雙環(huán)戊二烯改性不飽和聚酯樹脂合成新工藝

1、科技信息不飽和聚酯樹脂(簡稱UPR 是一種具有優(yōu)良機(jī)械性能、電性能和耐化學(xué)腐蝕性能的熱固性樹脂。但其應(yīng)用時易受空氣中氧的阻聚作用,固化收縮率較高,應(yīng)用受到很大限制。據(jù)研究報(bào)道,國內(nèi)外學(xué)者采用雙環(huán)戊二烯(簡稱DCPD 改性的不飽和聚酯樹脂(簡稱UPR 具有較好的耐熱性、氣干性、耐化學(xué)腐蝕性、低收縮性、低苯乙烯揮發(fā)性。DCPD 改性UPR 作為UPR 的重要品種在美國、歐洲國家和日本已大量生產(chǎn)并使用。國內(nèi)DCPD 主要來源于國內(nèi)乙烯工業(yè)的副產(chǎn)品C 5餾分和煤焦油中,產(chǎn)能超過4萬t/a ,大部分DCPD 作為燃料被燒掉,少部分主要用于生產(chǎn)UPR 。本研究采用“工業(yè)級”雙環(huán)戊二烯(含量75%80%為原

2、料,二異氰酸酯(MDI 作為交聯(lián)劑和支化劑,利用環(huán)保型有機(jī)酸為催化劑制備低粘度、低收縮性、耐化學(xué)腐蝕和無苯乙烯的環(huán)保型不飽和聚酯樹脂。產(chǎn)品綜合成本低,對于提高我國裂解C 5資源的化工利用和生產(chǎn)環(huán)保型高性能UPR 有重大的實(shí)際意義。1.實(shí)驗(yàn)部分1.1實(shí)驗(yàn)原理雙環(huán)戊二烯(簡稱DCPD 分子結(jié)構(gòu)中的共軛雙鍵,化學(xué)性質(zhì)非?；顫?在適當(dāng)?shù)姆磻?yīng)溫度下它可以與順丁烯二酸以11的摩爾比發(fā)生加成反應(yīng),生成雙環(huán)戊二烯順丁烯二酸的單酯: 此生成物可以和二元醇(如乙二醇、1,2-丙二醇反應(yīng),生成DCPD 型UPR : 1.2實(shí)驗(yàn)試劑及儀器設(shè)備:雙環(huán)戊二烯(DCPD:工業(yè)級,75%85%,吉化集團(tuán)公司;乙二醇(EG:分

3、析純,沈陽試劑一廠;1,2-丙二醇(PG :分析純,天津市博迪化工有限公司;順丁烯二酸酐(MA、鄰苯二甲酸酐(PA :分析純,天津市光復(fù)精細(xì)化工研究所;對苯二酚(HQ :分析純,遼寧省醫(yī)藥經(jīng)貿(mào)公司試劑廠;二異氰酸酯(MDI :分析純,煙臺萬華股份公司;蒸餾水:實(shí)驗(yàn)室自制。加熱、攪拌、溫控系統(tǒng):鞏義市英峪予化儀器廠;電子分析天平:AL104,MettlerToledo 集團(tuán);循環(huán)水式多用真空泵:SHB-III 型,鄭州長城科工貿(mào)有限公司;旋轉(zhuǎn)粘度計(jì):NDJ-1,上海群昶科學(xué)儀器有限公司;懸臂梁沖擊試驗(yàn)機(jī):AJU-22型,承德實(shí)驗(yàn)機(jī)廠;傅立葉變換紅外光譜:AVATAR-360,美國Nicolet

4、公司;核磁共振儀:300Hz ,瑞士Bruker 公司。1.3改性不飽和聚酯樹脂合成:本研究采用水解加成法制備DCPD 改性不飽和聚酯樹脂。按配比將順丁烯二酸酐、鄰苯二甲酸酐、DCPD 加入反應(yīng)器中,通N 2、升溫、攪拌,在100125下,在30min 內(nèi)滴加水,水解馬來酸酐。升溫至125140下,加成反應(yīng)2小時,生產(chǎn)雙環(huán)戊二烯馬來酸單酯。加入乙二醇、1,2-丙二醇、催化劑,升溫至150170,酯化縮聚反應(yīng),當(dāng)酸值達(dá)到3545mgKOH/g 時停止反應(yīng),再加入阻聚劑對苯二酚,反應(yīng)30min 。降溫至8090,加入MDI ,交聯(lián)、支化反應(yīng)1小時,制得深黃色,粘稠狀,DCPD 改性不飽和聚酯樹脂。

5、1.4樹脂與澆注體的性能測試1.4.1澆注體配制樹脂引發(fā)劑促進(jìn)劑=10040.4。稱取50g 樹脂,加入2g 引發(fā)劑,充分?jǐn)嚢韬?滴加0.2g 促進(jìn)劑,在35min 內(nèi)攪拌脫泡倒入自制模具中,室溫固化48h ,然后5060熟化3h 后待測。引發(fā)劑為過氧化苯甲酰(BPO 的鄰苯二甲酸二丁酯糊(50w%,促進(jìn)劑為N ,N-二甲基苯胺(DMA。1.4.2樹脂和澆注體性能測試酸值按GB/T28951982測試;黏度按GB/T7193.11987測試,不飽和聚酯樹脂80下反應(yīng)活性測定按GB/T7193.41987測試;固含量按GB/T7193.41987;樹脂澆注體沖擊試驗(yàn)按GB/T25711995測定

6、。1.4.3紅外(FT-IR 分析測定將DCPD 改性UPR 涂在KBr 片上,在紅外光譜儀上測定,掃描范圍4000400cm -1。1.4.4核磁共振(1H NMR 分析測定用核磁共振儀,以甲基硅烷為內(nèi)標(biāo),以氘代三氯甲烷(CDCl 3為溶劑進(jìn)行測定。2.實(shí)驗(yàn)結(jié)果與討論2.1DCPD 加入方式及加原料配比對樹脂性能的影響順丁烯二酸酐水解和順丁烯二酸與DCPD 的加成反應(yīng)都是強(qiáng)放熱反應(yīng),若把鄰苯二甲酸酐、順丁烯二酸酐、DCPD 和水按配比同時加入反應(yīng)器中進(jìn)行反應(yīng),當(dāng)順丁烯二酸酐水解反應(yīng)發(fā)生時,溫度迅速上升,必將引起順丁烯二酸與DCPD 的加成反應(yīng),這樣兩個放熱反應(yīng)同時進(jìn)行,系統(tǒng)溫度必將難以控制,

7、造成部分DCPD 分解成環(huán)戊二烯(CPD 。所以采用,DCPD 與MA 一起加熱熔融后滴加水;MA 和水加熱到90100水解后滴加DCPD 。兩種方法對比見表1。由表可見,種加料方式優(yōu)于種,反應(yīng)過程溫度容易控制,不會有DCPD 分解的現(xiàn)象出現(xiàn),選擇種加料方式。另外,DCPD 用量對不飽和聚酯樹脂摩爾質(zhì)量的控制起決定作用,DCPD 的用量直接影響樹脂的黏度,DCPD 的用量增加樹脂的黏度明顯下降,但DCPD 用量過大會嚴(yán)重影響樹脂的韌性。經(jīng)實(shí)驗(yàn)確定適宜的配比為,n (DCPD :n (順丁烯二酸酐=(0.60.8:1。表1DCPD 加入方式對反應(yīng)穩(wěn)定性的影響2.2酯化縮聚反應(yīng)催化劑的選擇表2不同

8、催化劑對樹脂性能的影響雙環(huán)戊二烯改性不飽和聚酯樹脂合成新工藝長春工業(yè)大學(xué)化學(xué)工程學(xué)院江海龍張龍摘要闡述了雙環(huán)戊二烯在不飽和聚酯樹脂生產(chǎn)中的重要意義,采用了水解法對“工業(yè)級”雙環(huán)戊二烯合成不飽和聚酯樹脂合成工藝進(jìn)行了研究,確定了適宜合成工藝。MDI 的加入代替了苯乙烯,改善了產(chǎn)品性能,制得了一種新型環(huán)保樹脂。關(guān)鍵詞雙環(huán)戊二烯二異氰酸酯不飽和聚酯樹脂水解加成法作者簡介:江海龍(1979-,男,長春工業(yè)大學(xué)化學(xué)工程學(xué)院工程碩士,白城師范學(xué)院教師,講師。DCPD 加入方式反應(yīng)現(xiàn)象體系色澤整個反應(yīng)過程溫度穩(wěn)定,易于控制淺棕黃色開始穩(wěn)定,滴入DCPD 后升溫快,較難控制深棕色Cata 類型用量w(cata

9、%樹脂外觀放熱峰溫度抗沖強(qiáng)度(kJ ·m -2邵氏硬度(HAH 3PO 40.08淺棕黃色透明149 1.9194.8H 3PO 40.10淺黃色透明146 1.8895.0甲磺酸0.08淺棕黃色透明135 1.9494.9甲磺酸0.10淺棕黃色透明137 1.8996.7對甲磺酸0.08淺棕紅色透明144 1.8591.3對甲磺酸0.10淺棕紅色透明1401.8791.9(下轉(zhuǎn)第508頁高校理科研究科技信息力學(xué)性能抗沖擊強(qiáng)度(kJ/m 2拉伸強(qiáng)度(MPa DCPD-UPR 3.758通用UPR3.660甲磺酸的酸性強(qiáng),與磷酸和對甲苯磺酸相當(dāng),但無氧化性,摩爾質(zhì)量小,熱穩(wěn)定性高,能減

10、少副反應(yīng)的發(fā)生。分別采用以上三種酸做催化劑,在相同反應(yīng)條件下進(jìn)行對比不同酸性催化劑用量對樹脂性能及顏色的影響,見表2。由表2可知,三種催化劑對產(chǎn)品的硬度、沖擊強(qiáng)度影響不大,磷酸和甲磺酸作催化劑對產(chǎn)品的性能和色澤有益,但磷酸后處理較難,易殘留在樹脂中腐蝕設(shè)備,使用甲磺酸還有降低放熱峰溫度的效果。所以,催化劑選用甲磺酸。2.3DCPD 改性UPR 的紅外(FT-IR 和核磁共振(1H NM R 圖譜分析圖1未固化DCPD 改性UPR 、已固化DCPD 改性UPR 的FT-IR 譜圖圖1a 、b 分別為DCPD 改性UPR 及其固化后的紅外光譜。讀圖1b 可知,脂基伸縮振動特征峰1720cm -1,

11、不飽和聚酯分子鏈節(jié)上的兩個端基-COOH 的特征峰1300cm -1和-OH 的特征峰1410cm -1明顯減弱,圖中存在共軛烯烴伸縮振動特征峰1645cm -1,說明雙鍵仍然存在。圖1a 中由于酯基不參與固化,所以1720cm -1和1728cm -1仍然存在,但由于C=C 雙鍵基團(tuán)參與固化交聯(lián)反應(yīng)而被消耗,因而1645cm -1,980cm -1,912cm -1,778cm -1峰在紅外譜圖上消失,表明C=C 已經(jīng)被消耗完全,樹脂已經(jīng)完全固化。DCPD 五元環(huán)上的雙鍵特征吸收峰1600cm -1仍然存在,降冰片環(huán)上的雙鍵特征吸收峰1575cm -1已經(jīng)消失,說明雙鍵已經(jīng)參加了加成反應(yīng)。2

12、.4DCPD 型樹脂的機(jī)械性能測試將樹脂澆注到自制的樣條槽中進(jìn)行固化并經(jīng)過熟化后處理,分別按照GB/T2571-1995制成尺寸為80×10×4mm 的無缺口樣條,在A-JU-22型懸臂梁沖擊實(shí)驗(yàn)機(jī)測定材料的抗沖擊性能;按照GB1447-83制成標(biāo)準(zhǔn)樣條,在Shimadzu AGS-H 型電子拉力機(jī)上測試材料的拉伸性能,拉伸速率為25mm/min 。DCPD-UPR 與通用不飽和聚酯樹脂澆注體的力學(xué)性能比較列于表3。由表中數(shù)據(jù)可知,該力學(xué)性能值基本滿足大部分制件對樹脂力學(xué)性能的要求。表3DCPD-UPR 及通用不飽和聚酯樹脂澆注體的力學(xué)性能3.結(jié)論(1確定了適宜的合成工藝:

13、加成溫度125140;酯化溫度150170;n (DCPD :n (順丁烯二酸酐=(0.60.8:1;催化劑為甲磺酸,用量為0.1%0.2%。(2產(chǎn)品經(jīng)過紅外分析表明,雙環(huán)戊二烯加成完全,五元環(huán)上雙鍵穩(wěn)定并仍然保留,確實(shí)為不飽和聚酯樹脂結(jié)構(gòu)。(3M DI 的加入代替了苯乙烯,得到一種新型環(huán)保樹脂,樹脂機(jī)械性能符合要求,可以作為生產(chǎn)和加工材料。參考文獻(xiàn)1焦揚(yáng)聲.雙環(huán)戊二烯改性的不飽和聚酯樹脂J .玻璃鋼/復(fù)合材料,1988(22趙之山,林宗基.端基封閉法合成雙環(huán)戊二烯改性不飽和聚酯J.石油化工,19953付麗華,賈德民.液化MDI 型聚氨酯/聚甲基丙烯酸甲酯/改性蒙脫土納米復(fù)合材料的力學(xué)性能與形

14、態(tài)D .廣西大學(xué)學(xué)報(bào)(自然科學(xué)版,2005(上接第506頁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 Catherine

15、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.The

16、 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.”“I

17、 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 to

18、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 w

19、as 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 Catheri

20、ne 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 courage

21、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 walke

22、d 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,213C

23、ourt 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 expected

24、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 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