CN106832203A - 轮胎用聚氨酯树脂及制备方法 - Google Patents
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Abstract
本发明公开了一种轮胎用聚氨酯及制备方法,所述树脂包含树脂A组分,树脂B1组分和树脂B2组分,树脂A组分包括聚多元醇A、交联剂、催化剂、发泡剂和匀泡剂;树脂B1包括异氰酸酯B1 100份,聚多元醇B1 10~40份,副反应阻止剂0.002~0.010份,树脂B2包括异氰酸酯B2 100份,聚多元醇B2 50~100份,副反应阻止剂0.002~0.010份,异氰酸酯B1为二苯基甲烷二异氰酸酯、碳化二亚胺改性二苯基甲烷二异氰酸酯、甲苯二异氰酸酯或萘二异氰酸酯,聚多元醇B1为聚己二酸系聚酯多元醇,异氰酸酯B2为二苯基甲烷二异氰酸酯、碳化二亚胺改性二苯基甲烷二异氰酸酯、甲苯二异氰酸酯或萘二异氰酸酯,聚多元醇B2为聚己二酸系聚酯多元醇或聚对苯二甲酸系聚酯多元醇。本发明可制得不同硬度聚氨酯轮胎。
Description
技术领域
本发明涉及一种轮胎用聚氨酯树脂及制备方法。
背景技术
聚氨酯全名聚氨基甲酸酯,是主链上含有重复氨基甲酸酯基团的大分子化合物的统称,是由二元或多元有机异氰酸酯与多元醇化合物相互作用而得到的高分子化合物。
用于生产聚氨酯轮胎的树脂一般为双组份原料——多元醇混合物和预聚物(简称AB料/AB组分或黑白料)。
不同性能要求的聚氨酯轮胎需要不同种类的AB料配合使用。对于聚氨酯轮胎生产企业,需要配备各种不同型号不同规格的原料以适应不同性能要求的轮胎的生产,而且每次更换原料需要清洗打样机台和物料罐体,生产成本高。
发明内容
本发明的目的在于提供一种轮胎用聚氨酯树脂及制备方法,以克服现有技术存在的缺陷。
本发明所述的轮胎用聚氨酯树脂,包含树脂A组分,树脂B1组分和树脂B2组分;
所述树脂A组分由如下重量份数的组分组成:
所述树脂B1组分由如下重量份数的组分组成:
异氰酸酯B1 100份;
聚多元醇B1 10~40份;
副反应阻止剂 0.002~0.010份;
所述树脂B2组分由如下重量份数的组分组成:
异氰酸酯B2 100份;
聚多元醇B2 50~100份;
副反应阻止剂 0.002~0.010份。
优选的:
所述树脂A组分由如下重量份数的组分组成:
优选的:
所述树脂B1组分由如下重量份数的组分组成:
异氰酸酯B1 100份;
聚多元醇B1 12~20份;
副反应阻止剂 0.002~0.010份;
优选的:
所述树脂B2组分由如下重量份数的组分组成:
异氰酸酯B2 100份;
聚多元醇B2 50~90份;
副反应阻止剂 0.002~0.010份。
所述树脂A组分中聚多元醇A为聚醚多元醇和聚合物多元醇的混合物,所述聚醚多元醇和聚合物多元醇的质量比为1∶1~4∶1。
所述聚醚多元醇为数均分子量6000~10000的聚氧化乙烯-氧化丙烯三元醇;
所述聚合物多元醇为数均分子量6000~10000的苯乙烯或丙烯腈接枝共聚氧化乙烯-氧化丙烯三元醇,固含量为40~50%。
所述交联剂为乙二醇、1,4-丁二醇、1,3-丙二醇,1,6-丁二醇中的一种或一种以上。
所述催化剂为三乙烯二胺的乙二醇溶液和70wt%的双(二甲氨基乙基)醚与30wt%一缩二丙二醇配成的溶液的混合物,所述三乙烯二胺的乙二醇溶液和70wt%的双(二甲氨基乙基)醚与30wt%一缩二丙二醇配成的溶液的混合物的质量比为1∶4~1∶1。
所述发泡剂为水;
所述匀泡剂为有机硅匀泡剂;
所述树脂B1组分中异氰酸酯B1为二苯基甲烷二异氰酸酯、碳化二亚胺改性二苯基甲烷二异氰酸酯、甲苯二异氰酸酯或萘二异氰酸酯中的一种或一种以上;
所述树脂B1组分中聚多元醇B1为聚己二酸系聚酯多元醇,优选乙二醇、二乙二醇、1,4-丁二醇中的一种或几种混合物与己二酸通过缩合共聚而成的聚己二酸系聚酯二元醇,数均分子量为1000~3000;
所述树脂B1组分中副反应阻止剂为磷酸;
所述树脂B2组分中异氰酸酯B2为二苯基甲烷二异氰酸酯、碳化二亚胺改性二苯基甲烷二异氰酸酯、甲苯二异氰酸酯或萘二异氰酸酯中的一种或一种以上;
所述树脂B2组分中聚多元醇B2为聚己二酸系聚酯多元醇或聚对苯二甲酸系聚酯多元醇,优选乙二醇、二乙二醇、1,4-丁二醇中的一种或几种混合物与己二酸或对苯二甲酸通过缩合共聚而成,数均分子量为1000~3000;
所述树脂B2组分中副反应阻止剂为磷酸。
所述的轮胎用聚氨酯树脂的制备方法,包括如下步骤:
(1)将聚多元醇A、交联剂、催化剂、发泡剂和匀泡剂在50~60℃下反应1.5~2.5h后,降温至40~45℃,混合1.0~1.5h,得到所述的聚氨酯树脂A组分;
(2)将异氰酸酯B1、聚多元醇B1和副反应阻止剂在65~75℃反应2~3h,即得聚氨酯树脂B1组分;
(3)将异氰酸酯B2、聚多元醇B2和副反应阻止剂在65~75℃反应2~3h,即得聚氨酯树脂B2组分。
所述轮胎用聚氨酯树脂,用于制备聚氨酯轮胎的方法包括如下步骤:
将温度为35~45℃的聚氨酯树脂A组分、温度为35~45℃的聚氨酯树脂B1组分和温度为35~45℃的聚氨酯树脂B2组分,在浇注机中混合后,注入35~45℃模具中反应3~5min成型,脱模,自然环境下放置2天熟化即得所述的聚氨酯轮胎。
聚氨酯树脂B1组分和聚氨酯树脂B2组分的质量比为1∶9~9∶1;
A组分活性氢摩尔数与B1组分和B2组分总的异氰酸酯基团摩尔数之比为1∶1。
本发明有益效果是:
本发明轮胎用聚氨酯树脂包含树脂A组分、树脂B1组分和树脂B2组分,通过调节B1组分和B2组分的质量比,可制得不同性能的聚氨酯轮胎。相比与普通的双组份聚氨酯树脂,本发明产品在生产聚氨酯轮胎过程中生产厂家无需配置各种不同原料,生产不同要求轮胎时,仅需调整B1和B2组份的配比,节约生产成本,减少资源浪费,提高生产效率,而且利用不同比例的两种预聚体组分(B1和B2)与A组分混合反应形成的聚氨酯树脂链段更加规整有序,制得的聚氨酯轮胎性能更佳。利用本发明生产的聚氨酯轮胎硬度可调范围宽,物性好、压缩变形率低,更适合连续生产操作,成本低,生产效率高。
具体实施方式
下面通过实施例对本发明进行具体的描述,只用于对本发明进行进一步说明,不能理解为对本发明保护范围的限定。实施例中采用的实施条件可以根据具体厂家的条件和要求做一些非本质的改进和调整。
实施例1
221.7kg的聚氧化乙烯-氧化丙烯三元醇(数均分子量为6000),55.4kg的苯乙烯接枝共聚氧化乙烯-氧化丙烯三元醇(数均分子量为6000),1.39kg乙二醇,0.22kg的三乙烯二胺的乙二醇溶液,0.89kg的70wt%的双(二甲氨基乙基)醚与30wt%一缩二丙二醇配成的溶液,2.77kg水和0.28kg有机硅匀泡剂在50℃下反应2.5h后,降温至40℃,混合1.5h,得到聚氨酯树脂A组分。
将45.4kg的二苯基甲烷二异氰酸酯,15.1kg的碳化二亚胺改性二苯基甲烷二异氰酸酯,0.76kg的聚己二酸乙二醇丁二醇酯二醇(数均分子量为1000)和0.0015kg的磷酸在65℃反应3h,即得聚氨酯树脂B1组分。
将4.54kg的二苯基甲烷二异氰酸酯,2.28kg的聚对苯二甲酸乙二醇酯二醇(数均分子量为1000)和0.0002kg的磷酸在65℃反应3h,即得聚氨酯树脂B2组分。
将温度为35℃的聚氨酯树脂A组分、温度为35℃的聚氨酯树脂B1组分和温度为35℃的聚氨酯树脂B2组分,在浇注机中混合后,注入35℃模具中反应5min成型,脱模,自然环境下放置2天熟化即得聚氨酯轮胎。
实施例2
221.7kg的聚氧化乙烯-氧化丙烯三元醇(数均分子量为6000),55.4kg的苯乙烯接枝共聚氧化乙烯-氧化丙烯三元醇(数均分子量为6000),1.39kg乙二醇,0.22kg的三乙烯二胺的乙二醇溶液,0.89kg的70wt%的双(二甲氨基乙基)醚与30wt%一缩二丙二醇配成的溶液,2.77kg水和0.28kg有机硅匀泡剂在50℃下反应2.5h后,降温至40℃,混合1.5h,得到聚氨酯树脂A组分。
将7.46kg的二苯基甲烷二异氰酸酯,2.48kg的碳化二亚胺改性二苯基甲烷二异氰酸酯,0.12kg的聚己二酸乙二醇丁二醇酯二醇(数均分子量为1000)和0.00032kg的磷酸在65℃反应3h,即得聚氨酯树脂B1组分。
将60.4kg的二苯基甲烷二异氰酸酯,30.2kg的聚对苯二甲酸乙二醇酯二醇(数均分子量为1000)和0.002kg的磷酸在65℃反应3h,即得聚氨酯树脂B2组分。
将温度为35℃的聚氨酯树脂A组分、温度为35℃的聚氨酯树脂B1组分和温度为35℃的聚氨酯树脂B2组分,在浇注机中混合后,注入35℃模具中反应5min成型,脱模,自然环境下放置2天熟化即得聚氨酯轮胎。
实施例3
101.0kg的聚氧化乙烯-氧化丙烯三元醇(数均分子量为10000),101.0kg的丙烯腈接枝共聚氧化乙烯-氧化丙烯三元醇(数均分子量为10000),2.02kg乙二醇,1.01kg的三乙烯二胺的乙二醇溶液,1.01kg的70wt%的双(二甲氨基乙基)醚与30wt%一缩二丙二醇配成的溶液,3.03kg水和4.04kg有机硅匀泡剂在60℃下反应1.5h后,降温至45℃,混合1.0h,得到所述的聚氨酯树脂A组分。
将48.3g的二苯基甲烷二异氰酸酯,12.1kg的碳化二亚胺改性二苯基甲烷二异氰酸酯,12.1kg的聚己二酸乙二醇丁二醇酯二醇(数均分子量为2000)和0.002kg的磷酸在75℃反应2h,即得聚氨酯树脂B1组分。
将4.34kg的二苯基甲烷二异氰酸酯,3.74kg的聚己二酸二乙二醇酯二醇(数均分子量为2000)和0.0002kg的磷酸在75℃反应2h,即得聚氨酯树脂B2组分。
将温度为45℃的聚氨酷树脂A组分、温度为45℃的聚氨酯树脂B1组分和温度为45℃的聚氨酯树脂B2组分,在浇注机中混合后,注入45℃箱泡中反应3min成型,脱模,自然环境下放置2天熟化即得聚氨酯轮胎。
实施例4
101.0kg的聚氧化乙烯-氧化丙烯三元醇(数均分子量为10000),101.0kg的丙烯腈接枝共聚氧化乙烯-氧化丙烯三元醇(数均分子量为10000),2.02kg乙二醇,1.01kg的三乙烯二胺的乙二醇溶液,1.01kg的70wt%的双(二甲氨基乙基)醚与30wt%一缩二丙二醇配成的溶液,3.03kg水和4.04kg有机硅匀泡剂在60℃下反应1.5h后,降温至45℃,混合1.0h,得到所述的聚氨酯树脂A组分。
将8.01kg的二苯基甲烷二异氰酸酯,2.00kg的碳化二亚胺改性二苯基甲烷二异氰酸酯,2.00kg的聚己二酸乙二醇丁二醇酯二醇(数均分子量为2000)和0.002kg的磷酸在75℃反应2h,即得聚氨酯树脂B组分。
将57.7kg的二苯基甲烷二异氰酸酯,50.1kg的聚己二酸二乙二醇酯二醇(数均分子量为2000)和0.009kg的磷酸在75℃反应2h,即得聚氨酯树脂B2组分。
将温度为45℃的聚氨酯树脂A组分、温度为45℃的聚氨酯树脂B1组分和温度为45℃的聚氨酯树脂B2组分,在浇注机中混合后,注入45℃箱泡中反应3min成型,脱模,自然环境下放置2天熟化即得聚氨酯轮胎。
实施例5
290.1kg的聚氧化乙烯-氧化丙烯三元醇(数均分子量为9000),145.1kg的苯乙烯接枝共聚氧化乙烯-氧化丙烯三元醇(数均分子量为9000),21.8kg乙二醇,1.31kg的三乙烯二胺的乙二醇溶液,2.61kg的70wt%的双(二甲氨基乙基)醚与30wt%一缩二丙二醇配成的溶液,5.66kg水和4.35kg有机硅匀泡剂在60℃下反应1.5h后,降温至45℃,混合1.0h,得到聚氨酯树脂A组分。
将83.6kg的二苯基甲烷二异氰酸酯,11.5kg的聚己二酸乙二醇酯二醇(数均分子量为3000)和0.008kg的磷酸在65℃反应3h,即得聚氨酯树脂B组分。
将28.5kg的二苯基甲烷二异氰酸酯,23.7kg的碳化二亚胺改性二苯基甲烷二异氰酸酯,43.0kg的聚己二酸丁二醇酯二醇(数均分子量为3000)和0.008kg的磷酸在65℃反应3h,即得聚氨酯树脂B2组分。
将温度为45℃的聚氨酯树脂A组分、温度为45℃的聚氨酯树脂B1组分和温度为45℃的聚氨酯树脂B2组分,在浇注机中混合后,注入45℃箱泡中反应3min成型,脱模,自然环境下放置2天熟化即得聚氨酯轮胎。
实施例6
200.0kg的聚氧化乙烯-氧化丙烯三元醇(数均分子量为8000),160.0kg的苯乙烯接枝共聚氧化乙烯-氧化丙烯三元醇(数均分子量为8000),36.0kg1,4-丁二醇,1.08kg的三乙烯二胺的乙二醇溶液,2.16kg的70wt%的双(二甲氨基乙基)醚与30wt%一缩二丙二醇配成的溶液,4.32kg水和4.68kg有机硅匀泡剂在50℃下反应2.5h后,降温至40℃,混合1.5h,得到聚氨酯树脂A组分。
将172.5kg的二苯基甲烷二异氰酸酯,10.05kg的聚己二酸乙二醇酯二醇(数均分子量为2000)和0.010kg的磷酸在75℃反应2h,即得聚氨酯树脂B组分。
将20.3kg的二苯基甲烷二异氰酸酯,14.2kg的碳化二亚胺改性二苯基甲烷二异氰酸酯,26.4kg的聚对苯二甲酸二乙二醇酯二醇(数均分子量为2000)和0.005kg的磷酸在75℃反应2h,即得聚氨酯树脂B2组分。
将温度为35℃的聚氨酯树脂A组分、温度为35℃的聚氨酯树脂B1组分和温度为35℃的聚氨酯树脂B2组分,在浇注机中混合后,注入35℃箱泡中反应5min成型,脱模,自然环境下放置2天熟化即得聚氨酯轮胎。
对比例1
221.7kg的聚氧化乙烯-氧化丙烯三元醇(数均分子量为6000),55.4kg的苯乙烯接枝共聚氧化乙烯-氧化丙烯三元醇(数均分子量为6000),1.39kg乙二醇,0.22kg的三乙烯二胺的乙二醇溶液,0.89kg的70wt%的双(二甲氨基乙基)醚与30wt%一缩二丙二醇配成的溶液,2.77kg水和0.28kg有机硅匀泡剂在50℃下反应2.5h后,降温至40℃,混合1.5h,得到聚氨酯树脂A组分。
将49.94kg的二苯基甲烷二异氰酸酯,15.1kg的碳化二亚胺改性二苯基甲烷二异氰酸酯,0.76kg的聚己二酸乙二醇丁二醇酯二醇(数均分子量为1000),2.28kg的聚对苯二甲酸乙二醇酯二醇(数均分子量为1000)和0.0017kg的磷酸在65℃反应3h,即得聚氨酯树脂B组分。
将温度为35℃的聚氨酯树脂A组分和温度为35℃的聚氨酯树脂B组分,在浇注机中混合后,注入35℃箱泡中反应5min成型,脱模,自然环境下放置2天熟化即得聚氨酯轮胎。对比例2
101.0kg的聚氧化乙烯-氧化丙烯三元醇(数均分子量为10000),101.0kg的丙烯腈接枝共聚氧化乙烯-氧化丙烯三元醇(数均分子量为10000),2.02kg乙二醇,1.01kg的三乙烯二胺的乙二醇溶液,1.01kg的70wt%的双(二甲氨基乙基)醚与30wt%一缩二丙二醇配成的溶液,3.03kg水和4.04kg有机硅匀泡剂在60℃下反应1.5h后,降温至45℃,混合1.0h,得到所述的聚氨酯树脂A组分。
将52.64kg的二苯基甲烷二异氰酸酯,12.1kg的碳化二亚胺改性二苯基甲烷二异氰酸酯,12.1kg的聚己二酸乙二醇丁二醇酯二醇(数均分子量为2000),4.34kg的聚己二酸二乙二醇酯二醇(数均分子量为2000)和0.0022kg的磷酸在75℃反应2h,即得聚氨酯树脂B组分。
将温度为45℃的聚氨酯树脂A组分和温度为45℃的聚氨酯树脂B组分,在浇注机中混合后,注入45℃箱泡中反应3min成型,脱模,自然环境下放置2天熟化即得聚氨酯轮胎。
实施例1~4和对比例1~2所制得的聚氨酯轮胎的各项性能测试如下:
表I
由实施例1和实施例2,实施例3和实施例4可知,在聚氨酯树脂A组分不变的前提下,简单调整树脂B1组分和B2组分的比例就可制得不同硬度、不同物性和不同压缩变形率聚氨酯轮胎,提高了生产效率,同时节约能源消耗,节约生产成本。对比实施例1和对比例1,实施例3和对比例2可知,利用本发明轮胎用聚氨酯树脂更易制得硬度较高压缩变形率更低,或者硬度较低压缩变形率也更低的聚氨酯轮胎。
尽管上述实施例已经对本发明的技术方案进行了详细地描述,但本发明的技术方案并不限于以上实施例,在不脱离本发明的思想和宗旨情况下,对本发明申请专利范围的内容所作的等效变化或修饰,都应为本发明的技术范畴。
Claims (10)
1.轮胎用聚氨酯树脂,其特征在于,包含树脂A组分,树脂B1组分和树脂B2组分;所述树脂A组分由如下组分组成:聚多元醇A、交联剂、催化剂、发泡剂和匀泡剂;
所述树脂B1组分含有由如下重量份数的组分:
异氰酸酯B1 100份;
聚多元醇B1 10~40份;
副反应阻止剂 0.002~0.010份;
所述树脂B2组分由如下重量份数的组分组成:
异氰酸酯B2 100份;
聚多元醇B2 50~100份;
副反应阻止剂 0.002~0.010份;
所述的异氰酸酯B1选自二苯基甲烷二异氰酸酯、碳化二亚胺改性二苯基甲烷二异氰酸酯、甲苯二异氰酸酯或萘二异氰酸酯中的一种或一种以上;
所述聚多元醇B1为聚己二酸系聚酯二元醇;
所述异氰酸酯B2为二苯基甲烷二异氰酸酯、碳化二亚胺改性二苯基甲烷二异氰酸酯、甲苯二异氰酸酯或萘二异氰酸酯中的一种或一种以上;
所述聚多元醇B2为聚己二酸系聚酯多元醇或聚对苯二甲酸系聚酯多元醇。
2.根据权利要求1所述的轮胎用聚氨酯树脂,其特征在于,所述树脂A组分由如下组分组成:
3.根据权利要求2所述的轮胎用聚氨酯树脂,其特征在于,所述树脂A组分由如下组分组成:
所述树脂A组分由如下重量份数的组分组成:
4.根据权利要求1所述的轮胎用聚氨酯树脂,其特征在于,所述树脂B1组分由如下重量份数的组分组成:
异氰酸酯B1 100份;
聚多元醇B1 12~20份;
副反应阻止剂 0.002~0.010份;
所述树脂B2组分由如下重量份数的组分组成:
异氰酸酯B2 100份;
聚多元醇B2 50~90份;
副反应阻止剂 0.002~0.010份;
所述的异氰酸酯B1选自二苯基甲烷二异氰酸酯、碳化二亚胺改性二苯基甲烷二异氰酸酯、甲苯二异氰酸酯或萘二异氰酸酯中的一种或一种以上;
所述聚多元醇B1为乙二醇、二乙二醇、1,4-丁二醇中的一种或几种混合物与己二酸通过缩合共聚而成,数均分子量为1000~3000;
所述异氰酸酯B2为二苯基甲烷二异氰酸酯、碳化二亚胺改性二苯基甲烷二异氰酸酯、甲苯二异氰酸酯或萘二异氰酸酯中的一种或一种以上;
所述聚多元醇B2为乙二醇、二乙二醇、1,4-丁二醇中的一种或几种混合物与己二酸或对苯二甲酸通过缩合共聚而成,数均分子量为1000~3000;
所述副反应阻止剂为磷酸。
5.根据权利要求2所述的轮胎用聚氨酯树脂,其特征在于,所述树脂A组分中聚多元醇A为聚醚多元醇和聚合物多元醇的混合物;所述聚醚多元醇和聚合物多元醇的质量比为1∶1~4∶1。
6.根据权利要求5所述的轮胎用聚氨酯树脂,其特征在于,所述聚醚多元醇为数均分子量6000~10000的聚氧化乙烯-氧化丙烯三元醇;
所述聚合物多元醇为数均分子量6000~10000的苯乙烯或丙烯腈接枝共聚氧化乙烯-氧化丙烯三元醇,固含量为40~50%;
所述交联剂为乙二醇、1,4-丁二醇、1,3-丙二醇,1,6-丁二醇中的一种或一种以上;
所述催化剂为三乙烯二胺的乙二醇溶液和70wt%的双(二甲氨基乙基)醚与30wt%一缩二丙二醇配成的溶液的混合物,所述三乙烯二胺的乙二醇溶液和70wt%的双(二甲氨基乙基)醚与30wt%一缩二丙二醇配成的溶液的混合物的质量比为1∶4~1∶1;
所述发泡剂为水;
所述匀泡剂为有机硅匀泡剂。
7.根据权利要求1~6任一项所述的轮胎用聚氨酯树脂,其特征在于,所述聚氨酯树脂B1组分和聚氨酯树脂B2组分的质量比为1∶9~9∶1;A组分活性氢摩尔数与B1组分和B2组分总的异氰酸酯基团摩尔数之比为1∶1。
8.根据权利要求1~7任一项所述的轮胎用聚氨酯树脂的制备方法,其特征在于,包括如下步骤:
(1)将聚多元醇A、交联剂、催化剂、发泡剂和匀泡剂在50~60℃下反应1.5~2.5h后,降温至40~45℃,混合1.0~1.5h,得到所述的聚氨酯树脂A组分;
(2)将异氰酸酯B1、聚多元醇B1和副反应阻止剂在65~75℃反应2~3h,即得聚氨酯树脂B1组分;
(3)将异氰酸酯B2、聚多元醇B2和副反应阻止剂在65~75℃反应2~3h,即得聚氨酯树脂B2组分。
9.据权利要求1~7任一项所述的轮胎用聚氨酯树脂的应用,其特征在于,用于制备聚氨酯轮胎。
10.根据权利要求9所述的应用,其特征在于,应用方法,包括如下步骤:将温度为35~45℃的聚氨酯树脂A组分、温度为35~45℃的聚氨酯树脂B1组分和温度为35~45℃的聚氨酯树脂B2组分,在浇注机中混合后,注入35~45℃模具中反应3~5min成型,脱模,自然环境下放置2天熟化即得所述的聚氨酯轮胎。
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CN108973534A (zh) * | 2018-07-20 | 2018-12-11 | 滁州市玉林聚氨酯有限公司 | 一种吸地防滑聚氨酯轮胎及其制备方法 |
CN110372842A (zh) * | 2019-07-30 | 2019-10-25 | 青岛双星轮胎工业有限公司 | 具有荧光效果的免充气轮胎配方及其制备方法 |
CN110746562A (zh) * | 2019-11-11 | 2020-02-04 | 湖北可兴鞋业有限公司 | 一种合成橡胶及其制备方法 |
CN111169060A (zh) * | 2018-11-12 | 2020-05-19 | 广州科济化学材料有限公司 | 一种外胎内浇注聚氨酯发泡免充气轮的制作工艺 |
CN111518381A (zh) * | 2020-05-29 | 2020-08-11 | 叶正芬 | 一种工程轮胎用双组分聚氨酯原液及其制备方法 |
CN109265974B (zh) * | 2018-08-02 | 2021-03-26 | 江苏唯源橡塑制品有限公司 | 一种轮椅用耐水耐高温pu轮胎及其制备方法 |
CN113292764A (zh) * | 2021-05-07 | 2021-08-24 | 湖北祥源新材科技股份有限公司 | 一种耐压缩聚氨酯泡棉及其制备方法 |
CN113512286A (zh) * | 2021-04-25 | 2021-10-19 | 苏州频发机电科技有限公司 | 一种高耐磨、抗老化的聚氨酯轮胎 |
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CN108973534A (zh) * | 2018-07-20 | 2018-12-11 | 滁州市玉林聚氨酯有限公司 | 一种吸地防滑聚氨酯轮胎及其制备方法 |
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CN111169060A (zh) * | 2018-11-12 | 2020-05-19 | 广州科济化学材料有限公司 | 一种外胎内浇注聚氨酯发泡免充气轮的制作工艺 |
CN110372842A (zh) * | 2019-07-30 | 2019-10-25 | 青岛双星轮胎工业有限公司 | 具有荧光效果的免充气轮胎配方及其制备方法 |
CN110746562A (zh) * | 2019-11-11 | 2020-02-04 | 湖北可兴鞋业有限公司 | 一种合成橡胶及其制备方法 |
CN111518381A (zh) * | 2020-05-29 | 2020-08-11 | 叶正芬 | 一种工程轮胎用双组分聚氨酯原液及其制备方法 |
CN113512286A (zh) * | 2021-04-25 | 2021-10-19 | 苏州频发机电科技有限公司 | 一种高耐磨、抗老化的聚氨酯轮胎 |
CN113292764A (zh) * | 2021-05-07 | 2021-08-24 | 湖北祥源新材科技股份有限公司 | 一种耐压缩聚氨酯泡棉及其制备方法 |
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