双环戊二烯改性不饱和聚酯树脂合成新工艺精.docx

1、双环戊二烯改性不饱和聚酯树脂合成新工艺精科技信息不饱和聚酯树脂(简称UPR 是一种具有优良机械性能、电性能和耐化学腐蚀性能的热固性树脂。但其应用时易受空气中氧的阻聚作用,固化收缩率较高,应用受到很大限制。据研究报道,国内外学者采用双环戊二烯(简称DCPD 改性的不饱和聚酯树脂(简称UPR 具有较好的耐热性、气干性、耐化学腐蚀性、低收缩性、低苯乙烯挥发性。DCPD 改性UPR 作为UPR 的重要品种在美国、欧洲国家和日本已大量生产并使用。国内DCPD 主要来源于国内乙烯工业的副产品C 5馏分和煤焦油中,产能超过4万t/a ,大部分DCPD 作为燃料被烧掉,少部分主要用于生产UPR 。本研究采用“

2、工业级”双环戊二烯(含量75%80%为原料,二异氰酸酯(MDI 作为交联剂和支化剂,利用环保型有机酸为催化剂制备低粘度、低收缩性、耐化学腐蚀和无苯乙烯的环保型不饱和聚酯树脂。产品综合成本低,对于提高我国裂解C 5资源的化工利用和生产环保型高性能UPR 有重大的实际意义。1.实验部分1.1实验原理双环戊二烯(简称DCPD 分子结构中的共轭双键,化学性质非常活泼,在适当的反应温度下它可以与顺丁烯二酸以11的摩尔比发生加成反应,生成双环戊二烯顺丁烯二酸的单酯: 此生成物可以和二元醇(如乙二醇、1,2-丙二醇反应,生成DCPD 型UPR : 1.2实验试剂及仪器设备:双环戊二烯(DCPD:工业级,75

3、%85%,吉化集团公司;乙二醇(EG:分析纯,沈阳试剂一厂;1,2-丙二醇(PG :分析纯,天津市博迪化工有限公司;顺丁烯二酸酐(MA、邻苯二甲酸酐(PA :分析纯,天津市光复精细化工研究所;对苯二酚(HQ :分析纯,辽宁省医药经贸公司试剂厂;二异氰酸酯(MDI :分析纯,烟台万华股份公司;蒸馏水:实验室自制。加热、搅拌、温控系统:巩义市英峪予化仪器厂;电子分析天平:AL104,MettlerToledo 集团;循环水式多用真空泵:SHB-III 型,郑州长城科工贸有限公司;旋转粘度计:NDJ-1,上海群昶科学仪器有限公司;悬臂梁冲击试验机:AJU-22型,承德实验机厂;傅立叶变换红外光谱:A

4、VATAR-360,美国Nicolet 公司;核磁共振仪:300Hz ,瑞士Bruker 公司。1.3改性不饱和聚酯树脂合成:本研究采用水解加成法制备DCPD 改性不饱和聚酯树脂。按配比将顺丁烯二酸酐、邻苯二甲酸酐、DCPD 加入反应器中,通N 2、升温、搅拌,在100125下,在30min 内滴加水,水解马来酸酐。升温至125140下,加成反应2小时,生产双环戊二烯马来酸单酯。加入乙二醇、1,2-丙二醇、催化剂,升温至150170,酯化缩聚反应,当酸值达到3545mgKOH/g 时停止反应,再加入阻聚剂对苯二酚,反应30min 。降温至8090,加入MDI ,交联、支化反应1小时,制得深黄色

5、,粘稠状,DCPD 改性不饱和聚酯树脂。1.4树脂与浇注体的性能测试1.4.1浇注体配制树脂引发剂促进剂=10040.4。称取50g 树脂,加入2g 引发剂,充分搅拌后,滴加0.2g 促进剂,在35min 内搅拌脱泡倒入自制模具中,室温固化48h ,然后5060熟化3h 后待测。引发剂为过氧化苯甲酰(BPO 的邻苯二甲酸二丁酯糊(50w%,促进剂为N ,N-二甲基苯胺(DMA。1.4.2树脂和浇注体性能测试酸值按GB/T28951982测试;黏度按GB/T7193.11987测试,不饱和聚酯树脂80下反应活性测定按GB/T7193.41987测试;固含量按GB/T7193.41987;树脂浇注

6、体冲击试验按GB/T25711995测定。1.4.3红外(FT-IR 分析测定将DCPD 改性UPR 涂在KBr 片上,在红外光谱仪上测定,扫描范围4000400cm -1。1.4.4核磁共振(1H NMR 分析测定用核磁共振仪,以甲基硅烷为内标,以氘代三氯甲烷(CDCl 3为溶剂进行测定。2.实验结果与讨论2.1DCPD 加入方式及加原料配比对树脂性能的影响顺丁烯二酸酐水解和顺丁烯二酸与DCPD 的加成反应都是强放热反应,若把邻苯二甲酸酐、顺丁烯二酸酐、DCPD 和水按配比同时加入反应器中进行反应,当顺丁烯二酸酐水解反应发生时,温度迅速上升,必将引起顺丁烯二酸与DCPD 的加成反应,这样两个

7、放热反应同时进行,系统温度必将难以控制,造成部分DCPD 分解成环戊二烯(CPD 。所以采用,DCPD 与MA 一起加热熔融后滴加水;MA 和水加热到90100水解后滴加DCPD 。两种方法对比见表1。由表可见,种加料方式优于种,反应过程温度容易控制,不会有DCPD 分解的现象出现,选择种加料方式。另外,DCPD 用量对不饱和聚酯树脂摩尔质量的控制起决定作用,DCPD 的用量直接影响树脂的黏度,DCPD 的用量增加树脂的黏度明显下降,但DCPD 用量过大会严重影响树脂的韧性。经实验确定适宜的配比为,n (DCPD :n (顺丁烯二酸酐=(0.60.8:1。表1DCPD 加入方式对反应稳定性的影

8、响2.2酯化缩聚反应催化剂的选择表2不同催化剂对树脂性能的影响双环戊二烯改性不饱和聚酯树脂合成新工艺长春工业大学化学工程学院江海龙张龙摘要阐述了双环戊二烯在不饱和聚酯树脂生产中的重要意义,采用了水解法对“工业级”双环戊二烯合成不饱和聚酯树脂合成工艺进行了研究,确定了适宜合成工艺。MDI 的加入代替了苯乙烯,改善了产品性能,制得了一种新型环保树脂。关键词双环戊二烯二异氰酸酯不饱和聚酯树脂水解加成法作者简介:江海龙(1979-,男,长春工业大学化学工程学院工程硕士,白城师范学院教师,讲师。DCPD 加入方式反应现象体系色泽整个反应过程温度稳定,易于控制浅棕黄色开始稳定,滴入DCPD 后升温快,较难

9、控制深棕色Cata 类型用量w(cata%树脂外观放热峰温度抗冲强度(kJ m -2邵氏硬度(HAH 3PO 40.08浅棕黄色透明149 1.9194.8H 3PO 40.10浅黄色透明146 1.8895.0甲磺酸0.08浅棕黄色透明135 1.9494.9甲磺酸0.10浅棕黄色透明137 1.8996.7对甲磺酸0.08浅棕红色透明144 1.8591.3对甲磺酸0.10浅棕红色透明1401.8791.9(下转第508页高校理科研究科技信息力学性能抗冲击强度(kJ/m 2拉伸强度(MPa DCPD-UPR 3.758通用UPR3.660甲磺酸的酸性强,与磷酸和对甲苯磺酸相当,但无氧化性,

10、摩尔质量小,热稳定性高,能减少副反应的发生。分别采用以上三种酸做催化剂,在相同反应条件下进行对比不同酸性催化剂用量对树脂性能及颜色的影响,见表2。由表2可知,三种催化剂对产品的硬度、冲击强度影响不大,磷酸和甲磺酸作催化剂对产品的性能和色泽有益,但磷酸后处理较难,易残留在树脂中腐蚀设备,使用甲磺酸还有降低放热峰温度的效果。所以,催化剂选用甲磺酸。2.3DCPD 改性UPR 的红外(FT-IR 和核磁共振(1H NM R 图谱分析图1未固化DCPD 改性UPR 、已固化DCPD 改性UPR 的FT-IR 谱图图1a 、b 分别为DCPD 改性UPR 及其固化后的红外光谱。读图1b 可知,脂基伸缩振

11、动特征峰1720cm -1,不饱和聚酯分子链节上的两个端基-COOH 的特征峰1300cm -1和-OH 的特征峰1410cm -1明显减弱,图中存在共轭烯烃伸缩振动特征峰1645cm -1,说明双键仍然存在。图1a 中由于酯基不参与固化,所以1720cm -1和1728cm -1仍然存在,但由于C=C 双键基团参与固化交联反应而被消耗,因而1645cm -1,980cm -1,912cm -1,778cm -1峰在红外谱图上消失,表明C=C 已经被消耗完全,树脂已经完全固化。DCPD 五元环上的双键特征吸收峰1600cm -1仍然存在,降冰片环上的双键特征吸收峰1575cm -1已经消失,说

12、明双键已经参加了加成反应。2.4DCPD 型树脂的机械性能测试将树脂浇注到自制的样条槽中进行固化并经过熟化后处理,分别按照GB/T2571-1995制成尺寸为80104mm 的无缺口样条,在A-JU-22型悬臂梁冲击实验机测定材料的抗冲击性能;按照GB1447-83制成标准样条,在Shimadzu AGS-H 型电子拉力机上测试材料的拉伸性能,拉伸速率为25mm/min 。DCPD-UPR 与通用不饱和聚酯树脂浇注体的力学性能比较列于表3。由表中数据可知,该力学性能值基本满足大部分制件对树脂力学性能的要求。表3DCPD-UPR 及通用不饱和聚酯树脂浇注体的力学性能3.结论(1确定了适宜的合成工

13、艺:加成温度125140;酯化温度150170;n (DCPD :n (顺丁烯二酸酐=(0.60.8:1;催化剂为甲磺酸,用量为0.1%0.2%。(2产品经过红外分析表明,双环戊二烯加成完全,五元环上双键稳定并仍然保留,确实为不饱和聚酯树脂结构。(3M DI 的加入代替了苯乙烯,得到一种新型环保树脂,树脂机械性能符合要求,可以作为生产和加工材料。参考文献1焦扬声.双环戊二烯改性的不饱和聚酯树脂J .玻璃钢/复合材料,1988(22赵之山,林宗基.端基封闭法合成双环戊二烯改性不饱和聚酯J.石油化工,19953付丽华,贾德民.液化MDI 型聚氨酯/聚甲基丙烯酸甲酯/改性蒙脱土纳米复合材料的力学性能

14、与形态D .广西大学学报(自然科学版,2005(上接第506页when he couldn t see her,he suddenly felt lonely and hollow.This psycholog-ical change of Henry reveals the change of his feeling towards Catherine.However,their relationship did not really develop until Henry was wounded and taken to the hospital where he met Catherin

15、e again.“When I saw her I was in love with her.Everything turned over inside of me,”he said,“I was crazy about her.”“God knows I had not wanted to fall in love with her.But God knows I had.”(Hemingway,70This was the turning point of Henry s feeling to Catherine and the real beginning of their love.T

16、he priest once told Henry,“When you love you wish to do things for.You wish to sacrifice for.You wish to serve.”(Hemingway,57While Cather-ine s idea of love was more specific:“I ll say just what you wish and I ll dowhat you wish.”“I want what you want.There isn t any me any more.Just what you want.”

17、“I m you.Don t make up a separate me.”(Hemingway,79This was her definition of love,that is,the combination of body and soul.It was her unselfish love that helped Henry recover quickly from the nightmare of the war and changed the former aimless and restless youth into a man com-mitted to love.Back t

18、o the front,the desperation of his friends and the defeats in the battlefields deepened Henry s weariness to the war.He though about Cather-ine all the time,even saw her in his dreams.He preyed,“That my sweet love Catherine down might rain.Blow her against to me.”(Hemingway,142His love for Catherine

19、 was so strong that he chose to jump into the icy river,before being executed and escaped.Henry could desert the war,but he would never desert his love.Compared with the passion of love,the war was pale and frag-ile.Floating down the river with a piece of wood,Henry abandoned everything except Cathe

20、rine and let the river take him to a new life.“Anger was washed away in the river along with any obligation.”The rest for him to do was to “Eat and drink and sleep with Catherine.”(Hemingway,167-168Nothing could separate them from now on.Henry returned to Catherine and found comfort,order and courag

21、e again.After staying in Stresa for several days,the couple fled to Switzerland,and begun their seclusive life.There was no war,no pain any more,only peace and love.That fall they lived in a brown wooden house on the side of a mountain with the kind M r.and M rs.Guttingen living down-stairs.They wal

22、ked down the mountain path in M ontreus,appreciated the beautiful scenery and played chess,enjoying each other s company.They be-came one flesh.“I don t live at all when I m not with you,”said Catherine.Henry replied,“I m no good when you re not there.I haven t any life at all anymore.”(Hemingway,21

23、3Court Greffi once told Henry that love was a “religious feeling.”(Hemingway,188Now they became the faith and support for each other.Catherine s haircut and Henry s new beard along with their life there signify a world they have longed for,devoid of war and filled with tranquil time.When the expecte

24、d date of childbirth approached,Henry andCatherine moved to a hotel in Lausanne,near the hospital.“We know the baby was very close now and it gave us both a feeling as though something were hurrying us and we could not lose any time together.”(Hemingway,220This seems to be a prophecy for the tragic

25、ending.Catherine delivered a dead baby and she died from hemorrhages.Love can be an antidote for the painful feelings of war,but it can not change the basic unforgiving hardness of the world.In an indifferent and un-caring universe,love between Henry and Catherine,though beautiful,is doomed to failu

26、re.Actually,the title of the novel is a pun.“Arms ”may refer to the weapons as well as the arms of a lover.Henry not only made his farewell to the war,but also to his love.A Farewell to Arms is a tragic love story.It develops with the themes of war and love,describing the fate and development of dif

27、ferent characters.The war is cruel,absurd and it is indifferent to man s plight.While the beautiful love brings people hope and helps them forget the painful experiences.References 1Hemingway,Ernest.A Farewell to Arms.Beijing:Foreign Lan-guage Teaching and R esearch Press,19922Donaldson,Scott.By Force of Will:The Life and Art of Ernest Hemingway.NewYork:Viking Penguin,19773王臻.战争与爱情的悲剧美学海明威永别了,武器解读J.湖南科技学院学报,2008,(014米田.通过永别了,武器看海明威的爱情观和反战立场J .作家,2009,(06人文社科