KR102008756B1 - Thermoplastic Polyurethane Composition and method thereof - Google Patents

Abstract

Thermoplastic polyurethane compositions according to the invention and methods for their preparation are disclosed. Thermoplastic polyurethane production method according to the present invention, the first step of preparing a copolymer consisting of 20 to 60% by weight: 80 to 40% by weight of two different polyols in the reactor; Injecting an excess of aromatic diisocyanate relative to the copolymer into the reactor, and then polymerizing the copolymer and the aromatic diisocyanate to generate a prepolymer; A third step of preparing a polyurethane by mixing a curing agent with the prepolymer; And a fourth step of aging the polyurethane. The thermoplastic polyurethane composition according to the present invention has the advantage of having both heat resistance and cold resistance.

Description

Thermoplastic polyurethane composition and preparation method thereof

The present invention relates to a thermoplastic polyurethane composition and a method for producing the same, and more particularly, to a thermoplastic polyurethane composition having a heat resistance and cold resistance at the same time and a method for producing the same.

Polyurethane is a generic name of a polymer compound in which urethane bonds are repeatedly contained in the main chain of the polymer and has a repeating structure of soft segments and hard segments. By controlling the ratio of soft and hard segments, polyurethanes can be designed in a variety of molecular designs, from elastomers with rubbery elasticity to rigid products such as engineering plastics. For example, when the ratio of the soft segments is increased, the polyurethane has a low hardness and soft rubber-like structure, wherein the entangled structure of the soft segments increases the elongation of the polyurethane. On the other hand, when the ratio of hard segments is increased, polyurethane has a structure of increasing hardness and increasing rigidity.

Polyurethanes contain an excess of isocyanates (e.g., TDI, MDI, NDI, etc.) in polyols having hydroxyl groups (-OH) at both ends (e.g. PPG, PTMG, Polyester diol, PCL diol, PC diol, etc.). It is prepared by polymerizing to make a prepolymer having an isocyanate group (-NCO) at the end and then addition polymerization with a chain extender (eg, amine, diol, etc.). Here, the polyol constitutes a soft segment, and the urethane or the like formed of a reaction with an isocyanate (TDI, MDI, NDI, etc.), amine, hydroxy, etc. constitutes a hard segment.

Polyurethane has a wide range of uses because it is possible to form polymers having various properties by changing the raw material composition of the hard and soft segments. For this reason, polyurethane has grown into an important industrial material with annual consumption of 10 million tons, and its application as a functional polymer is also actively developed. Typical applications of polyurethane include a wide variety of elastomers, engineering plastics, soft foams such as seat cushions, integral skin foams for automobile interiors, rigid foams used for building panels and various insulation materials, paints, adhesives, and functional fibers. .

As one of the polyurethane products, rod packing used in hydraulic equipment of construction machinery is a component that prevents leakage by matching with various materials and is frequently exposed to the harsh conditions such as high temperature, high pressure, and extreme depending on the operating environment of hydraulic equipment. . Since general rod packing is developed to have high heat resistance or high cold resistance, it is troublesome to replace it whenever the use environment of the rod packing changes from high temperature to extreme temperature or from extreme temperature to high temperature.

Korean Patent No. 1,631,375 Japanese Patent No. 4,338,261 Japanese Patent No. 4,076,589

The present invention has been made to solve the above-described problems, to provide a thermoplastic polyurethane composition and a method for producing the same having both heat resistance and cold resistance.

In addition, the present invention provides a method for producing a hybrid rod packing having both heat resistance and cold resistance.

Other objects of the present invention will become more apparent through the preferred embodiments described below.

 According to one aspect of the invention, the thermoplastic polyurethane manufacturing method comprises the first step of preparing a copolymer consisting of 20 to 60% by weight: 80 to 40% by weight of two different types of polyol in the reactor; Injecting an excess of aromatic diisocyanate relative to the copolymer into the reactor, and then polymerizing the copolymer and the aromatic diisocyanate to generate a prepolymer; A third step of preparing a polyurethane by mixing a curing agent with the prepolymer; And a fourth step of aging the polyurethane.

Here, the thermoplastic polyurethane manufacturing method may further include mixing an additive to the copolymer before the second step.

Here, the thermoplastic polyurethane manufacturing method may further comprise the step of heating the reactor to a temperature of 90 ℃ to 110 ℃ after mixing the additive.

Here, the thermoplastic polyurethane manufacturing method may further comprise the step of cooling the reactor to a temperature of 90 ℃ to 100 ℃ before the third step.

Here, the thermoplastic polyurethane manufacturing method may further comprise the step of dehydrating the copolymer before mixing the additive.

Herein, the aromatic diisocyanate may be 40 g to 65 g based on 100 g of the copolymer.

Here, the curing agent may be one or more of materials having 1,4-butanediol, HQEE and terminal OH groups.

Here, the fourth step may be at least 30 minutes at 80 ℃ to 110 ℃, 20 days or more at room temperature.

Here, the additive may be at least one of a dispersant, a sunscreen, a light stabilizer and a hydrolysis agent.

Here, the two different types of polyols may be polycarbonate polyols (PC) and polycaprolactone polyols (PCL).

Here, the aromatic diisocyanate may be 3,3'-dimethyl-4,4'-biphenylene diisocyanate (TODI).

According to another aspect of the invention, the thermoplastic polyurethane composition is a copolymer consisting of 20 to 60% by weight: 80 to 40% by weight of two different types of polyol, the copolymer and an excess of aromatic di Prepolymers produced by polymerizing isocyanates; And curing agents.

Here, the thermoplastic polyurethane composition may further include an additive consisting of at least one of a dispersant, a sunscreen, a light stabilizer, and a hydrolysis agent.

Here, the curing agent may be one or more of materials having 1,4-butanediol, HQEE and terminal OH groups.

Here, the aromatic diisocyanate may be 40 g to 65 g based on 100 g of the copolymer.

Here, the two different polyols may be PC and PCL.

Here, the aromatic diisocyanate may be TODI.

The thermoplastic polyurethane composition according to the present invention has the advantage of having both heat resistance and cold resistance.

In addition, the hybrid rod packing made of a thermoplastic polyurethane composition according to the present invention has the advantage that can be used simultaneously in high temperature and extreme environments.

1 is a flow chart showing a method of manufacturing a thermoplastic polyurethane composition according to an embodiment of the present invention.

As the invention allows for various changes and numerous embodiments, particular embodiments will be illustrated in the drawings and described in detail in the written description. However, this is not intended to limit the present invention to specific embodiments, it should be understood to include all transformations, equivalents, and substitutes included in the spirit and scope of the present invention. In the following description of the present invention, if it is determined that the detailed description of the related known technology may obscure the gist of the present invention, the detailed description thereof will be omitted.

Terms such as first and second may be used to describe various components, but the components should not be limited by the terms. The terms are used only for the purpose of distinguishing one component from another.

The terminology used herein is for the purpose of describing particular example embodiments only and is not intended to be limiting of the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this application, the terms "comprise" or "have" are intended to indicate that there is a feature, number, step, operation, component, part, or combination thereof described in the specification, and one or more other features. It is to be understood that the present invention does not exclude the possibility of the presence or the addition of numbers, steps, operations, components, components, or a combination thereof. Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings.

1 is a flow chart showing a method of manufacturing a thermoplastic polyurethane composition according to an embodiment of the present invention.

Referring to FIG. 1, step S110 is a step of preparing a copolymer including two different types of polyols in a predetermined ratio in a reactor. The two different types of polyols may include polyester polyols, polyether polyols, polycarbonate (PC) polyols, polycaprolacton (PCL) polyols, and polytetramethylene polyols. Can be selected from. For example, the two different types of polyols may be polycarbonate polyols and polycaprolactone polyols. In addition, the two types of polyol ratio may be 20 to 60% by weight: 80 to 40% by weight. For example, if the polyol A is 20% by weight, the polyol B is 80% by weight, if the polyol A is 50% by weight the polyol B is 50% by weight, or the polyol A is 60% by weight the polyol B is 50% by weight Can be.

In step S120, the copolymer may be subjected to a dehydration (water removal) and degassing (bubble removing) process. Dehydration and degassing process serves to prevent the addition reaction in the subsequent polymerization process.

Step S130 is a process of mixing the copolymer and the added additive by adding an additive into the reactor. Here, the additive may be at least one of a dispersant, a sunscreen, a light stabilizer, an antioxidant, a heat stabilizer and a hydrolysis agent. When a plurality of additives is added, the ratio between the plurality of additives may be variously set according to the embodiment.

In step S140, the reactor may be heated to a temperature of 90 ℃ to 110 ℃. Thereafter, an excessive amount of aromatic diisocyanate relative to the copolymer is introduced into the reactor in step S150, and the copolymer and the introduced aromatic diisocyanate are polymerized to generate a prepolymer. Here, the fructose aromatic diisocyanate may be 40 g to 65 g with respect to 100 g of the copolymer. In addition, the aromatic diisocyanate may be in powder form, and may be at room temperature. In addition, the aromatic diisocyanate may be 3,3'-dimethyl-4,4'-biphenylene diisocyanate (TODI). In addition, the polymerization of the copolymer and the aromatic diisocyanate may last for 30 minutes.

When the polymerization reaction is completed, the temperature in the reactor increases due to the heat of reaction (for example, rises from 105 ° C to 110 ° C). Since side reactions may occur during mixing of the curing agent at an elevated temperature, a process of cooling the reactor is performed in step S160. At this time, the cooling temperature may be 90 ℃ to 100 ℃.

Then, the polyurethane is prepared by adding and stirring the curing agent into the reactor (S170). Here, the curing agent may be at least one of 1.4 butanediol (1.4-Buthane Diol), bis 2-hydroxylethyl ether (HQEE) and a material having a terminal OH group. In addition, the stirring time may be within 2 minutes.

A process of ripening the polyurethane prepared in step S180 is performed. The aging process may be performed in an oven prepared at 80 ° C. to 110 ° C. for at least 30 minutes by putting a polyurethane prepared in a mold prepared in advance (for example, a mold having a thickness of 20 to 25 mm). Thereafter, the fermentation process may be carried out for 4 days or more at room temperature for 20 days.

Hereinafter, a specific embodiment of a thermoplastic polyurethane composition having both heat resistance and cold resistance according to an embodiment of the present invention will be described below.

<Example>

end. A copolymer (100 g, 2000 g / mol, hydroxyl group 56) composed of polycarbonate polyol and polycaprolactone was prepared.

I. Copolymer Dehydration and Defoaming

All. 1g each of additives, dispersant, antioxidant, heat stabilizer and hydrolysis agent, mixed with copolymer

la. Heating the reactor in the range of 90 ° C. to 100 ° C.

hemp. Prepolymer was added for 30 minutes with an excess of 49 g of TODI to form a prepolymer.

bar. Cool down the reactor to 90 ° C

four. Polyurethane was prepared by adding 1.4 butanediol (10.87g, 90g / mol) as a curing agent and stirring for 2 minutes.

Ah. The prepared polyurethane was put in a mold and aged in an oven at 110 ° C for 30 minutes and then divided into 4 parts for 20 days at room temperature (about 30 degrees).

Properties of the thermoplastic polyurethane composition according to the embodiment are shown in the table below.

Item unit Specifications PC: PCL = 1: 1 Test method Before ripening After ripening Hardness Shore a 94 ± 3 94 94 KS M 6518 The tensile strength Mpa 35 or more 57 57 KS M 6518 Tear strength KN / m 120 or more 158 161 KS M 6518 Elongation % More than 400 490 450 KS M 6518 100%
Modulus Mpa over 10 10.2 - KS M 6518 Hardness change rate Shore a - - 0 KS M 6518 The tensile strength
Rate of change % - - 14 KS M 6518 Elongation rate of change % - - 20 KS M 6518 Tear strength
Rate of change % - - 5.6 KS M 6518

Hereinafter, a method of manufacturing a hybrid rod packing having both heat resistance and cold resistance using the thermoplastic polyurethane composition according to the present invention will be described below.

end. Prepare the polyurethane after the above-mentioned aging process is completed

I. Pelletizing or granulating the polyurethane through a known pelletizer or grinder

All. Rod packing is manufactured by injection molding pelletized or granulated polyurethane

Preferred embodiments of the present invention described above are disclosed for purposes of illustration, and those skilled in the art will be able to make various modifications, changes, and additions within the spirit and scope of the present invention. Additions should be considered to be within the scope of the following claims.

Claims (17)

In the method for producing a polyurethane composition for producing a hybrid rod packing having both heat resistance and cold resistance at the same time,
Preparing a copolymer having a polycarbonate polyol (PC) and a polycaprolactone polyol (PCL) in a reactor in a ratio of 20 to 60 wt%: 80 to 40 wt%;
3,3'-dimethyl-4,4'-biphenylene diisocyanate (TODI) was introduced into the reactor, and the copolymer and the 3,3'-dimethyl-4,4'-biphenylene diisocyanate were added. A second step of polymerizing (TODI) to produce a prepolymer;
A third step of preparing a polyurethane by mixing a curing agent with the prepolymer; And
Including a fourth step of aging the polyurethane; including,
After the step of preparing the copolymer, a thermoplastic polyurethane manufacturing method comprising the step of dehydrating the copolymer to prevent the addition reaction that may occur during the polymerization of the copolymer.
The method according to claim 1,
The method of manufacturing a thermoplastic polyurethane further comprising the step of mixing an additive to the copolymer before the second step.
The method according to claim 2,
The method of manufacturing a thermoplastic polyurethane further comprises the step of heating the reactor to a temperature of 90 ℃ to 110 ℃ after mixing the additive.
The method according to claim 3,
The method of manufacturing a thermoplastic polyurethane further comprises the step of cooling the reactor to a temperature of 90 ℃ to 100 ℃ before the third step.
delete The method according to claim 1,
The aromatic diisocyanate is a thermoplastic polyurethane production method, characterized in that 40g to 65g with respect to 100g of the copolymer.
The method according to claim 1,
Wherein said curing agent is at least one of materials having 1,4-butanediol, HQEE and terminal OH groups.
The method according to claim 1,
The fourth step is a thermoplastic polyurethane manufacturing method comprising at least 30 minutes at 80 ℃ to 110 ℃, 20 days or more at room temperature.
The method according to claim 2,
The additive is a thermoplastic polyurethane manufacturing method, characterized in that at least one of a dispersant, a sunscreen, a light stabilizer and a hydrolysis agent.
delete delete In the polyurethane composition for producing a hybrid rod packing having both heat resistance and cold resistance,
Polycarbonate polyol (PC) and polycaprolactone polyol (PCL) each composed of 20 to 60% by weight: 80 to 40% by weight of the copolymer, and 3,3'-dimethyl-4,4'-biphenylene di Prepolymers produced by polymerizing isocyanates (TODI); And
A thermoplastic polyurethane composition comprising a curing agent;
The method according to claim 12,
A thermoplastic polyurethane composition further comprising an additive consisting of at least one of a dispersant, a sunscreen, a light stabilizer and a hydrolysis agent.
The method according to claim 13,
Wherein said curing agent is at least one of 1,4-butanediol, HQEE and a material having terminal OH groups.
The method according to claim 12,
The aromatic diisocyanate is a thermoplastic polyurethane composition, characterized in that from 40g to 65g with respect to 100g of the copolymer.
delete delete

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