苯乙烯丙烯酸化学改性醇酸树脂工艺优化研究

采用顺酐代替部分苯酐合成基础醇酸树脂，有利于后续的接枝改性，对合成工艺进行了优化研究；采用后苯乙烯化法，以大部分苯乙烯和少量丙烯酸及其酯类混合单体对顺酐基础醇酸树脂进行了化学改性，进行了改性工艺优化研究，确定了最佳工艺条件，并对改性机理进行了探讨。     

Factors influencing the stability and film properties of acrylic/alkyd water-reducible hybrid systems using a response surface technique

Acrylic-grafted-alkyd resins were prepared by free radical chemistry. Long, medium, and short oil alkyds were prepared using soybean oil, glycerol, phthalic anhydride (PA), and tetrahydrophthalic anhydride (THPA) and used as the alkyd phase. Acrylic co-monomer formulas containing methyl methacrylate (MMA), butyl acrylate (BA), methacrylic acid (MAA), and vinyl trimethoxysilane (VTMS) were polymerized in the presence of the different alkyds using 2,2′-azobisisobutyronitrile (AIBN) as the initiator to obtain the final grafted structures. Design of experiments was used to understand how different variables in the synthesis of the acrylated-alkyds affect the film performance. A Box–Behnkin design was used, varying the oil length of the alkyd phase, the degree of unsaturation in the polyester backbone, and acrylic to alkyd ratio. Acrylic–alkyd hybrid resins were reduced with an amine/water mixture. The hydrolytic stability of hybrid alkyd dispersed in water was evaluated. Cured films were prepared and basic coatings properties were also evaluated. It was found that the oil length of the alkyd is the most dominant factor for final coatings properties of the resins. The hydrolytic stability was dependent on the acrylic to alkyd ratio. The oil length of the alkyd backbone had a minimal effect on stability of the resin and film performance.     

水性苯丙共聚物改性醇酸树脂的制备及性能

以油酸、季戊四醇、邻苯二甲酸酐、苯甲酸为原料，采用丙二醇甲醚醋酸酯（PMA）为溶剂合成了基体醇酸树脂；用过氧化苯甲酰、过氧化苯甲酸叔丁酯双引发剂、分步引发烯类单体共聚，制备了一种苯丙烯树脂，并对醇酸树脂改性制得了水性醇酸树脂。考察了不同油度对水性醇酸树脂结构与性能的影响。通过FTIR、TGA、DLS分别对树脂的结构、稳定性和乳液性能进行了表征。测定了树脂的漆膜性能，包括耐水性、表干时间、硬度、电化学性能。结果表明，n（油酸）∶n（季戊四醇）∶n(邻苯二甲酸酐)∶n（苯甲酸）=1∶1∶1∶0.3，油度为47%时，聚合物乳液粒径为74.4 nm，PDI为0.262，胶膜的吸水率为14.5%，接触角为70.87?，有较好的耐水性。改性醇酸树脂的表干时间缩短为0.5 h，实干时间缩短为24 h，硬度达HB。     

Synthesis and properties of Ricinodendron heudelotii oil based hybrid alkyd–acrylate latexes via miniemulsion polymerization

Ricinodendron heudelotii (R. heudelotii) oil-based novel alkyd–acrylate hybrid latexes were synthesized as waterborne environmental friendly binder for coating systems. Long oil length alkyd resins were synthesized by two-stage alcoholysis–polyesterification reaction with variation of phthalic anhydride (PA) and maleic anhydride (MAH) proportion and further polymerized with methyl methacrylate (MMA) and butyl acrylate (BA) via miniemulsion polymerization. It is found that increasing the proportion of MAH in the alkyd resin enhances monomer conversion and total solid content of the hybrid latex. The latexes exhibited fast drying time at room temperature. The prepared latexes showed a bimodal particle size distribution motion. It is shown that the increase in MAH content in the alkyd moiety has a significant effect on the improved performance properties of hybrid latexes as well as latex films including, fast drying time at room temperature, highly crosslinked network, improved mechanical characteristics before and after UV exposure, better shore A hardness and hydrophobic water repellency contact angle. The results suggested that, the R. heudelotii oil-based alkyd–acrylate hybrid latexes have potential improved properties for manufacture of waterborne coatings and are usable as an alternative to petroleum-based coating systems.     

环氧改性水性醇酸树脂的制备

首先以亚麻酸、环氧树脂为原料制备环氧酯,再将环氧酯作为多元醇与亚麻酸、三羟甲基丙烷、苯酐、偏酐等进行酯化反应,经胺中和后得到一种环氧改性水性醇酸树脂,采用红外光谱对产物结构进行了表征并对其粒径分布作了分析,研究表明:醇酸树脂油度50%,终点酸值50～60,选用环氧树脂E-20与亚麻酸、三羟甲基丙烷、苯酐采用溶剂法反应,之后加入偏苯三酸酐采用熔融法反应可以得到干性好、硬度高、稳定性、水分散性和耐水性优良的环氧改性水性醇酸树脂。     

水溶性单体共聚法制备无皂苯丙乳液的研究

以苯乙烯(St)、丙烯酸(AA)、甲基丙烯酸甲酯(MMA)和丙烯酸丁酯(BA)为共聚单体,制备了无皂苯丙乳液;然后以AA含量、中和度、引发剂含量和软/硬单体配比等为试验因素,以乳液稳定性和粒径为考核指标,采用单因素试验法优选出制备无皂苯丙乳液的最佳工艺条件。结果表明:当w(引发剂)=1.2%和w(AA)=4.5%(均相对于单体总质量而言)、中和度为0.8、m(BA)∶m(St+MMA)=4∶6和反应温度为78℃时,可制得粒径为纳米级的高固含量稳定乳液。     

水溶性单体类型对BA-MMA-St微皂乳液聚合的影响

通过与水溶性单体、甲基丙烯酸（MAA）、丙烯酸（AA）、N-羟甲基丙烯酰胺（N-MA）、丙烯酰胺（AM）共聚，实现了BA-MMA-St的微皂乳液聚合。考察了水溶性单体（羧酸类单体、非离子水溶性单体）对微皂乳液聚合稳定性和化学稳定性的影响。实验结果表明：为了使水溶性单体键合在乳胶粒表面，实现乳胶粒的稳定化，其亲水性参数I／O应为3～5，水溶性单体还必须具有良好的聚合稳定性及与主单体良好的共聚性。     

水性上光油用苯丙共聚乳液的合成及性能表征

以苯乙烯(St)、丙烯酸丁酯(BA)和马来酸酐(MAH)为共聚单体,过硫酸钾(KPS)为引发剂,十二烷基硫酸钠(SDS)/壬基酚聚氧乙烯醚(OP-10)为复合乳化剂,采用半连续加料的乳液聚合法合成出一种水性上光油用苯丙共聚乳液。考察了玻璃化转变温度(Tg)、引发剂和乳化剂含量等对该乳液单体转化率、平均粒径、黏度和表干时间等影响,并对该乳液的热稳定性能进行了研究。结果表明:当w(引发剂)=0.6%、w(复合乳化剂)=1.2%和m(MAH)∶m(BA)∶m(St)=4.6∶36.3∶50.5时,该乳液具有良好的综合性能,完全满足水性上光油的使用要求,并且可在高温环境中使用。     

苯乙烯改性醇酸树脂合成研究

研究了采用顺丁烯二酸酐衍生物、苯乙烯与基体醇酸树脂反应制备苯乙烯改性醇酸树脂的方法、工艺条件和产品性能。该树脂涂膜快干、硬度高、耐水性好 ,同时具有与醇酸树脂相似的外观和耐冲击性能。     

Emulsion Semi-Batch Terpolymerization Process Using Hybrid Emulsifiers for Synthesizing New Emulsion Pressure Sensitive Adhesives (EPSAs)

In order to obtain a suitable formulation of designing direct synthesis of acrylic latexes to be used as emulsion pressure sensitive adhesives (EPSA), having high shear resistance together with high peel strength and tack, free radical emulsion polymerization of hard monomers, such as styrene (St), vinyl acetate monomer (VAM), methyl methacrylate (MMA) and butyl methacrylate (BMA), and soft monomers, butyl acrylate (BA) and 2-ethylhexyl acrylate (2-EHA) along with multifunctional monomers, namely acrylic acid (AA), were carried out. The effect of the type of hard and soft acrylic monomers, the type and level of emulsifiers, and the initiator concentration on the emulsion polymer stability and final properties of the EPSA were investigated. The results obtained showed an optimized composition. This composition led to a significant increase in shear strength and peel strength to 909 kPa and 0.45 N/mm, respectively, while the synthesized PSA was still too tacky, 5.5 cm, according to adhesion performance testing. For making this successful balance of the conflicting adhesion properties of PSA, a series of anionic and nonionic emulsifiers were investigated. It was interestingly found out that the hybrid emulsifiers (anionic coupling with nonionic) with the optimized compositions could enhance the stability of the emulsion system and improve the properties of PSA compared with the mono-emulsifier. We also tried to adjust the initiator concentration with the level of the optimized hybrid emulsifier, polyoxyethylene alkyl phenyl ether (K30), dioctyl sulfosuccinate (DOSS), and sodium vinyl sulfonate (SVS) with the ratio 2:1:1, resulting in a highly preferred proportion of the 0.5 part of the initiator versus 1.25 parts of the hybrid emulsifier in terms of the total weight of the monomers.     

核/壳型有机硅改性苯丙乳液印花粘合剂的合成及应用

以过硫酸钠(NaPS)为引发剂,苯乙烯(St)和丙烯酸丁酯(BA)为核单体,甲基丙烯酸甲酯(MMA)、丙烯酸异辛酯(EHA)、苯乙烯(St)、丙烯酸(AA)为壳单体,采用种子乳液聚合法,制备了硬壳软核型苯丙乳液,对其进行有机硅改性,得到核壳型有机硅改性苯丙乳液(简称硅丙乳液),将其用作涂料印花粘合剂。研究了核壳单体质量比、丙烯酸用量、乙烯基硅油用量对乳液性能及印花性能的影响;并用热失重分析仪和透射电镜进行了表征。较佳配方为:核/壳单体质量比为6∶4,AA质量分数为2.5%,乙烯基硅油质量分数为10%～15%。该乳液的理化性能较好,耐热性优于核/壳苯丙乳液,将其用于涂料印花,改善了堵网性,印花织物的干、湿摩擦牢度,皂洗牢度,手感以及表观得色量可以达到工业用华润粘合剂的水平。     

丙烯酸酯乳液胶粘剂的合成及其性能研究

以丙烯酸丁酯(BA)、甲基丙烯酸甲酯(MMA)、苯乙烯(St)、丙烯腈(AN)和丙烯酸(AA)为单体,十二烷基硫酸钠(SDS)为乳化剂,过硫酸钾(KPS)为引发剂,通过半连续乳液聚合方法合成了丙烯酸酯乳液胶粘剂。研究了软硬单体配比、不同硬单体以及功能单体AA对胶粘剂性能的影响。研究结果表明,当m(BA)∶m(MMA)∶m(AN+St)=75∶15∶10[其中m(AN)∶m(St)=1∶3]、w(AA)=2份时,制备的乳液胶粘剂具有较好的剪切强度、拉伸强度和耐水性。     

苯乙烯改性丙烯酸酯乳液压敏胶的研制

以丙烯酸丁酯、甲基丙烯酸甲酯、苯乙烯、丙烯酸-2-羟乙酯、丙烯酸为反应单体,十二烷基硫酸钠与聚乙二醇辛基苯基醚按质量比2：1组成复合乳化剂,过硫酸钾为引发剂,采用乳液聚合法,制备了苯乙烯改性丙烯酸酯乳液型压敏胶;对乳液型压敏胶进行了粒度分布、初粘性、180°剥离强度测试。研究结果表明,在反应温度为83±2℃、反应时间为6h、复合乳化剂用量为单体总质量的3～5％、引发剂用量为单体总质量的0．6～0．8％、单体质量比BA：MMA：St：HEA：AA为80：5：10：2：3的工艺条件下,可制得粒径分布窄、平均粒径小、初粘性好、剥离强度高的乳液型压敏胶。     

改性聚醋酸乙烯玻璃纤维网格布定型胶的研制

采用核/壳乳液聚合工艺,以醋酸乙烯(VAc)为主单体、甲基丙烯酸甲酯(MMA)和丙烯酸丁酯(BA)为改性单体、丙烯酸(AA)和N-羟甲基丙烯酰胺(NMA)为交联单体,合成出一种玻璃纤维定型用的改性聚醋酸乙烯(PVAc)粘合剂。研究结果表明:当聚合温度为75℃、m(AA)∶m(VAc)∶m(MMA)∶m(NMA)∶m(BA)=1∶35∶7∶1.5∶12时,改性PVAc乳液既具有优良的粘接性能,又具有很强的粘接性、耐水性、耐碱性和弹性,并可赋予玻璃纤维良好的定型防腐功效。     

弹性含氟树脂乳液的制备研究

以氟树脂乳液作为种子乳液,MMA、AA、BA作为改性单体制备了弹性含氟树脂乳液。研究了乳化剂用量、AA用量、改性单体用量对聚合反应及膜性能的影响。结果表明:随着乳化剂用量的增加,聚合稳定性、膜吸水率增加;随着AA用量的增加,乳液的冻融稳定性提高,膜吸水率增加,凝胶率降低;乳液的平均粒径、膜吸水率、膜弹性随着改性单体用量的增加而升高,膜的拉伸强度随着改性单体用量的增加而降低。当m(改性单体)∶m(固体氟树脂)=4∶6时,乳胶膜具有良好的低温柔韧性。     

马来酸酐改性多孔微球的制备及表征

为了提高多孔树脂微球的亲水性,扩大其应用范围,文章通过马来酸酐(MAH)与多孔苯乙烯-二乙烯基苯共聚微球悬挂双键的接枝聚合,制备了改性的多孔树脂微球。用扫描电镜、红外光谱法、酸碱滴定法等对产物进行了表征。考察了微球的交联度、引发剂、反应时间等因素对马来酸酐接枝率和改性微球形貌的影响。在以交联度55%的多孔微球为基球,基球与MAH质量比为5∶3,质量分数为3%的偶氮二异丁腈为引发剂,80℃、反应6 h时,制得了较好多孔形貌的改性微球。结果表明,马来酸酐为改性剂有利于保持多孔微球的多孔形貌。     

紫胶改性水性醇酸树脂的合成工艺研究

从改进树脂综合性能着手,研究了水性醇酸树脂的合成工艺。确定了以熔融法和分步加料来制备醇酸树脂。以紫胶部分替代三羟甲基丙烷,顺丁烯二酸酐/偏苯三酸酐部分替代苯酐,所得水性醇酸树脂的干燥性能、硬度和柔韧性等性能得以提高。紫胶用量以5%为宜。     

磷酸酯改性水性醇酸树脂的合成及性能研究

先采用马来酸酐和丙烯酸酯、磷酸酯自由基溶液共聚合成一种低相对分子质量的预聚物,再与单甘油酯、邻苯二甲酸酐、二羟甲基丙酸单体酯化合成一种改性的醇酸树脂,加入三乙胺中和成盐后,加水高速搅拌制得粒径分布在20～100 nm澄清透明的水分散醇酸树脂.使用傅里叶红外光谱仪、凝胶气相色谱、热分析等手段对目标产物的结构和性能进行了表征,使用碘量法测定了树脂中保留的双键的含量,测试了由该树脂制备的漆膜的性能.同时,在醇酸树脂结构中因引入磷酸酯功能单体提高了其漆膜的附着力和耐腐蚀性能.     

Waterborne hybrid alkyd–acrylic dispersion: Optimization of the composition using mixture experimental designs

VOC-free waterborne hybrid alkyd–acrylic (50/50 wt/wt) dispersions were synthesized by melt condensation reactions between acrylic pre-polymers bearing carboxylic groups and medium-oil alkyd resins, followed by a self-emulsification through the neutralization of the carboxylic groups by an aqueous ammonia solution. A mixture experimental design was used to investigate how formulation components of the hybrid alkyd–acrylic resin affect the properties of the hybrid dispersion in terms of the viscosity of the dispersion, particle size, hydrolytic stability, and coating performance, namely gloss and film hardness. It was found that the content of ionizable monomers is the dominant factor controlling the particle size. This latter was shown to meaningfully affect the gloss of the coating after drying. The viscosity of the dispersion was mainly governed by the content of the soybean oil fatty acid which also controlled the hardness of the coating film after drying. An optimal composition that fits the requirement of paint formulation in terms of particle size, viscosity, hardness, and gloss was defined on the basis of the results of the mixture experimental design.     

结合磷阻燃型苯丙共聚乳液胶粘剂的合成及性能研究

以苯乙烯(St)、丙烯酸丁酯(BA)、丙烯酸乙酯(EA)、甲基丙烯酸甲酯(MMA)、丙烯酸(AA)和含磷单体为共聚单体,采用预乳化种子乳液聚合法制备PSA(结合磷型苯丙共聚乳液胶粘剂),并在PSA中添加少量无机阻燃剂APP(聚磷酸铵)制备CPSA(复合型阻燃胶粘剂)。系统研究了含磷单体和APP含量对乳液稳定性、胶膜剥离强度、涂层阻燃性和热性能等影响。结果表明:当m(St+BA+EA+MMA+AA)=40 g、m(St)∶m(BA)∶m(EA)∶m(MMA)∶m(AA)=16∶90∶60∶24∶5、w(含磷单体)=4%和w(APP)=12%(相对于单体总质量而言)时,可制成稳定性、剥离强度和阻燃性能俱佳的CPSA。