乙二醇,平均分子量优选为1100~1200。因充电电缆对耐热要求极高,热稳定剂等助剂使用剂量较高,配方***粘度明显提高,造成加工困难,一般通过补偿润滑剂以解决加工环节上的障碍,如润滑剂补偿过多或者使用品种品质不当,后期有极大的析出风险。助剂的析出,极有可能导致体积电阻率下降,电绝缘能力受损。本发明采用的聚乙二醇,充分利用其表面活性剂的作用,一方面起到了物料包覆润滑效用,同时也有一定的增塑作用,有利于生产加工的可持续性。
优选的,所述抗氧剂为四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯和亚磷酸三(2,4-二叔丁基苯基)酯按重量比1:1形成的混合物。采用混合抗氧化剂解决了使用单一类别的受阻酚类抗氧化剂,在初期着色和后期老化力度找不到平衡的问题,使产品具备热稳定性、光稳定性及耐析出性。
优选的,所述光稳定剂为2-(2’,4’-二羟基苯基)-5,6-二羟基苯并三氮唑和1,6-二羟基苯并***按重量比1~2:1形成的混合物。添加该光稳定剂能够抑制或减弱光降解作用,提高制品的抗老化性能。
优选的,所述环氧基封端的聚硅氧烷的制备方法为:将双酚A型环氧树脂加入容器中,并加入甲苯作为溶剂,加热升温,当温度达到110℃以上时,加入辛酸锌作为催化剂,然后加入羟基封端的聚甲基苯基硅氧烷,保温2h~4h,反应过程中水和甲苯被不断蒸出,得到的固体产物在烘箱中烘干后得到环氧基封端的聚硅氧烷。
优选的,该新能源充电电缆用环保稳定剂还包括重量份数为1~5份的纳洛酮。纳洛酮化学名为17-烯丙基-4,5a-环氧基-3,14-二羟基***喃-6-酮,分子式为C19H21NO4,将纳洛酮引进配方中,发现其对稳定剂的性能具有较大的改善效果,其复杂的空间结构像一个保护网,能够防止稳定剂表面的氧化,使得稳定剂具有良好的稳定性能,大大延长稳定剂的使用寿命。此外,其在静止状态下能够保持稳定状态,且在低温下依然具有良好的流动性能,能够调节稳定剂的粘度,这一特性使其能够防止PVC片材在低温下发生老化龟裂现象。
相比于现有技术,本发明至少具有以下有益效果:
1)本发明添加的主稳定剂A硬脂酸铈,其热稳定性能要好于硬脂酸钙/锌等钙锌稳定剂,这是因为硬脂酸铈中的(铈Ceδ+)属于硬酸,与PVC分子链上的多个不稳定氯原子(Clδ-)之间有很强的配位能力,形成络合键,使PVC分子链趋于稳定。同时,铈有+3和+4两种化合价,且相互之间易于转化,所以也能捕捉自由基终止脱HCl反应。此外,铈原子还可以吸附若干个HCl分子,大大降低HCl浓度,有效减缓了PVC分子链的降解,提高了PVC的热稳定性。而且与钙锌稳定剂相比,硬脂酸铈稳定剂的最大扭矩和平衡扭矩小,这有利于生产加工过程中降低电耗;且硬脂酸铈稳定剂能延长塑化时间,这有利PVC塑化更完全。
2)本发明添加的主稳定剂B 2-氨基对苯二甲酸镧能够吸收PVC降解过程中放出的HCl,反应生成了LaCl3,减少了HCl对PVC降解的催化作用,从而提高PVC片材的热稳定性。
3)本发明添加的辅稳定剂环氧基封端的聚硅氧烷;其中,聚硅氧烷拥有优异的耐温性、耐化学腐蚀性以及耐候性等性能,其一般是由多官能度的有机硅醇或者有机硅氧烷缩合而成,具有三维交联网状结构,在该网状结构中,Si-O主链被Si上所连的R基团包覆其中,使得Si-O主链更加不容易受到杂质的攻击,因而主链不易断裂,所以其具有比其他树脂更加优异的热稳定性,其Si-O主链比C-C主链更加能承受住温度的侵蚀,而其良好的空间网络结构则使它在具有更加良好的耐温性的基础上,其他的性能也得到有效提高,如防脱落等,聚硅氧烷的使用使得本发明具有耐高温(200℃以上)、耐高湿、耐黄变等特性。而环氧基作为功能基团进入到有聚硅氧烷的封端部位,可以提高聚硅氧烷的反应活性和附着力,经过改性后的聚硅氧烷在低温下保持较好的柔顺性,具有固化收缩率小等优点。而且其透光率达到97%以上,完全能够透明度高的要求。
4)本发明添加的改质剂与普通的改质剂如MBS型抗冲改质剂不同,该改质剂用有机硅代替耐候性差的丁二烯,具有极佳的耐候性。同时,改质剂S具有核壳结构,其核为交联的苯乙烯和有机硅,壳为接枝的聚甲基丙烯酸甲酯。这种核壳结构使得产品作为单独粒子分散到树脂基材中,提高了冲击性能。有机硅材料的优良弹性,也可以使得聚氯乙烯改性过程中减小一部分增塑剂同样得到很好的柔软性,电绝缘性能明显提高。本发明采用的有机硅甲基苯基硅油为非水溶性,而亲水性硅油因吸潮是可以看作弱半导体,绝缘性能下滑明显。
5)本发明添加的混合增韧剂的能够对制品起到明显增韧及抗撕裂效果。
6)本发明添加的锌铝镧水滑石和钙铝镧水滑石可提高PVC的热稳定性及相容性。PVC主链受热后会逐步脱除HCl形成共轭多烯结构,制品颜色随之加深;在钙/锌水滑石复合热稳定体系中,加热前期水滑石层的镧通过配位作用稳定PVC链上的部分活性氯,同时水滑石层间距的增大能更多地吸附脱出的部分HCl,减慢共轭多烯的形成,保持样品初期白度。
7)相对于现有技术,使用本发明提供的新能源充电电缆用环保稳定剂,所得制品具有优秀的耐高温性能,优异的电绝缘性能;而且,使用该稳定剂制得的耐高温聚氯乙烯材料,可通用到电缆绝缘层和护套层,所制电缆具有耐磨性好、柔韧性高、抗撕裂、抗老化的优势。
具体实施方式
为使本发明的技术方案和优点更加清楚,下面将结合具体实施例,对本发明的技术方案进行清楚、完整地描述,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。
一种新能源充电电缆用环保稳定剂,包括以下重量份数的原料制成:
所述主稳定剂A为硬脂酸铈;
所述主稳定剂B为2-氨基对苯二甲酸镧;
所述辅稳定剂为环氧基封端的聚硅氧烷;
所述水滑石为锌铝镧水滑石和钙铝镧水滑石按重量比1:1形成的混合物;
所述改质剂为甲基丙烯酸甲酯-苯乙烯-有机硅聚合物,所述改质剂具有核壳结构,其核为交联的苯乙烯和有机硅,壳为接枝的聚甲基丙烯酸甲酯,所述有机硅甲基苯基硅油;
所述增韧剂为乙酰柠檬酸三丁酯和聚氧丙烯甘油醚按重量比2:1形成的混合物。
其中,环氧基封端的聚硅氧烷的制备方法为:将双酚A型环氧树脂加入容器中,并加入甲苯作为溶剂,加热升温,当温度达到110℃以上时,加入辛酸锌作为催化剂,然后加入羟基封端的聚甲基苯基硅氧烷,保温2h~4h,反应过程中水和甲苯被不断蒸出,得到的固体产物在烘箱中烘干后得到环氧基封端的聚硅氧烷。
其中,2-氨基对苯二甲酸镧的制备方法为:称取适量的2-氨基对苯二甲酸置于容器中,用稀氨水进行溶解,调节溶液pH为6~7,制成2-氨基对苯二甲酸氨水溶液。将容器置于60℃的恒温水浴锅中,搅拌,按n(氯化镧)∶n(2-氨基对苯二甲酸氨)=2∶3的摩尔比取2-氨基对苯二甲酸氨,用蠕动泵逐滴加入氯化镧溶液,滴加完毕后用稀氨水将溶液pH调至6~7,60℃水浴恒温搅拌4~5h。然后将容器静置,待冷却至室温,用真空泵进行抽滤,用去离子水洗涤3~5次,将所得配合物在75℃下进行烘干,得到2-氨基对苯二甲酸镧。
本发明添加的主稳定剂A硬脂酸铈,其热稳定性能要好于硬脂酸钙/锌等钙锌稳定剂,这是因为硬脂酸铈中的(铈Ceδ+)属于硬酸,与PVC分子链上的多个不稳定氯原子(Clδ-)之间有很强的配位能力,形成络合键,使PVC分子链趋于稳定。同时,铈有+3和+4两种化合价,且相互之间易于转化,所以也能捕捉自由基终止脱HCl反应。此外,铈原子还可以吸附若干个HCl分子,大大降低HCl浓度,有效减缓了PVC分子链的降解,提高了PVC的热稳定性。而且与钙锌稳定剂相比,硬脂酸铈稳定剂的最大扭矩和平衡扭矩小,这有利于生产加工过程中降低电耗;且硬脂酸铈稳定剂能延长塑化时间,这有利PVC塑化更完全。
本发明添加的主稳定剂B 2-氨基对苯二甲酸镧能够吸收PVC降解过程中放出的HCl,反应生成了LaCl3,减少了HCl对PVC降解的催化作用,从而提高PVC片材的热稳定性。
本发明添加的辅稳定剂环氧基封端的聚硅氧烷;其中,聚硅氧烷拥有优异的耐温性、耐化学腐蚀性以及耐候性等性能,其一般是由多官能度的有机硅醇或者有机硅氧烷缩合而成,具有三维交联网状结构,在该网状结构中,Si-O主链被Si上所连的R基团包覆其中,使得Si-O主链更加不容易受到杂质的攻击,因而主链不易断裂,所以其具有比其他树脂更加优异的热稳定性,其Si-O主链比C-C主链更加能承受住温度的侵蚀,而其良好的空间网络结构则使它在具有更加良好的耐温性的基础上,其他的性能也得到有效提高,如防脱落等,聚硅氧烷的使用使得本发明具有耐高温(200℃以上)、耐高湿、耐黄变等特性。而环氧基作为功能基团进入到有聚硅氧烷的封端部位,可以提高聚硅氧烷的反应活性和附着力,经过改性后的聚硅氧烷在低温下保持较好的柔顺性,具有固化收缩率小等优点。而且其透光率达到97%以上,完全能够透明度高的要求。
本发明添加的改质剂与普通的改质剂如MBS型抗冲改质剂不同,该改质剂用有机硅代替耐候性差的丁二烯,具有极佳的耐候性。同时,改质剂S具有核壳结构,其核为交联的苯乙烯和有机硅,壳为接枝的聚甲基丙烯酸甲酯。这种核壳结构使得产品作为单独粒子分散到树脂基材中,提高了冲击性能。有机硅材料的优良弹性,也可以使得聚氯乙烯改性过程中减小一部分增塑剂同样得到很好的柔软性,电绝缘性能明显提高。本发明采用的有机硅甲基苯基硅油为非水溶性,而亲水性硅油因吸潮是可以看作弱半导体,绝缘性能下滑明显。
本发明添加的混合增韧剂的能够对制品起到明显增韧及抗撕裂效果。
本发明添加的锌铝镧水滑石和钙铝镧水滑石可提高PVC的热稳定性及相容性。PVC主链受热后会逐步脱除HCl形成共轭多烯结构,制品颜色随之加深;在钙/锌水滑石复合热稳定体系中,加热前期水滑石层的镧通过配位作用稳定PVC链上的部分活性氯,同时水滑石层间距的增大能更多地吸附脱出的部分HCl,减慢共轭多烯的形成,保持样品初期白度。
相对于现有技术,使用本发明提供的新能源充电电缆用环保稳定剂,所得制品具有优秀的耐高温性能,优异的电绝缘性能;而且,使用该稳定剂制得的耐高温聚氯乙烯材料,可通用到电缆绝缘层和护套层,所制电缆具有耐磨性好、柔韧性高、抗撕裂、抗老化的优势。
优选的,还包括重量份数为5~10份的硅烷封端聚醚,所述硅烷封端聚醚为端基为三甲氧基硅烷、分子量30000~50000的硅烷封端聚醚。其中,硅烷封端聚醚树脂其主链为聚醚,端基为可水解的硅烷,固化时不起泡,同时其弹性好,具有优良的复原性,可吸收和补偿动态载荷,均匀传递受力,防止材料过早疲劳,而且,在湿气存在下,硅氧烷基水解,得到不稳定的硅醇,该不稳定的硅醇通过分子间脱水缩合或与基材表面羟基脱水缩合生成稳定的聚醚硅-氧-硅交联网状结构,而且由于Si-O键的键能比C-C键的键能高,因而加入硅烷封端聚醚后可以进一步提高PVC材料的耐热性和耐候性。
优选的,还包括重量份数为1~5份的1,3-二甲基-6-氨基尿嘧啶。1,3-二甲基-6-氨基尿嘧啶能吸收PVC生产过程中产生的HCl,还能取代不稳定氯原子,防止“锌烧”,大大增强PVC制品的长期稳定性。
优选的,还包括重量份数为1~5份的甘油锌和1~5份的季戊四醇。将其与主稳定剂A硬脂酸铈复配能够起协同作用,进一步提高热稳定性能。
优选的,还包括重量份数为1~4份的硬脂酰苯甲酰甲烷和2~8份的季戊四醇。将其与主稳定剂B 2-氨基对苯二甲酸镧复配能够起协同作用,进一步提高热稳定性能。
优选的,还包括重量份数为1~5份的丙烯酸酯类加工助剂,所述丙烯酸酯类加工助剂为甲基丙烯酸甲酯和丙烯酸甲酯按重量比1:1形成的混合物。加入混合丙烯酸酯类加工助剂,塑化加工性能优越,不黄变,透光率高;同时可改善压延PVC制品表面水波纹现象,提高表面光滑及平整度;还克服了PVC制品加工性能较差、塑化不佳的缺陷。
优选的,所述表面活性剂为平均分子量为800~1200的聚乙二醇,平均分子量优选为1100~1200。因充电电缆对耐热要求极高,热稳定剂等助剂使用剂量较高,配方***粘度明显提高,造成加工困难,一般通过补偿润滑剂以解决加工环节上的障碍,如润滑剂补偿过多或者使用品种品质不当,后期有极大的析出风险。助剂的析出,极有可能导致体积电阻率下降,电绝缘能力受损。本发明采用的聚乙二醇,充分利用其表面活性剂的作用,一方面起到了物料包覆润滑效用,同时也有一定的增塑作用,有利于生产加工的可持续性。
优选的,所述抗氧剂为四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯和亚磷酸三(2,4-二叔丁基苯基)酯按重量比1:1形成的混合物。采用混合抗氧化剂解决了使用单一类别的受阻酚类抗氧化剂,在初期着色和后期老化力度找不到平衡的问题,使产品具备热稳定性、光稳定性及耐析出性。
优选的,所述光稳定剂为2-(2’,4’-二羟基苯基)-5,6-二羟基苯并三氮唑和1,6-二羟基苯并***按重量比1~2:1形成的混合物。添加该光稳定剂能够抑制或减弱光降解作用,提高制品的抗老化性能。
优选的,该新能源充电电缆用环保稳定剂还包括重量份数为1~5份的纳洛酮。纳洛酮化学名为17-烯丙基-4,5a-环氧基-3,14-二羟基***喃-6-酮,分子式为C19H21NO4,将纳洛酮引进配方中,发现其对稳定剂的性能具有较大的改善效果,其复杂的空间结构像一个保护网,能够防止稳定剂表面的氧化,使得稳定剂具有良好的稳定性能,大大延长稳定剂的使用寿命。此外,其在静止状态下能够保持稳定状态,且在低温下依然具有良好的流动性能,能够调节稳定剂的粘度,这一特性使其能够防止PVC片材在低温下发生老化龟裂现象。
此外,本发明还提供一种所述的新能源充电电缆用环保稳定剂的制备方法,包括以下步骤:
1)按照重量份称取各原料;
2)将步骤1)称取的所有原料放入高速混料机在60~80℃下混料10-30分钟,其转速为1000-2000转/分钟,混合均匀;
3)将步骤2)混合物料冷却至35℃,即可获得所述新能源充电电缆用环保稳定剂。
为了进一步理解本发明,下面结合实施例对本发明提供的新能源充电电缆用环保稳定剂及其制备方法进行详细说明,但本发明的保护范围不受以下实施例的限制。
实施例1
本实施例提供一种新能源充电电缆用环保稳定剂,包括以下重量份数的原料制成:主稳定剂A 15份、主稳定剂B 15份、辅稳定剂5份、水滑石10份、抗氧剂2份、改质剂1份、表面活性剂1份、增韧剂1份、光稳定剂1份。
其中,所述主稳定剂A为硬脂酸铈;
所述主稳定剂B为2-氨基对苯二甲酸镧;
所述辅稳定剂为环氧基封端的聚硅氧烷;
所述水滑石为锌铝镧水滑石和钙铝镧水滑石按重量比1:1形成的混合物;
所述改质剂为甲基丙烯酸甲酯-苯乙烯-有机硅聚合物,所述改质剂具有核壳结构,其核为交联的苯乙烯和有机硅,壳为接枝的聚甲基丙烯酸甲酯,所述有机硅甲基苯基硅油;
所述增韧剂为乙酰柠檬酸三丁酯和聚氧丙烯甘油醚按重量比2:1形成的混合物。
所述表面活性剂为平均分子量为1100的聚乙二醇。
所述抗氧剂为四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯和亚磷酸三(2,4-二叔丁基苯基)酯按重量比1:1形成的混合物。
所述光稳定剂为2-(2’,4’-二羟基苯基)-5,6-二羟基苯并三氮唑和1,6-二羟基苯并***按重量比2:1形成的混合物。
该新能源充电电缆用环保稳定剂的制备方法,包括以下步骤:
1)按照重量份称取各原料;
2)将步骤1)称取的所有原料放入高速混料机在75℃下混料20分钟,其转速为1500转/分钟,混合均匀;
3)将步骤2)混合物料冷却至35℃,即可获得所述新能源充电电缆用环保稳定剂。
实施例2
与实施例1不同的是,本实施例提供一种新能源充电电缆用环保稳定剂,包括以下重量份数的原料制成:主稳定剂A 35份、主稳定剂B 35份、辅稳定剂10份、水滑石20份、抗氧剂8份、改质剂5份、表面活性剂5份、增韧剂5份、光稳定剂5份。
其中,所述主稳定剂A为硬脂酸铈;
所述主稳定剂B为2-氨基对苯二甲酸镧;
所述辅稳定剂为环氧基封端的聚硅氧烷;
所述水滑石为锌铝镧水滑石和钙铝镧水滑石按重量比1:1形成的混合物;
所述改质剂为甲基丙烯酸甲酯-苯乙烯-有机硅聚合物,所述改质剂具有核壳结构,其核为交联的苯乙烯和有机硅,壳为接枝的聚甲基丙烯酸甲酯,所述有机硅甲基苯基硅油;
所述增韧剂为乙酰柠檬酸三丁酯和聚氧丙烯甘油醚按重量比2:1形成的混合物。
所述表面活性剂为平均分子量为1200的聚乙二醇。
所述抗氧剂为四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯和亚磷酸三(2,4-二叔丁基苯基)酯按重量比1:1形成的混合物。
所述光稳定剂为2-(2’,4’-二羟基苯基)-5,6-二羟基苯并三氮唑和1,6-二羟基苯并***按重量比1:1形成的混合物。
其他同实施例1,这里不再赘述。
实施例3
与实施例1不同的是,本实施例提供一种新能源充电电缆用环保稳定剂,包括以下重量份数的原料制成:主稳定剂A 25份、主稳定剂B 25份、辅稳定剂8份、水滑石15份、抗氧剂5份、改质剂3份、表面活性剂3份、增韧剂3份、光稳定剂2份。
其他同实施例1,这里不再赘述。
实施例4
与实施例1不同的是,本实施例提供一种新能源充电电缆用环保稳定剂,还包括重量份数为8份的硅烷封端聚醚,所述硅烷封端聚醚为端基为三甲氧基硅烷、分子量30000~50000的硅烷封端聚醚。
其他同实施例1,这里不再赘述。
实施例5
与实施例1不同的是,本实施例提供一种新能源充电电缆用环保稳定剂,还包括重量份数为3份的1,3-二甲基-6-氨基尿嘧啶。
其他同实施例1,这里不再赘述。
实施例6
与实施例1不同的是,本实施例提供一种新能源充电电缆用环保稳定剂,还包括重量份数为2份的甘油锌和4份的季戊四醇。
其他同实施例1,这里不再赘述。
实施例7
与实施例1不同的是,本实施例提供一种新能源充电电缆用环保稳定剂,还包括重量份数为2份的硬脂酰苯甲酰甲烷和6份的季戊四醇。
其他同实施例1,这里不再赘述。
实施例8
与实施例1不同的是,本实施例提供一种新能源充电电缆用环保稳定剂,还包括重量份数为2份的丙烯酸酯类加工助剂,所述丙烯酸酯类加工助剂为甲基丙烯酸甲酯和丙烯酸甲酯按重量比1:1形成的混合物。
其他同实施例1,这里不再赘述。
实施例9
与实施例1不同的是,本实施例提供一种新能源充电电缆用环保稳定剂,还包括重量份数为3份的纳洛酮。
其他同实施例1,这里不再赘述。
实施例10
与实施例1不同的是,本实施例提供一种新能源充电电缆用环保稳定剂,还包括重量份数为8份的硅烷封端聚醚、3份的1,3-二甲基-6-氨基尿嘧啶。
其他同实施例1,这里不再赘述。
实施例11
与实施例1不同的是,本实施例提供一种新能源充电电缆用环保稳定剂,还包括重量份数为8份的硅烷封端聚醚、3份的纳洛酮。
其他同实施例1,这里不再赘述。
实施例12
与实施例1不同的是,本实施例提供一种新能源充电电缆用环保稳定剂,还包括重量份数为8份的硅烷封端聚醚、2份的甘油锌和4份的季戊四醇。
其他同实施例1,这里不再赘述。
实施例13
与实施例1不同的是,本实施例提供一种新能源充电电缆用环保稳定剂,还包括重量份数为8份的硅烷封端聚醚、2份的硬脂酰苯甲酰甲烷和6份的季戊四醇。
其他同实施例1,这里不再赘述。
实施例14
与实施例1不同的是,本实施例提供一种新能源充电电缆用环保稳定剂,还包括重量份数为2份的甘油锌、2份的硬脂酰苯甲酰甲烷和10份的季戊四醇。
其他同实施例1,这里不再赘述。
实施例15
与实施例1不同的是,本实施例提供一种新能源充电电缆用环保稳定剂,还包括重量份数为1,3-二甲基-6-氨基尿嘧啶、2份的甘油锌、2份的硬脂酰苯甲酰甲烷和10份的季戊四醇。
其他同实施例1,这里不再赘述。
分别对实施例1-15的稳定剂进行性能测试,测试结果见表1。
表1热稳定性、抗紫外性能测试结果
由表1的测试结果可知:
1)产品在200℃热稳定性测试时长均大于55min,表明具有良好的耐热性能;在紫外光吸光度(波长范围230-360nm)≤0.3测试中,本发明实施例均小于0.2,说明具备较佳的抗紫外老化性能。
2)对比实施例1、4、10~13可知,添加硅烷封端聚醚的热稳定性、抗紫外老化性能均比没添加的效果好,而且,当硅烷封端聚醚与1,3-二甲基-6-氨基尿嘧啶、甘油锌和季戊四醇、硬脂酰苯甲酰甲烷和季戊四醇、或纳洛酮复配时热稳定性、抗紫外老化效果更佳。
3)对比实施例1、5、10、15可知,加入1,3-二甲基-6-氨基尿嘧啶,产品的热稳定性、抗紫外老化效果均比没添加时效果好,而且当1,3-二甲基-6-氨基尿嘧啶与硅烷封端聚醚、或与甘油锌、硬脂酰苯甲酰甲烷和季戊四醇复配时热稳定性效果更加。
4)对比实施例1、9、11可知,加入纳洛酮,产品的热稳定性明显优于没有添加的性能,这是因为纳洛酮的三维网络结构,能够有效提高稳定剂的耐热性,而且当纳洛酮与硅烷封端聚醚复配时热稳定性更好。
5)对比实施例1、6、12、14~15可知,加入甘油锌和季戊四醇,产品的热稳定性均比没添加时效果好,而且当甘油锌和季戊四醇与硅烷封端聚醚、硬脂酰苯甲酰甲烷、或1,3-二甲基-6-氨基尿嘧啶复配时热稳定性效果更好。
6)对比实施例1、7、13、14~15可知,加入硬脂酰苯甲酰甲烷和季戊四醇,产品的热稳定性均比没添加时效果好,而且硬脂酰苯甲酰甲烷和季戊四醇与硅烷封端聚醚、甘油锌、或1,3-二甲基-6-氨基尿嘧啶复配时热稳定性效果更好。
根据上述说明书的揭示和教导,本发明所属领域的技术人员还能够对上述实施方式进行变更和修改。因此,本发明并不局限于上述的具体实施方式,凡是本领域技术人员在本发明的基础上所作出的任何显而易见的改进、替换或变型均属于本发明的保护范围。此外,尽管本说明书中使用了一些特定的术语,但这些术语只是为了方便说明,并不对本发明构成任何限制。
Claims (3)
1.一种新能源充电电缆用环保稳定剂,其特征在于,包括以下重量份数的原料制成:
所述主稳定剂A为硬脂酸铈;
所述主稳定剂B为2-氨基对苯二甲酸镧;
所述辅稳定剂为环氧基封端的聚硅氧烷;
所述水滑石为锌铝镧水滑石和钙铝镧水滑石按重量比1:1形成的混合物;
所述改质剂为甲基丙烯酸甲酯-苯乙烯-有机硅聚合物,所述改质剂具有核壳结构,其核为交联的苯乙烯和有机硅,壳为接枝的聚甲基丙烯酸甲酯,所述有机硅为甲基苯基硅油;
所述增韧剂为乙酰柠檬酸三丁酯和聚氧丙烯甘油醚按重量比2:1形成的混合物;
还包括重量份数为5~10份的硅烷封端聚醚,所述硅烷封端聚醚为端基为三甲氧基硅烷、分子量30000~50000的硅烷封端聚醚;
还包括重量份数为1~4份的硬脂酰苯甲酰甲烷和2~8份的季戊四醇;
所述表面活性剂为平均分子量为800~1200的聚乙二醇;
所述抗氧剂为四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯和亚磷酸三(2,4-二叔丁基苯基)酯按重量比1:1形成的混合物;
所述光稳定剂为2-(2’,4’-二羟基苯基)-5,6-二羟基苯并三氮唑和1,6-二羟基苯并***按重量比1~2:1形成的混合物;
所述环氧基封端的聚硅氧烷的制备方法为:将双酚A型环氧树脂加入容器中,并加入甲苯作为溶剂,加热升温,当温度达到110℃以上时,加入辛酸锌作为催化剂,然后加入羟基封端的聚甲基苯基硅氧烷,保温2h~4h,反应过程中水和甲苯被不断蒸出,得到的固体产物在烘箱中烘干后得到环氧基封端的聚硅氧烷。
2.根据权利要求1所述的新能源充电电缆用环保稳定剂,其特征在于:还包括重量份数为1~5份的1,3-二甲基-6-氨基尿嘧啶。
3.根据权利要求1所述的新能源充电电缆用环保稳定剂,其特征在于:还包括重量份数为1~5份的丙烯酸酯类加工助剂,所述丙烯酸酯类加工助剂为甲基丙烯酸甲酯和丙烯酸甲酯按重量比1:1形成的混合物。
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