CN115449333A - 橡胶地垫用聚氨酯粘合剂及其制备方法 - Google Patents

橡胶地垫用聚氨酯粘合剂及其制备方法 Download PDF

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CN115449333A
CN115449333A CN202211401651.2A CN202211401651A CN115449333A CN 115449333 A CN115449333 A CN 115449333A CN 202211401651 A CN202211401651 A CN 202211401651A CN 115449333 A CN115449333 A CN 115449333A
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王宝山
张华�
徐业峰
王善民
高朝阳
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Abstract

本发明属于聚氨酯胶黏剂技术领域,具体涉及橡胶地垫用聚氨酯粘合剂及其制备方法。所述橡胶地垫用聚氨酯粘合剂,由复合异氰酸酯、复合聚醚多元醇、氟碳树脂、蓖麻油、增塑剂、附着力促进剂、抗氧剂、紫外线吸收剂、杀菌防霉剂组成;其中复合异氰酸酯为MDI‑50、PAPI、液化MDI的混合物;复合聚醚多元醇为官能度为3、羟值为54~58mgKOH/g的聚醚多元醇A和官能度为6、羟值为26~30mgKOH/g的聚醚多元醇B的混合物。本发明的橡胶地垫用聚氨酯粘合剂,提高了产品在低模温条件下的脱模速度,且体系相容性好,储存稳定性好,同时有效提高了橡胶地垫的防腐性、耐磨性、耐候性和自清洁性。

Description

橡胶地垫用聚氨酯粘合剂及其制备方法
技术领域
本发明属于聚氨酯胶黏剂技术领域,具体涉及橡胶地垫用聚氨酯粘合剂及其制备方法。
背景技术
橡胶地垫,是利用特制的粘合剂将废弃的回收橡胶颗粒粘合后制成的特种聚合材料。橡胶地垫透气弹性好,拉伸强度高,可用于制作健身房地板、儿童乐园、过街天桥面层的铺设。常见的橡胶地垫制备方法为:将粉碎回收橡胶颗粒或彩色EPDM颗粒加入粘合剂混合均匀,放入120~160℃模具中固化成型,然后脱模冷却,室温熟化,即得。
在制备橡胶地垫时,采用的聚氨酯粘合剂一般采用甲苯二异氰酸酯(TDI)和聚醚多元醇、溶剂油配方体系,其粘结力较强,但是TDI、溶剂油易挥发,有刺激性气味,毒性大,危害环境和人体健康,而且TDI系列的粘合剂还存在生产效率低、产品质量稳定性差等问题。
此外,为了提高橡胶地垫的生产效率,聚氨酯粘合剂体系中一般还加入有机锡类金属催化剂,随着催化剂的加入,生产效率得到提高,同时也产生一系列的问题,例如粘合剂和橡胶颗粒混合后的静止适用期缩短,影响工人操作,制品的撕裂强度也有所下降,而且金属类催化剂对身体健康有影响。
发明内容
本发明要解决的技术问题是:提供一种橡胶地垫用聚氨酯粘合剂,提高了产品在低模温条件下的脱模速度,且体系相容性好,储存稳定性好,同时有效提高了橡胶地垫的防腐性、耐磨性、耐候性和自清洁性;本发明还提供其简单易行的制备方法。
本发明所述的橡胶地垫用聚氨酯粘合剂,由以下重量份数的原料组成:
复合异氰酸酯 20~45份,
复合聚醚多元醇 30~60份,
氟碳树脂 1~3份,
蓖麻油 1~3份,
增塑剂 8~20份,
附着力促进剂 0.1~0.5份,
抗氧剂 0.1~1份,
紫外线吸收剂 0.1~1份,
杀菌防霉剂 0.1~0.5份;
其中复合异氰酸酯为MDI-50(2,4和4,4’-二苯基甲烷二异氰酸酯混合物)、PAPI(多亚甲基多苯基异氰酸酯)、液化MDI(碳化二亚胺改性MDI)按质量比10:(2~4):(1~3)混合的混合物;
复合聚醚多元醇为官能度为3、羟值为54~58mgKOH/g的聚醚多元醇A和官能度为6、羟值为26~30mgKOH/g的聚醚多元醇B按质量比(2~3):1混合的混合物。
优选的,所述MDI-50、PAPI、液化MDI分别采用万华化学集团股份有限公司生产的MDI-50、PM-200、MDI-100L。
本发明采用上述三种异氰酸酯复配,其中MDI-50反应活性低、粘度低,能够赋予粘合剂粘度低、韧性好优点,但是单独使用会导致脱模时间长,并且不利于粘合剂粘结性的提高;液化MDI活性高,对潮气敏感,能够增加粘合剂的粘结性,但是单独使用会影响粘合剂的开放时间,不利于工人操作;PAPI具有较快的脱模时间,但合成粘合剂粘度大、做成制品脆、韧性不足。本发明在试验中发现,单独用其中一种异氰酸酯难以满足产品对工艺和性能要求,故本发明采用MDI-50、液化MDI前期聚合,后补加PAPI的方式,有效解决了各种异氰酸酯的不足,满足了产品的工艺和性能要求。
优选的,所述聚醚多元醇A为环氧丙烷-环氧乙烷共聚醚多元醇,环氧乙烷质量含量为5~15%;进一步优选为山东蓝星东大化工有限责任公司生产的聚醚多元醇EP-5631D。
优选的,所述聚醚多元醇B为环氧乙烷封端多元醇,环氧乙烷质量含量为5~15%;进一步优选为江苏长华聚氨酯科技有限公司生产的聚醚多元醇CHE-628。
常规粘合剂中一般都是使用低官能度(2官能度或3官能度)的聚醚多元醇,但是其合成的粘合剂交联度较低,不能满足低温快速脱模的要求。本发明采用6官能度聚醚多元醇B和3官能度聚醚多元醇A复配,其中6官能度聚醚多元醇B能够提高粘合剂反应基团的含量,使其在固化过程中分子量增加迅速,从而在较低模温下仍有很快的脱模速度。但是,高官能度聚醚多元醇会导致制品韧性变差,为此,本发明采用大分子量(数均分子量12000左右)的聚醚多元醇B,并通过合理控制高官能度聚醚多元醇的复配比例,在保留高官能度聚醚多元醇带来的优势的同时,避免了其带来的性能缺陷。同时,本发明还在粘合剂体系加入增塑剂,进一步提高制品的柔韧性,以平衡高官能度聚醚多元醇的加入对韧性的影响。
优选的,所述增塑剂为对苯二甲酸二辛酯(DOTP)。
优选的,所述抗氧剂为抗氧剂1076,巴斯夫股份公司生产。
优选的,所述紫外线吸收剂为紫外线吸收剂UV-9。
优选的,所述杀菌防霉剂为N-(2-苯丙咪唑基)-氨基甲酸甲酯。
优选的,所述氟碳树脂为羟基氟碳树脂,羟值为40mgKOH/g,进一步优选为山东华氟化工有限责任公司生产的HLR-1。
氟碳树脂有耐磨、防腐、强度高等诸多优点,但因其和聚氨酯体系相容性较差,所以不能共混使用,以往在涂料或油漆里面通过添加少量的氟碳树脂来提高聚氨酯材料的表面性能,但涂料在存储过程中也会出现分层、分离等现象。本发明通过加入羟基氟碳树脂提高产品的耐磨性,同时采用低极性聚醚多元醇提高氟碳树脂的相容性,低羟值聚醚多元醇能够引入较多的低极性聚醚链段,和氟碳树脂具有较好的相容性,如果采用高羟值低分子量聚醚多元醇,在合成过程中,会形成较多的氨基甲酸酯极性基团,从而影响氟碳树脂与体系的相容性。
优选的,所述附着力促进剂为改性氯化聚丙烯,优选杭州杰西卡化工有限公司生产的JSC-7500。
本发明所述的橡胶地垫用聚氨酯粘合剂的制备方法,包括以下步骤:
将复合聚醚多元醇、蓖麻油、抗氧剂、紫外线吸收剂投入反应釜中,升温至110~120℃,抽真空脱水1~1.5h,降温至45~55℃,加入氟碳树脂、MDI-50和液化MDI,升温至70~80℃,反应2~2.5h,加入PAPI、增塑剂、杀菌防霉剂、附着力促进剂,搅拌0.5~1.0h,降温,氮气封装,即得橡胶地垫用聚氨酯粘合剂。
本发明所述的橡胶地垫用聚氨酯粘合剂,用于制备橡胶地垫。
与现有技术相比,本发明具有以下有益效果:
(1)本发明选用低官能度聚醚多元醇和高官能度聚醚多元醇复配,通过高官能度聚醚多元醇提高粘合剂反应基团的含量,使其在固化过程中分子量增加迅速,从而在较低模温下仍有很快的脱模速度,并通过合理控制高官能度聚醚多元醇的复配比例,在保留高官能度聚醚多元醇带来的优势的同时,避免了其带来的性能缺陷,同时通过加入增塑剂,进一步提高制品的柔韧性,以平衡高官能度聚醚多元醇的加入对韧性的影响;
(2)本发明选用羟基氟碳树脂和异氰酸酯反应,将含羟基氟碳树脂预聚接枝到聚氨酯分子中,有机结合为一个整体,同时采用低极性聚醚多元醇提高氟碳树脂的相容性,解决了氟碳和聚氨酯相容性差导致的分离问题,氟碳树脂引入有效提高了橡胶地垫的防腐性、耐磨性和自清洁性;
(3)本发明采用MDI-50、PAPI、液化MDI复配,有效提高了粘合剂的耐水性和生产效率,使粘合剂体系在无催化剂条件下也可快速脱模;
(4)本发明通过加入附着力促进剂,有效提高了聚氨酯粘合剂对低表面能橡胶颗粒材料的粘结强度,同时通过加入抗氧剂、抗紫外线吸收剂、防霉杀菌助剂,改善了橡胶地垫的耐候性,使其在户外有较长的使用年限;
(5)本发明的聚氨酯粘合剂不含TDI、有机溶剂等有害挥发物质,且不使用有机金属催化剂,体系更加环保。
具体实施方式
下面结合实施例对本发明作进一步说明。实施例中所使用的原料,如无特别说明,均为市售常规原料;实施例中所使用的工艺方法,如无特别说明,均为本领域常规方法。
实施例中用到的部分原料如下:
MDI-50、PM-200、MDI-100L,万华化学集团股份有限公司;
EP-5631D、DL-2000,山东蓝星东大化工有限责任公司;
CHE-628,江苏长华聚氨酯科技有限公司;
JSC-7500,杭州杰西卡化工有限公司;
抗氧剂1076,巴斯夫股份公司;
UV-9,烟台恒诺新材料有限公司;
HLR-1,山东华氟化工有限责任公司。
实施例1
一种橡胶地垫用聚氨酯粘合剂,由以下重量份数的原料组成:
20份的MDI-50,8份的PM-200,2份的MDI-100L,30份的EP-5631D,15份的CHE-628,2份的HLR-1,1份的蓖麻油,12份的DOTP,0.2份的JSC-7500,0.5份的抗氧剂1076,0.1份的UV-9,0.1份的N-(2苯丙咪唑基)氨基甲酸甲酯。
制备方法如下:
将EP-5631、CHE-628、蓖麻油、抗氧剂1076、UV-9投入反应釜中,升温至110℃,抽真空脱水1.5h,降温至45℃,加入HLR-1、MDI-50和MDI-100L,升温至70℃,反应2.5h,加入PM-200、DOTP、N-(2-苯丙咪唑基)-氨基甲酸甲酯、JSC-7500,搅拌0.5h,降温,氮气封装,即得橡胶地垫用聚氨酯粘合剂。
实施例2
一种橡胶地垫用聚氨酯粘合剂,由以下重量份数的原料组成:
13份的MDI-50,4份的PM-200,3份的MDI-100L,24份的EP-5631D,8份的CHE-628, 1份的HLR-1,2份的蓖麻油,8份的DOTP,0.1份的JSC-7500,0.1份的抗氧剂1076,1份的UV-9,0.3份的N-(2苯丙咪唑基)氨基甲酸甲酯。
制备方法如下:
将EP-5631、CHE-628、蓖麻油、抗氧剂1076、UV-9投入反应釜中,升温至120℃,抽真空脱水1h,降温至55℃,加入HLR-1、MDI-50和MDI-100L,升温至80℃,反应2h,加入PM-200、DOTP、N-(2-苯丙咪唑基)-氨基甲酸甲酯、JSC-7500,搅拌0.5h,降温,氮气封装,即得橡胶地垫用聚氨酯粘合剂。
实施例3
一种橡胶地垫用聚氨酯粘合剂,由以下重量份数的原料组成:
30份的MDI-50,6份的PM-200,9份的MDI-100L,42份的EP-5631D,18份的CHE-628,3份的HLR-1,3份的蓖麻油,20份的DOTP,0.5份的JSC-7500,1份的抗氧剂1076,0.5份的UV-9,0.5份的N-(2苯丙咪唑基)氨基甲酸甲酯。
制备方法如下:
将EP-5631、CHE-628、蓖麻油、抗氧剂1076、UV-9投入反应釜中,升温至115℃,抽真空脱水1.5h,降温至50℃,加入HLR-1、MDI-50和MDI-100L,升温至75℃,反应2.5h,加入PM-200、DOTP、N-(2-苯丙咪唑基)-氨基甲酸甲酯、JSC-7500,搅拌1.0h,降温,氮气封装,即得橡胶地垫用聚氨酯粘合剂。
对比例1
本对比例采用2官能度聚醚多元醇和3官能度聚醚多元醇复配,与实施例1的不同之处仅在于,将聚醚多元醇CHE-628替换为等质量的聚醚多元醇DL-2000。
对比例2
本对比例增加6官能度聚醚多元醇CHE-628的配比,与实施例1的不同之处仅在于,采用20份的聚醚多元醇EP-5631D和20份的聚醚多元醇CHE-628。
对比例3
本对比例增加氟碳树脂的含量,与实施例3的不同之处仅在于,将氟碳树脂HLR-1的加入量增加到6份。
对比例4
本对比例的异氰酸酯仅采用MDI-50,与实施例3的不同之处仅在于,将PM-200和MDI-100L为等质量的MDI-50。
对比例5
市售TDI系列聚氨酯粘合剂HG2160,淄博华天橡塑科技有限公司生产。
将各实施例和对比例制备的聚氨酯粘合剂用于制备橡胶地垫,方法为:将橡胶颗粒和聚氨酯粘合剂按重量比100:6搅拌均匀,倒入已预热至120℃的模具内,然后脱模冷却,室温熟化,然后测试其性能。
其中,拉伸强度参照标准GB 36246-2018进行测试;表面硬度参照标准GB/T 531-92进行测试;冲击吸收参照标准GB/T 1697-2001进行测试;DIN磨耗参照标准GB/T 529-2008进行测试;操作时间和脱模时间测试条件为120℃模温、2cm厚度橡胶地垫;浸水强度保持率是将橡胶地垫样品在水中浸泡24h后测试拉伸强度保持率;耐脏性是将橡胶地垫样品在室外放置24h后表面变化;储存稳定性是粘合剂放置在室温密闭容器内,观察粘合剂分层变质时间。测试结果如表1所示。
表1 实施例和对比例各项性能测试结果
Figure DEST_PATH_IMAGE002
从表1可以看出,本发明制备的聚氨酯粘合剂,气味小,容易操作,脱模时间短,拉伸强度和耐磨性能、耐脏性均优于市售TDI系列聚氨酯粘合剂,延长了橡胶地垫的使用寿命。
通过对比实施例1和对比例1~2,可以看到高官能度聚醚多元醇CHE-628对脱模效率提高明显,但高比例的聚醚多元醇CHE-628会使胶水粘度升高,操作时间变短,影响工人操作,当EP-5631D和CHE-628的质量比在(2~3):1范围内时,既能提高脱模效率又能满足工人的操作时间;同时低羟值聚醚多元醇CHE-628的加入,提高了氟碳树脂的相容性,产品体系稳定不易分层。
通过对比实施例3和对比例3,可以看到当氟碳树脂添加过量时,其与粘合剂体系的相容性受到严重影响,储存稳定性下降,由于产品静置后分层严重,判定配方异常,未进行应用性能测试。
对比例4为MDI系列聚氨酯粘合剂,其无法满足快速脱模的使用要求。
对比例5为市售TDI系列聚氨酯粘合剂,有TDI刺激气味,同样无法满足快速脱模的使用要求。

Claims (10)

1.一种橡胶地垫用聚氨酯粘合剂,其特征在于:由以下重量份数的原料组成:
复合异氰酸酯 20~45份,
复合聚醚多元醇 30~60份,
氟碳树脂 1~3份,
蓖麻油 1~3份,
增塑剂 8~20份,
附着力促进剂 0.1~0.5份,
抗氧剂 0.1~1份,
紫外线吸收剂 0.1~1份,
杀菌防霉剂 0.1~0.5份;
其中复合异氰酸酯为MDI-50、PAPI、液化MDI按质量比10:(2~4):(1~3)混合的混合物;
复合聚醚多元醇为官能度为3、羟值为54~58mgKOH/g的聚醚多元醇A和官能度为6、羟值为26~30mgKOH/g的聚醚多元醇B按质量比(2~3):1混合的混合物。
2.根据权利要求1所述的橡胶地垫用聚氨酯粘合剂,其特征在于:所述聚醚多元醇A为环氧丙烷-环氧乙烷共聚醚多元醇,环氧乙烷质量含量为5~15%。
3.根据权利要求1所述的橡胶地垫用聚氨酯粘合剂,其特征在于:所述聚醚多元醇B为环氧乙烷封端多元醇,环氧乙烷质量含量为5~15%。
4.根据权利要求1所述的橡胶地垫用聚氨酯粘合剂,其特征在于:所述增塑剂为对苯二甲酸二辛酯。
5.根据权利要求1所述的橡胶地垫用聚氨酯粘合剂,其特征在于:所述抗氧剂为抗氧剂1076。
6.根据权利要求1所述的橡胶地垫用聚氨酯粘合剂,其特征在于:所述紫外线吸收剂为紫外线吸收剂UV-9。
7.根据权利要求1所述的橡胶地垫用聚氨酯粘合剂,其特征在于:所述杀菌防霉剂为N-(2-苯丙咪唑基)-氨基甲酸甲酯。
8.根据权利要求1所述的橡胶地垫用聚氨酯粘合剂,其特征在于:所述氟碳树脂为羟基氟碳树脂。
9.根据权利要求1所述的橡胶地垫用聚氨酯粘合剂,其特征在于:所述附着力促进剂为改性氯化聚丙烯。
10.一种权利要求1-9任一项所述的橡胶地垫用聚氨酯粘合剂的制备方法,其特征在于:包括以下步骤:
将复合聚醚多元醇、蓖麻油、抗氧剂、紫外线吸收剂投入反应釜中,升温至110~120℃,抽真空脱水1~1.5h,降温至45~55℃,加入氟碳树脂、MDI-50和液化MDI,升温至70~80℃,反应2~2.5h,加入PAPI、增塑剂、杀菌防霉剂、附着力促进剂,搅拌0.5~1.0h,降温,氮气封装,即得橡胶地垫用聚氨酯粘合剂。
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