CN109265645A - 一种汽车内饰用介孔改性聚氨酯树脂的制备方法 - Google Patents

一种汽车内饰用介孔改性聚氨酯树脂的制备方法 Download PDF

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CN109265645A
CN109265645A CN201811118917.6A CN201811118917A CN109265645A CN 109265645 A CN109265645 A CN 109265645A CN 201811118917 A CN201811118917 A CN 201811118917A CN 109265645 A CN109265645 A CN 109265645A
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余旺旺
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Nanjing Institute of Industry Technology
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Abstract

本发明公开了一种汽车内饰用介孔改性聚氨酯树脂及其制备方法,包括以下原料组分:前驱体、硅烷偶联剂、亚磷酸、2‑(2ˊ‑羟基‑5ˊ‑甲基苯基)苯并三氮唑、新型阻燃剂、二苯基甲烷二异氰酸酯、乙二醇、1,4‑丁二醇、聚酯二元醇、甲苯、N,N‑二甲基甲酰胺、催化剂、甲醇、碳酸氢铵,前驱体由硅酸铵、三乙烯四胺和锌氨络合物反应制得,锌氨络合物由硫酸锌、氨气和水反应制得,新型阻燃剂由草酸、水和尿素反应制得。该发明中的介孔材料可以提高聚氨酯制品的力学强度、增加聚氨酯表面官能度及亲水性,同时,介孔材料赋予聚氨酯优异的透明、防菌、阻燃、剥离强度、隔热、吸音等性能。

Description

一种汽车内饰用介孔改性聚氨酯树脂的制备方法
技术领域
本发明涉及一种汽车内饰用介孔改性聚氨酯树脂及其制备方法。
背景技术
聚氨酯树脂具有高强度、抗撕裂、耐磨、耐溶剂等特性,广泛应用于日常生活、工农业生产、医学等领域。因此,聚氨酯的合成及其应用越来越被人们重视。
目前,聚氨酯树脂存在防菌、阻燃、剥离强度、隔热、吸音效果不理想。
发明内容
本发明的目的在于提供一种汽车内饰用介孔改性聚氨酯树脂的制备方法,该方法通过改变反应物原料和加工方式,介孔改性聚氨酯树脂制备的合成革具有防菌、阻燃、剥离强度、隔热、吸音等性能。
为了实现上述目的,本发明的技术方案如下。
一种汽车内饰用介孔改性聚氨酯树脂,其特征在于:由以下原料组分反应制得:前驱体、硅烷偶联剂、亚磷酸、2-(2ˊ-羟基-5ˊ-甲基苯基)苯并三氮唑、新型阻燃剂、二苯基甲烷二异氰酸酯、乙二醇、1,4-丁二醇、聚酯二元醇、甲苯、N,N-二甲基甲酰胺、催化剂、甲醇、碳酸氢铵,原料质量份数比为5:0.5~1:0.3~0.8:0.2~0.5:1~5:37~83:7~15:3~10:100~180:100~200:270~526:0.3~1.6:0.3~0.6:3~8;其中,所述的前驱体由硅酸铵、三乙烯四胺和锌氨络合物反应制得,所述的硅酸铵、三乙烯四胺和锌氨络合物的份数比为10:12~20:50~70;所述的锌氨络合物由硫酸锌、氨气和水反应制得,所述的硫酸锌、氨气和水的份数比为10:30~60:20~50;所述的新型阻燃剂由草酸、水和尿素反应制得,所述的草酸、水和尿素的份数比为100:70~90:60~80。
本发明中,所述的硅烷偶联剂为丙基三甲氧基硅烷、乙烯基三乙氧基硅烷的一种或几种混合物;所述的催化剂是二月桂酸二丁基锡、三乙醇胺、辛酸亚锡中的一种;所述聚酯二元醇是聚己二酸乙二醇酯二元醇、聚己二酸丙二醇酯二元醇、聚苯二甲酸乙二醇酯二元醇、聚苯二甲酸乙二醇酯二元醇中的一种。
一种汽车内饰用介孔改性聚氨酯树脂的制备方法,其特征在于包括以下步骤:
(1)、将草酸、水和尿素按照份数比为100:70~90:60~80加入到反应器中,搅拌速度130~200r/min,维持体系温度25~46℃条件下反应1~3h,产物经乙醇洗涤、过滤、60℃,-0.1MPa干燥2h,得到新型阻燃剂;
(2)、将硫酸锌、氨气和水按照份数比为10:30~60:20~50加入到反应器中,搅拌速度80~150r/min,维持体系温度10~30℃条件下反应0.5~2h,产物经-30~-40℃冷冻干燥1~3h,得到锌氨络合物;所述的冷冻干燥的目的为了使锌氨络合物快速干燥的同时,降低氨气的挥发量。
(3)、将硅酸铵、三乙烯四胺和锌氨络合物按照份数比10:12~20:50~70加入到球型研磨机中,在温度20~30℃,100~150r/min条件下研磨反应1~3h,即得到前驱体;所述的三乙烯四胺的目的一方面,为了更好的分散硅酸铵和锌氨络合物;另一方面,为了修饰介孔材料表面。
(4)、前驱体、硅烷偶联剂、亚磷酸、2-(2ˊ-羟基-5ˊ-甲基苯基)苯并三氮唑、新型阻燃剂、二苯基甲烷二异氰酸酯、乙二醇、1,4-丁二醇、聚酯二元醇、甲苯、N,N-二甲基甲酰胺、催化剂、甲醇、碳酸氢铵按照份数比5:0.5~1:0.3~0.8:0.2~0.5:1~5:37~83:7~15:3~10:100~180:100~200:270~526:0.3~1.6:0.3~0.6:3~8加入到反应釜中,在温度65~80℃,90~130r/min条件下反应1~3h,即得到介孔材料改性聚氨酯树脂。
该发明的有益效果在于:
1、硅酸铵和锌氨络合物在聚氨酯合成过程中可以得到较好混合的同时,硅酸铵和锌氨络合物会分解生成纳米二氧化硅和纳米氧化锌,且两者在聚氨酯体体中得到很好的分散,改善介孔材料在聚氨酯中的团聚现象。又,硅酸铵和锌氨络合物分解过程中产生的氨气在纳米二氧化硅和氧化锌生成的过程中作为造孔剂,赋予生成的二氧化硅和氧化锌为介孔二氧化硅和介孔氧化锌;
2、由于介孔二氧化硅和介孔氧化锌在合成过程中,有氨气生成,氨气和有机胺可以修饰新生成的介孔材料表面,得到胺(氨)改性介孔材料;
3、在聚氨酯合成过程中,碳酸铵随着反应温度的升高,发生分解反应,生成二氧化碳、水、氨气,这些物质可以起到聚氨酯的发泡剂的作用,赋予聚氨酯树脂优异的弹性、吸音性能;
4、当聚氨酯在燃烧状态下时,一方面,亚磷酸作为还原剂,可以消耗氧气;另一方面,胺(氨)改性介孔材料会迁移至聚氨酯表面,与(亚)磷酸发生缩聚反应,在聚氨酯表面形成一层阻燃层;
5、当聚氨酯在燃烧状态时,一方面草酸-尿素阻燃剂受热分解生成二氧化碳、氨气等非助燃性气体,另一方面,草酸-尿素阻燃剂在高温时会发生聚合反应,在聚氨酯表面形成一层阻燃层;
6、介孔二氧化硅和氧化锌引入,由于银纹效应,提高了改性聚氨酯的力学性能。
该发明采用前驱体、新型阻燃剂、二苯基甲烷二异氰酸酯、乙二醇、1,4-丁二醇、聚酯二元醇、碳酸氢铵等原料,制备了具有优异防菌、阻燃、剥离强度、隔热、吸音效果等优势的汽车内饰用介孔改性聚氨酯树脂。
本发明可以提高聚氨酯制品的力学强度、增加聚氨酯表面官能度及亲水性,同时,介孔材料赋予聚氨酯优异的透明、防菌、阻燃、剥离强度、隔热、吸音等性能。
本发明可以应用在汽车、建筑、沙发、家居外包装、箱包、皮衣的防菌、阻燃、剥离强度、隔热、吸音等领域。
具体实施方式
下面结合实施例对本发明的具体实施方式进行描述,以便更好的理解本发明。
实施例1
(1)、称取100份草酸、82份水和67份尿素加入到反应器中,搅拌速度165r/min,维持体系温度30℃条件下反应2h,产物经500mL乙醇洗涤两次、过滤、60℃,-0.1MPa干燥2h,得到新型阻燃剂;
(2)、称取10份硫酸锌、45份氨气和39份水加入到反应器中,搅拌速度120r/min,维持体系温度26℃条件下反应1h,产物经-35℃冷冻干燥2h,得到锌氨络合物;
(3)、称取10份硅酸铵、16份三乙烯四胺和65份锌氨络合物加入到球型研磨机中,在温度26℃,130r/min条件下研磨反应2h,即得到前驱体;
(4)、称取5份前驱体、0.8份(2,3-环氧丙氧)丙基三甲氧基硅烷、0.5份亚磷酸、0.3份2-(2ˊ-羟基-5ˊ-甲基苯基)苯并三氮唑、3.5份新型阻燃剂、67份二苯基甲烷二异氰酸酯、12份乙二醇、7份1,4-丁二醇、150份聚己二酸丙二醇酯二元醇、155份甲苯、440份N,N-二甲基甲酰胺、0.9份二月桂酸二丁基锡、0.6份甲醇、5份碳酸氢铵加入到反应釜中,在温度70℃,110r/min条件下反应2h,即得到介孔材料改性聚氨酯树脂。表1是实施例1制得的汽车内饰用介孔改性聚氨酯树脂的性能参数。
实施例2
(1)、称取100份草酸、70份水和60份尿素加入到反应器中,搅拌速度130r/min,维持体系温度25℃条件下反应1h,产物经500mL乙醇洗涤两次、过滤、60℃,-0.1MPa干燥2h,得到新型阻燃剂;
(2)、称取10份硫酸锌、30份氨气和20份水加入到反应器中,搅拌速度80r/min,维持体系温度10℃条件下反应0.5h,产物经-30℃冷冻干燥1h,得到锌氨络合物;
(3)、称取10份硅酸铵、12份三乙烯四胺和50份锌氨络合物加入到球型研磨机中,在温度20℃,100r/min条件下研磨反应1h,即得到前驱体;
(4)、称取5份前驱体、0.5份乙烯基三乙氧基硅烷、0.3份亚磷酸、0.2份2-(2ˊ-羟基-5ˊ-甲基苯基)苯并三氮唑、1份新型阻燃剂、37份二苯基甲烷二异氰酸酯、7份乙二醇、3份1,4-丁二醇、100份聚苯二甲酸乙二醇酯二元醇、100份甲苯、270份N,N-二甲基甲酰胺、0.3份三乙醇胺、0.3份甲醇、3份碳酸氢铵加入到反应釜中,在温度65℃,90r/min条件下反应1h,即得到介孔材料改性聚氨酯树脂。
实施例3
(1)、称取100份草酸、90份水和80份尿素加入到反应器中,搅拌速度200r/min,维持体系温度46℃条件下反应3h,产物经500mL乙醇洗涤两次、过滤、60℃,-0.1MPa干燥2h,得到新型阻燃剂;
(2)、称取10份硫酸锌、60份氨气和50份水加入到反应器中,搅拌速度150r/min,维持体系温度30℃条件下反应2h,产物经-40℃冷冻干燥3h,得到锌氨络合物;
(3)、称取10份硅酸铵、20份三乙烯四胺和70份锌氨络合物加入到球型研磨机中,在温度30℃,150r/min条件下研磨反应3h,即得到前驱体;
(4)、称取5份前驱体、1份(甲基丙烯酰氧)丙基三甲氧基硅烷、0.8份亚磷酸、0.2~0.5份2-(2ˊ-羟基-5ˊ-甲基苯基)苯并三氮唑、5份新型阻燃剂、83份二苯基甲烷二异氰酸酯、15份乙二醇、10份1,4-丁二醇、180份聚己二酸丙二醇酯二元醇、200份甲苯、526份N,N-二甲基甲酰胺、1.6份二月桂酸二丁基锡、0.6份甲醇、8份碳酸氢铵加入到反应釜中,在温度80℃,130r/min条件下反应3h,即得到介孔材料改性聚氨酯树脂。
实施例4
(1)、称取100份草酸、73份水和66份尿素加入到反应器中,搅拌速度137r/min,维持体系温度28℃条件下反应3h,产物经500mL乙醇洗涤两次、过滤、60℃,-0.1MPa干燥2h,得到新型阻燃剂;
(2)、称取10份硫酸锌、35份氨气和28份水加入到反应器中,搅拌速度85r/min,维持体系温度13℃条件下反应0.8h,产物经-35℃冷冻干燥1h,得到锌氨络合物;
(3)、称取10份硅酸铵、15份三乙烯四胺和58份锌氨络合物加入到球型研磨机中,在温度23℃,110r/min条件下研磨反应3h,即得到前驱体;
(4)、称取5份前驱体、0.7份乙烯基三乙氧基硅烷、0.8份亚磷酸、0.3份2-(2ˊ-羟基-5ˊ-甲基苯基)苯并三氮唑、2份新型阻燃剂、56份二苯基甲烷二异氰酸酯、8份乙二醇、9份1,4-丁二醇、100份聚苯二甲酸乙二醇酯二元醇、120份甲苯、326份N,N-二甲基甲酰胺、0.7份三乙醇胺、0.5份甲醇、6份碳酸氢铵加入到反应釜中,在温度68℃,100r/min条件下反应1.5h,即得到介孔材料改性聚氨酯树脂。
实施例5
(1)、称取100份草酸、75份水和67份尿素加入到反应器中,搅拌速度146r/min,维持体系温度30℃条件下反应2h,产物经500mL乙醇洗涤两次、过滤、60℃,-0.1MPa干燥2h,得到新型阻燃剂;
(2)、称取10份硫酸锌、33份氨气和22份水加入到反应器中,搅拌速度90r/min,维持体系温度18℃条件下反应1.2h,产物经-33℃冷冻干燥2h,得到锌氨络合物;
(3)、称取10份硅酸铵、15份三乙烯四胺和57份锌氨络合物加入到球型研磨机中,在温度26℃,130r/min条件下研磨反应2h,即得到前驱体;
(4)、称取5份前驱体、0.7份(2,3-环氧丙氧)丙基三甲氧基硅烷、0.6份亚磷酸、0.4份2-(2ˊ-羟基-5ˊ-甲基苯基)苯并三氮唑、4份新型阻燃剂、80份二苯基甲烷二异氰酸酯、14份乙二醇、7份1,4-丁二醇、160份聚己二酸丙二醇酯二元醇、180份甲苯、470份N,N-二甲基甲酰胺、1.4份辛酸亚锡、0.5份甲醇、4份碳酸氢铵加入到反应釜中,在温度71℃,96r/min条件下反应2h,即得到介孔材料改性聚氨酯树脂。
实施例6
(1)、称取100份草酸、80份水和76份尿素加入到反应器中,搅拌速度150r/min,维持体系温度45℃条件下反应1h,产物经500mL乙醇洗涤两次、过滤、60℃,-0.1MPa干燥2h,得到新型阻燃剂;
(2)、称取10份硫酸锌、58份氨气和49份水加入到反应器中,搅拌速度147r/min,维持体系温度28℃条件下反应1.8h,产物经-39℃冷冻干燥2h,得到锌氨络合物;
(3)、称取10份硅酸铵、17份三乙烯四胺和66份锌氨络合物加入到球型研磨机中,在温度24℃,130r/min条件下研磨反应2h,即得到前驱体;
(4)、称取5份前驱体、0.8份乙烯基三乙氧基硅烷、0.6份亚磷酸、0.4份2-(2ˊ-羟基-5ˊ-甲基苯基)苯并三氮唑、3份新型阻燃剂、60份二苯基甲烷二异氰酸酯、9份乙二醇、5份1,4-丁二醇、160份聚己二酸乙二醇酯二元醇、170份甲苯、326份N,N-二甲基甲酰胺、1.6份二月桂酸二丁基锡、0.5份甲醇、6份碳酸氢铵加入到反应釜中,在温度73℃,123r/min条件下反应2h,即得到介孔材料改性聚氨酯树脂。
实施例7
(1)、称取100份草酸、84份水和73份尿素加入到反应器中,搅拌速度150r/min,维持体系温度37℃条件下反应2.5h,产物经500mL乙醇洗涤两次、过滤、60℃,-0.1MPa干燥2h,得到新型阻燃剂;
(2)、称取10份硫酸锌、53份氨气和46份水加入到反应器中,搅拌速度120r/min,维持体系温度26℃条件下反应1.7h,产物经-37℃冷冻干燥2.5h,得到锌氨络合物;
(3)、称取10份硅酸铵、17份三乙烯四胺和66份锌氨络合物加入到球型研磨机中,在温度21℃,124r/min条件下研磨反应2.8h,即得到前驱体;
(4)、称取5份前驱体、0.8份(甲基丙烯酰氧)丙基三甲氧基硅烷、0.6份亚磷酸、0.4份2-(2ˊ-羟基-5ˊ-甲基苯基)苯并三氮唑、3份新型阻燃剂、41份二苯基甲烷二异氰酸酯、7份乙二醇、8份1,4-丁二醇、140份聚苯二甲酸乙二醇酯二元醇、100份甲苯、270份N,N-二甲基甲酰胺、1.6份辛酸亚锡、0.3份甲醇、3份碳酸氢铵加入到反应釜中,在温度76℃,110r/min条件下反应1h,即得到介孔材料改性聚氨酯树脂。
实施例8
(1)、称取100份草酸、83份水和75份尿素加入到反应器中,搅拌速度170r/min,维持体系温度34℃条件下反应1.7h,产物经500mL乙醇洗涤两次、过滤、60℃,-0.1MPa干燥2h,得到新型阻燃剂;
(2)、称取10份硫酸锌、48份氨气和44份水加入到反应器中,搅拌速度116r/min,维持体系温度27℃条件下反应1.3h,产物经-32℃冷冻干燥3h,得到锌氨络合物;
(3)、称取10份硅酸铵、15份三乙烯四胺和65份锌氨络合物加入到球型研磨机中,在温度26℃,130r/min条件下研磨反应2h,即得到前驱体;
(4)、称取5份前驱体、0.7份乙烯基三乙氧基硅烷、0.7份亚磷酸、0.4份2-(2ˊ-羟基-5ˊ-甲基苯基)苯并三氮唑、4份新型阻燃剂、72份二苯基甲烷二异氰酸酯、9份乙二醇、6份1,4-丁二醇、158份聚己二酸乙二醇酯二元醇、130份甲苯、430份N,N-二甲基甲酰胺、1.5份二月桂酸二丁基锡、0.4份甲醇、5份碳酸氢铵加入到反应釜中,在温度73℃,126r/min条件下反应2.3h,即得到介孔材料改性聚氨酯树脂。
实施例9
(1)、称取100份草酸、81份水和77份尿素加入到反应器中,搅拌速度180r/min,维持体系温度29℃条件下反应2h,产物经500mL乙醇洗涤两次、过滤、60℃,-0.1MPa干燥2h,得到新型阻燃剂;
(2)、称取10份硫酸锌、36份氨气和40份水加入到反应器中,搅拌速度130r/min,维持体系温度17℃条件下反应1.9h,产物经-38℃冷冻干燥1.5h,得到锌氨络合物;
(3)、称取10份硅酸铵、17份三乙烯四胺和63份锌氨络合物加入到球型研磨机中,在温度26℃,130r/min条件下研磨反应2h,即得到前驱体;
(4)、称取5份前驱体、0.7份(甲基丙烯酰氧)丙基三甲氧基硅烷、0.5份亚磷酸、0.3份2-(2ˊ-羟基-5ˊ-甲基苯基)苯并三氮唑、4份新型阻燃剂、67份二苯基甲烷二异氰酸酯、12份乙二醇、7份1,4-丁二醇、180份聚苯二甲酸乙二醇酯二元醇、180份甲苯、390份N,N-二甲基甲酰胺、1.3份辛酸亚锡、0.4份甲醇、5份碳酸氢铵加入到反应釜中,在温度73℃,111r/min条件下反应2.6h,即得到介孔材料改性聚氨酯树脂。
实施例10
(1)、称取100份草酸、82份水和71份尿素加入到反应器中,搅拌速度180r/min,维持体系温度43℃条件下反应2.3h,产物经500mL乙醇洗涤两次、过滤、60℃,-0.1MPa干燥2h,得到新型阻燃剂;
(2)、称取10份硫酸锌、41份氨气和44份水加入到反应器中,搅拌速度134r/min,维持体系温度16℃条件下反应1.7h,产物经-38℃冷冻干燥2.3h,得到锌氨络合物;
(3)、称取10份硅酸铵、14份三乙烯四胺和63份锌氨络合物加入到球型研磨机中,在温度22℃,140r/min条件下研磨反应2.3h,即得到前驱体;
(4)、称取5份前驱体、0.7份(2,3-环氧丙氧)丙基三甲氧基硅烷、0.6份亚磷酸、0.5份2-(2ˊ-羟基-5ˊ-甲基苯基)苯并三氮唑、3份新型阻燃剂、63份二苯基甲烷二异氰酸酯、9份乙二醇、9份1,4-丁二醇、150份聚己二酸乙二醇酯二元醇、170份甲苯、350份N,N-二甲基甲酰胺、1.5份二月桂酸二丁基锡、0.4份甲醇、4份碳酸氢铵加入到反应釜中,在温度77℃,123r/min条件下反应2h,即得到介孔材料改性聚氨酯树脂。
实施例11
(1)、称取100份草酸、89份水和75份尿素加入到反应器中,搅拌速度190r/min,维持体系温度37℃条件下反应2h,产物经500mL乙醇洗涤两次、过滤、60℃,-0.1MPa干燥2h,得到新型阻燃剂;
(2)、称取10份硫酸锌、40份氨气和41份水加入到反应器中,搅拌速度86r/min,维持体系温度23℃条件下反应1.8h,产物经-36℃冷冻干燥1h,得到锌氨络合物;
(3)、称取10份硅酸铵、14份三乙烯四胺和60份锌氨络合物加入到球型研磨机中,在温度29℃,135r/min条件下研磨反应2h,即得到前驱体;
(4)、称取5份前驱体、0.7份(甲基丙烯酰氧)丙基三甲氧基硅烷、0.6份亚磷酸、0.3份2-(2ˊ-羟基-5ˊ-甲基苯基)苯并三氮唑、4份新型阻燃剂、46份二苯基甲烷二异氰酸酯、7份乙二醇、3份1,4-丁二醇、110份聚苯二甲酸乙二醇酯二元醇、100份甲苯、300份N,N-二甲基甲酰胺、1.5份辛酸亚锡、0.6份甲醇、5份碳酸氢铵加入到反应釜中,在温度75℃,97r/min条件下反应2h,即得到介孔材料改性聚氨酯树脂。
实施例12
(1)、称取100份草酸、81份水和72份尿素加入到反应器中,搅拌速度170r/min,维持体系温度30℃条件下反应1.5h,产物经500mL乙醇洗涤两次、过滤、60℃,-0.1MPa干燥2h,得到新型阻燃剂;
(2)、称取10份硫酸锌、35份氨气和21份水加入到反应器中,搅拌速度88r/min,维持体系温度18℃条件下反应1.5h,产物经-34℃冷冻干燥1h,得到锌氨络合物;
(3)、称取10份硅酸铵、16份三乙烯四胺和57份锌氨络合物加入到球型研磨机中,在温度25℃,140r/min条件下研磨反应3h,即得到前驱体;
(4)、称取5份前驱体、0.7份(2,3-环氧丙氧)丙基三甲氧基硅烷、0.4份亚磷酸、0.2份2-(2ˊ-羟基-5ˊ-甲基苯基)苯并三氮唑、3份新型阻燃剂、50份二苯基甲烷二异氰酸酯、7份乙二醇、4份1,4-丁二醇、120份聚苯二甲酸乙二醇酯二元醇、130份甲苯、270份N,N-二甲基甲酰胺、0.7份二月桂酸二丁基锡、0.5份甲醇、8份碳酸氢铵加入到反应釜中,在温度74℃,117r/min条件下反应1.5h,即得到介孔材料改性聚氨酯树脂。
表1实施例1制得的汽车内饰用介孔改性聚氨酯合成革树脂的性能参数
实施例1
氧指数% 35
剥离强度/kgf/cm 7.6
防霉菌
吸音
以上所述是该发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离该发明原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也视为该发明的保护范围。

Claims (2)

1.一种汽车内饰用介孔改性聚氨酯树脂,其特征在于:由以下原料组分反应制得:前驱体、硅烷偶联剂、亚磷酸、2-(2ˊ-羟基-5ˊ-甲基苯基)苯并三氮唑、新型阻燃剂、二苯基甲烷二异氰酸酯、乙二醇、1,4-丁二醇、聚酯二元醇、甲苯、N,N-二甲基甲酰胺、催化剂、甲醇、碳酸氢铵,原料质量份数比为5:0.5~1:0.3~0.8:0.2~0.5:1~5:37~83:7~15:3~10:100~180:100~200:270~526:0.3~1.6:0.3~0.6:3~8加入到反应釜中,在温度65~80℃,90~130r/min条件下反应1~3h;其中,所述的前驱体由硅酸铵、三乙烯四胺和锌氨络合物反应制得,所述的硅酸铵、三乙烯四胺和锌氨络合物的份数比为10:12~20:50~70;所述的锌氨络合物由硫酸锌、氨气和水反应制得,所述的硫酸锌、氨气和水的份数比为10:30~60:20~50加入到反应器中,搅拌速度80~150r/min,维持体系温度10~30℃条件下反应0.5~2h,产物经-30~-40℃冷冻干燥1~3h;所述的新型阻燃剂由草酸、水和尿素反应制得,所述的草酸、水和尿素的份数比为100:70~90:60~80加入到反应器中,搅拌速度130~200r/min,维持体系温度25~46℃条件下反应1~3h,产物经乙醇洗涤、过滤、60℃,-0.1MPa干燥2h。
2.根据权利要求1所述的汽车内饰用介孔改性聚氨酯树脂,其特征在于:所述的前驱体是由以下制备方法制得的:将硅酸铵、三乙烯四胺和锌氨络合物按照份数比10:15~17:57~65加入到球型研磨机中,在温度23~26℃,110~130r/min条件下研磨反应2~3h。
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102010496A (zh) * 2010-09-29 2011-04-13 上海汇得树脂有限公司 超软质湿法压花型聚氨酯树脂及其制备方法和应用
CN102634318A (zh) * 2012-05-02 2012-08-15 江苏华大新材料有限公司 一种耐低温溶剂型聚氨酯粘合剂及其制备方法
CN103031736A (zh) * 2012-12-20 2013-04-10 陕西科技大学 基于注流涂布的无溶剂多组分聚氨酯合成革的制备方法
CN104369516A (zh) * 2013-08-12 2015-02-25 佛山市高明区业晟聚氨酯有限公司 一种复合聚氨酯薄膜的制备方法

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1616354A (zh) * 2003-11-14 2005-05-18 湘潭大学 配位均匀沉淀法制备纳米氧化锌的方法
KR20070094312A (ko) * 2006-03-17 2007-09-20 마이크로코어텍(주) 나노 크기 기공을 함유한 실리카 비즈와 그의 제조 방법
CN100582012C (zh) * 2006-09-26 2010-01-20 中国科学院上海硅酸盐研究所 一种高度c轴取向的纳米多孔氧化锌薄膜及其制备方法
BR112012002056B1 (pt) * 2009-07-30 2019-12-17 Construction Research & Technology Gmbh composição e processo de fabricação da mesma
CN102718942A (zh) * 2012-06-13 2012-10-10 华东理工大学 一种耐磨耐黄变聚氨酯树脂的制备与应用
CN105153392A (zh) * 2015-11-01 2015-12-16 刘应才 一种汽车内饰用的阻燃聚氨酯泡沫材料的制备方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102010496A (zh) * 2010-09-29 2011-04-13 上海汇得树脂有限公司 超软质湿法压花型聚氨酯树脂及其制备方法和应用
CN102634318A (zh) * 2012-05-02 2012-08-15 江苏华大新材料有限公司 一种耐低温溶剂型聚氨酯粘合剂及其制备方法
CN103031736A (zh) * 2012-12-20 2013-04-10 陕西科技大学 基于注流涂布的无溶剂多组分聚氨酯合成革的制备方法
CN104369516A (zh) * 2013-08-12 2015-02-25 佛山市高明区业晟聚氨酯有限公司 一种复合聚氨酯薄膜的制备方法

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