CN105399924A - 一种可常温发泡的不黄变聚氨酯海绵的制备方法 - Google Patents
一种可常温发泡的不黄变聚氨酯海绵的制备方法 Download PDFInfo
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Abstract
本发明公开了一种可常温发泡的不黄变聚氨酯海绵的制备方法,以4,4′-二环己基甲烷二异氰酸酯或其预聚体、聚醚多元醇为主要原料,添加环保催化剂和其他辅料在常温下由传统聚氨酯海绵流水线反应发泡,经固化、熟化阶段得到不黄变聚氨酯海绵;本发明不黄变海绵可在常温下由传统聚氨酯海绵流水线得到,不需要加热原料及更改现有设备,具有设备投资少、能耗低等优点;另外,由于4,4′-二环己基甲烷二异氰酸酯不含有苯环结构,得到的聚氨酯海绵不黄变,具有优秀的抗老化、抗氧化和抗光照的能力,可广泛地应用于服装、鞋材、家私、电子、打印耗材、航空、汽车、医疗美容、包装、体育用品、生活用品领域。
Description
技术领域
本发明涉及聚氨酯海绵发泡技术领域,具体是一种以聚醚多元醇、4,4'-二环己基甲烷二异氰酸酯或其预聚体为主要原料在常温下进行反应发泡制备不黄变聚氨酯海绵的方法。
背景技术
聚氨酯海绵属于聚氨酯泡沫塑料当中的一种,属于软质聚氨酯泡沫塑料,因其具有多孔状蜂窝结构,所以具有质量轻、优良的柔软性、弹性及良好的耐水性等一系列优越性能,应用十分广泛,涉及很多行业,包括:服装、家私、航空、汽车、包装、体育及生活用品等等,而且其规模还在不断扩大;据目前为止,国内大多数海绵厂家还是以甲苯二异氰酸酯(TDI)或者二苯基甲烷二异氰酸酯(MDI)为原料生产聚氨酯海绵,由于TDI与MDI当中的异氰酸酯基与苯环直接相连,容易受到光照、氧气、氮氧化合物、漂白水等介质条件的影响,从而形成醌式发色基团,导致聚氨酯海绵发黄;为了防止TDI与MDI型海绵产生发黄,绝大多数生产厂家会往聚氨酯海绵配方中加入抗氧剂、光稳定剂以及荧光增白剂,以达到延缓或者掩盖聚氨酯海绵变黄,但添加辅料的办法只能暂时延缓黄变,不能从根本上解决聚氨酯海绵发黄的问题;中国专利CN104106938A和CN103908103A公开了采用甲苯二异氰酸酯(TDI)与多元醇反应发泡得到聚氨酯海绵,由于异氰酸酯使用了TDI,使得制备得到的聚氨酯海绵易受到热、氧和光照的影响,产生黄变及性能的降低;中国专利CN102336885A和CN103641986A公开了采用异佛尔酮二异氰酸酯(IPDI)与多元醇反应发泡制备高环境耐受性的聚氨酯海绵,虽然采用了脂环族的异氰酸酯,从根本上解决了聚氨酯海绵容易黄变问题,但是也是有明显的不足,一方面该专利为了提高IPDI的反应活性,将IPDI以及聚醚加热到40℃左右才能进行反应发泡,提高了料温,增加了能耗,反应不能有效的控制,得到的制品泡孔较粗,手感粗糙,回弹也差,制品容易出现白色熔接纹,另一方面IPDI分子量小、反应活性低,得到的聚氨酯海绵分子量低,使得其力学强度差,容易产生撕裂;基于上述原因,需要对现有技术的聚氨酯海绵的生产工艺进行改进,以提高其性能。
发明内容
本发明的目的在于提供一种可常温发泡的不黄变聚氨酯海绵的制备方法,以解决现有技术得到的芳香族聚氨酯海绵容易老化、氧化、耐光性能差和其他IPDI聚氨酯海绵需要加热发泡、反应活性低、产品质量不稳定的问题。
为实现上述目的,本发明提供如下技术方案:
一种可常温发泡的不黄变聚氨酯海绵的制备方法,包括一步法与预聚体法:
1、一步法制备可常温发泡的不黄变聚氨酯海绵,由以下重量份的原料反应发泡制成:
聚醚多元醇100份
4,4′-二环己基甲烷二异氰酸酯30~80份
水1.5~7份
硅油0.4~3.5份
碱性催化剂0.2~2.5份
金属催化剂0.2~1份
物理发泡剂0~10份
交联剂0.5~3份。
作为本发明进一步的方案:各原料的优选重量份数是:
聚醚多元醇100份
4,4′-二环己基甲烷二异氰酸酯40~70份
水2~6份
硅油1~3份
碱性催化剂0.4~1.5份
金属催化剂0.4~1份
物理发泡剂0~6份
交联剂0.8~2份。
2、预聚体法制备可常温发泡的不黄变聚氨酯海绵,由以下重量份的原料反应发泡制成:
聚醚多元醇100份
4,4′-二环己基甲烷二异氰酸酯预聚体50~90份
水1.5~7份
硅油0.4~3.5份
碱性催化剂0.2~2.5份
金属催化剂0.2~1份
物理发泡剂0~10份
交联剂0.5~3份。
作为本发明再进一步的方案:各原料的优选重量份数是:
聚醚多元醇100份
4,4′-二环己基甲烷二异氰酸酯预聚体60~90份
水2~6份
硅油1~3份
碱性催化剂0.4~1.5份
金属催化剂0.4~1份
物理发泡剂0~6份
交联剂0.8~2份。
作为本发明进一步的方案:所述聚醚多元醇的羟值为25~80mgKOH/g,分子量为2000~10000,其重量份数为100份,根据制品是否要求具有阻燃,选择阻燃型聚醚。
作为本发明再进一步的方案:所述水为去离子水或蒸馏水。
作为本发明再进一步的方案:所述硅油为商业硅油产品迈图L-580、L-5309、Y-10366、赢创B-8715、空气DC-2525、DC-6070、SI-1304、道康宁DC-868、DC-540、DK-580M、DC-898中的一种或几种的组合。
作为本发明再进一步的方案:所述碱性催化剂为三乙烯二胺、二甲基乙醇胺、二甲基环己胺、三乙胺、三乙醇胺、双(2-二甲胺基乙基)醚中的一种或几种的组合。
作为本发明再进一步的方案:所述金属催化剂为有机铋、有机锌、乙酰丙酮钛、乙酰丙酮钴、乙酰丙酮锆中的一种或几种的组合,
作为本发明再进一步的方案:所述物理发泡剂为正戊烷、正己烷、液态二氧化碳、石油醚、二氯乙烷、二氯甲烷以及氢化含氯氟烃中的一种或几种的组合。
作为本发明再进一步的方案:所述交联剂为1,4-丁二醇、丙三醇、丙二醇、乙二醇、三羟甲基丙烷、三乙醇胺、己二胺、苯二胺、二乙基甲苯二胺中的一种或几种的组合。
作为本发明再进一步的方案:所述4,4′-二环己基甲烷二异氰酸酯预聚体为过量的4,4′-二环己基甲烷二异氰酸酯与聚醚多元醇反应得到的预聚体,其中4,4′-二环己基甲烷二异氰酸酯中NCO与聚醚多元醇中摩尔比为n(NCO):n(OH)=1.1~1.4:1。
作为本发明再进一步的方案:本发明所述的可常温发泡的不黄变聚氨酯海绵的制备方法,包含一步法与预聚体法,预聚体法首先根据异氰酸酯基与羟基的摩尔比,反应得到4,4′-二环己基甲烷二异氰酸酯预聚体,其他步骤与一步法相同;具体步骤如下:
1.手工箱泡
1)根据海绵固化模具容积要求,按照上述配方各原料的重量份数称取相应的重量;
2)先将上述配方量的聚醚多元醇、水、硅油、碱性催化剂、金属催化剂、物理发泡剂、交联剂投入混合器中混合,搅拌速率100~400r/min,搅拌时间30~120s,搅拌均匀待用;
3)再将上述配方量的4,4′-二环己基甲烷二异氰酸酯或4,4′-二环己基甲烷二异氰酸酯预聚体投入上述混合器中,高速搅拌,搅拌速率200~600r/min,混合时间3~10s,混合后迅速倒入模具内常温反应发泡,经过固化、熟化阶段可得到本发明所述的不黄变聚氨酯海绵。
2.机泡
1)根据生产规模的要求,按照上述配方各原料的重量份数称取相应的重量;
2)分别将上述配方量的4,4′-二环己基甲烷二异氰酸酯或4,4′-二环己基甲烷二异氰酸酯预聚体和聚醚多元醇投入A和B发泡储料罐内;
3)再将上述配方量的水、硅油、碱性催化剂、金属催化剂、物理发泡剂、交联剂投入B发泡储料罐内混合,开启搅拌,搅拌速率100~400r/min,搅拌时间30~120s;
4)调节A、B发泡料液不同混合比率,不同流量的A、B发泡料液分别经过各自的高精度计量泵输送到混合头进行高速二次搅拌,使料液均匀地从灌注头喷出,喷出的泡沫由一定速率的传送带牵引,经过固化、熟化阶段即得到本发明所述的不黄变聚氨酯海绵。
与现有技术相比,本发明的有益效果是:本发明的原料采用4,4′-二环己基甲烷二异氰酸酯,相对异佛尔酮二异氰酸酯、甲苯二异氰酸酯和六亚甲基二异氰酸酯,其饱和蒸汽压更低,不易对人或环境造成伤害;相对中国专利CN102336885A中使用异佛尔酮二异氰酸酯,其反应发泡需要加热到40℃,本发明能够在常温下进行反应发泡,设备简单、能耗低,而且常温下反应发泡能够减小加热发泡所带来的副反应;本发明所制备的不黄变海绵不含有苯酚、荧光增白剂、TDI与MDI,不会对人体产生危害;本发明所制备的不黄变海绵经AATCC-16耐光照色牢度12小时测试、AATCC-23耐燃烧瓦斯气体褪色测试(一次循环)和AATCC-162耐氯水漂洗色牢度测试,其结果都达到了4级或以上,表明本发明产品具有优异的的抗老化、抗光照和抗氧化性能,能够增加聚氨酯海绵的使用寿命,减少废弃物的排放;本发明金属催化剂并未使用有毒性的有机锡催化剂,而是使用更加环保的金属催化剂,所得到的聚氨酯海绵更符合国际对环保和安全的要求;本发明制备的聚氨酯海绵具有优秀的环境耐受性,在光、热、氧条件下,不容易发黄,除此之外,HMDI还赋予了制品杰出的力学性能、耐氮氧化合物和耐氯水漂洗的性能,同时发泡反应可以在常温下进行,现有的发泡机不需要改造便可直接使用。
具体实施方式
下面结合具体实施方式对本专利的技术方案作进一步详细地说明。
实施例1
一步法制备可常温发泡的不黄变聚氨酯海绵,由以下重量份的原料组成:
聚醚多元醇GEP-560100份
4,4′-二环己基甲烷二异氰酸酯(HMDI)60份
水4份
迈图L-580(硅油)1.5份
三乙烯二胺(碱性催化剂)0.8份
有机铋(金属催化剂)0.3份
二氯甲烷MC(物理发泡剂)6份
三乙醇胺(交联剂)1.3份。
按照上述配方,根据手工泡固化模具的大小,先称取700gGEP-560聚醚多元醇、28g水、10.5gL-580硅油、5.6g三乙烯二胺、2.1g有机铋、42g二氯甲烷和9.1g三乙醇胺投入混合器内进行高速搅拌,转速200r/min,搅拌时间70s,搅拌均匀待用。
再称取420g4,4′-二环己基甲烷二异氰酸酯投入上述已搅拌均匀的混合液中,开启搅拌,搅拌速率500r/min,搅拌时间6s,搅拌结束后,快速倒入手工泡固化模具内,经固化、熟化阶段得到本发明所述的不黄变海绵。
依据AATCC-16耐光照色牢度12小时测试标准、AATCC-23耐燃烧瓦斯气体褪色测试(一次循环)标准和AATCC-162耐氯水漂洗色牢度测试标准,将所制备的不黄变海绵裁剪成标准样条,进行测试,测试结果见表1。
对比实施例1
甲苯二异氰酸酯代替HMDI采用一步法制备普通聚氨酯海绵,由以下重量份的原料组成:
聚醚多元醇GEP-560100份
甲苯二异氰酸酯40份
水4份
迈图L-580(硅油)1.5份
三乙烯二胺(碱性催化剂)0.8份
有机铋(金属催化剂)0.3份
二氯甲烷MC(物理发泡剂)6份
三乙醇胺(交联剂)1.3份
根据4,4′-二环己基甲烷二异氰酸酯和甲苯二异氰酸酯相对分子质量的差异,将60重量份数的4,4′-二环己基甲烷二异氰酸酯换算成甲苯二异氰酸酯,其重量份数为40份。
按照上述普通聚氨酯海绵的配方,根据手工泡固化模具的大小,先称取700gGEP-560聚醚多元醇、28g水、10.5gL-580硅油、5.6g三乙烯二胺、2.1g有机铋、42g二氯甲烷和9.1g三乙醇胺投入混合器内进行高速搅拌,转速200r/min,搅拌时间70s,搅拌均匀待用。
再称取280g甲苯二异氰酸酯投入上述已搅拌均匀的混合液中,开启搅拌,搅拌速率500r/min,搅拌时间6s,搅拌结束后,快速倒入手工泡固化模具内,经固化、熟化阶段得到对比实施例1的普通聚氨酯海绵。
依据AATCC-16耐光照色牢度12小时测试标准、AATCC-23耐燃烧瓦斯气体褪色测试(一次循环)标准和AATCC-162耐氯水漂洗色牢度测试标准,将所制备的普通聚氨酯海绵裁剪成标准样条,进行测试,测试结果见表1。
实施例2
预聚体法制备可常温发泡的不黄变聚氨酯海绵,由以下重量份的原料组成:
聚醚多元醇ACCLAIM8220N100份
4,4′-二环己基甲烷二异氰酸酯预聚体70份
水3份
赢创B-8715(硅油)1份
三乙烯二胺(碱性催化剂)0.6份
乙酰丙酮钛(金属催化剂)0.7份
液态二氧化碳(物理发泡剂)7份
1,4-丁二醇(交联剂)1份
按照n(NCO):n(OH)=1.3:1的摩尔比,预先反应得到4,4′-二环己基甲烷二异氰酸酯预聚体。
按照上述不黄变海绵的配方,根据手工泡固化模具的大小,称取700gACCLAIM8220N聚醚多元醇、21g水、7gB-8715硅油、4.2g三乙烯二胺、4.9g乙酰丙酮钛、49g液态二氧化碳和7g1,4-丁二醇投入混合器内进行高速搅拌,转速150r/min,搅拌时间90s,搅拌均匀待用。
再称取490g上述预先得到的4,4′-二环己基甲烷二异氰酸酯预聚体投入到上述已搅拌均匀的混合液中,开启搅拌,搅拌速率400r/min,搅拌时间7s,搅拌结束后,快速倒入手工泡固化模具内,经固化、熟化等阶段得到本发明所述的不黄变海绵。
实施例3
一步法制备可常温发泡的具有阻燃性的不黄变聚氨酯海绵,由以下重量份的原料组成:
聚醚多元醇NJ-330D100份
4,4′-二环己基甲烷二异氰酸酯(HMDI)70份
水5份
空气DC-6070(硅油)2份
二甲基环己胺(碱性催化剂)1份
有机锌(金属催化剂)0.4份
二氯乙烷(物理发泡剂)6份
丙三醇(交联剂)1.4份
如果不黄变海绵制品需要有一定的阻燃,可在配方中添加阻燃剂或使用阻燃聚醚,提高其阻燃效果。
按照上述不黄变海绵的配方,根据手工泡固化模具的大小,先称取700gNJ-330D阻燃聚醚多元醇、35g水、14gDC-6070硅油、7g二甲基环己胺、2.8g有机锌、42g二氯乙烷、9.8g丙三醇投入混合器内进行高速搅拌,转速220r/min,搅拌时间50s,搅拌均匀待用。
再称取490g4,4′-二环己基甲烷二异氰酸酯投入到上述已搅拌均匀的混合液中,开启搅拌,搅拌速率350r/min,搅拌时间9s,搅拌结束后,快速倒入手工泡固化模具内,经固化、熟化等阶段得到本发明所述的不黄变海绵,且该制品带有一定的阻燃性。
实施例4
一步法制备可常温发泡的不黄变聚氨酯海绵,由以下重量份的原料组成:
聚醚多元醇GEP-560100份
4,4′-二环己基甲烷二异氰酸酯(HMDI)60份
水4份
迈图L-580(硅油)1.5份
三乙烯二胺(碱性催化剂)0.8份
有机铋(金属催化剂)0.3份
二氯甲烷MC(物理发泡剂)6份
三乙醇胺(交联剂)1.3份
配方与实施例1配方一样,只是该实施例是用海绵发泡机进行发泡的。
按照上述不黄变海绵的配方,根据发泡机储料罐的大小,确定各配方原料所需的重量。
先称取100kgGEP-560聚醚多元醇、4kg水、1.5kgL-580硅油、0.8kg三乙烯二胺、0.3kg有机铋、6kg二氯甲烷和1.3kg三乙醇胺投入B储料罐内,开启高速搅拌,搅拌速率300r/min。
称取60kg4,4′-二环己基甲烷二异氰酸酯投入A储料罐内,同时也开启高速搅拌,搅拌速率300r/min。
调节A与B相对应的计量泵,使其流量比为1:1.2,调节传送带速率为10m/min。开启计量泵,A与B料液按照1:1.2的流量比进入混合头进行高速二次搅拌,使料液均匀地从灌注头喷出,喷出的泡沫由传送带牵引,经过固化、熟化等阶段即得到本发明所述的不黄变聚氨酯海绵。
实施例5
预聚体法制备可常温发泡的不黄变聚氨酯海绵,由以下重量份的原料组成:
聚醚多元醇JH-3031D100份
4,4′-二环己基甲烷二异氰酸酯预聚体80份
水3份
道康宁DC-540(硅油)1.2份
三乙胺(碱性催化剂)1份
乙酰丙酮钴(金属催化剂)0.3份
正己烷(物理发泡剂)7份
三羟甲基丙烷(交联剂)1.5份
按照n(NCO):n(OH)=1.4:1的摩尔比,预先反应得到4,4′-二环己基甲烷二异氰酸酯预聚体。
按照上述不黄变海绵的配方,根据发泡机储料罐的大小,确定各配方原料所需的重量。
称取100kgJH-3031D聚醚多元醇、3kg水、1.2kgDC-540硅油、1kg三乙胺、0.3kg乙酰丙酮钴、7kg正己烷和1.5kg三羟甲基丙烷投入B储料罐内,开启高速搅拌,搅拌速率300r/min。
称取80kg4,4′-二环己基甲烷二异氰酸酯预聚体投入A储料罐内,同时也开启高速搅拌,搅拌速率300r/min。
调节A与B相对应的计量泵,使其流量比为1:1.4,调节传送带速率为10m/min。开启计量泵,A与B料液按照1:1.4的流量比进入混合头进行高速二次搅拌,使料液均匀地从灌注头喷出,喷出的泡沫由传送带牵引,经过固化、熟化等阶段即得到本发明所述的不黄变聚氨酯海绵。
实施例1与对比实施例1测试结果进行灰卡评级,结果如表1所示:
灰卡评级结果由1~5,评级结果越高,其抗黄变能力越强。
灰卡评级结果由1~5,评级结果越高,其抗黄变能力越强。
由表1可知,不黄变聚氨酯海绵耐光照色牢度、耐燃烧瓦斯气体褪色色牢度和耐氯水漂洗色牢度级别都达到了4级或者以上,远远超过了普通聚氨酯海绵的级别,表明不黄变聚氨酯海绵抗黄变能力强。
对于本领域技术人员而言,显然本发明不限于上述示范性实施例的细节,而且在不背离本发明的精神或基本特征的情况下,能够以其他的具体形式实现本发明。因此,无论从哪一点来看,均应将实施例看作是示范性的,而且是非限制性的,本发明的范围由所附权利要求而不是上述说明限定,因此旨在将落在权利要求的等同要件的含义和范围内的所有变化囊括在本发明。不应将权利要求中的任何标记视为限制所涉及的权利要求。
此外,应当理解,虽然本说明书按照实施方式加以描述,但并非每个实施方式仅包含一个独立的技术方案,说明书的这种叙述方式仅仅是为清楚起见,本领域技术人员应当将说明书作为一个整体,各实施例中的技术方案也可以经适当组合,形成本领域技术人员可以理解的其他实施方式。
Claims (10)
1.一种可常温发泡的不黄变聚氨酯海绵的制备方法,包括一步法与预聚体法,其特征在于,采用以下步骤:
1)将聚醚多元醇、水、硅油、碱性催化剂、金属催化剂、物理发泡剂、交联剂投入混合器中进行高速搅拌,搅拌均匀,搅拌速率100~400r/min,搅拌时间30~120s;
2)将4,4′-二环己基甲烷二异氰酸酯或4,4′-二环己基甲烷二异氰酸酯预聚体与步骤1中的料液进行高速混合,搅拌速率200~600r/min,混合时间3~10s,混合后的料液快速倒入固化模具内或由混合头喷出,再由传送带传送,经固化、熟化等阶段得到不黄变聚氨酯海绵。
2.根据权利要求1所述的可常温发泡的不黄变聚氨酯海绵的制备方法,其特征在于,所述步骤1中,聚醚多元醇的羟值为25~80mgKOH/g,分子量为2000~10000,其重量份数为100份,根据制品是否要求具有阻燃,选择阻燃型聚醚。
3.根据权利要求1所述的可常温发泡的不黄变聚氨酯海绵的制备方法,其特征在于,所述步骤1中,水为去离子水或蒸馏水,重量份数为1.5~7份;硅油重量份数为0.4~3.5份。
4.根据权利要求1所述的可常温发泡的不黄变聚氨酯海绵的制备方法,其特征在于,所述步骤1中,碱性催化剂为三乙烯二胺、二甲基乙醇胺、二甲基环己胺、三乙胺、三乙醇胺、双(2-二甲胺基乙基)醚中的一种或几种的组合,重量份数为0.2~2.5份。
5.根据权利要求1所述的可常温发泡的不黄变聚氨酯海绵的制备方法,其特征在于,所述步骤1中,金属催化剂为有机铋、有机锌、乙酰丙酮钛、乙酰丙酮钴、乙酰丙酮锆中的一种或几种的组合,重量份数为0.2~1份。
6.根据权利要求1所述的可常温发泡的不黄变聚氨酯海绵的制备方法,其特征在于,所述步骤1中,物理发泡剂为正戊烷、正己烷、液态二氧化碳、石油醚、二氯乙烷、二氯甲烷以及氢化含氯氟烃中的一种或几种的组合,重量份数为0~10份。
7.根据权利要求1所述的可常温发泡的不黄变聚氨酯海绵的制备方法,其特征在于,所述步骤1中,交联剂为1,4-丁二醇、丙三醇、丙二醇、乙二醇、三羟甲基丙烷、三乙醇胺、己二胺、苯二胺、二乙基甲苯二胺中的一种或几种的组合,重量份数为0.5~3份。
8.根据权利要求1所述的可常温发泡的不黄变聚氨酯海绵的制备方法,其特征在于,所述步骤2中,4,4′-二环己基甲烷二异氰酸酯重量份数为30~80份。
9.根据权利要求1所述的可常温发泡的不黄变聚氨酯海绵的制备方法,其特征在于,所述步骤2中,4,4′-二环己基甲烷二异氰酸酯预聚体为过量的4,4′-二环己基甲烷二异氰酸酯与聚醚多元醇反应得到的预聚体,其中4,4′-二环己基甲烷二异氰酸酯中NCO与聚醚多元醇中OH摩尔比为n(NCO):n(OH)=1.1~1.4:1,4,4′-二环己基甲烷二异氰酸酯预聚体重量份数为50~90份。
10.根据权利要求1-9任一所述的可常温发泡的不黄变聚氨酯海绵的制备方法,其特征在于,所述各原料优选为聚醚多元醇100份、水1~6份、硅油1~3份、碱性催化剂0.4~1.5份、金属催化剂0.4~1份、物理发泡剂0~6份、交联剂0.8~2份、4,4′-二环己基甲烷二异氰酸酯40~70份、4,4′-二环己基甲烷二异氰酸酯预聚体60~90份。
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