有机硅/丁二醇扩链剂混合比对混合大二醇基聚氨酯弹性体的性能影响

以α,ω-双(γ-羟丙基)聚二甲基硅氧烷(BHPDMS)和聚氧四甲基二醇(PHMO)混合大二醇为软链段;以1,4-丁二醇(BDO)为主要扩链剂,1,3-双(4-羟丁基)-1,1,3,3-四甲基二硅氧烷(BHTD)为次级扩链剂,所有试样中硬链段均由4,4'-二苯基甲烷二异氰酸酯(MDI)和混合扩链剂所构成,且w(硬链段)=40%;采用两步溶液聚合法制备混合大二醇基芳香聚氨酯(PU)弹性体。通过力学性能测试、差示扫描量热法(DSC)和动力学热分析法(DMTA),研究了混合扩链剂中n(BDO)/n(BHTD)比值对该PU弹性体性能的影响。结果表明,当n(BDO):n(BHTD)=3:2时,所得PU弹性体具有优异的综合性能;引入BHTD扩链剂后,破坏了硬链段的有序性。     

混合大二醇基聚氨酯弹性体/环氧树脂互穿网络聚合物的研究

以α,ω-双(γ-羟丙基)聚二甲基硅氧烷(BHPDMS)和聚氧四甲基二醇(PHMO)混合大二醇作为软链段,首先通过两步溶液聚合法合成了-NCO封端的混合大二醇基聚氨酯(PU)弹性体预聚物(PUT);然后以PUT和环氧树脂(EP)预聚物为原料、1,3-双(γ-氨丙基)-1,1,3,3-四甲基二硅氧烷(BATS)为交联剂,采用同步溶液聚合法合成了PUT/EP互穿聚合物网络(PUT/EP I PN)。使用傅里叶红外光谱(FT-I R)法、动力学分析(DMA)法和扫描电子显微镜(SEM)法,对PUT和PUT/EP I PN进行分析和表征,并对其力学性能和表面疏水性进行测试。实验结果表明,PUT/EP I PN中不存在宏观相分离状态,仅发生微观相分离状态;当PUT/EP I PN中w(PUT)=50%时,PUT/EP I PN具有优异的综合力学性能和表面疏水性。     

PBA/MDI体系聚氨酯弹性体力学性能的研究

采用二步法以聚己二酸丁二醇酯(PBA)、4,4-′二苯基甲烷二异氰酸酯(MDI)和二元醇1,4-丁二醇(BDO)或混合扩链剂(二元醇和三元醇)合成了聚氨酯(PU)弹性体。研究了软段相对分子质量、预聚体-NCO质量分数和扩链剂对聚氨酯弹性体力学性能的影响。实验结果表明:PBA相对分子质量大,PU断裂伸长率和冲击弹性好;PU硬度、撕裂强度和模量随预聚体-NCO相对质量分数增加而增加;弹性体的交联密度过高,硬度和撕裂强度下降。     

双组分聚氨酯嵌缝密封剂的制备与性能研究

以TDI(甲苯二异氰酸酯)、N-220(聚醚二元醇)和N-330(聚醚三元醇)等为主要原料合成PU(聚氨酯)预聚体,并以此作为PU密封剂的甲组分;以MOCA(3,3′-二氯-4,4′-二氨基二苯甲烷)、EP330N(聚醚三元醇)、增塑剂邻苯二甲酸二辛酯(DOP)、轻质碳酸钙和辛酸亚锡等作为PU密封剂的乙组分。研究结果表明:以D3(PU类)为底涂剂,当R=n(-NCO)/n(-OH)=1.05～1.10、混合固化剂中n(MOCA中-OH)∶n(EP330N中-OH)=2∶1和w(DOP)=40%时,室温固化双组分PU密封剂具有良好的拉伸性能和定伸粘接性能,并且满足大变形、高位移量水泥伸缩缝的嵌缝工艺要求。     

聚碳酸酯二醇/蓖麻油基聚氨酯(脲)弹性体的制备及性能

以蓖麻油和聚碳酸酯二醇(PCDL)为共混软段,分别以1,4-丁二醇(BDO)和3,5-二甲硫基-2,4-二胺基甲苯(DMTDA)为扩链剂,用预聚体法合成出一系列聚氨酯(PU)和聚氨酯脲(PUU)弹性体,考察了异氰酸基(NCO)含量和PCDL用量对弹性体力学性能的影响,并对弹性体的热性能进行了分析。结果表明,随着预聚体中NCO含量的增加,PU、PUU弹性体的硬度和强度逐渐上升,当NCO质量分数为8%时,弹性体的拉伸强度最高,而扯断伸长率呈单调下降趋势;随着PCDL用量的增加,弹性体的拉伸强度先升高后下降,扯断伸长率和永久变形逐渐增加;用DMTDA为扩链剂制备的PUU比用BDO制备的PU具有更高的拉伸强度和撕裂强度;PCDL/蓖麻油基PUU的耐热性能优于纯蓖麻油基PUU,PUU的耐热性优于PU。     

H_(12)MDI聚氨酯弹性体微相分离研究

以4,4′-二环己基甲烷二异氰酸酯(H12MDI)/1,4-丁二醇(BDO)为聚氨酯硬段,分别以聚四氢呋喃醚二醇(PTMEG)、聚己二酸丁二醇酯(PBA)为软段合成了硬段含量(质量分数,下同)为23%～50%的聚氨酯弹性体。借助IR、DSC等分析手段研究了其微相分离结构,并针对所制备弹性体进行力学性能表征。结果表明,硬段含量对H12MDI基弹性体的软段玻璃化温度影响很小;硬段含量的增加,PTMEG型PU的微相分离程度随之先降低后增加,而PBA型PU的微相分离程度则随之降低;以PBA为软段的H12MDI基弹性体在硬段含量为40%时力学性能达到最优。     

PCL/MDI体系聚氨酯弹性体力学性能的研究

以聚己内酯二醇(PCL)和4,4′-二苯基甲烷二异氰酸酯(MDI)为原料,用二元醇1,4-丁二醇(BDO)和三元醇(TMP)混合物作扩链剂制备了聚氨酯(PU)弹性体,研究了预聚体NCO基含量、扩链剂用量和扩链系数对聚氨酯弹性体力学性能的影响。结果表明,聚氨酯弹性体的硬度、模量和强度随预聚体NCO基含量的增加而增加,扩链剂三元醇质量分数超过20%后,弹性体力学性能下降幅度较大,扩链系数大于0.95时,聚氨酯的力学性能急剧降低。     

阳离子型PDMS/PU无皂微乳液膜的结构与性能

在催化剂和助溶剂的作用下,采用一步法,以端羟基聚二甲基硅氧烷(PDMS)/聚醚二醇(PTMG)为软段,异佛尔酮二异氰酸酯(IPD I)为硬段(三羟甲基丙烷TMP为交联剂、N-甲基二乙醇胺MDEA为扩链剂)合成了一系列自乳化双软段PDMS/PU微乳液。将乳液流延成膜,综合研究了PDMS/PU中软硬段比例、溶剂、软段相对分子质量、TMP用量、MDEA用量、PDMS含量对成膜力学性能和耐水性的影响。结果表明,当n(NCO)/n(OH)=2.2,PTMG的相对分子质量为1 000,w(TMP)=3%,w(MDEA)=40%,w(PDMS)=15%,PDMS/PU膜的附着力为1级,光泽度101%,硬度H,耐冲击性50 cm,抗张强度33.8 MPa,柔韧性1级,胶膜吸水率随着w(PDMS)的增加,由11.2%降低到0.12%。     

PTMG／MDI体系聚氨酯弹性体的力学性能研究

以4,4′-二苯基甲烷二异氰酸酯（MDI）和聚四氢呋喃均聚醚（PTMG）为原料合成聚氨酯（PU）预聚体,再分别与BDO、MOCA、HQEE扩链剂及混合扩链剂制备Pu弹性体。讨论了预聚体NCO基含量、聚醚软段相对分子质量、三羟甲基丙烷（TMP）小分子醇含量及扩链剂类型对PU弹性体力学性能的影响。结果表明,提高预聚体NCO基含量可使PU弹性体的硬度、撕裂强度和300％模量明显提高;当预聚体NCO基含量基本相同时,软段Mn=2000比Mn=1000的PU冲击弹性高;混合扩链剂中的TMP质量分数超过30％时,弹性体的力学性能明显下降;BDO—PU的拉伸强度比HQEE-PU的强度高出70％以上,撕裂强度比HQEE—PU低了40％以上,硬度比MOCA-PU小。     

高性能聚氨酯密封材料的微相结构和热性能(Ⅱ)

采用聚碳酸酯二醇(PCDL)、聚四亚甲基醚二醇(PTMG)和4,4′-二苯基甲烷二异氰酸酯通过预聚体法和半预聚体法合成了一系列聚氨酯(PU)弹性体。采用示差热扫描量热,热失重和动态力学性能分析对PU弹性体的性能及多元醇结构和组成,合成方法对PU弹性体微相结构形态的影响进行了研究。结果表明,由预聚体法合成的弹性体的微相分离程度高于半预聚体法,二胺扩链的弹性体的硬段结晶性优于二醇扩链的弹性体,单一二醇合成弹性体的硬段的结晶性优于混合二醇合成的弹性体,几种弹性体的的硬段结晶性依次为PU-LF-950APU-PCDL≈PUPTMGPU-PCDL+PTMG。几种弹性体的热稳定性依次为PU-PCDLPU-PCDL+PTMG≈PU-PTMGPU-LF-950A。PU-LF-950A和PU-PTMG的低温性能优于PU-PCDL和PU-PCDL+PTMG。PU-LF-950A还具有较好的高温动态性能和微相分离程度。     

纳米蒙脱土-脂肪族聚氨酯弹性体的合成与制备

采用聚四氢呋喃醚（PTMG1000）为软段,4,4’-二环己基甲烷二异氰酸酯（HMD1）、异佛尔酮二异氰酸酯（1PD1）为硬段,层间距分别为1．95nm和2．40nm的2种有机蒙脱土,以插层聚合法制备出不同硬段含量和有机蒙脱土含量的纳米蒙脱土．脂肪族聚氨酯弹性体,并研究了硬段含量、有机蒙脱土含量、二异氰酸酯和有机蒙脱土种类对脂肪族聚氨酯弹性体力学性能的影响。结果表明,硬段含量对材料力学性能影响最大,其次是有机蒙脱土含量。当硬段质量分数达40％时,拉伸强度最高达14．06MPa;有机蒙脱土少量加入可有效提高材料的撕裂强度和断裂伸长率。以HMD1、PTMG1000和MMT2为原料,硬段质量分数为40％时,所合成的纳米蒙脱土-脂肪族聚氨酯弹性体具有较好的力学性能。     

Poly(dimethylsiloxane)/poly(hexamethylene oxide) mixed macrodiol based polyurethane elastomers. I. Synthesis and properties

The compatibilizing effect of poly(hexamethylene oxide) (PHMO) on the synthesis of polyurethanes based on α,ω‐bis(6‐hydroxyethoxypropyl) poly(dimethylsiloxane) (PDMS) was investigated. The hard segments of the polyurethanes were based on 4,4′‐methylenediphenyl diisocyanate (MDI) and 1,4‐butanediol. The effects of the PDMS/PHMO composition, method of polyurethane synthesis, hard segment weight percentage, catalyst, and molecular weight of the PDMS on polyurethane synthesis, properties, and morphology were investigated using size exclusion chromatography, tensile testing, and differential scanning calorimetry (DSC). The large difference in the solubility parameters between PDMS and conventional reagents used in polyurethane synthesis was found to be the main problem associated with preparing PDMS‐based polyurethanes with good mechanical properties. Incorporation of a polyether macrodiol such as PHMO improved the compatibility and yielded polyurethanes with significantly improved mechanical properties and processability. The optimum PDMS/PHMO composition was 80 : 20 (w/w), which yielded a polyurethane with properties comparable to those of the commercial material Pellethane™ 2363‐80A. The one‐step polymerization was sensitive to the hard segment weight percentage of the polyurethane and was limited to materials with about a 40 wt % hard segment; higher concentrations yielded materials with poor mechanical properties. A catalyst was essential for the one‐step process and tetracoordinated tin catalysts (e.g., dibutyltin dilaurate) were the most effective. Two‐step bulk polymerization overcame most of the problems associated with reactant immiscibility by the end capping of the macrodiol and required no catalysts. The DSC results demonstrated that in cases where poor properties were observed, the corresponding polyurethanes were highly phase separated and the hard segments formed were generally longer than the average expected length based on the reactant stoichiometry. Based on these results, we postulated that at low levels (∼ 20 wt %) the soft segment component derived from PHMO macrodiol was concentrated mainly in the interfacial regions, strengthening the adhesion between hard and soft domains of PDMS‐based polyurethanes. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 2026–2040, 2000     

Influence of soft segment composition on phase-separated microstructure of polydimethylsiloxane-based segmented polyurethane copolymers

Segmented polyurethane block copolymers were synthesized using 4,4′-methylenediphenyl diisocyanate (MDI) and 1,4-butanediol (BDO) as hard segments and various soft segments derived from poly(hexamethylene oxide) (PHMO) and poly(dimethylsiloxane) (PDMS)-based macrodiols and mixtures thereof. The microstructure and degrees of phase separation were characterized using a variety of experimental methods. Copolymers synthesized with the PDMS macrodiol and from PDMS/PHMO macrodiol mixtures were found to consist of three phases: a PDMS phase; hard domains; and a mixed phase of PHMO, PDMS ether end group segments and some dissolved hard segments. Two models were used to characterize the small-angle X-ray scattering from these copolymers: pseudo two-phase and core-shell models. Analysis using both methods demonstrates that as the PDMS content in the soft segment mixture increases, the greater the fraction of hard segments involved in hard domains than are dissolved in the mixed phase. Findings from analysis of the carbonyl region of FTIR spectra are also in agreement with greater hard/soft segment demixing in copolymers containing higher PDMS contents.     

The influence of composition ratio on the morphology of biomedical polyurethanes

Two series of thermoplastic polyurethane elastomers were synthesized from 4,4′‐methylenediphenyl diisocyanate (MDI), 1,4‐butanediol (BDO) chain extender, and each of poly(tetramethylene oxide) (PTMO) and poly(hexamethylene oxide) (PHMO) macrodiols. The PTMO and PHMO molecular weights were kept constant at 993 and 852 g/mol, respectively. In the PTMO‐based series, the composition ratio was varied between 48 and 58% (w/w) of macrodiol; 2 commercially available PTMO‐based polymers were also included. These were Pellethane 2363 80A® and its harder counterpart, Pellethane 2363 55D®. In the PHMO‐based series, the composition ratio was varied between 50 and 60% (w/w) of macrodiol. The materials were characterized by differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMTA), wide‐angle X‐ray diffraction (WAXD), and small‐angle X‐ray scattering (SAXS). Mechanical performance was also assessed by tensile testing, stress hysteresis, and hardness testing. Altering the composition ratio had a similar effect on morphology and properties for both the PTMO and PHMO‐based series. An increase in hard segment content was associated with increased hard microdomain crystallinity, hardness, and stiffness. In both series, he beginning of hard microdomain interconnectivity was observed at a composition ratio of 52% soft segment. That is to say, for the processing and annealing conditions employed, macrodiol contents of 52% and below began to produce continuous, rather than discrete, hard microdomains. Pellethane 80A® was shown to have a discrete hard microdomain morphology, while Pellethane 55D® was shown to incorporate interconnecting hard microdomains. It is suggested that the superior biostability performance of Pellethane 55D relative to Pellethane 80A may be related to its interconnecting hard microdomain texture. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 937–952, 1999     

1，3-丁二醇对PCL／MDI体系聚氨酯弹性体力学性能的影响

首先以聚己内酯多元醇（PCL）、4,4’-二苯基甲烷二异氰酸酯（MDI）、液化MDI和MDI-50为原料合成聚氨酯（PU）预聚体,再用混合扩链剂制备聚氨酯弹性体。讨论了预聚体异氰酸酯基（NCO）含量、异氰酸酯类型、1,3-丁二醇（1,3-BDO）含量、聚酯软段相对分子质量对聚氨酯弹性体力学性能的影响。结果表明：提高预聚体NC0基含量可使弹性体的硬度、300％定伸应力、拉伸强度和撕裂强度明显提高,拉断伸长率和冲击弹性则下降;纯MDI弹性体综合力学性能最好,液化MDI次之,MDI-50最差;提高1,3-BDO含量可使弹性体的硬度、撕裂强度和冲击弹性明显下降;软段相对分子质量为1000的聚氨酯弹性体的硬度、300％定伸应力、拉伸强度和撕裂强度较高,软段相对分子质量为2000的聚氨酯弹性体的拉断伸长率和冲击弹性较高。     

The effect of average soft segment length on morphology and properties of a series of polyurethane elastomers. I. Characterization of the series

A series of eight thermoplastic polyurethane elastomers were synthesized from 4,4′-methylene diphenyl diisocyanate (MDI) and 1,4-butanediol (BDO) chain extender, with poly(hexamethylene oxide) (PHMO) macrodiol soft segments. The soft segment molecular weights employed ranged from 433 g/mol to 1180 g/mol. All materials contained 60% (w/w) of the soft segment macrodiol. Differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMTA), wide angle x-ray diffraction (WAXD), and small angle x-ray scattering (SAXS) techniques were employed to characterize morphology. Tensile and Shore hardness tests were also performed. Materials were tested in the annealed state. It was found that an increase in segment length was accompanied by an increase in the degree of microphase separation, average interdomain spacing, hard domain order, hardness, stiffness, and opacity. DSC experiments showed the existence of several hard segment melting regions that were postulated to result from the disordering or melting of various hard segment length populations. For the system and composition ratio employed, it was found that optimum tensile properties (UTS and breaking strain) were achieved when a PHMO molecular weight of between 650 and 850 was utilized. © 1996 John Wiley & Sons, Inc.     

异氰脲酸酯基团对聚氨酯弹性体性能影响研究

引入异氰脲酸酯基团可提高聚氨酯弹性体的耐热性能,但同时对其他性能有一定影响。通过改变NCO含量考察异氰脲酸酯基团对聚氨酯弹性体的力学性能及耐溶剂性能的影响。力学性能测试结果表明,其硬度、拉伸强度和撕裂强度均在NCO质量分数为8％时达到极大值,分别为邵A60、10．33MPa和48．84kN／m,扯断伸长率随NCO含量增加单调减小,100％定伸强度单侧增大;耐溶剂实验表明,聚氨酯弹性体在NCO质最分数为8％时耐溶剂性能最好。     

1,3-丁二醇对PTMG/MDI体系聚氨酯弹性体力学性能的影响

以纯4,4′-二苯基甲烷二异氰酸酯（MDI）MDI-100、液化MDI（C-MDI）、MDI-50和四氢呋喃均聚醚（PTMG）为原料合成聚氨酯（PU）预聚体,再分别与KD和KC扩链剂制备PU弹性体。研究了1,3-BDO含量、异氰酸酯类型、预聚体NCO基含量、聚醚软段相对分子质量对PU弹性体力学性能的影响。结果表明,提高1,3-BDO含量可使PU弹性体的硬度、撕裂强度和冲击弹性明显下降;纯MDI弹性体综合力学性能最好,液化MDI次之,MDI-50最差;提高预聚体NCO基含量可使弹性体的硬度、300%定伸应力和撕裂强度明显提高,拉断伸长率和冲击弹性则下降;软段相对分子质量为1000时,PU弹性体的300%定伸应力、拉伸强度和撕裂强度均增加;软段相对分子质量为1800以上,拉断伸长率和冲击弹性增加。