CA1219987A - Process for the preparation of cellular and non- cellular polyurethanes - Google Patents
Process for the preparation of cellular and non- cellular polyurethanesInfo
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- CA1219987A CA1219987A CA000452232A CA452232A CA1219987A CA 1219987 A CA1219987 A CA 1219987A CA 000452232 A CA000452232 A CA 000452232A CA 452232 A CA452232 A CA 452232A CA 1219987 A CA1219987 A CA 1219987A
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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
- C08G18/42—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
-
- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4291—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from polyester forming components containing monoepoxy compounds
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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
- C08G18/4887—Polyethers containing carboxylic ester groups derived from carboxylic acids other than acids of higher fatty oils or other than resin acids
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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
- C08G2110/00—Foam properties
- C08G2110/0008—Foam properties flexible
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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
- C08G2110/00—Foam properties
- C08G2110/0041—Foam properties having specified density
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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
- C08G2110/00—Foam properties
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
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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
- C08G2410/00—Soles
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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
PROCESS FOR THE PREPARATION OF
CELLULAR OR NON-CELLULAR POLYURETHANES
Abstract of the Disclosure The invention relates to a process for the preparation of cellular or non-cellular polyurethanes through the reaction of organic polyisocyanates with a polyether-polyester polyol component containing di- to tetrafunctional polyether-polyester polyols having hydroxyl numbers of from 10 to 200, which are themselves prepared by esterifying conventional di- to tetrafunctional polyether polyols with carboxylic acid anhydrides, preferably aromatic carboxylic acid anhydrides, in the presence of selected catalysts to form carboxylic acid half esters, and oxy-alkylating the resulting carboxylic acid half esters with alkylene oxides in the presence of N-methylimidazole, triethylene diamine, triphenylphosphine or mixtures thereof with thiodlalkylene glycol as catalysts.
CELLULAR OR NON-CELLULAR POLYURETHANES
Abstract of the Disclosure The invention relates to a process for the preparation of cellular or non-cellular polyurethanes through the reaction of organic polyisocyanates with a polyether-polyester polyol component containing di- to tetrafunctional polyether-polyester polyols having hydroxyl numbers of from 10 to 200, which are themselves prepared by esterifying conventional di- to tetrafunctional polyether polyols with carboxylic acid anhydrides, preferably aromatic carboxylic acid anhydrides, in the presence of selected catalysts to form carboxylic acid half esters, and oxy-alkylating the resulting carboxylic acid half esters with alkylene oxides in the presence of N-methylimidazole, triethylene diamine, triphenylphosphine or mixtures thereof with thiodlalkylene glycol as catalysts.
Description
't3~
Case 1422 PROCESS FOR THE PREPARATION OF
CELLULAR AND NoN-cæLLuLAR POLYURETHANES
Back~round of the Invention l. Field of the Invention _ _ _ The ~ubject invention relates to a process for the preparation of cellular and non-cellular polyurethane~
having desirable physical propertie~. More particularly, the invention relate~ to the preparation of cellular and non-cellular polyure~hanes wherein selected polyether-polyester polyols, prepared utilizing specific oxyalkylation cataly~t~, are utilized a~ the polyol component of the polyurethanes .
Case 1422 PROCESS FOR THE PREPARATION OF
CELLULAR AND NoN-cæLLuLAR POLYURETHANES
Back~round of the Invention l. Field of the Invention _ _ _ The ~ubject invention relates to a process for the preparation of cellular and non-cellular polyurethane~
having desirable physical propertie~. More particularly, the invention relate~ to the preparation of cellular and non-cellular polyure~hanes wherein selected polyether-polyester polyols, prepared utilizing specific oxyalkylation cataly~t~, are utilized a~ the polyol component of the polyurethanes .
2. ~
The preparation of cellular or non-cellular polyurethanes through the reaction of organic polyi50-cyanates with organic polyhydroxyl compounds (polyolsl is well known. Particular attention is drawn, for example, to the monograph by J. H. Saunders and X. C. Frisch, High Polymers, Vol. XVI, "Pvlyurethanes," Pts. I and II (New York: Inter~cience Publishers, 1962, i964) and by R. Yieweg and A. Hochtlen, Kun~tstoff-Handbuck, Vol. VII, Polyurethane, (Munich, Carl Hanser Verlag, 1966).
Ester group-containing polyether polyols are frequently used as the polyol component for the preparation of flame-resistant, semi-rigid, or rigid polyurethane foams. The preparation of the~e polyether-polyester polyol~
is illustrated by reference to U. S. Pat~nts 3,585,185,
The preparation of cellular or non-cellular polyurethanes through the reaction of organic polyi50-cyanates with organic polyhydroxyl compounds (polyolsl is well known. Particular attention is drawn, for example, to the monograph by J. H. Saunders and X. C. Frisch, High Polymers, Vol. XVI, "Pvlyurethanes," Pts. I and II (New York: Inter~cience Publishers, 1962, i964) and by R. Yieweg and A. Hochtlen, Kun~tstoff-Handbuck, Vol. VII, Polyurethane, (Munich, Carl Hanser Verlag, 1966).
Ester group-containing polyether polyols are frequently used as the polyol component for the preparation of flame-resistant, semi-rigid, or rigid polyurethane foams. The preparation of the~e polyether-polyester polyol~
is illustrated by reference to U. S. Pat~nts 3,585,185,
3,639,541, and 3,639,542. For example, polyether polyols, which may contain pho~phoru~ compound~ as initiator mole-cules may be reacted with halogen-containing carboxylic a~id anhydride~, in particular tetrabromo~ or tetrachlorophthalic acid anhydride to form carboxylic acid half e~ters following which the free carboxylic acid group~ are oxyalkylated.
According to European Patent Application 468, polyether polyol mixkure~ having a functionality of from 2.8 to 4.5 are reacted with tetrachlorophthalic acid anhydride in a hydroxyl-to-anhydride-group ratio of from l:l to l.l:l to form tetrachlorophthalic acid half e3ters and said half ester~ are then oxyalkylated with from l mole equivalent to 1.5 mole-equivalent of alkylene oxide. The resulting chlorine-containing polyether-polyester polyol3 are sui~able for the preparation of rigid polyurethane or polyisocya-nurate foams.
The oxyalkylation of reaction productq prepared from carboxylic acid anhydrides and alcohols or amines in an equivalent ratio of from 0.1:1 to 2.0:1 with from 1.5 to 14 moles of alkylene oxide per mole equivalent o~ carboxylic acid anhydride is de~cribed in U. S. Patent 3,455,886.
These polyether-polye~ter polyols may al~o be utilized for the preparation of semi-rigid and rigid polyurethane foams.
~ Z~L~a3~37 The oxyalkylation de~cribed in the above r0~er-ences is generally performed in the pre~ence of basic ca~alystq, for example, alkali hydroxides or alkali alcohol-ates, al~hough occa~ionally acid catalysis is utilized. The di~advantage of the~e catalysts is that they not only accelerate the oxyalkylation of the carboxyl groups, they also catalyze polyoxyalkyla~ion at the expense of complete initial esteriication of the remaining acid functionality of the half esters. In order to assure that all the carboxyl groups are completely esterified, the oxyalkylation must generally be performed with a large excess of alkylene oxide over a long reaction time. A further disadvantage i~
that the catalysts must be separated from ths reaction mixture after completion of the reaction~ which necessitates lengthy and expensive purification operations.
In order to avoid post-reaction purification, in European Application 468 and German Application 1 568 249, the oxyalkylation of the carboxylic acid half esters is performed in the absence of catalysts. However, a large excess of alkylene oxide is still necessary in the non-catalytic oxyalkylation in order to esterify all the carboxyl groups. A further disadvantage is that the non-reacted alkylene oxides, up to 15 weight percent of the amounts originally used, must be qtrlpped. The ~tripping process, along with the need for proper disposal compromises the co~t effectiveness and environ~en~al ~oundness of this proce~O
In order to eliminate thi3 di~advantage, in German Patent 3,201,203, the carboxylic acid half esters are oxyalkyla~ed with one mole of alkylene o~ide per mole-equivalent of carboxyl group, in the pre~ence of a thio-dialkylene glycol a~ a catalyst. In thi3 proce~s, particu-larly good results are obtained when glutaric acid anhydride is used to prepare the carboxylic acid half esters.
However, if the polyols are reacted with other carboxylic acid anhydrides, ~uch a~ tetrahydro- or phthalic acid anhydride, and the carboxylic acid half-e~ter~ are subse-quently oxyalkylated, the re~ulting polye~ter or polyether-polye~ter polyols are difficult to proces3 into polyure-thanes in a reproducible manner. The process of the subject invention eliminate~ such defect3 by utilizing a process for the preparation of polyester or polyether-polyester polyol~
wherein the carboxylic acid half-ester~ are oxyalkylated in the presence of specific oxyalkylation catalyst~.
Summary of the Invention The object of the subject invention is to improve the mechanical propertie3 of cellular and non-cellular polyurethanes, by increasing the compre~sion hardness without negatively affecting propertie~ such as ten~ile strength and elongation, which generally behave in an opposite manner.
This pro~lem wa~ unexpectedly solved ~hrough the use of polyether-polyester polyol~ prepared through special methods as the polyol component of the polyurethane. The~e polyether-polye4ter polyols are prepared by reacting conventional polyether polyols with carboxylic acid anhy-drides, preferably aromatic carboxylic acid anhydride~, following which the re3ulting terminal carboxyl groups of the resultant half esters are oxyalkylated. The selection of specific cataly~ts according to the proces~ of this invention allows complete oxyalkylation of the half esters with the lowest po4sible amount~ of alkylene oxide.
Description of the Preferred Embodiments The subject of the invention is a proce~s for the preparation of cellular or non-cellular polyurethanes through the reaction of an organic polyiqocyanate with a polyol component in the presence of suitable catalysts and, ln some cases, chain extender~ or crosq-linking agents, blowing agents, and auxiliaries or additives, wherein the improvement compri~es utilizing as ~aid polyol component an isocyanate-reactive polyol containing from 30 percen~ to 100 parcent by weight of di- to tetrafunctional polyether-polyester polyols having hydroxyl number~ from 10 to 200 prepared by the process of:
a) esterifying di- to tetrafunctional polyether polyol~
having hydroxyl number~ from 15 to 250 with carboxylic acid anhydride3 to form carboxylic acid half esters, and b) oxyalkylating the carboxylic acid half e~ters with alkylene oxide~ in the pre~ence of a ca~alyst ~elected from the group consi~ting of:
i) N-methylimidazole, ii) triethylenediamine, iii) triphenylpho~phine, iv) mixtures of two or more of (i), (ii), and (iii), and v) a mixture of thiodialkylene glycol and at least one of (i), (ii), and (iii).
Polyisocyanates suitable for the preparation of said cellular or non-cellular polyurethanes of the subject invention are, for example, aliphatic, cycloaliphatic, aryl-aliphatic and preferably, aromatic polyisocyanates. Typical examples are: aliphatic diisocyanates such as ethylene diisocyanate, 1,4-tetramethylene dii~ocyanate, 1,6-hexa-methylene diisocyanate, and l,12-dodecane diisocyanate, cycloaliphatic dii~ocyanates such a~ 1,3-cyclohexane diisocyanate and 1,4-cyclohexane dii~ocyanate as well as various mixtures of the~e isomers, l-isocyanato-3,3,5-trimethyl-S~ ocyanatomethyl1cyclohexane, 2,4~ and 2,6-me~hylcyclohexane diisocyanate as well as various mixture~
of the~e isomers, 4,4'- and 2,4'-diisocyanatodicyclohexyl-methane: aromatic diisocyanates ~uch as 1,3- and 1,4-phenylene diisocyanate, 2,4- and 2,6-toluene diisocyanate as well as various mixtures of these isomer~, 2,2'-, 2,4'- and
According to European Patent Application 468, polyether polyol mixkure~ having a functionality of from 2.8 to 4.5 are reacted with tetrachlorophthalic acid anhydride in a hydroxyl-to-anhydride-group ratio of from l:l to l.l:l to form tetrachlorophthalic acid half e3ters and said half ester~ are then oxyalkylated with from l mole equivalent to 1.5 mole-equivalent of alkylene oxide. The resulting chlorine-containing polyether-polyester polyol3 are sui~able for the preparation of rigid polyurethane or polyisocya-nurate foams.
The oxyalkylation of reaction productq prepared from carboxylic acid anhydrides and alcohols or amines in an equivalent ratio of from 0.1:1 to 2.0:1 with from 1.5 to 14 moles of alkylene oxide per mole equivalent o~ carboxylic acid anhydride is de~cribed in U. S. Patent 3,455,886.
These polyether-polye~ter polyols may al~o be utilized for the preparation of semi-rigid and rigid polyurethane foams.
~ Z~L~a3~37 The oxyalkylation de~cribed in the above r0~er-ences is generally performed in the pre~ence of basic ca~alystq, for example, alkali hydroxides or alkali alcohol-ates, al~hough occa~ionally acid catalysis is utilized. The di~advantage of the~e catalysts is that they not only accelerate the oxyalkylation of the carboxyl groups, they also catalyze polyoxyalkyla~ion at the expense of complete initial esteriication of the remaining acid functionality of the half esters. In order to assure that all the carboxyl groups are completely esterified, the oxyalkylation must generally be performed with a large excess of alkylene oxide over a long reaction time. A further disadvantage i~
that the catalysts must be separated from ths reaction mixture after completion of the reaction~ which necessitates lengthy and expensive purification operations.
In order to avoid post-reaction purification, in European Application 468 and German Application 1 568 249, the oxyalkylation of the carboxylic acid half esters is performed in the absence of catalysts. However, a large excess of alkylene oxide is still necessary in the non-catalytic oxyalkylation in order to esterify all the carboxyl groups. A further disadvantage is that the non-reacted alkylene oxides, up to 15 weight percent of the amounts originally used, must be qtrlpped. The ~tripping process, along with the need for proper disposal compromises the co~t effectiveness and environ~en~al ~oundness of this proce~O
In order to eliminate thi3 di~advantage, in German Patent 3,201,203, the carboxylic acid half esters are oxyalkyla~ed with one mole of alkylene o~ide per mole-equivalent of carboxyl group, in the pre~ence of a thio-dialkylene glycol a~ a catalyst. In thi3 proce~s, particu-larly good results are obtained when glutaric acid anhydride is used to prepare the carboxylic acid half esters.
However, if the polyols are reacted with other carboxylic acid anhydrides, ~uch a~ tetrahydro- or phthalic acid anhydride, and the carboxylic acid half-e~ter~ are subse-quently oxyalkylated, the re~ulting polye~ter or polyether-polye~ter polyols are difficult to proces3 into polyure-thanes in a reproducible manner. The process of the subject invention eliminate~ such defect3 by utilizing a process for the preparation of polyester or polyether-polyester polyol~
wherein the carboxylic acid half-ester~ are oxyalkylated in the presence of specific oxyalkylation catalyst~.
Summary of the Invention The object of the subject invention is to improve the mechanical propertie3 of cellular and non-cellular polyurethanes, by increasing the compre~sion hardness without negatively affecting propertie~ such as ten~ile strength and elongation, which generally behave in an opposite manner.
This pro~lem wa~ unexpectedly solved ~hrough the use of polyether-polyester polyol~ prepared through special methods as the polyol component of the polyurethane. The~e polyether-polye4ter polyols are prepared by reacting conventional polyether polyols with carboxylic acid anhy-drides, preferably aromatic carboxylic acid anhydride~, following which the re3ulting terminal carboxyl groups of the resultant half esters are oxyalkylated. The selection of specific cataly~ts according to the proces~ of this invention allows complete oxyalkylation of the half esters with the lowest po4sible amount~ of alkylene oxide.
Description of the Preferred Embodiments The subject of the invention is a proce~s for the preparation of cellular or non-cellular polyurethanes through the reaction of an organic polyiqocyanate with a polyol component in the presence of suitable catalysts and, ln some cases, chain extender~ or crosq-linking agents, blowing agents, and auxiliaries or additives, wherein the improvement compri~es utilizing as ~aid polyol component an isocyanate-reactive polyol containing from 30 percen~ to 100 parcent by weight of di- to tetrafunctional polyether-polyester polyols having hydroxyl number~ from 10 to 200 prepared by the process of:
a) esterifying di- to tetrafunctional polyether polyol~
having hydroxyl number~ from 15 to 250 with carboxylic acid anhydride3 to form carboxylic acid half esters, and b) oxyalkylating the carboxylic acid half e~ters with alkylene oxide~ in the pre~ence of a ca~alyst ~elected from the group consi~ting of:
i) N-methylimidazole, ii) triethylenediamine, iii) triphenylpho~phine, iv) mixtures of two or more of (i), (ii), and (iii), and v) a mixture of thiodialkylene glycol and at least one of (i), (ii), and (iii).
Polyisocyanates suitable for the preparation of said cellular or non-cellular polyurethanes of the subject invention are, for example, aliphatic, cycloaliphatic, aryl-aliphatic and preferably, aromatic polyisocyanates. Typical examples are: aliphatic diisocyanates such as ethylene diisocyanate, 1,4-tetramethylene dii~ocyanate, 1,6-hexa-methylene diisocyanate, and l,12-dodecane diisocyanate, cycloaliphatic dii~ocyanates such a~ 1,3-cyclohexane diisocyanate and 1,4-cyclohexane dii~ocyanate as well as various mixtures of the~e isomers, l-isocyanato-3,3,5-trimethyl-S~ ocyanatomethyl1cyclohexane, 2,4~ and 2,6-me~hylcyclohexane diisocyanate as well as various mixture~
of the~e isomers, 4,4'- and 2,4'-diisocyanatodicyclohexyl-methane: aromatic diisocyanates ~uch as 1,3- and 1,4-phenylene diisocyanate, 2,4- and 2,6-toluene diisocyanate as well as various mixtures of these isomer~, 2,2'-, 2,4'- and
4,4'-diphenylmethane diisocyanate, and 1,5-naphthalene diisocyanate, aromatic polyisocyanates such a~ 4,4',4"-triphenylmethane trii~ocyanate, 2,4,6-triisocyanatobenzene, and polyphenylene polymethylene polyisocyanates. Modified polyi~ocyanate~ can al~o be u~ed, for example, ~ho3e described in U. S. Patent 3,492,330, carbodiimide-group-containing polyi~ocyanates ~German Patent 10 92 007), allophanate-group-containing polyisocyanates (British Paten~
994 890, Belgium Patent 761 626), i~ocyanurate-group-containing polylsocyanate~ (German Patents 10 22 789, 12 22 067, 10 27 394, 19 29 034, and 10 04 048), urethane-group-containing polyisocyanates, (Belgium Patent 752 261, U. S. Patent 3,394,164) biuret-group-containing polyisocya nates, (German Patent 11 01 394, British Patent 889 050), and ester-group-containing polyi~ocyanates (Briti3h Patents 965 474 and 10 72 9S6, U. S. Patent 3,567,763, and German Patent 12 31 688).
Preferably used are commercially available, aromatic di- and polyisocyanateA, which may contain urathane group~, such a~ 2,4- and 2,6-toluene dii~ocyanate and mixtures thereof, 2,2'-, 2,4'-, and 4,4l-diphenylmethane diisocyanate and mixtures thereof, mixturea of 2,2'-, 2,4'-, and 4,4'-diphenylmethane dii~ocyanate~ with polyphenylene polymethylene polyi~ocyanates (polymeric MDI), and mixture~
of toluene diiqocyanates and polymeric MDI. These di- and polyisocyanates can be used individually or in mixtures.
Es~ential to the ~ubject invention i~ the inclu-sion of di- to tetrafunctional, preferably 2.5- to tri-functional polyether-polyester polyols having hydroxyl number~ from 10 to 200, pr~ferably from 25 to 56, in the organic polyether-polyester polyol component prepared by the proces~ of esterifying conventional polyether polyols having functionalities of from 2 to 4, preferably from 2.5 to 3, and hydroxyl number~ from 15 to 250, preferably from 30 to 110, with carboxylic di- and/or monoanhydrides, preferably aromatic carboxylic acid monoanhydrides, preferably in the presence of esterification catalysts, to form carboxylic acid half ester~, followed by oxyalkylating the carboxylic acid half esters thus formed with alkylene oxides in the presence oE N-methylimidazole, triethylenediamine, ~ri-phenylphosphine, mixture~ thereof, or mixtures of one or more thereof with thiodialkylene glycol, a~ oxyalkylation catalyst~. Mixtures of N-methylimidazole and/or triethylene diamine and triphenylpho~phine are preferably u~ed.
The conventional polyether polyols suitable for use in the proce~s of the inv~n~ion having a functionality of from 2 to 4 and a hydroxyl number of from 15 to 250 may be prepared in accordance with known method~, for example, by polyoxyalkylating an initiator molecule containing from 2 to 4, pr~ferably from 2.5 to 3 active hydrogen a~om~, with one or more alkylen~ oxide~.or cyclic ethers having from 2 to 4 carbon atom3 in the alkylene radical, in the pre~ence of acid, or pref~rably, ba~ic cataly3ts such as alkali hydroxide~ or alkali alcoholates, or through the polymeriza-tion of tetrahydrofuran with ~uitable catalysts, for example, boron trifluoride etherate, antimony pentachloride, or fuller'~ earth.
Suitable alkylene oxide~ and cyclic ethers are, for example: oxetan~, 1,2-, 2,3-butylene oxide, styrene oxide, and preferably, ethylene oxide and propylene oxide.
Th~ alkylene oxides may be reacted singly, as mixtures, or sequentially, to form homopolymeric~ heteropolymeric, or block-polymeric alkylene oxide addition products.
Typical initiator molecules which may be used are: water, organic dicarboxylic acid~ ~uch a~ ~uccinic acid, adipic acid, phthalic acid, and terephthalic acid;
aliphatic and aromatic diamines, in some ca~es N-mono-, N,N-, and N,N'-dialkyl-substituted diamines having from 1 to 4 carbon atoms in the alkyl radical, for example, mono- and dialkyl-subs~ituted ethylene diamine, diethylene trlamine, triethylene tetramine, l,3-propylene diamine, 1,3~ and 1,4-butane diamine, 1,2-, 1,3-, 1,4-, 1,5-, and 1,6-hexa-methylene diamine, phenylene diamine, 2,4-, and 2,6-toluene diamine and 4,4'-, 2,4'-, and 2,2'-diaminodiphenylmethane;
monoamine~ such as methylamine, ethylamine, i~opropylamine, butylamine, benzylamine, aniline, toluidine~, and naphthyl-amines. Eqpecially useful compound~ are: N,N,N',N'-tetraki~(2-hydroxyethyl)ethylenediamine, N,N,N',N 7 -tetrakis-(2-hydroxypropyl)ethylenediamine, N,N,N',N",Nn-pentakis~2-hydroxyethyl3ethylenetriamine, phenyl diisopropanolamine, and higher molecular weight alkylene oxide adductq of aniline.
Additional initiator molecules are: alkanolamines such a~ ethanolamine, diethanolamine, N-methyl- and N-ethyl-diethanolamine, N-methyl- and N-ethyl- dipropanolamine, triethanolamine, hydrazine and hydrazide~, di- to te~ra-functional, preferably di- to tri-func~ional alcohol~, for example, ethylene glycol, 1,2- and 1,3-propylene glycol, diethylene glycol, dipropylene glycol, 1,4-butylene glycol, 1,6-hexamethylene glycol, glycerine, trimethylolpropane, and pentaerythritol.
The polyether polyoi~ can be utilized individually or in the form of mixtures. Preferably, polyether polyols are u~ed which contain not more than 30 weight percent, preferably not more ~han 5 ~o 10 weight percent ethylen~
oxide r~idues ba~ed on the total weight of alkylene oxide residues, said polyether polyol~ having hydroxyl numbers from 15 to 250. Particularly well ~uited are polyoxy-propylene ether glycols and/or triol~ having hydroxyl numbers from 30 to 110.
Aliphatic, optionally halogenated monoanhydrides cycloalipha~ic, optionally ~ubstituted di- and/or mono-anhydrides, and aromatic, optionally sub~tituted di- and/or mono- anhydride~, are utilized a~ the carboxylic acid anhydride~. Particularly well suited are aromatic, option-ally ~ub~tituted monoanhydrides. Typical carboxylic acid anhydrides are: aliphatic carboxylic acid anhydrides ~uch aq maleic acid anhydride, dichloromaleic acid anhydride, succinic acid anhydride, and glutaric acid anhydride, cyclo-aliphatic carboxylic acid anhydrides ~uch a~, for example, hexahydro- and tetrahydrophthalic acid anhydride, and preferably, aromatic carboxylic acid anhydrides such a3 tetrachlorophthalic acid anhydride, tetrabromophthalic acid anhydride, trimellitic acid anhydride, pyromellitic acid dianhydride, and phthalic acid anhydrid~. Phthalic acid anhydride i9 particularly well suited.
In order to prepare the carboxylic acid half eqter~, the conventional polyether polyols or polyether polyol mixtures and the carboxylic acid anhydride or ~L2~ 7 carboxylic acid anhydrid~ mixtur~ are e~terified at temperatures from 50 ~o 240C, prefer~bly fro~ 90 to 200C, for a period of from 0.5 to 8 hour~, preferably from 1 to 4 hours. ~he esterification takes place preferably in the presence of cataly~ts. From 0.25 to 1.05 mole-equiva-lents, and preferably from 0.95 ~o 1.0 mole-equivalents, carboxylic acid anhydride are present in the reaction mixture per mols-equivalent polyether polyol. Triphenyl-phosphine, N-methylimidazole, triethylene diamine or mixtures thereof have proven to be effective e~terification catalysts. Preferably used are N-methylimidazole and triethylenediamine. The catalysts are used in amounts from 0.05 to 2.0 part~ by weight, preferably from 0.1 to 0.4 parts by weight, per 100 parts by weight of the conventional polyether polyol/anhydride reaction mixture.
These same e~terification catalyst~ have been found to be most effectlve in the oxyalkylation reaction.
Thus, the previously fcrmed half-esters may be oxyalkylated directly, without removing the esterification catalyst. It may be preferable to add additional amounts of the same cataly~t as used for the esterification reaction, or to add one or more additional catalyst~. A ~hiodialkylene glycol such as thiodiethylene glycol may be used in conjunction with one of the aforementioned catalysts for the oxyalkyla-tion if desired.
The oxyalkylation take~ place in the pre~ence of from 0.05 to 2.0 part~ by weight, preferably fro~ 0.1 to 0.~
parts by weight of the oxyalkylation cataly~ts, ba~ed on 100 parts by weight of the carboxylic acid half ester. From 1 to 4 mole-equivalent3, preferably one mole-equivalent, of propylene oxide, mixtures of propylene oxide and ethylene oxide, or preferably, ethylene oxide alone, i3 added per mole-equivalent of carboxyl group. Triphenylpho~phine is preferred a~ the oxyalkylation catalyst.
lQ Particularly advantageou~ results are obtained when the carboxylic acid half ester i~ prepared in the pre~ence of N-methylimidazole and triethylenediamine, or mixtures thereof as cataly~ and additional triphenylphos-phine is added to the reaction mixture for the oxyalkyla-tion. Thi~ repre~ents a preferred embodimen~.
Thiodialkylene glycolq ~uitable for the oxyalky-lation catalysts po~es~ from 2 to 6, preferably 2 to 3, carbon atom~ in the alkylene radical. Typical examples are thiodihexylene glycol, thiodibutylene glycol, and, prefer-ably, thiodipropylene and/or thiodiethylene glycol.
The oxyalkylation of the carboxylic half ester i3 generally performed at temperatures from 80 to 160C, preferably from 90 to 130C, at standard pres~ure or, preferably, at elevated pre~sure. Eqpecially useful, for example, are preqsure~ from 0~5 to 10 bar, advantageously in ~2~
the presance of gase~ which ar~ inert under the reaction condition~, for example, nitrogen, helium, neon, etc., or mixtures thereofu After an acid number of les~ than 1 has been reached, the oxyalkyla~ion i~ stopped. If the reac~ion mixture still contains free monomeric alkylene oxide, the mixture i~ ~tripped at reduced pre3sure. It is not neces--~ary to remove the catalysts used for the preparation of the carboxylic acid half ester and for the oxyalkylation of the resulting polyether-polyeqter polyolq.
In order to prepare ~he cellular or non-cellular polyurethanes in accordance with the proce~q of the inven~
tion, the polyether-polye~ter polyols can be utilized individually or aq mixture~. Mixture~ of the polyether-polyester polyols and other polyols having a functionality o from 2 to 4, preferably from 2.5 to 3, and hydroxyl number~ from 10 to 200, preferably from 30 ~o 110, can be uqed in accordance with the subject invention. Such polyols may be, for example, hydroxyl-group containing polyesters, polyester amide~, polyacetals, polycarbonate~, and, prefer-ably, graft polymer polyether polyol~, polyether polyol filler di~persions, and conventional polyether polyol~, provided said mixture~ contain at least 30 weight percen~, preferably from 50 to ca. 100 weight percent polyether-polyester polyols prepared by the process of the invention ba~ed on the total weight of the polyol component.
In some cases, it may be de~irab}a to utilize, in addition to the polyether-polye~ter polyol component, additives such as chain extenders or cros~-linking agent~, to introduce rigid ~egmentq into the resulting poly-urethanes. Such additives are polyfunctional, particularly di- and trifunctional compounds having molecular weights from 17 to 600, preferably from 60 to 300. Suitable, for example, are: di- and trialkanolamines such a~ diethanol-amine and triethanolamine, aliphatic and aromatic diamines such as ethylenediamine, 1,4-butylenediamine, 1,6-hexa-methylenediamine, 4,4'-diaminodiphenylmethane, 3,3'-dialkyl-substituted-4,4'-diaminodiphenylmethanes, 3,3',5,5'-tetra-alkyl-substituted-4,4'-diaminodiphenylmethanes, 2,4- and 2,6-toluenediamine, and preferably, aliphatic diols and triols having from 2 to 6 carbon atoms, such as ethylene glycol, l,4-butylene glycol, 1,6-hexamethylene glycol, glycerine, and trime~hylol propane.
When chain extenders or cross-linking agents are used, they are generally used in amounts from 1 to 10, preferably from 1 to 4 parts by weight per 100 parts by weight polyether-polyester polyol component.
Blowing agents or their precursors, sometimes termed "reactive" blowing agents, may be utilized. ~hera the unqualified term "blowing agent~ is utilized in the subject invention, it is understood ~o includa both inert as ~2~ 7 well as reactive blowing a~ent~. Among the reactive blowing agent~ which can ~e utilized in the proce3~ of the invention for the prepara~ion of cellular polyurethane~ i8 water, which react~ wi~h i~ocyanate group~ to form carbon dioxide. The amount~ of water u~ed most ~ucce~sfully are from 0.5 to 20 parts by weight, preferably from 1.5 to 10 part~ by weight, and more preferably from 2 to 6 part~ by weight, based on 100 part3 by weight of the polyether-polyester polyol component.
Inert blowing agents may also be u~ed, either alone or mixed with water. Suitable liquid3 are those inert to the polyisocyanates and which posse~ boiling point~ les3 than 100C, preferably le~s than 50C, and mo~t preferably between -50C and 30C at atmo~pheric pressure, and which vaporize under the effect of the exothermic addition polymerization reaction. Typical blowing agent~ are hydrocarbons such a~ pentane, n-butane, iso-butane, and propane; ethers such as dimethyl ether and diethyl ether, ketones such a3 acetone and methylethyl ketone, ethyl acetate, and preferably, halogenated hydrocarbonq ~uch as methylene chloride, trichlorofluoromethane, dichlorodi-fluoromethane, dichloromonofluoro~e~hane, dichlorotetra-fluoroethane, and l,1,2-trichloro-1,2,2 trifluoroethane.
Mixture~ of these low boiling point liquid~ may al~o be utilized.
~2~ 7 ~ he desired amount of inert blowing agent can be determined ~imply, ba~ed on the amount of water which i~
pre~ent and the desired foam den~ity. In the ab~ence of water, this amount is approximately 1 to 4 parts by weight, preferably 3 to 15 part~ by weight, per 100 parts by weight polye~her-polye~ter polyol component. It may be desirable to mix the organic polyi~ocyanate with the blowing agent to thereby lower the viqco~ity of the polyi~ocyanate component.
In order to accelerate the reaction between the polyether-polyester polyol component, water, ~hain ex-tenders, or cross-linking agent~, and the organic polyisocy-anate~, standard polyurethane cataly~t~ may be incorporated into the reaction mixture. Basic polyurethane catalyst~ are preferably used, for example, tertiary amines such a~
dimethylbenzylamine, dicyclohexylmethylamine, dimethylcyclo-hexylamine, N,N,N',N'-tetramethyldiaminobutane, N,N,N',N'-tetramethyldiaminoethyl ether, bis(dimethylaminopropyl)urea, N-methyl- and N-ethylmorpholine, dimethylpiperazine, pyridine, l,2-dimethylimidazol~, l-azabicyclo[30300]0ctane, dimethylaminoethanol, Z-(dimethylaminoethoxy)ethanol, N,N',N"-tris(dialkylaminoalkyl)hexahydrotriazenes quch a~
N,N',N"-tri3(dimethylaminopropyl)-s-hexahydrotriazine and, in particular, triethylene diamin~ However, metal salt~
such a3 iron(II)chloride, zinc chloride, lead octoate, and, preferably tin ~alt~ ~uch a~ tin dioctoate, tin diethyl-hexanoata, and dibutyl tin dilaurate a~ well as mixtures of tertiary amines and organic tin salts are also suitable. It is desirable to use from 0.1 to 10 weight percent, prefer-ably from 0.5 to 5 w~ight percent, catalysts based on tertiary amines and/or from 0.01 ~o 0.5 weight percent, preferably from 0.05 to 0.25 weight percent metal salts, based on the weight of the polyether-polyester polyol component.
Auxiliaries or additive3 can also be incorporated in the reaction mixture. Typical example~ are surfactant~, foam stabilizers, cell regulators, fillers, colorants, pigments, flame retardants, anti-hydrolytic agent~, and fungistatic and bacteriostatic substances.
Surfactants which help to homogenize the various components and also regulate cell structure are e~pecially use~ul. Typical sur~actant3 are, for example, emulsifier~
~uch as the sodium salt~ of castor oil sulfates or of fatty acids. salts of fatty acids with amin~s, for example, maleic acid diethylamine or stearic acid diet~anolamine salts, ~0 salt~ of sulfonic acid~ such as alkali or ammonium salts of dodecylbenzene sulfonic acid or dinaphthylmethanedisulfonic acid and ricinoleic acid, foam ~tabilizers such as siloxane-oxyalkylene copolymer~ and other organic polysiloxane~, oxyethylated alkylphenols, oxyethylated fatty alcohols, paraffin oil, esters of castor oil, ricinoleic acid or ~2~ 3~
TurXey red oil, and cell regulators ~uch as paraffins, fatty a7coholY, and dimethylpolysiloxanes. The surfactant~ are generally pre~ent in amount~ from O.Ol to 5 parts by weight based on lOO part~ by weight polyether-polye~ter polyol component.
By the term fillers, in particular ~illers which have a reinforcing effect, is meant conventional organic and inorganic fillers, reinforcing agent~, weight-increasing agents, and agents for improving wear in paints, coatings, etc. Typical example~ are: inorganic fille~s 3uch as ~ilicate minerals, for ex~ple lamellar silicate~ such as antigorite, serpentina, horn blende, amphibolite, chryso-tile, and talcum; metal oxide~ such as kaolin, aluminum oxides, titanium oxides, and iron oxides, matal salt~ such as chalk, and barium sulfate, and inorganic pigments ~uch as cadmium sulfide, zinc sulfide, gla~s, ground asbestos, etc. Preferably, kaolin (China Clay), aluminum silicate, and coprecipitates of barium sulfate and aluminum silicate are u~ed, as well as natural and synth~tic fibrous minerals such as asbestos, wollastonite, and in particular, glass fibers of varying length~, which may be treated with size.
Typical organic filler~ are: carbon black, melamine, pine resin, cyclopentadianyl re~ins, and, preferably ~yrene-acrylonitrile-based graft polymers prepared through in ~itu polymerization of acrylonitrile-styrene mixtures in poly-ether polyols, similar to German patents 11 11 3g4, 12 22 669, (U~ S. Patent 3,304,273, 3,383,351, 3,523,093), 11 52 536, (Briti~h Patent 1,040,452) and 11 52 537 (British Pa~ent 987,618~ a~q well a~ filled polyether polyols in which agueous polymer di~persions are transformed into polyether polyol dispersions.
The inorganic and organic fillers may ~e used individually or as mixtures. Preferred are stable polyether polyol di~qparsions in which the fillers are raduced in si~e in the presence of polyether polyol~ in situ with high localized energy gradients to a particle size less than 7 ~m and are simultaneously dispersed by this action. Filled polyether polyol dispersions of this type are described, for example, in German Patents 28 50 609, 28 50 610, and 29 32 30~.
The inorganic and organic fillers are advanta-geously incorporated into the reaction mixture in amounts from 0~5 to 50 weight percent, preferably from 1 to 40 weight percent, based on the weight of the polyisocyanate-polyether-polyester polyol component reaction mixture.
Suitable flame retardants may also be added, such as, for example: tricresyl phosphate, tris-(2-chloroethyl)-phospha~e, tris-(chloropropyl)phosphate, and ~ris-(2,3-dibromopropyl)phosphate. Also used as flame retardants are inorganic flame retardant~ such as hydrated aluminum oxide~, -- ~0 --antimony trioxide, arsQnic oxide~, ammonium polyphosphate, and calcium ~ulfate as well as the e~terification products of low-molecular-weight mono- and polyfunctional alcohol~
and halogena~ed phthalic acid derivatives. In general, it has been found to be desirable to use from 5 to 50 parts by weight, preferably from 5 to 2~ parts by weight, of the above-cited flame retardanta per 100 parts by weight polyether-polyester polyol component.
Further information on other conventional aux-iliaries or additives may be found in the literature, in particular the monograph by J. H. Saunders and K. C. Frisch, "High Polymer~, n Vol. XVI, Pol~urethanes, Pts. 1 and 2, Interscience Publisher~: 1962/1964.
In order to prepare the polyurethanes in accor-dance with tAe process of the invention, the organic polyisocyanates and polyether-polyester polyol component, chain extenders, and cro~s-linking agents are reacted in the presence of catalysts, and in some cases, blowing agent3, auxiliaries and additives, at temperatures from 0 to 70C, preferably from 15 to 50C, at active hydrogen/isocyanate ratio~ of from 0.5 to 2:1, preferably from 0.8 to 1.6:1, and most preferably approximately 1:1.
The cellular or non-cellular polyurethanes can also be prepared using the prepolymer proce3s. To do this, the polyether-polyester polyol~ are tran~formed using 3~
ordinary method~ into i~ocyanate-group-containing prepoly-mers by the addi~ion of polyi~ocyanate~, preferably mixtures Oî 4,4'- and 2,4'-diphenylme hane diisocyanate~ or mix~ures of diphenylmethane diisocyanates and polyphenylene poly-methyl~ne polyisocyanate3 having a diphenylmethane diisocya-nate content in excess of 60 weight percent. The isocya-nate-group-~ontaining prepolymers can be reacted a~ such or in the form of a mixture with polyisocyanates, preferably a mixture o~ diphenylmethane diisocyanates and polyphenylene polymethylene polyisocyanate~, with additional polyether-polyester polyol component or wi~h conventional polyols, along with, in some case~, chain extender~ or cross-linking agents in the presence of catalyst~ and, in some cases, blowing agents, auxiliaries, and additive~.
Preferably, however, the cellular or non-cellular polyurethane3 are prepared in a one-shot process. Here the initial components, auxiliaries, and additive~ are added individually ~sing a mixing head with several feed noæzles and are mixed together inten~ively in a mixing chamber. It has been found to be particularly desirable to use a two-component proce~s, and to combine the polyether-polyester polyol component, cataly~ts, and, in ~ome case~, chain extenders, cro~-linking agent~, blowing agents, aux-iliaries, and additives on the ~o-called A component side, and to use as the B component the polyisocyanate, modified ~2~ '7 polyisocyanate and/or the isocyanate-grsup-containing prepolymers, in some casea in admixture wi~h blowing agents, and auxiliaries or additives. The advan~age oE the two-component procesq is that the A and B components need only to be intensively mixed together in the proper quantitative ratios to prepare ~he polyurethane~. The basic component3 can also be mixed together in a one-shot process with the aid of familiar reaction injection molding techniques (RIM), injected into molds, and cured in the closed molds to form polyurethane~.
The den~e, elastic, non-cellular or microcellular polyurethane~ prepared in accordance with the invention possess densities from 0.8 to 1.4 g/cm3, preferably from 1.1 to 1.2 g/cm3, and possess very good tensile strength, elongation, and tear streng~h. The products are suitable for the preparation of highly abrasion resis~ant poly-urethane molded parts such as rolls, sliding ~hoes, sliding corner~ for snow removal equipment, etc.
Elastic, cellular polyurethanes prepared by this procass may have densities of fro~ 0.2 to 1.2 g/cm3. Shoe soles preferably have a density from 0.3 ~o 0.7 g/cm3, while RIM molded parts preferably have a densi~y from 0.7 ~o 1.1 g/cm3. Both exhibit very good compression hardness, tensile ~trength, and elongation. The highly elastic, flexible foams having densities from 0.02 to 0.2 g/cm3 are ~ 23 -suitable for the production of upholstery cushion~, mat-tre~ses, automotive ~eat cushions, and neck ~upports, a~
well a~ particularly for molding foam~. Ela~tic poly-ur~thane~ find use~ a~ automotiv~ exterior part~, impact-ab~orbing moldings, bumper coating~, and in corner protec-tion application~.
The following material~ were u~ed to prepare the cellular or non-cellular polyurethane~ in the examples. The parts cited in the examples ~efer to parts by weight.
Polyol I:
A glycerine initiated polyoxypropylene polyoxy-ethylene block copolymer having a hydroxyl number of 35 and an ethylene oxide content of 15 weight percent~
Polyol II:
A glycerine initiated polyoxypropylene polyoxy-ethylene heteric copolymer having a hydroxyl number of 42 and an ethylene oxide content of 7Q welght percent in a random distribution.
Polyol III:
A glycerine initiated polyoxypropylene polyoxy~
ethylene heteric/block copolymer copolyether having a hydroxyl number of 56 and an e~hylene oxide content of 11 9~d weight percen~, of which ~hree-fif~hs are pre!~ent in a random dis~ribution and two-fifth~ a~ a terminal block.
Polyol IY:
Three thousand parts (1 mole) Polyol III were est~rified with 444 parts of (3 moles) phthalic acid anhydride in the pre~ence of 0.2 weight percent N-methyl-imidazole in a nitroy~n atmo~phere for 4 hours at 180C
while being agitated.
The reaction mixture was allowed ~o cool to lOS~C, following which 0.2 parts by weight thiodiethylene glycol was added, and an oxyethylation reaction wa3 performed at 2 bar nitrogen pressure with 132 parts (3 moles) ethylene oxide. At the end of oxyethylation, the volatile components were stripped at lOSC and 0.01 bar. The resulting poly-ether-polyester polyol had a hydroxyl number of 49 and could be u~qed for the preparation of polyurethanes without further purification.
Polyol ~:
A procedure similar to that used in the prepara-tion of Polyol IV was used, however, the equivalent amount of tetrahydrophthalic acid anhydride wa~ u~ed in place of ths phthalic acid anhydride and 0O2 weight perc~nt tri-phenylphosphine was used instead of thiodiethylen~ glycol - ~5 -3~3~
for the ethyoxylation. The re~ulting polyether-polyes~er polyol had a hydroxyl number of 51.
Pol~ol YI:
Thirty-two hundred parts (3 moles) of a polyoxy-propylene glycol having a hydroxyl number of 105 were heated to 180C under a nitrogen atomsphere with 888 part~ (6 moles) phthalic acid in the presence of 0.2 weight percent N-methylimidazole and agitated for four hours.
The reaction mixture was then allowed to cool to 105C, following which 0.2 weight percent thiodiethylene glycol was added, and the mix~ure was oxypropylated at 0.5 bar nitrogen pressure with 348 parts (6 moles) propylene oxide. After completion of the oxypropylation, the volatile components were stripped at 105C and 0~01 bar. The resulting polyether-polyester polyol pos3essed a hydroxyl number of al and could be used for the preparation of polyurethane without additional purification.
Isocyanate A: An isocyanate-group-containing prepolymer with an isocyanate content of 23 weight percent, prepared by the reaction of 100 part~ of a mixture comprising 4,4'- and 2,4'-diphenylmethane diisocyanate in a weight ratio of 75:25 and 39.5 part~ Polyol IV at 70C with two hours agitation~
~ 26 -~L2~
Isocyanate B: An isocyanate-group-containing prepolymer with an isocyanate content of 23 weight percent, prepared similarly to isocyanate A, however, 39.3 parts Polyol V were used instead of Polyol IV.
I~ocyanate C: An isocyanate-group-con~aining prepolymer with an isocyanate content of 23.3 weight percent, prepared similarly to isocyanate A, however, using 18.7 parts Polyol ~I instead of Polyol IV.
I~ocyanate D: An lsocyanate-group~containing prepolymer having an isocyanate content of 23 weight percent, prepared similarly to isocyanate A, however, using 38.8 parts Polyol III instead of Polyol IV.
Isocyanate E: A polyisocyanate mixture having an isocyanate content of 3~.6 weight percent, comprising: 40 parts of a mixture of 45 weight percent diphenylmethanediisocyanates and 55 weight percent polyphenylenepolymethylene polyisocya-nates (polymeric MDI), 45 parts 4,4'~diphenylmethane diisocyanate, and 15 parts 2,4'-diphenylmethane diisocyanate.
Isoc~anate F: An isocyanate-group-containing prepolymer with an isocyanate content of 23 weight percen~, prepared by the reaction of 100 part~ 4,4'-diphenylmethane diisocyana~e and 25~2 parts of a polyoxypropylene glycol having a hydroxyl number of 250, at 60C for four hours.
Example~ 1 3 and Comparative _x~
Preparation of elastic, cellular polyurethanea using isocyanate-group-containing prepolymer~ ba3ed on poly~ther-polyes~er polyols.
A Com~nent: A mixture compri~ing 86.4 part~
Polyol I, 4.0 parts Polyol II, 2.8 part~ water, 0.35 parts triethylenediamine (33 weight percent solution in dipro-pylene glycol~, 0.35 part bi~N,N'-dimethylamino)diethyl-ether, 0.1 part silicone stabilizer B 4690 (vendor:
Goldschmidt, Essen), and 6 part~ trichlorofluoromethane.
B Com~onent: Mixture comprising 40 part~ of a mixture of diphenylmethane dii~ocyanates and polyphenylene polymethylene polyisocyanate~ having an isocyanate content of 31 weight percent (polymeric MDI) and 60 par~ isocyanate as iden~ified in accordance with Table I.
The A and B Components were mixed intensively for eight seconds at an index of 100 at room ~emperature (23C);
800 g of the mixture was poured into an aluminum mold with internal dimension3 of 40 x 40 x 10 cm at 50C. The mold was closed and the reaction mix~ure was allowed to expand.
The isocyanates used and ~he mechanical propertie~
a~ measured on the resulting polyurethane flexible foams at a den~ity of 50 g/l are summarized in rable I.
TABLE I
Examples 1 2 3 Comp.
Example Isocyanate A B C D
_ ___ Tensile strength per DIN 53 571 [k-Pa]llO lO0 120 80 Elongation per DIN 53572 [~] 94 97 lOS 86 Tear strength per DIN 53 575 [N/mm]0.41 0.42 0.57 0.38 Compression hardness at 40~ deflection per DIN 53 577 [k-Pa]6.0 5 5 5.9 4.8 Exam~es 4 and_5 and Comparative_Example Preparation of elastic, cellular polyurethanes using polyether-polyester polyol~ in the A Component.
A Component: Mixture comprising 100 parts polyol per Table II, 2.8 parts water, 0.2 part silicone stabili~er B 46 90 (vendor: Goldschmidt, E~en), 0.4 part bis(N,N-di-methylamino) diethylether, and 0.35 part triethylenediamine (33 weight percent solu~ion in dipropylene glycol).
B Component: Isocyanate E.
The A and B Components were mixed intensively for eight seconds at an index of 105 at room temperature (~3C), 800 g of the mixture was filled into an aluminum mold with internal dimension~ of 40 x 40 x lO cm at 50C. The mold was closed and the reaction mixture was allowed to expand.
s~7 Th~ isocyanates used and the mechanical properties measured on the resulting polyurethane flexible foams at a density of 50 g/l are summarized in Table II.
TABLE II
Exa~les 4 5 Comp.
Example Polyol IV V III
Tensile strength per DIN 53 571 ~k-Pa] 200 180 140 Elongation per DIN 53 572 [96~ 122 133 115 Tear strength per DIN 53 575 ~N/nan] 0.70.61 0.49 Compression hardness at 4096 deflection per DIN 53 57~ [k-Pa] 7~9 5.8 4.5 Exame~e_6_and Compar tive Example Preparation of an Elastic, Dense Polyurethane A Component: Mixture comprising 100 parts of a .
polyol per Table III, 7 parts 1,4-butanediol, 0.7 part triethylenediamine (33 weight percent solution in dipro-pylene glycol), and 0.03 part dibutyl tin dilaurate.
B Component~ Isocyanate F.
The A and B Components were mixed intensively at room temperature (23C) at an index of 104 and the mixture was placed in an aluminum mold preheated to 50C and whose ~ 31 --~ 5~
interior dimension~ were 200 x 200 x 4 mm. The reactable polyurethane mixture cured in the closed mold very quickly to form an elastomer.
The polyol~ which were used and the mechanical properties of the resulting polyurethane elas~omer are listed in Table III.
TABLE III
Example 6 Comp.
Example Polyol IV III
Tensile strength per DIN 53 571 [k~Pa] 3.21 2.27 Elongation per DIN 53 572 ~ 140 80 Tear qtrength per DIN 53 575 [N/mm~ 8.9 6.0
994 890, Belgium Patent 761 626), i~ocyanurate-group-containing polylsocyanate~ (German Patents 10 22 789, 12 22 067, 10 27 394, 19 29 034, and 10 04 048), urethane-group-containing polyisocyanates, (Belgium Patent 752 261, U. S. Patent 3,394,164) biuret-group-containing polyisocya nates, (German Patent 11 01 394, British Patent 889 050), and ester-group-containing polyi~ocyanates (Briti3h Patents 965 474 and 10 72 9S6, U. S. Patent 3,567,763, and German Patent 12 31 688).
Preferably used are commercially available, aromatic di- and polyisocyanateA, which may contain urathane group~, such a~ 2,4- and 2,6-toluene dii~ocyanate and mixtures thereof, 2,2'-, 2,4'-, and 4,4l-diphenylmethane diisocyanate and mixtures thereof, mixturea of 2,2'-, 2,4'-, and 4,4'-diphenylmethane dii~ocyanate~ with polyphenylene polymethylene polyi~ocyanates (polymeric MDI), and mixture~
of toluene diiqocyanates and polymeric MDI. These di- and polyisocyanates can be used individually or in mixtures.
Es~ential to the ~ubject invention i~ the inclu-sion of di- to tetrafunctional, preferably 2.5- to tri-functional polyether-polyester polyols having hydroxyl number~ from 10 to 200, pr~ferably from 25 to 56, in the organic polyether-polyester polyol component prepared by the proces~ of esterifying conventional polyether polyols having functionalities of from 2 to 4, preferably from 2.5 to 3, and hydroxyl number~ from 15 to 250, preferably from 30 to 110, with carboxylic di- and/or monoanhydrides, preferably aromatic carboxylic acid monoanhydrides, preferably in the presence of esterification catalysts, to form carboxylic acid half ester~, followed by oxyalkylating the carboxylic acid half esters thus formed with alkylene oxides in the presence oE N-methylimidazole, triethylenediamine, ~ri-phenylphosphine, mixture~ thereof, or mixtures of one or more thereof with thiodialkylene glycol, a~ oxyalkylation catalyst~. Mixtures of N-methylimidazole and/or triethylene diamine and triphenylpho~phine are preferably u~ed.
The conventional polyether polyols suitable for use in the proce~s of the inv~n~ion having a functionality of from 2 to 4 and a hydroxyl number of from 15 to 250 may be prepared in accordance with known method~, for example, by polyoxyalkylating an initiator molecule containing from 2 to 4, pr~ferably from 2.5 to 3 active hydrogen a~om~, with one or more alkylen~ oxide~.or cyclic ethers having from 2 to 4 carbon atom3 in the alkylene radical, in the pre~ence of acid, or pref~rably, ba~ic cataly3ts such as alkali hydroxide~ or alkali alcoholates, or through the polymeriza-tion of tetrahydrofuran with ~uitable catalysts, for example, boron trifluoride etherate, antimony pentachloride, or fuller'~ earth.
Suitable alkylene oxide~ and cyclic ethers are, for example: oxetan~, 1,2-, 2,3-butylene oxide, styrene oxide, and preferably, ethylene oxide and propylene oxide.
Th~ alkylene oxides may be reacted singly, as mixtures, or sequentially, to form homopolymeric~ heteropolymeric, or block-polymeric alkylene oxide addition products.
Typical initiator molecules which may be used are: water, organic dicarboxylic acid~ ~uch a~ ~uccinic acid, adipic acid, phthalic acid, and terephthalic acid;
aliphatic and aromatic diamines, in some ca~es N-mono-, N,N-, and N,N'-dialkyl-substituted diamines having from 1 to 4 carbon atoms in the alkyl radical, for example, mono- and dialkyl-subs~ituted ethylene diamine, diethylene trlamine, triethylene tetramine, l,3-propylene diamine, 1,3~ and 1,4-butane diamine, 1,2-, 1,3-, 1,4-, 1,5-, and 1,6-hexa-methylene diamine, phenylene diamine, 2,4-, and 2,6-toluene diamine and 4,4'-, 2,4'-, and 2,2'-diaminodiphenylmethane;
monoamine~ such as methylamine, ethylamine, i~opropylamine, butylamine, benzylamine, aniline, toluidine~, and naphthyl-amines. Eqpecially useful compound~ are: N,N,N',N'-tetraki~(2-hydroxyethyl)ethylenediamine, N,N,N',N 7 -tetrakis-(2-hydroxypropyl)ethylenediamine, N,N,N',N",Nn-pentakis~2-hydroxyethyl3ethylenetriamine, phenyl diisopropanolamine, and higher molecular weight alkylene oxide adductq of aniline.
Additional initiator molecules are: alkanolamines such a~ ethanolamine, diethanolamine, N-methyl- and N-ethyl-diethanolamine, N-methyl- and N-ethyl- dipropanolamine, triethanolamine, hydrazine and hydrazide~, di- to te~ra-functional, preferably di- to tri-func~ional alcohol~, for example, ethylene glycol, 1,2- and 1,3-propylene glycol, diethylene glycol, dipropylene glycol, 1,4-butylene glycol, 1,6-hexamethylene glycol, glycerine, trimethylolpropane, and pentaerythritol.
The polyether polyoi~ can be utilized individually or in the form of mixtures. Preferably, polyether polyols are u~ed which contain not more than 30 weight percent, preferably not more ~han 5 ~o 10 weight percent ethylen~
oxide r~idues ba~ed on the total weight of alkylene oxide residues, said polyether polyol~ having hydroxyl numbers from 15 to 250. Particularly well ~uited are polyoxy-propylene ether glycols and/or triol~ having hydroxyl numbers from 30 to 110.
Aliphatic, optionally halogenated monoanhydrides cycloalipha~ic, optionally ~ubstituted di- and/or mono-anhydrides, and aromatic, optionally sub~tituted di- and/or mono- anhydride~, are utilized a~ the carboxylic acid anhydride~. Particularly well suited are aromatic, option-ally ~ub~tituted monoanhydrides. Typical carboxylic acid anhydrides are: aliphatic carboxylic acid anhydrides ~uch aq maleic acid anhydride, dichloromaleic acid anhydride, succinic acid anhydride, and glutaric acid anhydride, cyclo-aliphatic carboxylic acid anhydrides ~uch a~, for example, hexahydro- and tetrahydrophthalic acid anhydride, and preferably, aromatic carboxylic acid anhydrides such a3 tetrachlorophthalic acid anhydride, tetrabromophthalic acid anhydride, trimellitic acid anhydride, pyromellitic acid dianhydride, and phthalic acid anhydrid~. Phthalic acid anhydride i9 particularly well suited.
In order to prepare the carboxylic acid half eqter~, the conventional polyether polyols or polyether polyol mixtures and the carboxylic acid anhydride or ~L2~ 7 carboxylic acid anhydrid~ mixtur~ are e~terified at temperatures from 50 ~o 240C, prefer~bly fro~ 90 to 200C, for a period of from 0.5 to 8 hour~, preferably from 1 to 4 hours. ~he esterification takes place preferably in the presence of cataly~ts. From 0.25 to 1.05 mole-equiva-lents, and preferably from 0.95 ~o 1.0 mole-equivalents, carboxylic acid anhydride are present in the reaction mixture per mols-equivalent polyether polyol. Triphenyl-phosphine, N-methylimidazole, triethylene diamine or mixtures thereof have proven to be effective e~terification catalysts. Preferably used are N-methylimidazole and triethylenediamine. The catalysts are used in amounts from 0.05 to 2.0 part~ by weight, preferably from 0.1 to 0.4 parts by weight, per 100 parts by weight of the conventional polyether polyol/anhydride reaction mixture.
These same e~terification catalyst~ have been found to be most effectlve in the oxyalkylation reaction.
Thus, the previously fcrmed half-esters may be oxyalkylated directly, without removing the esterification catalyst. It may be preferable to add additional amounts of the same cataly~t as used for the esterification reaction, or to add one or more additional catalyst~. A ~hiodialkylene glycol such as thiodiethylene glycol may be used in conjunction with one of the aforementioned catalysts for the oxyalkyla-tion if desired.
The oxyalkylation take~ place in the pre~ence of from 0.05 to 2.0 part~ by weight, preferably fro~ 0.1 to 0.~
parts by weight of the oxyalkylation cataly~ts, ba~ed on 100 parts by weight of the carboxylic acid half ester. From 1 to 4 mole-equivalent3, preferably one mole-equivalent, of propylene oxide, mixtures of propylene oxide and ethylene oxide, or preferably, ethylene oxide alone, i3 added per mole-equivalent of carboxyl group. Triphenylpho~phine is preferred a~ the oxyalkylation catalyst.
lQ Particularly advantageou~ results are obtained when the carboxylic acid half ester i~ prepared in the pre~ence of N-methylimidazole and triethylenediamine, or mixtures thereof as cataly~ and additional triphenylphos-phine is added to the reaction mixture for the oxyalkyla-tion. Thi~ repre~ents a preferred embodimen~.
Thiodialkylene glycolq ~uitable for the oxyalky-lation catalysts po~es~ from 2 to 6, preferably 2 to 3, carbon atom~ in the alkylene radical. Typical examples are thiodihexylene glycol, thiodibutylene glycol, and, prefer-ably, thiodipropylene and/or thiodiethylene glycol.
The oxyalkylation of the carboxylic half ester i3 generally performed at temperatures from 80 to 160C, preferably from 90 to 130C, at standard pres~ure or, preferably, at elevated pre~sure. Eqpecially useful, for example, are preqsure~ from 0~5 to 10 bar, advantageously in ~2~
the presance of gase~ which ar~ inert under the reaction condition~, for example, nitrogen, helium, neon, etc., or mixtures thereofu After an acid number of les~ than 1 has been reached, the oxyalkyla~ion i~ stopped. If the reac~ion mixture still contains free monomeric alkylene oxide, the mixture i~ ~tripped at reduced pre3sure. It is not neces--~ary to remove the catalysts used for the preparation of the carboxylic acid half ester and for the oxyalkylation of the resulting polyether-polyeqter polyolq.
In order to prepare ~he cellular or non-cellular polyurethanes in accordance with the proce~q of the inven~
tion, the polyether-polye~ter polyols can be utilized individually or aq mixture~. Mixture~ of the polyether-polyester polyols and other polyols having a functionality o from 2 to 4, preferably from 2.5 to 3, and hydroxyl number~ from 10 to 200, preferably from 30 ~o 110, can be uqed in accordance with the subject invention. Such polyols may be, for example, hydroxyl-group containing polyesters, polyester amide~, polyacetals, polycarbonate~, and, prefer-ably, graft polymer polyether polyol~, polyether polyol filler di~persions, and conventional polyether polyol~, provided said mixture~ contain at least 30 weight percen~, preferably from 50 to ca. 100 weight percent polyether-polyester polyols prepared by the process of the invention ba~ed on the total weight of the polyol component.
In some cases, it may be de~irab}a to utilize, in addition to the polyether-polye~ter polyol component, additives such as chain extenders or cros~-linking agent~, to introduce rigid ~egmentq into the resulting poly-urethanes. Such additives are polyfunctional, particularly di- and trifunctional compounds having molecular weights from 17 to 600, preferably from 60 to 300. Suitable, for example, are: di- and trialkanolamines such a~ diethanol-amine and triethanolamine, aliphatic and aromatic diamines such as ethylenediamine, 1,4-butylenediamine, 1,6-hexa-methylenediamine, 4,4'-diaminodiphenylmethane, 3,3'-dialkyl-substituted-4,4'-diaminodiphenylmethanes, 3,3',5,5'-tetra-alkyl-substituted-4,4'-diaminodiphenylmethanes, 2,4- and 2,6-toluenediamine, and preferably, aliphatic diols and triols having from 2 to 6 carbon atoms, such as ethylene glycol, l,4-butylene glycol, 1,6-hexamethylene glycol, glycerine, and trime~hylol propane.
When chain extenders or cross-linking agents are used, they are generally used in amounts from 1 to 10, preferably from 1 to 4 parts by weight per 100 parts by weight polyether-polyester polyol component.
Blowing agents or their precursors, sometimes termed "reactive" blowing agents, may be utilized. ~hera the unqualified term "blowing agent~ is utilized in the subject invention, it is understood ~o includa both inert as ~2~ 7 well as reactive blowing a~ent~. Among the reactive blowing agent~ which can ~e utilized in the proce3~ of the invention for the prepara~ion of cellular polyurethane~ i8 water, which react~ wi~h i~ocyanate group~ to form carbon dioxide. The amount~ of water u~ed most ~ucce~sfully are from 0.5 to 20 parts by weight, preferably from 1.5 to 10 part~ by weight, and more preferably from 2 to 6 part~ by weight, based on 100 part3 by weight of the polyether-polyester polyol component.
Inert blowing agents may also be u~ed, either alone or mixed with water. Suitable liquid3 are those inert to the polyisocyanates and which posse~ boiling point~ les3 than 100C, preferably le~s than 50C, and mo~t preferably between -50C and 30C at atmo~pheric pressure, and which vaporize under the effect of the exothermic addition polymerization reaction. Typical blowing agent~ are hydrocarbons such a~ pentane, n-butane, iso-butane, and propane; ethers such as dimethyl ether and diethyl ether, ketones such a3 acetone and methylethyl ketone, ethyl acetate, and preferably, halogenated hydrocarbonq ~uch as methylene chloride, trichlorofluoromethane, dichlorodi-fluoromethane, dichloromonofluoro~e~hane, dichlorotetra-fluoroethane, and l,1,2-trichloro-1,2,2 trifluoroethane.
Mixture~ of these low boiling point liquid~ may al~o be utilized.
~2~ 7 ~ he desired amount of inert blowing agent can be determined ~imply, ba~ed on the amount of water which i~
pre~ent and the desired foam den~ity. In the ab~ence of water, this amount is approximately 1 to 4 parts by weight, preferably 3 to 15 part~ by weight, per 100 parts by weight polye~her-polye~ter polyol component. It may be desirable to mix the organic polyi~ocyanate with the blowing agent to thereby lower the viqco~ity of the polyi~ocyanate component.
In order to accelerate the reaction between the polyether-polyester polyol component, water, ~hain ex-tenders, or cross-linking agent~, and the organic polyisocy-anate~, standard polyurethane cataly~t~ may be incorporated into the reaction mixture. Basic polyurethane catalyst~ are preferably used, for example, tertiary amines such a~
dimethylbenzylamine, dicyclohexylmethylamine, dimethylcyclo-hexylamine, N,N,N',N'-tetramethyldiaminobutane, N,N,N',N'-tetramethyldiaminoethyl ether, bis(dimethylaminopropyl)urea, N-methyl- and N-ethylmorpholine, dimethylpiperazine, pyridine, l,2-dimethylimidazol~, l-azabicyclo[30300]0ctane, dimethylaminoethanol, Z-(dimethylaminoethoxy)ethanol, N,N',N"-tris(dialkylaminoalkyl)hexahydrotriazenes quch a~
N,N',N"-tri3(dimethylaminopropyl)-s-hexahydrotriazine and, in particular, triethylene diamin~ However, metal salt~
such a3 iron(II)chloride, zinc chloride, lead octoate, and, preferably tin ~alt~ ~uch a~ tin dioctoate, tin diethyl-hexanoata, and dibutyl tin dilaurate a~ well as mixtures of tertiary amines and organic tin salts are also suitable. It is desirable to use from 0.1 to 10 weight percent, prefer-ably from 0.5 to 5 w~ight percent, catalysts based on tertiary amines and/or from 0.01 ~o 0.5 weight percent, preferably from 0.05 to 0.25 weight percent metal salts, based on the weight of the polyether-polyester polyol component.
Auxiliaries or additive3 can also be incorporated in the reaction mixture. Typical example~ are surfactant~, foam stabilizers, cell regulators, fillers, colorants, pigments, flame retardants, anti-hydrolytic agent~, and fungistatic and bacteriostatic substances.
Surfactants which help to homogenize the various components and also regulate cell structure are e~pecially use~ul. Typical sur~actant3 are, for example, emulsifier~
~uch as the sodium salt~ of castor oil sulfates or of fatty acids. salts of fatty acids with amin~s, for example, maleic acid diethylamine or stearic acid diet~anolamine salts, ~0 salt~ of sulfonic acid~ such as alkali or ammonium salts of dodecylbenzene sulfonic acid or dinaphthylmethanedisulfonic acid and ricinoleic acid, foam ~tabilizers such as siloxane-oxyalkylene copolymer~ and other organic polysiloxane~, oxyethylated alkylphenols, oxyethylated fatty alcohols, paraffin oil, esters of castor oil, ricinoleic acid or ~2~ 3~
TurXey red oil, and cell regulators ~uch as paraffins, fatty a7coholY, and dimethylpolysiloxanes. The surfactant~ are generally pre~ent in amount~ from O.Ol to 5 parts by weight based on lOO part~ by weight polyether-polye~ter polyol component.
By the term fillers, in particular ~illers which have a reinforcing effect, is meant conventional organic and inorganic fillers, reinforcing agent~, weight-increasing agents, and agents for improving wear in paints, coatings, etc. Typical example~ are: inorganic fille~s 3uch as ~ilicate minerals, for ex~ple lamellar silicate~ such as antigorite, serpentina, horn blende, amphibolite, chryso-tile, and talcum; metal oxide~ such as kaolin, aluminum oxides, titanium oxides, and iron oxides, matal salt~ such as chalk, and barium sulfate, and inorganic pigments ~uch as cadmium sulfide, zinc sulfide, gla~s, ground asbestos, etc. Preferably, kaolin (China Clay), aluminum silicate, and coprecipitates of barium sulfate and aluminum silicate are u~ed, as well as natural and synth~tic fibrous minerals such as asbestos, wollastonite, and in particular, glass fibers of varying length~, which may be treated with size.
Typical organic filler~ are: carbon black, melamine, pine resin, cyclopentadianyl re~ins, and, preferably ~yrene-acrylonitrile-based graft polymers prepared through in ~itu polymerization of acrylonitrile-styrene mixtures in poly-ether polyols, similar to German patents 11 11 3g4, 12 22 669, (U~ S. Patent 3,304,273, 3,383,351, 3,523,093), 11 52 536, (Briti~h Patent 1,040,452) and 11 52 537 (British Pa~ent 987,618~ a~q well a~ filled polyether polyols in which agueous polymer di~persions are transformed into polyether polyol dispersions.
The inorganic and organic fillers may ~e used individually or as mixtures. Preferred are stable polyether polyol di~qparsions in which the fillers are raduced in si~e in the presence of polyether polyol~ in situ with high localized energy gradients to a particle size less than 7 ~m and are simultaneously dispersed by this action. Filled polyether polyol dispersions of this type are described, for example, in German Patents 28 50 609, 28 50 610, and 29 32 30~.
The inorganic and organic fillers are advanta-geously incorporated into the reaction mixture in amounts from 0~5 to 50 weight percent, preferably from 1 to 40 weight percent, based on the weight of the polyisocyanate-polyether-polyester polyol component reaction mixture.
Suitable flame retardants may also be added, such as, for example: tricresyl phosphate, tris-(2-chloroethyl)-phospha~e, tris-(chloropropyl)phosphate, and ~ris-(2,3-dibromopropyl)phosphate. Also used as flame retardants are inorganic flame retardant~ such as hydrated aluminum oxide~, -- ~0 --antimony trioxide, arsQnic oxide~, ammonium polyphosphate, and calcium ~ulfate as well as the e~terification products of low-molecular-weight mono- and polyfunctional alcohol~
and halogena~ed phthalic acid derivatives. In general, it has been found to be desirable to use from 5 to 50 parts by weight, preferably from 5 to 2~ parts by weight, of the above-cited flame retardanta per 100 parts by weight polyether-polyester polyol component.
Further information on other conventional aux-iliaries or additives may be found in the literature, in particular the monograph by J. H. Saunders and K. C. Frisch, "High Polymer~, n Vol. XVI, Pol~urethanes, Pts. 1 and 2, Interscience Publisher~: 1962/1964.
In order to prepare the polyurethanes in accor-dance with tAe process of the invention, the organic polyisocyanates and polyether-polyester polyol component, chain extenders, and cro~s-linking agents are reacted in the presence of catalysts, and in some cases, blowing agent3, auxiliaries and additives, at temperatures from 0 to 70C, preferably from 15 to 50C, at active hydrogen/isocyanate ratio~ of from 0.5 to 2:1, preferably from 0.8 to 1.6:1, and most preferably approximately 1:1.
The cellular or non-cellular polyurethanes can also be prepared using the prepolymer proce3s. To do this, the polyether-polyester polyol~ are tran~formed using 3~
ordinary method~ into i~ocyanate-group-containing prepoly-mers by the addi~ion of polyi~ocyanate~, preferably mixtures Oî 4,4'- and 2,4'-diphenylme hane diisocyanate~ or mix~ures of diphenylmethane diisocyanates and polyphenylene poly-methyl~ne polyisocyanate3 having a diphenylmethane diisocya-nate content in excess of 60 weight percent. The isocya-nate-group-~ontaining prepolymers can be reacted a~ such or in the form of a mixture with polyisocyanates, preferably a mixture o~ diphenylmethane diisocyanates and polyphenylene polymethylene polyisocyanate~, with additional polyether-polyester polyol component or wi~h conventional polyols, along with, in some case~, chain extender~ or cross-linking agents in the presence of catalyst~ and, in some cases, blowing agents, auxiliaries, and additive~.
Preferably, however, the cellular or non-cellular polyurethane3 are prepared in a one-shot process. Here the initial components, auxiliaries, and additive~ are added individually ~sing a mixing head with several feed noæzles and are mixed together inten~ively in a mixing chamber. It has been found to be particularly desirable to use a two-component proce~s, and to combine the polyether-polyester polyol component, cataly~ts, and, in ~ome case~, chain extenders, cro~-linking agent~, blowing agents, aux-iliaries, and additives on the ~o-called A component side, and to use as the B component the polyisocyanate, modified ~2~ '7 polyisocyanate and/or the isocyanate-grsup-containing prepolymers, in some casea in admixture wi~h blowing agents, and auxiliaries or additives. The advan~age oE the two-component procesq is that the A and B components need only to be intensively mixed together in the proper quantitative ratios to prepare ~he polyurethane~. The basic component3 can also be mixed together in a one-shot process with the aid of familiar reaction injection molding techniques (RIM), injected into molds, and cured in the closed molds to form polyurethane~.
The den~e, elastic, non-cellular or microcellular polyurethane~ prepared in accordance with the invention possess densities from 0.8 to 1.4 g/cm3, preferably from 1.1 to 1.2 g/cm3, and possess very good tensile strength, elongation, and tear streng~h. The products are suitable for the preparation of highly abrasion resis~ant poly-urethane molded parts such as rolls, sliding ~hoes, sliding corner~ for snow removal equipment, etc.
Elastic, cellular polyurethanes prepared by this procass may have densities of fro~ 0.2 to 1.2 g/cm3. Shoe soles preferably have a density from 0.3 ~o 0.7 g/cm3, while RIM molded parts preferably have a densi~y from 0.7 ~o 1.1 g/cm3. Both exhibit very good compression hardness, tensile ~trength, and elongation. The highly elastic, flexible foams having densities from 0.02 to 0.2 g/cm3 are ~ 23 -suitable for the production of upholstery cushion~, mat-tre~ses, automotive ~eat cushions, and neck ~upports, a~
well a~ particularly for molding foam~. Ela~tic poly-ur~thane~ find use~ a~ automotiv~ exterior part~, impact-ab~orbing moldings, bumper coating~, and in corner protec-tion application~.
The following material~ were u~ed to prepare the cellular or non-cellular polyurethane~ in the examples. The parts cited in the examples ~efer to parts by weight.
Polyol I:
A glycerine initiated polyoxypropylene polyoxy-ethylene block copolymer having a hydroxyl number of 35 and an ethylene oxide content of 15 weight percent~
Polyol II:
A glycerine initiated polyoxypropylene polyoxy-ethylene heteric copolymer having a hydroxyl number of 42 and an ethylene oxide content of 7Q welght percent in a random distribution.
Polyol III:
A glycerine initiated polyoxypropylene polyoxy~
ethylene heteric/block copolymer copolyether having a hydroxyl number of 56 and an e~hylene oxide content of 11 9~d weight percen~, of which ~hree-fif~hs are pre!~ent in a random dis~ribution and two-fifth~ a~ a terminal block.
Polyol IY:
Three thousand parts (1 mole) Polyol III were est~rified with 444 parts of (3 moles) phthalic acid anhydride in the pre~ence of 0.2 weight percent N-methyl-imidazole in a nitroy~n atmo~phere for 4 hours at 180C
while being agitated.
The reaction mixture was allowed ~o cool to lOS~C, following which 0.2 parts by weight thiodiethylene glycol was added, and an oxyethylation reaction wa3 performed at 2 bar nitrogen pressure with 132 parts (3 moles) ethylene oxide. At the end of oxyethylation, the volatile components were stripped at lOSC and 0.01 bar. The resulting poly-ether-polyester polyol had a hydroxyl number of 49 and could be u~qed for the preparation of polyurethanes without further purification.
Polyol ~:
A procedure similar to that used in the prepara-tion of Polyol IV was used, however, the equivalent amount of tetrahydrophthalic acid anhydride wa~ u~ed in place of ths phthalic acid anhydride and 0O2 weight perc~nt tri-phenylphosphine was used instead of thiodiethylen~ glycol - ~5 -3~3~
for the ethyoxylation. The re~ulting polyether-polyes~er polyol had a hydroxyl number of 51.
Pol~ol YI:
Thirty-two hundred parts (3 moles) of a polyoxy-propylene glycol having a hydroxyl number of 105 were heated to 180C under a nitrogen atomsphere with 888 part~ (6 moles) phthalic acid in the presence of 0.2 weight percent N-methylimidazole and agitated for four hours.
The reaction mixture was then allowed to cool to 105C, following which 0.2 weight percent thiodiethylene glycol was added, and the mix~ure was oxypropylated at 0.5 bar nitrogen pressure with 348 parts (6 moles) propylene oxide. After completion of the oxypropylation, the volatile components were stripped at 105C and 0~01 bar. The resulting polyether-polyester polyol pos3essed a hydroxyl number of al and could be used for the preparation of polyurethane without additional purification.
Isocyanate A: An isocyanate-group-containing prepolymer with an isocyanate content of 23 weight percent, prepared by the reaction of 100 part~ of a mixture comprising 4,4'- and 2,4'-diphenylmethane diisocyanate in a weight ratio of 75:25 and 39.5 part~ Polyol IV at 70C with two hours agitation~
~ 26 -~L2~
Isocyanate B: An isocyanate-group-containing prepolymer with an isocyanate content of 23 weight percent, prepared similarly to isocyanate A, however, 39.3 parts Polyol V were used instead of Polyol IV.
I~ocyanate C: An isocyanate-group-con~aining prepolymer with an isocyanate content of 23.3 weight percent, prepared similarly to isocyanate A, however, using 18.7 parts Polyol ~I instead of Polyol IV.
I~ocyanate D: An lsocyanate-group~containing prepolymer having an isocyanate content of 23 weight percent, prepared similarly to isocyanate A, however, using 38.8 parts Polyol III instead of Polyol IV.
Isocyanate E: A polyisocyanate mixture having an isocyanate content of 3~.6 weight percent, comprising: 40 parts of a mixture of 45 weight percent diphenylmethanediisocyanates and 55 weight percent polyphenylenepolymethylene polyisocya-nates (polymeric MDI), 45 parts 4,4'~diphenylmethane diisocyanate, and 15 parts 2,4'-diphenylmethane diisocyanate.
Isoc~anate F: An isocyanate-group-containing prepolymer with an isocyanate content of 23 weight percen~, prepared by the reaction of 100 part~ 4,4'-diphenylmethane diisocyana~e and 25~2 parts of a polyoxypropylene glycol having a hydroxyl number of 250, at 60C for four hours.
Example~ 1 3 and Comparative _x~
Preparation of elastic, cellular polyurethanea using isocyanate-group-containing prepolymer~ ba3ed on poly~ther-polyes~er polyols.
A Com~nent: A mixture compri~ing 86.4 part~
Polyol I, 4.0 parts Polyol II, 2.8 part~ water, 0.35 parts triethylenediamine (33 weight percent solution in dipro-pylene glycol~, 0.35 part bi~N,N'-dimethylamino)diethyl-ether, 0.1 part silicone stabilizer B 4690 (vendor:
Goldschmidt, Essen), and 6 part~ trichlorofluoromethane.
B Com~onent: Mixture comprising 40 part~ of a mixture of diphenylmethane dii~ocyanates and polyphenylene polymethylene polyisocyanate~ having an isocyanate content of 31 weight percent (polymeric MDI) and 60 par~ isocyanate as iden~ified in accordance with Table I.
The A and B Components were mixed intensively for eight seconds at an index of 100 at room ~emperature (23C);
800 g of the mixture was poured into an aluminum mold with internal dimension3 of 40 x 40 x 10 cm at 50C. The mold was closed and the reaction mix~ure was allowed to expand.
The isocyanates used and ~he mechanical propertie~
a~ measured on the resulting polyurethane flexible foams at a den~ity of 50 g/l are summarized in rable I.
TABLE I
Examples 1 2 3 Comp.
Example Isocyanate A B C D
_ ___ Tensile strength per DIN 53 571 [k-Pa]llO lO0 120 80 Elongation per DIN 53572 [~] 94 97 lOS 86 Tear strength per DIN 53 575 [N/mm]0.41 0.42 0.57 0.38 Compression hardness at 40~ deflection per DIN 53 577 [k-Pa]6.0 5 5 5.9 4.8 Exam~es 4 and_5 and Comparative_Example Preparation of elastic, cellular polyurethanes using polyether-polyester polyol~ in the A Component.
A Component: Mixture comprising 100 parts polyol per Table II, 2.8 parts water, 0.2 part silicone stabili~er B 46 90 (vendor: Goldschmidt, E~en), 0.4 part bis(N,N-di-methylamino) diethylether, and 0.35 part triethylenediamine (33 weight percent solu~ion in dipropylene glycol).
B Component: Isocyanate E.
The A and B Components were mixed intensively for eight seconds at an index of 105 at room temperature (~3C), 800 g of the mixture was filled into an aluminum mold with internal dimension~ of 40 x 40 x lO cm at 50C. The mold was closed and the reaction mixture was allowed to expand.
s~7 Th~ isocyanates used and the mechanical properties measured on the resulting polyurethane flexible foams at a density of 50 g/l are summarized in Table II.
TABLE II
Exa~les 4 5 Comp.
Example Polyol IV V III
Tensile strength per DIN 53 571 ~k-Pa] 200 180 140 Elongation per DIN 53 572 [96~ 122 133 115 Tear strength per DIN 53 575 ~N/nan] 0.70.61 0.49 Compression hardness at 4096 deflection per DIN 53 57~ [k-Pa] 7~9 5.8 4.5 Exame~e_6_and Compar tive Example Preparation of an Elastic, Dense Polyurethane A Component: Mixture comprising 100 parts of a .
polyol per Table III, 7 parts 1,4-butanediol, 0.7 part triethylenediamine (33 weight percent solution in dipro-pylene glycol), and 0.03 part dibutyl tin dilaurate.
B Component~ Isocyanate F.
The A and B Components were mixed intensively at room temperature (23C) at an index of 104 and the mixture was placed in an aluminum mold preheated to 50C and whose ~ 31 --~ 5~
interior dimension~ were 200 x 200 x 4 mm. The reactable polyurethane mixture cured in the closed mold very quickly to form an elastomer.
The polyol~ which were used and the mechanical properties of the resulting polyurethane elas~omer are listed in Table III.
TABLE III
Example 6 Comp.
Example Polyol IV III
Tensile strength per DIN 53 571 [k~Pa] 3.21 2.27 Elongation per DIN 53 572 ~ 140 80 Tear qtrength per DIN 53 575 [N/mm~ 8.9 6.0
Claims (12)
1. In a process for the preparation of cellular or non-cellular polyurethanes through the reaction of an organic polyisocyanate with a polyol component in the presence of suitable catalysts and, in some cases, chain extenders or cross-linking agents, blowing agents, and auxiliaries or additives, wherein the improvement comprises utilizing as said polyol component an isocyanate-reactive polyol containing from 30 percent to 100 percent by weight of di- to tetrafunctional polyether-polyester polyols having hydroxyl numbers from 10 to 200 prepared by the process of:
a) esterifying di- to tetrafunctional polyether polyols having hydroxyl numbers from 15 to 250 with carboxylic acid anhydrides to form carboxylic acid half esters, and b) oxyalkylating of the carboxylic acid half esters with alkylene oxides in the presence of a catalyst selected from the group consisting of:
i) N-methylimidazole, ii) triethylenediamine, iii) triphenylphosphine, iv) mixtures of two or more of (i), (ii), and (iii), and v) a mixture of thiodialkylene glycol and at least one of (i), (ii), and (iii).
a) esterifying di- to tetrafunctional polyether polyols having hydroxyl numbers from 15 to 250 with carboxylic acid anhydrides to form carboxylic acid half esters, and b) oxyalkylating of the carboxylic acid half esters with alkylene oxides in the presence of a catalyst selected from the group consisting of:
i) N-methylimidazole, ii) triethylenediamine, iii) triphenylphosphine, iv) mixtures of two or more of (i), (ii), and (iii), and v) a mixture of thiodialkylene glycol and at least one of (i), (ii), and (iii).
2. The process of claim 1, wherein the di- to tetrafunctional polyether polyols are esterified in the presence of N-methylimidazole, triethylenediamine or mixtures thereof as catalysts.
3. The process of claim 1, wherein (a) the di- to tetrafunctional polyether polyols are esterified with carboxylic acid anhydrides in the presence of N-methylimidazole, triethylenediamine or mixtures thereof as catalysts, and (b) the oxyalkylation of the carboxylic acid half esters with alkylene oxides is in the presence of a catalyst selected from the group consisting of:
i) N-methylimiaazole, ii) triethylenediamine, iii) triphenylphosphine, iv) mixtures of two or more of (i), (ii), and (iii), and v) a mixture of thiodialkylene glycol and at least one of (i), (ii), and (iii).
i) N-methylimiaazole, ii) triethylenediamine, iii) triphenylphosphine, iv) mixtures of two or more of (i), (ii), and (iii), and v) a mixture of thiodialkylene glycol and at least one of (i), (ii), and (iii).
4. The process of claim 1 wherein the oxyalkyla-tion of the carboxylic acid half esters is performed in the presence of a catalyst comprising N-methylimidazole, triethylenediamine, diphenylphosphine, or mixtures thereof.
5. The process of claim 1, wherein from 0.05 part by weight to 2.0 parts by weight N-methylimidazole, tri-ethylenediamine, triphenylphosphine, mixtures thereof, or mixtures thereof with thiodialkylene glycol are used per 100 parts by weight of the polyether polyol and carboxylic acid anhydride reaction mixture.
6. The process of claim 1, wherein the polyether polyols contain a maximum of 30 percent by weight of ethylene oxide residues.
7. The process of claim 1, wherein aromatic carboxylic acid anhydrides are used for the preparation of the carboxylic acid half esters.
8. The process of claim 7 wherein said aromatic carboxylic acid anhydride is phthalic acid anhydride.
9. The process of claim 1, wherein one mole-equivalent of polyether polyol is esterified with from 0.25 to 1.05 mole-equivalent of carboxylic acid anhydride to prepare the carboxylic acid half ester.
10. The process of claim 1, wherein said alkylene oxide is selected from the group consisting of a) ethylene oxide, b) propylene oxide, and c) mixtures thereof.
11. The process of claim 10 wherein a plurality of alkylene oxides are added sequentially.
12. The process of claim 1, wherein one mole-equivalent alkylene oxide is used per mole-equivalent of carboxylic acid group of the carboxylic acid half ester for the oxyalkylation.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19833315382 DE3315382A1 (en) | 1983-04-28 | 1983-04-28 | METHOD FOR PRODUCING ELASTIC, COMPACT OR CELLULAR POLYURETHANES |
| DEP3315382.5 | 1983-04-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1219987A true CA1219987A (en) | 1987-03-31 |
Family
ID=6197562
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000452232A Expired CA1219987A (en) | 1983-04-28 | 1984-04-17 | Process for the preparation of cellular and non- cellular polyurethanes |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0124071B1 (en) |
| CA (1) | CA1219987A (en) |
| DE (2) | DE3315382A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5151484A (en) * | 1991-01-26 | 1992-09-29 | Bayer Aktiengesellschaft | Isocyanate prepolymers containing ether and ester groups a process for their preparation and their use for the production of coating, sealing or casting composition |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3437915A1 (en) * | 1984-10-17 | 1986-04-17 | Bayer Ag, 5090 Leverkusen | METHOD FOR THE PRODUCTION OF POLYETHERESTER POLYOLS, CORRESPONDING PROCESS PRODUCTS AND THEIR USE |
| DE3613875A1 (en) * | 1986-04-24 | 1987-10-29 | Basf Ag | METHOD FOR PRODUCING POLYESTER POLYOLS |
| NZ234512A (en) * | 1989-07-19 | 1992-05-26 | Mitsui Toatsu Chemicals | Polyols prepared by adding alkylene oxide onto a compound containing at least one ester and/or amide linkage; polyurethane resins and foams prepared therefrom |
| US5397810A (en) * | 1989-07-19 | 1995-03-14 | Mitsui Toatsu Chemicals, Inc. | Polyol, polyurethane resin and utilization thereof |
| DE19601410B4 (en) * | 1996-01-17 | 2004-12-09 | Basf Ag | Process for the production of flexible polyurethane foams |
| FR2747389B1 (en) * | 1996-04-12 | 1998-06-05 | Witco | POLYESTER POLYOL, POLYURETHANE FOAM OBTAINED FROM SAID POLYESTER POLYOL AND USE THEREOF |
| AR017610A1 (en) * | 1997-11-13 | 2001-09-12 | Dow Chemical Co | PROCEDURE TO PREPARE POLYETER POLIETES USING IMIDAZOLS AS CATALYSTS |
| EP2551289A1 (en) * | 2011-07-26 | 2013-01-30 | Basf Se | Process for the continuous production of polyetherols |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2142161A1 (en) * | 1970-08-26 | 1972-03-02 | Dow Chemical Co | Process for the production of flexible polyurethane foams |
| JPS5040422B2 (en) * | 1972-04-14 | 1975-12-24 | ||
| US4229362A (en) * | 1979-04-16 | 1980-10-21 | The Dow Chemical Company | Esterification process |
| DE3201203A1 (en) * | 1982-01-16 | 1983-07-28 | Basf Ag, 6700 Ludwigshafen | METHOD FOR PRODUCING POLYESTER AND / OR POLYESTER-POLYETHER-POLYOLS |
| US4403093A (en) * | 1982-09-28 | 1983-09-06 | Ppg Industries, Inc. | Polyesters |
-
1983
- 1983-04-28 DE DE19833315382 patent/DE3315382A1/en not_active Withdrawn
-
1984
- 1984-04-17 CA CA000452232A patent/CA1219987A/en not_active Expired
- 1984-04-25 DE DE8484104608T patent/DE3477387D1/en not_active Expired
- 1984-04-25 EP EP84104608A patent/EP0124071B1/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5151484A (en) * | 1991-01-26 | 1992-09-29 | Bayer Aktiengesellschaft | Isocyanate prepolymers containing ether and ester groups a process for their preparation and their use for the production of coating, sealing or casting composition |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3477387D1 (en) | 1989-04-27 |
| EP0124071B1 (en) | 1989-03-22 |
| EP0124071A2 (en) | 1984-11-07 |
| DE3315382A1 (en) | 1984-10-31 |
| EP0124071A3 (en) | 1986-03-05 |
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