KR20100032124A - Method of forming polyurethane - Google Patents

Abstract

PURPOSE: A method for forming a light polyurethane mold is provided to prepare a polyurethane molded body with excellent flame resistance using light weight aggregates with big particles and to reduce used amount of the polyurethanes. CONSTITUTION: A method for forming a polyurethane mold comprises the steps of: (a) preparing a polyurethane prepolymer by mixing polyol, amine, diisocyanate and foaming agent; (b) making bubbles by stirring the polyurethane prepolymer; (c) preparing filler by mixing 8-90 parts by weight of prepolymer and 10-92 parts by weight of light weight aggregates; and (d) injecting the filler into a mold, and foaming and curing the filler.

Description

Manufacturing method of polyurethane molded object {METHOD OF FORMING POLYURETHANE}

The present invention relates to a method for producing a polyurethane molded article, and more particularly, to a method for producing a polyurethane molded article having flame resistance, including a lightweight aggregate.

Conventional building panels are filled with fillers such as styrofoam particle plates, polyurethane sponges, and glass wool as fillers therebetween.

However, Schirofoam particle plate of the above filler material is very weak to heat, and if a fire occurs, a large amount of toxic gas is generated, resulting in damage to life, property damage and release of air pollution, resulting in environmental damage. . In addition, the styrofoam filled inside the panel has a short life span of 4 to 5 years, and the filling effect of the panel is rapidly reduced in a short period of time, resulting in a weakening of the building as well as the soundproofing and insulation of the original purpose of use. .

Even when polyurethane is installed as a filler, it is vulnerable to heat and water, and in case of fire, it emits a large amount of harmful gas like styrofoam. In addition, glass wool (glass wool) in the production process and installation process of the non-combustible material or panel by generating the dust of the glass powder, the worker inhales the dust of the glass powder causes carcinogenesis, causing occupational diseases.

The present invention has been made to solve the above problems, and an object of the present invention is to provide a method for producing a polyurethane molded article having excellent flame resistance by mixing the foamed polyurethane prepolymer with a lightweight aggregate.

According to the present invention, there is provided a method for preparing a polyurethane prepolymer by mixing a polyol, an amine, a diisocyanate, and a blowing agent; Agitating and foaming the polyurethane prepolymer; Preparing a filler by mixing 8-90 parts by weight of the foamed polyurethane prepolymer and 10-92 parts by weight of the lightweight aggregate; Injecting the filler into a molding mold and foaming and curing the filler; There is provided a method of producing a polyurethane molded body comprising a.

The production method of the polyurethane molded product according to the present invention has the following effects.

First, it is excellent in flame resistance by using a lightweight aggregate having a large particle size.

Second, since the polyurethane foamed and mixed with the light aggregate, the amount of polyurethane is reduced because the amount of polyurethane is mainly applied to the surface of the light aggregate and the amount of penetration into the air gap between the light aggregate is reduced. Therefore, the polyurethane molded object which is light and excellent in flame resistance can be obtained. It also has the effect of reducing costs.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

Preparing a polyurethane prepolymer by mixing a polyol, an amine, a diisocyanate and a blowing agent (step a), stirring and foaming the polyurethane prepolymer (step b), and 8-90 parts by weight of the foamed polyurethane prepolymer And preparing a filler by mixing 10 to 92 parts by weight of the lightweight aggregate (step c), and inserting the filler into a molding mold and foaming and curing (d step).

The preparation of the polyurethane prepolymer by mixing polyols, amines, diisocyanates and blowing agents (step a) can take various forms. Polyols, amines, diisocyanates and blowing agents may all be mixed together, some polyols and diisocyanates may be mixed to make composition (A), and the remaining polyols and amines and blowing agents may be mixed to prepare other compositions (B) first. There is also a method of mixing the composition A and composition B to produce a prepolymer.

The polyol consists of at least one selected from the group consisting of polyester-polyols, polyether-polyols and diols, with polyester-polyols, polyether-polyols and diols having an average hydroxyl number of 10-900 mgKOH / g And having hydroxyl molecular weight of 1.5-6 and molecular weight of 140-20,000. The hydroxyl groups of polyols and diols cause urethane reactions with isocyanate groups of diisocyanates.

The amines are triethylenediamine (TEDA), diethylenetriamine (DETA), triethanolamine (TEA), pentamethyldiethylenetriamine (PMDETA), dimethylcyclohexylamine (DMCHA), tetramethyl hexane diamine (TMHDA), Dimethylthiotoluenediamine (DMTDA), 4,4'-methylene-bis- (2-methylaniline) (MMA), diethyltoluenediamine (DETDA), 4,4'-methylene-bis- (3-chloro-2.6 -Diethylaniline) (MCDEA), methylene-bis-orthochloroaniline (MBOCA), 4,4'-methylene-bis- (2.6-diethylaniline) (MDEA), methylenedianiline (MDA), 4,4 '-Methylene-bis- (2-chloro-6-ethylaniline) (MCEA), diethylamino propyl amine (DEAPA), isophorone diamine (IPDA), catamine, aldimine and oxazolidine Use one or more of them. Reaction with amines and diisocyanates results in urea bonds.

The diisocyanate is added in excess so that the remaining NCO is 3-28% by weight after the reaction. Diisocyanates include 2,4- / 2,6-toluene diisocyanate, diphenylmethane diisocyanate, 2,4 '-/ 4,4'-diphenylmethane diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, Any one or more selected from the group consisting of hydrogenated diphenylmethane diisocyanate and 1,6-hexamethylene diisocyanate is used.

The blowing agent is a material that forms bubbles during the polymer reaction, and is divided into two types of chemical blowing agents and physical blowing agents.

The former uses the activity of the isocyanate group of the diisocyanate and is foamed by the carbon dioxide produced by the reaction with water. Therefore, the water is used as a blowing agent. The latter forms bubbles by incorporating gas or generating heat of reaction using a decomposition or evaporating blowing agent. It does not participate in polymer reactions. Freon, hydrochlorofluorocarbon (HCFC), cyclopentane, etc. are used as physical blowing agents.

Catalysts may be added to facilitate the reaction of the polyurethane prepolymer. Catalysts are substances that promote chemical reactions and do not participate in the reaction. As the catalyst used in the preparation of the polyurethane prepolymer, tertiary amine catalysts and organic metal catalysts are used. As catalysts for promoting the isocyanate reaction with polyols, organometallic catalysts such as tin compounds and lead compounds, and some tertiary amines such as tetraethylenediamine (TEDA) and tetramethylenediamine (TMDA) are used.

DMPA can be added to impart hydrophilicity to the polyurethane prepolymer. DMPA is a structure having two -OH groups and -COOH. -OH acts as a chain extender by carrying out a urethane bond, and -COOH is poly-linked through an ionic bond with a neutralizing agent (usually tertiary amine) having a reverse charge. It serves to impart hydrophilicity to the urethane prepolymer. As a solvent for dissolving DMPA, one or more of N methyl 2 pyrrolidone (NMP), acetone, and anon can be selected and mixed. Such solvents also serve to control the viscosity of the polyurethane prepolymer. In addition to the method of mixing DMPA, other ionic diols may be used, or ionic groups may be introduced by chemical modification or grafting of functional groups to impart hydrophilicity.

The polyurethane prepolymer is a reaction retardant consisting of at least one selected from the group consisting of 2,4-pentanedione, methanesulfonic acid, benzenesulfonic acid, benzoyl chloride, acetic acid and phosphoric acid based on the total weight of the polyols, amines and diisocyanates. 0.01 to 1% by weight may be added. By adding a reaction retardant, water can be absorbed in the air to delay the reaction of the diisocyanate with water.

In addition, a flame retardant for improving the flame retardant effect, a foam stabilizer, an antioxidant, a pigment, and the like, which are additives for securing the mixing properties, stability, and the like of the raw materials, may be added.

Next, the step (b) of foaming by stirring the polyurethane prepolymer will be described. A foamed polyurethane prepolymer can be obtained by stirring the polyurethane prepolymer at high temperature under a nitrogen atmosphere at 40 ° C. When water is used as the blowing agent, foaming proceeds while the remaining NCO of water and diisocyanate reacts to generate CO ₂ gas. In the case of using a physical blowing agent such as Freon, hydrochlorofluorocarbon (HCFC), cyclopentane (cyclopentane), the foaming proceeds while evaporated by the heat of reaction. Stirring in a nitrogen atmosphere is intended to prevent the reaction of moisture in the air with the remaining NCO.

Next, the step (step c) of preparing the filler will be described. Fillers may be obtained by mixing lightweight aggregate with the foamed polyurethane prepolymer.

Lightweight aggregate is pulverized any one selected from the group consisting of vermiculite, pearlite, granite, clay blood box, silica, volcanic power, pumice and obsidian, or after mixing and grinding two or more, and then foaming by heating at 800-1300 ℃ It is made by cooling.

When heated to a high temperature, vermiculite, pearlite and the like soften, and the crystallized water expands to about 6 to 7 times its original size by evaporation, thereby decreasing its density. Crush the light aggregate thus obtained and use only thick grains of 0.1 ~ 10㎜. When using lightweight aggregate with particle size less than 0.1㎜, it is difficult to have flame resistance, so use only thick grains.

By using the foamed polyurethane prepolymer, the polyurethane prepolymer is applied to the surface of the lightweight aggregate, and the polyurethane prepolymer hardly penetrates into the voids between the lightweight aggregates. This is because the foaming prevents much of the surface of the lightweight aggregate from coming into contact with the polyurethane prepolymer and with the gas present in the interior of the polyupetane prepolymer, so that the wetting is not sufficient. Therefore, excellent polyurethane resistance and light polyurethane molded body can be obtained.

Finally, a step (d) of the filler is poured into the molding mold and foamed and cured. In order to foam and harden the filler at high speed, heated moisture is injected into the filler immediately before or simultaneously with the molding mold. The filler injected into the molding mold reacts with the injected hot water to expand and cure. When words, when spraying the heated water in the filling material, water is causing a residual NCO urea reaction and present in the polyurethane prepolymer, and in the process CO ₂ gas occurs, is cured while foaming up. When the polyurethane prepolymer is treated to be hydrophilic, moisture easily penetrates and the reaction proceeds quickly. Since foaming and curing are completed within 30 seconds, there is no need for a separate holding time for curing, and thus a manufacturing time is very short. The molding mold can be preheated to 20-120 ° C. to further shorten the foaming and curing time.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited only to these Examples.

Example 1

(Step a) 100 g of a polyether polyol (trade name: PP-2000, manufacturer: Korean Polyol) having an average hydroxyl number of 56 mgKOH / g and a hydroxyl functionality of 2 in a 3 L reactor in a nitrogen atmosphere capable of temperature control, Polyether polyol having an average hydroxyl number of 37 mgKOH / g and a hydroxyl functionality of 2 (product name: PP-3000, manufacturer: Korean Polyol) 100 g, a polyether polyol having an average hydroxyl number of 56 and a functionality of 3 (GP-2000 manufacturer: Korea Polyol) 70 g, 50 mg of polyether polyol (brand name: GP-3000, manufacturer: Korea Polyol) having an average hydroxyl number of 57 mgKOH / g and 3 functionalities, mixed, and toluene isocyanate Add 300 g of annette (trade name: TDI-80, manufacturer: BASF) by dropwise addition and react at 70-90 ° C. 50 g of 1.4 butanediol (brand name: 1.4BD, manufacturer name: Samsung Fine Chemicals) was added to the chain to extend the remaining NCO to 12% by weight.

100 g of polyether polyol (brand name: PP-2000, manufacturer: Korea Polyol) 100 g, Tris (2-chloroethyl) phosphate (brand name: TCPP manufacturer: Sungbo Chemical) 30g, blowing agent halogenated hydrocarbon : 70 g of HCFC141B, manufacturer: Ulsan Chemical), 25 g of foam stabilizer (trade name: B-8404, manufacturer: Goldschmidt), and 15 g of amine (trade name: aldimine, manufacturer: Kyungsung Industry) were separately prepared.

In the 8 L nitrogen atmosphere mixer capable of temperature control, the above prepared raw materials were added in steps 1 and 2 (step b), and foamed by stirring at high temperature at 40 ° C. The residual NCO after the reaction of the polyurethane prepolymer is 8.5% by weight.

(Step c) 4,200 L of lightweight aggregate was added to the foamed polyurethane prepolymer so that the polyurethane prepolymer was evenly applied to the aggregate surface.

(d) Put the mixed lightweight aggregate into the prepared mold, and spray and squeeze the heated moisture and compress and foam.

[Example 2]

(Step a) 100 g of polyester polyol (trade name: AK2001, manufacturer: Aekyung Emulsifier) having an average hydroxyl number of 300 mgKOH / g and a hydroxyl functionality of 2 in a 3 L reactor in a nitrogen atmosphere capable of temperature control. 100 g of polyethylene glycol having 55 mgKOH / g of hydroxyl number and hydroxyl functionality of 2 (brand name: PEG-1000T, manufacturer: Green Soft Chem), 50 g of 1.4 butanediol (trade name: 1.4BD manufacturer: Samsung Fine Chemicals) as a chain extender 40 g of a hydrophilic emulsifier dimethylol propionic acid (DMPA) and 40 g of solvent N methyl 2 pyrrolidone (NMP) (manufacturer: BASF) are mixed and dissolved, and a dibutyl tin dilaurate (DBTDL) catalyst (manufacturer: air product) is mixed with each other. 3 g were mixed to obtain an organic ion polyol.

 The temperature was raised to 70 ° C. and 600 g of isocyanate (MDI) (manufactured by BASF) was added dropwise to the organic ion polyol to obtain an NCO excess prepolymer. 150 g of acetone and 30 g of flame retardant (TCPP) were mixed and diluted therein.

100 g of polyethylene glycol (trade name: PEG-1000T, manufacturer: Green Softchem) having an average hydroxyl number of 55 mgKOH / g and a hydroxyl functionality of 2 in a 3 liter reactor in a nitrogen atmosphere capable of temperature control, a foaming agent silicone (brand name) : L-3002, manufacturer: Witco) 25 g, Tris (2-chloroethyl) phosphate (trade name: TCPP manufacturer: Sungbo Chemical) 30 g, amine (trade name: oxazolidine, manufacturer: ICL) 15 g, halogenated hydrocarbon (brand name HCFC141B Manufacturer: Ulsan Chemicals) 80 g was mixed.

The raw materials prepared in steps 1 and 2 under a nitrogen atmosphere in a 8 L mixer capable of temperature control were foamed by a high speed mixing reaction (step b) at a temperature of 40 ° C. The residual NCO after the reaction of the polyurethane prepolymer is 9% by weight.

(Step c) 5,000 liters of the fired aggregate selected in the granular state was added to the foamed polyurethane prepolymer and mixed at a low speed so that the polyurethane prepolymer was evenly applied to the aggregate surface.

(d) Put the mixed lightweight aggregate into the prepared mold, and spray and squeeze the heated moisture and compress and foam.

Example 3

(Step a) 200 g of a polyether polyol (trade name: PP-2000, manufacturer: Korean Polyol) having an average hydroxyl number of 56 mgKOH / g and a hydroxyl functionality of 2 in an 8 L reactor in a nitrogen atmosphere with temperature control. GP-1000 100g, 1.4g butanediol (brand name: 1.4BD manufacturer: Samsung Fine Chemicals) 50g, foaming agent (brand name: L-3002, manufacturer name: Witco) 25g, halogenated hydrocarbon (brand name: HCFC141B, manufacturer: Ulsan Chemical) ) 200 g of toluene isocyanate (trade name: TDI-80, manufacturer: BASF) was added to a mixture of 80 g and 25 g of an amine (trade name: aldimine, manufacturer: KK), and the remaining NCO was stirred at a temperature of 70-90 ° C. to 10.5. Polyurethane prepolymer (680 g) was obtained by weight.

(b step) foaming the polyurethane prepolymer by high speed agitation, (c step) adding 3,000 l of vermiculite, which is a lightweight stone, to the foamed prepolymer so that the polyurethane prepolymer is applied only to the surface, and then (d step) heating molding Put into mold and spray and press harden.

Table 1 shows the composition of the filler used in Examples 1 to 3.

TABLE 1

Example 1 Example 2 Example 3 Product Name Quantity Product Name Quantity Product Name Quantity Polyols and diols PP-2000 200 AK2001 200 g PP-1000 200 PP-3000 100 PET1000T 100 g GP-1000 100 GP-2000 70 1.4BD 50 1.4BD 50 GP-3000 80 1.4BD 50 Hydrophilic emulsifiers DMPA 40 menstruum NMP 40 Acetone 150 Isocyanate TDI-80 300 MDI 600 TDI-80 200 Flame retardant TCPP 30 TCPP 30 blowing agent HCFC141B 70 HCFC141B 80 HCFC141B 80 Foam stabilizer Silicon8404 25 Silicone 8404 25 Silicon8404 25 Amine Aldimine 15 Oxazolidine 15 Aldimine 25 catalyst DBTDL 3 Lightweight aggregate Effervescent vermiculite 4200ℓ Foam Pearlite 5,000ℓ Effervescent vermiculite 3,000ℓ

Claims (12)

In the method for producing a polyurethane molded article, (a) mixing a polyol, an amine, a diisocyanate and a blowing agent to prepare a polyurethane prepolymer; (b) stirring the polyurethane prepolymer to foam; (c) preparing a filler by mixing 8-90 parts by weight of the foamed polyurethane prepolymer with 10-92 parts by weight of the lightweight aggregate; And (d) injecting the filler into a molding mold and foaming and curing; Method for producing a polyurethane molded body comprising a. The method of claim 1, In step (a), The polyol is a method for producing a polyurethane molded body, characterized in that made of at least one selected from the group consisting of polyester-polyol, polyether-polyol and diol. The method of claim 2, The polyol has a mean hydroxyl number of 10-900mmKOH / g, a hydroxyl functional group of 1.5-6, a molecular weight of 140-20,000, the method for producing a polyurethane molded product. The method of claim 1, In step (a), The amine is triethylenediamine (TEDA), diethylenetriamine (DETA), triethanolamine (TEA), pentamethyldiethylenetriamine (PMDETA), dimethylcyclohexylamine (DMCHA), tetramethyl hexane diamine (TMHDA), Dimethylthiotoluenediamine (DMTDA), 4,4'-methylene-bis- (2-methylaniline) (MMA), diethyltoluenediamine (DETDA), 4,4'-methylene-bis- (3-chloro-2.6 -Diethylaniline) (MCDEA), methylene-bis-orthochloroaniline (MBOCA), 4,4'-methylene-bis- (2.6-diethylaniline) (MDEA), methylenedianiline (MDA), 4,4 '-Methylene-bis- (2-chloro-6-ethylaniline) (MCEA), diethylamino propyl amine (DEAPA), isophorone diamine (IPDA), catamine, aldimine and oxazolidine Method for producing a polyurethane molded product, characterized in that any one or more. The method of claim 1, In step (a), The diisocyanate is 2,4- / 2,6-toluene diisocyanate, diphenylmethane diisocyanate, 2,4 '-/ 4,4'-diphenylmethane diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate , At least one selected from the group consisting of hydrogenated diphenylmethane diisocyanate and 1,6-hexamethylene diisocyanate. The method of claim 1, In step (a), Preparation of polyurethane moldings further comprising adding at least one catalyst selected from the group consisting of tetraethylenediamine (TEDA), tetramethylenediamine (TMDA), dibutyltindilaurate (DBTDL) and tin (Tin) Way. The method of claim 6, The catalyst is a method for producing a polyurethane molded product, characterized in that the addition of 0.01 to 1.5% by weight relative to the polyol. The method of claim 1, In step (a), A method for producing a polyurethane molded body further comprising a flame retardant. The method of claim 1, In step (a), Method for producing a polyurethane molded product further comprising a foam stabilizer. The method of claim 1, In step (a), The blowing agent is a method for producing a polyurethane molded product, characterized in that any one or more selected from the group consisting of CFC, HCFC, cyclopentane, water. The method of claim 1, In the step (c), The lightweight aggregate is pulverized any one selected from the group consisting of vermiculite, pearlite, granite, clay blood box, silica, volcanic power, pumice and obsidian, or mixed and pulverized two or more, and then heated and foamed at 800-1300 ° C. After that, it is a lightweight foamed aggregate produced by cooling the method for producing a polyurethane molded body. The method of claim 11, Specific gravity of the lightweight aggregate is 0.05-0.2, the size of the particle production method of the polyurethane molded body, characterized in that 0.1-10mm.