CN1031853A - 氯氟代烷烃的稳定化 - Google Patents
氯氟代烷烃的稳定化 Download PDFInfo
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Abstract
3-丁烯-1-醇化合物可用于使除胺，氨基醇和含
氨基多元醇而外还含氯氟代烷烃的组合物稳定化。
Description
本发明涉及不饱和有机化合物进行含氯氟代烷烃和胺，氨基醇和/或含氨基多元醇并用于例如制备聚氨酯泡沫的混合物稳定化的应用，该混合物稳定化方法，混合物本身以及含稳定剂的氯氟代烷烃。
在制备聚氨酯泡沫时，将异氰酸酯与多元醇反应而进行高分子聚合，其中包括聚氨酯交联。若希望得到发泡聚合产物，则向异氰酸酯或多元醇或两者中加促进剂并且常为氯氟代烷烃。该促进剂借助聚合期间产生的反应热蒸发掉，从而得到低密度发泡产品。
当将制备聚氨酯泡沫所用的化合物于反应前相互直接混合时，则能很容易制成具有良好性能的泡沫材料。当然，实际上只有二异氰酸酯成分才能分开保存到发泡阶段。所有其它制备发泡物质所需要的催化剂如胺催化剂，乳化剂和促进剂或促进剂混合物需与多元醇预混。这种预混合物必须能够长期保存直到应用，这期间不能发生转化反应或分解而影响制成泡沫材料的质量。
但是，该法只有用无氨基多元醇即仅含碳、氢和氧元素的多元醇才能达到好的实施效果，其先决条件是预配制混合物在贮存过程中不能经受极端温度的影响。但在胺，氨基醇和以胺为基础的多元醇作用下即除上述碳、氢和氧元素而外还含氮并且例如以胺或醇胺为主的带游离羟基的聚醚多元醇作用下，胺，氨基醇或以胺为基础的多元醇和作为促进剂加入的氯氟代烷烃之间会发生反应。这样会形成氯化氢而降低PH值，并且因此而降低液态混合物的贮存稳定性。此外，溶液变得更暗，其粘度增加，从而只能制得劣质发泡材料或使混合物根本就不能用于泡沫材料的制造工艺。
从DE-PS 1207626已知，可向除氯氟代烷烃而外，还含以胺为基础的多元醇的混合物中加不饱和化合物，如丁二烯、异丙烯、2-甲基苯乙烯或4-18碳1-烯烃作为稳定剂，而不饱和含氧化合物如乙酸乙烯酯或甲基乙烯基酮在此却无效。
从DE-PS1518461已知，除了α-甲基苯乙烯而外，还可用茴香脑[＝1-（对甲氧苯基）-1-丙烯]，间二异丙烯基苯，1，3，5-三异丙烯基苯和1-（对甲氧苯基）-2-硝基-1-丙烯进行稳定化。
此外，DE-PS1618291说明了用对异丙烯基甲苯（对甲基-2-甲基苯乙烯）并且DE-PS3139401说明了用2，4-二苯基-4-甲基戊烯的异构体混合物（“二聚α-甲基苯乙烯”）阻止胺、氨基醇或含氨基的多元醇与氯氟代烷烃进行反应。
其不足之处是这些化合物仅在相当短的贮存时间内发挥其稳定作用，之后在某些情况下不能令人满意。一旦超过某一贮存时间，则胺、氨基醇或以胺为基础的多元醇与氯氟代烷烃之间就会不断发生反应。与非稳定混合物一样，通过该反应形成氯化氢而使PH值下降并导致粘度上升。该混合物会变色，沉淀盐酸盐而变得混浊并逐渐降低活性。这样老化后的混合物在发泡时起始时间，凝固时间和脱粘时间会不断延长。因此只能制成劣质泡沫材料即具有非均匀的且泡孔常常太大的暗色泡沫，不能用于制造泡沫材料。
另一缺点在于，存在的金属会催化并加速老化工艺，因而不断缩短制成的多元醇混合物在钢板或金属容器中按已知方法进行贮存时的最长贮存时间。混合物老化而使容器出现的腐蚀又会引起其它问题。
本发明的任务是克服现有技术的缺点，更具体地讲是提供用特定α-烯烃进行良好稳定化的混合物，其中含氯氟代烷烃和胺，包括氨基醇，和/或含氨基多元醇，该混合物适于制泡沫材料。这一任务是通过本发明的应用，方法和产品来完成的。
现已发现，应用3-丁烯-1-醇化合物可达到有效的稳定作用。本发明稳定含氯氟代烷烃和胺，包括氨基醇，和/或含氨基多元醇的组合物所采用的是下式Ⅰ的3-丁烯-1-醇。
式Ⅰ化合物的有效结构单元是端部双健与针对该双键而处于β位的羟基的结合。
R1和R2可相同或不同，可代表氢、直链或支链C1～C4烷基、苯基或由低级烷基，低级烯基和/或烷氧基取代的苯基。
优选的是R1为氢，R2为氢，甲基，乙基，丙基，丁基或苯基，如甲氧基，异丙烯基取代的苯基。R1为氢的化合物包括3-丁烯-1-醇，3-甲基-3-丁烯-1-醇，3-乙基-3-丁烯-1-醇，3-丙基-3-丁烯-1-醇，3-丁基-3-丁烯-1-醇或3-苯基-3-丁烯-1-醇。
优选的是R2为甲基，R1为氢、甲基、乙基、丙基、丁基或苯基，如甲氧基或异丙基取代的苯基。R2为甲基的化合物包括3-甲基-3-丁烯-1-醇，4-甲基-4-戊烯-2-醇，5-甲基-5-己烯-3-醇，2-甲基-1-庚烯-4-醇，2-甲基-1-辛烯-3-醇或1-苯基-3-甲基-3-丁烯-1-醇。
优选的是R1＝氢，R2＝甲基即所用化合物为3-甲基-3-丁烯-1-醇。
式Ⅰ化合物可按本发明用于稳定含氯氟代烷烃和胺，包括氨基醇，和/或含氨基多元醇的组合物。本发明稳定剂以氯氟代烷烃计为0.05-5优选为0.3-1.5重量%的3-甲基-3-丁烯-1-醇。在本发明的一个实施例中，以氯氟代烷烃计的3-甲基-3-丁烯-1-醇为0.75重量%。
本发明氯氟代烷烃作为促进剂可为已知化合物，如全囟代1-2碳烷烃，特别是三氯氟甲烷，1，1，2-三氯-1，2，2-三氟乙烷，1，1，1-三氯-2，2，2-三氟乙烷，四氯-1，2，-二氟乙烷，四氯-2，2-二氟乙烷以及其两种或多种化合物的混合物。特别适宜的是三氯氟甲烷。
本发明胺可用已知胺催化剂，如饱和或不饱和脂族，环脂族或杂环胺。具体例子是三乙胺，甲基-双-二甲基氨基乙基胺，N，N，N′，N′-四甲基乙二胺，三乙二胺，二甲基环己胺，N，N，N′，N′-四甲基-1，3-丁二胺，1，1，3，3-四甲基胍，1，2，4-三甲基哌嗪，N-环己基哌啶，4-二甲基氨基吡啶，N-甲基吗啉或吗啉。
此外，也可用其它常见胺如N-乙基吗啉，N，N′-二甲基苄胺，N，N-二甲基-（N，N′-二甲基氨基）哌嗪，N，N-二甲基哌嗪，十六（烷）基二甲基胺，二乙基环己胺，N-苯基环己胺的氯氟代烷烃混合物。
此外，本发明胺还可为已知氨基醇，例如-二甲基乙醇胺，二乙醇胺，N-甲基二乙醇胺，三乙醇胺，二异丙醇胺或N，N，N′，N′-四（2-羟丙基）乙二胺。此外，还可用其它常见氨基醇，如二乙基乙醇胺或1，4-双（2-羟丙基）-2-甲基哌嗪的氯氟代甲醇混合物。
所谓含氨基多元醇指的是以胺、醇胺或芳族胺为主的含羟基聚醚。这些以胺为基础的多元醇可为环氧乙烷和/或环氧丙烷与胺如二亚乙基三胺，乙二胺，三乙醇胺或亚甲苯二胺的反应产物。很显然，除了上述多元醇体系而外，本发明还可用其它常用多元醇体系。方案之一是用羟值为485-515的以胺为基础的多元醇。
本发明还包括含氯氟代烷烃和胺，包括氨基醇，和/或含氨基多元醇的组合物的稳定方法，其中以氯氟代烷烃计将0.05-5重量%的式（Ⅰ）化合物。在本发明的一个实施例中将0.75重量%的3-甲基-3-丁烯-1-醇加入混合物中。
此外，本发明还包括除氯氟代烷烃而外尚含有胺，包括氨基醇，和/或含氨基多元醇以及作为稳定剂的式（Ⅰ）化合物的组合物。在本发明的一个实施例中含有3-甲基-3-丁烯-1-醇作为稳定化合物。
因此，本发明还包括氯氟代烷烃或其混合物，其中含式（Ⅰ）化合物，而其量足以使含氯氟代烷烃和胺，包括氨基醇，和/或含氨基多元醇的组合物稳定化。
本发明用式（Ⅰ）化合物进行稳定化的组合物显示出有利的特性。这些组合物可以长时间保持稳定即PH值和粘度变化极小。贮存于钢罐中同样如此，因而对按常规方法在钢板容器或金属容器中的贮存特别有意义。本发明组合物优于本技术领域中采用的常见化合物按已知方式加以稳定化的组合物，表现在其稳定性和良好的可贮存性。此外，还可出人意料地保证制得高质量泡沫材料。
为了表明本发明作为稳定剂使用的化合物的优越性，可将3-甲基-3-丁烯-1-醇的作用与“二聚α-甲基苯乙烯”（从DE-PS3139401已知）的作用进行比较，这正如以下实施例所述。
以下实施例详细说明本发明，但并不限制其保护范围。
实施例：
以下试验中用本发明组合物Ⅰ（含3-甲基-3-丁烯-1-醇）和对比混合物（含“二聚α-甲基苯乙烯”）（配方均以重量份计）。
组合物号 Ⅰ Ⅱ
以胺为基础的聚醚 100.0 100.0
聚硅氧烷（Si共聚物） 0.8 0.8
二甲基环己胺 2.0 2.0
水 1.0 1.0
用0.75重量%二聚α-甲基苯乙烯
稳定后的三氯氟甲烷 - 30.0
用0.75%的3-甲基-3-丁烯-1-醇
稳定后的三氯氟甲烷 30.0 -
该组合物在玻璃容器中，贮存在钢罐内，50℃存放8星期，之后确定下表所列参数的特性。混合物50℃存放8星期相当于20℃存放10个月。
时间（星期） 组合物号
Ⅰ Ⅱ
PH值 0 10.8 10.9
8 9.2 8.5
粘度（m Pa.s） 0 128 120
8 138 169
起始时间（s） 0 17 17
8 17 30
凝固时间（s） 0 75 80
8 85 135
无粘时间（s） 0 110 115
8 110 180
Claims (10)
1、应用式Ⅰ的3-丁烯-1-醇化合物进行含氯氟代烷烃以及胺和/或含氨基多元醇的组合物稳定化
其中R1和/或R2为氢，直链或支链C1～C4烷基，苯基或取代苯基。
2、权利要求1的应用，其特征在于应用3-甲基-3-丁烯-1-醇。
3、权利要求1或2的应用，其特征在于3-丁烯-1-醇化合物用量以氯氟代烷烃计为0.05-5重量%，优选为0.3-1.5重量%。
4、权利要求1的应用，其特征在于胺为胺催化剂，如饱和或不饱和脂族，环脂族或杂环胺，优选为三乙胺，甲基-双-二甲基氨基乙基胺，N，N，N′，N′-四甲基乙二胺，三乙二胺，二甲基环己胺，N，N，N′，N′-四甲基-1，3-丁二胺，1，1，3，3-四甲基胍，12，4-三甲基哌嗪，N-环己基哌啶，4-二甲基氨基吡啶，N-甲基吗啉或吗啉。
5、权利要求1的应用，其特征在于的胺为氨基醇，优选为二甲基乙醇胺，二乙醇胺，N-甲基二乙醇胺，三乙醇胺，二异丙醇胺或N，N，N′，N′-四（2-羟丙基）乙二胺。
6、权利要求1的应用，其特征在于含氨基多元醇为以胺或醇胺为主的含羟基聚醚。
7、含氯氟代烷烃以及胺，氨基醇和/或含氨基多元醇的组合物的稳定方法，其特征在于向组合物中加0.05-5重量%的式（Ⅰ）化合物，优选为3-甲基-3-丁烯-1-醇。
8、含氯氟代烷烃和胺和/或含氨基多元醇以及作为稳定剂的式（Ⅰ）的组合物。
9、权利要求8的组合物，其特征在于不饱和化合物为3-甲基-3-丁烯-1-醇。
10、氯氟代烷烃，优选为三氯氟甲烷，1，1，2-三氯-1，2，2-三氟乙烷，1，1，1-三氯-2，2，2-三氟乙烷或这些化合物的组合物，其中含足够量用以使这些氯氟代烷烃与胺，氨基醇和/或含氨基多元醇的混合物稳定化的式（Ⅰ）化合物。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19873730221 DE3730221A1 (de) | 1987-09-09 | 1987-09-09 | Stabilisierung von chlorfluoralkanen |
| DEP3730221.3 | 1987-09-09 |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN93103531A Division CN1033231C (zh) | 1987-09-09 | 1993-03-30 | 含氯氟代烷烃的稳定组合物 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1031853A true CN1031853A (zh) | 1989-03-22 |
| CN1023708C CN1023708C (zh) | 1994-02-09 |
Family
ID=6335587
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN88106468A Expired - Fee Related CN1023708C (zh) | 1987-09-09 | 1988-09-06 | 用3-丁烯-丁醇化合物使氯氟代烷烃的组合物稳定 |
| CN93103531A Expired - Fee Related CN1033231C (zh) | 1987-09-09 | 1993-03-30 | 含氯氟代烷烃的稳定组合物 |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN93103531A Expired - Fee Related CN1033231C (zh) | 1987-09-09 | 1993-03-30 | 含氯氟代烷烃的稳定组合物 |
Country Status (18)
| Country | Link |
|---|---|
| US (1) | US4883913A (zh) |
| EP (1) | EP0306861B1 (zh) |
| JP (1) | JPH01103660A (zh) |
| CN (2) | CN1023708C (zh) |
| AR (1) | AR243582A1 (zh) |
| AT (1) | ATE84059T1 (zh) |
| DE (2) | DE3730221A1 (zh) |
| DK (1) | DK498888A (zh) |
| ES (1) | ES2052657T3 (zh) |
| FI (1) | FI89274C (zh) |
| GR (1) | GR3007416T3 (zh) |
| HK (1) | HK27794A (zh) |
| IL (1) | IL87711A (zh) |
| MY (1) | MY103392A (zh) |
| NO (1) | NO177317C (zh) |
| PH (1) | PH25602A (zh) |
| SG (1) | SG37793G (zh) |
| YU (1) | YU46551B (zh) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104755518A (zh) * | 2012-10-24 | 2015-07-01 | 气体产品与化学公司 | 改善具有含卤素发泡剂的聚氨酯体系的稳定性的胺催化剂 |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL284875A (zh) * | 1961-10-30 | |||
| US3297582A (en) * | 1963-06-10 | 1967-01-10 | Pennsalt Chemicals Corp | Trichloromonofluoromethanecontaining compositions |
| FR1420190A (fr) * | 1964-01-10 | 1965-12-03 | Allied Chem | Procédé de stabilisation des chlorofluoroalcanes vis-à-vis des alcools, au moyen de composés non saturés et compositions obtenues |
| US3352789A (en) * | 1964-01-10 | 1967-11-14 | Allied Chem | Stabilization of chlorofluoroalkanes |
| US3361833A (en) * | 1964-07-27 | 1968-01-02 | Kaiser Aluminium Chem Corp | Stabilized chlorofluorocarbon compositions |
| US3465052A (en) * | 1966-06-15 | 1969-09-02 | Daikin Ind Ltd | Stabilized chlorofluoroalkane compositions |
| JPS5785326A (en) * | 1980-11-14 | 1982-05-28 | Asahi Glass Co Ltd | Stabilization of flon |
| JPS5785325A (en) * | 1980-11-14 | 1982-05-28 | Asahi Glass Co Ltd | Stabilization of flon |
| DE3139401C2 (de) * | 1981-10-03 | 1985-12-12 | Hoechst Ag, 6230 Frankfurt | Stabilisieren von Polyether- oder Polyester-Formmassen gegen vorzeitige Reaktion |
-
1987
- 1987-09-09 DE DE19873730221 patent/DE3730221A1/de not_active Withdrawn
-
1988
- 1988-07-07 AR AR88311364A patent/AR243582A1/es active
- 1988-09-02 PH PH37497A patent/PH25602A/en unknown
- 1988-09-03 EP EP88114396A patent/EP0306861B1/de not_active Expired - Lifetime
- 1988-09-03 AT AT88114396T patent/ATE84059T1/de not_active IP Right Cessation
- 1988-09-03 ES ES88114396T patent/ES2052657T3/es not_active Expired - Lifetime
- 1988-09-03 DE DE8888114396T patent/DE3877098D1/de not_active Expired - Fee Related
- 1988-09-06 CN CN88106468A patent/CN1023708C/zh not_active Expired - Fee Related
- 1988-09-08 IL IL87711A patent/IL87711A/xx not_active IP Right Cessation
- 1988-09-08 NO NO884011A patent/NO177317C/no unknown
- 1988-09-08 US US07/241,468 patent/US4883913A/en not_active Expired - Fee Related
- 1988-09-08 DK DK498888A patent/DK498888A/da not_active Application Discontinuation
- 1988-09-08 JP JP63223683A patent/JPH01103660A/ja active Pending
- 1988-09-08 YU YU171188A patent/YU46551B/sh unknown
- 1988-09-08 MY MYPI88001001A patent/MY103392A/en unknown
- 1988-09-08 FI FI884139A patent/FI89274C/fi not_active IP Right Cessation
-
1993
- 1993-03-19 GR GR920403224T patent/GR3007416T3/el unknown
- 1993-03-30 CN CN93103531A patent/CN1033231C/zh not_active Expired - Fee Related
- 1993-04-06 SG SG377/93A patent/SG37793G/en unknown
-
1994
- 1994-03-24 HK HK277/94A patent/HK27794A/xx unknown
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104755518A (zh) * | 2012-10-24 | 2015-07-01 | 气体产品与化学公司 | 改善具有含卤素发泡剂的聚氨酯体系的稳定性的胺催化剂 |
| US10023681B2 (en) | 2012-10-24 | 2018-07-17 | Evonik Degussa Gmbh | Delay action catalyst for improving the stability of polyurethane systems having halogen containing blowing agents |
| US10196476B2 (en) | 2012-10-24 | 2019-02-05 | Evonik Degussa Gmbh | Amine catalyst for improving the stability of polyurethane systems having halogen containing blowing agents |
Also Published As
| Publication number | Publication date |
|---|---|
| IL87711A (en) | 1992-01-15 |
| NO177317B (no) | 1995-05-15 |
| US4883913A (en) | 1989-11-28 |
| IL87711A0 (en) | 1989-02-28 |
| EP0306861A2 (de) | 1989-03-15 |
| ATE84059T1 (de) | 1993-01-15 |
| HK27794A (en) | 1994-03-31 |
| NO884011L (no) | 1989-03-10 |
| AR243582A1 (es) | 1993-08-31 |
| EP0306861A3 (en) | 1990-08-16 |
| GR3007416T3 (zh) | 1993-07-30 |
| ES2052657T3 (es) | 1994-07-16 |
| DK498888D0 (da) | 1988-09-08 |
| CN1023708C (zh) | 1994-02-09 |
| SG37793G (en) | 1993-06-11 |
| DE3877098D1 (de) | 1993-02-11 |
| NO177317C (no) | 1995-08-23 |
| EP0306861B1 (de) | 1992-12-30 |
| CN1033231C (zh) | 1996-11-06 |
| YU46551B (sh) | 1993-11-16 |
| FI884139A0 (fi) | 1988-09-08 |
| YU171188A (en) | 1990-06-30 |
| DE3730221A1 (de) | 1989-03-30 |
| FI89274C (fi) | 1993-09-10 |
| DK498888A (da) | 1989-05-19 |
| FI884139A (fi) | 1989-03-10 |
| CN1079242A (zh) | 1993-12-08 |
| PH25602A (en) | 1991-08-08 |
| MY103392A (en) | 1993-06-30 |
| JPH01103660A (ja) | 1989-04-20 |
| FI89274B (fi) | 1993-05-31 |
| NO884011D0 (no) | 1988-09-08 |
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