JP2003301041A - Method for producing polyol and polymer dispersed polyol - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a polyol which can improve the moldability in producing a flexible polyurethane foam and can give the foam having good durability, hardness and vibration characteristics. <P>SOLUTION: The polyol is produced by continuously reacting an initiator with propylene oxide in an amount of 5-50 mass% and then with ethylene oxide and propylene oxide at random by using a double metal cyanide complex catalyst, and finally with ethylene oxide by using an alkali metal catalyst. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a high molecular weight polyoxyalkylene polyol or polymer-dispersed polyol. The polyoxyalkylene polyol or polymer-dispersed polyol obtained by the production method of the present invention is used as a raw material for an elastomer, a synthetic resin, a coating material, a sealing material, a surfactant, a lubricant, a diluent,
Widely used as a plasticizer. In particular, when used as a raw material for producing a flexible polyurethane foam (hereinafter referred to as a flexible foam), a flexible foam having improved mechanical properties such as hardness, moldability, vibration characteristics, and durability can be obtained.

[0002]

2. Description of the Related Art Conventionally, various studies have been made to improve the properties of flexible foams. For example, in order to improve the riding comfort performance of a seat cushion of an automobile or the like, improvements in impact resilience, vibration characteristics, durability, etc. are targeted. Further, in recent years, a flexible foam having a low impact resilience has been demanded along with a change in preference of the ride comfort performance of a user. Regarding vibration characteristics, the frequency range in which humans are sensitive (for example, 4 to 8 Hz, or 6
It is said that it is effective to improve the ride comfort performance by taking a particularly large attenuation of about 20 Hz). In order to improve these characteristics, it is considered effective to manufacture a seat cushion using a polyoxyalkylene polyol having a higher molecular weight.

Generally, a polyoxyalkylene polyol (hereinafter referred to as a polyol) used as a raw material for a flexible foam is a polyhydric alcohol prepared by using a sodium-based catalyst such as sodium hydroxide or a potassium-based catalyst such as potassium hydroxide. And the like as an initiator, and is produced by subjecting an alkylene oxide such as propylene oxide to ring-opening addition polymerization. In this production method, a monool having an unsaturated bond (unsaturated monool) is produced as a by-product, and the production amount of this unsaturated monool increases with a decrease in the hydroxyl value of the polyol (an increase in the molecular weight).

In the production of a polyol having a hydroxyl value of about 56 mgKOH / g, which is widely used as a raw material for flexible foams, the amount of unsaturated monool produced is not so large as to cause a serious problem. However, in the production of a polyol having a high molecular weight and a low hydroxyl value, the amount of unsaturated monool produced is a problem. When a flexible foam is produced using a polyol having a high degree of total unsaturation, there arise problems such as a decrease in hardness, deterioration of compression set, and deterioration of curing property during molding. Also, using a sodium-based catalyst or potassium-based catalyst,
When a polyol having a low hydroxyl value is to be produced, the total degree of unsaturation of the polyol is extremely high, and the production is very difficult.

As a method for producing a polyol having a low total degree of unsaturation and a low hydroxyl value, a method of ring-opening addition-polymerizing an alkylene oxide using a complex metal cyanide complex as a catalyst is disclosed in JP-A-2-276821. Proposed. Although the riding comfort performance is dramatically improved by using the high molecular weight polyol obtained by this production method,
There may be a problem in terms of moldability such as communication, which is required in addition to ride comfort performance. In fact, when a flexible foam is produced by using this polyol alone, the closed cell property is relatively high, and a problem may occur during the crushing treatment.

As a method of solving the problem of moldability, there is a method of producing a flexible foam using a polyol mixture of a polyol produced using a double metal cyanide complex catalyst and a polyol produced using potassium hydroxide as a raw material. It is proposed in Japanese Unexamined Patent Publication No. 8-231676.
However, in this method, as the polyol produced using the double metal cyanide complex catalyst, a polyoxyalkylene polyol produced by subjecting only propylene oxide to ring-opening addition-polymerization of ethylene oxide to an initiator is used. Therefore, the unsaturation degree of the polyol produced by using the potassium hydroxide catalyst was high, and the unsaturation degree of the entire polyol mixture was high, so that the durability of the foam was likely to be insufficient.

As another method, a mixed metal cyanide complex catalyst is used to supply a mixture of ethylene oxide and other alkylene oxide as an initiator to a ring-opening addition polymerization reaction system, and ethylene oxide is added to the polyol molecule. USP560 is a method of producing a polyol having a random addition structure with other alkylene oxides, and using this polyol to produce a flexible foam having good moldability.
5939, USP 5648559. However, when the present inventors produced flexible foams for automobile seats using the polyols of the examples described in the above publications, collapses (collaps) occurred inside and on the surface of the foams, and the foams could not be produced. .

[0008]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems, and when a flexible foam is produced from a polyol produced using a double metal cyanide complex catalyst as a raw material,
Good foam moldability is maintained, the physical properties such as hardness of the resulting foam, and vibration properties are good, and a raw polyol or a raw material polyol that gives a flexible foam having good durability, especially wet heat compression set characteristics A method for producing a polymer-dispersed polyol is provided.

[0009]

The present invention is a method for producing a polyoxyalkylene polyol by subjecting an initiator to ring-opening addition polymerization of propylene oxide and ethylene oxide in the presence of a catalyst. Propylene oxide is subjected to ring-opening addition polymerization with an initiator in the presence of a metal cyanide complex catalyst to form an oxypropylene block chain, and further ethylene oxide and propylene oxide are subjected to random ring-opening addition polymerization to form an oxyalkylene random chain. Then, the catalyst is converted to a polyoxyalkylene polyol obtained by ring-opening addition polymerization of ethylene oxide in the presence of an alkali metal catalyst to form an oxyethylene block chain, wherein the polyoxyalkylene polyol has a hydroxyl value of Is 5 to 56m
gKOH / g, the proportion of initiator residues is 25% by mass or less, the proportion of oxypropylene block chains is 5 to 50% by mass, the total oxyethylene group content is 5 to 60% by mass, and the primary hydroxyl group conversion rate is Is 60 mol% or more, and a method for producing a polyoxyalkylene polyol is provided.

The present invention also provides a method for producing a polymer-dispersed polyol, which comprises polymerizing a monomer having a polymerizable unsaturated group using the polyoxyalkylene polyol obtained by the above-mentioned production method as a dispersion medium. .

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION [Structure of Polyol (1)] The polyoxyalkylene polyol (hereinafter referred to as polyol (1)) in the present invention contains propylene oxide as an initiator in the presence of a double metal cyanide complex catalyst. Ring-opening addition polymerization is carried out to form an oxypropylene block chain, and further ethylene oxide and propylene oxide are subjected to ring-opening addition polymerization at random to form an oxyalkylene random chain, and then the catalyst is converted into the presence of an alkali metal catalyst. It is a polyoxyalkylene polyol obtained by ring-opening addition polymerization of ethylene oxide to form an oxyethylene block chain.

That is, the polyol (1) comprises an initiator residue (i) and an oxypropylene block chain (i) in the molecule.
i), an oxyalkylene random chain (iii), and an oxyethylene block chain (iv).

[Initiator Residue (i)] As the initiator of the polyol (1) in the present invention, polyhydric alcohols, amines, and active hydrogen compounds such as condensation compounds can be used. The initiator residue (i) refers to a portion of the polyol (1) derived from the initiator. This initiator residue (i)
The ratio is 25% by mass or less, preferably 2 to 20% by mass, based on the whole polyol (1).

Specific examples of the initiator include ethylene glycol, propylene glycol, 1,4-butanediol, glycerin, trimethylolpropane, pentaerythritol, diglycerin, meso-erythritol, methylglucoside, glucose, sorbitol and sucrose. Examples of the polyhydric alcohols include amines such as ethylenediamine, diethylenediamine, triethylenediamine, diaminodiphenylmethane, hexamethylenediamine, and propylenediamine; condensed compounds such as phenol resins and novolac resins.

Two or more kinds of these active hydrogen compounds may be used in combination. Among these active hydrogen compounds, polyhydric alcohols are preferable. Of these, polyhydric alcohols having 3 or more valences are preferable because the flexibility of a flexible foam made from a polyol produced by using the polyhydric alcohol as an initiator is likely to develop.

As the initiator, a compound obtained by subjecting the above compound to a small amount of ring-opening addition polymerization of alkylene oxide may be used. Propylene oxide is preferable as the alkylene oxide. The molecular weight of the compound is preferably 650 or more. The most preferable example of the initiator has a hydroxyl value of 150 to 250 obtained by ring-opening addition polymerization of propylene oxide with a polyhydric alcohol having a valence of 3 or more.
It is a compound of mgKOH / g.

[Oxypropylene block chain (ii)]
The polyol (1) in the present invention has an oxypropylene block chain (ii) formed using a double metal cyanide complex catalyst, adjacent to the initiator residue (i). The proportion of the oxypropylene block chain (ii) is 5 to 50% by mass, preferably 10 to 40% by mass, based on the whole polyol (1). Particularly, when the proportion of the oxypropylene block chain (ii) is 20 to 30% by mass, the hardness of the flexible foam can be controlled to be high, which is preferable. If the amount of oxypropylene block chains exceeds 50% by mass,
Moldability tends to deteriorate because the closed cell properties of the flexible foam become high, and hardness tends to be difficult to develop because the curability deteriorates, which is not preferable. Further, if the oxypropylene block chain (ii) is less than 5% by mass, the hardness of the flexible foam tends to be difficult to develop, which is not preferable.

When a compound obtained by ring-opening addition polymerization of propylene oxide with a polyhydric alcohol having a valence of 3 or more is used as the initiator, the initiator residue (i) is used.
It is not possible to distinguish the oxypropylene block chain possessed by and the oxypropylene block chain (ii) formed using the double metal cyanide complex catalyst by analyzing the obtained polyol (1). Therefore, when verifying as the polyol (1), the oxypropylene block chain (i) formed by using the oxypropylene block chain of the initiator residue (i) and the complex metal cyanide complex catalyst is used.
No distinction is made from i). That is, the total ratio of the initiator residue (i) and the oxypropylene block chain (ii) is preferably 5 to 75% by mass, more preferably 12 to 60% by mass, based on the entire polyol (1).

The oxypropylene block chain (i
polyol (1) in which i) is adjacent to the initiator residue (i)
When compared with other polyols, the former is preferable because the moldability is good. Further, this oxypropylene block chain (ii) is produced using the above-mentioned complex metal cyanide complex catalyst, but when other catalysts are used, unsaturated monool is by-produced, and the obtained flexible foam of polyol is used as a raw material. Durability tends to deteriorate, which is not preferable.

[Oxyalkylene Random Chain (ii
i)] The polyol (1) in the present invention has an oxyalkylene random chain (iii) formed by using a double metal cyanide complex catalyst, adjacent to the oxypropylene block chain (ii). The oxyalkylene random chain is a structure obtained by supplying ethylene oxide and propylene oxide into the reaction system at a predetermined ratio and randomly performing ring-opening addition polymerization. The proportion of the oxyalkylene random chain (iii) is preferably 5 to 90 mass% with respect to the entire polyol (1),
80 mass% is preferable.

The content of the oxyethylene group in the oxyalkylene random chain (iii) of the polyol (1) in the present invention is determined by the oxyalkylene random chain (iii).
3 to 35 mass% is preferable with respect to i), and 5 to 30 mass% is more preferable. That is, the ratio of ethylene oxide and propylene oxide supplied into the reaction system is 3/9 in terms of mass ratio (ethylene oxide / propylene oxide).
7-35 / 65 is preferable and 5 / 95-30 / 70 is more preferable. When the number of oxyethylene groups in the oxyalkylene random chain (iii) exceeds the range and is small or large, the flexible foam may have high closed cell properties and deteriorate moldability, which is not preferable.

When ethylene oxide and propylene oxide are supplied to the reaction system at a predetermined ratio, the ratio may be changed during the supply. By this method, the content of oxyethylene groups in the oxyalkylene random chain (iii) can be controlled at a desired portion in the molecule. For example, in the case where the ratio of ethylene oxide among the above ratios is increased in several steps and supplied, the polyol (1) having a higher content of oxyethylene groups as the molecular end of the polyol (1) is produced can be produced.

[Oxyethylene Block Chain (iv)] The polyol (1) in the present invention is adjacent to the oxyalkylene random chain (iii), that is, at the molecular end,
It has an oxyethylene block chain (iv) produced using an alkali metal catalyst. The content of the oxyethylene block chain (iv) is preferably 3 to 40% by mass, and more preferably 5 to 30% by mass, based on the entire polyol (1). When the oxyethylene block chain (iv) exceeds 40% by mass, shrinkage is likely to occur even after the crushing treatment, which is not preferable. The oxyethylene block chain (i
If v) is less than 3% by mass, collapsing of the foam is likely to occur during production of the flexible foam, which makes production difficult, which is not preferable.

[Compound Metal Cyanide Complex Catalyst] The polyol (1) in the present invention causes the above-mentioned specific alkylene oxide to undergo ring-opening addition polymerization with an initiator in the presence of the complex metal cyanide complex catalyst. Examples of the complex metal cyanide complex catalyst include compounds described in JP-B-46-27250. In particular, a complex containing zinc hexacyanocobaltate as a main component is preferable, and an ether and / or alcohol complex thereof is more preferable. By using this complex metal cyanide complex catalyst, the amount of unsaturated monool by-produced can be suppressed, and the durability of the flexible foam obtained from the resulting polyol as a raw material is improved, which is preferable.

The ether is not particularly limited, but a compound represented by the following formula (hereinafter, compound (X)
Is preferred). R ¹ -C (CH ₃ ) ₂ (OR ⁰ ) _n OH wherein R ¹ is a methyl group or an ethyl group, R ⁰ is an ethylene group or a group in which a hydrogen atom of the ethylene group is substituted with a methyl group or an ethyl group, n is an integer of 1 to 3. R
^{As 0} , a group selected from an ethylene group, a propylene group, an ethylethylene group, a 1,2-dimethylethylene group and a 1,1-dimethylethylene group is particularly preferable.

The compound (X) is specifically WO0.
The compound described in 0/02951 is mentioned.
Specifically, the following compounds are preferable.

When n is 1, ethylene glycol mono-
Preferred are tert-butyl ether, propylene glycol mono-tert-butyl ether, ethylene glycol mono-tert-pentyl ether and propylene glycol mono-tert-pentyl ether. n is 2
In the case of, diethylene glycol mono-tert-butyl ether and diethylene glycol mono-tert-pentyl ether are preferable. When n is 3, triethylene glycol mono-tert-butyl ether and triethylene glycol mono-tert-pentyl ether are preferable. Furthermore, as the compound (X), a compound in which n is 1 is particularly preferable, and a compound in which R ¹ is a methyl group is most preferable. Further, as the compound (X), two or more kinds of compounds can be used in combination.

The alcohol is not particularly limited, but for example, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, tert-butyl alcohol, pentanol,
Octanol is mentioned, and among them, it is preferable to use tert-butyl alcohol.

When the compound (X) is used in combination with another compound as the organic ligand, the compound that can be used in combination is tert-
Butyl alcohol, 1-butanol, 2-butanol,
1 or 2 selected from tert-pentyl alcohol, isopentyl alcohol, N, N-dimethylacetamide, glyme (ethylene glycol dimethyl ether), diglyme (diethylene glycol dimethyl ether), triglyme (triethylene glycol dimethyl ether), 2-propanol, and dioxane. It is preferably one or more compounds. The dioxane may be 1,4-dioxane or 1,3-dioxane, and 1,4-dioxane is preferable. As the compound used in combination, tert-butyl alcohol, tert-pentyl alcohol or glyme is particularly preferable.
-Butyl alcohol is most preferred.

Specifically, specific examples of the complex metal cyanide complex used in the present invention include zinc hexacyanocobaltate-ethylene glycol mono-tert-butyl ether complex, zinc hexacyanocobaltate-ethylene glycol mono-tert-butyl ether / ter.
Examples thereof include t-butyl alcohol complex, zinc hexacyanocobaltate-tert-butyl alcohol complex, and zinc hexacyanocobaltate-glyme complex. Among them, zinc hexacyanocobaltate-ethylene glycol mono-tert-butyl ether complex and zinc hexacyanocobaltate-ethylene glycol mono-t
The ert-butyl ether / tert-butyl alcohol complex is particularly preferred.

[Alkali Metal Catalyst] Examples of the alkali metal catalyst used for forming the oxyethylene block chain (iv) include sodium catalysts, potassium catalysts and cesium catalysts. Examples of the sodium-based catalyst include sodium metal, sodium alkoxide such as sodium methoxide, sodium hydroxide, sodium carbonate and the like. The same applies to potassium-based catalysts and cesium-based catalysts.

In the production of the polyol (1) in the present invention, as a method of converting the catalyst from the above-mentioned double metal cyanide complex catalyst to the alkali metal catalyst, the double metal cyanide complex catalyst is deactivated and then the alkali metal catalyst is deactivated. May be added to the reaction system, or the alkali metal catalyst may be directly added to the reaction system without deactivating. In the latter case,
The addition of the alkali metal catalyst deactivates the double metal cyanide complex catalyst. Examples of the deactivation treatment include treatment by adding water, acid or alkali, treatment by adding an adsorbent, and the like.

[Characteristics of Polyol (1)] The hydroxyl value of the polyol (1) in the present invention is 5 to 56 mgKOH.
/ G, but more preferably 10 to 42 mgKOH / g. When the hydroxyl value exceeds 56 mgKOH / g and is large and the molecular weight is low, the elasticity of the obtained flexible foam tends to be insufficient, which is not preferable. Also, the hydroxyl value is 5 mgKOH /
If it is less than g, the hardness of the resulting flexible foam is difficult to obtain, which is not preferable.

The number of hydroxyl groups of the polyol (1) in the present invention is preferably 2-8, more preferably 2.7-7,
Most preferred is 2.8 to 5.2. However, with the number of hydroxyl groups,
It means the average value of the number of active hydrogens of the initiator. Number of hydroxyl groups is 2
When it is less than 1, the resulting flexible foam tends to be soft and durability tends to deteriorate, which is not preferable. If the number of hydroxyl groups exceeds 8, the resulting flexible foam tends to be hard and mechanical properties such as elongation tend to deteriorate, such being undesirable.

The unsaturation degree of the polyol (1) in the present invention is preferably 0.03 meq / g or less, and 0.025 meq / g or less.
It is more preferably meq / g or less. Unsaturation is 0.03m
If it is larger than eq / g, that is, if the amount of unsaturated monool is large, durability and riding comfort performance of the resulting flexible foam are likely to deteriorate, which is not preferable. Here, the index of the durability of the flexible foam includes dry heat compression set and wet heat compression set. As the degree of unsaturation increases,
The value of the compression set becomes large and the durability tends to deteriorate. The resonance frequency is an index of the riding comfort performance of the flexible foam. There is a correlation that the transmissibility of 6 Hz, which is most uncomfortable for humans, decreases as the resonance frequency decreases, which is suitable as an index.

The total oxyethylene group content in the polyol (1) in the present invention (that is, all the oxyethylenes contained in the initiator residue (i), the oxyalkylene random chain (iii), and the oxyethylene block chain (iv)). The content of the group) is 5 to 60% by mass,
10 to 40 mass% is more preferable. In addition, the primary conversion rate of the terminal hydroxyl groups, which is the ratio of the primary hydroxyl groups in the terminal hydroxyl groups of the polyol derived from the oxyethylene block chain (iv) portion at the molecular terminal of the polyol (1) in the present invention, is 60 mol% or more. 80-95 mol% is more preferable.

[Polymer-dispersed polyol] The present invention also provides a method for producing a polymer-dispersed polyol in which polymer particles are stably dispersed in the above-mentioned polyol (1). Here, the polymer-dispersed polyol is a dispersion system in which polymer particles (dispersoids) are stably dispersed in a base polyol (dispersion medium). That is, the polymer-dispersed polyol in the present invention means the above-mentioned polyol (1).
It is a polymer-dispersed polyol having as a base polyol.

Examples of the polymer of the polymer fine particles include addition polymerization type polymers and condensation polymerization type polymers.
The addition-polymerization polymer is obtained, for example, by homopolymerization or copolymerization of monomers such as acrylonitrile, styrene, methacrylic acid ester, and acrylic acid ester. Further, as the polycondensation polymer, polyester, polyurea,
Examples include polyurethane and melamine.

The presence of polymer fine particles in the polyol suppresses the hydroxyl value of the polyol to a low level, and is effective in improving the physical properties such as hardness and air permeability of the flexible foam.
The content of the fine polymer particles in the polymer-dispersed polyol is not particularly limited, but is preferably 50% by mass or less,
3-40 mass% is more preferable. When the mass of the polyol is used for calculation, the mass of the polymer particles is not included.

[Use of Polyol (1)] The polyol (1) or the polymer-dispersed polyol in the present invention is
It is widely used as a raw material for flexible foams, elastomers, synthetic resins, paints, and sealing materials, and as a surfactant, lubricant, diluent, plasticizer, and the like. In particular, it is preferable to use it as a raw material for producing a flexible foam, since the moldability of the foam and the physical properties such as vibration characteristics and hardness of the resulting flexible foam are improved. As a method for producing a flexible foam, generally, a method of reacting a polyol compound and a polyisocyanate compound in the presence of a foaming agent and a catalyst, if necessary, in the presence of a foam stabilizer, a crosslinking agent, and a foam breaking agent. Is mentioned.

Polyol compound (including polymer-dispersed polyol) to be reacted when producing the flexible foam
As the polyol (1) in the present invention, and /
Alternatively, it is preferable to use a polyol mixture containing the polymer-dispersed polyol in the present invention. As the polyol mixture, only the polyol in the present invention (polyol (1) or the above polymer-dispersed polyol) may be used, or it may be used in combination with another polyol. The other polyol is not particularly limited as long as it is a polyol used when producing a flexible foam, but a polyoxyalkylene polyol is preferable, and a polyoxyalkylene polyol having a total oxypropylene group content of 40% by mass or more is preferable. Among the polyols reacted when producing the flexible foam, the content of the polyol in the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, and particularly preferably 50% by mass or more. Further, two or more kinds of the polyols of the present invention may be mixed and used. However, the above-mentioned polyol compound (mixture)
Does not include a crosslinking agent and a defoaming agent described later.

The hydroxyl value of the above-mentioned polyol mixture is 5 to 5.
56mgKOH / g is preferable, 10-42mgKOH
/ G is more preferable. The total unsaturation of the polyol mixture is preferably 0.05 meq / g or less,
Meq / g or less is more preferable, and 0.025 meq / g
The following are the most preferable. The average primary conversion rate of terminal hydroxyl groups of the above polyol mixture is preferably 60 mol% or more.

As the polyisocyanate compound,
Although not particularly limited, aromatic, alicyclic, aliphatic polyisocyanates having two or more isocyanate groups;
Examples include a mixture of two or more kinds of the above polyisocyanates; modified polyisocyanates obtained by modifying these. As a specific example, tolylene diisocyanate (T
DI), diphenylmethane diisocyanate (MD
I), polymethylene polyphenyl isocyanate (common name: crude MDI), xylylene diisocyanate (XDI), isophorone diisocyanate (IPD)
I), polyisocyanates such as hexamethylene diisocyanate (HMDI), prepolymer-type modified products, nurate-type modified products, urea-type modified products, carbodiimide-type modified products thereof and the like. Of these, TDI, M
DI, crude MDI, or modified forms thereof are preferred.

The amount of the polyisocyanate compound used is usually an isocyanate index (a value represented by 100 times the ratio of the number of isocyanate groups to the total number of all active hydrogens such as polyol, crosslinking agent, defoaming agent and water). The amount of the polyisocyanate compound used in the present invention is preferably 80 to 120, more preferably 85 to 110 in terms of isocyanate index.

The foaming agent is not particularly limited, but at least one selected from water and inert gas is preferable. Examples of the inert gas include air, nitrogen, carbon dioxide gas and the like. Of these, water is preferred. The amount of the foaming agent used is not particularly limited, but when water is used, it is preferably 10 parts by mass or less, more preferably 0.1 to 8 parts by mass with respect to 100 parts by mass of the polyol compound.

The catalyst is not particularly limited as long as it is a catalyst that accelerates the urethanization reaction. For example, triethylenediamine or bis (2-dimethylaminoethyl).
Tertiary amines such as ether, N, N, N ', N'-tetramethylhexamethylenediamine; potassium acetate, 2-
Examples thereof include carboxylic acid metal salts such as potassium ethylhexanoate; organic metal compounds such as dibutyltin dilaurate.

The foam stabilizer is not particularly limited, and examples thereof include a silicone type foam stabilizer and a fluorine type foam stabilizer. Of these, the silicone type foam stabilizer is preferable. By using these foam stabilizers, uniform bubbles can be formed.

The cross-linking agent is preferably a compound having two or more functional groups having active hydrogen such as hydroxyl group, primary amino group or secondary amino group. The hydroxyl value of the cross-linking agent is preferably 100 mgKOH / g or more, 15
0 mgKOH / g or more is more preferable, and 200 mgKO
H / g or more is particularly preferable. Two or more kinds of cross-linking agents may be used in combination.

Specific examples include ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, diethylene glycol, triethylene glycol, dipropylene glycol, glycerin, trimethylolpropane,
Pentaerythritol, diglycerin, dextrose, sorbitol, sucrose, monoethanolamine, diethanolamine, triethanolamine, bisphenol A, ethylenediamine, 3,5-diethyl-2,4 (or 2,6) -diaminotoluene (DET
DA), 2-chloro-p-phenylenediamine (CP
A), 3,5-bis (methylthio) -2,4 (or 2,6) -diaminotoluene, 1-trifluoromethyl-3,5-diaminobenzene, 1-trifluoromethyl-4-chloro-3, 5-diaminobenzene, 2,4-toluenediamine, 2,6-toluenediamine, bis (3,5-dimethyl-4-aminophenyl) methane,
Compounds such as 4,4′-diaminodiphenylmethane, m-xylylenediamine, 1,4-diaminohexane, 1,3-bis (aminomethyl) cyclohexane and isophoronediamine, and addition of a relatively small amount of alkylene oxide And the like.

As the above-mentioned defoaming agent, a polyoxyalkylene polyol having two or more hydroxyl groups, a hydroxyl value of 20 to 180 mgKOH / g and an oxyethylene group content of more than 60% by mass is preferable. The use of this foam breaking agent improves the moldability of the flexible foam, and specifically, the crushing load can be suppressed low, which is preferable. The amount of the defoaming agent used is preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the polyol compound.

In the production of flexible foams, in addition to the above, surfactants such as emulsifiers and foam stabilizers; antioxidants such as antioxidants and ultraviolet absorbers; fillers such as calcium carbonate and barium sulfate; flame retardants, Various known additives and auxiliaries such as plasticizers, colorants and antifungal agents can be used as necessary.

The flexible foam is preferably molded by directly injecting the reactive mixture into a mold using a low-pressure foaming machine or a high-pressure foaming machine. In particular, a method of molding in a closed mold (molding method) is preferable. The flexible foam in the present invention can be produced by either a cold cure method or a hot cure method, but the cold cure method is preferable.

The flexible foam produced by using the polyol (1) or the polymer-dispersed polyol in the present invention as a raw material is used for cushions, mattresses, seats and the like. In particular, it is suitable as a seat for vehicles such as automobiles.

[0054]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. The numerical values in the foaming prescription column in Examples and Comparative Examples represent parts by mass.

Examples X1 to X11 are production examples (examples) of the polyoxyalkylene polyol of the present invention, and Examples X12 to
Example X17 shows a production example (comparative example) of a comparative polyoxyalkylene polyol, and Example X18 shows a production example of a polyol used as a foam breaking agent. The properties of the polyol obtained in Production Example are shown in Table 1. Regarding the properties, the following items are shown. Ratio (unit: mass%) of oxypropylene block chains adjacent to the initiator (hereinafter referred to as "PO part (1)"), oxypropylene block chains not directly linked to the initiator (hereinafter referred to as "PO part (2)") Ratio (unit: mass%), ratio of oxyalkylene random chain (hereinafter referred to as “random part (1), random part (2)”) (unit: mass%), random part (1) and random part (2). ) And oxyethylene group content (represented as EO amount) in each part (unit: mass%), ratio of the terminal oxyethylene block chain (hereinafter referred to as “EO part”) (unit: mass%),
Hydroxyl value (unit: mgKOH / g), primary degree of terminal hydroxyl group (unit: mol%), degree of unsaturation (unit: meq /
g).

The hydroxyl value and the degree of unsaturation are measured according to JIS.
It carried out by the method based on K-1557. DM in production example
The C-METB complex catalyst indicates a zinc hexacyanocobaltate-ethylene glycol mono-tert-butyl ether complex catalyst, and the DMC-METB / TBA complex catalyst indicates a zinc hexacyanocobaltate-ethylene glycol mono-tert-butyl ether / tert-butyl alcohol. A complex catalyst is shown, a DMC-TBA complex catalyst shows a zinc hexacyanocobaltate-tert-butyl alcohol complex catalyst, and a DMC-glyme complex catalyst shows a zinc hexacyanocobaltate-glyme complex catalyst.

The initiator 1 is a hydroxyl value of 168 mg KOH / g obtained by adding propylene oxide to glycerin.
And the initiator 2 are compounds having a hydroxyl value of 234 mgKOH / g obtained by adding propylene oxide to glycerin.

Polyol Production Example (Example X1) “Production of Polyol A1” 1525 g of propylene oxide was added to about 120 using a DMC-METB complex catalyst in the presence of 1000 g of Initiator 1.
Then, 2833 g of an ethylene oxide / propylene oxide mixture containing 11.6% by weight of ethylene oxide was reacted at about 120 ° C. Next, potassium hydroxide was added to the reaction system to convert the catalyst to potassium hydroxide, and 1097 g of ethylene oxide was reacted at about 120 ° C. using this potassium hydroxide catalyst to complete the production. After the reaction, treatment with an adsorbent (synthetic magnesium silicate) and filtration were performed to obtain a polyol A1 having a hydroxyl value of 27.3 mgKOH / g.

Example X2 "Production of Polyol A2" Preparation of Polyol A1 was carried out in the same manner as in the production of Polyol A1 except that 2833 g of an ethylene oxide / propylene oxide mixture having an ethylene oxide content of 23.2% by mass was used. , Hydroxyl value is 27.8mg
A KOH / g polyol A2 was obtained.

(Example X3) "Production of Polyol B1" Propylene oxide (2279 g) was added to about 120 using a DMC-METB complex catalyst in the presence of Initiator 1 (1000 g).
C., and then 2278 g of an ethylene oxide / propylene oxide mixture containing 14.4% by weight of ethylene oxide was reacted at about 120.degree. C., and then 905 g of ethylene oxide was reacted at about 120.degree. C. using a sodium methoxide catalyst to complete the production. . After the reaction, treatment with an adsorbent (synthetic magnesium silicate) and filtration were performed to obtain a polyol B1 having a hydroxyl value of 27.6 mgKOH / g.

(Example X4) "Production of Polyol B2" The same procedure as in the production of Polyol B1 was repeated except that the DMC-METB / TBA complex catalyst was used instead of the DMC-METB complex catalyst in the production of Polyol B1.
7.8 mg KOH / g of polyol B2 was obtained.

(Example X5) "Production of Polyol B3" The same procedure as in the production of Polyol B1 was carried out except that a DMC-Glyme complex catalyst was used instead of the DMC-METB complex catalyst in the production of Polyol B1, and the hydroxyl value was 27.7 mg.
A KOH / g polyol B3 was obtained.

(Example X6) "Production of Polyol C" In the presence of 1000 g of Initiator 1, 2473 g of propylene oxide was added to about 120 using a DMC-METB complex catalyst.
C., 2174 g of an ethylene oxide / propylene oxide mixture containing 14.4% by weight of ethylene oxide was reacted at about 120.degree. C., and then 627 g of ethylene oxide was reacted at about 120.degree. C. using a sodium methoxide catalyst to complete the production. . After the reaction, treatment with an adsorbent (synthetic magnesium silicate) and filtration were performed to obtain a polyol C having a hydroxyl value of 28.1 mgKOH / g.

Example X7 "Production of Polyol D" In the presence of 1000 g of Initiator 1, 3137 g of propylene oxide was added to about 120 g using a DMC-METB complex catalyst.
C., then 1259 g of an ethylene oxide / propylene oxide mixture containing 14.4% by weight of ethylene oxide are reacted at about 120.degree. C., then using a potassium hydroxide catalyst about 878 g of ethylene oxide about 120 g.
The reaction was carried out at 0 ° C. to complete the production. After the reaction, the adsorbent (synthetic magnesium silicate) is treated and filtered to give a hydroxyl value of 2
8.3 mg KOH / g of polyol D was obtained.

(Example X8) "Production of Polyol E" Propylene oxide (630 g) was added at about 120 ° C using a DMC-METB complex catalyst in the presence of the initiator 1 (1000 g).
Ethylene oxide / ethylene oxide containing 11% by mass of ethylene oxide using a DMC-METB complex catalyst.
The production was completed by reacting 4014 g of the propylene oxide mixture at about 120 ° C. and then reacting 691 g of ethylene oxide at about 120 ° C. using a potassium hydroxide catalyst. After reaction, treatment with adsorbent (synthetic magnesium silicate),
Filtration was performed to obtain a polyol E having a hydroxyl value of 27.8 mgKOH / g.

Example X9 "Production of Polyol F1" 2833 of an ethylene oxide / propylene oxide mixture containing 11.6% by weight of ethylene oxide in the presence of 1000 g of Initiator 1 using a DMC-METB complex catalyst.
g at about 120 ° C., then 1525 g of propylene oxide at about 120 ° C., then about 1097 g of ethylene oxide using a potassium hydroxide catalyst.
The reaction was carried out at 0 ° C. to complete the production. After the reaction, the adsorbent (synthetic magnesium silicate) is treated and filtered to give a hydroxyl value of 2
7.9 mg KOH / g of polyol F1 was obtained.

(Example X10) "Production of polyol F2" In the production of the polyol F1, the same procedure as in the production of the polyol A was carried out except that 2833 g of an ethylene oxide / propylene oxide mixture having an ethylene oxide content of 23.2% by mass was used. Hydroxyl value is 26.9 mg KO
H / g of polyol F2 was obtained.

Example X11 "Production of Polyol G" In the presence of 1000 g of Initiator 1, 3817 g of propylene oxide was added to about 120 g using a DMC-METB complex catalyst.
C., followed by reaction of 591 g of an ethylene oxide / propylene oxide mixture containing 21.4% by weight of ethylene oxide at about 120.degree. C., and then 953 g of ethylene oxide at about 120.degree. C. using a potassium hydroxide catalyst.
Then, the reaction was completed and the production was completed. After the reaction, treatment with an adsorbent (synthetic magnesium silicate) and filtration were performed to obtain a hydroxyl value of 28.
1 mg KOH / g of polyol G was obtained.

(Example X12) "Production of Polyol H" In the presence of 1000 g of Initiator 1, 253 g of propylene oxide was heated to about 120 ° C using a DMC-METB complex catalyst.
Ethylene oxide / ethylene oxide containing 11% by mass of ethylene oxide using a DMC-METB complex catalyst.
The production was completed by reacting 4387 g of the propylene oxide mixture at about 120 ° C. and then reacting 695 g of ethylene oxide at about 120 ° C. using a potassium hydroxide catalyst. After reaction, treatment with adsorbent (synthetic magnesium silicate),
Filtration was performed to obtain a polyol H having a hydroxyl value of 27.9 mgKOH / g.

(Example X13) "Production of Polyol J" In the presence of 720 g of Initiator 2, 252 g of propylene oxide was reacted at about 120 ° C using a DMC-TBA complex catalyst, and then ethylene oxide containing 13% by mass of ethylene oxide. / Propylene oxide mixture 4487
g was reacted at about 120 ° C., and then 813 g of an ethylene oxide / propylene oxide mixture containing 40% by mass of ethylene oxide was reacted at about 120 ° C. to complete the production. After reaction, treatment with adsorbent (synthetic magnesium silicate),
Filtration was performed to obtain a polyol J having a hydroxyl value of 27.9 mgKOH / g.

(Example X14) "Production of Polyol K" Propylene oxide (5550 g) was added in an amount of about 120 using DMC-METB complex catalyst in the presence of initiator (1).
The reaction was carried out at 0 ° C., and then 1103 g of ethylene oxide was reacted at about 120 ° C. using a potassium hydroxide catalyst to complete the production. After reaction, adsorbent (synthetic magnesium silicate)
Treated and filtered, the hydroxyl value is 23.9mgKOH / g
Polyol K of was obtained.

Example X15 "Production of Polyol L1" In the presence of 1000 g of Initiator 1, 6467 g of propylene oxide was reacted at about 110 ° C. with a potassium hydroxide catalyst, and then 1423 g of ethylene oxide was added at about 110 ° C.
The reaction was carried out at 0 ° C. to complete the production. After the reaction, it is treated with an adsorbent (synthetic magnesium silicate) and filtered to give a hydroxyl value of 24.
mgKOH / g of polyol L1 was obtained.

(Example X16) "Production of polyol L2" In the presence of 1000 g of the initiator 1, 5378 g of propylene oxide was reacted at about 110 ° C using a potassium hydroxide catalyst, and then 1257 g of ethylene oxide was added at about 110 g.
The reaction was carried out at 0 ° C. to complete the production. After the reaction, the adsorbent (synthetic magnesium silicate) is treated and filtered to give a hydroxyl value of 2
7.9 mg KOH / g of polyol L2 was obtained.

Example X17 "Production of Polyol L3" In the presence of 1000 g of Initiator 1, 4416 g of propylene oxide were reacted at about 110 ° C. with a potassium hydroxide catalyst, then 904 g of ethylene oxide was added to about 110 g of ethylene oxide.
The reaction was carried out at 0 ° C. to complete the production. After the reaction, the adsorbent (synthetic magnesium silicate) is treated and filtered to give a hydroxyl value of 3
5.5 mg KOH / g of polyol L3 was obtained.

(Example X18) "Production of Polyol T" About 5000 g of an ethylene oxide / propylene oxide mixture containing 80% by mass of ethylene oxide in the presence of 1000 g of Initiator 1 was used with a potassium hydroxide catalyst.
The reaction was carried out at 0 ° C. to complete the production. After the reaction, the adsorbent (synthetic magnesium silicate) is treated and filtered to give a hydroxyl value of 2
7.9 mg KOH / g of Polyol T was obtained.

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[Table 1]

[0077]

[Table 2]

Flexible polyurethane foams were produced using the raw materials and blending amounts shown in Tables 2, 3 and 4. Of these, the mixture of all raw materials other than polyisocyanate (polyol system) and the polyisocyanate compound were each adjusted to a liquid temperature of 25 ± 1 ° C., the polyisocyanate compound was added to the polyol system, and the mixture was stirred and mixed with a high speed mixer for 5 seconds. Immediately heated to 60 ° C, length and width 400
The mixture was poured into an aluminum mold having a size of 100 mm and a height of 100 mm, and the mold was sealed. After curing for 6 minutes, the polyurethane foam was taken out, allowed to stand for 24 hours or more, and then various physical properties were measured. The measurement results are shown in Tables 3 and 4.

Crushing property was evaluated as an index of moldability. For evaluation of crushing property, a foam is molded (4
(00 mm x 400 mm x 100 mm),
Immediately, the workability when compressing the foam to 25% of the foam thickness and opening the foam cell was evaluated, and ◯ was evaluated as good and Δ was evaluated as somewhat poor. The load applied to the surface of 400 mm × 400 mm at the time of compression was evaluated as a crushing load (unit: N). The foam physical properties were measured in accordance with the following, and the core density was measured by cutting out from the center of the foam to a size of 100 mm in length and width and 50 mm in height.

The resonance frequency is 400 mm × 40
There is a correlation between a foam molded from a test piece mold having an inner size of 0 mm × 100 mm and a foam molded from a real mold of a seat cushion, and generally a seat cushion foam molded from the real mold. The resonance frequency of is about 0.2 ~
It tends to increase by about 1 Hz.

The unsaturation degree in Tables 3 and 4 is the total unsaturation degree (unit: meq / g) of the base polyol in the polyol and the polymer-dispersed polyol.

The standards used for measuring the physical properties of flexible foams are shown below. Total density (unit: kg / m ³ ), core density (unit: kg /
m ³ ), 25% hardness (ILD) (unit: N / 314 cm
² ), core impact resilience (unit:%), tear strength (N
/ Cm), tensile strength (kPa), elongation (%), dry heat compression set (unit:%), wet heat compression set (unit :)
%) Is a method based on JIS K6400. Hysteresis loss (unit:%) is a method based on JASO B407-87. Resonance frequency (unit: Hz), 6Hz transmissibility is JASO B407-87 (excitation amplitude: ± 2.5m
m, pressurizing plate: Tekken type, load: 490 N).

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[Table 3]

[0084]

[Table 4]

Examples 1 to 11 in Tables 3 and 4 are examples. Using a complex metal cyanide complex catalyst, propylene oxide is allowed to react continuously 5 to 50% by mass immediately after the initiator,
Then, the polyol (1) produced by reacting ethylene oxide and propylene oxide at random and finally reacting ethylene oxide with an alkali metal catalyst is used as a raw material, so that the moldability is good, physical properties such as hardness, and vibration. It is possible to obtain a foam having good properties and good durability, particularly good wet heat compression set. Particularly, in Examples 10 and 11, since Polyol T was used as the defoaming agent, the crushing load was suppressed to be low and good moldability was exhibited.

Examples 12 to 18 in Table 4 are comparative examples. Example 1
In Example 2 and Example 18, physical properties could not be measured because the foam cracked during the crushing treatment. Example 13 was synthesized using a potassium hydroxide catalyst in order to compensate for the poor moldability caused by the fact that the polyol K produced using the composite metal cyanide complex catalyst as a raw material does not have an oxyalkylene random chain. Since the polyol L2 is mixed and used as a raw material, the total unsaturation degree of the polyol is high and the durability is insufficient. Also, the moldability is not sufficient.

Since Example 14 uses a polyol produced with a potassium hydroxide catalyst, it has poor durability. Example 15
Since the oxypropylene block chain adjacent to the initiator uses 60% by mass of the polyol based on the entire polyol, the reactivity with the polyisocyanate becomes insufficient and the hardness is low, which is not preferable. Example 16 has insufficient hardness because the oxypropylene block chain adjacent to the initiator uses 4% by weight of polyol based on the total polyol.

In Example 17, since the end of the polyol L produced with the double metal cyanide complex catalyst was not completed by reacting ethylene oxide, collapsing occurred and a foam could not be produced, and the physical properties could be measured. There wasn't.

[0089]

EFFECT OF THE INVENTION By using the polyol having the specific structure of the present invention, it is possible to obtain a flexible polyurethane foam having improved moldability and excellent physical properties such as hardness and vibration characteristics. Further, since the polyol (1) in the present invention is produced by using the double metal cyanide complex catalyst, it has good durability, particularly physical properties such as wet heat compression set.

Front page continuation (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08G 101: 00) (72) Inventor Kayoko Sugiyama 1-633-2-801 Maruko-dori, Nakahara-ku, Kawasaki-shi, Kanagawa (72) Inventor Etsuko Akagi 9-30-204 F Term, Mitsuzawashita-cho, Kanagawa-ku, Yokohama, Kanagawa Prefecture (reference) 4J005 AA04 BB02 4J011 PA90 4J026 AB19 AC16 BA05 BA27 BA31 GA07 4J034 BA03 DA01 DB03 DB07 DG03 DG04 DG12 HA01 HA12 HC07 HC03 HC02 HC07 HC03 HC52 HC61 HC64 HC67 HC71 HC73 KB02 KC02 KC17 KD02 KD12 KE02 MA24 NA01 NA03 NA05 NA08 QB15 QC01 RA12 RA15

Claims (10)

[Claims] 1. A method for producing a polyoxyalkylene polyol by ring-opening addition polymerization of propylene oxide and ethylene oxide with an initiator in the presence of a catalyst, wherein the polyoxyalkylene polyol is in the presence of a double metal cyanide complex catalyst. In the initiator, propylene oxide is subjected to ring-opening addition polymerization to form an oxypropylene block chain, and further ethylene oxide and propylene oxide are subjected to random ring-opening addition polymerization to form an oxyalkylene random chain, and then the catalyst is converted. A polyoxyalkylene polyol obtained by ring-opening addition polymerization of ethylene oxide in the presence of an alkali metal catalyst to form an oxyethylene block chain, wherein the polyoxyalkylene polyol has a hydroxyl value of 5 to 5.
56 mgKOH / g, the proportion of the initiator residue is 25% by mass or less, the proportion of the oxypropylene block chain is 5 to 50% by mass, the total oxyethylene group content is 5 to 60% by mass, and the primary hydroxyl group of the terminal hydroxyl group Is 60 mol% or more, which is a polyoxyalkylene polyol. 2. In the formation of the oxyalkylene random chain, the ratio of ethylene oxide and propylene oxide to be subjected to ring-opening addition polymerization is 3/97 to 35/65 in mass ratio.
The method for producing a polyoxyalkylene polyol according to claim 1, which is within the range. 3. The method for producing a polyoxyalkylene polyol according to claim 1, wherein the complex metal cyanide complex catalyst has a compound represented by the following formula as at least a part of the organic ligand. R ¹ -C (CH ₃ ) ₂ (OR ⁰ ) _n OH where R ^{1 is a} methyl group or an ethyl group, R ⁰ is an ethylene group or a group in which a hydrogen atom of the ethylene group is substituted with a methyl group or an ethyl group, n is an integer of 1 to 3. 4. The proportion of oxyethylene block chains in the polyoxyalkylene polyol is 3 to 40% by mass.
A method for producing the polyoxyalkylene polyol according to claim 1, 2 or 3. 5. The method for producing a polyoxyalkylene polyol according to claim 1, wherein the proportion of the oxyalkylene random chain in the polyoxyalkylene polyol is 5 to 90% by mass. 6. A polymer-dispersed polyol, characterized by polymerizing a monomer having a polymerizable unsaturated group with the polyoxyalkylene polyol obtained by the production method according to claim 1 as a dispersion medium. Manufacturing method. 7. A method for producing a flexible polyurethane foam by reacting a polyol compound and a polyisocyanate compound in the presence of a foaming agent and a catalyst, wherein the polyol compound is used as the production according to any one of claims 1 to 5. A method for producing a flexible polyurethane foam, which comprises using a polyol mixture containing the polyoxyalkylene polyol obtained by the method and / or the polymer-dispersed polyol obtained by the production method according to claim 6. 8. The total unsaturation of the polyol compound is 0.05.
The method for producing a flexible polyurethane foam according to claim 7, which has a meq / g or less. 9. The method for producing a flexible polyurethane foam according to claim 7, wherein a flexible cell foam is added to produce a flexible polyurethane foam. 10. The method for producing a flexible polyurethane foam according to claim 7, 8 or 9, wherein the flexible polyurethane foam is produced in a closed mold.