WO1981000411A1 - Improvements relating to polyurethane catalysts - Google Patents

Improvements relating to polyurethane catalysts Download PDF

Info

Publication number
WO1981000411A1
WO1981000411A1 PCT/GB1980/000124 GB8000124W WO8100411A1 WO 1981000411 A1 WO1981000411 A1 WO 1981000411A1 GB 8000124 W GB8000124 W GB 8000124W WO 8100411 A1 WO8100411 A1 WO 8100411A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst system
represent
polyurethane
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.)
Ceased
Application number
PCT/GB1980/000124
Other languages
French (fr)
Inventor
B Willoughby
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
National Research Development Corp of India
Original Assignee
National Research Development Corp of India
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by National Research Development Corp of India filed Critical National Research Development Corp of India
Publication of WO1981000411A1 publication Critical patent/WO1981000411A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

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)

Abstract

Delayed action catalyst systems, principally for polyurethane production, of improved shelf life with greater potential for process control comprise: (i) a compound of the formula: (FORMULA) wherein: Q and Q' which may be the same or different, each represent C1 to C10 alkylene, C2 to C10 alkenylene or an arylene group; R1, R2, R3 and R4 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.

Description

IMPROVEMENTS RELATING TO POLYURETHANE CATALYSTS This invention relates to improved catalysts for the production of polyesters and polyurethanes.
In our OLS 2821306 we have described and claimed compounds of the formula: -.
Figure imgf000003_0002
wherein:
Q and Q' which ma be the same or different, each represent a group of the formula
Figure imgf000003_0003
or an arylene group;
R1, R2, R3 and R4, 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.
We have now determined that delayed action catalyst systems of improved shelf life with greater potential for process control comprise:
(i) a compound of the formula:
Figure imgf000003_0001
wherein: Q and Q' , which may be the same or different, each represent a C 1 to C 10 alkylene, C2 to C 10 alkenylene or an arylene group;
R1, R2, R3 and R4, 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: R5R6R7N wherein:
R5, R6, R7, which may be the same or different, each represent a C1 to C5 alkyl group, for example an ethyl group.
Triethylamine is found to be a convenient tertiary amine for use as component ( ii) .
In the above formulae R1, R2, R3 or R4suitably represents an unsubstituted alkyl group, for example a C1 to C6 alkyl group, preferably a C1 to C4 alkyl group. Generally, R1 and R2 will be identical and it is particularly preferred that they both represent butyl groups. Suitably, R3 and R4 will be identical. It is preferred that R3 and R4 both represent a methyl or an ethyl group.
Q and Q' , are preferably identical, most preferably a C1 to C4 linear alkylene group.
Preferably, x represents an integer less than 4, especially 1.
It is believed that when x = 1, and possibly when x > 1, these compounds exist in an associated form. When x = 1, the structure may be a dimer of the formula:
Figure imgf000004_0001
It is not known whether, at the low concentrations encountered in polyurethane-forming reactions, these compounds are associated or not.
Preferred delayed action catalyst systems of the invention are those in which one or, most preferably, both of R3 and of Q (R3 and R4 being identical and Q and Q' being identical) are C1 to C4 moieties. 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.
Preferably the weight ratio (i):(ii) is from 0.80:1 to 1.20:1.
The above mentioned 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. Such a process is, however, strongly temperature dependent. Thus, with the preferred catalyst systems of the invention, for example those derived from methyl glutarate half ester or methyl succinate half ester, it is highly desirable that 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. However, for less active catalyst systems of the invention, such as those claimed from n-dodecyl succinate half ester, excellent results may be attained by using an initial temperature of 40ºC to 50ºC for the homogeneous mixture. Broadly speaking, 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. 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. Thus, in general, it is found that both delay time and reaction time are reduced by increasing the quantity of component (i) . Thereafter, it is found that 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.
The following Examples illustrate the invention. In each case the 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.
Figure imgf000007_0001
Figure imgf000008_0001
In the accompanying Drawings several of the Examples (indicated by the reference number at the top of the respective curve) have their kinetic plots shown. Comparative plot 27 was effected with the conventional catalyst dibutyl tin dilaurate under the conditions shown in Table 2.

Claims

1. A catalyst system comprising: (i) a compound of the formula:
OOCQ'COOR.
wherein:
Figure imgf000010_0001
Q and Q' , which may be the same or different, each represent C 1 to C10 alkylene, C2 to C10 alkenylene or an arylene group;
R1, R2, R3and R4, 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.
2. A catalyst system according to Claim 1 wherein (ii) comprises a tertiary amine of the formula:
R5R6R7N wherein:
R5, R6and R7 , which may be the same or different, each, represent a C1to C5alkyl group.
3. A catalyst system according to Claim 2 wherein (ii) comprises triethylamine.
4. A catalyst system according to any preceding claim wherein R1 , R2 , R3 or R4, represents an unsubstituted alkyl group.
5. A catalyst system according to any preceding claim wherein R1,
R2, R3 or R4 represents a C1 to C6 alkyl group.
6. A catalyst system according to Claim 5 wherein R1, R2, R3or R4represents a C1to C4alkyl group.
7. A catalyst system according to any preceding claim wherein R1 and R2are identical.
8. A catalyst system according to Claim 7 wherein R1 and R2 represent butyl groups.
9. A catalyst system according to any preceding Claim wherein R3 and R4are identical.
10. A catalyst system according to Claim 9 wherein R3and R4 represent methyl or ethyl groups.
11. A catalyst system according to any preceding claim wherein
Q and Q' are identical.
12. A catalyst system according to Claim 11 wherein Q and Q' represent a C1 to C4 linear alkylene group.
13. A catalyst system according to any preceding claim wherein x represents an integer less than 4.
14. A catalyst system according to Claim 13 wherein x represents 1.
15. A catalyst system according to any preceding claim wherein the weight ratio (i):(ii) is from 0.8:1 to 1.2:1.
16. 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 according to any preceding claim; forming a homogeneous mixture of the reactants and catalyst system prior to polymerisation! and allowing the homogeneous mixture to polymerise to a polyurethane,
17. A process according to Claim 16 wherein the initial temperature of the homogeneous mixture is below 30ºC.
18. A polyurethane prepared using a catalyst system according to any of Claims 1 to 15.
19. A polyurethane according to Claim 18 which is an elastomer.
20. A polyurethane according to Claim 18 or 19 which is foamed.
PCT/GB1980/000124 1979-08-07 1980-08-06 Improvements relating to polyurethane catalysts Ceased WO1981000411A1 (en)

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
WO1981000411A1 true WO1981000411A1 (en) 1981-02-19

Family

ID=10507047

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1980/000124 Ceased WO1981000411A1 (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)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU619975B2 (en) * 1989-05-01 1992-02-06 Air Products And Chemicals Inc. Controlled release catalysts and curing agents for making polyurethane and/or polyisocyanurate product
EP0810245A1 (en) * 1996-05-28 1997-12-03 Elf Atochem North America, Inc. Catalyst for low temperature cure of blocked isocyanates
US10385177B2 (en) 2004-08-04 2019-08-20 Foam Supplies, Inc. Reactivity drift and catalyst degradation in polyurethane foam

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1242464A (en) * 1957-09-25 1960-09-30 Union Carbide Corp Process for accelerating the reaction of an isocyanate or isothiocyanate with an active hydrogen compound
FR1245085A (en) * 1958-11-24 1960-11-04 Union Carbide Corp Polyurethane foams and their manufacturing process
DE1195049B (en) * 1962-03-23 1965-06-16 Hans J Zimmer Verfahrenstechni Process for the production of poly (ethylene glycol terephthalate)
FR2336428A1 (en) * 1975-12-22 1977-07-22 M & T Chemicals Inc HIGHLY ELASTIC FOAM WITH IMPROVED AERATION AND REDUCED SHRINK PROPERTIES DUE TO THE USE OF CERTAIN TIN-BASED CATALYSTS AND ITS PREPARATION PROCESS
DE2821306A1 (en) * 1977-05-16 1978-12-21 Nat Res Dev ORGANOCIN NOXY DIESTERS AND PROCESS FOR THEIR PRODUCTION

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1242464A (en) * 1957-09-25 1960-09-30 Union Carbide Corp Process for accelerating the reaction of an isocyanate or isothiocyanate with an active hydrogen compound
FR1245085A (en) * 1958-11-24 1960-11-04 Union Carbide Corp Polyurethane foams and their manufacturing process
DE1195049B (en) * 1962-03-23 1965-06-16 Hans J Zimmer Verfahrenstechni Process for the production of poly (ethylene glycol terephthalate)
FR2336428A1 (en) * 1975-12-22 1977-07-22 M & T Chemicals Inc HIGHLY ELASTIC FOAM WITH IMPROVED AERATION AND REDUCED SHRINK PROPERTIES DUE TO THE USE OF CERTAIN TIN-BASED CATALYSTS AND ITS PREPARATION PROCESS
DE2821306A1 (en) * 1977-05-16 1978-12-21 Nat Res Dev ORGANOCIN NOXY DIESTERS AND PROCESS FOR THEIR PRODUCTION

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU619975B2 (en) * 1989-05-01 1992-02-06 Air Products And Chemicals Inc. Controlled release catalysts and curing agents for making polyurethane and/or polyisocyanurate product
EP0810245A1 (en) * 1996-05-28 1997-12-03 Elf Atochem North America, Inc. Catalyst for low temperature cure of blocked isocyanates
CN1105157C (en) * 1996-05-28 2003-04-09 北美埃尔夫爱托化学股份有限公司 Catalyst for low temp. cure of blocked isocyanates
US10385177B2 (en) 2004-08-04 2019-08-20 Foam Supplies, Inc. Reactivity drift and catalyst degradation in polyurethane foam

Also Published As

Publication number Publication date
EP0039331A1 (en) 1981-11-11
JPS56500966A (en) 1981-07-16

Similar Documents

Publication Publication Date Title
ES2000397A6 (en) A polyurethane-forming composition useful for backing textiles and a process for preparing polyurethane-backed textiles.
ES8500294A1 (en) Process for preparing an oligomer of a diisocyanate.
US4264745A (en) Fire-retardant polyurethane foam based on a bromine-containing polyester
KR940014497A (en) Thermoplastic Biodegradable Resin and Manufacturing Method Thereof
KR910020059A (en) Polyisocyanate-isocyanurate and preparation method thereof, use thereof
GB1453840A (en) Moulding composition
KR880001739A (en) Thermoplastic molding compositions
CH628910A5 (en) Process for the trimerisation and/or polymerisation of organic polyisocyanates
EP0113172A1 (en) Aromatic amino polyols and rigid polyurethane and polyisocyanurate foams obtainable therefrom
US3061557A (en) Method of reacting an active hydrogen containing compound with an isocyanate or isothiocyanate in contact with a polystannate catalyst
US3133113A (en) Method for preparing polycarbonate esters
US3730953A (en) Process for producing high molecular polyurethanes by reacting oxadiazinones with polyols in the presence of an organotin catalyst
IE41255B1 (en) A process for the production of cross-linked plastics
GB2203440A (en) Polyfunctional isocyanate crosslinking agents for propellant binders
WO1981000411A1 (en) Improvements relating to polyurethane catalysts
EP0117538A2 (en) Polyester polyols and a process for their production
KR850005459A (en) Catalyst Composition for Polyurethane Synthesis with Multi-aliphatic Isocyanates
US4962213A (en) Energetic azido curing agents
US4758606A (en) Polyester polyols prepared by reacting a polyhydric alkoxylated derivative with a polycarboxylic acid
US3139449A (en) Process for preparing organic isothiocyanate using phosphorus-containing catalysts
KR880006174A (en) Process for preparing cyclohexyl mono and diurethane and mono- and diisocyanates derived therefrom, novel monoisocyanates produced by the method and curable compositions comprising the same
GB1378974A (en) Pulverulent heat-hardenable coating amterial
US4136098A (en) Process for the production of cyclic esters of undecanedioic acid
KR960701913A (en) Novel Catalyst Package for use in RIM Systems Containing Acidic Additives
EP0113507B2 (en) Process of preparation of aromatic polyols and rigid polyurethane and polyisocyanurate foams obtainable therefrom

Legal Events

Date Code Title Description
AK Designated states

Designated state(s): JP US

AL Designated countries for regional patents

Designated state(s): DE FR GB

WWE Wipo information: entry into national phase

Ref document number: 1980901412

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 1980901412

Country of ref document: EP

WWW Wipo information: withdrawn in national office

Ref document number: 1980901412

Country of ref document: EP