JPS6017372B2 - Manufacturing method of polymer polyol - Google Patents

Description

Detailed Description of the Invention The present invention relates to a method for producing a polymer polyol, and particularly to a polymer polyol obtained by polymerizing a monomer having a polymerizable unsaturated group in a polyol having a specific polymerizable unsaturated group. The present invention relates to a manufacturing method of .

Compounds and mixtures obtained by polymerizing monomers with 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. Ru. There are two main types of polymer polyols; one is a polymer polyol obtained by polymerizing monomers in a polyol that does not substantially contain polymerizable unsaturated groups, and the other is a polyol that has polymerizable unsaturated groups. It is a polymer polyol obtained by polymerizing monomers in a polymer. 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, Kosho Hakama 521 Publication No. 343y and Special Publication No. 52-1383
It is described in Publication No. 4, etc.

In the inventions described in these publications, unsaturated polyols are produced by reacting a saturated polyol with an unsaturated polycarboxylic acid such as maleic anhydride and then adding an alkylene oxide, or by reacting a saturated polyol with an allyl glycidyl ether. It is manufactured by adding unsaturated epoxides such as

However, methods using unsaturated acids tend to leave unreacted carboxyl groups, and decomposition of ester groups in unsaturated polyols tends to occur during the production of polymer polyols, resulting in carboxyl groups. There is a problem that the polymer polyol tends to have a high acid value. 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. Furthermore, one of the problems with conventional unsaturated polyols is that the polymerizable unsaturated groups are difficult to copolymerize with monomers.
For example, in an unsaturated polyether ester polyol obtained by reacting a polyoxyalkyleneol with maleic anhydride and then reacting an alkylene oxide such as propylene oxide, the polymerizable unsaturated group is a polyether chain. exists between. Embedded in this polymer chain 2
The incorporated polymerizable unsaturated groups are not easily copolymerized by themselves or with polymerized 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. 2. The present inventor previously developed a nitrogen-containing bond-containing unsaturated polyol obtained by bonding an active hydrogen compound having a polymerizable unsaturated group to a polyol via a polyisocyanate compound, which solved each of the above two problems. Among these, we proposed 3 polymer polyols obtained by polymerizing monomers. However, in this case, if the unsaturated active hydrogen compound has two or more active hydrogens,
Since the unsaturated group may not be located at the end of the polyol, the activity of the unsaturated group is insufficient. On the other hand, if it has one active hydrogen, the number of hydroxyl groups in the 3-polyol is reduced, so there is a sufficient number of unsaturated groups. There was a problem that it could not be installed. Therefore, as a result of further investigation, the present inventor found that an unsaturated active hydrogen compound having at least two active hydrogens and one active hydrogen
An unsaturated polyol for producing a polymer polyol is used in combination with an unsaturated active hydrogen compound, which is bonded to a polyol via a polyisocyanate compound, to obtain a bound nitrogen-containing bond-containing unsaturated polyol. I saw it being used and put it out. Furthermore, it has been found that hydroxyl groups are particularly preferred as active hydrogen compounds. The nitrogen-containing bond-containing unsaturated polyol obtained by bonding an unsaturated polyhydroxy compound to a substantially saturated polyol via a polyisocyanate compound may have an unsaturated group located at the end. Therefore, 3 containing this hydroxyl group
The nitrogen-containing bond-containing unsaturated polyol obtained by bonding the components using a polyisocyanate compound not only has a large total number of unsaturated groups, but also has a large number of unsaturated groups disposed at the terminals. The present invention relates to a method for producing a polymer polyol by polymerizing a monomer in this nitrogen-containing 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. In the method for producing a polymer polyol, the unsaturated polyol is a substantially saturated polyol having at least two hydroxyl groups, an unsaturated polyhydroxy compound having at least two hydroxyl groups and at least one polymerizable unsaturated group. , and one hydroxyl group and at least one
Using a three-component hydroxyl group-containing compound of an unsaturated monohydroxy compound having three polymerizable unsaturated groups and a polycyasoanate compound having at least two isocyanate groups,
This is a method for producing a polymer polyol, which is a nitrogen-containing bond-containing unsaturated polyol obtained by bonding at least two of the three hydroxyl group-containing compounds via the polycysoanate compound.

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, and 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. be. Specifically, glycol, glycerin, trimethylolpropylene, bentaerythritol, sorbitol, dextrose and other polyhydric alcohols, jetanolamine, triethanolamine and other alkaline alcohols, bisphenol A, phenol-formaldehyde condensation other polyhydric phenols, ethylenediamine, diamine/diphenylmethane and other amines,
Examples include polyether polyols to which ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin and other alkylene oxides are added, as well as epoxides such as styrene oxide and glycidyl ether, and polyether polyols such as tetrahydrofuran polymers. Two or more of these can be used together,
In particular, in the case of diols, it is preferable to use them together with triols. Preferred polyether polyols are those having a molecular weight per OH group of 300 to 2,500, particularly those having a molecular weight of 600 to 2,000 per OH group.
Polyether polyols having 2 to 4 hydroxyl groups are preferred.
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 result from a side reaction in the addition reaction of alkylene oxides, particularly propylene oxide.
The present invention can use conventional polyether polyols having negligible amounts of unsaturated groups. As the unsaturated polyhydroxy compound, a compound having at least two hydroxyl groups and at least one polymerizable unsaturated group, such as an unsaturated polyhydric alcohol or an unsaturated polyhydric phenol, is used.

Particularly preferred are unsaturated polyhydric alcohols. This unsaturated polyhydric alcohol contains two or more hydroxyl groups, such as unsaturated polyether polyol, unsaturated polyester polyol, unsaturated polyether ester polyol, etc., in addition to unsaturated polyhydric alcohol in the usual sense. It is a compound. Examples of unsaturated polyhydric alcohols include 2-butene-1,4-diol, 3-butene-1,2-diol, glycerol allyl ether, trimethylolpropane allyl ether, bentaerythritol vinyl ether, and 2,5-dimethyl-3-diol. Hexene-2,5-diol, 1,5-hexadiene-3,4-diol, 1
There are polyhydric alcohols having one or more unsaturated bonds, such as , 4-butynediol, and the like. Unsaturated polyhydric alcohols in a broader sense include unsaturated polyhydric alcohols in a narrower sense.
unsaturated polyether polyols obtained by adding epoxides such as alkylene oxides to unsaturated active hydrogen compounds having at least two active hydrogen atoms, and allyl glycidyl to active hydrogen compounds having at least two active hydrogen atoms. Ether, 1-vinylcyclohexane-3,4-
Unsaturated polyether polyol obtained by adding epoxide, butadiene monoepoxide, and other epoxides having unsaturated groups alone or together with other epoxides.
An unsaturated polybasic acid is reacted with an unsaturated polyester polyol or polyol obtained from a polybasic acid and a polyhydric alcohol containing at least one residue of an unsaturated polybasic acid or an unsaturated polyhydric alcohol in the narrow sense. There are also unsaturated polyether ester polyols obtained by further reacting with epoxide. Of course, the present invention is not limited to these, and compounds having at least two hydroxyl groups and at least one polymerizable unsaturated group can be used. The unsaturated polyhydride having at least two hydroxyl groups according to the present invention.

As the xyl compound, Hirobishi's unsaturated polyhydric alcohols (hereinafter referred to as unsaturated polyhydric alcohols unless otherwise specified) are preferable, and unsaturated polyhydric alcohols in a narrow sense, especially unsaturated polyhydric alcohols having 3 to 10 carbon atoms, are preferable. Polyhydric alcohols are preferred.
As unsaturated polyhydric alcohols other than unsaturated polyhydric alcohols in the narrow sense, those having a relatively low molecular weight are preferred, and the molecular weight is not particularly limited, but 4000 or less, particularly 3000 or less is suitable. The number of hydroxyl groups in the unsaturated polyhydroxy compound is preferably from 2 to 8, particularly from 2 to 4, and particularly preferably from 2 to 4. In addition, the number of polymerizable unsaturated groups in one molecule is not particularly limited, but 1 to
4 is suitable, and 1 to 2 are particularly preferred. The most preferred unsaturated polyhydroxy compounds are 3-butene-1,2-diol or 2-butene-1,4-diol. Unsaturated monohydroxy compounds have one hydroxyl group and at least one
It is a compound having 2 polymerizable unsaturated groups.

The polymerizable unsaturated group is preferably a polymerizable double bond, and the number thereof is preferably one. This hydroxyl group is an alcoholic hydroxyl group or a phenolic hydroxyl group. As unsaturated monohydroxy compounds it is possible to use fin compounds. Examples include unsaturated monools, monoesters of unsaturated monocarboxylic acids and dihydric alcohols, monoesters of unsaturated dihydric alcohols and monocarboxylic acids, phenols having alkenyl side chain groups, and unsaturated polyether mo/ols. Especially as unsaturated monool, carbon number 3-6
Ethylene alcohols are preferred. Specific compounds include, for example, allyl alcohol, 2-buten-1-ol, 3-buten-2-ol, 3-buten-1-ol, and propargyl alcohol. 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. Yes, for example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate,
-Hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, etc. Examples of monoesters of unsaturated dihydric alcohols and monocarboxylic acids include mo/esters of putenediol. Examples of the phenol having an alkenyl side chain group include oxystyrene and hydroxyQ-methylstyrene. Other unsaturated monohydroxy compounds other than those mentioned above include, for example, N-
Examples include methylol acrylamide, monomethylaminoethyl, and methacrylate. Although the molecular weight is not particularly limited, it is preferably 1000 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, allyl alcohol and hydroxyQ-methylstyrene. The polyisocyanate compound is a compound having at least two isocyanate groups (one NCO), and includes aromatic polyisocyanates, aliphatic polyisocyanates, alicyclic polyisocyanates, and others.

Preferably, it is an aromatic bolysocyanate. Specifically, for example, tolylene diisocyanate (TDI)
, diphenylmethane diisocyanate (MDI), polymethylene polyphenyl isocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, hexamethylene diisocyanate, isophorone 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 polyisocyanate compound can react with the above-mentioned compound containing a hydroxyl group, and as a result, a nitrogen-containing bond such as a urethane bond or an allophanate bond is generated.

Usually, this nitrogen-containing bond is a urethane bond. The polycysoanate compound can react with any of the hydroxyl groups of the above three hydroxyl group-containing compounds. This reaction takes place in the presence of a catalyst.
Alternatively, the reaction occurs in the absence of the reaction at room temperature to elevated temperature, but the reaction conditions are not particularly limited. All of the isocyanate groups contained in the polyisocyanate compound react with hydroxyl groups to form nitrogen-containing bonds. It is disadvantageous that the number of isocyanate groups in the reaction system is greater than the number of hydroxyl groups and that the isocyanate groups remain in the final reaction product. That is, in order for the final reaction product to be a nitrogen-containing bond-containing unsaturated polyol, the number of hydroxyl groups in the system must be in excess of the number of isocyanate groups. One isocyanate group in the polyisocyanate compound reacts with a hydroxyl group in one of the three hydroxyl group-containing compounds mentioned above,
At least one other isocyanate group reacts with the hydroxyl group of the same or different hydroxyl group-containing compound. Therefore,
At least two molecules (that is, the same number as the number of isocyanate groups that the polyisocyanate compound has) of the three hydroxyl group-containing compounds are bonded by the polyisocyanate compound. One of the methods for producing a nitrogen-containing bond-containing unsaturated polyol is a method of reacting a mixture of the above three hydroxyl group-containing compounds with a polyisocyanate compound.
In this method, it is thought that compounds having various nitrogen-containing bonds are produced depending on the proportion of each of the three component hydroxyl group-containing compounds and the proportion of the polyisocyanate compound, and among the produced compounds, at least one unsaturated group and A compound having at least two hydroxyl groups is the nitrogen-containing bond-containing unsaturated polyol in the present invention. Among various nitrogen-containing bond-containing unsaturated polyols, those having 1 to 4 unsaturated bonds are preferred, and those having 1 to 2 unsaturated bonds are particularly preferred. Among the impurities generated,
Polyols without unsaturated groups (i.e., reaction products of substantially saturated polyols and polyisocyanate compounds)
Even if the amount produced is large, it does not pose a particular problem unless the viscosity of the reaction system is particularly increased. However, a compound in which an unsaturated polyhydroxy compound and an unsaturated monohydroxy compound are bonded via a polyisocyanate compound, or a reaction product between an unsaturated monohydroxy compound and a polyisocyanate compound contains one hydroxyl group or contains no hydroxyl group. Therefore, it is not preferable for the compound to exist in large amounts. Further, it is also undesirable that a large amount of unreacted unsaturated polyhydroxy compounds and unsaturated monohydroxy compounds remain. However, no problem arises when the substantially saturated polyol remains. In order to satisfy these requirements, it is preferable that the amount of the polyisocyanate compound used is approximately equal to or more than the total number of moles of the unsaturated polyhydroxy compound and the unsaturated monohydroxy compound. Practically speaking, a preferred nitrogen-containing unsaturated polyol is produced by bonding at least one molecule of an unsaturated polyhydroxy compound or an unsaturated monohydroxy compound to one molecule of a saturated polyol via a poly-IJ isocyanate compound.

However, there is no problem if the substantially saturated polyol is in excess and unreacted remains. Even if all of the unsaturated polyhydroxy compounds and unsaturated monohydroxy compounds used are bound to substantially saturated polyols, additional substantially saturated polyols may be present. When one molecule of unsaturated monohydroxy compound is bonded to one molecule of substantially saturated polyol, the number of hydroxyl groups in the resulting nitrogen-containing bond-containing unsaturated polyol decreases by one compared to the number of the original polyol. Therefore, when the saturated polyol is a diol, it becomes an unsaturated monool, and when it is a triol, it becomes an unsaturated diol.
Therefore, it is preferable to limit the amount of the unsaturated monohydroxy compound used relative to the substantially saturated polyol. It is preferable that the amount is equal to or higher than that. Further, as the substantially saturated polyol, it is preferable to use a mixture of a diol and a trivalent or higher polyol, or a trivalent or higher polyol alone or a mixture thereof, rather than a diol alone. The upper limit of the amount of polyisocyanate compound used is determined by the viscosity of the product containing the nitrogen-containing unsaturated polyol. Generally, as the amount of polyisocyanate compound used increases, the viscosity of the product increases. High viscosity products are produced in the next monomer monopolymerization step or in the step of producing polyurethane using the finished polymer polyol.
This causes various problems such as poor mixing. Therefore, its viscosity is usually below 2000P/25°C, especially 1000P/25°C.
- It is preferable that the amount of the polyisocyanate compound used is adjusted so that the temperature is 25°C or less. In the method of reacting the mixture of the three hydroxyl group-containing compounds with the polyisocyanate compound described above, it is preferable that the amount of each component used be limited as described above, but the more preferable amounts used are as follows. It is as follows.

First, the total number of moles of the unsaturated polyhydroxy compound and the unsaturated monohydroxy compound is 0.05 to 2.0 moles, particularly 0.1 to 1 mole, per mole of substantially saturated polyol.
．． It is 0 mole. The combination ratio of unsaturated polyhydroxy compound and unsaturated monohydroxy compound is 1/3 in molar ratio.
~10/1, particularly 1/2 and 8/1 are preferred. The polyisocyanate compound is preferably used in an amount of 1 to 2 mol, particularly 1 to 1.5 mol, per 1 mol of the total amount of the unsaturated polyhydroxy compound and the unsaturated monohydroxy compound. As a method other than the above, at least one component of the three hydroxyl group-containing compounds is reacted in advance with a polyisocyanate compound to form an isocyanate compound having a nitrogen-containing bond and at least one isocyanate group, and this There is a method of reacting with contained compounds.

This method is similar to the prepolymer method used to produce polyurethane from a polyol and a polyisocyanate compound. The hydroxyl group-containing compound to be reacted with the polyisocyanate compound in advance is preferably an unsaturated polyhydroxy compound, an unsaturated monohydroxy compound, or both. For example, a nitrogen-containing bond-containing unsaturated compound having isocyanate groups at both ends can be obtained from an unsaturated dihydroxy compound and a diisocyanate compound, and a nitrogen-containing bond-containing unsaturated compound having an isocyanate group can be obtained from an unsaturated monohydroxy compound and a diisocyanate compound. By reacting these with a substantially saturated polyol, a nitrogen-containing bond-containing unsaturated polyol can be obtained. When these previously isocyanated compounds are used alone, a polyisocyanate compound is additionally required to combine the other with the polyol. Particularly preferred is a method in which both an unsaturated polyhydroxy compound and an unsaturated monohydroxy compound are reacted in advance with a polyisocyanate compound and then reacted with a substantially saturated polyol. The amount of each component used in this method is preferably approximately the same as the conditions when using the mixture of the three hydroxyl group-containing compounds. Of the above two methods, a particularly preferred method is the former method using a mixture of three hydroxyl group-containing compounds.

The latter method yields a relatively controlled product with few impurities, but it is complicated with a large number of steps, and the reaction takes time. On the other hand, the former method not only yields almost the same product as the latter method depending on conditions such as the ratio of raw materials used, but also is extremely easy to produce. The present invention is not limited to the above two methods, and is not limited to these methods as long as similar products can be obtained by other methods. The nitrogen-containing bond-containing unsaturated polyol obtained by the above method may be a single compound, but in many cases it is a mixture of various compounds.

This may include unreacted unsaturated polyhydroxy compounds, unsaturated monohydroxy compounds, substantially saturated polyols, etc., and may also include nitrogen-containing bond-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. In addition, nitrogen-containing bond-containing unsaturated polyols or mixtures containing them are
It can also be used diluted with a polyol, and this polyol is usually a substantially saturated polyol, especially a polyol.
Ether polyols are used, but in some cases unsaturated polyols may also be used. A feature of this nitrogen-containing bond-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 polyhydroxy compounds and unsaturated monohydroxy compounds are unsaturated polyether ester polyols using unsaturated dibasic acids and unsaturated polyether polyols using allyl glycidyl ether as described in the above reference. It is possible to employ an unsaturated group that is more easily polymerized than the unsaturated group in . Moreover, the nitrogen-containing bond-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 it is not limited thereto. Specific monomers include acrylonitrile, styrene, acrylamide,
Preferably, but not limited to, acrylic ester, methacrylic ester, vinyl acetate, etc.
For example, styrene derivatives such as Q-methylstyrene, dimethylstyrene, and halogenated styrene, olefins such as putadiene and isoprene, acrylic derivatives such as methacrylonitrile, butyl acrylate, and benzyl methacrylate, vinyl halides such as vinyl chloride, maleic acid diesters, Unsaturated fatty acid esters such as itaconic acid esters and other monomers can be used. These monomers can not only be used alone. It can also be used 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 with other monomers. A polymerization initiator is usually required to graft-polymerize the above-mentioned monomers onto the nitrogen-containing bond-containing unsaturated polyol.

However, depending on the type of polymerization, 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 typically generates free radicals to initiate polymerization is used. Specifically, for example, azopisisobutyronitrile, benzoyl peroxide, diisopropyl peroxydicarbonate, acetyl peroxide, di-t-butyl peroxide, dicumyl peroxide, dilauriloyl peroxide. , persulfates, etc. Particularly preferred is azobisisobutyronitrile. The polymerization reaction is carried out at a temperature higher than the decomposition temperature of the polymerization initiator, usually from 80 to 160 qo. The monomer used in the leather is preferably about 6% by weight or less, particularly 10 to 5% by weight, based on the total amount of the monomer and the total polyol including the nitrogen-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 be subjected to post-treatment such as removing impurities such as decomposed products of the polymerization initiator. The polymer polyol obtained by 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, the use of acrylonitrile has been almost an essential requirement in conventional methods for producing polymer polyols using unsaturated polyols. In the present invention, although it is possible to use a monomer containing acrylonitrile, a polymer polyol with good dispersion stability can be obtained without using acrylonitrile at all. For example, styrene alone can be used to obtain polymer polyols with good stability. The polymer polyol obtained by the present invention is
It is usually an opaque dispersion.

Polymer polyols using styrene alone are white dispersions, while those using acrylonitrile are colored dispersions. Although a relatively transparent polymer polyol can be obtained depending on the reaction conditions, it is not necessary to use a particularly transparent polymer polyol as a polyurethane raw material, and a dispersion is sufficient. The polymer polyol obtained according to the present invention can be used as a raw material for polyurethane either alone or in combination with an active hydrogen compound such as another polyol that is normally used as a raw material for polyurethane.

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. In particular, polyether polyols are preferred. 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. Polymer polyol obtained by the present invention
The polyol component, which is composed of polyol alone or a mixture of polyols containing polyol, further includes a catalyst, a foam stabilizer, a blowing agent,
Fillers, crosslinkers, extenders, stabilizers, colorants and other additives may also be added. In the case of ordinary polyurethane foam production, catalysts, blowing agents, and foam stabilizers 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 a one-shot method and a prepolymer method can be used. The most suitable polyurethane is polyurethane foam, and the use of polymer polyols results in highly elastic foams, which are excellent, for example, as energy absorbing foams and foams for automobile seats. A feature of the polyurethane foam using the polymer polyol obtained according to 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, the energy-absorbing foam deforms slightly when stress is applied. 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. Although the present invention will be specifically explained using examples above, the present invention is not limited only to these examples.

Reference Examples 1 to 4 Comparative Examples 1 to 4 [Production of nitrogen-containing bond-containing unsaturated polyol] The method for producing the nitrogen-containing bond-containing unsaturated polyol used in the present invention and its production results will be described.

5. Into the autoclave, polyol, unsaturated polyhydric alcohol, and diisocyanate were added as shown in Table 1, and the mixture was kept at 80°C for 5 hours.

In both cases, transparent and viscous liquids were obtained. After confirming the absence of unreacted isocyanate groups by infrared absorption spectrum, the mixture was used as a raw material for producing a polymer polyol. Roughly ship turtle letter tomb sodatsu mi stomach.

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5 Into the autoclave, a predetermined amount of the nitrogen-containing bond-containing unsaturated polyol or ordinary polyoxyalkylene polyol produced in Table 1 shown in Table 2 was charged in advance, and a reduced pressure/nitrogen hawk exchange operation was carried out. After repeating the reaction at a predetermined temperature, the remaining nitrogen-containing unsaturated polyol or usually polyoxyalkylene polyol, a monomer having a polymerizable unsaturated group, and a polymerization initiator were mixed as shown in Table 2. The material was introduced into the autoclave while being rotated at a predetermined speed.

The unreacted polymerizable unsaturated monomer was removed under reduced pressure to obtain the desired polymer polyol. For comparison, when only a normal polyoxyalkylene polyol was used (Comparative Example-5), when styrene was used as a monomer. No separate homogeneous dispersion was obtained.

In addition, as in Comparative Examples 7 and 8, an unsaturated group polyol produced by reacting a normal polyoxyalkylene polyol with maleic acid was used (Comparative Example-6), and an unsaturated polyhydroxy compound was used only as in Comparative Examples 7 and 8. However, when only a small amount of an unsaturated monohydroxy compound was used as in Comparative Example 19, and styrene was used as a monomer, only particles with coarse particle diameters were produced. Ship ship Rushimaki old man rudder Tatsumitsuchi ya ○) Yamato \no go; Ototei Momogi gogomomori l Fukame Mikito etc. Mikumo car of three days.

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0 0 Tomi; Effect; Ryozari A flexible urethane foam was manufactured using the polymer polyol prepared by the experiment.

For comparison, a case will be described in which foaming is performed using polyoxypropylene triol (polyol B) having a molecular weight of 3000. Polyol or polymer polyol 10
Gunship, silicone L5201. Shigeru, Dabco3 Beni V (1 triethylene diamiso, 3 dipropylene glycol) 0
．． Total, T-9 (stannous octylate) 0.3g, water 4.
Table 3 shows the results of foaming by mixing TDI-80 (toluene diisocyanate) to an index of 105.

It can be seen that, compared to Comparative Example 10, the form properties of Application Examples 1 and 2 are superior, especially in terms of ILD.

Table 3 Application Examples 3 to 5 Comparative Examples 11 and 12 High elasticity foams were mold-foamed using the polymer polyols produced in Examples 1, 2, and 3 and Comparative Example 6 shown in Table 2.

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 the case of Comparative Example 11) 16 female, polyol 240g Silicone L53054
．． Crane, Dabo 3 Maru V2. Tsuru, water 1 Shigeru and TDI-80/
PAPI135 (Chemical Upjohn, crude phenylene diisocyanate) = 80/20 mixed isocyanate,
Mix so that the index is 105 and quickly
At 0:00 AM, the mold was placed in a 400 x side x 40 x 10 x 10 mm aluminum mold, 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, compared to Comparative Example 11, the foam physical properties of 0 using the polymer polyols of Examples 1, 2, and 3 are particularly excellent in terms of ILD.

In addition, in Comparative Example 16, the reaction was slower than in the Application Example, and the mold could not be removed in 10 minutes at room temperature, so it was allowed to stand for 15 minutes. It was found that the ILD of the foam was inferior (ILD, compression set haze). Table 4

Claims (1)

[Claims] 1. A method for producing a polyol by polymerizing a monomer having a polymerizable unsaturated group in a polyol containing an unsaturated polyol, wherein the unsaturated polyol is a substantially saturated polyol having at least two hydroxyl groups. polyol, an unsaturated polyhydroxy compound having at least two hydroxyl groups and at least one polymerizable unsaturated group, and an unsaturated monohydroxy compound having one hydroxyl group and at least one polymerizable unsaturated group. A nitrogen-containing bond obtained by using a component hydroxyl group-containing compound and a polyisocyanate compound having at least two isocyanate groups, and bonding at least two of the three component hydroxyl group-containing compounds via the polyisocyanate compound. A method for producing a polymer polyol, characterized in that the polyol contains an unsaturated polyol. 2. The manufacturing method according to claim 1, wherein the nitrogen-containing bond-containing unsaturated polyol is produced by reacting a mixture of three components of hydroxyl group-containing compounds with a polyisocyanate compound. 3. The method of claim 1, wherein the substantially saturated polyol is a polyether polyol.