CN112175568A - 一种高韧性高强度的厌氧胶及其制备方法 - Google Patents
一种高韧性高强度的厌氧胶及其制备方法 Download PDFInfo
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- 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
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- 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
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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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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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
- C08G18/70—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
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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Abstract
本发明是一种高韧性高强度的厌氧胶及其制备方法，厌氧胶包括如下重量份的组分：聚氨酯甲基丙烯酸酯40—75；丙烯酸酯单体15—30；螯合剂0.01—1.0；稳定剂0.005—0.1；促进剂0.1—2.0；助促时剂0.1－1.0；增韧剂1.0—20.0；引发剂1.0—3.0；触变剂2.0—5.0。制备厌氧胶时：将自制的聚氨酯甲基丙烯酸酯，丙烯酸酯单体搅拌均匀；加入螯合剂、稳定剂，促进剂和助促时剂搅拌；加入增韧剂，触变剂搅拌均匀；降温加入引发剂，冷却出料。本发明通过添加聚四氟乙烯赋予厌氧胶更优良的韧性、强度性能，本发明制备的厌氧胶在‑100度时仍柔软，即使温度下降到‑196℃，也可保持5％的伸长率。
Description
技术领域
本发明涉及厌氧胶技术领域，尤其涉及一种高韧性高强度的厌氧胶及其制备方法。
背景技术
厌氧胶又名绝氧胶、嫌气胶、螺纹胶、机械胶，是利用氧对自由基阻聚原理制成的单组份密封粘和剂，主要应用于螺纹锁固、金属粘接、管道密封、平面密封、圆柱固持、砂孔堵漏等方面。目前市场上厌氧胶主要有两种技术路线：环氧丙烯酸型－粘接强度高，耐温耐介质性较好，但韧性抗冲击性较差；聚氨酯丙烯酸脂型－粘接强度低，耐介质特别是耐酸碱性差，且行业内普遍使用的TDI由于蒸汽压高、易挥发、具有强烈的刺激气味，对人体健康及环境有较大的危害。
发明内容
针对现有技术不足，本发明提供一种高韧性高强度的厌氧胶。由于聚氨酯丙烯酸酯具有固化收缩率低、柔韧性好的特点，本发明中的厌氧胶使用环保型聚氨酯甲基丙烯酸酯作为原料，本发明在合成聚氨酯甲基丙烯酸酯时采用贮存稳定性好，蒸汽压低，高弹性且抗撕裂性强的MDI50来合成聚氨酯甲基丙烯酸酯预聚体；在此基础上加入柔韧性好，强度高的丙烯酸单体和增韧剂，生产出的厌氧胶具有韧性好、强度高、耐酸碱等优点。
本发明还提供了一种高韧性高强度的厌氧胶的制备方法。
本发明为实现上述目的，采用以下技术方案：
本发明是通过以下技术方案实现的：
一种高韧性高强度的厌氧胶，包括如下重量份的组分：
本发明所述的聚氨酯甲基丙烯酸酯由二苯基甲烷二异氰酸酯MDI50、聚四氢呋喃醚二醇(分子量1000)和甲基丙烯酸羟乙酯合成。其中二苯基甲烷二异氰酸酯MDI50、聚四氢呋喃醚二醇、甲基丙烯酸羟乙酯的质量比为(20-40)：(30-60)：(10-40)；二月桂酸二丁基锡加入量为所述聚氨酯甲基丙烯酸酯总质量的(0.01—1.0)％。
本发明所述的聚氨酯甲基丙烯酸酯合成方法如下：向干燥的的反应釜中加入二苯基甲烷二异氰酸酯MDI50，并加热至30-40℃，开启搅拌(300r/min)；向反应釜中加入聚四氢呋喃醚二醇(分子量1000)，搅拌均匀，并保温反应3-4小时；加热升温至60-70℃，加入甲基丙烯酸羟乙酯和二月桂酸二丁基锡，并保温反应2-3小时；降温至20-30℃，加入对甲氧基苯酚，搅拌0.5小时，冷却至常温，出料即得到所需的聚氨酯甲基丙烯酸酯。
更具体的是聚氨酯甲基丙烯酯合成中所用的原料二苯基甲烷二异氰酸酯MDI50也可以选择已二异氰酸酯(HDI)，异佛尔酮二异氰酸酯(IPDI)，二环已基甲烷二异氰酸酯(HDMI)等中的一种或多种混合物；优选MDI50是因为MDI50含有2,4－MDI和4,4－MDI两种分子结构，而2,4－MDI苯环2位上的NCO基团因空间位阻效应，使其活性比苯环4位上的NCO基团活性低的多，从而在反应过程中更容易控制；聚四氢呋喃醚二醇(分子量1000)也可以选择聚四氢呋喃醚二醇(2000)、聚丙二醇(1500)等；甲基丙烯酸羟乙酯可以选择甲基丙烯酸羟丙酯、甲基丙烯酸异冰片酯等。
本发明中的丙烯酸酯单体为乙氧化双酚A二甲基丙烯酸酯、聚乙二醇二甲基丙烯酸酯、二缩三乙二醇二甲基丙烯酸酯中一种或多种；
进一步优选的，所述的丙烯酸酯单体为聚乙二醇二甲基丙烯酸酯；
本发明中的螯合剂为乙二胺四乙酸、乙二胺四乙酸二钠、乙二胺四乙酸四钠、乙二铵四乙酸四铵中的一种或多种；
进一步优选的，所述的螯合剂为乙二胺四乙酸二钠；
本发明的稳定剂为对苯二酚、1,4苯醌、萘醌中一种或多种；
进一步优选的，所述的稳定剂为1,4苯醌；
本发明中的促进剂为三乙铵、邻苯甲硫酰亚胺、乙酰苯肼、抗坏血酸、二茂铁中的一种或多种；
进一步优选的，所述的促进剂为邻苯甲硫酰亚胺；
本发明中的助促进剂为N,N二甲基对甲苯胺、苯甲酰肼，马来酸酐，丙烯酸、甲基丙烯酸中的一种或多种；
进一步优选的，所述的助促进剂为N,N二甲基对甲苯胺；
本发明中的增韧剂为聚醋酸乙烯酯、富马酸双酚A聚酯、聚四氟乙烯粉中的一种或多种；
进一步优选的，所述的增韧剂为聚四氟乙烯粉；
本发明中的引发剂为叔丁基过氧化氢、过氧化苯甲酰、异丙苯过氧化氢中的一种或多种；
进一步优选的，所述的引发剂为异丙苯过氧化氢；
本发明中的触变剂为气相白炭黑、氢化蓖麻油、氧化钙中一种或多种；
进一步优先的，所述的触变剂为气相白炭黑；
本发明一种高韧性高强度的厌氧胶生产过程包括以步骤：
1、按重量份将自制的聚氨酯甲基丙烯酸酯，丙烯酸酯单体加入反应釜中搅拌均匀；
2、加入螯合剂、稳定剂，促进剂和助促时剂搅拌，至固体颗粒完全溶解；
3、加入增韧剂，触变剂搅拌均匀；
4、降温至40℃以下，加入引发剂，搅拌均匀，冷却至室温，出料。
本发明的有益效果：
1、本发明的聚氨酯甲基丙烯酸酯合成原料MDI50毒性低，对人体刺激性小，属行业倡导使用环保原料；固化过程中异氰酸酯基团与金属表面的极性基团通过化学作用提高厌氧胶的初粘力，且异氰酸根基团在聚合过程中体积收缩率小，使粘结强度下降程度减小，柔韧性增强，使厌氧胶的韧性和强度得到提高。
2、本发明中聚四氟乙烯赋予厌氧胶更优良的韧性、强度性能。聚四氟乙烯具有耐腐、耐化学试剂、耐磨、韧性和强度高的性能。在-100度时仍柔软，即使温度下降到-196℃，也可保持5％的伸长率。
具体实施方式
以下结合具体实施例进一步描述本发明，但本发明并不局限以下实施例。
本发明中聚氨酯甲基丙烯酸酯按以下步骤制备：
向干燥的反应釜中加入30份二苯基甲烷二异氰酸酯MDI50，并加热至30-40℃，开启搅拌(300r/min)；向反应釜中加入50份聚四氢呋喃醚二醇(分子量1000)，搅拌均匀，并保温反应3-4小时；加热升温至60-70℃，加入20份甲基丙烯酸羟乙酯；缓慢滴入0.05份二月桂酸二丁基锡，并保温反应2-3小时；降温至20-30℃，加入对甲氧基苯酚，搅拌0.5小时，冷却至常温，出料即得到所需的聚氨酯甲基丙烯酸酯。
实施例1
| 原料名称 | 重量份数 |
| 聚氨酯甲基丙烯酸酯 | 60.00 |
| 聚乙二醇二甲基丙烯酸酯 | 20.00 |
| 乙二胺四乙酸二钠 | 0.25 |
| 1,4苯醌 | 0.10 |
| 邻苯甲硫酰亚胺 | 1.60 |
| N,N二甲基对甲苯胺 | 1.00 |
| 聚四氟乙烯粉 | 11.00 |
| 异丙苯过氧化氢 | 3.00 |
| 气相白炭黑 | 3.00 |
制备方法：
1、按重量份将自制的聚氨酯甲基丙烯酸酯60份，聚乙二醇二甲基丙烯酸酯20份加入反应釜中搅拌均匀；
2、加入乙二胺四乙酸二钠0.25份，1,4苯醌0.10份，邻苯甲硫酰亚胺1.6份和N,N二甲基对甲苯胺1.0份充分搅拌，至固体颗粒完全溶解；
3、加入聚四氟乙烯粉11份，气相白炭黑3.0份，搅拌混合均匀；
4、降温至40℃以下，加入异丙苯过氧化氢3.0份，搅拌均匀，冷却至室温，出料。
实施例2
| 原料名称 | 重量份数 |
| 聚氨酯甲基丙烯酸酯 | 50.00 |
| 聚乙二醇二甲基丙烯酸酯 | 25.00 |
| 乙二氨四乙酸二钠 | 0.25 |
| 1，4苯醌 | 0.10 |
| 邻苯甲硫酰亚胺 | 1.60 |
| N,N二甲基对甲苯胺 | 1.00 |
| 聚四氟乙烯粉 | 16.00 |
| 异丙苯过氧化氢 | 3.00 |
| 气相白炭黑 | 3.00 |
制备方法：
1、按重量份比将自制的聚氨酯甲基丙烯酸酯50份，聚乙二醇二甲基丙烯酸酯25份加入反应釜中搅拌均匀；
2、加入乙二胺四乙酸二钠0.25份，1，4苯醌0.10份，邻苯甲硫酰亚胺1.6份和N,N二甲基对甲苯胺1.0份充分搅拌，至固体颗粒完全溶解；
3、加入聚四氟乙烯粉16份，气相白炭黑3.0份，搅拌混合均匀；
4、降温至40℃以下，加入异丙苯过氧化氢3.0份，搅拌均匀，冷却至室温，出料。
实施例3
制备方法：
1、按重量份比将自制的聚氨酯甲基丙烯酸酯70份，聚乙二醇二甲基丙烯酸酯15份加入反应釜中搅拌均匀；
2、加入乙二胺四乙酸二钠0.25份，1，4苯醌0.10份，邻苯甲硫酰亚胺1.6份和N,N二甲基对甲苯胺1.0份充分搅拌，至固体颗粒完全溶解；
3、加入聚四氟乙烯粉6份，气相白炭黑3.0份，搅拌混合均匀；
4、降温至40℃以下，加入异丙苯过氧化氢3.0份，搅拌均匀，冷却至室温，出料。
实施例4
| 原料名称 | 重量百分比 |
| 聚氨酯甲基丙烯酸酯 | 71.00 |
| 聚乙二醇二甲基丙烯酸酯 | 25.00 |
| 乙二氨四乙酸二钠 | 0.25 |
| 1,4苯醌 | 0.10 |
| 邻苯甲硫酰亚胺 | 1.60 |
| N,N二甲基对甲苯胺 | 1.00 |
| 聚四氟乙烯粉 | 1.00 |
| 异丙苯过氧化氢 | 3.00 |
| 气相白炭黑 | 3.00 |
制备方法：
1、按重量份比将自制的聚氨酯甲基丙烯酸酯71份，聚乙二醇二甲基丙烯酸酯25份加入反应釜中搅拌均匀；
2、加入乙二胺四乙酸二钠0.25份，1,4苯醌0.10份，邻苯甲硫酰亚胺1.6份和N,N二甲基对甲苯胺1.0份充分搅拌，至固体颗粒完全溶解；
3、加入聚四氟乙烯粉1.0份，气相白炭黑3.0份，搅拌混合均匀；
4、降温至40℃以下，加入异丙苯过氧化氢3.0份，搅拌均匀，冷却至室温，出料。
比较例1
市场上出售的醇酸型平面密封厌氧胶518；
性能测试：
1、固化定位时间：据HB 5325-1993航空用厌氧胶固化速度试验方法，试验件不能移动的时间，即为固化定位时间；
2、剪切强度：据GB/T 18747.2厌氧胶粘剂扭矩强度和剪切强度的测定进行测定；
3、气密性测试：据HB 5313航空用厌氧胶液体密封性试验方法，涂胶24小时后，测式试件的接口的气密性；
4、断裂伸长率：据JB/T7311-2016标准时行测试；
5、稳定性:将单组分厌氧胶放置在5毫升玻璃小试管里,在水浴82℃下放置2小时,如果不凝胶,表示可以常温下保存2年；
从上表可以看出：本发明中的实施例与市售对比例相比，本发明的厌氧胶固化定位速度快，柔韧性强，剪切强度高，克服了厌氧胶存在的聚合物弹性低的缺点，从而可大大拓展其应用领域。
上面对本发明进行了示例性描述，显然本发明具体实现并不受上述方式的限制，只要采用了本发明的方法构思和技术方案进行的各种改进，或未经改进直接应用于其它场合的，均在本发明的保护范围之内。
Claims (10)
1.一种高韧性高强度的厌氧胶，其特征在于，包括如下重量份的组分：
2.根据权利要求1所述的一种高韧性高强度的厌氧胶，其特征在于，所述的聚氨酯甲基丙烯酸酯由二苯基甲烷二异氰酸酯MDI50、聚四氢呋喃醚二醇(分子量1000)和甲基丙烯酸羟乙酯合成，其中二苯基甲烷二异氰酸酯MDI50、聚四氢呋喃醚二醇、甲基丙烯酸羟乙酯的质量比为(20-40)：(30-60)：(10-40)；二月桂酸二丁基锡加入量为所述聚氨酯甲基丙烯酸酯总质量的(0.01—1.0)％。
3.根据权利要求2所述的一种高韧性高强度的厌氧胶，其特征在于，所述的二苯基甲烷二异氰酸酯MDI50也可以选择已二异氰酸酯(HDI)，异佛尔酮二异氰酸酯(IPDI)，二环已基甲烷二异氰酸酯(HDMI)中的一种或多种混合物，所述的聚四氢呋喃醚二醇(分子量1000)也可以选择聚四氢呋喃醚二醇(2000)、聚丙二醇(1500)；所述的甲基丙烯酸羟乙酯可以选择甲基丙烯酸羟丙酯、甲基丙烯酸异冰片酯。
4.根据权利要求1所述的一种高韧性高强度的厌氧胶，其特征在于，所述的丙烯酸酯单体为乙氧化双酚A二甲基丙烯酸酯、聚乙二醇二甲基丙烯酸酯、二缩三乙二醇二甲基丙烯酸酯中一种或多种。
5.根据权利要求1所述的一种高韧性高强度的厌氧胶，其特征在于，所述的螯合剂为乙二胺四乙酸、乙二胺四乙酸二钠、乙二胺四乙酸四钠、乙二铵四乙酸四铵中的一种或多种。
6.根据权利要求1所述的一种高韧性高强度的厌氧胶，其特征在于，所述的稳定剂为对苯二酚、1,4苯醌、萘醌中一种或多种。
7.根据权利要求1所述的一种高韧性高强度的厌氧胶，其特征在于，所述的促进剂为三乙铵、邻苯甲硫酰亚胺、乙酰苯肼、抗坏血酸、二茂铁中的一种或多种。
8.根据权利要求1所述的一种高韧性高强度的厌氧胶，其特征在于，所述的助促进剂为N,N二甲基对甲苯胺、苯甲酰肼，马来酸酐，丙烯酸、甲基丙烯酸中的一种或多种；所述的增韧剂为聚醋酸乙烯酯、富马酸双酚A聚酯、聚四氟乙烯粉中的一种或多种。
9.根据权利要求1所述的一种高韧性高强度的厌氧胶，其特征在于，所述的引发剂为叔丁基过氧化氢、过氧化苯甲酰、异丙苯过氧化氢中的一种或多种；所述的触变剂为气相白炭黑、氢化蓖麻油、氧化钙中一种或多种。
10.一种高韧性高强度的厌氧胶的制备方法，其特征在于，包括以下步骤：
(1)按重量份将自制的聚氨酯甲基丙烯酸酯，丙烯酸酯单体加入反应釜中搅拌均匀；
(2)加入螯合剂、稳定剂，促进剂和助促时剂搅拌，至固体颗粒完全溶解；
(3)加入增韧剂，触变剂搅拌均匀；
(4)降温至40℃以下，加入引发剂，搅拌均匀，冷却至室温，出料。
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| CN117050712A (zh) * | 2023-07-27 | 2023-11-14 | 广东中粘新材料科技有限公司 | 一种耐低温的无溶剂聚氨酯胶粘剂 |
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