JPS6354727B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing polymer polyols. More specifically, the present invention relates to a method for producing a polymer polyol with good fluidity, which provides a polyurethane with low water absorption and good weather resistance. Conventionally, polymer polyols have been produced by polymerizing ethylenically unsaturated monomers in polyether polyols in the presence of radical generators. However, the polyurethane produced using this polymer polyol has the disadvantage of high water absorption, and its physical properties are not necessarily satisfactory. The inventors
As a result of extensive research into a method for producing a polymer polyol that does not have the above-mentioned problems, the present invention was achieved. That is, in producing a polymer polyol from a polyol and an ethylenically unsaturated monomer, the present invention
The polyols include (A) polyoxypropylene and/or polyoxyethylene polyol, (B) hydroxyl group-containing vinyl polymer, and (C) polyester polyol and/or polyester polyol if necessary.
This is a method for producing a polymer polyol, characterized by using a polyol composition comprising a polyether polyol. Examples of the hydroxyl group-containing vinyl polymer (B) used in the present invention include acrylic polyols. Acrylic polyol is an acrylic (co)polymer into which a hydroxyl group is introduced, and includes a (co)polymer of a hydroxyl group-containing monomer and another polymerizable monomer. Examples of hydroxyl group-containing monomers include hydroxyalkyl (meth)acrylates [hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxyhexyl (meth)acrylate, etc.], allyl alcohol,
Examples include monoallyl ether of polyhydric alcohol. Preferably hydroxyalkyl (meth)
It is acrylate. Other polymerizable monomers include unsaturated carboxylic acid esters such as alkyl (meth)acrylates [methyl; ethyl; n-, iso, or t-butyl; 2-ethylhexyl;
lauryl (meth)acrylate, etc.], fumaric acid ester, maleic acid ester: aromatic vinyl monomers (styrene, alkylstyrene, etc.), vinyl halides (vinyl chloride, etc.), vinyl esters (vinyl acetate, etc.), unsaturated nitriles [(meta)
Acrylonitrile, etc.], unsaturated amides [(meth)
acrylamide, etc.], unsaturated carboxylic acids or anhydrides [(meth)acrylic acid, maleic anhydride,
Examples include crotonic acid, itaconic acid, etc. Preferred are alkyl (meth)acrylates. Regarding acrylic polyols, Japan Rubber Association Journal, Vol. 45, No. 5, 1972, pp. 77-78; JP-A-Sho
No. 48-1099; Special Publication No. 56-15417; Special Publication No. 15417-
No. 19273; Special Publication No. 56-15417; Special Publication No. 39-29379
No.: US Pat. No. 3,028,367 and Japanese Patent Application No. 1983-65,757 and can be used. Vinyl acetate (co)polymer hydrolysis can also be used. The hydroxyl value of vinyl polymers containing hydroxyl groups is usually 20~
200, preferably 30-150. Molecular weight is usually
1000-10000, preferably 1000-5000. The number of functional groups is usually 2 or more, preferably 2 to 4. The polyoxypropylene and/or polyoxyethylene polyol (A) used in the present invention includes active hydrogen atom-containing compounds such as polyhydric alcohols, amines/polyhydric phenols, and polycarboxylic acids, and propylene oxide and/or ethylene. It is a compound with a structure in which an oxide is added. The above polyhydric alcohols include ethylene glycol, propylene glycol, 1.4-butanediol, 1.6-hexanediol, diethylene glycol, neopentyl glycol, glycerin,
Examples include trimethylolpropane, pentaerythritol, sorbitol, and sucrose. Examples of amines include monoamines such as ammonia and butylamine; aliphatic polyamines such as ethylenediamine, trimethylenediamine, and diethylenetriamine; alicyclic polyamines such as piperazine and N-aminoethylpiperazine; phenylenediamine, tolylenediamine, and xylylenediamine. Examples include aromatic polyamines such as amine, diphenylmethanediamine, and polyphenylmethanepolyamine, and alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine. Examples of polyvalent phenols include polyvalent phenols such as pyrogallol and hydroquinone, as well as bisphenols such as bisphenol A. Examples of polycarboxylic acids include aliphatic polycarboxylic acids such as succinic acid and adipic acid; and aromatic polycarboxylic acids such as phthalic acid, terephthalic acid and trimellitic acid. Two or more kinds of the above-mentioned active hydrogen atom-containing compounds can also be used. The method for adding propylene oxide or ethylene oxide to the active hydrogen atom-containing compound may be any conventional method, and either block or random addition method may be used. Preferred polyether polyols (A) are compounds having a structure in which propylene oxide or propylene oxide and ethylene oxide are added to a polyhydric alcohol, and particularly preferred are polyhydric alcohols (especially propylene glycol, glycerin, and trimethylolpropane). Compounds with a structure in which propylene oxide and ethylene oxide are added to, especially polyoxypropylene/polyoxyethylene polyols containing terminal oxyethylene groups (chipped type and balanced type)
It is. The terminal oxyethylene group content is usually 8 to 30
% by weight, preferably 10-25% by weight. If the terminal oxyethylene group content is less than 8% by weight, the curing properties during polyurethane production will be poor, and if it exceeds 30% by weight, the water absorption of the polyurethane will increase. In addition, the oxyethylene group content in the whole (A) is usually 10
~35% by weight. In the polyol composition, the hydroxyl value of (A) polyoxypropylene and/or polyoxyethylene polyol is 150 or less, preferably 15-60, more preferably 20-45. If a polymer polyol obtained with a hydroxyl value exceeding 150 is used in a urethane molded product, the molded product will have poor elasticity. As the polyester polyol and polyester/polyether polyol (C), which may be used as necessary, examples include condensed polyester polyols obtained by reacting polyols with dicarboxylic acids (or dicarboxylic acid anhydrides and alkylene oxides), and ring-opening polymerization of lactones. Examples include polyester polyols obtained by. The above polyols include low molecular weight polyols such as ethylene glycol, propylene glycol, 1.6-
Diols such as hexanediol, diethylene glycol, neopetyl glycol, bis(hydroxymethyl)cyclohexane, bis(hydroxyethyl)benzene; trimethylolpropane, glycerin, etc.; polyether polyols (polyalkylene glycols, etc.) and mixtures thereof. Examples of dicarboxylic acids include succinic acid, glutaric acid, adipic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, terephthalic acid, dimer acid, and mixtures thereof. Also, special public service in 1977-
A polyester/polyether polyol obtained by reacting a polyoxyalkylene polyol described in No. 10078 with a polycarboxylic acid anhydride and a cyclic ether compound can also be used. The hydroxyl value of the above-mentioned polyester and polyester/polyether polyol is usually 35 to 110. (A) in the polyol composition is usually 20 to 95% (wt%
represents. (same below) Preferably 30 to 90%, particularly preferably 50 to 80%. If (A) is less than 20%, the fluidity of the polyol will be poor and the physical properties (especially temperature characteristics) of the polyurethane will be poor. If it exceeds 95%, the water absorption and physical properties of polyurethane will not be satisfactory. The content of (B) in the polyol composition is usually 5 to 80%, preferably 20 to 50%. If (B) is less than 5%, the water absorption and physical properties of the polyurethane will be insufficient, and if it exceeds 80%, the fluidity of the polyol will be poor and the physical properties of the polyurethane will be poor. The ratio of (B) and (C) is usually 1:9 to 10: by weight.
0, preferably 3:7 to 10:0. The hydroxyl value of the polyol composition is usually 200 or less,
Preferably it is 10-130, more preferably 15-110. The ethylenically unsaturated monomers used in the present invention include the following. (a) Acrylic acid, methacrylic acid and their derivatives: acrylonitrile, methacrylonitrile, acrylic acid, methacrylic acid and their salts, methyl acrylate, methyl methacrylate,
Dimethylaminoethyl methacrylate, acrylic amide, methacrylic amide, etc. (b) Aromatic vinyl monomers: styrene, α-methylstyrene, etc. (c) Olefinic hydrocarbon monomers: ethylene, propylene, butadiene, isobutylene, isoprene, 1,4-pentadiene, etc. (d) Vinyl ester monomers: vinyl acetate, etc. (e) Vinyl halide monomers: vinyl chloride, vinylidene chloride, etc. (f) Vinyl ether monomers: vinyl methyl ether, etc. Among these, preferred are acrylonitrile, methyl methacrylate , styrene, and butadiene, and particularly preferred are acrylonitrile and a combination of acrylonitrile and styrene. In the production of polymer polyols, the ratio of the polyol composition to the monomer (or polymer) used can vary over a wide range, but usually the ethylenically unsaturated monomer (or polymer) is used per 100 parts by weight of the polyol composition. combination) 2 to 70 parts by weight, preferably 5
~40 parts by weight. When polymerizing a mixture of styrene and acrylonitrile, styrene:
The blending ratio of acrylonitrile is preferably 10:90 to 60:40 (weight ratio). A known method may be used to produce a polymer polyol from a polyol composition and an ethylenically unsaturated monomer. Method of polymerization in the presence of
No. 3383351, Special Publication No. 39-24737, Special Publication No. 47-
No. 47999, JP-A-50-15894). The reaction (polymerization) temperature is usually 50 to 170°C, preferably 90 to 150°C. As the polymerization catalyst (radical generator) used in the polymerization reaction, azo compounds, peroxides, persulfates, perborates, etc. can be used, but azo compounds are preferred in practical terms. The amount used is not particularly limited, and is, for example, 0.1 to 20 parts by weight, preferably 0.1 to 15 parts by weight, per 100 parts by weight of the ethylenically unsaturated monomer (or polymer). The above polymerizations can also be carried out in the presence of solvents such as toluene, xylene and the like. The polymer polyol obtained by the present invention has 1) a lower oxygen concentration in the molecule than a polymer polyol obtained from polyoxypropylene and/or polyoxyethylene polyol or a polymer polyol obtained from a hydroxyl group-containing vinyl monomer; 2) The decrease in oxygen concentration reduces the degree of UV degradation and improves weather resistance. 3) Polyurethane obtained only from hydroxyl group-containing vinyl polymers is polyoxypropylene. The urethane of the present invention has very good water absorption properties compared to polyurethanes obtained from polymer polyols made from polyoxyethylene polyols and/or polyoxyethylene polyols, but has the disadvantage that the flexibility of the urethanes is significantly reduced. It has water absorption and flexibility. 4) A uniform solution can be obtained by using a polyester polyol that is incompatible with polyoxypropylene and/or polyoxyethylene polyol as a polymer polyol. 5) Excellent heat resistance (heat sag), water absorption, and weather resistance when polyurethane is produced. The polymer polyols obtained according to the invention are suitable as raw materials for the production of polyurethanes. In producing polyurethane, the above polymer polyols may be used alone or in combination with other polymer polyols or/and crosslinking agents,
It is carried out by reacting with an organic polyisocyanate. As the organic polyisocyanate used for polyurethane production, those conventionally used for polyurethane production can be used. For example, aliphatic polyisocyanates (hexamethylene diisocyanate, lysine diisocyanate, etc.), alicyclic polyisocyanates (hydrogenated diphenylmethane diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, etc.), aromatic polyisocyanates [tolylene diisocyanate (TDI)] , diphenylmethane diisocyanate (MDI), naphthylene diisocyanate, xylylene diisocyanate, etc.] and mixtures thereof. Among these, the preferred ones are:
Among the aromatic diisocyanates, particularly preferred are TDI and MDI. These polyisocyanates are crude polyisocyanates, such as crude TDI, crude MDI [crude diaminodiphenylmethane {condensation product of formaldehyde and aromatic amines or mixtures thereof: diaminophenylmethane and small amounts (e.g. 5 to 20% by weight)] Phosgenated product of polyallyl polyisocyanate (PAPI)] or modified polyisocyanate (for example, liquefied MDI)
It can also be used as a prepolymer containing free isocyanates obtained by reacting excess polyisocyanates (TDI, MDI, etc.) with polyols (carbodiimide-modified, trihydrocarbyl phosphate-modified, etc.), or used in combination (for example, modified A combination of polyisocyanate and prepolymer) can also be used. The polyols used in the production of the above prepolymer include polyols having an equivalent weight of 30 to 200, such as glycols such as ethylene glycol, propylene glycol, diethylene glycol, and dipropylene glycol; triols such as trimethylolpropane and glycerin; and pentaerythritol and sorbitol. Highly functional polyols; and alkylene oxide (ethylene oxide and/or propylene oxide) adducts thereof. Among these, those having 2 to 3 functional groups are preferred. The free isocyanate group content of the above-mentioned modified polyisocyanates and prepolymers is usually 10
~33%, preferably 15-30%, particularly preferably
It is 25-30%. As the crosslinking agent that may be used in combination, low-molecular polyols and polyamines can be used. Examples of low-molecular polyols include triethanolamine, diethanolamine, ethylene glycol, diethylene glycol, butanediol, trimethylolpropane, and glycerin. Examples of polyamines include tolylene diamine, xylylene diamine, diaminodiphenyl metal, and methylenebis-0-chloroaniline. The amount of crosslinking agent used can be varied depending on the required degree of rigidity, etc. In the case of low-molecular polyols, it is usually 50% by weight or less, preferably 5 to 40% by weight of the total polyol.
% amount is used. When polyamines are used, they are used in smaller amounts, for example up to 10%, preferably from 2 to 5%, based on the total of polyol and amine. If the amount of the crosslinking agent is larger than the above, the urethane becomes too rigid and the temperature characteristics deteriorate. Other polymeric polyols that may be used include polyether polyols, polyester polyols, other polymer polyols, and the like. The polyether polyol may be of a commonly used type, including compounds having at least two active hydrogen atoms [polyhydric alcohols, amines, polyhydric phenols, polycarboxylic acids mentioned as starting materials in (A) above] ] and alkylene oxide (propylene oxide, ethylene oxide, butylene oxide, etc.) adducts. When used in combination with other polymer polyols, the polymer polyol accounts for usually 5% by weight or more, preferably 20% or more, more preferably 50% by weight or more of the total polymer polyol (total of the above polymer polyol and other polymer polyols). % or more is used. When producing polyurethane using a polymer polyol, it may be foamed to produce polyurethane foam, or polyurethane resin (elastomer, sealant, sheet, paint, adhesive) may be produced without foaming. . Foaming is usually carried out using a foaming agent, but foaming can also be carried out by introducing a gas such as air during molding. As the blowing agent, water and/or a halogen-substituted aliphatic hydrocarbon blowing agent (fluorocarbons such as trichloromonofluoromethane) can be used. The amount of blowing agent used can be varied depending on the required physical properties, usage, etc., but in general, in the case of water, it is usually 6 parts or less, preferably 4 parts per 100 parts of polyol.
below. In the case of fluorocarbons, the amount is usually 30 parts or less, preferably 15 parts or less. When producing polyurethane molded articles by the RIM method, the amount of blowing agent is preferably 0.5 parts or less for water and 10 parts or less for fluorocarbons per 100 parts of polyol. Both blowing agents can also be used in combination. The ratio of polyisocyanate and active hydrogen atom-containing compound (polymer polyol, crosslinking agent, water) may be the same as that of ordinary polyurethane (resin, foam) (for example, 95 to 120 as an NCO index, especially 100).
~110). It is also possible to form polyisocyanurates (resins, foams) using isocyanate in excess (for example as an index of 120 to 1000, especially 150 to 500). Further, if necessary, the reaction can be carried out in the presence of catalysts (tertiary amines, organic tin compounds, organic lead compounds, etc.), surfactants (silicone surfactants, etc.), and other auxiliaries. If necessary, pigments, fillers, flame retardants, solvents, thixotropic agents, etc. can also be added. The polyurethane manufacturing method may be the same as conventional methods, and either the one-shot method or the prepolymer method (quasi-prepolymer method) can be applied. For example, special public relations
No. 24737, Special Publication No. 15108, No. 133417, No. 55
The foam manufacturing method described in JP-A-46-5750, etc., JP-A-50-23497, JP-A-49-99597, JP-A-53-42294, JP-A-53-16796, etc. The methods for producing elastomers, sheets, or sealants described above can be used, and the catalysts, surfactants and other auxiliary agents, equivalent ratios, amounts added, etc. described therein can also be used. The polyurethane manufacturing method is particularly useful for molding using the RIM method, but other methods such as
Molding other than RIM method (open mold molding,
It can also be applied to various methods such as integral molding with composite materials (cold cure and hot cure), slab method, on-site construction, spray method, injection, coating, and impregnation. A method for producing a polyurethane molded product by molding using the RIM method can be carried out by a conventional method.
For example, a polyol, a crosslinking agent, a catalyst, if necessary a blowing agent (water and/or fluorocarbons), a pigment, and a foam stabilizer are added and mixed uniformly to form part A, and part B is an organic isocyanate prepared in advance. ,
Fill the A and B liquid tanks of the high pressure foaming machine. Connect the injection nozzle of the high-pressure foaming machine to the injection port of the mold in advance, and mix liquids A and B with the mixing head.
The liquids are mixed and poured into a sealed mold, and after hardening, the mold is removed. The present invention will be explained below with reference to Examples, but the present invention is not limited thereto. Parts in the examples represent parts by weight. Example 1 A polyether polyol with a hydroxyl value of 42 was added to Kolben (3466 parts of propylene oxide to 134 parts of trimethylolpropane, then ethylene oxide)
(obtained by adding 400 parts) 30 parts and hydroxyl value 30
70 parts of hydroxyl group-containing vinyl polymer were respectively charged, the temperature was raised to 120 to 140°C with stirring, and then 1 part of azobisisobutyronitrile dissolved in 10 parts of acrylonitrile was added dropwise little by little over 3 hours. . After the dropwise addition, the mixture was incubated at the same temperature for 1 hour to obtain the polymer polyol () of the present invention. Example 2 Polyether polyol with a hydroxyl value of 28 (obtained by adding 4828 parts of propylene oxide to 92 parts of glycerin and then 1080 parts of ethylene oxide) 80
and 20 parts of a hydroxyl group-containing vinyl polymer with a hydroxyl value of 100.
20 parts of acrylonitrile and 1 part of azobisisobutyronitrile were reacted in the same manner as in Example 1 to obtain the polymer polyol (2) of the present invention. Example 3 50 parts of the polyether polyol with a hydroxyl value of 28 obtained in Example 2 and a hydroxyl group-containing vinyl polymer with a hydroxyl value of 150 (manufactured by Nippon Carbide Industries, Nicalite H480,
The same applies below) to a polyol composition mixed with 50 parts of
The polymer polyol () of the present invention was prepared by reacting in the same manner as in Example 1 using 25 parts of a monomer premixed with acrylonitrile and styrene in a weight ratio of 8:2 and 1 part of azobisisobutyronitrile. Obtained. Example 4 70 parts of the polyether polyol with a hydroxyl value of 28 obtained in Example 2, 20 parts of a hydroxyl group-containing vinyl polymer with a hydroxyl value of 150, and a polyester with a hydroxyl value of 45 (200 parts of ethylene glycol and 1.4-butanediol)
150-200 parts of a mixture of 200 parts and 755 parts of adipic acid
This product was obtained by reacting in the same manner as in Example 1, using 20 parts of acrylonitrile and 1 part of azobisisobutyronitrile in a polyol composition prepared by mixing 10 parts of (obtained by reacting at °C for about 20 hours). A polymer polyol () according to the invention was obtained. Example 5 70 parts of the polyether polyol with a hydroxyl value of 28 obtained in Example 2, 20 parts of a hydroxyl group-containing vinyl polymer with a hydroxyl value of 150, and a polyester/polyether polyol with a hydroxyl value of 46 (1 mol of propylene glycol with a hydroxyl value of 56) After esterifying and 2 moles of phthalic anhydride at about 150℃ for 2 hours under an alkali catalyst, about
Obtained by adding 2 moles of ethylene oxide at 120°C. 20 parts of acrylonitrile and 1 part of azobisisobutyronitrile were used to react a polyol composition prepared by mixing 10 parts of azobisisobutyronitrile in the same manner as in Example 1 to obtain the polymer polyol (2) of the present invention. Comparative Example 1 A comparative polymer polyol (A ) was obtained. Comparative Example 2 A comparative polymer polyol (B) was obtained by reacting in the same manner using the polyether polyol having a hydroxyl value of 28 obtained in Example 2 instead of the hydroxyl group-containing vinyl polymer of Comparative Example 1. . Example 6 The appearance and analytical values of the polymer polyols ~, A, and B obtained in Examples 1 to 5 and Comparative Example 1 are as shown in Table 1.

[Molding prescription]

Polymer polyol 100 1.4-butanediol 30 Black toner 4 Diflon-11u 7 DABCO 33LV 1.0 DTD 0.08 Millionate MTL NCO Index 105 (Note) Black toner; carbon black dispersed in polyether polyol. Daiflon-11u; Freon manufactured by Daikin Industries, Ltd.
11 DABCO 33LV; Amine catalyst DTD manufactured by Sankyo Air Products; Dibutyltin dilaurate millionate manufactured by Sankyoki Gosei; Modified MDI manufactured by Nippon Polyurethane [Urethane molding conditions] Polymer polyol and auxiliary agents such as crosslinking agent and catalyst Charge the mixed polyol component and isocyanate component into the raw material tank of a high-pressure foaming machine, and
After mixing liquid and B liquid with a high pressure foaming machine, the thickness is 2.5mm and the width is 300mm.
A urethane molded product was created by injecting it into a temperature-controlled sealed mold with a length of 1000 mm. Discharge rate (Kg/min) Approx. 40 Discharge pressure (Kg/cm ² ) Approx. 160 Injection time (sec) Approx. 1.8 Raw material temperature (℃) Polyol component/Isocyanate component 50/40 Mold temperature (℃) 70±2 Mold release time (Seconds) 30 Reference Examples 5 to 8 and Comparative Example 2 Polyurethane molded products were manufactured using polymer polyols ~ and A under the same molding conditions as above and according to the following formulation. [Molding recipe] Polymer polyol 100 Ethylene glycol 20 Black toner 4 Freon-11 7 DTD 0.15 Millionate MTL NCO Index 105 Tables 2 and 3 show the physical property measurement results of the polyurethane molded products obtained in the above reference examples and comparative examples. Shown below. The physical property measurement method is as follows. Immediately after the molded polyurethane was released from the mold, it was annealed at 120°C for 1 hour, and then left at room temperature for 3 days or more before measurement. Tensile strength: According to JIS K-6402. Elongation: Same as above Bending modulus: Sample size 25mm x 70mm x
Measured with 2.5mm (t), span 40mm, and punch diameter 5R. Heat sag: sample size 25mm x 150mm x 2.5
mm(t) with 100mm overhang
After leaving at 120°C for 1 hour, measure the sagging distance after cooling at room temperature for 30 minutes. Brittle temperature: According to JIS K-6301. Water absorption: Sample size 100mm x 200mm x 2.5mm
(t) Weight change rate after immersion in a water tank at 40°C for 10 days.

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Claims (1)

[Claims] 1. In producing a polymer polyol from a polyol and an ethylenically unsaturated monomer, as the polyol (A) polyoxypropylene and/or polyoxyethylene polyol, (B) a hydroxyl group-containing vinyl polymer and (C) a method for producing a polymer polyol, which comprises using, if necessary, a polyol composition comprising a polyester polyol and/or a polyester/polyether polyol. 2. The manufacturing method according to claim 1, wherein the polyol composition is a polyol composition containing 20 to 95% by weight of (A). 3. The manufacturing method according to claim 1 or 2, wherein the polyol composition is a polyol composition containing 5 to 80% by weight of (B). 4. Claims 1 to 3, wherein (A) of the polyol composition is a polyoxypropylene/polyoxyethylene polyol containing a terminal oxyethylene group.
The manufacturing method described in any of paragraphs. 5. The manufacturing method according to claim 4, wherein the terminal oxyethylene group-containing polyoxypropylene/polyoxyethylene polyol has a terminal oxyethylene group content of 8 to 30% by weight. 6. The manufacturing method according to any one of claims 1 to 5, wherein the polyol composition has a hydroxyl value of 10 to 130.