超支化聚酯的水溶性及交联剂应用

以顺丁烯二酸酐和甘油为原料合成了多官能团中间体,以季戊四醇为核分子进一步反应合成具有良好水溶性的端羟基超支化聚酯。当n(顺丁烯二酸酐)∶n(甘油)=1∶1,n(原料)∶n(季戊四醇)=100∶1和150∶1时,所得产物室温下具有良好水溶性。初步探索了超支化端羟基聚酯作为水性涂料交联剂,可使丙烯酸酯乳液性能明显提高。     

以季戊四醇为核的超支化不饱和聚酰胺酯的合成

以顺丁烯二酸酐（MA）和二乙醇胺（DEA）为原料合成超支化不饱和聚酰胺酯AB2型单体。通过季戊四醇和AB2型单体进行酯化反应合成支化不饱和聚酰胺酯HBP。考查了反应温度、催化剂用量、反应时间对反应产率的影响。最佳工艺条件为：温度140℃,反应时间5h,催化剂对甲苯磺酸用量为反应物量的1.5%。     

Synthesis and Characterization of a Novel Low‐Viscosity Unsaturated Hyperbranched Polyester Resin

Hyperbranched thermosetting resin is the best additive for toughening and reinforcing linear thermosetting resin. A novel low‐viscosity unsaturated hyperbranched polyester resin (UHPR) is synthesized by the reaction between maleic anhydride monoisooctyl alcohol ester and a hydroxyl‐ended hyperbranched polyester resin (HPR) prepared from phthalic anhydride (PA) and trimethylolpropane (TMP). The structure of HPR is characterized by FT‐IR and ¹H NMR, and its degree of branching is deduced by comparing with the ¹H NMR spectrum of a model compound. The molecular weights of HPR and UHPR are determined by theoretical calculation and MALDI‐TOF MS measurements. This low‐viscosity (< 10 000 cP) novel UHPR can be applied in the field of environment‐friendly coatings and in toughening and reinforcing linear unsaturated polymers.     

丙烯酸改性聚酯水分散体纺织涂层的制备

采用新戊二醇、二甘醇、邻苯二甲酸酐、顺丁烯二酸酐等为原料合成了主链上含有双键的聚酯,然后采用含一定亲水基团的丙烯酸混合单体接枝改性聚酯树脂,提高了聚酯树脂的水溶性和成膜性能.由此制备出一种性能优良的环保型纺织涂层.用红外光谱表征了产物的分子结构.讨论了顺丁烯二酸酐用量及中和剂的选择对水分散体性能的影响.     

松香基UV固化超支化聚酯丙烯酸酯的合成

采用季戊四醇作为聚酯内核与二羟甲基丙酸(DMPA)发生酯化反应后,再与以松香为原料合成的马来海松酸酐(MPA)反应合成富含末端基团的超支化聚酯大分子(HBP),再分别将2-羟乙基丙烯酸酯(2-HEA)和五缩六乙二醇丙烯酸单酯(PEA-6)引入到HBP结构中,得到新型UV固化超支化树脂(HBR)。采用红外光谱对产物结构进行了表征,对固化膜进行了热重分析,通过动态力学谱测试了其粘弹性,并对涂膜的其他基本性能进行了测定。结果表明,所得树脂大都具有较低的粘度,漆膜硬度较好,对金属、塑料底材附着力较好。随着PEA-6用量的增加,产物的硬度和热力学稳定性能下降,柔韧性增加。     

Synthesis and characterization of unsaturated polyesters based on the aminolysis of poly(ethylene terephthalate)

The depolymerization of poly(ethylene terephthalate) via an aminolysis process was studied. An excess of ethanol amine in the presence of sodium acetate as a catalyst was used to produce bis(2‐hydroxyl ethylene) terephthalamide (BHETA). Unsaturated polyester (UP) resins were obtained by the reaction of BHETA with different long‐chain dibasic acids such as decanedioic acid, tetradecanoic acid, and octadecanoic acid in conjunction with maleic anhydride as a source of unsaturation. The chemical structure of the UP resins was confirmed by ¹H‐NMR. The vinyl ester resins were used as crosslinking agents for UP. The curing behavior and mechanical properties of the UP resins with vinyl ester were evaluated at different temperatures ranging from 25 to 55°C. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

浅色高软化点马来松香季戊四醇酯的制备

以精制松香、马来酸酐和季戊四醇为原料,制备浅色高软化点马来松香季戊四醇酯。重点讨论了不同还原剂、催化剂、减色剂、原料配比及反应时间等因素对产品性能的影响。研究表明最佳合成条件为：马来酸酐、还原剂SHHP、催化剂R-1、减色剂M-6的用量分别为精制松香质量的13%、0.3‰、3‰、3‰,精制松香和马来酸酐加成反应60 min,马来松香和季戊四醇酯化反应150 min,所得产品颜色为加纳色号3号,酸值为9.8 mg/g,软化点为159 ℃。     

超支化聚合物的研究及应用

以二异丙醇胺（DIPA）及酸酐为原料合成了含有一个羧基、两个羟基的AB2型单体,采用AB2型单体自缩聚的方法合成了超支化聚酰胺酯,然后用甲基丙烯酸对超支化聚酰胺酯的端基功能改性。然后将超支化单体与马来酸酐、甲基丙烯酸共聚合成阻垢分散剂。     

有机硅烷偶联剂改性紫外光固化超支化聚醚基水性聚氨酯的性能

采用超支化聚酯Boltorn H 20与丁二酸酐反应,制备了亲水性超支化聚酯,然后与甲基丙烯酸酯基改性的聚醚基聚氨酯预聚体和3-异氰酸酯基丙基三乙氧基硅烷(IPTS)反应,合成了有机硅烷偶联剂改性紫外光固化聚醚基超支化水性聚氨酯(WHPU)。考察了有机硅烷偶联剂用量对WHPU的耐酸性、固化时间、凝胶质量分数、附着力、水接触角、水吸附率、乳液粒径分布及热稳定性的影响。结果表明,当IPTS与Boltorn H 20中羟基的摩尔比为6/16时,固化后的WHPU膜的凝胶质量分数为92%,在玻璃表面的附着力达到0级;与不含有机硅烷偶联剂的WHPU相比,该涂膜的水接触角和热稳定性分别提高了34°和22℃,其吸水率从13.8%降低到4.3%。     

超支化水性聚氨酯乳液的制备及性能研究

以顺丁烯二酸酐改性的超支化聚酯Boltorn H20、聚四氢呋喃2000和异佛尔酮二异氰酸酯为主要原料合成了超支化水性聚氨酯乳液,研究了改性超支化聚酯Boltorn H20的合成,以及改性超支化聚酯中羧基含量、初聚—NCO/—OH物质的量比、催化剂用量等对制备水性聚氨酯的影响,并探讨了亲水基团含量、乳化温度、中和度等因素对乳液及涂膜性能的影响,进一步使用傅里叶红外和热重分析分别对超支化聚氨酯涂膜的结构和热稳定性能进行了表征及测试。结果表明,在不加催化剂,初聚—NCO/—OH物质的量比为2∶1,亲水基团含量为2.05%的条件下,合成得到的含固量为30%的超支化水性聚氨酯乳液稳定性好。由此得到的超支化聚氨酯薄膜的耐水性和热稳定性较好。     

Hyperbranched unsaturated polyester resin for application in impregnation coatings

A new kind of water-soluble hyperbranched unsaturated polyester resin (HBUP) was prepared to enhance the rate of curing, to increase the adhesive strength and to decrease the dielectric constant of the water-soluble insulating impregnation coating comprising water-soluble unsaturated alkyd resin and amino resin. The HBUP was synthesized from pentaerythritol as the core molecule, which was then esterified with dimethylol propionic acid (DMPA). In addition, the terminal hydroxyl groups of HBUP were modified by acrylic acid and maleic anhydride. The hyperbranched structure and C=C double bonds of HBUP resin were investigated by Fourier transform infrared (FTIR) and nuclear magnetic resonance (¹³C-NMR and ¹H-NMR) spectroscopies. The reaction rate of the water-soluble insulating impregnation coating was accelerated by addition of HBUP which was demonstrated by the surface drying test and differential scanning calorimetry (DSC). The electrical and mechanical properties of the water-soluble insulating impregnation coating were also studied. It was shown that the addition of HBUP resin could reduce the permittivity of the coating which was at its lowest level when the HBUP content was 5 wt%, whereas the breakdown voltage, volume resistivity and adhesive strength of the coating were improved.     

Synthesis and characterization of new hydrogels on the basis of water‐soluble maleic anhydride copolymers with γ‐aminopropyltriethoxysilane

This work describes the synthesis and macromolecular reactions of maleic anhydride (MA)–acrylic acid (AA) binary reactive copolymers with γ‐aminopropyltriethoxysilane (APTS) as a polyfunctional crosslinker. Copolymers with a given composition of MA–AA (47.17–52.83 wt %) were synthesized by radical binary copolymerization with benzoyl peroxide as an initiator in p‐dioxane at 70°C in nitrogen atmosphere and initial monomer ratio of 1 : 1. It is shown that the network structure is formed in MA–AA/APTS in water by intermolecular reaction between the anhydride unit and the amine group, as well as between the etoxysilyl fragment and free carboxyl groups of the acrylic acid and maleic anhydride unit. Swelling parameters such as beginning time of hydrogel formation, initial rate of swelling, swelling rate constant, equilibrium swelling, and equilibrium water content were determined for copolymer/APTS/water systems with various copolymer/crosslinker ratios. Formation of a hyperbranched network structure through the fragmentation of side‐chain reactive groups in the studied systems was confirmed by FTIR, TGA, and DSC methods. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 4009–4015, 2003     

含三嗪环的超支化聚酯丙烯酸酯的合成和应用

以丙烯酸甲酯和二乙醇胺为原料,制得N,N-二羟乙基-3-胺基丙酸甲酯（DAMP）;接着,用DAMP与三羟乙基异氰脲酸酯（THEIC）经酯交换反应,合成出一种超支化聚酯多元醇;再以该多元醇与丙烯酸通过酯化反应,制备了可UV固化的超支化聚酯丙烯酸酯。实验结果表明：以对甲苯磺酸为催化剂,当THEIC与DAMP的物质的量比为1∶9时,可制得二代超支化聚酯多元醇;该聚酯丙烯酸酯的玻璃化温度为53.0℃,与环氧丙烯酸酯（9104）混合组成的组合物,具有固化速度快、固化膜柔韧性佳的特点;附着力可达0级,摆杆硬度为0.751。     

萜烯基聚酯丙烯酸酯的合成及性能研究

以萜烯马来酸酐(TMA)、DCPD、顺酐(MA)、乙二醇(EG)、丙二醇(PG)、丙烯酸(AA)为主要原料,通过三步法合成了聚酯丙烯酸酯。通过红外光谱分析仪、动态机械分析仪和TG研究了不同原料配比、缩聚反应时间、阻聚剂用量对涂膜性能的影响。结果表明,该光固化涂膜具有良好的力学性能、耐化学性能和耐热性,且固化速度快,可单独作为UV固化的预聚物使用。     

Preparation and characterization of hyperbranched polyester capillary columns used for the separation of basic proteins

A series of hyperbranched polyesters with pentaerythritol as the core were synthesized and coated on the inner surface of fused‐silica capillaries by chemical bonding. Three kinds of basic proteins were selected for studying the behavior of the adsorption to fused‐silica capillaries. Comparative studies of the coating materials were conducted, and the experimental results showed that the coated columns with hyperbranched polyesters could suppress the electroosmotic flow greatly and effectively prevent adsorption in the pH range of 4–6; they were superior to capillaries coated with traditional hydroxypropyl cellulose. Furthermore, research was conducted to study the effect of hyperbranched polyester generation on the column efficiency. The results showed that higher column efficiency was obtained on a capillary column coated with the sixth generation of the hyperbranched polyester at pH 5.0. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Microgel formation and thermo‐mechanical properties of UV‐curing unsaturated polyester acrylates

The effect of internal and terminal unsaturation on the properties of the acrylated polyester films was investigated. Four types of acrylated polyester resin were prepared using adipic acid, maleic anhydride, neopentyl glycol, trimethylolpropane, and acrylic acid. Terminal and internal double bond content as well as branching was adjusted by the molar quantities of trimethylolpropane and maleic anhydride, respectively. A reactive diluent, trimethylolpropane triacrylate (TMPTA), was also used. A three‐factor, three‐level Box‐Behnken design was used to investigate complex nonlinear relationships. Dynamic mechanical, fracture toughness, and tensile properties were evaluated with respect to the amount of terminal and internal unsaturation, and reactive diluent concentration. It was found that microgel formation extensively affects the final UV‐cured film properties. Small quantities of microgels function as micro‐support units, whereas high extent of microgelation causes phase separation through cluster formation and hence, decreases the mechanical properties. It is essential to control the extent of microgelation and phase separation to optimize product performance. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

New high performance waterborne organic–inorganic hybrid materials from UV curing

The third generation glycerol based hyperbranched polyester (HBPE-3G) was synthesized by reacting glycerol and 2,2-bis(hydroxymethyl)propionic acid in a stoichiometric molar ratio. This polyester was used as preparation for waterborne hyperbranched UV cured polyurethane–silica hybrid coatings. The acrylic terminated waterborne coatings were prepared by modifying some of the hydroxyl groups HBPE-3G to acidic groups by reacting with maleic anhydride. The remaining hydroxyl groups were reacted with NCO terminated acrylate. Then the prepolymer was neutralized with triethyl amine and dispersed in water. The waterborne hybrid formulations were prepared by mixing 3, 5 and 10% of trimethoxysilylpropyl methacrylate (TMSPM) into the acrylic terminated waterborne coatings. The films were casted and cured under UV light. The various film properties were studied by XRD, AFM, TGA and DMTA instruments. TGA result suggests that the onset degradation temperature and final mass residue increase with increasing TMSPM concentration. DMTA results show that the storage modulus and glass transition temperature increase for the hybrid formulations with increasing TMSPM concentration. The structural characterization of the hybrid coatings was performed using FTIR spectroscopy. The tensile test demonstrated that the mechanical properties improve with the increasing TMSPM content. Surface morphology was studied by atomic force microscopy (AFM). AFM study revealed that TMSPM was crosslinked homogenously through the polymer matrix. The TGA and DMTA data suggest that higher thermal stability and glass transition temperature (T_g) for the TMSPM hybrid films compared to their pure counterparts were obtained with increasing the TMSPM content.     

可聚合端羧基超支化聚胺酯的合成与表征

以丙烯酸甲酯、二乙醇胺、三羟甲基丙烷、马来酸酐等为原料,通过3步合成反应合成了一种可聚合端羧基超支化聚胺酯。通过羟值和酸值监测反应进行的程度,确定其最佳合成条件为:反应温度为70℃,催化剂用量为1%,反应时间为3.5 h,并用红外光谱对产物结构进行表征。     

螯合分散剂的合成和性能研究

以马来酸酐（MA）和丙烯酸（AA）为单体,以（NH4）2S2O8为引发剂采用水溶液聚合方法合成了马来酸酐-丙烯酸共聚物螯合分散剂。实验结果表明增加马来酸酐用量可以提高产品的分散性,增加丙烯酸用量产品螯合Ca^2＋性能好。据此确定了最佳产品合成条件：m（MA）：m（AA）=1：3,引发剂（NH4）2S2O8的质量为单体质量的4％,聚合温度为85℃,反应时间为3h。产物为透明、淡黄色、稍有粘稠状的液体,具有良好的螯合分散性。     

Synthesis and characterization of a thermotropic liquid crystalline hyperbranched polyester

BACKGROUND: Hyperbranched polymers have received increasing attention in the fields of medicine, homogeneous catalysis and materials science. Hydroxyl‐functional aliphatic polyesters are one of the most widely investigated families of hyperbranched polymers. The research reported here is based on the preparation of a novel hyperbranched polyester and the modification of its terminal hydroxyl groups by biphenyl mesogenic units. RESULTS: 2,2,6,6‐Tetramethylolcyclohexanol as a core and 8‐[4′‐propoxy(1,1‐biphenyl)yloxy]octanoic acid as a mesogenic unit were synthesized. A hyperbranched polyester (HPE) was synthesized in one step and subsequently substituted by reaction of its terminal hydroxyl groups with the biphenyl mesogenic units to yield a novel liquid crystalline hyperbranched polyester (HPE‐LC). The chemical structures of all compounds were confirmed using Fourier transform infrared, ¹H NMR and ¹³C NMR spectroscopy. The thermal behavior and the mesogenic properties of the biphenyl mesogenic unit and HPE‐LC were investigated using differential scanning calorimetry, polarized optical microscopy and wide‐angle X‐ray diffraction. The results demonstrated that the degree of branching of the HPE is ca 0.63. Both HPE‐LC and the biphenyl mesogenic unit exhibit mesomorphic properties, but HPE‐LC has a lower isotropic transition temperature and a wider transition temperature range than the biphenyl mesogenic unit. CONCLUSION: A novel liquid crystalline hyperbranched polyester was successfully synthesized, which exhibits mesomorphic properties. This polymer has good solubility in highly polar solvents and good thermal stability. Copyright © 2009 Society of Chemical Industry