WO2020138723A1 - Method for manufacturing polymer nanoclay composite having excellent heat resistance and flame retardancy - Google Patents

Abstract

The present disclosure pertains to a method for manufacturing a polymer nanoclay composite having excellent heat resistance and flame retardancy, the method comprising: a raw material mixing step of mixing a polymer resin, nanoclay, and a compatibilizer; a heating and stirring step of heating and stirring the mixture prepared through the raw material mixing step; and a cooling step of cooling the mixture heated and stirred through the mixing and heating step. The polymer nanoclay composite manufactured through the procedure has improved heat resistance and flame retardancy and exhibits excellent productivity as well as being environmentally friendly because it contains no halogen-based ingredients.

Description

Method of manufacturing a polymer nanoclay composite with excellent heat resistance and flame retardancy

The present invention relates to a method for preparing a polymer nanoclay composite having excellent heat resistance and flame retardancy, and more particularly, improved heat resistance due to an increase in decomposition temperature, and not only exhibits excellent flame retardancy due to the coexistence of an insert type structure and a peel type structure. , Since it is manufactured by mixing all raw materials at one time, it exhibits excellent productivity, and does not contain halogen-based components.

Research on composites of polymers and nanoclays has been conducted since Toyota's Central Research and Development in 1997 developed nanocomposites obtained by completely peeling a hydrophilic nylon-laden clay with a hydrophilic surface, and applied it to automobile timing belt covers and automobile fuel lines. have.

Plastic materials, especially polymer composites reinforced with inorganic fillers, are replacing competitive materials such as metals, ceramics, and woods in various industries due to their excellent mechanical properties, excellent formability, and light weight. In particular, polymer composite materials with light weight, dimensional stability, and heat resistance required in the fields of automotive materials, electrical, and electronic materials are expanding in use, and due to the advent of hybrid vehicles, additional lightweight efforts and recycling characteristics due to the advent of the eco-friendly era The demand for this excellent polymer composite is rapidly increasing. As a method of improving light weight and recyclability while maintaining the improved physical properties of such a polymer composite material, polymers and nanoclay composites have recently emerged, and various approaches have been proposed. These polymer and nanoclay composites are superior in terms of overall mechanical properties and light weight, such as stiffness, compared to conventional polypropylene composites containing general inorganic additives such as talc, while their impact strength is markedly lowered to that of conventional composites. The expansion is quite limited.

In addition, conventionally, when manufacturing the polymer and the nanoclay composite, there was a problem in that productivity is low because the raw materials must be classified and mixed for each manufacturing step.

As a conventional patent related to the manufacture of such a nanoclay composite, Korean Patent Registration No. 10-087285 is a nanoclay masterbatch comprising 20 to 70% by weight of polypropylene resin, 40 to 50% by weight of nanoclay, and 10 to 40% by weight of modified polymer. As a composition for production, the modified polymer has a weight average molecular weight of 30,000 to 100,000, and is a maleic anhydride graft polypropylene resin containing 4 to 8 parts by weight of maleic anhydride relative to 100 parts by weight of polypropylene resin, the master The bending elastic modulus of the batch is 30,000-50,500 Kg/cm ² , and the composition for preparing a nanoclay masterbatch having a heat deflection temperature of 100-140°C, 1-50% by weight of the nanoclay masterbatch, and 50-99% by weight of polypropylene resin % High stiffness polypropylene/nanoclay composites. In addition, Korean Patent No. 10-0882307 discloses a nanoclay-polyol composite in which a diol having a carboxyl group is inserted between layers to prepare a peeled nanoclay-polyol composite, and then the peeled nanoclay-polyol composite, diisocyanate, foaming agent, blowing agent, and catalyst Polyurethane insulating foam produced by a simple process of foaming is a simplified process compared to the prior art discloses a method of manufacturing a polyurethane insulating foam having improved mechanical properties and heat insulating properties and improved storage stability without the use of a separate organic solvent. However, these patents still have the problems as described above.

The object of the present invention is to improve the heat resistance due to the increase of the decomposition temperature, not only exhibits excellent flame retardancy due to the coexistence of the insert-type structure and the peel-type structure, but also shows excellent productivity because it is produced by mixing all raw materials at once, and halogen-based components This is to provide a method for producing an environmentally friendly polymer nanoclay complex that does not contain.

The object of the present invention is a raw material mixing step of mixing a polymer resin, a nanoclay and a compatibilizer, a heating stirring step of heating and stirring the mixture prepared through the raw material mixing step, and cooling the heated and stirred mixture through the heating stirring step. It is achieved by providing a method for producing a polymer nanoclay composite having excellent heat resistance and flame retardancy, characterized by comprising a cooling step.

According to a preferred feature of the present invention, the raw material mixing step is made by mixing 100 parts by weight of the polymer resin, 1 to 15 parts by weight of the nanoclay, and 1 to 15 parts by weight of the compatibilizer.

According to a more preferred feature of the present invention, the polymer resin is made of at least one selected from the group consisting of polyolefin, nitrile butadiene rubber and ethylene propylene diene monomer.

According to a more preferred feature of the invention, the compatibilizer is made of polyethylene graft maleic anhydride.

According to a still more preferred feature of the present invention, the heating and stirring step is performed by heating and stirring the mixture prepared through the raw material mixing step at a temperature of 120 to 200°C and a speed of 200 to 500 rpm for 1 to 5 minutes.

The method for preparing a polymer nanoclay composite having excellent heat resistance and flame retardancy according to the present invention improves heat resistance due to an increase in decomposition temperature, and not only exhibits excellent flame retardancy due to the coexistence of an insert type structure and a peel type structure, but also mixes all raw materials at once Because it is produced by showing excellent productivity, it does not contain halogen-based components, it shows an excellent effect of providing an environmentally friendly polymer nanoclay composite.

1 is a flow chart showing a method of manufacturing a polymer nanoclay composite excellent in heat resistance and flame retardancy according to the present invention.

Hereinafter, the preferred embodiment of the present invention and the physical properties of each component will be described in detail, but it is intended to be described in detail so that a person skilled in the art to which the present invention pertains can easily implement the invention. This does not mean that the technical spirit and scope of the present invention is limited.

The method for preparing a polymer nanoclay composite having excellent heat resistance and flame retardancy according to the present invention is a raw material mixing step (S101) for mixing a polymer resin, a nanoclay and a compatibilizer, and a heating stirring of the mixture prepared through the raw material mixing step (S101) It consists of a heating stirring step (S103) and a cooling step (S105) for cooling the mixture heated and stirred through the heating stirring step (S103).

The raw material mixing step (S101) is a step of mixing a polymer resin, a nanoclay and a compatibilizer, and is made by mixing 100 parts by weight of a polymer resin, 1 to 15 parts by weight of a nanoclay, and 1 to 15 parts by weight of a compatibilizer. The resin exhibits a particle size of 0.01 to 0.1 millimeters, and a thermoplastic one may be used, preferably one or more selected from the group consisting of polyolefin, nitrile butadiene rubber and ethylene propylene diene monomer, and the polyolefin is polyethylene or polypropylene. It is more preferably made.

If the particle size of the polymer resin is less than 0.01 millimeter, it is easily scattered, contaminating the workplace, and agglomeration occurs between the polymer resins, so that it is not evenly mixed with the nanoclay, and when the particle size of the polymer resin exceeds 0.1 millimeter, the nano May not mix evenly with clay.

The nanoclay contains 1 to 15 parts by weight, and serves to improve heat resistance and flame retardancy in the polymer nanoclay composite according to the present invention. Montmorillonite, hectorite, bentonite, vermiculite, and ball cornite can be used. The montmorillonite is a form modified with an organic compound, specifically, Cloisite ^® 10A, Cloisite ^® 15A, Cloisite ^® 20A, Cloisite ^® 25A, Cloisite ^® 30B, Cloisite ^® 93A, etc. of Southern Clay Products may be used.

In addition, when the nanoclay is contained, the polymer nanoclay complex has an increase in decomposition temperature of 50% or more (increased from 50 to 150°C), thereby improving heat resistance, and the composite structure of the complex (Intercalation structure and exporalation structure) Coexistence} improves flame retardancy and improves flame propagation blocking power.

The polymer nanoclay composite of the present invention has a form in which a polymer is intercalated between nanoclay layers (insertion type, intercalation) and a nanoclay layered structure is exfoliation unlike the structure in a conventional mixture or compound. ), the flame retardancy and shielding properties are improved.

When the content of the nanoclay is less than 1 part by weight, the effect of improving mechanical properties such as compressive strength of the polymer nanoclay composite having excellent heat resistance and flame retardancy is negligible. When the content of the nanoclay exceeds 15 parts by weight, the polymer resin As the dispersion effect is lowered, agglomeration between nanoclay components occurs, and thus the physical properties of the polymer nanoclay composite may be deteriorated.

The compatibilizer is mixed with 1 to 15 parts by weight, and is made of polyethylene graft maleic anhydride, so that the polymer resin and nanoclay have excellent affinity and can be evenly mixed, so that the polymer nanoclay exhibits homogeneous properties. It serves to provide a complex.

If the content of the compatibilizer is less than 1 part by weight, the above effect is negligible, and when the content of the compatibilizer exceeds 15 parts by weight, the effect of the above is not significantly improved, and the polymer nanoclay complex is contained in an excessive amount. It can reduce the physical properties of.

The heating and stirring step (S103) is a step of heating and stirring the mixture prepared through the raw material mixing step (S101), the mixture prepared through the raw material mixing step (S101) temperature of 120 to 200 ℃ and 200 to 500rpm Heat stirring for 1 to 5 minutes at a rate of.

When the mixture made of a polymer resin, a nanoclay and a compatibilizer is stirred at the above temperature and speed, the polymer resin is melted and the molten polymer resin is evenly mixed with the nanoclay due to the action of the use agent, so that the polymer has excellent heat resistance and flame retardancy. Nanoclay complexes are provided.

At this time, if the temperature of the heating and stirring step is less than 120°C, melting of the polymer resin may not proceed as a material, and when the temperature of the heating and stirring step exceeds 200°C, a phenomenon in which the polymer resin is carbonized may occur.

In addition, if the stirring speed is less than 200 rpm, the mixing degree of the polymer resin and the nanoclay may be lowered, and even if the stirring speed exceeds 500 rpm, the mixing degree of the polymer resin and the nanoclay is not significantly improved, thereby improving energy efficiency. It is preferable to maintain a stirring speed of 200 to 500 rpm as described above.

The cooling step (S105) is a step of cooling the mixture that is heated and stirred through the heating and stirring step (S103), and is a step of slowly cooling the mixture that is heated and stirred through the heating and stirring step (S103) to room temperature.

After the cooling step (S105), the production of a polymer nanoclay composite excellent in heat resistance and flame retardancy according to the present invention is completed.

Hereinafter, a method of manufacturing a polymer nanoclay composite having excellent heat resistance and flame retardancy according to the present invention and physical properties of the polymer nanoclay composite prepared through the manufacturing method will be described with reference to examples.

<Example 1>

100 parts by weight of a polymer resin (low density polyethylene, particle size of 0.05 millimeters), 12.35 parts by weight of nanoclay (Cloisite® 10A), 12.35 parts by weight of a compatibilizer (polyethylene graft maleic anhydride) were prepared to prepare a mixture, and the mixture was 150°C The mixture was heated and stirred at a rate of 350 rpm for 3 minutes, and the mixture was heated and slowly cooled to room temperature for 10 minutes to prepare a polymer nanoclay composite having excellent heat resistance and flame retardancy.

<Example 2>

The same procedure as in Example 1, but containing 13.5 parts by weight of the nanoclay to prepare a polymer nanoclay composite excellent in heat resistance and flame retardancy.

<Example 3>

The same procedure as in Example 1, but containing 15 parts by weight of nanoclay to prepare a polymer nanoclay composite excellent in heat resistance and flame retardancy

<Comparative Example 1>

Low density polyethylene.

<Comparative Example 2>

Nanoclay (Cloisite® 10A).

<Comparative Example 3>

Polyethylene graft maleic anhydride.

<Comparative Example 4>

The same procedure as in Example 1, but containing 5.25 parts by weight of the nanoclay and the compatibilizer was not used to prepare a polymer nanoclay composite.

<Comparative Example 5>

The same procedure as in Example 1 was carried out, but the polymer nanoclay composite was prepared by containing 0.5 parts by weight of the nanoclay.

The heat resistance and flame retardancy of the components prepared through Example 1 and Comparative Examples 1 to 4 were measured and are shown in Table 1 below.

{However, the heat resistance is shown in Table 1 below by measuring the decomposition temperature and residual flow rate for the polymer nanoclay composites prepared through Example 1 and Comparative Examples 1 to 4.

In addition, by measuring the weight change according to the temperature of the components prepared through Example 1 and Comparative Examples 1 to 4 are shown in Figure 3 below, the results of scanning by XRD are shown in Figures 4 to 5 below, IR Spectrum The results taken with are shown in FIGS. 6 to 7 below.

<Table 1>

As shown in Table 1 above, it can be seen that the polymer nanoclay composites prepared through Example 1 of the present invention have high decomposition temperature and high residual amount compared to the components of Comparative Examples 1 to 4, thereby exhibiting excellent heat resistance.

In addition, the flame retardancy of the polymer nanoclay composites prepared through Examples 1 to 3 and Comparative Example 5 was measured and is shown in Table 2 below.

{However, the flame retardancy was measured based on the method of performing the vertical combustion test of the "combustibility test of plastic material" in UL (Underwriters Laboratories Incorpoartion) Subject 94 in the vertical phase (V0). The thickness of the polymer nanoclay composite used was It was 1/16inch.}

<Table 2>

As shown in Table 2, it can be seen that the polymer nanoclay composites prepared through Examples 1 to 3 of the present invention have excellent flame retardancy.

Therefore, the method for preparing a polymer nanoclay composite having excellent heat resistance and flame retardancy according to the present invention improves heat resistance due to an increase in decomposition temperature, and not only exhibits excellent flame retardancy due to the coexistence of an insert-type structure and a peelable-type structure, but also provides all raw materials. Since it is manufactured by mixing at one time, it exhibits excellent productivity and does not contain halogen-based components, thus exhibiting an excellent effect of providing an environmentally friendly polymer nanoclay composite.

Claims (5)

1. A raw material mixing step of mixing a polymer resin, a nanoclay and a compatibilizer;

   A heating stirring step of heating and stirring the mixture prepared through the raw material mixing step; And

   Method of manufacturing a polymer nanoclay composite excellent in heat resistance and flame retardancy, characterized in that consisting of; cooling step of cooling the mixture heated by stirring through the heating stirring step.
2. The method according to claim 1,

   The raw material mixing step is 100 parts by weight of a polymer resin, 1 to 15 parts by weight of the nanoclay, 1 to 15 parts by weight of a compatibilizer.
3. The method according to claim 1 or 2,

   The polymer resin is a polyolefin, nitrile butadiene rubber and ethylene propylene diene monomer, at least one selected from the group consisting of a heat-resistant and flame-retardant polymer nanoclay composite manufacturing method.
4. The method according to claim 1 or 2,

   The compatibilizer is a method for producing a polymer nanoclay composite having excellent heat resistance and flame retardancy, characterized in that it consists of polyethylene graft maleic anhydride.
5. The method according to claim 1,

   The heating and stirring step is a polymer nanoclay composite having excellent heat resistance and flame retardancy, characterized in that the mixture prepared through the raw material mixing step is heated and stirred at a temperature of 120 to 200°C and a speed of 200 to 500 rpm for 1 to 5 minutes. Method of manufacturing.

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