丙烯酸改性氯化聚丙烯的合成和粘接性能的研究

丙酸改性氯化聚丙烯的合成和粘接性能的研究zHAN∥E2004,25(4)Study on synthesis and adhesiveness of modifiedchlorinated polypropylene with acrylic acidFU He-qing, HUANG Hong, ZHANG Xin-ya, CHEN Huan-qin(Research Institute of Chemical Engineering, South China University of Technology, Guangzhou, Guangdong 510640)Abstract: Grafting of acrylic acid(AA) on chlorinated polypropylene (CPP) by free radical processwas carried out at different temperatures and hours using toluene as solvent. The effect of temperature,time, initiator concentration and the ratio of chlorinated polypropylene and acrylic acid on the adhesivenesswas studied. The optimum processing conditions were that the reaction temperature was 100 C, reactiontime was 3. 5 h, based on 100 parts chlorinated polypropylene 3 parts of acrylic acid and 0. 30 parts benzoperoxide(BPO)were used. The adhesiveness of modified chlorinated polypropylene with acrylic acid wasbetter than that of chlorinated polypropylene.Key words: chlorinated polypropylene; grafting; modification; acrylic acid; adhesiveness中图分类号:TQ325.1+4文獻标识码:A文章编号:1001-5922(2004)03-0008-03pylene by free radical process was carried out.Due to the low cost, versatile properties, poly- Effect of reaction temperature, time and initiatorpropylene is one of the most important polymer concentration on adhesiveness was systematicallyidely used in household and industrial fields. studied. The adhesiveness of grafting modified ofof dyeing, low impact strength, poor compatibility better than that of chlorinated polypropylenesHowever, lack of chemical functionalities, difficulty chlorinated polypropylene with acrylic acid wwith other polymers, poor adhesion and non-polarity of the polypropylene its further application 2 Experimentalhas been restricted in the field of adhesive, printing 2. 1 Materials and instrumentationink and coating. This can be overcome thiCPP, toluene (CP grade ), benzoyl peroxideChemical modification of(BPO)(CP grade), acrylic acid(AA)(CP gradepropylene through grafting copolymerization offers were purchased from Guangzhou Jinzhujiangthe polarity of polytd, Hengyang Chemical Agent Faory, Guangzhou Xingang Chemical Co, LtdChlorinated polypropylene is the product of Guangzhou Donghong Chemical Agent Factory, re-polypropylene's chlorination modification, but its spectivelyadhesion can't suit for special need in adhesive and2 Experimental procedurecoating field. In order to improve its property,100 g CPP was dissolved in toluene in a four-grafting of acrylic acid on the chlorinated polypro- neck reactive flask with mechanical stirrer, drop-ng funnel, and thermo pocket. The initiator收稿日期:2004-02-作者简介:傅和青(1968-),男,发表论文20多篇,主要研究项目solved in为改性聚合物m中国煤化工ixture. The reactionCNMHG研究报告及专论粘接2004,25(4)temperature was from 80 C to 110 C, and the re- hand, further increases in reaction time might causeaction time was from lh to 5 h After completion of the cross linking reaction and other side reactionthe reaction, the adhesiveness of the product was therefore resulting in shearing strength decreasing.determined3.2 Effect of reaction temperature on the shear-2.3 Determination of the adhesiveness of the prod-ing strengthPolypropylene film was rubbed down withsand paper, then was immersed in chromic acid, after 15min, took out, washed with water and drieduntil it was clean and dry. The prepared polypropylene film was smeared with 0. 0lcm adhesion of日and was placed for 3min, clamped and cured at120.C for 2h, took out and cooled at room-tem-perature, then determined the shearing strengthFig 2 Effect of reaction temperature on the shearing strengthFig 2 shows that as the temperature increa-3 Results and discussionses, the shearing strength increases fast at first but3. 1 Effect of reaction time on the shearing strengthafter over 100C it decreases. The reason is that atunder 100c the temperature is low and the con-centration of free radical is low, then with increas-ing temperature, the number and the mobility offree radicals generated at high temperature in-crease, so that there is more acrylic acid grafts on1.8the chlorinated polypropylene After over 100Cthe free radicals decreases and the acrylic acid graf-ted on the chlorinated polypropylene decreases and4.04.5side reaction increases, therefore the shearingFig. 1 Effect of reaction time on the shearing strengthstrength of the product decreases.3. 3 Effect of BPO amount on shearing strengthFig. l illustrates the effect of reaction time onhe shearing strength. It can be seen from the fig.222l that as the reaction time increases the shearingstrength increases fast before 3. 5h, and after 3. 5hthe shearing strength decreases. The reason is thatbefore 3. 5h polymerizing reaction is at the step ofchain initiation and chain growth, at which themain reaction is the formation and growth free rad-0100.150.20025030035I concentration of the free radical increases fastBP0/%Fig 3 Effect of BPO amount on shearing strengthand there is more free radical reacts with chlorinated polypropylene. After3. 5h, it goes into step ofThe results obtained in the study of effect ofhain termination, there is less free radical which initiator concentration on the shearing strength arereacts with chlorinated polypropylene, on the other given中国煤化工 t as increasingCNMHG丙烯酸改性氯化聚丙烯的合成和粘接性能的研究ZHANJIE2004,25(4)concentration of BPO, the shearing strength initial- of the free radical increases fast and there is morely increases fast, passes through the maximum, free radical reacts with chlorinated polypropylenehen decreases. This is a typical behavior observed When the concentration of acrylic acid exceedsin grafting processes occurring via chain transfer 3%, the increased free radical concentration in themechanism. Initially the shearing strength increa- solution increases homopolymerization and otherses due to increased availability of free radicals for side reactions, and hence decreases the shearinggrafting of acrylic acid, but, when concentration of strength. And it is also illustrates that the adheBPO exceeds a certain limit, increased free radicals siveness of modified chlorinated polypropyleneconcentration in the solution increases the reaction with acrylic acid was better than that of chlorinatedgradationand other side reaction, and hence de- polypropylenecreases shearing strength.3.4 Effect of AA amount on shearing strength4 ConclusionThe modified chlorinated polypropylene withacrylic acid was prepared using BPO as the initiator, toluene as solvent, at different reaction conditions. The optimum processing conditions werethat the reaction temperature was 100 C, reactiontime was 3. 5 h, based on 100 parts chlorinated polpropylene 3 parts of acrylic acid and 0. 30 partBPO were used. The adhesiveness of the acrylicFig. 4 Effect of quantity of AA on shearing strengththan that of chlorinated polypropylene.Fig. 4 illustrates the effect of acrylic acid conentration on the shearing strength. It was ob- [1]FU He-qing, HUANG Hong, LAN Ren-hua, et al. Melt-served that as increasing concentration of acrylicGrafting for Maleic Anhydride onto Polypropylene withacid, the shearing strength initially increases andthe Assistantin Chinese)[J]. Modern Chemicalthen passes through the maximum, when the conIndustry,2003,23(7):27-29centration of acrylic acid exceeds 3%, the shearing [2JLi Ying, Xie Xu-Ming, Guo Bao- Hua. Study on styrene-strength decreases. The reason is that when theassisted melt free-radical grafting of maleic anhydride on-olymerizing reaction is at the step of chain initia-to polypropylene []. Ploymer, 2001, 42: 3419-3 425.tion and chain growth at first, and the concentration[3]DANG Soft Propylene Polymer Blend with High MeltStrength[P].US:6225411,2001-5-1.丙烯酸改性氯化聚丙烯的合成和粘接性能的研究傅和青,黄洪,张心亚,陈焕钦(华南理工大学化工学院化工所,广东广州510640)摘:氯化聚丙婶是聚丙的氯化改性产物,通过改性,其硬度、耐磨性、耐酸性、耐盐水性能比聚丙烯都好,耐热、耐老化性也优于聚丙坤。但其性能尤其是粘辏性能还不能满足其在胶粘剂等方面的要,为了进一步提高氯化聚丙烯的粘接性能拓宽其应用顿城需对氯化聚丙烯改性。接枝共聚法是一种很好的化学改性方法。本文以丙烯酸(AA)作为挟枝单体,以过氧化萃甲酰(BPO)为引发剂,以甲菶为溶剂,采用液相接枝共聚法将丙烯酿单体接枝到氯化聚丙烯大分子链上,得到丙烯酸改性氯化聚丙坤产物。系统研究了反应温度、反应时间、引发剂过氧化苇甲酰用量和丙蛐酸单体用量等因素对丙烯酸接枝改性的氯化聚丙烯产物粘擴性能的影响,得出了较佳的工艺条件是反应温度T=100℃,反应时间t=3.5h,原料质量配比为100份氯化聚丙烯、3份丙烯酸和0.3份的过氧化二笨甲酰。研究还表明,丙烯酸改性的氯化聚丙烯的粘接性能优于氯化聚丙烯的粘接性能关鵪词:氯化聚丙烯;楼枝;改性;丙烯酸;粘接性能中国煤化工CNMHG