DE69529488T3 - Preparation of polyoxyalkylene polyols, polymeric polyols and soft polyurethane foams - Google Patents

Description

BACKGROUND OF THE INVENTION

1. Field of the invention

The The present invention relates to a polymer polyol and method for Preparation of a polyoxyalkylene polyol, a polymer polyol and a flexible polyurethane foam. In particular, it relates to A method for producing a polyoxyalkylene polyol having a hydroxyl value from 10 to 35 mg KOH / g, a monool content less than or equal to 15 mole% and a head-to-tail binding selectivity greater than or equal to 96% resulting from the addition polymerization of propylene oxide gives and a method for producing the polyol. The invention also provides a process for reacting an organic polyisocyanate with the above-mentioned Polyoxyalkylenpolyol in the presence of a catalyst, a surfactant, a foaming agent, a crosslinking agent and other additives for making a Flexible polyurethane foam with improved wet aging compression set ready. The invention further relates to a polymer polyol comprising (a) a polyoxyalkylene polyol having a hydroxyl value of 10 to 35 mg KOH / g, a Monoolanteil less than or equal to 15 mol% and a head-to-tail binding selectivity greater than or equal to 96%, resulting from the addition polymerization of propylene oxide and (b-1) polymer particles present in the polyoxyalkylene polyol in the range of greater than or equal to 5 weight percent to less than 30 weight percent or (b-2) polymer particles present in the polyoxyalkylene polyol in the range of greater than or equal to 30 weight percent to less than or equal to 60 weight percent are dispersed and a glass transition temperature from 90 to 120 ° C exhibit. The invention relates to processes for preparing the polymer polyol and a method for producing a flexible polyurethane foam, comprising reacting an organic polyisocyanate compound with a polyoxyalkylene polyol containing at least one of the above mentioned Polymer polyols, in the presence of a foaming agent, a catalyst, a surfactant, a crosslinking agent and other additives.

2. State of the art

When Catalyst is used in the preparation of polyoxyalkylene polyols for polyurethane raw materials and others mainly Potassium hydroxide used. It is well known that when propylene oxide as an alkylene oxide is subjected to addition polymerization, side reactions occur in which monools are formed, and when the molecular weight of polyoxyalkylene polyols increased will, the amount of monool will increase. It is believed that if the polyol is a big one Has amount of monools, crosslinking and polymerization in the Urethane reaction of a polyoxyalkylene polyol with an organic Polyisocyanate compound can be prevented and the mechanical properties of the obtained flexible polyurethane foam and elastomer deteriorated become.

at a conventional one Processes such as the addition polymerization of propylene oxide to a Hydrogen compound by using a potassium hydroxide catalyst exceeds the monool portion of polymerized polyoxyalkylene polyol having a Hydroxyl value of less than or equal to 35 mg KOH / g 15 mol% and it is essentially impossible a polyoxyalkylene polyol having a hydroxyl value of less than or to produce 28 mg KOH / g.

USP 3,829,505, JP-A-2-115211 (Tokkaihei) and JP-A-3-14812 (Tokkaihei) disclose methods for using catalysts derived from alkali metal catalysts are different, such as a double metal cyanide complex catalyst in the addition polymerization of propylene oxide as an alkylene oxide to release the aforementioned Problems. In particular, JP-A-3-14812 (Tokkaihei) discloses in U.S.P. Comparative Examples that double metal cyanide complex catalysts superior to the catalysts containing alkali metal hydroxide are. However, there is a problem that these catalysts are very are expensive and uneconomic on an industrial scale, and when the addition polymerization of ethylene oxide as an alkylene oxide accomplished the process needs further steps of removal of the Catalyst and others Polymerization with an alkali metal hydroxide or its alkoxide.

Polyoxyalkylene polyols containing minor amounts of monools tend to have a higher viscosity. When a double metal cyanide complex catalyst is used, they tend to have a very high viscosity. This appears to result from their lower head-to-tail binding selectivity in the addition polymerization of propylene oxide as an alkylene oxide. If they have a higher viscosity, problems with dimensional stability and mixing properties occur in the mechanical molding of flexible polyurethane foams, and high Mo polyoxyalkylene polyols Molecular weight are of limited use in this context.

It However, it is expected that a polymer polyol acting as a matrix a polyoxyalkylene polyol with a large amount of monools as above mentioned, has a polyurethane foam having deteriorated physical Properties results.

Around the aforementioned To solve problems, USP 3,829,505, JP-A-02-115211 (Tokkaihei) and JP-A-03-014812 (Tokkaihei) a process for producing a polyoxyalkylene polyol in which a catalyst other than an alkali metal catalyst is, like a double metal cyanide complex catalyst, as a catalyst in the addition polymerization of propylene oxide used as alkylene oxide and also disclose a polymer polyol, wherein the above-mentioned Polyoxyalkylenpolyol is a matrix. There is a trend that a polyoxyalkylene polyol having a small amount of monools has a higher viscosity. The preparation of a polyoxyalkylene polyol by applying a Double metal cyanide complex catalyst causes a significant Viscosity increase of Polyoxyalkylene. The viscosity increase is due to the low Head-to-tail binding selectivity in the Addition polymerization of propylene oxide as an alkylene oxide. Therefore It is expected that a polymer polyol resulting from the process of radical polymerization of an ethylenically unsaturated Monomer in a polyoxyalkylene polyol, also a clear high viscosity having. When a polymer polyol has high viscosity, there is an obstacle for molding and mixing in mechanical molding for manufacturing a flexible polyurethane foam to stabilize and an application limit a polymer polyol, wherein the high molecular weight polyoxyalkylene polyol represents a matrix.

polymer polyols have deteriorated dispersion stability and higher viscosity. In particular, if the polymer content is greater than or equal to 30% by weight, such tendencies are clear. It is essentially impossible to produce a polymer polyol that has a high polymer concentration in a polyoxyalkylene polyol as a matrix by using the mentioned above Has metal complex catalyst.

It is also known, a chain transfer agent to release such problems as deteriorated dispersion stability and higher viscosity of highly concentrated Polymer polyol, apply. USP 3,953,393 and JP-A-01-221403 (Tokkaihei) disclose methods of preparing low viscosity polymer polyols Use of alkylmercaptans as chain transfer agents. polymer polyols according to this However, procedures are bad-smelling and it is difficult to get one available To obtain polymer polyol, because a highly concentrated polymer polyol no sudden Avoid viscosity increase can.

JP-A-58-210917 (Tokkaisho) discloses a method of using mercaptans Ketones, alcohols, aldehydes, halogenated compounds, benzene derivatives and especially isopropyl alcohol as a chain transfer agent. The procedure however, is insufficient to increase the viscosity of highly concentrated polymer polyol to diminish. JP-A-63-146912 (Tokkaisho) discloses a method for using amines, such as morpholines, as reaction regulators, and the method differs from that of the present Invention because a special polyol is used.

Because flexible polyurethane foams a medium elasticity exhibit and excellent in the impact-absorbing property they are for bedding, Furniture, Slices for Motor vehicles, upholstery of furniture, and so on. They are usually through the slab or Hot-mold foaming produced. You have poor flexibility and a low one Elasticity, so they can appreciate the convenience of rubber latex foam a cushioning material is lacking. Polyurethane foams with high elasticity were designed to be the conventional ones flexible polyurethane foams in the aforementioned To improve properties. You are going through the procedure for Reacting polyisocyanate with a polyoxyalkylene polyol and a partially used by the polyoxyalkylene polyol polymer polyol produced. The polymer polyol is made by polymerizing an ethylenic unsaturated Monomers, such as acrylonitrile and styrene, in a polyoxyalkylene polyol, and subsequently Foam, leaving the foam as it is at temperatures of Room temperature up to 100 ° C for one short period received. Adjusting the obtained foams the people by their excellent amenity and theirs Comfort impresses, so that the foams are often used for upholstery used by motor vehicles and so on.

The for upholstery foams used by automobiles have excellent rigidity; this means Hardness and mechanical properties, but they are inferior in wet aging life (subsequently represented by the term wet aging compression set).

JP-A-63-75021 (Tokkaisho), JP-A-02-115211 (Tokkaihei), JP-A-03-068620 (Tokkaihei) and JP-A-03-014812 (Tokkaihei) disclose methods for improving of polyurethane foams in wet aging compression set. JP-A-63-75021 (Tokkaisho) discloses that the Use in combination with a special crosslinking agent a polyurethane foam in wet aging compression set improved to such an extent however too high amounts of it the foam in the mechanical properties, such as elongation and tear strength, deteriorate, and there is a limit to the improvement of polyurethane foam in wet aging compression set. JP-A-02-115211 (Tokkaihei), JP-A-03-068620 (Tokkaihei) and JP-A-03-014812 (Tokkaihei) disclose that the use of a polyoxyalkylene polyol with a low Degree of full-time unsaturation a polyurethane foam in wet aging compression set improved. These polyoxyalkylene polyols are used in the presence of Diethylzinc, metal porphyrin or a double metal cyanide complex catalyst, as in the aforementioned Descriptions disclosed, made. According to the results, which by the inventors have been double checked however, was the flexible polyurethane foam composed of a polyoxyalkylene polyol, which using the above-mentioned double metal cyanide complex catalyst is produced, not in the wet aging compression set improved, as the inventors expected.

EP-A-0 403,313 discloses that BaOH is used as a polymerization catalyst of propylene oxide is used to produce a low polyether polyol To obtain monool content.

SUMMARY THE INVENTION

tasks The present invention provides (i) a method for preparing a polyoxyalkylene polyol having a low molecular weight Monool fraction and high head-to-tail binding selectivity, even if polymerization by addition of an alkylene oxide to a Active hydrogen compound is carried out, (ii) a polymer polyol, that in viscosity is low and excellent in dispersion stability, (iii) a method for producing the same and (iv) a method for producing a flexible polyurethane foam, the less closed Having cells and improved properties, such as hardness, wet aging compression set and impact resilience, having.

The Inventors looked for ways to solve the problems mentioned above to solve and found the amount of alkali metal hydroxide catalyst, the reaction temperature and the reaction pressure required to make a special Polyoxyalkylenpolyol produce. They found that at the use of the above-mentioned polyoxyalkylene polyol As a matrix of polymer polyol, its polymer concentration is important within a predetermined range and the glass transition temperature of the polymer within a predetermined range, if the polymer concentration is high, and they were successful at Making a flexible polyurethane foam by applying the Polyoxyalkylenpolyols and the polymer polyol.

One aspect of the present invention is a process for producing a polyoxyalkylene polyol having an oxypropylene group content of at least 70% by weight, adding propylene oxide to an active hydrogen compound, and conducting addition polymerization in the presence of an alkali metal hydroxide catalyst having a purity of at least 90% by weight and at least one compound from the group consisting of cesium hydroxide and rubidium hydroxide, in an amount of 0.05 to 0.5 mole per mole of the active hydrogen compound at a temperature of 60 to 98 ° C and at a reaction pressure of less than or equal to 490 kPa (4 kg / cm ² ).

According to one Second aspect of the present invention is a method for Preparation of a Polyoxyalkylenpolyols with a hydroxyl value of 10 to 35 mg KOH / g, a monool content of less than or equal to 15 mole%, based on the polyoxyalkylene polyol, of a head-to-tail binding selectivity of at least 96% and an oxypropylene group content of at least 70% by weight, derived from addition polymerization of propylene oxide.

One Third aspect of the present invention is a method for Making a flexible polyurethane foam, reacting a Polyisocyanate compound with a polyoxyalkylene polyol according to the second Aspect of the invention having a hydroxyl value of 10 to 35 mg KOH / g, a monool content of less than or equal to 15 mol%, based to the polyoxyalkylene polyol, a head-to-tail binding selectivity of at least 96% and an oxypropylene group content of at least 70% by weight, which originates from an addition polymerization of propylene oxide, in Presence of a catalyst, a surfactant, a foaming agent and a crosslinking agent.

One fourth aspect of the present invention is a polymer polyol, a polyoxyalkylene polyol according to the second Aspect of the invention having a hydroxyl value of 10 to 35 mg KOH / g, a monool content of less than or equal to 15 mol%, based to the polyoxyalkylene polyol, and a head-to-tail binding selectivity greater than or equal to 96% and an oxypropylene group content of at least 70 weight percent, that of an addition polymerization of propylene oxide and polymer particles present in the polyoxyalkylene polyol in U.S.P. Range greater than or equal to 5% by weight or less dispersed as 30 weight percent.

One fifth Aspect of the present invention is a polymer polyol containing a Polyoxyalkylenepolyol according to the second Aspect of the invention having a hydroxyl value of 10 to 35 mg KOH / g, a monool content of less than or equal to 15 mol%, based to the polyoxyalkylene polyol, an oxypropylene group content of at least 70% by weight, greater than a head-to-tail binding selectivity or equal to 96%, of an addition polymerization of propylene oxide and polymer particles present in the polyoxyalkylene polyol in the Range of greater than or equal to 30 weight percent to less than or equal to 60 weight percent are dispersed, and a glass transition temperature from 90 to 120 ° C comprise.

According to the present Invention may be a polymer polyol by polymerizing an ethylenically unsaturated Monomers in a Polyoxyalkylenpolyol according to the second aspect of this Invention, for example in the presence of a chain transfer agent, getting produced.

The Polymer polyol of the present invention has as a matrix Polyoxyalkylenepolyol according to the second Aspect of the invention, which has a low Monoolanteil and a high head-to-tail binding selectivity and properties such as low Viscosity, and improves various properties of polyurethane foams.

Also when polymer polyols are high in concentration, if with conventional compared with this invention, it is possible to obtain polymer polyols, the low in viscosity, free from flocculation of particles and excellent in dispersion stability.

The polyoxyalkylene polyols and polymer polyols thus obtained give polyurethane foams which have some closed cells so crushed foams do not with difficulties, such as tearing, Suffer. The polyurethane foams are in properties, like hardness, Compression set under wet ages and heat and impact resilience, excellent.

DESCRIPTION THE PREFERRED EMBODIMENTS

Polyoxyalkylene polyols

The Active hydrogen compounds include polyhydric alcohols From 2 to 8 hydroxyl groups, preferably from 3 to 8 hydroxyl groups, sugars, aliphatic amine compounds, alkanolamines, polyamines, aromatic Amine compounds, polyhydric phenols and polyoxyalkylene polyols, these compounds as starters and a molecular weight of 250 to 1000, a. Preferred are ethylene glycol, diethylene glycol, Propylene glycol, dipropylene glycol, 1,4-butylene glycol, glycerol, diglycerol, Hexanetriol, trimethylolpropane, pentaerythritol, sorbitol, dextrose, Sucrose, methylglycoxide, bisphenol-A, bisphenol-F, dihydroxydiphenylether, Dihydroxybiphenyl, hydroquinone, resorcinol, phloroglucinol, naphthalenediol, Aminophenol, aminonaphthol, phenol-formaldehyde condensates, N-methyl-N, N-diethanolamine, N-ethyl-N, N-diisopropanolamine, monoethanolamine, diethanolamine, triethanolamine, Ethylenediamine, propylenediamine, hexamethylenediamine, bis (p-aminocyclohexyl) methane, aniline, toluidines, Tolylenediamines, diphenylmethanediamine, naphthalenediamine. They are individually or used in combination.

The Alkali metal hydroxide catalysts include potassium hydroxide, sodium hydroxide, Lithium hydroxide, rubidium hydroxide and cesium hydroxide, the one Purity greater than or equal to 90% by weight and at least one compound, selected from the group consisting of cesium hydroxide and rubidium hydroxide.

The Alkylene oxides consist of propylene oxide and at least one alkylene oxide, selected from the group consisting of ethylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, Styrene oxide and other alkylene oxides having at least 3 carbon atoms. They are used under the condition that addition polymerization of propylene oxide gives a product containing oxypropylene groups of at least 70% by weight, preferably at least 80% by weight, having.

The Polyoxyalkylene polyols are added by adding an alkylene oxide the above-mentioned active hydrogen compound and polymerizing in the presence of the alkali metal hydroxide catalyst receive. They have a hydroxyl value of 10 to 35 mg KOH / g, one Mono fraction less than or equal to 15 mol%, based on the polyoxyalkylene polyol, and a head-to-tail binding selectivity greater than or equal to 96%. in the Fall of hydroxyl values of less than 10 mg KOH / g become polyoxyalkylene polyols and polymer polyols, wherein vinyl polymer particles in the polyoxyalkylene polyols are dispersed as matrices, very high in viscosity and are as starting materials for flexible polyurethane foams not suitable. In their reaction with organic isocyanates, under Formation of prepolymers, the products are also very high in viscosity and not suitable for use.

in the Case of polyoxyalkylene polyols having such low hydroxyl values polymerization is accompanied by a Monoolanteilerhöhung. It deteriorates flexible polyurethane foams in the compression set at high humidity and temperature and impact resilience and deteriorates polyurethane elastomers in the mechanical properties, so the monol fraction must be less than or equal to 15 mol%. In the case of hydroxyl values of more than 35 mg KOH / g, some have conventional Polyols have a monool content of about 15 mole%; but also at low Molecular weights do not have flexible polyurethane foams as above mentioned, increased Properties.

If a polyoxyalkylene polyol having such a lower monool proportion which results from the addition polymerization of propylene oxide gives a head-to-tail binding selectivity of less than 96 percent, the binding selectivity decreases accompanied by significant increase in viscosity. This causes problems in molding a flexible polyurethane foam and reacting with an organic isocyanate to form a Prepolymer.

The The following conditions are used in the preparation of the above mentioned Necessary high molecular weight polyoxyalkylene polyols whose Structure was regulated. In the addition polymerization of propylene oxide to an active hydrogen compound is the amount of alkali metal hydroxide catalyst 0.05 to 0.5 mol per mole of the active hydrogen compound, preferably 0.1 to 0.3 mol. The reaction temperature is 60 to 98 ° C, preferably 70 to 90 ° C. When the concentration of the catalyst per mole of the active hydrogen compound is greater than 0.5 mol, the proportion of monool in the product is usually exceed 15 mol%, too when the reaction of addition polymerization of propylene oxide at 60 to 98 ° C extends and their head-to-tail binding selectivity is often less than 96 percent is such that the catalyst concentration is greater than 0.5 mol unsuitable is.

If the concentration of catalyst per mole of active hydrogen compound less than 0.05 moles, runs the addition polymerization of propylene oxide is slow and it is difficult to polymerize to a hydroxyl value of 10 to 35 mg KOH / g. If also an alkali metal hydroxide catalyst to an intermediate polymer, which by addition of propylene oxide to an active hydrogen compound in Presence of catalyst is given is the total amount alkali metal hydroxide catalyst also in the above-mentioned range.

The reaction pressure is less than or equal to 4 kg / cm ² (490 kPa) in the addition polymerization of propylene oxide to an active hydrogen compound in the presence of alkali metal hydroxide catalyst. Reaction pressures greater than 4 kg / cm ² (490 kPa) are inappropriate because the monool fraction of polyoxyalkylene polyol increases, and at lower hydroxyl levels, the monool fraction exceeds 15 mole%.

If the addition polymerization of alkylene oxide, that of propylene oxide is different, such as ethylene oxide and 1,2-butylene oxide, alone or in combination with propylene oxide, to an active hydrogen compound in the presence an alkali metal hydroxide catalyst is carried out, the reaction condition except for mentioned above Conditions or within those.

Method, such as neutralization by using inorganic acids, such as hydrochloric acid and phosphoric acid, organic acids, like acetic acid, Carbon dioxide and so on, adsorption by using an adsorbent, Wash by using water or a mixture of water and an organic solvent, and ion exchange by using an ion exchange resin, make it possible the above catalyst of crude polyoxyalkylene polyol by adding an alkylene oxide to an active hydrogen compound, in the presence thereof and to obtain a desired product.

Polymer polyols

polyoxyalkylene are shown below.

The Polyoxyalkylene polyols prepared according to the second aspect of the invention, have a hydroxyl value of 10 to 35 mg KOH / g and a Monoolanteil less than or equal to 15 mole%, based on the polyoxyalkylene polyol, and a head-to-tail binding selectivity greater than or equal to 96 percent, which results from the addition polymerization of propylene oxide. They are used singly or in combination.

in the Case of hydroxyl values of less than 10 mg KOH / g are polyoxyalkylene polyols and polymer polyols with the polyoxyalkylene polyols as matrices and vinyl type dispersed polymer particles are very high in viscosity and not suitable for use as flexible polyurethane foams. In the case of polyoxyalkylene polyols with such low hydroxyl values, the monool fraction of the Polyols according to the addition polymerization, so that flexible polyurethane foams in the compression set under high humidity and heat and in the bounce springback Reduce. It is necessary to reduce their monool share to less than or equal to 15 mol%. In the case of hydroxyl values of more as 35 mg KOH / g, some conventional polyols have a mono-ol content of about 15 mole%. Even if they have a low molecular weight, do not give a flexible polyurethane foam which in the above mentioned Properties is improved.

in the Case of less than 96 percent head-to-tail binding selectivity resulting from addition polymerization of propylene oxide, as in polyoxyalkylene polyols with such low monol shares increases the low Head-to-tail binding selectivity greatly increases the viscosity of a Polyoxyalkylenpolyols and a problem in molding a flexible Polyurethane foam occurs.

polymer polyols are shown below.

The ethylenically unsaturated Monomers have at least one ethylenically unsaturated group with others is polymerizable. They close Acrylonitrile, methacrylonitrile, acrylic acid, phenyl acrylate, methyl methacrylate, methacrylic anhydride, Acrylamide, styrene, methylstyrene, phenylstyrene, chlorostyrene, butadiene, 1,4-pentadiene and vinyl acetate or mixtures thereof. acrylonitrile or a mixture of acrylonitrile and styrene is preferred.

The weight ratio of acrylonitrile-to-styrene is preferably in the range of 100: 0 until 10:90. When the polymer concentration is greater than or equal to 30% by weight is the range of 90:10 to 30:70 is preferred to increase the viscosity to diminish.

The ethylenically unsaturated Monomers usually become in the range of 5 to 60 percent by weight per the sum of the polyol and the monomer used to control the polymer concentration thereof in the range from 5 to 60 percent by weight.

If the polymer concentration of the polymer polyol in the range of more than or equal to 5 weight percent or less than 30 weight percent is, the polymer polyol is prepared ge according to known methods. The conditions of this case can the same as those using a chain transfer agent be. When the ethylenically unsaturated Monomer is acrylonitrile alone, the glass transition temperature is according to the general Thermal analysis unclear and can not be measured. If the monomer, however is a mixture of acrylonitrile and styrene, the temperature is in the range of 105 to 130 ° C. When the polymer concentration is greater than or equal to 30 weight percent and less than or equal to 60 weight percent is, becomes a chain transfer agent used.

worin R₁, R₂ und R₃ ausgewählt sind aus der Gruppe, bestehend aus Wasserstoffatom, einer Alkylgruppe mit 1 bis 10 Kohlenstoffatomen und einer Hydroxyalkylgruppe mit 2 bis 10 Kohlenstoffatomen, die gleich oder verschieden voneinander sein können, jedoch nicht alle Wasserstoffatome darstellen; oder von der allgemeinen Formel (2) ist:

worin X ein Sauerstoffatom oder eine Gruppe NR₂ darstellt, R₁ eine Alkylgruppe mit 1 bis 10 Kohlenstoffatomen oder eine Hydroxyalkylgruppe mit 2 bis 10 Kohlenstoffatomen darstellt und R₂ ein Wasserstoffatom, eine Alkylgruppe mit 1 bis 10 Kohlenstoffatomen oder eine Hydroxyalkylgruppe mit 2 bis 10 Kohlenstoffatomen darstellt. Sie schließen Amine, wie Triethylamin, Tripropylamin, Tributylamin, N,N-Diethylethanolamin, N-Methylmorpholin und N-Ethylmorpholin, ein. Triethylamin und N-Methylmorpholin sind bevorzugter.The chain transfer agents are usually amine compounds, for example of the general formula (1),

wherein R ₁ , R ₂ and R _{3 are} selected from the group consisting of hydrogen atom, an alkyl group having 1 to 10 carbon atoms and a hydroxyalkyl group having 2 to 10 carbon atoms which may be the same or different from each other but are not all hydrogen atoms; or of the general formula (2) is:

wherein X represents an oxygen atom or a group NR ₂ , R _{1 represents} an alkyl group having 1 to 10 carbon atoms or a hydroxyalkyl group having 2 to 10 carbon atoms, and R _{2 represents} a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a hydroxyalkyl group having 2 to 10 carbon atoms represents. They include amines such as triethylamine, tripropylamine, tributylamine, N, N-diethylethanolamine, N-methylmorpholine and N-ethylmorpholine. Triethylamine and N-methylmorpholine are more preferred.

The Amount of chain transfer agent depends on the glass transition temperature of the polymer controlled by the use of the means for holding the temperature in the range of 90 to 120 ° C, preferably 95 to 115 ° C, from. in the Case of glass transition temperatures less than 90 ° C are polyurethane foams in properties, such as hardness, deteriorates, and at glass transition temperatures greater than 120 ° C is it impossible, To obtain polymers that are low in viscosity and excellent in dispersion stability are as desired. The amount of chain transfer agent to realize such a glass transition temperature is that the molecular weight of the polymer in the range of 30,000 to 140,000 and in the range of 0.5 to 30 parts by weight, preferably 1 to 20 parts by weight per 100 parts by weight of the ethylenically unsaturated Monomers, stops.

The Polymerization catalysts are those used for the vinyl polymerization reaction are well known. They close Peroxides, such as hydroperoxide, benzoyl peroxide, acetyl peroxide, t-butyl peroxide and di-t-butyl peroxide, azo compounds such as azobisisobutyronitrile, Peroxo compounds, such as persulfates, succinic acid, and diisopropyl peroxydicarbonate, one.

The Catalysts are in the range of 0.01 to 5 weight percent, preferably 0.1 to 2.0 percent by weight, per total weight polyoxyalkylene polyol and ethylenically unsaturated monomer.

It is possible, to carry out the polymerization in the presence of a dispersion stabilizer to disperse the polymer particles. The dispersion stabilizers shut down unsaturated Carbon-carbon bonds containing polyether ester polyols, modified polyols having an acrylic group at the end thereof Methacrylic group and an allyl group as disclosed in JP-B-49-046556 (Tokkosho), a.

The Polymer polyols are prepared by employing the above-mentioned polyoxyalkylene polyols, ethylenically unsaturated Monomers, chain transfer agents and catalysts produced.

The Polymerization reaction may be batchwise or in continuous Way executed become. The polymerization temperature is dependent on the type of catalyst and generally at a level greater than or equal to the decomposition temperature of the catalyst, preferably from 60 to 200 ° C, more preferably 90 to 160 ° C, certainly. The polymerization reaction can be carried out under pressure set system or in a normal pressure system.

To completion the polymerization reaction, the resulting polymer polyol, such as it is applied as a starting material for polyurethane foams become. It is more preferable to unreacted under reduced pressure Monomers, decomposition products of catalyst and chain transfer agent to remove and apply the polymer polyol.

Polyurethane foams

All the aforementioned Polyoxyalkylenpolyole can used as polyoxyalkylene polyols for producing polyurethane foams become.

All the above-mentioned polymer polyols can be used as the polymer polyols as they are. Polyols containing polymer polyols include the aforementioned polymer polyols or gems the polymer polyols with other polyoxyalkylene polyols. Polymer polyols having a viscosity of less than or equal to 3 Pa · s (3,000 cP) are preferred. Other polyoxyalkylene polyols are not particularly limited, but conventional ones can be used. It is also possible to use the same polyoxyalkylene polyol as that for producing a polymer polyol, if necessary.

The organic polyisocyanates include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, mixtures of these isocyanates, by weight of 80:20 (80:20 TDI) and 65:35 (65:35 TDI), crude tolylene diisocyanate (crude TDI), 4,4'-diphenylmethane diisocyanate (4,4'-MDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI), 2,2'-diphenylmethane diisocyanate (2,2'-MDI), mixtures of diphenylmethane diisocyanate isomers (MDI), polymethylene polyphenyl isocyanate (crude MDI), toluidine diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, Isophorone diisocyanate, dicyclohexylmethane diisocyanate and carbodiimido-modified Products thereof, biuret-modified products, dimers, trimers and Prepolymers thereof. You can individually or in combination.

The foaming shut down Water, trichloromonofluoromethane, dichlorodifluoromethane, 2,2-dichloro-1,1,1-trifluoroethane, 1,1-dichloro-1-fluoroethane, methylene chloride, trichlorotrifluoroethane, Dibromotetrafluoroethane. They are used individually or in combination used. Applying water alone is from the standpoint of environmental protection prefers. The amount is in the range of 0.01 to 10 parts by weight per 100 parts by weight of polyoxyalkylene polyol.

The Urethane reaction catalysts are well known and not particularly limited. The amine catalysts include triethylamine, tripropylamine, Polyisopropanolamine, tributylamine, trioctylamine, hexamethyldimethylamine, N-methylmorpholine, N-ethylmorpholine, N-octadecylmorpholine, monoethanolamine, Diethanolamine, triethanolamine, N-methyldiethanolamine, N, N-dimethylethanolamine, Diethylenetriamine, N, N, N ', N'-tetramethylethylenediamine, N, N, N ', N'-tetramethylpropylenediamine, N, N, N ', N'-tetramethylbutanediamine, N, N, N ', N'-tetramethyl-1,3-butanediamine, N, N, N ', N'-tetramethylhexamethylenediamine, Bis [2- (N, N-dimethylamino) ethyl] ether, N, N-dimethylbenzylamine, N, N-dimethylcyclohexylamine, N, N, N ', N'-pentamethyldiethylenetriamine, Triethylenediamine, formate and other salts of triethylenediamine, Oxyalkylene adducts of amino groups, such as primary and secondary amines, cyclic aza compounds such as N, N-dialkylpiperazines, various N, N ', N "-trialkylaminoalkylhexahydrotriazines, β-aminocarbonyl catalysts, disclosed in JP-B-52-043517 (Tokkosho) and β-aminonitrile catalysts in JP-B-53-014278 (Tok kosho). Organometallic catalysts include tin acetate, Tin octylate, tin oleate, tin laurate, dibutyltin diacetate, dibutyltin dilaurate, Dibutyltin dichloride, lead octanoate, lead naphthenate, nickel naphthenate and cobalt naphthenate. You can used singly or in combination. The amount is in Range from 0.0001 to 10.0 parts by weight per 100 parts by weight Compounds with active hydrogen atoms.

The Surfactants are well known surfactants Organosilicon agents. They include L-520, L-532, L-540, L-544, L-550, L-3550, L-5305, L-3600, L-3601, L-5305, L-5307, L-5309, L-5710, L-5720, L-5740M and L-6202 from Nippon Unica Co., Ltd., SH-190, SH-194, SH-200, Toray's SPX-253, PX-274C, SF-2961, SF-2962, SPX-280X and SPX-294A Silicone Co., Ltd., F-114, F-121, F-122, F-220, F-230, F-258, F260B, F-317, F-341, F-601, F-606, X-20-200 and X-20-201 from Shinetsu Silicone Co., Ltd., TFA-4200 and TFA-4202 from Toshiba Silicone Co., Ltd., B-4113 from Goldschmidt Co., Ltd., SRX-253, SRX-274C, SF-2961 and SF-2962 from Toray-Dow Corning Co., a. The amount thereof is in the range of 0.1 to 10 Parts by weight, preferably 0.1 to 5 parts by weight, per 100 parts by weight the total weight of the compound, the active hydrogen atoms and a polyisocyanate.

The Close crosslinking agent monomeric polyols, such as ethylene glycol, propylene glycol, diethylene glycol, Triethylene glycol and 1,3-butanediol, alkanolamines such as triethanolamine and diethanolamine, aliphatic polyamines such as ethylenediamine, diethylenetriamine and triethylenetetramine, aromatic polyamines, such as methyleneorthochloramine, 4,4'-diphenylmethane diamine, Aniline, 2,4'-tolylenediamine and 2,6'-tolylenediamine, and compounds obtained by addition of ethylene oxide and propylene oxide to these active hydrogen compounds to a hydroxyl value of greater than or equal to 200 mg KOH / g. Other connections with a hydroxyl value greater than or equal to 200 mg KOH / g, obtained by adding ethylene oxide and propylene oxide to hydroquinone, resorcinol and aniline, too be used. They are in the range of 0.1 to 10 parts by weight, per 100 parts by weight of polyoxyalkylene polyol.

stabilizers, fillers, coloring Materials and flame retardants can, if necessary, in addition to the aforementioned Materials are applied.

The process for producing polyurethane foam will be described below. predetermined Amounts of polyoxyalkylene polyol, foaming agent, catalyst, surfactant, crosslinking agent and other additives are blended in predetermined amounts to obtain a resinous premix. The amounts of the organic polyisocyanate compound, polyoxyalkylene polyol and crosslinking agent are determined so that the ratio per equivalent weight (NCO / H) of the group NCO in the polyisocyanate compound to the active hydrogen atom in the resinous premix is in the range of 0.7: 1.4. The resinous premix and the polyisocyanate compound are adjusted at a predetermined temperature, for example, 20 to 25 ° C, followed by rapid mixing and pouring into a mold having a set temperature, for example, 30 to 70 ° C. The reaction mixture is foamed, filled into the mold and cured in an oven whose predetermined temperature is, for example, in the range of room temperature to 100 ° C for a predetermined period of time, for example, 5 to 30 minutes, and the foam is removed from the mold to to obtain a flexible polyurethane foam.

EXAMPLES

The The present invention will be explained more specifically below by examples and Comparative examples explained.

hydroxyl value: Esterification was carried out using a pyridine solution of phthalic anhydride accomplished and excess phthalic anhydride was prepared by adding a sodium hydroxide solution according to the method of JIS K 1557 examined.

monol:

• Equipment: High-pressure liquid chromatograph (HPLC) from Nihon Bunko Co.
• filler from column separation: Aminopropyl group, chemically bonded type of silica filler
• Eluent: a mixture of hexane and 2-propanol
• Flow rate: 1 ml / min

One Liquid chromatogram of polyoxyalkylene polyol was drawn to increase the area ratio of triol to monool, based on the peak area intensity detected with a differential refractometer.

The Liquid chromatograms of triol and monool, which have different molecular weights from each other had, were under the same conditions as the above mentioned drawn. A calibration curve was obtained according to the elution peak times on the chromatograms, pulled. The molecular weights of the triol and monools in polyoxyalkylene polyol were calculated according to the curve. The Mono shares (mol%) were calculated according to the area ratio and calculated molecular weights, based on the triol and monool. The diol component in polyoxyalkylene polyol was hardly detected and ignored when calculating the monolayer.

The head-to-tail binding selectivity or HT binding selectivity. The ¹³ C nuclear magnetic resonance (NMR) spectrum was measured using dichloroform as the solvent and ¹³ C-NMR equipment (400 Hz, Nihon Bunko Co.). The head-to-tail binding selectivity was determined as a function of the ratio (16.9-17.4 ppm) of the methyl group of oxypropylene segments in head-to-tail bonds to the signals (17.7-18.5 ppm ) of the methyl group of oxypropylene segments in head-to-head bonds.

A

= ein Integralwert der Methylgruppe in Kopf-zu-Kopf-Bindungen

B

= ein Integralwert der Methylgruppe in Kopf-zu-Schwanz-Bindungen

F = ((0,5A/(0,5A + B)) × 100 The calculation formula F is shown below.

A

= an integral value of the methyl group in head-to-head bonds

B

= an integral value of the methyl group in head-to-tail bonds

F = ((0.5A / (0.5A + B)) × 100

Of the Origin of each signal, referring to the data in the F.C. Schilling and A. E. Tonelli (Macromolecules 19, 1337-1343, (1986)) written report, determined.

Viscosity: It was measured with a rotary viscometer at 25 ° C according to the method of JIS K 1557 certainly.

Polymer concentration: Methanol was added to a polymer polyol to give the resulting To disperse the mixture well. The resulting mixture was used for determination the weight of methanol insoluble solid particles centrifuged. In the case of a polymer polyol consisting of acrylonitrile alone, the polymer concentration was determined by a method of detection Nitrogen content according to elemental analysis and calculating the polymer concentration.

Tg (Glass transition temperature): It was made by applying Perkin-Elmer DSC-7 thermal analysis apparatus Co. in nitrogen atmosphere at a rinse temperature velocity of 20 ° K / min certainly.

Evaluation of polyoxyalkylene polyols

1. Preparation of polyoxyalkylene polyols

example 1

Polyoxyalkylene polyol A: To 1 mole of glycerol was added 0.13 mol of cesium hydroxide, dehydration was carried out at 100 ° C for 6 hours, and addition polymerization of propylene oxide was carried out at a reaction temperature of 95 ° C at a reaction pressure of less than or equal to 3.5 kg / cm ² (440 kPa) to obtain a polyoxypropylene polyol having a hydroxyl value of 33 mg KOH / g. To the polyoxypropylene polyol was added 15% by weight of ethylene oxide, based on the weight of the polyol, at 100 ° C to obtain a polyoxyalkylene polyol having a hydroxyl value of 28 mg KOH / g. The viscosity was 1.14 Pa · s (1140 cP) at 25 ° C.

Of the Mono fraction, based on the above-mentioned area ratio of triol to monool, was 13.0 mol%. The diol component in the polyoxyalkylene polyol was Hard to prove and was in the calculation of the Monool share ignored. The H-T bond selectivity was 96.7 mole%. The results are in Table 1.

Example 2

Polyoxyalkylene polyol B: To 1 mol of glycerol was added 0.43 mol of cesium hydroxide, dehydration was carried out at 100 ° C for 6 hours, and addition polymerization of propylene oxide was carried out at a reaction temperature of 65 ° C at a reaction pressure of less than or equal to 2.0 kg / cm ² (300 kPa) to obtain a polyoxypropylene polyol having a hydroxyl value of 50 mg KOH / g. To the polyoxypropylene polyol was added propylene oxide at a reaction temperature of 75 ° C at a reaction pressure of less than or equal to 3 kg / cm ² (300 kPa) to obtain a polyoxypropylene polyol having a hydroxyl value of 28 mg KOH / g. The proportion of monool product obtained according to Example 1 was 11.9 mol%, the viscosity was 1.25 Pa · s (1250 cP) at 25 ° C and the HT binding selectivity was 96.2 mol%. The results are in Table 1.

Example 3

Polyoxyalkylene polyol C: To 1 mol of glycerol was added 0.23 mol of cesium hydroxide, dehydration was carried out at 100 ° C for 6 hours, and addition polymerization of propylene oxide was carried out at a reaction temperature of 80 ° C at a reaction pressure of less than or equal to 3.5 kg / cm ² (440 kPa) to obtain a polyoxypropylene polyol having a hydroxyl value of 28 mg KOH / g. To the polyoxypropylene polyol was added 15% by weight of ethylene oxide by weight of polyol at 100 ° C to give a polyoxyalkylene polyol having a hydroxyl value of 24 mg KOH / g. The proportion of monool product obtained according to Example 1 was 8.0 mol%, the viscosity was 1.65 Pa · s (1650 cP) at 25 ° C and the HT binding selectivity was 96.3 mol%. The results are in Table 1.

Example 4

Polyoxyalkylene polyol E: To 1 mol of adduct of pentaerythritol with propylene oxide having a hydroxyl value of 450 mg KOH / g was added 0.23 mol of cesium hydroxide, dehydration was carried out at 100 ° C for 6 hours, and addition polymerization of propylene oxide was carried out at a reaction temperature of 80 ° C at a reaction pressure of less than or equal to 3.5 kg / cm ² (440 kPa) to obtain a polyoxypropylene polyol having a hydroxyl value of 50 mg KOH / g. To the polyoxypropylene polyol was propylene oxide at a reaction temperature of 90 ° C at a reaction pressure of less than or equal to 3.5 kg / cm ² (440 kPa) added to obtain a polyoxypropylene polyol having a hydroxyl value of 29 mg KOH / g. To the polyoxypropylene polyol was added 15% by weight of ethylene oxide, based on the weight of the polyol, at 100 ° C to obtain a polyoxyalkylene polyol having a hydroxyl value of 25 mg KOH / g. The proportion of monool product obtained according to Example 1 was 14.3 mol%, the viscosity was 1.8 Pa · s (1800 cP) at 25 ° C and the HT binding selectivity was 96.4 mol%. The results are in Table 1.

Example 5

Polyoxyalkylene polyol F: To 1 mol of glycerol was added 0.13 mol of cesium hydroxide, dehydration was carried out at 100 ° C for 6 hours, and addition polymerization of propylene oxide was carried out at a reaction temperature of 60 ° C at a reaction pressure of less than or equal to 2.0 kg / cm ² (300 kPa) to obtain a polyoxypropylene polyol having a hydroxyl value of 50 mg KOH / g. To the polyoxypropylene polyol was added propylene oxide at a reaction temperature of 60 ° C at a reaction pressure of less than or equal to 2.0 kg / cm ² (300 kPa) to give a polyoxypropylene polyol having a hydroxyl value of 16 mg KOH / g. The proportion of monool product obtained according to Example 1 was 14.6 mol%, the viscosity was 2.3 Pa · s (2300 cP) at 25 ° C, and the HT binding selectivity was 97.0 mol%. The results are in Table 1.

Example 6

Polyoxyalkylene polyol G: To 1 mole of glycerol was added 0.23 mole of cesium hydroxide and 0.10 mole of rubidium hydroxide, dehydration was carried out at 100 ° C for 6 hours, and addition polymerization of propylene oxide was carried out at a reaction temperature of 80 ° C at a reaction pressure of less at or equal to 2.5 kg / cm ² (350 kPa) to obtain a polyoxypropylene polyol having a hydroxyl value of 50 mg KOH / g. To the polyoxypropylene polyol was added propylene oxide at a reaction temperature of 80 ° C at a reaction pressure of less than or equal to 2.5 kg / cm ² (350 kPa) to obtain a polyoxypropylene polyol having a hydroxyl value of 33 mg KOH / g. The proportion of monool product obtained according to Example 1 was 10.5 mol%, the viscosity was 0.95 Pa · s (950 cP) at 25 ° C and the HT binding selectivity was 96.3 mol%. The results are in Table 2.

Example 7

Polyoxyalkylene polyol H: To 1 mole of glycerol was added 0.23 mole of cesium hydroxide, dehydration was carried out at 100 ° C for 6 hours, and addition polymerization of propylene oxide was carried out at a reaction temperature of 80 ° C at a reaction pressure of less than or equal to 3.5 kg / cm ² (440 kPa) to obtain a polyoxypropylene polyol having a hydroxyl value of 33 mg KOH / g. To the polyoxypropylene polyol was added 15% by weight of ethylene oxide, based on the total weight of polyol, at 100 ° C to obtain a polyoxyalkylene polyol having a hydroxyl value of 28 mg KOH / g. The proportion of monool product obtained according to Example 1 was 7.2 mol%, the viscosity was 1.29 Pa · s (1290 cP) at 25 ° C and the HT binding selectivity was 96.4 mol%. The results are in Table 2.

Example 8

Polyoxyalkylene polyol I: To 1 mol of glycerol was added 0.23 mol of cesium hydroxide, dehydration was carried out at 100 ° C for 6 hours, and addition polymerization of propylene oxide was carried out at a reaction temperature of 80 ° C at a reaction pressure of less than or equal to 3.5 kg / cm ² (440 kPa) to obtain a polyoxypropylene polyol having a hydroxyl value of 25 mg KOH / g. To the polyoxypropylene polyol was added 15% by weight of ethylene oxide, based on the total weight of polyol, at 100 ° C to give a polyoxyalkylene polyol having a hydroxyl value of 21 mg KOH / g. The proportion of monool product obtained according to Example 1 was 10.5 mol%, the viscosity was 1.95 Pa · s (1950 cP) at 25 ° C and the HT binding selectivity was 97.0 mol%. The results are in Table 2.

Example 9

Polyoxyalkylene polyol J: To 1 mole of glycerol was added 0.23 mole of cesium hydroxide, dehydration was carried out at 100 ° C for 6 hours, and addition polymerization of propylene oxide was carried out at a reaction temperature of 80 ° C at a reaction pressure of less than or equal to 3.5 kg / cm ² (440 kPa) to obtain a polyoxypropylene polyol having a hydroxyl value of 20 mg KOH / g. To the polyoxypropylene polyol was added 15 weight percent ethylene oxide, based on the total weight polyol, at 100 ° C to obtain a polyoxyalkylene polyol having a hydroxyl value of 17 mg KOH / g. The proportion of monool product obtained according to Example 1 was 14.0 mol%, the viscosity was 2.38 Pa · s (2380 cP) at 25 ° C and the HT binding selectivity was 97.2 mol%. The results are in Table 2.

Example 10

Polyoxyalkylene polyol K: To 1 mol of pentaerythritol was added 0.23 mol of cesium hydroxide, dehydration was carried out at 100 ° C for 6 hours, and addition polymerization of propylene oxide was carried out at a reaction temperature of 80 ° C at a reaction pressure of less than or equal to 3.5 kg / cm ² (440 kPa) to obtain a polyoxypropylene polyol having a hydroxyl value of 33 mg KOH / g. To the polyoxypropylene polyol was added 15% by weight of ethylene oxide, based on the total weight of polyol, at 100 ° C to obtain a polyoxyalkylene polyol having a hydroxyl value of 28 mg KOH / g. The proportion of monool product obtained according to Example 1 was 9.5 mol%, the viscosity was 1.42 Pa · s (1420 cP) at 25 ° C and the HT binding selectivity was 96.5 mol%. The results are in Table 2.

Comparative Example 1

Polyoxyalkylene polyol L: To 1 mole of glycerol was added 0.37 mol of potassium hydroxide, dehydration was carried out at 100 ° C for 6 hours, and addition polymerization of propylene oxide was carried out at a reaction temperature of 115 ° C at a reaction pressure of less than or equal to 5 kg / cm ² (590 kPa) to obtain a polyoxypropylene polyol having a hydroxyl value of 33 mg KOH / g. To the polyoxypropylene polyol was added 15% by weight of ethylene oxide, based on the total weight of polyol, at 100 ° C to obtain a polyoxyalkylene polyol having a hydroxyl value of 28 mg KOH / g. The proportion of monool product obtained according to Example 1 was 29.3 mol%, the viscosity was 1.15 Pa · s (1150 cP) at 25 ° C and the HT binding selectivity was 96.3 mol%. The results are in Table 3.

Comparative Example 2

Polyoxyalkylene polyol M: To 1 mole of glycerol was added 6.93 g of so-called double metal cyanide complex catalyst comprising cobalt zinc cyanide, zinc chloride, water and dimethoxyethanol (DMC catalyst), and addition polymerization of propylene oxide was carried out at a reaction temperature of 90 ° C a reaction pressure of less than or equal to 4 kg / cm ² (590 kPa) to obtain a polyoxypropylene polyol having a hydroxyl value of 33 mg KOH / g. The reaction mixture was contacted with aqueous ammonia to extract the DMC catalyst and was washed with water. To the reaction mixture was added 0.23 mol of potassium hydroxide per mole of glycerin in the polyoxypropylene polyol, dehydration was carried out at 100 ° C for 6 hours. To the reaction mixture was added 15% by weight of ethylene oxide, based on the weight of polyol, to obtain a polyoxyalkylene polyol having a hydroxyl value of 28 mg KOH / g. The monool product content obtained in Example 1 was 9.6 mole%, the viscosity was 3.08 Pa · s (3080 cP) at 25 ° C and the HT binding selectivity was 85.4 mole%. The results are in Table 3.

Comparative Example 3

Polyoxyalkylene polyol N: To 1 mole of glycerol was added 0.23 mole of cesium hydroxide, dehydration was carried out at 100 ° C for 6 hours, and addition polymerization of propylene oxide was carried out at a reaction temperature of 80 ° C at a reaction pressure of less than or equal to 3.5 kg / cm ² (440 kPa) to obtain a polyoxypropylene polyol having a hydroxyl value of 50 mg KOH / g. To the polyoxypropylene polyol was added propylene oxide at a reaction temperature of 100 ° C at a reaction pressure of less than or equal to 3.5 kg / cm ² (440 kPa) to obtain a polyoxypropylene polyol having a hydroxyl value of 28 mg KOH / g. The proportion of monool product obtained in Example 1 was 22.9 mol%, the viscosity was 1.2 Pa · s (1200 cP) at 25 ° C, and the HT binding selectivity was 97.5 mol%. The results are in Table 3.

Comparative Example 4

Polyoxyalkylene polyol O: To 1 mole of glycerol was added 0.53 moles of cesium hydroxide, dehydration was carried out at 100 ° C for 6 hours, and addition polymerization of propylene oxide was carried out at a reaction temperature of 90 ° C at a reaction pressure of less than or equal to 3.5 kg / cm ² (440 kPa) to obtain a polyoxypropylene polyol having a hydroxyl value of 117 mg KOH / g. To the polyoxypropylene polyol was propylene oxide at a reaction temperature of 90 ° C at a reaction pressure of is less than or equal to 3.5 kg / cm ² (440 kPa) to obtain a polyoxypropylene polyol having a hydroxyl value of 31 mg KOH / g. The monool product content obtained in Example 1 was 22.7 mole%, the viscosity was 1.16 Pa · s (1160 cP) at 25 ° C and the HT bond selectivity was 95.4 mole%. The results are in Table 3.

Comparative Example 5

Polyoxyalkylene Polyol P: To 1 mol of glycerol was added 0.23 mol of cesium hydroxide, dehydration was carried out at 100 ° C for 6 hours, and addition polymerization of propylene oxide was carried out at a reaction temperature of 95 ° C at a reaction pressure of less than or equal to 4 kg / cm ² (490 kPa) to obtain a polyoxypropylene polyol having a hydroxyl value of 117 mg KOH / g. To the polyoxypropylene polyol was added propylene oxide at a reaction temperature of 95 ° C at a reaction pressure of less than or equal to 4.5 kg / cm ² (540 kPa) to obtain a polyoxypropylene polyol having a hydroxyl value of 28 mg KOH / g. The proportion of monool product obtained in Example 1 was 17.7 mole%, the viscosity was 1.11 Pa · s (1110 cP) at 25 ° C and the HT binding selectivity was 96.9 mole%. The results are in Table 3.

All the polyoxyalkylene polyols of Examples and Comparative Examples were added by adding water and phosphoric acid after completion of the reaction neutralized and dried under reduced pressure to form To remove crystals of alkali metal phosphates by filtration. Their hydroxyl values, viscosity, proportion monool and H-T binding selectivity were determined according to the above mentioned Procedures examined.

• EO a.p.t.: EO-Additionspolymerisationstemperatur

Tabelle 2

• EO a.p.t.: EO-Additionspolymerisationstemperatur

Tabelle 3

• EO a.p.t.: EO-Additionspolymerisationstemperatur

The data of Examples and Comparative Examples are summarized in Tables 1 to 3. In the tables, Starter A is glycerol and Starter B is an adduct (hydroxyl value 450 mg KOH / g) of pentaerythritol with propylene oxide. Catalyst A is cesium hydroxide, Catalyst B potassium hydroxide, Catalyst C rubidium hydroxide and Catalyst D so-called double metal cyanide complex catalyst (DMC catalyst) comprising cobalt zinc cyanide, zinc chloride, water and dimethoxyethanol. PO is propylene oxide and EO is ethylene oxide. Table 1

• EO apt: EO addition polymerization temperature

Table 2

• EO apt: EO addition polymerization temperature

Table 3

• EO apt: EO addition polymerization temperature

2. Preparation of Polymer Polyols

Production Example 1

Polymer Polyol C: A one-liter autoclave equipped with a thermometer, a stirrer and a liquid feeder was charged and filled with polyoxyalkylene polyol C obtained in Example 3, and the contents were heated to 120 ° C with stirring. A mixture of the polyol, AIBN and AN, previously mixed at a ratio shown in Table 4, was introduced continuously to continuously obtain a polymer polyol at the discharge port. The reaction pressure was 3.5 kg / cm ² (440 kPa) and the residence time was 50 minutes. After the state became constant, the thus obtained reaction mixture was subjected to suction treatment at 120 ° C at 2670 Pa (20 mmHg) for 4 hours under reduced pressure, thereby removing unreacted monomers and recovering polymer polyol C. The results are shown in Table 4.

Production Example 2

Polymer Polyol L: A one-liter autoclave equipped with a thermometer, a stirrer and a liquid feeder was charged and filled up with polyoxyalkylene polyol L obtained in Comparative Example 1, and the contents were heated to 120 ° C with stirring. The mixture of the polyol, AIBN and AN, previously mixed at a ratio in Table 4, was continuously fed to obtain a polymer polyol from the discharge port. The reaction pressure was 3.5 kg / cm ² (440 kPa) and the residence time was 50 minutes. After the state became constant, the thus-obtained reaction mixture was subjected to suction treatment at 120 ° C at 2670 Pa (20 mmHg) for 4 hours under reduced pressure, thereby removing unreacted monomers and recovering polymer polyol L. The results are shown in Table 4.

Production Example 3

Polymer Polyol M: A one-liter autoclave equipped with a thermometer, a stirrer and a liquid feeder was charged and filled up with polyoxyalkylene polyol L obtained in Comparative Example 2, and the contents were heated to 120 ° C with stirring. A mixture of the polyol, AIBN and AN, previously mixed at a ratio in Table 4, was continuously charged to continuously obtain a polymer polyol from the discharge port. The reaction pressure was 3.5 kg / cm ² (440 kPa) and the residence time was 50 minutes. After the state became constant, the reaction mixture thus obtained was subjected to suction treatment at 120 ° C at 2670 Pa (20 mmHg) for 4 hours under reduced pressure, thereby removing unreacted monomers and recovering polymer polyol M. The results are shown in Table 4 ,

• Die Einheiten der Ausgangmaterialien und des Katalysators sind in Gewichtsteilen.

The polymer polyols of Preparation Examples 1 to 3 were evaluated according to the above-mentioned methods to obtain hydroxyl values and viscosity. The polymer concentration was obtained by measuring the nitrogen content according to elemental analysis and calculating the polymer concentration. AIBN and AN are simple abbreviations of azobisisobutyronitrile and acrylonitrile, respectively. Table 4

• The units of the starting materials and the catalyst are in parts by weight.

3. Production of polyurethane foams

• Katalysator-1: Minico L-1020 (Handelsname), ein Aminkatalysator von Katsuzai Chemical Co., 33% Diethylenglycollösung von Triethylendiamin
• Katalysator-2: Niax A-1 (Handelsname), ein Aminkatalysator von ARCO Co.
• Vernetzungsmittel-1: KL-210 (Handelsname), ein Amin-Vernetzungsmittel mit einem Hydroxylwert von 830 mg KOH/g von Mitsui Toatsu Chemicals Inc.
• Tensid: SRX-274C (Handelsname), ein Tensid von Toray-Dow Corning Co.
• Isocyanat-1: Cosmonate TM-20 (Handelsname), ein Gemisch von TDI-80 und Polymeric MDI (Gewichtsverhältnis von 80:20) von Mitsui Toatsu Chemicals Inc.

The following materials and so forth have been used, which are different from the above-mentioned polyoxyalkylene polyols and polymer polyols.

• Catalyst-1: Minico L-1020 (trade name), an amine catalyst from Katsuzai Chemical Co., 33% diethylene glycol solution of triethylenediamine
• Catalyst 2: Niax A-1 (trade name), an amine catalyst from ARCO Co.
• Crosslinker-1: KL-210 (trade name), an amine crosslinking agent having a hydroxyl value of 830 mg KOH / g by Mitsui Toatsu Chemicals Inc.
• Surfactant: SRX-274C (trade name), a surfactant from Toray-Dow Corning Co.
• Isocyanate-1: Cosmonate TM-20 (trade name), a mixture of TDI-80 and Polymeric MDI (weight ratio of 80:20) from Mitsui Toatsu Chemicals Inc.

The Properties were made according to the rules from JIS K-6301 and JIS K-6401 measured. The densities in Examples and Comparative Examples mean densities over everything.

Example 12

The seven ingredients described below were mixed to form a resinous premix. Polyoxyalkylene polyol C 60 parts by weight Polymer polyol C 40 parts by weight water 3.0 parts by weight Catalyst-1 0.5 parts by weight Catalyst 2 0.1 parts by weight Crosslinking agent-1 3.0 parts by weight surfactant 1.0 parts by weight

Mix of 107.6 parts by weight of the above-mentioned resinous premix with 39 parts by weight of isocyanate-1 was carried out. The mixture was in a Metal mold (400 mm × 400 mm × 100 mm), previously at 60 ° C was set. The mold was covered to carry out foaming. The Form was in a hot air oven for 7 minutes at 100 ° C heated to harden the foam and the foam was removed from the mold. The properties of the thus obtained foam are given in Table 5. The equivalent weight ratio (NCO / H) the NCO group of isocyanate to the active hydrogen atom of resinous premix was 1.00.

Examples 13 to 17

The the same procedure as in Example 12 was carried out with with the exception that polyoxyalkylene polyols E, H, I, J and K instead of polyoxyalkylene polyol C of Example 12 were used.

The equivalent weight ratio (NCO / H) the NCO group of Isocyanate to the active hydrogen atom of the resinous premix was 1.00. The properties of the resulting foam are shown in Table 5 indicated.

Comparative Example 6

The the same procedure as in Example 12 was carried out with with the exception that polyoxyalkylene polyol L instead of polyoxyalkylene polyol C was used and polymer polyol L instead of polymer polyol C. of Example 12 was used.

The equivalent weight ratio (NCO / H) the NCO group of Isocyanate to the active hydrogen atom of resinous premix was 1.00. The properties of the resulting foam are shown in Table 5 specified.

Comparative Example 7

The the same procedure as in Example 12 was carried out with with the exception that polyoxyalkylene polyol M instead of polyoxyalkylene polyol C was used and Polymerpolyol M instead of Polymerpolyol C of Example 12 was used.

The equivalent weight ratio (NCO / H) the NCO group of the Isocyanate to the active hydrogen atom of resinous premix was 1.00. The properties of the resulting foam are shown in Table 5 indicated.

• CO.6 und CO.7 bedeuten Vergleichsbeispiele 6 bzw. 7.

The foam of Comparative Example 7 (double metal cyanide complex catalyst) had a very large number of closed cells and much larger cell size than the foams of the other examples. Table 5

• CO.6 and CO.7 are comparative examples 6 and 7, respectively.

The foams of Examples 12 to 14 and 17 had a density in the range of 54 to 55 kg / m ³ and a 50% wet aging compression set in the range of 7 to 8% when they had a 25% ILD in the range of 18 to 20 kg / 314 cm ² had. The foams of Comparative Examples 6 to 7 had almost the same density and hardness but had a 50% wet aging compression set in the range of 14 to 18%. These data showed that the flexible polyurethane foams of the present examples are improved in wet aging compression set.

Evaluation of polymer polyols

1. Preparation of polyoxyalkylene polyols

• Polyole A bis E: Polyoxyalkylenpolyole in Herstellungsbeispielen 1 bis 5
• Katalysator a: Cäsiumhydroxid
• Katalysator b: Kaliumhydroxid
• Katalysator c: ein Katalysator, umfassend Zinkcobaltcyanid-Verbindung, Zinkchlorid, Wasser und Dimethoxyethanol, sogenannter Doppelmetall-Cyanid-Komplexkatalysator
• PO: Propylenoxid
• EO: Ethylenoxid
• AN: Acrylnitril
• St: Styrol
• TEA: Triethylamin
• AIBN: Azobisisobutyronitril
• Polymerpolyole a bis i: Polymerpolyole in Beispielen 18 bis 22 und Vergleichsbeispielen 8 bis 11
• Wasser: Ionen-ausgetauschtes Wasser
• L-1020: ein Katalysator, erzeugt von Katsuzai Chemicals Co.
• X-DM: ein Katalysator, erzeugt von Katsuzai Chemicals Co.
• KL-210: ein Vernetzungsmittel, erzeugt von Mitsui Toatsu Chemicals Inc.
• L-5309: ein Tensid, erzeugt von Nippon Unicar Co.
• TM-20: ein Gemisch, bestehend aus TDI-80/20 (ein Gemisch, bestehend aus 2,4-Tolylendiisocyanat und 2,6-Tolylendiisocyanat bei einem Gewichtsverhältnis von 80:20) und Cosmonate MDI-CR, erzeugt von Mitsui Toatsu Chemicals Inc., bei einem Gewichtsverhältnis von 80:20
• Eigenschaften der Schäume: Sie wurden gemäß den Verfahren von JIS K-6301 und JIS K-6401 bestimmt.

Starting materials, abbreviations and analysis methods in Examples and Comparative Examples are explained below.

• Polyols A to E: Polyoxyalkylenpolyole in Preparation Examples 1 to 5
• Catalyst a: cesium hydroxide
• Catalyst b: potassium hydroxide
• Catalyst c: a catalyst comprising zinc cobalt cyanide compound, zinc chloride, water and dimethoxyethanol, so-called double metal cyanide complex catalyst
• PO: propylene oxide
• EO: ethylene oxide
• AN: acrylonitrile
• St: styrene
• TEA: triethylamine
• AIBN: azobisisobutyronitrile
• Polymer polyols a to i: polymer polyols in Examples 18 to 22 and Comparative Examples 8 to 11
• Water: ion-exchanged water
• L-1020: a catalyst produced by Katsuzai Chemicals Co.
• X-DM: a catalyst produced by Katsuzai Chemicals Co.
• KL-210: a crosslinking agent produced by Mitsui Toatsu Chemicals Inc.
• L-5309: a surfactant produced by Nippon Unicar Co.
• TM-20: a mixture consisting of TDI-80/20 (a mixture consisting of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate at a weight ratio of 80:20) and cosmonates MDI-CR produced by Mitsui Toatsu Chemicals Inc., at a weight ratio of 80:20
• Properties of the foams: They were determined according to the methods of JIS K-6301 and JIS K-6401.

1. Production of polyoxyalkylene polyols

Preparation Examples 1 and 2 and comparative preparation examples 3 and 4.

To Glycerol was added to catalyst a or b and dehydration was at 100 ° C executed for 6 hours. propylene oxide was to run of addition polymerization under the conditions given in Table 6 and 15 percent by weight of ethylene oxide, based on total weight of the polyoxyalkylene polyol obtained were used to carry out Addition polymerization added. After completion of the reactions were water and phosphoric acid for neutralization and drying under reduced pressure. The formed crystals of alkali metal phosphates were passed through Filtration removed to obtain polyols A to D. The properties are in Table 6.

Comparative Production Example 5

To glycerol was added 6.93 g of catalyst c, and propylene oxide was added to carry out addition polymerization under the conditions in Table 6. The catalyst c was extracted with ammonia water. The obtained polyoxyalkylene polyol was purified by washing with water. To the polyol was added 0.23 moles of potassium hydroxide per mole of glycerol, and dehydration was carried out at 100 ° C for 6 hours. Ethylene oxide was added to perform addition polymerization under the conditions in Table 6. The formed crystal of alkali metal phosphate was removed by filtration to give Polyol E. The properties are shown in Table 6. Table 6

In the first row of this table are M1 and M2 manufacturing examples 1 and 2. CM3, -4, -5 are comparative preparation examples 3, 4 and 5.

2. Production of polymer polyols

Examples 18 to 22 and Comparative Examples 8 to 11

• Anmerkungen: „nein" bedeutet: flockulierte Teilchen wurden nicht gefunden.

Each polyol sample was placed in a one-liter autoclave equipped with a thermometer, a stirrer, a liquid feeder, and the contents were heated to 120 ° C with stirring. A mixture of the polyol, AIBN, AN, St, TEA previously mixed in a ratio in Tables 7 and 8, was fed continuously. The obtained polymer polyol was continuously obtained from the discharge port. The reaction pressure was 3.5 kg / cm ² (440 kPa) and the residence time was 50 minutes. After the state became constant, the reaction mixtures thus obtained were subjected to suction treatment at 120 ° C at 2670 Pa (20 mmHg) for 4 hours under reduced pressure to remove unreacted monomers and TEA to obtain polymer polyols a to i. The results are in Tables 7 and 8. Table 7

• Notes: "no" means flocculated particles were not found.

• Anmerkungen: „nein" bedeutet Teilchen wurden nicht gefunden und „gefunden" bedeutet Teilchen wurden gefunden.

The units of the starting materials, the catalyst and the additives are parts by weight. Table 8

• Notes: "no" means particles were not found and "found" means particles were found.

The Units of starting materials, catalyst and additives are parts by weight.

3. Production of polyurethane foams

Examples 23 to 24 and Comparative Examples 12 to 13

• Anmerkungen: „nein" bedeutet Risse wurden nicht gefunden und „gefunden" bedeutet Risse wurden gefunden.

Polymer polyols, polyols, water, L-1020, X-DM, KL-210 and L-5309 were blended at ratios in Table 9 to form resinous premixes and set at 25 ° C. TM-20 whose ratio by equivalent weight of NCO group to active hydrogen atoms in the resinous premix was 1.00 was set at 25 ° C. The ratio of TM-20 to the resinous premix, previously mixed, was adjusted to obtain a foam having an intended density. The mixture was rapidly mixed with stirring for 6 seconds, followed by pouring it into an aluminum test mold previously heated to 60 ° C and coated with a commercial mold release agent. The mold was covered and sealed with clamps to cure the contents. Three minutes after the start of blending, the staples were removed and a cured flexible polyurethane foam was removed from the mold to determine the level of closed cell contents in accordance with the strength that appears as the hand depresses the foam. Thereafter, the foam was compacted and pressed with a roll at a compression ratio in the thickness of 20 percent based on the initial thickness thereof. These procedures were repeated to obtain other samples. Twenty-four hours later, the properties were determined. The properties thereof are shown in Table 9. Table 9

• Comments: "no" means cracks were not found and "found" means cracks were found.

The Units of starting materials, catalyst and additives are parts by weight.

Claims (25)

A process for producing a polyoxyalkylene polyol having an oxypropylene group content of at least 70% by weight, adding propylene oxide to an active hydrogen compound and conducting addition polymerization in the presence of an alkali metal hydroxide catalyst having a purity of at least 90% by weight and at least one compound selected from the group consisting of cesium hydroxide and rubidium hydroxide, in an amount of 0.05 to 0.5 mole per mole of the active hydrogen compound at a temperature of 60 to 98 ° C and at a reaction pressure of less than or equal to 490 kPa (4 kg / cm ² ). The method of claim 1, wherein the active hydrogen compound Contains 2 to 8 hydroxyl groups. The method of claim 1, wherein the polyoxyalkylene polyol a hydroxyl value of 10 to 35 mg KOH / g, a monool fraction of less than or equal to 15 mole%, based on the polyoxyalkylene polyol, and has a head-to-tail binding selectivity of at least 96%. Process for producing a flexible polyurethane foam, reacting a polyisocyanate compound with a polyoxyalkylene polyol, formed by a process according to claim 3 in the presence of a catalyst, a surfactant, a foaming agent and a crosslinking agent. The method of claim 4, wherein a portion of the polyoxyalkylene polyol with a polymer polyol obtained by polymerizing an ethylenic unsaturated Monomers in a polyoxyalkylene polyol as a matrix is substituted is. The method of claim 4, wherein the foaming agent Water is. The method of claim 4, wherein the active hydrogen compound Contains 2 to 8 hydroxyl groups. Polymer polyol, which is a polyoxyalkylene, formed by a method according to claim 3, and polymer particles, which in the polyoxyalkylene polyol in the range greater than or equal to 5 weight percent to less than 30% by weight. Process for preparing the polymer polyol after Claim 8, wherein the method comprises polymerizing an ethylenic unsaturated Monomers in a polyoxyalkylene polyol having a hydroxyl value of 10 to 35 mg KOH / g, a monool content of less than or equal to 15 mole%, based on the polyoxyalkylene polyol, of a head-to-tail binding selectivity greater than or equal to 96% and an oxypropylene group content of at least 70 weight percent includes. The method of claim 9, wherein the polyoxyalkylene polyol by addition polymerization of an alkylene oxide to an active hydrogen compound having 2 to 8 hydroxyl groups in the presence of an alkali metal catalyst, which has a purity of at least 90% by weight and at least one compound selected from the group consisting of cesium and rubidium hydroxide, is obtained. The method of claim 10, wherein the alkylene oxide at least two compounds selected from the group consisting of ethylene oxide, propylene oxide and butylene oxide. The method of claim 10, wherein the proportion of Propylene oxide at least 70 weight percent, based on the total weight to alkylene oxide, and the polyoxyalkylene polyol is at least 5 weight percent terminal oxyethylene group contains. The method of claim 9, wherein the ethylenic unsaturated Monomer acrylonitrile or a mixture of acrylonitrile and styrene represents. Process for producing a flexible polyurethane foam, reacting an organic polyisocyanate compound with a A polyol containing a polymer polyol comprising a polyoxyalkylene polyol according to Claim 8, comprising. Polymer polyol, which is a polyoxyalkylene, formed by a method according to claim 3, and polymer particles, which in the polyoxyalkylene polyol in the range greater than or equal to 30 Percent by weight to less than or equal to 60 weight percent dispersed are, and a glass transition temperature from 90 to 120 ° C comprise. A method for producing a polymer polyol after Claim 15, wherein the method comprises polymerizing an ethylenic unsaturated Monomers in the presence of a chain transfer agent in the polyoxyalkylene polyol includes. The process of claim 16 wherein the polyoxyalkylene polyol is prepared by addition polymerization of an alkylene oxide to an active hydrogen compound having from 2 to 8 hydroxyl groups in the presence of an alkali metal catalyst having a purity of at least 90% by weight and at least one compound selected from the group consisting of cesium hydroxide and rubidium hydroxide. contains, received becomes. The method of claim 17, wherein the alkylene oxide at least two compounds selected from the group consisting of ethylene oxide, propylene oxide and butylene oxide. The method of claim 17, wherein the proportion of Propylene oxide at least 70 weight percent, based on the total weight to alkylene oxide, and the polyoxyalkylene polyol is at least 5 weight percent terminal oxyethylene group contains. The method of claim 17, wherein the ethylenic unsaturated Monomer acrylonitrile or a mixture of acrylonitrile and styrene represents. The method of claim 17, wherein the chain transfer agent represents an amine compound. A process according to claim 21, wherein the amine compound has the general formula (1):

wherein R ₁ , R ₂ and R _{3 are} selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and a hydroxyalkyl group having 2 to 10 carbon atoms which may be the same or different from each other but are not all hydrogen atoms; or of the general formula (2) is:

wherein X represents an oxygen atom or a group NR ₂ , R _{1 represents} an alkyl group having 1 to 10 carbon atoms or a hydroxyalkyl group having 2 to 10 carbon atoms, and R _{2 represents} a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a hydroxyalkyl group having 2 to 10 carbon atoms represents. The method of claim 21, wherein the amine compound Represents triethylamine. The method of claim 21, wherein the amine compound Represents N-methylmorpholine. Process for producing a flexible polyurethane foam, reacting an organic polyisocyanate compound with a A polyol containing a polymer polyol according to claim 15, in the presence a foaming agent, a catalyst, a surfactant and a crosslinking agent.