JPH07330843A - Polymer polyol, method for producing the same, and method for producing a flexible high-elasticity polyurethane foam - Google Patents

Abstract

(57) [Summary] [Provision] To provide a polymer polyol having a low viscosity and good dispersion stability, and a polyurethane foam having low closed cell properties at the time of foaming and excellent physical properties such as hardness, permanent set under heat and humidity, and impact resilience. [Structure] Hydroxyl value is 10 to 35 mg KOH / g, monool maximum content is 15 mol%, and head-to-tail (Hea) by propylene oxide addition polymerization is further used.
d-to-Tail) In a polyoxyalkylene polyol with a minimum bond selectivity of 96%, the polymer concentration is 3
When the amount is 0% by weight or more and 60% by weight or less, the chain transfer agent (amine compound) is present, and when the amount is 5% by weight or more and less than 30% by weight, the chain transfer agent (amine compound) is not present, and ethylenically unsaturated. A polymer (acrylonitrile or a mixture of acrylonitrile and styrene) is polymerized to produce a polymer polyol. Next, the polymer polyol and the organic polyisocyanate compound are reacted in the presence of a foaming agent, a catalyst, a foam stabilizer, a cross-linking agent and other auxiliaries to produce a flexible high elasticity polyurethane foam.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a polymer polyol,
The present invention relates to a method for producing the same and a method for producing a flexible high elasticity polyurethane foam. More specifically, the hydroxyl value is 10 to 3
5 mg KOH / g, monool maximum content 15 mol%
Further, the polymer particles are dispersed in a polyoxyalkylene polyol having a minimum head-to-tail bond selectivity of 96% by addition polymerization of propylene oxide in an amount of 5% by weight or more and less than 30% by weight. And a polyoxyalkylene polyol having a glass transition temperature of 90 to 120 ° C.
A polymer polyol having 30% by weight or more and 60% by weight or less of dispersed polymer particles, a method for producing the same, and a polyol containing an organic polyisocyanate compound containing a polymer polyol consisting of one or more of these, a foaming agent, a catalyst, and a conditioning agent. The present invention relates to a method for producing a flexible high-elasticity polyurethane foam, which comprises reacting in the presence of a foaming agent, a cross-linking agent and other auxiliaries.

[0002]

2. Description of the Related Art A method for producing a polymer polyol by polymerizing an ethylenically unsaturated monomer in a polyoxyalkylene polyol as a polyurethane raw material or the like is known. Potassium hydroxide is mainly used as a catalyst in the production of this polyoxyalkylene polyol, and when a high molecular weight is obtained by the addition of propylene oxide, which is an alkylene oxide, a monool is produced by a side reaction and its production amount increases with an increase in the molecular weight. Is well known. Further, when the monool content in the polyoxyalkylene polyol is high, crosslinking during the urethanization reaction with the organic polyisocyanate compound, hindering the increase in the molecular weight, and degrading the mechanical properties of the flexible and highly elastic polyurethane foam or elastomer may occur. Conceivable. Therefore, similar deterioration of physical properties of polyurethane foam and the like is expected for polymer polyols using such a polyoxyalkylene polyol having a high monool content as a matrix.

In order to solve the above problems, a method of using a catalyst other than an alkali metal, for example, a double metal cyanide complex catalyst as a catalyst for propylene oxide addition polymerization as an alkylene oxide (USP 3,829,505,
(JP-A-2-115211 and JP-A-3-14812)
Has been proposed, and a polymer polyol using this as a matrix is also disclosed. When the monool content in the polyoxyalkylene polyol is reduced, the viscosity of the polyoxyalkylene polyol tends to increase, but when a double metal cyanide complex catalyst is used as the catalyst, the polyoxyalkylene polyol The viscosity was remarkably increased, and this was due to head-to-
It is considered that the tail (Head-to-Tail) bond selectivity is low. Therefore, it is considered that the viscosity of the polymer polyol obtained by radically polymerizing the ethylenically unsaturated monomer in this polyoxyalkylene polyol also significantly increases. When the viscosity of the polymer polyol is high, problems may occur in terms of molding stability and mixability during mechanical foam molding during the production of flexible polyurethane foam, and polymers using high molecular weight polyoxyalkylene polyol as a matrix. There are also restrictions on the use of polyols. On the other hand, polymer polyols generally have poor dispersion stability and high viscosity. This tendency becomes remarkable especially when the polymer concentration is 30% or more, and it is practical to produce a polymer polyol having a high polymer concentration using the polyoxyalkylene polyol obtained by the above-mentioned double metal cyanide complex catalyst. Impossible.

It is also known to use a chain transfer agent in order to solve the problems of deterioration of dispersion stability and increase of viscosity when the concentration is increased. A method for obtaining a low-viscosity polymer polyol by using an alkyl mercaptan as a chain transfer agent has been proposed (US Pat. No. 3,953,393, JP-A-01-221403). However, these methods have a problem of odor of the obtained polymer polyol, and it is difficult to obtain a practical polymer polyol because it is impossible to suppress a rapid increase in viscosity when the polymer concentration is increased. Further, a method using mercaptan, ketone, alcohol, aldehyde, halogen compound, benzene derivative, especially isopropyl alcohol as a chain transfer agent has been proposed (JP-A-58-21).
No. 0917). However, this method is not sufficient to reduce the viscosity of high-concentration polymer polyols. Further, a method using amines such as morpholine as a reaction modifier has been proposed (JP-A-63-146912), but it differs from the present invention because a specific polyol is used.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polymer polyol having a low viscosity and good dispersion stability and a low closed-cell property at the time of foaming using the polymer polyol, and hardness, permanent set at the time of wet heat, and impact resilience. It is to provide a polyurethane foam having excellent physical properties such as.

[0006]

[Means for Solving the Problems] The inventors of the present invention have conducted extensive studies to achieve the above object, and when a specific polyoxyalkylene polyol is used and a specific polymer concentration is maintained and the polymer concentration is high, Have found that the above object can be achieved by maintaining the glass transition temperature of the polymer within a specific range.

That is, the first gist of the present invention is that the hydroxyl value is 1
0-35mgKOH / g, maximum monol content 15m
ol%, and further, head-to-tail (Head-to-Tai) by propylene oxide addition polymerization.
1) A polymer polyol characterized in that polymer particles are dispersed in a polyoxyalkylene polyol having a bond minimum selectivity of 96% in an amount of 5% by weight or more and less than 30% by weight. The second gist is a hydroxyl group. Value 10-35mgK
OH / g, the maximum content of monool is 15 mol%,
Furthermore, 30 weight parts of polymer particles having a glass transition temperature of 90 to 120 ° C. in a polyoxyalkylene polyol having a minimum head-to-tail bond selectivity of 96% by propylene oxide addition polymerization. % Or more and 60% by weight or less is a polymer polyol characterized by being dispersed. The third gist is
It has a hydroxyl value of 10 to 35 mg KOH / g, a maximum monol content of 15 mol%, and a head-to-tail (Head-to-tail) obtained by addition polymerization of propylene oxide.
-Tail) A method for producing a polymer polyol, which comprises polymerizing an ethylenically unsaturated monomer in a polyoxyalkylene polyol having a minimum bond selectivity of 96%, and a fourth gist is a hydroxyl group. Value 10-35mgK
OH / g, the maximum content of monool is 15 mol%,
Further, in a polyoxyalkylene polyol having a minimum head-to-tail bond selectivity of 96% by propylene oxide addition polymerization, in the presence of a chain transfer agent, an ethylenically unsaturated monomer A fifth aspect is a method for producing a polymer polyol characterized by carrying out polymerization, wherein the fifth aspect includes a polyol containing a polymer polyol and an organic polyisocyanate compound as a foaming agent, a catalyst, a foam stabilizer, a cross-linking agent and other auxiliary agents. A method for producing a flexible high-elasticity polyurethane foam, which comprises reacting in the presence of an agent.

Method for Producing Polymer Polyol First, the polyoxyalkylene polyol will be described. Polyoxyalkylene polyol has a hydroxyl value of 10
~ 35mgKOH / g, maximum monol content 15mo
1%, and further, head-to-tail by propylene oxide addition polymerization (Head-to-Tail)
A hydroxyl group in the presence of an alkali metal catalyst, which is a polyoxyalkylene polyol having a minimum bonding selectivity of 96% and contains at least one compound selected from cesium hydroxide and rubidium hydroxide having a purity of 90% by weight or more. It is obtained by addition-polymerizing an alkylene oxide to the active hydrogen compound of the number 2 to 8. When the hydroxyl value is less than 10 mgKOH / g, the viscosity of the polyoxyalkylene polyol or the polymer polyol in which vinyl polymer particles are dispersed by using this as a matrix becomes too high, and it cannot be practically used for flexible high elasticity polyurethane foam. On the other hand, in such a low hydroxyl value polyoxyalkylene polyol, the monool content increases with the increase in the molecular weight, and the compression set and rebound resilience at the time of wet heat in the flexible high elasticity polyurethane foam decrease, so the monool content As 15mo
It should be kept below 1%. Also, the hydroxyl value is 35 mg.
When KOH / g is exceeded, existing polyols have a monol content of about 15 mol%. However, even when the molecular weight is low, the above-mentioned properties of flexible high elasticity polyurethane foam and the like are improved. unacceptable. Further, in such a low monool content polyoxyalkylene polyol, a head-to-tail (Head-to-tail) obtained by propylene oxide addition polymerization.
Tail) When the minimum bond selectivity is less than 96%, the viscosity of the polyoxyalkylene polyol increases remarkably with a decrease in the head-to-tail bond selectivity, resulting in the molding of a flexible high elastic polyurethane foam. Sometimes it causes problems.

As the active hydrogen compound, ethylene glycol, diethylene glycol, propylene glycol,
Dipropylene glycol, 1,4-butylene glycol and other diols, glycerin, hexanetriol, trimethylolpropane, pentaerythritol, sorbitol, sucrose and other polyols, bisphenol A, bisphenol F, dihydroxydiphenyl ether, dihydroxybiphenyl, hydroquinone, resorcin , Phloroglucin, naphthalenediol, aminophenol, aminonaphthol, aromatic compounds such as phenol formaldehyde condensate, methyldiethanolamine, ethyldiisopropanolamine, triethanolamine, ethylenediamine, hexamethylenediamine,
Bis (p-aminocyclohexyl) methane, aniline,
One or a mixture of two or more of amine compounds such as toluidine, tolylenediamine, diphenylmethanediamine and naphthalenediamine is used. As the alkylene oxide, one kind or a mixture of two or more kinds such as ethylene oxide, propylene oxide and butylene oxide is used, and the polyoxypropylene group content by propylene oxide addition polymerization is 70% by weight or more,
The alkylene oxide is preferably selected so that a polyoxyalkylene polyol having a terminal oxyethylene group content of 5% by weight or more can be obtained by ethylene oxide addition polymerization. Addition polymerization is carried out at an alkali metal hydroxide catalyst concentration of 0.05 to 0.5 mol with respect to 1 mol of an active hydrogen compound at 60 to 98 ° C. and a maximum reaction pressure of 4 kg / cm ^2.
It is performed under the condition of (490 kPa). One kind or a mixture of two or more kinds of the polyoxyalkylene polyol thus obtained can be used.

Next, the polymer polyol will be described. As the ethylenically unsaturated monomer, one having at least one polymerizable ethylenically unsaturated group is suitable. For example, one kind of acrylonitrile, methacrylonitrile, acrylic acid, phenyl acrylate, methyl methacrylate, methacrylic anhydride, acrylamide, styrene, methylstyrene, phenylstyrene, chlorostyrene, butadiene, 1,4-pentadiene, vinyl acetate, etc. Alternatively, a mixture of two or more kinds may be used. Preferred is acrylonitrile alone or a mixture of acrylonitrile and styrene. The weight ratio of acrylonitrile / styrene is preferably 100/0 to 10/90. When the polymer concentration is 30% or more, the viscosity increase is small 90/1
0-30 / 70 is preferable.

The amount of the ethylenically unsaturated monomer used is usually 5 to 60% by weight based on the total amount of the polyoxyalkylene polyol and the monomer, which results in a polymer concentration of 5 to 5.
It is maintained at 60% by weight. When the polymer concentration is 5% by weight or more and less than 30% by weight, the polymer polyol can be produced by a conventionally known production method. The conditions in this case may be the same as when using a chain transfer agent. When the ethylenically unsaturated monomer is only acrylonitrile, the glass transition temperature by general thermal analysis is unclear and cannot be measured.
In the case of acrylonitrile and styrene, the glass transition temperature of the polymer is 105-130 ° C. When the polymer concentration is 30% by weight or more and 60% by weight or less, a chain transfer agent is used.

The chain transfer agent is usually an amine compound. The amine compound has the general formula (1):

[0013]

[Chemical 3] (In the formula, R ₁ , R ₂ and R ₃ are H and have 1 to 10 carbon atoms.
And an alkyl group having 2 to 10 carbon atoms, which may be the same or different, but not all of them are H at the same time. ) Or an amine compound represented by the general formula (2):

[0014]

[Chemical 4] (In the formula, X represents O and NR ₂ , and R ₁ has 1 to 1 carbon atoms.
0 represents an alkyl group having 0 to 2 carbon atoms, and R ₂ represents H, an alkyl group having 1 to 10 carbon atoms, and a hydroxyalkyl group having 2 to 10 carbon atoms. ) Is a compound represented by. Specific examples include, for example, triethylamine, tripropylamine, tributylamine, N,
Examples thereof include amines such as N-diethylethanolamine, N-methylmorpholine and N-ethylmorpholine.

The amount of the chain transfer agent used is determined according to the glass transition temperature of the polymer adjusted by the chain transfer agent, and the glass transition temperature is 90 to 120 ° C., preferably 95.
The amount of chain transfer agent used is adjusted to ˜115 ° C. When the glass transition temperature is less than 90 ° C, the physical properties such as hardness in the case of using polyurethane foam are deteriorated, and when the glass transition temperature exceeds 120 ° C, the intended polymer polyol having low viscosity and good dispersion stability can be obtained. Absent. The amount of the chain transfer agent that gives the glass transition temperature is an amount that adjusts the molecular weight of the polymer to 30,000 to 140,000, and is 0.5 to 100 parts by weight of the ethylenically unsaturated monomer. 30 parts by weight, preferably 1 to 20
Parts by weight.

As the catalyst, a well-known catalyst for vinyl polymerization reaction is used. For example, peroxides such as hydrogen peroxide, benzoyl peroxide, acetyl peroxide, t-butyl peroxide, di-t-butyl peroxide, azo compounds such as azobisisobutyronitrile,
Alternatively, a persulfate, persuccinic acid, and a peroxide compound such as di-isopropylperoxy dicarbonate may be used. The catalyst is added in an amount of 0.01 to 5% by weight, preferably 0.1 to 2.0% by weight, based on the total weight of the polyoxyalkylene polyol and the ethylenically unsaturated monomer.

It is also possible to carry out the polymerization in the presence of a dispersion stabilizer for the purpose of stably dispersing the polymer particles. As such a dispersion stabilizer, JP-B-49-46556
Examples thereof include carbon-carbon unsaturated bond-containing polyether ester polyols as described in JP-A No. 2003-242242, modified polyols having an acryl group, a methacryl group, an allyl group, etc. at their terminals.

The polymer polyol is produced by the polyoxyalkylene polyol, the ethylenically unsaturated monomer,
Polymerization reaction is carried out using a chain transfer agent and a catalyst. The polymerization reaction can be carried out batchwise or continuously. The polymerization temperature is determined according to the type of the catalyst, but is not lower than the decomposition temperature of the catalyst, preferably 60 to 200 ° C., more preferably 90.
Perform at ~ 160 ° C. Further, the polymerization reaction can be carried out under pressure or under normal pressure. After the completion of the polymerization reaction, the obtained polymer polyol can be used as it is as a raw material for polyurethane, but it is preferable to use it after removing unreacted monomers, decomposition products of catalysts, chain transfer agents and the like under reduced pressure.

Polyurethane foam As the polymer polyol, all of the above-mentioned ones can be applied as they are. The polyol containing a polymer polyol is the above polymer polyol or a mixture of the above polymer polyol and another polyoxyalkylene polyol, and preferably has a viscosity of 3000 cps or less. Other polyoxyalkylene polyols are not particularly limited, but those conventionally used in the art can be used. Further, the polyoxyalkylene polyol used in the production of the polymer polyol can be used if necessary.

The organic polyisocyanate compound is, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, or 80/20 of both isocyanates.
Weight ratio (80 / 20-TDI) or 65/35 weight ratio (65 / 35-TDI) mixture, crude tolylene diisocyanate (crude TDI), 4,4'-diphenylmethane diisocyanate (4,4'-MDI), 2,4'-
Diphenylmethane diisocyanate (2,4'-MD
I), 2,2'-diphenylmethane diisocyanate (2,2'-MDI), isomer mixture of diphenylmethane diisocyanate (MDI), polymethylene polyphenyl isocyanate (crude MDI), toluidine diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, Isophorone diisocyanate,
These are dicyclohexylmethane diisocyanate, and carbodiimide-modified, buret-modified, dimer, trimer, or prepolymers of these isocyanates. The organic polyisocyanate compound is used alone or in combination of two or more.

The blowing agent is water, trichloromonofluoromethane, dichlorodifluoromethane or 2,2-dichloro-.
1,1,1-trifluoroethane, 1,1-dichloro-
1-fluoroethane, methylene chloride, trichlorotrifluoroethane, dibromotetrafluoroethane, trichloroethane, pentane, n-hexane and the like are one kind or a mixture of two or more kinds.

The urethanization reaction catalyst is conventionally known and is not particularly limited. For example, as an amine-based catalyst, triethylamine, tripropylamine, polyisopropanolamine, tributylamine, trioctylamine, hexamethyldimethylamine, N-methylmorpholine, 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-1,3
-Butanediamine, N, N, N ', N'-tetramethylhexamethylenediamine, bis [2- (N, N-dimethylamino) ethyl] ether, N, N-dimethylbenzylamine, N, N-dimethylcyclohexyl Amine,
Of N, N, N ′, N′-pentamethyldiethylenetriamine, triethylenediamine, formate salts and other salts of triethylenediamine, oxyalkylene adducts of amino groups of primary and secondary amines, N, N-dialkylpiperazines Such aza ring compounds, various N, N ′, N ″-
Examples thereof include trialkylaminoalkylhexahydrotriazines, β-aminocarbonyl catalysts in JP-B-52-43517, β-aminonitrile catalysts in JP-B-53-14278, and the like. Further, as the organometallic catalyst, tin acetate, tin octylate, tin oleate, tin laurate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, lead octanoate, lead naphthenate, nickel naphthenate, naphthene. Examples thereof include cobalt acid. These catalysts are used alone or in combination of two or more, and the amount thereof is 0.0001 to 10.0 parts by weight based on 100 parts by weight of the compound having active hydrogen.

The foam stabilizer is a conventionally known organic silicon surfactant, such as L-520 and L manufactured by Nippon Unicar Co., Ltd.
-532, L-540, L-544, L-550, L-
3550, L-5305, L-3600, L-360
1, L-5305, L-5307, L-5309, L-
5710, L-5720, L-5740M, L-620
2nd grade, SH-190, SH- manufactured by Torre Silicone Co., Ltd.
194, SH-200, SPX-253, PX-274
C, SF-2961, SF-2962, SPX-280
A, SPX-294A, F-1 manufactured by Shin-Etsu Silicone Co., Ltd.
14, F-121, F-122, F-220, F-23
0, F-258, F-260B, F-317, F-34
1, F-601, F-606, X-20-200, X-
20-201, TFA-420 manufactured by Toshiba Silicone Co., Ltd.
0, TFA-4202, Gold Schmitt B
-4113 etc. are mentioned. The amount of these foam stabilizers used is the total amount of the compound having active hydrogen and polyisocyanate 1
It is 0.1 to 5 parts by weight with respect to 00 parts by weight.

The cross-linking agents include monomer polyols such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, 1,3-butanediol and 1,3-butanediol, alkanolamines such as triethanolamine and diethanolamine, Aliphatic polyamines such as ethylenediamine, diethylenetriaminetriethylenetetramine, methyleneorthochloramine, 4,4'-diphenylmethanediamine, aniline, 2,4'-tolylenediamine, 2,6'-tolylenediamine, and other aromatic polyamines And a compound having a hydroxyl value of 200 mgKOH / g or more obtained by adding ethylene oxide, propylene oxide or the like to these active hydrogen compounds. Hydroxyl value of 200 mgKOH / g obtained by adding ethylene oxide, propylene oxide, etc. to hydroquinone, resorcin, aniline, etc.
The above compounds can also be used.

In the present invention, stabilizers, fillers, colorants, flame retardants and the like can be used, if necessary, in addition to the above.

The method for producing the polyurethane foam is as follows. Polyols, including polymer polyols,
A resin solution is prepared by mixing predetermined amounts of a foaming agent, a catalyst, a foam stabilizer, a cross-linking agent and other auxiliaries. The amounts of the organic polyisocyanate compound, the polyol and the cross-linking agent used are determined so that the equivalent ratio (NCO / H) of the NCO group in the organic polyisocyanate compound and the active hydrogen in the resin liquid is 0.70 to 1.40. . The resin solution and the organic polyisocyanate compound are adjusted to a predetermined temperature, for example 20 to 25 ° C., then rapidly mixed and poured into a mold whose temperature is adjusted to a predetermined temperature, for example 30 to 70 ° C. After the reaction mixture is foam-filled in the mold, it is cured in an oven at a predetermined temperature, for example, 60 to 205 ° C. for a predetermined time, for example, 1 to 20 minutes, and the foam is demolded to obtain a desired polyurethane foam.

[0027]

EXAMPLES The present invention will be described below with reference to examples. Raw materials, abbreviations, and analytical methods used in Examples and Comparative Examples are described below. Polyols A to E: Polyoxyalkylene polyols obtained in Production Examples 1 to 5. Catalyst a; cesium hydroxide. Catalyst b; potassium hydroxide. Catalyst c; zinc-cobalt cyanide compound and zinc chloride, water,
So-called complex metal cyanation complex catalyst consisting of dimethoxyethanol. PO: propylene oxide. EO: ethylene oxide. Hydroxyl value: Esterified with pyridine solution of phthalic anhydride, and titrate excess phthalic anhydride with sodium hydroxide solution (according to JIS K 1557 method). Monool content: A high performance liquid chromatograph (HPLC) device manufactured by JASCO, using a silica-based separation column with an aminopropyl group chemically bonded, and using a hexane / 2-propanol mixture as an eluent (flow rate 1 ml / min) The liquid chromatogram of polyoxyalkylene polyol was taken, and the area ratio of triol and monool was determined from the peak area intensity detected by the differential refractometer. Further, the values of the molecular weights of triol and monool in the polyoxyalkylene polyol were obtained from the calibration curve prepared from the elution peak times of the liquid chromatograms of triol and monool having different molecular weights obtained under the same conditions. The monool content (mol%) was calculated from the values of the area ratio and the molecular weight of the above triol and monool. Since the diol component in the polyoxyalkylene polyol was hardly detected, it was ignored when the monool content was calculated. Head - toe - tail (Head-to-Tail) bond selectivity; manufactured by JEOL 400MHzC ¹³ nuclear magnetic resonance (N
MR) apparatus, using heavy chloroform as a solvent, and taking a C ¹³ NMR spectrum of this polyoxyalkylene polyol to obtain a Head-to-T (Head-to-T).
ayl) -bonded oxypropylene segment methyl group signal (16.9 to 17.4 ppm) and head-to-head (head-to-head) oxypropylene segment methyl group signal (17.7).
˜18.5 ppm). Viscosity; measured according to JIS K 1557. AN; acrylonitrile. St: Styrene. TEA; triethylamine. AIBN; azoisobutyronitrile. Polymer concentration: It is determined by adding methanol to the polymer polyol and thoroughly dispersing it, and then centrifuging to measure the weight of the methanol-insoluble matter. However, in the case of a polymer polyol containing acrylonitrile alone, it is determined from the nitrogen content by elemental analysis. Tg (glass transition temperature); DSC manufactured by Perkin Elmer
Using -7, it is determined by thermal analysis under a nitrogen atmosphere at a heating rate of 20 K / min. Polymer polyols a to i: Examples 1 to 5, Comparative Examples 1 to 1
The polymer polyol obtained in 4. Water; ion-exchanged water. L-1020; catalyst made by Active Material Chemical Co., Ltd. X-DM: Active Material Chemical Co. catalyst. KL-210; a cross-linking agent manufactured by Mitsui Toatsu Chemicals, Inc. L-5309; surfactant manufactured by Nippon Unicar Co., Ltd. TM-20; TDI-80 / 20 (mixture of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate in a weight ratio of 80:20) and Mitsui Toatsu Co., Ltd. Cosmonate MDI-CR in a weight ratio. 80/20 mixture. Physical properties of foam; JIS K-6301, JIS K-
Measured according to 6401.

1. Production of Polyoxyalkylene Polyol Production Examples 1 to 4 Catalyst I or II was added to glycerin, dehydration was performed at 100 ° C for 6 hours, and then propylene oxide was addition-polymerized under the conditions shown in Table 1, and then 15 wt% of this polyoxyalkylene polyol was used. % Ethylene oxide was addition polymerized. After completion of the reaction, water and phosphoric acid were added to neutralize, followed by drying under reduced pressure, and the produced crystals of alkali metal phosphate were removed by filtration to obtain polyols A to D. The physical property values are shown in Table 1. Production Example 5 6.93 g of catalyst C was added to glycerin, and propylene oxide was addition-polymerized under the conditions shown in Table 1. The catalyst (c) was extracted with aqueous ammonia, the polyoxypropylene polyol was purified by washing with water, potassium hydroxide was added so as to be 0.23 mol with respect to 1 mol of glycerin, and dehydration under reduced pressure was carried out at 100 ° C. for 6 hours. Next, ethylene oxide was subjected to addition polymerization under the conditions shown in Table 1. After completion of the reaction, water and phosphoric acid were added to neutralize, followed by drying under reduced pressure, and the produced alkali metal phosphate crystal was removed by filtration to obtain a polyol E. The physical property values are shown in Table 1.

[0029]

[Table 1]

2. Production of Polymer Polyols Examples 1 to 5, Comparative Examples 1 to 4 A 1 liter autoclave equipped with a thermometer, a stirrer, and a liquid feeder was charged with the polyol in a liquid-filled state and heated to 120 ° C while stirring. Polyol, AIBN, AN, St, TE mixed in advance in the ratios shown in Tables 2 and 3
The mixed solution of A was continuously charged, and a polymer polyol was continuously obtained from the outlet. At this time, the reaction pressure is 3.5k
The g / cm ² (440 kPa) and the residence time were 50 minutes. After reaching a steady state, the reaction solution obtained was heated to 120 ° C,
Unreacted monomers and TEA were removed by vacuum suction treatment at 20 mmHg for 4 hours to obtain polymer polyols a to i. The results are shown in Tables 2 and 3.

[0031]

[Table 2]

[0032]

[Table 3]

3. Production of Polyurethane Foam Examples 6-7, Comparative Examples 5-6 Polymer polyol, polyol, water, L-1020,
X-DM, KL-210, and L-5309 were mixed with stirring at a ratio shown in Table 4 to prepare a resin premix, which was adjusted to 25 ° C. TM-20 adjusted to 25 ° C. in such an amount that the equivalent ratio of NCO group and active hydrogen of resin premix becomes 1.00
Then, the amount of the resin premix prepared above was adjusted so that a foam having the desired density was obtained, and the mixture was vigorously stirred and mixed for 6 seconds, and heated to 60 ° C. in advance to apply a commercially available release agent. After pouring into an aluminum test mold, the lid was closed, the clamp was closed, and the foam was cured. 3 from the start of stirring
After minutes, the mold was unclamped, the cured flexible polyurethane foam was released from the mold, and the closed cell property was evaluated by the magnitude of the force when the foam was pressed by hand. After that, 80% of the thickness was compressed by using a roller for crushing. Two
Various physical properties were measured after 4 hours. Table 4 shows the physical properties of the foam.
Shown in.

[0034]

[Table 4]

[0035]

The polymer polyol of the present invention has a low monol content and a head-to-tail (Head-t).
Since the polyoxyalkylene polyol having a high o-Tail) bond selectivity is used as a matrix, it has a characteristic of low viscosity and can improve physical properties in a wide range of polyurethane applications. Further, even when the polymer concentration is increased, it is possible to obtain a polymer polyol having a lower viscosity than the conventional one, no particle aggregation, and good dispersion stability. The polymer polyol obtained in this manner provides a polyurethane foam excellent in physical properties such as hardness, wet heat strain, and impact resilience without causing problems such as cracking in the foam after crushing due to low closed cell properties during foaming. .

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication C08G 18/63 NEQ 65/02 NQF C08J 9/02 CFF 9/14 CFF // (C08G 18/48 101: 00) C08L 75:04 (72) Inventor, Made by Izugawa, Mitsui Toatsu Chemical Co., Ltd., 2-1-1, Tangodori, Minami-ku, Nagoya-shi, Aichi

Claims (10)

[Claims] 1. A hydroxyl value of 10 to 35 mg KOH / g, a maximum content of monool is 15 mol%, and a minimum head-to-tail bond selectivity by propylene oxide addition polymerization is 96%.
5. A polymer polyol, characterized in that polymer particles are dispersed in the polyoxyalkylene polyol which is, in an amount of 5% by weight or more and less than 30% by weight. 2. A hydroxyl value of 10 to 35 mg KOH / g, a maximum content of monool is 15 mol%, and a minimum head-to-tail bond selectivity by propylene oxide addition polymerization is 96%.
The polymer polyol having a glass transition temperature of 90 to 120 ° C. dispersed in the polyoxyalkylene polyol which is 30% by weight or more and 60% by weight or less. 3. A hydroxyl value of 10 to 35 mg KOH / g, a maximum content of monool is 15 mol%, and a minimum head-to-tail bond selectivity by propylene oxide addition polymerization is 96%.
The method for producing a polymer polyol according to claim 1, wherein the ethylenically unsaturated monomer is polymerized in the polyoxyalkylene polyol which is 4. A hydroxyl value of 10 to 35 mg KOH / g, a maximum monool content of 15 mol%, and a minimum head-to-tail bond selectivity by propylene oxide addition polymerization of 96%.
3. The method for producing a polymer polyol according to claim 2, wherein the ethylenically unsaturated monomer is polymerized in the presence of a chain transfer agent in the polyoxyalkylene polyol. 5. The polyoxyalkylene polyol is 9
Obtained by addition-polymerizing an alkylene oxide with an active hydrogen compound having 2 to 8 hydroxyl groups in the presence of an alkali metal catalyst containing at least one compound selected from cesium hydroxide and rubidium hydroxide having a purity of 0% by weight or more. The method for producing a polymer polyol according to claim 3, wherein the polymer polyol is a polymer polyol. 6. The method for producing a polymer polyol according to claim 3, wherein the ethylenically unsaturated monomer is acrylonitrile or a mixture of acrylonitrile and styrene. 7. The method for producing a polymer polyol according to claim 4, wherein an amine compound is used as the chain transfer agent. 8. An amine compound represented by the general formula (1): (In the formula, R ₁ , R ₂ and R ₃ are H and have 1 to 10 carbon atoms.
And an alkyl group having 2 to 10 carbon atoms, which may be the same or different, but not all of them are H at the same time. ) Or an amine compound represented by the general formula (2) [Chemical Formula 2] (In the formula, X represents O and NR ₂ , and R ₁ has 1 to 1 carbon atoms.
0 represents an alkyl group having 0 to 2 carbon atoms, and R ₂ represents H, an alkyl group having 1 to 10 carbon atoms, and a hydroxyalkyl group having 2 to 10 carbon atoms. 8. The method for producing a polymer polyol according to claim 7, which is a compound represented by 9. The method for producing a polymer polyol according to claim 7, wherein the amine compound is triethylamine. 10. A reaction comprising a polyol containing at least one of the polymer polyols according to claim 1 and an organic polyisocyanate compound in the presence of a foaming agent, a catalyst, a foam stabilizer, a cross-linking agent and other auxiliary agents. A method for producing a flexible high-elasticity polyurethane foam, which comprises: