玻纤网格布用有机硅改性聚丙烯酸酯乳液的制备
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摘要
玻璃纤维网格布具有耐高温、强度高、比重轻、吸湿低及延伸小等优异特性,使其在建筑方面的应用日益增多,但是玻璃纤维网格布容易受到水泥中碱性介质的浸蚀,而使网布的强度下降。通过改变玻璃纤维的化学成分可以增加其耐碱率,但这种方法会加大成本;在网布的表面涂上高分子涂层可以提高网布抗碱腐蚀和承受复杂应力的能力。目前织物涂层普遍存在强度低、易腐蚀、手感差、涂层表面易粘连等缺点,不能很好地满足工业上的要求。针对这些缺点,本文采用核壳乳液聚合的方法合成了一种玻璃纤维网格布用耐碱涂层,在丙烯酸酯壳层聚合物分子链上引入有机硅偶联剂,利用硅烷偶联剂使共聚物产生一定程度交联,从而有效地克服了传统乳液涂层中存在的耐碱性能差这一缺陷。此外,在偶联剂交联基础上,又在壳层共聚物分子链上引入一定数量的支化型有机硅MATS,进一步提高共聚物膜的表面疏水性能,降低其吸水率。论文的主要研究内容有:
通过核壳乳液聚合的方法,并引入有机硅偶联剂进行共聚,制备了具有较好的柔软性、不粘连、强度高、耐碱保留率高的乳液涂层,满足了产品工业化应用的性能要求。
研究了单体配比、核壳比、乳化剂用量、N-羟甲基丙烯酰胺及有机硅偶联剂用量等工艺参数对产品性能的影响,确定制备乳液的最佳工艺条件为:核、壳的Tg分别为-40℃和20℃,壳/核为5:4,核、壳层N-羟甲基丙烯酰胺用量分别为为1.5%和3.0%,核层KH-570用量为6.0%,制得的乳液涂层各项性能较好。
利用红外光谱(FT-IR)对共聚物结构进行了表征,确认有机硅与丙烯酸酯发生了共聚;共聚物胶膜DSC测试结果表明,有机硅的用量较大时聚合物的核和壳的Tg分别为-39℃和24℃,较理论值有所偏高;利用透射电子显微镜(TEM)观察改性聚丙烯酸酯胶膜,确认成功制备出了具有典型核壳结构的有机硅改性聚丙烯酸树脂。
合成了具有支化结构的高硅含量反应性有机硅单体甲基丙烯酰氧基丙基三(三甲基硅氧基)硅烷(MATS),并用1H-NMR、FT-IR对其结构进行了表征。以γ-甲基丙烯酰氧基丙基三甲氧基硅烷(KH-570)为交联单体以具有支化型大体积疏水基团的有机硅单体MATS为功能单体同丙烯酸酯单体进行壳层共聚,合成了稳定的交联型高硅含量硅丙乳液。MATS的加入使得有机硅改性聚丙烯酸酯聚合物的耐水性和粘结力有所提高;聚合物交联度减小,网布耐碱强度保留率降低。
Fiberglass mesh had good properties such as high temperature resistance,high strength, low density and so on. So more and more fiberglass mesh were applied in architecture,but the mesh was corrupted by alkali from cement and the strength of fiberglass was poor.By changing the chemical dosage of fiberglass mesh,the alkali resistance could be enhanced,but it made the cost too high.It could improve the abiility of alkali resistance and strength of fiberglass mesh by coating the mesh with em emulsion polymer.Most of the coating were poor strength,easy corroding,bad handle,tackiness and others defects.In this paper,an alkali resistant emulsion binder was prepared by core-shell polymerization and introducing an alkoxysilan to copolymerize with shell polymer.crosslinking agent KH-570 was used to correct these shortcomings in conventional emulsion.A stable copolymer emulsion with high MATS content was prepared by seeded semibatch emulsion polymerization.The hydroscopici -ty of the films of the latexes were tested.The branched large group of MATS can effectivel decrease the surface energy of the films,provide the copolymer excellent water-resistance. Results were as follows:
A coating binder was prepared by core-shell polymerization and an organosilicon coppler was copolymerized in it.The emulsion coating had good properties such as softness,ad -hesive resistance,high strength,alkali resistance and was satisfied with the property of product.
The performance of the coating binder is mainly influenced by the Tg of core polymer and shell polymer,the ratio of core polymer to shell polymer, the dosage of NMA,the dosage of emulsifiers,the dosage of KH-570.The best technology conditions were as follows:Tg of core polymer-45℃,Tg of shell polymer 20℃,the ratio of shell polymer to core polymer dosage of NMA in core polymer about 1.5%,dosage of KH-570 6.0%,dosage of emulsifiers 3.0%.
Alkoxysilane and acrylate were polymerized by means of FT-IR andspectra;The results of DSC tests showed the Tg of the core polymer and shell polymer were -39℃and 24℃, slightly higher than numerical value in theory for the alkoxysilan; By TEM observation,the polymer with core-shell structure was prepared.
Stable copolymer emulsions with high silicon content were prepared by seeded semibatch emulsion polymerization,in which KH-570 acted as a crosslinker and MATS [γ-methacryloxy -propyl tris-(trimethylsiloxy)silane] was used as a reactive organosilicon monomer with branched Si-O-Si groups.The properties of the copolymer latex were measured.The property of the water-resistance and adhesive joint strength were improved which crosslinking rate and alkali resistant keeping rate of fiber glass mesh were reduced.
通过核壳乳液聚合的方法,并引入有机硅偶联剂进行共聚,制备了具有较好的柔软性、不粘连、强度高、耐碱保留率高的乳液涂层,满足了产品工业化应用的性能要求。
研究了单体配比、核壳比、乳化剂用量、N-羟甲基丙烯酰胺及有机硅偶联剂用量等工艺参数对产品性能的影响,确定制备乳液的最佳工艺条件为:核、壳的Tg分别为-40℃和20℃,壳/核为5:4,核、壳层N-羟甲基丙烯酰胺用量分别为为1.5%和3.0%,核层KH-570用量为6.0%,制得的乳液涂层各项性能较好。
利用红外光谱(FT-IR)对共聚物结构进行了表征,确认有机硅与丙烯酸酯发生了共聚;共聚物胶膜DSC测试结果表明,有机硅的用量较大时聚合物的核和壳的Tg分别为-39℃和24℃,较理论值有所偏高;利用透射电子显微镜(TEM)观察改性聚丙烯酸酯胶膜,确认成功制备出了具有典型核壳结构的有机硅改性聚丙烯酸树脂。
合成了具有支化结构的高硅含量反应性有机硅单体甲基丙烯酰氧基丙基三(三甲基硅氧基)硅烷(MATS),并用1H-NMR、FT-IR对其结构进行了表征。以γ-甲基丙烯酰氧基丙基三甲氧基硅烷(KH-570)为交联单体以具有支化型大体积疏水基团的有机硅单体MATS为功能单体同丙烯酸酯单体进行壳层共聚,合成了稳定的交联型高硅含量硅丙乳液。MATS的加入使得有机硅改性聚丙烯酸酯聚合物的耐水性和粘结力有所提高;聚合物交联度减小,网布耐碱强度保留率降低。
Fiberglass mesh had good properties such as high temperature resistance,high strength, low density and so on. So more and more fiberglass mesh were applied in architecture,but the mesh was corrupted by alkali from cement and the strength of fiberglass was poor.By changing the chemical dosage of fiberglass mesh,the alkali resistance could be enhanced,but it made the cost too high.It could improve the abiility of alkali resistance and strength of fiberglass mesh by coating the mesh with em emulsion polymer.Most of the coating were poor strength,easy corroding,bad handle,tackiness and others defects.In this paper,an alkali resistant emulsion binder was prepared by core-shell polymerization and introducing an alkoxysilan to copolymerize with shell polymer.crosslinking agent KH-570 was used to correct these shortcomings in conventional emulsion.A stable copolymer emulsion with high MATS content was prepared by seeded semibatch emulsion polymerization.The hydroscopici -ty of the films of the latexes were tested.The branched large group of MATS can effectivel decrease the surface energy of the films,provide the copolymer excellent water-resistance. Results were as follows:
A coating binder was prepared by core-shell polymerization and an organosilicon coppler was copolymerized in it.The emulsion coating had good properties such as softness,ad -hesive resistance,high strength,alkali resistance and was satisfied with the property of product.
The performance of the coating binder is mainly influenced by the Tg of core polymer and shell polymer,the ratio of core polymer to shell polymer, the dosage of NMA,the dosage of emulsifiers,the dosage of KH-570.The best technology conditions were as follows:Tg of core polymer-45℃,Tg of shell polymer 20℃,the ratio of shell polymer to core polymer dosage of NMA in core polymer about 1.5%,dosage of KH-570 6.0%,dosage of emulsifiers 3.0%.
Alkoxysilane and acrylate were polymerized by means of FT-IR andspectra;The results of DSC tests showed the Tg of the core polymer and shell polymer were -39℃and 24℃, slightly higher than numerical value in theory for the alkoxysilan; By TEM observation,the polymer with core-shell structure was prepared.
Stable copolymer emulsions with high silicon content were prepared by seeded semibatch emulsion polymerization,in which KH-570 acted as a crosslinker and MATS [γ-methacryloxy -propyl tris-(trimethylsiloxy)silane] was used as a reactive organosilicon monomer with branched Si-O-Si groups.The properties of the copolymer latex were measured.The property of the water-resistance and adhesive joint strength were improved which crosslinking rate and alkali resistant keeping rate of fiber glass mesh were reduced.
引文
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2.姜肇中,高建枢,王惟峰.玻璃纤维的发展和应用[J].玻璃钢/复合材料,1997, 6:5—10
3.刘泽黎.耐碱玻璃纤维制品的研制[J].玻璃纤维,1997,6:9—12
4.边天佑.耐碱玻璃纤维和GRC制品的现状与发展趋势[J].玻璃纤维,1998,5:16—20
5.刘泽黎.耐碱玻璃纤维制品的研制[J].玻璃纤维,1997,6:9—12
6. H.瓦尔森,C.A.芬奇.合成聚合物乳液的应用(第3卷)[M].曹同玉等译.北京:化学工业出版社,2004:179—214
7.徐祖顺,易吕凤,肖卫东.织物用胶粘剂及粘接技术[M].北京:化学工业出版社,2004
8. Philip L Schell.Polyamide and acrylic polymer coated glass fiber reinforcements, reinforc -ed polymeric composites and a method of reinforcing a polymeric material[P].US580431 3,1998
9. Mankell Kurt O,Noone Michael J,Tessari Domenic J.Hydrophobic, anti-microbial insulati -on products and a hydrophobic, anti-microbial coating composition for preparing the sa -me[P].W049981 A2,2002
10. Momotake,Hiroyuki,Kadota Toshiya.Glass fiber for reinforcing rubber[P].JP244785,2004
11.肖利明,赵建国,杨永社.新型玻璃纤维浸润剂合成技术[J].河北师范大学学报,1996,20 (2):72—75
12. Owens-Corning Fiberglass Coip.Method and compositions for coating glass fibers[P].GB 892091,1960
13. Helbing Clarence.Fiber glass binder compositions and process there of[P].W060043,1999
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