GB2107336A - A method of manufacturing flexible polyurethane forms and a novel polyol composition for use therein - Google Patents
A method of manufacturing flexible polyurethane forms and a novel polyol composition for use therein Download PDFInfo
- Publication number
- GB2107336A GB2107336A GB08218711A GB8218711A GB2107336A GB 2107336 A GB2107336 A GB 2107336A GB 08218711 A GB08218711 A GB 08218711A GB 8218711 A GB8218711 A GB 8218711A GB 2107336 A GB2107336 A GB 2107336A
- Authority
- GB
- United Kingdom
- Prior art keywords
- polyol
- optionally
- alkali metal
- metal salt
- weight
- 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- Withdrawn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
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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
- C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
- C08G18/4841—Polyethers containing oxyethylene units and other oxyalkylene units containing oxyethylene end groups
-
- 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
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- 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
- C08G18/22—Catalysts containing metal compounds
- C08G18/225—Catalysts containing metal compounds of alkali or alkaline earth metals
-
- 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
-
- 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
- C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
-
- 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
- C08G2110/00—Foam properties
- C08G2110/0008—Foam properties flexible
-
- 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
- C08G2110/00—Foam properties
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
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
A method of manufacturing flexible polyurethane foams comprises mixing together in the presence of an alkali metal salt, (a) a polyisocyanate or isocyanate-ended prepolymer thereof, (b) a polyoxyalkylene polyol having a molecular weight of not less than 3000 and containing oxypropylene and optionally oxyethylene units, (c) water, (d) a catalyst for foam formation and (e) optionally minor amounts of other conventional polyurethane ingredients; the amount by weight of component (b) used being from 20 to 50 times the amount of weight of component (c) and the isocyanate index of components (a), (b), (c) and (d) taken together being from 80 to 120. The invention also relates to a polyol composition which comprises a polyoxyalkylene polyol having a molecular weight of not less than 3000 and containing oxypropylene and optionally oxyethylene units, in admixture with an alkali metal salt and optionally water, a catalyst for polyurethane foam formation and minor amounts of other conventional ingredients. The alkali metal salt is typically potassium formate or acetate and is used to lower the density of the foam.
Description
SPECIFICATION
A method of manufacturing flexible polyurethane foams and a novel polyol composition for use therein
This invention relates to flexible polyurethane foams, especially those foams known as high resilience urethane foams. More particularly, the invention relates to a method of manufacturing such foams, a novel polyol composition for use in their manufacture and the foams themselves.
High resilience urethane foams are known for use in cushioning applications in the automobile and furnishing industries. They may be made by mixing together a polyisocyanate or isocyanateended prepolymer with a polyoxyalkylene polyol containing oxypropylene and optionally oxyethylene units, water, a catalyst for foam formation and optionally other conventional polyurethane foam ingredients. The manufacture of such foams is described in, for example,
European Patent Specifications Nos. 0010850 and 0022617.
The present invention is concerned with reducing the density of these foams.
According to one aspect of the present invention there is provided a method of manufacturing flexible polyurethane foams which comprises mixing together in the presence of an alkali metal salt, (a) a polyisocyanate or isocyanate-ended prepolymer thereof, (b) a polyoxyalkylene polyol having a molecular weight of not less than 3000, preferably of from 4000 to 7000, andXcontaining oxypropylene and optionally oxyethylene units, (c) water, (d) a catalyst for foam formation and (e) optionally minor amounts of other conventional polyurethane ingredients; the amount by weight of component (b) used being from 20 to 50 times the amount of weight of component (c) and the
Isocyanate Index of components (a), (b), (c) and
(d) taken together being from 80 to 120, preferably from 95 to 105. The invention also includes the foams so obtained.
Potassium acetate and alkali metal hydroxides
are known catalysts for the trimerisation of
isocyanates and for the formation of rigid or semirigid polyurea foams. Potassium acetate is also known to catalyse the reaction between carboxylic acids and isocyanates, and alkali metal hydroxides the reaction between isocyanates and water and hydroxy compounds.
It has now surprisingly been found that the use of alkali metal salts in making high resilience water blown flexible foams, particularly those
based on diphenylmethane diisocyanate (MDI), gives a lower density foam than with for example, a tertiary amine catalyst alone. This is the more surprising because alkali metal salts have no
apparent effect in conventional water blown tolylene diisocyanate (TDI)-based flexible foams
of the type in which polysiloxane-oxyalkylene surfactants are used. While alkali metal
hydroxides have a similar effect, they are
unsuitable because of their detrimental effect on the hydrolytic stability of the foam.
Any alkali metal salt may be used in the invention, particularly one which is highly soluble in water. Salts of organic acids are preferred, especially fatty acids and notably the formates and acetates of sodium and potassium. Salts of higher fatty acids, such as potassium octoate and stearate, are also useful. The amount of alkali metal salt required to obtain a benefit is usefully about 0.1% by weight of the polyol component (b). More than about 0.1%, for example 0.5%, has little further effect in lowering foam density.
Component (a) may be any polyisocyanate or isocyanate-ended prepolymer thereof known to be used in the manufacture of high resilience foams. These include TDI, MDI and mixtures thereof and prepolymers made therefrom. Of especial interest are MDI-based polyisocyanates which include pure 4,4'-MDI and mixtures of this isomer with the 2,4'-isomer. Also included are the so-called crude MDI compositions, particularly those containing from 30 to 95%, especially from 40 to 80%, by weight of MDI, the remainder being largely polymethylene polyphenyl polyisocyanates of functionality greater than twb. Such compositions are obtained by the phosgenation of crude diaminodiphenylmethane.
Isocyanate-ended prepolymers of polyisocyanates and their methods of preparation are fully described in relevant literature. Of particular interest are the prepolymers prepared by reacting a polyoxyalkylene diol or triol, especially polypropylene glycol of molecular weight about 2000, and mixtures thereof with other polyoxyalkylene diols and triols, especially poly(oxypropylene-oxyethylene) random polymers having a larger ethylene oxide than propylene oxide content, with an excess of a MDI-based polyisocyanate. Also the prepolymer may be blended with a different
MDI. For example, a prepolymer made by reacting a polyoxyalkylene diol or triol with a substantially pure MDI can be blended with a crude MDI.A further possibility is to blend the prepolymer with another prepolymer made by reacting a MDI with another polyol, for example another polyoxyalkylene polyol or a monomeric polyol such as a glycol or a mixture of monomeric polyols.
The polyoxyalkylene polyol, referred to above as component (b), may be a polyoxypropylene polyol or a poly(oxypropylene-oxyethylene)polyol or a mixture thereof. Such polyols and methods for their preparatioh have been fully described in the prior art. They are obtained by reacting ethylene and propylene oxides with active hydrogen-containing initiators. Many are commerically available. The poly(oxypropyleneoxyethylene)polyols are preferably ethylene oxidetipped polyoxypropylene polyols which contain from 10 to 25%, especially from 16 to 22% of oxyethylene units based on the total oxyalkylene units present.
The polyoxyalkylene polyol is most suitably a diol or triol or a mixture thereof. It has a molecular weight of not less than 3000, and preferably of from 4000 to 7000.
The water, component (c), is used as a blowing agent in making the flexible foams of the invention. The amount used will depend inter alia on the desired density of the foam and whether auxiliary blowing agents are employed. It is important only that there should be used from 20 to 50 times by weight more of the component (b) polyol than water.
Any catalyst suitable for the formation of polyurethane foams may be used as component (d). Such catalysts have been fully described in the relevant literature and include, in particular, tertiary amines. Organic metal compounds, for example tin compounds, may also be used.
Examples of suitable tertiary amines are N,Ndimethylcyclohexylamine, N,N-dimethylbenzylamine, N,N-dimethylethanolamine and 1,4-diazabicyclo[2.2.2]-octane. Examples of organic metal compounds are stannous octoate and dibutyltin dilaurate. A mixture of catalysts, for example a mixture of amines or an amine and a tin compound, may also be used.
Other conventional polyurethane ingredients which may optionally be used as component (e) include surfactants, fillers, fire-retarders, pigments and dyes. They are used in minor amounts; that is to say in amounts which will not significantly alter the structure of the foam.
Suitable amounts are known to polyurethane technicians and documented in relevant literature.
The foams of the invention are essentially water blown foams. However, it may be desirable to use an auxiliary blowing agent to lower further the foam density. A low boiling solvent, for example, trichlorofluoromethane, may therefore be added in amount of, for example, 5 to 1 5 parts by weight for each 100 parts of polyol used.
The Isocyanate Index of components (a), (b), (c) and (d) taken together is from 80 to 120, preferably from 95 to 105.
By the term "Isocyanate Index" is meant one hundred times the ratio of free isocyanate groups to isocyanate-reactive groups present before
reaction takes place.
The components of the foam-forming reaction mixture may be mixed together in any convenient manner using any of the mixing equipment described in relevant literature for the purpose. If desired, mutually inert individual components
may be pre-blended so as to reduce the number of component streams requiring to be brought together in a final mixing step. It is often convenient to have a two-stream system whereby one stream comprises the polyisocyanate or
prepolymer and the second comprises all the
other components of the reaction mixture.
Thus according to another aspect of the present invention there is provided a polyol composition which comprises a polyoxyalkylene polyol having a molecular weight of not less than 3000, preferably of from 4000 to 7000 and containing oxypropylene and optionally oxyethylene units, in admixture with an alkali metal salt and optionally water, a catalyst for polyurethane foam formation and minor amounts of other conventional ingredients as hereinbefore defined.
In a preferred composition the polyol is an ethylene oxide-tipped polyoxypropylene polyol containing from 10 to 25%, especially from 1 6 to 22% of oxyethylene units based on the total oxyethylene units present. It is further preferred that the alkali metal salt is the salt of an organic acid especially a fatty acid and particularly a formate or acetate of sodium or potassium.
The invention is of particular interest in the manufacture of high resilience, cold-cure urethane foams especially those derived from
MDI-based polyisocyanates. Such foams are used for seating mouldings in the furniture and automotive industries.
Claims (4)
1. A method of manufacturing flexible polyurethane foams which comprises mixing together in the presence of an alkali metal salt, (a) a polyisocyanate or isocyanate-ended prepolymer thereof, (b) a polyoxyalkylene polyol having a molecular weight of not less than 3000, preferably of from 4000 to 7000, and containing oxypropylene and optionally oxyethylene units, (c) water, (d) a catalyst for foam formation and (e) optionally minor amounts of other conventional polyurethane ingredients; the amount by weight of component (b) used being from 20 to 50 times the amount of weight of component (c) and the
Isocyanate Index of components (a), (b), (c) and (d) taken together being from 80 to 1 20.
2. A polyol composition which comprises a polyoxyalkylene polyol having a molecular weight of not less than 3000, preferably of from 4000 to 7000, and containing oxypropylene and optionally oxyethylene units, in admixture with an alkali metal salt and optionally water, a catalyst for polyurethane foam formation and minor amounts of other conventional ingredients.
3. A flexible polyurethane foam made by the
method claimed in claim 1.
4. A flexible polyurethane foam made by reacting together a polyisocyanate and a polyol, characterised in that as the polyol there is used the polyol composition ciaimed in claim 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB08218711A GB2107336A (en) | 1981-10-13 | 1982-06-29 | A method of manufacturing flexible polyurethane forms and a novel polyol composition for use therein |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8130881 | 1981-10-13 | ||
| GB08218711A GB2107336A (en) | 1981-10-13 | 1982-06-29 | A method of manufacturing flexible polyurethane forms and a novel polyol composition for use therein |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB2107336A true GB2107336A (en) | 1983-04-27 |
Family
ID=26280957
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08218711A Withdrawn GB2107336A (en) | 1981-10-13 | 1982-06-29 | A method of manufacturing flexible polyurethane forms and a novel polyol composition for use therein |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2107336A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0398304A1 (en) * | 1989-05-17 | 1990-11-22 | ENICHEM S.p.A. | Flexible polyurethane foams and process for preparing them |
| GB2264501A (en) * | 1992-02-28 | 1993-09-01 | Basf Corp | Poly(urethane-urea) microcellular elastomer compositions |
| US5510053A (en) * | 1994-12-29 | 1996-04-23 | Basf Corporation | Water-blown polyurethane sealing devices and compositions for producing same |
| US5532285A (en) * | 1994-12-29 | 1996-07-02 | Basf Corporation | Water-blown polyurethane sealing devices and compositions for producing same |
| EP0743334A1 (en) * | 1995-05-10 | 1996-11-20 | C.O.I.M. S.p.A. | Polyester polyols, particularly for the production of rigid polyurethane foams |
| EP0803522A1 (en) * | 1996-04-23 | 1997-10-29 | Bayer Ag | Process for the preparation of moulded articles according to the RIM process |
| JP2013543905A (en) * | 2010-10-27 | 2013-12-09 | バイエル・インテレクチュアル・プロパティ・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング | Hydrophilic aliphatic polyurethane foam |
-
1982
- 1982-06-29 GB GB08218711A patent/GB2107336A/en not_active Withdrawn
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0398304A1 (en) * | 1989-05-17 | 1990-11-22 | ENICHEM S.p.A. | Flexible polyurethane foams and process for preparing them |
| US5098937A (en) * | 1989-05-17 | 1992-03-24 | Montedipe S.R.L. | Flexible polyurethane foams and process for preparing them |
| AU627025B2 (en) * | 1989-05-17 | 1992-08-13 | Ecp Enichem Polimeri S.R.L. | Flexible polyurethane foams and process for preparing them |
| GB2264501A (en) * | 1992-02-28 | 1993-09-01 | Basf Corp | Poly(urethane-urea) microcellular elastomer compositions |
| US5382646A (en) * | 1992-02-28 | 1995-01-17 | Basf Corporation | Poly(urethane-urea) microcellular elastomer compositions |
| US5530034A (en) * | 1994-12-29 | 1996-06-25 | Basf Corporation | Water-blown polyurethane sealing devices and compositions for producing same |
| US5510053A (en) * | 1994-12-29 | 1996-04-23 | Basf Corporation | Water-blown polyurethane sealing devices and compositions for producing same |
| US5532285A (en) * | 1994-12-29 | 1996-07-02 | Basf Corporation | Water-blown polyurethane sealing devices and compositions for producing same |
| US5532403A (en) * | 1994-12-29 | 1996-07-02 | Basf Corporation | Water-blown polyurethane sealing devices and compositions for producing same |
| US5539009A (en) * | 1994-12-29 | 1996-07-23 | Basf Corporation | Water-blown polyurethane sealing devices and compositions for producing same |
| US5539010A (en) * | 1994-12-29 | 1996-07-23 | Basf Corporation | Water-blown polyurethane sealing devices and compositions for producing same |
| US5672635A (en) * | 1994-12-29 | 1997-09-30 | Basf Corporation | Water-blown polyurethane sealing devices and compositions for producing same |
| EP0743334A1 (en) * | 1995-05-10 | 1996-11-20 | C.O.I.M. S.p.A. | Polyester polyols, particularly for the production of rigid polyurethane foams |
| EP0803522A1 (en) * | 1996-04-23 | 1997-10-29 | Bayer Ag | Process for the preparation of moulded articles according to the RIM process |
| JP2013543905A (en) * | 2010-10-27 | 2013-12-09 | バイエル・インテレクチュアル・プロパティ・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング | Hydrophilic aliphatic polyurethane foam |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0022617B1 (en) | Polyisocyanate compositions and their use in the preparation of polyurethane foams | |
| EP0392788B1 (en) | Isocyanate composition and process for making flexible foams therefrom | |
| US4261852A (en) | Liquid polyisocyanate compositions | |
| KR100210563B1 (en) | An isocyanate-terminated prepolymer and flexible polyurethane foam prepared therefrom | |
| DE69307800T2 (en) | Reaction system for the production of microcellular elastomers | |
| JP3605154B2 (en) | Method for producing foamed polyurethane molded article without using CFC | |
| DE4203918A1 (en) | METHOD FOR THE PRODUCTION OF FLUOROCHLORINE-HYDROGEN-FREE POLYURETHANE SOFT FOAMS USING POLYISOCYANATE MIXTURES ON DIPHENYLMETHANE DIISOCYANIZATE POLYISOCYANIZED ASYANIZED ASYANIZED ASYANIZED ASYANATE BASE | |
| US4144386A (en) | Process for the production of flexible polyurethane foams | |
| DE69801421T2 (en) | ISOCYANATE COMPOSITIONS FOR PRODUCING POLYURETHANE FOAMS WITH A LOW DENSITY | |
| KR100977664B1 (en) | Prepolymer, Polyol Composition and Process for Making a Flexible Foam | |
| DE69019651T2 (en) | Chemical blowing agent. | |
| DE69506470T2 (en) | Flexible polyurethane foam and process for its production | |
| US5356943A (en) | Rigid foams | |
| DE2402734A1 (en) | METHOD FOR MANUFACTURING CELLULAR POLYURETHANES | |
| DE69010982T2 (en) | Flexible polyurethane foams and processes for their production. | |
| GB2107336A (en) | A method of manufacturing flexible polyurethane forms and a novel polyol composition for use therein | |
| GB2109803A (en) | High molecular weight polyether polyols | |
| EP0480090B1 (en) | Polyisocyanate compositions and their use in the preparation of flexible polyurethane foams | |
| EP0358328A1 (en) | Novel isocyanate-prepolymer compositions | |
| DE4032148A1 (en) | Cellular moulded plastics for e.g. shoe sole prodn. - by reaction of polyether di- and tri:ol(s) with isocyanate semi-prepolymer, using water as sole blowing agent | |
| DE60315298T2 (en) | METHOD FOR PRODUCING A MOLDED POLYURETHANE MATERIAL | |
| GB2099440A (en) | Rigid polymeric foams | |
| EP0339848A1 (en) | Process for making polyurethane foams | |
| US3471418A (en) | Urethane sponge prepared from crude polyisocyanates | |
| KR100525352B1 (en) | Manutacturing method of non-yellowing flexible polyurethane foam |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |