CN106675496A - 一种高粘结力的水性聚氨酯粘合剂 - Google Patents

一种高粘结力的水性聚氨酯粘合剂 Download PDF

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CN106675496A
CN106675496A CN201611227116.4A CN201611227116A CN106675496A CN 106675496 A CN106675496 A CN 106675496A CN 201611227116 A CN201611227116 A CN 201611227116A CN 106675496 A CN106675496 A CN 106675496A
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aqueous polyurethane
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polyurethane adhesive
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张炎斌
魏风军
郝会霞
李亚超
李东海
闫新亮
董豪杰
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Abstract

一种高粘结力的水性聚氨酯粘合剂，由耐水组合物与水性聚氨酯乳液共混制得，水性聚氨酯乳液的制备方法：将羟基单体和亲水扩链剂混合升温、脱水、降温，再加入异氰酸酯单体，经升温、保温即可；所述的羟基单体为聚醚多元醇、聚酯多元醇或两者的混合物；所述的亲水扩链剂为含有羧基、磺酸基团或者是磺酸盐基团的小分子多元醇，其质量占异氰酸酯单体、羟基单体、亲水扩链剂三者总质量的10.5％‑12.5％；所述的异氰酸酯单体为芳香族多异氰酸酯、脂肪族多异氰酸酯或脂环族多异氰酸酯，R1值为1.2‑1.8。本发明解决了现有技术中耐高温性能、耐水性能和耐户外老化性能较差的技术问题，粘结力强，满足生产的需要。

Description

一种高粘结力的水性聚氨酯粘合剂
技术领域
本发明涉及高分子材料技术领域，具体涉及一种高粘结力的水性聚氨酯粘合剂。
背景技术
水性聚氨酯粘合剂是水性粘合剂中的重要一类，具有聚氨酯材料的优良性能。水性聚氨酯粘合剂含有极性很强、化学活泼性很高的异氰酸酯基和氨酯基，使之具有优良的化学粘结力，其不污染环境，应用领域、用途也愈来愈广。但其耐高温性能、耐水性能和耐户外老化性能较差，从而导致使用水性聚氨酯粘合剂的产品出现脱胶情况，不能满足提高产品质量的需要，因此需要对现有的水性聚氨酯粘合剂进行改进，以达到需要。
发明内容
本发明的目的是提供一种高粘结力的水性聚氨酯粘合剂，解决了现有技术中耐高温性能、耐水性能和耐户外老化性能较差的技术问题，粘结力强，满足生产的需要。
为了解决上述技术问题，本发明所采用的技术方案是：一种高粘结力的水性聚氨酯粘合剂，是由耐水组合物与水性聚氨酯乳液共混制得，所述水性聚氨酯乳液的制备方法为，将羟基单体和亲水扩链剂混合升温至145-150℃，脱水，15-20min后，降温至50-70℃，加入计量的异氰酸酯单体，升温至80-90℃，保温2-2.5h即可；所述的羟基单体为聚醚多元醇、聚酯多元醇或两者的混合物；所述的亲水扩链剂为含有羧基、磺酸基团或者是磺酸盐基团的小分子多元醇，其质量占异氰酸酯单体、羟基单体、亲水扩链剂三者总质量的10.5％-12.5％；所述的异氰酸酯单体为芳香族多异氰酸酯、脂肪族多异氰酸酯或脂环族多异氰酸酯，其中控制R1值为1.2-1.8；
所述耐水组合物的制备方法包括以下步骤，a、按照重量比取5-15份芋头粉、0.5-1份二乙烯三胺五乙酸五钠、1-2份纳米氧化镨、35-37份聚乙烯醇、0.5-1份丁酮酸钠盐、0.03-0.05份木质素偶联剂、2-4份糠醇和0.5-1份改性硅藻土作为原材料；b、从原材料中取改性芋头粉、聚乙烯醇和糠醇混合并加热至35-40℃，然后再依次加入改性硅藻土、丁酮酸钠盐和木质素偶联剂进行搅拌，搅拌速度为500-510r/min，升温至45-50℃，然后加入二乙烯三胺五乙酸五钠和纳米氧化镨，以600-610r/min速度搅拌20-30min，然后保温2-3h即可。
所述耐水组合物的原材料中还含有0.1-0.3份氯化钙以及0.5-1份硬脂酸钙。
所述芋头粉还可经过改性处理，其改性方法为将芋头粉加入到其重量2-4倍且浓度为0.12-0.14g/ml硝酸铈铵水溶液中，并在30-35℃温度下搅拌2-3h以制成芋头粉浆，再将芋头粉浆进行抽滤并用水洗涤直至水中不含硝酸铈铵，得到改性芋头粉。
所述改性硅藻土的制备方法为，取硅藻土并将其加入到为其重量3-5倍的水中混合均匀，再加入为硅藻土重量8％-10％的锡偶联剂，用硫酸调节pH为5-6，然后加入为硅藻土重量1％-3％的桃叶珊瑚苷，混合均匀，调节温度至60-65℃并保温2-3h，再加入为硅藻土重量4％-6％的硬脂酸搅拌均匀，然后在110-105℃条件下烘干至恒重，得到改性硅藻土。
所述制备改性硅藻土的过程中，加入锡偶联剂后，再加入为硅藻土重量2％-3％的y-氯丙基三甲氧基硅烷，然后再用硫酸调节PH为5-6。
所述水性聚氨酯乳液的具体制备方法为，按照重量比取70-80份多异氰酸酯和15-20份聚醚多元醇并将二者混合，然后在温度为55-60℃的条件下反应2-2.5h，再用含羧基亲水性基团的多官能基小分子进行扩链和交联，其中，多官能基小分子为二元醇、二元胺、三元醇、三元胺中的任意一种或任意一种以上的混合，任意一种以上混合时为任意配比；含羧基亲水性基团的多官能基小分子的加入量为多异氰酸酯的10-50％；其最后的NCO/OH摩尔比为1.0-3.5，扩链剂中[-OH]与多元醇中[-OH]摩尔比为1.0-3.5；然后调节PH值为6.5-7.5，待5-10分钟后冷却至40℃以下再加冰水分散，得水性聚氨酯乳液，固含量的质量百分数为10-25％。
本发明具有以下有益效果：
一、本发明所述的一种高粘结力的水性聚氨酯粘合剂，耐高温性能、耐水性能和耐户外老化性能强，粘结力强，使用该水性聚氨酯粘合剂的产品不易出现脱胶情况，满足了提高产品质量的需要；
二、本发明中耐水组合物使用的改性芋头粉是由芋头粉经硝酸铈铵改性得到，改性后的芋头粉，醛基量增加，但仍然保留伯醇，可以和聚乙烯醇分子间形成氢键，进而使本发明结构致密，粘结力更强，且耐水组合物中含有乙烯三胺五乙酸五钠、丁酮酸钠盐和纳米氧化镨，能够极大的改善混合材料的性能，使其耐水性能和耐高温性能极佳，并进一步降低了本发明所述高粘结力的水性聚氨酯粘合剂的透湿率并且大大增强了其耐高温性能，有效改善了因过强的界面作用导致断裂伸长率降低的现象；
三、耐水组合物中的改性硅藻土是由硅藻土经改性后得到，从而使得改性硅藻土摩擦系数、结晶成核能力和吸附能力均大大降低，使其更容易与高分子材料进行共混制备水性聚氨酯粘合剂，且加入改性硅藻土使耐水组合物共混过程更快更均匀，并使本发明所述的高粘结力的水性聚氨酯粘合剂的稳定性更高，保持时间长，粘结性更强，改性硅藻土提高了本发明中金属阳离子的活性，使本发明用于粘合时干燥时间更短；
四、对硅藻土进行改性时，向硅藻土中加入桃叶珊瑚苷，桃叶珊瑚苷含有多个极性官能团，性质活泼，在锡偶联剂和硅藻土的作用下产生了与戊二醛相似的双醛结构，从而使生成的改性硅藻土更加均匀；
五、本发明安全无毒，其耐热温度提高了23℃，抗冲击强度提高了55.2％，韧性提高了23.1％，胶合强度提高了45％。
具体实施方式
结合以下具体实施例，对本发明作进一步的详细说明，本发明的保护范围不局限于以下实施例。实施本发明的过程、条件、试剂、实验方法等，除以下专门提及的内容之外，均为本领域的普遍知识和公知常识，本发明没有特别限制内容。
实施例1
一种高粘结力的水性聚氨酯粘合剂，是由耐水组合物与水性聚氨酯乳液共混制得，所述水性聚氨酯乳液的制备方法为，将羟基单体和亲水扩链剂混合升温至145℃，脱水，15min后，降温至50℃，加入计量的异氰酸酯单体，升温至80℃，保温2h即可；所述的羟基单体为聚醚多元醇、聚酯多元醇或两者的混合物；所述的亲水扩链剂为含有羧基、磺酸基团或者是磺酸盐基团的小分子多元醇，其质量占异氰酸酯单体、羟基单体、亲水扩链剂三者总质量的10.5％；所述的异氰酸酯单体为芳香族多异氰酸酯、脂肪族多异氰酸酯或脂环族多异氰酸酯，其中控制R1值为1.2；
所述耐水组合物的制备方法包括以下步骤，a、按照重量比取5份芋头粉、0.5份二乙烯三胺五乙酸五钠、1份纳米氧化镨、35份聚乙烯醇、0.5份丁酮酸钠盐、0.03份木质素偶联剂、2份糠醇和0.5份改性硅藻土作为原材料；b、从原材料中取改性芋头粉、聚乙烯醇和糠醇混合并加热至35℃，然后再依次加入改性硅藻土、丁酮酸钠盐和木质素偶联剂进行搅拌，搅拌速度为500r/min，升温至45℃，然后加入二乙烯三胺五乙酸五钠和纳米氧化镨，以600r/min速度搅拌20min，然后保温2h即可。
所述芋头粉还可经过改性处理，其改性方法为将芋头粉加入到其重量2倍且浓度为0.12g/ml硝酸铈铵水溶液中，并在30℃温度下搅拌2h以制成芋头粉浆，再将芋头粉浆进行抽滤并用水洗涤直至水中不含硝酸铈铵，得到改性芋头粉。
所述改性硅藻土的制备方法为，取硅藻土并将其加入到为其重量3-5倍的水中混合均匀，再加入为硅藻土重量8％的锡偶联剂，用硫酸调节pH为5，然后加入为硅藻土重量1％的桃叶珊瑚苷，混合均匀，调节温度至60℃并保温2h，再加入为硅藻土重量4％的硬脂酸搅拌均匀，然后在105℃条件下烘干至恒重，得到改性硅藻土。
所述水性聚氨酯乳液的具体制备方法为，按照重量比取70份多异氰酸酯和15份聚醚多元醇并将二者混合，然后在温度为55℃的条件下反应2h，再用含羧基亲水性基团的多官能基小分子进行扩链和交联，其中，多官能基小分子为二元醇、二元胺、三元醇、三元胺中的任意一种或任意一种以上的混合，任意一种以上混合时为任意配比；含羧基亲水性基团的多官能基小分子的加入量为多异氰酸酯的10％；其最后的NCO/OH摩尔比为1.0，扩链剂中[-OH]与多元醇中[-OH]摩尔比为1.0；然后调节PH值为6.5，待5分钟后冷却至40℃以下再加冰水分散，得水性聚氨酯乳液，固含量的质量百分数为10％。
以上为基础技术方案，可在以上基础上做进一步的改进：
如，所述耐水组合物的原材料中还含有0.1份氯化钙以及0.5份硬脂酸钙。
又如，所述制备改性硅藻土的过程中，加入锡偶联剂后，再加入为硅藻土重量2％的y-氯丙基三甲氧基硅烷，然后再用硫酸调节PH为5。
实施例2
一种高粘结力的水性聚氨酯粘合剂，是由耐水组合物与水性聚氨酯乳液共混制得，所述水性聚氨酯乳液的制备方法为，将羟基单体和亲水扩链剂混合升温至147℃，脱水，18min后，降温至60℃，加入计量的异氰酸酯单体，升温至85℃，保温2.3h即可；所述的羟基单体为聚醚多元醇、聚酯多元醇或两者的混合物；所述的亲水扩链剂为含有羧基、磺酸基团或者是磺酸盐基团的小分子多元醇，其质量占异氰酸酯单体、羟基单体、亲水扩链剂三者总质量的11.5％；所述的异氰酸酯单体为芳香族多异氰酸酯、脂肪族多异氰酸酯或脂环族多异氰酸酯，其中控制R1值为1.4；
所述耐水组合物的制备方法包括以下步骤，a、按照重量比取10份芋头粉、0.8份二乙烯三胺五乙酸五钠、1.5份纳米氧化镨、36份聚乙烯醇、0.7份丁酮酸钠盐、0.04份木质素偶联剂、3份糠醇和0.8份改性硅藻土作为原材料；b、从原材料中取改性芋头粉、聚乙烯醇和糠醇混合并加热至38℃，然后再依次加入改性硅藻土、丁酮酸钠盐和木质素偶联剂进行搅拌，搅拌速度为505r/min，升温至47℃，然后加入二乙烯三胺五乙酸五钠和纳米氧化镨，以605r/min速度搅拌25min，然后保温2.5h即可。
所述芋头粉还可经过改性处理，其改性方法为将芋头粉加入到其重量3倍且浓度为0.13g/ml硝酸铈铵水溶液中，并在33℃温度下搅拌2.5h以制成芋头粉浆，再将芋头粉浆进行抽滤并用水洗涤直至水中不含硝酸铈铵，得到改性芋头粉。
所述改性硅藻土的制备方法为，取硅藻土并将其加入到为其重量4倍的水中混合均匀，再加入为硅藻土重量9％的锡偶联剂，用硫酸调节pH为5.5，然后加入为硅藻土重量2％的桃叶珊瑚苷，混合均匀，调节温度至63℃并保温2h，再加入为硅藻土重量5％的硬脂酸搅拌均匀，然后在108℃条件下烘干至恒重，得到改性硅藻土。
所述水性聚氨酯乳液的具体制备方法为，按照重量比取75份多异氰酸酯和17份聚醚多元醇并将二者混合，然后在温度为58℃的条件下反应2.5h，再用含羧基亲水性基团的多官能基小分子进行扩链和交联，其中，多官能基小分子为二元醇、二元胺、三元醇、三元胺中的任意一种或任意一种以上的混合，任意一种以上混合时为任意配比；含羧基亲水性基团的多官能基小分子的加入量为多异氰酸酯的30％；其最后的NCO/OH摩尔比为2.5，扩链剂中[-OH]与多元醇中[-OH]摩尔比为2.5；然后调节PH值为7，待8分钟后冷却至40℃以下再加冰水分散，得水性聚氨酯乳液，固含量的质量百分数为15％。
以上为基础技术方案，可在以上基础上做进一步的改进：
如，所述耐水组合物的原材料中还含有0.2份氯化钙以及0.8份硬脂酸钙。
又如，所述制备改性硅藻土的过程中，加入锡偶联剂后，再加入为硅藻土重量2.5％的y-氯丙基三甲氧基硅烷，然后再用硫酸调节PH为5.5。
实施例3
一种高粘结力的水性聚氨酯粘合剂，是由耐水组合物与水性聚氨酯乳液共混制得，所述水性聚氨酯乳液的制备方法为，将羟基单体和亲水扩链剂混合升温至150℃，脱水，20min后，降温至70℃，加入计量的异氰酸酯单体，升温至90℃，保温2.5h即可；所述的羟基单体为聚醚多元醇、聚酯多元醇或两者的混合物；所述的亲水扩链剂为含有羧基、磺酸基团或者是磺酸盐基团的小分子多元醇，其质量占异氰酸酯单体、羟基单体、亲水扩链剂三者总质量的12.5％；所述的异氰酸酯单体为芳香族多异氰酸酯、脂肪族多异氰酸酯或脂环族多异氰酸酯，其中控制R1值为1.8；
所述耐水组合物的制备方法包括以下步骤，a、按照重量比取15份芋头粉、1份二乙烯三胺五乙酸五钠、2份纳米氧化镨、37份聚乙烯醇、1份丁酮酸钠盐、0.05份木质素偶联剂、4份糠醇和1份改性硅藻土作为原材料；b、从原材料中取改性芋头粉、聚乙烯醇和糠醇混合并加热至40℃，然后再依次加入改性硅藻土、丁酮酸钠盐和木质素偶联剂进行搅拌，搅拌速度为510r/min，升温至50℃，然后加入二乙烯三胺五乙酸五钠和纳米氧化镨，以610r/min速度搅拌30min，然后保温3h即可。
所述芋头粉还可经过改性处理，其改性方法为将芋头粉加入到其重量4倍且浓度为0.14g/ml硝酸铈铵水溶液中，并在35℃温度下搅拌3h以制成芋头粉浆，再将芋头粉浆进行抽滤并用水洗涤直至水中不含硝酸铈铵，得到改性芋头粉。
所述改性硅藻土的制备方法为，取硅藻土并将其加入到为其重量5倍的水中混合均匀，再加入为硅藻土重量10％的锡偶联剂，用硫酸调节pH为6，然后加入为硅藻土重量3％的桃叶珊瑚苷，混合均匀，调节温度至65℃并保温3h，再加入为硅藻土重量6％的硬脂酸搅拌均匀，然后在110℃条件下烘干至恒重，得到改性硅藻土。
所述水性聚氨酯乳液的具体制备方法为，按照重量比取80份多异氰酸酯和20份聚醚多元醇并将二者混合，然后在温度为60℃的条件下反应2.5h，再用含羧基亲水性基团的多官能基小分子进行扩链和交联，其中，多官能基小分子为二元醇、二元胺、三元醇、三元胺中的任意一种或任意一种以上的混合，任意一种以上混合时为任意配比；含羧基亲水性基团的多官能基小分子的加入量为多异氰酸酯的50％；其最后的NCO/OH摩尔比为3.5，扩链剂中[-OH]与多元醇中[-OH]摩尔比为3.5；然后调节PH值为7.5，待10分钟后冷却至40℃以下再加冰水分散，得水性聚氨酯乳液，固含量的质量百分数为25％。
以上为基础技术方案，可在以上基础上做进一步的改进：
如，所述耐水组合物的原材料中还含有0.3份氯化钙以及1份硬脂酸钙。
又如，所述制备改性硅藻土的过程中，加入锡偶联剂后，再加入为硅藻土重量3％的y-氯丙基三甲氧基硅烷，然后再用硫酸调节PH为6。

Claims (6)

1.一种高粘结力的水性聚氨酯粘合剂，其特征在于：是由耐水组合物与水性聚氨酯乳液共混制得，所述水性聚氨酯乳液的制备方法为，将羟基单体和亲水扩链剂混合升温至145-150℃，脱水，15-20min后，降温至50-70℃，加入计量的异氰酸酯单体，升温至80-90℃，保温2-2.5h即可；所述的羟基单体为聚醚多元醇、聚酯多元醇或两者的混合物；所述的亲水扩链剂为含有羧基、磺酸基团或者是磺酸盐基团的小分子多元醇，其质量占异氰酸酯单体、羟基单体、亲水扩链剂三者总质量的10.5％-12.5％；所述的异氰酸酯单体为芳香族多异氰酸酯、脂肪族多异氰酸酯或脂环族多异氰酸酯，其中控制R1值为1.2-1.8；
所述耐水组合物的制备方法包括以下步骤，a、按照重量比取5-15份芋头粉、0.5-1份二乙烯三胺五乙酸五钠、1-2份纳米氧化镨、35-37份聚乙烯醇、0.5-1份丁酮酸钠盐、0.03-0.05份木质素偶联剂、2-4份糠醇和0.5-1份改性硅藻土作为原材料；b、从原材料中取改性芋头粉、聚乙烯醇和糠醇混合并加热至35-40℃，然后再依次加入改性硅藻土、丁酮酸钠盐和木质素偶联剂进行搅拌，搅拌速度为500-510r/min，升温至45-50℃，然后加入二乙烯三胺五乙酸五钠和纳米氧化镨，以600-610r/min速度搅拌20-30min，然后保温2-3h即可。
2.如权利要求1所述的一种高粘结力的水性聚氨酯粘合剂，其特征在于：所述耐水组合物的原材料中还含有0.1-0.3份氯化钙以及0.5-1份硬脂酸钙。
3.如权利要求1所述的一种高粘结力的水性聚氨酯粘合剂，其特征在于：所述芋头粉还可经过改性处理，其改性方法为将芋头粉加入到其重量2-4倍且浓度为0.12-0.14g/ml硝酸铈铵水溶液中，并在30-35℃温度下搅拌2-3h以制成芋头粉浆，再将芋头粉浆进行抽滤并用水洗涤直至水中不含硝酸铈铵，得到改性芋头粉。
4.如权利要求1所述的一种高粘结力的水性聚氨酯粘合剂，其特征在于：所述改性硅藻土的制备方法为，取硅藻土并将其加入到为其重量3-5倍的水中混合均匀，再加入为硅藻土重量8％-10％的锡偶联剂，用硫酸调节pH为5-6，然后加入为硅藻土重量1％-3％的桃叶珊瑚苷，混合均匀，调节温度至60-65℃并保温2-3h，再加入为硅藻土重量4％-6％的硬脂酸搅拌均匀，然后在105-110℃条件下烘干至恒重，得到改性硅藻土。
5.如权利要求4所述的一种高粘结力的水性聚氨酯粘合剂，其特征在于：所述制备改性硅藻土的过程中，加入锡偶联剂后，再加入为硅藻土重量2％-3％的y-氯丙基三甲氧基硅烷，然后再用硫酸调节PH为5-6。
6.如权利要求1所述的一种高粘结力的水性聚氨酯粘合剂，其特征在于：所述水性聚氨酯乳液的具体制备方法为，按照重量比取70-80份多异氰酸酯和15-20份聚醚多元醇并将二者混合，然后在温度为55-60℃的条件下反应2-2.5h，再用含羧基亲水性基团的多官能基小分子进行扩链和交联，其中，多官能基小分子为二元醇、二元胺、三元醇、三元胺中的任意一种或任意一种以上的混合，任意一种以上混合时为任意配比；含羧基亲水性基团的多官能基小分子的加入量为多异氰酸酯的10-50％；其最后的NCO/OH摩尔比为1.0-3.5，扩链剂中[-OH]与多元醇中[-OH]摩尔比为1.0-3.5；然后调节PH值为6.5-7.5，待5-10分钟后冷却至40℃以下再加冰水分散，得水性聚氨酯乳液，固含量的质量百分数为10-25％。
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108148230A (zh) * 2017-12-13 2018-06-12 北京中选耐磨设备有限公司平顶山分公司 一种旋流器用耐冲刷橡胶内衬及其制备方法
CN111363494A (zh) * 2018-12-13 2020-07-03 赢创运营有限公司 亲水化组合物、其制备方法及其用途
CN112266297A (zh) * 2020-10-30 2021-01-26 中诚国联（河南）生物科技有限公司 含有精甲霜灵和噁霉灵的药肥颗粒剂及其应用
CN112829417A (zh) * 2021-01-04 2021-05-25 厦门市雅宝汇装饰石材有限公司 一种铝塑板及其复合加工工艺
CN115124964A (zh) * 2022-07-27 2022-09-30 北京长润化工有限公司 一种湿固化聚氨酯热熔胶及其制备方法和应用

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1876746A (zh) * 2006-07-10 2006-12-13 武汉理工大学 一种天然高分子复合水性聚氨酯粘合剂及其制备方法

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1876746A (zh) * 2006-07-10 2006-12-13 武汉理工大学 一种天然高分子复合水性聚氨酯粘合剂及其制备方法

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CN108148230A (zh) * 2017-12-13 2018-06-12 北京中选耐磨设备有限公司平顶山分公司 一种旋流器用耐冲刷橡胶内衬及其制备方法
CN111363494A (zh) * 2018-12-13 2020-07-03 赢创运营有限公司 亲水化组合物、其制备方法及其用途
CN112266297A (zh) * 2020-10-30 2021-01-26 中诚国联（河南）生物科技有限公司 含有精甲霜灵和噁霉灵的药肥颗粒剂及其应用
CN112829417A (zh) * 2021-01-04 2021-05-25 厦门市雅宝汇装饰石材有限公司 一种铝塑板及其复合加工工艺
CN115124964A (zh) * 2022-07-27 2022-09-30 北京长润化工有限公司 一种湿固化聚氨酯热熔胶及其制备方法和应用
CN115124964B (zh) * 2022-07-27 2024-03-26 北京长润化工有限公司 一种湿固化聚氨酯热熔胶及其制备方法和应用

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