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。