羧酸盐、磺酸盐复配型高固含水性聚氨酯的制备

以聚己内酯(PCL)、聚氧化丙烯二醇(PPG)、聚四亚甲基醚二醇(PTMG)、六亚甲基二异氰酸酯(HDI)、异佛尔酮二异氰酸酯(IPDI)和聚乙二醇单甲醚(MPEG)为主要原料,以二羟甲基丙酸(DMPA)和乙二胺基乙磺酸钠(A-95)为亲水扩链剂,采用预聚体-丙酮法合成羧酸盐、磺酸盐复配型高固含水性聚氨酯,并研究了DMPA、A-95用量对乳液性能的影响。研究结果表明:当w(DMPA)=0.98%、w(A-95)=1.97%时,聚氨酯乳液固含量可达到50%,且黏度低、粒径小、稳定性好和力学性能适中。     

纳米SiO_2改性水性聚氨酯乳液的制备及性能研究

以硅烷偶联剂(KH-550)作为纳米二氧化硅(nano-SiO2)的表面处理剂,以甲苯二异氰酸酯(TDI)、聚醚二元醇(N-220)、二羟甲基丙酸(DMPA)和nano-SiO2等为主要原料,制备nano-SiO2改性WPU(水性聚氨酯)乳液。着重探讨了DMPA的加料方式、DMPA和nano-SiO2用量等对WPU乳液稳定性、粒径分布、耐水性和力学性能等影响。结果表明:采用先加入DMPA后扩链的加料方式,可制得外观及稳定性均较好的WPU乳液;当w(DMPA)=5%、w(改性nano-SiO2)=2.0%时,WPU乳液及其胶膜的综合性能较好。     

环氧改性聚酯聚醚型水性聚氨酯的合成及性能研究

选用环氧树脂E-44为改性剂,以异佛尔酮二异氰酸酯(IPDI)、聚醚多元醇(PPG-220)、聚酯多元醇(POL-220)、二羟甲基丙酸(DMPA)等为主要原料合成了一系列环氧树脂改性的水性聚氨酯乳液。探讨了聚酯多元醇、DMPA和环氧树脂加入量对乳液和膜性能的影响。通过傅里叶变换红外光谱(FT-IR)、接触角及拉伸测试研究了改性树脂的结构、耐水性和力学性能;通过差示扫描量热法(DSC)和热重(TG)分析研究了聚合物膜的热性能。实验结果表明:当w(聚酯)=20.0%,w(DMPA)=3.9%,w(E-44)=8%时,获得综合性能优良的改性水性聚氨酯。     

改性水性聚氨酯汽车内饰胶的合成

采用丙酮法,并以聚醚二元醇(N220)、甲苯二异氰酸酯(TDI-80)、1,4-丁二醇(BDO)和二羟甲基丙酸(DMPA)等为原料,制备了聚氨酯(PU)预聚体;然后以丙烯酸酯为改性剂合成出水性聚氨酯(WPU)乳液。实验结果表明,当w(丙烯酸酯单体)=25%、w(DMPA)=3.8%时,可得到高性能的改性WPU乳液;由该乳液制得的胶粘剂可以满足汽车内饰材料的粘接要求。     

提高水性聚氨酯耐水性的研究

为了制备耐水性能较好的水性聚氨酯(WPU),以聚酯二元醇(PBA)、甲苯二异氰酸酯(TDI)和二羟甲基丙酸(DMPA)等为主要原料合成了WPU乳液,着重探讨了DMPA含量、R值[即n(-NCO)/n(-OH)]和交联剂对WPU胶膜耐水性能的影响。实验结果表明,当w(DMPA)=4%、R=1.5时,制得的WPU胶膜耐水性较好;采用不同的室温交联剂对WPU进行交联改性,当w(氮丙啶型交联剂A)=3%时(相对于WPU乳液干固量而言),WPU胶膜的吸水率降低至3%左右,并具有较好的持久耐水性。     

环氧树脂改性高度支化水性聚氨酯的合成与性能研究

用甲苯-2,4-二异氰酸酯(TDI)、聚碳酸酯二醇(PCDL)、二羟甲基丙酸(DMPA)等为原料,制备了线性水性聚氨酯(LWPU,A2),并通过"A2+B3"的方式,将其滴加到聚醚胺(T403)的四氢呋喃–异丙醇(THF–IPA)溶液(B3)中,合成出端氨基高度支化水性聚氨酯(HBWPU)。用核磁共振仪表征了HBWPU的结构,证实合成成功。考察了TDI、DMPA和T403的用量对HBWPU的乳液粒径、外观和力学性能的影响,得到最优配方为:n(NCO)∶n(OH)=1.3,w(DMPA)=6.0%,n(B3)∶n(A2)=0.8。以双酚A型环氧树脂(EP)改性最优配方所得的HBWPU,用红外光谱研究了产物HBWPU/EP的结构,通过热重分析(TGA)和应力-应变曲线探讨了EP用量对其热稳定性和力学性能的影响。结果表明,引入EP明显提升了HBWPU的热稳定性及力学性能。当m(EP)∶m(HBWPU)=0.2,HBWPU/EP的拉伸强度达38.30 MPa,断裂伸长率为252%。但当EP用量过多,拉伸强度反而下降。     

丙烯酸酯改性水性聚氨酯乳液的合成及胶膜性能

以异佛尔酮二异氰酸酯(IPDI)、聚碳酸酯二醇(PCDL)、二羟甲基丙酸(DMPA)、三乙胺(TEA)、甲基丙烯酸甲酯(MMA)、丙烯酸丁酯(BA)为原料,采用原位乳液聚合法制备水性聚氨酯-丙烯酸酯(WPUA)复合乳液。考察了聚氨酯(PU)质量分数、m(MMA)∶m(BA)、初始—NCO与—OH摩尔比等因素对WPUA复合乳液及其胶膜性能的影响。结果显示,当w(PU)=80%、初始n(—NCO)/n(—OH)=6.0、w(DMPA)=5%、m(MMA)∶m(BA)=4∶6时,所得WPUA乳液性能稳定,其胶膜吸水率降低至9.80%,相比较未改性的聚氨酯胶膜的吸水率24.75%,其吸水率降低了60.4%;改性胶膜的拉伸强度达到28.9 MPa,是未改性聚氨酯胶膜的1.53倍,制备出了性能稳定、具有优异耐水性和物理机械性能的WPUA复合乳液。     

纳米SiO_2改性水性聚氨酯胶粘剂的制备及性能

以PBA(聚酯二元醇)、IPDI(异佛尔酮二异氰酸酯)、DMPA(2,2-二羟甲基丙酸)和BDO(1,4-丁二醇)为原料,DBTDL(二月桂酸二丁基锡)为催化剂,TEA(三乙胺)为中和剂,乙二胺为扩链剂,水为介质,采用共混法和原位聚合法合成了纳米SiO_2(纳米二氧化硅)改性WPU(水性聚氨酯)胶粘剂。研究结果表明:纳米SiO_2能有效提高WPU胶膜的热稳定性,并且采用原位聚合法制得的纳米SiO_2改性WPU胶粘剂之性能优于共混法;当w(纳米SiO_2)=2.0%、w(DMPA)=4.7%(均相对于预聚体质量而言)和R=n(—NCO)/n(—OH)=3.0时,采用原位聚合法制得的纳米SiO_2改性WPU胶粘剂的综合性能相对最佳。     

环氧改性高固含水性聚氨酯消光树脂的制备及性能研究

用聚四氢呋喃醚二醇(PTMG)、异佛尔酮二异氰酸酯(IPDI)、间苯二甲基异氰酸酯(mXDI)、二羟甲基丙酸(DMPA)为预聚物反应单体,以2-[(2-氨基乙基)氨基]乙磺酸钠(A95)和乙二胺为扩链剂,利用预聚体分散法制备高固含水性聚氨酯(WPU)消光树脂乳液及胶膜,分析了乳液表观黏度、乳化工艺、R值[n(—NCO)∶n(—OH)]、磺酸盐扩链剂的用量等因素对乳液固含量的影响,探讨了环氧改性高固含水性聚氨酯消光树脂的性能。当乳化转速为3 500 r/min左右,中和度为90%左右,R值为1.9时,A95含量为30%时,环氧树脂含量为7.5%时,能够制得固含量为40%以上的WPU乳液稳定性好,性能优异。     

羧酸型水性聚氨酯分散液的制备与性能研究

以聚己二酸丁二醇酯二醇(PBA3000)、异佛尔酮二异氰酸酯(IPDI)和2,2-二羟甲基丙酸(DMPA)为主要原料,合成了羧酸型水性聚氨酯(WPU)。结果表明:一步法和两步法制成的WPU分散液及其胶膜特性相近,但一步法制备工艺更加简单;随着DMPA含量不断增加,预聚过程中体系黏度和分散液电导率上升,WPU胶膜的拉伸强度、硬度和吸水率增大,断裂伸长率和分散液粒径(100 nm)减小;当n(PBA)∶n(DMPA)=2∶3时,R值越大,预聚过程中体系黏度越低,WPU胶膜的拉伸强度和硬度越大,而断裂伸长率和吸水率越小;当w(-COOH)=1.09%～2.37%时,WPU分散液的稳定性较好。     

Facile preparation and characterization of low-gloss waterborne polyurethane coatings using amine-based chain extenders

A novel waterborne polyurethane (WPU) coating with a self-roughed surface is prepared using a general prepolymer emulsion polymerization method. A rough surface is formed by crosslinking the WPU particles through the introduction of a polyfunctional amine-based chain extender. Ethylenediamine, diethylenetriamine (DETA) and triethylenetetramine (TETA) with different functional groups are used as chain extenders, and their effect on the surface morphology and gloss of WPU films is investigated. DETA and TETA form a rough surface on the WPU film by crosslinking the polymer chains and promoting phase separation between soft and hard segments. A rough surface reflects light diffusely, resulting in a decrease in the gloss of the film. Overall, the chain extension improves the thermal stability and tensile strength of the WPU film. In particular, the WPU film with DETA, exhibiting the highest chain extension effect, shows the lowest gloss value, the highest tensile strength and thermal stability. The present series of WPU materials, prepared without matting agents and special treatment processes, can be an effective alternative for producing low-gloss coatings. © 2022 The Authors. Polymer International published by John Wiley & Sons Ltd on behalf of Society of Industrial Chemistry.     

苯酐聚酯多元醇合成水性聚氨酯的研究

以苯酐聚酯二元醇(APP)为主要原料合成了水性聚氨酯(WPU)树脂,探讨了n(-NCO)/n(-OH)比值及扩链剂等对WPU成膜性能的影响。研究结果表明,适度交联可提高WPU胶膜的拉伸强度和耐水性;当w(二羟甲基丙酸)=3.3%、n(-NCO)/n(-OH)=4.0和w(乙二胺)=1.0%时,WPU胶膜的综合性能最好;与其他多元醇[如聚四氢呋喃多元醇(PTMEG)、聚醚多元醇(N-220)和聚酯多元醇(PS)等]合成的WPU树脂相比,用APP合成的WPU树脂,其成膜光泽和断裂伸长率较好、综合性能最优。     

硅烷偶联剂封端改性水性聚氨酯的研究

以聚醚多元醇(GE210)、异佛尔酮二异氰酸酯(IPDI)和α,α-二羟甲基丙酸(DMPA)为原料合成了基础聚氨酯(PU)预聚体,然后以1,4-丁二醇进一步扩链制得了水性聚氨酯(WPU)乳液,最后以偶联剂γ-氨丙基三甲氧基硅烷对PU分子进行封端,得到了稳定的改性PU乳液。通过对偶联剂的用量和封端条件等研究,确定了适合硅烷改性WPU的方式。实验结果表明,当w(硅烷偶联剂)=4%～5%时(占树脂的质量分数),硅烷偶联剂封端改性WPU乳液具有较低的表面张力,其胶膜的力学性能和耐水耐溶剂性能均相当优异。     

有机硅改性磺酸/羧酸型水性聚氨酯的研究

以聚醚多元醇(N-210)和2,4-甲苯二异氰酸酯(TDI)为原料,以自制的磺酸型亲水单体1,2-二羟基-3-丙磺酸钠(DHPA)和二羟甲基丙酸(DMPA)为扩链剂,采用氨丙基三甲氧基硅烷和氨乙基氨丙基三甲氧基硅烷对纯水性聚氨酯(WPU)进行改性,并对有机硅改性WPU胶膜的性能进行了研究。结果表明:WPU分别经两种不同结构的有机硅改性后,其胶膜的力学性能略高于未改性WPU,但耐水性和耐热性则明显高于未改性WPU。     

硅烷偶联剂改性高固含量水性聚氨酯的合成

以聚四氢呋喃二醇、聚己二酸乙二酯和异佛尔酮二异氰酸酯等为主要原料,以硅烷偶联剂KH550为改性剂,2,2-二羟甲基丙酸(DMPA)和(1,3-二氨基)-丁基磺酸钠(HSJ)为亲水扩链剂,采用自乳化和外乳化相结合的方法合成阴离子型高固含量硅烷偶联剂改性水性聚氨酯(WPU)乳液。考察了乳化剂、扩链剂、硅烷偶联剂用量,异氰酸酯基与羟基摩尔比(R值)等对乳液和胶膜性能的影响。通过傅里叶变换红外光谱、热重分析和接触角测试分析了改性前后WPU的结构。结果表明:DMPA,HSJ,乳化剂,硅烷偶联剂的质量分别占总固体质量的1.60%,0.26%,1.60%,1.50%,R值为1.20时,可得到固含量54%、黏度低、稳定性好、耐水、耐热性能优异的WPU乳液。     

有机氟硅共改性水性聚氨酯乳液的合成及其性能

将异佛尔酮二胺(IPDA)和甲基丙烯酸十二氟庚酯(DFMA)进行Micheal加成反应,合成端仲胺基的有机氟化合物(DFMA-IPDA)。以该化合物为扩链剂、聚醚改性聚二甲基硅氧烷(PDMS)为二元醇,与异佛尔酮二异氰酸酯(IPDI)、聚氧化丙烯二醇(PPG)、二羟甲基丙酸(DMPA)聚合制备了有机氟和硅改性的水性聚氨酯(WPU),研究了有机氟和/或硅用量对WPU乳液性能和胶膜性能的影响。结果表明:用该方法合成的DFMA-IPDA纯度达99.2%,和一定量的PDMS共改性可合成稳定的WPU乳液。随两者用量的增加,WPU乳液的平均粒径增大,胶膜的热稳定性、耐水性提高,表面水接触角增大。PDMS可提高WPU胶膜的柔性,而DFMA-IPDA可提高胶膜的韧性。用PDMS和DFMA-IPDA共改性能获得综合性能优异的WPU,当扩链剂完全采用DFMA-IPDA,PDMS用量为4%时,WPU胶膜的吸水率为4.5%,水接触角达到102.3°。     

阴离子型水性聚氨酯的合成及其性能研究

以甲苯二异氰酸酯(TDI)、聚丙二元醇(N210)为主要原料,二羟甲基丙酸(DMPA)为亲水性扩链剂,1,4-丁二醇(BDO)和乙二胺(EDA)为小分子扩链剂,采用预聚体法合成了系列阴离子型水性聚氨酯乳液。讨论了硬段含量、DMPA用量、-NCO／-OH物质的量比值及扩链剂用量对水性聚氨酯乳液及胶膜性能的影响,得出了制备阴离子型水性聚氨酯的最佳配方。     

尿素对水性聚氨酯性能的影响

以异佛尔酮二异氰酸酯（IPDI）、聚醚220、聚酯二元醇为主要原料,二羟甲基丙酸（DMPA）为亲水性扩链剂,并分别用乙二胺和尿素作扩链剂,合成阴离子型水性聚氨酯乳液。对比2种扩链剂对水性聚氨酯乳液黏度、膜吸水性及玻璃化转变温度（Tg）的影响.结果表明,增加乙二胺的用量,能提高聚氨酯乳液黏度,降低其膜的吸水性,增大聚合物Tg．而增加尿素的用量对聚氨酯乳液黏度和聚合物Tg没有明显影响,但提高了膜吸水性。说明尿素没有起到扩链作用,但可以作为封端剂在聚氨酯分子末端引入胺基。     

Synthesis and characterization of ambient-temperature self-crosslinked waterborne polyurethanes with a novel diol chain extender bearing two ketone groups

A series of ambient-temperature self-crosslinked waterborne polyurethanes denoted as WBPUs were successfully synthesized by incorporating a novel diol chain extender bearing two ketone groups, 2,2-bis(4-(2-hydroxypropoxy levulinate)phenyl)-propane (BHLPP), which was prepared using 2,2-bis(4-(2,3-epoxypropoxy)phenyl)-propane and levulinic acid, with 4,4-methylenedicyclohexyl diisocyanate, poly-neopentylene adipate glycol, and dimethylolpropionic acid. After post-adding adipic dihydrazide (ADH), self-crosslinking was achieved by the reaction between the ketone (–CO–) of BHLPP and the hydrazine (–NHNH₂) of ADH during film formation. For comparison, noncrosslinked waterborne polyurethane (WPU) without BHLPP and ADH was prepared. The structure of BHLPP was characterized by IR and NMR. The properties of the WPU and WBPU dispersions were investigated by measuring the stability, particle size, and morphology. The effects of the ratio of n(–NHNH₂)/n(–CO–) and the content of BHLPP were studied in terms of hardness, water resistance, solvent resistance, and thermal properties of WPU and WBPU films. The WBPU dispersions exhibited excellent stability, bimodal distribution, and regular spheroid morphology. The optimal ratio of n(–NHNH₂)/n(–CO–) for ketone–hydrazine self-crosslinking was 0.75:1. Importantly, the WBPU films showed superior hardness, water resistance, solvent resistance, and thermal properties to WPU film.     

Flame Retardant Modified Bio-Based Waterborne Polyurethane Dispersions Derived from Castor Oil and Soy Polyol

Although tremendous efforts have been dedicated to developing environmentally friendly bio-based waterborne polyurethane (WPU) dispersions from vegetable oil, the fabrication of WPU dispersions solely derived from vegetable oil-based polyol with excellent comprehensive properties is still challenging. In the present work, novel bio-based WPU dispersions derived from castor oil and soy polyol is successfully modified by phosphorus-nitrogen chain extender [bis(2-hydroxyethyl)amino]-methyl-phosphonic acid dimethyl ester (BH). The structure and properties of the dispersions and films are characterized systematically by Fourier transform infrared spectroscopy, thermogravimetric analysis , mechanical test, and limiting oxygen index (LOI), etc. The results indicate that bio-based WPU films display moderate mechanical performance by adjusting BH content, and the WPU film containing 100% BH with 47.8% biobased content has a tensile strength of 8 MPa and the highest Young's modulus of 62.3 MPa. The incorporation of BH can increase the production of char residue. The flame retardancy of WPU films increase gradually with the BH molar content, and the LOI value of the WPU100 with 1.53 wt% phosphorus content can reach as high as 28.1%. This work may provide a new approach to develop high biobased content, eco-friendly, flame retardant WPU for application in the surface coating industry.