低游離度TDI三聚體的合成
低游離度TDI三聚體的合成
jiabeneryiqingsuanzhi(tdi)zaicuihuazuoyongxiakeyifashengsanjufanying,xingchenghanyiqingniaosuanzhihuandesanjuti。tdisanjutijuyouhuifaxingdi、duxingxiao、guannengdugao、rewendingxinghao、naifushixinghaodengyoudian,changzuoweijuanzhiguhuajibeiguangfanyingyongzaituliao、zhanhejizhong。zai20shiji70niandai,guowaiduojiagongsikaishigongyehuashengchanyingyongzheleichanpin,rubayer、basf、dowdeng。muqiangaoxingneng、diyoulidantidetdisanjutirengranxuyaodaliangyilaijinkou。
benyanjiuyicuihuaji nt cat p100hecheng tdi sanjutijuanzhiguhuaji,shiyanjieguobiaoming: gaicuihuajijuyoucuihuasulvkuai、huoxinggao、fanyingwendudidengyoudian。zai40 ℃xia,yidijiafangshicuihuafanying,8 h jiukeyidadaofanyingzhongdian,dedaodiyoulidantihanliang tdi sanjuti。
原料及試劑
jiabeneryiqingsuandantitdi(80/20):gongyepin,basf;cusuandingzhi:fenxichun,guangzhoufanyuliqianghuagongchang;nt cat dmp-30:gongyepin,xindianhuaxue;nt cat k-15:gongyepin,xindianhuaxue;nt cat p100: xindianhuaxue;
合成工藝
zaidanqibaohudetiaojianxia,wangzhuangyoujiaoban、wendujiyijihuiliulengningguandeganzaosikouyuandishaopingzhongjiaru tdi( 80/20) danti 100 g,cusuandingzhi100 g。jiaoban5 ~10 min,jiareshengwenzhi40 ℃,dijia0. 5 gcuihuajidecusuandingzhirongye( cusuandingzhi10 ml) 。dijiawanbihou,kongzhiwenduzai40 ~80 ℃zhijian,baowenfanyingyue8 h,meige1 hcedingyicifanyingrongyede—ncozhi,dang—ncohanliangjiangdidao8.5% ~ 9% shi,jiaru1 gbenjiaxianlv,jixufanying0.5 h,tingzhijiarejiaoban,jiangwenchuliao,dedaoqianhuangsetoumingyeti。
zaishangshugongyijichushang,dijiayushedingliangdechun,baowenfanying30 ~60 min,dui tdi sanjutijinxinggaixingchuli。
催化劑種類、用量及滴加方式的影響
cuihuajidexuanzeshitdisanjufanyingdeguanjian。changyongdetdisanjucuihuajibaokuoshuan、youjijinshuhuahewu、youjilinhuahewu、jianjinshusuosuanyandeng。xuanyongdmp-30、k-15hep100dui50%cusuandingzhidetdirongyefenbiecuihuafanying,jieguorubiao1hetu2suoshi。
表1 不同催化劑(0.5%添加量)對TDI三聚反應的影響
催化劑種類 | 無 | K-15 | DMP-30 | P100 |
反應溫度/℃ | 70 | 80 | 70 | 70 |
反應時間/h | 24 | 26 | 6 | 5 |
w(—NCO)/% | 24.2 | 12.3 | 10.4 | 6.8 |
產品外觀 | 無色透明 | 黃色透明 | 微黃透明 | 近水白透明 |
youbiao1hetu2kejian,bujiacuihuajideqingkuangxia,tdidesanjufanyingbufasheng;k-15cuihuasanjudexiaoguojiaocha,wendujiaogao、fanyingshijianchang,rongyichanshenggengduodeduojutijiegou;junweishuanleicuihuajidedmp-30hep100cuihuaxiaoguojiaohao,xiangbizhixiap100decuihuaxingnenggengqiang,duanshijianneijiunengxunsufanying,jiangdi—ncozhi,erqieshiyanhuanbiaomingzai40 ℃xiaqirengranjuyouhengaodecuihuahuoxing。yinci,xuanyongp100zuoweicuihuaji。tu3ship100cuihuajiyongliangfenbiezhantdidantizongzhiliangde2%、0.5%ji0.8%shiduitdisanjufanyingdeyingxiang。
圖2 3 種催化劑的催化效率對比

diyoulidutdisanjutidehecheng
congtu3kandao,zaiqitatiaojianxiangtongdeqingkuangxia,suizhup100yongliangdezengjia,fanyingsulvjiakuai,tongshi—ncojituanhanliangyousuojianshao。cuihuajiyongliangtaishaoshi,jishiyanchangfanyingshijian,—ncohanliangrenggaoyu12%;ercuihuajiyongliangguogaoshi,daliangcanliudecuihuajizaiyidingchengdushangyingxianglechanpindexingneng。shiyanbiaoming,p100yongliangwei0.5%jiaoheshi。
圖3 催化劑用量對TDI三聚反應的影響

diyoulidutdisanjutidehecheng
lingwai,cuihuajidedijiafangshiyehuiyingxiangsanjufanying。shiyanbiaoming,ruoyicixingjiarucuihuaji,dantimashangjuliefanying,daliangfangre,jubuwendukeshangsheng10 ℃,fanyingwuhuoxingdezengjiakenengdaozhichanwudexiangduifenzizhiliangzengjia、fenbubiankuan,shengchengdaliangdegaojuwu,shichanwudenianduzengjia、yansejiashen、chanpinxingnengxiajiang。ercaiyongcusuandingzhixishicuihuajihouzhudidijiadefangshi,nenghenhaodikongzhifanyingwendu。
結論
caiyongp100weicuihuajihechengtdisanjuti,shiyanbiaominggaicuihuajicuihuahuoxinggao、cuihuasulvkuai,cuihuaxiaoguojiao dmp-30 hek-15hao。