高固体分涂料用含羟基星形丙烯酸酯树脂的制备及性能

以占单体物质的量0.01%的低铜盐用量催化剂体系进行电子转移活化再生催化剂原子转移自由基聚合(ARGET ATRP), 制备了丙烯酸丁酯、甲基丙烯酸甲酯和丙烯酸羟丙酯为单体的线形和六臂星形共聚物。采用折光指数-激光-黏度三检测联用GPC, ¹H NMR和DSC对聚合物的分子结构、共聚组成和玻璃化转变行为进行了研究。将聚合物配制成涂料用树脂溶液, 流变行为研究表明星形聚合物溶液黏度最低。在高固含量时, 星形聚合物降低黏度的优势更明显。在适合喷涂施工的黏度下, 六臂星形共聚物比普通自由基聚合得到的商品化丙烯酸酯树脂的固含量可提高10%。采用异氰酸酯固化剂固化得到的漆膜性能测试表明, 星形聚合物对应清漆的表干时间很短, 同时力学性能达到良好水平。     

Synthesis and photopolymerization of acrylic acrylate copolymers

Acrylate‐functionalized copolymers were synthesized by the modification of poly(butyl acrylate‐co‐glycidyl methacrylate) (BA/GMA) and poly(butyl acrylate‐co‐methyl methacrylate‐co‐glycidyl methacrylate). ¹³C‐NMR analyses showed that no glycidyl methacrylate block longer than three monomer units was formed in the BA/GMA copolymer if the glycidyl methacrylate concentration was kept below 20 mol %. We chemically modified the copolymers by reacting the epoxy group with acrylic acid to yield polymers with various glass‐transition temperatures and functionalities. We studied the crosslinking reactions of these copolymers by differential scanning calorimetry to point out the effect of chain functionality on double‐bond reactivity. Films formed from acrylic acrylate copolymer precursors were finally cured under ultraviolet radiation. Network heterogeneities such as pendant chains and highly crosslinked microgel‐like regions greatly influenced the network structure and, therefore, its viscoelastic properties. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 753–763, 2002     

Preparation and coating properties of an acrylic melamine resin containing silicone segments

The aim of this study was the preparation of novel water repellent UV curable materials using acrylic modified melamine (AM) and poly-dimethylsiloxane (PDMS). UV curable acrylic melamines containing silicone segments (SiAMs) were synthesized by condensation of methylolmelamine, 2-hydroxyethyl acrylate, and carbinol-modified PDMS. The SiAM films with a 0.3 wt% PDMS segment that were cured by UV irradiation had higher transparency than that of a blended sample. Examination with a scanning electron microscope revealed that the blend sample has cohesion of the silicone segments, while such a phenomenon was not observed in the composite samples (SiAMs). From these results, it was confirmed that aggregation of the silicone segments was prevented by introducing the silicone segments into the acrylic melamine. By introducing 0.3 wt% of PDMS segments into AM, good water-shedding properties were confirmed, while several of the most attractive features of AM, such as hardness, adhesion, and refractive index, were maintained.     

氟硅烷改性水性丙烯酸二级分散体的制备与涂层性能

将1,1,3,3-四甲基-1,3-二乙烯硅氮烷(DVDZ)和甲基丙烯酸六氟丁酯(EINECS)进行Micheal加成反应,合成2,2,3,4,4,4-六氟丁基-3-(二(二甲基(乙烯基)硅基)氨基)-2-甲基丙酸酯(DVE)功能有机氟硅单体,与甲基丙烯酸甲酯(MMA)、甲基丙烯酸羟乙酯(HEMA)等单体混合,以偶氮二异丁腈(AIBN)为引发剂,异丙醇(IPA)为溶剂,合成氟硅烷改性水性丙烯酸二级分散体。然后,将其与异氰酸酯固化剂混合,制备了双组分水性聚氨酯(2K-WPU)涂膜。通过FTIR、1HNMR、TG、SEM、XPS对DVE和2K-WPU进行表征和检测,结果表明:随着DVE质量分数的增加,丙烯酸二级分散体的粒径增大,黏度降低,涂膜的耐水性增强,铅笔硬度和附着力减弱。当DVE质量分数为6%时,吸水率为8.2%,接触角为91.5?,热失重10%和50%时的温度分别为220.9和438.5℃,涂膜耐热、耐水和耐酸碱等性能均有提升。     

用电子转移活化再生原子转移自由基聚合制备含氟丙烯酸酯共聚物及其表征

在水分散介质中,以非离子乳化剂Tween-80和十二烷基磺酸钠作为复合乳化剂,通过电子转移活化再生原子转移自由基聚合,采用ab二次引发乳液聚合法制备了含氟丙烯酸酯三元共聚物,用傅里叶变换红外光谱、拉曼光谱、核磁共振波谱及凝胶渗透色谱等对其结构、组成和相对分子质量及其分布进行了表征。结果表明,含氟丙烯酸酯聚合物的分子结构及组成可控,转化率高达95%,相对分子质量分布较窄。优选憎水性配体和惰性乳化剂可提高反应的可控性。     

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。     

Preparation of acrylic copolymers and crosslinking agents and properties as a film

Copolymers of butyl acrylate (BA)‐methyl methacrylate (MMA)‐acrylic acid (AA) and intraparticle crosslinking agents containing N‐methylol acrylamide (NMA) and ethylene glycol dimethacrylate (EGDMA) were prepared by emulsion copolymerization. After that, films were prepared from the mixture of copolymers and the interparticle crosslinking agents. The interparticle crosslinking agents were prepared from hexamethylene diisocyanate and aziridine ethanol. Mixtures of the copolymer and the interparticle crosslinking agent were cast to films and crosslinked in a convection oven. The effects of the contents of the intra/interparticle crosslinking agents were also evaluated. By increasing the contents of EGDMA, roughness of the films was increased because of the effects of EGDMA acting as an intraparticle crosslinking agent. By increasing the contents of the interparticle crosslinking agent, roughness was also increased by the reaction between the copolymers and interparticle crosslinking agent. Tensile strength and water and chemical resistance of the film were increased, whereas elongation of film was decreased by increasing the contents of interparticle crosslinking agents. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

水性丙烯酸酯汽车涂料制备及其漆膜性能研究

合成了水性丙烯酸树脂并用其配制了汽车罩光清漆,研究了硬/软单体配比、丙烯酸单体的用量、芳香酯单体的用量、氨基树脂固化剂/丙烯酸树脂的配比及固化条件对漆膜性能的影响。结果发现,硬/软单体配比为39/35,丙烯酸质量分数为6%,甲基丙烯酸苄酯(BNMA)质量分数为12%,固化剂/树脂配比为40/100,固化温度及时间分别为140℃和30 min时,固化漆膜具有优良的综合性能,其光泽度达到98(60°),冲击强度为0.50 kJ/m,硬度为2H,附着力为0级,耐溶剂、耐紫外老化性能良好。FT-IR分析显示氨基树脂/丙烯酸树脂漆膜固化后表征羟基和甲氧基的吸收峰强度显著变弱,表明氨基树脂和丙烯酸树脂发生了交联固化。     

肠溶型药物包衣用丙烯酸树脂的制备工艺

采用乳液聚合法制备肠溶型药物包衣用丙烯酸树脂,采用甲基丙烯酸与甲基丙烯酸甲酯作为共聚单体、过硫酸钾作为引发剂、十二烷基硫酸钠及OP-10复配作为乳化剂、苯乙烯的二聚体作为分子量调节剂、碳酸氢钠作为pH值调节剂,考察了乳化剂配比及用量、引发剂及分子量调节剂的用量、反应温度、加料方式、相比等因素的影响,最终确定了实验制备药物包衣用丙烯酸树脂的最佳条件。利用乌氏粘度计测定其相对分子量,并作了红外光谱测试,结果表明,乳液符合国家药典要求。该制备过程避免了有机溶剂的使用,有明显的经济和环保效益。     

胃溶型丙烯酸树脂乳液的制备

采用乳液聚合法,以甲基丙烯酸甲酯(MMA)和甲基丙烯酸二甲氨基乙酯(DM)为单体,制备了可直接用于药物包衣的胃溶型丙烯酸树脂乳液。结果表明,当温度为65℃,单体摩尔比为1∶1,引发剂和乳化剂用量分别为0.6%和0.3%,采用单体连续滴加法时,可制得稳定的乳液,聚合物分子量为14.9万。在180℃以下,产品的失重率基本不随温度而变,而在180℃以上,失重率随温度升高而增加。聚合物膜在缓冲溶液中的失重率随pH的增加而减小,当pH为1.0和2.0时,膜几乎全部溶解,pH为3.0时,膜的失重率为65.0%,在pH为4.0时,失重率迅速降低到32.8%,到pH为7.0时,膜已基本不溶。     

三聚氰胺改性脲醛树脂粉体胶粘剂的研制

用三聚氰胺改性脲醛树脂改善了胶粘剂的耐沸水性,并有效地降低了游离甲醛含量。三聚氰胺改性脲醛树脂粉体胶粘剂应用更广泛,性能更可靠。     

影响丙烯酸树脂粘度的工艺研究

在涂料用丙烯酸酯树脂的合成中,通过研究不同引发剂在不同工艺条件下对树脂产物的影响,以及不同溶剂对树脂的溶解性能,为生产实践中设计和控制树脂粘度寻找了一些方法,也为制作某些特性树脂而选用合成工艺、引发剂和溶剂提供了思路。     

Preparation and physical properties of transparent organic–inorganic nanohybrid materials based on urethane dimethacrylate

The aim of this study was to prepare transparent organic–inorganic nanohybrid materials with improved physical properties in comparison with the matrix polymer. Polymerizable silica nanoparticles were synthesized via the reaction of silanol groups on the surface of silica nanoparticles (particle diameter ≈ 12 nm) with isocyanate groups of 2‐(methacryloyloxy)ethyl isocyanate (MOI) in ethyl acetate. In addition, the matrix monomer, urethane dimethacrylate, was prepared by the reaction of an MOI isocyanate group with the hydroxyl group of 2‐hydroxyethyl methacrylate, and novel organic–inorganic nanohybrid materials were obtained at various silica contents with bulk polymerization. The surface treatment of the silica nanoparticles and preparation of the matrix monomer were carried out in a one‐pot reaction. The prepared hybrid materials retained high transparency, and the elastic modulus and surface hardness improved with increasing silica content. Moreover, the strength of the material containing 20 wt % silica was up to 30 MPa higher than that of the matrix polymer. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

醋丙乳液的研制

介绍了丙烯酸酯改性聚醋酸乙烯酯乳液的合成方法,利用种子乳液聚合合成了一种高性能醋酸乙烯-丙烯酸丁酯共聚乳液,确定了最佳的聚合配方和聚合工艺,经实验测试,乳液性能良好,尤其是乳液的耐水性和耐寒性得到改善。     

水溶性丙烯酸树脂的制备研究

用于水性油墨的水溶性丙烯酸树脂由丙烯酸丁酯(BA)、甲基丙烯酸甲酯(MMA)、丙烯酸(AA)三种单体采用传统的自由基溶液聚合方式合成,通过大量的对比实验筛选了各种不同的反应条件,获得了最佳合成工艺,包括引发剂、溶剂、加料方式、聚合时间和温度。对影响树脂性能的指标如共聚物组成、玻璃化转变温度Tg等各种因素,采用DSC、IR等分析方法进行了详尽的分析和表证。     

Viscoelastic properties and coating performance of acrylic copolymers crosslinked with melamine resin

For 8 carboxy and hydroxy functional acrylic copolymers crosslinked with melamine resin, glass transition temperature (T_g), molecular weight of chain segments between crosslinked point (M_c), and polymer-solvent interaction parameters (χ_g ) were determined by dynamic mechanical measurements and swelling measurements. T_g increases and M_c decreases with the increase of hydroxyl value and the molecular weight of acrylic copolymers. T_g decreases and M_c increases with the increase of alkyl chain length of acrylate in acrylic copolymers. The film hardness, T_g and polarity of methyl methacrylate (MMA) containing acrylic-melamine-cured films are higher than those of styrene-containing acrylic-melamine-cured films, but both films are almost the same in the degree of crosslinking (maximum loss tangent, tan δ_max, and M_c). T_g increases and M_c decreases with the increase of melamine resin content for acrylic-melamine coatings. The cured film consists of the acrylic-melamine segments and the melamine-melamine segments at crosslinking points. The carboxy group enhances the crosslinking reactions at low temperatures. All films crosslinked have single glass transition temperatures and broad damping peaks, which show good compatibility. The values of χ_g of acrylic copolymer-melamine films in polar and nonpolar solvents depend on the polarity of acrylic composition and the degree of crosslinking. χ_g values of carboxy functional acrylic-melamine film in any solvents are smaller than that of carboxy and hydroxy functional acrylic-melamine film. χ_g values of MMA-containing acrylic-melamine film in polar solvents are smaller than those of styrene-containing acrylic-melamine film, but χ_g values of MMA-containing acrylic-melamine film in nonpolar solvents are larger than those of styrene-containing acrylic-melamine film. χ_g values of acrylic-melamine film in polar and nonpolar solvents increase with the increase of alkyl chain length of acrylate. The χ_g values of acrylic-melamine coatings in toluene are less than 0.3 and smaller than those of alkyd coatings.     

高羟基含氟丙烯酸乳液的合成及性能研究

以丙烯酸酯类单体作为原料,以过硫酸钾为引发剂,采用预乳化半连续乳液聚合方式合成了高羟基丙烯酸乳液,并在后期补加氧化还原体系引发剂,提高了单体的转化速率。系统地研究了乳化剂用量、羟基单体、氟单体、硅单体含量等因素对涂膜性能的影响。最后,将制备的丙烯酸羟基组分同水性固化剂配制成双组分水性丙烯酸聚氨酯清漆,并分析清漆的性能。     

槽液稳定性好的高硬度丙烯酸阳极电泳涂料的研制

在混合溶剂中加入甲基丙烯酸、各种甲基丙烯酸酯单体以及引发剂AIBN和链转移剂DDM,在85℃下反应合成了丙烯酸树脂。分别研究了不同酸值和羟值的丙烯酸单体、不同Tg的丙烯酸树脂以及各种助溶剂和中和剂对漆膜性能的影响。获得了丙烯酸阳极电泳涂料的最佳配方:丙烯酸共聚树脂的酸值为65 mg KOH/g、羟值为69 mg KOH/g、Tg为20℃,溶剂是体积比为1∶1的丙二醇单甲醚和异丙醇的混合物,中和剂是二乙醇胺。该电泳涂料具有良好的槽液稳定性和起泡消泡性。制得的涂膜外观平整、丰满、光亮,厚度为18~20μm,硬度为5 H,冲击强度为500 N/cm2,附着力为1级,柔韧性为1 mm,耐烟雾实验超过400 h。     

纸塑复合用丙烯酸酯乳液胶粘剂的制备

采用半连续法制备了一种纸塑复合用丙烯酸酯乳液胶粘剂,讨论了乳化剂的用量、松香乳液的用量、交联剂的用量等因素对胶粘剂性能的影响。结果表明,当乳化剂的用量为4.5%、松香乳液用量为10%,胶粘剂的性能较好;另外,加入一定量的交联剂,可显著提高该胶粘剂的耐水性。     

Viscoelastic properties and coating performance of water-soluble acrylic copolymers crosslinked with melamine resin

Acrylic copolymers with different amounts of carboxyl and hydroxyl groups for obtaining practical performance of melamine-cured acrylic coatings was investigated. Property testing results indicated that glass transition temperature (T_g) and shear modulus increased, and molecular weight between crosslinks (M_c) decreased with the increase of hydroxyl and carboxyl number in the acrylic copolymers. The degree of crosslinks influenced the resistance to solvent and chemicals at a lower baking temperature. Compared with acrylic acid, itaconic acid as a carboxyl monomer was more effective in inducing a lower baking schedule. The water-soluble acrylic copolymer, which is neutralized with triethylamine, consists of 20 wt % methylmethacrylate, 55 wt % buthylacrylate, 15 wt % hydroxyethyl methacrylate, and 10 wt % itaconic acid. The copolymer showed higher crosslinks when cured with methoxymethyl melamine formaldehyde resin under a relatively lower baking schedule at 135°C for 30 min. It also has excellent solvent and chemical resistance. This coating film has a T_g value of 39°C, modulus of 2 × 10⁸ dyne/cm² in the rubbery state, and M_c value of 464. Also the acrylic copolymer films with M_c < 900 have good properties for solvent, acid, and alkali resistance. © 1995 John Wiley & Sons, Inc.