CN111136851A - 一种高强度耐腐蚀制品及其制备方法 - Google Patents
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Abstract
本发明公开了一种高强度耐腐蚀制品的制备方法,所述的高强度耐腐蚀制品包括热固性树脂,以及包覆于热固性树脂中的金属;所述的热固性树脂表面致密,内部具有泡孔,且泡孔尺寸由内而外从和金属表面接触的内表面至树脂的外表面逐渐缩小。本发明产品抗压能力强、耐腐蚀能力强且易清洁。
Description
技术领域
本发明涉及一种高强度耐腐蚀制品及其制备方法。
背景技术
卫浴地漏材料以不锈钢、铜锌合金等金属材料及塑料材质为主,其中普通塑料(PP/ABS/PVC)地漏质感差,密度小,不耐高温、不耐划伤;不锈钢地漏、电镀地漏不耐酸性腐蚀,容易生锈;金属材质表面处理工艺(喷涂等)易脱落。
针对以上问题,本体地漏应运而生:
1.高性能热塑性材料:聚苯硫醚(PPS)、聚甲醛(POM)、对苯二甲酸四次甲基酯(PBT) 等;这些高性能热塑性材料性能优异,但存在质感差、塑料质感强,耐冲击一般,能耗大等缺点;
2.特种陶瓷地漏:例如氧化锆陶瓷地漏;但其存在强度低、耐冲击性能差,耐污性不足,能耗大等。
3.其他热固性材料:注塑或者模压后,脆性大、强度低,耐污性不佳/外观质量不佳等。
发明内容
本发明的主要目的,在于提供一种高强度(抗压)耐腐蚀制品。
本发明解决其技术问题的所采用的技术方案是:
一种高强度耐腐蚀制品的制备方法,包括如下步骤:
1)将金属样品加工成所需形状;
2)树脂原料制备成待发泡团状复合树脂,并形成待发泡团状树脂-金属-待发泡团状树脂三明治结构放入模具中;其中,所述的树脂原料中包括不饱和聚酯和发泡剂,且发泡剂的发泡温度大于不饱和聚酯的最低热固成型温度;
3)模具合模、加热使复合树脂固化成型,在此过程中采用包括电磁加热在内的方式加热金属,其中,模具的加热温度低于金属的加热温度,且等于或高于不饱和聚酯的最低热固成型温度;金属的加热温度等于或大于发泡剂的发泡温度。
优选地,发泡剂的发泡温度高于不饱和聚酯的最低热固成型温度,且低于不饱和聚酯的最高热固成型温度。
优选地,金属的加热温度比发泡剂的发泡温度高0.1-10℃。
在本发明中,所述的高强度耐腐蚀制品包括地漏、台盆、置物架、小便斗等中的至少一种。
优选地,所述的金属包括铁或不锈钢中的至少一种。
优选地,按质量比,所述的树脂原料包括:
不饱和聚酯30%-50%;增强纤维20%~40%、发泡剂:0.5%~4%;
气相白炭黑:0.5%~1.5%;含氟化合物:1%~8%;增稠剂:0.05%-0.1%;
低收缩剂1%-8%:引发剂:0.5%-3%;其他助剂1.5%~3%;
无机改性填料余量;
其中,所述的不饱和聚酯包括邻苯型、间苯型、双酚A型、新戊二醇型中的一种或者其组合;
无机改性填料包括碳酸钙、硫酸钡、水合氧化铝、纳米陶瓷粉中的至少一种,粒径为200 目-800目;
增强纤维包括玻纤/碳纤/芳纶纤维中的至少一种,4-10mm;
发泡剂为核壳聚合物、偶氮二甲酰胺(AC)、超临界气体中的至少一种;所述的超临界气体可以是二氧化碳、氮气。
气相白炭黑,粒径5-800nm;
含氟化合物:包括甲基丙烯酸含氟酯、氟硅烷中的至少一种;
在本发明的优选实施例中,
增稠剂包括氢氧化钙、氧化镁中的至少一种;
低收缩剂包括PMMA(聚甲基丙烯酸甲酯)/PE(聚乙烯)/PS(聚苯乙烯)中的至少一种;
引发剂为过氧化物;
其他助剂包括阻聚剂、内脱模剂、着色剂等中的至少一种;
无机填料包括碳酸钙、硫酸钡、水合氧化铝、纳米陶瓷粉中的至少一种。
优选地,金属固定于模具中,其中模具上/下模具有电磁加热装置,可以对嵌入至树脂中的金属嵌入模块进行隔空加热。
优选地,对金属及树脂进行加热时,模具进行排气保压50s-300s。
优选地,步骤2)中,树脂制备成待发泡团状复合树脂,并形成发泡团状树脂-金属-待发泡团状树脂三明治结构放入模具中。
优选地,待发泡团状复合树脂的制备方法包括:
(1)混炼捏合:将不饱和聚酯均匀混合搅拌4-6h,加入包括填料、疏水气相白炭黑、引发剂/阻聚剂、玻纤在内的原料进行混炼捏合5-15min,温度控制≤30℃,制备均匀的团状树脂;
(2)发泡捏合:将发泡剂和其它树脂成分立刻缓慢加入至上述团状树脂,采用捏合机进一步捏合3-5min,制备待发泡团状复合树脂。
优选地,发泡剂选用核壳聚合物,且经过如下的表面处理:将核壳聚合物表面喷洒硅烷偶联剂,搅拌均匀后将处理的核壳聚合物定量浸泡至聚酯体系中,并采用超声波均匀分散、搅拌10-20min,温度控制≤30℃。
热固性树脂的常规加热方法是采用由外至内进行传热成型,针对于该种材料采用传统加热处理方式,上模固化过程中小分子析出释放气体,容易出现表面质量不佳、气痕严重、耐污、耐腐蚀性能较差等问题,本发明采用嵌入式金属结构,将金属结构包覆嵌入至制品内部进行内外同时加热处理,既能显著提升产品的强度、避免腐蚀,又能够显著改善产品表面质量,提升产品表面致密性、提升耐污、耐腐蚀性能;同时本发明采用微孔发泡结构实现“双三明治”结构,成本节约、密度降低的同时能够提升材料的韧性及抗冲击性能。其原理为:
1.微纳孔发泡结构-增韧:
微孔结构能够在产品受到冲击时产生大量银纹,这个过程会吸收大量的能量,减缓冲击带来的伤害:当微孔较为均匀的分布在材料内部时,应力场不在是均匀的,冲击点处的力会通过微纳孔结构向其他微孔结构进行消耗,逐渐产生大量银纹,使应力扩散中止,不至于产生破坏性的裂纹或开裂,宏观表现即材料在受到外力冲击或者高低温内应力时,材料内部可自我消化缓冲,韧性增强,不至于产生产品破裂等现象;优选核壳聚合物,避免AC或超临界气体在玻纤表面形成成核点,形成缺陷;
2.双“三明治”结构-增韧/降本/降密度:
内嵌加热金属结构,内外加热单元同时工作,促使内部先发泡先成型、表面结皮,构造泡孔三明治结构:上/下模固化温度低于发泡温度,上/下表面无发泡,缓慢流平后结皮定型,表面结皮致密均匀,内部由内而外进行发泡,泡孔尺寸由内而外逐渐减小,形成“三明治”结构,同时内嵌金属结构,外包覆热固性改性树脂,形成更稳定的“三明治”结构整体结构更稳定;
3.表面结皮-耐污/耐腐蚀/气痕改善:
上下模具温度低于发泡材料的膨胀温度(即发泡温度),在模压过程中,团状树脂流动性强,在模具的压力下平整铺展开来,并固化成型,表面致密均匀、显著改善传统模压气痕严重等缺陷;同时由于制品厚度较大,单纯上下模具加热会出现内部固化速度慢或不固化产生内部开裂,该种固化工艺能够有效解决该问题;
本发明的制品耐腐蚀性能优异、强度高、表面质量好、密度低成本低;其中采用核壳聚合物微孔发泡结构能够较好的提升产品的强度及耐冲击性能,采用金属嵌入结构加热方式既可以显著提升产品的强度和承载力,又可以通过该种制备工艺改善产品表面缺陷、提升产品质量及产品耐腐蚀耐腐蚀性能。
附图说明
下面结合附图和实施例对本发明作进一步说明。
图1为本发明的原理示意图;
图2为实施例1的地漏产品(左)和现有的地漏产品(右)对比实物图
具体实施方式
实施例1
以地漏产品为例,本发明的技术方案如下:
基础方案配方:
不饱和聚酯40%:AROPOL MR14029树脂
无机改性填料余量:硫酸钡
玻璃纤维30%:泰安玻璃纤维有限公司,玻纤长度5mm-8mm
核壳聚合物发泡剂:2%:北京沪锦科技有限公司、PG16发泡剂
气相白炭黑:1%:赢创德固赛疏水气相白炭黑
甲基丙烯酸含氟酯:5%:美国Aldrich公司
增稠剂:0.1%氧化镁
低收缩剂:PMMA/PE/PS,在本实施例中采用PMMA,使用量为5%
引发剂:TBPB过氧化苯甲酸叔丁酯,1.5%;购买于阿科玛公司、TBPO过氧化-2-乙基已酸叔丁酯,1.5%,购买于阿克苏公司
其他助剂1.5%
导热金属结构:不锈钢、铁等,冲压或者浇注成型,厚度0.5mm
制备方法:
1)核壳聚合物表面处理:将核壳聚合物表面喷洒硅烷偶联剂,搅拌均匀后将处理的核壳聚合物定量浸泡至不饱和聚酯体系中,并采用超声波均匀分散、搅拌15min,温度控制≤30℃;
2)气相白炭黑表面处理:将气相白炭黑加入去离子水中搅拌均匀,再添加10%~20%的硅烷偶联剂升温充分回流反应,烘箱100℃烘烤制备疏水改性气相白炭黑;
3)混炼捏合:将不饱和聚酯均匀混合搅拌5h,加入填料(含水率≤0.1%)、疏水气相白炭黑、引发剂/阻聚剂、玻纤(含水率≤0.1%)等进行混炼捏合10min,温度控制≤30℃,制备均匀的团状树脂;
4)发泡捏合:将步骤1)中分散的核壳聚合物+树脂体系立刻缓慢加入至上述团状树脂 (均匀加入),采用捏合机进一步捏合4min,完成制备待发泡团状复合树脂,放置在25℃保存;
5)金属样片成型:将金属样品冲压成型制备嵌入结构模块;
6)金属嵌入模块表面处理:采用喷砂/化学蚀刻工艺对金属嵌入结构模块进行表面粗化处理,之后采用超声波清洗,在高温烘箱中进行预处理>1h;
7)模压成型:模具预热,依次将待发泡团状树脂、金属嵌入模块、待发泡团状树脂放入模具中固定(三明治结构),其中金属嵌入模块可固定至模具中,模具的上/下模具有电磁加热装置,可以对嵌入至树脂中的金属嵌入模块进行隔空加热。之后,将模具和金属都先加热至树脂的热固成型温度,再利用电磁加热装置单独将金属温度提高5-20度。排气保压50s-300s;
8)飞边处理:取出冷却后进行飞边处理。
结果
本发明地漏耐腐蚀性能好/疏水性佳,不易受外界环境腐蚀及污染,强度高、抗冲击性能好、疏水易洁,相对于传统不锈钢地漏产品性能优势大,同时该材料地漏采用模压或注塑工艺,产品结构可设计性强、外观颜色可设计,具有不锈钢或金属地漏无法达到的性能;
实施例2
以小便斗产品为例,本发明的技术方案如下:
基础方案配方:
不饱和聚酯45%:AROPOL MR14029树脂
无机改性填料:硫酸钡余量%
玻璃纤维18%:泰安玻璃纤维有限公司4-6mm
核壳聚合物发泡剂:0.5%:北京沪锦科技有限公司PG18发泡剂
气相白炭黑:1.5%:赢创德固赛疏水气相白炭黑
甲基丙烯酸含氟酯:3.5%:美国Aldrich公司
增稠剂:0.08%氢氧化钙、氧化镁
低收缩剂:PMMA
引发剂:TBPB过氧化苯甲酸叔丁酯,购买于阿科玛公司,1.5%、TBPO过氧化-2-乙基已酸叔丁酯,购买于阿克苏公司,1.5%;
其他助剂1.5%
导热金属结构:不锈钢冲压成型,厚度1.5mm
制备方法:
1)核壳聚合物表面处理:将核壳聚合物表面喷洒硅烷偶联剂,搅拌均匀后将处理的核壳聚合物定量浸泡至不饱和聚酯体系中,并采用超声波均匀分散、搅拌15min,温度控制≤30℃;
2)气相白炭黑表面处理:将气相白炭黑加入去离子水中搅拌均匀,再添加10%~20%的硅烷偶联剂升温回流反应,烘箱100℃烘烤制备疏水改性气相白炭黑;
3)混炼捏合:将不饱和聚酯均匀混合搅拌5h,加入填料(含水率≤0.1%)、疏水气相白炭黑、引发剂/阻聚剂、玻纤(含水率≤0.1%)等进行混炼捏合10min,温度控制≤30℃,制备均匀的团状树脂;
4)发泡捏合:将步骤1中分散的核壳聚合物+树脂体系立刻缓慢加入至上述团状树脂(均匀加入),采用捏合机进一步捏合4min,完成制备待发泡团状复合树脂,放置在25℃保存;
5)金属样片成型:将金属样品冲压成型制备嵌入结构模块,并加工焊接支撑结构,用于安装与墙面;
6)金属嵌入模块表面处理:采用喷砂/化学蚀刻工艺对金属嵌入结构模块进行表面粗化处理,之后采用超声波清洗,在高温烘箱中进行预处理>1h;
7)模压成型:模具预热,依次将待发泡团状树脂、金属嵌入模块、待发泡团状树脂放入模具中固定(三明治结构),其中金属嵌入模块可固定至模具中,其中模具上/下模具有电磁加热装置,可以对嵌入至树脂中的金属嵌入模块进行隔空加热。之后,将模具和金属都先加热至树脂的热固成型温度,再利用电磁加热装置单独将金属温度提高5-20度。排气保压 50s~300s;
8)飞边处理:取出冷却后进行飞边处理。
本方案材料小便斗产品密度低、抗冲击性能高,不易破碎,便于运输,同时该小便斗疏水性好易清洁,耐腐蚀性能佳,不易发生腐蚀及生锈,相对于普通陶瓷小便斗和不锈钢小便斗,具有明显的综合性能优势;同时该材料相对于不锈钢小便斗和陶瓷小便斗,具有尺寸稳定性更好、颜色可设计性强、生产能耗低等一系列优点。
Claims (10)
1.一种高强度耐腐蚀制品的制备方法,包括如下步骤:
1)将金属样品加工成所需形状;
2)树脂原料制备成待发泡团状复合树脂,并形成待发泡团状树脂-金属-待发泡团状树脂三明治结构放入模具中;其中,所述的树脂原料中包括不饱和聚酯和发泡剂,且发泡剂的发泡温度大于不饱和聚酯的最低热固成型温度;
3)模具合模、加热使复合树脂固化成型,在此过程中采用包括电磁加热在内的方式加热金属,其中,模具的加热温度低于金属的加热温度,且等于或高于不饱和聚酯的最低热固成型温度;金属的加热温度等于或大于发泡剂的发泡温度。
2.如权利要求1所述的一种高强度耐腐蚀制品的制备方法,其特征在于:发泡剂的发泡温度高于不饱和聚酯的最低热固成型温度,且低于不饱和聚酯的最高热固成型温度。
3.如权利要求1所述的一种高强度耐腐蚀制品的制备方法,其特征在于:金属的加热温度比发泡剂的发泡温度高0.1-10℃。
4.如权利要求1所述的一种高强度耐腐蚀制品的制备方法,其特征在于:金属的加热温度比模具的加热温度高5-20℃。
5.根据权利要求1所述的一种高强度耐腐蚀制品的制备方法,其特征在于:所述的树脂原料按质量比,包括:
不饱和聚酯:30%-50%;增强纤维:20%~40%、发泡剂:0.5%~4%;
气相白炭黑:0.5%~1.5%;含氟化合物:1%~8%;增稠剂:0.05%-0.1%;
低收缩剂:1%~10%;引发剂:0.5%~3%;其他助剂:1.5%~3%;
无机改性填料:余量;
其中,所述的不饱和聚酯包括邻苯型、间苯型、双酚A型、新戊二醇型中的至少一种;
无机改性填料包括碳酸钙、硫酸钡、水合氧化铝、纳米陶瓷粉中的至少一种,粒径为200目-800目;
增强纤维包括玻纤/碳纤/芳纶纤维中的至少一种,长度为4-10mm;
发泡剂为核壳聚合物、偶氮二甲酰胺、超临界气体中的至少一种;
气相白炭黑,粒径5-800nm;
含氟化合物:包括甲基丙烯酸含氟酯、氟硅烷中的至少一种。
6.根据权利要求5所述的一种高强度耐腐蚀制品的制备方法,其特征在于:
增稠剂包括氢氧化钙、氧化镁中的至少一种;
低收缩剂包括PMMA/PE/PS中的至少一种;
引发剂为过氧化物、苯乙烯、甲基丙烯酸甲酯、邻苯二甲酸二丙烯酯中的至少一种;
其他助剂包括阻聚剂、内脱模剂、着色剂中的至少一种;
无机填料包括碳酸钙、硫酸钡、水合氧化铝、纳米陶瓷粉中的至少一种。
7.根据权利要求1所述的一种高强度耐腐蚀制品的制备方法,其特征在于:金属固定于模具中,其中模具的上/下模具有可以对嵌入至树脂中的金属嵌入模块进行隔空加热的电磁加热装置。
8.根据权利要求1所述的一种高强度耐腐蚀制品制备方法,其特征在于:对金属及树脂进行加热时,模具进行排气0.5s-3s,然后合模保压50s-300s。
9.根据权利要求1所述的一种高强度耐腐蚀制品的制备方法,其特征在于:
待发泡团状复合树脂的制备方法包括:
(1)混炼捏合:将聚酯体系均匀混合搅拌4-6h,加入包括填料、疏水气相白炭黑、引发剂/阻聚剂、玻纤在内的原料进行混炼捏合5-15min,温度控制≤30℃,制备均匀的团状树脂;
(2)发泡捏合:将发泡剂和其它树脂成分立刻缓慢加入至上述团状树脂,采用捏合机进一步捏合3-5min,制备待发泡团状复合树脂。
10.根据权利要求5所述的一种高强度耐腐蚀制品的制备方法,其特征在于:发泡剂采用核壳聚合物,且经过如下处理:将核壳聚合物表面喷洒硅烷偶联剂,搅拌均匀后将处理的核壳聚合物定量浸泡至聚酯体系中,并采用超声波均匀分散、搅拌10-20min,温度控制≤30℃。
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CN112976459A (zh) * | 2021-02-05 | 2021-06-18 | 广州辰东新材料有限公司 | 用于制备低介电树脂金属复合体的微发泡纳米注塑方法 |
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