JPS6011965B2 - 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, and in particular to a method for producing a polyO-mer polyol by polymerizing a monomer having a polymerizable unsaturated group in a specific unsaturated polyol. .

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 foterms 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. A monomer having a polymerizable unsaturated group (hereinafter referred to as a monomer) in a polyol having a polymerizable unsaturated group (hereinafter referred to as an unsaturated polyol)
Regarding polymer polyols obtained by polymerizing
It is described in Publication No. 3834, etc.

In the inventions described in these publications, unsaturated polyols are produced by reacting saturated polyols with unsaturated polycarboxylic acids such as maleic anhydride and then adding alkylene oxide, or by reacting saturated polyols with allyl glycidyl ether, etc. It is manufactured by adding unsaturated epoxide. However, methods using unsaturated acids tend to reduce the acid value due to the fact that unreacted carboxyl groups tend to remain, and that the ester groups of unsaturated polyols tend to decompose and form carboxyl groups 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, conventionally known unsaturated polyols cannot be used satisfactorily due to technical problems and economic reasons. As a result of various research studies to solve the above-mentioned problems, the present inventors have discovered an unsaturated polyol or A polymer polyol obtained by polymerizing a monomer having a polymerizable unsaturated group in a polyol mixture containing it has been developed.The present invention relates to a method for producing this polymer polyol. In a method for producing a liquid polymer polyol by polymerizing a monomer having a polymerizable unsaturated group in a polyol or a polyol mixture containing the same, the unsaturated polyol or the polyol mixture containing the same contains at least two active hydrogen atoms. an unsaturated active hydrogen compound having at least one polymerizable unsaturated group, a polyisocyanate compound having at least two isocyanate groups, and a substantially saturated polyether polyol having at least two hydroxyl groups;
or a polyol mixture containing the same, or an unsaturated active hydrogen compound in which at least two of the active hydrogens are hydroxyl groups, and the polyisocyanate compound. A method for producing a polymer polyol, which is a mixture of a nitrogen-containing bond-containing unsaturated polyol and the substantially saturated polyether polyol. The nitrogen-containing bonds in unsaturated polyols are produced by the reaction between isocyanate groups and active hydrogen-containing groups.

Examples of the active hydrogen-containing group include a hydroxyl group, an amino group, a carboxylic acid group, and a -SH group, with a hydroxyl group being particularly suitable. Specific nitrogen-containing bonds include, for example, urethane bonds, urea bonds, bullet bonds, allophanate bonds, and urethane bonds and urea bonds are particularly suitable. This nitrogen-containing bond is present in polyisocyanate compounds having at least two isocyanate groups and active hydrogen compounds having at least two active hydrogens, i.e. unsaturated active hydrogen compounds and/or substantially saturated polyethers. polyol,
It is caused by a reaction with Since a polyisocyanate compound is used, at least two nitrogen-containing bonds are generated. The polymerizable unsaturated group derived from the unsaturated active hydrogen compound is carbon-
A carbon double bond or triple bond that can be polymerized by itself or with other polymerizable unsaturated groups. The nitrogen-containing bond-containing unsaturated polyol has at least two hydroxyl groups. Therefore, when the unsaturated active hydrogen compound contains at least two hydroxyl groups, a nitrogen-containing bond-containing unsaturated polyol can be obtained from the unsaturated active hydrogen compound and the polyisocyanate compound. However, since it is usually difficult to obtain an unsaturated polyol with a low viscosity using these alone, it is necessary to dissolve or disperse them in a substantially saturated polyether polyol before use. If the unsaturated active hydrogen compound does not contain two or more hydroxyl groups, a compound having at least two hydroxyl groups is required. Therefore, in the present invention, the nitrogen-containing bond-containing unsaturated polyol is preferably produced from an unsaturated active hydrogen compound (which may contain a hydroxyl group), a substantially saturated polyether polyol, and a polyisocyanate compound. Ru. Each of these three raw materials may be used alone or in combination of two or more. An unsaturated active hydrogen compound is a compound having at least two active hydrogens and at least one unsaturated group as described above.

Preferably it is an unsaturated polyol having at least two hydroxyl groups. Hereinafter, this unsaturated polyol will be mainly referred to as an unsaturated polyhydric alcohol to distinguish it from others. Therefore, the meaning of unsaturated polyhydric alcohol in the present invention is broader than the usual meaning as shown below. Examples of unsaturated active hydrogen compounds other than unsaturated polyhydric alcohols include unsaturated polybasic acids, unsaturated amines, unsaturated polythiols, or active hydrogen-containing groups such as hydroxyl groups, carboxyl groups, amino groups, and monoSH groups. There are unsaturated compounds containing one or more types of different types. Examples of unsaturated active hydrogen compounds other than unsaturated polyhydric alcohols include maleic acid,
These include fumaric acid, itaconic acid, acrylamide, and paravinylaniline. Unsaturated polyhydric alcohols are compounds containing two or more hydroxyl groups, such as unsaturated polyether polyols, unsaturated polyester polyols, and unsaturated polyether ester polyols, in addition to unsaturated polyhydric alcohols in the usual sense. .

Examples of unsaturated polyhydric alcohols in the narrow sense include 2-butene-1,4-diol, 3-butene-1,2-diol, glycerol allyl ether, trimethylolpropane allyl ether, bentaerythritol vinyl ether, 2,5-dimethyl-3-hexene-2・5-diol, 1,5-hexadiene-3,4-diol, 1.
There are polyhydric alcohols having one or more unsaturated bonds, such as 4-butine diol. Unsaturated polyhydric alcohols in a broader sense include unsaturated polyhydric alcohols in a narrower sense and unsaturated polyesters obtained by adding epoxides such as alkylene oxides to other unsaturated active hydrogen compounds having at least two active hydrogens. -terpolyol, at least 2
Allyl glycidyl ether, 1-vinylcyclohexane-3,4-epoxide, putadiene monoepoxide, and other unsaturated group-containing epoxides are added to active hydrogen compounds having active hydrogens alone or together with other epoxides. unsaturated polyether polyol obtained by
Unsaturated polyester polyol obtained from a polybasic acid and polyhydric alcohol containing at least one residue of an unsaturated polybasic acid or an unsaturated polyhydric alcohol in the narrow sense, or after reacting a polyol with an unsaturated polybasic acid Furthermore, there are unsaturated polyether ester polyols obtained by reacting eboxide. 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. As the unsaturated active hydrogen compound having at least two active hydrogens in the present invention, unsaturated polyhydric alcohols in the broad sense described above (hereinafter referred to as unsaturated polyhydric alcohols unless otherwise specified) are preferable, particularly unsaturated polyhydric alcohols in the narrow sense. saturated polyhydric alcohol,
In particular, unsaturated polyhydric alcohols having 3 to 10 carbon atoms are preferred. As unsaturated polyhydric alcohols other than unsaturated polyhydric alcohols in the narrow sense, those with relatively low molecular weight are preferable, and the molecular weight is not particularly limited, but is 4000 or less,
In particular, 3000 or less is suitable. The number of active hydrogens in the unsaturated active hydrogen compound is preferably 2 to 8, particularly 2 to 4, and particularly 2. Further, the number of polymerizable unsaturated groups in one molecule is not particularly limited, but 1 to 4 is appropriate, and 1 to 2 is particularly preferable. The most preferred unsaturated active hydrogen compound is 3-butene-1,2-diol or 2-phthene-1,4-diol. The polyisocyanate compound is a compound having at least two isocyanate groups (one NCO), and may have a polymerizable unsaturated group as mentioned above, but it is usually a compound that does not have it. be.

Examples of polyisocyanate compounds include aromatic polyisocyanates, aliphatic polyisocyanates, alicyclic polyisocyanates, and aromatic polyisocyanates are preferred. Specifically, for example, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polymethylene polyphenyl isocyanate (PAPI), naphthalene diisocyanate,
Examples include triphenylmethisotriisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate. As the isocyanate compound, it is possible to use a modified polyisocyanate compound that has been modified using an active hydrogen compound such as a polyhydric alcohol or an amine, or using another method. Although the nitrogen-containing bond-containing unsaturated polyol can be obtained from the above-described unsaturated active hydrogen compound and polyisocyanate compound, the present invention further uses a substantially saturated polyether polyol.

This substantially saturated polyether polyol is
For example, there are polyether polyols made by adding alkylene oxide to active hydrogen-containing compounds such as polyhydroxy compounds and phosphoric acid amines, and polyether polyols made from cyclic phenolic polymers. Specifically, glycol, glycerin, trimethylolpropane, bentaerythritol, sorbitol, dextrose and other polyhydric alcohols, diethanolamine, triethanolamine and other alkanolamines, bisphenol A
, phenol-formaldehyde condensates, other polyhydric phenols, ethylenediamine, diaminodiphenylmethane and other amines, ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin and other alkylene oxides, and even styrene oxide. There are polyether polyols with added epoxides such as glycidyl ether, and polyether polyols such as tetrahydrofuran polymers. Two or more of these can also be used in combination. Preferred polyether polyols are polyether polyols having a molecular weight per OH group of 300 to 2,500, and particularly preferred are polyether polyols having a molecular weight per OH group of 600 to 2,000 and a number of hydroxyl groups of 2 to 4. These substantially saturated polyether polyols usually have a higher molecular weight than the unsaturated active hydrogen compound. This high molecular weight polyol is a polyol having substantially no polymerizable unsaturated groups.

The above-mentioned polyether polyol "usually has no polymerizable unsaturated groups in its constituent compounds (for example, polyhydroxy compounds or alkylene oxides), or even if it does have it, it can be polymerized to form a polyol during polyol production. , is considered to contain no polymerizable unsaturated groups.
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. Various methods can be used to produce the nitrogen-containing unsaturated polyol from the above raw materials.

First, a case will be described in which two types, an unsaturated active hydrogen compound and a polyisocyanate compound, are reacted and then mixed with a substantially saturated polyol. In this case, as the unsaturated active hydrogen compound, it is necessary to use at least a compound having a hydroxyl group such as an unsaturated zero-hydric alcohol. For example, a nitrogen-containing bond-containing unsaturated diol having two hydroxyl groups can be produced by reacting an unsaturated diol with a diisocyanate compound. In this case, the number of hydroxyl groups must be greater than the number of isocitaanate groups, but if the ratio of the numbers is close to 1, the molecular weight may increase and the necessary liquid nitrogen-containing unsaturated polyol may not be obtained. Conversely, even if the number of isocyanate groups is small, there is little risk that the presence of unreacted unsaturated polyhydric alcohol will cause any problems. Further, if a low molecular weight unsaturated polyhydric alcohol is used, it tends to be solid or highly viscous, so in this case, a relatively high molecular weight unsaturated polyhydric alcohol is preferable. The resulting nitrogen-containing bond-containing polyol can be mixed into the substantially saturated tapolyol in any proportion. When using an unsaturated active hydrogen compound, a polyisocyanate compound, and a substantially saturated polyether polyol as raw materials, the easiest and preferred method is to use an unsaturated active hydrogen compound and a substantially saturated polyether polyol. mixture with polysocyanate
This method involves reacting two compounds.

For example, when TDI is added to a mixture of butene diol and polyoxyalkylene triol and reacted, the desired nitrogen-containing bond-containing unsaturated polyol can be obtained. This nitrogen-containing bond-containing unsaturated polyol is rarely a single compound, but is usually a mixture of various compounds, and often also contains a saturated polyol. For example, when producing an unsaturated diol containing a urethane bond by this method using an unsaturated diol, a saturated diol, and a diisocyanate compound as raw materials, the unsaturated diol residue is A, the saturated diol residue is B, and the diisocyanate compound residue and its both ends are When the urethane bond is represented by - and the hydroxyl group is represented by OH, the following urethane bond-containing diol is thought to be produced as a relatively simple compound. HOA-BOH, HOA-AO
H, HOB-BOH, HOA-A-AOH, HOA-A
-BOH, HOA-B-AOH, HOB-A-BOH,
HOA-B-BOH, HOB-B-BOH and of course A
It is conceivable that a product in which four or more and B are bonded in this way is produced, and unreacted unsaturated diols or saturated diols may also remain. Among these, a compound containing at least an unsaturated diol residue is one of the nitrogen-containing bond-containing unsaturated polyols in the present invention. By using an unsaturated active hydrogen compound having an active hydrogen of Z3 or more, a substantially saturated polyol, and a polyisocyanate compound having 3 or more isocyanate groups in the same machine, more complex nitrogen-containing bond-containing unsaturated polyols can be produced. can get.
In the above method using a mixture of a Z-unsaturated active hydrogen compound and a substantially saturated polyether polyol, the amounts of these and the polyisocyanate compound used are not particularly limited as long as a nitrogen-containing unsaturated polyol is produced. However, it is not preferable that the nitrogen-containing bond 2-containing unsaturated polyol becomes a highly viscous liquid or solid. Therefore, it is not preferable that the molecular weight of the nitrogen-containing bond-containing unsaturated polyol becomes too high, and the number of unsaturated groups in one molecule is preferably about 1 to 4, particularly 1 to 2. Therefore, it is preferable that on average about 0.2 to 4 molecules, particularly 0.3 to 2 molecules, of the unsaturated active hydrogen compound are bonded to one molecule of the substantially saturated polyether polyol. In addition, since the polyisocyanate compound binds between these two, it is preferable to use about one molecule or more per molecule of the unsaturated active hydrogen compound, and the upper limit is 4
Preferably, it is on the order of molecules. Therefore, the amount used per mole of substantially saturated polyether polyol is about 0.2 to 4 moles, especially 0.3 to 2 moles of unsaturated active hydrogen compound.
It is preferably about 0.2 to 4 mol, particularly 0.3 to 2 mol, of the polyisocyanate compound, and approximately equimolar or more to the unsaturated active hydrogen compound. In addition, since there is little problem with unreacted substantially saturated polyether polyol remaining, the ratio of the unsaturated active hydrogen compound to the polyisocyanate compound may be even smaller, and even substantially less. Since saturated polyether polyols may be bonded together with a polyisocyanate compound, the proportion of the polyisocyanate compound may be high depending on the case. As a method other than using a mixture of an unsaturated active hydrogen compound and a substantially saturated polyether polyol, one of them is reacted with a polyisocyanate compound in advance to obtain a reactant in which polyisocyanate groups remain. , and then reacted with the other to obtain a nitrogen-containing bond-containing unsaturated polyol.

For example, an unsaturated diol and a diisocyanate compound may be reacted to produce a product having isocyanate groups, and this may be reacted with a substantially saturated polyenal polyol to obtain the desired unsaturated polyol. In addition, a nitrogen-containing bond-containing unsaturated polyol can be produced by reacting these three components using various methods. One of the features of the present invention is that unsaturated polyols are extremely easy to produce.

For example, in the production of unsaturated polyether polyols described in the above-mentioned publications, heating of at least about 100 q0 is required to react the polyol with maleisic acid and further react with propylene oxide,
Since the reaction of propylene oxide requires a catalyst, it is necessary to remove the catalyst after the reaction. Furthermore, a reactor such as an autoclave and post-treatment such as stripping after the reaction are required. In contrast, in the present invention, the reaction occurs at room temperature to 1
It can be carried out at 00°C, does not require a special reactor or catalyst, and usually the desired unsaturated polyol can be obtained simply by mixing the raw materials. Moreover, it is usually special 0
The next polymerization operation can be carried out without the need for further post-treatment. The nitrogen-containing bond-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 polyether polyols, and may include nitrogen-containing bond-containing polyols containing no unsaturated groups. This mixture can be directly applied to the next polymerization operation, but
Further, it can be applied to zero after removing removable impurities. Further, the nitrogen-containing bond-containing unsaturated polyol or a mixture containing the same can be used after being diluted with a polyol, and as this polyol, a substantially saturated polyable polyol is usually used. Monomers having a polymerizable unsaturated group usually have one polymerizable double bond.
However, the monomers that are unique to the present invention may be used, but are not limited thereto.

Specific monomers are preferably acrylonitrile, styrene, acrylamide, acrylate ester, methacrylate ester, vinyl acetate, etc., but are not limited to these, for example, Q-methylstyrene, dimethylstyrene, halogenated styrene, etc. Styrene derivatives, olefins such as ptagene, isoprene, and methacrylates. Acrylic derivatives such as nitrile, butyl acrylate and benzyl methacrylate, vinyl halides such as vinyl chloride, unsaturated fatty acid esters such as maleate ester and itaconate diester, and other monomers can be used. These monomers can be used not only alone, but also in combination with other monomers to form copolymers. 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 a nitrogen-containing bond-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 typically generates free radicals to initiate polymerization is used. Specifically, for example, azopisisobutylonitrile, benzoyl/dioxide, diisopropyl peroxydicarbonate, acetyl peroxide, di-t-butyl peroxide, dicumyl peroxide, diuraryloyl peroxide, persulfate, etc. There is. 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 amount of the monomer used 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 of the present invention is characterized by good dispersion stability.

Conventional polymer polyols using saturated polyols do not have sufficient dispersion stability, and it is 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, even in conventional methods for producing polymer polyols using unsaturated polyols, the use of acrylonitrile has been almost an indispensable requirement. In the present invention, although monomers containing acrylonitrile can of course be used, 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 of the present invention is usually a liquid dispersion in which opaque finely divided solids are dispersed.

Polymer polyols using styrene alone are white dispersions, while those using acrylonitrile are colored dispersions. Although it is possible to obtain a relatively transparent polymer polyol 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 obtained polymer polyol of 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. Particularly preferred are polyether polyols. Polyether polyols refer to polyether polyols produced by adding alkylene oxide to polyhydric alcohols, amines, and other so-called initiators, and substantially saturated polyether polyols such as tetrahydrofuran polymers. It is included in the scope. The polyol component consisting of the polymer polyol of the present invention alone or a mixture of polyols containing the same may further contain catalysts, foam stabilizers, blowing agents, fillers, crosslinking agents, chain extenders, stabilizers, colorants, and other additives. Agents may also be added. In the case of ordinary polyurethane foam production, catalysts, blowing agents, and foam stabilizers are often considered essential components. As the catalyst, amiso-based catalysts such as tertiary amines and organometallic compounds such as organotin compounds are suitable.
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 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. In other words, when stress is applied to the energy absorbing form, it deforms slightly. Also,
Since it has a nitrogen-containing bond, the reaction rate can be improved in urethanization, and the use of amine catalysts can also 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 [Manufacture of nitrogen-containing bond-containing unsaturated polyol] The method for manufacturing the nitrogen-containing bond-containing unsaturated polyol used in the present invention and its manufacturing results will be described.

5. Into the autoclave, polyol, unsaturated polyhydric alcohol, and diisocyanate were added as shown in Table 1, and the autoclave was kept at 80 qo for about 7 hours.

In each case, a transparent and slightly viscous liquid was 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. Tatsumi S 3. Lower level Tatsudeki K place Kabubu Hina■ Ki Mikumo member.

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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 the pressure reduction and nitrogen substitution operations were carried out at a predetermined temperature. After repeating this process, as shown in Table 2, the remaining nitrogen-containing bond-containing unsaturated polyol or normal polyoxyalkylene polyol, and the monomer polymerization initiator having a polymerizable unsaturated group were mixed together at a predetermined rate. The mixture was introduced into the autoclave while being stirred.

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

For comparison, a sample using an unsaturated group-containing polyol produced by reacting a normal polyoxyalkylene polyol with maleic acid was also listed. Nansho Ran Kama S 3. Lower Cherry Blossoms/Do Shibu* Hair Spirit House Poison S Sanzogumo Kasumi Takou Yukigumo Do 3 Yukigumo Gosori Sakura Main Pithole ○ Yusuke Dokudouun Hoichi Sakura ” ↑ 2 Lower Nosoku Reference Example 7~ 8. Comparative Reference Example 1 [Flexible foam foaming test] A flexible urethane foam was manufactured using the polymer polyols manufactured in Examples 5 and 6 shown in Table 2.

For comparison, a case in which foaming was performed using only polyoxypropylene triol (polyol B) having a molecular weight of 3000 will also be described. Polyol or polymer polyol 100%, silicone L5201.2%, Dabo3
Round V (Triethylene diamine 1, dipropylene glycol 3) 0.39, T-9 (stannous octylate) 0.
Table 3 shows the results of foaming by intensively mixing TDI Mountain 80 (tolylene diisocyanate) to an index of 105 on 3 evenings and 4.0 evenings on Wednesday.

It can be seen that, compared to Comparative Reference Example 1, the foam properties of Reference Examples 7 and 8 are superior, especially regarding the peak D.

Table 3: Flexible foam foam test results Reference Examples 9 to 11, Comparative Reference Examples 2 to 3 [High elastic foam foaming test] Polymer polyols produced in Examples 1, 2, 3 and Comparative Example 2 in Table 2 were used. A highly elastic foam was then molded.

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 Reference Example 2) 160 minutes, Polyol 2
409, Silicone L53054.4 evening, Dabo 3 round V2.4 evening, Wednesday 12 evening, TDI-80/PAPI13
5 (manufactured by Kasei Upjohn Co., Ltd., crude phenylene diisocyanate) = 80/20 mixed isocyanate was mixed to have an index of 105 and the temperature was quickly adjusted to 50 mm. Aluminum 40 mm x 40 mm x 10 mm. It was placed in a mold on the side of the ship, 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 foam physical properties of Reference Examples 9 to 11 are superior to Comparative Reference Example 2, especially with respect to ratio D.

Further, in Comparative Reference Example 3, the reaction was slower than in Examples, and the mold could not be removed in 1 minute at room temperature, so it was left for 18 minutes. It was found that the ILD and compression set of the foam were also slightly inferior. Table-4 High elasticity foam physical property test results Reference Examples 12-13 Examples 9-10 [Unsaturated polyurethane polyol-based polymer polyol] - Same method as Reference Examples 1-6 except for changing the type of unsaturated polyhydric alcohol The following nitrogen-containing bond-containing unsaturated polyol was produced.

Table 5 Using these unsaturated polyols, polymer polyols were produced in the same manner as in Examples 1 to 8.

Claims (1)

[Claims] 1. A method for producing a liquid polymer polyol by polymerizing a monomer having a polymerizable unsaturated group in an unsaturated polyol or a polyol mixture containing the same, wherein the unsaturated polyol or the polyol mixture containing the same is , an unsaturated active hydrogen compound having at least two active hydrogens and at least one polymerizable unsaturated group, a polyisocyanate compound having at least two isocyanate groups, and a substantially saturated polyisocyanate compound having at least two hydroxyl groups. a nitrogen-containing bond-containing unsaturated polyol obtained by reacting a polyether polyol or a polyol mixture containing the same, or reacting the unsaturated active hydrogen in which at least two of the active hydrogens are hydroxyl groups with the polyisocyanate compound. A method for producing a polymer polyol, which is a mixture of the obtained nitrogen-containing bond-containing unsaturated polyol and the substantially saturated polyether polyol. 2. The method for producing a polymer polyol according to claim 1, wherein the unsaturated active hydrogen compound is an unsaturated polyhydric alcohol. 3. The method for producing a polymer polyol according to claim 1, wherein the polyisocyanate compound is an aromatic diisocyanate compound. 4. The nitrogen-containing bond-containing unsaturated polyol is a nitrogen-containing bond-containing unsaturated polyol obtained by adding and reacting a polyisocyanate compound to a mixture of an unsaturated active hydrogen compound and a substantially saturated polyether polyol. A method for producing a polymer polyol according to claim 1.