KR100882307B1 - Preparation method of nanoclay reinforced polyurethane insulation foams - Google Patents

Abstract

A preparation method of nanoclay reinforced polyurethane insulation foams is provided to improve adiabaticity, mechanical strength and storage stability while not using the organic solvent, to simplify a manufacturing process by applying nanoclay peeled by using diol having a carboxy radical to polyurethane insulation foams. A preparation method of nanoclay reinforced polyurethane insulation foams comprise a step for manufacturing a mixture by mixing (i) at least one or two polyols 100.0 parts by weight selected from solbitol polyol, toluene diamine polyol, ethylenediamine polyol and sucrose/glycerine polyol, (ii) diol 0.05~2.0 parts by weight having a carboxy radical selected from a dimethylol propionic acid, dimethylol butanoic acid and their mixture, and (iii) tertiary amine 0.04~2.0 parts by weight; a step for manufacturing a nanoclay-polyol composite which is exfoliated by inserting diol having a carboxy radical in an interlayer, by mixing the mixed solution 100.0 parts by weight, and nanoclay 0.5~15 parts by weight selected from montmorillonite, hectorite, bentonite, vermiculate and volkonskoite; and a step for manufacturing polyurethane foam by mixing and foaming (i) the nanoclay-polyol composite 100.0 parts by weight, (ii) diisocyanate 100~180 parts by weight selected from crude-4,4'- diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, crude-2,6-toluene diisocyanate, 2,6-toluene diisocyanate and 2,4-toluene diisocyanate, (iii) surfactant 0.5~5 parts by weight as an additive for foaming, (iv) foaming agent 8~50 parts by weight and (v) foaming catalyst 0.2~2 parts by weight.

Description

Preparation Method of Nanoclay Reinforced Polyurethane Insulation Foam {Preparation method of Nanoclay Reinforced Polyurethane Insulation Foams}

The present invention provides a polyurethane insulation foam containing nanoclay exfoliated using a diol having a neutralized carboxyl group, which not only improves insulation and mechanical strength but also simplifies the manufacturing process and improves storage stability without using an organic solvent. It relates to a manufacturing method.

Styrofoam, urethane foam, glass fiber and epoxy resin insulators are the most common thermal insulation materials using foam foam, and their substrates are made of thermoplastic resins that are weak to heat, and thus are susceptible to fire.

Among these, the polyurethane insulation foam of the related art may use additives such as glass fiber to supplement mechanical properties in terms of application, but in this case, the insulation property is poor, the manufacturing process is complicated, storage stability is poor, and organic solvents are used. Since there is a problem such as environmental pollution, various researches on the production method of the polyurethane insulation foam which improves the mechanical strength without reducing the thermal insulation, and improve the storage stability while simplifying the manufacturing process.

The following is a detailed description of various well-known technologies for polyurethane insulation foams.

Korean Patent Registration No. 642685 discloses a clay-polyurethane nanocomposite and a method for manufacturing the same, but this requires attention during the experiment process since unwanted by-products may occur during the reaction of the layered clay with the diisocyanate. There is an unavoidable problem of using a solvent in the reaction.

Korean Patent Registration No. 599197 discloses a clay-polyurethane foam nanocomposite for heat pipe insulation and a method of manufacturing the same, but the process is complicated by the addition of a physical method such as applying ultrasonic waves during the reaction of the layered clay and diisocyanate. .

Polyurethane / clay nanocomposites form: processing, structure and properties Literature clay is modified from toluene to thibutyldimethoxytin in order to effectively remove the layered clay. However, toluene, which is a solvent used to peel the layered clay, not only has a bad effect on the physical properties of the foam but also has limitations due to environmental regulations, so it is required to exclude its use.

The present invention has conducted a variety of in-depth studies to fundamentally solve these problems of the conventional polyurethane insulation foam nanocomposites. It is to prepare a polyurethane insulation foam that contains the nanoclay peeled using a diol having a carboxyl group in the polyurethane insulation foam to improve the mechanical strength and insulation and improve the storage stability without using an organic solvent.

The present invention is a method for producing a polyurethane insulation foam by foaming a polyol, diisocyanate, foam stabilizer, blowing agent and catalyst,

The polyol component was mixed with 100 parts by weight of polyol, 0.05 to 2.0 parts by weight of diol having a carboxyl group, and 0.05 to 2.0 parts by weight of amine to prepare a mixed solution, 100 parts by weight of the mixed solution and 0.5 to 15 parts by weight of nanoclay. There is a feature in the method for producing a polyurethane insulation foam using a nanoclay-polyol composite in which diols having a carboxyl group are inserted into and separated from each other by intercalation.

In addition, the present invention is a polyurethane insulation foam prepared by the above method, the compressive strength is in the range of 1.2 ~ 1.8 MPa, the thermal conductivity is in the range of 0.02 ~ 0.025 Kcal / mhr ℃, storage stability 0.02 ~ 0.09 range (XRD after 15 days Another characteristic is the polyurethane insulation foam, which is the θ change value of.

As described above, in the method of manufacturing the exfoliated polyurethane insulation foam nanocomposite of the present invention, the diol having a carboxyl group is inserted between the clay layers to make the peeling more easily, thereby improving dispersibility and improving heat insulation and mechanical strength. This technology not only improves the manufacturing process, but also enables the production of polyurethane insulation foam nanocomposites with improved storage stability without the use of organic solvents. It can be applied to various industrial purposes.

The present invention is a method for producing a polyurethane insulation foam by foaming a polyol, diisocyanate, in order to improve the mechanical, thermal properties and long-term stability of the insulation foam using a diol and an amine having a carboxyl group as a polyol component between layers Inserted and exfoliated nanoclay-polyol complexes were used.

Looking at the manufacturing method of the polyurethane insulation foam according to the invention in more detail as follows.

A mixed solution is prepared by mixing a polyol with a diol having a carboxyl group and an amine. The mixing is carried out at a temperature of 20 to 40 ° C. for 1 to 5 hours under conditions of a speed of 300 to 700 rpm.

The polyol is generally used in the art, but is not particularly limited, and specifically, one or two or more selected from sorbitol polyol, toluenediamine polyol, ethylenediamine polyol, and sucrose / glycerine polyol may be used.

The diol having the carboxyl group is generally used in the art, but is not particularly limited, and specifically, dimethylol propionic acid, dimethylol butanoic acid, and mixtures thereof may be used. The diol having such a carboxyl group is used in the range of 0.05 to 2.0 parts by weight, preferably 0.05 to 0.67 parts by weight, based on 100 parts by weight of the polyol. If the amount is less than 0.05 parts by weight, the degree of insertion between the clay layers is small and 3.0 parts by weight. When the amount is exceeded, it is preferable to maintain the above range because a problem occurs that the diol having an unreacted carboxyl group remains as an impurity.

The amine is used to increase the clay intercalation effect by neutralizing the diol having a carboxyl group may specifically use a tertiary amine. At this time, the pH is maintained in the range of about 7-8 using an amine. The amine is used in an amount of 0.04 to 2.0 parts by weight, preferably 0.046 to 0.456 parts by weight, based on 100 parts by weight of polyol. When the amount of the amine is less than 0.04 parts by weight, the carboxyl group is not effectively neutralized, and thus the insertion effect is reduced in the nanoclay. When it exceeds 2.0 parts by weight, it is preferable to maintain the above range because the problem of soaking increases.

Next, the mixed solution and the nanoclay are mixed to prepare a nanoclay-polyol complex in which a diol having a carboxyl group is inserted between layers to be peeled off. The mixing is carried out at 50 to 70 ° C. for 1 to 5 hours under conditions of 1000 to 3000 rpm.

The nanoclay is not particularly limited to those commonly used in the art, and specifically, montmorillonite, hectorite, bentonite, vermiculite, and volconscote may be used. The montmorillonite may be a form modified with organic compounds, specifically Cloisite® 10A, Cloisite® 15A, Cloisite® 20A, Cloisite® 25A, Cloisite® 30B, Cloisite® 93A, and the like, manufactured by Southern Clay Products.

The nanoclay is used in the range of 0.5 to 15 parts by weight, preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the mixed solution. If the amount is less than 0.5 parts by weight, there is no effect of compensating mechanical properties such as compressive strength. When the amount exceeds 15 parts by weight, the dispersion effect of the clay is reduced, so that the aggregates of clay increase, so that a problem of deterioration of mechanical properties such as compressive strength occurs, so it is preferable to maintain the above range.

Next, a polyurethane insulation foam is prepared by mixing and foaming the nanoclay-polyol composite, diisocyanate, foam stabilizer, foaming agent, and catalyst prepared above. At this time, the mixing and foaming is carried out under the conditions of 20 to 40 ℃, 2000 to 8000 rpm, it is generally good to perform by one-shot method.

The diisocyanate is generally used in the art and is not particularly limited, but specifically, crude-4,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, and crude-2,6 -Toluene diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, etc. can be used. The diisocyanate is used in the range of 100 to 180 parts by weight of diisocyanate, preferably 119 to 151 parts by weight, based on 100 parts by weight of the nanoclay-polyol composite. If the amount of the diisocyanate is less than 100 parts by weight, mechanical properties such as compressive strength may be used. If it falls and exceeds 180 parts by weight, it is preferable to maintain the above range because unreacted diisocyanate remains and a problem of lowering mechanical properties occurs.

The foam stabilizer is generally used in the art, but is not particularly limited, and specifically, a silicone foam stabilizer may be used, and more preferably, B 8462®, B 8409®, and B 8404® products, such as those manufactured by Goldschmidt AG, may be used. Can be. Such foam stabilizers are used in the range of 0.5 to 5 parts by weight, preferably 0.5 to 3 parts by weight, based on 100 parts by weight of the nanoclay-polyol composite. When the amount is less than 0.5 parts by weight, the amount of closed cells is reduced and irregular cells are used. It is preferable to maintain the above range because a large number of structures will adversely affect the mechanical strength and the like, and if it exceeds 5 parts by weight, the cell wall will become thinner and the mechanical strength will drop.

The blowing agent is not particularly limited to those generally used in the art, but it is preferable to use an environment-friendly chlorine group without destroying the ozone layer. Specifically, HCFC-based blowing agent, pentane-based blowing agent, water, and the like may be used. Preferably, water, HFC 365mfc® from Solvay Chemicals, HFC 245fa® from Honeywell Specialty Chemicals, cyclopentane products are preferably used. The blowing agent is used in the range of 8 to 50 parts by weight, preferably 8 to 30 parts by weight with respect to 100 parts by weight of the nanoclay-polyol composite. When the amount of the blowing agent is less than 8 parts by weight, the cell production is reduced and heat insulation is deteriorated. If it exceeds 50 parts by weight, it is preferable to maintain the above range because a problem occurs that the mechanical properties are degraded at a low density. At this time, when water is used as the blowing agent, it is preferable to use it in the range of 1 to 6 parts by weight.

The catalyst is used to promote the resination reaction and the foaming reaction and to adjust the reaction time to meet the process characteristics, but is not particularly limited, specifically, tertiary amines such as dimethylene cyclohexaneamine, triethylenediamine is mainly used, Thibutyltin, tin-containing octaoate, and the like. The catalyst is used in the range of 0.2 to 2 parts by weight, preferably 0.2 to 1.5 parts by weight, based on 100 parts by weight of the nanoclay-polyol composite. If the amount of the catalyst is less than 0.2 part by weight, the resination reaction does not sufficiently occur and the foam When this easily tears and exceeds 2 parts by weight, the shrinkage of the foam occurs, so it is preferable to maintain the above range.

Polyurethane insulation foam prepared by the above process has a compressive strength of 1.2 ~ 1.8 MPa range, thermal conductivity of 0.02 ~ 0.025 Kcal / mhr ℃ range, storage stability 0.02 ~ 0.09 range (the θ change value of XRD after 15 days) Keep it.

Hereinafter, the present invention will be described in more detail based on the following examples, but the present invention is not limited to the examples.

Example 1

In a detachable 500 ml round four-necked flask equipped with a stirrer, 0.45 g of dimethylol butanoic acid was dissolved in 60 g of sorbitol polyol at 100 rpm for 30 minutes to completely dissolve, followed by adding 0.31 g of triethylamine (tertiary amine) to 500 After neutralizing at rpm for 3 hours, 3 g of Nanoclay Cloisite® 30B (Southern Clay Products Co., Ltd.) was added thereto, and stirred at 2000 rpm for 3 hours to prepare the nanoclay-solitol polyol complex in which the dimethylol butanoic acid was inserted between the layers. It was. At this time, the identification of the nanoclay was confirmed by XRD photographs, it showed 2θ = 1.80. The smaller the value of 2θ, the more it indicates peeling, and it is preferable to maintain the range of 0 to 2.

63 g of the exfoliated nanoclay-solitol polyol complex, 40 g of toluenediamine polyol, 119 g of 4,4'-diphenylmethane diisocyanate, 12 g of foam HFC 365 mfc® (manufactured by Solvay Chemicals), foam stabilizer B 8462® ( 2 parts by weight of Goldschmidt AG), 0.6 g of triethylenediamine was foamed by 3000 rpm at room temperature (20 ° C.) by one-shot method, and then cured at room temperature (20 ° C.) for 1 week to prepare a polyurethane insulation foam.

Examples 2-4 and Comparative Examples 1-3

The same procedure as in Example 1, except that the polyurethane insulation foam was prepared using the components shown in Table 1.

Experimental Example

The dispersion properties, mechanical and thermal properties of the polyurethane insulation foams prepared by the methods of Examples 1 to 4 and Comparative Examples 1 to 3 were measured, and the results are shown in Table 3 below. At this time, the sample was measured in a liquid state.

[Measurement of physical properties]

1. XRD: X 'pert pro (Philips) was used, measured at 1 ~ 10 ° C at room temperature.

2. Compressive strength: LRX Plus (LLOYD Instruments) was used and measured in accordance with ASTM D 1621 at room temperature.

3. Thermal conductivity: HC-074 (LaserComp) was used, measured in accordance with ASTM C 518.

4. Storage stability: The storage stability was measured by XRD θ change after 15 days.

division Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 XRD (2θ) 1.80 1.67 0.95 1.85 1.80 2.0 4.6 - Compressive strength (MPa) 0.91 1.12 1.01 0.82 1.15 0.89 0.71 0.61 Thermal Conductivity (Kcal / mhr ℃) 0.0234 0.0241 0.0227 0.0249 0.0274 0.0237 0.0255 0.0251 Storage stability 0.02 0.03 0.08 0.09 0.02 0.13 0.41 -

As shown in Table 3, the polyurethane insulation foam prepared in Examples 1 to 5 according to the present invention is a nanoclay in which the dimethylol butanoic acid intercalated between the nanoclay layers is exfoliated by expanding the interlayer spacing as described in the XRD measurement. It was confirmed that polyol complex formation was possible. Using such a nanoclay-polyol composite, it was confirmed that the compressive strength, thermal conductivity and storage stability are superior to Comparative Examples 1 to 3.

Figure 1 shows the synthesis of eco-friendly polyurethane insulation foam nanocomposite according to an embodiment of the present invention.

Claims (8)

In the method for producing a polyurethane foam by mixing and foaming a polyol component and a diisocyanate component with a foam stabilizer, a foaming agent and a catalyst as a conventional foaming additive, Diol having 0.05 to carboxyl group selected from dimethylol propionic acid, dimethylol butanoic acid and mixtures thereof in 100 parts by weight of one or two or more polyols selected from sorbitol polyol, toluenediamine polyol, ethylenediamine polyol and sucrose / glycerin polyol Mixing 2.0 parts by weight and 0.04 to 2.0 parts by weight of tertiary amine to prepare a mixed solution; To 100 parts by weight of the mixed solution, 0.5 to 15 parts by weight of nanoclays selected from montmorillonite, hectorite, bentonite, vermiculite, and bolconscote were mixed, and a diol having a carboxyl group was inserted between layers to remove the nanoclay-polyol complex. Manufacturing process; And 100 parts by weight of the nanoclay-polyol composite, crude-4,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, crude-2,6-toluene diisocyanate, 2,6 -100 to 180 parts by weight of diisocyanate selected from toluene diisocyanate and 2,4-toluene diisocyanate, 0.5 to 5 parts by weight of foam stabilizer, 8 to 50 parts by weight of blowing agent, and 0.2 to foaming catalyst as usual foaming additives. Mixing and foaming 2 parts by weight to prepare a polyurethane foam; Polyurethane insulation foam manufacturing method comprising a. delete delete delete delete delete The method of claim 1, wherein the mixing and foaming for producing the polyurethane foam is carried out under the conditions of 20 to 40 ℃, 2000 to 8000 rpm. Polyurethane insulation foam prepared by the method of claim 1, Polyurethane insulation foam, characterized in that the compressive strength is in the range of 1.2 to 1.8 MPa, the thermal conductivity is in the range of 0.02 to 0.025 Kcal / mhr ° C, and the storage stability is in the range of 0.02 to 0.09 (the θ change value of XRD after 15 days).

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