长玻纤增强反应注射成型PU泡沫塑料的力学性能

利用高压喷灌机开展了长玻纤增强硬质聚氨酯泡沫塑料(RPUF)的成型技术研究。结果表明:RPUF的弯曲模量随着玻纤用量的增加而增大;密度为0.75 g/cm3的RPUF的弯曲强度随玻纤用量的增加而减小,密度为0.95g/cm3的RPUF的弯曲强度随玻纤用量的增加而增大,当玻纤质量分数大于40%时,弯曲强度开始下降;在载荷垂直于玻纤的分布方向,RPUF的压缩模量随着玻纤用量的增加先增大后减小,在载荷平行于玻纤分布方向,压缩模量随着玻纤用量的增加而增大;RPUF的压缩强度随着玻纤用量的增加而减小;RPUF的压缩强度和压缩模量在载荷平行于玻纤分布方向明显高于载荷垂直于玻纤分布方向;随着玻纤用量和长度的增加,RPUF的冲击强度均明显提高。     

反应型阻燃剂及全水发泡剂对硬质聚氨酯泡沫塑料阻燃性能的影响研究

以多元醇、异氰酸酯、发泡剂等添加剂为原料,并加入含卤结构型阻燃聚醚多元醇,制备出阻燃硬质聚氨酯泡沫塑料(RPUF),考察了配方中阻燃多元醇及发泡剂水的用量对RPUF的阻燃等性能的影响。研究结果表明,阻燃聚醚多元醇能显著提高RPUF的阻燃性能,氧指数随着其用量的增加而增大,水发泡剂的用量直接影响RPUF的密度、力学性能和阻燃性能。     

阻燃聚氨酯硬质泡沫的研究

以聚醚4110为主要原料,研究了阻燃聚酯(或聚醚)多元醇、反应型阻燃剂和添加型阻燃剂对聚氨酯硬质泡沫(RPUF)综合性能的影响。结果表明,阻燃多元醇、反应型阻燃剂的使用对RPUF阻燃性能都有一定的改善作用,添加型阻燃剂的引入则可大幅提高RPUF的阻燃性能,只是固体粉末阻燃剂的添加与阻燃多元醇和反应型阻燃剂相比对泡沫体的压缩强度影响较大。     

植物油多元醇改性硬质聚氨酯泡沫性能的研究

采用植物油多元醇、聚醚多元醇、异氰酸酯和发泡剂HCFC-141b等为主要原料,制备得到植物油聚氨酯泡沫塑料,探讨了植物油多元醇加入量对泡沫塑料压缩强度、屈服强度、弹性模量和动态粘弹性能影响.结果表明,随着植物油多元醇加入量增加,泡沫塑料的压缩强度和弯曲模量逐渐减小,弹性模量呈先缓慢上升后下降趋势.作为硬泡应用时,植物油多元醇添加量应小于20份,可提高阻尼性能.     

笼状硫代磷酸酯对聚氨酯泡沫性能的影响

以多异氰酸酯、硫代笼状季戊四醇磷酸酯(SPEPA)、聚醚多元醇为主要原料,采用一步法和自由发泡工艺制备SPEPA阻燃硬质聚氨酯泡沫塑料(RPUF)。通过电子扫描显微镜(SEM)、氧指数、冲击强度、压缩强度、热稳定性等测试,研究了SPEPA对泡沫的泡孔结构、阻燃性能、力学性能及热稳定性的影响。结果表明:随SPEPA含量的增加,SPEPA改性RPUF的平均泡孔直径减小,且SPEPA在一定程度上提高了RPUF的阻燃性能。阻燃RPUF的力学性能呈先上升后下降趋势,当SPEPA质量分数为5%时,力学性能最好。SPEPA阻燃RPUF获得了较高的热稳定性,残炭量从9.3%增加至33.1%。     

可膨胀石墨与含磷阻燃剂对聚氨酯硬泡性能影响研究

通过试验研究比较了可膨胀石墨(EG)、含磷阻燃聚醚多元醇(F-7190)和磷酸三乙酯(TEP)对硬质聚氨酯泡沫塑料(RPUF)氧指数和燃烧性能的影响,同时考察了这几种阻燃剂对RPUF的压缩强度、导热系数等物理性能的影响。结果表明,EG的阻燃效果最好,F-7190、TEP的添加对含EG的RPUF极限氧指数的提高有促进作用,不同膨胀倍率的EG对RPUF的阻燃效果和物理性能的影响不同。RPUF的压缩强度随F-7190含量的增加略有增加,随TEP、EG含量的增加而减小。RPUF的导热系数随F-7190、TEP和EG含量的增加而增大,但存在一定的差异,其中EG的影响最大。     

组合多元醇对硬质聚氨酯泡沫塑料力学性能的影响

将中等羟值聚醚多元醇、低羟值聚醚多元醇、聚合物多元醇和苯酐聚酯多元醇分别与基础聚醚多元醇复配,制备了全水发泡硬质聚氨酯泡沫塑料,研究了4种不同组合多元醇对制品力学性能的影响,发现低羟值多元醇的加入使泡孔直径明显减小;过低羟值的TMN3050的加入对力学性能的提高不利;TMN700使泡沫体的压缩强度略为增加,冲击强度大幅提高,弯曲强度略为下降;聚合物多元醇TPOP36/28在低添加量下,制得硬泡泡孔直径明显减小,压缩强度和冲击强度大幅增加,弯曲强度降低;苯酐聚酯多元醇PS400A,使泡孔直径减小,制得硬泡的密度和力学性能大幅降低。     

水对硬质聚氨酯泡沫塑料性能的影响研究

采用一步法合成了硬质聚氯酯泡沫塑料(PUF-R),考察了水的用量对PUF-R的表观芯密度、导热系数、拉伸强度、弯曲强度、压缩强度等性能影响,并利用扫描电子显微镜观察了泡孔形态.结果表明,随着水用量的增加,RPUF的密度、导热系数、拉伸强度、弯曲强度、压缩强度逐渐降低,储能模量随之下降,而泡孔直径则逐渐增大.     

含磷二元醇/APP阻燃硬质聚氨酯泡沫的性能

以聚醚多元醇、多次甲基多异氰酸酯、含磷二元醇(P-polyol)和聚磷酸铵(APP)为主要原料,制备出综合性能较好的阻燃硬质聚氨酯泡沫塑料(RPUF)。结果表明:P-polyol与APP复配,可在提高RPUF阻燃性能的同时,增强力学性能,提高热稳定性;当P-polyol的添加量为31.8份、APP的添加量为95.0份时,改性RPUF的极限氧指数(LOI)增大至27.0%,烟密度等级(SDR)降低为24.0%;且此时的冲击强度和压缩强度均高于纯RPUF。微型燃烧量热(MCC)、热重(TG)和扫描电镜(SEM)测试表明:P-polyol与APP的复配改性使RPUF生成了连续致密的炭层,残炭率提高,稳定性增强;其总热释放量为22.7 kJ/g、热释放峰值为132 W/g,相比纯RPUF有明显下降。     

汽车用微孔聚氨酯弹性体的研究

研究了以聚醚多元醇、二异氰酸酯、醇胺交联剂和水制备微孔聚氨酯弹性体的力学性能和压缩负荷性能。结果表明：随异氰 酸酯指数Ｒ的提高,微孔聚氨酯弹性体的硬度、拉伸强度和冲击弹性增加,而伸长率则下降;增加异氰酸酯指数和密度微孔弹性体的压缩负荷显著提高,压缩变定性能改善。当Ｒ为１．０５时,呈现出最佳性能。     

大豆油多元醇的制备及其在聚氨酯硬泡中的应用

通过实验制备出大豆油多元醇Soy-450,并应用于聚氨酯硬泡中,通过改变Soy-450的替代用量来研究其对硬泡性能的影响。随着Soy-450替代量的增加,发泡性能和尺寸稳定性有所下降,密度增大;当替代量为10~50份时,具有更高的垂直压缩强度;与石油基硬泡相比,大豆油基硬泡具有更好的热稳定性。     

新型含磷阻燃型桐油基聚氨酯硬泡的制备及性能表征

桐油与甘油在甲醇钠为催化剂的条件下发生醇解反应得到桐油醇解产物（GTO）,GTO经环氧化得到环氧化桐油醇解产物（EGTO）,EGTO与9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物（DOPO）发生开环反应生成新型含磷阻燃型桐油基多元醇（PTOP）。PTOP部分取代聚醚多元醇（PPG4110）与异氰酸酯及助剂反应,通过一步法制备聚氨酯硬泡（RPUF）。采用万能试验机、热导率测定仪、热重分析仪和锥形量热仪分别考察RPUF的力学性能、热稳定性和燃烧行为。结果表明：随着PTOP替代石油基多元醇的比率增大,RPUF的压缩强度、密度、热导率先增大后减小,热稳定性提高,极限氧指数（LOI）由18.1%提高至26.0%,而总放热量先减小后增大,这主要是由于PTOP结构中的DOPO基团具有阻燃作用而PTOP结构中含有的桐油基脂肪链易于燃烧且热释放量较大。以上结果表明PTOP部分取代PPG4110制备的RPUF具有良好的阻燃性能和热稳定性。     

Nanoclay reinforced rigid polyurethane foams

Clay was intercalated and exfoliated by neutralized dimethylol butanoic acid (DMBA) and used to fabricate rigid polyurethane foam (RPUF)/clay nanocomposites. Cream time, gel time, and tack‐free time increased with the addition and increasing amount of clay whereas foam density and compression strength decreased. Cell size, closed cell content, volume change upon heating and cooling, and thermal conductivity of the foam decreased with the addition and increasing amount of clay with a minimum at 2 pphp (parts per 100 polyol by weight). The glass transition and decomposition temperatures increased with increasing clay content due to the restricted motion of chains and barrier property of the clay platelets. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

硅钙镁晶须增强RPUF复合材料的制备与性能研究

研究了硅钙镁（SCM）晶须在硬质聚氨酯泡沫塑料（RPUF）基体中的分散状况及SCM晶须用量对SCM晶须／RPUF复合材料的力学性能、表皮结构和尺寸稳定性的影响。结果表明：SCM晶须在RPUF基体中具有较好的分散性；随着SCM晶须用量的增加，复合材料的压缩性能逐渐提高，直至晶须用量超过60g／100g聚醚后，复合材料的压缩性能开始下降；复合材料的冲击强度随着SCM晶须用量的增加明显下降；复合材料的表皮随晶须用量的增加越来越致密；在一定用量范围内，SCM晶须可改善复合材料的尺寸稳定性。     

Bio-based flame-retardant rigid polyurethane foam with high content of soybean oil polyols containing phosphorus

Rigid polyurethane foam (RPUF) is prepared from petroleum-based polyols and isocyanate, which consumes a large amount of petroleum. To alleviate the consumption of petroleum, it is necessary to synthesize green and sustainable polyols. However, the greatest disadvantage of RPUF is its flammability. To reduce the risk of fire caused by RPUF, phosphorylated soybean oil polyol (Polyol-P) and phenyl phospho-soybean oil polyol (Polyol-PPOA) were synthesized by ring-opening reactions of epoxy soybean oil with phosphoric acid and phenylphosphonic acid, respectively. A flame-retardant RPUF was prepared via polymeric 4,4-diphenylmethane diisocyanate (p-MDI), which reacted after mixing Polyol-P and Polyol-PPOA with polyether polyol-330N in different proportions. Scanning electron microscopy (SEM) showed that the cell sizes of the RPUF-P and RPUF-PPOA increased first and then decreased and the cell number decreased first and then increased with the increase in the contents of Polyol-P and Polyol-PPOA. Mechanical property tests showed that the compressive strength of the RPUF-P4 reached 0.1 MPa, and the compressive strength of the RPUF-PPOA4 reached 0.07 MPa. The limiting oxygen index values of the RPUF-P4 and RPUF-PPOA4 were 20.9% and 24.3%, respectively. The UL 94 of the RPUFs indicated that the rating of the RPUF-PPOA3 was improved to V-1. The results showed that the flame-retardancy mechanism of the Polyol-P and Polyol-PPOA in the RPUF was based on the charred surface as a physical barrier, which slowed down the decomposition of RPUF and prevented heat and mass transfer between the gas and the condensed phase.     

催化剂DABCO8154对硬质聚氨酯泡沫塑料性能的影响

采用一步法合成聚氨酯硬质泡沫塑料,考察了催化剂DABCO8154对聚氨酯塑料发泡体系的发泡时间、表观密度、热稳定性能、力学性能等的影响。随着DABCO8154用量的增加,发泡时间缩短,表观密度先下降后提高。压缩性能、弯曲性能随着DABCO8154含量增加逐渐降低。随着DABCO8154的加入,制品热稳定性提高。     

硬质聚氨酯泡沫动静态劈裂拉伸的试验研究

利用双立柱微机控制电子万能试验机并结合应变分析测量系统对密度为0.54 g/cm3和0.62 g/cm3的2种硬质聚氨酯泡沫（RPUF）进行准静态劈裂以及利用分离式霍普金森压杆对密度为0.62 g/cm3的RPUF进行动态劈裂,试验研究主要考虑应变率、密度和长径比3个影响因素。结果表明,在RPUF的准静态劈裂试验中,其抗拉强度、弹性模量均随应变率的增大而提高,而随长径比的增大却呈现降低的趋势;此外,RPUF的抗拉强度与密度也有着密切关系,即材料密度越大,抗拉强度越高,而对于较高密度的材料,当应变率达到一定值后,其抗拉强度的变化不再明显;在动态劈裂试验中,RPUF的DIF值随应变率的增大而明显升高且呈非线性增长的趋势,而抗拉强度、弹性模量均随长径比的增大而降低。     

端羟基液体橡胶改性RPUF的结构与力学性能

制备了3种端羟基液体橡胶改性硬质聚氨酯泡沫塑料(RPUF)。研究了所制备材料的形态结构,以及泡沫材料的冲击韧性、屈服强度模量、缓冲吸能特性和阻尼性能与材料密度、液体橡胶的含量和液体橡胶的种类之间的关系。结果表明,粘度较低的端羟基聚丁二烯改性的硬质聚氨酯泡沫具有更好的冲击韧性;粘度较高、含极性氰基端羟基聚丁二烯丙烯腈改性的硬质聚氨酯泡沫塑料具有较低的屈服强度、模量和缓冲能量吸收值,具有较高的力学损耗。为高阻尼硬质聚氨酯泡沫塑料的制备奠定了基础。     

大豆油基聚氨酯的研究及应用进展

综述了大豆油基聚氨酯的制备方法及应用,以大豆油为绿色原料,通过环氧化得到环氧大豆油,利用环氧大豆油开环制得大豆油基多元醇,再用此多元醇与异氰酸酯反应得到大豆油基聚氨酯泡沫、大豆油基聚氨酯乳液以及溶剂型大豆油基聚氨酯树脂。同时介绍了大豆油基聚氨酯在泡沫、涂料、胶粘剂等领域的具体应用。     

Reactivity of the raw materials and their effects on the structure and properties of rigid polyurethane foams

Formulations for rigid polyurethane foams (RPUFs) based on crude 4,4′‐diphenylmethane diisocyanate, polyether polyol, triethylenediamine, 1,4‐butane diol, poly(siloxane ether), methylene chloride, and water were studied. The stoichiometric ratios of various foam ingredients and their effects on physical properties such as the cream time, gel time, tack‐free time, and density of the RPUF samples were studied. The results indicated that the rate of RPUF formation increased with the catalyst (triethylenediamine and tin) and water content. The density of the RPUF samples blown with water, methylene chloride, and a mixture of water and methylene chloride decreased from 240.1 to 33.4 kg/m³ with an increase in the blowing agent contents. However, the RPUF density increased with increasing contents of 1,4‐butane diol. The cell morphology and thermal properties of the RPUF samples were investigated with scanning electron microscopy, thermogravimetric analysis, derivative thermogravimetry, and differential thermal analysis. Scanning electron microscopy results revealed an average increase in the cell size of the RPUF samples from 162 to 278 μm with increased water content. A thermal behavior study indicated that the RPUF samples decomposed in nitrogen and degraded in air through two and three weight‐loss stages, respectively. Foam pyrolysis in nitrogen and combustion in air led to 15 and 0% char residue, respectively. The results indicated that the thermal stability of the RPUFs was better in nitrogen than in an air atmosphere. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007