聚丙烯酸酯吸油膨胀橡胶的合成及性能研究

以丙烯酸乙酯（EA）、丙烯酸十二酯（LA）和甲基丙烯酸羟乙酯（HEMA）为单体,采用乳液聚合的方法制备了含羟基的丙烯酸酯共聚物,塑炼后与多缩水甘油酯交联剂和白炭黑进行混炼、硫化,制得吸油膨胀橡胶（OSR）。研究了单体配比、乳化剂用量、交联剂用量对OSR吸油膨胀性能和力学性能的影响,并研究了吸油时间对OSR吸油膨胀性能的影响。结果表明：随着LA单体比例的增加,OSR的硬度和拉伸强度降低,吸油膨胀率增大。随着交联剂用量的增加,OSR的硬度、拉伸强度和断裂伸长率增大,吸油膨胀率随着交联剂用量的增加呈先升后降的趋势。随着吸油时间的增加,OSR的吸油膨胀率增大,在10h后吸油膨胀率几乎不变。     

乳液聚合交联改性提高疏水性氟代丙烯酸酯的力学性能

为了改善丙烯酸酯的力学性能,以丙烯酸酯为主要单体,甲基丙烯酸十二氟庚酯为功能单体,1,4-丁二醇二丙烯酸酯(BDDA)为交联剂,采用核壳乳液聚合法合成了水性含氟丙烯酸酯。考察了反应条件,并对乳液的稳定性、粒径,以及乳液膜的拉伸强度、断裂伸长率、硬度、水接触角和化学结构进行了表征。结果表明,BDDA的加入可以有效提高乳液膜的拉伸强度、断裂伸长率及硬度。当BDDA占单体质量3%时,乳液的平均粒径为63.8 nm,转化率为99.2%,乳液膜的综合性能最好,分别为:吸水率4.9%,水接触角98.8°,拉伸强度1.94 MPa,断裂伸长率743.6%,硬度45.6 HA。其拉伸强度和断裂伸长率分别是未改性含氟丙烯酸酯乳液膜的1.73倍和1.46倍。     

氟硅共聚改性提高聚丙烯酸酯力学和疏水性能的研究

为改善聚丙烯酸酯表面能高、力学性能较差的缺点,以丙烯酸酯为主要单体,甲基丙烯酸十二氟庚酯、四甲基四乙烯基环四硅氧烷为功能单体,采用核壳乳液聚合法合成了水性聚氟硅丙烯酸酯。结果表明,四甲基四乙烯基环四硅氧烷可有效提高乳液膜的疏水角、断裂伸长率以及硬度;其质量分数为5%时,乳液的平均粒径为166.8 nm,转化率为98.6%;乳液膜的综合性能最好,其吸水率为3.9%,水接触角为131.3°,拉伸强度为2.3 MPa,断裂伸长率为929.7%,硬度为46.6 HA;与氟硅丙烯酸树脂相比,断裂伸长率提高了58.7%,水接触角提高了11.8%。     

聚丙烯酸酯无皂乳液的构建及对水性油墨性能的影响

以丙烯酸（AA）、丙烯酸丁酯（BA）、甲基丙烯酸甲酯（MMA）、丙烯酸羟丙酯（HPA）、2-甲基丙烯酸羟乙酯（HEMA）、乙烯基三异丙氧基硅烷（A-173）为单体,过氧化苯甲酰（BPO）、过氧化苯甲酸叔丁酯（TBPB）为引发剂,合成了丙烯酸酯大分子乳化剂,再通过无皂乳液聚合法合成了聚丙烯酸酯无皂乳液,将其与颜料等混合制备了水性油墨。采用FTIR、DSC、TEM、SEM对聚合物的结构及性能进行了表征,考察了不同BPO用量对丙烯酸酯大分子乳化剂的影响,不同AA添加量对乳液及水性油墨的影响。结果表明：当BPO用量为单体总质量的4.18%时,丙烯酸酯大分子乳化剂具有最低表面张力40.43 mN/m;当AA添加量为单体总质量的1.00%时,聚丙烯酸酯无皂乳液具有合格的储存稳定性,乳胶膜拉伸强度可达5.00MPa,断裂伸长率为200%,玻璃化转变温度为18.5℃,所制备的水性油墨黏度为23.79 mPa·s,附着牢度90.75%,耐摩擦性4.5级。     

交联单体种类及其用量对丙烯酸酯乳胶聚合行为的影响

本研究分别以二乙烯基苯（ DVB）、乙二醇二甲基丙烯酸酯（ EGDMA）、双环戊烯基丙烯酸酯（DCPA）、三烯丙基异氰脲酸酯（TAIC）、甲基丙烯酸烯丙酯（AMLA）、马来酸二烯丙酯（ DAM）为交联单体,采用乳液聚合技术制备了丙烯酸丁酯 -丙烯酸异辛酯（ BA-EHA）共聚物乳胶,系统研究了不同交联剂种类和用量对乳液聚合单体动力学和乳胶性能的影响。结果表明：交联单体的引入会直接影响丙烯酸酯乳胶聚合动力学,随交联单体用量的增加,最终乳胶的粒径减小,粒子数目增大。同时,交联单体的加入使乳胶膜的吸水率下降,凝胶率和玻璃化转变温度增大。 6种交联单体中,具有等活性双键的三烯丙基异氰脲酸酯（TAIC）对丙烯酸酯的交联效果最佳。     

环氧改性丙烯酸酯结构胶的研制

采用低挥发性、低刺激性单体甲基丙烯酸羟乙酯、乙氧基乙氧基乙基丙烯酸酯,使用柔性环氧丙烯酸酯替代橡胶作增韧剂,制备了一种低气味高韧性丙烯酸酯结构胶。该结构胶气味小,初固时间5 min,24h固化后剪切强度28MPa,伸长率30%,拉伸强度24 MPa。     

耐候型ASA树脂的制备及其性能研究

采用悬浮聚合法,以丙烯酸丁酯、苯乙烯和丙烯腈为原料,合成了一系列丙烯酸丁酯-苯乙烯-丙烯腈(ASA)树脂。考察了橡胶相聚丙烯酸丁酯(PBA)、交联剂二甲基丙烯酸乙二醇酯(EGDMA)、接枝剂甲基丙烯酸烯丙酯(ALMA)和摩尔质量调节剂十二烷基硫醇(TDDM)的用量对ASA树脂的冲击强度的影响;PBA质量分数对ASA树脂的拉伸强度和断裂伸长率的影响。结果表明:PBA质量分数达到20%后,ASA树脂的冲击强度大幅增加;EGDMA、ALMA和TDDM的质量分数分别为0.43%、0.4%和1%时,ASA树脂的冲击强度达到最大值;随PBA增加,ASA树脂的拉伸强度减小,断裂伸长率变大。     

多元共聚高吸油树脂合成及性能研究

以(甲基)丙烯酸酯类、苯乙烯为主要共聚单体,双甲基丙烯酸乙二醇酯(EGDMA)、二乙烯基苯(DVB)等为交联剂,采用悬浮共聚工艺合成了一系列高吸油树脂.研究了树脂共聚单体组成、丙烯酸单体链长、交联剂种类、交联度、引发剂量以及聚合工艺等因素对吸油树脂吸油量等性能的影响.结果表明:采用EGDMA交联时以丙烯酸十四酯的效果最佳,采用DVB交联时以丙烯酸十二酯效果最佳;交联剂种类及交联度大小对树脂吸油性能及树脂形态有明显影响;树脂交联度的大小明显影响树脂共聚物的转化率与可溶性分率,也明显影响树脂产品的收率.在最佳合成条件下制备的高吸油树脂具有较佳的吸油性能,对甲苯的吸附量可达17.32 g/g树脂.     

紫外光固化丙烯酸酯胶粘剂的研制

用甲基丙烯酸甲酯、丙烯酸丁酯、丙烯酸-β羟丙酯等单体共聚成光敏树脂（预聚物），加入适量甲基丙烯酸丙酯和光敏剂即得紫外光固化胶粘剂。当加入适量多官能丙烯酸酯（如季戊四醇三丙烯酸酯）时，可大大缩短胶的光固化时间。该胶对诸多基材粘接良好。     

水性丙烯酸酯汽车涂料树脂的制备与粘度的研究

合成了用于配制水性汽车罩光清漆的丙烯酸酯涂料树脂,研究了丙烯酸单体、含芳香酯基团单体、引发剂、链转移剂和聚合温度对树脂水溶性和粘度的影响,并用红外光谱表征了树脂的结构。结果表明,增加丙烯酸单体的用量会提高丙烯酸酯树脂的水溶性和粘度,而增加含芳香酯基团的甲基丙烯酸苄酯（BNMA）单体、引发剂和链转移剂的用量和提高聚合温度可降低树脂的粘度。该树脂与氨基树脂（HMMM）固化剂配制的漆膜性能优良,可以用作汽车原厂漆（OEM）。     

高级脂肪酸酯-醋酸乙烯酯共聚改性研究

介绍了醋酸乙烯酯。在丙烯酸类单体共聚改性的基础上,引入一种高级脂肪酸酯类单体参与共聚．探讨了共聚合成乳液及其粘接强度和耐水性。研究结果表明,改性后的胶粘剂降低了最低成膜温度,并经胶合板的JAS2类检测标准耐温水试验显示,试件的耐水性和粘接强度得到提高。     

全氟内交联型聚醋酸乙烯酯乳液的制备及其膜耐水性研究

为了大幅度提高聚醋酸乙烯酯的耐水性,本文采用全氟烷基乙基丙烯酸酯单体(FA)对其进行改性,并通过羟甲基丙烯酰胺(HMA)进行内交联,以醋酸乙烯酯(VAc)、丙烯酸(AA)、丙烯酸丁酯(BA)为主要单体,以聚乙烯醇(PVA)为保护胶体,通过无皂乳液聚合法制备了全氟内交联型聚醋酸乙烯酯乳液。同时考察了全氟单体和交联剂用量比对乳液粒径、流变性和涂膜耐水性的影响,并确定了它们的最适宜条件。研究结果表明,乳液为非牛顿流体,且具有一定的假塑性和触变性,表观黏度随切变速率的变化规律呈现切力变稀特征,当全氟单体用量为6%和交联剂用量为2.5%时,全氟内交联型聚醋酸乙烯酯膜具有良好的稳定性和耐水性。     

丙烯酸系多元共聚乳液的研制

介绍了以丙烯酸酯为主要原料制备的多元共聚乳液，并探讨了单体、浓度和温度对共聚乳液性能的影响。     

Stabilization of Acrylic Esters

Acrylic acid (AA) and its esters are monomers which can easily be polymerized. In order to avoid the unintentional polymerization during the manufacture and storage, the acrylic esters are stored under air‐atmosphere to which 15 ppm (g g^–1) hydroquinone monomethylether (MeHQ) has been added. The consumption of the stabilizers, oxygen (O₂) and MeHQ, play an important role in the prognosis of the stability of the monomers. In earlier works the O₂/MeHQ‐consumption of acrylic acid during the inhibition period without radical‐starter‐addition was examined [1]. In this paper it could be shown that the examinations on acrylic acid are not transferable to different acrylic esters. The O₂‐consumption rates in the acrylic esters are approximately ten times smaller than in acrylic acid, depending on temperature and monomer. The inhibition periods of the acrylic esters are about the factor ten greater in comparison to acrylic acid. A correlation between the concentration of the C=C double bond in the esters and the O₂‐consumption is possible with the measurements of the O₂‐consumption in the different acrylic esters as a function of temperature. The O₂‐consumption of any acrylic ester can be calculated in this way on the basis of the C=C double bond concentration. The same applies to the inhibition period (the time up to the start of the polymerization). An estimation of the stability is possible with these two parameters.     

有机电致发光显示器用框胶封装材料的研制

以聚氨酯丙烯酸树脂、环氧丙烯酸/聚氨酯丙烯酸混合树脂、氨基甲酸酯丙烯酸聚硅氧烷树脂和环氧丙烯酸树脂分别作为基体树脂,制备有机电致发光显示器(OLED)用框胶封装材料。结果表明:氨基甲酸酯丙烯酸聚硅氧烷树脂基框胶的综合性能较好,其粘接强度为33.5 MPa、玻璃化转变温度为135.02℃、水汽穿透率为9.3 g/(m2.d)和氧气穿透率为0.021 mL/(m2.d),满足OLED用框胶封装材料的使用要求。     

Crosslinking of unsaturated polyester resins by combinations of vinyl esters and methacrylates

The replacement of styrene by other crosslinking monomers in unsaturated polyester resins has been investigated because of the possible toxicity of this monomer and the strong smoke evolution of burning polyester materials. A theoretical study has been carried out to provide criteria for the applicability of classes of monomers in polyester curing. From this study it appeared that vinyl esters, vinyl ethers, N-vinyl lactams, and styrenes are suitable, whereas acrylic and methacrylic esters and allylic or olefinic compounds are not. Combinations of vinyl esters and (meth)acrylic esters of polyols should generate IPN-like structures. Polyesters cured by this combination of monomers gave materials with increased stiffness and strength relative to those obtained with the separate monomers and on the same level as styrene-cured polyesters.     

Reactions of conjugated fatty acids. V. Preparation and properties of diels-alder adducts and their esters fromtrans,trans-conjugated fatty acids derived from soybean oil

Summary Soybean fatty acids were conjugated with alkali, and the contained, conjugated dienoic acids were isomerized with iodine to thetrans,trans configuration. Adducts were prepared from thesetrans,trans-conjugated acids by condensation with maleic anhydride and acrylic acid. The adducts were isolated, purified, and converted to esters by using a variety of alcohols, including methyl, ethyl,n-propyl,n-butyl, and allyl alcohols. Esters made from saturated alcohols were converted into the corresponding epoxy derivatives. All of the esters (except allyl) and all of the epoxy esters were compatible with an equal weight of polyvinyl chloride and appeared to be primary plasticizers for this plastic. The epoxy esters were effective in inhibiting heat deterioration of polyvinyl chloride. Presented at fall meeting. American Oil Chemists' Society, September 23–26, 1956, Chicago, Ill.     

淀粉与乙烯基单体的接枝共聚改性

评述了丙烯腈、丙烯酰胺、丙烯酸、丙烯酸酯类及苯乙烯等几种较常见的乙烯基单体与淀粉的接枝共聚反应,重点讨论了淀粉糊化、引发剂和单体的浓度、种类及配比、反应温度、时间等因素对接枝共聚反应的影响,同时介绍了淀粉与乙烯基单体接枝共聚物的应用。     

卷铝用改性丙烯酸树脂的合成

采用丙烯酸酯类单体、功能性单体——丙烯酸β-羟乙酯(HEA)、三羟甲基丙烷三丙烯酸酯(TMPTA)和季戊四醇三丙烯酸酯(PETA),合成了热固性丙烯酸树脂。与丁醇醚化的氨基树脂(582-2)、颜填料及助剂配合,制成了适用于铝箔的卷铝涂料。该涂料显示出优异的附着力、耐MEK擦拭和良好的T弯等性能。     

Synthèse de monomères acryliques et méthacryliques derivés de biocides. Etude de leur homo et copolymérisation

In order to provide macromolecular biocides for the preparation of binders used in paint formulations, different biocidal agents, mainly phenols, are transformed in acrylic and methacrylic monomers. Their free radical homo and copolymerization (styrene, acrylic acid esters) behaviour is studied. Characteristics as monomer or homo and copolymer are obtained by classical techniques: infra-red, NMR of proton and carbon 13, size exclusion chromatography.