JP2654173B2 - Process for producing polymer polyols and polyurethanes - Google Patents

Description

The present invention relates to a method for producing a polymer polyol and a method for producing a polyurethane using the same.

More specifically, an allyl glycidyl ether and a saturated dicarboxylic anhydride are added to a polyether polyol,
Further, the allyl group-containing polyether ester polyol obtained by reacting the alkylene oxide is polymerized with a peroxide radical catalyst to produce a high molecular weight polyether polyol, which is mixed into the polyether polyol, and the The present invention relates to a method for producing a polymer polyol obtained by polymerizing an unsaturated group-containing monomer and a method for producing a polyurethane using the same.

[Conventional technology]

Compounds and mixtures obtained by polymerizing ethylenically unsaturated group-containing monomers in polyether polyols or polyester polyols are called polymer polyols,
Used as a raw material for polyurethane foams and polyurethane elastomers.

Conventionally, polymer polyols generally have poor dispersion stability and high viscosity, but polyurethanes using them have excellent physical properties and are therefore widely used in the production of polyurethanes.

In the production of highly practical polymer polyols, acrylonitrile alone or a combination of acrylonitrile and an ethylenically unsaturated group-containing monomer such as styrene is used as the ethylenically unsaturated group-containing monomer (high acrylonitrile ratio). The polymer concentration of the polymer polyol obtained by polymerization was at most about 20% by weight.

Polyurethane foams and polyurethane elastomers using these polymer polyols are characterized in that the polymer particles in the polymer polyol act as organic fillers, so that the resulting polyurethane product can easily increase hardness or elastic modulus. Show.

In the production of the polymer polyol, acrylonitrile alone or a mixed monomer of acrylonitrile / styrene having a high acrylonitrile ratio is used as the ethylenically unsaturated group-containing monomer, and the obtained polymer polyol is yellow or pale yellow. In addition, the polyurethane foam produced therefrom also had a disadvantage that it was colored pale yellow and did not become a white foam.

However, recently, a white foam having high hardness has been desired, and the production of a higher quality polymer polyol has been required.

In order to achieve such an object, it has become necessary to further increase the polymer concentration in the polymer polyol and to use an acrylonitrile / styrene mixed monomer having a high styrene ratio.

However, when the concentration of the polymer is increased (30% by weight or more), a sharp increase in viscosity occurs, and when acrylonitrile and styrene are combined as monomers, the affinity with polyol decreases when the ratio of styrene increases. As a result, the dispersion stability was extremely reduced, and aggregation and separation were caused.

Therefore, the polymer concentration is high (30% by weight or more) and
It was very difficult to obtain a polymer polyol having a low viscosity and good dispersion stability under the condition of a high styrene ratio.

As a method for solving these problems, for example, a method of producing a polymer polyol by polymerizing an ethylenically unsaturated group-containing monomer in a polyol having a polymer unsaturated group is disclosed in Japanese Patent Publication Nos. 51-37228 and JP-B-51-40915.

The unsaturated polyols described in these publications are produced by a method of reacting a saturated polyol with an unsaturated polycarboxylic acid such as maleic anhydride, or a method of adding an alkylene oxide after the reaction.

However, the method using an unsaturated acid causes polymerization or addition reaction of the unsaturated group of the unsaturated carboxylic acid used, and the concentration of the unsaturated group does not become constant. In addition, the copolymerization with the unsaturated group-containing monomer becomes uniform, and it is difficult to stably produce the copolymer.

[Problems to be solved by the invention]

The present inventors have conducted intensive studies to find a method for producing a polymer polyol that has solved the above-mentioned problems.As a result, the polymer concentration is high, and the styrene ratio is high, and the viscosity is low and the dispersion stability is good. The present inventors have found a method for producing a polymer polyol and have reached the present invention.

That is, when producing a polymer polyol, in order to stably disperse the polymer particles, by previously copolymerizing an ethylenically unsaturated group-containing monomer with a polyol containing a polymer unsaturated group to form a graft, It is based on a completely new idea that a stable dispersion can be obtained and the above problems can be solved.A so-called emulsifier is synthesized in advance, and this emulsifier is partially added to the polyether polyol. This is a method for stably dispersing the polyol particles.

Since this emulsifier basically does not contain a polymerizable unsaturated group, it does not take part in the copolymerization with the ethylenically unsaturated group-containing monomer during the polymer polyol production reaction, and a product whose properties are always stable can be obtained. It has the characteristic that it can be done.

Another feature is that a polymer of an allyl glycidyl ether group is used as a component of an emulsifier having an affinity for polymer particles, and the same / or another polyether polyol is used as an emulsifier component having an affinity for a dispersion medium. Since the emulsifier is used, the structure of the emulsifier can be freely designed according to the composition of the polymer to be stabilized or the composition of the polyether polyol as the dispersion medium, and the stabilization of the polymer polyol is easy.

Further, by introducing an ester skeleton into the emulsifier using a saturated dicarboxylic anhydride, a polymer polyol having higher hardness can be produced.

It has been found that the polyurethane foam obtained using the above-mentioned polymer polyol becomes a white and hard foam as compared with a polyurethane foam using a known polymer polyol.

[Means for solving the problem]

That is, the present invention, a part of the polyether polyol,
A method for producing a polymer polyol by graft polymerization with an ethylenically unsaturated group-containing monomer, comprising the steps of: (1) reacting polyether polyol (A) with allyl glycidyl ether and a saturated dicarboxylic anhydride, and then reacting alkylene oxide; A first-stage reaction step of polymerizing the allyl group-containing polyetherester polyol obtained by using a peroxide-based radical catalyst to obtain a high-molecular-weight polyether polyol (B); and (2) the first-stage reaction step The polyether polyol (C) is added to the high molecular weight polyether polyol (B) obtained in the step (1) in such a ratio that the concentration of B becomes 1 to 40% by weight, and then the ethylenically unsaturated group is added using a radical catalyst. A second reaction step of graft-polymerizing with the contained monomer (D). The present invention relates to a method for producing riol.

The polyether polyol (A) of the present invention comprises ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin, diglycerin, trimethylolpropane, pentaerythritol,
One or more polyhydric alcohols such as sucrose and sorbitol may be combined with one or more alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide.
A polyether polyol obtained by reacting a species or two or more species, and having a molecular weight of 3000 to 7000, preferably 4000 to 60
A range of 00 is used.

The amount of the allyl glycidyl ether used in the present invention is 0.5 to 5 mol, preferably 1 to 2 mol, per 1 mol of the polyether polyol (A).

When the amount of the allyl glycidyl ether is 0.5 mol or less, when graft polymerization is performed using a radical catalyst,
A polymer polyetherester polyol sufficient to stably disperse polymer particles cannot be obtained. In addition, in the case of 5 mol or more, even with the use of a small amount of a radical catalyst, a rapid grafting reaction occurs, and the viscosity is increased or fixed.
It becomes difficult to control the viscosity (molecular weight) of the high molecular weight polyetherester polyol.

Examples of the saturated carboxylic anhydride used in the present invention include succinic anhydride, phthalic anhydride, glutaric anhydride and the like. The amount of the saturated dicarboxylic anhydride used is 0.5 to 5 mol per 1 mol of the polyether polyol (A),
Preferably it is 1-2 mol.

When the amount of the saturated dicarboxylic anhydride used is 0.5 mol or less, a polymer polyol having sufficient curing cannot be obtained. If it is more than 5 moles, the viscosity of the produced polymer polyol increases remarkably and the viscosity of the high-molecular-weight polyetherester polyol itself also increases. Poor filtration or blockage during filtration.

When the polyether polyol (A) is reacted with allyl glycidyl ether and saturated dicarboxylic anhydride, and then reacted with alkylene oxide to obtain an allyl group-containing polyether ester polyol, a catalyst is used to accelerate the reaction. Is preferred.

Specific examples of the catalyst include hydroxides, oxides and salts of alkali metals and alkaline earth metals such as sodium hydroxide, potassium hydroxide and lithium chloride.

The reaction is carried out at a temperature of 80 to 160 ° C., preferably 110 to 130 ° C., and the obtained polyetherester polyol is purified by a usual method.

Next, a high molecular weight polyetherester polyol is produced by using a peroxide radical catalyst for the allyl group-containing polyetherester polyol.

As the peroxide-based radical catalyst, benzoyl peroxide, propionyl peroxide, t-butyl hydroperoxide, dicumyl peroxide, di-t-butyl peroxide and the like are used.

The amount of the catalyst is 0.01 to 5.0% by weight, preferably 0.05 to 1.0% by weight, based on the allyl group-containing polyether polyol.

The temperature of the polymerization reaction varies depending on the type of catalyst, but is not lower than the decomposition temperature and is 70 to 200 ° C, preferably 120 to 187 ° C.

The present invention has a high polymer concentration (20 to 60% by weight) and
When producing a polymer polyol under high styrene conditions, use a high molecular weight polyether ester polyol obtained by polymerizing an allyl group-containing polyether ester polyol with a peroxide radical catalyst as a dispersion stabilizer for the polymer. It is characterized by. That is, in the polyether polyol (C), a high-molecular-weight polyether ester polyol is dissolved as a dispersion stabilizer, and a monomer having an ethylenically unsaturated group is polymerized with a radical catalyst in the polyether polyol (C). Obtain good polymer polyols.

The addition amount of the high molecular weight polyether ester polyol as a dispersion stabilizer is 1 to 40% by weight, preferably 5 to 20% by weight, based on the polyether polyol (C). When the addition amount is 1% by weight or less, the dispersion stability of the polymer polyol is extremely lowered, and aggregation, separation and the like occur. Also,
When added in an amount of 40% by weight or more, the dispersion stability is good, but it is not practical to use it as a raw material for polyurethane because the viscosity is significantly increased.

The polyether polyol (C) is one or two polyhydric alcohols such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin, diglycerin, trimethylolpropane, pentaerythritol, sucrose, and sorbitol.
A polyether polyol obtained by reacting one or more alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, etc., with a molecular weight of 2,000 to 6,000, preferably 3,000 to 50.
A range of 00 is used.

As the ethylenically unsaturated group-containing monomer, butadiene, 1,4-pentadiene, styrene, methylstyrene,
Examples include phenylstyrene, chlorostyrene, acrylic acid, methyl methacrylate, methacrylic anhydride, acrylonitrile, methacrylonitrile, phenyl acrylate, acrylamide, and vinyl acetate. Preferably, acrylonitrile alone, styrene alone, or a combination of acrylonitrile and styrene is used.

The polymerization ratio of acrylonitrile / styrene is 100/0 to 0
/ 100, preferably 50/50 to 10/90. The amount of monomer used is 20 to the total amount of polyether polyol and monomer.
It is 60% by weight, preferably 30 to 50% by weight.

As the radical catalyst, a well-known vinyl polymerization reaction catalyst is added in an amount of 0.01 to 5% by weight, preferably 0.1 to 2.0% by weight. Examples of radical catalysts include peroxides such as hydrogen peroxide, benzoyl peroxide, acetyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, and azo such as azobisisobutyronitrile. Compound or persulfate, persuccinic acid, di-
It is a peroxide compound such as isopropylperoxy dicarbonate, but is preferably azobisisobutyronitrile.

The polymerization reaction of the polymer polyol according to the present invention can be carried out by a batch system or a continuous system.

The polymerization temperature varies depending on the type of the radical catalyst, but is not lower than the decomposition temperature and is in the range of 60 to 200C, preferably 90 to 160C.

The polymer polyol obtained after the completion of the polymerization reaction can be used as a raw material of the polyurethane as it is, but it is preferable to use it as a raw material of the polyurethane after reducing the pressure of unreacted monomers and decomposition products of the radical catalyst after the reaction. .

The polyisocyanate used in the present invention is, for example, 2,4
-Tolylene diisocyanate, 2,6-tolylene diisocyanate, 80/20 weight ratio of both isocyanates (80/20
-TDI) or a mixture in a 65/35 weight ratio (65/35 TDI), crude tolylene diisocyanate (crude TDI), 4,4'-diphenylmethane diisocyanate (4,4'-MDI), 2,4'-
Diphenylmethane diisocyanate (2,4'-MDI), 2,
2'-diphenylmethane diisocyanate (2,4'-MD
I), an isomer mixture of diphenylmethane diisocyanate (MDI), polymethylene polyphenyl isocyanate (crude MDI), toluidine diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and carbodiimide modified products of these isocyanates. Bullet modified products, dimers, trimers, and prepolymers.

The polyisocyanate may be used alone or in a mixture. The polyisocyanate particularly suitable for the present invention is a mixture of a carbodiimide-modified isomer mixture of diphenylmethane diisocyanate and polymethylene polyphenyl polyisocyanate.

The crosslinking agent used in the present invention is a monomer polyol such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, trimethylene glycol, 1,3- and 1,4-butanediol, and triethanolamine. Alkanolamines such as diethanolamine, aliphatic polyamines such as ethylenediamine, diethylenetriamine and triethylenetetramine, methylene orthochloroaniline, 4,4 ′
-Diphenylmethanediamine, aniline, 2,4-tolylenediamine, aromatic polyamines such as 2,6-tolylenediamine, and hydroxyl values obtained by adding ethylene oxide, propylene oxide, etc. to these active hydrogen compounds, 200 mg KOH / g or more compounds.

In addition, a compound having a hydroxyl value of 200 mgKOH / g or more obtained by adding ethylene oxide and / or propylene oxide to hydroquinone, resorcin, aniline, or the like can also be used.

The polyisocyanate, polyol and crosslinking agent are used such that the equivalent ratio (NCO / H) between the NCO group in the polyisocyanate and the active hydrogen in the polyol and the crosslinking agent is 0.70 to 1.40.

The catalyst which can be used in combination in the present invention is a conventionally known catalyst and is not particularly limited. For example, as an amine-based urethanization catalyst, triethylamine, tripropylamine, triisopropanolamine, tributylamine, hexadecyldimethylamine, N-methyl Morpholine, N-ethylmorpholine, N-octadecylmorpholine, monoethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N, N-dimethylethanolamine, diethylenetriamine, N, N, N ', N'
-Tetramethylethylenediamine, N, N, N ', N'-tetramethylpropylenediamine, N, N, N', N'-tetramethylbutanediamine, N, N, N ', N'-tetramethyl-1, Three
-Butanediamine, N, N, N ', N'-tetramethylhexamethylenediamine, bis [2- (N, N-dimethylamino) ethyl] ether, N, N-dimethylbenzylamine, N, N-dimethylcyclohexyl Amines, N, N, N ',
Azacycles such as N ", N" -pentamethyldiethylenetriamine, triethylenediamine, formate and other salts of triethylenediamine, oxyalkylene adducts of amino groups of primary and secondary amines, N, N-dialkylpiperazines Compounds, various N, N ', N "-trialkylaminoalkylhexahydrotriazines, β-
Aminocarbonyl catalyst, β-aminonitrile catalyst of JP-B-53-14279, etc., as an organometallic urethanization catalyst, tin acetate, tin octylate, tin oleate, tin laurate, dibutyltin diacetate, dibutyltin dilaurate, Examples include dibutyltin dichloride, lead octoate, lead naphthenate, nickel naphthenate, and cobalt naphthenate. These catalysts are used alone or as a mixture, and the amount is 0.0001 to 10.0 parts based on 100 parts of the compound having active hydrogen.

The blowing agent in the present invention may be one or more of water, trichloromonofluoromethane (F11), dichlorodifluoromethane, methylene chloride, trichlorotrifluoroethane, dibromotetrafluoroethane, trichloroethane, pentane, n-hexane and the like. It is a mixture.

The foam stabilizer in the present invention is a conventionally known organosilicon surfactant, for example, L-52 manufactured by Nippon Unicar Co., Ltd.
0, L-532, L-540, L-544, L-550, L3500, L-
5305, L-3600, L-3601, L-5305, L-5307, L-
5309, L-5710, L-5720, L-5740M, L-6202, etc., and SH-190, SH-192, SH
-194, SH-200, SRX-253, SRX-274C, SF-2961, SF
-2962, SRX-280A, SRX-294A, etc., and F-114, F-121, F-122, F-220, F-
230, F-258, F-260B, F-317, F-341, F-60
1, F-606, X-20-200, X-20-201, etc., manufactured by Toshiba Silicone Co., Ltd., TFA-4200, TFA-4202, etc.
B-4113 or the like manufactured by Goldschmidt.

The amount of the foam stabilizer used is 0.1 to 5 parts by weight based on 100 parts by weight of the total amount of the compound having active hydrogen and the polyisocyanate.

In the present invention, in addition to the above, a stabilizer, a filler, a coloring agent and the like can be used if necessary.

To carry out the present invention, a polyol, a crosslinking agent, a foam stabilizer,
A predetermined amount of a catalyst, a foaming agent and other auxiliaries are mixed to form a resin component. The polyisocyanate is mixed to form a polyisocyanate component.

According to the method of the present invention, a polymer polyol having a high styrene ratio and a high polymer concentration can be produced with low viscosity and high stability.

Further, the polyurethane foam produced by using this as a raw material not only has high hardness and can withstand a high load, but also becomes a white foam, thereby improving the product value.

〔Example〕

Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

Examples 1 to 5 Production of high molecular weight polyetherester polyol (dispersion stabilizer) A predetermined amount of polyol A and potassium hydroxide was charged into a container equipped with a thermometer and a stirrer, and the temperature was raised to 120 ° C.

After the temperature was reached, a predetermined amount of allyl glycidyl ether and a saturated dicarboxylic anhydride was charged, and a predetermined amount of ethylene oxide was continuously charged, followed by stirring at the same temperature for 4 hours.

Thereafter, the temperature was lowered to 80 ° C., predetermined amounts of phosphoric acid and water were added, and the mixture was stirred for 30 minutes to neutralize. After neutralization, a predetermined amount of an adsorbent was added, and after a dehydration treatment at 20 mmHg for 4 hours, a filter aid was added, followed by filtration to obtain an allyl group-containing polyetherester polyol.

A predetermined amount of the allyl group-containing polyether S-polyol and the radical initiator were charged into a container equipped with a thermometer and a stirrer, and the temperature was raised to a predetermined temperature.

After reaching the temperature, after stirring for a predetermined time at the same temperature, 20
Decompression treatment was performed at 30 mmHg for 30 minutes to remove decomposition products of the initiator to obtain a high molecular weight polyetherester polyol.

 Table 1 shows the results of Examples (1 to 5).

Comparative Example 1 As a comparative example, a high molecular weight polyether polyol was obtained under the same reaction conditions without adding a saturated dicarboxylic anhydride and ethylene oxide.

 Table 1 shows the results of Comparative Example 1.

Examples 6 to 10 and Comparative Examples 2 to 3 Production of polymer polyol A pressure-resistant container equipped with a thermometer and a stirrer was charged with a predetermined amount of polyol B, and the inside of the container was replaced with nitrogen several times.

Under stirring, the internal temperature was raised to 100 ° C., and after reaching the temperature, a predetermined amount of a mixture of each of the polyol B, the high molecular weight polyetherester polyol (dispersion stabilizer) obtained in Reference Example 1, styrene, acrylonitrile, and AIBN was added. , And were continuously supplied by a pump for 4 hours.

After continuing stirring at the same temperature for 30 minutes, a reduced pressure treatment was performed at 20 mmHg for 3 hours to obtain a white emulsion polymer polyol having good dispersion stability.

Table 2 shows the results of Examples (6 to 10), Comparative Examples 2 and 3.

Examples of the foaming of the present invention are shown below.

The following raw materials were used in the examples. Hereinafter, "part" indicates "part by weight".

Polyol D; Polymer polyol of acrylonitrile / styrene polymerized in polyether polyol obtained by addition polymerization of propylene oxide to glycerin 45 mg KOH / g Polyol E: Obtained by addition polymerization of propylene oxide and ethylene oxide to glycerin Acrylonitrile / styrene polymerized in polyether polyol, polymer polyol having hydroxyl value of 45 mgKOH / g L-6202; Nippon Unicar, Organosilicon L-5740M; foaming agent SO; Stanas octoate TDI-80 / 20; toluene diisocyanate (80% of 2,4-isomer and 20% of 2,6-isomer) TEDA; triethylenediamine N-MM; N-methylmorpholine Examples 11 to 15, Comparative Examples 4 to 5 180 parts of polyol B, 420 parts of the polyol of Examples 6 to 10 in Table 2 or the polyol of Comparative Example 2, L-6202 4.8
Part, H ₂ O16.2 parts TEDA0.36 parts, premixed N-MM 1.20 parts, to which was added SO1.20 parts, after high speed mixing, immediately predetermined TDL-80/20 (Table 3 ), And further mixed at high speed, poured into a box with an inner size of 300 x 300 x 150 mm, and left overnight.

Table 3 shows the physical properties of the obtained foam. In this example, the equivalent ratio (NCO / H) between the isocyanate group and the active hydrogen is 1.10.

As compared with Comparative Examples 4 and 5, the hardness was improved in all Examples.

Examples 16 and 17 and Comparative Examples 6 and 7 The polyols of Examples 6 and 9 in Table 2 or 186 parts of the polyol of Comparative Example 2, 434 parts of the polyol B, L-5740 M8.7
, 24.8 parts of water, 0.50 part of TEDA catalyst and 1.24 part of N-MM catalyst in advance, add 0.74 part of SO to this, and after high-speed mixing, immediately TDI-80 / 20 (shown in Table-4) The mixture is further mixed at a high speed, poured into a mold having an internal size of 400 × 400 × 100 mm adjusted to 40 ° C. in advance, and the lid is closed to foam.

After heating and hardening in an oven at 180 ° C. for 12 minutes, the foam is removed from the mold.

Table 4 shows the physical properties of the obtained foam. In this embodiment, the equivalent ratio (NCO / H) between the isocyanate group and the active hydrogen is 1.00.

Comparative Example 6 and Comparative Example 7 using 186 parts of polyol E
As compared with the examples, the hardness was improved in all the examples.

(Effects of the Invention) As shown in the examples, polyurethane foam produced using the polymer polyol obtained in the present invention,
It is clear from Tables 3 and 4 that foams having higher hardness than those shown in the comparative examples were obtained.

Claims (6)

(57) [Claims] 1. A method for producing a polymer polyol by graft-polymerizing a part of a polyether polyol with an ethylenically unsaturated group-containing monomer, wherein (1) an allyl glycidyl ether and a saturated dicarboxylic acid are added to the polyether polyol (A). A first-stage reaction in which an allyl group-containing polyetherester polyol obtained by reacting an anhydride and then an alkylene oxide is polymerized using a peroxide-based radical catalyst to obtain a high molecular weight polyether polyol (B) And (2) a polyether polyol (C) was added to the high-molecular-weight polyether polyol (B) obtained in the first-stage reaction step in such a manner that the concentration of B became 1 to 40% by weight. After that, the second step is carried out by graft polymerization with an ethylenically unsaturated group-containing monomer (D) using a radical catalyst. A process for producing a polymer polyol. 2. The polyether polyol (A) has a molecular weight
The method for producing a polymer polyol according to claim 1, wherein the amount is from 3,000 to 7000. 3. The method according to claim 1, wherein the ethylenically unsaturated group-containing monomer (D) is a mixture of acrylonitrile and styrene. 4. The polyether polyol (C) has a molecular weight
The method for producing a polymer polyol according to claim 1, wherein the number is from 2000 to 6000. 5. The process for producing a polymer polyol according to claim 1, wherein the total amount of the ethylenically unsaturated group-containing monomer (D) is 20 to 60% by weight in the polymer polyol. 6. A method for producing polyurethane, comprising reacting the polymer polyol produced by the method according to claim 1 with polyisocyanate to produce polyurethane.