CN115386064A - 一种柔软高弹水性聚氨酯及其制备方法 - Google Patents
一种柔软高弹水性聚氨酯及其制备方法 Download PDFInfo
- Publication number
- CN115386064A CN115386064A CN202211212967.7A CN202211212967A CN115386064A CN 115386064 A CN115386064 A CN 115386064A CN 202211212967 A CN202211212967 A CN 202211212967A CN 115386064 A CN115386064 A CN 115386064A
- Authority
- CN
- China
- Prior art keywords
- parts
- waterborne polyurethane
- isophorone diisocyanate
- stirring
- modified
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0033—Xanthan, i.e. D-glucose, D-mannose and D-glucuronic acid units, saubstituted with acetate and pyruvate, with a main chain of (beta-1,4)-D-glucose units; Derivatives thereof
-
- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- 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
- C08G18/3225—Polyamines
- C08G18/3228—Polyamines acyclic
-
- 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
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
-
- 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
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
-
- 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
- C08G18/4081—Mixtures of compounds of group C08G18/64 with other macromolecular compounds
-
- 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
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- 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
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6484—Polysaccharides and derivatives thereof
-
- 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
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6492—Lignin containing materials; Wood resins; Wood tars; Derivatives thereof
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
- C08G18/724—Combination of aromatic polyisocyanates with (cyclo)aliphatic polyisocyanates
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
- C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Emergency Medicine (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Biochemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
本发明公开了一种柔软高弹水性聚氨酯及其制备方法,由包括以下重量份的原料制成:聚四氢呋喃醚二醇:65‑85份;改性异佛尔酮二异氰酸酯:20‑40份;六亚甲基二异氰酸酯:10‑20份;甲苯二异氰酸酯:20‑30份;二羟甲基丙酸:4‑8份;邻氨基苯磺酸:5‑10份;水:100‑120份;催化剂:2‑5份;增稠剂:1‑6份;消泡剂:2‑4份;所述改性异佛尔酮二异氰酸酯由异佛尔酮二异氰酸酯、滑石粉和黄原胶改性制得。本申请具有提高水性聚氨酯的柔软性。
Description
技术领域
本发明涉及水性聚氨酯领域,尤其是涉及一种一种柔软高弹水性聚氨酯及其制备方法。
背景技术
水性聚氨酯是以水代替有机溶剂作为分散介质的新型聚氨酯体系,水性聚氨酯以水为溶剂,有着无污染、安全可靠、机械性能优良、相容性好、易于改性等优点。
现有的,市场上的水性聚氨酯材料柔软度不高,当水性聚氨酯遇水、清洁剂或在湿度高的情况下,会加速聚氨酯的水解、裂化;因此,市场上需要一款柔软性高的水性聚氨酯涂料。
发明内容
为了提高水性聚氨酯的柔软性,本申请提供一种柔软高弹水性聚氨酯及其制备方法。
第一方面,本申请提供的一种柔软高弹水性聚氨酯采用如下技术方案:
一种柔软高弹水性聚氨酯,由包括以下重量份的原料制成:
聚四氢呋喃醚二醇:65-85份;
改性异佛尔酮二异氰酸酯:20-40份;
六亚甲基二异氰酸酯:10-20份;
甲苯二异氰酸酯:20-30份;
二羟甲基丙酸:4-8份;
邻氨基苯磺酸:5-10份;
水:100-120份;
催化剂:2-5份;
增稠剂:1-6份;
消泡剂:2-4份;
所述改性异佛尔酮二异氰酸酯由异佛尔酮二异氰酸酯、滑石粉和黄原胶改性制得。
通过采用上述技术方案,本申请通过水作为水性聚氨酯的溶剂,通过滑石粉和黄原胶对异佛尔酮二异氰酸酯进行改性,黄原胶自身是稳定的粘稠胶体,与滑石粉混合可以提高滑石粉的分散性能,使黄原胶和滑石粉可以均匀与异佛尔酮二异氰酸酯混合,滑石粉可以填充在异佛尔酮二异氰酸酯内,改性后的异佛尔酮二异氰酸酯在参与制备水性聚氨酯的反应过程中更加平稳,可以防止水性聚氨酯凝聚,进而改善水性聚氨酯的柔顺性;
同时本申请中加入六亚甲基二异氰酸酯、甲苯二异氰酸酯和改性异佛尔酮二异氰酸酯,作为制备水性聚氨酯的材料,甲苯二异氰酸酯和改性异佛尔酮二异氰酸酯均具有环状结构,六亚甲基二异氰酸酯的结构对称,三者共同配合形成交联网状结构,可以有效增加水性聚氨酯的柔软度同时使水性聚氨酯具有优异的弹性;聚四氢呋喃醚二醇中的醚键可以为制备水性聚氨酯提供良好的耐水解性能,且分子量较大,可以增加分子链段长度,制备出来的水性聚氨酯具有大量活性基团,进而使水性聚氨酯获得良好的柔软度;
二羟甲基丙酸和邻氨基苯磺酸作为亲水扩链剂,在聚氨酯链段引入基团,提高水分子进入聚氨酯分子链的速度,进而提高水性聚氨酯乳液的稳定性。
优选的,所述异佛尔酮二异氰酸酯的制备方法为:将异佛尔酮二异氰酸酯和黄原胶加入到乙醇溶液中,加热搅拌,加入滑石粉进行超声振荡,洗涤后烘干,得到所述改性异佛尔酮二异氰酸酯;所述异佛尔酮二异氰酸酯、滑石粉和黄原胶的重量配比为1:(0.32-0.4):(0.6-0.72)。
通过采用上述技术方案,本申请通过滑石粉和黄原胶对异佛尔酮二异氰酸酯进行改性,滑石粉具有良好的润滑性,滑石粉可以填充到异佛尔酮二异氰酸酯内,异佛尔酮二异氰酸酯的粘度较低,而黄原胶具有高粘度的特性,使滑石粉均匀紧密附着在异佛尔酮二异氰酸酯上,使制得的水性聚氨酯具有良好的柔顺性,同时滑石粉填充在异佛尔酮二异氰酸酯内,可以提高水性聚氨酯的拉伸强度。
优选的,所述水性聚氨酯还包括有以下重量份数:
松香树脂:15-25份;
1,6-己二胺:4-8份;
壳聚糖:6-10份。
通过采用上述技术方案,松香树脂具有羧基活性基团,加入1,6-己二胺扩链剂参与扩链,使水性聚氨酯具有更良好的粘结力,加入壳聚糖会与水性聚氨酯发生反应,形成网状交联结构,增强了分子间的相互作用,松香树脂、1,6-己二胺和壳聚糖共同配合可以提高水性聚氨酯的回弹性。
优选的,所述松香树脂、1,6-己二胺、壳聚糖和聚四氢呋喃醚二醇的重量比为(3-3.5):1:(1-1.2):(11.6-12)。
通过采用上述技术方案,当松香树脂、1,6-己二胺、壳聚糖和聚四氢呋喃醚二醇在特定配比时,可以提高水性聚氨酯的力学性能,使水性聚氨酯具有良好的回弹性能,同时使水性聚氨酯形成特殊的网状结构,进而水性聚氨酯具有良好的抑菌效果。
优选的,所述改性异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯和甲苯二异氰酸酯的重量比为(2.4-2.5):1:(1.4-1.5)。
通过采用上述技术方案,当改性异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯和甲苯二异氰酸酯在特定的重量配比时,改性异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯和甲苯二异氰酸酯三者共同配合,更容易与聚四氢呋喃醚二醇和水发生反应,使制得的水性聚氨酯具有良好的柔软性和力学性能,进而提高水性聚氨酯的拉伸强度。
优选的,所述黄原胶为改性黄原胶,所述改性黄原胶的制备方法为:将20-30重量份黄原胶与8-12重量份二甲基甲酰胺在乙醇溶液中搅拌,再将10-15重量份甘露醇和4-8重量份氰基硼氢化钠搅拌后洗涤干燥后得到所述改性黄原胶。
通过采用上述技术方案,本申请通过二甲基甲酰胺和氰基硼氢化钠对黄原胶进行改性,使二甲基甲酰胺和氰基硼氢化钠分散在黄原胶上,氰基硼氢化钠可以激发异佛尔酮二异氰酸酯的活性,使改性后的黄原胶再对异佛尔酮二异氰酸酯改性时,制得的改性异佛尔酮二异氰酸酯的粘结性能较高,进而提高水性聚氨酯的柔软性和弹力。
优选的,所述二甲基甲酰胺、甘露醇和氰基硼氢化钠的重量比为1:(1.3-1.4):(0.45-0.5)。
通过采用上述技术方案,当二甲基甲酰胺、甘露醇和氰基硼氢化钠在特定的重量配比时,甘露醇可以改善改性黄原胶的流动性,使二甲基甲酰胺和氰基硼氢化钠对黄原胶改性的效果更显著,同时二甲基甲酰胺、甘露醇和氰基硼氢化钠三者共同配合对黄原胶改性后,改性黄原胶用于对异佛尔酮二异氰酸酯进行改性,改善水性聚氨酯乳液的流动性,进而提高水性聚氨酯的柔软性的同时还可以提高水性聚氨酯的抑菌性。
优选的,所述催化剂为三亚乙基二胺和二丁基锡二月桂酸酯中的一种;所述增稠剂为淀粉和海藻胶中的一种;所述消泡剂为二甲基硅油和棕榈酸中的一种。
通过采用上述技术方案,选用合适的催化剂,增稠剂和消泡剂可以制得柔软高弹的水性聚氨酯。
第二方面,本申请提供一种柔软高弹水性聚氨酯的制备方法采用如下技术方案:
一种柔软高弹水性聚氨酯的制备方法,包括以下步骤:
S1.将聚四氢呋喃醚二醇、六亚甲基二异氰酸酯和二羟甲基丙酸混合加热溶解后冷却,得到预聚液;
S2.将预聚液、改性异佛尔酮二异氰酸酯、甲苯二异氰酸酯、水和催化剂混合搅拌,边搅拌边加入邻氨基苯磺酸进行扩链反应,得到搅拌液;
S3.将增稠剂和消泡剂加入搅拌液中搅拌后得到所述水性聚氨酯。
通过采用上述技术方案,将各种原料分步骤进行混合,可以使各种原料充分混合,进而得到柔软高弹的水性聚氨酯。
优选的,S1.将聚四氢呋喃醚二醇、六亚甲基二异氰酸酯和二羟甲基丙酸混合加热溶解后冷却,得到预聚液;
S2.将预聚液、改性异佛尔酮二异氰酸酯、甲苯二异氰酸酯、水和催化剂混合搅拌,边搅拌边加入邻氨基苯磺酸进行扩链反应,得到搅拌液;
S3.将松香树脂、1,6-己二胺、壳聚糖、增稠剂和消泡剂加入搅拌液中搅拌后得到所述水性聚氨酯。
通过采用上述技术方案,将松香树脂、1,6-己二胺、壳聚糖加入搅拌液中,有助于提高水性聚氨酯的弹性。
综上所述,本申请具有以下技术效果:
1.本申请中加入六亚甲基二异氰酸酯、甲苯二异氰酸酯和改性异佛尔酮二异氰酸酯,作为制备水性聚氨酯的材料,甲苯二异氰酸酯和改性异佛尔酮二异氰酸酯均具有环状结构,六亚甲基二异氰酸酯的结构对称,三者共同配合形成交联网状结构,可以有效增加水性聚氨酯的柔软度同时使水性聚氨酯具有优异的弹性;聚四氢呋喃醚二醇中的醚键可以为制备水性聚氨酯提供良好的耐水解性能,且分子量较大,可以增加分子链段长度,制备出来的水性聚氨酯具有大量活性基团,进而使水性聚氨酯获得良好的柔软度;
2.本申请通过滑石粉和黄原胶对异佛尔酮二异氰酸酯进行改性,滑石粉具有良好的润滑性,滑石粉可以填充到异佛尔酮二异氰酸酯内,异佛尔酮二异氰酸酯的粘度较低,而黄原胶具有高粘度的特性,使滑石粉均匀紧密附着在异佛尔酮二异氰酸酯上,使制得的水性聚氨酯具有良好的柔顺性,同时滑石粉填充在异佛尔酮二异氰酸酯内,可以提高水性聚氨酯的拉伸强度;3.本申请通过二甲基甲酰胺和氰基硼氢化钠对黄原胶进行改性,使二甲基甲酰胺和氰基硼氢化钠分散在黄原胶上,氰基硼氢化钠可以激发异佛尔酮二异氰酸酯的活性,使改性后的黄原胶再对异佛尔酮二异氰酸酯改性时,制得的改性异佛尔酮二异氰酸酯的粘结性能较高,进而提高水性聚氨酯的柔软性和弹力。
具体实施方式
以下结合实施例和对比例对本申请作进一步详细说明。
制备例1
一种改性黄原胶的制备方法:
将20kg黄原胶溶解在5L的乙醇溶液中,在转速为20rad/min,温度为30℃的条件下边搅拌边加入8kg二甲基甲酰胺,搅拌4h;
再加入10kg甘露醇和4kg氰基硼氢化钠在温度为30℃、转速为25rad/min的条件下搅拌6h;用乙醇洗涤后在温度为40℃的条件下干燥6h,得到所述改性黄原胶。
制备例2
一种改性黄原胶的制备方法:
将30kg黄原胶溶解在5L的乙醇溶液中,在转速为20rad/min,温度为30℃的条件下边搅拌边加入12kg二甲基甲酰胺,搅拌4h;
再加入15kg甘露醇和8kg氰基硼氢化钠在温度为30℃、转速为25rad/min的条件下搅拌6h;用乙醇洗涤后在温度为40℃的条件下干燥6h,得到所述改性黄原胶。
制备例3
一种改性黄原胶的制备方法:
将25kg黄原胶溶解在5L的乙醇溶液中,在转速为20rad/min,温度为30℃的条件下边搅拌边加入10kg二甲基甲酰胺,搅拌4h;
再加入12.5kg甘露醇和6kg氰基硼氢化钠在温度为30℃、转速为25rad/min的条件下搅拌6h;用乙醇洗涤后在温度为40℃的条件下干燥6h,得到所述改性黄原胶。
制备例4
一种改性黄原胶的制备方法,与制备例3的不同之处在于,二甲基甲酰胺的投入量为10kg,甘露醇的投入量为13kg,氰基硼氢化钠的投入量为4.5kg。
制备例5
一种改性黄原胶的制备方法,与制备例3的不同之处在于,二甲基甲酰胺的投入量为10kg,甘露醇的投入量为14kg,氰基硼氢化钠的投入量为5kg。
实施例
实施例1
一种柔软高弹水性聚氨酯的制备方法:
S1.将65kg聚四氢呋喃醚二醇、10kg六亚甲基二异氰酸酯和4kg二羟甲基丙酸加入三口烧瓶中,升温至60℃,在转速为50rad/min的条件下搅拌溶解1h后冷却至室温,得到预聚液;
S2.将预聚液、20kg改性异佛尔酮二异氰酸酯、20kg甲苯二异氰酸酯、100kg水和2kg催化剂在温度为80℃,转速为60rad/min混合搅拌1h后,继续搅拌,边搅拌边加入5kg邻氨基苯磺酸进行扩链反应,继续搅拌2h后,得到搅拌液;
S3.将1kg增稠剂和2kg消泡剂加入搅拌液中在温度为60℃,转速为60rad/min的条件下搅拌30min后冷却至室温,得到水性聚氨酯。
其中,一种改性异佛尔酮二异氰酸酯的制备方法为:
将20kg异佛尔酮二异氰酸酯和10kg制备例1中制得的黄原胶加入到乙醇溶液中,在温度为35℃,转速为80rad/min的条件下加热搅拌15min,再加入6kg滑石粉在43kHz的条件下进行超声振荡30min,再用无水乙醇洗涤3次后在温度为55℃的条件下烘干3h,得到改性异佛尔酮二异氰酸酯。
实施例2-3
实施例2和实施例3与实施例1的区别在于柔软高弹水性聚氨酯的原料种类及用量的差异,具体参照表1所示:
表1
实施例4
一种柔软高弹水性聚氨酯的制备方法,与实施例3的不同之处在于,改性异佛尔酮二异氰酸酯的投入量为36kg、六亚甲基二异氰酸酯的投入量为15kg、甲苯二异氰酸酯的投入量为21kg。
实施例5
一种柔软高弹水性聚氨酯的制备方法,与实施例3的不同之处在于,改性异佛尔酮二异氰酸酯的投入量为37.5kg、六亚甲基二异氰酸酯的投入量为15kg、甲苯二异氰酸酯的投入量为22.5kg。
实施例6
一种柔软高弹水性聚氨酯的制备方法,与实施例5的不同之处在于,在改性异佛尔酮二异氰酸酯的制备过程中,将制备例1中制得的改性黄原胶等量替换成制备例2中制得的改性黄原胶。
实施例7
一种柔软高弹水性聚氨酯的制备方法,与实施例5的不同之处在于,在改性异佛尔酮二异氰酸酯的制备过程中,将制备例1中制得的改性黄原胶等量替换成制备例3中制得的改性黄原胶。
实施例8
一种柔软高弹水性聚氨酯的制备方法,与实施例5的不同之处在于,在改性异佛尔酮二异氰酸酯的制备过程中,将制备例1中制得的改性黄原胶等量替换成市售的黄原胶。
实施例9
一种柔软高弹水性聚氨酯的制备方法,与实施例7的不同之处在于,在改性异佛尔酮二异氰酸酯的制备过程中,将制备例3中制得的改性黄原胶等量替换成制备例4中制得的改性黄原胶。
实施例10
一种柔软高弹水性聚氨酯的制备方法,与实施例7的不同之处在于,在改性异佛尔酮二异氰酸酯的制备过程中,将制备例3中制得的改性黄原胶等量替换成制备例5中制得的改性黄原胶。
实施例11
一种柔软高弹水性聚氨酯的制备方法,与实施例10的不同之处在于,在改性异佛尔酮二异氰酸酯的制备过程中,异佛尔酮二异氰酸酯的投入量为30kg、滑石粉的投入量为18kg、制备例5中制得的改性黄原胶的投入量为24kg。
实施例12
一种柔软高弹水性聚氨酯的制备方法,与实施例10的不同之处在于,在改性异佛尔酮二异氰酸酯的制备过程中,异佛尔酮二异氰酸酯的投入量为25kg、滑石粉的投入量为8kg、制备例5中制得的改性黄原胶的投入量为15kg。
实施例13
一种柔软高弹水性聚氨酯的制备方法,与实施例10的不同之处在于,在改性异佛尔酮二异氰酸酯的制备过程中,异佛尔酮二异氰酸酯的投入量为25kg、滑石粉的投入量为10kg、制备例5中制得的改性黄原胶的投入量为18kg。
实施例14
一种柔软高弹水性聚氨酯的制备方法,与实施例13的不同之处在于,在S3步骤中,还加入有松香树脂15kg,1,6-己二胺4kg和壳聚糖6kg。
实施例15
一种柔软高弹水性聚氨酯的制备方法,与实施例13的不同之处在于,在S3步骤中,还加入有松香树脂25kg,1,6-己二胺8kg和壳聚糖10kg。
实施例16
一种柔软高弹水性聚氨酯的制备方法,与实施例15的不同之处在于,在S3步骤中,还加入有松香树脂18kg,1,6-己二胺6kg和壳聚糖6.4kg,聚四氢呋喃醚二醇的投入量为70kg。
实施例17
一种柔软高弹水性聚氨酯的制备方法,与实施例15的不同之处在于,在S3步骤中,还加入有松香树脂21kg,1,6-己二胺6kg和壳聚糖7.2kg,聚四氢呋喃醚二醇的投入量为72kg。
实施例18
一种柔软高弹水性聚氨酯的制备方法,与实施例15的不同之处在于,在S3步骤中,还加入有松香树脂25kg。
实施例19
一种柔软高弹水性聚氨酯的制备方法,与实施例15的不同之处在于,在S3步骤中,还加入1,6-己二胺8kg。
实施例20
一种柔软高弹水性聚氨酯的制备方法,与实施例15的不同之处在于,在S3步骤中,还加入壳聚糖10kg。
实施例21
一种柔软高弹水性聚氨酯的制备方法,与实施例15的不同之处在于,在S3步骤中,还加入松香树脂35kg,1,6-己二胺2kg和壳聚糖8kg。
对比例
对比例1
一种柔软高弹水性聚氨酯的制备方法,与实施例1的不同之处在于,将改性异佛尔酮二异氰酸酯等量替换成市售的异佛尔酮二异氰酸酯。
对比例2
一种柔软高弹水性聚氨酯的制备方法,与实施例1的不同之处在于,将六亚甲基二异氰酸酯等量替换成改性异佛尔酮二异氰酸酯。
对比例3
一种柔软高弹水性聚氨酯的制备方法,与实施例1的不同之处在于,将甲苯二异氰酸酯等量替换成改性异佛尔酮二异氰酸酯。
对比例4
一种柔软高弹水性聚氨酯的制备方法,与实施例1的不同之处在于,在改性异佛尔酮二异氰酸酯的制备过程中,不加入黄原胶。
性能检测试验
将实施例1-20和对比例1-4中制得的水性聚氨酯各100kg,加入2kg聚碳化二亚胺交联剂在转速为40rad/min的条件下搅拌30min,得到胶浆,将胶浆涂在涤纶面料上,胶浆的厚度为0.45cm,在室温干燥。
柔软性测试:根据GB/T 1731-2020《漆膜、腻子膜柔韧性测定法》测试实施例1-20和对比例1-4中制得的水性聚氨酯通过加入交联剂固化,测试所能承受的最小轴棒的半径。其中,轴棒的半径越小,漆膜的柔韧性越好,此处轴棒半径小于3mm即满足要求。
回弹性测试:根据GB/T6670-97标准使用落球回弹试验机测试实施例1-20和对比例1-4中制得的水性聚氨酯通过加入交联剂固化,测试水性聚氨酯的回弹性能。
拉伸强度测试:根据GB/T528-1998使用万能拉伸试验机测试实施例1-20和对比例1-4中制得的水性聚氨酯通过加入交联剂固化后,测试水性聚氨酯的拉伸强度。
抑菌性测试:按照ASTM E2149-10《在动态接触条件下测定稳态抗菌剂的抗菌行为》检测指标为大肠杆菌ATCC25922,测试实施例1-20和对比例1-4中制得的水性聚氨酯,测试其对大肠杆菌的抑菌效果
表2
根据实施例1-3和对比例1-4的数据对比可得,本申请中加入六亚甲基二异氰酸酯、甲苯二异氰酸酯和改性异佛尔酮二异氰酸酯,作为制备水性聚氨酯的材料,同时通过黄原胶和滑石粉对异佛尔酮二异氰酸酯进行改性,改性后的异佛尔酮二异氰酸酯在参与制备水性聚氨酯的反应过程中更加平稳,可以防止水性聚氨酯凝聚,进而改善水性聚氨酯的柔顺性。
根据实施例3-5的数据对比可得,当改性异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯和甲苯二异氰酸酯在特定的重量配比时,改性异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯和甲苯二异氰酸酯三者共同配合,使制得的水性聚氨酯具有良好的柔软性和力学性能,进而提高水性聚氨酯的拉伸强度。
根据实施例5-8的数据对比可得,本申请通过二甲基甲酰胺和氰基硼氢化钠对黄原胶进行改性,使制得的改性异佛尔酮二异氰酸酯的粘结性能较高,进而提高水性聚氨酯的柔软性和弹力。
根据实施例5和实施例9-10的数据对比可得,当二甲基甲酰胺、甘露醇和氰基硼氢化钠在特定的重量配比时,改善水性聚氨酯乳液的流动性,进而提高水性聚氨酯的柔软性的同时还可以提高水性聚氨酯的抑菌性。
根据实施例10-12的数据对比可得,本申请通过滑石粉和黄原胶对异佛尔酮二异氰酸酯进行改性,在提高水性聚氨酯的柔软性和回弹性的同时还可以提高水性聚氨酯的拉伸强度。
根据实施例12-20的数据对比可得,加入松香树脂、1,6-己二胺和壳聚糖共同配合可以提高水性聚氨酯的回弹性;当松香树脂、1,6-己二胺、壳聚糖和聚四氢呋喃醚二醇在特定的配比时,既能提高水性聚氨酯的回弹性能也可以提高水性聚氨酯的抑菌效果,若分别单独加入松香树脂、1,6-己二胺和壳聚糖,制得的水性聚氨酯的回弹性能和抑菌效果均不佳。
具体实施例仅仅是对本申请的解释,其并不是对本申请的限制,本领域技术人员在阅读完本说明书后可以根据需要对本实施例做出没有创造性贡献的修改,但只要在本申请的权利要求范围内都受到专利法的保护。
Claims (10)
1.一种柔软高弹水性聚氨酯,其特征在于:由包括以下重量份的原料制成:
聚四氢呋喃醚二醇:65-85份;
改性异佛尔酮二异氰酸酯:20-40份;
六亚甲基二异氰酸酯:10-20份;
甲苯二异氰酸酯:20-30份;
二羟甲基丙酸:4-8份;
邻氨基苯磺酸:5-10份;
水:100-120份;
催化剂:2-5份;
增稠剂:1-6份;
消泡剂:2-4份;
所述改性异佛尔酮二异氰酸酯由异佛尔酮二异氰酸酯、滑石粉和黄原胶改性制得。
2.根据权利要求1所述的一种柔软高弹水性聚氨酯,其特征在于:所述异佛尔酮二异氰酸酯的制备方法为:将异佛尔酮二异氰酸酯和黄原胶加入到乙醇溶液中,加热搅拌,加入滑石粉进行超声振荡,洗涤后烘干,得到所述改性异佛尔酮二异氰酸酯;所述异佛尔酮二异氰酸酯、滑石粉和黄原胶的重量配比为1:(0.32-0.4):(0.6-0.72)。
3.根据权利要求1所述的一种柔软高弹水性聚氨酯,其特征在于:所述水性聚氨酯还包括有以下重量份数:
松香树脂:15-25份;
1,6-己二胺:4-8份;
壳聚糖:6-10份。
4.根据权利要求1所述的一种柔软高弹水性聚氨酯,其特征在于:所述松香树脂、1,6-己二胺、壳聚糖和聚四氢呋喃醚二醇的重量比为(3-3.5):1:(1-1.2):(11.6-12)。
5.根据权利要求1所述的一种柔软高弹水性聚氨酯,其特征在于:所述改性异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯和甲苯二异氰酸酯的重量比为(2.4-2.5):1:(1.4-1.5)。
6.根据权利要求2所述的一种柔软高弹水性聚氨酯,其特征在于:所述黄原胶为改性黄原胶,所述改性黄原胶的制备方法为:将20-30重量份黄原胶与8-12重量份二甲基甲酰胺在乙醇溶液中搅拌,再将10-15重量份甘露醇和4-8重量份氰基硼氢化钠搅拌后洗涤干燥后得到所述改性黄原胶。
7.根据权利要求6所述的一种柔软高弹水性聚氨酯,其特征在于:所述二甲基甲酰胺、甘露醇和氰基硼氢化钠的重量比为1:(1.3-1.4):(0.45-0.5)。
8.根据权利要求1所述的一种柔软高弹水性聚氨酯,其特征在于:所述催化剂为三亚乙基二胺和二丁基锡二月桂酸酯中的一种;所述增稠剂为淀粉和海藻胶中的一种;所述消泡剂为二甲基硅油和棕榈酸中的一种。
9.一种柔软高弹水性聚氨酯的制备方法,其特征在于:用于制备权利要求1-8任一所述的一种柔软高弹水性聚氨酯,包括以下步骤:
S1.将聚四氢呋喃醚二醇、六亚甲基二异氰酸酯和二羟甲基丙酸混合加热溶解后冷却,得到预聚液;
S2.将预聚液、改性异佛尔酮二异氰酸酯、甲苯二异氰酸酯、水和催化剂混合搅拌,边搅拌边加入邻氨基苯磺酸进行扩链反应,得到搅拌液;
S3.将增稠剂和消泡剂加入搅拌液中搅拌后得到所述水性聚氨酯。
10.根据权利要求9所述的一种柔软高弹水性聚氨酯的制备方法,其特征在于:
S1.将聚四氢呋喃醚二醇、六亚甲基二异氰酸酯和二羟甲基丙酸混合加热溶解后冷却,得到预聚液;
S2.将预聚液、改性异佛尔酮二异氰酸酯、甲苯二异氰酸酯、水和催化剂混合搅拌,边搅拌边加入邻氨基苯磺酸进行扩链反应,得到搅拌液;
S3.将松香树脂、1,6-己二胺、壳聚糖、增稠剂和消泡剂加入搅拌液中搅拌后得到所述水性聚氨酯。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202211212967.7A CN115386064A (zh) | 2022-09-30 | 2022-09-30 | 一种柔软高弹水性聚氨酯及其制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202211212967.7A CN115386064A (zh) | 2022-09-30 | 2022-09-30 | 一种柔软高弹水性聚氨酯及其制备方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN115386064A true CN115386064A (zh) | 2022-11-25 |
Family
ID=84128837
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202211212967.7A Withdrawn CN115386064A (zh) | 2022-09-30 | 2022-09-30 | 一种柔软高弹水性聚氨酯及其制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN115386064A (zh) |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110922563A (zh) * | 2019-12-18 | 2020-03-27 | 辽宁恒星精细化工有限公司 | 一种泳衣印花用水性聚氨酯胶浆乳液及制备方法 |
CN113896853A (zh) * | 2021-11-29 | 2022-01-07 | 辽宁恒星精细化工有限公司 | 一种高固含量热塑性水性聚氨酯乳液及其制备方法 |
-
2022
- 2022-09-30 CN CN202211212967.7A patent/CN115386064A/zh not_active Withdrawn
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110922563A (zh) * | 2019-12-18 | 2020-03-27 | 辽宁恒星精细化工有限公司 | 一种泳衣印花用水性聚氨酯胶浆乳液及制备方法 |
CN113896853A (zh) * | 2021-11-29 | 2022-01-07 | 辽宁恒星精细化工有限公司 | 一种高固含量热塑性水性聚氨酯乳液及其制备方法 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN107903865B (zh) | 一种含除水剂的单组份湿气固化聚氨酯密封胶及其制备方法 | |
CN103483539B (zh) | 聚(碳酸酯-醚)型水性聚氨酯、水性聚氨酯胶粘剂及其制备方法 | |
CN102702471A (zh) | 一种无溶剂水性聚氨酯分散体的制备方法 | |
CN1190456C (zh) | 适于动态应用的聚氨酯脲弹性体 | |
JPH1060272A (ja) | カルボキシル基含有樹脂用ポリカルボジイミド硬化剤組成物、これを用いた接着剤及び塗料 | |
CN104974703A (zh) | 一种双组份超支化聚氨酯胶粘剂及其制备方法 | |
JP2010024319A (ja) | ポリウレタンビーズの製造方法 | |
CN115386064A (zh) | 一种柔软高弹水性聚氨酯及其制备方法 | |
CN113105608B (zh) | 一种具有高力学强度的自愈性超支化聚氨酯及其制备方法与应用 | |
CN105085890A (zh) | 一种亲水性超支化的封闭型异氰酸酯及其制备方法和其在涂料中的应用 | |
CN112341925B (zh) | 一种抗流挂无溶剂型单组分聚氨酯防水涂料及制备方法 | |
CN114075331A (zh) | 聚乙醇酸组合物及其制备方法与应用 | |
CN114276747B (zh) | 一种耐超低温易施工单组分聚氨酯防水涂料及其制备方法 | |
JP7509512B2 (ja) | 不織布製造用ポリアミドイミド樹脂組成物 | |
CN111925494B (zh) | 一种高粘性水性聚氨酯及其制备方法 | |
CN107686548B (zh) | 水性纯聚脲的制备方法 | |
CN110835396B (zh) | 一种改善水性纳米涂层柔韧性树脂及其制备方法 | |
CN104211898A (zh) | 一种端氨基水性聚氨酯分散体及其制备方法 | |
WO2009099039A1 (ja) | 安定化されたポリアミドイミド樹脂溶液及びその製造方法 | |
CN113789147A (zh) | 双组份氯丁聚氨酯复合橡胶粘合剂及其制备方法 | |
CN109337546B (zh) | 一种高性能陶瓷复合涂料及其制备方法 | |
CN111826070A (zh) | 一种耐磨水性涂料及其制备方法 | |
CN110862491A (zh) | 一种多链交叉网络型水性聚氨酯的制备方法 | |
KR101874301B1 (ko) | 핫멜트 접착제용 폴리우레탄 수지 및 이를 포함하는 2액형 폴리우레탄 핫멜트 접착제 및 핫멜트 접착제용 폴리우레탄 수지의 제조방법. | |
CN115926163A (zh) | 一种水性聚酰胺酰亚胺树脂分散液及其制备方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
WW01 | Invention patent application withdrawn after publication |
Application publication date: 20221125 |
|
WW01 | Invention patent application withdrawn after publication |