不饱和聚酯型聚氨酯涂料的研制

采用两步法由二元醇、二元酸酐和甲苯二异氰酸酯(TDI)合成了一种不饱和聚酯型聚氨酯(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:顺丁烯二酸酐摩尔比为1.2:0.7:0.3,反应温度为205℃,反应时间8h,酸值在40mgKOH/g以下时,得到UPPU涂膜性能较好,硬度6H,附着力1级,柔韧性0.5mm,抗冲击性35cm。     

聚氨酯改性不饱和聚酯树脂的制备

利用二步法由二元醇、二元酸及TDI合成一种聚氨酯改性不饱和聚酯树脂,第一步由二元醇和二元酸合成以羟基封端的不饱和聚酯,第二步利用不饱和聚酯的—OH与TDI的—NCO反应合成聚氨酯改性不饱和聚酯,使得树脂分子链段上既有不饱和链节又含有聚氨酯基团,结合了聚氨酯涂料和不饱和聚酯涂料的优点,使其涂膜性能优异。试验发现TDI加入量为10%时效果最佳。     

聚氨酯型不饱和聚酯涂料的研究

通过对反应过程中和涂膜酸值和粘度测定以及涂膜性能测定和红外光谱分析研究了聚氨酯型不饱和聚酯树脂的反应温度、反应时间、醇酸比、TDI用量、饱和酸与不饱和酸配比、交联剂聚苯乙烯用量等对涂料性能的影响。研究表明:反应温度170℃,反应时间3 h,乙二醇、邻苯二甲酸酐与顺丁烯二酸酐物质的量比为1.4:3:7,—NCO与—OH物质的量比为1:1,每15 g树脂中加入交联剂苯乙烯5 g,固化体系0.3 g,填料10 g,可制得物理力学性能较好的聚氨酯型不饱和聚酯涂料,涂膜硬度为5 H,附着力1级,柔韧性0.5 mm,抗冲击性50 cm。     

固体不饱和聚酯树脂的合成工艺

采用二步熔融缩聚法制得了固体不饱和聚酯树脂(UP),研究了UP的不饱和酸含量、醇酸比及合成反应温度、反应时间对反应的影响,并通过物理力学性能测试及耐热性测试研究了不同原料配比的UP产物对粉末涂料涂膜和粘结永磁塑料性能的影响。结果表明,适用于粉末涂料和粘结永磁塑料的UP树脂原料乙二醇、对苯二甲酸与反丁烯二酸的物质的量配比分别为2.1∶1∶1和2.42∶1∶1.3。适合的反应温度为210～220℃,反应时间8 h。     

不饱和聚酯聚氨酯纳米复合材料的研究

采用混合二元醇、二元酸通过缩聚反应合成不饱和聚酯树脂(UPR),UPR与甲苯二异氰酸酯(TDI)经逐步加聚得到不饱和聚酯型聚氨酯树脂(UPPU),UPPU与γ-缩水甘油醚氧丙基三甲氧基硅烷(KH560)改性的纳米凹凸棒土复合得到不饱和聚酯型聚氨酯纳米凹凸棒复合材料。通过SEM、FT-IR、TG等方法对不饱和聚酯聚氨酯纳米复合材料进行了表征。结果表明,当KH-560用量及改性纳米凹凸棒土用量为UPPU质量的2%时,纳米复合材料的热稳定性和韧性有了很大的提高。     

常温固化不饱和聚酯聚氨酯涂料的研制

本实验选用顺酐、苯酐和一缩二乙二醇为原料,采用逐步聚合法合成不饱和聚酯树脂(UPR);继而用所合成的UPR和聚乙二醇(PEG)、甲苯二异氰酸酯(TDI)经逐步加聚合成不饱和聚酯聚氨酯树脂(UPPU);再加入活性稀释剂苯乙烯、引发剂过氧化甲乙酮与颜填料制备得到常温固化型不饱和聚酯聚氨酯涂料。     

气干性耐腐蚀不饱和树脂的研究

采用顺酐和二醇制得耐腐蚀不饱和树脂,再将其与由三羟甲基丙烷二烯丙基醚(TMPDE)、TDI和苯乙烯反应得到的含有气干性基团的预聚物接枝聚合得到气干性耐腐蚀不饱和树脂。研究了预聚物加入量对树脂气干性以及接枝聚合反应温度和时间对反应程度的影响,并测试了产品的耐腐性和力学性能。结果表明,自制的耐腐蚀不饱和树脂、TDI、TMPDE及苯乙烯的质量配比为10∶1∶1∶2,聚合反应温度75～85℃,反应时间2.0 h时得到的不饱和树脂性能最佳,无缺口冲击强度为7.56 kJ/m2,弯曲强度为71.7 MPa,弯曲模量为3.21 GPa,热变形温度为110℃,产品可耐强酸、强碱、强氧化介质的长期腐蚀,气干性好,固化优良。     

封端不饱和聚酯树脂的合成及性能研究

在合成通用型不饱和聚酯(UP)树脂的基础上,反应后期分别用环己醇、苯甲酸及环己醇/苯甲酸进行封端处理,得到封端改性UP树脂.对封端前后UP树脂的性能进行了研究,发现封端后UP树脂的性能与通用型UP树脂的性能基本相当,但耐腐蚀性明显提高,其中酸值50 mg KOH/g时封端的UP树脂的耐腐蚀性比酸值80 mgKOH/g时封端强,而采用环己醇/苯甲酸同时封端后耐腐蚀性提高得更为明显.     

支化结构不饱和聚酯的合成及性能研究

以乙二醇、季戊四醇(丙三醇)、反丁烯二酸为原料合成了含支化结构的不饱和聚酯(RP),对产物进行了红外表征,并通过GPC、DSC和TGA测试对其性能进行了研究。结果表明,季戊四醇(丙三醇)用量为反丁烯二酸物质的量的5%为宜,最佳反应温度为190～200℃,RP树脂数均分子质量为线形UP树脂的5倍左右。RP树脂相比UP树脂固化快,其最大放热温度、热稳定性和冲击性能均有所提高,其中冲击强度提高33%。此外,丙三醇型RP树脂较季戊四醇型反应易于控制,反应程度高。     

高性能PU/UP不饱和聚酯家具涂料的研制

用天然松香与二元醇、二元酸和甲苯二异氰酸酯(TDI)合成了不饱和聚氨酯树脂,再加入稀释剂苯乙烯配制成家具涂料。采用国标方法对家具涂料的柔软性、硬度、抗冲击性、固化收缩率、附着力等物理性能进行测试。结果表明,不同二元醇对合成UP/PU树脂家具涂料的性能影响较大,其中乙二醇型UP/PU的聚酯家具涂料且具有优良的抗冲击性、硬度较高、附着力好、固化收缩率低等优越性能。     

Effects of chemical composition and structure of unsaturated polyester resins on the miscibility, cured sample morphology and mechanical properties of styrene/unsaturated polyester/low-profile additive ternary systems: 2. Mechanical properties

The effects of three series of unsaturated polyester (UP) resins with different chemical composition or structure on the mechanical properties of three low-shrink UP resins containing thermoplastic polyurethane, poly(vinyl acetate) and poly(methyl methacrylate) respectively have been investigated by an integrated approach of static phase characteristics–cured sample morphology–reaction conversion–property measurements. The three series of UP resins synthesized include: maleic anhydride (MA)–neopentyl glycol (NPG)–diethylene glycol (DEG) types, with various molar ratios of NPG and DEG; MA–1,2-propylene glycol (PG) types with and without modification by a saturated dibasic aromatic anhydride or acid, such as phthalic anhydride (PA) or isophthalic acid; and MA–PA–PG types modified by a second glycol, such as DEG, 2-methyl-1,3-propanediol or NPG, to partially replace PG. Based on the Takayanagi mechanical models, the effects of glycol ratios, saturated dibasic aromatic acid modification, second glycol modification, C=C unsaturation of UP and molecular weight of UP on the mechanical properties will be discussed.     

Effects of chemical structure of polyurethane‐based low‐profile additives on the miscibility,curing behavior,volume shrinkage,glass transition temperatures,and mechanical properties for styrene/unsaturated polyester/low‐profile additive ternary systems. II: Glass transition temperatures and mechanical properties

The effects of three series of thermoplastic polyurethane‐based (PU) low‐profile additives (LPA) with different chemical structures and molecular weights on the glass transition temperatures and mechanical properties for thermoset polymer blends made from styrene (ST), unsaturated polyester (UP), and LPA have been investigated by an integrated approach of static phase characteristics‐cured sample morphology‐reaction conversion‐property measurements. The three series of PU used were made from 2,4‐tolylene di‐isocyanate (2,4‐TDI) and varied diols, namely polycaprolactone diol (PCL), poly(diethylene adipate) diol (PDEA), and poly(propylene glycol) diol (PPG), respectively, while the two UP resins employed were synthesized from maleic anhydride (MA) and 1,2‐propylene glycol (PG) with and without modification by phthalic anhydride (PA). Based on the Takayanagi mechanical models, factors that control the glass transition temperature in each phase region of cured samples, as identified by the method of thermally stimulated currents (TSC), and mechanical properties will be discussed. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 558–568, 2000     

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.     

聚氨酯胶黏剂用苯酐聚酯多元醇的研制

以苯酐、二甘醇、新戊二醇为原料,合成了苯酐聚酯多元醇。简述了合成聚酯多元醇的工艺,对反应温度、醇酸物质的量比、真空度、出水速率和催化剂等对合成聚酯树脂的影响进行了探讨,结果表明,当控制反应温度在250℃左右,醇酸物质的量比为1.164,真空度>0.09MPa,出水速率为50mL/h,催化剂质量分数为0.04%时,合成的苯酐聚酯多元醇能够满足生产聚氨酯胶黏剂的应用要求。并对所做聚酯用红外光谱和核磁共振氢谱表征。     

Oxazoline polyester coating resins

Oxazoline polyester resins were prepared by reaction of oxazoline diols from linseed acids and tris (hydroxymethyl) aminomethane with each of five dibasic acids (adipic, dimer, fumaric, itaconic and maleic). Certain resins were dissolved in isopropyl alcohol to give solutions infinitely water dilutable when the free carboxyl was neutralized with an amine. Film properties of resins cast on steel plates were investigated. Drying characteristics, hardness, color stability and solvent resistance of some of these films equaled or excelled those of a commercial soy alkyd resin, although their initial color was darker. The resins prepared from itaconic and maleic acids have potential value as water-solubilizable coating vehicles. Presented at the 151st ACS Meeting, Pittsburgh, March 1966. No. Utiliz. Res. Dev. Div., ARS, USDA.