低游离度TDI三聚体的合成
低游离度TDI三聚体的合成
JIABENERYIQINGSUANZHI(TDI)ZAICUIHUAZUOYONGXIAKEYIFASHENGSANJUFANYING,XINGCHENGHANYIQINGNIAOSUANZHIHUANDESANJUTI。TDISANJUTIJUYOUHUIFAXINGDI、DUXINGXIAO、GUANNENGDUGAO、REWENDINGXINGHAO、NAIFUSHIXINGHAODENGYOUDIAN,CHANGZUOWEIJUANZHIGUHUAJIBEIGUANGFANYINGYONGZAITULIAO、ZHANHEJIZHONG。ZAI20SHIJI70NIANDAI,GUOWAIDUOJIAGONGSIKAISHIGONGYEHUASHENGCHANYINGYONGZHEILEICHANPIN,RUBayer、BASF、DowDENG。MUQIANGAOXINGNENG、DIYOULIDANTIDETDISANJUTIRENGRANXUYAODALIANGYILAIJINKOU。
BENYANJIUYICUIHUAJI NT CAT P100HECHENG TDI SANJUTIJUANZHIGUHUAJI,SHIYANJIEGUOBIAOMING: GAICUIHUAJIJUYOUCUIHUASULVKUAI、HUOXINGGAO、FANYINGWENDUDIDENGYOUDIAN。ZAI40 ℃XIA,YIDIJIAFANGSHICUIHUAFANYING,8 h JIUKEYIDADAOFANYINGZHONGDIAN,DEDAODIYOULIDANTIHANLIANG TDI SANJUTI。
原料及试剂
JIABENERYIQINGSUANDANTITDI(80/20):GONGYEPIN,BASF;CUSUANDINGZHI:FENXICHUN,GUANGZHOUFANYULIQIANGHUAGONGCHANG;NT CAT DMP-30:GONGYEPIN,XINDIANHUAXUE;NT CAT K-15:GONGYEPIN,XINDIANHUAXUE;NT CAT P100: XINDIANHUAXUE;
合成工艺
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。
催化剂种类、用量及滴加方式的影响
CUIHUAJIDEXUANZESHITDISANJUFANYINGDEGUANJIAN。CHANGYONGDETDISANJUCUIHUAJIBAOKUOSHUAN、YOUJIJINSHUHUAHEWU、YOUJILINHUAHEWU、JIANJINSHUSUOSUANYANDENG。XUANYONGDMP-30、K-15HEP100DUI50%CUSUANDINGZHIDETDIRONGYEFENBIECUIHUAFANYING,JIEGUORUBIAO1HETU2SUOSHI。
表1 不同催化剂(0.5%添加量)对TDI三聚反应的影响
催化剂种类 | 无 | K-15 | DMP-30 | P100 |
反应温度/℃ | 70 | 80 | 70 | 70 |
反应时间/h | 24 | 26 | 6 | 5 |
w(—NCO)/% | 24.2 | 12.3 | 10.4 | 6.8 |
产品外观 | 无色透明 | 黄色透明 | 微黄透明 | 近水白透明 |
YOUBIAO1HETU2KEJIAN,BUJIACUIHUAJIDEQINGKUANGXIA,TDIDESANJUFANYINGBUFASHENG;K-15CUIHUASANJUDEXIAOGUOJIAOCHA,WENDUJIAOGAO、FANYINGSHIJIANZHANG,RONGYICHANSHENGGENGDUODEDUOJUTIJIEGOU;JUNWEISHUANLEICUIHUAJIDEDMP-30HEP100CUIHUAXIAOGUOJIAOHAO,XIANGBIZHIXIAP100DECUIHUAXINGNENGGENGQIANG,DUANSHIJIANNEIJIUNENGXUNSUFANYING,JIANGDI—NCOZHI,ERQIESHIYANHAIBIAOMINGZAI40 ℃XIAQIRENGRANJUYOUHENGAODECUIHUAHUOXING。YINCI,XUANYONGP100ZUOWEICUIHUAJI。TU3SHIP100CUIHUAJIYONGLIANGFENBIEZHANTDIDANTIZONGZHILIANGDE2%、0.5%JI0.8%SHIDUITDISANJUFANYINGDEYINGXIANG。
图2 3 种催化剂的催化效率对比

DIYOULIDUTDISANJUTIDEHECHENG
CONGTU3KANDAO,ZAIQITATIAOJIANXIANGTONGDEQINGKUANGXIA,SUIZHEP100YONGLIANGDEZENGJIA,FANYINGSULVJIAKUAI,TONGSHI—NCOJITUANHANLIANGYOUSUOJIANSHAO。CUIHUAJIYONGLIANGTAISHAOSHI,JISHIYANZHANGFANYINGSHIJIAN,—NCOHANLIANGRENGGAOYU12%;ERCUIHUAJIYONGLIANGGUOGAOSHI,DALIANGCANLIUDECUIHUAJIZAIYIDINGCHENGDUSHANGYINGXIANGLECHANPINDEXINGNENG。SHIYANBIAOMING,P100YONGLIANGWEI0.5%JIAOHESHI。
图3 催化剂用量对TDI三聚反应的影响

DIYOULIDUTDISANJUTIDEHECHENG
LINGWAI,CUIHUAJIDEDIJIAFANGSHIYEHUIYINGXIANGSANJUFANYING。SHIYANBIAOMING,RUOYICIXINGJIARUCUIHUAJI,DANTIMASHANGJULIEFANYING,DALIANGFANGRE,JUBUWENDUKESHANGSHENG10 ℃,FANYINGWUHUOXINGDEZENGJIAKENENGDAOZHICHANWUDEXIANGDUIFENZIZHILIANGZENGJIA、FENBUBIANKUAN,SHENGCHENGDALIANGDEGAOJUWU,SHICHANWUDENIANDUZENGJIA、YANSEJIASHEN、CHANPINXINGNENGXIAJIANG。ERCAIYONGCUSUANDINGZHIXISHICUIHUAJIHOUZHUDIDIJIADEFANGSHI,NENGHENHAODIKONGZHIFANYINGWENDU。
结论
CAIYONGP100WEICUIHUAJIHECHENGTDISANJUTI,SHIYANBIAOMINGGAICUIHUAJICUIHUAHUOXINGGAO、CUIHUASULVKUAI,CUIHUAXIAOGUOJIAO DMP-30 HEK-15HAO。