环氧树脂/丙烯酸树脂/纳米SiO_2复合型胶粘剂的研究
摘要
环氧树脂做为国内外高品级涂附磨具的胶粘剂，常用来制备透明耐水砂纸、超薄涂层等涂附产品。它的性能优劣将在很大程度上影响涂附磨具的质量。环氧树脂胶粘剂具有粘接强度高、耐热、收缩率低等优点，并且还有优良的耐有机溶剂、耐碱性能，而现有环氧树脂胶粘剂存在透明性较差、耐水性不佳、涂附工艺实施困难，混溶性较差、脆性较大等缺点，严重影响了透明耐水砂纸的生产和使用。国内对这方面有针对性的研究非常缺乏，所以本实验以涂附磨具的环氧树脂胶粘剂为研究对象，通过理论研究和具体实验，提高环氧树脂的透明性、耐水性、耐热性、耐磨性，从而制备一种透明、易混合的高性能环氧树脂胶粘剂。
本文针对环氧树脂目前存在的性能缺点，主要从两个方面进行改性研究。首先，通过溶液聚合，合成丙烯酸树脂Poly(MMA／BA／MAA)，通过Poly(MMA／BA／MAA)中羧基与环氧基的化学反应，将它作为环氧树脂的大分子固化剂，提高环氧树脂的透明性、耐水性、减少脆性。在实验中分别对单体配比、引发剂、溶剂、升温速度等因素进行具体实验分析，并对EP／Poly(MMA／BA／MAA)胶粘剂的粘结性能、结构、热性能进行了测试。
通过红外光谱分析证明了Poly(MMA／BA／MAA)与环氧树脂确实化学反应，形成了交联固化体系。丙烯酸树脂中MAA中羧基的极性影响了聚合物溶液的均一性，所以MAA：MMA+BA的摩尔比小于1：7；MMA和BA的配比影响了Poly(MMA／BA／MAA)链段的“软硬”程度和极性，影响粘结强度。随MMA含量的增加，对极性较大的铁片的粘结强度增加而对极性较弱的铝片的粘结强度减小并出现粘结强度的极大值；对极性较弱的基体以MMA：BA：MAA=3：5：1的配比为最好。引发剂浓度和单体浓度影响聚合反应速度，引发剂的最佳用量在1.5％，单体浓度在45％，溶剂以甲苯和二甲苯的混合溶剂为最好，这种混合溶剂具有
对丙烯酸树脂单体和聚合物良好的溶解性，能保证胶粘剂有良好的流
平性和挥发性。以EP/Poly(MMA/BA/拟A)胶粘剂的耐水砂纸对铝材的
磨削量比国家标准提高了29%，耐热性提高了15℃。
第二步，将纳米5102与EP/Poly(MMA/BA/MAA)树脂共混，制备复
合胶粘剂进行研究，对纳米5102、偶联剂、纳米粒子分散性对复合胶
粘剂粘结性能的影响进行了实验研究，同时实验测试了复合胶粘剂的
热性能和以该胶粘剂制备的耐水砂纸磨削性能。
通过分析偶联剂KH一550对纳米材料的分散性影响，从理论上分析
论证了纳米粒子的分散状态:以共混方式制备的纳米复合物中纳米粒
子并不是真正分散成单颗粒状态，而是以第二聚集体的形式存在于聚
合物体系中，但这种松散聚集状态对环氧树脂仍起到了很好的改性效
果。对偶联剂和纳米5102用量的配合提出了自己的观点:偶联剂对纳
米粒子起到了强化分散和稳定作用，但是随纳米5102用量变化，纳米
复合胶粘剂粘结性能极大值处的偶联剂用量也在变化，而不是一成不
变的。在偶联剂用量不超过4%时纳米5102用量3%粘结强度最好，此时
偶联剂主要以化学偶联作用附着在纳米材料表面，在偶联剂用量超过
4%时纳米5102用量增加到5%，此时偶联剂还有阻隔纳米粒子聚集的作
用。通过测试，这种EP/Poly(MMA邝A/MAA)/nln一510:胶粘剂的耐热性比
纯环氧树脂体系提高了63℃，对铝棒的磨削量比国家标准提高了42%。
本实验制备的EP/P oly(M拟/BA/MAA)/nm一5 1 02复合型胶粘剂，通过
实验证明具有优异的透明性、磨削性、耐水性、耐热性和粘结强度，
与现有的耐水砂纸相比，明显超出原有的相关性能，达到了实验的预
期目的。
In this paper, the modification ways of epoxy resin adhesive in glassy waterproof abrasive paper have studied. Epoxy resin adhesive has many good properties: high shear strength, small shrinkage, solvent resistance, resistance of alkali and so on. But epoxy adhesive often has low clarity, bad water resistence, bad coating technique, difficulty of mixing because of using low-molecular weight PA or polyethylene polyamine as curing agent. Then the abrasive paper has bad abrasive properties. Now the modification ways of epoxy resin are studied in this paper to improve abrasive properties, clarity, water resistance and to make mixing process easy.
There are two ways which are used in this paper to modify epoxy adhesive together. At first, acrylic resin is composed ?Poly(MMA/BA/MAA). Because -COOH group in Poly(MMA/BA/MAA) can react with epoxy group in epoxy resin, epoxy resin can be cured and modified by Poly(MMA/BA/MAA). During this period, it is studied that synthetic reaction speed and conversion change with monomer concentration, monomer proportion, initiator, solvent selection, temperature.
It is found that MAA can effect the intermiscibility of copolymer and solvent. When MAA content is more than 1:7(MAA: MMA+BA =1:7), copolymer became to separate from the solution and the solution became cloudy because of polymer polarity increasing. Synthetic reaction speed increases with initiator content and monomer content. From the experiment we have get the conclusion: "the best content is: initiator 1.5% and monomer 45%. There are four different solvents which are used to find the suitable intermiscibility and volatility on copolymer. Finally toluene and xylene mixture is the best.
Infra-red absorption spectroscope is used to study copolymer's structure, thermal instrument to study copolymer's thermal properties, and measure the sample's shear strength. In the experiment, it is found that shear strength curve go up with MMA content increasing when using iron sample, and shear strength curve go up at first and then go down at MAA proportion of 3:5(MMA: BA) when using aluminium sample. It is MAA content of 1:8 that shear strength has the biggest value. The essential reason of this phenomenon is that copolymer and sample have different polarity when MAA content have changed. From TG curve of EP/Poly(MMA/BA/MAA) and EP we have found that the epoxy resin adhesive modified with copolymer have improved its temperature of decomposition of 15?
At second, nm-SiO surface is modified by supersonic wave to separate nm-SiOj accumulation and coupling agent to keep separation. In this process, the relationship between shear strength and nm-SiCh proportion, coupling agent proportion is studied, including the abrasive paper's abrasive property and TG curve of EP/Poly(MMA/BA/MAA)/nm-SiO2 adhesive .
There are two curves of shear strength which one uses coupling agent KH-550 and the other does not use. The curve which use coupling agent has increased much higher than the curve which not use coupling agent. Then the effect of stability on nm-SiO surface treatment is studied. It can be seen that coupling agent KH-550 is benefit for stability of nm-SiO and coupling agent have the best concentration because of the curve having the biggest value of shear strength.
When effect of shear strength on nm-SiO2 content is studied, it is found that the curve also have got a biggest pot. So the conclusion is: when coupling agent content is 2% or 4% and nm-SiO content is 3% the shear strength curve has the biggest value, when coupling agent content is 6%
or 8% and nm-SiO content is 5% the shear strength curve has the biggest value.
In order to study this phenomenon, a theory fomula is used to calculate the value of KH-550/nm-SiO. It is 70.5.It is much bigger than factual value. So it can be said that nm-SiOj is separated in small accumulate which is not same as the structure of not having surface treatment.
The abrasive weight experiment shows that the paper has improved its abrasive property with using EP/Poly(MMA/BA/MAA) or EP/Poly(MMA/BA/MAA)/n
本文针对环氧树脂目前存在的性能缺点，主要从两个方面进行改性研究。首先，通过溶液聚合，合成丙烯酸树脂Poly(MMA／BA／MAA)，通过Poly(MMA／BA／MAA)中羧基与环氧基的化学反应，将它作为环氧树脂的大分子固化剂，提高环氧树脂的透明性、耐水性、减少脆性。在实验中分别对单体配比、引发剂、溶剂、升温速度等因素进行具体实验分析，并对EP／Poly(MMA／BA／MAA)胶粘剂的粘结性能、结构、热性能进行了测试。
通过红外光谱分析证明了Poly(MMA／BA／MAA)与环氧树脂确实化学反应，形成了交联固化体系。丙烯酸树脂中MAA中羧基的极性影响了聚合物溶液的均一性，所以MAA：MMA+BA的摩尔比小于1：7；MMA和BA的配比影响了Poly(MMA／BA／MAA)链段的“软硬”程度和极性，影响粘结强度。随MMA含量的增加，对极性较大的铁片的粘结强度增加而对极性较弱的铝片的粘结强度减小并出现粘结强度的极大值；对极性较弱的基体以MMA：BA：MAA=3：5：1的配比为最好。引发剂浓度和单体浓度影响聚合反应速度，引发剂的最佳用量在1.5％，单体浓度在45％，溶剂以甲苯和二甲苯的混合溶剂为最好，这种混合溶剂具有
对丙烯酸树脂单体和聚合物良好的溶解性，能保证胶粘剂有良好的流
平性和挥发性。以EP/Poly(MMA/BA/拟A)胶粘剂的耐水砂纸对铝材的
磨削量比国家标准提高了29%，耐热性提高了15℃。
第二步，将纳米5102与EP/Poly(MMA/BA/MAA)树脂共混，制备复
合胶粘剂进行研究，对纳米5102、偶联剂、纳米粒子分散性对复合胶
粘剂粘结性能的影响进行了实验研究，同时实验测试了复合胶粘剂的
热性能和以该胶粘剂制备的耐水砂纸磨削性能。
通过分析偶联剂KH一550对纳米材料的分散性影响，从理论上分析
论证了纳米粒子的分散状态:以共混方式制备的纳米复合物中纳米粒
子并不是真正分散成单颗粒状态，而是以第二聚集体的形式存在于聚
合物体系中，但这种松散聚集状态对环氧树脂仍起到了很好的改性效
果。对偶联剂和纳米5102用量的配合提出了自己的观点:偶联剂对纳
米粒子起到了强化分散和稳定作用，但是随纳米5102用量变化，纳米
复合胶粘剂粘结性能极大值处的偶联剂用量也在变化，而不是一成不
变的。在偶联剂用量不超过4%时纳米5102用量3%粘结强度最好，此时
偶联剂主要以化学偶联作用附着在纳米材料表面，在偶联剂用量超过
4%时纳米5102用量增加到5%，此时偶联剂还有阻隔纳米粒子聚集的作
用。通过测试，这种EP/Poly(MMA邝A/MAA)/nln一510:胶粘剂的耐热性比
纯环氧树脂体系提高了63℃，对铝棒的磨削量比国家标准提高了42%。
本实验制备的EP/P oly(M拟/BA/MAA)/nm一5 1 02复合型胶粘剂，通过
实验证明具有优异的透明性、磨削性、耐水性、耐热性和粘结强度，
与现有的耐水砂纸相比，明显超出原有的相关性能，达到了实验的预
期目的。
In this paper, the modification ways of epoxy resin adhesive in glassy waterproof abrasive paper have studied. Epoxy resin adhesive has many good properties: high shear strength, small shrinkage, solvent resistance, resistance of alkali and so on. But epoxy adhesive often has low clarity, bad water resistence, bad coating technique, difficulty of mixing because of using low-molecular weight PA or polyethylene polyamine as curing agent. Then the abrasive paper has bad abrasive properties. Now the modification ways of epoxy resin are studied in this paper to improve abrasive properties, clarity, water resistance and to make mixing process easy.
There are two ways which are used in this paper to modify epoxy adhesive together. At first, acrylic resin is composed ?Poly(MMA/BA/MAA). Because -COOH group in Poly(MMA/BA/MAA) can react with epoxy group in epoxy resin, epoxy resin can be cured and modified by Poly(MMA/BA/MAA). During this period, it is studied that synthetic reaction speed and conversion change with monomer concentration, monomer proportion, initiator, solvent selection, temperature.
It is found that MAA can effect the intermiscibility of copolymer and solvent. When MAA content is more than 1:7(MAA: MMA+BA =1:7), copolymer became to separate from the solution and the solution became cloudy because of polymer polarity increasing. Synthetic reaction speed increases with initiator content and monomer content. From the experiment we have get the conclusion: "the best content is: initiator 1.5% and monomer 45%. There are four different solvents which are used to find the suitable intermiscibility and volatility on copolymer. Finally toluene and xylene mixture is the best.
Infra-red absorption spectroscope is used to study copolymer's structure, thermal instrument to study copolymer's thermal properties, and measure the sample's shear strength. In the experiment, it is found that shear strength curve go up with MMA content increasing when using iron sample, and shear strength curve go up at first and then go down at MAA proportion of 3:5(MMA: BA) when using aluminium sample. It is MAA content of 1:8 that shear strength has the biggest value. The essential reason of this phenomenon is that copolymer and sample have different polarity when MAA content have changed. From TG curve of EP/Poly(MMA/BA/MAA) and EP we have found that the epoxy resin adhesive modified with copolymer have improved its temperature of decomposition of 15?
At second, nm-SiO surface is modified by supersonic wave to separate nm-SiOj accumulation and coupling agent to keep separation. In this process, the relationship between shear strength and nm-SiCh proportion, coupling agent proportion is studied, including the abrasive paper's abrasive property and TG curve of EP/Poly(MMA/BA/MAA)/nm-SiO2 adhesive .
There are two curves of shear strength which one uses coupling agent KH-550 and the other does not use. The curve which use coupling agent has increased much higher than the curve which not use coupling agent. Then the effect of stability on nm-SiO surface treatment is studied. It can be seen that coupling agent KH-550 is benefit for stability of nm-SiO and coupling agent have the best concentration because of the curve having the biggest value of shear strength.
When effect of shear strength on nm-SiO2 content is studied, it is found that the curve also have got a biggest pot. So the conclusion is: when coupling agent content is 2% or 4% and nm-SiO content is 3% the shear strength curve has the biggest value, when coupling agent content is 6%
or 8% and nm-SiO content is 5% the shear strength curve has the biggest value.
In order to study this phenomenon, a theory fomula is used to calculate the value of KH-550/nm-SiO. It is 70.5.It is much bigger than factual value. So it can be said that nm-SiOj is separated in small accumulate which is not same as the structure of not having surface treatment.
The abrasive weight experiment shows that the paper has improved its abrasive property with using EP/Poly(MMA/BA/MAA) or EP/Poly(MMA/BA/MAA)/n
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