JPH0459815A - Production of polymer polyol - Google Patents

Abstract

PURPOSE:To obtain the title composition having excellent heat resistance and rigidity by reacting a specific polyol with an epoxy resin and an epoxy curing agent under a specific condition, while stirring and uniformly and stably dispersing a cured material of epoxy resin into the polyol. CONSTITUTION:(A) A polyol having 200-20,000 hydroxyl equivalent and 2-8 average functional groups is made to react with (B) an epoxy resin (preferably bisphenol A type epoxy resin) and (C) an epoxy curing agent (e.g. ethylenediamine) and/or an epoxy curing catalyst (e.g. imidazole) preferably at 30-180 deg.C, while stirring under a condition to make the number of circulations, a value obtained by dividing flow rate of delivery by an amount of liquid stirred, for 0-3/minute to give the objective composition wherein particles of the cured material of epoxy resin are dispersed into the component A.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing a polymer polyol composition that can be used in producing a urethane-based composite resin having excellent moldability and physical properties.

[Prior Art] Conventionally, a method is known in which a polymer polyol produced by radical polymerization of monomers such as acrylonitrile and styrene in a polyol is used as a raw material for a urethane-based synthetic resin.

[Problem to be solved by the invention] However, in this method, when the polymer content is increased,
The viscosity increased significantly, making it difficult to increase hardness and heat resistance. Furthermore, a polymer polyol in which a cured epoxy resin is uniformly dispersed as a polymer component in a polyol has not been found so far.

[Means for Solving the Problems] The present inventors have conducted extensive studies to obtain a polymer polyol in which a cured epoxy resin is uniformly and stably dispersed in a polyol, and as a result, they have arrived at the present invention. That is, the present invention provides (a) hydroxyl group equivalent of 200 to 20,000 and 1
a polyol having an average number of functional groups per molecule of 2 to 8;
(b) Epoxy resin and (c) epoxy curing agent and/or epoxy curing catalyst are stirred and reacted under conditions such that the number of circulation is 0 to 3/min. Dispersed polymer polyol (
Polymer polyol) and flow rate (V
) and tube diameter (D) (llt (V/D) are 0.001
This is a method for producing a polymer polyol (polymer polyol) in which the reaction is caused to flow under conditions of ~4/min.

The polyols used in the present invention include polyether polyols, polyester polyols, polydiene polyols and their hydrogenated products, and acrylic polyols having a hydroxyl equivalent of 200 to 20,000 and an average number of functional groups per molecule of 2 to 8. Examples include one type or a mixture of two or more types selected from the group consisting of:

As polyether polyols, active hydrogen atom-containing compounds [OB, N11a, N11l, C0O
Compounds having active hydrogen atom-containing groups such as H, such as polyhydric alcohols, polyhydric phenols, amines, and phosphoric acids.

Examples include polyethers having two or more hydroxyl groups in the molecule, which are obtained by adding alkylene oxide to [carboxylic acids].

The active hydrogen atom-containing compounds used in the production of the above polyether include (1) aliphatic and alicyclic polyhydric alcohols, such as alkylene glycols (having 2 to 8 carbon atoms) [ethylene glycol, propylene glycol, 1,4-butane; Glycols such as diol, l,3-butane glycol, neopentyl glycol, l,tohexanediol, cyclohexanediol, cyclohexane dimetatool, etc.:
Tri- to octa-hydric alcohols such as glycerin, trimethylolpropane, trimethylolethane, hexanetriol, pentaerythritol, diglycerin, α-methylglucoside, sorbitol, xylitol, mannitol, glucose, fructose, sucrose: (2) polyhydric alcohols; phenols, such as; hydroquinone,
Catechol, resorcinol, pyrogallol, bisphenols (bisphenol A1, bisphenol sulfone, bisphenol F, etc.), phenol-formaldehyde condensate (novolac resin, intermediate for resol resin); (3) Aliphatic, alicyclic, aromatic and heterocyclic mono- and polyamines of the formula, such as; ammonia; mono-, di- and tri-alkanolamines such as ethanolamine and/or propatoolamine;
Mono- and di-alkyl (1 to 20 carbon atoms) amines,
Alkylene (alkylene has 2 to G carbon atoms) diamine (ethylene diamine, hexamethylene diamine, etc.), polyalkylene (alkylene has 2 to B carbon atoms) polyamine (
Aliphatic amines such as diethylenetriamine, triethylenetetramine, bishexamethylenetriamine, etc.; aromatic amines such as aniline, phenylenediamine, diaminotoluene, xylylenediamine, methylenedianiline, diethyl diamine, tyltrylenediamine, diphenyl ether diamine, etc. ; Alicyclic amines such as isophorone diamine and dicyclohexylmethane diamine: piperazine, aminoethyl J reviperazine, and others JP 55-21044
Heterocyclic amines described in the publication: (4) Aliphatic, alicyclic and aromatic dicarboxylic acids such as adipic acid, tetrahydrophthalic acid, hexahydrophthalic acid and phthalic acid; (5) Phosphoric acids Examples include: orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, polyphosphoric acid, phosphorous acid, etc.; and acidic esters thereof (dibutylpyrophosphoric acid, etc.); and mixtures of two or more thereof.

Among these, polyhydric alcohols, especially dihydric to trihydric alcohols, are preferred.

Examples of the alkylene oxide added to the active hydrogen-containing compound include ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO),
, 2,3- and 1,3-butylene oxide, tetrahydrofuran, styrene oxide, epichlorohydrin, etc., and two or more of these (e.g. EO and PO)
combinations (random and/or random).

Examples of polyester polyols include alkylene (alkylene having 2 to 6 carbon atoms) glycol [ethylene glycol, propylene glycol, 1,4-butanediol, 3-butanediol, neopentyl glycol, cyclohexanediol, cyclohexane dimetatool] and 2ai carboxylic acids such as malonic acid, succinic acid, adipic acid, maleic acid, fumaric acid, azelaic acid, phthalic acid, isophthalic acid, and terephthalic acid; A condensed polyester polyol having a hydroxyl group at the end derived from an anhydride type or a mixture of two or more types, and
Examples include polycaprolactone polyols obtained by ring-opening polymerization of ε-caprolactone using a divalent or trivalent low molecular weight polyol as an initiator.

As polydiene polyols and their hydrogenated products,
Examples include polybutadiene polyol, hydrogenated polybutadiene polyol, polyisoprene diol, and hydrogenated polyisoprene diol.

As the acrylic polyol, alkyl methacrylate,
Examples include copolymers of one or more (meth)acrylic monomers such as alkyl acrylates, styrene, and acrylonitrile and hydroxyethyl (meth)acrylate.

The molecular weight of these polyols is usually 400-40.

000, preferably 1,000 to 20,000.

As the epoxy resin that can be used in the present invention, ordinary ones such as "New Epoxy Resin" [written by Hiroshi Kakiuchi, published by Shokodo Co., Ltd., May 10, 1985]] pages 5-97, "Basic Synthesis "Chemistry of Resins (New Edition)" [written by Tadahiro Miwa, Gihodo, published in 1975, pp. 371-392, "Epoxy Resins" [McGraw-Hill Book Company, 1957
Those described on page 29 of the 2010 issue can be used, and specific examples include the following.

(1) Phenol ether epoxy resins [e.g. bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol AD epoxy resin, halogenated bisphenol A epoxy resin, phenol novolak epoxy resin, cresol novolac epoxy resin, halogenated (2) Ether-based epoxy resins (e.g., condensates of epichlorohydrin with polyols, polyether polyols, etc.); (3) Ester-based epoxy resins [
Copolymers of glycidyl (meth)acrylate and ethylenically unsaturated monomers (acrylonitrile, etc.);
4) Glycidylamine-based epoxy resins [e.g. aniline, diaminodiphenylmethane, aminophenols,
Condensates of amines such as xylylene diamine, halogenated aniline, and bisaminomethylcyclohexane with epichlorohydrin, etc.; (5) Non-glycidyl epoxy resins [ring epoxy resins, epoxidized polybutadiene,
epoxidized soybean oil, etc.]; and mixtures of two or more thereof. Among these, the preferred one is (1)
and (4).

In the present invention, examples of the curing agent that can be used for curing the epoxy resin include amino compounds.

Specific examples include (1) aliphatic polyamines, such as alkylene diamines such as ethylene diamine, tetramethylene diamine, hexamethylene diamine, diethylene triamine, iminobispropylamine, bis(hexamethylene) triamine, triethylenetetramine;
Polyalkylene (alkylene has 2 to 6 carbon atoms) polyamines such as tetraethylenepentamine and pentaethylenehexamine, alkyl (1 to 3 carbon atoms) aminopropylamine, aminoethylethanolamine, iminobispropylamine, etc. ~4) or hydroxyalkyl (alkyl having 2 to 4 carbon atoms) amine compounds, aromatic ring-containing aliphatic amines such as xylylene diamine, tetrachloro-p-xylylene diamine, polyoxytetramethylene polynamine, polyoxypropylene polyamine (2) alicyclic or heterocyclic-containing aliphatic polyamines, such as menthanediamine, di-aminoethylpiperazine, 1,3-
Diaminocyclohexane, isophorone diamine, hydrogenated methylene dianiline, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro [5°5]
undecane, etc., (3) aromatic polyamines such as phenylenediamine, toluenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, benzidine, 4,4'-bis(0-toluidine), thiodianiline, dianisidine, methylenebis(o-chloroaniline)
, bis(3,4-diaminophenyl)sulfone, diaminoditolylsulfone, 2. (4) Polyamide polyamines such as triaminopyridine, 4-chloro-〇-phenylenediamine, 4-methoxy-tomethyl-phenylenediamine, -monoaminobenzylamine, 4,4'-diamino-3,3'-dimethyldiphenylmethane, etc. (Condensates of the above polyamines and dimer acids) (5) Benzoguanamine and/or alkylguanamine and modified products thereof, and (6) dicyandiamide.

The epoxy curing agent is usually used in an amount close to the equivalent (about the same number of equivalents) as the epoxy group of the epoxy resin, but either may be present in excess (for example, about 10% or more).

Epoxy curing catalysts can be used with or in place of epoxy curing agents. Specific examples of epoxy curing catalysts include (1) tertiary amines, such as pyridine, quinoline, imidazole, N, trimethylcyclohexylamine;

Triethylamine, N-methylmorpholine, toethylmorpholine, triethylenediamine, N, trimethylamyline, N, dimethylbenzylamine, tris(N
, N-dimethylaminomethyl)phenol, etc. (2)
Quaternary ammonium compounds, such as tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride, tetramethylammonium hydroxide, etc. (3)
Basic alkali metal compounds, such as sodium methoxide, caustic potash.

(4) Metal halides, such as potassium 2-ethylhexanoate, such as 5nC14, FeC15l 1tc
h,, 5bC1s+BF,, ZnC15t
Zn9r2. (5) organometallic compounds such as triethylaluminum, aluminum isopropoxide, tetraisopropyl titanate, diethylzinc, n-butoxylithium, zinc acetate, lead 2-ethylhexanoate, acetylacetonate compounds ( (6) phosphorus compounds, such as trialkylphosphine, trialkylphosphine oxide, phosphonium salts, etc., (7) boron compounds, such as trialkyl-, triaryl- or tricyclo Examples include alkyl borates and the like.

The curing catalyst is used in an amount normally used for curing epoxy resins, usually 0.5 to 20% by weight, preferably 0.5 to 10% by weight of the epoxy resin.

The proportion of cured epoxy resin particles in the composition of the present invention is
It is usually 5 to 80% by weight, preferably 10 to 70% by weight.

In producing the composition of the present invention, other additives may be used as necessary. This additive includes flame retardants (
(phosphorus compounds, halogen compounds, antimony compounds, etc.)
, colorants (pigments, dyes), internal mold release agents, anti-aging agents, antioxidants, plasticizers, bactericides and fillers [carbon black, zinc oxide, calcium oxide, lead dioxide, titanium oxide, cane earth, glass] Examples include fibers and their crushed products (cut glass, milled glass, glass flakes, etc.), glass balloons, organic balloons, talc, mica, etc.

The reaction temperature when producing the composition of the present invention is usually 20 to
The temperature is 200°C, preferably 30°C to 30°C.

The composition of the present invention can be produced by a conventional method,
For example, a curing agent and/or curing catalyst may be added to a mixture and dissolved epoxy resin in a polyol at a constant temperature, or the polyol, epoxy resin, curing agent and/or curing catalyst may be mixed and dissolved. They may be mixed at the same time and then reacted at a constant temperature.

The composition of the present invention can be produced using either a batch method or a continuous method.

An important factor in producing the polymer polyol of the present invention is the degree of stirring after uniformly mixing the polyol, epoxy resin, and epoxy curing agent and/or epoxy curing catalyst. If the shear is too large, stirring of the liquid will cause too much turbulence in the system (if this occurs, the epoxy resin cured particles produced by the reaction will aggregate, making it impossible to obtain a dispersion).

When producing the composition of the present invention in a patch-type reaction tank,
A stirrer may also be used. The stirrer may be of any type, such as a propeller-type stirrer, a paddle-type stirrer, a turbine-type stirrer, and the like.

The number of circulations, which is an indicator of the degree of stirring, is usually 0 to 37.
minutes, preferably 0 to 27 minutes. If the number of circulation exceeds 37 minutes, the polymer components will aggregate and no polymer polyol will be obtained.

The number of circulations referred to here is the value obtained by dividing the discharge flow rate by the amount of stirring liquid. Note that the discharge flow rate is expressed as the product of the discharge area of the stirring blade and the discharge speed ("Kagakusei", September 1981 issue, page 15).

When producing the composition of the invention in a continuous manner, tubes are used. The tube diameter is usually 1 to 100 cm.

The length of the tube is typically 0.1"lOm.

Flow velocity (v) and pipe diameter (D) (7) Ratio (V/D)! t, 0.
0.001 to 4/min, preferably 0.01 to 37 min. If V/D exceeds 4/min, the polymer components will aggregate and no polymer polyol will be obtained.

The particle size of the cured product particles present in the polymer polyol of the present invention can be varied depending on the type of polyol used, the type of epoxy resin, curing agent and/or curing catalyst, and the amount of stirring, but is usually 0.1 ~500μ praise.

[Examples] The present invention will be specifically explained below using Examples, but the present invention is not limited to these Examples. The composition of the raw materials used in the Examples and Comparative Examples is as follows.

Note that parts and % represent parts by weight and % by weight, respectively.

(1) Polyol Polyol (a): 92 parts of glycerin with PO5゜1
Trifunctional polyether polyol (molecular weight 6,000) to which a mixture of 00 parts and EO 800 parts was added Polyol (b): Hydrogenated polyisoprene glycol (2) with a molecular weight of 2500 Epoxy resin: Epoxy resin (a): Bisphenol A Glycidyl ether (epoxy equivalent 19o) Epoxy resin (b): Tetraglycidyldiaminodiphenylmethane (epoxy equivalent 125) (3) Epoxy curing agent Curing agent (a): Diaminodiphenylmethane (active hydrogen equivalent 49-5) 1M agent (b) Nidiaminodicyclohexylmethane (active hydrogen equivalent 52.5) Example 1 Polyol (a) 700 in a container with stirring and temperature control
After adding 238 parts of epoxy resin (A) and 82 parts of curing agent (A) and mixing them uniformly, 100 parts of epoxy resin (A) was added and mixed uniformly.
The temperature was raised to ℃. Thereafter, the reaction temperature was kept at 100-130° C. and the reaction was carried out for 5 hours with the number of circulations being 07 minutes (stirring stopped).

Finally, remove low volatile matter using a vacuum pump to obtain a polymer concentration of 30%.
% of milky white polymer polyol was obtained.

Examples 2 to 4 Polymer polyols (1) and (2) were produced in the same manner as in Example 1 under the conditions shown in Table 1.

Comparative Example 1 Polyol (a) 700 in a container with stirring and temperature control
1, 238 parts of epoxy resin (A), and 62 parts of curing agent (A) were added, mixed uniformly, and heated to 100°C with gentle stirring.
The temperature rose to . Thereafter, the reaction was carried out for 5 hours while maintaining the reaction temperature at 100-130"C with a circulation rate of 5/min (vigorous stirring).

Finally, the particles of the polymer polyol obtained by removing low volatile matter using a vacuum pump were aggregated, and the particles and liquid were separated.

Table 1 After heating to 100℃ Diameter 5 CL Length 3 m
lc/min (v/d=0.2) in a stainless steel tube.
It was run with water and reacted. Finally, low volatile components were removed using a vacuum pump to obtain a milky white polymer polyol I with a polymer concentration of 30%.

Examples 5 to 7 Polymer polyols (1) and (2) were produced in the same manner as in Example 1 under the conditions shown in Table 1.

Comparative Example 2 The length of the tube was set to elm, and the flow rate was set to 25c/min (V/d=
When the reaction was carried out in the same manner as in Example 4 except for step 5), the tube was clogged about 1 hour after the start of the reaction and no polymer polyol was obtained.

Unmeasurable wealth Example 4 700 parts of polyol (a), 238 parts of epoxy resin (a)
and 62 parts of curing agent (A) were uniformly dissolved and mixed at approximately 70°C Table 2 It is stably dispersed and contains a larger amount of hard particles than conventional polymer polyols using monomers such as acrylonitrile-styrene. Therefore, when used as a polyurethane resin, the heat resistance and rigidity are superior to those using conventional polymer polyols.

Therefore, - the polymer polyol produced by the method of the present invention is useful as a raw material for producing soft and rigid polyurethane foams, semi-rigid and rigid polyurethane elastomers, etc., and its practical value cannot be measured at all [Effects of the invention]

Claims (1)

[Claims] 1. (a) a polyol having a hydroxyl equivalent of 200 to 20,000 and an average number of functional groups per molecule of 2 to 8; (b)
The epoxy resin and (c) the epoxy curing agent and/or the epoxy curing catalyst are stirred and reacted under conditions such that the number of circulation is 0 to 3 minutes.(a) Particles of the cured epoxy resin are dispersed in the mixture. A method for producing polymer polyols. 2. (a) a polyol having a hydroxyl equivalent of 200 to 20,000 and an average number of functional groups per molecule of 2 to 8; (b)
Epoxy resin and (c) epoxy curing agent and/or epoxy curing catalyst are introduced into the tube at a flow rate (V) and a tube diameter (D).
A method for producing a polymer polyol, wherein particles of a cured epoxy resin are dispersed in (a), which is reacted by flowing under conditions such that the ratio (V/D) of (V/D) is 0.001 to 4/min.