研究与开发(239～240)PPΠPOEΠPE共混改性的研究赵枫1,杨琪2,杨云波2(1.牡丹江第三热电厂,黑龙江牡丹江157013;2.牡丹江石油化工厂,黑龙江牡丹江157009)摘要:介绍了新型热塑性弹性体乙烯-辛烯共聚物(POE)的结构与性能的特点,采用配比合适的均聚聚丙烯(PP)和共聚PP为基体树脂,通过POE,PE对PP增韧改性研究,确定最佳的增韧剂和具有较好的协同效应的共混体系,结果表明:POE为PP的最好增韧剂,PPΠPOEΠPE三元共混体系具有较好的协同效应。

关键词:聚烯烃弹性体;聚丙烯;增韧;共混中图分类号:T Q316.6 文献标识码:B 文章编号:1009-0045(2002)04-0239-02 聚丙烯(PP)作为一种通用塑料,具有密度小、无毒、耐腐蚀、力学均衡性好、价格低等优点,但其缺口敏感性特别显著,缺口冲击强度较低,尤其在低温时更为突出。

根据橡胶增韧塑料的机理,橡胶与塑料应构成“海岛”结构,即橡胶相必须以一定的粒径均匀分布在塑料连续相中以达到增韧塑料的目的。

人们往往采用EPDM, E VA和S BS等一些橡胶或热塑性弹性体对PP进行改性,以改进PP的缺口冲击韧性,但热稳定性、刚性却不够理想。

聚烯烃弹性体(POE)与上述传统的增韧材料相比,对PP的增韧改性效果则更为显著。

本文以配比合适的均聚PP和共聚PP为基体树脂,以POE为主增韧剂,在保证共混材料刚性、冲击强度较高的前提下加入少量PE 作为辅助增韧剂,以减少POE的用量,降低成本。

1　实验部分①1.1　主要原料均聚PP4018,辽阳化纤公司产品;共聚PP1647,北京燕山石化公司产品;PE,大庆石化总厂产品;POE8150,美国DOW化学公司产品;抗氧剂1010、168,北京化工三厂产品。

1.2　主要设备同向双螺杆挤出机,型号TSS J-58Π48D,成都晨光塑料机械厂产品;注塑机,C J-150NC,广东震德塑料机械厂产品;熔体流动速率仪,VPXRZ-400C,吉林大学科教仪器厂产品;电子万能试验机,CSS1101C,机械部长春试验机研究所产品;冲击试验机,RESI L25,意大利CE AST公司产品;调温,调湿箱,P L-2G,上海爱斯佩克环境仪器公司产品。

1.3　试样制备将原材料干燥后按工艺配比进行共混,经同向双螺杆挤出机挤出,温度为210℃,主机转速为240rΠmin,挤出后水冷,干燥,切粒筛分。

在温度为50℃的条件下干燥1h,在注塑机上按AST M 标准注塑样条,在调温、调湿箱里进行样条处理72h后进行检测。

1.4　性能测试熔体流动速率按IS O1133测定,测试温度为(230±1)℃;缺口冲击强度按IS O180测定,测试温度为(23±1)℃;拉伸强度,断裂伸长率按IS O527测定;弯曲性能按IS O178测定。

2　结果与讨论2.1　POE的组成和特性POE是一种饱和的乙烯-辛烯共聚物,由美国DOW化学公司采用茂金属催化剂使乙烯和辛烯聚合而得的一种热塑弹性体。

POE的特性:非常窄的分子质量分布和一定的结晶度,使其既具有弹性体的性能又能像热塑　①收稿日期:2002-01-15;修回日期:2002-03-07作者简介:赵枫(1969-),女,黑龙江牡丹江人,工程师,已发表论文5篇。

第20卷　第4期2002年7月 石化技术与应用Petrochemical T echnology&ApplicationV ol.20　N o.4 Jul.2002性塑料一样便于加工;有较高的剪切敏感性和熔体强度,加之与其他聚烯烃相容性好,可以实现高挤出速率;没有不饱和双键,耐候性能优于其他弹性体,在低温下仍有较好的韧性。

2.2　POE含量对均聚PP性能的影响均聚PP加入POE进行增韧时,对均聚PP的性能影响见表1。

表1　POE对均聚PP的性能影响项目w(POE)Π% 1015202530熔体流动速率(10m in)Πg10.59.89.28.4 6.6屈服拉伸强度ΠMPa2725231918断裂伸长率Π%>500>500>500>500>500弯曲强度ΠMPa3533302825弯曲弹性模量ΠMPa11931095972893740缺口冲击强度Π(J・m-1)63110321539601 由表1可以看出,POE对于均聚PP增韧效果完全符合增韧理论。

熔体流动速率、屈服拉伸强度、弯曲强度和弯曲弹性模量均随着增韧剂POE 含量的增加而下降,而缺口冲击强度随着增韧剂POE含量的增加而提高,只有断裂伸长率未发生变化。

造成这种现象的原因可能是POE本身较小的内聚能和其长的侧已基在分子间起的连结、缓冲,减小银纹因受力发展成裂纹的综合结果。

均聚PP共混物的脆韧转变点在POE含量为25%左右,同时不难看出,随着体系冲击强度的提高,共混材料的刚性也下降较显著,相对材料成本很高。

2.3　共聚PP对均聚PPΠPOE性能的影响为在提高PP冲击强度的同时保证共混材料具有一定的刚性,并充分考虑共混体系的材料成本以及加工性能,将共聚PP加入到共混体系中,把POE的质量分数定为16%不变,然后逐渐加入不同质量分数的共聚PP,最终选出均聚PP与共聚PP的配合比。

所得共混体系的性能见表2。

表2　共聚PP对均聚PPΠPOE共混物的性能影响项目w(PP)Π% 1215243042熔体流动速率(10m in)Πg9.28.97.57.1 6.6屈服拉伸强度ΠMPa2726252423断裂伸长率Π%>500>500>500>500>500弯曲强度ΠMPa3432302928弯曲弹性模量ΠMPa117611361092981962缺口冲击强度Π(J・m-1)125132286326549 由表2可以看出,共混体系随着共聚PP的含量增加,体系的冲击强度得到改善,是同等质量分数POE增韧均聚PP的几倍,在得到同样冲击强度的共混材料时,完全可以降低POE的加入量,从而达到降低成本的目的,同时3共混材料的弯曲强度和弯曲模量等刚性指标还得到了一定的保证,这说明共聚PP是一种很好的相容剂,也是一种良好的增韧剂。

有关研究结果表明: POE对不同的PP共混物进行增韧时,都易得到粒径较小的分散相和较窄的粒径分布,平均粒径(d)为0.34μm,粒径分布为0.2～0.6μm,其粒径越小,分布越窄,共混物冲击性能越好且共混物可在较低的弹性体含量时呈现脆韧转变。

由表2可以看出,正是共聚PP这个相容剂对整个体系的作用,使得POE在PP中分散性更好,在POE质量分数为16%的条件下,就达到了以均聚PP为基体树脂时,POE质量分数需25%以上的条件要求。

从表2可确定均聚PP与共聚PP的质量分数比大致为1∶1。

2.4　PE对共聚PPΠ均聚PPΠPOE性能的影响在PP共混改性研究中,常发现采用三元共混增韧体系效果更好,因此,在本共混体系中将POE的质量分数降为10%,加入质量分数为10%的PE,共混体系中w(PE)∶w(共聚PP)∶w(均聚PP)∶w(POE)为10∶40∶40∶10,其性能测试见表3。

表3　PE对共聚PPΠ均聚PPΠPOE共混体系性能的影响项目共混体系熔体流动速率(10m in)Πg 5.6屈服拉伸强度ΠMPa24断裂伸长率Π%500弯曲强度ΠMPa38弯曲弹性模量ΠMPa968缺口冲击强度Π(J・m-1)576 由表3可以看出,随着PE的加入,共混体系的冲击强度并不随增韧剂POE的适当减少而降低,共混体系的刚性也没有较大的变化,而材料的成本却降低了,因此,可以肯定PE的加入起到了一种辅助增韧剂的作用,可使PP球晶形态不完整,分割成晶片,不能生成球晶,加上PE的熔点比PP低30～40℃,在熔体冷却时,部分增韧剂(下转第254页)2　计算结果分析从工况1和工况2的计算结果可以看出,由于实际进料温度的降低使28#板以下的气、液负荷均有较大程度的增加,特别是45#板以下液体负荷增加了30个百分点,气体负荷增加了40个百分点,再沸器热负荷增加了40个百分点,这样大的增幅必然会影响到全塔的正常操作和塔的生产能力,这就是导致生产达不到设计生产能力的原因。

工况3仅将第1股进料的温度作为操作温度,则28#到57#板的液体负荷仅增加4个百分点,气体负荷仅增加5个百分点,再沸器负荷增加4个百分点,说明第1股进料(10#板)温度的变化对塔的操作条件影响并不大,不至于影响到塔的正常操作。

工况4的情况是将第2股进料提高到设计温度,其余基本为实际操作条件,结果从28#到57#板的液体负荷仅增加19个百分点,气体负荷仅增加18个百分点,再沸器负荷增加12个百分点。

这些变化也在设计允许的范围之内,不会影响到塔的生产能力。

计算结果说明,第2股进料的温度对塔的操作影响很大。

3　改造及改造后的效果根据以上的分析,确定了提高第2股进料温度的改造方法,这样就可以降低从28#到53#板的气液负荷以及降低再沸器的热负荷,使该塔能够在设计负荷范围内正常稳定地操作。

实际上第2股进料温度没有达到设计温度是由于冷箱中通道的堵塞造成的。

本来该股料要经过冷箱,回收这股冷量,经检查发现该通道有堵塞,流体流动不畅,使之达不到设计的温度。

改造时只好增加了一条旁通管线,同时,为了提高第2股进料温度,采用了丙烯制冷中的43℃的液体丙烯作为热剂,回收这股物料的冷量,以降低能耗。

总的节能情况如下:再沸器减少蒸汽能耗2424400k JΠh;第2股进料加热回收0℃冷量558448k JΠh。

该改造措施实施后,效果很好。

图1为1组实际的操作数据,括号内为设计值,括号前为目前操作值。

图1　脱乙烷塔4　结论a.用PRO-Ⅱ软件,对脱乙烷塔的不正常操作工况进行了模拟计算,发现塔负荷加不上去的主要原因是第2股料进料温度太低(比设计值低10℃)。

b.通过改造第2股进料管线,进一步回收其中冷量的方法,使该塔通过能力提高,达到稳定正常操作的目的。

c.实现该改造有明显的节能作用。

(上接第240页)POE包覆在PE的外层,从而增加了增韧剂的有效体积分数,最终达到了细化PP晶体、增韧改性、降低成本,提高刚性的目的。

3　结论a.POE是良好的热塑性弹性体,用其增韧PP,其综合效果好。

b.基体树脂种类及含量同增韧剂一样,都是决定共混材料性能的关键因素,共聚PP在均聚PPΠPOE共混体系中可起到相容剂和辅助增韧剂的作用。

c.在共混体系中少量加入PE可以减少增韧剂POE的含量,从而提高刚性,降低成本。

R esearch of catalytic removal of sulfur compounds for oil by using sup2 ported active carbon:Ⅱ.R egeneration experimental research ZHANGJin-chang,W ANG Y an-hui,CHE N Biao-hua,LI Cheng-yue (K ey Laboratory o f Science and Technology o f Controllable Chemical Reac2 tions,Ministry o f Education,Beijing Univer sity o f Chemical Technology,Bei2 jing,100029,China)Abstract:The regeneration technologic conditions for the preparation of s or2 bent Z BDS were studied.The research was carried out in fixed bed reactor at 120～160℃by using N2,steam and steam m ixed with N2.It was showed that the regeneration conditions by using60%(v)m ixed with N2at140℃and2400h-1conditions was ideal,the multi regenerated s orbent had better ability of rem oval of sulfur com pounds.The SE M results did not show much difference between the fresh s orbent and third regenerated s orbent,which al2 s o indicated that the regenerated s orbent had better ability of rem oval of sul2 fur com pounds.Those results provided the basis for this s orbent to be used in the petrochem ical industries.K ey w ords:desulfurization s orbent;regeneration;active carbon;desulfuriza2 tionDevelopment of chemical ultra-stable Y of vanadium resistance PANG X in-mei,S UN Shu-hong,DING W ei(Petrochemical Research Institute o f Lanzhou Petrochemical Company,Pet2 roChina,Lanzhou,730060,China)Abstract:A novel chem ical ultra-stable Y zeolite was introduced,which had0.1%～17.0%of RE2O3and was characterized by the methods of XRD and IR.The characterization results showed that RE on the zeolite were tw o types:one was RE2O3and the other was RE3+ion.The results showed that the novel zeolite had excellent vanadium resistance and g ood products selectivity,especially,for gas oline,dry gas and coke.K ey w ords:chem ical ultra-stable Y;cracking catalyst;RE2O3;vanadium resistanceStudy on technical process of degrad ation of w aste plastics for produc2 ing gasoline and diesel FuelLI Y a-hong1,LI W en-hong2,QIN Qian2,W ANG Y an-li2,HUA Chao2 (1.Xi’an Petroleum Institute,Xi’an,710065,China;2.Northwest Uni2 ver sity,Xi’an,710069,China)Abstract:The technical process of hot cracking,catalytic cracking and cata2 lytic upgrading for producing gas oline and diesel fuel with waste plastics such as PE,PP and PS were studied.The optimum conditions of reactin pro2 cess was obtained.The results showed that the gas oline(N o.80)was pro2 duced by using SH-1catalysts at the380℃,with yield86.0%;the gas o2 line(N o.93)was produced by using JD-01catalyst,with yield82.0%. K ey w ords:waste plastic;cracking reaction;catalytic upgrading;technical process;gas oline;diesel fuelStudy on process for synthesizing furazolidone by carbonylation of dimethyl carbonateLI G ui-xian1,LI Shao-bai2(1.College o f Petrochemical Engineering,Gansu Univer sity o f Technology, Lanzhou,730050,China;2.College o f Chemisty and Chemical Engineering, Lanzhou Univer stiy,Lanzhou,730000,China)Abstract:By establishing the reas onable process for synthetising furaz oli2 done with the carbonylation of DMC,many effect factors such as carbonyla2 tion agent,catalyst and its yield,reaction ratio,reaction time and reaction distillation etc on the carbonylation reaction were investigated.Based on these researches,the optimal process conditions were determ ined.K ey w ords:dimethyl carbonate;carbonylation reaction;furaz olidone;option2 al condition Properties and application of amine salt of acidity isooctyl-phosphite W U Jing,FU X i-sheng,ZHANGLong-hua(Research and Development center o f Lanzhou Lube Oil Company,Lanzhou, 730060,China)Abstract:The synthetic method and properties of im proved product of am ine salt of acidity is ooctyl-phosphite EPΠAW additive were introduced,and the application of this additive used into vehicle gear oil was als o discussed.Ex2 perimental results revealed that the im proved additive had g ood extreme pre2 ssure were resistance and s olution ability in hydrogenation oil.The80WΠ90 heavy loading vehicle gear oil with4.8%additive package reached the standard of API G L-5.K ey w ords:additive;gear oil;applicationModification of PPΠPOEΠPE blendsZHAO Feng1,Y ANG Qi2,Y ANG Y un-bo2(1.Mudanjiang No.3Electrical Plant Mudanjing,157013,China;2.Mu2 danjiang Petrochemical Factory Mudanjiang,157009,China)Abstract:The properties and structure of a nwe therm oplastic elastomer POE were studied.The optimum toughening agent and blending system were ob2 tained with proper hom opolymerized PP and copolymerized PP as base res2 ins,by com paring the toughening m odification with POE and PE.The results showed that POE was the best toughening agent and the PPΠPOEΠPE blend2 ing system had g ood synergistic effect.K ey w ords:poly olefine elastomer;polypropylene;toughening;blending Application of hot circulation regeneration of pyrolysis gasoline second2 ary,hydrogenation catalystW U Hao1,LI S i-qin2(1.Ethylene Industry Company o f Maoming Petrochemical Corporation,SIN2 OPEC,Maoming,525021,China;2.Petrochemical Research Institute o f Lanzhou Petrochemical company,Petro China,Lanzhou,730060,China) Abstract:The pyrolysis gas oline secondary hydrogenation catalyst was stu2 dided by hot circulation regeneration.The industrial test showed that the running period of the catalyst increased from6m onths to16m onths with g ood effect.K ey w ords:pyrolysis gas oline;hydrogenation;catalyst;regeneration Analysis on inactivation reasons of p alladium catalyst in pyrolysis gaso2 line hydrogenationY ANG Bai-cheng(Ethylene Industry Company o f Maoming Petrochemical Corporation,SIN2 OPEC,Maoming,525021,China)Abstract:The factors affecting the service life of palladium catalyst in pyrol2 ysis gas oline hydrogenation were found out by the analysis on the running circumstance of primary hydrogneation catalyst in pyrolysis gas oline hydroge2 nation unit.The method for increasing the service life of catalyst was prop2 osed.K ey w ords:pyrolysis gas oline;hydrogenation;palladium catalyst;inactiva2 tionProduction technology of catalytic cracking by increasing heavy oil ra2 tionLIU Huai-yuan,W U K ai(Re finery o f Lanzhou Petrochemical company,petro china,Lanzhou, 730060,China)Abstract:The technological rem oulding was carried out in a1.2M tΠa heavy oil catalytic cracking unit by incresing the heavy oil ratio from41.52%to 52.20%.The processing of heavy oil increased149.5%ktΠa,the yield of product reached79.2%,the product structure could be adjusted,and g ood econom ic effectiveness was obtained.ABSTRACTS PETROCHE MICA L TECHNO LOGY&APP LICATIONBim ontlhy V olume20, N o.4 Jul 2002。