丙烯酸酯有机硅复合改性水性聚氨酯的合成

以聚四氢呋喃二元醇（PTMG）和异佛尔酮二异氰酸酯（IPDI）为基本原料,在R值为2.5、DM-PA质量分数为6%、PU/PA质量比为8∶2的基础上,通过进一步变化羟基硅油PDMS的质量分数来研究有机硅改性对水性聚氨酯性能的影响,从而合成出丙烯酸酯有机硅复合改性的水性聚氨酯。探讨了不同质量分数的有机硅对乳液及涂膜性能的影响。结果表明,有机硅质量分数为10%或者13%时,得到的丙烯酸酯有机硅复合改性的水性聚氨酯综合性能较佳。     

耐指纹涂层用聚合物乳液成膜物的制备与性能研究

以丙烯酸酯类为主要单体,环氧树脂和有机硅大分子乳液为改性剂,R303为主要乳化剂,通过乳液聚合方法合成了耐指纹涂料用聚合物乳液成膜物,讨论了乳化剂、环氧树脂和有机硅对乳液及涂膜性能的影响。结果表明,采用阳/非离子复合乳化体系可以制得酸性环境下使用的聚合物乳液,涂膜烘烤过程中活泼的环氧基团与其它基团的交联会大幅度提高涂膜的耐腐蚀性和硬度,有机硅参与聚和后会进一步改善涂层的耐水耐腐蚀性,当m(R303)∶m(OP-10)为3∶1,E-51质量分数为10%,乙烯基有机硅乳液质量分数为5%时,合成的乳液成膜物有较好的综合性能。     

A／U-g-A型核壳聚氨酯-丙烯酸酯复合乳液的合成

通过加入双官能团单体甲基丙烯酸-β-羟乙酯(HEMA),采用溶液聚合法和原位乳液聚合法,把聚氨酯与丙烯酸(AA)、丙烯酸丁酯(BA)和苯乙烯(St)等丙烯酸酯单体接枝共聚,合成了PUA为壳、PA为核的聚氨酯-丙烯酸酯(PUA)复介乳液.研究了壳层PA/Pu、总PA/PU、核壳比、BA/St、壳层HEMA/PA和链转移剂含量对乳液制备过程、乳液及涂膜性能的影响.研究结果表明:PUA中的PA、BA、St、HEMA,链转移剂和DMPA与AA中的-COOH的含量(壳层PUA的质量分数)分别为55.6%、25%、17.8%、9%、1%和7%,核壳质量比为1:4时,复合乳液涂膜结构规整,各项性能较好.PUA胶粒的平均粒径在100 nm左右时,分布更均匀.     

阳离子有机硅聚氨酯自交联乳液的制备和应用

制备一种可以改善手感和防水性的有机硅改性聚氨酯自交联乳液.制备分为3个步骤聚醚与2,4-甲苯二异氰酸酯发生预聚,得到以-NCO为端基的预聚体,用小分子扩链剂扩链,再加入羟基硅油进行改性,最后加阳离子型扩链剂反应制得含有叔胺基的预聚体,加有机酸成盐,乳化得蓝光乳白微透明乳液.这种自乳化阳离子有机硅聚氨酯乳液可明显提高涂膜的光亮性、柔软性、抗水性和手感等.     

核壳型水性聚氨酯-聚丙烯酸酯复合乳液的制备及其影响因素

用丙烯酸酯改性水性聚氨酯(PU)制备了具有核壳结构的PU-聚丙烯酸酯(PA)复合乳液,对其结构进行了表征,研究了亲水性扩链荆二羟甲基丙酸(DMPA)用量、NCO/OH(摩尔比)、乳化剂用量、核壳质量比对乳液和涂膜性能的影响.结果表明,所制备的乳液为核壳型PU-PA复合乳液;当DMPA的质量分数为5.5%-6.0%、NCO-OH总摩尔比为1.3-1.4、NCO/OH初始摩尔比为4.5-5.5、乳化荆质量分数为1.0%、核壳质量比为30/70时,可得到性能较佳的PU-PA复合乳液和涂膜.     

蓖麻油和环氧树脂改性水性聚氨酯-丙烯酸酯的合成与表征

以甲苯二异氰酸酯(TD I)、聚醚型多元醇(N210)、2,2-二羟甲基丙酸(DMPA)、甲基丙烯酸甲酯(MMA)等为主要原料,蓖麻油(C.O.)和脂肪族环氧树脂(RE)为交联剂,以原位乳液聚合法制备出聚氨酯-丙烯酸酯(PUA)复合乳液。以无皂乳液聚合法合成了聚丙烯酸酯乳液(PA),再与聚氨酯(PU)乳液机械混合得到PU/PA共混乳液。探讨了蓖麻油C.O.、RE对复合乳液及涂膜性能的影响,烯丙氧基羟丙基磺酸钠(COPS-1)用量对共混乳液和涂膜性能的影响。结果表明,C.O.、RE分别占PU干质量的5.0%～7.0%和2.0%～3.0%,COPS-1占单体总质量的2.0%时,乳液和涂膜综合性能较好。PUA比PU/PA柔韧性好、断裂伸长率高及附着力好,硬度低,成本高。红外光谱分析发现,PUA与PU/PA中—NH—全部形成氢键。TEM观察到,PUA形成核-壳结构的粒子,粒径较小。通过AFM扫描发现,PUA存在硬段与软段的微相分离。     

聚脲交联改性丙烯酸酯弹性乳液的制备与性能研究

为了在性能上对聚脲交联改性后的丙烯酸酯乳液(PUA)和纯丙乳液(以)进行比较,文章以丙酮为溶剂,通过端氨基聚醚和甲苯二异氰酸酯的缩合反应合成了端异氰酸酯基聚脲预聚物,由于丙酮与胺基的可逆缩合反应,降低了胺基与异氰酸酯基反应的活性,从而可以更好地控制反应速度,降低副反应的发生几率.聚脲预聚体经丙烯酸羟乙基酯双键封端制备了含有2个双键的聚氨酯脲大单体,以其为外交联剂,通过与甲基丙烯酸甲酯、丙烯酸丁酯的乳液共聚反应制备了聚氨酯脲改性的纯丙弹性乳液,对乳液涂膜进行了FT-IR,DSC和TGA的表征.研究表明:PUA涂膜比PA涂膜具有更好的热稳定性、机械性能、耐低温性以及耐溶剂性.     

单组分室温固化乳液涂料的研制

制备了单组分伯胺基/环氧基室温固化乳液涂料:运用局在化技术,将伯胺基团固定于乳胶粒的核层,以乙二醇二甲基丙烯酸酯(EGDMA)为交联剂制备乳胶粒的中间网络层,以甲基丙烯酸缩水甘油酯(GMA)为单体制备乳胶粒的壳层。采用红外光谱、透射电镜、涂膜力学性能等测试手段研究了乳化剂MS-1、UPA用量对乳液聚合稳定性的影响以及熟化温度、UPA、EGDMA用量对涂膜拉伸强度、耐溶剂性的影响。并提出了耐溶剂性涂膜的互穿网络(IPN)结构形成过程的模型。结果表明:不饱和伯胺(UPA)可与苯乙烯、(甲基)丙烯酸酯发生乳液共聚。当MS-1用量不低于总单体质量的3.2%,UPA用量不超过总单体质量的1.5%时,可以得到稳定的乳液。当UPA质量分数为0.8%,EGDMA质量分数为0.2%时,涂膜的拉伸强度最大。涂膜的耐溶剂性对EGD-MA用量更为敏感。     

有机硅改性核壳型丙烯酸酯乳液的制备与性能

以甲基丙烯酸甲酯(MMA)、丙烯酸丁酯(BA)和丙烯酸(AA)为主要单体,采用半连续种子乳液聚合法并通过加入适量有机硅A-174制备了具有软核硬壳结构的核壳乳液。研究了有机硅A-174质量分数和加入方式对乳液聚合和膜性能的影响,采用傅里叶变换红外光谱(FT-IR)、粒度分析、热重分析(TGA)、差式扫描量热(DSC)、原子力显微镜(AFM)、光学接触角测量仪等分析手段对乳液及涂膜进行表征。结果表明,当有机硅A-174质量分数为4%且与30%的壳单体预乳化后加入时,得到乳胶粒平均粒径为97. 8 nm、转化率为93%、凝胶率为0. 8%的有机硅改性核壳丙烯酸酯乳液,此时涂膜的综合性能最佳,吸水率为10. 5%,水接触角为72. 6°,质量损失50%时的热分解温度为407. 7℃。     

氨基硅油微乳液改性水性聚氨酯的合成和性能

合成了水性聚氨酯乳液和氨基硅油(AEAPS)微乳液改性水性聚氨酯乳液,研究了两种水性聚氨酯的性能及在织物上的涂层效果。结果表明,当氨基硅油相对于聚丙二醇的质量百分比为8.18%时,有机硅改性水性聚氨酯乳液的离心稳定性好,乳液胶膜表面硅原子的质量分数为0.92%;该有机硅改性水性聚氨酯软段相与硬段相的微观相分离增大,乳液胶膜的耐水性能和热稳定性提高;该有机硅改性水性聚氨酯乳液作为织物涂层剂时,可以赋予织物柔软、滑爽的风格。     

Enhanced heat stability and storage modulus in novel PTMO-intercalated clay platelets/PTMO-based polyurethane nanocomposites

Amine-telechelic poly(tetramethylene oxide) (PTMO) was trimethylated to a quaternary ammonium (QA)-capped PTMO as a bivalent organic macrocation. This QA-capped PTMO (QAPTMO) was used for intercalation of montmorillonite (MMT) platelets with 69 % ion exchange yield and 4.03 nm d-spacing. Then, segmented polyurethanes (SPU) with PTMO soft segments were synthesized in the presence of the QAPTMO-intercalated MMT filler in different contents. According to the X-ray and SEM analyses, the polyaddition reaction could result in a full exfoliation of the clay platelets. Two model composites including SPU polymer loaded by unmodified MMT and tetradecyltrimethylammonium bromide (TTAB)-intercalated MMT were also synthesized analogously. The SPU/QAPTMO-MMT composites possessing 5.0 and 7.0 wt.% of the filler obviously showed a better thermal behavior in comparison with SPU/TTAB-MMT and SPU/Na-MMT composites. In addition, a significant increase in the storage moduli of the polyurethane matrices occurred due to the QAPTMO-MMT particles, particularly in the 5.0 wt.% loading content of the filler.     

3-羟乙基-1,3-噁唑烷的合成和表征及其初步应用

以甲醛和二乙醇胺为原料,采用加成缩合反应合成了化合物3-羟乙基-1,3-噁唑烷。毛细管气相色谱(GC)研究表明可通过减压蒸馏提纯产物。采用傅里叶变换红外光谱(FT-IR)、13C核磁共振谱(13CNMR)对产物的结构进行了表征。将所合成的3-羟乙基-1,3-噁唑烷用作单组分湿固化聚氨酯体系的潜固化剂,抑泡效果明显,固化后样品的伸长率提高了10倍以上。     

长链聚硅氧烷接枝（甲基）丙烯酸酯聚合物乳液的制备及其性能

该文首先合成了聚硅氧烷阴离子乳液和链中含硅烷偶联剂的（甲基）丙烯酸酯聚合物乳液两种不同的乳液,然后通过乳液接枝共聚的方法,利用硅烷偶联剂水解基团与聚硅氧烷正离子之间的反应合成了一种高硅含量的硅丙聚合物乳液。测试结果表明,有机硅质量分数为20％的聚合物乳液涂膜性能最佳,与不含有机硅的聚合物乳液涂膜相比,其水表面接触角由 77.5。增加到95。,24小时吸水率由4.9％下降到2.3％,耐水性大大增加,同时玻璃化转变温度由8.53℃下降到-1.36℃,聚合物分子链的柔顺性有所提高,说明此方法合成的高硅含量硅丙乳液涂膜可作为一类具有优良耐水性及良好的表面疏水性的功能材料得以应用。     

Microphase separation and surface properties of segmented polyurethane-Effect of hard segment content

A series of segmented polyurethanes (SPU), based on 4,4′-diphenylmethane diisocyanate and 1,4-butanediol as hard segments (HS) and poly(propylene glycol) (Mn = 1000) as soft segments, were synthesized. Relationships between microphase separation and the surface and adhesive properties were characterized by thermal analysis, X-ray diffraction, contact angle, electron spectroscopy for chemical analysis, T-peel and tensile test measurements. Microphase separation occurred for SPU with an HS content of more than 50 wt% and influenced not only the bulk properties, but also the surface properties. Young's modulus and tensile strength increased abruptly for SPU with an HS content of more than 50wt%. Surface free energy also increased in a stepwise manner at an HS content of about 50wt%. The optimum HS content of SPUs for adhesion, based on T-peel test results, also gave good thermal and mechanical properties.     

硅烷封端羟基硅油改性端硅氧烷聚氨酯密封胶的研究

用2,4-甲苯二异氰酸酯(TDI)、α,ω-二羟基聚二甲基硅氧烷、聚醚多元醇和硅烷偶联剂为原料,分别制备了硅烷封端的羟基硅油(SHS)和端硅氧烷聚氨酯(SPU),并将其共混制备出硅烷封端羟基硅油改性的SPU密封胶。用红外光谱对预聚体进行了表征,考察了密封胶的力学性能。结果表明,添加的硅烷封端羟基硅油与SPU的质量比为50∶100时,SPU密封胶在保持高拉伸强度的同时,断裂伸长率比未添加硅烷封端羟基硅油的密封胶提高了46.7%。通过改变硅烷偶联剂的种类、填料和催化剂的种类和添加量,找到了偶联剂、填料和催化剂对硅烷封端羟基硅油改性SPU密封胶力学性能的影响规律。     

Nonwovens with antimicrobial properties

A new organosilicon modifier was synthesized. The effect of the modifier content on the biocidal and physicomechanical properties of the nonwoven material was investigated. When the content of the product on the fibre increased to 15 wt. %, its physicochemical properties increased. It was found that nonwovens fabricated from a cotton and polyester fibre blend (70:30) treated with the modifier in the amount of 1-3 wt. % has antimicrobial properties.     

Microstructure and water vapor transport properties of functionalized carbon nanotube‐reinforced dense‐segmented polyurethane composite membranes

This work investigates the influence of functionalized multiwall carbon nanotube (MWNT) on microstructure and water vapor transport properties of segmented polyurethane (SPU) membranes. SPUs were reinforced with four different concentration of MWNT viz. 0.25, 0.50, 1.0, and 2.5 wt%. Presence of the microcrystals in all SPU‐MWNT composite membranes was detected by wide angle X‐ray diffraction (WAXD). The percent crystallinity of SPU‐MWNT at 0.25 wt% content of MWNT was increased slightly when compared with the pristine SPU sample. However, further increase of MWNT decreases the order structure. Glass transition temperature was increases with increasing MWNT content in the SPUs, which signifies that MWNT could also affect the amorphous region of SPU. WAXD and transmission electron microscopy (TEM) results evidenced the interaction between SPUs and MWNT. In comparing the water vapor transport properties of MWNT‐SPU composite membranes, it was observed that at 0.25 wt% of MWNT in SPU, water vapor transport property increases slightly at soft segment crystal melting temperature. Further increase of MWNT content has no significant influence on the water vapor transport properties. However, at 2.5 wt% of MWNT in SPU matrix, water vapor transport was decreases due to the increase of stiffness in the polymer chains. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Synthesis of 2‐phenyl‐3‐hydroxyethanyl‐1,3‐oxazolidine and its application as latent curing agents

A kind of new compound of 2‐phenyl‐3‐hydroxyethanyl‐1,3‐oxazolidine was successfully synthesized by addition–condensation reaction of phenyl aldehyde and β‐hydroxylethanolamine and purified by vacuum distillation. Its purity was examined by gas chromatographic analysis. Its structure was confirmed by ¹³C NMR and FTIR. When this compound was added as a latent curing agent in single‐component moisture‐curable polyurethane system (SPU), bubbles of SPU formed during curing was obviously restrained, and the elongation at break of the cured SPU contained a certain content of 2‐phenyl‐3‐hydroxyethanyl‐1,3‐oxazolidine was increased to 16 times when compared with that uncontained this oxazolidine derivative. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Relation between the phase structure and surface structure of films made from polyurethane dispersions

Segmented polyurethane dispersions (SPUD) having carboxyl groups in soft segments (SS) or hard segments (HS) were synthesized. Phase, surface, and interface structures of films made from those SPUD were examined by differential scanning calorimeter (DSC), contact angle, and X-ray photoelectron spectroscopy (XPS) measurements. Segmented polyurethanes (SPU) with the same structures as SPUD were also synthesized in the organic solvent system, and the properties and behaviors of these SPU films were compared with the SPUD films. It was indicated by the DSC measurements that the film made from SPUD having carboxyl groups in the soft segments (S-SPUD) had higher crystallinity and crystal growth rate than the film made from SPUD having carboxyl groups in the hard segments (H-SPUD) in spite of steric hindrance. On the other hand, the film made from SPU having carboxyl groups in the hard segments (H-SPU) had higher crystallinity than the film made from SPU having carboxyl groups in the soft segments (S-SPU). Further, the crystal growth rate of SPU was faster than that of SPUD, regardless of the position of carboxyl groups. These results indicated that the phase structure of SPUD film was affected by the phase structure in the dispersion particle. Surface and interface structure of SPUD film was rearranged with a change of the phase structure. But the degree of this change was higher in the surface structure than in the interface structure. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 741–748, 1999     

有机硅季铵盐抗菌整理剂的合成工艺研究

首先以八甲基环四硅氧烷、氨乙基氨丙基甲基二甲氧基硅烷为原料合成氨基聚硅氧烷,最佳反应温度为130℃、反应时间为4 h;再经季铵化制得有机硅季铵盐抗菌整理剂,最佳反应条件为：反应温度80℃、反应时间4 h、氨基聚硅氧烷与季铵化试剂摩尔比1：2.0。织物抗菌整理实验表明,整理后的织物具有良好的抗菌性能,当抗菌整理剂用量为1...