KR100187524B1 - Preparation of polyoxyalkylene polyols, polymer polyols and flexible polyurethane foams - Google Patents

Abstract

Propylene oxide was added to the active hydrogen compound in the presence of 0.05 to 0.5 mole alkali metal hydroxide catalyst per mole of active hydrogen compound, and the hydroxyl value was 10 to 35 mgKOH / g, the monool content was 15 mol% or less, head-to-band A low viscosity polyoxyalkylene polyol having a head-to-tail bond selectivity of 96% or more is prepared.

Polymer polyols are prepared by polymerizing ethylenically unsaturated monomers in polyoxyalkylene polyols. Flexible polyurethane foams are prepared by reacting polyoxyalkylene polyols or polymer polyols with organic polyisocyanate compounds in the presence of blowing agents, catalysts, surfactants (foaming agents), crosslinkers and other additives.

The polyurethane foam obtained in this way has fewer independent bubble cells and has more excellent physical properties such as hardness, wet heat durability, and impact resistance.

Description

Polymer Polyols and Methods for Making the Same

The present invention relates to a process for producing polyoxyalkylene polyols, polymer polyols and flexible polyurethane foams. Specifically, the present invention has a hydroxyl value of 10 to 35 mgKOH / g and a monool maximum content of 15 mol% obtained by addition polymerization of alkylene oxide to an active hydrogen compound in the presence of an alkali metal hydroxide catalyst. And polyoxyalkylene polyols having a minimum selectivity of 96% of head-to-tail bonds by propylene oxide addition polymerization, methods for producing the same, and polyoxyalkylene polyols and organic polyisocyanates Method for producing a flexible polyurethane foam having improved heat and moisture resistance by reacting the compound in the presence of a blowing agent, a catalyst, a foaming agent, a crosslinking agent and other auxiliaries, or having a hydroxyl value of 10 to 35 mgKOH / g and a maximum monool content of 15 The polymer particles are dispersed in an amount of 5% by weight or more and less than 30% by weight in a polyoxyalkylene polyol having a mol% of 96% of a head-to-tail bond minimum selectivity by propylene oxide addition polymerization. A polymer polyol comprising 30% by weight or more and 60% by weight or less of polymer particles having a glass transition temperature of 90 to 120 ° C in the polymer polyol and the polyoxyalkylene polyol, a method for producing the polymer polyol and one or more of these A method for producing a flexible polyurethane foam comprising reacting a polyol containing and a polyisocyanate compound in the presence of a blowing agent, a catalyst, a foam stabilizer, a crosslinking agent and other auxiliaries.

Potassium hydroxide is mainly used as a catalyst for the production of polyoxyalkylene polyols used in polyurethane raw materials, and at the time of high molecular weight by addition of propylene oxide, which is an alkylene oxide, monool is formed by side reactions to increase molecular weight. It is well known that the production amount increases together. In addition, when the monool content in a polyoxyalkylene polyol is high, it will prevent crosslinking and high molecular weight at the time of urethanation reaction with an organic polyisocyanate compound, and it is thought that the mechanical property of a flexible polyurethane foam or an elastomer will fall. Can be.

In the addition polymerization of propylene oxide to an active hydrogen compound using a potassium hydroxide catalyst, in the prior art, the monool content in the high molecular weight polyoxyalkylene polyol having a hydroxyl value of 35 mgKOH / g or less exceeds 15 mol%, and It was practically impossible to produce polyoxyalkylene polyols having a hydroxyl value of 28 mgKOH / g or less.

In order to solve the above problems, a method using a catalyst other than an alkali metal, for example, a bimetal cyanide complex catalyst, as an alkylene oxide as a catalyst for the addition polymerization of propylene oxide (USP 3,829,505, Japan) JP-A 2-115211 and JP-A 3-14812) have been proposed.

In particular, Japanese Patent Application Laid-Open No. 3-14812 emphasizes the superiority of the complex metal cyanide complex catalyst by using an alkali metal as a comparative example. These catalysts are extremely expensive and economically poor in industrial use, and in the case of addition polymerization of ethylene oxide as alkylene oxide, it is necessary to polymerize again using alkali metal hydroxide or its alkoxide after removal of the catalyst. And the like.

When the monool content in the polyoxyalkylene polyol is reduced, the viscosity of the polyoxyalkylene polyol tends to increase, whereas when a bimetal cyanide catalyst is used as the catalyst, the viscosity increase of the polyoxyalkylene polyol is increased. This is considered to be due to the low selectivity of the head-to-tail bond in the propylene oxide addition polymerization as the alkylene oxide. If the viscosity of the polyol is high, there will be problems in terms of molding stability and mixing properties during mechanical foam molding in the production of flexible polyurethane foam, or in terms of the use of the high molecular weight polyoxyalkylene polyol. .

Similarly with respect to the polymer polyol using a polyoxyalkylene polyol having a high monool content as a matrix, physical property degradation such as polyurethane foam is expected.

In order to solve the above problems, a method of using a catalyst other than an alkali metal, such as a complex metal cyanide complex catalyst, as a catalyst in the addition polymerization of propylene oxide as alkylene oxide (USP 3,829,505, Japanese Patent Laid-Open No. 2-) 115211, Japanese Patent Laid-Open No. 3-14812, has been proposed, and a polymer polyol having this as a matrix is also disclosed. When the monool content in the polyoxyalkylene polyol is reduced, the viscosity of the polyoxyalkylene polyol tends to increase, whereas when a bimetal cyanide complex catalyst is used as the catalyst, the viscosity increase of the polyoxyalkylene polyol is increased. It is remarkable, and it is considered that this is because the head-to-tail bond selectivity in propylene oxide addition polymerization as alkylene oxide is low. Therefore, it is considered that the viscosity increase will be remarkable also with respect to the polymer polyol obtained by radical polymerization of the ethylenically unsaturated monomer in this polyoxyalkylene polyol. When the viscosity of the polymer polyol is high, there is a problem in terms of molding stability and mixing properties during the mechanical foam molding during the production of the flexible polyurethane foam, or the polymer polyol using the high molecular weight polyoxyalkylene polyol in the matrix. There are also restrictions on use.

Polymeric polyols generally have poor dispersion stability and high viscosity. Especially in the case of a polymer concentration of 30% or more, this tendency becomes remarkable, and it is practically impossible to produce a polymer polyol having a high polymer concentration using the polyoxyalkylene polyol obtained with the above-mentioned bimetal cyanide complex catalyst.

It is also known to use a chain transfer agent to solve the problem of deterioration of dispersion stability and viscosity increase at high concentration. A method of obtaining a low viscosity polymer polyol using an alkylmercaptan as a chain transfer agent has been proposed (US Patent No. 3,953,393 and Japanese Patent Application Laid-Open No. 01-221403). However, the polymer polyols obtained by these methods have a problem of odor, and it is difficult to obtain a practical polymer polyol because the sudden increase in viscosity when the polymer concentration is made high cannot be suppressed.

In addition, a method of using mercaptan, ketone, alcohol, aldehyde, halogen compound, benzene derivative, especially isopropyl alcohol as a chain transfer agent has been proposed (Japanese Patent Application Laid-Open No. 58-210917). However, this method is insufficient for low viscosity of high concentration of polymer polyols.

Moreover, although the method of using amines, such as morpholine, as a reaction regulator is proposed (it is Unexamined-Japanese-Patent No. 63-146912), since it uses a specific polyol, it differs from this invention.

Soft polyurethane foams are widely used in bedding, furniture, automobile seats, furniture cushions, and the like because they have moderate elasticity and excellent shock absorption performance. Flexible polyurethane foams are usually produced by slab foaming or hot mold foaming. However, since these foams are inflexible and have low elasticity, they have the drawback that they do not feel the same as they would when sitting on a rubber latex foam. In order to remedy this drawback, highly elastic polyurethane foams have been developed. This foam is a polymer polyol obtained by polymerizing ethylenically unsaturated monomers such as acrylonitrile and styrene in a polyoxyalkylene polyol as a part of the polyoxyalkylene polyol, and reacted with polyisocyanate to terminate the foaming. It is prepared by leaving it for a short time at ℃. This highly elastic polyurethane foam is widely used for cushions of passenger cars because of its excellent feel when sitting.

Polyurethane foam requires elasticity, i.e. hardness and mechanical strength, for use in many cushions in passenger cars, but the problem with conventional products is that it is inferior to the moisture resistance and durability (usually expressed as wet set). .

As a method for improving the moisture-resistant heat resistance of a polyurethane foam, Unexamined-Japanese-Patent No. 63-75021, Unexamined-Japanese-Patent No. 02-115211, Unexamined-Japanese-Patent No. 03-068620, 03-014812, etc. are mentioned, for example. However, the use of special crosslinking agents, such as Japanese Patent Application No. 63-75021, can improve the heat and moisture resistance to some extent.However, if the number of used parts is too high, the mechanical strength such as elongation and tear strength is lowered. There is a limit. In addition, Japanese Patent Application Laid-Open No. 02-115211, Japanese Patent Laid-Open No. 03-068620, Japanese Patent Laid-Open No. 03-014812 and the like disclose a content of improving the heat and moisture resistance by using a polyoxyalkylene polyol having a low total unsaturated.

These polyoxyalkylene polyols are prepared using diethyl zinc, metal porphyrins, bimetal cyanide complex catalysts, and the like, as specified in the above patent publications. However, according to the present inventors further testing, the soft polyurethane foam produced by the polyoxyalkylene polyol using the complex cyanide complex catalyst or the like results in the improved moisture and heat resistance as expected by the present inventors. Could not.

An object of the present invention is a polyoxyalkylene polyol having a low monool content and a high head-to-tail bond selectivity even when high molecular weight is obtained by addition polymerization of alkylene oxide to an active hydrogen compound. Polymer polyols with low viscosity and good dispersion stability, and methods for their preparation, and the production of flexible polyurethane foams prepared using the same, having low independent foaming properties during foaming and excellent physical properties such as hardness, permanent deformation upon deformation, and repulsive elasticity To provide a way.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to achieve the said objective, the present inventors used this polyoxyalkylene polyol by manufacturing specific polyoxyalkylene polyol by specifying alkali metal hydroxide catalyst concentration, reaction temperature, and reaction pressure. When the polymer concentration is high while maintaining the specific polymer concentration, it was found that the above object can be achieved by maintaining the glass transition temperature of the polymer in a specific range.

That is, the first object of the present invention is to produce propylene oxide under the conditions of reaction temperature of 60-98 ° C. and reaction maximum pressure of 4Kg / cm ² in the presence of 0.05-0.5 mole alkali metal hydroxide catalyst per mole of active hydrogen compound. A method of producing a polyoxyalkylene polyol, characterized in that the addition polymerization,

The second object of the present invention is a hydroxyl value of 10 to 35 mgKOH / g, monool maximum content of 15 mol%, and the head-to-tail binding minimum selectivity by propylene oxide addition polymerization Polyoxyalkylene polyol, characterized in that 96%,

The third object of the present invention is the hydroxyl value of 10 to 35 mgKOH / g, the monool maximum content of 15 mol%, the head-to-tail binding minimum selectivity by propylene oxide addition polymerization is 96% It is a method for producing a flexible polyurethane foam, characterized in that the polyoxyalkylene polyol and the polyisocyanate compound are reacted in the presence of a catalyst, foam stabilizer, foaming agent, crosslinking agent, and other auxiliaries,

The fourth object of the present invention is a hydroxyl value of 10 to 35 mgKOH / g, the monool maximum content of 15 mol%, the head-to-tail binding minimum selectivity by propylene oxide addition polymerization is 96 It is a polymer polyol characterized by dispersing 5% by weight or more and less than 30% by weight of the polymer particles in the polyoxyalkylene polyol which is%,

Fifth objective is polyoxy with a hydroxyl value of 10 to 35 mgKOH / g, a monool maximum content of 15 mol%, and a head-to-tail bond minimum selectivity of 96% by propylene oxide addition polymerization. A polymer polyol characterized by dispersing 30% by weight or more and 60% by weight or less of polymer particles having a glass transition temperature of 90 to 120 ° C in the alkylene polyol,

The sixth object is polyoxy with a hydroxyl value of 10 to 35 mgKOH / g, a monool maximum content of 15 mol%, and a head-to-tail binding minimum selectivity by propylene oxide addition polymerization of 96%. A method for producing a polymer polyol, characterized in that the polymerization of ethylenically unsaturated monomers in an alkylene polyol,

The seventh object is polyoxy with a hydroxyl value of 10 to 35 mgKOH / g, a monool maximum content of 15 mol%, and a head-to-tail binding minimum selectivity of 96% by propylene oxide addition polymerization. A method of producing a polymer polyol, wherein the alkylene polyol is polymerized with an ethylenically unsaturated monomer in the presence of a chain transfer agent.

Eighth object is a method for producing a flexible polyurethane foam, characterized in that the polyol containing the polymer polyol and the organopolyisocyanate compound are reacted in the presence of a blowing agent, a catalyst, a foam stabilizer, a crosslinking agent and other auxiliaries.

Process for preparing polyoxyalkylene polyol

Examples of the active hydrogen compound include polyhydric alcohols, sugars, aliphatic amine compounds, alkanolamines, polyamines, aromatic amine compounds, polyhydric phenol compounds having a hydroxyl group of 2 to 8, preferably 3 to 8, and a molecular weight of 250 containing these compounds as initiators. And polyoxyalkylene polyols of -1000 and the like. Preferably, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butylene glycol, glycerin, diglycerin, hexanetriol, trimethylolpropane, pentaerythritol, sorbitol, dextrose, sucrose , Methylglycoside, bisphenol A, bisphenol F, dihydroxydiphenyl ether, dihydroxybiphenyl, hydroquinone, resorcin, fluoroglycine, naphthalin diol, aminophenol, aminonaphthol, phenolformaldehyde condensate , Methyldiethanolamine, ethyldiisopropanolamine, monoethanolamine, diethanolamine, triethanolamine, ethylenediamine, propylenediamine, hexamethylenediamine, bis (p-aminocyclohexyl) methane, aniline, toluidine, torrylenediamine, 1 type, 2 or more types of compound, etc. are mentioned among compounds, such as diphenylmethanediamine and naphthalin diamine.

Examples of the alkali metal hydroxide catalyst include potassium hydroxide, sodium hydroxide, lithium hydroxide, rubidium hydroxide, cesium hydroxide, and the like. Among them, at least one compound selected from cesium hydroxide and rubidium hydroxide with a purity of 90% by weight or more is used. Particular preference is given to the catalysts involved.

As the alkylene oxide, one or more kinds of compounds selected from ethylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, styrene oxide, and other alkylene oxide having 3 or more carbon atoms together with propylene oxide may be used. The alkylene oxide used together is mentioned, It is used to contain an oxypropylene group, Preferably it is 70 weight% or more, More preferably, 80 weight% or more by propylene oxide addition polymerization. The polyoxyalkylene polyol obtained by addition polymerization of alkylene oxide to the above active hydrogen compound in the presence of an alkali metal hydroxide catalyst has a hydroxyl value of 10 to 35 mgKOH / g, a monool maximum content of 15 mol%, and propylene jade. Head-to-Tail coupling minimum selectivity by seed addition polymerization is characterized by 96%. If the hydroxyl value is less than 10 mgKOH / g, the viscosity of the polyoxyalkylene polyol or the polymer polyol in which the vinyl polymer particles are dispersed using this as a matrix becomes too high, and it is practically impossible to use for flexible polyurethane foam applications. Even when prepolymerized by reaction with, it is impossible to use because of its high viscosity.

On the other hand, in the polyoxyalkylene polyol having such a low hydroxyl value, the monool content increases as the molecular weight is increased, and the mechanical properties of compressive permanent deformation, rebound elasticity or polyurethane elastomer during wet heat in a flexible polyurethane foam are increased. Since it falls, it is necessary to maintain monool content at 15 mol% or less. In addition, when the hydroxyl value exceeds 35 mgKOH / g, the monool content of about 15 mol% also exists in the existing polyol, but even if the molecular weight is low in this way, the improvement of the said characteristic in a flexible polyurethane foam etc. is confirmed. It doesn't work.

Also, when the head-to-tail bond selectivity by propylene oxide addition polymerization in such low monool polyoxyalkylene polyol is less than 96%, the head-to-tail -to-Tail) The viscosity increase of the polyoxyalkylene polyol due to the decrease in the bond selectivity becomes remarkable, and a problem occurs in the use of prepolymerized by forming a flexible polyurethane foam or by reaction with an organic polyisocyanate compound.

In the production of the above structure-controlled high molecular weight polyoxyalkylene polyol, it is necessary to select and carry out the following conditions. That is, the alkali metal hydroxide catalyst concentration at the time of the propylene oxide addition polymerization to the active hydrogen compound is preferably 0.05 to 0.5 mol, particularly preferably 0.1 to 0.3 mol with respect to 1 mol of the active hydrogen compound. Moreover, reaction temperature becomes like this. Preferably it is 60-98 degreeC, Especially preferably, it is the range of 70-90 degreeC. When the alkali metal hydroxide catalyst concentration per mole of active hydrogen compound exceeds 0.5 mole, the monool content tends to exceed 15 mol% even when propylene oxide addition polymerization is carried out at a reaction temperature of 60 to 98 ° C. It is not preferable because the head-to-tail coupling selectivity may be less than 96%. When the alkali metal hydroxide catalyst concentration per mole of active hydrogen compound is less than 0.05 mole, the propylene oxide addition polymerization reaction rate is slow, and it is difficult to increase the molecular weight to 10 to 35 mgKOH / g hydroxyl group. Also, in the case where an alkali metal hydroxide catalyst is added to an intermediate polymer obtained by the propylene oxide addition reaction to an active hydrogen compound in the presence of an alkali metal hydroxide catalyst and the propylene oxide addition polymerization is carried out, the sum of the alkali metal hydroxide catalyst concentrations is in the above range. It is performed under the conditions which make it enter inside.

In the presence of an alkali metal hydroxide catalyst, the reaction maximum pressure at the time of propylene oxide addition polymerization to the active hydrogen compound is preferably ⁴ Kg / cm ² (490 KPa) or less. When the reaction pressure exceeds 4 Kg / cm ² (490 KPa), the monool content in the polyoxyalkylene polyol increases, which is not preferable because it becomes more than 15 mol% when it becomes a low hydroxyl group.

In the presence of an alkali metal hydroxide catalyst, the active hydrogen compound is additionally polymerized with alkylene oxides other than propylene oxide, for example, ethylene oxide, 1,2-butylene oxide, etc., alone or in combination with propylene oxide. The reaction conditions in this case may be outside or within the range of the above reaction conditions.

The catalyst in the crude polyoxyalkylene polyol obtained by addition polymerization of alkylene oxide to an active hydrogen compound in the presence of an alkali metal hydroxide catalyst is used for neutralization by an acidic acid such as hydrochloric acid, organic acid such as phosphoric acid, acetic acid, carbon dioxide, etc. The product can be obtained by removal by a method such as removal by adsorption, washing with water or water / organic solvent, or ion exchange with ion exchange resin.

Manufacturing method of polymer polyol

A polyoxyalkylene polyol is demonstrated.

The polyoxyalkylene polyol used has a hydroxyl value of 10 to 35 mgKOH / g, a monool maximum content of 15 mol%, and a head-to-tail bond minimum selectivity by propylene oxide addition polymerization of 96. It is a polyoxyalkylene polyol which is% and is obtained by the above-mentioned method. One kind or a mixture of two or more kinds of these polyoxyalkylene polyols can be used.

If the hydroxyl value is less than 10 mgKOH / g, the viscosity of the polyoxyalkylene polyol or the polymer polyol in which the vinyl polymer particles are dispersed using this as a matrix becomes too high and cannot be used practically for flexible polyurethane foam applications. On the other hand, the polyoxyalkylene polyol having such a low hydroxyl value increases the monool content as the molecular weight is increased, and the compressive permanent deformation and the rebound elasticity at the time of wet heat in the flexible polyurethane foam are lowered. It is necessary to keep it in mol% or less. When the hydroxyl value is more than 35 mgKOH / g, the monool content of about 15 mol% is also present in existing polyols. However, even when the molecular weight is low, the improvement of the above characteristics in the flexible polyurethane foam or the like can be confirmed. none.

Also, when the head-to-tail bond minimum selectivity by propylene oxide addition polymerization in such low monool polyoxyalkylene polyol is less than 96%, the head-to-tail (Head-to-Tail) The viscosity increase of the polyoxyalkylene polyol due to the decrease in the bond selectivity is remarkable, and a problem occurs in forming a flexible polyurethane foam.

A polymer polyol is demonstrated.

It is suitable that an ethylenically unsaturated monomer has at least 1 ethylenically unsaturated group which can superpose | polymerize. For example, acrylonitrile, methacrylonitrile, acrylic acid, phenol acrylate, methyl methacrylate, methacrylic anhydride, acrylamide, styrene, methylstyrene, phenylstyrene, chlorostyrene, butadiene, 1,4-pentadiene 1 type, or 2 or more types of mixtures are mentioned among vinyl acetate. Preferably acrylonitrile alone or a mixture of acrylonitrile and styrene.

The ratio of acrylonitrile / styrene is preferably 100/0 to 10/90 by weight. In the case where the polymer concentration is 30% or more, 90/10 to 30/70 having a small increase in viscosity is preferable.

The use amount of the ethylenically unsaturated monomer is usually 5 to 60% by weight based on the total amount of the polyoxyalkylene polyol and the monomer, thereby maintaining the polymer concentration at 5 to 60% by weight. The polymer is usually dispersed in fine particles having a diameter of 0.1 to 10 m.

When the polymer concentration is 5% by weight or more and less than 30% by weight, the polymer polyol can be produced by a conventionally known production method. The conditions in this case may be the same as in the case of using a chain transfer agent. When the ethylenically unsaturated monomer is acrylonitrile alone, the glass transition temperature by general thermal analysis is unclear and cannot be measured. In the case of acrylonitrile and styrene, the glass transition temperature of the polymer is 105 to 130 ° C. A chain transfer agent is also used when the polymer concentration is 30% by weight to 60% by weight.

Chain transfer agents are usually amine compounds. The amine compound is an amine compound represented by the general formula (1),

(In formula, R <_1> , R <_2> and R <_3> represent H, a C1-C10 alkyl group, and a C2-C10 hydroxyalkyl group, These may mutually be same or different, but they are not all H at the same time.)

Or it is a compound represented by General formula (2).

(Wherein X represents 0 and NR ₂ , R ₁ represents an alkyl group having 1 to 10 carbon atoms, a hydroxyalkyl group having 2 to 10 carbon atoms, R ₂ represents H, an alkyl group having 1 to 10 carbon atoms, and a carbon group having 2 to 10 carbon atoms). Hydroxyalkyl group.)

Specific examples include amines such as triethylamine, tripropylamine, tributylamine, N, N-diethylethanolamine, N-methylmorpholine, and N-ethylmorpholine.

The amount of the chain transfer agent is determined according to the glass transition temperature of the polymer controlled by the chain transfer agent, and an amount of the chain transfer agent is used so that the glass transition temperature is controlled to 90 to 120 ° C, preferably 95 to 115 ° C. If the glass transition temperature is lower than 90 ° C., the physical properties such as hardness are lowered when the polyurethane foam is used. If the glass transition temperature is higher than 120 ° C., a polymer polyol having good dispersion stability at low viscosity cannot be obtained. . The amount of the chain transfer agent for obtaining such a glass transition temperature is an amount for adjusting the molecular weight of the polymer to 30,000 to 140,000, 0.5 to 30 parts by weight, preferably 1 to 20 parts by weight based on 100 parts by weight of the ethylenically unsaturated monomer. .

As a catalyst, a well-known catalyst for vinyl polymerization reaction is used. For example, hydrogen peroxide, benzoyl peroxide, acetyl peroxide, t-butyl peroxide, peroxides such as di-t-butyl peroxide, azo compounds such as azobisisobutylonitrile, or persulfates, peric acid, di Peroxide compounds, such as isopropyl peroxy dicarbonate, are mentioned.

The catalyst is added in an amount of 0.01 to 5% by weight, preferably 0.1 to 2.0% by weight, based on the total weight of the polyoxyalkylene polyol and the ethylenically unsaturated monomer.

It is also possible to carry out polymerization in the presence of a dispersion stabilizer for the purpose of stably dispersing the polymer particles. Examples of such dispersion stabilizers include carbon-carbon unsaturated bond-containing polyether ester polyols, such as those described in Japanese Patent Application Publication No. 49-46556, and modified polyols having an acryl group, methacryl group, aryl group, and the like at their ends. Can be.

The polymer polyol is produced by carrying out a polymerization reaction using the polyoxyalkylene polyol, ethylenically unsaturated monomer, a chain transfer agent, and a catalyst.

The polymerization reaction can be carried out batchwise or continuously. The polymerization temperature is determined according to the type of catalyst, but is carried out at a decomposition temperature of the catalyst, preferably at 60 to 200 ° C, more preferably at 90 to 160 ° C. The polymerization reaction can be performed by a pressure gauge or an atmospheric pressure gauge.

After the completion of the polymerization reaction, the obtained polymer polyol can be used as a raw material of polyurethane as it is, but it is preferable to use it after removing the unreacted monomer, the decomposition product of the catalyst, the chain transfer agent, and the like under reduced pressure.

Method of manufacturing polyurethane foam

The polyoxyalkylene polyol mentioned above can be used as a polyoxyalkylene polyol.

As the polymer polyol, all of the foregoing can be applied as it is. The polyol containing a polymer polyol refers to the polymer polyol or a mixture of the polymer polyol and other polyoxyalkylene polyols, and preferably has a viscosity of 3000 cps or less. Although it does not specifically limit as other polyoxyalkylene polyol, What is conventionally used in the art can be used.

Moreover, it is also possible to use the polyoxyalkylene polyol used for manufacture of a polymer polyol as needed.

The organic polyisocyanate compound used in the present invention may be, for example, 2,4-torylene diisocyanate, 2,6-torylene diisocyanate, 80/20 weight ratio (80 / 20-TDI) or 65/35 weight ratio of these isocyanates ( 65 / 35-TDI), crude toylene diisocyanate (prepared TDI), 4,4'-diphenylmethane diisocyanate (4,4'-MDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI), 2,2'-diphenylmethane diisocyanate (2,2'-MDI), an isomer mixture of diphenylmethane diisocyanate (MDI), polymethylene polyphenylisocyanate (prepared MDI), Toluidine diisocyanate, xylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexyl methane diisocyanate and carbodiimide modified, biuret modified, dimer, trimer or prepolymer thereof. An organopolyisocyanate compound is used 1 type or in mixture of 2 or more types.

Blowing agents include water, trichloromonofluoromethane, dichlorodifluoromethane, 2,2-dichloro-1, 1,1-trifluoroethane, 1,1-dichloro-1-fluoroethane, methylene chloride, trichloro Although it is 1 type, or 2 or more types of mixtures, such as rotrifluoroethane, dibromotetrafluoroethane, trichloroethane, pentane, and n-hexane, it is preferable to use water independently from a viewpoint of environmental protection. The use amount of blowing agent is 0.01-10 weight part with respect to 100 weight part of polyoxyalkylene polyols.

The urethanation reaction catalyst used in the present invention is conventionally known and there is no particular limitation. For example, as an amine catalyst, triethylamine, tripropylamine, polyisopropanolamine, tributylamine, trioctylamine, hexamethyldimethylamine, N-methylmorpholine, N-ethylmorpholine, and N-octadecyl Morpholine, 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 of the first and second amines, N, N-dialkyl Aza ring, such as piperazine Compounds, various N, N ', N-trialkylaminoalkylhexahydrotriazines, β-aminocarbonyl catalyst of JP 52-43517, β-amino nitrile catalyst of JP 53-14278, etc. Can be mentioned. Further, as the organometallic catalyst, tin acetate, octylate tin, oleate tin, lauryl acid tin, dibutyl tin diacetate, dibutyl tin dilaurate, dibutyl tin dichloride, zinc octanoate, zinc naphthenate, naphthenic acid Nickel, cobalt naphthenate, etc. are mentioned. These catalysts are used 1 type or in mixture of 2 or more types, and the use amount is 0.0001-10.0 weight part with respect to 100 weight part of compounds which have active hydrogen.

A foam stabilizer is a conventionally well-known organosilicon surfactant, for example, L-520, L-532, L-540, L-544, L-550, L-3550, L-5305, and L-3600 made by Nippon Unicas Co., Ltd. , L-3601, L-5305, L-5307, L-5309, L-5710, L-5720, L-5740M, L-6202, SH-190, SH-194, SH- made by Toray Silicon Corporation 200, SPX-253, PX-274C, SF-2961, SF-2962, SPX-280A, SPX-294A, F-114, F-121, F-122, F-220, F-230 made by Shin-Etsu Silicone , F-258, F-260B, F-317, F-341, F-601, F-606, X-20-200, X-20-201, TFA-4200, TFA-4202 made by Toshiba Silicone Co., Ltd. And B-4113 manufactured by Gold Schmidt, SRX-253 manufactured by Toray Dow Corning, SRX-274C, SF-2961, SF-2962 and the like. The use amount of these foam stabilizers is 0.1-10 weight part with respect to 100 weight part of total amounts of the compound which has active hydrogen, and a polyisocyanate, Preferably it is 0.1-5 weight part.

Crosslinking agents Alkenolamines, such as monomer polyols, such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, and 1, 3- butanediol, triethanolamine, and diethanolamine, ethylenediamine, diethylenetriamine, and triethylenetetramine Aromatic polyamines such as aliphatic polyamines, methyleneorthochloroamine, 4,4'-diphenylmethanediamine, aniline, 2,4'-torylenediamine, 2,6'-torylenediamine, and active hydrogen compounds thereof It is a compound whose hydroxyl group obtained by adding ethylene oxide, propylene oxide, etc. to 200 mgKOH / g or more. In addition, a compound having a hydroxyl value of 200 mgKOH / g or more obtained by adding ethylene oxide, propylene oxide or the like to hydroquinone, resorcin, aniline, or the like can also be used. The usage-amount is 0.1-10 weight part with respect to 100 weight part of polyoxyalkylene polyols.

In the present invention, stabilizers, fillers, colorants, flame retardants and the like may be used as necessary in addition to the above.

The manufacturing method of the polyurethane foam is as follows.

A resin solution is prepared by mixing a predetermined amount of a polyoxyalkylene polyol, a blowing agent, a catalyst, a foam stabilizer, a crosslinking agent, and other auxiliaries. The amount of the organic polyisocyanate compound, the polyoxyalkylene polyol and the crosslinking agent is determined so that the equivalent ratio (NCO / H) between the NCO in the organic polyisocyanate compound and the active hydrogen in the resin solution is 0.7 to 1.4. The resin solution and the organic polyisocyanate compound are adjusted to a predetermined temperature, for example, 20 to 25 ° C, and then rapidly mixed, and poured into a mold temperature-controlled at a predetermined temperature, for example, 30 to 70 ° C. After the reaction mixture is foam-filled into the mold, the mixture is left to cure for 5 to 30 minutes in a predetermined temperature, for example, at room temperature to 100 ° C, and then the foam is demolded to obtain a flexible polyurethane foam.

Example

Hereinafter, an Example and a comparative example are given and this invention is demonstrated.

The hydroxyl value is esterified with a pyridine solution of phthalic anhydride, and excess phthalic anhydride is titrated with a sodium hydroxide solution (according to the method of JIS K 1557).

Monool content: A high-performance liquid chromatography (HPLC) device using a Japanese spectroscopy, using an aminopropyl group-bonded silica-based separation column, using a mixed solution of hexane / 2-propanol as an eluent (flow rate of 1 ml / min) A liquid chromatogram of alkylene polyol was obtained, and the area ratio of triol and monool was determined from the peak area intensity detected by the differential refraction system. The molecular weight values of the triol and monool in the polyoxyalkylene polyol were determined by a calibration curve prepared from the elution peak times of the liquid chromatograms of triols and monools having different molecular weights obtained under the same conditions. Monool content (mol%) was computed from the value of the area ratio and molecular weight with respect to the above triol and monool. Since the diol component in polyoxyalkylene polyol was hardly detected, it was ignored at the time of calculating monool content.

Head-to-Tail Bond Selectivity: C ¹³ NMR spectrum of this polyoxyalkylene polyol using heavy chloroform as a solvent using a 40 MHz C ¹³ nuclear magnetic resonance (NMR) device manufactured by Nippon Electronics To obtain a signal of the methyl group of the oxypropylene segment of the head-to-tail bond (16.9 to 17.4 ppm) and the methyl group of the oxypropylene segment of the head-to-head bond. It calculated | required from ratio of the signal of (17.7-18.5 ppm).

Calculation F is

A = integral of the methyl groups of the head-to-head bond

B = integral of the methyl groups of the head-to-tail bond

F = (0.5 A / (0.5 A + B)) × 100

In addition, each signal is attributed to Macromolecules 19. 1337-1343 (1986). F.C.Schilling, A.E. Reference is made to the values described in Jonelli's literature.

Viscosity: Measured value at 25 ° C. using a rotary viscometer (measured according to JIS K 1557).

Polymer Concentration: After dispersing well by adding methanol to the polymer polyol, centrifugation is performed to determine the weight of methanol insoluble content. However, the polymer polyol which consists of acrylonitrile alone was calculated | required from the nitrogen content by elemental analysis.

Tg (glass transition temperature): It was calculated | required by the thermal analysis using the DSC-7 by Parkin Elmer company under nitrogen atmosphere and the temperature increase rate of 20 K / min.

Evaluation of Polyoxyalkylene Polyols

1. Preparation of Polyoxyalkylene Polyols

Example 1

Polyol A: cesium hydroxide was added to a 0.13mol relative to 1mol of glycerin, the combined addition of from 100 ℃ 6 sigan dehydration after propylene oxide and the reaction temperature 95 ℃, maximum reaction pressure ^{3.5kg / cm 2 (440 KPa)} , a hydroxyl 33 mgKOH / g polyoxypropylene polyol was obtained. Subsequently, 15 wt% of ethylene oxide was added to this polyoxypropylene polyol at 100 ° C to obtain a polyoxyalkylene polyol having a hydroxyl value of 28 mgKOH / g. The viscosity was 1140 cps / 25 degreeC.

It was 13.0 mol% when the monool content (mol%) was computed from the value of the area ratio and molecular weight with respect to above-mentioned triol and monool. In addition, since the diol component in polyoxyalkylene polyol was hardly detected, it was ignored at the time of calculating monool content. H-T bond selectivity was 96.7 mol%. The results are shown in Table 1.

Example 2

Polyol B: After putting the cesium hydroxide to a 0.43mol glycerin 1mol dehydrated at 100 ℃ 6-hour reaction of propylene oxide the temperature 65 ℃, the combined addition of the reaction at a maximum pressure ^{2.0kg / cm 2 (300 KPa)} , a hydroxyl value of 50 mgKOH / g polyoxypropylene polyol was obtained. The propylene oxide was further polymerized at a reaction temperature of 75 ° C. and a reaction maximum pressure of 3 kg / cm ² (400 KPa) to obtain a polyoxypropylene polyol having a hydroxyl value of 28 mgKOH / g. The monool content obtained by the method similar to Example 1 was 11.9 mol%, the viscosity was 1250 cps / 25 degreeC, and HT bond selectivity was 96.2 mol%. The results are shown in Table 1.

Example 3

Polyol C: cesium hydroxide was added to a 0.23mol glycerin 1mol, the combined addition of from 100 ℃ 6 sigan dehydration after propylene oxide and the reaction temperature 80 ℃, maximum reaction pressure ^{3.5Kg / cm 2 (440 KPa)} , a hydroxyl value of 28 A mgKOH / g polyoxypropylene polyol was obtained. Subsequently, 15 wt% of ethylene oxide was added to this polyoxypropylene polyol at 100 ° C. to obtain a polyoxyalkylene polyol having a hydroxyl value of 24 mgKOH / g. The monool content obtained by the method similar to Example 1 was 8.0 mol%, the viscosity was 1650 cps / 25 degreeC, and HT bond selectivity was 96.3 mol%. The results are shown in Table 1.

Example 4

Polyol D: 0.23 mol of potassium hydroxide was added to 1 mol of glycerin, and dehydrated at 100 DEG C for 6 hours, after which the propylene oxide was polymerized by addition at a reaction temperature of 70 DEG C and a maximum pressure of 3.5 kg / cm ² (440 KPa). A mgKOH / g polyoxypropylene polyol was obtained. Subsequently, 15 wt% of ethylene oxide was added to this polyoxypropylene polyol at 100 ° C to obtain a polyoxyalkylene polyol having a hydroxyl value of 29 mgKOH / g. The monool content obtained by the method similar to Example 1 was 13.7 mol%, the viscosity was 1100 cps / 25 degreeC, and HT bond selectivity was 96.5 mol%. The results are shown in Table 1.

Example 5

Polyol E: 0.23 mol of cesium hydroxide was added to 1 mol of propylene oxide adduct of pentaerythritol having a hydroxyl value of 450 mgKOH / g, and dehydrated at 100 DEG C for 6 hours. addition polymerization at / cm ² (440 KPa) afforded a polyoxypropylene polyol having a hydroxyl value of 50 mgKOH / g. The propylene oxide was further polymerized at a reaction temperature of 90 ° C. and a reaction maximum pressure of 3.5 kg / cm ² (440 KPa) to obtain a polyoxypropylene polyol having a hydroxyl value of 29 mgKOH / g. Subsequently, 15 wt% of ethylene oxide was added to this polyoxypropylene polyol at 100 ° C to obtain a polyoxyalkylene polyol having a hydroxyl value of 25 mgKOH / g. The monool content obtained by the method similar to Example 1 was 14.3 mol%, the viscosity was 1800 cps / 25 degreeC, and HT bond selectivity was 96.4 mol%. The results are shown in Table 1.

Example 6

Polyol F: cesium hydroxide was added to a 0.13mol glycerin 1mol, the combined addition of from 100 ℃ 6 sigan dehydration after propylene oxide and the reaction temperature 60 ℃, maximum reaction pressure ^{2.0kg / cm 2 (300 KPa)} , a hydroxyl value of 50 A mgKOH / g polyoxypropylene polyol was obtained. The propylene oxide was further polymerized at a reaction temperature of 60 ° C. and a reaction maximum pressure of 2.0 kg / cm ² (300 KPa) to obtain a polyoxypropylene polyol having a hydroxyl value of 16 mg KOH / g. The monool content obtained by the method similar to Example 1 was 14.6 mol%, the viscosity was 2300 cps / 25 degreeC, and HT bond selectivity was 97.0 mol%. The results are shown in Table 1.

Example 7

Polyol G: 0.23 mol of cesium hydroxide and 0.10 mol of rubidium hydroxide are added to 1 mol of glycerin, and dehydrated at 100 ° C. for 6 hours at a reaction temperature of 80 ° C. and a maximum reaction pressure of 2.5 kg / cm ² (350 KPa). The addition polymerization yielded a polyoxypropylene polyol having a hydroxyl value of 50 mgKOH / g. The propylene oxide was further polymerized at a reaction temperature of 80 ° C. and a reaction maximum pressure of 2.5 kg / cm ² (350 KPa) to obtain a polyoxypropylene polyol having a hydroxyl value of 33 mgKOH / g. Monool content obtained by the method similar to Example 1 was 10.5 mol%, the viscosity 950cps / 25 degreeC, and HT bond selectivity 96.3mol%. The results are shown in Table 2.

Example 8

Polyol H: cesium hydroxide was added to a 0.23mol glycerin 1mol, the combined addition of from 100 ℃ 6 sigan dehydration after propylene oxide and the reaction temperature 80 ℃, maximum reaction pressure ^{3.5kg / cm 2 (440 KPa)} , a hydroxyl value of 33 A mgKOH / g polyoxypropylene polyol was obtained. Subsequently, 15 wt% of ethylene oxide was added to this polyoxypropylene polyol at 100 ° C to obtain a polyoxyalkylene polyol having a hydroxyl value of 28 mgKOH / g. The monool content obtained by the method similar to Example 1 was 7.2 mol%, the viscosity was 1290 cps / 25 degreeC, and HT bond selectivity was 96.4 mol%. The results are shown in Table 2.

Example 9

Polyol I: cesium hydroxide was added to a 0.23mol glycerin 1mol, the combined addition of from 100 ℃ 6 sigan dehydration after propylene oxide and the reaction temperature 80 ℃, maximum reaction pressure ^{3.5kg / cm 2 (440 Kpa)} , a hydroxyl value of 25 A mgKOH / g polyoxypropylene polyol was obtained. Subsequently, 15 wt% of ethylene oxide was added to this polyoxypropylene polyol at 100 ° C to obtain a polyoxyalkylene polyol having a hydroxyl value of 21 mgKOH / g. The monool content obtained by the method similar to Example 1 was 10.5 mol%, the viscosity was 1950 cps / 25 degreeC, and HT bond selectivity was 97.0 mol%. The results are shown in Table 2.

Example 10

Polyol J: 0.23 mol of cesium hydroxide was added to 1 mol of glycerin, and dehydrated at 100 ° C. for 6 hours. The propylene oxide was added and polymerized at a reaction temperature of 80 ° C. and a maximum pressure of 3.5 kg / cm ² (440 KPa). / g polyoxypropylene polyol was obtained. Subsequently, 15 wt% of ethylene oxide was added to this polyoxypropylene polyol at 100 ° C to obtain a polyoxyalkylene polyol having a hydroxyl value of 17 mgKOH / g. The monool content obtained by the method similar to Example 1 was 14.0 mol%, the viscosity was 2380 cps / 25 degreeC, and HT bond selectivity was 97.2 mol%. The results are shown in Table 2.

Example 11

Polyol K: combined in 1mol of pentaerythritol was added to a 0.23mol cesium hydroxide, in addition to 100 ℃ 6 hours after dehydration of propylene oxide at a reaction temperature of 80 ℃, maximum reaction pressure ^{3.5kg / cm 2 (440 KPa)} , a hydroxyl group 33 mgKOH / g of polyoxypropylene polyol was obtained. Subsequently, 15 wt% of ethylene oxide was added to this polyoxypropylene polyol at 100 ° C to obtain a polyoxyalkylene polyol having a hydroxyl value of 28 mgKOH / g. Monool content obtained by the method similar to Example 1 was 9.5 mol%, the viscosity was 1420 cps / 25 degreeC, and HT bond selectivity was 96.5 mol%. The results are shown in Table 2.

Comparative Example 1

Polyol L: 0.37 mol of potassium hydroxide was added to 1 mol of glycerin, and dehydrated at 100 ° C. for 6 hours. The propylene oxide was added and polymerized at a reaction temperature of 115 ° C. and a reaction maximum pressure of 5 kg / cm ² (590 kPa). / g polyoxypropylene polyol was obtained. Subsequently, 15 wt% of ethylene oxide was added to this polyoxypropylene polyol to obtain a polyoxyalkylene polyol having a hydroxyl value of 28 mgKOH / g. Monool content obtained by the method similar to Example 1 was 29.3 mol%, the viscosity was 1150 cps / 25 degreeC, and HT bond selectivity was 96.3 mol%. The results are shown in Table 3.

Comparative Example 2

Polyol M: 6.93 g of a so-called complex metal cyanocomplex catalyst (DMC catalyst) consisting of zinc cobalt cyanide, zinc chloride, water, and dimethoxyethanol is added to 1 mol of glycerine, and propylene oxide is reacted at a reaction temperature of 90 캜 and a maximum pressure of the reaction. Addition polymerization at 4 kg / cm ² (490 kPa) yielded a polyoxypropylene polyol having a hydroxyl value of 33 mgKOH / g. The DMC catalyst was extracted with ammonia water, washed with water, 0.23 mol of potassium hydroxide was added to 1 mol of glycerin contained in the polyoxypropylene polyol, and dehydrated at 100 DEG C for 6 hours. % Addition polymerization was performed to obtain a polyoxyalkylene polyol having a hydroxyl value of 28 mgKOH / g. Monool content obtained by the method similar to Example 1 was 9.6 mol%, the viscosity was 3080 cps / 25 degreeC, and HT bond selectivity was 85.4 mol%. The results are shown in Table 3.

Comparative Example 3

Polyol N: cesium hydroxide was added to a 0.23mol glycerin 1mol, the combined addition of from 100 ℃ 6 sigan dehydration after propylene oxide and the reaction temperature 80 ℃, maximum reaction pressure ^{3.5kg / cm 2 (440 kPa)} , a hydroxyl value of 50 A mgKOH / g polyoxypropylene polyol was obtained. The propylene oxide was further polymerized at a reaction temperature of 100 ° C. and a reaction maximum pressure of 3.5 kg / cm ² (440 kPa) to obtain a polyoxypropylene polyol having a hydroxyl value of 28 mgKOH / g. Monool content obtained by the method similar to Example 1 was 22.9 mol%, the viscosity was 1200 cps / 25 degreeC, and HT bond selectivity was 97.5 mol%. The results are shown in Table 3.

Comparative Example 4

Polyol O: after putting the cesium hydroxide of 0.53mol dehydrated at 100 ℃ 6 hours in glycerol 1mol reaction of propylene oxide the temperature 90 ℃, the combined addition of the reaction at a maximum pressure ^{3.5kg / cm 2 (440 kPa)} , a hydroxyl value of 117 mgKOH / g polyoxypropylene polyol was obtained. The propylene oxide was further polymerized at a reaction temperature of 90 ° C. and a reaction maximum pressure of 3.5 kg / cm ² (440 KPa) to obtain a polyoxypropylene polyol having a hydroxyl value of 31 mgKOH / g. Monool content obtained by the method similar to Example 1 was 22.7 mol%, the viscosity was 1160 cps / 25 degreeC, and HT bond selectivity was 95.4 mol%. The results are shown in Table 3.

Comparative Example 5

Polyol P: cesium hydroxide was added to a 0.23mol 1mol the glycerin, adding the sum of 6 hours at 100 ℃ dehydrated propylene oxide at a reaction temperature of 95 ℃, maximum reaction pressure ^{4kg / cm 2 (490 kPa)} , a hydroxyl value of 117 mgKOH / g polyoxypropylene polyol was obtained. The propylene oxide was further polymerized at a reaction temperature of 95 ° C. and a reaction maximum pressure of 4.5 kg / cm ² (540 kPa) to obtain a polyoxypropylene polyol having a hydroxyl value of 28 mgKOH / g. The monool content obtained by the method similar to Example 1 was 17.7 mol%, the viscosity was 1110 cps / 25 degreeC, and HT bond selectivity was 96.9 mol%. The results are shown in Table 3.

The polyoxyalkylene polyols of Examples and Comparative Examples were all neutralized by adding water and phosphoric acid after the completion of the reaction, and then dried under reduced pressure. The crystals of the resulting alkali metal phosphate were removed by filtration, and the hydroxyl value, viscosity, Monool content and HT binding selectivity were measured.

Examples and Comparative Examples are summarized in Tables 1 to 3, but Initiator A in the table is glycerin and Initiator B are propylene oxide adducts (450 mgKOH / g hydroxyl value of pentaerythritol). Catalyst A represents cesium hydroxide, catalyst B represents potassium hydroxide, catalyst C represents rubidium hydroxide, and catalyst D is a so-called complex metal cyanocomplex (DMC catalyst) consisting of zinc cobalt cyanide, zinc chloride, water and dimethoxyethanol. .

PO stands for propylene oxide and EO stands for ethylene oxide.

Table 1

Polyol Example 1 2 3 4 5 6 A B C D E F Initiator A (mol) Initiator B (mol) Catalyst A (mol) Catalyst B (mol) Catalyst C (mol) Catalyst D (g) 1 1 1 1-1----1 -0.13 0.43 0.23-0.23 0.13---0.23------------- PO addition polymerization temperature First half reaction (℃) Maximum half pressure after reaction (kgf / cm2) Second half reaction After hydroxyl addition (mgKOH / g) 95 65 80 70 80 60 95 75 80 70 90 60 3.5 2.0 3.5 3.5 3.5 2.0 3.5 3.0 3.5 3.5 3.5 2.033 28 28 33 29 16 EO addition polymerization temperature (℃) Maximum pressure (kgf / ㎠) 100-80 100 100 -3.5-3.5 3.5 3.5- Hydroxyl value (mgKOH / g) viscosity (cps / 25 ℃) monool content (mol%) H-T bond selectivity (mol%) 28 28 24 29 25 171 140 1250 1650 1100 1800 230013.0 11.9 8.0 13.7 14.3 14.696.7 96.2 96.3 96.5 96.4 97.0

TABLE 2

Polyol Example 7 8 9 10 11 G H I J K Initiator A (mol) Initiator B (mol) Catalyst A (mol) Catalyst B (mol) Catalyst C (mol) Catalyst D (g) 1 1 1 1-----0.23 0.23 0.23 0.23 0.23-----0.10-------- PO addition polymerization temperature Overall reaction (℃) Maximum pressure after reaction Maximum reaction (kgf / ㎠) Hydroxyl value after addition of PO (mgKOH / g) 80 80 80 80 80 80 80 80 80 802.5 3.5 3.5 3.5 3.52.5 3.5 3.5 3.5 3.533 33 25 20 33 EO addition polymerization temperature (℃) Maximum pressure (kgf / ㎠) -100 100 100 100- 3.5 3.5 3.5 3.5 Hydroxyl value (mgKOH / g) viscosity (cps / 25 ℃) monool content (mol%) H-T bond selectivity (mol%) 34 28 21 17 28950 1290 1950 2380 142010.5 7.2 10.5 14.0 9.596.3 96.4 97.0 97.2 96.5

TABLE 3

Polyol Comparative Example 1 2 3 4 5L M N O P Initiator A (mol) Initiator B (mol) Catalyst A (mol) Catalyst B (mol) Catalyst C (mol) Catalyst D (g) 1 1 1 1 1------0.23 0.53 0.230.37--------6.93--- PO addition polymerization temperature Overall reaction (℃) Maximum pressure after reaction Maximum reaction (kgf / ㎠) Hydroxyl value after addition of PO (mgKOH / g) 115 90 80 90 95 115 90 100 90 955.0 4.0 3.5 3.5 4.05.0 4.0 3.5 3.5 4.533 33 28 31 28 EO addition polymerization temperature (℃) Maximum pressure (kgf / ㎠) 100 100---5.0 4.0--- Hydroxyl value (mgKOH / g) viscosity (cps / 25 ℃) monool content (mol%) H-T bond selectivity (mol%) 28 28 28 31 281150 3080 1200 1160 11 1029.3 9.6 22.9 22.7 17.796.3 85.4 97.5 95.4 96.9

2. Preparation of Polymer Polyols

Preparation Example 1

Polymer polyol (C): The polyol C obtained in Example 3 was filled in liquid state in a 1 liter autoclave with a thermometer, a stirring device, and a liquid feeding device, and the temperature was raised to 120 ° C while stirring. A mixture of polyol C, azobisisobutylonitrile, and acrylonitrile mixed in advance in the ratio shown in Table 4 was continuously charged to obtain a polymer polyol continuously at the outlet. At this time, the reaction pressure was 3.5kg / cm ² , and the residence time was 50 minutes. After reaching the steady state, the obtained reaction solution was aspirated under reduced pressure at 120 ° C. at 20 mmHg for 4 hours to remove unreacted monomer to obtain a polymer polyol. The results are shown in Table 4.

Preparation Example 2

Polymer polyol L: The polyol L obtained in the comparative example 1 was filled in the liquid state in 1 liter autoclave with a thermometer, a stirring apparatus, and a liquid feeding apparatus, and it heated up to 120 degreeC, stirring. A mixture of polyol L, azobisisobutyronitrile and acrylonitrile mixed in advance in the ratio shown in Table 4 was continuously charged to obtain a polymer polyol continuously at the outlet. At this time, the reaction pressure was 3.5kg / cm ² , and the residence time was 50 minutes. After reaching the steady state, the obtained reaction solution was aspirated under reduced pressure at 120 ° C. at 20 mmHg for 4 hours to remove unreacted monomer to obtain a polymer polyol. The results are shown in Table 4.

Preparation Example 3

Polymer polyol M: The polyol M obtained by the comparative example 2 was filled in the liquid state in 1 liter autoclave with a thermometer, a stirring apparatus, and a liquid feeding apparatus, and it heated up to 120 degreeC, stirring. The mixed liquid of polyol M, azobisisobutylonitrile, and acrylonitrile previously mixed in the ratio shown in Table 4 was continuously charged to obtain a polymer polyol continuously at the outlet. At this time, the reaction pressure was 3.5kg / cm ² , and the residence time was 50 minutes. After reaching the steady state, the resultant reaction solution was aspirated under reduced pressure at 120 ° C. and 20 mmHg for 4 hours to remove unreacted monomer to obtain a polymer polyol. The results are shown in Table 4.

The hydroxyl value and viscosity were measured by the method mentioned above about the polymer polyol obtained by manufacture examples 1-3. The polymer concentration was also determined from the nitrogen content by elemental analysis. Standard AIBN stands for azobisisobutylonitrile and AN stands for acrylonitrile.

Table 4

Polymer polyol Preparation Example 1 2 3C L M Polyol (part by weight) Polyol (part by weight) Polyol (part by weight) AIBN (part by weight) AN (part by weight) 77.6--77.6--77.60.35 0.35 0.3522.4 22.4 22.4 Hydroxyl value (mg KOH / g) viscosity (cps / 25 ℃) polymer concentration (wt%) 19.5 22.8 22.84 800 3600 954021.0 20.6 20.9

3. Preparation of Polyurethane Foam

In addition to the polyoxyalkylene polyol and polymer polyol, the raw materials shown below were used.

(Catalyst-1) Minico L-1020: amine catalyst made from lubricant chemical company

(33% diethylene glycol solution of triethylenediamine)

(Catalyst-2) Niax A-1: Amine catalyst made by ARCO

(Crosslinker-1) KL-210: An amine crosslinking agent with a hydroxyl value of 830 mgKOH / g, manufactured by Mitsui Oatsu Chemical Co., Ltd.

(Foaming agent-1) SRX-274C: foaming agent made by Toray Dow Corning Silicone Co., Ltd.

(Isocyanate-1) Cosmonate TM-20: A mixture of 80:20 weight ratio of TD1-80 and polymeric MDI, manufactured by Mitsui Otsu Chemical Co., Ltd.

Physical properties were measured according to JIS K-6301 and JIS K-6401. The density in an Example and a comparative example shows an overall density.

Example 12

The 7 components shown below were mixed and the resin liquid was created.

Polyol C 60 parts by weight

Polymer polyol C 40 parts by weight

3.0 parts by weight of water

0.5 parts by weight of catalyst -1

0.1 parts by weight of catalyst -2

Crosslinking agent -1 3.0 parts by weight

Foam stabilizer -1 1.0 parts by weight

39 parts by weight of isocyanate-1 was mixed with 107.6 parts by weight of the resin solution, and immediately injected into a mold having an internal dimension of 400 × 400 × 100 mm previously adjusted to 60 ° C., and the lid was closed and foamed. After 7 minutes of heat curing in a hot air oven at 100 ° C., the foam was taken out of the mold. The physical properties of the obtained foam are shown in Table 5.

The equivalent ratio (NCO / H) of the isocyanate and the active hydrogen of the resin solution was 1.00.

Examples 13-17

The same procedure as in Example 12 was carried out except that the polyol C in Example 12 was changed to polyols E, H, I, J, and K.

The equivalent ratio (NCO / H) of the isocyanate and the active hydrogen of the resin solution was set to 1.00. The physical properties of the obtained foam are shown in Table 5.

Comparative Example 6

The same procedure as in Example 12 was carried out except that the polyol C in Example 12 was changed to polyol L and the polymer polyol C was changed to polymer polyol L.

The equivalent ratio (NCO / H) of the isocyanate and the active hydrogen of the resin solution was set to 1.00. The physical properties of the obtained foam are shown in Table 5.

Comparative Example 7

It carried out by the same method as Example 12 except having changed the polyol C in Example 12 into polyol M, and the polymer polyol C into polymer polyol M.

The equivalent ratio (NCO / H) of the isocyanate and the active hydrogen of the resin solution was set to 1.00. The physical properties of the obtained foam are shown in Table 5.

Compared to the foam obtained in Example, the foam obtained in Comparative 7 (using a composite metal cyanocomplex catalyst) was very strong in terms of independent foaming, and the cell of the foam was also coarse.

Table 5

Example 12 13 14 15 16 17 Comparative Example 6 7 Polyol Polymer Polyol C E H I J K C C C C C C L ML M (Physical Properties) Density (kg / ㎥) Hardness 25% ILD (kg / 314㎠) Wet Heat Durability 50% Wet Set% 54.0 54.5 54.1 54.3 54.2 54.318.0 18.5 19.1 17.5 16.4 19.27.5 7.7 8.0 7.4 7.4 7.9 54.4 54.918.6 18.214.1 18.0

In Examples 12 to 14 and 17, the 50% wet set was 7 to 8% at a foam density of 54 to 55 kg / m ³ and 25% ILD of 18 to 29 kg / 314 cm ² . On the other hand, in Comparative Examples 6-7, 50% wet set showed 14-18% in almost the same density and hardness. From this result, it is understood that the flexible polyurethane foam shown in this example is effective for improving the moisture resistance and heat resistance.

Evaluation of Polymer Polyols

The raw material, abbreviation, and analysis method which were used for the Example and the comparative example are demonstrated below.

Polyols A to E: Polyoxyalkylene polyols obtained in Production Examples 1 to 5.

Catalyst (a): Cesium hydroxide.

Catalyst (b); Potassium hydroxide.

Catalyst (C); A so-called complex metal cyanocomplex catalyst comprising a zinc cobalt cyanide compound, zinc chloride, water, and dimethoxyethanol.

PO; Propylene oxide.

EO; Ethylene oxide.

AN; Acrylonitrile.

St; Styrene.

TEA; Triethylamine.

AIBN; Azoisobutylonitrile.

Polymer polyols a to i; Polymer polyols obtained in Examples 18 to 22 and Comparative Examples 8 to 11.

Water; Ion exchange water.

L-1020; Catalyst made by lubricant chemicals.

X-DM; Catalyst made by lubricant chemicals.

KL-210; Crosslinking agent made by Mitsui Oatsu Chemical Co., Ltd.

L-5309; A surfactant made by Nippon Unicas.

TM-20; A mixture of TDI-80 / 20 (a mixture of 80 to 20 weight ratio of 2,4-tolylene diisocyanate and 2,6-torylene diisocyanate) with a weight ratio of 80 to 20 with Cosmonate MDI-CR manufactured by Mitsui Oatsu Corporation.

Foam properties; Measured according to JIS K-6301 and JIS K-6401.

1. Preparation of Polyoxyalkylene Polyols

Production Examples 1-4

Catalyst (A) or (B) was added to glycerin, followed by dehydration at 100 DEG C for 6 hours, followed by addition polymerization of propylene oxide under the conditions shown in Table 6, followed by 15 wt% of ethylene oxide based on this polyoxyalkylene polyol. Was addition polymerized. After completion of the reaction, water and phosphoric acid were added, neutralized, dried under reduced pressure, and the produced crystals of alkali metal phosphate were removed by filtration to obtain polyols A to D. Physical properties are shown in Table 6.

Preparation Example 5

6.93 g of catalyst (C) was added to glycerin, and propylene oxide was polymerized under the conditions shown in Table 6. The catalyst (C) was extracted with ammonia water, washed with water to purify the polyoxypropylene polyol, and potassium hydroxide was added to 0.23 mol with respect to 1 mol of glycerin, followed by dehydration under reduced pressure at 100 ° C for 6 hours. Ethylene oxide was then polymerized under the conditions shown in Table 6. After completion of the reaction, water and phosphoric acid were added to neutralize, dried under reduced pressure, and crystals of the resulting alkali metal phosphate were removed by filtration to obtain polyol E. Physical properties are shown in Table 6.

Table 6

Preparation Example 1 Preparation Example 2 Preparation Example 3 Preparation Example 4 Preparation Example 5 Polyol A B C D E Glycerin mol catalyst (A) mol catalyst (B) mol catalyst (C) g 1.000.23-- 1.000.23-- 1.00-0.37- 1.00-0.37- 1.00-0.236.93 PO addition reaction temperature ℃ maximum pressure kgf / ㎠ hydroxyl value (mg KOH / g) EO addition reaction temperature ℃ maximum pressure kgf / ㎠ 803.537803.5 803.528803.5 1154.0371154.0 1154.0281154.0 904.028904.0 Hydroxyl value (mg KOH / g) monool content (mol%) head-to-tail selectivity (%) viscosity (cps / 25 ° C) 33.86.796.81100 23.58.096.41650 33.424.096.3900 24.035.596.41400 24.011.086.43300

2. Preparation of Polymer Polyols

Examples 18-22, Comparative Examples 8-11

The 1-liter autoclave equipped with a thermometer, a stirrer, and a liquid feeding device was filled with a polyol in a fully liquid state, and the temperature was raised to 120 ° C while stirring. The mixed liquid of the polyol, AIBN, AN, St, and TEA mixed in advance at the ratio shown in Tables 7 and 8 was continuously charged to obtain a polymer polyol continuously at the outlet. At this time, the reaction pressure was 3.5kg / cm ² (440 kPa), and the residence time was 50 minutes. After the steady state was reached, the reaction solution was aspirated under reduced pressure at 120 ° C. at 20 mmHg for 4 hours, and unreacted monomer and TEA were removed to obtain polymer polyols ai. The results are shown in Tables 7 and 8.

TABLE 7

Example 18 19 20 21 22 Polymer polyol a d e f g Polyol A (parts by weight) Polyol B (parts by weight) -77.60 47.55- 53.33- 53.33- -46.86 AN (parts by weight) St (parts by weight) TEA (parts by weight) AIBN (parts by weight) 22.40--0.35 41.9610.494.000.26 37.349.331.000.26 30.3416.331.000.26 42.5110.634.000.26 Hydroxyl value (mg KOH / g) viscosity (cps / 25 ℃) polymer concentration (wt%) Tg (℃) 19.5480021.0- 19.7660047.699 18.6684044.8115 18.6650044.0118 15.31320050.099 Agglomerated particles none none none none none

Table 8

Comparative Example 8 9 10 11 Polymer polyol a c h i Polyol A (parts by weight) Polyol C (parts by weight) Polyol D (parts by weight) Polyol E (parts by weight) --77.60- --- 75.97 -53.33-- 53.33 --- AN (parts by weight) St (parts by weight) TEA (parts by weight) AIBN (parts by weight) 22.40--0.35 18.975.07-0.35 37.349.33-0.26 37.349.33-0.26 Hydroxyl value (mg KOH / g) viscosity (cps / 25 ℃) polymer concentration (wt%) Tg (℃) 19.8410020.8- 18.11200022.3112 18.51450044.2123 18.91500044.0125 Agglomerated particles none has exist has exist has exist

3. Preparation of Polyurethane Foam

Examples 23-24, Comparative Examples 12-13

Polymer polyol, polyol, water, L-1020, X-DM, KL-210, L-5309 were stirred and mixed at the ratio shown in Table 9 to make a resin premix and adjusted to 25 ° C. The amount of NCO and the active hydrogen equivalent of the resin premix is adjusted to 1.00 at 25 ° C, and the amount used is adjusted so as to obtain a foam having a desired density for the resin premix that has been adjusted. After injection into a test mold made of aluminum, which was heated to 60 ° C in advance and commercially available a release agent was applied, the lid was closed, sealed with a clamp, and foamed and cured. Three minutes after the start of the stirring, the mold was clamped, the cured flexible polyurethane foam was demolded, and the independent foamability was evaluated by the magnitude of the force when the foam was pressed by hand. The rollers were then crushed by compressing the thickness by 80%. After 24 hours, various physical properties were measured. Foam properties are shown in Table 9.

Table 9

Example 23 Comparative Example 12 Example 24 Comparative Example 13 Polymer Polyol a Polymer Polyol b Polymer Polyol e Polymer Polyol h 40 --- -40-- --28- --- 28 Polyol (parts by weight) 60 60 72 72 Water (parts by weight) L-1020 (parts by weight) X-DM (parts by weight) L-5309 (parts by weight) XL-210 (parts by weight) 3.30.40.31.03.0 3.30.40.31.03.0 3.50.40.31.03.0 3.50.40.31.03.0 Independent foaming evaluation Foam foam density over crushing (kg / ㎥) Hardness 25% ILD (kg / 314㎠) Tensile strength (kg / ㎠) Elongation (%) Tear strength (kg / ㎠) Wet heat durability 50% Wet ( Resilient (%) Core Small None 5021.521200.609.374 Small None 5021.371050.5311.371 Small None 50241.151140.6416.276 5021.041120.5820.673

The polyoxyalkylene polyol of the present invention is prepared using an alkali metal hydroxide catalyst, has a low monool content, and is compared with a method using a bimetal cyanide catalyst or the like, which has been conventionally used. -to-Tail) Due to the high selectivity of the bond, it has low viscosity and can improve physical properties in a wide range of polyurethane applications.

The polymer polyol of the present invention is characterized by low viscosity because it has a polyoxyalkylene polyol having a low monool content and a high Head-to-Tail bond selectivity as a matrix, and is suitable for a wide range of polyurethane applications. This can bring about improved physical properties. In addition, even when the polymer concentration is increased, it is possible to obtain a polymer polyol having a lower viscosity than the conventional one, no particle aggregation, and good dispersion stability.

The polyoxyalkylene polyols and polymer polyols obtained in this way have low foaming properties at the time of foaming, so that there is no problem of cracking in the foam after crushing. Provides excellent polyurethane foam.

Claims (16)

Polyoxyalkylene having a hydroxyl value of 10 to 35 mgKOH / g, a monool maximum content of 15 mol%, and a head-to-tail coupling minimum selectivity by propylene oxide addition polymerization of 96% A polymer polyol, wherein said polymer particles are dispersed at least 5% by weight and less than 30% by weight in said polyol. Polyoxyalkylene having a hydroxyl value of 10 to 35 mgKOH / g, a monool maximum content of 15 mol%, and a head-to-tail coupling minimum selectivity by propylene oxide addition polymerization of 96% The method for producing the polymer polyol of claim 1, wherein the polyol is polymerized with an ethylenically unsaturated monomer. 3. The polyoxyalkylene polyol according to claim 2, wherein the polyoxyalkylene polyol is alkylated to an active hydrogen compound having 2 to 8 hydroxyl groups in the presence of an alkali metal catalyst comprising at least one of compounds selected from cesium hydroxide and rubidium hydroxide having a purity of 90% by weight or more. A method for producing a polymer polyol, which is obtained by addition polymerization of lenoxide. The method for producing a polymer polyol according to claim 3, wherein the alkylene oxide is at least two kinds selected from the group consisting of ethylene oxide, propylene oxide and butylene oxide. The method for producing a polymer polyol according to claim 3, wherein an alkylene oxide having a content of propylene oxide of 70% by weight or more is used, and ethylene oxide used in the end cap of the polyoxyalkylene polyol is 5% by weight or more. . The method of claim 2, wherein the ethylenically unsaturated monomer is acrylonitrile or a mixture of acrylonitrile and styrene. Polyoxyalkylene having a hydroxyl value of 10 to 35 mgKOH / g, a monool maximum content of 15 mol%, and a head-to-tail coupling minimum selectivity by propylene oxide addition polymerization of 96% A polymer polyol, wherein the polymer particles having a glass transition temperature of 90 to 120 ° C. are dispersed in a polyol of 30% by weight to 60% by weight. Polyoxyalkylene having a hydroxyl value of 10-35 mgKOH / g, a monool maximum content of 15 mol%, and a head-to-tail bond minimum selectivity of 96% by propylene oxide addition polymerization A method for producing the polymer polyol of claim 7, wherein the polyol is polymerized with an ethylenically unsaturated monomer in the presence of a chain transfer agent. The polyoxyalkylene polyol according to claim 8, wherein the polyoxyalkylene polyol is alkylated to an active hydrogen compound having 2 to 8 hydroxyl groups in the presence of an alkali metal catalyst comprising at least one of compounds selected from cesium hydroxide and rubidium hydroxide having a purity of 90% by weight or more. A method for producing a polymer polyol, characterized in that obtained by addition polymerization of lenoxide. The method for producing a polymer polyol according to claim 9, wherein the alkylene oxide is at least two kinds selected from the group consisting of ethylene oxide, propylene oxide and butylene oxide. The method for producing a polymer polyol according to claim 9, wherein an alkylene oxide having a content of propylene oxide of 70% by weight or more is used, and ethylene oxide used in the end cap of the polyoxyalkylene polyol is 5% by weight or more. . 9. A process according to claim 8 wherein the ethylenically unsaturated monomer is acrylonitrile or a mixture of acrylonitrile and styrene. The method for producing a polymer polyol according to claim 8, wherein an amine compound is used as a chain transfer agent. The compound according to claim 13, wherein the amine compound is of formula (1) (In Formula (1), R <_1> , R <_2> and R <_3> represent H, a C1-C10 alkyl group, and a C2-C10 hydroxyalkyl group, These may mutually be same or different, but all are H It is not.) Amine compound represented by the formula, or general formula (2) (In Formula (2), X represents O or NR ₂ , R ₁ represents an alkyl group having 1 to 10 carbon atoms, a hydroxyalkyl group having 2 to 10 carbon atoms, and R ₂ represents H, an alkyl group having 1 to 10 carbon atoms and carbon number. 2-10 hydroxyalkyl group.) Method for producing a polymer polyol, characterized in that the compound represented by. The method for producing a polymer polyol according to claim 13, wherein the amine compound is triethylamine. The method for producing a polymer polyol according to claim 13, wherein the amine compound is N-methylmorpholine.