丙烯酸改性水性聚氨酯的研究

以低聚物多元醇、DMPA、IPDI等为原料,采用先溶液聚合,后乳化的方式制备了水性形状记忆聚氨酯。讨论了DMPA的用量、低聚合物醇含量、软段的种类等因素对水性形状记忆聚氨酯(WPU)及乳液性能的影响,并通过在水性聚氨酯中引入丙烯酸来配制乳液,使改性后的乳液既保留PU的优良性能,也对涂膜性能的改善以及PU成本的降低大有好处,同时还能减少溶液性SMPU对环境的危害,获得环保型的材料,拓宽SMPU的应用领域。     

水性聚氨酯胶粘剂的研制

以低聚物多元醇、二异氰酸酯和二羟甲基丙酸为主要原料制备了一种阴离子水性聚氨酯胶粘剂。探讨了不同种类的多元醇和异氰酸酯对预聚体的合成和乳液性能的影响,实验中发现用三乙胺做中和剂时存在着一个临界浓度。选用多种助剂最后配制得到了综合性能优良的水性聚氨酯胶粘剂。     

扩链剂结构对脂肪族水性PU性能的影响

以六亚甲基二异氰酸酯(HDI)和聚环氧丙烷醚二醇(PPG)为主要原料,二羟甲基丙酸(DMPA)为亲水性扩链剂合成了聚氨酯预聚体,再经过不同小分子扩链剂扩链、乳化制备水性聚氨酯(WPU)乳液,然后与自制交联剂HM交联成膜.研究了不同扩链剂对聚氨酯乳液稳定性及涂膜力学性能的影响.结果表明,以脂肪族二醇扩链的WPU乳液的外观好于芳香族二酚,而芳香族二酚扩链的WPU涂膜力学性能优于脂肪族二醇.     

煤化工领域用的可降解聚乙醇酸的制备及应用性能

针对传统聚氨酯材料难降解,难处理的问题,提出以聚乙醇酸基多元醇为主要原料制备可降解聚氨酯泡沫和阻燃聚氨酯泡沫,并对其性能进行研究。结果表明,当聚乙醇酸基多元醇添加量为60%时,聚氨酯泡沫性能最佳,此时表观密度和导热系数分别为70.4kg·m^-3和0.055W·(m·K)^-1,压缩强度为610k Pa。当甲基膦酸二甲酯阻燃剂添加量为多元醇总质量的15%时,材料达到难燃材料标准,可起到一定的阻燃作用。     

脂肪族水性聚氨酯的合成研究

以六亚甲基二异氰酸酯(HDI)、聚酯多元醇、二羟甲基丙酸(DMPA)、乙二胺为主要原料,采用预聚体法制备了脂肪族水性聚氨酯(PU)乳液,研究了HDI与聚酯多元醇摩尔比(R值)、DMPA用量及中和度对PU乳液及胶膜性能的影响。结果表明,当R值为3.00～3.25、DMPA质量分数为3.28%左右、中和度为100%时,所合成的PU乳液稳定性最好,胶膜的综合性能最佳。     

油溶性单组分聚氨酯灌浆材料的研制

以聚醚多元醇、蓖麻油、多亚甲基多苯基多异氰酸酯(PAPI)和助剂等为原料,制得了单组分油溶性聚氨酯(PU)灌浆材料。研究了PU预聚体的配方、反应条件、蓖麻油及增塑剂的用量对该灌浆材料性能的影响。研究结果表明,当蓖麻油用量为混合醇质量的70%时,该灌浆材料所形成的固结物压缩强度较高(为32.5MPa),适用于加固地表和防水兼备的工程。     

核壳乳液聚合法制备聚丙烯酸酯-聚氨酯复合乳液

以聚四氢呋喃二醇(PTMG-1000)和异佛尔酮二异氰酸酯(IPDI)为基本原料,二羟甲基丙酸(DMPA)作为亲水扩链剂,甲基丙烯酸-β-羟乙酯(HEMA)作为偶联剂与甲基丙烯酸甲酯(MMA)反应,采用核壳乳液共聚法,制备了聚丙烯酸酯-聚氨酯复合乳液(WPUA);通过红外光谱、透射电镜对WPUA乳液粒子的结构进行观察,探讨了DMPA用量、聚氨酯预聚体R值、聚氨酯(PU)链段与聚丙烯酸酯(PA)链段质量比等因素对乳液外观、粘度、稳定性等性能的影响;结果表明,当DM-PA用量为6份,R值为2.5,PU链段与PA链段质量比为70∶30时,所得WPUA表观性能较为优异。     

聚氨酯胶粘剂讲座（连载三）

第三章原料 1 含活性氢原子的化合物聚氨酯胶粘剂中常用的、能与异氰酸酯基反应的含活性氢基团的低聚物一般为含羟基的化合物。常用的低聚物多元醇有聚酯、聚醚,有时也用到蓖麻油、聚丁二烯二元醇或其加氢化合物二醇、聚异丁烯二醇、聚丁腈二醇、聚ε—己内酯、聚碳酸酯、有机硅多元醇等,它们的分子量通常在500～3000之间,官能度2～3。表1为低聚物多元醇的种类及其结构式。 1.1 聚醚在聚氨酯胶粘剂制备中最常用的聚醚是聚氧化丙烯二醇及三醇。     

聚氨酯弹性体软段对其力学性能的影响

先用4,4'-二苯基甲烷二异氰酸酯(MDI)与不同相对分子质量不同种类低聚物多元醇合成预聚体,再以1,4-丁二醇(BDO)为扩链剂制备聚氨酯弹性体,考察了软段对聚氨酯弹性体力学性能的影响.结果 表明:当预聚体NCO含量相同时,聚酯型聚氨酯弹性体的力学性能整体优于聚醚型的,随低聚物多元醇相对分子质量的增加,聚氨酯弹性体的...     

扩链交联剂对水性聚氨酯乳液性能的影响

分别以一缩二乙二醇(DEG)、乙二醇(EG)、1,4-丁二醇(BDO)、乙二胺(EDA)及三羟甲基丙烷(TMP)为扩链交联剂,液化MDI为异氰酸酯组分,聚醚二醇(PPG)为低聚物多元醇组分,采用预聚体法制备了一系列水性聚氨酯(WPU)。通过万能材料试验机、热重分析(TG)、差示扫描量热仪(DSC)等表征手段研究了扩链交联剂对水性聚氨酯乳液及胶膜性能的影响。结果表明:BDO型WPU乳液粒径最小,黏度最大,稳定性最好;TMP型WPU胶膜具有最大拉伸强度,DEG型WPU胶膜具有最大断裂伸长率;TMP型WPU胶膜耐热性最好。     

Preparation and characteristics of polyurethane made with polyhydric alcohol‐liquefied rice husk

The limited availability of fossil resource is causing the urgent need to get renewable chemicals. Solvent liquefaction can convert rice husk into bio‐based chemicals. Rice husk was liquefied in polyhydric alcohol catalyzed by sulfuric acid under atmospheric pressure. The viscosity, residue content, and weight average molecular weight (M_w) of liquefied rice husk were 3089 cps, 23.6% and 4100, respectively. Prolonging the liquefaction time decreased the residue content and increased the average molecular weight. Polyurethane (PU) foams were successfully prepared from the liquefied rice husk with different molar ratios of NCO to OH (NCO/OH). The mechanical properties of PU foams showed that the compressive strength in the vertical direction is higher than that in the horizontal direction. With Increase of the NCO/OH molar ratio from 1.0 to 2.0, compressive strength in the vertical direction of PU foams increased from 70.6 to 114.7 kPa at 10% strain. Thermal analysis results showed that thermal stability of liquefied rice husk‐based PU resins was better than that of fossil‐ and liquefied wood‐ based PU resins. Increasing the NCO/OH molar ratio and inorganic residue of rice husk can help to increase thermal stability. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45910.     

软段对水性聚氨酯木器涂料性能的影响

合成了系列水性聚氨酯乳液,研究了低聚物多元醇种类及分子量不同对水性聚氨酯涂料性能的影响。结果表明:聚酯型水性聚氨酯随着软段分子量的增大结晶程度增加,机械强度和硬度较聚醚型高,耐水性较好;结构规整,易结晶的软段合成出的聚氨酯树脂力学性能和耐水性能都较好;而有机硅氧烷改性可以提高聚氨酯材料的耐水性。     

无溶剂型双组分有机硅改性PU胶粘剂的制备与性能研究

以聚醚二元醇(DL-1000)、4,4′-二苯基甲烷二异氰酸酯(MDI)为主要原料合成端-NCO基PU(聚氨酯)预聚体;然后以γ-氨丙基三乙氧基硅烷(KH-550)对其进行嵌段共聚改性,并以3,3′-二氯-4,4′-二氨基二苯基甲烷(MOCA)/蓖麻油作为复合固化剂,制备出无溶剂型双组分有机硅改性PU胶粘剂。研究结果表明:硅烷键已引入PU胶粘剂中;随着KH-550含量的不断增加,胶粘剂的黏度增大、固化时间缩短、室温剪切强度下降且耐热性增强;通过调节不同KH-550含量,可制备出不同性能要求的胶粘剂;该胶粘剂的玻璃化转变温度(-45.9℃)相对较低,说明其耐寒性相对较好。     

Preparation of semirigid polyurethane foam with liquefied bamboo residues

Bamboo residues were liquefied by using a solvent mixture consisting of polyethylene glycol 400 and crude glycerol (4/1, w/w) with 98% sulfuric acid as catalyst at 160°C for 120 min. The liquefied bamboo had hydroxyl values from 178 to 200 mg KOH/g and viscosities from 507 to 2201 mPa S. The obtained bamboo‐based polyols were reacted with various amounts of polyaryl polymethylene isocyanate (PAPI), using distilled water as blowing agent, silicone as surfactant, and triethylenediamine and dibutyltine dilaurate as cocatalyst to produce semirigid polyurethane (PU) foams. The [NCO]/[OH] ratio was found to be an important factor to control the mechanical properties of PU foams. At a fixed [NCO]/[OH] ratio, both density and compressive strength of PU foams decreased with the increase of bamboo content. The microstructure of PU foams indicates that [NCO]/[OH] ratios are important for cell formation and chemical reactions. The uniformity and cell structure of the foams are comparable to their corresponding compressive strengths. Moreover, the thermogravimetry analysis showed that all the semirigid PU foams had approximately the same degradation temperature of about 250 to 440°C. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

车身反光贴用聚氨酯胶粘剂的研制

以结晶性聚酯多元醇、直链二醇扩链剂、异氰酸酯和纳米助剂等为主要原料,制备出一种高粘接强度、耐老化性能优良的车身反光贴用PU(聚氨酯)胶粘剂。分析了聚酯多元醇的种类及其Mr(相对分子质量)、扩链剂、异氰酸酯、纳米助剂和催化剂等对PU胶粘剂性能的影响。结果表明:当结晶性聚酯多元醇为Mr=3 000的聚己二酸-1,4-丁二醇酯、扩链剂为1,6-己二醇(HDO)、异氰酸酯为1,6-己二异氰酸酯(HDI)、催化剂为有机铋类(BiCAT 8108)且w(催化剂)=0.03%(相对于反应物总质量而言)、n(聚酯多元醇)∶n(扩链剂)=1∶0.3和w(气相白炭黑)=0.2%～0.3%(相对于反应物总质量而言)时,PU胶粘剂的综合性能相对最好。     

高速铁路用道碴胶的制备

以含活泼氢多元醇为主剂、含-NCO基团的PU(聚氨酯)预聚体为固化剂,制成的双组分道碴胶不能满足在湿度较大环境中的施工要求。通过对A组分进行改性,可获得力学性能优良的道碴胶。研究结果表明:当空气湿度从50%增至80%时,自制改性道碴胶的压缩强度、粘接强度和断裂伸长率分别从48.6 MPa、4.4 MPa和13.8%降至46.6 MPa、4.2 MPa和13.7%,而同类产品则从54.0 MPa、3.7 MPa和3.2%变成23.5 MPa、1.9 MPa和7.6%;当固化温度为5~15℃时,自制改性道碴胶的固化时间比同类产品缩短了1 h以上。因此,自制改性道碴胶在高速铁路中具有广泛的应用前景。     

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。     

Synthesis and properties of polyurethane wood adhesives derived from crude glycerol-based polyols

Crude glycerol, a waste stream of the biodiesel production process, is low-cost renewable feedstock for the production of chemicals and polymers. In this study, polyurethane (PU) adhesives were synthesized from crude glycerol-based polyols (CG-based polyols) for wood bonding applications. Effects of different variables, including hydroxyl values of CG-based polyols, chain extenders, and the molar ratio of NCO/OH on the properties of PU adhesives were investigated. The chemical structures of PU adhesives were characterized, and their thermal, mechanical, and chemical resistance properties were evaluated. The experimental results indicated that an increase of the NCO/OH molar ratio (1.3) substantially improved bonding strength by up to 38 MPa. Higher thermal stability and stronger chemical resistance to hot and cold water and to alkali and acid solutions were observed comparing to vegetable oil-based adhesives. However, the effect of the hydroxyl value of polyols on bonding strength was not significant. Additionally, bond strength of crude glycerol-based PU adhesives was comparable to that of some commercial PU wood adhesives. All these properties demonstrated the potential of CG for PU wood adhesive applications, particularly for fast-curing uses.     

Hydrophilic UV-curable PU resins for PET micro-fiber applications

Hydrophilic UV-curable PU oligomers (UV-PU) were prepared by mixing either the toluene diisocyanates (TDI) with polyethylene glycol-1000, or the isophorone diisocyanate (IPDI) with polypropylene glycol-1000 and dimethylol propanic acid (DMPA), to produce the desired carboxylic acid bearing or non-ionic PU oligmer (NCO-PU), separately. The 2-hydroxyethyl methacrylate (HEMA) was then added into the NCO-PU oligomer to form acrylate-terminated (UV-curable) PU oligomer (UV-PU). The reactive diluents, such as 1,6-hexanediol diacrylate (HDDA), trimethylolpropane tricarylate (TMPTA) and others were used to adjust the viscosity of UV-PU and to control the concentration of acrylic group. The hydrophilic UV-curable PU system was formulated and applied on PET micro-fiber and then cured by an UV-radiation at ambient temperature. The physical, thermal, and mechanical properties, in particular, the hydrophilic properties of UV-curable PU treated PET micro-fibers will be discussed.     

环境友好型阻燃高回弹聚氨酯软泡性能

开发环境友好型聚氨酯是目前聚氨酯（polyurethane,PU）泡沫塑料领域的热点课题。在PU中引入大豆分离蛋白质（soy protein isolate,SPI）,采用阻燃聚醚制备了环境友好型阻燃高回弹聚氨酯软泡。研究了SPI的不同添加方式及用量对聚氨酯软泡物理、力学、阻燃和生物降解性能的影响。结果表明,SPI以添加的方式而不是替代聚醚的方式加入软泡性能更好;少量添加SPI可以提高PU软泡的开孔率、密度、压陷硬度、舒适因子、回弹率和断裂伸长率,对压缩永久变形率、拉伸强度和极限氧指数影响不大。SPI改变了PU的硬段结构,可以有效促进聚氨酯泡沫的生物降解。