CN107011812B - 一种无甲醛环保型玻璃棉胶黏剂 - Google Patents
一种无甲醛环保型玻璃棉胶黏剂 Download PDFInfo
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- CN107011812B CN107011812B CN201710366537.3A CN201710366537A CN107011812B CN 107011812 B CN107011812 B CN 107011812B CN 201710366537 A CN201710366537 A CN 201710366537A CN 107011812 B CN107011812 B CN 107011812B
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- glass wool
- formaldehyde
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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
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
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- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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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
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- C—CHEMISTRY; METALLURGY
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- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- C—CHEMISTRY; METALLURGY
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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Abstract
本发明公开了一种无甲醛环保型玻璃棉胶黏剂，其各组成的配比为：三缩四乙二醇二甲基丙烯酸酯50～60份、环氧丙烯酸双酯20～35份、过硫酸钾2～4份、水溶性丙烯酸树脂50‑70份、三乙胺1～2份、糖精0.1～0.5份、氢醌0.5～1份、丙烯酸树脂粉末1～1.5份、无机填料0.5～3份、水200～300份。本发明使用水性无甲醛的环保丙烯酸树脂系统替代传统的有毒有害三醛树脂，与三醛树脂不同，本发明的产品不含甲醛，并且在高温分解过程中，仅产生二氧化碳和水，不产生诸如二噁英之类的致癌物，是一种环保的玻璃棉胶黏剂。
Description
技术领域
本发明属于高分子聚合物领域，具体涉及一种无甲醛环保型玻璃棉胶黏剂。
背景技术
玻璃棉属于玻璃纤维中的一个类别，是一种人造无机纤维。采用石英砂、石灰石、白云石等天然矿石为主要原料，配合一些纯碱、硼砂等化工原料熔成玻璃。在融化状态下，借助外力吹制式甩成絮状细纤维，纤维和纤维之间为立体交叉，互相缠绕在一起，呈现出许多细小的间隙。这种间隙可看作孔隙。离心玻璃棉具有防火、保温、易于切割等优良特性。
离心玻璃棉属于多孔吸声材料，具有良好的吸声性能。是建筑吸声最常用的材料之一。常用于作为成吸声吊顶板或吸声墙板。离心玻璃棉能够吸声的原因不是由于表面粗糙，而是因为具有大量的内外连通的微小孔隙和孔洞。当声波入射到离心玻璃棉上时，声波能顺着孔隙进入材料内部，引起空隙中空气分子的振动。由于空气的粘滞阻力和空气分子与孔隙壁的摩擦，声能转化为热能而损耗。
玻璃棉胶黏剂是玻璃棉生产过程中必不可少的环节之一，在玻璃棉制品中使用一定量的玻璃棉胶黏剂对玻璃棉制品的成形是非常重要的。它可以稳定产品的几何尺寸，使产品表面光滑，增加产品的强度和回弹性能，除此之外，还可以减少粉尘，并减少产品对皮肤的刺激。目前玻璃棉所用胶黏剂主要是热固性酚醛树脂。
酚醛树脂是苯酚和甲醛在酸性或碱性的催化剂作用下，通过缩聚反应生成的。在酸性催化剂作用下，苯酚过量时生成线型热塑性树脂；在碱性催化剂作用下，甲醛过量时生成体型热固性树脂，酚醛就是苯酚和甲醛的发泡物，在这个过程中不可避免的要使用到苯酚和甲醛，甲醛对人体有害处，而酚醛中近20％的原料就是甲醛。众所周知，甲醛对人们的健康有着极大的危害：皮肤直接接触甲醛可引起过敏性皮炎、色斑、坏死，吸入高浓度甲醛时可诱发支气管哮喘。还有对皮肤粘膜的刺激作用，甲醛是原浆毒物质，能与蛋白质结合、高浓度吸入时出现呼吸道严重的刺激和水肿、眼刺激、头痛。最为危险的是甲醛的致突变作用：高浓度甲醛属于基因毒性物质，能引起哺乳动物细胞核的基因突变、染色体损伤断裂。研究发现，长期接触甲醛增大了患上霍奇金淋巴瘤、多发性骨髓瘤、骨髓性白血病等特殊癌症的几率。因此，急需开发一种无甲醛、无VOC的环保玻璃棉胶黏剂，以适应现代玻璃棉生产的需要。
水性胶黏剂是以树脂为粘结基体材料，以水为溶剂或分散剂，取代对环境有污染的有毒有机溶剂，而制备成的一种环境友好型胶黏剂。现有水基胶粘剂不含有毒的有机溶剂，生产过程和产品中没有有毒物质挥发和残留，对人体、环境无危害，安全环保，大大减少了生产及使用过程中挥发性有机化合物的排放，为改善周边大气环境作出了积极的贡献，极大地降低了环境污染的治理费用，节约能源，对环境的改善具有重要的意义。
发明内容
发明目的：针对现有技术中的玻璃棉胶黏剂的不足之处，即含有甲醛，不利于人体健康，不利于环境保护，本发明采用水性无甲醛的环保丙烯酸树脂系统替代传统的有毒有害三醛树脂，提供了一种无甲醛环保型玻璃棉胶黏剂。
技术方案：本发明所提供的玻璃棉胶黏剂胶由三缩四乙二醇二甲基丙烯酸酯、环氧丙烯酸双酯、过硫酸钾、水溶性丙烯酸树脂、三乙胺、糖精、氢醌、丙烯酸树脂粉末、无机填料和水组成。
对于本发明的配方来说，主要成分为作为双酯单体的三缩四乙二醇二甲基丙烯酸酯和作为改性树脂的环氧丙烯酸双酯，以过硫酸钾为引发剂，以三乙胺为促进剂、以糖精为助促进剂加速其固化。本发明以水溶性丙烯酸树脂为基础胶黏剂，在配方中用于提供基础的粘结力，三缩四乙二醇二甲基丙烯酸酯、环氧丙烯酸双酯和丙烯酸树脂粉末的加入不但提高了玻璃棉胶黏剂的粘结力，而且制备的产品具有更良好的回弹性。
对于本发明来说配比也非常重要，本发明优化了单体的配比，提高了树脂基体的内聚强度，从而大幅提高玻璃棉胶黏剂的粘结力，而且制备的产品具有更良好的回弹性、耐水洗和耐磨性能，具体的本发明所述玻璃棉胶黏剂各组成的配比为：三缩四乙二醇二甲基丙烯酸酯50～60份、环氧丙烯酸双酯20～35份、过硫酸钾2～4份、水溶性丙烯酸树脂50～70份、三乙胺1～2份、糖精0.1～0.5份、氢醌0.5～1份、丙烯酸树脂粉末1～1.5份、无机填料0.5～3份、水200～300份。
本发明所述的水溶性丙烯酸树脂是一种至少包含了低分子量丙烯酸聚合物和多元醇的混合物，所述的低分子量丙烯酸聚合物是以丙烯酸或甲基丙烯酸为单体聚合反应得到的，其数均分子量为500～30000，优选为800～10000，更优选为800～5000，所述的多元醇为乙二醇、丙二醇、一缩二乙二醇、1,4-丁二醇、1,2,3-环已三醇、1,2,4-丁三醇、1,2,3-丁三醇、1,2,5-戊三醇、甘油中的任意一种或多种，所述多元醇中的羟基与丙烯酸聚合物中的羧基的摩尔比为0.8∶1.2～1.2∶0.8。所述的水溶性丙烯酸树脂的固含量为30～60％，PH值为2.0-4.0。
具体的，本发明所述的丙烯酸树脂粉末是以丙烯酸酯单体混合物和聚乙烯醇为原料，以过氧化苯甲酰为引发剂反应后，烘干、粉碎得到的。所述的丙烯酸树脂粉末的原料的配比为丙烯酸酯单体混合物80～120份、聚乙烯醇5～9份、水60～80份。
所述的丙烯酸酯单体混合物为甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丁酯、丙烯酸丁酯、甲基丙烯酸异丁酯、丙烯酸十二烷基酯、丙烯酸十八烷基酯中的任意一种或几种与甲基丙烯酸、丙烯酸、丙烯酰胺、丙烯腈、甲基丙烯酰胺、苯乙烯中的任意一种或几种的混合物。本发明中固体丙烯酸树脂粉末的加入在一定程度上提高了玻璃棉胶黏剂的粘结力，而且制备的产品具有更良好的回弹性。
对于本发明来说无机填料的使用也较为关键，所述的无机填料为膨润土、六钛酸钾晶须、硅微粉、纳米三氧化二铝中的一种或多种。对于常规技术来说加入填料可以起到增稠作用，还可改善胶液的触变性能，以控制胶液的流动性。进一步的研究发现，有些聚合物分子间的相互作用力较弱，内聚能低，因此力学性能不高。我们优选六钛酸钾晶须，除了上述提到的作用以外，还能起到补强效果，填料粒子的活性表面可与若干大分子链相结合形成交联结构，当其中一条分子链受到应力时，可通过交联点将应力分散传递到其他分子上。可以提高本产品可以提高胶黏剂的内聚强度、黏合力耐热性，降低胶黏剂的固化收缩率和热膨胀系数等。
更进一步的尝试，发现，如果在本发明中添加气相白炭黑，可以改善其流淌性，如果在本发明的配方中添加苯醌，可以改善储存期。然而他们的加入量必须得到控制，较适宜的范围是白炭黑0.5～1份、苯醌1.0～1.5份，最优的加入量是白炭黑0.8份、苯醌1.2份。
对于本发明来说，还可以添加偶联剂、憎水剂、防尘油中的一种或几种组合。偶联剂可在无机物质和有机物质的界面之间架起“分子桥”，把两种性质悬殊的材料牢固的结合在一起，改善了粘结剂的润湿性能，增加了界面的粘结性能，消除了内应力，提高使用寿命；憎水剂可有效阻止水分子吸附在玻璃纤维表面，提高玻璃棉的憎水性能；防尘油用于玻璃棉中可有效减少生产和切割、加工、搬运的过程中产生大量飞扬的粉尘。偶联剂、憎水剂和防尘油的用量为0.1～3份。
对于本发明来说，最佳的配方：三缩四乙二醇二甲基丙烯酸酯50份、环氧丙烯酸双酯20份、过硫酸钾2份、水溶性丙烯酸树脂50份、三乙胺1份、糖精0.1份、氢醌0.5份、以丙烯酸丁酯和甲基丙烯酸为单体混合物的丙烯酸树脂粉末1份、六钛酸钾晶须0.5份、水200份、苯醌1.2份、气相白炭黑0.8份。
有益效果：本发明制得的玻璃棉胶黏剂具有优异的柔顺性，脆性小、韧性好，粘度适中，耐水性、耐老化性能优越，无游离甲醛释放，达到环保节能的要求。
本发明为水溶性而非溶剂型，绿色环保，且具有良好的储存稳定性，相比于现有技术，本发明的所提供的玻璃棉胶黏剂无需低温保存，储存和运输方便。因此，具有很好的市场应用前景。
本发明使用水性无甲醛的环保丙烯酸树脂系统替代传统的有毒有害三醛树脂，与三醛树脂不同，本发明的产品不含甲醛，并且在高温分解过程中，仅产生二氧化碳和水，不产生诸如二噁英之类的致癌物，是一种环保的玻璃棉胶黏剂。
具体实施方式：
实施例1
丙烯酸丁酯和甲基丙烯酸混合物80份、聚乙烯醇5份、水80份反应，干燥，粉粹，得到丙烯酸树脂粉末。
实施例2
甲基丙烯酸丁酯和丙烯酰胺混合物120份、聚乙烯醇9份、水80份反应，干燥，粉粹，得到丙烯酸树脂粉末。
实施例3
甲基丙烯酸甲酯和丙烯腈混合物80份、聚乙烯醇9份、水80份反应，干燥，粉粹，得到丙烯酸树脂粉末。
在以下4-21的实施例中，所述的水溶性丙烯酸树脂的数均分子量为1200，固含量为52％，PH值为3.0，其包含的多元醇为1,2,4-丁三醇，多元醇中的羟基与丙烯酸聚合物中的羧基的摩尔比为0.95。
实施例4
玻璃棉胶黏剂配方：三缩四乙二醇二甲基丙烯酸酯50份、环氧丙烯酸双酯20份、过硫酸钾2份、水溶性丙烯酸树脂50份、三乙胺1份、糖精0.1份、氢醌0.5份、实施例1所得的丙烯酸树脂粉末1份、膨润土0.5份、水200份。
将三缩四乙二醇二甲基丙烯酸酯50份、环氧丙烯酸双酯20份、过硫酸钾2份和适量的水混合，再加入丙烯酸1份、三乙胺1份、糖精0.1份、对苯二酚0.5份，反应后，再加入丙烯酸树脂粉末1份、膨润土0.5份和适量的水混合，得到。
实施例5
玻璃棉胶黏剂配方：三缩四乙二醇二甲基丙烯酸酯60份、环氧丙烯酸双酯35份、过硫酸钾4份、水溶性丙烯酸树脂60份、三乙胺2份、糖精0.5份、氢醌1份、实施例1所得的丙烯酸树脂粉末1.5份、硅微粉3份、水300份。
制备方法与实施例4相同。
实施例6
玻璃棉胶黏剂配方：三缩四乙二醇二甲基丙烯酸酯50份、环氧丙烯酸双酯20份、过硫酸钾2份、水溶性丙烯酸树脂55份、三乙胺1份、糖精0.1份、氢醌0.5份、实施例1所得的丙烯酸树脂粉末1份、六钛酸钾晶须0.5份、水200份。
制备方法与实施例4相同。
实施例7
玻璃棉胶黏剂配方：三缩四乙二醇二甲基丙烯酸酯60份、环氧丙烯酸双酯35份、过硫酸钾4份、水溶性丙烯酸树脂65份、三乙胺2份、糖精0.5份、氢醌1份、实施例1所得的丙烯酸树脂粉末1.5份、纳米三氧化二铝3份、水300份
制备方法与实施例4相同。
实施例8～11
配方分别与实施例4～5基本相同，不同之处在于，将实施例1所得的丙烯酸树脂粉末替换为实施例2所得到的丙烯酸树脂粉末。
制备方法与实施例4相同。
实施例12～15
配方分别与实施例4～5基本相同，不同之处在于，将实施例1所得的丙烯酸树脂粉末替换为实施例3所得到的丙烯酸树脂粉末。
制备方法与实施例4相同。
实施例16
玻璃棉胶黏剂配方：三缩四乙二醇二甲基丙烯酸酯50份、环氧丙烯酸双酯20份、过硫酸钾2份、水溶性丙烯酸树脂60份、三乙胺1份、糖精0.1份、氢醌0.5份、实施例1所得的丙烯酸树脂粉末1份、六钛酸钾晶须0.5份、水200份、苯醌1份。
将三缩四乙二醇二甲基丙烯酸酯50份、环氧丙烯酸双酯20份、过硫酸钾2份和适量的水混合，再加入丙烯酸1份、三乙胺1份、糖精0.1份、对苯二酚0.5份，反应后，再加入丙烯酸树脂粉末1份、膨润土0.5份、苯醌1份和适量的水混合，得到。
实施例17
玻璃棉胶黏剂配方：三缩四乙二醇二甲基丙烯酸酯50份、环氧丙烯酸双酯20份、过硫酸钾2份、水溶性丙烯酸树脂70份、三乙胺1份、糖精0.1份、氢醌0.5份、实施例1所得的丙烯酸树脂粉末1份、六钛酸钾晶须0.5份、水300份、苯醌1.5份。
制备方法与实施例16相同。
实施例18
玻璃棉胶黏剂配方：三缩四乙二醇二甲基丙烯酸酯50份、环氧丙烯酸双酯20份、过硫酸钾2份、水溶性丙烯酸树脂55份、三乙胺1份、糖精0.1份、氢醌0.5份、实施例1所得的丙烯酸树脂粉末1份、六钛酸钾晶须0.5份、水200份、气相白炭黑0.5份。
将三缩四乙二醇二甲基丙烯酸酯50份、环氧丙烯酸双酯20份、过硫酸钾2份和适量的水混合，再加入丙烯酸1份、三乙胺1份、糖精0.1份、对苯二酚0.5份，反应后，再加入丙烯酸树脂粉末1份、膨润土0.5份、气相白炭黑0.5份和适量的水混合，得到。
实施例19
玻璃棉胶黏剂配方：三缩四乙二醇二甲基丙烯酸酯50份、环氧丙烯酸双酯20份、过硫酸钾2份、水溶性丙烯酸树脂50份、三乙胺1份、糖精0.1份、氢醌0.5份、实施例1所得的丙烯酸树脂粉末1份、六钛酸钾晶须0.5份、水200份、气相白炭黑1份。
制备方法与实施例18相同。
实施例20
玻璃棉胶黏剂配方：三缩四乙二醇二甲基丙烯酸酯50份、环氧丙烯酸双酯20份、过硫酸钾2份、水溶性丙烯酸树脂70份、三乙胺1份、糖精0.1份、氢醌0.5份、实施例1所得的丙烯酸树脂粉末1份、六钛酸钾晶须0.5份、水200份、苯醌1.5份、气相白炭黑0.5份。
将三缩四乙二醇二甲基丙烯酸酯50份、环氧丙烯酸双酯20份、过硫酸钾2份和适量的水混合，再加入丙烯酸1份、三乙胺1份、糖精0.1份、对苯二酚0.5份，反应后，再加入丙烯酸树脂粉末1份、膨润土0.5份、苯醌1.5份、气相白炭黑0.5份和适量的水混合，得到。
实施例21
玻璃棉胶黏剂配方：三缩四乙二醇二甲基丙烯酸酯50份、环氧丙烯酸双酯20份、过硫酸钾2份、水溶性丙烯酸树脂50份、三乙胺1份、糖精0.1份、氢醌0.5份、实施例1所得的丙烯酸树脂粉末1份、六钛酸钾晶须0.5份、水200份、苯醌1.2份、气相白炭黑0.8份。
制备方法与实施例20相同。
采用GB/T2912.1-1998、ISO3251：2008、标准对实施例1～21进行检测，检测结果如下表所示：
实施例22～24
将实施例14、实施例16、实施例20中所得到的玻璃棉胶黏剂喷涂于玻璃棉，分别得到产品1，产品2，产品3。
对上述的产品1，产品2，产品3进行性能测试，所得结果如下表所示：
Claims (7)
1.一种无甲醛环保型玻璃棉胶黏剂，其特征在于所述的玻璃棉胶黏剂由三缩四乙二醇二甲基丙烯酸酯、环氧丙烯酸双酯、过硫酸钾、水溶性丙烯酸树脂、三乙胺、糖精、氢醌、丙烯酸树脂粉末、无机填料和水组成；
所述的玻璃棉胶黏剂各组成的配比为：三缩四乙二醇二甲基丙烯酸酯50～60份、环氧丙烯酸双酯20～35份、过硫酸钾2～4份、水溶性丙烯酸树脂50～70份、三乙胺1～2份、糖精0.1～0.5份、氢醌0.5～1份、丙烯酸树脂粉末1～1.5份、无机填料0.5～3份、水200～300份；
所述的水溶性丙烯酸树脂是一种至少包含了低分子量丙烯酸聚合物和多元醇的混合物，所述的低分子量丙烯酸聚合物是以丙烯酸或甲基丙烯酸为单体聚合反应得到的，其数均分子量为500～30000，；所述的多元醇为乙二醇、丙二醇、一缩二乙二醇、1,4-丁二醇、1,2,3-环已三醇、1,2,4-丁三醇、1,2,3-丁三醇、1,2,5-戊三醇、甘油中的任意一种或多种；所述多元醇中的羟基与丙烯酸聚合物中的羧基的摩尔比为0.8∶1.2～1.2∶0.8；所述的水溶性丙烯酸树脂的固含量为30～60％，PH值为2.0-4.0；
所述的丙烯酸树脂粉末是以丙烯酸酯单体混合物和聚乙烯醇为主要原料，以过氧化苯甲酰为引发剂反应后，烘干、粉碎得到的。
2.根据权利要求1所述的无甲醛环保型玻璃棉胶黏剂，其特征在于所述的丙烯酸树脂粉末的原料的配比为丙烯酸酯单体混合物80～120份、聚乙烯醇5～9份、水60～80份。
3.根据权利要求1所述的无甲醛环保型玻璃棉胶黏剂，其特征在于所述的丙烯酸酯单体混合物为甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丁酯、丙烯酸丁酯、甲基丙烯酸异丁酯、丙烯酸十二烷基酯、丙烯酸十八烷基酯中的任意一种或几种与甲基丙烯酸、丙烯酸、丙烯酰胺、丙烯腈、甲基丙烯酰胺、苯乙烯中的任意一种或几种的混合物。
4.根据权利要求1所述的无甲醛环保型玻璃棉胶黏剂，其特征在于所述的无机填料为膨润土、六钛酸钾晶须、硅微粉、纳米三氧化二铝中的一种或多种。
5.根据权利要求1所述的无甲醛环保型玻璃棉胶黏剂，其特征在于还含有苯醌，配比为1～1.5份。
6.根据权利要求1所述的无甲醛环保型玻璃棉胶黏剂，其特征在于还含有气相白炭黑，配比为0.5～1份。
7.根据权利要求1所述的无甲醛环保型玻璃棉胶黏剂，其特征在于还含有偶联剂、憎水剂、防尘油中的一种或几种组合。
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