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如何正確提高丙烯酸與硅PU面層韌性的指數

2013-10-23 14:00:07  來源:  字號:【69免費視頻:  69免費視頻:  69免費視頻:】  瀏覽:197

以上(shang)四個(ge)聚(ju)(ju)(ju)(ju)(ju)酯(zhi)(zhi)(zhi)(zhi)樣的(de)(de)(de)(de)顏色、粘度(du)、固含(han)(han)、酸(suan)(suan)(suan)值都(dou)能(neng)(neng)作到同一(yi)規范范圍內(nei)。用聚(ju)(ju)(ju)(ju)(ju)酯(zhi)(zhi)(zhi)(zhi)1和(he)(he)聚(ju)(ju)(ju)(ju)(ju)酯(zhi)(zhi)(zhi)(zhi)2改(gai)(gai)(gai)性(xing)(xing)(xing)的(de)(de)(de)(de)丙(bing)(bing)(bing)烯酸(suan)(suan)(suan)樹(shu)(shu)脂(zhi)(zhi)(zhi)與 TDI加(jia)成(cheng)物和(he)(he)醇(chun)(chun)酸(suan)(suan)(suan)樹(shu)(shu)脂(zhi)(zhi)(zhi)的(de)(de)(de)(de)混(hun)溶(rong)性(xing)(xing)(xing)較(jiao)差,而用聚(ju)(ju)(ju)(ju)(ju)酯(zhi)(zhi)(zhi)(zhi)3和(he)(he)聚(ju)(ju)(ju)(ju)(ju)酯(zhi)(zhi)(zhi)(zhi)4改(gai)(gai)(gai)性(xing)(xing)(xing)的(de)(de)(de)(de)丙(bing)(bing)(bing)烯酸(suan)(suan)(suan)樹(shu)(shu)脂(zhi)(zhi)(zhi)與TDI加(jia)成(cheng)物和(he)(he)醇(chun)(chun)酸(suan)(suan)(suan)樹(shu)(shu)脂(zhi)(zhi)(zhi)的(de)(de)(de)(de)混(hun)溶(rong)性(xing)(xing)(xing)確較(jiao)好,從聚(ju)(ju)(ju)(ju)(ju)酯(zhi)(zhi)(zhi)(zhi)樹(shu)(shu)脂(zhi)(zhi)(zhi)的(de)(de)(de)(de)配方分(fen)析,聚(ju)(ju)(ju)(ju)(ju)酯(zhi)(zhi)(zhi)(zhi)1和(he)(he)聚(ju)(ju)(ju)(ju)(ju)酯(zhi)(zhi)(zhi)(zhi) 2分(fen)子(zi)結(jie)構上(shang)的(de)(de)(de)(de)可供(gong)引發共聚(ju)(ju)(ju)(ju)(ju)的(de)(de)(de)(de)雙(shuang)(shuang)鍵不足(zu),導致聚(ju)(ju)(ju)(ju)(ju)酯(zhi)(zhi)(zhi)(zhi)樹(shu)(shu)脂(zhi)(zhi)(zhi)與丙(bing)(bing)(bing)烯酸(suan)(suan)(suan)樹(shu)(shu)脂(zhi)(zhi)(zhi)發生(sheng)共聚(ju)(ju)(ju)(ju)(ju)的(de)(de)(de)(de)幾率少,此(ci)樹(shu)(shu)脂(zhi)(zhi)(zhi)仍由聚(ju)(ju)(ju)(ju)(ju)酯(zhi)(zhi)(zhi)(zhi)樹(shu)(shu)脂(zhi)(zhi)(zhi)與較(jiao)多(duo)未改(gai)(gai)(gai)性(xing)(xing)(xing)的(de)(de)(de)(de)丙(bing)(bing)(bing)烯酸(suan)(suan)(suan)樹(shu)(shu)脂(zhi)(zhi)(zhi)組成(cheng),所以,與TDI加(jia)成(cheng)物和(he)(he)醇(chun)(chun)酸(suan)(suan)(suan)樹(shu)(shu)脂(zhi)(zhi)(zhi)的(de)(de)(de)(de)混(hun)溶(rong)性(xing)(xing)(xing)仍較(jiao)差。聚(ju)(ju)(ju)(ju)(ju)酯(zhi)(zhi)(zhi)(zhi)3和(he)(he)聚(ju)(ju)(ju)(ju)(ju)酯(zhi)(zhi)(zhi)(zhi)4分(fen)子(zi)結(jie)構上(shang)可供(gong)引發共聚(ju)(ju)(ju)(ju)(ju)的(de)(de)(de)(de)雙(shuang)(shuang)鍵較(jiao)聚(ju)(ju)(ju)(ju)(ju)酯(zhi)(zhi)(zhi)(zhi)1和(he)(he)聚(ju)(ju)(ju)(ju)(ju)酯(zhi)(zhi)(zhi)(zhi)2明(ming)(ming)顯要多(duo),聚(ju)(ju)(ju)(ju)(ju)酯(zhi)(zhi)(zhi)(zhi)樹(shu)(shu)脂(zhi)(zhi)(zhi)與丙(bing)(bing)(bing)烯酸(suan)(suan)(suan)樹(shu)(shu)脂(zhi)(zhi)(zhi)發生(sheng)共聚(ju)(ju)(ju)(ju)(ju)改(gai)(gai)(gai)性(xing)(xing)(xing)的(de)(de)(de)(de)幾率大,改(gai)(gai)(gai)性(xing)(xing)(xing)后的(de)(de)(de)(de)丙(bing)(bing)(bing)烯酸(suan)(suan)(suan)樹(shu)(shu)脂(zhi)(zhi)(zhi)與TDI加(jia)成(cheng)物和(he)(he)醇(chun)(chun)酸(suan)(suan)(suan)樹(shu)(shu)脂(zhi)(zhi)(zhi)的(de)(de)(de)(de)混(hun)溶(rong)性(xing)(xing)(xing)較(jiao)佳,丙(bing)(bing)(bing)烯酸(suan)(suan)(suan)樹(shu)(shu)脂(zhi)(zhi)(zhi)的(de)(de)(de)(de)應用范圍明(ming)(ming)顯變(bian)得更加(jia)廣闊。但相同配方、相同工藝、相同的(de)(de)(de)(de)轉(zhuan)化率時,聚(ju)(ju)(ju)(ju)(ju)酯(zhi)(zhi)(zhi)(zhi)4改(gai)(gai)(gai)性(xing)(xing)(xing)的(de)(de)(de)(de)丙(bing)(bing)(bing)烯酸(suan)(suan)(suan)樹(shu)(shu)脂(zhi)(zhi)(zhi)粘度(du)明(ming)(ming)顯高(gao)于前三個(ge)試(shi)樣,說(shuo)明(ming)(ming)聚(ju)(ju)(ju)(ju)(ju)酯(zhi)(zhi)(zhi)(zhi)4分(fen)子(zi)結(jie)構上(shang)雙(shuang)(shuang)鍵已開始過(guo)量,不適于作高(gao)固含(han)(han)低粘度(du)丙(bing)(bing)(bing)烯酸(suan)(suan)(suan)樹(shu)(shu)脂(zhi)(zhi)(zhi),聚(ju)(ju)(ju)(ju)(ju)酯(zhi)(zhi)(zhi)(zhi)3比較(jiao)理想的(de)(de)(de)(de)改(gai)(gai)(gai)性(xing)(xing)(xing)聚(ju)(ju)(ju)(ju)(ju)酯(zhi)(zhi)(zhi)(zhi)配方,最終 選擇了聚(ju)(ju)(ju)(ju)(ju)酯(zhi)(zhi)(zhi)(zhi)3作為丙(bing)(bing)(bing)烯酸(suan)(suan)(suan)樹(shu)(shu)脂(zhi)(zhi)(zhi)的(de)(de)(de)(de)共聚(ju)(ju)(ju)(ju)(ju)半成(cheng)品,達到比較(jiao)理想的(de)(de)(de)(de)綜合性(xing)(xing)(xing)能(neng)(neng)。 

應(ying)(ying)用(yong)領域廣范,丙烯酸(suan)(suan)樹(shu)脂(zhi)(zhi)綜(zong)合(he)性(xing)(xing)能優異(yi)。但中高羥值的丙烯酸(suan)(suan)樹(shu)脂(zhi)(zhi)由于(yu)極性(xing)(xing)大,跟醚(mi)化(hua)度高的氨基(ji)(ji)樹(shu)脂(zhi)(zhi)、醇(chun)酸(suan)(suan)樹(shu)脂(zhi)(zhi)、TDI加(jia)成物(wu)固化(hua)劑混(hun)溶性(xing)(xing)較差,使丙烯酸(suan)(suan)樹(shu)脂(zhi)(zhi)的通用(yong)性(xing)(xing)受到(dao)明(ming)顯的限(xian)制。本(ben)文通過(guo)聚酯與丙烯酸(suan)(suan)樹(shu)脂(zhi)(zhi)的共聚反應(ying)(ying),有(you)效的解決羥基(ji)(ji)丙烯酸(suan)(suan)樹(shu)脂(zhi)(zhi)與高、中、低醚(mi)化(hua)度氨基(ji)(ji)樹(shu)脂(zhi)(zhi)、醇(chun)酸(suan)(suan)樹(shu)脂(zhi)(zhi)、TDI加(jia)成物(wu)固化(hua)劑的混(hun)溶性(xing)(xing)問題(ti),拓(tuo)寬(kuan)了丙烯酸(suan)(suan)樹(shu)脂(zhi)(zhi)的應(ying)(ying)用(yong)范圍。

關鍵詞(ci):丙烯(xi)酸樹脂;高、中、低醚化(hua)度的氨基(ji)樹脂;醇酸樹脂;聚酯;TDI加成物固化(hua)劑(ji);混溶性(xing)。

硬(ying)度、柔韌性(xing)、光澤(ze)等(deng)指標亦可調節,   溶劑型丙(bing)烯酸樹(shu)脂(zhi)由于Tg值、羥值、酸值都可以調整。這給樹(shu)脂(zhi)的(de)(de)(de)應用(yong)提供了較大(da)的(de)(de)(de)方便,拓(tuo)寬了該(gai)樹(shu)脂(zhi)的(de)(de)(de)應用(yong)領域(yu),滿足 人們多(duo)種多(duo)樣和不斷提高的(de)(de)(de)需求(qiu),所以,丙(bing)烯酸樹(shu)脂(zhi)在(zai)國內還不過三十年的(de)(de)(de)歷史,油漆應用(yong)領域(yu)卻(que)發展到僅(jin)次于醇酸樹(shu)脂(zhi)第二(er)大(da)用(yong)量樹(shu)脂(zhi)體系,近年來國際原油 價格(ge)不時上漲,但對丙(bing)烯酸樹(shu)脂(zhi)的(de)(de)(de)發展和應用(yong)都未造(zao)成明顯的(de)(de)(de)沖擊,目前(qian),該(gai)樹(shu)脂(zhi)還無(wu)替代品(pin),丙(bing)烯酸樹(shu)脂(zhi)仍然是國內樹(shu)脂(zhi)領域(yu)研發的(de)(de)(de)重(zhong)點。    

   1 實驗局(ju)部     

   1.1原(yuan)材(cai)料和(he)助劑(ji)   

KoH標液、酸堿指示劑。       新戊二醇:工業級、三羥甲基丙烷:工業級、己二酸:工業級、間苯二甲酸:工業級、鄰苯二甲酸酐:工業級、1010抗氧劑(汽巴)順丁烯二酸酐:工業級、二甲苯:工業級、丁醇:工業級、丙烯酸丁酯:工業級、甲基丙烯酸甲酯:工業級、苯乙烯:工業級、甲基丙烯酸:工業級、丙烯酸羥乙酯:工業級、醋酸丁酯:工業級、過氧化苯甲酸叔丁酯:工業級、氮氣(N2.

   1.2 主要儀器(qi)和設備 YH電(dian)加熱(re)器(qi)、JJ-1増力(li)(li)電(dian)動攪(jiao)拌器(qi)、電(dian)子臺稱(0-2000gGZX-9070MBE數顯(xian)鼓(gu)風干(gan)燥箱、SYD-6536石油(you)產品蒸餾實驗(yan)器(qi)、電(dian)子天(tian)平(ping)(0.0001NDJ-4旋轉(zhuan)式粘度計、重力(li)(li)式噴槍、Wgg60-E4光澤計、漆膜劃格器(qi)。

   1.3實(shi)驗方法(fa)

   1.3.1 聚酯的合成     

10-13份三羥甲基丙烷,5-7份己二酸,12-16份間苯二甲酸,10-14份鄰苯二甲酸酐,2-3份二甲苯,0.1-0.3份1010抗氧劑投人反應釜中,通N2升 溫(wen)至(zhi)(zhi)(zhi)(zhi)150℃,保溫(wen)1小時后,以(yi)每小時升溫(wen)20℃速度升溫(wen)至(zhi)(zhi)(zhi)(zhi)220℃,保溫(wen)酯化反應酸值至(zhi)(zhi)(zhi)(zhi)10-12mgKoH/g后,降溫(wen)至(zhi)(zhi)(zhi)(zhi)145℃左(zuo)右,加(jia) 0.4-1.2份順丁烯二酸酐,145℃左(zuo)右保溫(wen)1小時,然后以(yi)每小時升溫(wen)20℃的速度升溫(wen)至(zhi)(zhi)(zhi)(zhi)180℃,保溫(wen)酯化反應至(zhi)(zhi)(zhi)(zhi)酸值于 14-16mgKoH/g,   將(jiang)18-20份新戊二醇。降溫(wen)至(zhi)(zhi)(zhi)(zhi)120℃左(zuo)右,加(jia)40份左(zuo)右二甲(jia)苯(ben)混合(he)溶劑兌稀,過濾,備用。    

   1.3.2 聚酯改性(xing)羥基丙烯(xi)酸(suan)樹脂(zhi)的(de)合成(cheng)     

10-15份丁醇,20-30份不(bu)飽和聚酯(zhi)(zhi)(zhi)投入(ru)反應釜中,升(sheng)溫(wen)回流20min將(jiang)10-14份苯乙(yi)烯(xi)(xi),13-15份丙烯(xi)(xi)酸(suan)乙(yi) 酯(zhi)(zhi)(zhi),5-8份甲(jia)(jia)基丙烯(xi)(xi)酸(suan)甲(jia)(jia)酯(zhi)(zhi)(zhi),6-10份丙烯(xi)(xi)酸(suan)羥(qian)丙酯(zhi)(zhi)(zhi),0.4-0.8份丙烯(xi)(xi)酸(suan),0.3-0.5份叔戊酯(zhi)(zhi)(zhi),0.3-0.5份過氧化苯甲(jia)(jia)酸(suan)叔丁酯(zhi)(zhi)(zhi)投入(ru)高位槽 攪拌15min,   將(jiang)10-15份二(er)甲(jia)(jia)苯。通(tong)N2,勻速(su)滴加(jia)用(yong)3小時,滴加(jia)完畢后用(yong)2份左右的二(er)甲(jia)(jia)苯沖洗高位槽,然(ran)后在120-130℃保溫(wen)反應5小時,降溫(wen)至(zhi)80℃,停(ting)N2,調 整粘度,粘度合格后,過濾,包(bao)裝。

 

 

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