GB1584780A - Polyurethane compositions - Google Patents
Polyurethane compositions Download PDFInfo
- Publication number
- GB1584780A GB1584780A GB41032/76A GB4103276A GB1584780A GB 1584780 A GB1584780 A GB 1584780A GB 41032/76 A GB41032/76 A GB 41032/76A GB 4103276 A GB4103276 A GB 4103276A GB 1584780 A GB1584780 A GB 1584780A
- Authority
- GB
- United Kingdom
- Prior art keywords
- parts
- weight
- mixture
- polyurethane compositions
- polyester
- 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.)
- Expired
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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
- C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
- C08G18/8009—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203
- C08G18/8012—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203 with diols
- C08G18/8019—Masked aromatic polyisocyanates
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/797—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing carbodiimide and/or uretone-imine groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0016—Plasticisers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/02—Halogenated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
Description
(54) NEW POLYURETHANE COMPOSITIONS
(71) We, IMPERIAL CHEMICAL INDUSTRIES LIMITED, Imperial
Chemical House, Millbank, London SW1P 3JF, a British Company, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: This invention relates to new and improved polyurethane compositions.
Our U.K. Application No. 51876/73 (Serial No. 1,451,775) describes and claims a process for the manufacture of polyurethane elastomers wherein a polyester having a viscosity within the range 100 to 250 centistokes at 100"C, a hydroxyl value within the range 50 to 100 mg KOH/g and an acid value less than 2.0 mg KOH/g, which has been formed by condensing adipic acid with a molecular excess of a mixture of polyols consisting of ethylene and propylene glycols in a molar ratio of from 65: 35 to 75:25 together with a polyol having 3 or more hydroxyl groups and a molecular weight below 500, the amount of the latter being such as to give up to 0.2 branch point per 1000 units of molecular weight of the polyester, is reacted under substantially anhydrous conditions as sole isocyanate-reactive component with a diphenylmethane diisocyanate composition at a NEO: OOH ratio of 0.88:1 to 1.20 to 1. The elastomers obtained have a amrbination of hardness and resilience which make them valuable for the manufacture of newspaper, textile, metallurgy or printers' rollers, solid tyres, conveyer belting, thick sheet, seals and shock absorbers.
It has now been found that by incorporating a plasticiser in the elastomers of
Specification No. 1,451,775 obtained from diphenyl methane diisocyanate compositions which are liquid at ambient temperatures, a novel series of solid polyurethane compositions are obtained which have high resilience, low compression set, good tear strength and tensile strength, and which can be used as tyre-filling compositions with good load bearing properties and low heat build-up.
Thus, the present invention provides solid polyurethane compositions comprising a plasticiser and the reaction product of a polyester as hereinbefore defined and a composition of diphenylmethane diisocyanates or reaction products thereof which is liquid at ambient temperatures.
As examples of diphenyimethane diisocyanate compositions which may be used, there may be mentioned:
(a) reaction products of pure 4,4'-diisocyanatodiphenylmethane or mixtures
thereof with the 2,2 '-isomer which have had small amounts of urethane or
uretonimine groups incorporated by reaction with glycols or heating in the
presence of catalysts.
(b) mixtures of 4,4'-and 2,4'-diisocyanatodiphenylmethane containing up to
50%, preferably up to 30%, by weight of the latter;
(c) mixtures of (a) or (b) with up to 70%, but preferably not more than 55%
by weight of the mixtures of poly(isocyanatophenyl) methylene compounds
obtained by reacting aniline with formaldehyde and subjecting the reaction
product to the action of phosgene.
Particularly useful compositions are (1) a mixture of aproximately equal parts by weight of the mixtures of poly(isocyanatophenyl)methylene compounds mentioned under (c) and the urethane made by reacting approximately 90 parts by weight of a mixture of 70-95 parts by weight of 4,4'-dlisocyanatodiphenyl methane and 5-30 parts by weight of 2,4'-diisocyanatodiphenylmethane with approximately 10 parts by weight of a mixture of diethylene, 1,3-butylene and 1,2-propylene glycols in equimolar proportions and (2) a mixture of approximately equal parts by weight of (a) the urethane made by reacting approximately 90 parts by weight of 4,4'-diisocyanatodiphenyl methane with approximately 10 parts by weight of the mixed glycols in (1) above with (b) the uretonimine made by heating 4,4'-diisocyanatodiphenylmethane in the presence of l-phenyl-3-methyl-2-phospholene oxide until the isocyanate content is approximately 29% by weight.
The polyurethanes in the compositions can be made by the "two-stage" process in which all the isocyanate is mixed with a part of the polyester and the reaction product is subsequently reacted with the remainder of the polyester. It is preferred however to react all the polyester with all the isocyanate in a single reaction. The plasticiser should be added to the reactants or a mixture thereof which is still liquid.
In a preferred process the plasticiser is distributed between the diisocyanate com- ponent and the polyester component in such a way that the two components are as nearly equal in volume as possible. This expedient facilitates the mixing of the two components. It is preferred that a catalyst be present though it is ngt essential where heat curing of the solid elastomer is possible. Metal salts or complexes or tertiary amine catalysts or mixtures of these can be used but tertiary amines are preferred.
A particularly useful amine is triethylene diamine. The preferred catalyst usage is 0.01-0.3 % by weight on the combined diisocyanate and polyester weight.
As examples of plasticisers which may be present, there may be mentioned the phthalate and phosphate esters of C4-C,, alcohols well known in the plasticiser art.
Additionally halogenated hydrocarbons known as secondary plasticisers in the art may be used. The preferred class, where fire-retardant properties are desirable, include the phosphates, in particular halogen-containing phosphates, and the halogenated hydrocarbons. Typical phosphates are tricresyl phosphate, trixylyl phosphate and tris(2-chloroethyl)phosphate. Commercially available chlorinated paraffin waxes typify the halogenated hydrocarbons. Typical phthalates are dibutyl phthalate, di-2-ethylhexyl phthalate, and the esters of phthalic anhydride with the commercially available mixed alcohols such as iso octanol, nonanol, isodecanol and tridecanol. A particularly preferred plasticiser is a phthalate made from a mixture of aliphatic and araliphatic alcohols. Typically this is butyl benzyl phthalate. Quantities of plasticiser to be used preferably lie in the range 5-30% by weight of the combined polyester and isocyanate weights.
In addition to use as a tyre-filling composition as mentioned above, the new colmpositions can be used for the manufacture of newspaper, metallurgy or printers' rollers, thick sheet, seals, shock absorbers and as encapsulating materials.
The invention is illustrated, but not limited by the following Examples in which parts are by weight.
Example 1.
Part A 100 parts of polyester (obtained as described below)
40 parts of butyl benzyl phthalate
0.2 part of 1,4-diaza-[2,2,2]-bicyclo-octane Part B 20 parts of isocyanate composition, described below
27 parts of butyl benzyl phthalate
Parts A and B (both at 250C) were mixed together for 2 minutes, degassed for 5 minutes and then cast into an open steel mould at 250C. This mix had a pot-life (for 250 gm mass) of 90 minutes. The castings cured to 32 Shore A hardness over 7 days at ambient temperature. The cure of some castings was accelerated by heating them for 1 hour at 65"C when the elastomers reached 33 Shore A hardness. The physical properties of the cured cast elastomers were as follows: Hardness 33 Shore A
Tangent Modulus at 100% Elongation 0.2 MN/m2
Tensile Strength k 1.0 MN/m2
Elongation at Break 300%
Tear Strength Resilience at 25"C 60% N/2.3 mm Compression Set (25% Compression, 60% 22 hours at 700C) 5.4% The polyester used in the above Example was obtained by condensation of 2620 parts of ethylene glycol, 1370 parts of 1,2-propylene glycol, 143 parts of trimethylol propane and 7750 parts of adipic acid to give a polyester having an acid value between 1 and 2 mg KOH/g, hydroxyl value 64 mg KOH/g a viscosity of 203 centistokes at 100"C and 0.113 branch points per 1000 units of molecular weight.
The isocyanate composition used consisted of a mixture of 40 parts of a mixture of methylene bridged poly(phenylisocyanates) containing 48.4 % by weight of 4,4'and 3.8% by weight of 2,4'-diisocyanato diphenylmethanes and 60 parts of the reaction product of 56.5 parts of a mixture of 0.833 moles of 4,4'-, 0.006 moles of 2,2'and 0.161 moles of 2,4-diisocyanatodiphenyl methanes with 3.5 parts of a 1:1:1 molar mixture of 1,2+propylene, 1,3-butylene and diethylene glycols.
Example 2.
Part A 100 parts of polyester (as used in Example 1)
40 parts of butyl benzyl phthalate
0.5 parts of 1,4- diaza- [2,2,2]-bicyclo-octane Part B 19 parts of isocyanate composition (as described below)
28 parts of butyl benzyl phthalate
Parts A and B (both at 25 0C) were mixed together for 2 minutes, degassed for 5 minutes and then cast into an open steel mould at 25 0C. This mix had a pot-life for 250 gm mass of 15 minutes. The castings cured to 34 Shore A hardness over 7 days at ambient temperature.
The isocyanate composition used is a mixture of equal parts by weight of
(a) the reaction product of 100 parts of 4,4'-diisocyanatodiphenylmethane and
9.19 parts of a 1:1:1 molar mixture of 1,2-propylene, 1,3-butylene and
diethylene glycols.
(b) the reaction product obtained by heating 4,4'-diisocyanatodiphenylmethane
in the presence of luphenyl-3-methyl-2-phospholene oxide until the NCO
content has dropped to 29% by weight.
WHAT WE CLAIM IS:- 1. Solid polyurethane compositions comprising a plasticiser and the reaction product of a polyester having a viscosity within the range 100 to 250 centistokes at 100"C, a hydroxyl value within the range 50 to 100 mg KOH/g and an acid value less than 2.0 mg KOH/g, which has been formed by condensing adipic acid with a molecular excess of a mixture of polyols consisting of ethylene and propylene glycols in a molar ratio of from 65 : 35 to 75: 25 together with a polyol having 3 or more hydroxyl groups and a molecular weight below 500, the amount of the latter being such as to give up to 0.2 branch point per 1000 units of molecular weight of the polyester, and a composition of diphenylmethane diisocyanates or reaction products thereof which is liquid at ambient temperatures.
2. Solid polyurethane compositions as claimed in claim 1 wherein the liquid diphenyl methane diisocyanate composition used is a mixture of approximately equal parts by weight of
(a) mixtures of poly(isocyanatophenyl)methylene compounds obtained by reacting aniline with formaldehyde and subjecting the reaction product to the action of phosgene; and (b) the urethane made by reacting approximately 90 parts by weight of a mixture of 70-95 parts by weight of 4,4'-diisocyanatodiphenyl methane and 5-30 parts by weight of 2,4'-diisocyanatodiphenylmethane with approximately 10 parts by weight of a mixture of diethylene, 1,3ibutylene and 1,2tpropylene glycols in equimolar proportions.
3. Solid polyurethane compositions as claimed in claim 1 wherein the liquid diphenyl methane diisocyanate composition used is a mixture of approximately equal parts by weight of
(a) the urethane made by reacting approximately 90 parts by weight of 4,4'diisocyanatodiphenylmethane with approximately 10 parts by weight of a mixture of diethylene, 1,3wbutylene and 1,2-propylene glycols in equimolar proportions; and
(b) the uretonimine made by heating 4,4'-diisocyanatodiphenylmethane in the presence of l-phenyl-3-methyl-2-phospholene oxide until the isocyanate content is approximately 29% by weight.
4. Solid polyurethane compositions as claimed in any preceding claim wherein the plasticiser is a phthalate or phosphate ester of a C4-C13 alcohol or a halogenated hydrocarbon.
5. Solid polyurethane compositions as claimed in claim 4 wherein the plasticiser is a phthalate mixed ester of aliphatic and araliphatic alcohols.
**WARNING** end of DESC field may overlap start of CLMS **.
Claims (9)
- **WARNING** start of CLMS field may overlap end of DESC **.The polyester used in the above Example was obtained by condensation of 2620 parts of ethylene glycol, 1370 parts of 1,2-propylene glycol, 143 parts of trimethylol propane and 7750 parts of adipic acid to give a polyester having an acid value between 1 and 2 mg KOH/g, hydroxyl value 64 mg KOH/g a viscosity of 203 centistokes at 100"C and 0.113 branch points per 1000 units of molecular weight.The isocyanate composition used consisted of a mixture of 40 parts of a mixture of methylene bridged poly(phenylisocyanates) containing 48.4 % by weight of 4,4'and 3.8% by weight of 2,4'-diisocyanato diphenylmethanes and 60 parts of the reaction product of 56.5 parts of a mixture of 0.833 moles of 4,4'-, 0.006 moles of 2,2'and 0.161 moles of 2,4-diisocyanatodiphenyl methanes with 3.5 parts of a 1:1:1 molar mixture of 1,2+propylene, 1,3-butylene and diethylene glycols.Example 2.Part A 100 parts of polyester (as used in Example 1)40 parts of butyl benzyl phthalate 0.5 parts of 1,4- diaza- [2,2,2]-bicyclo-octane Part B 19 parts of isocyanate composition (as described below)28 parts of butyl benzyl phthalate Parts A and B (both at 25 0C) were mixed together for 2 minutes, degassed for 5 minutes and then cast into an open steel mould at 25 0C. This mix had a pot-life for 250 gm mass of 15 minutes. The castings cured to 34 Shore A hardness over 7 days at ambient temperature.The isocyanate composition used is a mixture of equal parts by weight of (a) the reaction product of 100 parts of 4,4'-diisocyanatodiphenylmethane and 9.19 parts of a 1:1:1 molar mixture of 1,2-propylene, 1,3-butylene and diethylene glycols.(b) the reaction product obtained by heating 4,4'-diisocyanatodiphenylmethane in the presence of luphenyl-3-methyl-2-phospholene oxide until the NCO content has dropped to 29% by weight.WHAT WE CLAIM IS:- 1. Solid polyurethane compositions comprising a plasticiser and the reaction product of a polyester having a viscosity within the range 100 to 250 centistokes at 100"C, a hydroxyl value within the range 50 to 100 mg KOH/g and an acid value less than 2.0 mg KOH/g, which has been formed by condensing adipic acid with a molecular excess of a mixture of polyols consisting of ethylene and propylene glycols in a molar ratio of from 65 : 35 to 75: 25 together with a polyol having 3 or more hydroxyl groups and a molecular weight below 500, the amount of the latter being such as to give up to 0.2 branch point per 1000 units of molecular weight of the polyester, and a composition of diphenylmethane diisocyanates or reaction products thereof which is liquid at ambient temperatures.
- 2. Solid polyurethane compositions as claimed in claim 1 wherein the liquid diphenyl methane diisocyanate composition used is a mixture of approximately equal parts by weight of (a) mixtures of poly(isocyanatophenyl)methylene compounds obtained by reacting aniline with formaldehyde and subjecting the reaction product to the action of phosgene; and (b) the urethane made by reacting approximately 90 parts by weight of a mixture of 70-95 parts by weight of 4,4'-diisocyanatodiphenyl methane and 5-30 parts by weight of 2,4'-diisocyanatodiphenylmethane with approximately 10 parts by weight of a mixture of diethylene, 1,3ibutylene and 1,2tpropylene glycols in equimolar proportions.
- 3. Solid polyurethane compositions as claimed in claim 1 wherein the liquid diphenyl methane diisocyanate composition used is a mixture of approximately equal parts by weight of (a) the urethane made by reacting approximately 90 parts by weight of 4,4'diisocyanatodiphenylmethane with approximately 10 parts by weight of a mixture of diethylene, 1,3wbutylene and 1,2-propylene glycols in equimolar proportions; and (b) the uretonimine made by heating 4,4'-diisocyanatodiphenylmethane in the presence of l-phenyl-3-methyl-2-phospholene oxide until the isocyanate content is approximately 29% by weight.
- 4. Solid polyurethane compositions as claimed in any preceding claim wherein the plasticiser is a phthalate or phosphate ester of a C4-C13 alcohol or a halogenated hydrocarbon.
- 5. Solid polyurethane compositions as claimed in claim 4 wherein the plasticiser is a phthalate mixed ester of aliphatic and araliphatic alcohols.
- 6. Solid polyurethane compositions as claimed in claim 5 wherein the plasticiseris butyl benzyl phthalate.
- 7. Solid polyurethane compositions as claimed in any preceding claim wherein the amount of plasticiser used lies in the range 5 to 50or, by weight of the combined weights of polyester and isocyanate composition.
- 8. Solid polyurethane compositions as claimed in claim 1, substantially as herein described with reference to any of the Examples.
- 9. The use of a solid polyurethane composition as claimed in any preceding claim as a tyre-filling composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB41032/76A GB1584780A (en) | 1977-12-07 | 1977-12-07 | Polyurethane compositions |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB41032/76A GB1584780A (en) | 1977-12-07 | 1977-12-07 | Polyurethane compositions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB1584780A true GB1584780A (en) | 1981-02-18 |
Family
ID=10417800
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB41032/76A Expired GB1584780A (en) | 1977-12-07 | 1977-12-07 | Polyurethane compositions |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB1584780A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0134455A1 (en) * | 1983-06-30 | 1985-03-20 | BASF Aktiengesellschaft | Use of thermoplastic polyurethanes containing plasticizers for the manufacture of foils and moulded articles |
| EP0193346A2 (en) * | 1985-02-22 | 1986-09-03 | Genesco Inc. | Process for forming a hot melt composition |
-
1977
- 1977-12-07 GB GB41032/76A patent/GB1584780A/en not_active Expired
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0134455A1 (en) * | 1983-06-30 | 1985-03-20 | BASF Aktiengesellschaft | Use of thermoplastic polyurethanes containing plasticizers for the manufacture of foils and moulded articles |
| EP0193346A2 (en) * | 1985-02-22 | 1986-09-03 | Genesco Inc. | Process for forming a hot melt composition |
| EP0193346A3 (en) * | 1985-02-22 | 1988-01-07 | Genesco Inc. | Hot melt composition and process for forming the same |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR0157982B1 (en) | Thermoplastic polyurethanes | |
| US3591561A (en) | Process of production of polyurethane elastomer from a mixture of a lactone polyester polyol and a low molecular weight aliphatic diol | |
| US5177118A (en) | Manufacture of fire retardant foams | |
| WO2013100633A1 (en) | Method for the preparation of microcellular polyurethane elastomers | |
| US3012991A (en) | Chemical reactions | |
| US4448905A (en) | Alcohol substituted amides as chain extenders for polyurethanes | |
| US4235977A (en) | Cross-linked polyurethane elastomers and microcellular foams | |
| EP0031650B1 (en) | Process for preparing liquid polyisocyanate compositions, and their use | |
| US4670068A (en) | Polyfunctional isocyanate crosslinking agents for propellant binders | |
| US3471445A (en) | Curable urethane compositions | |
| EP0031207A1 (en) | Process for preparing liquid polyisocyanate compositions, and their use | |
| EP0422811B1 (en) | Process for producing a flexible polyurethane foam | |
| EP0398304B1 (en) | Flexible polyurethane foams and process for preparing them | |
| US4386032A (en) | Liquid polyisocyanate compositions | |
| US3014894A (en) | Polyurethane plastics | |
| GB1584780A (en) | Polyurethane compositions | |
| US3681288A (en) | Storage-stable polyurethane prepolymers containing malonitrile | |
| US5817734A (en) | Prepolymers with low TDI content | |
| US3661862A (en) | Process for the preparation of polyurethane mastics | |
| KR100407028B1 (en) | Cellular polyurethane elastomer | |
| EP0486034B1 (en) | Flexible polyurethane foams and process for preparing them | |
| US4115301A (en) | Cross-linker for flexible and semi-flexible polyurethane foams | |
| JP3476001B2 (en) | Flame retardant polyurethane resin composition | |
| EP0594292B1 (en) | Polyols and their use for the manufacture of polyurethanes. | |
| JPS6315935B2 (en) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PS | Patent sealed | ||
| 732 | Registration of transactions, instruments or events in the register (sect. 32/1977) | ||
| PCNP | Patent ceased through non-payment of renewal fee |