JPH0688021A - Production of polyol composition and production of polyurethane molding from the composition - Google Patents

Abstract

PURPOSE:To provide a process for producing a polyurethane molding whereby vegetable residues can be used as a starting material, the residues can be used without liquefaction, and the obtained molding has good strengths and good surface appearance and does not cause the separation of vegetable residues and to provide a polyol composition as a starting material for such a polyurethane molding. CONSTITUTION:A polyol composition is obtained by frictionally crushing vegetable residues such as coffee bean extraction residues in the presence of a liquid polyol such as polypropylene glycol or polyethylene glycol by the wet process with a grinder. The frictional crushing is preferably carried out in two stages composed of coarse grinding and fine grinding. In obtaining a polyurethane molding by reacting a polyol component with a polyisocyanate component, the above polyol composition is used as at least part of the polyol component.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a polyol composition using plant residues such as coffee bean extraction residue, and further to produce a biodegradable polyurethane molded article using the polyol composition. It is about how to do it.

[0002]

2. Description of the Related Art A large amount of molded products such as polystyrene foam and polyurethane foam have been manufactured as cushioning materials and heat insulating materials. There is an urgent need to develop a molded product having

For such a purpose, the following studies have been made on the polyurethane compounded with the wood material.

Japanese Patent Publication No. Sho 50-9814 A method for producing a polyurethane foam using a lignin sulfonate as a filler.

JP-A-51-86597 A method for producing a flame-retardant polyurethane foam in which 10 to 150 parts by weight of lignin sulfonate is added to 100 parts by weight of polyol.

[Patent Document 1] Japanese Unexamined Patent Publication No. 57-190014 A polyhydroxylated sulfite lignin obtained by dissolving solid sulfite lignin in a polyol, diamine or alkanolamide and then reacting with alkylene oxide is used as a polyol for polyurethane. A composition for polyurethane used as one component.

JP-A-58-96619 A method for producing a polyurethane foam using a lignin-based polyol obtained by adding an epoxide to a lignin derivative as part or all of the polyol.

Japanese Patent Application Laid-Open No. 61-171744 A wood-based foam obtained by foaming and hardening a solution of chemically decorated wood dissolved in an organic solvent having an active group capable of polymerizing.

[Patent Document 1] JP-A-64-36628 DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention A wood solution prepared by dissolving a wood material in an organic solvent having an active group capable of polymerizing in the presence of an anhydride of a dibasic acid, a crosslinking agent or a curing agent, and If necessary, a method for producing a wood-based foam in which a foaming agent is added to foam and cure.

Japanese Unexamined Patent Publication No. 64-45440 Wood which is chemically decorated by dissolving a wood material in an organic compound having an active group capable of polymerizing and introducing a substituent into a hydroxyl group of the obtained wood solution. A method for producing a wood-based foam, in which a solution is obtained and a medicinal-chemically-decorated wood solution is foamed and cured.

JP-A-1-289823 A polyurethane containing a cellulosic substance, a hemicellulose type substance or a lignin type substance as a hard segment.

-Paper and Paper Cooperative Magazine, Vol. 44, No. 8, 849-
Page 855 Kraft lignin, sorbosis lignin, eucalyptus lignin or wood flour is liquefied and then reacted with polyisocyanate to produce polyurethane.

[0013]

Among the above, the method of "liquefying" a wood material as a polyol component and reacting this with a polyisocyanate component to obtain polyurethane involves complicated steps for liquefying a wood material. However, there is a problem that the cost is high.

This method is also limited in that only the liquefiable portion of the wood material can be used. Since the purpose of developing biodegradable molded products is not only to prevent pollution when the molded products are discarded, it is also important to effectively use wastes that are by-produced in large amounts such as plant extraction residues. ,
The fact that only a part of the wood-based material is available means that the intended purpose cannot be fully achieved.

Among the above, the method of using the wood material as the "filler" in the production of polyurethane is preferable from the viewpoint of effectively utilizing the waste by-produced in a large amount such as plant extraction residue. However, since the wood material does not substantially react with the polyisocyanate, it does not act as a polyol and is merely mixed in the molded product as a filler. Therefore, there are problems that the strength of the obtained molded product is lowered, the surface condition is deteriorated, and the wood material falls off from the molded product.

[0016] Therefore, the inventor of the present invention, based on the idea that the above-mentioned problem when the wood material is used as the filler lies in the particle size, removes plant residue such as coffee bean extraction residue. As much as possible, the inventors conducted extensive research into using the finely pulverized product as a filler in the production of polyurethane.

However, even when a state-of-the-art pulverizing system such as an impact type ultrafine pulverizer and an ultra-low temperature pulverizing system using liquid nitrogen is adopted and sufficient preliminary drying and deoiling are performed in advance, the target Faced with problems such as not being able to obtain particles with a particle size, causing overloading of the equipment, or making hard deposits inside the equipment, making continuous operation difficult, and achieving the intended purpose. There wasn't.

Under such a background, the present invention makes it possible to use a plant residue as a raw material and to use the plant residue without liquefying it, and when the molded product has good strength and surface condition, It is an object of the present invention to provide a method for producing a polyurethane molded product in which plant residues do not fall off, and a polyol composition as a raw material for the polyurethane molded product.

[0019]

The method for producing the polyol composition of the present invention is characterized in that the plant residue is wet-milled using a grinder in the presence of a liquid polyol.

Further, in the method for producing a polyurethane molded product of the present invention, when the polyol component and the polyisocyanate component are reacted to obtain a polyurethane molded product, the above-mentioned polyol composition is used as at least a part of the polyol component. It is a feature.

The present invention will be described in detail below.

<Production of Polyol Composition> As plant residues, those which are conventionally poorly disposed, for example, coffee bean extraction residue, sugar residue extraction residue, food oil production residue extraction residue, The extraction residue obtained by extracting and removing useful components from plants such as tea leaves is preferably used. In addition to extraction residue, wood flour, bamboo flour, pulp, walnut shell,
Rice husks, buckwheat husks, palm husks, bean husks and the like can also be used. The plant residue has a moisture content of 15% by weight on a wet basis.
Hereafter, it is desirable to use a dried product, especially to 10% by weight or less.

Examples of the liquid polyol include ethylene glycol, diethyl glycol, triethylene glycol,
Polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, trimethylene glycol, 1,
A relatively low viscosity polyhydric alcohol such as 4-butanediol, 1,6-hexanediol, glycerin and trimethylolpropane is preferably used.

The polyol composition of the present invention is produced by wet-milling a plant residue in the presence of a liquid polyol using a grinder.

As the grinder that is the heart of the grinder, it is preferable to use a non-porous or ceramic-like grinder from the viewpoint of permeability, strength (prevention of cracking), and growth of microorganisms. Incidentally, a general ceramic grinder has a porosity of about 40%, and water permeates instantly.

Grinding means that an object to be processed is "ground" by centrifugal force, impact, shearing force, etc. generated when passing through the gap between two grindstones.

Although the ratio of the plant residue to the liquid polyol can be set variously, the weight ratio is 80:20 to 40: 6.
It is desirable to set the ratio to 0, particularly 70:30 to 50:50. With such a ratio, the smoothest fine pulverization can be achieved, and the load on the apparatus is also within the allowable range.

It is particularly preferable that the grinding using a grinder is carried out in two stages, firstly coarse crushing and then finely crushing.
This is because when such a two-step method (or a multi-step method of more than that) is adopted, the most satisfactory results can be obtained in terms of load, throughput and fine pulverization.

By the above-mentioned wet milling, the average particle size of the plant residue after milling can be reduced to 90 μm or less, further 75 μm or less, especially 40 μm or less, and above all 10 μm or less.

<Production of Polyurethane Molded Product> A polyurethane molded product is obtained by reacting a polyol component and a polyisocyanate component. In the present invention, the above-mentioned polyol composition is used as at least a part of the polyol component. .

Examples of the polyol component which can be used with this polyol composition include ethylene glycol, diethyl glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol and trimethylene glycol. , 1,4
In addition to relatively low-viscosity polyhydric alcohols such as butanediol, 1,6-hexanediol, glycerin, and trimethylolpropane, for example, pentaerythritol, polyester polyols, polyether polyols, polybutadiene polyols or hydrogenated products thereof, polyolefins Polyols, castor oil or castor oil derivative-based polyols, alkylene oxide adducts of bisphenols, N, N, N ′, N′-tetrakis (2-hydroxypropyl) ethylenediamine and the like are used.

On the other hand, as the polyisocyanate component, tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, diphenyl sulfone diisocyanate,
Triphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 3-
Isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate, 3-isocyanate ethyl-
3,5,5-Trimethylcyclohexyl isocyanate, 3-isocyanate ethyl-3,5,5-triethylcyclohexyl isocyanate, diphenylpropane diisocyanate, phenylene diisocyanate, cyclohexylylene diisocyanate, 3,3'-diisocyanate dipropyl ether, triphenylmethane tri Examples thereof include isocyanate, diphenyl ether-4,4′-diisocyanate, and dimers and trimers of these polyisocyanates.

The proportion of the plant residue can be set in a wide range, but it is desirable to set it to 5 to 60 parts by weight based on 100 parts by weight of the total amount of the polyol component and the polyisocyanate component. When the proportion of plant residues is extremely low, the meaning of blending plant residues for the purpose of imparting biodegradability and effective use of plant residues is lost. On the other hand, when the proportion of the plant residue is extremely large, the mechanical properties of the obtained polyurethane molded product will deteriorate.

A foaming agent can be used in the urethanization reaction. As the foaming agent, water, carbon dioxide, air, hydrocarbon, methylene chloride, chlorofluorocarbon, alternative chlorofluorocarbon, etc. are used. A thermal decomposition type foaming agent such as azodicarbonamide, ammonium carbonate or sodium bicarbonate can also be used.

Other compounding agents such as foam stabilizers, solvents, reactive diluents, fillers, pigments, antioxidants, leveling agents, dispersants, antisettling agents, wetting agents, thickeners, preservatives and deodorants. A foaming agent, a flame retardant, an ultraviolet absorber and the like can be added as required.

The polyurethane molded product thus obtained is useful for various purposes such as cushioning materials or cushioning materials, heat insulating materials, building materials, various molded products, and packaging containers. In addition, the formation of a laminate layer, a coating layer, or a filled cured product of the polyurethane is also included in the molded product.

[0037]

According to the present invention, when the plant residue is wet-milled in the presence of the liquid polyol using a grinder, the milling is carried out smoothly and the plant residue is finely pulverized to the utmost limit. The material becomes fully compatible with the liquid polyol. Therefore, although the plant residue is essentially in the form of being dispersed in the liquid polyol, it does not cause sedimentation or separation phenomenon, and is activated by fine pulverization to partially react the OH groups of the plant residue. Will be shown. That is, in the polyol composition of the present invention, not only the liquid polyol but also the finely ground plant residue comes to play the role of the polyol.

As a result, when this polyol composition is used as at least a part of the polyol component in the reaction between the polyol component and the polyisocyanate component, the plant residue is essentially liquefied, but the strength is not increased. It is possible to obtain a polyurethane molded product which is large in size, has a good surface condition, and has no plant residue falling off.

[0039]

EXAMPLES The present invention will be further described with reference to examples. Hereinafter, “parts” means parts by weight.

Example 1 Extraction residue of coffee beans generated in a canned coffee manufacturing plant (dried to a moisture content of 7% by weight on a wet basis, not oiled) 600 parts of a molecular weight of 1000
Was added to and mixed with 500 parts of polypropylene glycol.

This mixture was roughly crushed using a grinder manufactured by Masuyuki Sangyo Co., Ltd. under the following conditions. Grinder Company's non-porous ceramic grinder for coarse crushing Clearance 15mm Temperature 56 ° C Time 3 minutes Capacity 220kg / hr

The coarsely crushed product was refined under the following conditions using a grinder manufactured by Masuyuki Sangyo Co., Ltd. Grinder Company's non-porous ceramic grinder for refining Clearance 2-3 mm Temperature 77 ° C Time 8 minutes Capacity 38kg / hr

The polyol composition thus obtained (a ground product of a mixture of the extraction residue of coffee beans and polypropylene glycol, the particle size of the plant residue is 30 μm or less) 1
00 parts, polymerized MDI (diphenylmethane diisocyanate) as an example of polyisocyanate component
80 parts, 3 parts water as a foaming agent, 3 silicone type foam stabilizers
Parts and 0.4 parts of dibutyltin dilaurate as a catalyst were mixed and stirred vigorously, and allowed to stand at room temperature. The mixture self-heated and foamed to obtain a light brown foam having a specific gravity of 0.026.

The resulting foam was cut into the shape of a cushioning material or a heat insulating material. This one has the necessary strength and elasticity, and also during the above cutting and actual use,
No dropout of residual powder from the foam was observed.

When the collapsed state was observed by burying the foam thus produced in soil, partial collapse was already observed after one month, and the collapse was almost completed after three months.

Example 2 430 parts of coffee bean extraction residue (dried to a moisture content of 7% by weight on a wet basis and not oiled) were put into 270 parts of polyethylene glycol having a molecular weight of 400 and mixed. .

The mixture was roughly crushed using a grinder manufactured by Masuyuki Sangyo Co., Ltd. under the following conditions. Grinder Company's non-porous ceramic grinder for coarse crushing Clearance 15mm Temperature 58 ℃ Time 1 minute 30 seconds Capacity 280kg / hr

The coarsely crushed product was refined using a grinder manufactured by Masuyuki Sangyo Co., Ltd. under the following conditions. Grinder Company's non-porous ceramic grinder for refining Clearance 6mm Temperature 96 ℃ Time 4 minutes Capacity 105kg / hr

Polyol composition thus obtained (ground product of mixture of extraction residue of coffee beans and polyethylene glycol, particle size of plant residue is 30 μm or less) 10
0 parts, polymerized MDI (diphenylmethane diisocyanate) 6 as an example of polyisocyanate component
0 parts, 3 parts water as a foaming agent, 3 silicone foam stabilizers
Parts and 0.4 parts of dibutyltin dilaurate as a catalyst were mixed and stirred vigorously, and allowed to stand at room temperature. The mixture self-heated and foamed to obtain a light brown foam having a specific gravity of 0.038.

This foam had the same strength, elasticity, residual powder drop-off prevention property, and biodegradability as in Example 1.

[0051]

INDUSTRIAL APPLICABILITY In the present invention, since the plant residue can be used without liquefying, a complicated process for liquefying can be omitted at all, and a polyurethane molded product can be manufactured at low cost. Moreover, since the entire amount of plant residues can be used, a large amount of by-product waste can be effectively used. Deoiling treatment from plant residues can also be omitted.

The obtained polyurethane molded product is preferable in terms of strength and surface condition, and there is no fear that plant residues fall off from the molded product. Moreover, since the presence of the plant residue imparts a preferable biodegradability to the molded product, even if the molded product is discarded by a route other than the regular processing route, it will eventually collapse and disappear. Also, when this is incinerated, the incineration is performed smoothly.

Claims (6)

[Claims] 1. A plant residue in the presence of a liquid polyol,
A method for producing a polyol composition, which comprises wet-milling using a grinder. 2. The method according to claim 1, wherein the average particle size of the plant residue after milling is 90 μm or less. 3. The method according to claim 1, wherein the milling is carried out in two stages, first of which is coarse crushing and then of fine crushing. 4. The method according to claim 1, wherein the plant residue is an extraction residue obtained by extracting and removing useful components from plants. 5. The method according to claim 1, wherein the weight ratio of the plant residue to the liquid polyol is 80:20 to 40:60. 6. A method for producing a polyurethane molded article, wherein the polyol composition according to claim 1 is used as at least a part of the polyol component when a polyurethane molded article is obtained by reacting a polyol component and a polyisocyanate component. Law.