CN110845696A - 一种水性聚氨酯树脂及其制备方法 - Google Patents
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Abstract
一种水性聚氨酯树脂及其制备方法,属于高分子材料技术领域,包括如下重量份数的物质:聚合物多元醇160‑330份,蓖麻油20‑40份,有机蒙脱土2‑5份,硅烷偶联剂0.5‑1.2份,聚二异氰酸酯56‑100份,羟甲基酸7.2‑14.8份,羟基型小分子多元醇7‑21份,催化剂0.2‑0.4份,丙酮80‑140份,中和剂5.5‑7.5份,去离子水600‑1120份,助剂8‑15份。本发明通过硅烷偶联剂与蒙脱土进行插层改性反应,使蒙脱土的片层间距打开更有利于高分子链的插层,同时使水分散蒙脱土与有机相的相容性更好,有利于乳液的稳定,同时增强了材料的耐水和耐碱性能。
Description
技术领域
本发明属于高分子材料领域,具体地说是一种水性聚氨酯树脂及其制备方法。
背景技术
水性聚氨酯以水代替有机溶剂作为分散介质,除具有溶剂型聚氨酯的优异性能外,水性聚氨酯具有无毒、对环境友好等优点,并具有良好的耐候性、耐油脂等性能。随着人们对环境保护要求的提升,对水性树脂替代溶剂型树脂制备合成革的呼声也越来越高。欧共体新的生态标准液对有毒有害溶剂的可使用范围有了新的界定,同时我国环保部门对皮革行业的污水排放中甲苯、DMF等含量作了限定。这对溶剂型合成革的生产和应用将是巨大的考验,而对水性聚氨酯在合成革领域的发展将起到巨大的推动作用。
水性聚氨酯用于合成革行业,将可实现该产业的清洁生产和安全生产。但是就目前来说,合成革用水性聚氨酯还达不到应用的要求。水性聚氨酯含有大量的亲水基团,干燥成膜后遇水易溶胀。这是由于水一旦渗入到水性聚氨酯大分子中与聚氨酯分子中的极性基团结合形成氢键并诱发聚氨酯链段的溶胀,使得聚氨酯分子链间作用力减弱,表现为拉伸强度及撕裂强度极大程度的降低。
水性聚氨酯产品的耐水性、耐溶剂性、机械强度、丰满性等较差,一定程度上限制了其的应用领域。为了进一步改善水性聚氨酯的综合性能和拓宽其应用范围,需对其进行有效的改性处理。
发明内容
本发明提供一种水性聚氨酯树脂,用以解决现有技术中的缺陷。
本发明通过以下技术方案予以实现:
一种水性聚氨酯树脂,包括如下重量份数的物质:
聚合物多元醇160-330份,蓖麻油20-40份 ,有机蒙脱土2-5份,硅烷偶联剂0.5-1.2份,聚二异氰酸酯56-100份,羟甲基酸7.2-14.8份,羟基型小分子多元醇7-21份,催化剂0.2-0.4份,丙酮80-140份,中和剂5.5-7.5份,去离子水600-1120份,助剂8-15份。
如上所述的一种水性聚氨酯树脂,所述的聚合物多元醇数均分子量为1000-8000。
如上所述的一种水性聚氨酯树脂,所述的聚合物多元醇为聚四氢呋喃醚二元醇、聚氧化丙烯二元醇、聚氧化丙烯三元醇、聚己内酯二元醇的其中一种或两种以上以任意比例混合。
如上所述的一种水性聚氨酯树脂,所述的硅烷偶联剂为乙烯基三甲氧基硅烷、3-氨基丙基三乙氧基硅烷、γ-(2,3-环氧丙氧)丙基三甲氧基硅烷中的其中一种或两种以上以任意比例混合。
如上所述的一种水性聚氨酯树脂,所述聚二异氰酸酯为异佛尔酮二异氰酸酯、甲苯二异氰酸酯、4,4-二环己基甲烷二异氰酸酯的其中一种或两种以上以任意比例混合。
如上所述的一种水性聚氨酯树脂,所述羟甲基酸为二羟甲基丙酸和二羟甲基丁酸的其中一种。
如上所述的一种水性聚氨酯树脂,所述羟基型小分子多元醇为一缩二乙二醇、新戊二醇、1,6-己二醇、1,8-辛二醇、三羟甲基丙烷中的其中一种或两种以上以任意比例混合。
如上所述的一种水性聚氨酯树脂,中和剂为氢氧化钠、二甲氨基乙醇、三乙胺中的一种或两种以上以任意比例混合。
如上所述的一种水性聚氨酯树脂,所述的催化剂为辛酸亚锡、有机铋酸盐中的其中一种。
如上所述的一种水性聚氨酯树脂,所述的所述中和剂使用前与去离子水以1:1的比例进行稀释。
如上所述的一种水性聚氨酯树脂,所述的催化剂为有机铋酸盐。
如上所述的一种水性聚氨酯树脂,所述的催化剂为新癸酸铋。
如上所述的一种水性聚氨酯树脂,所述的所述助剂为润湿剂、流平剂、柔软助剂、消泡剂中的一种或两种以上以任意比例混合。
如上所述的一种水性聚氨酯树脂,所述的润湿剂、流平剂为聚醚改性聚硅氧烷类。
如上所述的一种水性聚氨酯树脂,所述的柔软助剂为三元共聚硅油类。
如上所述的一种水性聚氨酯树脂,所述的消泡剂为聚氧丙烯氧化乙烯甘油醚类。
如上所述的一种水性聚氨酯树脂,所述的
一种水性聚氨酯树脂的制备方法,包括如下步骤:
步骤一:有机蒙脱土改性:准确称取硅烷偶联剂,配置成10%水溶液,室温下水解20-30min;准确称取入蒙脱土,配成5-10%的水溶液,室温下溶胀2-3h,用高速分散机搅拌分散30-60min,然后将蒙脱土水溶液转移到反应器中,向反应器中缓慢滴加提前水解好的硅烷偶联剂水溶液,在50-75℃的温度下,反应2-3.5h,反应完成后冷却至室温,过滤,用蒸馏水洗涤抽滤,将滤渣放入烘干器中在100-120℃的温度下烘干2h,干燥器停止加热冷却至室温,取出干燥后的滤渣研磨成粉末即得改性有机蒙脱土;
步骤二:向反应器中加入聚合物多元醇、蓖麻油,在110℃的温度下抽真空脱水0.5小时;
步骤三:脱水完成后,降温至60℃,向反应器中加入聚二异氰酸酯、改性有机蒙脱土,升温至75-90℃,聚合反应2-3h;
步骤四:降温至60-70℃,加入羟甲基酸、羟基型小分子多元醇、丙酮、催化剂,升温至75-85℃,反应2.5-3.5h;
步骤五:降温至50-55℃,加入中和剂,搅拌均匀,加入去离子水,分散均匀;
步骤六:升温至65-70℃,真空脱除丙酮,即得聚氨酯水分散体;
步骤七:在步骤六所得水分散体中加入助剂,分散均匀,得水性聚氨酯树脂。
本发明的优点是:
1、本发明通过硅烷偶联剂与蒙脱土进行插层改性反应,使蒙脱土的片层间距打开更有利于高分子链的插层,同时使水分散蒙脱土与有机相的相容性更好,有利于乳液的稳定,同时增强了材料的耐水和耐碱性能;
2、同时高分子链与蒙脱土分子的插层作用限制了聚氨酯分子链的自由运动,相应提高了材料的力学性能、耐热稳定性以及尺寸稳定性,增加材料的手感丰满性;
3、无机粒子对高分子链的支撑作用使材料的透水气性有一定程度的增加;
4、本发明以水为分散介质,生产过程清洁环保,使用过程安全无异味,对环境友好,对生产使用人员身体健康无害;
5、本发明采用的催化剂是铋磺酸基催化剂,属新一代无毒,绿色环保型催化剂,代替了目前生产水性聚氨酯乳液普遍使用的含有机锡类的催化剂,残留在聚氨酯乳液中的有机锡重金属催化剂不仅会造成环境污染,还可导致生物体畸形和慢性中毒,该类催化剂已被欧盟等发达国家列入禁止使用的名单;而有机铋催化剂不仅仅属于合成聚氨酯材料的新型无毒、绿色环保型催化剂,还可以使制得的聚氨酯产品具有较窄的分子量分布和较低的粘度,在水性聚氨酯乳液中还可减少水与 -NCO 基的副反应。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚,下面将结合本发明实施例,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
实施例1
步骤一:准确称取聚氧化丙烯三元醇(数均分子量为3000)60g,聚四氢呋喃醚二元醇(数均分子量为1000)100g,蓖麻油20g ,有机蒙脱土2g,乙烯基三甲氧基硅烷0.5g,甲苯二异氰酸酯56g,二羟甲基丙酸7.2g,三羟甲基丙烷4g,一缩二乙二醇3g,新癸酸铋0.2g,丙酮80g,三乙胺5.5g,去离子水600g,润湿剂3g,消泡剂0.5g,柔软助剂4.5g;
步骤二:有机蒙脱土改性:取乙烯基三甲氧基硅烷,配置成10%水溶液,室温下水解20min;取入蒙脱土,配成5%的水溶液,室温下溶胀2h,用高速分散机搅拌分散30min,然后将蒙脱土水溶液转移到装有搅拌器、测温装置、滴加装置的圆底烧瓶中,向圆底烧瓶中缓慢滴加提前水解好的硅烷偶联剂水溶液,在50℃的温度下,反应3.5h,反应完成后冷却至室温,过滤,用蒸馏水洗涤抽滤,将滤渣放入烘干器中在100℃的温度下烘干2h,干燥器停止加热冷却至室温,取出干燥后的滤渣研磨成粉末即得改性有机蒙脱土;
步骤三:向圆底烧瓶中加入聚氧化丙烯三元醇、聚四氢呋喃醚二元醇、蓖麻油,在110℃的温度下抽真空脱水0.5小时;
步骤四:脱水完成后,降温至60℃,向圆底烧瓶中加入甲苯二异氰酸酯、改性有机蒙脱土,升温至75℃,聚合反应2h;
步骤五:降温至60℃,向圆底烧瓶中加入二羟甲基丙酸、三羟甲基丙烷、一缩二乙二醇、丙酮、新癸酸铋,升温至75℃,反应3h;
步骤六:降温至50℃,向圆底烧瓶中加入三乙胺,搅拌均匀,加入去离子水,分散均匀;
步骤七:升温至65℃,真空脱除丙酮,即得聚氨酯水分散体;
步骤八:在步骤七所得水分散体中加入润湿剂、消泡剂、柔软助剂,分散均匀,得水性聚氨酯树脂,记为实施例1。
实施例2
步骤一:准确称取聚氧化丙烯三元醇(数均分子量为3000)48g,聚氧化丙烯二元醇(数均分子量为8000)200g,聚己内酯二元醇(数均分子量为1000)82g,蓖麻油26g ,有机蒙脱土5g,γ-(2,3-环氧丙氧)丙基三甲氧基硅烷1.2g,异佛尔酮二异氰酸酯89g,二羟甲基丙酸14.8g,三羟甲基丙烷3g,新戊二醇3.1g,1,6-己二醇5.4g,新癸酸铋0.4g,丙酮140g,氢氧化钠1.2g,二甲氨基乙醇5.5g,去离子水1120g,流平剂4.6g,消泡剂0.8g,柔软助剂9.6g;
步骤二:有机蒙脱土改性:取γ-(2,3-环氧丙氧)丙基三甲氧基硅烷,配置成10%水溶液,室温下水解30min;取入蒙脱土,配成10%的水溶液,室温下溶胀3h,用高速分散机搅拌分散50min,然后将蒙脱土水溶液转移到装有搅拌器、测温装置、滴加装置的圆底烧瓶中,向圆底烧瓶中缓慢滴加提前水解好的硅烷偶联剂水溶液,在75℃的温度下,反应2h,反应完成后冷却至室温,过滤,用蒸馏水洗涤抽滤,将滤渣放入烘干器中在120℃的温度下烘干2h,干燥器停止加热冷却至室温,取出干燥后的滤渣研磨成粉末即得改性有机蒙脱土;
步骤三:向圆底烧瓶中加入聚氧化丙烯三元醇、聚氧化丙烯二元醇、聚己内酯二元醇、蓖麻油,在110℃的温度下抽真空脱水0.5小时;
步骤四:脱水完成后,降温至60℃,向圆底烧瓶中加入异佛尔酮二异氰酸酯、改性有机蒙脱土,升温至90℃,聚合反应2h;
步骤五:降温至70℃,向圆底烧瓶中加入二羟甲基丙酸、三羟甲基丙烷、新戊二醇、1,6-己二醇、丙酮、新癸酸铋,升温至85℃,反应3.5h;
步骤六:降温至55℃,向圆底烧瓶中加入氢氧化钠、二甲氨基乙醇,搅拌均匀,加入去离子水,分散均匀;
步骤七:升温至70℃,真空脱除丙酮,即得聚氨酯水分散体;
步骤八:在步骤七所得水分散体中加入润湿剂、消泡剂、柔软助剂,分散均匀,得水性聚氨酯树脂,记为实施例2。
实施例3
步骤一:准确称取聚氧化丙烯二元醇(数均分子量为4000)80g,聚四氢呋喃二元醇(数均分子量为1000)100g,蓖麻油40g ,有机蒙脱土2.5g,3-氨基丙基三乙氧基硅烷0.6g,4,4-二环己基甲烷二异氰酸酯100g,二羟甲基丁酸10.8g,三羟甲基丙烷6g,1,8-辛二醇15g,新癸酸铋0.3g,丙酮120g,二甲氨基乙醇6.5g,去离子水825g,润湿剂3.5g,消泡剂0.56g,柔软助剂5.7g;
步骤二:有机蒙脱土改性:取3-氨基丙基三乙氧基硅烷,配置成10%水溶液,室温下水解30min;取入蒙脱土,配成8%的水溶液,室温下溶胀2.5h,用高速分散机搅拌分散50min,然后将蒙脱土水溶液转移到装有搅拌器、测温装置、滴加装置的圆底烧瓶中,向圆底烧瓶中缓慢滴加提前水解好的硅烷偶联剂水溶液,在65℃的温度下,反应3h,反应完成后冷却至室温,过滤,用蒸馏水洗涤抽滤,将滤渣放入烘干器中在120℃的温度下烘干2h,干燥器停止加热冷却至室温,取出干燥后的滤渣研磨成粉末即得改性有机蒙脱土;
步骤三:向圆底烧瓶中加入聚氧化丙烯二元醇、聚四氢呋喃醚二元醇、蓖麻油,在110℃的温度下抽真空脱水0.5小时;
步骤四:脱水完成后,降温至60℃,向圆底烧瓶中加入4,4-二环己基甲烷二异氰酸酯、改性有机蒙脱土,升温至85℃,聚合反应3h;
步骤五:降温至65℃,向圆底烧瓶中加入二羟甲基丁酸、三羟甲基丙烷、1,8-辛二醇、丙酮、新癸酸铋,升温至80℃,反应3h;
步骤六:降温至55℃,向圆底烧瓶中加入二甲氨基乙醇,搅拌均匀,加入去离子水,分散均匀;
步骤七:升温至70℃,真空脱除丙酮,即得聚氨酯水分散体;
步骤八:在步骤七所得水分散体中加入润湿剂、消泡剂、柔软助剂,分散均匀,得水性聚氨酯树脂,记为实施例3。
实施例4
步骤一:准确称取聚氧化丙烯三元醇(数均分子量为3000)36g,聚四氢呋喃二元醇(数均分子量为1000)80g,聚己内酯二元醇(数均分子量为2000)60g,蓖麻油33g ,有机蒙脱土3.6g,3-氨基丙基三乙氧基硅烷0.9g,异佛尔酮二异氰酸酯90g,二羟甲基丁酸10.6g,三羟甲基丙烷3.6g,1,6-己二醇10g,一缩二乙二醇5g,新癸酸铋0.3g,丙酮120g,三乙胺7.5g,去离子水770g,润湿剂2.5g,流平剂2.5g,消泡剂0.6g,柔软助剂6.5g;
步骤二:有机蒙脱土改性:取3-氨基丙基三乙氧基硅烷,配置成10%水溶液,室温下水解30min;取入蒙脱土,配成8%的水溶液,室温下溶胀2.5h,用高速分散机搅拌分散50min,然后将蒙脱土水溶液转移到装有搅拌器、测温装置、滴加装置的圆底烧瓶中,向圆底烧瓶中缓慢滴加提前水解好的硅烷偶联剂水溶液,在75℃的温度下,反应3h,反应完成后冷却至室温,过滤,用蒸馏水洗涤抽滤,将滤渣放入烘干器中在110℃的温度下烘干2h,干燥器停止加热冷却至室温,取出干燥后的滤渣研磨成粉末即得改性有机蒙脱土;
步骤三:向圆底烧瓶中加入聚氧化丙烯三元醇、聚四氢呋喃醚二元醇、聚己内酯二元醇、蓖麻油,在110℃的温度下抽真空脱水0.5小时;
步骤四:脱水完成后,降温至60℃,向圆底烧瓶中加入异佛尔酮二异氰酸酯、改性有机蒙脱土,升温至90℃,聚合反应2.5h;
步骤五:降温至65℃,向圆底烧瓶中加入羟甲基丁酸、三羟甲基丙烷、1,6-己二醇、一缩二乙二醇、丙酮、新癸酸铋,升温至85℃,反应2.5h;
步骤六:降温至55℃,向圆底烧瓶中加入三乙胺,搅拌均匀,加入去离子水,分散均匀;
步骤七:升温至68℃,真空脱除丙酮,即得聚氨酯水分散体;
步骤八:在步骤七所得水分散体中加入润湿剂、消泡剂、柔软助剂,分散均匀,得水性聚氨酯树脂,记为实施例4。
对比例:
山东天庆科技发展有限公司市场现有的产品水性聚氨酯树脂PUQ-7105。
对实施例1-4以及对比实施例进行固含量、拉伸强度、断裂伸长率、耐热性、耐水性、耐碱性、手感丰满性的性能检测,其检测如下表一所示。
1. 检测项目 | 2. 实施例1 | 3. 实施例2 | 4. 实施例3 | 5. 实施例4 | 6. 对比例 |
7. 固含量/% | 8. 29.63 | 9. 29.81 | 10.30.36 | 11.30.19 | 12.30.28 |
13. 拉伸强度/MPa | 14.25.16 | 15.24.68 | 16.24.36 | 17.25.68 | 18.18.45 |
19. 断裂伸长率/% | 20.805 | 21. 916 | 22. 890 | 23. 852 | 24.925 |
25. 耐热性/140℃,2h | 26. 黄变,不流挂 | 27. 不黄变,不流挂 | 28. 不黄变,不流挂 | 29. 不黄变,不流挂 | 30. 不黄变,流挂 |
31. 耐水性/24h | 32. 增重9.89% | 33. 增重3.56% | 34. 增重7.68% | 35. 增重5.63% | 36. 增重42.31% |
37. 耐碱性/5%NaOH,24h | 38. 增重20.62% | 39. 增重12.68% | 40. 增重15.97% | 41. 增重16.64% | 42. 增重103.64% |
43. 手感丰满性 | 44. 良 | 45. 优 | 46. 优 | 47. 良 | 48. 差 |
表一 各实施例与对比例树脂性能检测的结果
由表一可以看出:实施例1、2、3、4拉伸强度均比对比例要高,但是断裂伸长率略微偏低;实施例1、2、3、4耐热性、耐水性、耐碱性均比对比例要好。实施例1、2、3、4胶膜手感比较丰满,浸渍后合成革回弹性好,饱满性好,对比例胶膜手感较差,有塑感,肉感差,浸渍后合成革回弹差,饱满性差。由此可得,蒙脱土改性水性聚氨酯对于胶膜的拉伸强度、耐热性、耐水性、耐碱性、手感丰满性均有不同程度的提高。
所采用检测方法如下:
固含量测试方法:按照轻工部标准QB/T2415-1998《制革用水乳型聚氨酯涂饰剂》检测。
力学性能测试方法:按照国家标准GB/T16421-1996《塑料拉伸性能小试样试验方法》检测。
耐热性测试方法:将胶膜裁成5cm*10cm的形状,将其悬挂于140℃带有鼓风功能的烘箱中,加热2小时,拿出,冷却至室温,观察其色度和形状变化。
耐水性、耐碱性测试:将胶膜裁成2cm*2cm的正方形,测定样品质量(M1), 浸泡在25℃左右的蒸馏水/5%NaOH水溶液中,24h后取出,用滤纸快速擦干表面,立即称取质量(M2),按下式计算增重率:Ww= (M2-M1)/ M1×100%。
最后应说明的是:以上实施例仅用以说明本发明的技术方案,而非对其限制;尽管参照前述实施例对本发明进行了详细的说明,本领域的普通技术人员应当理解:其依然可以对前述各实施例所记载的技术方案进行修改,或者对其中部分技术特征进行等同替换;而这些修改或者替换,并不使相应技术方案的本质脱离本发明各实施例技术方案的精神和范围。
Claims (10)
1.一种水性聚氨酯树脂,其特征在于:包括如下重量份数的物质:
聚合物多元醇160-330份,蓖麻油20-40份 ,有机蒙脱土2-5份,硅烷偶联剂0.5-1.2份,聚二异氰酸酯56-100份,羟甲基酸7.2-14.8份,羟基型小分子多元醇7-21份,催化剂0.2-0.4份,丙酮80-140份,中和剂5.5-7.5份,去离子水600-1120份,助剂8-15份。
2.根据权利要求1所述的一种水性聚氨酯树脂,其特征在于:所述的聚合物多元醇数均分子量为1000-8000。
3.根据权利要求1所述的一种水性聚氨酯树脂,其特征在于:所述的聚合物多元醇为聚四氢呋喃醚二元醇、聚氧化丙烯二元醇、聚氧化丙烯三元醇、聚己内酯二元醇的其中一种或两种以上以任意比例混合。
4.根据权利要求1所述的一种水性聚氨酯树脂,其特征在于:
所述的硅烷偶联剂为乙烯基三甲氧基硅烷、3-氨基丙基三乙氧基硅烷、γ-(2,3-环氧丙氧)丙基三甲氧基硅烷中的其中一种或两种以上以任意比例混合;
所述聚二异氰酸酯为异佛尔酮二异氰酸酯、甲苯二异氰酸酯、4,4-二环己基甲烷二异氰酸酯的其中一种或两种以上以任意比例混合;
所述羟甲基酸为二羟甲基丙酸和二羟甲基丁酸的其中一种;
所述羟基型小分子多元醇为一缩二乙二醇、新戊二醇、1,6-己二醇、1,8-辛二醇、三羟甲基丙烷中的其中一种或两种以上以任意比例混合;
中和剂为氢氧化钠、二甲氨基乙醇、三乙胺中的一种或两种以上以任意比例混合;
所述的催化剂为辛酸亚锡、有机铋酸盐中的其中一种。
5.根据权利要求4所述的一种水性聚氨酯树脂,其特征在于:所述的所述中和剂使用前与去离子水以1:1的比例进行稀释。
6.根据权利要求4所述的一种水性聚氨酯树脂,其特征在于:所述的催化剂为有机铋酸盐。
7.根据权利要求4所述的一种水性聚氨酯树脂,其特征在于:所述的催化剂为新癸酸铋。
8.根据权利要求1所述的一种水性聚氨酯树脂,其特征在于:所述的所述助剂为润湿剂、流平剂、柔软助剂、消泡剂中的一种或两种以上以任意比例混合。
9.根据权利要求8所述的一种水性聚氨酯树脂,其特征在于:
所述的润湿剂、流平剂为聚醚改性聚硅氧烷类;
所述的柔软助剂为三元共聚硅油类;
所述的消泡剂为聚氧丙烯氧化乙烯甘油醚类。
10.一种水性聚氨酯树脂的制备方法,其特征在于:包括如下步骤:
步骤一:有机蒙脱土改性:准确称取硅烷偶联剂,配置成10%水溶液,室温下水解20-30min;准确称取入蒙脱土,配成5-10%的水溶液,室温下溶胀2-3h,用高速分散机搅拌分散30-60min,然后将蒙脱土水溶液转移到反应器中,向反应器中滴加提前水解好的硅烷偶联剂水溶液,在50-75℃的温度下,反应2-3.5h,反应完成后冷却至室温,过滤,用蒸馏水洗涤抽滤,将滤渣放入烘干器中在100-120℃的温度下烘干2h,干燥器停止加热冷却至室温,取出干燥后的滤渣研磨成粉末即得改性有机蒙脱土;
步骤二:向反应器中加入聚合物多元醇、蓖麻油,在110℃的温度下抽真空脱水0.5小时;
步骤三:脱水完成后,降温至60℃,向反应器中加入聚二异氰酸酯、改性有机蒙脱土,升温至75-90℃,聚合反应2-3h;
步骤四:降温至60-70℃,加入羟甲基酸、羟基型小分子多元醇、丙酮、催化剂,升温至75-85℃,反应2.5-3.5h;
步骤五:降温至50-55℃,加入中和剂,搅拌均匀,加入去离子水,分散均匀;
步骤六:升温至65-70℃,真空脱除丙酮,即得聚氨酯水分散体;
步骤七:在步骤六所得水分散体中加入助剂,分散均匀,得水性聚氨酯树脂。
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109790266A (zh) * | 2016-09-29 | 2019-05-21 | 第一工业制药株式会社 | 水分散体 |
CN115612279A (zh) * | 2022-10-25 | 2023-01-17 | 宁波聚泰新材料科技有限公司 | 一种用于通信电缆/光缆的tpu发泡复合材料及其制备方法 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101698744A (zh) * | 2009-10-30 | 2010-04-28 | 青岛科技大学 | 一种阳离子水性聚氨酯/有机蒙脱土复合树脂及其制备方法 |
CN102344699A (zh) * | 2011-07-05 | 2012-02-08 | 天津大学 | 纳米二氧化硅修饰蒙脱土粒子制备及应用于原位法生成改性水性聚氨酯树脂的方法 |
WO2016091059A1 (zh) * | 2014-12-11 | 2016-06-16 | 宝山钢铁股份有限公司 | 一种热镀铝锌钢板用表面处理剂、热镀铝锌钢板及其制造方法 |
CN108531059A (zh) * | 2018-04-21 | 2018-09-14 | 郭平 | 一种耐紫外线辐射的蒙脱土插层改性聚氨酯涂料 |
-
2019
- 2019-12-03 CN CN201911218345.3A patent/CN110845696A/zh active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101698744A (zh) * | 2009-10-30 | 2010-04-28 | 青岛科技大学 | 一种阳离子水性聚氨酯/有机蒙脱土复合树脂及其制备方法 |
CN102344699A (zh) * | 2011-07-05 | 2012-02-08 | 天津大学 | 纳米二氧化硅修饰蒙脱土粒子制备及应用于原位法生成改性水性聚氨酯树脂的方法 |
WO2016091059A1 (zh) * | 2014-12-11 | 2016-06-16 | 宝山钢铁股份有限公司 | 一种热镀铝锌钢板用表面处理剂、热镀铝锌钢板及其制造方法 |
CN108531059A (zh) * | 2018-04-21 | 2018-09-14 | 郭平 | 一种耐紫外线辐射的蒙脱土插层改性聚氨酯涂料 |
Non-Patent Citations (1)
Title |
---|
侯孟华等: "水性聚氨酯/硅烷蒙脱土纳米复合材料的制备与性能", 《石油化工》 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109790266A (zh) * | 2016-09-29 | 2019-05-21 | 第一工业制药株式会社 | 水分散体 |
CN115612279A (zh) * | 2022-10-25 | 2023-01-17 | 宁波聚泰新材料科技有限公司 | 一种用于通信电缆/光缆的tpu发泡复合材料及其制备方法 |
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