CN110746923A - 一种用于人造草坪的阻燃耐热双组分聚氨酯草坪背胶 - Google Patents
一种用于人造草坪的阻燃耐热双组分聚氨酯草坪背胶 Download PDFInfo
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Abstract
本发明公开了一种用于人造草坪的阻燃耐热双组分聚氨酯胶粘剂及其制备方法。本发明所述双组份聚氨酯胶粘剂由A组分与B组分按4~6:1的重量比混合制得,所述A组分主要成分为含羟基的多元醇化合物,其粘度为3000‑7000mPa•s,羟值为50‑200mgKOH/g;所述B组分主要成分为含‑NCO基团的化合物,NCO值为20‑35%,粘度为100‑900mPa•s。本发明所述双组分聚氨酯胶粘剂具有更优异的回弹性、耐低温耐水解性能、较高的阻燃性能;添加支化聚醚‑聚酯多元醇,提高了胶层的耐热性能;不使用任何有机溶剂,具有环保性,气味低,无污染,同时又具有优良的粘结性,可很好地适用于各种高端人造草坪的制造。
Description
技术领域
本发明涉及一种胶粘剂,更具体的说是涉及一种用于人造草坪的阻燃耐热双组分聚氨酯草坪背胶及其制备方法。
背景技术
人造草坪是由草丝、基布以及牢固草丝在基布上的胶粘剂组成,草丝一般是簇绒在基布上,人造草坪比天然草坪具有更加优异的性能,它护养简单,排水迅速,全天候可用以及场地平整度优异,广泛应用于运动场地,公用练习休闲场所、室内美化以及景观铺设。然而使用过程中除了草丝性能差异之外,最主要的就是草丝在基布上的牢固性、耐热性及阻燃性,这对于胶粘剂的选择尤为重要。
聚氨酯胶粘剂(PU)具有大量极性基团,分子可设计性,软硬度可调节等优势,对多种基材具有很强的粘结性,同时,通过交联与结晶,提高其内聚力以及粘结强度,具有更优异的防老化性、耐水解性与抗侵蚀性能,已广泛使用于人造草坪背涂,具有较高的拔出力。但目前市场上的聚氨酯草坪胶均不能经受60-80℃的较高温度,铺设的草坪在夏季强烈阳光照射下,胶层变软,草丝拔出力下降明显,导致草丝脱落严重,甚至出现局部草坪破损或裸露的问题,影响了整体草坪的美观性和使用寿命。同时,由于室内运动场地的流行,许多材料都需要达到一定的阻燃标准,对胶粘剂也提出了阻燃性的要求。
发明内容
本发明的目的是提供一种用于人造草坪的阻燃耐热双组分聚氨酯背胶,它具有较高的粘结强度、较好的耐热性,并且具有优异的阻燃性,可以满足室内场地的阻燃要求。本发明的另一个目的是提供一种用于人造草坪的阻燃耐热双组分聚氨酯草坪背胶的制备方法。
本发明是通过以下技术方案实现的:
一种用于人造草坪的阻燃耐热双组分聚氨酯胶粘剂,由A组分与B组分按4~6:1的重量比混合制得,所述A组分主要成分为含羟基的多元醇化合物,其粘度为3000-7000mPa·s,羟值为50-200mgKOH/g;所述B组分主要成分为含-NCO基团的化合物,NCO值为20-35%,粘度为100-900mPa·s。
所述A组分由以下组分按重量份数组成:
所述B组分由以下组分按重量份数组成:
多异氰酸酯 60~85份,
聚合物二元醇 15~40份;
所述高分子量聚醚多元醇为聚氧化丙烯多元醇,其重均分子量为3000~6000,官能度为3,羟值为30-100mgKOH/g,为市售商购产品;
所述聚合物聚醚多元醇为乙烯基单体接枝改性聚醚多元醇的化合物,简称聚合物聚醚多元醇,其固含量为30-50%,羟值为20-50mgKOH/g,为市售商购产品;优选使用蓝星东大HPOP-42、钟山化工H-45、上海高桥GPOP-2042;
所述阻燃聚醚多元醇为含磷类或氮类的聚醚多元醇,磷或氮的含量为5-25wt%,其重均分子量为1000-3000,其官能度2,羟值为50-200mgKOH/g,为市售商购产品;
所述支化聚醚-聚酯多元醇为一种100%固含的支化的油脂化学聚醚-聚酯多元醇,其羟值为100-400mgKOH/g,官能度为2.5-4.0,为市售商购产品;优选使用BASF公司的Sovermol 805、815、750、760牌号的产品;
所述无机填料由重质碳酸钙、轻质碳酸钙中任意一种与硅微粉、石英粉、云母粉中任意一种按照重量比2-4:1混合而成;所述重质碳酸钙优选400目重质碳酸钙或800目重质碳酸钙;
所述阻燃剂为液体无卤含磷类阻燃剂,磷的含量为5-35wt%,分解温度大于180℃;优选为阻燃剂DEEP、阻燃剂DMPP、阻燃剂TBEP、阻燃剂TCP中的任意一种;
所述色浆为白色、黑色、蓝色、绿色的无溶剂聚氨酯专用色浆,为市售商购产品;
所述助剂为分散剂和硅烷偶联剂按照重量比1:4-6配置的混合物,分散剂为BYK-969或BYK-985,硅烷偶联剂为KH-550或KH-560,二者按比例加入混合均匀即可;
所述催化剂为有机胺类与有机锌或有机铋类催化剂按重量比1:2-4混合使用,优选双(二甲氨基乙基)醚或三亚乙基二胺与异辛酸锌或异辛酸铋混合;
所述多异氰酸酯选自多亚甲基多苯基异氰酸酯(聚合MDI)、4,4'-二苯基甲烷二异氰酸酯(纯MDI)、2,4'-二苯基甲烷二异氰酸酯与4,4'-二苯基甲烷二异氰酸酯的混合物(MDI-50),碳化二亚胺改性二苯基甲烷二异氰酸酯(液化MDI)中的任意一种或两种混合;
所述聚合物二元醇为聚氧化丙烯二元醇、聚己内酯二元醇、聚四氢呋喃二元醇中任意一种或两种任意组合,其重均分子量为2000-3000,羟值为50-200mgKOH/g,为市售商购产品,组合物的羟值亦为50-200mgKOH/g。
本发明所述一种用于人造草坪的阻燃耐热双组分聚氨酯胶粘剂的制备方法,具体包括如下步骤:
(1)A组分的制备:将高分子量聚醚多元醇、聚合物聚醚多元醇、阻燃聚醚多元醇和支化聚醚-聚酯多元醇加入反应釜中,升温到110-120℃,边搅拌边抽真空脱水2-3h,水分指标控制在200ppm以下;降温至40-50℃,加入无机填料,以600-1500r/min的速度高速分散搅拌1-2h,然后加入阻燃剂、色浆、助剂、催化剂,继续搅拌均匀,检测粘度合格出料,即得该双组分聚氨酯胶粘剂的A组分;
(2)B组分的制备:向聚合釜中快速加入多异氰酸酯及聚合物二元醇,缓慢升温至80℃,并在通干燥氮气状态下搅拌反应2-3小时,测定-NCO值和粘度,合格后降温到室温下出料,得到B组份;
(3)双组分聚氨酯胶粘剂的制备:将步骤(1)制得的组分A与步骤(2)制得的组分B按比例混合制得所述双组份聚氨酯胶粘剂。
本发明提供的双组分聚氨酯胶粘剂采用高分子量聚醚多元醇和聚合物聚醚多元醇为主基料,相比聚酯多元醇具有更优异的回弹性、耐低温耐水解性能;添加阻燃聚醚多元醇,并搭配液体阻燃剂,大大提高胶体的阻燃性能;添加支化聚醚-聚酯多元醇,提高了胶层的耐热性能,长期60-80℃+70-90%湿度环境下粘结强度衰减小;不使用任何有机溶剂,具有环保性,气味低,无污染,同时又具有优良的粘结性,可很好地适用于各种高端人造草坪的制造。
具体实施方式
以下通过具体实施例说明本发明,但是本发明并不仅仅限定于这些实施例。若没有特别说明,所有原料均为市售商购产品。
实施例1
一种用于人造草坪的阻燃耐热双组分聚氨酯胶粘剂的制备方法包括如下步骤:
(1)A组分的制备:
A组分的原料按重量份计如下所述:
将上述高分子量聚醚多元醇、聚合物聚醚多元醇、阻燃聚醚多元醇和支化聚醚-聚酯多元醇加入反应釜中,升温到110-120℃,边搅拌边抽真空脱水2-3h,水分指标控制在200ppm以下;降温至40-50℃,加入无机填料,以600-1500r/min的速度高速分散搅拌1-2h,然后加入阻燃剂、色浆、助剂、催化剂,继续搅拌均匀,检测粘度合格出料,即得该双组分聚氨酯胶粘剂的A组分;
(2)B组分的制备:
B组分的原料按重量份计如下所述:
聚合MDI 85份,
聚氧化丙烯二元醇(重均分子量3000) 15份,
向聚合釜中快速加入85份多异氰酸酯、15份聚合物二元醇,缓慢升温至80℃,并在通干燥氮气状态下搅拌反应2-3小时,测定-NCO值和粘度,合格后降温到室温下出料,得到B组份;
(3)将步骤(1)制得的A组分与步骤(2)制得的B组分按比例混合制得本发明所述双组分聚氨酯胶粘剂。
实施例2
一种用于人造草坪的阻燃耐热双组分聚氨酯胶粘剂的制备方法包括如下步骤:
(1)A组分的制备:
A组分的原料按重量份计如下所述:
将上述高重均分子量聚醚多元醇、聚合物聚醚多元醇、阻燃聚醚多元醇和支化聚醚-聚酯多元醇加入反应釜中,升温到110-120℃,边搅拌边抽真空脱水2-3h,水分指标控制在200ppm以下;降温至40-50℃,加入无机填料,以600-1500r/min的速度高速分散搅拌1-2h,然后加入阻燃剂、色浆、助剂、催化剂,继续搅拌均匀,检测粘度合格出料。即制得该双组分聚氨酯胶粘剂的A组分;
(2)B组分的制备:
B组分的原料按重量份计如下所述:
MDI-50 80份,
聚己内酯二元醇(重均分子量2000) 20份,
向聚合釜中快速加入80份多异氰酸酯、20份聚合物二元醇,缓慢升温至80℃,并在通干燥氮气状态下搅拌反应2-3小时,测定-NCO值和粘度,合格后降温到室温下出料,得到B组份;
(3)将步骤(1)制得的A组分与步骤(2)制得的B组分按比例混合制得本发明所述双组分聚氨酯胶粘剂。
实施例3
一种用于人造草坪的阻燃耐热双组分聚氨酯胶粘剂的制备方法包括如下步骤:
(1)A组分的制备:
A组分的原料按重量份计如下所述:
将上述高重均分子量聚醚多元醇、聚合物聚醚多元醇、阻燃聚醚多元醇和支化聚醚-聚酯多元醇加入反应釜中,升温到110-120℃,边搅拌边抽真空脱水2-3h,水分指标控制在200ppm以下;降温至40-50℃,加入无机填料,以600-1500r/min的速度高速分散搅拌1-2h,然后加入阻燃剂、色浆、助剂、催化剂,继续搅拌均匀,检测粘度合格出料。即制得该双组分聚氨酯胶粘剂的A组分;
(2)B组分的制备:
B组分的原料按重量份计如下所述:
纯MDI 67份,
聚四氢呋喃醚二元醇(重均分子量3000) 33份,
向聚合釜中快速加入67份多异氰酸酯、33份聚合物二元醇,缓慢升温至80℃,并在通干燥氮气状态下搅拌反应2-3小时,测定-NCO值和粘度,合格后降温到室温下出料,得到B组份;
(3)将步骤(1)制得的A组分与步骤(2)制得的B组分按比例混合制得本发明所述双组分聚氨酯胶粘剂。
实施例4
一种用于人造草坪的阻燃耐热双组分聚氨酯胶粘剂的制备方法包括如下步骤:
(1)A组分的制备:
A组分的原料按重量份计如下所述:
将上述高重均分子量聚醚多元醇、聚合物聚醚多元醇、阻燃聚醚多元醇和支化聚醚-聚酯多元醇加入反应釜中,升温到110-120℃,边搅拌边抽真空脱水2-3h,水分指标控制在200ppm以下;降温至40-50℃,加入无机填料,以600-1500r/min的速度高速分散搅拌1-2h,然后加入阻燃剂、色浆、助剂、催化剂,继续搅拌均匀,检测粘度合格出料。即制得该双组分聚氨酯胶粘剂的A组分;
(2)B组分的制备:
B组分的原料按重量份计如下所述:
纯MDI 55份,
液化MDI 20份,
聚氧化丙烯二元醇(重均分子量2000) 25份,
向聚合釜中快速加入75份多异氰酸酯、25份聚合物二元醇,缓慢升温至80℃,并在通干燥氮气状态下搅拌反应2-3小时,测定-NCO值和粘度,合格后降温到室温下出料,得到B组份;
(3)将步骤(1)制得的A组分与步骤(2)制得的B组分按比例混合制得本发明所述双组分聚氨酯胶粘剂。
对比例1
用普通聚醚三元醇N330(重均分子量3000)替代聚合物多元醇(固含量40%),其他同实施例1;
对比例2
用非阻燃的普通聚醚二元醇N220(重均分子量2000)代替含磷阻燃聚醚二元醇(重均分子量2000),去掉阻燃剂DEEP,其他同实施例1;
对比例3
用蓖麻油替代Sovermol 815,其他同实施例1。
性能测试
将各实施例制备的组分A和组分B按照重量比5:1混合,涂布在需要背胶的人造草坪上,涂胶量控制在800g/m2,经过100-110-120-130℃设置的四段烘道传动干燥固化8min后自然冷却放置24h后测试。
(1)常温草丝拔出力:用万能拉力机测试,取3次平均值,单位:N
(2)高温草丝拔出力:将涂胶的人造草坪放置80℃烘箱中24h后,取出立刻测试草丝拔出力,取3次平均值,单位:N
(3)低温草丝拔出力:将涂胶的人造草坪放置-50℃冷冻氮气中24后,取出立刻测试草丝拔出力,取3次平均值,单位:N
(4)阻燃性能:将组分A和组分B按照重量比5:1混合,倒入直径10cm、深度4mm圆盘中,放入130℃烘箱中固化5min,得到厚度约4mm、直径约10mm的圆形固化胶块,常温自然放置24h,用打火机对着胶块边缘燃烧20sec、30sec,然后拿开打火机,观察是否熄灭。
测试结果如下表1:
表1各实施例及对比例性能测试
编号 | 常温拔出力 | 高温拔出力 | 低温拔出力 | 燃烧20sec | 燃烧30sec |
实施例1 | 62.3N | 52.6N | 61.2N | 离火自熄 | 离火自熄 |
实施例2 | 58.6N | 50.4N | 58.0N | 离火自熄 | 离火自熄 |
实施例3 | 60.4N | 51.5N | 59.8N | 离火自熄 | 离火自熄 |
实施例4 | 61.5N | 51.8N | 60.9N | 离火自熄 | 离火自熄 |
对比例1 | 56.8N | 42.1N | 50.1N | 离火自熄 | 离火自熄 |
对比例2 | 59.2N | 44.0N | 58.5N | 不熄灭 | 不熄灭 |
对比例3 | 60.1N | 33.7N | 59.2N | 离火自熄 | 不熄灭 |
由表1中数据可以看出,实施例1-4和对比例1-3的常温草丝拔出力均较好;高温拔出力方面,实施例1-4的衰减小于20%,且衰减后仍然大于50N,还可以满足使用要求;对比例1-3的衰减大于20%,尤其是对比例3,衰减大于40%,已无法满足使用要求。这是因为对比例3中没有使用支化聚醚-聚酯多元醇原料,使得其耐高温性能很差。低温拔出力方面,实施例1-4和对比例1-3均表现出较好的耐低温性能,这是因为均使用高分子量聚醚多元醇或普通聚醚多元醇作为主料;对比例1低温拔出力衰减约10%,这是因为没有使用聚合物多元醇,而采用普通聚醚多元醇N330替代,这说明采用聚合物多元醇具有更好的耐低温性能,同时又具有优良的粘结性。
阻燃性能测试结果表明,实施例1-4的阻燃性能非常好,燃烧20sec和燃烧30sec均可离火自熄;对比例1燃烧20sec和30sec也可以离火自熄,但对比例3燃烧20sec可离火自熄、燃烧30sec不能熄灭,对比例2的阻燃性能很差,这是因为对比例2没有使用阻燃聚醚多元醇和阻燃剂,根本没有阻燃效果。
Claims (9)
1.一种用于人造草坪的阻燃耐热双组分聚氨酯胶粘剂,其特征在于,由A组分与B组分按4~6:1的重量比混合制得,所述A组分主要成分为含羟基的多元醇化合物,其粘度为3000-7000mPa·s,羟值为50-200mgKOH/g;所述B组分主要成分为含-NCO基团的化合物,NCO值为20-35%,粘度为100-900mPa·s。
2.根据权利要求1所述的一种用于人造草坪的阻燃耐热双组分聚氨酯胶粘剂,其特征在于,所述A组分由以下组分按重量份数组成:
所述B组分由以下组分按重量份数组成:
多异氰酸酯 60~85份,
聚合物二元醇 15~40份;
所述高分子量聚醚多元醇为聚氧化丙烯多元醇,其重均分子量为3000~6000,官能度为3,羟值为30-100mgKOH/g,为市售商购产品;
所述聚合物聚醚多元醇为乙烯基单体接枝改性聚醚多元醇的化合物,其固含量为30-50%,羟值为20-50mgKOH/g,为市售商购产品;
所述阻燃聚醚多元醇为含磷类或氮类的聚醚多元醇,磷或氮的含量为5-25wt%,其重均分子量为1000-3000,其官能度2,羟值为50-200mgKOH/g,为市售商购产品;
所述支化聚醚-聚酯多元醇为一种100%固含的支化的油脂化学聚醚-聚酯多元醇,其羟值为100-400mgKOH/g,官能度为2.5-4.0,为市售商购产品;
所述无机填料由重质碳酸钙、轻质碳酸钙中任意一种与硅微粉、石英粉、云母粉中任意一种按照重量比2-4:1混合而成;
所述阻燃剂为液体无卤含磷类阻燃剂,磷的含量为5-35wt%,分解温度大于180℃;
所述色浆为无溶剂聚氨酯专用色浆,为市售商购产品;
所述助剂为分散剂和硅烷偶联剂按照重量比1:4-6配置的混合物,分散剂为BYK-969或BYK-985,硅烷偶联剂为KH-550或KH-560;
所述催化剂为有机胺类与有机锌或有机铋类催化剂按重量比1:2-4混合;
所述多异氰酸酯选自多亚甲基多苯基异氰酸酯(聚合MDI)、4,4'-二苯基甲烷二异氰酸酯(纯MDI)、2,4'-二苯基甲烷二异氰酸酯与4,4'-二苯基甲烷二异氰酸酯的混合物(MDI-50),碳化二亚胺改性二苯基甲烷二异氰酸酯(液化MDI)中的任意一种或两种混合;
所述聚合物二元醇为聚氧化丙烯二元醇、聚己内酯二元醇、聚四氢呋喃二元醇中任意一种或两种任意组合,其重均分子量为2000-3000,所述聚合物二元醇的羟值为50-200mgKOH/g,为市售商购产品。
3.根据权利要求2所述的一种用于人造草坪的阻燃耐热双组分聚氨酯胶粘剂,其特征在于,所述聚合物聚醚多元醇选自蓝星东大HPOP-42、钟山化工H-45或上海高桥GPOP-2042。
4.根据权利要求2所述的一种用于人造草坪的阻燃耐热双组分聚氨酯胶粘剂,其特征在于,所述支化聚醚-聚酯多元醇使用BASF公司的Sovermol 805、815、750或760牌号的产品。
5.根据权利要求2所述的一种用于人造草坪的阻燃耐热双组分聚氨酯胶粘剂,其特征在于,所述重质碳酸钙为400目重质碳酸钙或800目重质碳酸钙。
6.根据权利要求2所述的一种用于人造草坪的阻燃耐热双组分聚氨酯胶粘剂,其特征在于,所述阻燃剂选自阻燃剂DEEP、阻燃剂DMPP、阻燃剂TBEP、阻燃剂TCP中的任意一种。
7.根据权利要求2所述的一种用于人造草坪的阻燃耐热双组分聚氨酯胶粘剂,其特征在于,所述色浆为白色、黑色、蓝色、绿色的无溶剂聚氨酯专用色浆,为市售商购产品。
8.根据权利要求2所述的一种用于人造草坪的阻燃耐热双组分聚氨酯胶粘剂,其特征在于,所述催化剂为双(二甲氨基乙基)醚或三亚乙基二胺与异辛酸锌或异辛酸铋按重量比1:2-4混合。
9.权利要求2至8任一项所述的一种用于人造草坪的阻燃耐热双组分聚氨酯胶粘剂的制备方法,其特征在于,具体包括如下步骤:
(1)A组分的制备:将高分子量聚醚多元醇、聚合物聚醚多元醇、阻燃聚醚多元醇和支化聚醚-聚酯多元醇加入反应釜中,升温到110-120℃,边搅拌边抽真空脱水2-3h,水分指标控制在200ppm以下;降温至40-50℃,加入无机填料,以600-1500r/min的速度高速分散搅拌1-2h,然后加入阻燃剂、色浆、助剂、催化剂,继续搅拌均匀,检测粘度合格出料,即得该双组分聚氨酯胶粘剂的A组分;
(2)B组分的制备:向聚合釜中快速加入多异氰酸酯及聚合物二元醇,缓慢升温至80℃,并在通干燥氮气状态下搅拌反应2-3小时,测定-NCO值和粘度,合格后降温到室温下出料,得到B组份;
(3)双组分聚氨酯胶粘剂的制备:将步骤(1)制得的组分A与步骤(2)制得的组分B按比例混合制得所述双组份聚氨酯胶粘剂。
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