GB2109803A - High molecular weight polyether polyols - Google Patents
High molecular weight polyether polyols Download PDFInfo
- Publication number
- GB2109803A GB2109803A GB08133316A GB8133316A GB2109803A GB 2109803 A GB2109803 A GB 2109803A GB 08133316 A GB08133316 A GB 08133316A GB 8133316 A GB8133316 A GB 8133316A GB 2109803 A GB2109803 A GB 2109803A
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- Prior art keywords
- molecular weight
- polyol
- high molecular
- diphenylmethane diisocyanate
- polyether polyols
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- 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
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5096—Polyethers having heteroatoms other than oxygen containing silicon
-
- 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
- C08G18/28—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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
- C08G18/4247—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids
- C08G18/4252—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids derived from polyols containing polyether groups and polycarboxylic acids
-
- 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
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
- C08G18/5036—Polyethers having heteroatoms other than oxygen having nitrogen containing -N-C=O groups
- C08G18/5045—Polyethers having heteroatoms other than oxygen having nitrogen containing -N-C=O groups containing urethane 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
- 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
- C08G2110/0041—Foam properties having specified density
- C08G2110/0058—≥50 and <150kg/m3
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- 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
These polyols are obtained by reacting a polyoxyalkylene polyol with a polyfunctional hydroxyl-reactive compound, typically a diisocyanate, in the molar ratio of from 4:3 to 4:1. The polyoxyalkylene polyol has a molecular weight greater than 5000 and up to 10,000 and contains propylene oxide and optionally ethylene oxide residues, the latter in amounts of from 0 to 40%. Diphenylmethane diisocyanate-based high resilience polyurethane foams formed therefrom exhibit a more latex-like feel and improved tear strength and elastomers formed therefrom are generally stronger.
Description
SPECIFICATION
High molecular weight polyether polyols
This invention relates to novel polyether polyols and their use in the manufacture of polyurethane foams and elastomers.
According to the invention, we provide high molecular weight polyether polyols which are obtained by reacting a polyoxyalkylene polyol with a polyfunctional, especially a difunctional, hydroxylreactive compound in the molar ratiooffrom 4:3 to 4:1, especially from 4:3 to 2:1,the polyoxyalkylene polyol having a molecular weight greater than 5000 and up to 10,000 and containing propylene oxide and optionally ethylene oxide residues, the latter in an amount of from 0 to 40%, preferably 10% to 25%, by weight of the total alkylene oxide residues present.
The polyoxyalkylene polyol may be a polyoxypropylene polyol or a poly(oxypropyleneoxyethylene)polyol or a mixture thereof. Such polyols and methods for their preparation have been fully described in the relevant literature, many of the polyols being commercially available. The poly(oxypropylene-oxyethylene)polyols include ethylene oxide-tipped polyoxypropyiene polyols and other random or block copolymers obtained by reacting ethylene and propylene oxides with active hydrogen-containing initiators. Normally they will be triols having a nominal hydroxyl equivalent weight in the range of from 1 700 to 3300 and hydroxyl numbers of from 34 to 17. Triols which we have found to be particularly useful are those, especially ethylene oxide tipped oxypropylated glycerols, having a nominal hydroxyl equivalent weight of about 2000 and a hydroxyl number of about 28.
The purpose of the polyfunctional hydroxyl-reactive compound is to join together molecules of the polyoxyalkylene polyol. It may have a functionality of two, three or four. Preferably it has a functionality of two. Thus in the preferred high molecular weight polyols one, two or three molecules of the compound join together two, three or four molecules, respectively of the polyoxyalkylene polyol according to the molar ratio in which they are reacted. The polyfunctional hydroxyl-reactive compound may be any such compound which will fulfil this purpose. For example, it may be a polybasic acid or polyisocyanate which will join together molecules of the polyoxyalkylene polyol by way of ester or urethane linkages, respectively.Suitable polybasic acids include those aliphatic dicarboxylic acids used in the manufacture of polyester polyols, for example succinic, glutaric, adipic, suberic, azelaic and sebacic acids and mixtures thereof. Polyisocyanates which may be used include any of those commonly used in the manufacture of polyurethane products and, in particular, diisocyanates such as tolylene diisocyanates, especially technical mixtures of 2,4- and 2,6-tolylene diisocyanates in the ratio of, for instance, 80:20 and 65:35, and diphenylmethane diisocyanates as hereinafter described.
Other suitable polyfunctional hydroxyl-reactive compounds include acid chlorides and siloxanes containing at least two hydrogen atoms bonded directly to a silicon atom.
The preferred high molecular weight polyether polyols of the invention are believed to be polyether polyols having a molecular weight of from 10,000 to 40,000, preferably 12,000 to 18,000, and a formula: Y+XY)x in which X is the residue of a difunctional hydroxyl-reactive organic compound, Y is Z[(C2H40)m(C3H60)n]y in which the alkylene oxide residues are ordered or randomly arranged and Z is the residue of an initiator having y active hydrogen atoms, and x, y, m and n are integers or m is zero, x being 1,2 or 3; y being 2, 3 or 4, preferably 3; and m/n being 0 to 0.9, preferably 0.14 to 0.44. These polyols have hydroxyl numbers of from 24 to 8, preferably from 22 to 1 5.
In particular we would mention high molecular weight polyols obtained by reacting an ethylene oxide tipped oxypropylated glycerol having a nominal hydroxy equivalent weight of about 2000 and a hydroxyl number of about 28 with a difunctional hydroxyl-reactive organic compound in the molar ratio of 2:1.
The high molecular weight polyols are conveniently prepared by adding gradually the polyfunctional hydroxyl-reactive compound to the polyalkylene polyol while stirring at an elevated temperature, for example at 80 to 900 C. A suitable catalyst may be used to speed reaction of enable the reaction to be carried out at a lower temperature. After adding the polyfunctional hydroxyl-reactive compound stirring is continued until reaction is complete.
We have found that the high molecular weight polyols of the present invention are of particular value in the manufacture of high resilience, cold-cure urethane foams and of elastomers derived from a diphenylmethane diisocyanate (MDI) based polyisocyanate.
Currently high resilience urethane foams are made with polyethers having a molecular weight of about 5000 to 6000. By using our high molecular weight polyols, MDI-based polyurethane foams can be obtained which have a more latex-like feel. This improved "feel" can be quantified in terms of the foam's SAG factor, i.e. the ratio of the loads required to produce deflections of the foam of 65% and 25%. This is of importance when the foams are to be used for seating and other cushioning applications in which latex-like properties are generally desirable. In addition, these high resilience foams show advantage in respect of improved tear strength.
Thus according to a further aspect of our invention we provide a method of making polyurethane foams which comprises mixing together a high molecular weight polyol, as hereinbefore defined, a diphenylmethane diisocyanate-based polyisocyanate or a prepolymer thereof, water and a catalyst for foam formation, optionally in the presence of other conventional polyurethane foam ingredients.
In yet another aspect of our invention we provide a method of making polyurethane elastomers which comprises mixing together a high molecular weight polyol, as hereinbefore defined, a diphenylmethane diisocyanate-based polyisocyanate or a prepolymer thereof, a chain extending agent and a catalyst, optionally in the presence of a low-boiling solvent as blowing agent and other conventional elastomer ingredients.
The invention also includes the polyurethane foams and elastomers so obtained. Elastomers derived from the high molecular weight polyols of our invention exhibit improved strength generally.
In using the phrase "a diphenylmethane diisocyanate-based polyisocyanate" we include pure 4,4'diphenylmethane diisocyanate as well as mixtures of this isomer with the 2,4'-isomer. Uretonimine modified pure diphenylmethane diisocyanate and mixtures thereof with, for example, a prepolymer of diphenylmethane diisocyanate and a monomeric polyol or mixture of monomeric polyols, are particularly usefui in preparing the elastomers of the invention. We also include the so-called crude diphenylmethane diisocyanate compositions, particularly those containing from 30 to 95%, preferably from 40 to 80%, by weight of diphenylmethane diisocyanates, the remainder being largely polymethylene polyphenyl polyisocyanates of functionality greater than two. Such compositions may be obtained by phosgenation of crude diaminodiphenylmethane as is fully described in the relevant literature.Further, we include mixtures of these diphenylmethane diisocyanates with other polyisocyanates, such as tolylene diisocyanates, and the diphenylmethane diisocyanates when modified, for example, by reaction with monomeric polyols.
Prepolymers of the diphenylmethane diisocyanate-based polyisocyanate and their methods of preparation are well known. Any such prepolymer may be used in the present invention. In particular, we would mention propolymers 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 diphenylmethane diisocyanate-based polyisocyanate. Also the prepolymer may be blended with a different diphenylmethane diisocyanate. For example, a prepolymer made by reacting a polyoxyalkylene diol or triol with a substantially pure diphenylmethane diisocyanate can be blended with a crude diphenylmethane diisocyanate.A further possibility is to blend the prepolymer with another prepolymer made by reacting a diphenylmethane diisocyanate with another polyol, for example another polyoxyalkylene polyol or a monomeric polyol such as a glycol or a mixture of monomeric polyols.
In general, the composition of a foam-forming reaction mixture should be such that the ratio of isocyanate groups to active hydrogen atoms is within the range of 0.7:1 to 1.2:1 and especially within the range of 0.8:1 to 1.1:1.
The chain extending agent used in making the elastomers of the invention will usually be a glycol or diamine. Preferably it is a glycol. Suitable glycols include ethylene glycol, I ,4-, 1 ,3- and 2,3-butane diols, diethylene glycol and dipropylene glycol. The amount used will normally be approximately equal to that required to react with the isocyanate groups of the MDI-based polyisocyanate not required for reaction with the high molecular weight polyol.
in making the foams of the invention, water is used as a blowing agent in an appropriate amount to give a foam of the desired density. It is appropriate to use from 1.0 to 5.5%, especially from 1.5 to 4.0%, by weight of water based on the weight of the high molecular weight polyol. In making the elastomers of the invention, a low-boiling solvent, such as a fluorocarbon, may be used to reduce density. Such a blowing agent may also be used in addition to the water used in making the foams.
Catalysts which may be used in have been fully described in the relevant literature and include tertiary amines and organic metal compounds, particularly tin compounds. Examples of suitable tertiary amines include N,N-dimethylcyclohexylamine, N,N-dimethylbenzylamine, N,N-dimethylethanolamine and 1 ,4-diazabicyclo[2.2.2]octane. Organic metal compounds which may be used as catalysts include stennous octoate and dibutyltin dilaurate. It is often advantageous to use a mixture of catalysts, for example a mixture of amines or an amine and a tin compound.
Other conventional polyurethane foam ingredients include surfactants, for example siloxaneoxyalkylene copolymers, fillers, fire-retardants, pigments, dyes and additional blowing agents.
The components of both the foam-forming and elastomer-forming reaction mixtures may be mixed together in any convenient manner, for example by using any of the mixing equipment described in the relevant literature for the purpose. If desired, mutually inert individual components may be preheated so as to reduce the number of component streams requiring to be brought together in the final mixing step. It is often convenient to have a two-stream system whereby one stream comprises the polyisocyanate and the second comprises all the other components of the reaction mixture.
If desired, the density of the foams of the invention can be modified by overpacking, that is to say foaming the reaction mixture in a closed mould having a volume less than that which would be occupied by the resultant foam if the reaction mixture were allowed to rise freely.
The invention is illustrated but not limited by the following Examples in which all parts and percentages are by weight.
EXAMPLE 1
A high molecular weight polyol having a hydroxyl number of 21 is prepared by adding gradually over 20 minutes 52 parts of an isomeric mixture of diphenylmethane diisocyanate containing approximately 80% 4,4'- and 20% 2,4'- and a trace of 2,2'-isomer to 2500 parts of an ethylene oxide tipped oxypropylated glycerol having an oxyethylene content of 16% and a molecular weight of 6000 (hydroxyl number 28). The reaction mixture is stirred throughout the addition and for 120 minutes afterwards and the temperature maintained between 80 and 900 C.
A polyol blend is prepared by mixing together 100 parts of the high molecular weight polyol prepared as described above, 3.0 parts of water, 10 parts of trichlorofluoromethane, 1.0 part of a 33% solution of triethylene diamine in dipropylene glycol, 0.1 part of a 70% solution of bis(2dimethylaminoethyl)ether in dipropylene glycol and 1.0 part of Silicone Oil B41 13.
This is called Polyol Blend A.
By way of comparison, a polyol blend is prepared in the same way as Polyol Blend A except that 100 parts of the ethylene oxide tipped oxypropylated glycerol used to prepare the high molecular weight polyol is used instead of the 1 00 parts of the high molecular weight polyol itself. This is called
Polyol Blend B.
Foams are made from each of Polyol Blends A and B by mixing 100 parts of the blends with 58.4 and 61.2 parts, respectively, of a diphenylmethane diisocyanate-based polyisocyanate obtained by blending 27 parts of a crude diphenylmethane diisocyanate containing approximately 50% of diphenylmethane diisocyanate isomers with 73 parts of a prepolymer which is the reaction product of an 80/20 mixture of diphenylmethane-4,4'- and 2,4'-diisocyanates and polypropylene glycol of molecular weight 2000. The Isocyanate Index is 90.
The foams so obtained have the following properties:
Foam made from Foam made from
Property Polyol Blend A Polyol Blend B
Density (kg/m3) 43 41
Tear strength (N/m) 280 240
The foam made from Polyol Blend A has a more latex-like feel than that made from Polyol Blend B.
EXAMPLE 2
An elastomer is prepared by mixing together the following ingredients:
Parts
The high molecular weight polyol prepared as described in Example 1 100
Ethylene glycol 12
33% solution of triethylene diamine in dipropylene glycol 0.45
FOMREZ UL29 (a tin catalyst) 0.05
An isocyanate based on a prepolymer of pure MDI and mixed glycols 71.3
and a uretonimine modified pure MDI
The Isocyanate Index is 1 to. The elastomer is designated "Elastomer I".
By way of comparison, an elastomer, designated "Elastomer II", is prepared in the same way as
Elastomer I except that 100 parts of the ethylene oxide tipped oxypropylated glycerol used to prepare the high molecular weight polyol is used instead of the 100 parts of the high molecular weight polyol itself.
The elastomers have the following properties:
Property Elastomer I Elastomer II Density (kg/m3) 1131 1154
Hardness (Shore D) 46 45
Tensile strength (mN/m2 1 5.6 13.4
Tensile strength (mN/m2) 1 5.6 13.4
Elongation (%) 200 160
Flexural Modulus (nM/m2) 103 92
EXAMPLE 3
The procedure of Example 2 is repeated except that the amount of ethylene glycol used is reduced to 6 parts and the amount of isocyanate correspondingly reduced to 40 parts to maintain an Isocyanate
Index of 1 00. In this Example the elastomer obtained from the high molecular weight polyol is designated "Elastomer Ill" and the polyol obtained from the lower molecular weight polyol for comparative purposes is designated "Elastomer IV".
The elastomers have the following properties:
Property Elastomer III Elastomer IV
Density (kg/m3) 950 870
Hardness (Shore D) 23 19
Tensile strength (mN/m2) 4.8 3.3
Elongation (%) 160 120
Tear strength (kN/m) 23 1 7 Tear modulus (mPa) 2.1 1.8
RESULTS
It will be seen from Example 1 that a foam made from a high molecular weight polyol of the invention has advantages in respect of tear strength and a more latex-like feel over an equivalent foam made from a lower molecular weight poiyol outside the scope of the invention.
Examples 2 and 3 show that generally stronger elastomers are obtained by using a high molecular weight polyol of the invention.
Claims (6)
1. High molecular weight polyether polyols which are obtained by reacting a polyoxyalkylene polyol with a polyfunctional hydroxyl-reactive compound in the molar ratio of from 4:3 to 4:1, the polyoxyalkylene polyol having a molecular weight greater than 5000 and up to 10,000 and containing propylene oxide and optionally ethylene oxide residues, the latter in an amount of from 0 to 40% by weight of the total alkylene oxide residues present.
2. Polyether polyols having a molecular weight of from 10,000 to 40,000 and a formula: Y+XY)x in which X is the residue of a difunctional hydroxyl-reactive organic compound, Y is Z[(C2H4O)m(CaH6O)njy in which the alkylene oxide residues are ordered or randomly arranged and Z is the residue of an initiator having y active hydrogen atoms, and x, y, m and n are integers or m is zero, x being 1,2 or 3; y being 2, 3 or 4; and m/n being 0 to 0.9.
3. A method of making polyurethane foams which comprises mixing together a polyol, as claimed in claims 1 or 2, a diphenylmethane diisocyanate-based polyisocyanate or a prepolymer thereof, water and a catalyst for foam formation, optionally in the presence of other conventional polyurethane foam ingredients.
4. A method of making polyurethane elastomers which comprises mixing together a high molecular weight polyol, as claimed in claims 1 or 2, a diphenylmethane diisocyanate-based polyisocyanate or a prepolymer thereof, a chain extending agent and a catalyst, optionally in the presence of a low-boiling solvent as blowing agent and other conventional elastomer ingredients.
5. Polyurethane foams whenever made by a method according to claim 3.
6. Polyurethane elastomers whenever made by a method according to claim 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB08133316A GB2109803A (en) | 1981-02-26 | 1981-11-04 | High molecular weight polyether polyols |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8106120A GB2093852A (en) | 1981-02-26 | 1981-02-26 | Polymeric materials |
| GB8114007 | 1981-05-07 | ||
| GB08133316A GB2109803A (en) | 1981-02-26 | 1981-11-04 | High molecular weight polyether polyols |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB2109803A true GB2109803A (en) | 1983-06-08 |
Family
ID=27261126
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08133316A Withdrawn GB2109803A (en) | 1981-02-26 | 1981-11-04 | High molecular weight polyether polyols |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2109803A (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2139238A (en) * | 1983-05-05 | 1984-11-07 | Mobay Chemical Corp | Flexible polyurethane foams |
| GB2249793A (en) * | 1990-11-16 | 1992-05-20 | Basf Corp | Integral-skin rigid urethane foam |
| EP0509271A2 (en) * | 1991-04-15 | 1992-10-21 | BASF Aktiengesellschaft | Siloxi-Polytetrahydrofuran |
| EP0555742A2 (en) * | 1992-02-11 | 1993-08-18 | BASF Aktiengesellschaft | Process for the preparation of fluorchlorhydrocarbon-free flexible polyurethane foams using urethane groups containing polyisocyanate blends based on diphenylmethane-diisocyanate as well as likewise modified polyisocyanate blends |
| EP0676434A1 (en) * | 1994-04-06 | 1995-10-11 | BASF Aktiengesellschaft | Process for the preparation of highly elastic, flexible polyurethane foams devoid of fluorochlorohydrocarbons and urethane groups modified polyisocyanate mixtures based on diphenylmethane diisocyanate suitable therefor |
| EP0745627A2 (en) * | 1995-05-29 | 1996-12-04 | Dow Mitsubishi Chemical Ltd. | A process for preparing open-cellular polyurethane modified polyisocyanurate foam |
| EP1127685A2 (en) * | 2000-02-21 | 2001-08-29 | Benecke-Kaliko AG | Pressure- and vacuum-deformable grained composite sheet, process for making it and its use |
| US8901187B1 (en) | 2008-12-19 | 2014-12-02 | Hickory Springs Manufacturing Company | High resilience flexible polyurethane foam using MDI |
| US8906975B1 (en) | 2009-02-09 | 2014-12-09 | Hickory Springs Manufacturing Company | Conventional flexible polyurethane foam using MDI |
| CN110283293A (en) * | 2019-06-24 | 2019-09-27 | 红宝丽集团股份有限公司 | The imitative latex polyurethane flexible foam prepared using terminal isocyanate group performed polymer |
| US20210292463A1 (en) * | 2020-03-18 | 2021-09-23 | Northwestern University | Dynamic polyurethane networks with post-recycling retention of cross-linking densities and mechanical properties |
-
1981
- 1981-11-04 GB GB08133316A patent/GB2109803A/en not_active Withdrawn
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2139238A (en) * | 1983-05-05 | 1984-11-07 | Mobay Chemical Corp | Flexible polyurethane foams |
| GB2249793A (en) * | 1990-11-16 | 1992-05-20 | Basf Corp | Integral-skin rigid urethane foam |
| EP0509271A2 (en) * | 1991-04-15 | 1992-10-21 | BASF Aktiengesellschaft | Siloxi-Polytetrahydrofuran |
| EP0509271A3 (en) * | 1991-04-15 | 1992-11-25 | Basf Aktiengesellschaft | Siloxi-polytetrahydrofuran |
| EP0555742A2 (en) * | 1992-02-11 | 1993-08-18 | BASF Aktiengesellschaft | Process for the preparation of fluorchlorhydrocarbon-free flexible polyurethane foams using urethane groups containing polyisocyanate blends based on diphenylmethane-diisocyanate as well as likewise modified polyisocyanate blends |
| EP0555742A3 (en) * | 1992-02-11 | 1993-10-27 | Basf Ag | Process for the preparation of fluorchlorhydrocarbon-free flexible polyurethane foams using urethane groups containing polyisocyanate blends based on diphenylmethane-diisocyanate as well as likewise modified polyisocyanate blends |
| US5494941A (en) * | 1992-02-11 | 1996-02-27 | Basf Aktiengesellschaft | Preparation of chlorofluorocarbon-free flexible polyurethane foams using diphenylmethane diisocyanate-based polyisocyanate mixtures containing urethane groups, and modified polyisocyanate mixtures of the type |
| EP0676434A1 (en) * | 1994-04-06 | 1995-10-11 | BASF Aktiengesellschaft | Process for the preparation of highly elastic, flexible polyurethane foams devoid of fluorochlorohydrocarbons and urethane groups modified polyisocyanate mixtures based on diphenylmethane diisocyanate suitable therefor |
| EP0745627A2 (en) * | 1995-05-29 | 1996-12-04 | Dow Mitsubishi Chemical Ltd. | A process for preparing open-cellular polyurethane modified polyisocyanurate foam |
| EP0745627A3 (en) * | 1995-05-29 | 1997-07-16 | Dow Mitsubishi Chemical Ltd | A process for preparing open-cellular polyurethane modified polyisocyanurate foam |
| CN1082063C (en) * | 1995-05-29 | 2002-04-03 | 三菱化成陶氏株式会社 | Process for preparing open-cellular polyurethane modified polyisocyanurate foam |
| EP1127685A2 (en) * | 2000-02-21 | 2001-08-29 | Benecke-Kaliko AG | Pressure- and vacuum-deformable grained composite sheet, process for making it and its use |
| EP1127685A3 (en) * | 2000-02-21 | 2002-05-02 | Benecke-Kaliko AG | Pressure- and vacuum-deformable grained composite sheet, process for making it and its use |
| US8901187B1 (en) | 2008-12-19 | 2014-12-02 | Hickory Springs Manufacturing Company | High resilience flexible polyurethane foam using MDI |
| US8906975B1 (en) | 2009-02-09 | 2014-12-09 | Hickory Springs Manufacturing Company | Conventional flexible polyurethane foam using MDI |
| CN110283293A (en) * | 2019-06-24 | 2019-09-27 | 红宝丽集团股份有限公司 | The imitative latex polyurethane flexible foam prepared using terminal isocyanate group performed polymer |
| CN110283293B (en) * | 2019-06-24 | 2021-12-24 | 红宝丽集团股份有限公司 | Latex-like polyurethane soft foam prepared from isocyanate-terminated prepolymer |
| US20210292463A1 (en) * | 2020-03-18 | 2021-09-23 | Northwestern University | Dynamic polyurethane networks with post-recycling retention of cross-linking densities and mechanical properties |
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