氯化聚丙烯的制备与性能研究

本文针对聚丙烯(PP)粘合性差、较难染色、低温呈脆性、收缩率大等缺陷,采用溶液法对聚丙烯进行氯化改性,以AIBN(BPO)为引发剂,氯苯为溶剂,进行自由基引发接枝反应制取氯化聚丙烯(CPP)。通过滴定法得出氯化度的值,并对反应时间、反应温度、引发剂浓度等条件进行考察,得出最优氯化工艺条件,采用红外技术(FT-IR)对CPP加以表征,从溶解性能方面加以分析,进一步阐述了氯化度对其性能的影响。实验结果表明,该法可以得到氯原子的接枝产物,在反应温度120℃,反应时间5h时,CPP的氯化度最高可达52%,氯化度越高溶解度越高。     

氯化聚烯烃大分子改性聚丙烯的研究

利用Haake流变仪,以氯化聚烯烃(氯化聚乙烯CPE、氯化聚丙烯CPP)为大分子改性剂,与聚丙烯(PP)进行熔融复合,并加入三氧化二锑(AO)作为阻燃协效剂,得到一系列不同组成的聚合物复合材料。测试结果表明,CPP对CPE具有增容作用,两者的引入不但可同时提高复合材料的拉伸强度与冲击强度,而且也显著提高了复合材料的阻燃性能。在氯化聚烯烃含量为20%时,CPP/CPE质量比为1/9时复合材料的拉伸强度比纯PP增加了40%,CPP/CPE质量比为9/1时复合材料的冲击强度比纯PP增加了165%,氧指数比纯PP增加了41%,水平燃烧达到FH-1级。     

氯化聚丙烯/丙烯酸酯接枝物的合成和性能研究

采用溶液法用混合单体甲基丙烯酸甲酯（MMA）、丙烯酸丁酯（BA）对氯化聚丙烯（CPP）进行接枝改性,制备出不同接枝率的改性CPP,并对接枝产物进行了傅里叶变换红外光谱分析,探讨了改性CPP在PP底材上得附着性能。结果表明：改性CPP在PP板材上具有良好的附着力;随着接枝率的提高,改性CPP与丙烯酸树脂的相容性增强。     

氯化聚丙烯对PP/PVC共混物性能的影响

以氯化聚丙烯(CPP)为增容剂,探讨了CPP不同含量下PP/PVC体系的力学性能、相容性、流变性能以及对应的微观结构,并与氯化聚乙烯(CPE)增容剂进行了比较。发现添加5份CPP可明显改善PP和PVC两相界面相容性,与PP/PVC体系相比,拉伸强度提高了61%,无缺口冲击强度提高了100%。此时CPP还起到了一定的增塑作用,共混体系加工性能较好。与CPE相比,含有CPP的共混体系拉伸强度较高。     

改性CPP的表征及其对PP附着性能的影响

采用混合单体甲基丙烯酸甲酯(MMA)、丙烯酸丁酯(BA)和2-甲基丙烯酸(MAA)对氯化聚丙烯(CPP)进行接枝改性,制备了几种不同接枝率的改性CPP,并用红外光谱和热分析仪对其进行了表征,探讨了改性CPP在PP基材上的附着性能。结果表明:改性CPP在PP塑料上具有良好的附着力;随着接枝率的提高,改性CPP与丙烯酸树脂的相容性增强,其混合液在PP塑料上的附着力达到100%,可用来制备直接涂覆的PP涂料。     

改性氯化聚丙烯的性能与应用

氯化聚丙烯(CPP)被广泛用作聚丙烯(PP)塑料上涂层的附着力促进剂。向CPP中引入含氧的极性基团可以大幅度提高其与丙烯酸树脂的相容性,改善涂层对PP底材的附着力。通过红外光谱、紫外-可见光谱、X-射线光电子能谱和X-射线衍射等方法分析了一种新型的基于CPP的附着力促进剂,并与市场上普遍使用的同类产品进行了比较,考察了由此新型附着力促进剂制备的PP底漆、色漆和金属涂料的性能。     

氯化聚丙烯/马来酸酐接枝物的合成和性能研究

以甲基环己烷为溶剂、过氧化二苯甲酰(BPO)为引发剂,加入马来酸酐(MAH)以及苯乙烯(St)对氯化聚丙烯(CPP)进行接枝改性。系统研究了单体MAH、St、过氧化二苯甲酰(BPO)对MAH接枝率的影响,并对其影响因素进行了分析。用红外光谱(FTIR)表征了产物结构,用滴定的方法测定了接枝率,实验结果表面:最佳反应条件为BPO/CPP投料比为10%,St/MAH投料比为1∶1,MAH/CPP投料比为20%,反应温度为100℃,反应时间为2 h。通过聚丙烯(PP)板涂装底漆附着力测试表明,当氯化聚丙烯接枝马来酸酐(CPP-g-MAH)接枝率达到3.14%时涂层附着力等级可达到0级。     

超声波对制备改性氯化聚丙烯乳液的影响

采用超声波处理为分散手段,通过自乳化法制备了改性氯化聚丙烯(CPP)乳液。比较了机械搅拌和超声乳化工艺对制备CPP乳液性能的影响;研究了超声波作用时间、作用功率对乳液性能的影响以及对乳液粒径及其分布的影响,结果表明,超声波的作用功率为400 W,作用时间为6 min时,得到的CPP乳液具有良好的稳定性,而且乳液涂膜在PP塑料上的附着力达到0级。     

氯化聚丙烯改性及其粘附性能研究

以甲苯为溶剂,过氧化二苯甲酰(BPO)为引发剂,通过自由基聚合,采用马来酸酐(MAH)接枝改性氯化聚丙烯(CPP),并对产物结构进行了FTIR表征。研究了反应温度、反应时间、MAH和BPO用量对改性氯化聚丙烯胶粘剂粘附性能的影响;得出较佳的工艺条件为:反应温度θ=90℃,反应时间t=3 0h,原料质量配比为m(CPP)∶m(MAH)∶m(BPO)=100∶3∶0 3。     

氯化聚丙烯的磺化改性研究与应用

以氨基磺酸为磺化剂对氯化聚丙烯(CPP)进行磺化改性,研究了氨基磺酸的用量、反应温度和时间对磺化度的影响,获得了较佳的反应条件:m(NH2SO3H)/m(CPP)=0.08,温度60℃,时间8.0h。在此条件下可制得磺化度为1.56mol/kg的磺化CPP。通过红外光谱对磺化CPP进行了表征。将磺化改性的CPP与丙烯酸酯聚合,制备了水性磺化CPP–丙烯酸酯乳液。以此乳液制备金属防腐涂料,所得涂膜附着力0~1级,硬度3B~2B,柔韧性>2mm,在3%NaCl溶液中浸泡45d和盐雾腐蚀试验300h后完好。该磺化改性CPP可用于制备水性金属防腐涂料。     

聚丙烯水相悬浮热氯化

研究了等规聚丙烯(IPP)水相悬浮热氯化,考察了氯化时间和温度、IPP粒径、搅拌转速、通氯速率等条件对氯化反应的影响。发现氯含量随氯化温度的升高而增大,随IPP粒径的减小而呈线性增大;在IPP充分分散条件下搅拌和通氯速率对氯化几无影响。扫描电镜(SEM)照片显示,氯化反应首先发生在粒子表面,氯化产物将粒子表面孔隙填充,增加了氯向粒子内部扩散的阻力,致使粒子内部的氯化反应缓慢。     

Electrical properties of chlorinated atactic polypropylene (CAPP) and PVC–DOP–CAPP system

The electrical properties, such as dielectric properties and volume resistivity, of chlorinated atactic polypropylene(CAPP), obtained by thermal chlorination of APP, have been studied. The results show that dielectric constant, loss tangent, and volume resistivity of the chlorinated samples increase with the increase in degree of chlorination. The effect of CAPP as secondary plasticizer in the PVC–DOP system has also been studied. Dielectric study of PVC compounds shows a single relaxation peak, indicating no phase separation. In the case of PVC compounds, it has been observed that with the increase in CAPP content in PVC compounds dielectric constant and loss tangent decrease whereas volume resistivity increases. The increase in volume resistivity was further supported by the increase in activation energy value, obtained from volume resistivity vs. 1/T plot.     

丙烯酸(酯)的含氯化开发及其在氯产品中的应用

结合国内外的相应实例,介绍了丙烯酸(酯)的含氯化开发,即直接氯化或间接含氯处理的进展。阐述了丙烯酸酯类在氯化橡胶、氯丁胶粘剂、氯化聚丙烯、聚氯乙烯加工中的应用。     

无溶剂光氯化悬浮法制备低氯化度的氯化等规聚丙烯

用无溶剂光氯化悬浮法进行等规聚丙烯 (IPP)氯化反应 ,考察了反应时间、引发剂、通氯量、悬浮剂和金属盐等因素对氯化速度的影响 ,以偶氮二异丁腈为引发剂 ,m(IPP)∶m(H2 O) =1∶1 5,通氯量为 40mL min ,反应时间 1 0h ,可得到氯质量分数在 2 5%左右的氯化聚丙烯。金属离子可明显缩短其诱导期 ,但反应后期 ,金属离子的存在对氯化反应起抑制作用。     

Study of structure and thermal properties of polypropylene and chlorinated polypropylene by infrared spectroscopy and differential scanning calorimetry

The infrared spectra of chlorinated polypropylene (CPP) are interpreted and tentative assignments of C—Cl stretching vibration of CPP are proposed. Recently, infrared spectrophotometry has been applied as a useful tool for the investigation of polymer transitions. The solid-state transition in isotactic polypropylene (IPP) was studied by infrared method in the range of ?50° to 30°C; and from the temperature dependence of the peak absorbance, transition at -10°C was detected. This temperature of -10°C agrees well with the T_g2 detected by other methods. From these results, it is presumed that T_g2 is attributed to a motion (thermal expansion) of IPP segments in either crystalline and amorphous region. The thermal transition of chlorinated isotactic polypropylene (CIPP) was also examined with differential scanning calorimetry and infrared method, and two thermal transitions were observed. A higher transition (T_H) has a minimum at a degree of chlorination of about 39 wt-%; and a lower transition (T_L) changes linearly with increasing degree of chlorination. Infrared results indicate that T_H may be associated with a motion (thermal expansion) in chlorinated segments, and T_L may be associated with a motion in unchlorinated segments. These results of infrared studies also suggest that CIPP may have a block structure.     

Chlorinated atactic polypropylene as a plasticizer for poly(vinyl chloride)

Atactic polypropylene, a byproduct obtained in the manufacture of isotactic polypropylene, has been chlorinated under various reaction conditions. The chlorination reaction is reasonably fast so as to give a product of 53-43% chlorine content in 3 h. The chlorinated product has been incorporated in poly(viny1 chloride) formulations with a view to study its plasticizing activity. Generally this type of compound acts only as a secondary plasticizer; hence it has been used in combination with di(2-ethylhexyl)phthdate, a primary plasticizer. Different proportions of these two plasticizers have been added to poly(vinyl chloride) resin to obtain a series of formulations. These compounds were evaluated, and it appears that the addition of chlorinated atactic polypropylene (APPC) helps in easy processing and increases the throughput. The increasing concentration of APPC showed an upward trend in die head pressure and torque indicating an increase in melt viscosity. The results of physical properties evaluation show that APPC acts as a reinforcing agent and also imparts permanence to the plasticizers.     

Surface chlorination of polypropylene film by CHCI3 plasma

Polypropylene films were treated with the CHCI₃ plasma, and their chemical composition was analyzed with XPS and ART IR spectroscopy. The CHCI₃ plasma irradiation made polypropylene films hydrophilic. The advancing contact angle decreases from 95° for the untreated to about 73° for the CHCI₃ plasma-treated films. In the CHCI₃ plasma irradiation, the chlorination occurs, and C? Cl, C? Cl₂, and C? Cl₃ units are formed in the polypropylene films. Simultaneously with the chlorination, unsaturated units (C?C and conjugated C?C units) are formed from dehydrogen chlorination of the chlorinated products, but the oxygen incorporation into the films is low. The CHCI₃ plasma is preferred in chlorination of polypropylene films to the CCl₄ plasma. © 1994 John Wiley & Sons, Inc.     

Head-to-head polymers: 19. Chlorination of cis-1,4-polybutadiene

Chlorination of cis-1,4-polybutadiene (PB) has been studied in detail. It was found that chlorination must be carried out in an oxygen free atmosphere at polymer concentrations below 0.5%, and at temperatures below room temperature in mixed solvents with dichloromethane as the major component. In the initial stage of chlorine addition to the double bonds of cis-1,4-polybutadiene, block structures of chlorinated segments are formed. The chlorine addition to the cis-butadiene units was not stereospecific and the final chlorination product had nearly a 1:1 ratio of the threo- and erythro structure of the CHCICHCI-units. Microphase separation in partially chlorinated PB was observed by d.s.c., dynamic-mechanical measurement, and transmission electron microscopy. It was concluded that partially chlorinated PB, whose degree of chlorination was lower than 65 mole %, was composed of almost pure cis-1,4-PB domains and a separate phase which consists ofCH₂CHCICHCICH₂units with perhaps as much as 10% of cis-1,4-PB units incorporated in this phase. If the degree of chlorination is more than 90 mole % one phase exists.     

CPP-g-GMA对聚丙烯及其复合材料涂装性能的改善

本文研究了自制的CPP-g-GMA(氯化聚丙烯接枝甲基丙烯酸缩水甘油酯)对聚丙烯的粘接作用,并以CPP-g-GMA为底漆、双组分丙烯酸清漆为面漆对聚丙烯及其复合材料进行了涂装,探讨了CPP-g-GMA对涂层附着力的影响及其与接枝率的关系.结果表明,GMA的接枝可在一定程度上改善CPP与聚丙烯的粘接作用,能有效提高聚丙烯及其复合材料与丙烯酸漆的附着力,随着接枝率的增加,提高的幅度增大,在接枝率为2.31%时附着力等级可达到最高的0级.