JPS595608B2 - Method for producing polymer polyol - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a polymer polyol, particularly a polymer characterized by polymerizing a monomer having a polymerizable unsaturated group in a polyol having a specific polymerizable unsaturated group. This invention relates to a method for producing polyol.

Compounds and mixtures obtained by polymerizing monomers having polymerizable unsaturated groups in polyols such as polyether polyols and polyester polyols are called polymer polyols, and are used as raw materials for polyurethanes such as polyurethane foams and polyurethane elastomers.

There are two types of polymer polyols, one of which is a polymer polyol obtained by polymerizing monomers in a polyol that does not substantially contain polymerizable unsaturated groups.
Others are polymer polyols obtained by polymerizing monomers in polyols having polymerizable unsaturated groups. Although the latter polymer polyol is considered to be superior in terms of dispersion stability, etc., it still has aspects that cannot be said to be sufficient in terms of ease of production and economic efficiency. The present invention relates to the latter type of polymer polyol. Regarding polymer polyols obtained by polymerizing monomers having polymerizable unsaturated groups (hereinafter referred to as monomers) in polyols having polymerizable unsaturated groups (hereinafter referred to as unsaturated polyols), for example, Japanese Patent Publication No. 52-3439 Publication No. and Special Publication No. 52-13
It is described in Publication No. 834, etc.

In the inventions described in these publications, unsaturated polyols can be produced by reacting a saturated polyol with an unsaturated polycarboxylic acid such as maleic anhydride and then adding xylene oxide to the anhydride, or by reacting a saturated polyol with allyl glycidyl ether, etc. It is manufactured by adding unsaturated epoxide. However, methods using unsaturated acids tend to reduce the acid value because unreacted carboxyl groups tend to remain, and carboxyl groups are easily generated due to decomposition of ester groups in unsaturated polyols during the polymer polyol production stage. There is a problem that it tends to become a high polymer polyol. Use of a polymer polyol with a high acid value tends to interfere with the urethanization reaction during polyurethane production, making it impossible to obtain a good polyurethane. In addition, one of the problems with conventional unsaturated polyols is that
The first problem is that the polymerizable unsaturated group is difficult to copolymerize with the monomer.

For example, in unsaturated polyether ester polyols obtained by reacting polyoxyalkylene polyols with maleic anhydride and then reacting them with alkylene oxides such as propylene oxide, the polymerizable unsaturated groups are present between the polyether chains. do. The polymerizable unsaturated groups embedded in the polymer chain are not easily copolymerized by themselves or with other monomers. Therefore, it is considered that the polymerizable unsaturated group in the unsaturated polyol is more easily copolymerized with the monomer when it is present at or near the end of the polyol. The present inventor conducted research and examination to find an unsaturated polyol that solved the above problems, and as a result, discovered a new unsaturated polyol, and eventually discovered a new polymer polyol.

This unsaturated polyol comprises a substantially saturated polyol having at least two hydroxyl groups, an unsaturated active hydrogen compound having one active hydrogen and at least one polymerizable unsaturated group, and a polyisocyanate compound. It is a nitrogen-containing bonded gold-containing unsaturated polyol obtained by bonding through a nitrogen-containing bond. The present invention relates to a method for producing a polymer polyol obtained by polymerizing monomers in this unsaturated polyol, that is,
A method for producing a polymer polyol by polymerizing a monomer having a polymerizable unsaturated group in a polyol containing an unsaturated polyol alone or a mixture thereof and having an average number of hydroxyl groups of 1.7 or more. The saturated polyol is a substantially saturated polyol having at least two hydroxyl groups, an unsaturated active hydrogen compound having one active hydrogen and at least one polymerizable unsaturated group, and at least two isocyanates. This is a method for producing a polymer polyol, characterized in that it is a nitrogen-containing bonded gold-containing unsaturated polyol obtained by bonding via a polyisocyanate compound having a group. Nitrogen-containing bonds are generated by the reaction between isocyanate groups and active hydrogen-containing groups,
Examples include urethane bonds, urea bonds, biuret bonds, and allophanate bonds.

When the active hydrogen-containing group is a hydroxyl group, urethane bonds are mainly formed, and when it is an amino group, urea bonds are mainly formed. Other active hydrogen-containing groups include -COOH, -S
There are H, etc. This nitrogen-containing bond is generated by the reaction between the hydroxyl group in the substantially saturated polyol and the isocyanate group of the polyisocyanate compound, and the one generated by the reaction between one active hydrogen-containing group in the unsaturated active hydrogen compound and the polyisocyanate group. Some are generated by reaction with isocyanate groups of compounds. It is also possible that substantially saturated polyols or unsaturated active hydrogen compounds are bonded to each other via a polyisocyanate compound. Unsaturated active hydrogen compound is 1
It is a compound having active hydrogen atoms and at least one polymerizable unsaturated group.

Examples of the group containing active hydrogen include a hydroxyl group, an imino group, a carboxyl group, an SH group, and a hydroxyl group is particularly preferred. Further, the polymerizable unsaturated group is preferably a polymerizable double bond, and the number of polymerizable unsaturated groups in one molecule is preferably one. That is, a preferred unsaturated active hydrogen compound is an unsaturated monohydroxy compound having one polymerizable double bond. This hydroxyl group is an alcoholic hydroxyl group or a phenolic hydroxyl group. Various compounds can be used as unsaturated monohydroxy compounds. For example, unsaturated monools, monoesters of unsaturated monocarboxylic acids and dihydric alcohols, monoesters of unsaturated dihydric alcohols and monocarboxylic acids, phenols with alkenyl side groups, unsaturated polyether monoesters, There are oars, etc. As the unsaturated monol, particularly preferred is an ethylene alcohol having 3 to 6 carbon atoms. Specific compounds include, for example, allyl alcohol, 2-buten-1-ol, 3-buten-2-ol, 3-buten-1-ol, and propargyl alcohol. Examples of monoesters of unsaturated monocarboxylic acids and dihydric alcohols include monoesters of acrylic acid, methacrylic acid, crotonic acid, itaconic acid and other unsaturated monocarboxylic acids and ethylene glycol, propylene glycol, butylene glycol and other dihydric alcohols. esters, such as 2-hydroxyethyl acrylate, 2
Examples include -hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, and 4-hydroxybutyl acrylate. Examples of the phenol having an alkenyl side chain group include oxystyrene and hydroxy α-methylstyrene. Examples of monoesters of unsaturated dihydric alcohols and monocarboxylic acids include monoesters of butenediol. Examples of other unsaturated monohydroxy compounds and active hydrogen compounds other than those mentioned above include N-methylolacrylamides and monomethylaminoethyl methacrylate. Although the molecular weight is not particularly limited, it is preferably 1,000 or less, particularly 500 or less. Among these, particularly preferred compounds are monoesters of acrylic acid or methacrylic acid and ethylene glycol, propylene glycol or butylene glycol, or allyl alcohol and human
-Methylstyrene. As the substantially saturated polyol, various high molecular weight polyols used as raw materials for polyurethane can be used. for example,
Typical examples include polyether polyols and polyester polyols, as well as hydrocarbon polymers having hydroxyl groups at the ends. Preferred are polyether polyols, such as polyether polyols prepared by adding alkylene oxide to active hydrogen-containing compounds such as polyhydroxy compounds, phosphoric acid, and amines, and polyether polyols made of cyclic ether polymers.
Specifically, glycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, dextrose and other polyhydric alcohols, diethanolamine, triethanolamine and other alkanolamines, bisphenol A, phenol-formaldehyde condensates, and other polyhydric alcohols. Polyether polyols made by adding ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin and other alkylene oxides, and epoxides such as styrene oxide and glycidyl ether to phenol, ethylene diamine, diaminodiphenylmethane and other amines, and tetrahydrofuran polymers. There are polyether polyols such as Two or more of these can be used in combination, and in the case of diols, it is particularly preferable to use them in combination with triols. Preferred polyether polyols are polyether polyols having a molecular weight of 300 to 2,500 per OH group, and particularly preferred are polyether polyols having a molecular weight of 600 to 2,000 per OH group and a number of hydroxyl groups of 2 to 4. This high molecular weight polyol is a polyol having substantially no polymerizable unsaturated groups.

The above-mentioned polyether polyols and polyester polyols usually do not have polymerizable unsaturated groups in their constituent compounds (for example, polyhydroxy compounds or alkylene oxides), or even if they do have them, they are polymerized during polyol production. If so, it is considered that it does not contain a polymerizable unsaturated group. However, in some cases, unsaturated groups may be generated during polyol production due to side reactions.
For example, a normal polyether polyol produced by adding an alkylene oxide that does not have a polymerizable unsaturated group to an active hydrogen-containing compound that does not have a polymerizable unsaturated group may contain a small amount of unsaturated groups. Are known. This is believed to occur as a side reaction in the addition reaction of alkylene oxides, especially propylene oxide.
The present invention can use conventional polyether polyols having negligible amounts of unsaturation.
The polyisocyanate compound is a compound having at least two isocyanate groups (-NCO), such as aromatic polyisocyanate, aliphatic polyisocyanate,
There are alicyclic polyisocyanates and others.

Preferably, it is an aromatic polyisocyanate. Specifically, for example, tolylene diisocyanate (TDI)
, diphenylmethane diisocyanate (MDI), polymethylene polyphenyl isocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, hexamethylene diisocyanate, isoborone diisocyanate, and the like. As these isocyanate compounds, it is also possible to use modified polyisocyanate compounds that have been modified using compounds having active hydrogen such as polyhydric alcohols and amines, or using other methods. The method for producing the nitrogen-containing unsaturated polyol using these raw materials is not particularly limited. However, preferred methods include a method in which an isocyanate compound is added to a mixture of an unsaturated active hydrogen compound and a substantially saturated polyol and reacted, and a method in which an unsaturated active hydrogen compound and a polyisocyanate compound are reacted to form an isocyanate compound. This method involves producing a compound having a nato group and reacting it with a substantially saturated polyol. The former method is the simplest method and is the most preferred method because it can yield the desired nitrogen-containing, bonded, gold-containing unsaturated polyol. In a method in which a polyisocyanate compound is added to a mixture of an unsaturated active hydrogen compound having one active hydrogen and a substantially saturated polyol and reacted, various nitrogen-containing compounds are thought to be produced.

That is, one isocyanate group in the polyisocyanate compound can react with one active hydrogen in the active hydrogen compound or one of the two or more hydroxyl groups of the polyol. Therefore, it is conceivable that two or more isocyanate groups in one molecule of a polyisocyanate compound may react only with the active hydrogen compound or only with the polyol,
A compound in which at least one is an active hydrogen compound and at least one other is reacted with a polyol is the nitrogen-containing gold-containing unsaturated polyol in the present invention. For example, when a diisocyanate compound is added to a mixture of an unsaturated monohydroxy compound having one polymerizable unsaturated group and a polyether triol and the mixture is reacted, the most preferable nitrogen-containing gold-containing unsaturated polyol is diisocyanate. One isocyanate group of the compound reacts with the hydroxyl group of the unsaturated monohydroxy compound, and the other isocyanate group reacts with one hydroxyl group of the polyether triol, resulting in two urethane bonds and one polymerizable unsaturated group. It is a diol having In addition, there are compounds in which two molecules of unsaturated monohydroxy compound react with one molecule of diisocyanate compound, and two or three hydroxyl groups of polyether triol each react with one molecule of diisocyanate compound, and each A compound having 4 or 6 urethane bonds and 2 to 3 unsaturated groups in which the other isocyanate group of the isocyanate compound has reacted with an unsaturated monohydroxy compound, produced from a polyether triol and a diisocyanate compound Compounds without unsaturated groups and compounds with various other urethane bonds are produced. Further, unreacted unsaturated monohydroxy compounds and polyether triols may remain. Among these, the presence of a compound having at least two hydroxyl groups produced from a polyether triol and a diisocyanate compound and unreacted polyether triol poses almost no problem even if the amount thereof is large. However, a large amount of a compound having no hydroxyl group or a compound having only one hydroxyl group is unsuitable as a raw material for polyurethane. Similarly, when polyols or polyisocyanate compounds other than those mentioned above are used as raw materials, it is not preferable that many compounds having one or less hydroxyl groups are produced. Therefore, the average number of hydroxyl groups in the produced nitrogen-containing gold-containing unsaturated polyol or the polyol mixture containing the same is required to be 1.7 or more, preferably 2 or more. Therefore, as the raw material polyol, it is preferable to use a mixture of a diol and a polyol with a valence of 3 or more, or a polyol with a valence of 3 or more, singly or in a mixture, rather than using only a diol. The amount of the unsaturated active hydrogen compound and polyisocyanate compound to be used relative to the substantially saturated polyol is not particularly limited as long as the average number of hydroxyl groups in the product is 1.7 or more, particularly 2 or more.

Preferably, on average 1.5 per molecule of polyol
The amount used is such that not more than 1, especially not more than 1 unsaturated active hydrogen compound is bound. The lower limit is not particularly limited, but is 0.
About 1 is preferable. Furthermore, if we take polyether polyol and unsaturated monohydroxy compound which are commonly used as an example, for 100 parts by weight of polyether polyol,
Preference is given to using 2 to 20 parts by weight of unsaturated monohydroxy compound. Further, it is preferable to use the polyisocyanate compound in an amount of approximately equal mole or more, particularly 1 to 2 times the mole of the unsaturated active hydrogen compound. In this case, a further excess of the polyisocyanate compound is less of a problem, as long as the reaction products of the polyol and the polyisocyanate compound do not become particularly undesirable, for example, unless the viscosity of the product becomes too high. . Next, a method will be described in which an unsaturated active hydrogen compound and a polyisocyanate compound are reacted in advance and then reacted with a substantially saturated polyol.

Unsaturated active hydrogen compound and polyisocyanate compound (When these substances are reacted, a compound having one nitrogen-containing bond and one or more isocyanate groups is produced. This unsaturated group and at least one isocyanate group are formed.) When the compound is reacted with a substantially saturated polyol, the desired nitrogen-containing bound gold-containing unsaturated polyol can be obtained. Both must have one isocyanate group, preferably unsaturated active hydrogen compound 1
It is preferable to react the polyisocyanate compound in an amount of 1 mol or more per mol. Further, the excess of the polyisocyanate compound is not limited as long as it does not cause particular inconvenience when reacted with a polyol as in the above method. However, it is not preferable that the unsaturated active hydrogen compound becomes excessive and a large amount of products having no isocyanate groups are produced.
This product is then reacted with a substantially saturated polyol to cause the isocyanate groups of the product to react with the hydroxyl groups of the polyol. Therefore, when one molecule of this product reacts with one molecule of polyol, a compound having the number of hydroxyl groups one less than the number of hydroxyl groups in the polyol is produced. As in the previous method, it is necessary that the average number of hydroxyl groups in this product be at least 1.7, especially at least 2.0. A feature of this method is that a nitrogen-containing, bonded, gold-containing unsaturated polyol with less impurities can be obtained compared to the above-mentioned method. The nitrogen-containing gold-containing unsaturated polyol obtained by the above method may be a single compound, but in most cases it is a mixture of various compounds.

This may include unreacted unsaturated active hydrogen compounds, substantially saturated polyols, and may include nitrogen-containing gold-containing polyols containing no unsaturated groups. This mixture can be applied as is to the next polymerization operation, or it can be applied after further removal of removable impurities. Also,
Nitrogen-containing gold-containing unsaturated polyols or mixtures containing them can also be used diluted with a polyol, and this polyol is usually a substantially saturated polyol, especially a polyether polyol, but in some cases may be an unsaturated polyol. A feature of this nitrogen-containing bonded gold-containing unsaturated polyol is that the unsaturated groups contained therein are easily copolymerized with monomers. This is because the unsaturated group is located at or near the end of the molecular chain of the polyol. In addition, unsaturated active hydrogen compounds having active hydrogen, such as unsaturated monohydroxy compounds,
An unsaturated group that is more easily polymerized than the unsaturated group in the unsaturated polyether ester polyol using an unsaturated dibasic acid or the unsaturated polyether polyol using allyl glycidyl ether described in the above-mentioned references can be used. Moreover, the nitrogen-containing bonded gold-containing unsaturated polyol of the present invention is characterized in that it can be produced more easily than these known unsaturated polyols. As the monomer having a polymerizable unsaturated group, a monomer having one polymerizable double bond is usually used, but the monomer is not limited thereto.

Preferred examples of monomers include acronitrile, styrene, acrylamide, acrylic esters, methacrylic esters, vinyl acetate, etc., but are not limited to these. For example, α-methylstyrene, dimethylstyrene, halogenated styrene, etc. styrene derivatives, olefins such as butadiene and isoprene, acrylic derivatives such as methacrylonitrile, butyl acrylate and benzyl methacrylate, vinyl halides such as vinyl chloride, unsaturated fatty acid esters such as maleic acid diester and itaconic acid diester, and other monomers. can be used. These monomers can be used not only alone, but also in combination with other monomers to form a copolymer. The most preferred monomers are acrylonitrile alone, styrene alone, acrylonitrile and styrene, or a combination of acrylonitrile or styrene-based monomers with other monomers. A polymerization initiator is usually required to graft-polymerize the above-mentioned monomer onto the nitrogen-containing gold-containing unsaturated polyol.

However, in some cases, graft polymerization can also be carried out using heat or radiation without using a polymerization initiator. As the polymerization initiator, a type of polymerization initiator that generates free radicals to initiate polymerization is used. Specifically, for example, azobisisobutyronitrile, benzoyl peroxide, diisopropyl peroxydicarbonate, acetyl peroxide, di-t-butyl peroxide, dicumyl peroxide, dilauriloyl peroxide, persulfate, etc. There is. Particularly preferred is azobisisobutyronitrile. The polymerization reaction is carried out at a temperature higher than the decomposition temperature before the start of polymerization, usually from 80 to 160°C.

The amount of the monomer used is preferably about 60% by weight or less, particularly 10 to 50% by weight, based on the total amount of the monomer and the entire polyol including the nitrogen-containing gold-containing unsaturated polyol used.
The polymer polyol obtained after the completion of the polymerization reaction can be used as it is as a raw material for polyurethane, but it may also be subjected to post-treatment such as removing impurities such as decomposed products of the polymerization initiator. The polymer polyol of the present invention is characterized by good dispersion stability.

Conventional polymer polyols using saturated polyols did not have sufficient dispersion stability, and it was necessary to use acrylonitrile, which has good dispersion stability, as one of the monomer components. That is, a good polymer polyol could not be obtained unless the majority or all of the monomers were acrylonitrile. Furthermore, in most conventional methods for producing polymer polyols using unsaturated polyols, the use of acrylonitrile has been an essential requirement. In the present invention, a monomer containing acrylonitrile can of course be used, but a polymer polyol with good dispersion stability can be obtained without using acrylonitrile at all. For example, Styrene 7 alone can be used to obtain a polymer polyol with good stability. The polymer polyols of this invention are generally opaque dispersions.

Polymer polyols using styrene alone are white dispersions, while those using acrylonitrile are colored dispersions. Depending on reaction conditions 5 and the like, a relatively transparent polymer polyol can be obtained, but it is not necessary to use a particularly transparent polymer polyol as a polyurethane raw material, and a dispersion is sufficient. The obtained polymer polyol of the present invention is used as a raw material for polyurethane either alone or in combination with an active hydrogen compound used as a raw material for solid polyurethane such as other polyol 4.
The active hydrogen compound to be combined with this polymer polyol is preferably a polyhydroxy compound containing at least two hydroxyl groups, such as a polyether polyol or a polyester polyol. Particularly preferred are polyether polyols. Polyether polyols include polyether polyols produced by adding alkylene oxide to polyhydric alcohols, amines, and other so-called initiators, and those included in the range referred to as substantially saturated polyols, such as tetrahydrofuran polymers. It is. The polyol component consisting of the polymer polyol of the present invention alone or a mixture of polyols containing the same may further include a catalyst, a foam stabilizer, a blowing agent, a filler, a crosslinking agent,
Chain extenders, stabilizers, colorants and other additives may also be added. In the case of ordinary polyurethane foam production, catalysts, blowing agents, and foaming agents are often considered essential components. Suitable catalysts include amine catalysts such as tertiary amines and organometallic compounds such as organotin compounds. Water, trichlorofluoromethane, methylene chloride, and other halogenated hydrocarbons are suitable as blowing agents. As the foam stabilizer, an organosilicon compound-based surfactant is suitable. Other raw materials for polyurethane are polyisocyanate compounds as described above. Polyurethane is obtained by reacting the above polyol component with this polyisocyanate component. As a method for producing polyurethane, conventional methods such as one shot method and prepolymer one method can be used. As the polyurethane, polyurethane foam is most suitable, and the use of polymer polyols results in highly elastic foams, which are excellent, for example, as energy absorbing foams and foams for seats in automobiles and the like. A feature of the polyurethane foam using the polymer polyol of the present invention is that a harder foam can be obtained compared to polyurethane foam using the conventional polymer polyol. This stiff foam is a more desirable physical property for energy absorbing foam applications. That is, there is less deformation when stress is applied to the energy absorbing foam. Furthermore, since it has a nitrogen-containing bond, the reaction rate in urethanization can be improved, and the use of amine catalysts can be reduced. EXAMPLES The present invention will be specifically explained below using Examples, but the present invention is not limited only to these Examples.

Reference Examples 1 to 6 [Method for producing nitrogen-containing bound gold-containing unsaturated polyol] The production method and the production results for the nitrogen-containing alloy-containing unsaturated polyol used in the present invention will be described.

As shown in Table 1, a polyol, an unsaturated active hydrogen compound, and dicyanate were charged into a 5-t autoclave and held at 80° C. for about 4 hours.

In both cases, transparent and slightly viscous liquids were obtained.

After confirming the absence of unreacted isocyanate groups by infrared absorption spectrum, the product was used as a raw material for producing a polymer polyol. Examples 1 to 9 Comparative Examples 1 to 2 A method for producing a polymer polyol composition according to the present invention and its production results will be described.

In a 5 ton autoclave, the specified amount shown in Table 2,
After charging the nitrogen-containing gold-containing unsaturated polyol or ordinary polyoxyalkylene polyol produced in Table 1 in advance and repeating the vacuum nitrogen purging operation at a predetermined temperature,
As shown in Table 2, a mixture of the remaining nitrogen-containing gold-containing unsaturated polyol or normal polyoxyalkylene polyol, a monomer having a polymerizable unsaturated group, and a polymerization starter is stirred at a predetermined speed. was introduced into the autoclave.

Unreacted polymerizable unsaturated monomers were removed under reduced pressure to obtain the desired polymer polyol. As a comparison, when using only a regular polyoxyalkylene polyol, a separated and homogeneous dispersion was not obtained when styrene was used as the monomer.

In addition, when a polyol containing an unsaturated group produced by reacting a normal polyoxyalkylene polyol with maleic acid was evaluated for comparison, an emulsion with a white appearance was obtained, but the dispersion particles I found that it was a little rough. 1) Polyollipolyol A Polyoxypropylene ethylene triol polyol E Equimolar anti-L1 product of polyol A and maleic acid and polyol A (50/50) mixture 2) AIBN: Azobisisobutyronitrile Reference Examples 7, 8, Comparative Reference Example 1 A flexible urethane foam was manufactured using the polymer polyols manufactured in Examples 6 and 7 in Table 2.

For comparison, a case in which only polyoxypropylene triol (polyol B) having a molecular weight of 3000 is used and foamed is also described. Polyol or polymer polyol 1009, silicone L52Ol. 2g, Dab
cO33LV Polyol D A mixture of the polyol produced in Reference Example-1 and polyol A (50/50) (1 part triethylene diamine, 3 parts dipropylene glycol)
) 0.39, T-9 (stannous octylate) 0.39,
4.0g water, TDI-80 (toluene isocyanate)
Table 3 shows the results of foaming by stirring and mixing to obtain an index of 105.

It can be seen that compared to Comparative Reference Example 1, the formal physical properties of Reference Examples 7 and 8 are superior, especially regarding LLD. Reference Examples 9 to 11, Comparative Reference Examples 2 to 3 The polymer polyols produced in Examples 1, 2, and 3 and Comparative Example 2 shown in Table 2 were used to mold foam into highly elastic foams.

For comparison, a case of foaming using polyoxypropylene ethylene triol (polyol A) having a molecular weight of 5000 will also be described.

Polymer polyol (polyol A in case of Comparative Reference Example-2) 1609, polyol 240g, silicone L5
3O54.49, DabcO33L2.49, water 12y
&CTDI-80/PAPI135 (Chemical addition, crude phenylene diisocyanate) = 80/20 mixed isocyanate was mixed to give an index of 105, and the temperature was quickly adjusted to 50°C. Aluminum 400
The molded product was put into a mold of m clouds x 4 Oou x 100 U1, and after being left at room temperature for 10 minutes, the mold form was taken out.

The physical properties of the foam are shown in Table 4. It can be seen that the physical properties of the foams using the polymer polyols produced in Examples 1, 2, and 3 are excellent, especially in terms of ILD, as compared to Comparative Reference Example-2.

Claims (1)

[Scope of Claims] 1 A polymer polyol is obtained by polymerizing a monomer having a polymerizable unsaturated group in a polyol that is an unsaturated polyol alone or a polyol mixture containing the unsaturated polyol and has an average number of hydroxyl groups of 1.7 or more. In the method for producing an unsaturated polyol, an unsaturated active hydrogen compound having one active hydrogen and at least one polymerizable unsaturated group is added to a substantially saturated polyol having at least two hydroxyl groups. 1. A method for producing a polymer polyol, which is a nitrogen-containing bond-containing unsaturated polyol obtained by bonding via a polyisocyanate compound having at least two isocyanate groups. 2. The method of claim 1, wherein the substantially saturated polyol is a polyether polyol. 3. The method according to claim 1, wherein the unsaturated active hydrogen compound is an unsaturated monohydroxy compound. 4. The nitrogen-containing bond-containing unsaturated polyol alone or the polyol mixture containing the same is obtained by adding a polyisocyanate compound to a mixture of a substantially saturated polyol and an unsaturated active hydrogen compound and reacting the mixture. The method according to claim 1.