CN107245162A - 一种聚氨酯降解方法及其降解产物在塑胶跑道乙组分中的应用 - Google Patents
一种聚氨酯降解方法及其降解产物在塑胶跑道乙组分中的应用 Download PDFInfo
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Abstract
本发明公开了一种聚氨酯降解方法及其降解产物在聚氨酯塑胶跑道乙组分中的应用。本方法是一种以有机酸作为降解剂,在催化剂的作用下降解聚氨酯弹性体,所将制得的降解产物可代替全新聚醚多元醇应用于聚氨酯塑胶跑道乙组分。本发明无需使用大量的降解剂,无需抽真空,降解过程中的馏分主要是原料自带的水分,且降解后胺类副产物大大减少,无需加入针对胺类副产物的处理剂,达到降低三废、提高产率、简化工艺和节省成本的目的,降解产物能完全替代全新聚醚多元醇应用于聚氨酯塑胶跑道乙组分,从而大大降低聚氨酯塑胶跑道组合料成本。
Description
技术领域
本发明涉及聚氨酯技术领域,更具体地涉及一种聚氨酯降解方法及其降解产物在塑胶跑道乙组分中的应用。
背景技术
目前公开报道的聚氨酯降解方法主要有醇解法、水解法、胺解法、碱解法,其中最具有产业化价值的是醇解法。醇解过程的基本反应是利用烷基二醇为降解剂,在150-250℃温度范围内,使聚氨酯废料中的氨基甲酸酯基断裂,即氨基甲酸酯基团与烷基二醇进行酯交换反应,氨基甲酸酯基团被短的醇链取代,释放出长链多元醇。常用的醇解剂包括乙二醇、二乙二醇、二甘醇、丙二醇、二丙二醇、丁二醇、聚乙二醇、聚丙二醇等。
由于聚氨酯结构的复杂,参与反应的基团比较多,还会发生很多副反应,主要的副反应是在醇解剂的作用下,脲基断裂生成胺和多元醇。为了降解完全,醇解剂往往需要大大过量,一般不少于聚氨酯废料的40%。过量的醇解剂在降解完成后往往需要抽真空除去,费事费力且会产生大量无用馏分。此外,降解过程会产生大量的胺类副产物,需要加入各种处理剂与其反应,使其转化成低反应活性的物种,如美国专利5,556,889中,降解完后,加入环氧脂肪油处理胺类副产物;M. Modesti等人在解聚过程中加入六亚甲基四胺处理胺类副产物。这样一来造成工艺复杂、综合产率低(一般不足70%)、成本较高。
因此既能简化降解回收工艺又能降低生产成本,降解产物还能制备性能优异的聚氨酯塑胶跑道乙组分产品,具有十分重要的环保和经济价值。
发明内容
本发明旨在克服上述现有技术需要抽真空、胺类副产物较多、工艺复杂、成本高昂的问题,提供一种新的聚氨酯的降解方法。
本发明的另一目的在于提供一种聚氨酯降解产物在聚氨酯塑胶跑道乙组分中的应用。
为解决上述技术问题,本发明所采用的技术方案是:
一种聚氨酯降解方法,包括如下步骤:
S1.将聚氨酯弹性体废料、有机酸降解剂和催化剂按重量比100份:20~25份:1~1.5份的比例配成聚氨酯降解体系;
S2.将配成的降解体系加热到200℃~210℃得到聚氨酯降解产物;
所述有机酸降解剂为二元羧酸;所述催化剂为酰化催化剂或Lewis酸类催化剂。
利用有机二元羧酸作为降解剂,在催化剂的作用下,降解聚氨酯弹性体废料,过程中无需抽真空,降解过程中的馏分主要是原料自带的水分,且解聚后胺类副产物大大减少,无需加入针对胺类副产物的处理剂,工艺简单,产率大大提高,生产成本降低。
进一步地,所述二元羧酸含有4个以上的碳原子。
进一步地,所述二元羧酸或酸酐优选为丁二酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸或苯甲酸酐。
进一步地,所述酰化催化剂优选为4-二甲氨基吡啶或1-羟基苯并***。
进一步地,所述Lewis酸类催化剂优选为三氯化铁或三溴化铝或二氯化锌。
一种聚氨酯塑胶跑道乙组分,包括以下按重量份计算的组分:
经所述降解方法得到的聚氨酯降解产物125~135份;
硫化剂15~25份;
氯化石蜡270~290份;
滑石粉540~570份;
甲苯或二甲苯25~35份。
本发明所述方法得到的聚氨酯降解产物胺值低(AN≤20),羟值适中(HV=50~90),反应活性适中,可完全替代全新聚醚多元醇应用于聚氨酯塑胶跑道乙组分,制备的乙组分的硬度、伸长率和拉伸长度均达到塑胶跑道国家标准。
优选地,所述硫化剂优选为3,3,-二氯-4,4,-二氨基二苯基甲烷(MOCA)。
所述聚氨酯塑胶跑道乙组分的制备方法包括如下步骤:
S1. 将聚氨酯弹性体废料降解产物、硫化剂预混合,加热融化,控制温度不超过110℃;
S2. 加入氯化石蜡、滑石粉和甲苯或二甲苯搅拌均匀。
与现有技术相比,本发明的有益效果是:
本发明提供一种新的聚氨酯的降解方法,其利用有机酸作为降解剂,降解过程中无需抽真空,无需加入胺类副产物处理剂,简化了工艺,提高了产率和经济效益。所得降解产物胺值低(AN≤20)、羟值适中(HV=50~90)、反应活性适中,可完全替代全新聚醚多元醇应用于聚氨酯塑胶跑道乙组分,所制的产品性能优异,成本低廉,具有极高的推广价值。
具体实施方式
下面结合具体实施方式对本发明作进一步的说明,但实施例并不对本发明做任何形式的限定。除非另有说明,本发明实施例采用的原料试剂为常规购买的原料试剂。
实施例1
S1.将聚氨酯弹性体废料、苯甲酸酐和4-二甲氨基吡啶按重量比100份:20份:1份的比例配成聚氨酯降解体系;
S2.将配成的降解体系加热到200℃-210℃得到聚氨酯降解产物。
实施例2
S1.将聚氨酯弹性体废料、苯甲酸酐和1-羟基苯并***按重量比100份:25份:1份的比例配成聚氨酯降解体系;
S2.将配成的降解体系加热到200℃-210℃得到聚氨酯降解产物。
实施例3
S1.将聚氨酯弹性体废料、丁二酸和1-羟基苯并***按重量比100份:20份:1.5份的比例配成聚氨酯降解体系;
S2.将配成的降解体系加热到200℃-210℃得到聚氨酯降解产物。
实施例4
S1.将聚氨酯弹性体废料、戊二酸和三氯化铁按重量比100份:25份:1.25份的比例配成聚氨酯降解体系;
S2.将配成的降解体系加热到200℃-210℃得到聚氨酯降解产物。
实施例5
S1.将聚氨酯弹性体废料、庚二酸和三溴化铝按重量比100份:23份:1.5份的比例配成聚氨酯降解体系;
S2.将配成的降解体系加热到200℃-210℃得到聚氨酯降解产物。
实施例6
S1.将聚氨酯弹性体废料、辛二酸和二氯化锌按重量比100份:24份:1.1份的比例配成聚氨酯降解体系;
S2.将配成的降解体系加热到200℃-210℃得到聚氨酯降解产物。
实施例7
S1.将聚氨酯弹性体废料、壬二酸和4-二甲氨基吡啶按重量比100份:25份:1份的比例配成聚氨酯降解体系;
S2.将配成的降解体系加热到200℃-210℃得到聚氨酯降解产物。
实施例8
S3.将实施例1所制得的聚氨酯降解产物130份、硫化剂MOCA20份预混合,加热融化,控制温度不超过110℃;
S4.加入氯化石蜡、滑石粉和二甲苯搅拌均匀。
实施例9
S3.将实施例2所制得的聚氨酯降解产物130份、硫化剂MOCA20份预混合,加热融化,控制温度不超过110℃;
S4.加入氯化石蜡、滑石粉和甲苯搅拌均匀。
对实施例1-7的降解产物的指标进行了检测,检测指标结果见表1。
对实施例8-9制备的聚氨酯塑胶跑道乙组分性能进行测试,其测试参考GB/T14833-93,测试结果见表2。
表1降解产物检测指标
检测指标 | 实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例5 | 实施例6 | 实施例7 |
羟值/mg KOH/g | 65 | 64 | 66 | 72 | 80 | 85 | 71 |
胺值/mg KOH/g | 12 | 13 | 11 | 10 | 15 | 13 | 12 |
酸值/mg KOH/g | 2 | 1 | 1 | 2 | 3 | 3 | 2 |
水分含量/% | 0.2 | 0.3 | 0.2 | 0.5 | 0.3 | 0.3 | 0.3 |
粘度/m Pa s | 5300 | 5500 | 5700 | 6000 | 5800 | 5600 | 5500 |
表2塑胶跑道乙组分测试结果
检测项目 | 塑胶跑道应满足的国家标准 | 实施例1 | 实施例2 |
硬度(邵A)/度 | 45-60 | 54 | 56 |
伸长率/% | ≥90 | 300 | 360 |
拉伸强度/MPa | ≥0.7 | 1.22 | 1.32 |
乙组成本(元/公斤) | —— | 2.92 | 3.02 |
根据上表的测试结果可知,利用有机酸降解聚氨酯废料的方法获得的降解产物制备出的聚氨酯塑胶跑道乙组分能够满足国家标准,且能节省原材料成本。
Claims (7)
1.一种聚氨酯降解方法,其特征在于,包括如下步骤:
S1.将聚氨酯弹性体废料、有机酸降解剂和催化剂按重量比100份:20~25份:1~1.5份的比例配成聚氨酯降解体系;
S2.将配成的降解体系加热到200℃~210℃得到聚氨酯降解产物;
所述有机酸降解剂为二元羧酸或酸酐;所述催化剂为酰化催化剂或Lewis酸类催化剂。
2.如权利要求1 所述的聚氨酯降解方法,其特征在于,所述二元羧酸或酸酐为丁二酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸或苯甲酸酐。
3.如权利要求1所述的聚氨酯降解方法,其特征在于,所述酰化催化剂为4-二甲氨基吡啶或1-羟基苯并***。
4.如权利要求1所述的聚氨酯降解方法,其特征在于,所述Lewis酸类催化剂为三氯化铁、三溴化铝或二氯化锌。
5.一种聚氨酯塑胶跑道乙组分,其特征在于,包括以下按重量份计算的组分:
经权利要求1方法得到的聚氨酯降解产物125~135份;
硫化剂15~25份;
氯化石蜡270~290份;
滑石粉540~570份;
甲苯或二甲苯25~35份。
6.如权利要求5所述的聚氨酯塑胶跑道乙组分,其特征在于,所述硫化剂为3,3,-二氯-4,4,-二氨基二苯基甲烷。
7.权利要求5或6所述的聚氨酯塑胶跑道乙组分的制备方法,其特征在于,包括如下步骤:
S3.将聚氨酯降解产物、硫化剂预混合,加热融化,控制温度不超过110℃;
S4.加入氯化石蜡、滑石粉和甲苯或二甲苯搅拌均匀。
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