EP0039331A1 - Improvements relating to polyurethane catalysts - Google Patents
Improvements relating to polyurethane catalystsInfo
- Publication number
- EP0039331A1 EP0039331A1 EP19800901412 EP80901412A EP0039331A1 EP 0039331 A1 EP0039331 A1 EP 0039331A1 EP 19800901412 EP19800901412 EP 19800901412 EP 80901412 A EP80901412 A EP 80901412A EP 0039331 A1 EP0039331 A1 EP 0039331A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- catalyst system
- polyurethane
- represent
- alkyl group
- different
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 38
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 14
- 239000004814 polyurethane Substances 0.000 title claims abstract description 14
- 230000003111 delayed effect Effects 0.000 claims abstract description 9
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 125000000732 arylene group Chemical group 0.000 claims abstract description 4
- 125000006832 (C1-C10) alkylene group Chemical group 0.000 claims abstract description 3
- 125000004450 alkenylene group Chemical group 0.000 claims abstract description 3
- 150000001412 amines Chemical class 0.000 claims abstract description 3
- 239000008240 homogeneous mixture Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 150000003512 tertiary amines Chemical class 0.000 claims description 3
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 229920001228 polyisocyanate Polymers 0.000 claims description 2
- 239000005056 polyisocyanate Substances 0.000 claims description 2
- 229920005862 polyol Polymers 0.000 claims description 2
- 150000003077 polyols Chemical class 0.000 claims description 2
- 229920001971 elastomer Polymers 0.000 claims 1
- 239000000806 elastomer Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000004886 process control Methods 0.000 abstract description 2
- 150000002148 esters Chemical class 0.000 description 9
- IBMRTYCHDPMBFN-UHFFFAOYSA-N Mono-Me ester-Pentanedioic acid Natural products COC(=O)CCCC(O)=O IBMRTYCHDPMBFN-UHFFFAOYSA-N 0.000 description 6
- WXUAQHNMJWJLTG-VKHMYHEASA-N (S)-methylsuccinic acid Chemical compound OC(=O)[C@@H](C)CC(O)=O WXUAQHNMJWJLTG-VKHMYHEASA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- FJEKUEUBQQWPBY-UHFFFAOYSA-N 1$l^{2}-stanninane Chemical compound C1CC[Sn]CC1 FJEKUEUBQQWPBY-UHFFFAOYSA-N 0.000 description 1
- LWYAUHJRUCQFCX-UHFFFAOYSA-N 4-dodecoxy-4-oxobutanoic acid Chemical compound CCCCCCCCCCCCOC(=O)CCC(O)=O LWYAUHJRUCQFCX-UHFFFAOYSA-N 0.000 description 1
- UZNLHJCCGYKCIL-UHFFFAOYSA-N 6-ethoxy-6-oxohexanoic acid Chemical class CCOC(=O)CCCCC(O)=O UZNLHJCCGYKCIL-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000196 viscometry Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/161—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22
- C08G18/163—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22 covered by C08G18/18 and C08G18/22
- C08G18/165—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22 covered by C08G18/18 and C08G18/22 covered by C08G18/18 and C08G18/24
Definitions
- This invention relates to improved catalysts for the production of polyesters and polyurethanes.
- Q and Q' which ma be the same or different, each represent a group of the formula or an arylene group
- R 1 , R 2 , R 3 and R 4 which may be the same or different, each represent a substituted or unsubstituted alkyl group; n represents zero or an integer from 1 to 10, and x represents zero or an integer less than 6.
- Such compounds are delayed action catalysts for polyester and polyurethane production.
- delayed action catalyst systems of improved shelf life with greater potential for process control comprise:
- Q and Q' which may be the same or different, each represent a C 1 to C 10 alkylene, C 2 to C 10 alkenylene or an arylene group;
- R 1 , R 2 , R 3 and R 4 which may be the same or different , each represent a substituted or unsubstituted alkyl group; and x represents zero or an integer less than 6 ; and (ii ) an amine .
- Component (ii) of the catalyst system is suitably a tertiary amine, preferably one of the formula: R 5 R 6 R 7 N wherein:
- R 5 , R 6 , R 7 which may be the same or different, each represent a C 1 to C 5 alkyl group, for example an ethyl group.
- Triethylamine is found to be a convenient tertiary amine for use as component ( ii) .
- R 1 , R 2 , R 3 or R 4 suitably represents an unsubstituted alkyl group, for example a C 1 to C 6 alkyl group, preferably a C 1 to C 4 alkyl group.
- R 1 and R 2 will be identical and it is particularly preferred that they both represent butyl groups.
- R 3 and R 4 will be identical. It is preferred that R 3 and R 4 both represent a methyl or an ethyl group.
- Q and Q' are preferably identical, most preferably a C 1 to C 4 linear alkylene group.
- x represents an integer less than 4, especially 1.
- Preferred delayed action catalyst systems of the invention are those in which one or, most preferably, both of R 3 and of Q (R 3 and R 4 being identical and Q and Q' being identical) are C 1 to C 4 moieties.
- R 3 and of Q R 3 and R 4 being identical and Q and Q' being identical
- examples include the derivatives of ethyl adipate half ester, methyl glutarate half ester and methyl succinate half ester, especially methyl glutarate half ester and methyl succinate half ester.
- weight ratio (i):(ii) is from 0.80:1 to 1.20:1.
- compositions of the invention are delayed action catalyst systems for the production of polyurethane.
- Component (i) of the catalyst systems of the invention may be prepared in accordance with the disclosure of our OLS 2821306. It is particularly preferred that the reagents are anhydrous; for example the organic solvent is preferably sodium-dried.
- This invention also provides a delayed action process for the preparation of a polyurethane, which process comprises introducing a polyol and a polyisocyanate into a reaction vessel in the presence of a delayed action catalyst system as herein described; forming a homogeneous mixture of the reactants and catalyst system prior to polymerisation; and allowing the homogeneous mixture to polymerise to a polyurethane.
- a delayed action process for the preparation of a polyurethane, which process comprises introducing a polyol and a polyisocyanate into a reaction vessel in the presence of a delayed action catalyst system as herein described; forming a homogeneous mixture of the reactants and catalyst system prior to polymerisation; and allowing the homogeneous mixture to polymerise to a polyurethane.
- the initial temperature of the homogeneous mixture is not greater than 30oC, preferably from 20oC to 25oC; if the initial temperature is higher, there is a possibility that the catalyst system will immediately be activated and no delay period observed.
- excellent results may be attained by using an initial temperature of 40oC to 50oC for the homogeneous mixture.
- the selection of catalyst component (i) will depend on the desired initial temperature of the homogeneous mixture, the reactant bulk, and, to a lesser extent, reactor geometry and composition. This may readily be determined by routine experiment by one skilled in the art.
- the catalyst systems of this invention may also be used at higher temperatures at which no delay period is observed.
- catalyst component (i) Once catalyst component (i) has been selected, it is possible to optimise the system (a) by the amount of (i) present and (b) by the weight ratio (i):(ii) present, thereby giving great control over the process of this invention.
- both delay time and reaction time are reduced by increasing the quantity of component (i) .
- the effect of an increased amount of component (i) can be tempered by reducing the weight ratio (i):(ii).
- This invention provides a polyurethane prepared using a catalyst system of the present invention.
- stannoxane used as component (i) prepared by reacting equimolar quantities of the half ester with dibutyl tin dioxide in anhydrous toluene, and the viscometry apparatus, were as disclosed in our OLS 2821306.
- Comparative plot 27 was effected with the conventional catalyst dibutyl tin dilaurate under the conditions shown in Table 2.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB7927505 | 1979-08-07 | ||
| GB7927505 | 1979-08-07 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP0039331A1 true EP0039331A1 (en) | 1981-11-11 |
Family
ID=10507047
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP19800901412 Withdrawn EP0039331A1 (en) | 1979-08-07 | 1980-08-06 | Improvements relating to polyurethane catalysts |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0039331A1 (en)) |
| JP (1) | JPS56500966A (en)) |
| WO (1) | WO1981000411A1 (en)) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5177117A (en) * | 1989-05-01 | 1993-01-05 | Air Products And Chemicals, Inc. | Controlled release catalysts and curing agents for making polyurethane and/or polyisocyanurate product |
| CA2207146A1 (en) * | 1996-05-28 | 1997-11-28 | Atofina Chemicals, Inc. | Catalyst for low temperature cure of blocked isocyanates |
| KR20070053708A (ko) | 2004-08-04 | 2007-05-25 | 포움 서플라이즈 인코포레이션 | 폴리우레탄 폼에서의 반응도 변동 및 촉매 분해 |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE595337A (en)) * | 1957-09-25 | |||
| BE584911A (en)) * | 1958-11-24 | |||
| DE1195049B (de) * | 1962-03-23 | 1965-06-16 | Hans J Zimmer Verfahrenstechni | Verfahren zur Herstellung von Poly-(aethylenglykolterephthalat) |
| GB1533308A (en) * | 1975-12-22 | 1978-11-22 | M & T Chemicals Inc | High resiliency polyurethane foam with breathability and reduced shrinkage by use of certain tin catalysts |
| GB1604224A (en) * | 1977-05-16 | 1981-12-02 | Rubber & Plastic Res Ass | Polyurethane catalysts |
-
1980
- 1980-08-06 JP JP50175180A patent/JPS56500966A/ja active Pending
- 1980-08-06 WO PCT/GB1980/000124 patent/WO1981000411A1/en not_active Application Discontinuation
- 1980-08-06 EP EP19800901412 patent/EP0039331A1/en not_active Withdrawn
Non-Patent Citations (1)
| Title |
|---|
| See references of WO8100411A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS56500966A (en)) | 1981-07-16 |
| WO1981000411A1 (en) | 1981-02-19 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| 17P | Request for examination filed |
Effective date: 19810821 |
|
| AK | Designated contracting states |
Designated state(s): DE FR GB |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
|
| 18D | Application deemed to be withdrawn |
Effective date: 19831118 |
|
| RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: WILLOUGHBY, BRYAN GODFREY |