CA2193032A1 - Low-viscosity polymer polyols, a process for their production, and their use for the production of polyurethane plastic foams - Google Patents
Low-viscosity polymer polyols, a process for their production, and their use for the production of polyurethane plastic foamsInfo
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- CA2193032A1 CA2193032A1 CA 2193032 CA2193032A CA2193032A1 CA 2193032 A1 CA2193032 A1 CA 2193032A1 CA 2193032 CA2193032 CA 2193032 CA 2193032 A CA2193032 A CA 2193032A CA 2193032 A1 CA2193032 A1 CA 2193032A1
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- Prior art keywords
- polyol
- production
- weight
- primary hydroxyl
- unsaturated
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
-
- 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
- C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
- C08G18/635—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers onto unsaturated polymers
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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)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Polymerisation Methods In General (AREA)
Abstract
A process is described for the production of stable agglomerate-free low-viscosity polymer polyols by free-radical polymerization of ethylenically unsaturated monomers, such as styrene and/or acrylonitrile, with polyol compounds. This process requires that prior to the start of the free-radical polymerization, an olefinically unsaturated compound which is capable of reacting with primary hydroxyl groups is added to a base polyol which contains at least 2 wt-% of a polyol containing primary hydroxyl end groups, and then, the free-radical polymerization is carried out. Suitable olefinically unsaturated compounds include unsaturated cyclic or acyclic anhydrides, unsaturated acid chlorides and/or unsaturated epoxides. Also, a process for the production of polyurethane plastics from the polyisocyanate polyaddition process is described wherein the isocyanate-reactive component comprises the polymer polyols produced from the above described process.
Description
Mo~562 LeA 31,486 -US
LOW-VISCOSITY POLYMER POLYOLS, A PROCESS
FOR THEIR PRODUCTION, AND THEIR USE FOR THE
PRODUCTION OF POLYURETHANE PLASTIC FOAMS
BACKGROUND OF THE INVENTION
The present invention relates to a process for the production of polymer polyols having low viscosity, the polymer polyols produced by this process, and to their use in the production of polyurethane plastic foams.
The expression "polymer polyols", which are also commonly referred to as graft copolymer dispersion, is understood to mean products that can be obtained by polymerization of olefinic monomers in polyether polyols ("base polyols"). In this broad sense, the olefinic monomers principally consist of ethylenically unsaturated compounds such as styrene and/or acrylonitrile.
Polymer polyols are employed, for example, in the production of soft polyurethane plastic foams.
The production of polymer polyols is described in, for example, U.S. Patents 3,383,351 and 3,304,273, or in DE-A 1,152,536 and DE-A
1,152,537.
In the ideal case, the polymer polyols are relatively low-viscosity, finely divided, non-settling dispersions of the polymerizate (which preferably comprises an acrylonitrile/styrene graft copolymer) in the essentially unchanged polyether polyol (i.e. base polyol). Characteristic features associated with quality and processability of the polymer polyols are low-viscosity, storage stability (resistance to sedimentation) and fineness of dispersal. These properties are influenced above all by the type and the relative proportions of the starting materials. In particular, Mo-4562 -2-the solids content (proportion of monomers in the formulation) and the monomer ratio (e.g. styrene/ acrylonitrile ratio) have a considerable influence on the quality of the product.
The most important aims in the production of polymer polyols are 5 the attainment of high solids contents (at least 40%) with a viscosity that is as low as possible, and, simultaneously, with excellent product stability.
In order to achieve product stability, i.e. the prevention of the formation of undesirable agglomerated polymer particles that precipitate out of the continuous phase or the base polyol, the polymer particles have to be 10 stabilized during production of the polymer polyol. This stabilization can be achieved by the incorporation of a portion of the molecules of the base polyether into the polymer that is formed in-situ. In this sense, the - effectiveness of the stabilization is favored by, for example, a molecular weight of the base polyether that is as high as possible and by a 15 proportion of acrylonitrile in the monomer mixture that is as high as possible. Whereas a high acrylonitrile content increases the intrinsic color of the polymer polyols and the tendency towards discoloration of soft foams produced therewith and is therefore undesirable, the viscosity of the polymer polyols is increased by the use of base polyols of higher 20 molecular weight.
In accordance with the state of the art, the most important way of stabilizing polymer polyols is through the concomitant use of compounds which are compatible with the base polyol phase and which contain ethylenically unsaturated, polymerizable groups (i.e. macromonomers or 25 macromers). These so-called macromonomers copolymerize with the vinyl monomers, so that the polymer particles arising are sterically stabilized by polyether side-chains and are consequently protected against agglomeration and sedimentation.
The production of polymer polyols with concomitant use of 30 macromonomers is described, for example, in U.S. Patents 3,652,639, ~lg~032 Mo-4562 -3-3,823,201, 4,342,840, 4,390,645, 4,454,255 (Reissue 33,291) 4,460,715 and 5,093,412. The ethylenically unsaturated double bonds are, for example, introduced into polyether polyols by reaction with cyclic, unsaturated carboxyiic anhydrides such as maleic anhydride and subsequent reaction with ethylene oxide or propylene oxide; by esterification with acrylic or methacrylic derivatives; by reaction with allyl glycidyl ether; by reaction with an unsaturated isocyanate such as isocyanatoalkyl acrylate and isocyanatoalkyl methacrylate, 1-(1-isocyanato-1-methylethyl)-3-(1-methylethenyl)-benzene or NCO-functional adducts formed from a polyisocyanate and hydroxyethyl acrylate or hydroxypropyl acrylate.
With all the specified processes the macromonomer has to be synthesized prior to the actual production of polymer polyol. This results in logistical problems, for example, since an adequate quantity of macromonomer always has to be produced and stored in addition to the base polyol for the production of polymer polyol.
It is therefore of interest to develop processes which produce low-viscosity polymer polyols with high solids contents and that do not require the use of previously produced macromonomers.
It has surprisingly been found this object can be achieved with the process according to the invention.
SUMMARY OF THE INVENTION
The present invention comprises a process for the production of stable polymer polyols comprising:
25 1 ) mixing a) a base polyol component comprising i) at least 2% by weight, based on 100% by weight of the base polyol component, of at least one polyether polyol containing at least one primary hydroxyl end group, preferably containing predominately primary hydroxyl end groups, and b) an olefinically unsaturated compound which is capable of Mo4562 -4-reacting with primary hydroxyl groups, and 2) polymerizing the mixture from 1) with c) a mixture of at least two ethylenically unsaturated monomers, in the presence of a free-radical catalyst to form a polymer polyol.
The polyol which accounts for at least a portion of the base polyol component and which contains at least one primary hydroxyl group per molecule is preferably a polyether polyol. Suitable polyether polyols containing at least one primary hydroxyl groups include, for example, the known addition products of cyclic ethers such as, for example, ethylene oxide, propylene oxide, styrene oxide, butylene oxide with starter compounds such as, for example, polyhydroxy compounds including alkylene glycols, glycerine, trimethylolpropane, pentaerythritol, sorbitol, amines such as ethylene diamine or toluylene diamines. These polyols should have functionalities between 1 and 6 and an OH number from 10 to 100. It is preferred that this polyether polyol contain predominately primary hydroxyl end groups.
Typically, the ethylenically unsaturated monomers are present in a quantity of from about 20 to 65% by weight, based on the weight of the end product.
Polymerization may, optionally, be carried out in the presence of a low-molecular regulator (i.e. chain transfer agent), and/or also, optionally, in an organic solvent.
In accordance with the invention it is preferred that:
1) the monomers are ethylenically unsaturated monomers, such as, for example, styrene and/or acrylonitrile, Mo-4562 -5 2) ethylenically unsaturated monomers comprise a mixture of styrene and acrylonitrile in a weight ratio of 20:80 to 80:20, most preferably 25:75 to 75:25, 3) the base polyol component comprises at least one so-called "conventional base polyol" having at least two hydroxyl groups, and most preferably comprises at least one polyether polyol having a functionality of 2.5 to 6 and an OH
number up to 100, 4) the base polyol component comprises at least one polyol having at least one primary hydroxyl end group, more preferably a polyether polyol having a functionality of 1 to 6 and an OH number from 10 to 100, most preferably 20 to - 100, 5) the olefinically unsaturated compound is added to the base polyol component in a quantity of from 0.05 to 1.5% by weight, preferably of from 0.1 to 1.0% by weight, based on the total weight of the base polyol component a).
It is particularly preferred that the polyols used as "conventional base polyols" containing at least two hydroxyl groups are polyether 20 polyols such as, for example, the known addition products of cyclic ethers such as, for example, ethylene oxide, propylene oxide, styrene oxide, butylene oxide, with starter compounds such as, for example, polyhydroxy compounds such as, for example, alkylene glycols, glycerine, trimethylolpropane, pentaerythritol, sorbitol, or amine compounds such as, 25 for example, ethylene diamine or toluylene diamines. The polyether polyols used as "base polyols" more preferably have functionalities of 2.5 to 6 and OH numbers of from 20 to 100. The polyether chains are preferably constructed from propylene-oxide and ethylene-oxide units.
However, suitable "conventional base polyols" may also be polyester 30 polyols with functionalities of, preferably, 2.5 to 6 and OH numbers of from 20 to 100.
-Mo-4562 -6-Prior to the start of the actual radical polymerization, an olefinically unsaturated compound such as, for example, a compound containing double bonds which is capable of reacting with primary hydroxyl end groups, is added to the reaction mixture, optionally in the presence of catalysts. Such compounds include, for example, unsaturated cyclic or acyclic anhydrides such as maleic anhydride or methacrylic anhydride, unsaturated acid chlorides such as methacrylic chloride, and unsaturated epoxides such as methacrylic glycidyl ester.
Suitable catalysts which are optionally used concomitantly include, for example, amines such as, for example, dimethylaminopyridine, or hydroxides such as, for example, potassium hydroxide.
The polymer polyols are produced by the free-radical polymerization of ethylenically unsaturated monomers or mixtures of ethylenically unsaturated monomers in a base polyol component as described above. Some examples of suitable ethylenically unsaturated monomers include compounds such as butadiene, styrene, a-methylstyrene, methylstyrene, ethylstyrene, acrylonitrile, methacrylonitrile, methyl methacrylate, acrylic ester. These are preferably mixtures of styrene and acrylonitrile. The quantity of ethylenically unsaturated monomers present is from 20 to 65% by weight, based on the total quantity of finished product. With regard to the respective quantities of styrene to acrylonitrile, these are preferably present in a weight ratio of from 20:80 to 80:20, and most preferably of from 70:30 to 30:70 (parts by weight).
Although it possible theoretically to select an unsaturated compound which would satisfy the description of both component b) the olefinically unsaturated compound and component c) the ethylenically unsaturated monomer, in practice, it is not possible to use the same ~ 21g3032 Mo~562 -7-unsaturated compound simultaneously as component b) and component c). In practicing the present invention, component b) and component c) are always different compounds.
The free-radical polymerization is initiated with conventional radical-forming initiators. Suitable examples of such initiators include organic peroxides such as, for example, benzoyl peroxide, tert.-butyl octotate, didesanoyl peroxide; azo compounds such as, for example, azo isobutyronitrile or 2,2'-azobis(2-methyl-butyronitrile).
Low-molecular weight regulators can be optionally added. These are also commonly referred to as chain transfer agents. Suitable compounds to be used as low-molecular weight regulators include, for example, alcohols such as methanol, ethanol, isopropanol, butanols and butanediol, mercaptans, allyl compounds, and enol ethers such as, for example, (cyclohex-3-enylidenemethoxymethyl)benzene.
It is also possible that a suitable solvent be used in the polymerization reaction. Suitable solvents include, for example, hydrocarbons such as toluene, ethylbenzene, isopropylbenzene and xylenes, or ketones such as acetone and methyl ethyl ketone. Preferred solvents are toluene and/or ethylbenzene.
The process according to the invention may be implemented either discontinuously or continuously.
With a discontinuous process, it is necessary to heat the base polyol component which contains the polyol having at least one (preferably predominantly) primary hydroxy end group, and, optionally, the low-molecular weight regulator, prior to the actual radical polymerization in a reactor equipped with a stirrer. During this heating process, the compound containing double bonds (i.e. the olefinically unsaturated compound) which is capable of reacting with primary hydroxy end groups is added, optionally, together with the catalyst.
Mo4562 -8-Then, a mixture of the ethylenically unsaturated monomers, the free-radical initiator, optionally, solvent and, optionally, a portion of the base polyol to be employed is charged.
With a continuous process, prior to the charging of the mixture 5 containing the ethylenically unsaturated monomers, the free-radical initiator, optionally, solvent and, optionally, a portion of the base polyol to be employed into the base polyol component (i.e. the mixture of the base polyol and a polyol having at least one (preferably predominantly) primary hydroxy end groups, and, optionally, the low-molecular weight regulator, 10 and the compound containing the double bonds (i.e. olefinically unsaturated compound) which is capable is capable of reacting with primary hydroxy end groups is charged, optionally together with the catalyst.
The product (i.e. polymer polyol or graft copolymer dispersion) is 15 drawn off continuously through an overflow.
The temperature at which the polymerization is carried out is typically from about 80 to 140C, preferably from 90 to 130C.
After completion of the polymerization reaction, the product is freed in the normal manner of readily volatile components such as, for 20 example, residual monomers, solvent and regulator residues by vacuum distillation.
The polymer polyols (i.e. graft copolymer dispersions) produced by the process according to the invention are particularly suitable for the production of polyurethane plastics via the polyisocyanate polyaddition 25 process. They are free of polymer agglomerates of any sort, and are stable and of low viscosity.
The present invention also relates to stable, low-viscosity polymer polyols which are produced by the process according to the invention and the use of these polymer polyols as a polyol component in the Mo-4562 -9-production of polyurethane plastics in accordance with the polyisocyanate polyaddition process.
Polyurethane plastics, preferably soft, flexible polyurethane foams, are produced by reaction of:
5 a) organicpolyisocyanates, with b) the polymer polyols of the present invention, optionally, in the presence of c) additional relatively high-molecular and/or low-molecular compounds containing hydrogen atoms that are reactive with respect to isocyanates, d) catalysts, e) water and/or low-boiling hydrocarbons by way of foaming agent, and 15 fl auxiliary substances and/or additives.
Suitable polyisocyanate starting components include the aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates such as those described, for example, by W Siefken in Justus Liebigs Annalen der Chemie, 362, pages 75 to 136. These include, for example, those 20 polyisocyanates corresponding to the general formula:
Q(NC)n wherein:
n: represents 2 to 5, preferably 2 to 3, and Q: represents an aliphatic hydrocarbon residue with 2 to 18, preferably 6 to 10 carbon atoms, a cycloaliphatic hydrocarbon residue with 4 to 15, preferably 5 to 10 carbon atoms, an aromatic hydrocarbon residue with 6 to 15, preferably 6 to 13 carbon atoms.
Mo-4562 -10-Suitable examples of such polyisocyanates include those described in, for example, DE-OS 2 832 253, at pages 10 to 11.
Particularly preferred, as a rule, are the polyisocyanates that are readily available commercially. These include compounds such as, for 5 example 2,4- and 2,6-toluylene diisocyanate, as well as any mixtures of these isomers ("TDI"), diphenylmethane diisocyanate ("MDI") and polyphenylpolymethylene polyisocyanates such as are produced by aniline-formaldehyde condensation and subsequent phosgenation, and polyisocyanates comprising carbodiimide groups, urethane groups, 10 allophanate groups, isocyanurate groups, urea groups or biuret groups.
These are commonly referred to as "modified polyisocyanates". In particular, such modified polyisocyanates include those derived from 2,4-- and/or 2,6-toluylene diisocyanate or 4,4'- and/or 2,4'-diphenylmethane diisocyanate.
The polymer polyols produced according to the present invention are used as some or all of the isocyanate-reactive component to be reacted with the isocyanate component.
In addition to the polymer polyols produced according to the present invention, some of the isocyanate-reactive component may 20 comprise compounds having at least 2 hydrogen atoms which are capable of reacting with the NCO group of the isocyanate component.
These compounds typically have molecular weights of 40 to 10,000 g/mol, and are preferably polyether polyols. Suitable polyether polyols include, for example, the known addition products, of cyclic ethers such 25 as ethylene oxide, propylene oxide, styrene oxide and butylene oxide with suitable starter compounds such as, for example, polyhydroxy compounds such as alkylene glycols, glycerine, trimethylolpropane, pentaerythritol and sorbitol, and/or amines such as ethylene diamine or toluylene diamines. It is also possible that the starter compounds 2ls3n32 Mo-4562 -1 1-themselves, which are generally relatively low molecular weight compounds, are present in conjunction with the polymer polyols.
In the process of producing polyurethanes from the polymer polyols of the present invention, it is also possible that catalysts are used 5 to catalyze the reaction between the polyurethane forming reactants.
Suitable catalysts include those which are conventional and well known in the field of polyurethane chemistry.
In an optional embodiment, a foaming agent comprising water and/or low-boiling hydrocarbons such as, for example, low-boiling alkanes 10 such as pentane, cycloalkanes such as cyclopentane, and alkenes may be added to the reaction mixture. Also, gases may be introduced into the reaction mixture under pressure such as, for example, carbon dioxide;
- Auxiliary substances and additives, for instance surface-active additives such as emulsifiers and foam stabilizers.
Also, suitable for use as additives in the production of polyurethanes are, for example, reaction retarders, cell regulators of the type known as such, such as parafffins, fatty alcohols or dimethylpolysiloxanes, and pigments or dyestuffs, and flameproofing agents of the type known as such. Furthermore, stabilizers may be added to counter the effects of ageing and weathering, as well as plasticizers and substances that act fungistatically and bacteriostatically.
Suitable examples of surface-active additives and foam stabilizers, reaction retarders, stabilizers, flame-retardant substances, plasticizers, dyestuffs, and substances that act fungistatically and bacteriostatically which are optionally to be used in the production of polyurethanes, as well as details relating to the method of application and mode of operation of these additives, are described in the Kunststoff-Handbuch, Volume Vll, published by G Oertel, Carl Hanser Verlag, Munchen, 1993, for example on pages 104 to 127.
The soft polyurethane foams are produced in a manner known as 2193~32 Mo4562 -12-such, as described for example in the Kunststoff-Handbuch, Volume Vll, published by G Oertel, Carl Hanser Verlag, Munchen, 1993, for example on pages 139 to 263.
The following examples are intended to illustrate the invention in 5 more detail without, however, restricting its scope.
Examples The following compounds were used as starting materials in the examples:
Polyol A: polypropylene oxide/ethylene oxide ether based on sorbitol, and having a molecular weight of 12,020 and containing primary OH end groups Polyol B: polypropylene oxide/ethylene oxide ether based on trimethyolpropane, and having a mlolecul~r weight of 6,000 g/mol and containing predominantly primary OH end groups Polyol C: polypropylene oxide/ethylene oxide ether based on glycerine, and having a molecular weight of 3,000 and containing predominantly secondary OH end groups Polyol D: polypropylene oxide/ethylene oxide ether based on trimethylolpropane, and having a molecular weight of 4,800 g/mol and containing predominantly primary OH end groups Polyol E: the reaction product of maleic anhydride with Polyol B in a molar ratio of 0.75:1 Polyol F: polypropylene oxide/ethylene oxide ether based on trimethylolpropane, and having a molecular weight of 3,700 g/mol Enol ether: (cyclohex-3-enylidenemethoxymethyl)benzene MM: methacrylic anhydride Mo4562 -1 3-MSA: maleic anhydride Catalyst 1: a catalyst mixture consisting of dimethylethanol amine and bis-N,N-dimethylaminoethyl ether Catalyst 2: tin octoate Stabilizer: a polyether siloxane, commercially available from Goldschmidt, Essen Isocyanate: toluylene diisocyanate comprising 80% by weight of the 2,4-isomer and 20% by weight of the 2,6-isomer Example 1:
Production of a polymer polyol corresponding to the process according to the invention:
A mixture of 465 g Polyol C, 30 g Polyol A and 0.1 g dimethylaminopyridine was heated to 125C. During the heating process, 1 g methacrylic anhydride in 35 g toluene were added. While maintaining 15 the temperature at 125C, 263 g styrene, 142 g acrylonitrile, 6 g 2,2'-azobis(2-methylbutyronitrile) and 100 g toluene were charged over a 2 hour period, with stirring. Then, after an additional 10 minutes, 0.4 g 2,2'-azobis(2-methylbutyronitrile) in 10 g toluene were added so as to complete the conversion. After a post-reaction time of 1 hour, residual 20 monomers and solvent were filtered via a filter cloth with a mesh width of 100 ,um. The product was a white, agglomerate-free dispersion with a viscosity of 5,200 mPa.s/25C and a solids content of 45% by weight.
Examples 2 to 10:
Examples 2 to 9 show the production of polymer polyols by the 25 process according to the invention. The process used to produce these polymer polyols was essentially the same as that used in Example 1 as described above, with the exception that the specific starting compounds and quantities (in grams) of these compounds were as set forth in Table 1.
Example 10 is a comparative example. it also used a process 21930~2 Mo-4562 -1 4-which essentially corresponded to that in Example 1 as described above, with the exception that the specific starting compounds and quantities (in grams) of these compounds were as set forth in Table 1. This example demonstrates that if the reaction product of a compound such as, for 5 example, maleic anhydride with a polyol with predominantly primary OH
end groups is used conjunction with the process for the production of polymer polyols as described above, a stable product does not form.
Table 1:
Example Polyol A 30 22 22 30 22 Polyol B 22 22 Polyol C 465 518 518 518 518 465 518 465 Polyol D 540 Polyol E 30 MM 1 1 1.5 1.5 MSA 1.5 1.5 0.5 Styrene 263 216 216 216 216 263 216 216 216 Acrylonitrile 142 144 144 144 144 144 144 144 144 Toluene 135 120 120 120 120 135 120 135 120 Isopropanol 30 r~
Enol ether 9 8 8 8 8 Solids (wt. %) 45 40 40 40 40 45 40 40 40 Viscosity (mPa s/25C) 4900 3500 4400 3500 3700 5400 4100 5700 1): the viscosity could not be measured; no stable product was formed 21g3032 Mo-4562 -1 6-The examples demonstrate that products having differing solid contents can be produced; that different regulators (Examples 2, 5, 8, 9 and 7) can be employed; that regulators are not essential to the process (Examples 3, 4, 6); and that active polymer polyols (with primary OH end 5 groups) can also be produced (Example 9).
Examples 11 to 16:
The polymer polyols produced in accordance with the present process were used in a process for the production of polyurethane plastic foams. The specific foam formulation for each example is set forth in 10 Table 2 below.
All the components, except for the polyisocyanate, were mixed intensively with one another. Then, the polyisocyanate was added while stirring, and the reaction mixture was poured into an open mold where it frothed up, and thus formed the polyurethane plastic foam.
219~032 Mo-4562 -17-Table 2:
Foaming Examples (quantities in parts by weight) Examples Polyol F 50 50 50 50 50 50 Polymer polyol 50 (Example 2) Polymer polyol 50 (Example 3) Polymer polyol 50 (Example 4) Polymer polyol 50 (Example 5) lOPolymer polyol 50 (Example 6) Polymer polyol 50 (Example 7) Water 4.5 4.5 4.5 4.5 4.5 4.5 Stabilizer Catalyst 1 0.2 0.2 0.2 0.2 0.2 0.2 15 Catalyst 2 0.05 0.05 0.05 0.05 0.05 0.05 Characteristic 108 108 108 108 108 108 number Bulk density 26.3 25.4 27.6 25.4 26.3 28.3 (kg/m3) Compression 6.57 6.26 6.79 6.29 6.72 7.32 hardness (kPa) .
Mo~562 -1 8-Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of 5 the invention except as it may be limited by the claims.
LOW-VISCOSITY POLYMER POLYOLS, A PROCESS
FOR THEIR PRODUCTION, AND THEIR USE FOR THE
PRODUCTION OF POLYURETHANE PLASTIC FOAMS
BACKGROUND OF THE INVENTION
The present invention relates to a process for the production of polymer polyols having low viscosity, the polymer polyols produced by this process, and to their use in the production of polyurethane plastic foams.
The expression "polymer polyols", which are also commonly referred to as graft copolymer dispersion, is understood to mean products that can be obtained by polymerization of olefinic monomers in polyether polyols ("base polyols"). In this broad sense, the olefinic monomers principally consist of ethylenically unsaturated compounds such as styrene and/or acrylonitrile.
Polymer polyols are employed, for example, in the production of soft polyurethane plastic foams.
The production of polymer polyols is described in, for example, U.S. Patents 3,383,351 and 3,304,273, or in DE-A 1,152,536 and DE-A
1,152,537.
In the ideal case, the polymer polyols are relatively low-viscosity, finely divided, non-settling dispersions of the polymerizate (which preferably comprises an acrylonitrile/styrene graft copolymer) in the essentially unchanged polyether polyol (i.e. base polyol). Characteristic features associated with quality and processability of the polymer polyols are low-viscosity, storage stability (resistance to sedimentation) and fineness of dispersal. These properties are influenced above all by the type and the relative proportions of the starting materials. In particular, Mo-4562 -2-the solids content (proportion of monomers in the formulation) and the monomer ratio (e.g. styrene/ acrylonitrile ratio) have a considerable influence on the quality of the product.
The most important aims in the production of polymer polyols are 5 the attainment of high solids contents (at least 40%) with a viscosity that is as low as possible, and, simultaneously, with excellent product stability.
In order to achieve product stability, i.e. the prevention of the formation of undesirable agglomerated polymer particles that precipitate out of the continuous phase or the base polyol, the polymer particles have to be 10 stabilized during production of the polymer polyol. This stabilization can be achieved by the incorporation of a portion of the molecules of the base polyether into the polymer that is formed in-situ. In this sense, the - effectiveness of the stabilization is favored by, for example, a molecular weight of the base polyether that is as high as possible and by a 15 proportion of acrylonitrile in the monomer mixture that is as high as possible. Whereas a high acrylonitrile content increases the intrinsic color of the polymer polyols and the tendency towards discoloration of soft foams produced therewith and is therefore undesirable, the viscosity of the polymer polyols is increased by the use of base polyols of higher 20 molecular weight.
In accordance with the state of the art, the most important way of stabilizing polymer polyols is through the concomitant use of compounds which are compatible with the base polyol phase and which contain ethylenically unsaturated, polymerizable groups (i.e. macromonomers or 25 macromers). These so-called macromonomers copolymerize with the vinyl monomers, so that the polymer particles arising are sterically stabilized by polyether side-chains and are consequently protected against agglomeration and sedimentation.
The production of polymer polyols with concomitant use of 30 macromonomers is described, for example, in U.S. Patents 3,652,639, ~lg~032 Mo-4562 -3-3,823,201, 4,342,840, 4,390,645, 4,454,255 (Reissue 33,291) 4,460,715 and 5,093,412. The ethylenically unsaturated double bonds are, for example, introduced into polyether polyols by reaction with cyclic, unsaturated carboxyiic anhydrides such as maleic anhydride and subsequent reaction with ethylene oxide or propylene oxide; by esterification with acrylic or methacrylic derivatives; by reaction with allyl glycidyl ether; by reaction with an unsaturated isocyanate such as isocyanatoalkyl acrylate and isocyanatoalkyl methacrylate, 1-(1-isocyanato-1-methylethyl)-3-(1-methylethenyl)-benzene or NCO-functional adducts formed from a polyisocyanate and hydroxyethyl acrylate or hydroxypropyl acrylate.
With all the specified processes the macromonomer has to be synthesized prior to the actual production of polymer polyol. This results in logistical problems, for example, since an adequate quantity of macromonomer always has to be produced and stored in addition to the base polyol for the production of polymer polyol.
It is therefore of interest to develop processes which produce low-viscosity polymer polyols with high solids contents and that do not require the use of previously produced macromonomers.
It has surprisingly been found this object can be achieved with the process according to the invention.
SUMMARY OF THE INVENTION
The present invention comprises a process for the production of stable polymer polyols comprising:
25 1 ) mixing a) a base polyol component comprising i) at least 2% by weight, based on 100% by weight of the base polyol component, of at least one polyether polyol containing at least one primary hydroxyl end group, preferably containing predominately primary hydroxyl end groups, and b) an olefinically unsaturated compound which is capable of Mo4562 -4-reacting with primary hydroxyl groups, and 2) polymerizing the mixture from 1) with c) a mixture of at least two ethylenically unsaturated monomers, in the presence of a free-radical catalyst to form a polymer polyol.
The polyol which accounts for at least a portion of the base polyol component and which contains at least one primary hydroxyl group per molecule is preferably a polyether polyol. Suitable polyether polyols containing at least one primary hydroxyl groups include, for example, the known addition products of cyclic ethers such as, for example, ethylene oxide, propylene oxide, styrene oxide, butylene oxide with starter compounds such as, for example, polyhydroxy compounds including alkylene glycols, glycerine, trimethylolpropane, pentaerythritol, sorbitol, amines such as ethylene diamine or toluylene diamines. These polyols should have functionalities between 1 and 6 and an OH number from 10 to 100. It is preferred that this polyether polyol contain predominately primary hydroxyl end groups.
Typically, the ethylenically unsaturated monomers are present in a quantity of from about 20 to 65% by weight, based on the weight of the end product.
Polymerization may, optionally, be carried out in the presence of a low-molecular regulator (i.e. chain transfer agent), and/or also, optionally, in an organic solvent.
In accordance with the invention it is preferred that:
1) the monomers are ethylenically unsaturated monomers, such as, for example, styrene and/or acrylonitrile, Mo-4562 -5 2) ethylenically unsaturated monomers comprise a mixture of styrene and acrylonitrile in a weight ratio of 20:80 to 80:20, most preferably 25:75 to 75:25, 3) the base polyol component comprises at least one so-called "conventional base polyol" having at least two hydroxyl groups, and most preferably comprises at least one polyether polyol having a functionality of 2.5 to 6 and an OH
number up to 100, 4) the base polyol component comprises at least one polyol having at least one primary hydroxyl end group, more preferably a polyether polyol having a functionality of 1 to 6 and an OH number from 10 to 100, most preferably 20 to - 100, 5) the olefinically unsaturated compound is added to the base polyol component in a quantity of from 0.05 to 1.5% by weight, preferably of from 0.1 to 1.0% by weight, based on the total weight of the base polyol component a).
It is particularly preferred that the polyols used as "conventional base polyols" containing at least two hydroxyl groups are polyether 20 polyols such as, for example, the known addition products of cyclic ethers such as, for example, ethylene oxide, propylene oxide, styrene oxide, butylene oxide, with starter compounds such as, for example, polyhydroxy compounds such as, for example, alkylene glycols, glycerine, trimethylolpropane, pentaerythritol, sorbitol, or amine compounds such as, 25 for example, ethylene diamine or toluylene diamines. The polyether polyols used as "base polyols" more preferably have functionalities of 2.5 to 6 and OH numbers of from 20 to 100. The polyether chains are preferably constructed from propylene-oxide and ethylene-oxide units.
However, suitable "conventional base polyols" may also be polyester 30 polyols with functionalities of, preferably, 2.5 to 6 and OH numbers of from 20 to 100.
-Mo-4562 -6-Prior to the start of the actual radical polymerization, an olefinically unsaturated compound such as, for example, a compound containing double bonds which is capable of reacting with primary hydroxyl end groups, is added to the reaction mixture, optionally in the presence of catalysts. Such compounds include, for example, unsaturated cyclic or acyclic anhydrides such as maleic anhydride or methacrylic anhydride, unsaturated acid chlorides such as methacrylic chloride, and unsaturated epoxides such as methacrylic glycidyl ester.
Suitable catalysts which are optionally used concomitantly include, for example, amines such as, for example, dimethylaminopyridine, or hydroxides such as, for example, potassium hydroxide.
The polymer polyols are produced by the free-radical polymerization of ethylenically unsaturated monomers or mixtures of ethylenically unsaturated monomers in a base polyol component as described above. Some examples of suitable ethylenically unsaturated monomers include compounds such as butadiene, styrene, a-methylstyrene, methylstyrene, ethylstyrene, acrylonitrile, methacrylonitrile, methyl methacrylate, acrylic ester. These are preferably mixtures of styrene and acrylonitrile. The quantity of ethylenically unsaturated monomers present is from 20 to 65% by weight, based on the total quantity of finished product. With regard to the respective quantities of styrene to acrylonitrile, these are preferably present in a weight ratio of from 20:80 to 80:20, and most preferably of from 70:30 to 30:70 (parts by weight).
Although it possible theoretically to select an unsaturated compound which would satisfy the description of both component b) the olefinically unsaturated compound and component c) the ethylenically unsaturated monomer, in practice, it is not possible to use the same ~ 21g3032 Mo~562 -7-unsaturated compound simultaneously as component b) and component c). In practicing the present invention, component b) and component c) are always different compounds.
The free-radical polymerization is initiated with conventional radical-forming initiators. Suitable examples of such initiators include organic peroxides such as, for example, benzoyl peroxide, tert.-butyl octotate, didesanoyl peroxide; azo compounds such as, for example, azo isobutyronitrile or 2,2'-azobis(2-methyl-butyronitrile).
Low-molecular weight regulators can be optionally added. These are also commonly referred to as chain transfer agents. Suitable compounds to be used as low-molecular weight regulators include, for example, alcohols such as methanol, ethanol, isopropanol, butanols and butanediol, mercaptans, allyl compounds, and enol ethers such as, for example, (cyclohex-3-enylidenemethoxymethyl)benzene.
It is also possible that a suitable solvent be used in the polymerization reaction. Suitable solvents include, for example, hydrocarbons such as toluene, ethylbenzene, isopropylbenzene and xylenes, or ketones such as acetone and methyl ethyl ketone. Preferred solvents are toluene and/or ethylbenzene.
The process according to the invention may be implemented either discontinuously or continuously.
With a discontinuous process, it is necessary to heat the base polyol component which contains the polyol having at least one (preferably predominantly) primary hydroxy end group, and, optionally, the low-molecular weight regulator, prior to the actual radical polymerization in a reactor equipped with a stirrer. During this heating process, the compound containing double bonds (i.e. the olefinically unsaturated compound) which is capable of reacting with primary hydroxy end groups is added, optionally, together with the catalyst.
Mo4562 -8-Then, a mixture of the ethylenically unsaturated monomers, the free-radical initiator, optionally, solvent and, optionally, a portion of the base polyol to be employed is charged.
With a continuous process, prior to the charging of the mixture 5 containing the ethylenically unsaturated monomers, the free-radical initiator, optionally, solvent and, optionally, a portion of the base polyol to be employed into the base polyol component (i.e. the mixture of the base polyol and a polyol having at least one (preferably predominantly) primary hydroxy end groups, and, optionally, the low-molecular weight regulator, 10 and the compound containing the double bonds (i.e. olefinically unsaturated compound) which is capable is capable of reacting with primary hydroxy end groups is charged, optionally together with the catalyst.
The product (i.e. polymer polyol or graft copolymer dispersion) is 15 drawn off continuously through an overflow.
The temperature at which the polymerization is carried out is typically from about 80 to 140C, preferably from 90 to 130C.
After completion of the polymerization reaction, the product is freed in the normal manner of readily volatile components such as, for 20 example, residual monomers, solvent and regulator residues by vacuum distillation.
The polymer polyols (i.e. graft copolymer dispersions) produced by the process according to the invention are particularly suitable for the production of polyurethane plastics via the polyisocyanate polyaddition 25 process. They are free of polymer agglomerates of any sort, and are stable and of low viscosity.
The present invention also relates to stable, low-viscosity polymer polyols which are produced by the process according to the invention and the use of these polymer polyols as a polyol component in the Mo-4562 -9-production of polyurethane plastics in accordance with the polyisocyanate polyaddition process.
Polyurethane plastics, preferably soft, flexible polyurethane foams, are produced by reaction of:
5 a) organicpolyisocyanates, with b) the polymer polyols of the present invention, optionally, in the presence of c) additional relatively high-molecular and/or low-molecular compounds containing hydrogen atoms that are reactive with respect to isocyanates, d) catalysts, e) water and/or low-boiling hydrocarbons by way of foaming agent, and 15 fl auxiliary substances and/or additives.
Suitable polyisocyanate starting components include the aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates such as those described, for example, by W Siefken in Justus Liebigs Annalen der Chemie, 362, pages 75 to 136. These include, for example, those 20 polyisocyanates corresponding to the general formula:
Q(NC)n wherein:
n: represents 2 to 5, preferably 2 to 3, and Q: represents an aliphatic hydrocarbon residue with 2 to 18, preferably 6 to 10 carbon atoms, a cycloaliphatic hydrocarbon residue with 4 to 15, preferably 5 to 10 carbon atoms, an aromatic hydrocarbon residue with 6 to 15, preferably 6 to 13 carbon atoms.
Mo-4562 -10-Suitable examples of such polyisocyanates include those described in, for example, DE-OS 2 832 253, at pages 10 to 11.
Particularly preferred, as a rule, are the polyisocyanates that are readily available commercially. These include compounds such as, for 5 example 2,4- and 2,6-toluylene diisocyanate, as well as any mixtures of these isomers ("TDI"), diphenylmethane diisocyanate ("MDI") and polyphenylpolymethylene polyisocyanates such as are produced by aniline-formaldehyde condensation and subsequent phosgenation, and polyisocyanates comprising carbodiimide groups, urethane groups, 10 allophanate groups, isocyanurate groups, urea groups or biuret groups.
These are commonly referred to as "modified polyisocyanates". In particular, such modified polyisocyanates include those derived from 2,4-- and/or 2,6-toluylene diisocyanate or 4,4'- and/or 2,4'-diphenylmethane diisocyanate.
The polymer polyols produced according to the present invention are used as some or all of the isocyanate-reactive component to be reacted with the isocyanate component.
In addition to the polymer polyols produced according to the present invention, some of the isocyanate-reactive component may 20 comprise compounds having at least 2 hydrogen atoms which are capable of reacting with the NCO group of the isocyanate component.
These compounds typically have molecular weights of 40 to 10,000 g/mol, and are preferably polyether polyols. Suitable polyether polyols include, for example, the known addition products, of cyclic ethers such 25 as ethylene oxide, propylene oxide, styrene oxide and butylene oxide with suitable starter compounds such as, for example, polyhydroxy compounds such as alkylene glycols, glycerine, trimethylolpropane, pentaerythritol and sorbitol, and/or amines such as ethylene diamine or toluylene diamines. It is also possible that the starter compounds 2ls3n32 Mo-4562 -1 1-themselves, which are generally relatively low molecular weight compounds, are present in conjunction with the polymer polyols.
In the process of producing polyurethanes from the polymer polyols of the present invention, it is also possible that catalysts are used 5 to catalyze the reaction between the polyurethane forming reactants.
Suitable catalysts include those which are conventional and well known in the field of polyurethane chemistry.
In an optional embodiment, a foaming agent comprising water and/or low-boiling hydrocarbons such as, for example, low-boiling alkanes 10 such as pentane, cycloalkanes such as cyclopentane, and alkenes may be added to the reaction mixture. Also, gases may be introduced into the reaction mixture under pressure such as, for example, carbon dioxide;
- Auxiliary substances and additives, for instance surface-active additives such as emulsifiers and foam stabilizers.
Also, suitable for use as additives in the production of polyurethanes are, for example, reaction retarders, cell regulators of the type known as such, such as parafffins, fatty alcohols or dimethylpolysiloxanes, and pigments or dyestuffs, and flameproofing agents of the type known as such. Furthermore, stabilizers may be added to counter the effects of ageing and weathering, as well as plasticizers and substances that act fungistatically and bacteriostatically.
Suitable examples of surface-active additives and foam stabilizers, reaction retarders, stabilizers, flame-retardant substances, plasticizers, dyestuffs, and substances that act fungistatically and bacteriostatically which are optionally to be used in the production of polyurethanes, as well as details relating to the method of application and mode of operation of these additives, are described in the Kunststoff-Handbuch, Volume Vll, published by G Oertel, Carl Hanser Verlag, Munchen, 1993, for example on pages 104 to 127.
The soft polyurethane foams are produced in a manner known as 2193~32 Mo4562 -12-such, as described for example in the Kunststoff-Handbuch, Volume Vll, published by G Oertel, Carl Hanser Verlag, Munchen, 1993, for example on pages 139 to 263.
The following examples are intended to illustrate the invention in 5 more detail without, however, restricting its scope.
Examples The following compounds were used as starting materials in the examples:
Polyol A: polypropylene oxide/ethylene oxide ether based on sorbitol, and having a molecular weight of 12,020 and containing primary OH end groups Polyol B: polypropylene oxide/ethylene oxide ether based on trimethyolpropane, and having a mlolecul~r weight of 6,000 g/mol and containing predominantly primary OH end groups Polyol C: polypropylene oxide/ethylene oxide ether based on glycerine, and having a molecular weight of 3,000 and containing predominantly secondary OH end groups Polyol D: polypropylene oxide/ethylene oxide ether based on trimethylolpropane, and having a molecular weight of 4,800 g/mol and containing predominantly primary OH end groups Polyol E: the reaction product of maleic anhydride with Polyol B in a molar ratio of 0.75:1 Polyol F: polypropylene oxide/ethylene oxide ether based on trimethylolpropane, and having a molecular weight of 3,700 g/mol Enol ether: (cyclohex-3-enylidenemethoxymethyl)benzene MM: methacrylic anhydride Mo4562 -1 3-MSA: maleic anhydride Catalyst 1: a catalyst mixture consisting of dimethylethanol amine and bis-N,N-dimethylaminoethyl ether Catalyst 2: tin octoate Stabilizer: a polyether siloxane, commercially available from Goldschmidt, Essen Isocyanate: toluylene diisocyanate comprising 80% by weight of the 2,4-isomer and 20% by weight of the 2,6-isomer Example 1:
Production of a polymer polyol corresponding to the process according to the invention:
A mixture of 465 g Polyol C, 30 g Polyol A and 0.1 g dimethylaminopyridine was heated to 125C. During the heating process, 1 g methacrylic anhydride in 35 g toluene were added. While maintaining 15 the temperature at 125C, 263 g styrene, 142 g acrylonitrile, 6 g 2,2'-azobis(2-methylbutyronitrile) and 100 g toluene were charged over a 2 hour period, with stirring. Then, after an additional 10 minutes, 0.4 g 2,2'-azobis(2-methylbutyronitrile) in 10 g toluene were added so as to complete the conversion. After a post-reaction time of 1 hour, residual 20 monomers and solvent were filtered via a filter cloth with a mesh width of 100 ,um. The product was a white, agglomerate-free dispersion with a viscosity of 5,200 mPa.s/25C and a solids content of 45% by weight.
Examples 2 to 10:
Examples 2 to 9 show the production of polymer polyols by the 25 process according to the invention. The process used to produce these polymer polyols was essentially the same as that used in Example 1 as described above, with the exception that the specific starting compounds and quantities (in grams) of these compounds were as set forth in Table 1.
Example 10 is a comparative example. it also used a process 21930~2 Mo-4562 -1 4-which essentially corresponded to that in Example 1 as described above, with the exception that the specific starting compounds and quantities (in grams) of these compounds were as set forth in Table 1. This example demonstrates that if the reaction product of a compound such as, for 5 example, maleic anhydride with a polyol with predominantly primary OH
end groups is used conjunction with the process for the production of polymer polyols as described above, a stable product does not form.
Table 1:
Example Polyol A 30 22 22 30 22 Polyol B 22 22 Polyol C 465 518 518 518 518 465 518 465 Polyol D 540 Polyol E 30 MM 1 1 1.5 1.5 MSA 1.5 1.5 0.5 Styrene 263 216 216 216 216 263 216 216 216 Acrylonitrile 142 144 144 144 144 144 144 144 144 Toluene 135 120 120 120 120 135 120 135 120 Isopropanol 30 r~
Enol ether 9 8 8 8 8 Solids (wt. %) 45 40 40 40 40 45 40 40 40 Viscosity (mPa s/25C) 4900 3500 4400 3500 3700 5400 4100 5700 1): the viscosity could not be measured; no stable product was formed 21g3032 Mo-4562 -1 6-The examples demonstrate that products having differing solid contents can be produced; that different regulators (Examples 2, 5, 8, 9 and 7) can be employed; that regulators are not essential to the process (Examples 3, 4, 6); and that active polymer polyols (with primary OH end 5 groups) can also be produced (Example 9).
Examples 11 to 16:
The polymer polyols produced in accordance with the present process were used in a process for the production of polyurethane plastic foams. The specific foam formulation for each example is set forth in 10 Table 2 below.
All the components, except for the polyisocyanate, were mixed intensively with one another. Then, the polyisocyanate was added while stirring, and the reaction mixture was poured into an open mold where it frothed up, and thus formed the polyurethane plastic foam.
219~032 Mo-4562 -17-Table 2:
Foaming Examples (quantities in parts by weight) Examples Polyol F 50 50 50 50 50 50 Polymer polyol 50 (Example 2) Polymer polyol 50 (Example 3) Polymer polyol 50 (Example 4) Polymer polyol 50 (Example 5) lOPolymer polyol 50 (Example 6) Polymer polyol 50 (Example 7) Water 4.5 4.5 4.5 4.5 4.5 4.5 Stabilizer Catalyst 1 0.2 0.2 0.2 0.2 0.2 0.2 15 Catalyst 2 0.05 0.05 0.05 0.05 0.05 0.05 Characteristic 108 108 108 108 108 108 number Bulk density 26.3 25.4 27.6 25.4 26.3 28.3 (kg/m3) Compression 6.57 6.26 6.79 6.29 6.72 7.32 hardness (kPa) .
Mo~562 -1 8-Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of 5 the invention except as it may be limited by the claims.
Claims (13)
1. A process for the production of stable low-viscosity polymer polyols comprising 1) mixing a) a base polyol component comprising i) at least 2% by weight, based on 100% by weight of the base polyol component, of at least one polyol containing at least one primary hydroxyl end group per molecule, and b) an olefinically unsaturated compound which is capable of reacting with primary hydroxyl groups, and
2) polymerizing the mixture from 1) with c) a mixture of ethylenically unsaturated monomers, in the presence of a free-radical catalyst to form a polymer polyol.
2. The process of Claim 1, wherein said olefinically unsaturated compound is selected from the group consisting of unsaturated cyclic anhydrides, unsaturated acyclic anhydrides, unsaturated acid chlorides, unsaturated epoxides and mixtures thereof.
2. The process of Claim 1, wherein said olefinically unsaturated compound is selected from the group consisting of unsaturated cyclic anhydrides, unsaturated acyclic anhydrides, unsaturated acid chlorides, unsaturated epoxides and mixtures thereof.
3. The process of Claim 2, wherein said olefinically unsaturated compounds are mixed with said base polyol component at a temperature of between 20 and 120°C.
4. The process of Claim 3, wherein said olefinically unsaturated compounds are mixed with said base polyol component at a temperature of between 30 and 80°C.
5. The process of Claim 1, wherein said olefinically unsaturated compound is added in a quantity of from 0.05 to 1.5% by weight, based on 100% by weight of the base polyol component.
6. The process of Claim 5, wherein said olefinically unsaturated compound is added in a quantity of from 0.1 to 1% by weight, based on 100% by weight of the base polyol component.
7. The process of Claim 1, wherein said polyol containing primary hydroxyl end groups contains predominately primary hydroxyl groups.
8. The process of Claim 1, wherein said ethylenically unsaturated monomers comprise a mixture of styrene and acrylonitrile.
9. The process of Claim 8, wherein styrene and acrylonitrile are present in a weight ratio of 20:80 to 80:20.
10. The process of Claim 8, wherein styrene and acrylonitrile are present in a weight ratio of 25:75 to 75:25.
11. The process of Claim 1, wherein said polyol containing at least one primary hydroxyl end group per molecule is a polyether polyol having a functionality of 1 to 6 and an OH number of from 10 to 100.
12. The stable, low-viscosity polymer polyol produced by the process of Claim 1.
13. In a process for the production of polyurethane plastics via the polyisocyanate polyaddition process comprising reacting a polyisocyanate with an isocyanate-reactive component and optionally a crosslinker and/or chain extender, the improvement wherein said isocyanate-reactive component comprises the polymer polyol produced by the process of Claim 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE1995147632 DE19547632A1 (en) | 1995-12-20 | 1995-12-20 | Low-viscosity polymer polyols, a process for their preparation and their use in the production of polyurethane foams |
| DE19547632.8 | 1995-12-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2193032A1 true CA2193032A1 (en) | 1997-06-21 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2193032 Abandoned CA2193032A1 (en) | 1995-12-20 | 1996-12-16 | Low-viscosity polymer polyols, a process for their production, and their use for the production of polyurethane plastic foams |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0780410A1 (en) |
| JP (1) | JPH09183825A (en) |
| CA (1) | CA2193032A1 (en) |
| DE (1) | DE19547632A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115232257A (en) * | 2021-04-22 | 2022-10-25 | 中国石油化工股份有限公司 | Preparation method of low-viscosity polymer polyol, obtained polymer polyol and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6214958B1 (en) * | 1999-07-21 | 2001-04-10 | Arco Chemical Technology, L.P. | Process for preparing comb-branched polymers |
| DE102004017294A1 (en) * | 2004-04-05 | 2005-10-20 | Basf Ag | Process for the production of polyurethane foams |
| DE102006029588A1 (en) * | 2006-06-26 | 2007-12-27 | Bayer Materialscience Ag | Purification of polymer-polyol used for polyurethane production, involves stripping with superheated steam in a packed column at moderate temperature, using a liquid distributor with a high drip-point density |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3304273A (en) | 1963-02-06 | 1967-02-14 | Stamberger Paul | Method of preparing polyurethanes from liquid, stable, reactive, filmforming polymer/polyol mixtures formed by polymerizing an ethylenically unsaturated monomer in a polyol |
| GB1022434A (en) | 1961-11-28 | 1966-03-16 | Union Carbide Corp | Improvements in and relating to polymers |
| DE1152536B (en) | 1962-03-30 | 1963-08-08 | Bayer Ag | Process for the production of foams containing urethane groups |
| DE1152537B (en) | 1962-06-02 | 1963-08-08 | Bayer Ag | Process for the production of homogeneous plastics containing urethane groups |
| BE759006A (en) | 1969-11-20 | 1971-05-17 | Marles Kuhlmann Wyandotte | COPOLYMERS GRAFTS AND PREPARATION OF POLYURETHANES |
| US3823201A (en) | 1972-12-04 | 1974-07-09 | Basf Wyandotte Corp | Highly-stable graft copolymer dispersions in polyols containing unsaturation and polyurethanes prepared therefrom |
| DE2832253A1 (en) | 1978-07-22 | 1980-01-31 | Bayer Ag | METHOD FOR PRODUCING MOLDED FOAMS |
| US4390645A (en) | 1979-11-23 | 1983-06-28 | The Dow Chemical Company | Stable dispersions of polymers in polyfunctional compounds having a plurality of active hydrogens and polyurethanes therefrom |
| US4460715A (en) | 1979-11-23 | 1984-07-17 | The Dow Chemical Company | Stable dispersions of polymers in polyfunctional compounds having a plurality of active hydrogens and polyurethanes produced therefrom |
| US4342840A (en) | 1979-12-25 | 1982-08-03 | Asahi Glass Company, Ltd. | Process for producing polymer polyol |
| US4394491A (en) * | 1980-10-08 | 1983-07-19 | The Dow Chemical Company | Addition polymerizable adduct of a polymeric monoahl and an unsaturated isocyanate |
| IN167010B (en) * | 1985-12-23 | 1990-08-18 | Kellogg M W Co | |
| US4745153A (en) * | 1986-12-17 | 1988-05-17 | The Dow Chemical Company | Low viscosity, high solids polymer polyols prepared using a preformed dispersant |
| US5093412A (en) | 1989-08-23 | 1992-03-03 | Basf Corporation | Macromers for graft polyols and the polyols prepared therefrom |
-
1995
- 1995-12-20 DE DE1995147632 patent/DE19547632A1/en not_active Withdrawn
-
1996
- 1996-12-09 EP EP96119694A patent/EP0780410A1/en not_active Withdrawn
- 1996-12-16 CA CA 2193032 patent/CA2193032A1/en not_active Abandoned
- 1996-12-18 JP JP8353781A patent/JPH09183825A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115232257A (en) * | 2021-04-22 | 2022-10-25 | 中国石油化工股份有限公司 | Preparation method of low-viscosity polymer polyol, obtained polymer polyol and application |
| CN115232257B (en) * | 2021-04-22 | 2023-09-29 | 中国石油化工股份有限公司 | Preparation method of low-viscosity polymer polyol, polymer polyol obtained by preparation method and application of polymer polyol |
Also Published As
| Publication number | Publication date |
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| DE19547632A1 (en) | 1997-06-26 |
| JPH09183825A (en) | 1997-07-15 |
| EP0780410A1 (en) | 1997-06-25 |
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