KR101003552B1 - polymer adhesive from high density polyethylene power and preparing method - Google Patents

Abstract

The present invention relates to a polymer adhesive prepared using high density polyethylene (HDPE, High Density Polyethylene) powder and a method for producing the same, and more particularly, to a radical generation step, a polyethylene injection step, a first heating step, a spraying step, a circulation step, and It relates to a polymer adhesive comprising a second heating step and a method of manufacturing the same.

In addition, the present invention has an environmentally friendly advantage without generating a gas harmful to the human body during operation because it proceeds through the reaction of the gas phase and solid phase does not use a solvent.

High Density, Polyethylene, Polymer, Powder, Adhesive, Monomer, Dispersant, Grafting

Description

Polymer adhesive using high density polyethylene powder and its manufacturing method {polymer adhesive from high density polyethylene power and preparing method}

The present invention relates to a polymer adhesive capable of adhering fibers, metals, concrete, and polar polymers, and a method for manufacturing the same, wherein a high density polyethylene powder is irradiated with an electron beam accelerator to generate radicals and grafting monomers. It relates to a polymer adhesive modified physical properties and a method of manufacturing the same.

In the case of the polymer adhesive used in the prior art was mostly manufactured in the form of pellets (Pellet). However, these pellet-type polymer adhesives were inconvenient to use due to the limitation of co-extrusion through an extruder, and a method using a twin screw was used as a modified method. There was a problem that the working environment is contaminated due to the harmful steam generated by the decomposition of the acid proceeds or the evaporation of the solvent due to high heat generated in the process.

An object of the present invention is to solve the above-mentioned problems, the polymer adhesive is a solvent is not used because the process of grafting the monomer through the irradiation of high-density polyethylene powder with an electron beam accelerator to produce a radical and gas phase, solid phase reaction and It is to provide a manufacturing method.

Another object of the present invention is to provide a polymer adhesive having excellent adhesion to fibers, metals, concrete and polar polymers, and a method of manufacturing the same.

Still another object of the present invention is to provide a polymer adhesive having excellent chemical resistance, heat resistance, moisture resistance, impact resistance and durability, and a method of manufacturing the same.

An object of the present invention as described above, a radical generation step of generating a radical by irradiating an electron beam to the high-density polyethylene powder, a polyethylene input step of introducing the high-density polyethylene powder passed through the radical generation step to the first reactor, the polyethylene input step described above The first heating step of heating the high density polyethylene powder to a temperature of 70 to 80 ℃, the spraying step of spraying 0.2 to 55 parts by weight of the additive in the first reactor described above, the high density polyethylene powder is a circulator A polymer adhesive using a high density polyethylene powder comprising a circulation step of circulating using a second step of transferring the high density polyethylene powder that has passed through the above-mentioned circulation step to a second reactor and heating to a temperature of 100 to 200 ° C. It is achieved by the manufacturing method.

According to a preferred feature of the present invention, the irradiation range of the electron beam in the above-described radical generation step is 3 to 30 kGy (kilogray).

According to a further preferred feature of the present invention, the particle size of the aforementioned high density polyethylene powder is 200 microns or less.

According to a further preferred feature of the present invention, the above-mentioned additive comprises 0.1 to 40 parts by weight of monomer and 0.1 to 15 parts by weight of dispersant.

According to a still further preferred feature of the present invention, the monomers described above comprise at least one selected from the group consisting of dibutyl maleic acid and maleic anhydride.

According to a further preferred feature of the present invention, the above-mentioned dispersant is to comprise at least one selected from the group consisting of acetone and xylene.

According to a still further preferred feature of the present invention, the above-mentioned additive further comprises 1 to 10 parts by weight of an initiator, and the above-mentioned initiator is a group consisting of dibutyl peroxide, benzoyl peroxide and 2,2-azobisisobutylonitrile It is to include one or more selected from.

According to a further preferred feature of the present invention, the above-mentioned circulation step is performed for 25 to 35 minutes, and during the spraying step, it is to circulate 3 to 8% by weight of the high density polyethylene powder using the circulator.

In addition, the above object of the present invention can also be achieved by providing an adhesive prepared by the method for producing a polymer adhesive using the high-density polyethylene powder described above.

According to the polymer adhesive using the high-density polyethylene powder according to the present invention and a method for manufacturing the same, there is an excellent effect to improve the environmental friendliness by providing a polymer adhesive that is not used solvent.

It also exhibits excellent adhesion to fibers, metals, concrete and polar polymers.

In addition, it exhibits excellent effects of chemical resistance, heat resistance, moisture resistance, impact resistance and durability.

In the following, preferred embodiments of the present invention and the physical properties of each component will be described in detail, which is intended to explain in detail enough to be able to easily carry out the invention by one of ordinary skill in the art, This does not mean that the technical spirit and scope of the present invention is limited.

Method for producing a polymer adhesive using a high density polyethylene powder according to the present invention comprises a radical generation step (S101) for generating a radical by irradiating an electron beam to the high density polyethylene powder (S101), the high-density polyethylene powder through the above-described radical generation step (S101) 1 polyethylene injection step (S103) to be introduced into the reactor 10, the first heating step (S105) for heating the high-density polyethylene powder passed through the above-described polyethylene injection step (S103) to a temperature of 70 to 80 ℃, the first described above The spraying step (S107) for spraying 0.2 to 55 parts by weight of the additive in the reactor, while continuing the spraying step (S107) described above, the high-density polyethylene powder is circulated by using the circulator 11 (S109) and the above-mentioned circulation step It comprises a second heating step (S111) for transferring the high density polyethylene powder passed through (S109) to the second reactor 20 and heated to a temperature of 100 to 200 ℃ The.

The radical generation step (S101) is a step of forming a radical in the high-density polyethylene by irradiating an electron beam of 3 to 30 kGy to the high-density polyethylene powder described above using a direct current type high voltage electron beam accelerator (ELV-0.5 Type). The irradiation of the electron beam proceeds at an irradiation rate in the range of 1 to 1 × 10 ³ Megared (Mrgarad) per minute and crosslinking of the ethylene polymer chain without causing crosslinking in an environment where the concentration of active oxygen is 15 vol% or less.

The above-described polyethylene input step (S103) is a step of introducing the high-density polyethylene powder in which the radical is formed through the above-described radical generation step (S101) into the first reactor 10, which is a gas phase reactor, and the first reactor 10 described above. The reaction should proceed in the absence of free radicals, and in order to remove the free radicals, a small amount of nitrogen is introduced into the first reactor 10 and sealed and left for 5 minutes.

The above-described first heating step (S105) is a step of heating the high-density polyethylene powder introduced into the first reactor 10 through the above-described polyethylene input step (S103) to a temperature of 70 to 80 ℃, the above heating temperature is high density Polyethylene powder is the most suitable temperature for the grafting reaction with the monomers.

The above spraying step (S107) is a step of spraying 0.2 to 55 parts by weight of the additive, the above-mentioned additive comprises 0.1 to 40 parts by weight of monomer and 0.1 to 15 parts by weight of the dispersant, the monomer described above is dibutyl maleic acid and anhydrous And at least one selected from the group consisting of maleic acid and the aforementioned dispersant comprises at least one selected from the group consisting of acetone and xylene.

The above-described additive is sprayed into the gas phase through a nozzle having an inner diameter of 1 to 3 microns installed in the first reactor 10, and the sprayed gaseous additive is applied to the aforementioned high density polyethylene powder.

The above-mentioned circulation step (S109) is a step of circulating the high density polyethylene powder using the circulator 11 in the first reactor 10 to which the additive is applied through the above-described spraying step (S107), in the first reactor 10 3 to 8% by weight of the high density polyethylene powder is introduced into the first reactor 10 through the circulation pipe again using a rotary feeder circulator 11 to undergo a spraying step (S107).

The high density polyethylene powder accumulated on the lower surface is moved back to the upper surface through the circulation step (S109), while the aforementioned spraying step (S107) is continuously performed during the circulation step (S109). If the process (S109) is continued for 25 to 35 minutes, the additive is evenly applied to the high density polyethylene powder.

The above-described second heating step (S111) is a step of transferring the high-density polyethylene powder passed through the above-mentioned circulation step (S109) to the second reactor 20 and heating it for 100 minutes at a temperature of 100 to 200 ° C. As a result, the radicals remaining in the high density polyethylene powder are removed and stabilized, and the acetone and acid materials applied to the high density polyethylene powder are evaporated.

After the second heating step S111 described above, the polymer adhesive using the high density polyethylene powder is cooled with nitrogen gas.

Polymer adhesive using a high-density polyethylene powder prepared by the above-described process is used by heating to a temperature of 60 to 70 ℃ the available temperature.

In addition, the adhesive prepared by the method of preparing a polymer adhesive using the high density polyethylene powder according to the present invention includes 60 to 100 parts by weight of HDPE (Linear High Density Polyethylene) powder irradiated with an electron beam accelerator, and 0.2 to 55 parts by weight of an additive. It is done by

Here, the high density polyethylene powder is linear with almost no branched chain, the molecular weight is 200,000 or less, and 60 to 100 parts by weight is added. The high density polyethylene powder described above has a chemical resistance, heat resistance, moisture resistance, impact resistance and durability to the polymer adhesive. Will be provided.

In addition, when the electron beam of 3 to 30 kGy is irradiated to the aforementioned high density polyethylene powder by using an electron beam accelerator, monomers are added to form the radicals in the high density polyethylene.

The particle size of the high-density polyethylene that passed through the above process is less than 200 microns.

In addition to the high density polyethylene described above, a polyolefin (Poly Olefin) -based polymer material having 4 to 10 carbon atoms may be used.

The aforementioned additive comprises 0.1 to 40 parts by weight of monomers grafted onto the HDPE powder and 0.1 to 15 parts by weight of the dispersant.

The monomer described above is added in an amount of 0.1 to 40 parts by weight and includes at least one selected from the group consisting of dibutyl maleic acid and maleic anhydride, and is grafted by reacting with radicals formed on the high density polyethylene powder.

In addition to the above-mentioned monomers, unsaturated carboxylic acids, unsaturated carboxylic acid anhydrides, unsaturated carboxylic acid ethers, unsaturated carboxylic acid amides, unsaturated carboxylic acid imides and unsaturated carboxylic acid metal salts and the like may be used.

The dispersant described above is added in an amount of 0.1 to 15 parts by weight, and includes at least one selected from the group consisting of acetone and xylene, and serves to increase the solubility of the aforementioned high density polyethylene and the aforementioned monomer.

The adhesive prepared by the method of preparing the polymer adhesive using the high density polyethylene powder described above may further include 1 to 10 parts by weight of an initiator. The above-mentioned initiator may be dibutyl peroxide, benzoyl peroxide and 2,2-azobisisobutyl. It comprises one or more selected from the group consisting of nitriles, and these initiators serve to improve the hydrophobicity of the HDPE powder, reduce the size of the dispersed phase, and increase the reaction area between the HDPE powder and the grafted monomer. do.

Hereinafter, a description will be given of an example of a method for producing a polymer adhesive using a high density polyethylene according to the present invention.

≪ Example 1 >

100 parts by weight of the high density polyethylene powder was put in a first reactor washed with nitrogen gas and heated to 75 ° C., 6.0 parts by weight of maleic anhydride, 0.5 parts by weight of xylene, 10 parts by weight of acetone and 1.5 parts by weight of dibutyl peroxide were mixed. It is formed and sprayed into the gas phase through a spray nozzle having an inner diameter of 2 microns installed in the first reactor, the high-density polyethylene powder applied to the spray liquid is returned to the first reactor through the circulation pipe using a rotary feeder circulator After the circulating step was carried out for 30 minutes, the high-density polyethylene powder passed through the circulation step was transferred to the second reactor and heated to a temperature of 160 ℃ for 30 minutes to cool with nitrogen gas to prepare a polymer adhesive using a high-density polyethylene powder.

<Example 2>

In the same manner as in Example 1, maleic anhydride was substituted with dibutyl maleic acid to prepare a polymer adhesive using high density polyethylene powder.

<Example 3>

The polymer adhesive using the high density polyethylene powder prepared in Example 1 was extruded using an extruder having an L / D = 36, a cylinder and die temperature of 190 ° C., and a screw rotation speed of 60 rpm. Adhesive was prepared.

<Example 4>

In the same manner as in Example 3, maleic anhydride was substituted with dibutyl maleic acid to prepare a polymer adhesive using high density polyethylene powder.

<Example 5>

Proceed in the same manner as in Example 1, a high-density polyethylene powder was irradiated with an electron beam of 3 kGy using a direct current high voltage electron beam accelerator (ELV-0.5 Type) to prepare a polymer adhesive using a high density polyethylene powder.

<Example 6>

Proceed in the same manner as in Example 1, a high-density polyethylene powder was irradiated with a 5 kGy electron beam using a direct current high voltage electron beam accelerator (ELV-0.5 Type) to prepare a polymer adhesive using a high density polyethylene powder.

<Example 7>

Proceed in the same manner as in Example 1, a polymer adhesive using a high density polyethylene powder was prepared by irradiating a 10 kGy electron beam to a high density polyethylene powder using a direct current type high voltage electron beam accelerator (ELV-0.5 Type).

<Example 8>

Proceed in the same manner as in Example 1, a high-density polyethylene powder was irradiated with an electron beam of 15 kGy using a direct current high voltage electron beam accelerator (ELV-0.5 Type) to prepare a polymer adhesive using a high density polyethylene powder.

Example 9

Proceed in the same manner as in Example 1, a high-density polyethylene powder was irradiated with a 20 kGy electron beam using a direct current high voltage electron beam accelerator (ELV-0.5 Type) to prepare a polymer adhesive using a high density polyethylene powder.

<Example 10>

Proceed in the same manner as in Example 1, a high-density polyethylene powder was irradiated with a 25 kGy electron beam using a DC-type high voltage electron beam accelerator (ELV-0.5 Type) to prepare a polymer adhesive using high density polyethylene powder.

<Example 11>

Proceed in the same manner as in Example 1, a high-density polyethylene powder was irradiated with an electron beam of 30 kGy using a DC-type high voltage electron beam accelerator (ELV-0.5 Type) to prepare a polymer adhesive using a high density polyethylene powder.

After the polymer adhesive using the high-density polyethylene powder prepared in Examples 1 to 11 was heated to a temperature of 60 to 70 ℃ the usable temperature, the adhesion process was performed and the adhesive strength is shown in Table 1 below.

Table 1>

As shown in Table 1, it can be seen that the adhesion is improved depending on the extrusion process and the electron beam irradiation amount.

1 is a flow chart illustrating a manufacturing process of a polymer adhesive using a high density polyethylene powder according to the present invention.

Figure 2 is a block diagram showing the manufacturing process of the polymer adhesive using a high density polyethylene powder according to the present invention.

Figure 3 is a photograph of bonding stainless steel to a polyethylene cylinder using a polymer adhesive using a high density polyethylene powder according to the present invention.

Figure 4 is a photograph of bonding carbon steel to a polyethylene cylinder using a polymer adhesive using a high density polyethylene powder according to the present invention.

*** Description of the symbols for the main parts of the drawings ***

10; First reactor

11; cycle

20; Second reactor

Claims (9)

Radical generation step of generating a radical by irradiating the electron beam to the high-density polyethylene powder; A polyethylene input step of introducing the high density polyethylene powder, which has undergone the radical generation step, into a first reactor; A first heating step of heating the high-density polyethylene powder passed through the polyethylene injection step at a temperature of 70 to 80 ° C .; Spraying step of spraying 0.2 to 55 parts by weight of the additive in the first reactor; A circulation step of circulating the high density polyethylene powder using a circulator while continuing the spraying step; And And a second heating step of transferring the high density polyethylene powder passed through the circulation step to a second reactor and heating to a temperature of 100 to 200 ° C., The additive comprises 0.1 to 40 parts by weight of monomer and 0.1 to 15 parts by weight of dispersant, The monomer comprises at least one selected from the group consisting of dibutyl maleic acid and maleic anhydride, The dispersant is a method for producing a polymer adhesive using a high density polyethylene powder, characterized in that it comprises one or more selected from the group consisting of acetone and xylene. The method according to claim 1, The irradiation range of the electron beam in the radical generation step is a method for producing a polymer adhesive using a high density polyethylene powder, characterized in that 3 to 30 kGy (kilogray). The method according to claim 1, The particle size of the high density polyethylene powder is a method for producing a polymer adhesive using a high density polyethylene powder, characterized in that less than 200 microns. delete delete delete The method according to claim 1 The additive further comprises 1 to 10 parts by weight of initiator, Wherein said initiator comprises at least one selected from the group consisting of dibutyl peroxide, benzoyl peroxide and 2,2-azobisisobutylonitrile. The method according to claim 1, The circulation step is made for 25 to 35 minutes, during the spraying step of the polymer adhesive using a high density polyethylene powder, characterized in that for circulating 3 to 8% by weight of the high density polyethylene powder using a circulator. delete

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