Synthesis of four-component acrylic-modified water-reducible alkyd resin: investigation of dilution ratio effect on film properties and thermal behaviors

This study investigated the effect of the dilution ratio on film properties of acrylic-modified water-reducible alkyd resins. First, new four-component acrylic-modified alkyd resins based on 1,3-propanediol containing 40% of the equivalent amount of acrylic copolymer to alkyd resin were synthesized using the fatty acid method. The synthesized acrylic-modified alkyd resin was then dissolved in isopropyl alcohol (IPA) at various ratios and further diluted using distilled water at various ratios to obtain by-weight percentages of 70/50, 70/60, and 80/60 of solid content to IPA and water, respectively. Films of the modified alkyd resins were prepared, and cured at 150°C for 1 h, then their physical and chemical surface coating properties and thermal behaviors were investigated. The best results were obtained for the by-weight percentages of 80/60.     

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。     

新型改性醇酸树脂涂料的制备及性能研究

采用脂肪酸一步法合成了端羟基醇酸树脂,并给出了甲苯二异氰酸酯(TDI)改性醇酸树脂的制备工艺。从树脂涂料的固含量、表面干燥时间、硬度等方面考察了n(—NCO)∶n(—OH)、二羟甲基丙酸(DMPA)和三乙胺的用量、初期及中期聚合温度的影响,并对其进行了红外表征。实验结果表明:n(—NCO)∶n(—OH)=1.8,w(DMPA)≈5%,三乙胺在改性反应前加入,用量为1.7g(每20g样品),初期聚合温度30℃、中期聚合温度80~85℃时,制得的涂料综合性能优异。     

自干型环氧丙烯酸改性水性醇酸树脂的制备与性能

在酯化反应中后期加入环氧树脂E-20,合成环氧改性醇酸树脂后,再加入苯乙烯(St)、甲基丙烯酸甲酯(MMA)、丙烯酸丁酯(BA)和甲基丙烯酸(MAA)进行共聚接枝,获得了自干型环氧丙烯酸改性水性醇酸树脂。分析了加入环氧树脂时酸值、环氧树脂用量、丙烯酸单体总用量、各单体用量比例、引发剂过氧化苯甲酰(BPO)用量和反应温度等对产物性能的影响。结果表明:在酸值为35~40 mg KOH/g时加入8%~12%E-20,丙烯酸类单体总量为20%[其中w(St)∶w(MMA)=1∶1,w(软单体)∶w(硬单体)=1∶3],BPO用量为单体量的6%,温度控制在115°C,得到的改性树脂水分散性良好,干燥速度快,漆膜硬度、附着力、耐水性和耐盐水性等性能均优于未改性醇酸树脂漆膜。     

Electrochemical and anti‐corrosion behaviors of water dispersible graphene/acrylic modified alkyd resin latex composites coated carbon steel

A type of water dispersible graphene (PG) has been synthesized by nucleophilic ring‐opening reaction of the primary amine group in 3‐(1‐(2‐aminopropoxy) propan‐2‐ylamino) propane‐1‐sulfonate sodium (PPS) with epoxy groups on the basal plane of graphene oxide (GO), followed by in situ reduction with hydrazine hydrate. The PG is employed as nanoscale reinforcement fillers in waterborne acrylic modified alkyd resin (AMAR) coatings. The stability and corrosion resistance of the waterborne PG/AMAR nanocomposite coatings are investigated. SEM and stability of nanocomposite indicated that the PG sheet is uniformly distributed in AMAR nano‐emulsion. Potentiodynamic polarization and electrochemical impedance spectroscopy studies indicated that the PG/AMAR composite coatings exhibit higher corrosion resistance in simulated body fluid (SBF) compared with pure AMAR coatings and GO/AMAR coatings. In addition, the stability and corrosion resistance of the composite materials reach optimum when the PG content is 1%. PPS functionalized graphene (PG) displays prospective application in anticorrosion field. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44445.     

Preparation and characterization of water reducible alkyd resin/colloidal silica nanocomposite coatings

In this study, water reducible alkyd resins containing different amounts of colloidal silica were synthesized for the first time. In order to achieve this, alkyd resin, which has an oil content of 35%, was prepared with tall oil fatty acid, isophthalic acid, trimellitic anhydride, and trimethylolpropane. The alkyd resin was neutralized with triethylamine, and was dissolved in an isobutyl alcohol-isopropyl alcohol-butyl glycol mixture to produce 75% (wt.) solution, which was called stock alkyd resin. The stock alkyd resin was diluted with water to 50% (wt.) concentration with water and colloidal silica mixture in order to prepare an alkyd solution containing 0%, 5%, 10%, 15% and 20% colloidal silica. Then the effect of the silica nanoparticle addition on the surface coating properties, thermal behaviors and surface morphologies of water reducible alkyd resins was investigated. As a result, the addition of colloidal silica has improved surface coating properties and thermal behaviors of nanocomposite water reducible alkyd resin.     

端羟基聚丁二烯改性醇酸树脂的合成与性能研究

利用梓油和桐油以及带端羟基的聚丁二烯(下文简称丁羟)合成了具有快干特征的醇酸树脂。利用该树脂配制的涂料不仅干性好,且涂层光泽高、鲜映性好,保色保光性优异,可用于农业机械、工程机械等涂装。     

有机丙硅树脂的合成与性能

有机丙硅树脂是由有机硅,丙烯酸及丙烯酸酯类以不同方式合成的,因为它具有独特的性能,使它在许多领域得到广泛的应用。因此,近几年来有许多这方面的报导。     

Synthesis of water‐reducible acrylic–alkyd resins based on modified palm oil

Water‐reducible acrylic–alkyd resins were synthesized from the reaction between monoglycerides prepared from modified palm oil and carboxy‐functional acrylic copolymer followed by neutralization of carboxyl groups with diethanolamine. Modified palm oil was produced by interesterification of palm oil with tung oil at a weight ratio of 1 : 1, using sodium hydroxide as a catalyst, whereas carboxy‐functional acrylic copolymer was prepared by radical copolymerization of n‐butyl methacrylate and maleic anhydride. The amount of acrylic copolymer used was from 15 to 40% by weight, and it was found that homogeneous resins was obtained when the copolymer content was 20–35 wt %. All of the prepared water‐reducible acrylic–alkyd resins were yellowish viscous liquids. Their films were dried by baking at 190°C and their properties were determined. These films showed excellent water and acid resistance and good alkali resistance. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1170–1175, 2005     

Stability and film properties of tung oil modified soybean alkyd emulsion

A series of tung oil modified soybean alkyd emulsions are prepared by an inversion emulsified technique. In these alkyd resins, the tung oil contents are about 0, 12.5, and 25.0 wt % (based on the total oil). Using IGEPAL CO‐630 as the surfactant, a very stable alkyd emulsion can be obtained. With the increase of the tung oil contents in alkyd emulsions, the initial droplet sizes of the emulsions increase dramatically. Aging under 50°C can eliminate the difference in droplet sizes; the final droplet sizes of the emulsions are about 50 nm. The alkyd resins also have good hydrolytic stability. The tung oil contents in the alkyd resins also strongly influences the film properties; suitable tung oil content improves the film gloss. An atomic force microscopy investigation shows that the film from the alkyd emulsion is more water sensitive; after a 50‐h deionized water immersion, the film surface appears to have a lot of dents. This indicates that the film surface may be very rich in surfactant species. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1698–1706, 2000     

条件对丙烯酸-丙烯酰胺共聚合成树脂的影响

以丙烯酸、丙烯酰胺为原料，过氧化异丙苯为引发剂，N，N-五甲基二丙烯酰胺为交联剂，制备了吸水树脂，讨论了制备条件的影响。     

The effects of anhydride type and amount on viscosity and film properties of alkyd resin

In this study, a modified method for preparing low viscosity alkyd resin was suggested. For this purpose the preparation of sunflower oil-based alkyd resins were achieved into two steps. First sunflower oil and glycerol were reacted to form partial glycerides, and then, after removing free glycerol, esterification reaction was achieved between partial glycerides and anhydride. Glutaric, maleic, phthalic and succinic anhydride were used. Sunflower oil alkyd resins were also prepared by classical method. The results obtained were compared with each other. By the modified method low viscosity and good film properties resins could be prepared.     

水性发用聚丙烯酸定型树脂的合成及性能

以丙烯酸(AA)、丙烯酰胺(AM)、甲基丙烯酸二甲氨基乙酯(DMAEMA)和丙烯酸丁酯(BA)为聚合单体,N-羟甲基丙烯酰胺(NMA)为交联剂,采用溶液聚合法制备了水性发用聚丙烯酸定型树脂,并应用于配制睹喱.探讨了单体组成和交联剂用量对树脂性能的影响.当m(AA):m(AM):m(DMAEMA):m(BA)=1.0:0.07:0.07:0.15,NMA用量为单体总质量的0.06%时,制得树脂无色透明,w=10%水溶液表观黏度2042 mPa·s;配制成睹喱后,卷曲保持率为73%,梳理时基本无白屑.     

Preparation of acrylic copolymer latex modified by fluorine,silicon, and epoxy resin

A series of modified acrylic copolymer latices have been prepared through a semicontinuous emulsion copolymerization process with a variety of hydrocarbon monomers and (perfluoroalkyl) methyl methacrylate, vinyltriethoxysilicone, and phenol‐formaldehyde epoxy resin. The composition of copolymer was analyzed by fluoride ion selective electrode analysis, ¹⁹F NMR, FTIR, crosslinking degree determination, and epoxy‐acetone method. The results showed that the fluorine monomer, silicon monomer and epoxy resin had copolymerized with acrylic monomers. The optimum mass ratio between the curing agent TEA and epoxy resin was 1.36 : 6. The determination results of stabilities (electrolyte stability, freeze‐thaw stability, high temperature stability and mechanical stability) of latices showed that the incorporation of fluorine monomer and silicon monomer improved freeze‐thaw stability and mechanical stability, whereas the epoxy resin did not have obvious effect on the stabilities. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

噁唑烷酮改性环氧树脂的性能

采用4,4-二苯基甲烷二异氰酸酯(MDI)对双酚A环氧树脂和脂肪族环氧树脂进行噁唑烷酮化共改性,研究了MDI及作为活性稀释剂的脂肪族环氧用量对改性产物黏度及树脂固化物力学性能、耐热性的影响。结果表明,低改性比和稀释剂可以有效降低唑烷酮改性环氧树脂黏度,当改性比为4∶1时,树脂固化物拉伸强度、弯曲强度达到75.4 MPa和158.2 MPa,分别比环氧树脂固化物提高了64%和57%,断裂延伸率和冲击强度有较大提高,具有高强高韧的特点。稀释剂含量对Tg影响较小,各改性树脂Tg在108～118℃之间,与纯环氧树脂的耐热性相当。     

正交优化水性丙烯酸树脂的合成及性能研究

合成了碱溶性聚丙烯酸乙酯/丙烯酸丁酯/甲基丙烯酸[P(EA/BA/MAA)]无规共聚物,研究其对单体甲基丙烯酸甲酯(MMA)和丙烯酸乙酯(EA)的乳化稳定能力.以合成的[P(EA/BA/MAA)]作为高分子乳化剂,进行甲基丙烯酸甲酯/丙烯酸乙酯/甲基丙烯酸/甲基丙烯酸-β-羟乙酯[P(MMA/EA/MAA/HEMA)]乳液聚合反应;并通过正交试验对乳液的聚合参数进行优化,得到了最佳合成条件;在此条件下合成的乳液稳定性好、吸水性低,转化率高.采用FT-IR、TEM对聚合物乳液的结构进行了表征;TEM图片证实,乳胶粒子呈明显的核/壳结构,平均粒径80 nm.     

Synthesis and properties of novel acrylic polyester hyper-dispersant

3-Pentadecylphenyl acrylate (PDPA) was synthesized from renewable sources (the cashew nut shell liquid), by using a novel organic chemical intermediate that can be used to copolymerize with vinyl monomers. A novel acrylic polyester hyper-dispersant was prepared by polymerization of methacrylic acid (MAA), butyl acrylate (BA), and PDPA. The acrylic polyester hyper-dispersants were used to disperse titanium dioxide in non-polar solvent system, and the dispersion performance was studied. The viscosity and particle size of suspensions were affected by monomer ratio and molecular weight; the results showed that the optimum monomer ratio and molecular weight were MAA:BA:PDPA = 1:10:1.2 (wt%) and 6000, respectively. The optimum amount weight of MAA of acrylic polyester should be around 10% (wt%).     

Investigation of the thermal properties of novel adamantane‐modified polybenzoxazine

Two novel structures of adamantane‐modified benzoxazines were synthesized from 4‐(1‐adamantyl)‐phenol through the incorporation of adamantane as a pendant group into the polybenzoxazine backbone. Both ¹H‐NMR and Fourier transform infrared spectra were used to characterize these structures. The rigid structure of the adamantane tended to hinder the chain mobility (boat anchor effect) and substantially enhanced the thermal properties, including the glass‐transition temperature and decomposition temperature, especially for poly(6‐adamantyl‐3‐methyl‐3,4‐dihydro‐2H‐1,3‐benzoxazine). In the poly(6‐adamantyl‐3‐phenyl‐3,4‐dihydro‐2H‐1,3‐benzoxazine) system, however, the opposite result for the glass‐transition temperature was observed and it was interpreted as lower crosslinking density. The phenyl group was bulkier than the methyl group, and the movement of the molecular chain was hindered between bridging points during the curing process; this resulted in a lower crosslinking density and a lower glass‐transition temperature than those of poly(6‐adamantyl‐3‐methyl‐3,4‐dihydro‐2H‐1,3‐benzoxazine). © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 932–940, 2004     

双重改性酚醛树脂的合成及性能研究

以环氧大豆油(ESO)和苯胺对酚醛树脂进行改性,得到分子结构中含有苯并噁嗪环的环氧豆油醚化增韧酚醛树脂预聚体,并通过红外光谱对其结构进行了表征。采用非等温差示扫描量热法及热重分析法分别对该预聚体的热固化温度及固化产物的耐热性进行了研究。同时研究了环氧大豆油不同添加量对改性树脂的冲击强度及弯曲强度的影响。研究结果表明,改性树脂的固化物失重5%时的温度为323℃,比纯酚醛树脂高80℃左右;而冲击强度在ESO添加量40%时为4.61 kJ/m2,是普通酚醛树脂的3~4倍。     

Bismaleimide modified bis propargyl ether bisphenol A resin: Synthesis,cure, and thermal properties

Bis propargyl ether bisphenol A (PBPA) was synthesized and blended with 4,4′‐bismaleimide diphenyl methane (BDM) at different molar ratios. The cure behavior of the blend resins was measured by DSC and FTIR spectra. The results indicated that the onset cure temperatures of the blend resins were about 20–30°C lower than that of pure PBPA, and the cure exothermic enthalpy of the resins also significantly reduced from 1320 (PBPA) to 493 J/g (PBPA–BDM (1.0:2.0)). The thermal stabilities and dynamic mechanical properties of the cured resins were characterized by TGA and DMA, respectively. The thermal stability of the resins improved markedly with the increase in BDM content, and the glass transition temperature increased from 306°C for PBPA–BDM (1.0:0.5) to 358°C for PBPA–BDM (1.0:2.0). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3610–3615, 2006