CN109679418B - 氟碳漆用聚氨酯弹性体及其制备方法 - Google Patents
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Abstract
本发明涉及聚氨酯弹性体技术领域,具体涉及一种氟碳漆用聚氨酯弹性体及其制备方法。所述的氟碳漆用聚氨酯弹性体,包括A组分和B组分;A组分包括氟碳树脂99.5‑99.8%,催化剂0.2‑0.5%;B组分包括聚醚多元醇52.5‑65.3%,二异氰酸酯17.2‑35.5%,抗氧剂0.2‑0.3%,增塑剂0‑30%;A组分和B组分的混合质量比为100‑190:100。本发明的氟碳漆用聚氨酯弹性体解决了氟碳漆涂料抗老化性差、保光保色性不好、施工比例难控制的问题,实现了氟碳漆的安全美观性,减少清洁和维护的费用,大大拓展了氟碳漆的应用领域;本发明还提供其制备方法。
Description
技术领域
本发明涉及聚氨酯弹性体技术领域,具体涉及一种氟碳漆用聚氨酯弹性体及其制备方法。
背景技术
氟碳树脂是以氟烯烃为基本单体进行均聚或共聚,或以此为基础与其他单体进行共聚以及侧链含有氟碳键单体自聚或共聚而得的、分子结构中含有较多C-F化学键的一类树脂。而氟碳漆则是以此为基础的、同时也包含其他树脂改性的一类新型涂料。作为一种高科技功能性涂料,氟碳涂料的发展经历了热熔型、常温交联固化型和水溶性3个发展阶段。
国内氟碳漆行业起步较晚,但是发展很快,随着氟碳漆技术的进步和施工应用技术的完善,氟碳漆优异的性价比使它在各个领域越来越具有竞争力,尤其在铁路防腐领域的优势越来越明显。氟碳漆是一种多组分的油漆,主要成分包括主漆、固化剂和稀释剂,施工时需要按照规定的比例混合,才能达到理想的漆膜效果,但如果采用不配套固化剂,则会影响氟碳漆的交联反应,产生硬度不够、不干、成膜开裂、弹性不好、保光性不好、抗老化性差、对环境污染严重,同时也存在浪费资源、浪费能源等问题。
专利CN201210505355.7中公开了一种常温氟碳漆及其制备方法,包括甲组份和乙组分,甲组份包括氟树脂、热塑性丙烯酸树脂、高沸点溶剂、超耐候颜料和助剂,B组分为市售常规固化剂,产品可常温固化,施工工艺简单;但其加入高沸点溶剂,高沸点溶剂挥发较慢,导致固化时间较长,且溶剂挥发对环境造成污染。专利CN201310461557.8中公开了一种水性防腐蚀装饰氟碳漆及其制备方法,采用水分散氟碳树脂和水、颜料和助剂作为A组分,与三聚氰酰胺类固化剂混合后进行施工,产品耐腐蚀效果好,保光保色性好;但其低温柔韧性较差,强度一般,仅限用于装饰涂料,不能满足铁路、桥梁等对机械性能要求较高的领域使用。
而聚氨酯弹性体是一种介于橡胶与塑料的材料,其原材料品种繁多,配方多种多样,可调的范围较广。其具有优良的耐磨性、良好的力学强度及耐油、耐低温、耐臭氧老化等性能,因而得到广泛应用。将聚氨酯弹性体的优良性能与氟碳漆的性能相结合,扩大氟碳漆的应用领域,有很大的实用性和必要性。
发明内容
针对现有技术的不足,本发明的目的是提供一种氟碳漆用聚氨酯弹性体,解决了氟碳漆涂料抗老化性差、保光保色性不好、施工比例难控制的问题,实现了氟碳漆的安全美观性,减少清洁和维护的费用,大大拓展了氟碳漆的应用领域;本发明还提供其制备方法。
本发明所述的氟碳漆用聚氨酯弹性体,包括A组分和B组分;
A组分包括以下质量百分比的原料:
氟碳树脂 99.5-99.8%;
催化剂 0.2-0.5%;
B组分包括以下质量百分比的原料:
A组分和B组分的混合质量比为100-190:100。
氟碳树脂由四氟乙烯、三氟氯乙烯、氟乙烯等共聚而成,羟值为55-60mgKOH/g,酸值为5-8mgKOH/g,含氟量为25-30%。
催化剂为铋类催化剂、锌类催化剂或锡类催化剂,优选为铋类催化剂。
聚醚多元醇为2官能度、数均分子量650-2000的聚四氢呋喃多元醇,2官能度、数均分子量400-4000的聚醚多元醇,3官能度、数均分子量3000-6000的聚醚多元醇中的一种或两种以上的混合物。
优选地,2官能度、数均分子量650-2000的聚四氢呋喃多元醇为PTMG650,PTMG1000,PTMG2000;
优选地,2官能度、数均分子量400-4000的聚醚多元醇为DL-400,DL-1000,DL-2000,DL-3000,DL-4000;
优选地,3官能度、数均分子量3000-6000的聚醚多元醇为EP-330N、MN-3050、EP-3600。
二异氰酸酯为二苯基甲烷二异氰酸酯(MDI)、异氟尔酮二异氰酸酯(IPDI)、六亚甲基二异氰酸酯(HDI)中的一种或两种以上的混合物,其中MDI优选为MDI-50、MDI-100或H12MDI。
抗氧剂为抗氧剂1076、抗氧剂1010、抗氧剂1035、抗氧剂PDP中的一种或两种以上的混合物。
增塑剂为苯甲酸酯类增塑剂、对苯二甲酸二辛酯(DOTP)、邻苯二甲酸二辛酯(DOP)、邻苯二甲酸二甲基乙二醇酯(DMEP)或邻苯二甲酸二异丁酯中的一种或两种以上的混合物。
本发明所述的氟碳漆用聚氨酯弹性体的制备方法,包括以下步骤:
(1)将氟碳树脂和催化剂混合均匀,即得A组分;
(2)将聚醚多元醇、增塑剂混合,升温至100-120℃,真空脱水至水分含量<0.05%;降温至40-60℃,依次加入二异氰酸酯、抗氧剂,在80-90℃条件下反应4-5h,真空脱气泡,得到异氰酸根含量为4.3-8.0%的预聚物,即为B组分;
(3)将A组分和B组分混合,固化,即得氟碳漆用聚氨酯弹性体。
B组分是由聚醚多元醇和二异氰酸酯反应得到的以NCO基团封端的聚合物,而氟碳树脂是四氟乙烯等与其它带官能团的碳氢烯烃在溶剂中的共聚产物,其大分子链的羟基官能团可以与二异氰酸酯反应,形成交联网状结构,将聚醚多元醇的分子链引入到氟碳漆的分子链中,提高氟碳漆的低温柔韧性等性能。
与现有技术相比,本发明有以下有益效果:
(1)本发明采用聚氨酯预聚物作为固化剂,与氟碳树脂按照一定比例混合,实现了氟碳树脂材料的常温固化,并将聚氨酯弹性体优良的耐磨性、良好的力学强度及耐油、耐低温、耐臭氧老化等性能引入到氟碳漆材料中,大大提高了氟碳漆的耐候性、耐摩擦、耐沾污、耐酸、耐碱及力学稳定性能;
(2)本发明采用双组份配方,原料安全无毒,具有比例可调、成本低、粘度低、操作时间可控等优点,便于施工操作,扩大了氟碳漆材料的应用领域。
具体实施方式
以下结合实施例对本发明做进一步说明,但本发明的保护范围不仅限于此,该领域专业人员对本发明技术方案所作的改变,均应属于本发明的保护范围内。
实施例1
原料及其质量百分比如下:
A组分:
氟碳树脂CF-803 99.5%;
铋类催化剂CX-18 0.5%;
B组分:
(1)将氟碳树脂CF-803和铋类催化剂CX-18混合均匀,即得A组分;
(2)将聚四氢呋喃多元醇PTMG2000、聚醚多元醇MN-3050、增塑剂DOTP混合,升温至100℃,真空脱水至水分含量<0.05%;降温至60℃,依次加入IPDI、抗氧剂1076,在90℃条件下反应5h,真空脱气泡,得到异氰酸根含量为4.3%的预聚物,即为B组分;
(3)将A组分和B组分按质量比A:B=100:100混合,即得氟碳漆用聚氨酯弹性体。
实施例2
原料及其质量百分比如下:
A组分:
氟碳树脂CF-803 99.7%;
锡类催化剂T-9 0.3%;
B组分:
(1)将氟碳树脂CF-803和锡类催化剂T-9混合均匀,即得A组分;
(2)将聚四氢呋喃多元醇PTMG2000、聚醚多元醇DL-2000、增塑剂DOTP混合,升温至120℃,真空脱水至水分含量<0.05%;降温至40℃,依次加入IPDI、抗氧剂1076,在80℃条件下反应4h,真空脱气泡,得到异氰酸根含量为5.0%的预聚物,即为B组分;
(3)将A组分和B组分按质量比A:B=120:100混合,即得氟碳漆用聚氨酯弹性体。
实施例3
原料及其质量百分比如下:
A组分:
氟碳树脂CF-803 99.7%;
锡类催化剂T-9 0.3%;
B组分:
(1)将氟碳树脂CF-803和锡类催化剂T-9混合均匀,即得A组分;
(2)将聚四氢呋喃多元醇PTMG2000、增塑剂DOP混合,升温至100℃,真空脱水至水分含量<0.05%;降温至60℃,依次加入H12MDI、抗氧剂PDP,在90℃条件下反应4h,真空脱气泡,得到异氰酸根含量为6.5%的预聚物,即为B组分;
(3)将A组分和B组分按质量比A:B=150:100混合,即得氟碳漆用聚氨酯弹性体。
实施例4
原料及其质量百分比如下:
A组分:
氟碳树脂CF-803 99.8%;
铋类催化剂CX-18 0.2%;
B组分:
聚四氢呋喃多元醇PTMG1000 64.3%;
IPDI 35.5%;
抗氧剂PDP 0.2%。
(1)将氟碳树脂CF-803和铋类催化剂CX-18混合均匀,即得A组分;
(2)将聚四氢呋喃多元醇PTMG1000升温至100℃,真空脱水至水分含量<0.05%;降温至60℃,依次加入IPDI、抗氧剂PDP,在90℃条件下反应3h,真空脱气泡,得到异氰酸根含量为8.0%的预聚物,即为B组分;
(3)将A组分和B组分按质量比A:B=190:100混合,即得氟碳漆用聚氨酯弹性体。
对比例1
本对比例与实施例1相比,不同点仅在于B组分采用市售常规固化剂三聚氰酰胺。
对比例2
本对比例在氟碳树脂中加入助剂进行改性,固化剂采用拜耳N75,具体步骤如下:
A组分:
B组分:
固化剂(拜耳N75)。
将氟碳树脂CF-803、热塑性丙烯酸树脂BM44、乙二醇丁醚和气相二氧化硅混合,高速分散30min,然后研磨至细度≤17μm,即得A组分;将A组份和B组分按质量比6:1进行混合,即可喷涂使用。
将实施例1-4和对比例1-2的产品进行性能测试,测试方法如下:
(1)硬度:硬度使用邵氏A硬度计,根据GB/T-531测试标准测量;
(2)拉伸强度和断裂伸长率:使用万能拉力机,按照GB/T-528测试标准测量;
(3)附着力:应用划格法,间隔1mm,根据GB/T-9286测试标准测量;
(3)玻璃化转变温度:使用DSC差示扫描量热仪,按照GB/T-29611测试标准测量;
(4)耐盐雾性、酚黄测试、保光性由第三方机构进行检测。
测试结果如表1所示:
表1实施例1-4和对比例1-2产品的性能测试结果
从表1可以看出,本发明使用聚氨酯预聚体作为氟碳树脂的固化剂,对比传统的拜耳N75(脂肪族异氰酸酯三聚体)和三聚氰酰胺固化剂,由于引入了部分软段聚醚多元醇分子链,降低了体系的官能度,能够更好的提升氟碳漆的力学性能和低温柔顺性,产品的耐候性和附着力也保持一定的优越性。
Claims (6)
1.一种氟碳漆用聚氨酯弹性体,其特征在于:由A组分和B组分组成;
所述A组分由以下质量百分比的原料组成:
氟碳树脂CF-803 99.5-99.8%;
催化剂 0.2-0.5%;
所述B组分由以下质量百分比的原料组成:
聚醚多元醇 52.5-65.3%;
二异氰酸酯 17.2-35.5%;
抗氧剂 0.2-0.3%;
增塑剂 0-30%;
所述A组分和B组分的混合质量比为100-190:100;
聚醚多元醇为2官能度、数均分子量400-4000的聚醚多元醇,3官能度、数均分子量3000-6000的聚醚多元醇中的一种或两种的混合物;
B组分原料制备得到的预聚物的异氰酸根含量为4.3-8.0%。
2.根据权利要求1所述的氟碳漆用聚氨酯弹性体,其特征在于:所述的催化剂为铋类催化剂、锌类催化剂或锡类催化剂。
3.根据权利要求1所述的氟碳漆用聚氨酯弹性体,其特征在于:二异氰酸酯为二苯基甲烷二异氰酸酯、异氟尔酮二异氰酸酯、六亚甲基二异氰酸酯中的一种或两种以上的混合物。
4.根据权利要求1所述的氟碳漆用聚氨酯弹性体,其特征在于:抗氧剂为抗氧剂1076、抗氧剂1010、抗氧剂1035、抗氧剂PDP中的一种或两种以上的混合物。
5.根据权利要求1所述的氟碳漆用聚氨酯弹性体,其特征在于:增塑剂为苯甲酸酯类增塑剂、对苯二甲酸二辛酯、邻苯二甲酸二辛酯、邻苯二甲酸二甲基乙二醇酯或邻苯二甲酸二异丁酯中的一种或两种以上的混合物。
6.一种权利要求1-5任一项所述的氟碳漆用聚氨酯弹性体的制备方法,其特征在于:包括以下步骤:
(1)A组分:将氟碳树脂和催化剂混合均匀,即得A组分;
(2)B组分:将聚醚多元醇、增塑剂混合,升温至100-120℃,真空脱水至水分含量<0.05%;降温至40-60℃,依次加入二异氰酸酯、抗氧剂,在80-90℃条件下反应4-5h,真空脱气泡,得到预聚物,即为B组分;
(3)将A组分和B组分混合,即得氟碳漆用聚氨酯弹性体。
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