CN111849337A - 一种以油性消光树脂为核的自消光乳液制备方法 - Google Patents
一种以油性消光树脂为核的自消光乳液制备方法 Download PDFInfo
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Abstract
本发明提供了一种以油性消光树脂为核的自消光乳液制备方法,包括以下步骤:S1.在强极性水溶性溶剂中,将结晶性聚酯多醇与结晶性二异氰酸酯反应,生成结晶性聚氨酯预聚物;加入二元醇,用残留的‑NCO接枝有机硅多元醇,继续反应,生成油性消光树脂;S2.采用低粘度含EO多元醇,并加入二元醇、羧基二元醇、铋催化剂、抗氧剂和IPDI,制备得到低粘度水性预聚物;S3.将S1的油性消光树脂加入到S2的低粘度水性预聚物中,并加入成盐剂和扩链剂进行乳化,乳化后以水稀释,加入后扩链剂进行扩链后,得到实心型自消光乳液。该制备通过先制备油性消光树脂,并与低粘度水性预聚物进行共乳化,使得乳液成膜时保持球形、同时不中空,涂层能保证高消光和高黑度效果。
Description
技术领域
本发明涉及有机聚合物合成的技术领域,尤其是涉及一种以油性消光树脂为核的自消光乳液制备方法。
背景技术
水性乳液形成的涂膜大多是光亮的,为实现消光效果,多加入消光剂;而最常用的消光剂是二氧化硅。二氧化硅作为消光剂具有化学性质稳定、消光效率高、透明性好和加入量少的优点;但是,二氧化硅在用作水性消光剂时,在降低涂料光泽度的同时也带来不少缺点,比如,乳液的稳定性降低、黏度增大;制得的涂层脆性增大、易破碎脱落,另外,抗蚀性和耐刮性、耐弯折性等性能特性也有所下降。
在一些乳液制备方法中,在制备过程中使用助剂或者经有机改性的二氧化硅消光剂,使二氧化硅消光剂稳定且均匀分散在WPU分散体中,但这样会使得导致生产工艺繁琐且成本增加。目前,也有不少不添加消光剂的自消光乳液研究。
比如,公开号为WO 2012020026 A1的专利申请,其描述了一种单组份水性聚氨酯分散体及其制备方法。该分散体是一种非离子型水性聚氨酯/聚脲分散体,乳胶粒子粒径大,分布宽,极易再分散,乳胶成膜后极易产生低光泽,而且不需要加入任何的消光剂。但这些专利的技术方案中,也存在没有考虑到的技术问题,比如水性乳液在未成膜时是球状,但在成膜过程会变形,不会保持球状,也就不能在成膜后有消光效果;也有的专利提及中空微球,涂膜可以可保持球状,有消光效果,但这种乳液的表面泛白,不能达到高黑度的消光效果。
因此,如何在不外加消光剂的情况下,使乳液在成膜时保持球形且不是中空状,以获得良好的消光效果,是本领域的技术人员需要解决的技术问题。
发明内容
为了解决现有技术存在的上述问题,本发明提供了一种以油性消光树脂为核的自消光乳液制备方法,通过先制备油性消光树脂,然后与低粘度水性预聚物进行共乳化,使得乳液成膜时保持球形、同时不中空,涂层能保证高消光和高黑度效果。
为了实现上述目的,本发明提供了如下技术方案:
一种以油性消光树脂为核的自消光乳液制备方法,包括以下步骤:
S1.油性消光树脂的制备:在强极性水溶性溶剂中,将结晶性聚酯多醇与结晶性二异氰酸酯反应,生成结晶性聚氨酯预聚物;加入二元醇,用残留的-NCO 接枝有机硅多元醇,继续反应,生成油性消光树脂;
S2.低粘度水性预聚物的制备:采用低粘度含EO多元醇,并加入二元醇、羧基二元醇、铋催化剂、抗氧剂和IPDI,反应制备得到低粘度水性预聚物;
S3.共乳化:将S1的油性消光树脂加入到S2的低粘度水性预聚物中,并加入成盐剂和扩链剂进行乳化,乳化后以水稀释,加入后扩链剂进行扩链后,得到实心型自消光乳液。
在上述的制备方法中,S1在制备油性消光树脂时,利用聚合物之间的不相容特性,将高结晶聚合物(结晶性聚酯多醇与结晶性二异氰酸酯)内部的微相聚集,和非结晶性聚合物有机硅多元醇组合,利用极性的聚氨酯与非极性的有机硅之间的不相容性,制备油性消光树脂。而且,制备得到的油性消光树脂在后续的乳化前就已经是完整的高性能油性树脂。
在S2中,制备得到低粘度水性预聚物,并与油性消光树脂后续进行共乳化; IPDI与低粘度含EO多元醇生成低粘度易乳化预聚物,使之与S1混合后保持适合乳化的较低粘度。
在S3的共乳化过程中,以高分子量的油性树脂为核结构,可以完整保持油性树脂的品质,在此基础上,以阴离子树脂和非离子树脂为基础乳液,先用二氨基磺酸盐乳化扩链,继续用二胺或水合肼低温再扩链,制备得到自消光产品。
作为本发明技术方案的进一步描述,所述自消光乳液按重量份数,包括以下组分:油性消光树脂 8-50份,低粘度水性预聚物 10-50份,成盐剂 0.5-10 份,扩链剂 0.2-20份,后扩链剂 0.2-5份,水 30-85份。
作为本发明技术方案的进一步描述,按总配方的质量百分比,包括以下反应物:
强极性水溶性溶剂 30-85%,
结晶性聚酯多醇 2-30%,
结晶性二异氰酸酯 2-30%,
二元醇 1-20%,
有机硅多元醇 2-30%,
低粘度含EO多元醇 2-30%,
羧基二元醇 1-10%,
铋催化剂 0.02-2%,
抗氧剂 0.02-2%,
成盐剂 0.5-10%,
扩链剂 0.2-20%,
后扩链剂 0.2-5%,
水 30-85%。
作为本发明技术方案的进一步描述,所述强极性水溶性溶剂为DMF或 PMA。
作为本发明技术方案的进一步描述,所述结晶性聚酯多醇为PBA3000、 PCL3000或PCD3000的至少一种;所述结晶性二异氰酸酯为MDI100、H12MDI 或HDI的至少一种。
作为本发明技术方案的进一步描述,所述二元醇为1.4-BDO或1.6-HDO,所述羧基二元醇为DMPA或DMBA。
有机硅多元醇,羟基含量为56-110mgKOH/g,如道康宁公司SF8427(羟基含量56KOH/g)。
作为本发明技术方案的进一步描述,低粘度含EO多元醇为PTMG1000、PPG 或PEG的至少一种,其规格型号可以选用Ymer N120(瑞典帕斯托公司),或者 Unisafe C-1100(日本油脂株式会社)。PTMG1000为非结晶性多元醇。
作为本发明技术方案的进一步描述,所述扩链剂为水溶性扩链剂氨基磺酸钠盐,所述后扩链剂为IPDA、EA或水合肼的至少一种。
水溶性扩链剂氨基磺酸钠盐具体为2-[(2-氨乙基)氨基]乙磺酸钠(A95)(50%水溶液)。
作为本发明技术方案的进一步描述,所述铋催化剂为铋催化剂K24,所述抗氧剂为抗氧剂I-1010。
本发明还提供了一种自消光乳液产品,通过上述的以油性消光树脂为核的自消光乳液制备方法制备得到。这种自消光乳液产品,消光力强,黑雾透感好,手感粉蜡柔和,抗粘性好,可做成普通型和不易黄变型。
产品主要应用于塑胶,纸张纸品、纺织涂层、皮革、印花PU表面处理,其附着力好、触感柔和,具有优越手感,也可运用到其他弹性消光涂料行业和哑光产品领域。本发明的自消光乳液产品,与传统外加消光剂的乳液产品、其他水性自消光树脂以及空心型水性消光树脂相比:
A.与传统外加消光剂的乳液产品相比,具有相容性好、耐刮擦、手感柔和、消光度高和透感强的优点。
B.与其他水性自消光树脂相比,本发明的前期工艺已实现了高分子内核,相对成熟简单,产品稳定;而其他工艺以后扩链实现高分子,不可控因素多,产品分子量分布广,难控制分子量大小,最终产品的性能难以稳定。
C.与空心型水性消光树脂相比,产品实心,透明度高,表现为高消光度和高黑度。
基于上述的技术方案,本发明取得的技术效果为:
(1)本发明提供的以油性消光树脂为核的自消光乳液制备方法,通过油性消光树脂与低粘度的水性预聚体共乳化后扩链得到实心型自消光乳液,其前段为油性树脂制备工艺,分子量可准确控制,使水性产品性能在开始时得到保证;后段中能将油性消光树脂成品直接乳化,也可将其他高分子树脂乳化,水性化后能保持大部分原性能。这种前段的油脂扩链+利用预聚物乳化+后扩链工艺,可解决大多数水性产品分子量不高和分子量不稳定问题。
(2)本发明在制备水性自消光乳液过程中,无需外加消光粉即可达到消光效果,比传统加入消光粉的产品稳定性更好,手感更柔和,具有更透明的消光性;而且乳液内核为高分子消光树脂,防止像其他核壳型消光乳液出现空心泛白现象。
(3)本发明制备得到的水性自消光乳液,具有成膜性优异、消光性强、不含哑粉以及分子内消光的优点,形成的涂膜触感柔软,该乳液可单独使用或配合其他水性聚氨酯分散体使用。
具体实施方式
为了便于理解本发明,下面将结合具体的实施例对本发明进行更全面的描述。本发明给出了的较佳实施方式。但是,本发明可以以许多不同的形式来实现,并不限于本文所描述的实施方式。相反地,提供这些实施方式的目的是使对本发明的公开内容理解的更加透彻全面。
除非另有定义,本文所使用的所有的技术和科学术语与属于本发明的技术领域的技术人员通常理解的含义相同。本文中在本发明的说明书中所使用的术语只是为了描述具体的实施方式的目的,不是旨在于限制本发明。
实施例1
一种以油性消光树脂为核的自消光乳液制备方法,包括以下步骤:
S1.油性消光树脂的制备:在强极性水溶性溶剂中,将结晶性聚酯多醇与结晶性二异氰酸酯反应制备第一段产物,生成结晶性聚氨酯;在第二段中,加入二元醇,用残留的-NCO接枝有机硅多元醇,继续反应,利用极性的聚氨酯与非极性的有机硅之间的不相容性,生成油性消光树脂;
S2.低粘度水性预聚物的制备:采用低粘度含EO多元醇,并加入二元醇、羧基二元醇、铋催化剂、抗氧剂和IPDI,反应制备得到低粘度水性预聚物;
S3.共乳化:将S1的油性消光树脂加入到S2的低粘度水性预聚物中,并加入成盐剂和扩链剂进行乳化,乳化后以水稀释,加入后扩链剂进行扩链后,得到实心型自消光乳液。
上述的自消光乳液按重量份数,包括以下组分:油性消光树脂 8-50份,低粘度水性预聚物 10-50份,成盐剂 0.5-10份,扩链剂 0.2-20份,后扩链剂 0.2-5 份,水 30-85份。
该制备方法直接用成品油性消光树脂作为乳化前材料,加入低粘度水性预聚物进行共乳化,得到实心型自消光乳液。该油性消光树脂在乳化前已经是完整高性能油性树脂,在此基础上,以阴离子树脂和非离子树脂为基础乳液,先用二氨基磺酸盐乳化扩链,继续用二胺或水合肼低温再扩链,制备得到自消光产品。
制备得到的产品,无需外加消光粉而达到消光效果,比传统加入消光粉的产品稳定性更好,手感更柔和,具有更透明的消光性。
制备得到的产品,其具体性能参数如下:
实施例2
一种自消光乳液,由以下制备方法制备得到:
(1)制备高分子油性消光树脂
取DMF 200g、PCD3000 150g和H12MDI13g,在80℃反应2小时,加入 1,4-BDO 27g、H12MDI 78g、DMF 100g和SF8427 50g,并逐步加入H12MDI 5.2g 以提高粘度,最后加入DMF434g,调整粘度至3000-5000mPa.S,不挥发份30 ±2%,平均分子量约40000。
(2)制备低粘度水性预聚物
取IPDI 174g、Ymer N120(瑞典帕斯托公司)180g、DMPA18g、1,4-BDO 20g、 K24(铋催化剂)1g、I1010(抗氧剂)1g,投入500mL三口烧瓶中,升温到90-95℃反应,待NCO值降至1.2-1.3mmol/g时降温,备用。
(3)制备实心型自消光乳液
取低粘度水性预聚物100g、高分子油性消光树脂100g、TEA 3g混合,加入水100g、2-[(2-氨乙基)氨基]乙磺酸钠(A95)6g,先行混合,乳化后加EA 2.8g (先加水50g稀释)后,扩链剂EA以大量水稀释并少量分段逐步加入,扩链得到实心型自消光乳液。该自消光乳液为阴非离子型,消光度高,为含PCD多元醇脂肪族聚氨酯,耐水解,耐候性优秀。
实施例3
一种自消光乳液,由以下制备方法制备得到:
(1)制备高分子油性消光树脂
取DMF 200g、PBA3000 150g和MDI100 12.5g,在80℃反应2小时,加入 1,4-BDO27g、MDI100 75g和DMF 100g,SF8427(分子量2000,二羟基)50g,逐步加入MDI100 5g提高粘度,最后加DMF 434g,调整粘度3000-5000mPa.S,不挥发份30±2%,平均分子量约30000。
(2)制备低粘度水性预聚物
取IPDI 174g、Unisafe C-1100(日本油脂株式会社)180g、DMPA18g、1,4-BDO 20g、K24(铋催化剂)1g和I1010(抗氧剂)1g投入500ml三口烧瓶中,升温到 85-90℃反应,待NCO值降至1.2-1.3mmol/g时降温,备用。
(3)制备实心型自消光乳液
取低粘度水性预聚物100g、高分子油性消光树脂100g,并加入成盐剂TEA3g,于高速分散条件下逐渐加入水100和A95 6g(先混合),待乳化后加入 EA 2.8g(先加入水50)后扩链反应,扩链剂EA以大量水稀释并少量分段逐步加入,得到实心自消光乳液,该产品雾度黑度优秀,手感佳,成本低。
实施例4
一种自消光乳液,由以下制备方法制备得到:
(1)制备高分子油性消光树脂
取DMF 200g、PBA3000 150g和H12MDI13g,在80℃反应2小时,加入 1,4-BDO 27g、H12MDI 78g、DMF 100g和SF8427 50g,逐步加入H12MDI 5.2g 以提升粘度,最后加入DMF434g,调整粘度3000-5000mPa.S,不挥发份30±2%,平均分子量约30000。
(2)制备低粘度水性预聚物
取PMA 100g、HMDI 41.6g、IPDI 106.6g、EGO 16g、DMPA 16g、 PEBA1000 80g、YmerN120(瑞典帕斯托公司)80g、K24(铋催化剂)1g投入投入500ml三口烧瓶中,升温到85-90℃反应,待NCO值降至0.9-1.1mmol/g时降温,备用。
(3)制备实心型自消光乳液
取低粘度水性预聚物100g、高分子油性消光树脂100g,并加入成盐剂 TEA3g,混合均匀后加入水100g,A95 4.8g(先混合),乳化后加水合肼1.5, IPDA 1.4、水50g(先混合),扩链剂水合肼和IPDA以大量水稀释并少量分段逐步加入,搅拌均匀得到成品。该产品为阴非离子乳液,对PH值不敏感,能提高水性化后的保存时间。
实施例5
一种自消光乳液,由以下制备方法制备得到:
(1)制备高分子油性消光树脂
取DMF 200g、PCD3000 150g和H12MDI 13g,在80℃反应2小时,加入 1,4-BDO 27g,H12MDI 78g,DMF 100g和SF8427 50g,逐步加入H12MDI 5.2g, DMF 434g,调整粘度3000-5000mPa.s,不挥发份30±2%,平均分子量约40000。
(2)制备低粘度水性预聚物
取PMA 100g、H12MDI 41.6g、IPDI 106.6g、EGO 16g、DMPA 16g、 PCL1000 80g、Unisafe C-1100(日本油脂株式会社))80g、K24(铋催化剂)1g 投入投入500ml三口烧瓶中,升温到85-90℃反应,待NCO值降至0.9-1.1mmol/g 时降温,备用。
(3)制备实心型自消光乳液
取低粘度水性预聚物100g、高分子油性消光树脂100g,并加入成盐剂 TEA3g,于高速分散条件下加入水100g,A95 4.8g的混合物,乳化后逐渐加入 IPDA 6.4g(先溶于50水中),扩链剂IPDA以水稀释并少量分段逐步加入,搅拌均匀得到成品.该产品耐水解,耐候性能较好,能提高水性化后的产品性能。
以上内容仅仅为本发明所作的举例和说明,其描述较为具体和详细,但并不能因此而理解为对本发明专利范围的限制。应当指出的是,对于本领域的普通技术人员来说,在不脱离本发明构思的前提下,还可以做出若干变形和改进,这些显而易见的替换形式均属于本发明的保护范围。
Claims (10)
1.一种以油性消光树脂为核的自消光乳液制备方法,其特征在于,包括以下步骤:
S1.油性消光树脂的制备:在强极性水溶性溶剂中,将结晶性聚酯多醇与结晶性二异氰酸酯反应,生成结晶性聚氨酯预聚物;加入二元醇,用残留的-NCO接枝有机硅多元醇,继续反应,生成油性消光树脂;
S2.低粘度水性预聚物的制备:采用低粘度含EO多元醇,并加入二元醇、羧基二元醇、铋催化剂、抗氧剂和IPDI,反应制备得到低粘度水性预聚物;
S3.共乳化:将S1的油性消光树脂加入到S2的低粘度水性预聚物中,并加入成盐剂和扩链剂进行乳化,乳化后以水稀释,加入后扩链剂进行扩链后,得到实心型自消光乳液。
2.根据权利要求1所述的自消光乳液制备方法,其特征在于,所述自消光乳液按重量份数,包括以下组分:油性消光树脂 8-50份,低粘度水性预聚物 10-50份,成盐剂 0.5-10份,扩链剂 0.2-20份,后扩链剂 0.2-5份,水 30-85份。
3.根据权利要求1所述的自消光乳液制备方法,其特征在于,按总配方的质量百分比,包括以下反应物:
强极性水溶性溶剂 30-85%,
结晶性聚酯多醇 2-30%,
结晶性二异氰酸酯 2-30%,
二元醇 1-20%,
有机硅多元醇 2-30%,
低粘度含EO多元醇 2-30%,
羧基二元醇 1-10%,
铋催化剂 0.02-2%,
抗氧剂 0.02-2%,
成盐剂 0.5-10%,
扩链剂 0.2-20%,
后扩链剂 0.2-5%,
水 30-85%。
4.根据权利要求1-3任一所述的自消光乳液制备方法,其特征在于,所述强极性水溶性溶剂为DMF或PMA。
5.根据权利要求1-3任一所述的自消光乳液制备方法,其特征在于,所述结晶性聚酯多醇为PBA3000、PCL3000或PCD3000的至少一种;所述结晶性二异氰酸酯为MDI100、H12MDI或HDI的至少一种。
6.根据权利要求1-3任一所述的自消光乳液制备方法,其特征在于,所述二元醇为1.4-BDO或1.6-HDO,所述羧基二元醇为DMPA或DMBA。
7.根据权利要求1-3任一所述的自消光乳液制备方法,其特征在于,低粘度含EO多元醇为PTMG1000、PPG或PEG的至少一种。
8.根据权利要求1-3任一所述的自消光乳液制备方法,其特征在于,所述扩链剂为水溶性扩链剂氨基磺酸钠盐,所述后扩链剂为IPDA、EA或水合肼的至少一种。
9.根据权利要求1-3任一所述的自消光乳液制备方法,其特征在于,所述铋催化剂为铋催化剂K24,所述抗氧剂为抗氧剂I-1010。
10.一种自消光乳液,其特征在于,采用权利要求1-3任一所述的自消光乳液制备方法制得。
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