JPH0135012B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing adsorptive polyurethane foams. Conventional polyurethane foams use water as a foaming method, carbon dioxide gas generated by the reaction between water and organic polyisocyanate, or low-boiling volatile substances such as trichloromonofluoromethane as foaming agents. The blowing agent is vaporized by making the temperature of the reaction system equal to or higher than the boiling point of the blowing agent due to the heat of reaction between the hydrogen-containing compound and the organic polyisocyanate and/or the reaction heat due to the trimerization reaction of the organic polyisocyanate itself. This has been utilized or a combination of water and a blowing agent has been used. With these conventional foaming methods, it has been difficult to uniformly disperse and incorporate the adsorbent into the polyurethane foam and maintain adsorption performance for the following reasons. (1) If an adsorbent is mixed into the urethane raw material before foaming, the adsorbent will adsorb water or low-boiling point volatile substances as a foaming agent, making it impossible to obtain a polyurethane foam with the desired density, resulting in serious problems. If it is excessive, all the foaming agent will be absorbed by the adsorbent and no foam will be obtained. (2) In order to obtain a polyurethane foam with a desired density, if a large excess of blowing agent is added in anticipation of the amount that will be adsorbed by the adsorbent, the adsorption capacity of the resulting polyurethane foam will be significantly reduced. , the effect of mixing the adsorbent does not appear, and the mixed adsorbent becomes a mere filler. (3) The adsorbent also well adsorbs amine catalysts conventionally used as catalysts for urethane foaming. Since the amount of the amine catalyst used is adsorbed by the adsorbent, it becomes difficult to control the urethane foaming reaction, and in extreme cases, the entire amount of the amine catalyst used is adsorbed by the adsorbent, resulting in foaming. does not occur. A first object of the present invention is to provide a polyurethane foam that has excellent adsorption performance for decolorizing, deodorizing, dehumidifying, desalting, etc. by incorporating an adsorbent. In contrast to conventional methods for producing polyurethane foam, in which foam formation, expansion and curing occur almost simultaneously, the present invention typically involves a foam formation step of inert gas dispersion by mechanical stirring, followed by foam formation. The foam formulation and manufacturing process have been improved to include two stages: heating and curing to complete the reaction. That is, in the present invention, an inert gas is used as a foam forming agent without using water and a low-boiling volatile substance as blowing agents that have been conventionally used, and an amine is used as a blowing catalyst in the conventional method. Although conventional catalysts were mainly used, metal catalysts are used in the present invention. That is, the present invention involves adding a mixture of a compound having two or more active hydrogens, an organic polyisocyanate compound, a catalyst, a foam stabilizer, other auxiliary agents, and an adsorbent to the entire mixture by mechanical stirring. A method for producing a soft to semi-rigid adsorptive polyurethane foam, comprising dispersing an active gas substantially uniformly to form a substantially structurally stable foam, and then thermoforming the foam. be. The adsorbent of the present invention can be uniformly dispersed and included in the urethane foam without deteriorating its adsorption performance. Compounds with two or more active hydrogens used in the present invention include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, trimethylene glycol, 1,3- and 1,4-butanediol, etc. Monomeric polyols, aliphatic polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, methylene orthochloroaniline, 4,4'-diphenylmethanediamine, 2,4-tolylene diamine, 2,6-tolylene diamine, etc. Alkanolamines such as aromatic polyamines, triethanolamine, diethanolamine, water, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, trimethylene glycol, 1,3- and 1,4 butanediol, 1,5-pentanediol, 1,2-hexylene glycol, 1,10-decanediol, 1,2-cyclohexanediol, 2-butene-1,4-diol, 3-cyclohexane-1,1-dimethanol, 4-methyl-
3-Cyclohexane-1,1-dimethanol, 3
-methylene-1,5-pentanediol, (2-
hydroxyethoxy)-1-propanol, 4-
(2-hydroxyethoxy)-1-butanol, 5
-(2-hydroxypropoxy)-1-pentanol, 1-(2-hydroxymethoxy)-2-hexanol, 1-(2-hydroxypropoxy)-2-
Octanol, 3-allyloxy-1,5-pentanediol, 2-allyloxymethyl-2-methyl-1,3-pentanediol, [4,4-bentroxy)-methyl]-1,3-propanediol,
3-(o-propenylphenoxy)1,2-propanediol, 2,2'-diisopropylidenebis(p-phenyleneoxy)diethanol, glycerin, 1,2,6-hexanetriol, 1,
1,1-trimethylolethane, 1,1,1-trimethylolpropane, 3-(2-hydroxyethoxy)-1,2-propanediol, 3-(2-
hydroxypropyl)-1,2-propanediol, 2,4-dimethyl-2-(2-hydroxyethoxy)-methylpentanediol 1,5,1,
1,1-tris[2-hydroxyethoxy)methyl]-ethane, 1,1,1-tris[(2-hydroxypropoxy)-methyl]propane, pentaerythritol, sorbitol, sucrose, lactose, α-methylglucoside, α-hydroxyalkyl glucoside, novolac resin, phosphoric acid, benzene phosphoric acid,
Polyphosphoric acid (e.g. tripolyphosphoric acid and tetrapolyphosphoric acid), phenol-aniline-formaldehyde ternary condensation product, aniline-formaldehyde condensation product, caprolactone, etc., aliphatic polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, methylene Aromatic polyamines such as orthochloroaniline, 4,4'-diphenylmethanediamine, 2,4-tolylenediamine, 2,6-tolylenediamine, alkanolamines such as triethanolamine, diethanolamine, ethylene oxide, propylene oxide polyether polyols obtained by adding one or more of , tetrahydrofuran, styrene oxide, etc., or polytetramethylene ether glycol, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, dipropylene Glycol, trimethylene glycol, 1,
3- and 1,4-butanediol, tetramethylene glycol, neopentyl glycol, hexamethylene glycol, decamethylene glycol,
One or more compounds having at least two hydroxyl groups such as glycerin, trimethylolpropane, pentaerythritol, and sorbitol, and malonic acid, maleic acid, succinic acid, adipic acid, tartaric acid, pimelic acid, and sebacic acid. , oxalic acid, phthanolic acid, terephthanolic acid, hexahydrophthanolic acid, aconitic acid, trimellitic acid, hemimellitic acid, etc., and one or more compounds having at least two carboxyl groups, Also, ring-opened polymers of cyclic esters such as polycaprolactone, and
39-24737, Special Publication No. 41-3473, Special Publication No. 43-22108,
Tokuko Sho 44-8230, Tokuko Sho 47-15108, Tokko Shou 47-
47597, JP-A-47-47999, JP-A-48-34991, JP-A-51-50398, JP-A-51-70286, etc. by polymerizing ethylenically unsaturated compounds in polyether polyols and/or polyester polyols described in Ethylenically unsaturated compounds suitable for preparing such compositions include acrylonitrile, styrene, and the like. Furthermore, 1,2-polybutadiene glycol and 1,4-polybutadiene glycol are used. The various active hydrogen-containing compounds described above may be used alone or in combination of two or more. Its hydroxy value is 25~
120mgKOH/g is appropriate, and the produced polyurethane foam will be soft to semi-hard. The organic polyisocyanate compound used in the present invention is a known compound and is not particularly limited, but for example, 2,4-tolylene diisocyanate, 2,6
-Tolylene diisocyanate, mixture of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate with isomer ratios of 80/20 and 65/35, crude tolylene diisocyanate, diphenylmethane-
4,4'-diisocyanate, polyphenylmethylene polyisocyanate (known as crude MDI), various known modified diphenylmethane-4,4'-diisocyanates modified with carbodiimide groups, dianisidine diisocyanate, toluidine diisocyanate, xylylene diisocyanate, etc. Isocyanate, isophorone diisocyanate, bis(2-
isocyanatoethyl) fumarate, bis(2-isocyanatoethyl) fumarate, bis(2-isocyanatoethyl) carbonate, bis(2-isocyanatoethyl) carbonate, 1,6-hexamethylene diisocyanate, 1,4-tetramethylene Diisocyanate, 1,10-decamethylene diisocyanate, cumene-2,4-diisocyanate, 4-methoxy-1,3-phenylene diisocyanate, 4-chloro-1,3-phenylene diisocyanate, 4-bromo-1,3- phenylene diisocyanate, 4-ethoxy-1,3-phenylene diisocyanate, 2,4'-diisocyanat diphenyl ether, 5,6-dimethyl-1,
3-phenylene diisocyanate, 2,4-dimethyl-1,3-phenyl diisocyanate,
4,4'-diisocyanatophenyl ether, bis5,6-(2-isocyanatoethyl)bicyclo[2,2,1]hebut-2-ene, penzidine diisocyanate, 4,6-dimethyl-1,3 −
Phenyl diisocyanate, 9,10-anthracene diisocyanate, 4,4'-diisocyanatodibenzyl, 3,3-dimethyl-4,4'-diisocyanatodiphenylmethane, 2,6-dimethyl-
4,4'-diisocyanatodiphenyl, 2,4-diisocyanatostilbene, 3,3'-dimethyl-
4,4'-diisocyanatodiphenyl, 3,3'-dimethoxy-4,4'-diisocyanatodiphenyl,
1,4-anthoradiisocyanate, 2,5-fluorene diisocyanate, 1,8-naphthalene diisocyanate, 2,6-diisocyanatobenzfuran, 2,4,6-toluene diisocyanate. These organic polyisocyanate compounds and prepolymers having an NCO terminal group from the active hydrogen-containing compound described above are used alone or in combination. The catalyst used in the present invention is preferably a catalyst that does not promote the urethane reaction much at temperatures below 60°C, but promotes the reaction when heated above 70°C; examples of these include Japanese Patent No. 938508;
Nickel acetylacetonate, diacetonitrile diacetylacetonate nickel, diphenylnitrile diacetylacetonate nickel, bis(triphenylphosphine) diacetylacetonate nickel shown in Japanese Patent Publication No. 53-43237, Patent Application Sho 53-43237
Copper acetylacetonates shown in No. 54-126411, ferrous and ferric acetylacetonates and molybdenum oxide acetylacetonates shown in Japanese Patent Application No. 54-153031. Known urethanization catalysts can also be used in the present invention, such as amine-based urethanization catalysts (triethylamine, tripropylamine, triisopropanolamine, tributylamine, trioctylamine, hexadecyldimethyl Amine, N-methylmorpholine,
N-ethylmorpholine, N-octadecylmorpholine, monoethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N,N-dimethylethanolamine, diethylenetriamine, N,N,N',
N'-tetramethylethylenediamine, N,N,
N', N'-tetramethylpropylene diamine, 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-dimethylpenzylamine, N,N-dimethylbenzidylamine, N,N-dimethylcyclohexylamine,
N,N,N',N'',N''-pentamethyldiethylenetriamine, triethylenediamine, formate and other salts of triethylenediamine, amino group oxyalkylene adducts of primary and secondary amines, N,N
-Azacyclic compounds such as dialkylpiperazines, various N,N',N''-trialkylaminoalkylhexahydrotriazines, Japanese Patent Publication No. 1973-
43517 β-Aminocarbonyl Catalyst, Special Publication 1973-
14279 β-aminonitrile catalyst, etc.). Organometallic urethanation catalysts (tin acetate, tin octoate, tin oleate, tin laurate, dibutyltin, diacetate, dibutyltin dilaurate, dibutyltin dichloride, lead octoate, lead naphthenate, nickel naphthenate, naphthenic acid) cobalt, etc.). In the present invention, the above acetylacetonate catalyst,
The urethanization catalyst and the organometallic urethanization catalyst may be used alone or in combination of two or more. These catalysts can be used after being diluted with a solvent, an active hydrogen compound as a urethane raw material, and an organic polyisocyanate compound, if necessary. The amount of the catalyst used is 0.0001 to 10 parts per 100 parts by weight of the active hydrogen compound (hereinafter, parts are by weight). As the foam stabilizer used in the present invention, known foam stabilizers that are widely used for foaming urethane foam can be used. Examples of these are organosilicon surfactants and USP3821130
Examples include polyether surfactants such as those described in . Adsorbents used in the present invention include activated carbon,
Activated clay, acid clay, silica gel, natural and synthetic zeolite, activated alumina, aluminum silicate, magnesium silicate, etc. Decolorization, deodorization, dehumidification, desalination, recovery of materials, purification, catalysts, chemical analysis,
All adsorbents widely used in industrial applications such as water softening and water softening are used. Adsorbents are used in powder or particulate form.
The amount of adsorbent added is 10% for the urethane foam.
From weight percentage (hereinafter % indicates weight %)
500 percent is used. In the present invention, other auxiliary agents such as known dyes, pigments, lubricants, etc. may be mixed. In the present invention, an inert gas is substantially added to the mixture of a compound having two or more active hydrogens, an organic polyisocyanate compound, a catalyst, a foam stabilizer, a foaming aid, etc., and an adsorbent by mechanical stirring. Equipment for uniformly dispersing and forming a substantially structurally stable foam includes Hobart mixers;
Examples include Kenwood mixers, OAKES mixers, SKG mixers, and EASE mixers. The polyurethane foam with excellent adsorption performance of the present invention can be used for purifying exhaust gas; dehumidifying packaging containers (precision measuring instruments, fruits, confectionery, etc.), packaging containers, shoe insoles, etc.
Deodorization of hospital bed cushions, seats, automobile interior parts, etc., water purifiers, industrial waste fluids, decolorization of liquids in manufacturing processes, desalination in the purification process of manufacturing processes, adsorption recovery in the recovery process, and water treatment. Used for water softening, catalysts in chemical reactions, chemical analysis, etc. Next, the present invention will be specifically explained using examples. Example 1 48 parts of a polymer polyol (hydroxyl value 32) synthesized from polyoxypropylene polyoxyethylene glycol with a hydroxyl value of 39.8, acrylonitrile, and styrene, EP-550N (manufactured by Mitsui Nisso Urethane Co., Ltd., polyoxypropylene polyoxy TDI was added to a polyol mixture consisting of 144 parts of ethylene glycol, hydroxyl value 54) and 8 parts of diethylene glycol.
-80 (Mitsui Nisso Urethane Co., Ltd., tolylene diisocyanate 2, 4 units/2, 6 units/mixing ratio (weight) of 80/20) and MN-1000 (Mitsui Nisso Urethane Co., Ltd. polyoxypropylene glycol, Hydroxyl value
Prepolymer synthesized from 168) (NCO: 28%)
Add 50 parts and further 1.0 part of copper acetylacetonate,
After adding 8 parts of L-520 (organosilicon surfactant manufactured by Nippon Unicar Co., Ltd.) and 200 parts of powdered activated carbon, and mixing these mixtures uniformly for about 1 minute, The mixture was mixed using a mold for about 10 minutes to incorporate air and form a fine and uniform foam. This foam was poured into a 200 mm x 200 mm mold to a thickness of about 2 mm, and cured at 120° C. for 10 minutes. The density of the obtained urethane foam was 300Kg/m ³ . The adsorption properties of the cured sheet were evaluated by the following method. When dry clean air is sent to a urethane foam sheet saturated with adsorbed gases (ethyl mercaptan, triethylamine, hydrogen sulfide) at room temperature and at 1 atm, the weight ratio (%) of the remaining adsorbed gas to the urethane foam sheet is adsorbed. Retention rate. The adsorption retention rates for various gases were ethyl mercaptan (20%), triethylamine (2%), and hydrogen sulfide (2.5%). Example 2 A urethane foam sheet was produced in the same manner as in Example 1. However, powdered activated alumina was used as the adsorbent instead of activated carbon. The adsorption retention rates of the urethane foam sheet of this example were ethyl mercaptan (15%), triethylamine (1.5%), and hydrogen sulfide (1.5%). Example 3 A urethane foam sheet was prepared in the same manner as in Example 1. However, powdered silica gel was used as the adsorbent instead of activated carbon. This urethane foam sheet 15.3ml (contains 2g of silica gel)
heavy metal ions (mercury, cadmium, lead)
500 ml of an aqueous solution containing 500 mg was passed through, and the residual heavy metal concentration, unit adsorption amount, and removal rate of the filtered solution were determined. The results of the heavy metal ion adsorption test are shown in Table 1. 【table】

Claims (1)

[Claims] 1. Inert gas is substantially uniformly dispersed throughout the mixture of a compound having two or more active hydrogens, an organic polyisocyanate compound, a catalyst, a foam stabilizer, other auxiliary agents, and an adsorbent by mechanical stirring. Let me,
1. A method for producing a soft to semi-rigid adsorptive polyurethane foam, comprising forming a substantially structurally stable foam and then thermoforming the foam.