室温自交联核壳结构丙烯酸酯乳液的合成及应用研究
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摘要
聚丙烯酸酯乳液是一类容易制备、性能忧良、应用广泛且符合环保要求的聚合物乳液。本论文采用核壳乳液聚合法制得了带有活泼酮基的硬核软壳结构的自交联丙烯酸酯乳液,利用酮基与酰肼基的反应,进一步得到室温固化的胶膜。为了进一步提高乳液的综合性能,采用多重交联体系对乳液进行改性。试验过程中考察了聚合条件、乳化剂、交联体系及交联单体用量、固化条件等对乳液性能的影响。将该乳液成功应用于粘结经酚醛树脂处理过的波纹纸,并考察了聚合物玻璃化温度、有机硅氧烷单体种类及用量、成膜助剂种类及用量等对乳液胶黏剂耐沸水性能及蒸煮后粘结强度的影响,得出了最佳的工艺及配方;论文在设计乳胶粒结构及乳液交联体系方面具有一定的创新性。
合成试验表明,核壳型聚合物适宜的聚合条件是:复合乳化剂用量为2～2.8wt%,且m(CO-436)︰m(CO-630)︰m(COPS-1)= 1～1.5︰0.8～1︰0.2～0.3;DDM用量为0.1～0.2wt%;采用先热引发后氧化还原的双重引发剂体系且反应期APS为0.4wt%,后处理期THBP为0.1wt%、SFS为0.1wt%;AA用量为1～3wt%,m(GMA +HEA)=2～3wt%;DAAM全加在壳层,且m(DAAM)=1.5～2wt%、m(ADH)/m(DAAM)=0.8～1,核壳比为4/6～6/4;此时所得乳液固含量及转化率高,胶膜交联度高、聚合物分子量分布宽,胶膜吸水率低,乳液性能最优。
采用FTIR、DSC、TEM等方法对聚合物乳液进行了表征,运用粒度分析仪测试了乳胶粒粒径及其分布,并通过GPC测试聚合物分子量及其分布。FTIR图谱表示酮羰基与酰肼基发生交联反应生成了腙;DSC曲线表明聚合物具有两个明显的玻璃化转变温度,分别为18.2℃和44.5℃;TEM照片显示乳胶粒具有明显的核壳双层结构。
应用试验表明,采用不同种类的有机硅氧烷单体对乳液胶黏剂进行改性均能有效提高胶黏剂的耐沸水性能,但C-1757的用量(4wt%)是Z-6040(0.5wt%)的8倍左右时才能达到相同的改性效果;成膜助剂能改善乳液胶黏剂对基材的渗透性,进而改善蒸煮后胶膜的起泡问题;自制乳液与市场同类产品美国Rohm & Haas公司研制的AC-261P纯丙乳液性能相当,但自制乳液吸水率更低,蒸煮后胶膜起泡更少,市场应用前景巨大。
Polyacrylate emulsion is known as an environmental-friendly emulsion with excellentperformance, which is easy to prepare and widely applicable. Self-crosslinking acrylicemulsion with hard core-soft shell structure and active keto-carbonyl group was synthesizedby core-shell emulsion polymerization, and film was cured at ambient temperature thoughreaction of ketone and hydrazide. To further improve comprehensive performances,multi-crosslinking system was used to modify emulsion. Various factors influential foremulsion performance were discussed during the experiment such as polymerizationconditions, crosslinking system and cross-linking monomer dosage, curing conditions, etc.Resultant emulsion was applied to bond phenolic resin-coated corrugated paper. Severalfactors were found to be influential for boiling water-resistance properties and adhesion of theemulsion after being boiled, such as polymer glass transition temperature, type and amount oforganic siloxane monomer, type and amount of film forming additive, etc. Optimum processand formula were obtained. Some innovative ideas in latex structure design and crosslinkingsystem of emulsion are proposed in this paper.
As is indicated from experimental results, optimum polymerization condition wasdetermined as follows: hybrid emulsifier constitutes of m(CO-436), m(CO-630) andm(COPS-1) at a ratio of 1~1.5︰0.8~1︰0.2~0.3, at a total dosage of 2~2.8 wt%. Dosage ofDDM is 0.1~0.2 wt%. A combination of thermal initiation (0.4 wt% of APS) and redoxinitiator system (0.1 wt% of THBP, 0.1 wt% of SFS) was adopted to initiate thepolymerization. Dosage of AA and functional monomer mixture (GMA+HEA) were set at1~3wt% and 2~3wt% respectively. DAAM were all added to the shell, at dosage of 1.5~2wt%. m(ADH)/ m(DAAM) ratio was controlled at 0.8~1, m(core)/ m(shell) ratio is designedat 4/6~6/4. All weight ratios above are based on total monomer content. At conditions above,emulsions with high solid content and conversion rate, as well as highlycross linked film withwide molecular weight distribution and low water absorption could be prepared.
Several testing methods such as FTIR, DSC and TEM were adopted to characterize theemulsion. Emulsion particle size and molecular weight distribution were determined byparticle size analyzer and GPC respectively. FTIR spectra confirmed the crosslink reaction between ketone and hydrazino group. Two glass transition temperatures at 18.2℃and 44.5℃could be clearly observed in DSC curve of the resultant emulsion sample. Obviouscore-shell structure was shown in TEM images.
It is suggested from application experiments that different kinds of organic siloxanemonomer were used to modify emulsion for improving boiling water-resistance. To achieveequivalent modification effect, C-1757 (4wt %) has to be added at dosage of eight times ofZ-6040(4wt %). Film forming additive could improve the permeability of the latex onsubstrate, and also help alleviate blistering of film during boiling water. As is compared withRohm & Haas AC-261P, self-prepared latex exhibit better performances such as lower waterabsorption and slighter blistering, thus having a huge potential application prospect.
合成试验表明,核壳型聚合物适宜的聚合条件是:复合乳化剂用量为2～2.8wt%,且m(CO-436)︰m(CO-630)︰m(COPS-1)= 1～1.5︰0.8～1︰0.2～0.3;DDM用量为0.1～0.2wt%;采用先热引发后氧化还原的双重引发剂体系且反应期APS为0.4wt%,后处理期THBP为0.1wt%、SFS为0.1wt%;AA用量为1～3wt%,m(GMA +HEA)=2～3wt%;DAAM全加在壳层,且m(DAAM)=1.5～2wt%、m(ADH)/m(DAAM)=0.8～1,核壳比为4/6～6/4;此时所得乳液固含量及转化率高,胶膜交联度高、聚合物分子量分布宽,胶膜吸水率低,乳液性能最优。
采用FTIR、DSC、TEM等方法对聚合物乳液进行了表征,运用粒度分析仪测试了乳胶粒粒径及其分布,并通过GPC测试聚合物分子量及其分布。FTIR图谱表示酮羰基与酰肼基发生交联反应生成了腙;DSC曲线表明聚合物具有两个明显的玻璃化转变温度,分别为18.2℃和44.5℃;TEM照片显示乳胶粒具有明显的核壳双层结构。
应用试验表明,采用不同种类的有机硅氧烷单体对乳液胶黏剂进行改性均能有效提高胶黏剂的耐沸水性能,但C-1757的用量(4wt%)是Z-6040(0.5wt%)的8倍左右时才能达到相同的改性效果;成膜助剂能改善乳液胶黏剂对基材的渗透性,进而改善蒸煮后胶膜的起泡问题;自制乳液与市场同类产品美国Rohm & Haas公司研制的AC-261P纯丙乳液性能相当,但自制乳液吸水率更低,蒸煮后胶膜起泡更少,市场应用前景巨大。
Polyacrylate emulsion is known as an environmental-friendly emulsion with excellentperformance, which is easy to prepare and widely applicable. Self-crosslinking acrylicemulsion with hard core-soft shell structure and active keto-carbonyl group was synthesizedby core-shell emulsion polymerization, and film was cured at ambient temperature thoughreaction of ketone and hydrazide. To further improve comprehensive performances,multi-crosslinking system was used to modify emulsion. Various factors influential foremulsion performance were discussed during the experiment such as polymerizationconditions, crosslinking system and cross-linking monomer dosage, curing conditions, etc.Resultant emulsion was applied to bond phenolic resin-coated corrugated paper. Severalfactors were found to be influential for boiling water-resistance properties and adhesion of theemulsion after being boiled, such as polymer glass transition temperature, type and amount oforganic siloxane monomer, type and amount of film forming additive, etc. Optimum processand formula were obtained. Some innovative ideas in latex structure design and crosslinkingsystem of emulsion are proposed in this paper.
As is indicated from experimental results, optimum polymerization condition wasdetermined as follows: hybrid emulsifier constitutes of m(CO-436), m(CO-630) andm(COPS-1) at a ratio of 1~1.5︰0.8~1︰0.2~0.3, at a total dosage of 2~2.8 wt%. Dosage ofDDM is 0.1~0.2 wt%. A combination of thermal initiation (0.4 wt% of APS) and redoxinitiator system (0.1 wt% of THBP, 0.1 wt% of SFS) was adopted to initiate thepolymerization. Dosage of AA and functional monomer mixture (GMA+HEA) were set at1~3wt% and 2~3wt% respectively. DAAM were all added to the shell, at dosage of 1.5~2wt%. m(ADH)/ m(DAAM) ratio was controlled at 0.8~1, m(core)/ m(shell) ratio is designedat 4/6~6/4. All weight ratios above are based on total monomer content. At conditions above,emulsions with high solid content and conversion rate, as well as highlycross linked film withwide molecular weight distribution and low water absorption could be prepared.
Several testing methods such as FTIR, DSC and TEM were adopted to characterize theemulsion. Emulsion particle size and molecular weight distribution were determined byparticle size analyzer and GPC respectively. FTIR spectra confirmed the crosslink reaction between ketone and hydrazino group. Two glass transition temperatures at 18.2℃and 44.5℃could be clearly observed in DSC curve of the resultant emulsion sample. Obviouscore-shell structure was shown in TEM images.
It is suggested from application experiments that different kinds of organic siloxanemonomer were used to modify emulsion for improving boiling water-resistance. To achieveequivalent modification effect, C-1757 (4wt %) has to be added at dosage of eight times ofZ-6040(4wt %). Film forming additive could improve the permeability of the latex onsubstrate, and also help alleviate blistering of film during boiling water. As is compared withRohm & Haas AC-261P, self-prepared latex exhibit better performances such as lower waterabsorption and slighter blistering, thus having a huge potential application prospect.
引文
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