浅谈双环戊二烯改性不饱和聚酯树脂的生产工艺

采用双环戊二烯改性不饱和聚酯树脂,使得不饱和聚酯树脂具有很多独特的优异性能。主要介绍以双环戊二烯与顺丁烯二酸酐合成双环戊二烯马来酸单酯为基础,经进一步扩链（加入多元醇酯化）之后得到不饱和聚酯树脂的合成过程。剖析了生产设备、生产工艺流程。     

海洋操作平台钢结构用防护涂料的制备与性能

以聚己内酯、新戊二醇与顺丁烯二酸酐合成了聚酯树脂,然后与六亚甲基二异氰酸酯(HDI)反应以提高支化度,引入有机硅后再同丙烯酸单体反应制得丙烯酸改性聚酯树脂。以此丙烯酸改性聚酯树脂和适量的颜填料为甲组分、拜耳3390固化剂为乙组分,开发了适用于海洋气候的钢结构表面防护涂层。研究了顺丁烯二酸酐含量、丙烯酸改性聚酯树脂羟基含量、n(─NCO)∶n(─OH)值和聚合条件对面漆性能的影响。当顺丁烯二酸酐的用量为聚酯树脂的5%,自制的丙烯酸改性聚酯树脂羟基含量为4.5%±0.3%,n(─NCO)∶n(─OH)=1.1~1.4时,所制备的丙烯酸改性聚酯树脂面漆配以环氧富锌底漆及环氧云母氧化铁中涂漆得到的涂层体系能够满足海上平台钢结构的防护要求。     

由工业级双环戊二烯制备浅色不饱和聚酯树脂

以工业级双环戊二烯(DCPD,纯度75%~85%)为原料,采用滴加顺丁烯二酸酐(MA)法制备浅色(Gardner色度<3)的DCPD改性不饱和聚酯树脂(UPR)。并就2种不同工艺合成的DCPD不饱和聚酯树脂的性能作了对比。     

聚乙二醇改性不和饱和聚酯树脂

利用一步法熔融缩聚,由顺丁烯二酸酐、邻苯二甲酸酐、丙二醇和不同分子量的聚乙二醇合成了一系列不饱和聚酯树脂并研究了经苯乙烯交联后的不饱和聚酯树脂浇铸体的性能。拉伸和弯曲性能随聚乙二醇分子量的增加而降低,而冲击强度、伸长率和吸水性则增加。本研究对不饱和聚酯中聚乙二醇分子链长对它的浇铸体性能的影响,有更好的了解。     

利用废聚酯薄膜制备不饱和聚酯树脂工艺研究

以废聚酯薄膜(PET)为原料制得了不饱和聚酯树脂(UPR),通过产物酸值测定研究了反应温度、催化剂种类对聚酯薄膜降解反应的影响,通过固化性能测试及其浇注体和玻璃钢制品的力学和热性能测试确定了废聚酯薄膜的用量,并将制品的性能与邻苯型196#不饱和聚酯树脂作了比较。结果表明:采用有机锡类和醋酸锌的复合催化剂,反应温度210～225℃,废聚酯薄膜与顺丁烯二酸酐物质的量比1:2.7时UPR产品性能最优,其力学性能、耐热性和耐腐蚀性均优于196#UPR。     

封端不饱和聚酯树脂的制备与表征

以顺丁烯二酸酐与邻苯二甲酸酐的摩尔比为7：3,制备了一种以环己醇封端的不饱和聚酯树脂,固化剂和促进剂用量分别为1%和2%,凝胶时间和固化时间分别为4 min和13 min。用聚合放热峰温、红外光谱和热重-差热对不饱和聚酯树脂进行了表征。     

DCPD改性UPR的合成新工艺及性能研究

采用催化水解加成法研究了“工业级”双环戊二烯为主要原料合成不饱和聚酯树脂的新工艺及性能。双环戊二烯的含量低于80％，研究了各种影响因素，得出主要工艺条件：加成温度为120～140℃，酯化温度为170～180℃，n（顺丁烯二酸酐）：n（邻苯二甲酸酐）=（5～6）：1，n（DCPD）：n（顺丁烯二酸酐）=（0．5～0．8）：1，催化剂用量为0．1％～0．2％，树脂收率达93．5％～94．8％。     

新型的聚酯层压材料

最近美国市场上出现一种新型的聚酯树脂层压材料,商品名称“Hetron”。这种层压材料,是用一种新的聚酯树脂与玻璃纤维(也可以用合成纤维)制成的。用于制造“Hetron”的聚酯树脂,不用异苯二甲酸(即间苯二甲酸)、二酚基丙烷等为原料,而是由六氯环戊二烯与顺丁烯二酸酐合成。反应方程式如下:     

低成本一步法合金灰树脂的制备及应用研究

为替代进口合金灰树脂,采用丙二醇、乙二醇、二乙二醇、季戊四醇、四氢苯酐、己二酸、反丁烯二酸、顺丁烯二酸酐和苯乙烯等常规原材料,通过一步法合成了不饱和聚酯树脂;通过改变原料用量、配比和固化体系的协同作用制备成合金灰,研究了其固化体系和固化性能;采用动态差示扫描量热法(DSC)确定自制合金灰树脂的固化温度。比较自制合金灰树脂与进口树脂性能发现:其附着性、表干性和打磨性等主要技术指标与进口树脂相当,可完全替代进口树脂,降低国内合金灰成本。     

国内专利摘要

热塑性丙烯酸聚酯树脂本发明是有关生产涂料用的一种热塑性聚酯树脂的制造方法。过去不饱和聚酯漆是双组分混合后使用的涂料,要现配配用,给施工带来较大不便。本发明是以顺丁烯二酸酐、松香为原料,以三苯基膦为酯化催化剂,与乙二醇或丙二醇在170～240℃下进行     

高固体分卷材涂料用聚酯的研制

通过引入叔碳酸缩水甘油酯单体,并采取分步聚合法工艺合成高固体分聚酯树脂,制得了施工 VOC满足环保要求的卷材涂料。探讨了不同二元酸类型、叔碳酸缩水甘油酯用量、相对分子质量及合成工艺对聚酯树脂及漆膜性能的影响。实验结果表明：采用分步法聚酯合成工艺,第一步选用甲基丙二醇及己二酸、六氢苯酐及苯酐合成的端羧基聚酯,酸超量 40%;第二步中引入叔碳酸缩水甘油酯及三羟甲基丙烷及甲基丙二醇,醇超量 50%,可得到数均相对分子质量为 1 862、固含量为 81%、黏度（ 23 ℃）为 1 860 mPa·s的高固体分聚酯树脂,以此树脂配制的白色卷材面漆性能良好,施工 VOC为 305 g/L,满足低于 420 g/L的要求。     

SYNTHESIS OF UNSATURATED POLYESTER RESIN—EFFECT OF CHOICE OF REACTANTS AND THEIR RELATIVE PROPORTIONS

Unsaturated polyesters are synthesized in the laboratory by the condensation of saturated and unsaturated anhydrides with glycols. The condensate obtained is mixed with styrene monomer to get an unsaturated polyester resin formulation. The properties of the polyester resin synthesized are affected by the synthesis parameters. In this study, the parameters investigated are the effect of choice of reactants and their relative proportions. Properties such as tensile strength, tensile modulus, elongation-at-break, toughness, impact strength, surface hardness, abrasion resistance, and water absorption were tested after curing the resin. Various combinations of (a) maleic anhydride and phthalic anhydride, (b) propylene glycol and ethylene glycol, and (c) propylene glycol and diethylene glycol were used to investigate the effect on the properties of the synthesized resin. The combinations of the anhydrides and glycols that give optimum properties are identified. The results show that most of the properties are maximum at 60% maleic anhydride composition in a mixture of maleic anhydride and phthalic anhydride. Similarly, a better balance of properties is obtained when propylene glycol is mixed with 30% ethylene glycol or 20% diethylene glycol.     

Synthesis of Unsaturated Polyester Resin—Effect of Sequence of Addition of Reactants

Abstract

Unsaturated polyesters were synthesized in the laboratory by the condensation of maleic anhydride and phthalic anhydride with propylene glycol. The condensate obtained was mixed with styrene monomer to get an unsaturated polyester resin formulation. The properties of the polyester resin synthesized were found to be affected by the synthesis parameters. In this study, the effect of sequence of addition of reactants on the properties of resin was investigated. Properties such as tensile strength, tensile modulus, elongation at break, toughness, impact strength, surface hardness, abrasion resistance, and water absorption were evaluated after curing the resin. Propylene glycol necessary for esterification of both the anhydride fractions was initially reacted with phthalic anhydride. Later, the esterification was completed by reaction with maleic anhydride. This sequence of addition of reactants was found to give the best mechanical properties among all possible methods of reactant addition. Moreover, it was found that this sequence of addition of reactants gives the shortest reaction time.     

New aspects of unsaturated polyester resin synthesis. Part 2. Reactant sequence distribution and its effect on cure kinetics

The distribution of unsaturations in the prepolymer of a typical unsaturated polyester (UP) resin (maleic anhydride, phthalic anhydride and 1,2‐propylene glycol) has been shown to influence the kinetics of the cure process with styrene monomer. Segments containing double bonds in close proximity appear to lower the reactivity of the resin due to steric hindrance, as indicated by the fact that the rate of cure and the final degree of cure, measured by differential scanning calorimetry (DSC), increase as the average sequence length (SL) of maleic units decreases. This implies that the reactivity of UP resins may be improved by synthesis of prepolymers with certain reactant sequence‐length distributions. The copolymer formed by the melt condensation process of maleic anhydride, phthalic anhydride and 1,2‐propylene glycol in the absence of a transesterification catalyst has a non‐random structure with a tendency towards blockiness. This was established using ¹H NMR analysis in tandem with deterministic and Monte Carlo modelling techniques. Copyright © 2003 Society of Chemical Industry     

含乳酸酯链节的不饱和聚酯(续)

本文叙述了直接用乳酸与顺丁烯二酸酐及1．2—丙二醇合成含乳酸酯链节的不饱和聚酯的方法,以及含乳酸酯链节的不饱和聚酯与普通不饱和聚酯均交联后进行的加速水解对比实验,结果表明含乳酸酯链节的不饱和聚酯水解降解的程度较高,特别是用甲基丙烯酸甲酯交联者。     

聚氨酯型不饱和聚酯树脂的合成及其性能的研究

采用两步法由二元醇、二元酸酐和甲苯二异氰酸酯(TDI)合成了一种聚氨酯型不饱和聚酯树脂(UPPU)。第一步由二元醇和二元酸酐合成出以—OH封端的不饱和聚酯(UP);第二步利用UP的—OH与TDI的—NCO的高反应活性由UP与TDI合成UPPU。同时研究了反应温度、反应时间、原料配比等对UPPU树脂涂膜性能的影响。结果表明,当乙二醇:邻苯二甲酸酐:顺丁烯二酸酐物质的量比为1.2:0.7:0.3,反应温度为205℃,反应时间8 h,酸值在40mgKOH/g以下时,得到UPPU树脂涂膜性能较好。     

Modification of unsaturated polyesters using polyethylene glycol

Abstract

The fracture toughness and impact resistance of rigid unsaturated polyesters can be modified by various physical and chemical methods. In this study, flexible unsaturated polyesters were prepared by condensation polymerisation of maleic anhydride, phthalic anhydride and propylene glycol in the presence of polyethylene glycol. By this method, copolymers of unsaturated polyesters with polyethylene glycols of different molecular weights were prepared. A two stage process was used for the synthesis, which resulted in segmental structures containing alternating rigid cross-linked segments and linear soft segments displaced regularly in the polymer chain. Properties such as tensile strength, tensile modulus, elongation at break, toughness, impact strength, surface hardness, abrasion resistance and water absorption were tested after the resin was cured in appropriate moulds and compared with those of the control resin. Polyethylene glycols of lower molecular weight (～ 200) impart flexibility to the polyester chains and increase fracture toughness and impact resistance of rigid unsaturated polyester without seriously affecting other properties. Glass reinforced specimens prepared using the modified resin also show improved toughness and elongation at break.     

热塑性聚氨酯用苯酐聚酯多元醇的合成及表征

介绍了一种以苯酐和新戊二醇为原料制备热塑性聚氨酯用聚酯多元醇的方法,重点讨论了在实验室制备过程中,醇酸比、酯化反应温度、真空度和酯化时间对聚酯树脂合成的影晌;对该聚酯树脂分别用红外光谱和核磁共振氢谱进行结构表征,并从理论上讨论了其耐水解稳定性。     

Thermal properties of chlorendic acid based polyester resins

Polyester resins were prepared from chlorendic acid, maleic anhydride, and ethylene- and/or propylene-glycol. The resins were cured at room temperature with two different crosslinking agents including styrene and methyl methacrylate. The thermal behaviour of these polyester resins and their cured products was studied. From the thermogravimetric data it was observed that the polyester resins cured with styrene are thermally more stable than the methyl methacrylate cured products. It was also observed that the polyester resin prepared from propylene glycol is thermally more stable relatively than the ethylene glycol based polyester resin. The activation energies of thermal degradation of the resins and their cured products were calculated. The implications of these results are discussed.