CN113969130A - 一种氧化石墨烯原位聚合改性双组分聚氨酯胶黏剂及其制备方法 - Google Patents
一种氧化石墨烯原位聚合改性双组分聚氨酯胶黏剂及其制备方法 Download PDFInfo
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- CN113969130A CN113969130A CN202111178547.7A CN202111178547A CN113969130A CN 113969130 A CN113969130 A CN 113969130A CN 202111178547 A CN202111178547 A CN 202111178547A CN 113969130 A CN113969130 A CN 113969130A
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- polyurethane adhesive
- graphene oxide
- adhesive
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 53
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- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 12
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- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 claims description 2
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/08—Polyurethanes from polyethers
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
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- 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
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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
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- 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
- C08G18/3237—Polyamines aromatic
- C08G18/324—Polyamines aromatic containing only one aromatic ring
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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
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- C08G18/3278—Hydroxyamines containing at least three hydroxy groups
- C08G18/3281—Hydroxyamines containing at least three hydroxy groups containing three hydroxy groups
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- 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
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- C08G18/3865—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms containing groups having one sulfur atom between two carbon atoms
- C08G18/3868—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms containing groups having one sulfur atom between two carbon atoms the sulfur atom belonging to a sulfide group
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- 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
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- C08G18/4804—Two or more polyethers of different physical or chemical nature
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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
- 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
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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Abstract
本发明涉及胶黏剂技术领域,具体涉及一种氧化石墨烯原位聚合改性双组分聚氨酯胶黏剂及其制备方法,该胶黏剂由A、B双组分组成。其中,聚氨酯胶黏剂A组分由聚醚二元醇、聚醚三元醇、扩链剂A、无机填料、除水稳定剂、粘接促进剂混合而成;聚氨酯胶黏剂B组分由聚醚二元醇、聚醚三元醇、二异氰酸酯、异氰酸酯改性氧化石墨烯、扩链剂B、抗氧剂、催化剂反应得到低聚物组合物。本发明所述的聚氨酯胶粘剂A组分和B组分按一定重量比例混合后,在室温或加热条件下可交联固化,具有免底涂剂,粘接强度和硬度高,耐磨性好的特点,可用于金属、复合材料及高分子材料之间的界面粘接及表面防护。
Description
技术领域
本发明涉及胶黏剂技术领域,具体涉及一种氧化石墨烯原位聚合改性双组分聚氨酯胶黏剂及其制备方法。
背景技术
聚氨酯胶黏剂具有较好的弹性、粘接强度和耐腐蚀性,在工程上获得广泛应用。但是目前国内所研制的聚氨酯胶黏剂强度、耐磨性、耐候性等性能偏低,大多数用于建筑、服装等领域。但是,对于粘接强度、耐磨、耐疲劳和耐候性要求比较高的航空、机械、交通等领域,主要以环氧等结构胶黏剂为主,聚氨酯胶黏剂的研究和应用相对较少。采用高性能纳米材料改性聚氨酯是提高性能的有效方法之一,常用的二氧化硅、碳纳米管、石墨烯等纳米材料,但由于纳米材料易团聚、分散困难,与聚氨酯胶粘剂混合后虽然一定程度上提高了聚氨酯的部分性能,但改性后的胶粘剂稳定性差,难以实现工业化制备及应用。
发明内容
为了克服现有聚氨酯胶黏剂的不足,本发明的目的在于提供一种氧化石墨烯原位聚合改性双组分聚氨酯胶黏剂,通过氧化石墨烯的表面化学反应及原位聚合反应,改善氧化石墨烯在胶黏剂中不易分散、稳定性差的问题,制备的胶黏剂具有免底涂剂、粘接强度高、耐磨性优异等优点。
本发明的目的通过下述技术方案实现:
本发明提供一种氧化石墨烯原位聚合改性双组分聚氨酯胶黏剂,所述的胶黏剂包括A、B两组分,其中,A组分是由以下重量份数的原料混合而成:聚醚二元醇5-15份,聚醚三元醇30-60份,无机填料10-30份,扩链剂A 0.01-20份,粘接促进剂0.01-10份,除水稳定剂0.01-5份;B组分是由以下重量份数的聚合反应而成:聚醚二元醇10-60份,聚醚三元醇5-20份,二异氰酸酯10-45份,异氰酸酯改性石墨烯0.01-10份,扩链剂B 0.01-20份,抗氧剂0.01-2份,催化剂 0.01-5份。
进一步的,所述的A组分中,聚醚二元醇为聚氧化丙烯二元醇为平均分子量为500-2000的聚氧化丙烯二元醇;所述聚醚三元醇为平均分子量在3000-6000 的聚氧化丙烯三元醇;所述的无机填料为纳米碳酸钙、高岭土、硅微粉、炭黑、气相二氧化硅中的至少一种;所述的扩链剂A为1,4-丁二醇、乙二醇、一缩二乙二醇、1,6己二醇、三羟甲基丙烷、3,5-二甲硫基甲苯二胺、3,5-二乙基甲苯二胺、三乙醇胺中的至少一种;所述粘接促进剂为环氧硅烷偶联剂、氨基硅烷偶联剂、巯基硅烷偶联剂中的至少一种;所述除水稳定剂为噁唑烷类除水剂、对甲基苯磺酰异氰酸酯、原甲酸三乙酯、氧化钙中的至少一种。
进一步的,所述的B组分中,聚醚二元醇为聚氧化丙烯二元醇为平均分子量为500-2000的聚氧化丙烯二元醇;聚醚三元醇为平均分子量在3000-6000的聚氧化丙烯三元醇;二异氰酸酯为甲苯二异氰酸酯、二环己基甲烷二异氰酸酯、异佛尔酮二异氰酸酯、二苯基甲烷二异氰酸酯、六亚甲基二氰酸酯中的至少一种;扩链剂B为1,4-丁二醇、乙二醇、一缩二乙二醇、1,6己二醇、三羟甲基丙烷、 3,5-二甲硫基甲苯二胺、3,5-二乙基甲苯二胺、三乙醇胺中的至少一种;催化剂为有机锡类催化剂、叔胺类催化剂、有机锌类催化剂和有机铋类催化剂中的至少一种;所述的抗氧剂为2,6-二叔丁基对甲酚(抗氧剂264)、β(3,5二叔丁基-4-羟基苯基--丙酸十八醇酯(又称抗氧剂1076)、四[β-(3-5-二叔丁基-4-羟基苯基)丙酸] 季戊四醇酯(抗氧剂1010)、三(壬基代苯基)亚磷酸酯(简称TNP)、三(2,4-二叔丁基苯基)亚磷酸酯(简称TBP)、二亚磷酸双十八酯季戊四醇酯(简称DPD)、四 (2,4-二叔丁基苯基)4,4'-联苯撑二磷酸酯、硫代二丙酸二月桂酸酯(简DLTDP)中的至少一种;粘接促进剂为环氧硅烷偶联剂、氨基硅烷偶联剂、巯基硅烷偶联剂中的至少一种。
进一步的,所述的B组分中,异氰酸酯改性石墨烯由氧化石墨烯与异氰酸酯反应制备而成。
本发明还提供了一种氧化石墨烯原位聚合改性双组分聚氨酯胶黏剂的制备方法,其包括以下步骤:
(1)A组分的制备:按照重量份数计,将聚醚三元醇、聚醚二元醇加入反应器混合,升温至100-120℃,抽真空除水2h,然后降温至室温,加入扩链剂A、无机填料、粘接促进剂、除水稳定剂,在压力为-0.095~0.1Mpa的真空状态下脱除气泡,搅拌均匀后,用干燥的氩气解除真空,将制的混合物放入到密闭容器,即制得聚氨酯胶黏剂A组分.
(2)制备异氰酸酯改性石墨烯:将10份氧化石墨烯与30-50份四氢呋喃混合,密封条件下在细胞破碎机中超声分散2h;加入10-20份二环己基甲烷二异氰酸酯和0.01-10份催化剂,30℃继续超声反应2h;将产物用四氢呋喃溶液离心洗涤多次,去除未反应的异氰酸酯;将沉淀物转入70℃真空烘箱中干燥24h,即得到异氰酸酯改性石墨烯,转入密闭容器中隔绝空气和湿气留存待用;
(3)B组分的制备:按照重量份数计,将聚醚二元醇、聚醚三元醇、抗氧剂混合,升温至100-120℃,抽真空除水2h,然后降温至60-80℃,再加入二异氰酸酯和催化剂反应,在氩气保护下70-80℃反应3h后;加入异氰酸酯改性石墨烯反应2h,再加入扩链剂B,反应1.5h后;用红外光谱仪测试,直至NCO值无变化时反应结束,降至室温,制得石墨烯原位聚合改性聚氨酯胶黏剂B组分,转入密闭容器中隔绝空气和湿气密封保存。
本发明所述氧化石墨烯原位聚合改性双组分聚氨酯胶黏剂,其使用时将A 组分和B组分按照1:0.8-1.2重量比例室温混合均匀后,均匀涂于清洁后的金属、复合材料、高分子材料等表面后,必要时施加一定的压力确保胶粘剂与粘接界面充分接触后,24-48小时可完全固化达到最佳的粘接强度。
本发明有益效果在于:本发明采用氧化石墨烯原位聚合改性聚氨酯胶黏剂具有提高的力学强度、耐磨性和耐候性等综合性能。由于本发明创新性采用二环己基甲烷二异氰酸酯与氧化石墨烯表面极性基团反应,在石墨烯表面实现了有机基团接枝改性,克服了石墨烯片层易团聚的问题;进一步,将异氰酸酯改性氧化石墨烯在胶黏剂制备过程中进一步原位反应聚合,将氧化石墨烯以化学键的形式连接在胶黏剂聚合物分子结构中,从而彻底解决了氧化石墨烯团聚和分散不均匀的问题,使制得胶黏剂具有储存稳定性好,固化后硬度和强度高、免底涂、适应性好等特点。
具体实施方式
为了便于本领域技术人员的理解,下面结合实施例对本发明作进一步的说明,实施方式提及的内容并非对本发明的限定。
实施例1:
一种氧化石墨烯原位聚合改性双组分聚氨酯胶黏剂的制备方法,包括如下三个步骤:
步骤1:制备聚氨酯胶黏剂A组分
向2L行星搅拌釜中加入15份聚醚二元醇(相对分子量2000),加入35份聚醚三元醇(相对分子量5000),升温至100-120℃真空脱水2h,检测液料水分含量小于100ppm后。加入9份A(3,5-二甲硫基甲苯二胺)作为扩链剂、0.6份气相二氧化硅、7.2份炭黑、0.6份氧化钙作为除水稳定剂、3.6份γ-(2,3环氧丙氧) 丙基三甲氧基硅烷作为粘接促进剂。在压力为-0.095-0.1Mpa的真空状态下搅拌均匀,然后用干燥的氩气解除真空,制得聚氨酯胶黏剂A组分,置于干燥的密闭容器中备用。
所述步骤1中,气相二氧化硅、炭黑均预先干燥至水分含量小于500ppm。
步骤2:制备异氰酸酯改性氧化石墨烯
在250ml三口瓶中,将2份氧化石墨烯与50份四氢呋喃混合,密封条件下在细胞破碎机中超声分散2h,之后加入40份二环己基甲烷二异氰酸酯和0.02 份催化剂二月桂酸二丁基锡,30℃继续超声反应2h,将产物用四氢呋喃溶液离心洗涤多次,去除未反应的异氰酸酯,最后将沉淀物转入70℃真空烘箱中干燥 24h,即得到异氰酸酯改性氧化石墨烯,转入密闭容器中隔绝空气和湿气留存待用。
步骤3:制备氧化石墨烯原位聚合改性聚氨酯胶黏剂B组分
在干燥的500mL四口瓶中加入36份聚醚二元醇(相对分子量2000),加入 8份聚醚三元醇(相对分子量5000),再加入0.15份抗氧剂1010,升温至100-120℃真空脱水2h,检测液料水分含量小于100ppm后,降温至60-80℃,加入24.5份二环己基甲烷二异氰酸酯,加入0.034份二月桂酸二丁基锡作为催化剂,在氩气保护下保温反应3h,加入2份异氰酸酯改性氧化石墨烯反应2h,再加入2份1,6 己二醇作为扩链剂,反应1.5h后;用红外光谱仪测试,直至NCO值无变化时反应结束,降温至室温出料,制得氧化石墨烯原位聚合改性聚氨酯胶黏剂B组分,置于干燥的密闭容器中备用。
由步骤1制得A组分和由步骤2、3制得B组分,分别以一定包装形式密封包装,使用时按照A:B=1:0.8-1.2重量比例,室温混合均匀后,均匀涂于清洁后的金属、复合材料、高分子材料等表面后,必要时施加一定的压力确保胶粘剂与粘接界面充分接触后,24-48小时可完全固化达到最佳的粘接强度。
实施例2
一种氧化石墨烯原位聚合改性双组分聚氨酯胶黏剂的制备方法,包括如下三个步骤:
步骤1:制备聚氨酯胶黏剂A组分
向2L行星搅拌釜中加入5份聚醚二元醇(相对分子量2000),加入60份聚醚三元醇(相对分子量5000),升温至100-120℃,真空脱水2h,检测液料水分含量小于100ppm后。加入20份3,5-二乙基甲苯二胺作为扩链剂、1份气相二氧化硅、20份高岭土、2份原甲酸三乙酯作为除水稳定剂、3份γ-氨丙基三乙氧基硅烷作为粘接促进剂。在压力为-0.095-0.1Mpa的真空状态下搅拌均匀,然后用干燥的氩气解除真空,制得聚氨酯胶黏剂A组分,置于干燥的密闭容器中备用。
所述步骤1中,气相二氧化硅、高岭土均预先干燥至水分含量小于500ppm。
步骤2:制备异氰酸酯改性氧化石墨烯
在250ml三口瓶中,将2份氧化石墨烯与50份四氢呋喃混合,密封条件下在细胞破碎机中超声分散2h,之后加入40份二环己基甲烷二异氰酸酯和0.02 份催化剂二月桂酸二丁基锡,30℃继续超声反应2h,将产物用四氢呋喃溶液离心洗涤多次,去除未反应的异氰酸酯,最后将沉淀物转入70℃真空烘箱中干燥 24h,即得到异氰酸酯改性氧化石墨烯,转入密闭容器中隔绝空气和湿气留存待用。
步骤3:制备氧化石墨烯原位聚合改性聚氨酯胶黏剂B组分
在500ML四口瓶中加入60份聚醚二元醇(相对分子量2000),加入5份聚醚三元醇(相对分子量5000),再加入1份抗氧剂264,升温至100-120℃真空脱水2h,检测液料水分含量小于100ppm后,降温至60-80℃,加入45份复配二环己基甲烷二异氰酸酯和二苯基甲烷二异氰酸酯,加入0.5份辛酸亚锡作为催化剂,在氩气保护下保温反应3h,加入5份异氰酸酯改性氧化石墨烯反应2h,再加入5份1,4丁二醇作为扩链剂B,反应1.5h后;用红外光谱仪测试,直至NCO 值无变化时反应结束,降温至室温出料,制得氧化石墨烯原位聚合聚氨酯胶黏剂B组分,置于干燥的密闭容器中备用。
由步骤1制得A组分和由步骤2、3制得B组分,分别以一定包装形式密封包装,使用时按照A:B=1:0.8-1.2重量比例,室温混合均匀后,均匀涂于清洁后的金属、复合材料、高分子材料等表面后,必要时施加一定的压力确保胶粘剂与粘接界面充分接触后,24-48小时可完全固化达到最佳的粘接强度。
实施例3
一种氧化石墨烯原位聚合改性双组分聚氨酯胶黏剂的制备方法,包括如下三个步骤:
步骤1:制备聚氨酯胶黏剂A组分
向2L行星搅拌釜中加入10份聚醚二元醇(相对分子量2000),加入45份聚醚三元醇(相对分子量5000),升温至100℃真空脱水2h,检测液料水分含量小于100ppm后。加入18份3,5-二甲硫基甲苯二胺和三乙醇胺复配的扩链剂、加入20份纳米碳酸钙、5份硅微粉、1份噁唑烷类除水剂、6份乙烯基三甲氧基硅烷作为粘接促进剂。在压力为-0.095-0.1Mpa的真空状态下搅拌均匀,然后用干燥的氩气解除真空,制得聚氨酯胶黏剂A组分,置于干燥的密闭容器中备用。
所述步骤1中,纳米碳酸钙、硅微粉均预先干燥至水分含量小于500ppm。
步骤2:制备异氰酸酯改性氧化石墨烯
在250ml三口瓶中,将2份氧化石墨烯与50份四氢呋喃混合,密封条件下在细胞破碎机中超声分散2h,之后加入40份二环己基甲烷二异氰酸酯,以及0.02 份二月桂酸二丁基锡作为催化剂,30℃继续超声反应2h,将产物用四氢呋喃溶液离心洗涤多次,去除未反应的异氰酸酯,最后将沉淀物转入70℃真空烘箱中干燥24h,即得到异氰酸酯改性氧化石墨烯,转入密闭容器中隔绝空气和湿气留存待用。
步骤3:制备氧化石墨烯原位聚合改性聚氨酯胶黏剂B组分
在500ML四口瓶中加入40份聚醚二元醇(相对分子量2000),加入20份聚醚三元醇(相对分子量5000),再加入1份抗氧剂1076,升温至100-120℃真空脱水2h,检测液料水分含量小于100ppm后,降温至60-80℃,加入50份二苯基甲烷二异氰酸酯,0.05份异辛酸锌作为催化剂,在氩气保护下保温反应3h,加入5份异氰酸酯改性氧化石墨烯反应2h,再加入6份三羟甲基丙烷作为扩链剂,反应1.5h后;用红外光谱仪测试,直至NCO值无变化时反应结束,降温至室温出料,制得氧化石墨烯原位聚合聚氨酯胶黏剂B组分,置于干燥的密闭容器中备用。
由步骤1制得A组分和由步骤2、3制得B组分,分别以一定包装形式密封包装,使用时按照A:B=1:0.8-1.2重量比例,室温混合均匀后,均匀涂于清洁后的金属、复合材料、高分子材料等表面后,必要时施加一定的压力确保胶粘剂与粘接界面充分接触后,24-48小时可完全固化达到最佳的粘接强度。
实施例4:
一种氧化石墨烯原位聚合改性双组分聚氨酯胶黏剂的制备方法,包括如下三个步骤:
步骤1:制备聚氨酯胶黏剂A组分
向2L行星搅拌釜中加入15份聚醚二元醇(相对分子量2000),加入50份聚醚三元醇(相对分子量5000),升温至100-120℃真空脱水2h,检测液料水分含量小于100ppm后。加入16份3,5-二甲硫基甲苯二胺作为扩链剂、加入20份纳米碳酸钙、5份硅微粉、1份对甲基苯磺酰异氰酸酯、6份二(γ-三甲氧基甲硅烷基丙基)胺作为粘接促进剂。在压力为-0.095-0.1Mpa的真空状态下搅拌均匀,然后用干燥的氩气解除真空,制得聚氨酯胶黏剂A组分,置于干燥的密闭容器中备用。
所述步骤1中,纳米碳酸钙、硅微粉均预先干燥至水分含量小于500ppm。
步骤2:制备异氰酸酯改性氧化石墨烯
在250ml三口瓶中,将2份氧化石墨烯与50份四氢呋喃混合,密封条件下在细胞破碎机中超声分散2h,之后加入40份二环己基甲烷二异氰酸酯和0.02 份催化剂二月桂酸二丁基锡,30℃继续超声反应2h,将产物用四氢呋喃溶液离心洗涤多次,去除未反应的异氰酸酯,最后将沉淀物转入70℃真空烘箱中干燥 24h,即得到异氰酸酯改性氧化石墨烯,转入密闭容器中隔绝空气和湿气留存待用。
步骤3:制备氧化石墨烯原位聚合改性聚氨酯胶黏剂B组分
在500ML四口瓶中加入35份聚醚二元醇(相对分子量2000),加入20份聚醚三元醇(相对分子量5000),再加入1份复配的抗氧剂1076和抗氧剂1010,升温至100-120℃真空脱水2h,检测液料水分含量小于100ppm后,降温至 60-80℃,加入40份二苯基甲烷二异氰酸酯,以及0.05份异辛酸铋作为催化剂,在氩气保护下保温反应3h,降温至60-80℃,加入5份异氰酸酯改性氧化石墨烯反应2h;加入3份三乙醇胺作为扩链剂,反应1.5h后。用红外光谱仪测试,直至NCO值无变化时反应结束,降温至室温出料,制得氧化石墨烯原位聚合聚氨酯胶黏剂B组分,置于干燥的密闭容器中备用。
由步骤1制得A组分和由步骤2、3制得B组分,分别以一定包装形式密封包装,使用时按照A:B=1:0.8-1.2重量比例,室温混合均匀后,均匀涂于清洁后的金属、复合材料、高分子材料等表面后,必要时施加一定的压力确保胶粘剂与粘接界面充分接触后,24-48小时可完全固化达到最佳的粘接强度。
实施例5
一种氧化石墨烯原位聚合改性双组分聚氨酯胶黏剂的制备方法,包括如下三个步骤:
步骤1:制备聚氨酯胶黏剂A组分
向2L行星搅拌釜中加入10份聚醚二元醇(相对分子量2000),加入56份聚醚三元醇(相对分子量5000),升温至100-120℃真空脱水2h,检测液料水分含量小于100ppm后。加入15份3,5-二甲硫基甲苯二胺作为扩链剂、16份炭黑、 1份氧化钙作为除水稳定剂、6份γ-(2,3环氧丙氧)丙基三甲氧基硅烷作为粘接促进剂。在压力为-0.095-0.1Mpa的真空状态下搅拌均匀,然后用干燥的氩气解除真空,制得聚氨酯胶黏剂A组分,置于干燥的密闭容器中备用。
所述步骤1中,炭黑预先干燥至水分含量小于500ppm。
步骤2:制备异氰酸酯改性氧化石墨烯
在250ml三口瓶中,将2份氧化石墨烯与50份四氢呋喃混合,密封条件下在细胞破碎机中超声分散2h,之后加入40份二环己基甲烷二异氰酸酯和0.02 份催化剂二月桂酸二丁基锡,30℃继续超声反应2h,将产物用四氢呋喃溶液离心洗涤多次,去除未反应的异氰酸酯,最后将沉淀物转入70℃真空烘箱中干燥 24h,即得到异氰酸酯改性氧化石墨烯,转入密闭容器中隔绝空气和湿气留存待用。
步骤3:制备氧化石墨烯原位聚合改性聚氨酯胶黏剂B组分
在500L四口瓶中加入35份聚醚二元醇(相对分子量2000),加入10份聚醚三元醇(相对分子量5000)和0.5份抗氧剂1010,升温至100-120℃真空脱水 2h,检测液料水分含量小于100ppm后,降温至60-80℃,加入36份二苯基甲烷二异氰酸酯和0.1份二月桂酸二丁基锡作为催化剂,在氩气保护下保温反应3h,降温至60-80℃,加入6份异氰酸酯改性氧化石墨烯;加入3份1,6己二醇作为扩链剂,反应1.5h后。用红外光谱仪测试,直至NCO值无变化时反应结束,降温至室温出料,制得氧化石墨烯原位聚合改性聚氨酯胶黏剂B组分,置于干燥的密闭容器中备用。
由步骤1制得A组分和由步骤2、3制得B组分,分别以一定包装形式密封包装,使用时按照A:B=1:0.8-1.2重量比例,室温混合均匀后,均匀涂于清洁后的金属、复合材料、高分子材料等表面后,必要时施加一定的压力确保胶粘剂与粘接界面充分接触后,24-48小时可完全固化达到最佳的粘接强度。
对比例1
一种双组分聚氨酯胶黏剂的制备方法,包括如下步骤:
步骤1:制备聚氨酯胶黏剂A组分
向2L行星搅拌釜中加入59份聚醚二元醇(相对分子量2000),加入98份聚醚三元醇(相对分子量5000),升温至100-120℃真空脱水2h,检测液料水分含量小于100ppm后。加入40份纳米碳酸钙、5份气相二氧化硅、20份炭黑、5 份γ-(2,3环氧丙氧)丙基三甲氧基硅烷作为粘接促进剂、22份辛酸亚锡和三乙醇胺复配催化剂,在压力为-0.095-0.1Mpa的真空状态下搅拌均匀,然后用干燥的氩气解除真空,制得聚氨酯胶黏剂A组分,置于干燥的密闭容器中备用。
所述步骤1中,纳米碳酸钙、气相二氧化硅、炭黑均预先干燥至水分含量小于500ppm。
步骤2:制备聚氨酯胶黏剂B组分
在500ML四口瓶中加入20份聚醚二元醇(相对分子量2000),加入120份聚醚三元醇(相对分子量5000),加入21份邻苯二甲酸二丁酯,升温至100-120℃真空脱水2h,检测液料水分含量小于100ppm后,降温至60-80℃,加入72份二环己基甲烷二异氰酸酯和1份二月桂酸二丁基锡催化剂,在氩气保护下保温反应3h。用红外光谱仪测试,待反应至NCO值无变化时,降温至室温出料,制得聚氨酯胶黏剂B组分,置于干燥的密闭容器中备用。
由步骤1制得A组分和由步骤2制得B组分,分别以一定包装形式密封包装,使用时按照A:B=1:0.8-1.2重量比例,室温混合均匀后,均匀涂于清洁后的金属、复合材料、高分子材料等表面后,必要时施加一定的压力确保胶粘剂与粘接界面充分接触后,24-48小时可完全固化达到最佳的粘接强度。
对比例2
一种双组分聚氨酯胶黏剂的制备方法,包括如下步骤:
步骤1:制备聚氨酯胶黏剂A组分
向2L行星搅拌釜中加入34份聚醚二元醇(相对分子量2000),加入135份聚醚三元醇(相对分子量5000),升温至100-120℃真空脱水2h,检测液料水分含量小于100ppm后。降温至常温加入20份3,5-二乙基甲苯二胺作为扩链剂、 36份炭黑、2.5份原甲酸三乙酯作为除水稳定剂、12份γ-(2,3环氧丙氧)丙基三甲氧基硅烷作为粘接促进剂,在压力为-0.095-0.1Mpa的真空状态下搅拌均匀,然后用干燥的氩气解除真空,制得聚氨酯胶黏剂A组分,置于干燥的密闭容器中备用。
所述步骤1、2中,气相二氧化硅、炭黑均预先干燥至水分含量小于500ppm。
步骤2:制备聚氨酯胶黏剂B组分:
在2L四口瓶中加入80份聚醚二元醇(相对分子量2000),加入720份聚醚三元醇(相对分子量5000),升温至100-120℃真空脱水2h,检测液料水分含量小于100ppm后,降温至60-80℃,加入420份二苯基甲烷二异氰酸酯和2份二月桂酸二丁基锡催化剂,在氩气保护下保温反应3h,待反应至NCO值无变化时,加入60份气相二氧化硅,在压力为-0.095-0.1Mpa的真空状态下搅拌均匀,用干燥的氩气解除真空,降温至室温出料,制得聚氨酯胶黏剂B组分,置于干燥的密闭容器中备用。
由步骤1制得A组分和由步骤2制得B组分,分别以一定包装形式密封包装,使用时按照A:B=1:0.8-1.2重量比例,室温混合均匀后,均匀涂于清洁后的金属、复合材料、高分子材料等表面后,必要时施加一定的压力确保胶粘剂与粘接界面充分接触后,24-48小时可完全固化达到最佳的粘接强度。
主要测试方法:
(1)硬度:按照GB/T531.1-2008标准,采用邵氏硬度计进行测量。
(2)适用期:按照GB/T7123-2015标准进行测定。
(3)固化24h后与环氧基材180度剥离强度按照ASTMD3330标准进行测定。
(4)固化24h后与聚氨酯膜90度剥离强度按照ASTMD3330标准进行测定。
(5)锥状磨损:按照ASTMD4060进行测定。实施例和对比例性能数据如表1所示。
表1:实施例和对比例的性能数据
由上述数据对比可知,本发明的氧化石墨烯原位聚合改性双组分聚氨酯胶黏剂,和对比例未经氧化石墨烯原位改性的胶黏剂比,具有更高的硬度、更好的耐磨性、粘接强度,因而应用时具备高硬度、室温固化、免底涂、适应性好的特点。
与现有普通聚氨酯胶黏剂比较,本发明具有更好的耐磨性、粘接强度和硬度,上述实施例为本发明较佳的实现方案,除此以外,本发明还可以其它方式实现,在不脱离本发明构思的前提下任何显而易见的替换均在本发明的保护范围之内。
Claims (6)
1.一种氧化石墨烯原位聚合改性双组分聚氨酯胶黏剂,其特征在于,该胶黏剂包括A、B两组分,其中,A组分由以下重量份数的原料混合而成:聚醚二元醇5-15份,聚醚三元醇30-60份,无机填料10-30份,扩链剂A0.01-20份,粘接促进剂0.01-10份,除水稳定剂0.01-5份;B组分由以下重量份数的聚合反应而成:聚醚二元醇10-60份,聚醚三元醇5-20份,二异氰酸酯10-45份,异氰酸酯改性石墨烯0.01-10份,扩链剂B 0.01-20份,抗氧剂0.01-2份,催化剂0.01-5份。
2.根据权利要求1所述的一种氧化石墨烯原位聚合改性双组分聚氨酯胶黏剂,其特征在于,所述的A组分中,聚醚二元醇为聚氧化丙烯二元醇为平均分子量为500-2000的聚氧化丙烯二元醇;所述聚醚三元醇为平均分子量在3000-6000的聚氧化丙烯三元醇;所述的无机填料为纳米碳酸钙、高岭土、硅微粉、炭黑、气相二氧化硅中的至少一种;所述的扩链剂A为1,4-丁二醇、乙二醇、一缩二乙二醇、1,6己二醇、三羟甲基丙烷、3,5-二甲硫基甲苯二胺、3,5-二乙基甲苯二胺、三乙醇胺中的至少一种;所述粘接促进剂为环氧硅烷偶联剂、氨基硅烷偶联剂、巯基硅烷偶联剂中的至少一种;所述除水稳定剂为噁唑烷类除水剂、对甲基苯磺酰异氰酸酯、原甲酸三乙酯、氧化钙中的至少一种。
3.根据权利要求1所述的一种氧化石墨烯原位聚合改性双组分聚氨酯胶黏剂,其特征在于,所述的B组分中,聚醚二元醇为聚氧化丙烯二元醇为平均分子量为500-2000的聚氧化丙烯二元醇;聚醚三元醇为平均分子量在3000-6000的聚氧化丙烯三元醇;二异氰酸酯为甲苯二异氰酸酯、二环己基甲烷二异氰酸酯、异佛尔酮二异氰酸酯、二苯基甲烷二异氰酸酯、六亚甲基二氰酸酯中的至少一种;扩链剂B为1,4-丁二醇、乙二醇、一缩二乙二醇、1,6己二醇、三羟甲基丙烷、3,5-二甲硫基甲苯二胺、3,5-二乙基甲苯二胺、三乙醇胺中的至少一种;催化剂为有机锡类催化剂、叔胺类催化剂、有机锌类催化剂和有机铋类催化剂中的至少一种;所述的抗氧剂为2,6-二叔丁基对甲酚(抗氧剂264)、β(3,5二叔丁基-4-羟基苯基--丙酸十八醇酯(又称抗氧剂1076)、四[β-(3-5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯(抗氧剂1010)、三(壬基代苯基)亚磷酸酯(简称TNP)、三(2,4-二叔丁基苯基)亚磷酸酯(简称TBP)、二亚磷酸双十八酯季戊四醇酯(简称DPD)、四(2,4-二叔丁基苯基)4,4'-联苯撑二磷酸酯、硫代二丙酸二月桂酸酯(简DLTDP)中的至少一种;粘接促进剂为环氧硅烷偶联剂、氨基硅烷偶联剂、巯基硅烷偶联剂中的至少一种。
4.根据权利要求1所述的一种氧化石墨烯原位聚合改性双组分聚氨酯胶黏剂,其特征在于,所述的B组分中,异氰酸酯改性石墨烯由氧化石墨烯与异氰酸酯反应制备而成。
5.一种氧化石墨烯原位聚合改性双组分聚氨酯胶黏剂的制备方法,其特征在于,包括以下步骤:
(1)A组分的制备:按照重量份数计,将聚醚三元醇、聚醚二元醇加入反应器混合,升温至100-120℃,抽真空除水2h,然后降温至室温,加入扩链剂A、无机填料、粘接促进剂、除水稳定剂,在压力为-0.095~0.1Mpa的真空状态下脱除气泡,搅拌均匀后,用干燥的氩气解除真空,将制的混合物放入到密闭容器,即制得聚氨酯胶黏剂A组分;
(2)制备异氰酸酯改性石墨烯:将10份氧化石墨烯与30-50份四氢呋喃混合,密封条件下在细胞破碎机中超声分散2h;加入10-20份二环己基甲烷二异氰酸酯和0.01-10份催化剂,30℃继续超声反应2h;将产物用四氢呋喃溶液离心洗涤多次,去除未反应的异氰酸酯;将沉淀物转入70℃真空烘箱中干燥24h,即得到异氰酸酯改性石墨烯,转入密闭容器中隔绝空气和湿气留存待用;
(3)B组分的制备:按照重量份数计,将聚醚二元醇、聚醚三元醇、抗氧剂混合,升温至100-120℃,抽真空除水2h,然后降温至60-80℃,再加入二异氰酸酯和催化剂反应,在氩气保护下70-80℃反应3h后;加入异氰酸酯改性石墨烯反应2h,再加入扩链剂B,反应1.5h后;用红外光谱仪测试,直至NCO值无变化时反应结束,降至室温,制得石墨烯原位聚合改性聚氨酯胶黏剂B组分,转入密闭容器中隔绝空气和湿气密封保存。
6.根据权利要求1所述的一种氧化石墨烯原位聚合改性双组分聚氨酯胶黏剂,其特征在于,A组分和B组分分别以一定包装形式密封包装,使用时按照1:0.8-1.2重量比例室温混合均匀后,均匀涂于清洁后的金属、复合材料、高分子材料等表面后,必要时施加一定的压力确保胶粘剂与粘接界面充分接触后,24-48小时可完全固化达到最佳的粘接强度。
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