KR100293163B1 - Manufacturing method of 1-component polyurethane foam composition - Google Patents

Abstract

1. TECHNICAL FIELD OF THE INVENTION

The present invention relates to a method for producing a one-component polyurethane foam composition, in particular, a one-component polyurethane foam useful as a heat insulating material, soundproofing material, packaging material, cushioning material, sealing material, etc., which bubbles are generated by reaction with water and have bubbles therein after curing. It relates to a method for preparing the composition.

2. Technical problem to be solved by the invention

It is an object of the present invention to provide a method for producing a one-part polyurethane foam composition with good storage stability and ease of use.

3. Summary of the Solution of the Invention

A first step of removing water from the polyol (A) according to a conventional method such as heating or vacuum defoaming, mixing a reaction stabilizer, a reaction accelerator, a polymerization inhibitor and a silicone oil into a can, and an excess of diisocyanate (B). Injecting a solvent and a blowing agent comprises a second step of reacting the remaining NCO to 3.5 to 20% by weight based on the total weight of the polyol (A) and diisocyanate (B).

4. Important uses of the invention

Packed in high-pressure can, it is used for construction of insulation, soundproofing, packing, cushioning and sealing materials at the place of use.

Description

[Name of invention]

Production of One Liquid Foamable Polyurethane Composition

Detailed description of the invention

[Purpose of invention]

[Technical field to which the invention belongs and the prior art in that field]

The present invention relates to a method for producing a one-component polyurethane foam composition, in particular, a one-component polyurethane foam useful as a heat insulating material, soundproofing material, packaging material, cushioning material, sealing material, etc., which bubbles are generated by reaction with water and have bubbles therein after curing. It relates to a method for preparing the composition.

Polyurethane is obtained by the reaction of diol and diisocyanate. Industrially, diisocyanates include toluene diisocyanate (TDI), methylene diphenyl diisocyanate (MDI), and hexamethylene diisocyanate (HDI). As the diol, poly (ethylene oxide), poly (propylene oxide), polyester glycol, etc. are used in addition to ethylene glycol, propylene glycol, 1,4-butanediol, and 1,3-butanediol.

Polyurethane can be produced in various physical properties, ranging from elastomers to hard plastics, depending on the type of diisocyanate and diol selected. Excess isocyanates generate carbon dioxide when reacted with water or carboxylic acids, Urethane foam is also produced.

In particular, the polyurethane foam (foam-containing foam) containing the foam has a good thermal insulation, soundproofing and shock-absorbing properties are widely used as a heat insulating material, sound insulation and sealing materials (sealing), cushioning materials and packaging materials such as ceramics. However, since one-part urethane prepolymer has poor storage stability, it is sometimes used to prepare a polyurethane foam composition by reacting diol or polyol with diisocyanate directly at the site of use, but in this case, workability is poor and proper quality control is achieved. it's difficult.

Thus, efforts have been focused on the production of one-part polyurethane foam compositions. For example, German Patent Application Publication No. DE-4341264 discloses that the bubbles produced by reacting a polyol with an excess of isocyanate are small and uniform, and have water and moisture. A method for preparing a one-part polyurethane foam composition with improved permeability is described, but there is no mention of storage stability.

EP-66830 discloses a one-part polyurethane foam composition which reduces the size and improves the uniformity of bubbles produced by reacting polyester and / or poly-ether-polyols with polyisocyanates, but with regard to storage stability. There is no mention.

Federal Republic of Germany Patent Application DE-2842242 describes a process for preparing one-part polyurethane foam compositions prepared by reacting polyols with an excess of isocyanates, with a storage stability of at least 6 months at room temperature.

Federal Republic of Germany DE-4025843 describes a one-part polyurethane foam composition prepared by reacting with a polymer containing polyester and / or poly-ether and isocyanate groups, the storage stability of which is described as being at least 6 months at room temperature. have.

[Technical problem to be achieved]

It is an object of the present invention to provide a method for producing a one-part polyurethane foam composition with good storage stability and ease of use.

[Configuration and Function of Invention]

The method for producing a one-component polyurethane foam composition of the present invention comprises the first step of removing water from the polyol (A) according to a conventional method and injecting a reaction stabilizer, a reaction promoter, a silicone oil and a polymerization inhibitor into a can; A diisocyanate (B), a solvent, and a blowing agent are injected into the can, and the second step is performed to react the remaining NCO to 3.5 to 20% by weight based on the total weight of the polyol (A) and the diisocyanate (B).

Polyols (A) are those having 2 to 8 hydroxyl groups, and polyols of various structural formulas including ethylene glycol, propylene glycol, poly (ethylene oxide), poly (propylene oxide), polyester glycol, or mixtures thereof. Can be.

If water is contained in the polyol (A), since the water contained reacts with the diisocyanate (B), the water should be removed to 0.5 weight% or less, preferably 0.1 weight% or less before mixing with the diisocyanate.

Moisture removal is performed by the conventional method of heating or vacuum defoaming a polyol (A), and it is more effective by blowing dry air or nitrogen at the time of heating or vacuum defoaming.

Diisocyanate (B) uses toluene diisocyanate (TDI), methylene diphenyl diisocyanate (MDI), hexamethylene diisocyanate (HDI), or a mixture thereof, so that the remaining NCO group is 3.5 to 20% by weight after the reaction. Excess is used relative to the polyol (A).

The reaction stabilizer, the reaction promoter and the polymerization inhibitor are mixed with the polyol (A) and injected into the can, and are cured as soon as the polyol (A) and the diisocyanate (B) are mixed without mixing them.

As a reaction stabilizer, 0.01 to 1% by weight of benzoyl chloride based on the total weight of the polyol (A) and the diisocyanate (B), and 1 based on the total weight of the polyol (A) and the diisocyanate (B) as the reaction accelerator. DMDEE (dimorpholinodiethyl ether) (trade name: Jeffcat, manufactured by Huntsmann) is used.

In addition, when adding phosphoric acid, formic acid, or MSA (methane sulfonic acid) as a polymerization inhibitor, when phosphoric acid is added, 0.01 to 0.1% by weight based on the total weight of the polyol (A) and the diisocyanate (B) is used.

HCFC (hydrochlorofluoro carbon) is used as a blowing agent. It is mixed with a solvent. Dimethyl isocyanate (DME) or odorless LPG is used as the solvent. The reaction is initiated and cured when diisocyanate (B) is injected into the can and shaken before injection of the blowing agent and solvent.

The present invention is characterized in that the whole process is carried out in the can except for the dehydration and mixing of the polyol (A).

The invention will be further clarified by the following examples.

Example 1

220 g of a mixture of polyols of 180 g of H-4701, 20 g of H-490 and 20 g of H-3000D (above Kumho Chemical Co., Ltd.) were heated to 110 ° C. to remove moisture and cooled to 50 ° C., followed by benzoyl chloride as a reaction stabilizer. 0.16g, DMDEE (dimorpholinodiethyl ether) (trade name: Jeffcat, Huntsmann) 2.6g, silicone oil (trade name: Silicone Surfactant 8404, Pelron) 5g and 0.08g phosphoric acid with polymerization inhibitor It was.

Next, 300 g of methylene diphenyl diisocyanate (MDI), 75 g of HCFC as a blowing agent, and 50 g of odorless LPG as a solvent were injected into a can, and the reaction was started by shaking. Remaining NCO after the reaction was 10.9 wt% based on the total weight of the polyol mixture and MDI.

As a result of foaming after 12 hours after completion of the reaction, surface curing and complete curing at 80% humidity and 25 ° C were achieved in 15 minutes and 12 hours, respectively. Volume of resin) was measured at 40. Foam density is 22 ± 5kg / m ³ , thermal conductivity is 0.021 ± 0.005kcal / m · h ℃, bending strength is 6.5 ± 0.5N / cm ² , water absorption is 3 ± 0.5g / 100cm ³ , and compressive strength is 4.2 ± 0.5N / cm ^2, tensile strength was measured by each 3 ± 0.5N / cm ^2.

As a result of measuring the preservation period, the period of preservation without gelation at room temperature was one year and June. After that, the gelation progressed slowly, but in the case of shaking, the retention period was extended by six months.

In addition, when stored at a low temperature of 5 ℃ or less, the gelation did not occur for more than two years, the longer the shelf life.

Example 2

Using a mixture of 30 g of H-1000, 7 g of H-450, and 140 g of H-4701 (above Kumho Chemical Co., Ltd.), the amount of benzoyl chloride is 0.03 g, the amount of dimorpholinodiethyl ether (DMDEE) is 3 g, and the amount of blowing agent HCFC is used. Except that 80g was carried out under the same conditions as in Example 1.

The results are shown in Table 1 together with the comparative example.

Example 3

Under the same conditions as in Example 2, except that a mixture of 30 g of H-2000D, 10 g of H-482 and 150 g of H-4701 (above Kumho Chemical Co., Ltd.) was used as a polyol, and the amount of the blowing agent HCFC was 90 g. Was performed.

The results are shown in Table 1 together with the comparative example.

Comparing Examples 1-3 with Comparative Examples, the physical properties such as foaming degree, strength, water absorption amount, thermal conductivity, and the like are almost similar, but the composition of the present invention is excellently long in storage stability.

[Effects of the Invention]

Because it reacts directly in the high-pressure can, there is no need for a separate packaging process, and the storage stability is good, so it can be stored for a long time, and it can be used for construction of insulation, soundproofing, packaging, cushioning and sealing materials at the place of use.

Claims (1)

In preparing a polyurethane foam composition by reacting a polyol (A) with an excess of diisocyanate (B), water is removed from the polyol (A) and based on the total weight of the polyol (A) and the diisocyanate (B) First to be mixed into 0.01 to 1% by weight of benzoyl chloride, 1 to 7% by weight of dimorpholinodiethyl ether (DMEE), silicone oil and phosphoric acid based on the total weight of polyol (A) and diisocyanate (B) Steps; Excess diisocyanate (B), solvent and blowing agent are added to the can to make the remaining NCO 3.5 to 20% by weight or more after the reaction, and the residual NCO is 3.5 based on the total weight of the polyol (A) and the diisocyanate (B). Method for producing a one-part polyurethane foam composition comprising a second step of reacting to ~ 20% by weight.