CN106188563B - 一种端酰肼基树枝状聚氨酯分散体及其制备方法与应用 - Google Patents
一种端酰肼基树枝状聚氨酯分散体及其制备方法与应用 Download PDFInfo
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- CN106188563B CN106188563B CN201610606469.9A CN201610606469A CN106188563B CN 106188563 B CN106188563 B CN 106188563B CN 201610606469 A CN201610606469 A CN 201610606469A CN 106188563 B CN106188563 B CN 106188563B
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- Prior art keywords
- diisocyanate
- hydrazide
- dendritic
- glycol
- polyurethane dispersion
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- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 8
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- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 claims description 2
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 2
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- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
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- ULMZOZMSDIOZAF-UHFFFAOYSA-N 3-hydroxy-2-(hydroxymethyl)propanoic acid Chemical compound OCC(CO)C(O)=O ULMZOZMSDIOZAF-UHFFFAOYSA-N 0.000 claims description 2
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 2
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
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- TUOBEAZXHLTYLF-UHFFFAOYSA-N [2-(hydroxymethyl)-2-(prop-2-enoyloxymethyl)butyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(CC)COC(=O)C=C TUOBEAZXHLTYLF-UHFFFAOYSA-N 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
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- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 2
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- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
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- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 3
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/002—Dendritic macromolecules
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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Abstract
本发明公开了一种端酰肼基的树枝状聚氨酯分散体及其制备方法与应用。该聚氨酯分散体的制备方法如下:（1）以大分子二元醇、离子性或潜在离子型二元醇和二异氰酸酯为原料制备NCO封端预聚物a;（2）向a中加入带羟基的乙烯基单体和阻聚剂，反应得到乙烯基封端聚合物b;（3）将b加入枝状酰肼的醇溶液中，反应得到c;(4)用非极性溶剂将c从醇溶液中絮凝出来，滤除上层醇溶液，下层聚合物用丙酮溶解后加水分散，除去丙酮得到端酰肼基树枝状聚氨酯分散体。该聚氨酯分散体分子量大于或等于20000g/mol，酰肼含量大于或等于30mmol/100g树脂，与含酮羰基的丙烯酸酯乳液混合可制备室温自交联聚氨酯丙烯酸酯复合乳液。
Description
技术领域
本发明属于精细化学品及其制备方法领域，具体涉及一种端酰肼基树枝状聚氨酯分散体及其制备方法与应用。
背景技术
水性聚氨酯分散体以水为分散介质，不含有机溶剂，不会排放VOC污染环境，是一种绿色环保的环境友好型产品，可以应用到胶黏剂、涂料、纺织助剂、医药卫生、建筑材料和印刷等领域。然而单一的水性聚氨酯分散体往往存在涂膜干燥速度慢、对非极性基材润湿性差以及乳液成膜后存在耐水性和耐溶剂性差、硬度低、耐高温性能不佳等缺点，因此对聚氨酯分散体进行改性，提高其性能，扩大其应用范围成为研究热点，在聚氨酯分子链上引入活性基团是最常用的改性方式。随着酮肼交联体系研究和应用的发展，在聚氨酯分子链上引入酮羰基和肼基成为聚氨酯官能团化的一个研究热点。
由于羰基与羟基、异氰酸酯没有反应活性，合成含酮羰基的二元醇扩链剂，从而将酮羰基引入聚氨酯分子链的主链或支链上，而且引入的酮羰基量不受聚氨酯分子量的影响，此类研究已有大量文献报道。WO1997011103A1用二乙醇胺与二烯酮反应制备了含酮羰基的二元醇，并将其用作小分子扩链剂，成功地将酮羰基引入到聚氨酯的主链上。WO2008016843A1通过乙酰丙酸与环氧化亚麻子油的开环反应制备了含多元酮和羟基的低聚物，然后通过该低聚物中羟基与异氰酸酯反应将酮羰基引入聚氨酯链，成功制备了含多元酮的聚氨酯分散体。最后通过添加小分子二元酰肼如己二酰肼合成了室温自交联的聚氨酯分散体。固化后的胶膜有很好的抗划伤性和耐溶剂性。
但是肼及其酰肼类衍生物与异氰酸酯的反应活性大，因此不能通过扩链剂的方式引入到聚氨酯分子链的支链上，一般是将其作为小分子扩链剂通过后扩链的方法对聚氨酯进行扩链与封端，从而将肼基引入聚氨酯分子链的末端，但在聚氨酯分子链末端引入肼基，其能引入的肼基最大量与聚氨酯的分子量存在反比的关系，从而限制了其应用。
US5137967用水合肼代替小分子二元胺作为扩链剂，制备了肼基聚氨酯分散体，并加入适量的三聚氰胺甲醛树脂，199℃加热两分钟，涂膜不会发生黄变。US20090318634用肼的衍生物酰肼代替水合肼作为扩链剂，乙酸甲酯代替丙酮作为溶剂，制备了酰肼基聚氨酯分散体，不仅解决了胶膜的黄变问题，还降低了水相中肼的残余量，从而解决残余肼的环境污染问题。CN101792592A通过丙酮法将己二酰肼的水溶液作为扩链剂加入到分散后的聚氨酯预聚体中得到扩链型肼基聚氨酯分散体；然后依次加入双丙酮丙烯酰胺和乙烯基单体，于搅拌下引发制得聚氨酯丙烯酸酯共聚乳液；最后将两种乳液混合制备了一种室温自交联型侧链含氟烷基的水性聚氨酯丙烯酸酯复合乳液，该复合乳液在室温下快速自交联，固化物的力学性能和耐化学品性能优异。
上述发明很好地解决了肼基聚氨酯分散体容易黄变和游离肼基残余量的问题，并成功将其应用到室温自交联的聚氨酯丙烯酸酯复合乳液中。但并未能解决肼基聚氨酯分散体存在的肼基含量与聚氨酯分子量之间的矛盾关系。本发明通过将树枝状多酰肼引入乙烯基封端的聚氨酯分子链成功制备了兼顾高分子量和高肼基含量的聚氨酯分散体。
发明内容
针对线形聚氨酯酰肼基含量与分子量成反比的矛盾关系，本发明提供了一种端酰肼基树枝状聚氨酯分散体及其制备方法与应用，通过引入树枝状多酰肼的方法来制备同时兼顾一定分子量和酰肼含量的聚氨酯分散体。该聚氨酯分散体分子量大于或等于20000g/mol，酰肼含量大于或等于30mmol/100g树脂，与含酮羰基的丙烯酸酯乳液混合可制备室温自交联聚氨酯丙烯酸酯复合乳液。
本发明实现上述目的技术方案如下。
一种端酰肼基树枝状聚氨酯分散体的制备方法，步骤如下：
(1)取用量为原料30wt％～60wt％的大分子二元醇、3wt％～5wt％的离子性或潜在离子型二元醇混合后升温至100～130℃真空脱水1～2h，降温至60～70℃，搅拌下加入用量为原料20wt％～30wt％的二异氰酸酯和0.01wt％～0.04wt％的催化剂升温至70～90℃反应1h～2h，之后加入少量高沸点溶剂降低黏度，再加入用量为原料1wt％～5wt％的小分子二元醇，扩链0.5h～1.5h，得到NCO封端预聚物a；
(2)将反应体系降温至60℃～70℃，向NCO封端预聚物a中加入用量为原料1.07wt％～2.14wt％的带羟基的乙烯基单体和用量为乙烯基单体0.05wt％～0.2wt％的阻聚剂，反应2h～4h，得到乙烯基封端聚合物b；
(3)将反应体系降温至20℃～40℃，用适量的低分子一元醇溶解乙烯基封端聚合物b，并加入用量为原料4.6wt％～12.6wt％的树枝状多酰肼的低分子醇溶液中反应7h～12h，得到产物c；
(4)在20℃～40℃下，用非极性溶剂将产物c从醇溶液中絮凝出来，滤除上层醇溶液，下层聚合物用非极性溶剂洗涤至中性，然后用丙酮溶解后加水分散，减压除去丙酮得到目标产物端酰肼基树枝状聚氨酯分散体；其中大分子二元醇、离子性或潜在离子型二元醇、二异氰酸酯、小分子二元醇、带羟基的乙烯基单体和树枝状多酰肼为原料。
进一步地，步骤(1)所述大分子二元醇为聚己二酸新戊二醇酯二醇，聚己二酸乙二醇酯二醇，聚己二酸丁二醇酯二醇，聚己二酸己二醇酯二醇，聚乙二酸乙二醇酯二醇，聚乙二酸丁二醇酯二醇，聚乙二醇，聚丙二醇，聚丁二醇，聚四氢呋喃醚二醇，聚己内酯二醇和聚碳酸酯二醇中的一种或几种；本发明优选聚己二酸新戊二醇酯二醇。所述大分子二元醇的分子量为500-3000。
进一步地，步骤(1)中的离子性二元醇为磺酸盐聚醚二元醇，1,4-二羟基丁烷-2-磺酸钠，1,2-二羟基-3-丙磺酸钠，2,2-二羟甲基丁酸-3’-磺酸钠-丙酯中的一种或几种；所述潜在离子型二元醇为2,2-二羟甲基乙酸，2,2-二羟甲基丙酸，2,2-二羟甲基丁酸和2,2-二羟甲基戊酸中的一种或几种；本发明优选离子型多元醇磺酸盐聚醚二元醇(SPPG)。
进一步地，步骤(1)所述二异氰酸酯为异佛尔酮二异氰酸酯、2,4-甲苯二异氰酸酯、1,6-六亚甲基二异氰酸酯、2,6-甲苯二异氰酸酯、2,2,4-三甲基-1,6-六亚甲基二异氰酸酯、1,4-苯二异氰酸酯、1,4-环己烷二异氰酸酯、1,5-萘二异氰酸酯、1,5-戊烷二异氰酸酯和1,3-苯二亚甲基二异氰酸酯中的一种或几种。本发明优选异佛尔酮二异氰酸酯。
进一步地，步骤(1)所述催化剂是二月桂酸二丁基锡，辛酸钾，辛酸亚锡和羧酸铋中的任意一种；本发明优选二月桂酸二丁基锡。
进一步地，步骤(1)所述高沸点溶剂为二甲基甲酰胺，二甲基乙酰胺和N-甲基吡咯烷酮中的一种或几种；本发明优选二甲基乙酰胺。
进一步地，步骤(1)所述小分子二元醇为乙二醇，丙二醇，丁二醇，新戊二醇和戊二醇中的一种或几种。本发明优选丁二醇。
进一步地，步骤(2)所述带羟基的乙烯基单体为丙烯酸羟乙酯、丙烯酸羟丙酯、甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯、季戊四醇三丙烯酸酯和三羟甲基丙烷二丙烯酸酯中的一种或几种；所述阻聚剂为对苯二酚、对羟基苯甲醚、2,5-二叔丁基对苯二酚和2-叔丁基对苯二酚中的一种或几种。本发明优选甲基丙烯酸羟乙酯、季戊四醇三丙烯酸酯或其混合物。
进一步地，步骤(3)所述树枝状多酰肼的低分子醇溶液中的树枝状多酰肼的结构式如下：
其中，R1、R2是相同或者不同的C2-C10的烷基或芳香基。进一步地所述树枝状多酰肼是H2N-R1(R2)-NH2与丙烯酸甲酯迈克尔加成后的产物，再经肼解所得。本发明优选R1、R2是C6烷基。
进一步地，步骤(3)所述低分子一元醇为甲醇和乙醇中的一种或几种。
进一步地，步骤(4)所述非极性溶剂为石油醚、己烷、甲苯或二甲苯。
由以上所述的制备方法制得的一种端酰肼基树枝状聚氨酯分散体。
以上所述的一种端酰肼基树枝状聚氨酯分散体应用于制备室温自交联聚氨酯丙烯酸酯复合乳液。
与现有技术相比，本发明具有如下优点与技术效果：
1、本发明通过将树枝状多酰肼引入乙烯基封端的聚氨酯分子链成功制备了兼顾高分子量和高肼基含量的聚氨酯分散体，成功解决了肼基聚氨酯分散体存在的肼基含量与聚氨酯分子量之间的矛盾关系。
2、本发明的聚氨酯分散体与含酮羰基的丙烯酸酯乳液混合制备的室温自交联聚氨酯丙烯酸复合乳液有着良好的耐水性，耐醇性，铅笔硬度及机械性能。
具体实施方式
以下通过实施例对本发明作进一步的说明，但本发明的实施方式不限于此。
实施例1(树枝状多酰肼的制备)
树枝状多酰肼的合成参照文献(《树枝状多酰肼固化剂的制备与性能》2013，29：125～128)。简述如下：在250mL三口烧瓶中加入11.6g(0.10mol)己二胺和40mL甲醇,冰水浴下逐滴滴加51.6g(0.6mol)丙烯酸甲酯,滴加完后移走冰水浴，温度升至室温后继续搅拌22h,在72℃、133Pa条件下减压蒸馏,除去过量的甲醇和丙烯酸甲酯,得淡黄色液体43.6g，产率94.8％,即为0.5G(0.5代)己二胺为核的树枝状大分子。再加入40mL甲醇,23.3g水合肼(85wt％)，50℃搅拌回流3h,降温析出白色固体,用甲醇重结晶烘干，得白色晶体42.2g，即为1.0G末端四个酰肼基的树枝状多酰肼(HZ-1)，产率91.7％。按照上述合成方法，得到2.0G末端八个酰肼基的树枝状多酰肼(HZ-2)。
实施例2(端酰肼基树枝状聚氨酯分散体的制备)
在装有冷凝管、搅拌器、温度计的500ml三口圆底烧瓶中分别加入60.0g聚己二酸新戊二醇酯二醇1000(PNA1000)、3.36g磺酸盐聚醚二元醇(SPPG)，120℃下真空脱水1.5h，降温至60℃，加入26.55g异佛尔酮二异氰酸酯(IPDI)，0.02g二月桂酸二丁基锡(DBTDL)作为催化剂，升温至80℃，反应1.5h，以二正丁胺法滴定-NCO剩余量，至-NCO含量达到理论值(4.8wt％)，然后加入10g二甲基乙酰胺调节反应物粘度，再加入4.18g 1,4-丁二醇(BDO)反应1.0h至-NCO含量达到另一理论值(0.445wt％)，降温至65℃，加入1.3g甲基丙烯酸羟乙酯(HEMA)、0.001g对羟基苯甲醚(MEHQ)反应3h至-NCO红外光谱特征峰消失。降温至35℃，并用100g无水乙醇溶解聚合物，再加入含4.60g实施例1中制备的末端含四个酰肼基的树枝状多酰肼(HZ-1)的乙醇溶液，35℃反应7h至-C＝C红外光谱特征峰完全消失，用石油醚将聚合物从乙醇中絮凝出来，过滤除去过量的酰肼乙醇溶液，聚合物用冷的石油醚、乙醇洗涤数次。减压除去残留的溶剂，聚合物用30g丙酮溶解后加入162g去离子水，在1000r/min转速下分散20min，减压除去丙酮得到固含量为38％，数均分子量Mn＝20000g/mol，酰肼含量30mmol/100g树脂的聚氨酯分散体PUD1。
实施例3(端酰肼基树枝状聚氨酯分散体的制备)
在装有冷凝管、搅拌器、温度计的500ml三口圆底烧瓶中分别加入60.0g聚己二酸新戊二醇酯二醇1000(PNA1000)、3.36g磺酸盐聚醚二元醇(SPPG)，120℃下真空脱水1.5h，降温至60℃，加入24.62g异佛尔酮二异氰酸酯(IPDI)，0.02g二月桂酸二丁基锡(DBTDL)作为催化剂，升温至80℃，反应1.5h，以二正丁胺法滴定-NCO剩余量，至-NCO含量达到理论值(4.08wt％)，然后加入10g二甲基乙酰胺调节反应物粘度，再加入3.4g 1,4-丁二醇(BDO)反应1.0h至-NCO含量达到另一理论值(0.462wt％)，降温至65℃，加入0.975g甲基丙烯酸羟乙酯(HEMA)、0.745g季戊四醇三丙烯酸酯(PETA)、0.001g对羟基苯甲醚(MEHQ)反应3h至-NCO红外光谱特征峰消失。降温至35℃，并用100g无水乙醇溶解聚合物，再加入含6.9g实施例1中制备的末端含四个酰肼基的树枝状多酰肼(HZ-1)的乙醇溶液，35℃反应7h至-C＝C红外光谱特征峰完全消失，用石油醚将聚合物从乙醇中絮凝出来，过滤除去过量的酰肼乙醇溶液，聚合物用冷的石油醚、乙醇洗涤数次。减压除去残留的溶剂，聚合物用30g丙酮溶解后加入162g去离子水，在1000r/min转速下分散20min，减压除去丙酮得到固含量为38％，数均分子量Mn＝20000，酰肼含量45mmol/100g树脂的聚氨酯分散体PUD2。
实施例4(端酰肼基树枝状聚氨酯分散体的制备
在装有冷凝管、搅拌器、温度计的500ml三口圆底烧瓶中分别加入60.0g聚己二酸新戊二醇酯二醇1000(PNA1000)、3.36g磺酸盐聚醚二元醇(SPPG)，120℃下真空脱水1.5h，降温至60℃，加入24.02g异佛尔酮二异氰酸酯(IPDI)，0.02g二月桂酸二丁基锡(DBTDL)作为催化剂，升温至80℃，反应1.5h，以二正丁胺法滴定-NCO剩余量，至-NCO含量达理论值(3.32wt％)，然后加入10g二甲基乙酰胺调节反应物粘度，再加入1.68g 1,4-丁二醇(BDO)反应1.0h至-NCO含量达到另一理论值(0.480wt％)，降温至65℃，加入0.65g甲基丙烯酸羟乙酯(HEMA)、1.49g季戊四醇三丙烯酸酯(PETA)、0.002g对羟基苯甲醚(MEHQ)反应3h至-NCO红外光谱特征峰消失。降温至35℃，并用100g无水乙醇溶解聚合物，再加入含9.2g实施例1中制备的末端含四个酰肼基的树枝状多酰肼(HZ-1)的乙醇溶液，35℃反应7h至-C＝C红外光谱特征峰完全消失，用石油醚将聚合物从乙醇中絮凝出来，过滤除去过量的酰肼乙醇溶液，聚合物用冷的石油醚、乙醇洗涤数次。减压除去残留的溶剂，聚合物用30g丙酮溶解后加入162g去离子水，在1000r/min转速下分散20min，减压除去丙酮得到固含量为38％，数均分子量Mn＝20000g/mol，酰肼含量60mmol/100g树脂的聚氨酯分散体PUD3。
实施例5(端酰肼基树枝状聚氨酯分散体的制备
在装有冷凝管、搅拌器、温度计的500ml三口圆底烧瓶中分别加入60.0g聚己二酸新戊二醇酯二醇1000(PNA1000)、3.36g磺酸盐聚醚二元醇(SPPG)，120℃下真空脱水1.5h，降温至60℃，加入20.58g异佛尔酮二异氰酸酯(IPDI)，0.02g二月桂酸二丁基锡(DBTDL)作为催化剂，升温至80℃，反应1.5h，以二正丁胺法滴定-NCO剩余量，至-NCO含量达理论值(2.46wt％)，然后加入10g二甲基乙酰胺调节反应物粘度，再加入1.76g 1,4-丁二醇(BDO)反应1.0h至-NCO含量达到另一理论值(0.50wt％)，降温至65℃，加入1.3g甲基丙烯酸羟乙酯(HEMA)、0.001g对羟基苯甲醚(MEHQ)反应3h至-NCO红外光谱特征峰消失。降温至35℃，并用100g无水乙醇溶解聚合物，再加入含12.6g实施例1中制备的末端含四个酰肼基的树枝状多酰肼(HZ-2)的乙醇溶液，35℃反应7h至-C＝C红外光谱特征峰完全消失，用石油醚将聚合物从乙醇中絮凝出来，过滤除去过量的酰肼乙醇溶液，聚合物用冷的石油醚、乙醇洗涤数次。减压除去残留的溶剂，聚合物用30g丙酮溶解后加入162g去离子水，在1000r/min转速下分散20min，减压除去丙酮得到固含量为38％，数均分子量Mn＝20000，酰肼含量70mmol/100g树脂的聚氨酯分散体PUD4。
实施例6(端酰肼基树枝状聚氨酯分散体的制备)
在装有冷凝管、搅拌器、温度计的500ml三口圆底烧瓶中分别加入60.0g聚己二酸新戊二醇酯二醇1000(PNA1000)、3.36g磺酸盐聚醚二元醇(SPPG)，120℃下真空脱水1.5h，降温至60℃，加入26.62g异佛尔酮二异氰酸酯(IPDI)，0.02g二月桂酸二丁基锡(DBTDL)作为催化剂，升温至80℃，反应1.5h，以二正丁胺法滴定-NCO剩余量，至-NCO含量达到理论值(4.80wt％)，然后加入10g二甲基乙酰胺调节反应物粘度，再加入4.35g 1,4-丁二醇(BDO)反应1.0h至-NCO含量达到另一理论值(0.223wt％)，降温至65℃，加入0.325g甲基丙烯酸羟乙酯(HEMA)、0.745g季戊四醇三丙烯酸酯(PETA)、0.001g对羟基苯甲醚(MEHQ)反应3h至-NCO红外光谱特征峰消失。降温至35℃，并用100g无水乙醇溶解聚合物，再加入含4.6g实施例1中制备的末端含四个酰肼基的树枝状多酰肼(HZ-1)的乙醇溶液，35℃反应7h至-C＝C红外光谱特征峰完全消失，用石油醚将聚合物从乙醇中絮凝出来，过滤除去过量的酰肼乙醇溶液，聚合物用冷的石油醚、乙醇洗涤数次。减压除去残留的溶剂，聚合物用30g丙酮溶解后加入162g去离子水，在1000r/min转速下分散20min，减压除去丙酮得到固含量为38％，数均分子量Mn＝40000g/mol，酰肼含量30mmol/100g树脂的聚氨酯分散体PUD5。
实施例7(含酮羰基丙烯酸酯乳液的制备)
将25g甲基丙烯酸甲酯(MMA)，21.5g丙烯酸正丁酯(BA)，1.0g甲基丙烯酸(MAA)，2.5g双丙酮丙烯酰胺(DAAM)组成的混合单体加入到溶有0.25g烷基酚聚氧乙烯醚(OP-10)、0.25十二烷基硫酸钠(SDS)的25g水溶液中搅拌20min，制得单体预乳液；将0.15g过硫酸铵(APS)溶于15g去离子水制得引发剂溶液。在装有搅拌器、温度计、恒压滴液漏斗的500mL四口烧瓶中加入0.25g烷基酚聚氧乙烯醚(OP-10)、0.25十二烷基硫酸钠(SDS)和41g去离子水，搅拌均匀后升温至80℃，然后加入5.0wt％的单体预乳液和50wt％的引发剂溶液反应20min得到蓝色透明的种子乳液，之后在3h内滴加剩余的单体预乳液和引发剂溶液。滴加完毕后，80℃保温30min，降温至50℃用稀氨水调节pH为7，过滤后即得双丙酮丙烯酰胺(DAAM)含量为5.0wt％的含酮羰基丙烯酸酯乳液。调整DAAM用量，按照上述步骤分别制得DAAM含量为5.0wt％，7.5wt％、10wt％、11.67wt％的含酮羰基丙烯酸酯乳液。分别记为PA1，PA2，PA3，PA4。
室温自交联聚氨酯丙烯酸酯复合乳液的制备及性能测试：
取实施例2，3，4，5，6中的端酰肼基的树枝状聚氨酯分散体PUD1，PUD2，PUD3，PUD4和PUD5分别与含酮羰基的丙烯酸酯乳液按一定比例混合得到一系列室温自交联聚氨酯丙烯酸酯复合乳液。
所得室温自交联聚氨酯丙烯酸酯复合乳液其组成及性能如表1所示：
表1
测试按照如下方法进行：
硬度：按照国标GB/T6739-2006“色漆和清漆铅笔法测定漆膜硬度”进行测试。
吸水率：已知质量干膜G1，在水中浸泡24h，取出并用滤纸擦干胶膜表面水分，立即称重质量为G2，则吸水率为：[(G2-G1)/G1]*100％。
吸醇性：已知质量干膜m1，在无水乙醇中浸泡24h，取出并用滤纸擦干胶膜表面乙醇，立即称重质量为m2，则吸醇率为：[(m2-m1)/m1]*100％。
拉伸强度：按照国标GB13022-91“塑料拉伸性能试验方法”进行测试。
从上述测试结果可知，本发明制备的端酰肼基树枝状聚氨酯分散体同时具备高的酰肼含量和较高分子量，用其与含酮羰基的丙烯酸酯乳液混合制备的室温自交联聚氨酯丙烯酸复合乳液有着良好的耐水性，耐醇性，铅笔硬度及机械性能。特别地，从中可以看出聚氨酯的分子量和酰肼基含量对复合乳液的性能有着重要影响，在一定范围内聚氨酯分散体的分子量越高，酰肼基含量越高，固化后胶膜性能越好。
Claims (5)
1.一种端酰肼基树枝状聚氨酯分散体的制备方法，其特征在于，步骤如下：
(1)取用量为原料30wt% ~ 60wt%的大分子二元醇、3wt% ~ 5wt%的离子型 或潜在离子型二元醇混合后升温至100℃ ~ 130℃真空脱水1h ~ 2h，降温至60 ~ 70℃，搅拌下加入用量为原料20wt% ~ 30wt%的二异氰酸酯和0.01wt% ~ 0.04wt%的催化剂升温至70 ~ 90℃反应1h ~ 2h，之后加入高沸点溶剂降低黏度，再加入用量为原料1wt% ~ 5wt%的小分子二元醇，扩链1h ~ 1.5h，得到NCO封端预聚物a;所述大分子二元醇为聚己二酸新戊二醇酯二醇，聚己二酸乙二醇酯二醇，聚己二酸丁二醇酯二醇，聚己二酸己二醇酯二醇，聚乙二酸乙二醇酯二醇，聚乙二酸丁二醇酯二醇，聚乙二醇，聚丙二醇，聚丁二醇，聚四氢呋喃醚二醇，聚己内酯二醇和聚碳酸酯二醇中的一种或几种；所述大分子二元醇的分子量为500-3000；离子型 二元醇为二羟基磺酸盐；所述潜在离子型二元醇为2, 2-二羟甲基乙酸，2, 2-二羟甲基丙酸，2, 2-二羟甲基丁酸和2, 2-二羟甲基戊酸中的一种或几种；所述二异氰酸酯为异佛尔酮二异氰酸酯、2, 4-甲苯二异氰酸酯、1, 6-六亚甲基二异氰酸酯、2, 6-甲苯二异氰酸酯、2, 2, 4-三甲基-1, 6-六亚甲基二异氰酸酯、1, 4-苯二异氰酸酯、1, 4-环己烷二异氰酸酯、1, 5-萘二异氰酸酯、1, 5-戊烷二异氰酸酯和1, 3-苯二亚甲基二异氰酸酯中的一种或几种；所述催化剂是二月桂酸二丁基锡，辛酸钾，辛酸亚锡和羧酸铋中的任意一种；所述高沸点溶剂为二甲基甲酰胺，二甲基乙酰胺和N-甲基吡咯烷酮中的一种或几种；所述小分子二元醇为乙二醇，丙二醇，丁二醇，新戊二醇和戊二醇中的一种或几种；
(2)将反应体系降温至60℃ ~ 70℃，向NCO封端预聚物a中加入用量为原料1.07wt% ~2.14wt%的带羟基的乙烯基单体和用量为乙烯基单体0.05wt% ~ 0.2wt%的阻聚剂，反应2h~ 4h，得到乙烯基封端聚合物b;所述带羟基的乙烯基单体为丙烯酸羟乙酯、丙烯酸羟丙酯、甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯、季戊四醇三丙烯酸酯和三羟甲基丙烷二丙烯酸酯中的一种或几种；所述阻聚剂为对苯二酚、对羟基苯甲醚、2，5-二叔丁基对苯二酚和2-叔丁基对苯二酚中的一种或几种；
(3)将反应体系降温至20℃ ~ 40℃，用低分子一元醇溶解乙烯基封端聚合物b，并加入用量为原料4.6wt% ~ 12.6wt%的树枝状多酰肼的低分子醇溶液中反应7h ~ 12h，得到产物c; 所述树枝状多酰肼的低分子醇溶液中的树枝状多酰肼的结构式如下：
其中，R1、R2是相同或者不同的C2-C10的烷基或芳香基；
(4)在20℃ ~ 40℃条件下，用非极性溶剂将产物c从醇溶液中絮凝出来，滤除上层醇溶液，下层聚合物用非极性溶剂洗涤至中性，然后用丙酮溶解后加水分散，减压除去丙酮得到目标产物端酰肼基树枝状聚氨酯分散体；其中大分子二元醇、离子型 或潜在离子型二元醇、二异氰酸酯、小分子二元醇、带羟基的乙烯基单体和树枝状多酰肼为原料，各原料用量之和为100wt%。
2.根据权利要求1所述的制备方法，其特征在于，步骤（3）所述低分子一元醇为甲醇和乙醇中的一种或几种。
3.根据权利要求1所述的制备方法，其特征在于，步骤（4）所述非极性溶剂为石油醚、己烷、甲苯或二甲苯。
4.由权利要求1-3任一项所述的制备方法制得的一种端酰肼基树枝状聚氨酯分散体。
5.权利要求4所述的一种端酰肼基树枝状聚氨酯分散体应用于制备室温自交联聚氨酯丙烯酸酯复合乳液。
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| KR102246054B1 (ko) | 2016-03-18 | 2021-04-28 | 피피지 인더스트리즈 오하이오 인코포레이티드 | 다층 코팅 및 이의 제조 방법 |
| CN106188563B (zh) * | 2016-07-27 | 2020-07-28 | 华南理工大学 | 一种端酰肼基树枝状聚氨酯分散体及其制备方法与应用 |
| ES2960080T3 (es) * | 2018-10-26 | 2024-02-29 | Basf Se | Formulación aglutinante acuosa a base de poliuretanos funcionalizados |
| CN110527109B (zh) * | 2019-09-03 | 2021-06-11 | 北京大学口腔医学院 | 一种多羟基超支化聚合物及制备方法以及其在牙科复合树脂中的应用 |
| CN111593598B (zh) * | 2020-04-13 | 2021-12-31 | 仙鹤股份有限公司 | 一种施胶均匀的人造革离型原纸的制备方法 |
| CN115536544B (zh) * | 2021-06-30 | 2024-03-12 | 中石化南京化工研究院有限公司 | 具有破乳功能的化合物及其制备方法和应用 |
| CN113817133A (zh) * | 2021-09-18 | 2021-12-21 | 湖南松井新材料股份有限公司 | 可室温自交联水性非离子型聚氨酯分散体及其制备方法和应用 |
| CN114891174B (zh) * | 2022-06-29 | 2024-06-25 | 万华化学集团股份有限公司 | 一种水性聚氨酯树脂及其制备方法 |
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| CN101240101A (zh) * | 2007-09-30 | 2008-08-13 | 合肥安大天辐新材料有限公司 | 酮肼交联型丙烯酸酯-聚氨酯复合纺织乳液的制备方法及用途 |
| CN103113532A (zh) * | 2013-01-24 | 2013-05-22 | 陕西科技大学 | 常温自交联水性聚氨酯乳液的制备方法 |
| CN103980792A (zh) * | 2014-05-30 | 2014-08-13 | 陕西科技大学 | 一种室温酮肼交联无voc水性涂料及其制备方法 |
| CN106188563A (zh) * | 2016-07-27 | 2016-12-07 | 华南理工大学 | 一种端酰肼基树枝状聚氨酯分散体及其制备方法与应用 |
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| CN103113532A (zh) * | 2013-01-24 | 2013-05-22 | 陕西科技大学 | 常温自交联水性聚氨酯乳液的制备方法 |
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