Rheological behavior and thermal properties of poly(butyl acrylate‐co‐2‐ethylhexyl acrylate)‐grafted vinyl chloride resin

The rheological behavior and thermal properties of a poly(butyl acrylate‐co‐2‐ethylhexyl acrylate) [P(BA‐EHA)]‐grafted vinyl chloride (VC) composite resin [P(BA‐EHA)/poly(vinyl chloride) (PVC)] and its materials were investigated. The rheological behavior, thermal stability, and Vicat softening temperature (VST) of P(BA‐EHA)/PVC were measured with capillary rheometry, thermal analysis, and VST testing, respectively. The effects of the P(BA‐EHA) content and the polymerization temperature of grafted VC on the rheological behavior of the composite resin were examined. The weight loss of the composite resin and its extracted remainder via heating were analyzed. The influence of the content and crosslinking degree of P(BA‐EHA) and the polymerization temperature of the grafted VC on VST of the materials was determined. The results indicated the pseudoplastic‐flow nature of the composite resin. The flow property of the modified PVC resin was improved because of the incorporation of the acrylate polymer. The molecular weight of PVC greatly influenced the flow behavior and VST of the composite resin and its materials. The flowability of the composite resin markedly increased, and the VST of its materials decreased as the polymerization temperature of the grafted VC increased. The initial degradation temperature of the composite resin increased as the P(BA‐EHA) content increased. The VST of the samples was enhanced a little as the content of the crosslinking agent increased in P(BA‐EHA). As expected, the composite resin, with good impact resistance, had better heating stability and flowability than pure PVC, whereas the VST of the material decreased little with increasing P(BA‐EHA) content. Therefore, P(BA‐EHA)/PVC resins prepared by seeded emulsion polymerization have excellent potential for widespread applications. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 419–426, 2005     

Synthesis of thermally stable high gloss water dispersible polyurethane/polyacrylate resins

Design and synthesis of some new thermally stable polyurethane/polyacrylate blend resins with high gloss and excellent chemical resistivity has been accomplished. Thus, polyurethane was synthesized from polyethylene glycol (PEG) and hexamethylene diisocyanate (HDI) using the conventional prepolymer method. The double bond functionality is introduced by blocking the prepolymer isocyanate groups with acrylamide so as to utilize acrylic acid as a chain extender to make the resin water dispersible. Polyacrylates are prepared by free radical (emulsion seed) polymerization of methylmethacrylate (MMA), 2-ethylhexylacrylate (2EHA), butylacrylate (BA) and acrylic acid using potassium persulfate (KPS) as an initiator. The morphology of polyurethane and polyacrylate is investigated using FTIR spectroscopy and the thermal stability by TGA. The luster of resin is checked by novo gloss meter. Chemical resistivity of the resin films is determined by immersing the films in different solvents. The rationale of current work was to synthesize some high gloss blend resins from some commonly available monomers, having excellent properties suitable for commercial applications.     

环氧改性含磷苯丙防锈乳液的合成

采用常规乳液聚合方法,以环氧树脂改性含有磷酸酯功能单体的苯丙乳液来制备水性防锈乳液。苯乙烯(St)、丙烯酸丁酯(BA)等为共聚单体,引入环氧树脂及具有抗闪蚀功能的磷酸酯功能单体,考察了乳化剂、引发剂、环氧树脂、磷酸酯单体不同用量对乳液及其漆膜的影响,并对乳液的粒径、固含量及漆膜的耐盐水性、附着力等性能进行测试,逐步优化聚合工艺来合成具有高效防锈的新型环氧防锈乳液。研究表明,乳化剂用量、引发剂用量、环氧树脂用量、磷酸酯单体用量分别为单体总量的1.5%、0.6%、7%、3%时,可制得性能较好的水性环氧改性含磷苯丙防锈乳液。     

Preparation and performance of new antifouling resins containing BIT group

New acrylate grafting epoxy antifouling resins containing benzoisothiazoline ketone (BIT) group were successfully synthesized, and their structures and performances were determined. Experimental data indicated that the new acrylate grafting epoxy antifouling resins have a strong bonding to the cured epoxy resin coating through chemical reaction and self-stratifying. And the paint prepared by using the new resin as matrix has excellent self-polishing and antifouling properties. Especially its antifouling period could be modified by changing the weight ratio of the usage of the mixed monomers and epoxy resin in the preparing process of the acrylate grafting epoxy antifouling resins.     

水性羟基丙烯酸树脂的制备与研究

以甲基丙烯酸甲酯(MMA)、苯乙烯(St)和丙烯酸丁酯(BA)等为主要单体,引入丙烯酸(AA)、丙烯酸羟基乙酯(HEA)与甲基丙烯酸异冰片酯(IBOMA)等作为功能单体,通过半连续溶液聚合工艺,最后加水分散制得水性羟基丙烯酸树脂。利用FT-IR、透光度、粘度分析研究了单体配比、引发剂(BPO)用量、温度、链转移剂(DDM)用量、功能单体用量等因素对树脂性能的影响。结果表明,当AA、HEA、IBOMA、BPO和DDM的质量分数分别为3%、12%、10%、3%和2%,聚合反应温度100℃时可获得粘度为5 Pa.s,固含量约45%的水性羟基丙烯酸树脂。     

A novel type of Si‐containing acrylic resins: Synthesis,characterization, and film properties

A novel type of Si‐containing acrylic resins was prepared by two steps and investigated their usage as surface coatings materials. At first a reactive polysiloxane intermediate Z‐6018 was reacted with 2‐hydroxyethyl methacrylate (HEMA) in toluene at 110°C under N₂ atmosphere. After the condensation reaction was stopped, reacted with different acrylic ester monomers such as ethyl acrylate (EA) and methyl methacrylate (MMA) at different mole ratio (1/3 and 1/4) by the free radical addition polymerization. Structures of Si‐containing acrylic resins were characterized by Fourier Transform Infrared Spectrometer (FTIR) and thermal properties of these resins were investigated by thermogravimetric analysis and differential scanning calorimetry DSC techniques. Surface coating properties of the films prepared from these resin were also determined. The results showed that all films are flexible, glossy or semi gloss and have excellent drying and adhesion properties. All films also exhibit abrasion resistances moderately. Water resistance of the films was generally modified by cured in oven and alkaline resistance of the films prepared from resins containing ethyl acrylate units are excellent. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

高性能水性印花涂料的制备

以丙烯酸甲酯(MA)、丙烯酸乙酯(EA)、丙烯酸丁酯(BA)、环氧树脂和乳化剂分别制备核、壳预乳化剂,然后通过种子乳液聚合法制备了具有核壳结构的聚合乳液。以环氧树脂E-44和有机硅氧烷KH-570对聚合乳液进行改性,制备了印花涂料用乳液。研究了乳化剂和核壳单体的配比以及不同改性剂用量对乳液稳定性和成膜性能的影响。结果表明,制备乳液的较佳条件为:复合乳化剂[m(十二烷基硫酸钠)∶m(非离子型乳化剂OS-15)=1∶3]的质量分数为4%,核单体组成为m(MA)∶m(EA)∶m(BA)=1∶1∶3、质量分数为30%～40%,壳单体组成为m(MA)∶m(EA)∶m(BA)=2∶1∶1,改性剂环氧树脂E-44和有机硅氧烷KH-570的用量分别为2%和6%。当烘焙工艺条件为140℃/3min时,制得的印花涂料涂膜在弹性、手感、牢度等性能指标方面均达到了设计要求。     

涂料用有机硅改性丙烯酸树脂的合成与研究

以溶液聚合法合成了有机硅改性丙烯酸树脂,选择不同种类的硅单体进行实验,研究了硅单体用量对涂膜吸水率的影响以及不同软硬丙烯酸类单体比例对涂膜柔韧性及吸水率的影响,并对涂膜进行了红外分析和扫描电镜分析。结果表明：由接枝反应改性的有机硅丙烯酸酯涂料具有优良的性能。     

Preparation and characterization of poly(butyl acrylate‐co‐2‐ethylhexyl acrylate) grafting of vinyl chloride resin with good impact resistance

Crosslinked poly(butyl acrylate‐co‐2‐ethylhexyl acrylate) [P(BA–EHA)] latex was synthesized by seeded emulsion polymerization. P(BA–EHA)/poly(vinyl chloride) (PVC) composite latex was prepared using P(BA–EHA) latex as the seed. The effects of the amount of P(BA–EHA) on the latex particle diameters and mechanical properties of the materials are discussed. The grafting efficiency (GE) of P(BA–EHA)‐grafted vinyl chloride (VC) in the synthesized resin was investigated, and the GE increased with an increasing P(BA–EHA)/VC ratio. The morphology of P(BA–EHA)/PVC was characterized using TEM, SEM, and DMA. TEM indicated that the particles of the P(BA–EHA)/PVC composite latex have a clear core–shell structure. DMA illustrated that the compatibility between P(BA–EHA) and PVC was well improved. With an increasing P(BA–EHA) content, the loss peak in the low‐temperature range became stronger than that of pure PVC, and the maximum values of the loss peaks gradually shifted to higher temperature. SEM showed that the fractured surface of the composite sample exhibited better toughness of the material. The notched impact strength of the material with 4.2 wt % P(BA–EHA) was 11 times that of PVC. TEM showed that P(BA–EHA) was uniformly dispersed in the PVC matrix and that the interface between the two phases was indistinct. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 643–649, 2003     

反光膜用聚丙烯酸酯压敏胶的合成

以醋酸乙烯酯(VAc)为硬单体、丙烯酸异辛酯(EHA)和丙烯酸丁酯(BA)为软单体、丙烯酸(AA)和丙烯酸羟丙酯(HPA)为交联单体、过氧化苯甲酰(BPO)为引发剂和乙酸乙酯为溶剂,制备了反光膜用溶剂型聚丙烯酸酯PSA(压敏胶)。考察了各单体和引发剂含量对PSA性能的影响。结果表明:当w(VAc)=15%、m(EHA)∶m(BA)=3∶1、w(AA)=4%、w(HPA)=6%和w(BPO)=0.8%时,PSA的综合性能优异,并且完全满足反光膜的使用要求。     

氟改性双组分水性丙烯酸聚氨酯涂料性能研究

以甲基丙烯酸十二氟庚酯（DFMA）、丙烯酸（AA）、甲基丙烯酸羟乙酯（HEMA）、甲基丙烯酸甲酯（MMA）和丙烯酸丁酯（BA）为原料,采用溶液聚合法合成了一系列氟含量不同的水性羟基丙烯酸树脂。将含氟水性羟基丙烯酸树脂、亲水性异氰酸酯固化剂和助剂混合制备氟改性双组分水性丙烯酸聚氨酯（2K—WPU）涂料。利用傅里叶变换红外光谱（FT-IR）对其结构进行了表征,并对涂料的接触角、吸水率和清漆性能分别进行了测试。结果表明,该水性树脂粒径在28．2～68．1nm之间,粒径分布均匀。当水性羟基丙烯酸树脂组成中DFMA质量分数从0增加至20％时,所制备氟改性2K-WPu涂料的水接触角从70．3。增大到97．6。,吸水率从11．4％降低至6．31％,涂膜的耐水性显著提高。清漆性能测试表明,所制氟改性2K．WPu的各项性能优异。     

水基改性环氧树脂涂料的合成研究

研究了以环氧树脂Ｅ－ ４４（ 简称为环氧树脂） 为主要原料, 对水基改性环氧树脂涂料———环氧磷酸酯 丙烯酸接枝共聚物的合成反应, 探讨了丙烯酸及其酯, 苯乙烯和引发剂的用量,接枝反应温度, 接枝反应时间等因素对该接枝共聚物水分散稳定性的影响, 确定了较佳的工艺条件。并对该接枝共聚物进行了有关的产品性能和应用性能检测。     

环氧改性醇溶性丙烯酸酯干式复膜胶的研制

介绍了一种新型环氧改性醇溶性丙烯酸酯干式复膜胶的制备方法和性能。首先以环氧树脂E-44和丙烯酸(AA)为原料,合成了一种丙烯酸环氧单酯(EA);再以乙醇为溶剂,采用半连续加料法合成了醋酸乙烯酯(VAc)、丙烯酸丁酯(BA)、丙烯酸2-乙基己酯(2-EHA)和EA四元共聚物。该复膜胶合成的适宜条件为:m(VAc)∶m(BA)∶m(2-EHA)∶m(EA)=40∶25∶20∶15,w(引发剂)=1.0%,反应温度为73℃,反应时间为7h。实验结果表明,该复膜胶可用于制备塑料复合薄膜,具有环保、无毒、剥离强度高和快速固化等特点,适用于快速干式复合薄膜的生产线。     

木器高光面漆用丙烯酸酯树脂的制备与性能研究

以甲基丙烯酸甲酯(MMA)和丙烯酸丁酯(BA)为主单体,多种交联体系为功能单体,采用水性固体丙烯酸树脂(SR-675、QZ-7001、QZ-7002)和聚合型乳化剂NRS-10搭配作为体系的表面活性剂,通过预乳化半连续乳液聚合工艺合成了木器高光面漆用丙烯酸酯树脂。探究了水性固体丙烯酸树脂酸值、T_g、相对分子质量以及用量;NRS-10用量、引发剂(APS)用量和树脂T_g对树脂及涂膜性能的影响。结果表明:当采用水性固体丙烯酸树脂SR-675且用量占单体总量的20%(下同)、NRS-10占0.5%、APS占0.75%,树脂T_g设计为40 ℃时,合成的丙烯酸酯树脂制备成木器面漆,涂膜光泽高、附着力好、耐水性好,铅笔硬度可达2H。     

高固体份含氟丙烯酸酯树脂的合成及性能研究

通过丙烯酸酯类单体与含氟丙烯酸单体的溶液聚合,制备了高固体份低粘度的含氟多羟基丙烯酸树脂。讨论了反应温度、引发剂、氟单体、羟基值等因素对树脂分子量、黏度以及性能的影响。通过优化条件,结果表明制备的含氟丙烯酸树脂,数均分子量小于6000,分子量分布<1.5,羟基含量>30 mgKOH/g,高固体份低粘度特性显著。通过与固化剂N75按质量比1∶5配制成涂料,常温固化成膜后,测定其各项性能均优于普通丙烯酸聚氨酯树脂涂料。     

Resultant synergism in the shear resistance of acrylic pressure‐sensitive adhesives prepared by emulsion polymerization of n‐butyl acrylate/2‐ethyl hexyl acrylate/acrylic acid

Acrylic emulsion pressure‐sensitive adhesives (PSAs) were synthesized by the copolymerization of n‐butyl acrylate with various levels of 2‐ethyl hexyl acrylate (2EHA) and a small constant amount of acrylic acid. The effect of varying the n‐butyl acrylate/2EHA monomer composition on the kinetic behavior of the polymerization and the characteristics of the copolymers prepared in a batch process were investigated. The results showed that increasing the amount of 2EHA in the monomer caused the polymerization rate and the glass‐transition temperature of the acrylic copolymers to decrease. Increasing the amount of 2EHA caused the gel content of the copolymers to decrease, reaching a minimum at 50 wt %; thereafter, the gel content increased at higher 2EHA levels. For the acrylic emulsion, the peel‐fracture energy of the PSAs decreased as the amount of 2EHA in the monomer was increased up to 50 wt %. At higher 2EHA levels, the peel‐fracture energy was relatively constant. Interestingly, a synergistic effect of increased shear resistance at 25 wt % 2EHA was observed without a significant trade‐off in terms of the peel and tack properties. This behavior was attributed to a good interconnection between the microgels and the free polymer chains inside the contacting particles in the adhesive film. Cooperation between various levels of 2EHA in the copolymer structure simultaneously changed the crosslink molecular weight (M_c) of the microgels and the entanglement molecular weight (M_e) of the free chains in the adhesive network morphology. The adhesive performance of the PSAs was found to be correlated with their M_c/M_e values as the 2EHA proportion was varied. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

碱溶性丙烯酸树脂在水性木器漆乳液制备中的应用

以碱溶性丙烯酸树脂作为乳化剂,以丙烯酸丁酯、甲基丙烯酸甲酯、甲基丙烯酸正丁酯、丙烯酸2-乙基己酯为共聚单体,双丙酮丙烯酰胺为交联单体,过硫酸钾为引发剂,系统研究了碱溶性丙烯酸树脂的相对分子质量、酸值、用量及配伍,交联单体的用量对乳液聚合稳定性,乳液粒径及分布,涂膜的耐水性、耐醇性、硬度及最低成膜温度的影响。结果表明:当低酸值低相对分子质量碱溶性丙烯酸树脂与高酸值高相对分子质量碱溶性丙烯酸树脂复配且质量比为7:3~9:1,总量为单体的16%~26%时,聚合稳定性均较好且粒径可控制在50~80 nm之间。涂膜室温养护7 d的硬度可达到3H,耐水白可达400 h,经60°白酒浸泡7 d涂膜无变化,表明这种乳液可适合用作木器家具涂料的成膜物质。     

聚丙烯酸酯涂料的制备

以甲基丙烯酸甲酯(MMA)、丙烯酸丁酯(BA)、丙烯酸(AA)为单体,以十二烷基苯磺酸钠为乳化剂,当m(BA)∶m(MMA)∶m(AA)=33∶17∶1,通过乳液聚合制得丙烯酸酯类乳液,再加入填料及各种助剂,经过高速搅拌、均质而出料。并且讨论了乳化剂及引发剂用量对乳液聚合、乳液及涂料性能的影响。     

Synthesis and characterization of tall oil fatty acids-based alkyd resins and alkyd–acrylate copolymers

The polymerization and properties of environmentally friendly waterborne binders for wood coatings were studied. Conjugated and non-conjugated tall oil fatty acids-based alkyd resins were synthesized and further copolymerized via miniemulsion polymerization with acrylates (butyl acrylate and methyl methacrylate). The ratio between alkyd resin and acrylate monomers was varied and the effect on copolymerization and the copolymer binder properties, such as particle size, molecular weight, grafting of acrylate to alkyd resin and reaction of double bonds, were studied. It was observed that the use of MMA influenced on the degree of grafting of acrylate and monomer conversion because the steric hindrances prevent MMA to react with alkyd double bonds as eagerly as BA. The increasing amount of alkyd resin was noticed to decrease the polymerization rate. The research showed that it was possible to prepare stable hybrids, alkyd–acrylate copolymers, with varied chemical composition.     

Metal ion retention properties of water‐insoluble polymers containing carboxylic acid groups

Crosslinked poly(acrylic acid), PAA, and poly(2‐acrylamidoglycolic acid), PAAG, were synthesized by radical polymerization. Both resins contain carboxylic acid groups. PAA at basic pH exists basically as an acrylate anion and PAAG shows three atoms or groups, carboxylic acid, hydroxyl, and amide groups, that can act as ion exchanger or chelating groups. Both resins are studied as adsorbents to trace metal ions from saline aqueous solutions and natural sea water and their properties by Batch equilibrium procedure are compared. The metal ions studied under competitive and noncompetitive conditions were Cu(II), Pb(II), Cd(II), and Ni(II). The effects of pH, time of contact, amount of resin, temperature, and salinity were studied. Resin PAA shows a high affinity (>80%) for Cu(II) and Cd(II) and resin PAAG shows also a high affinity for Ni(II), Pb(II), and Cd(II). By treatment of the metal ion‐loaded resin with 4M HNO₃ it is possible to recover completely the Cu(II) ions from resin PAA and Ni(II) and Pb(II) from resin PAAG. The metal ion retention properties were studied with natural sea water. For those natural sea waters containing Cu(II) and Cd(II), the resins showed a high affinity for Cd(II) ions. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 697–705, 2006