KR100246147B1 - Process for preparation of polymer with isocyanate function - Google Patents

Abstract

1. TECHNICAL FIELD OF THE INVENTION

The present invention relates to a thermoplastic polymer having an isocyanate group and a method for producing the same.

2. The technical problem to be solved by the invention

The present invention provides a reactive compatibilizer comprising an isocyanate group in a thermoplastic polymer molecule such as a thermoplastic resin or an elastomer to reduce the interfacial tension between disperse and continuous phases between dissimilar polymer polymers during polymer blending and to impart strong adhesion to the interface. It is an object of the present invention to provide a thermoplastic polymer having an isocyanate group capable of maximizing a commercialization effect and a method for producing the same.

3. Summary of Solution to Invention

In order to achieve the above object, the present invention provides a thermoplastic polymer having an isocyanate group characterized in that the compound having the structure of formula (1) is constituted in a molecule.

[Formula 1]

In Formula 1, A is a monovalent radical derived from an unsaturated compound having a hydroxy group, a carboxyl group, an amine group, an amide group, a urethane group, a urea group, etc., and D is an aliphatic or aromatic diisocyanate compound together with two substituted isocyanate groups. Divalent radicals derived from cyclic aliphatic or aromatic compounds.

4. Important uses of the invention

The present invention has use as a compatibilizer in polymer blending and as an adhesive resin in coextrusion of thermoplastic resins.

Description

Method for producing a thermoplastic polymer having an isocyanate group

The present invention relates to a method for producing a thermoplastic polymer having an isocyanate group. More particularly, by forming an isocyanate group in a molecule of a thermoplastic polymer such as a thermoplastic resin or an elastomer, excellent physical properties can be expressed even when mixed with a heterogeneous resin. A method for producing a thermoplastic polymer having an isocyanate group.

Generally, homopolymers have unique properties determined by their chemical structures, and in some cases, polymers having properties that share the characteristics of each homopolymer are required.

For this reason, heterogeneous homopolymers have been conventionally used as polymer blends for the above-mentioned purposes by polymer blending, and thus blends between two or three component thermoplastic resins or these resins and elastomers Blends with can not only combine the advantages of the polymers, but also because the production method is simple and low cost, the amount of use is increasing in each industry.

However, in the case of blending an engineering resin such as polyamide or polyester together with a polyolefin resin or an elastomer which lacks compatibility between blend components in the preparation of the thermoplastic resin and the elastomer blend. Insufficient adhesive strength between the and continuous phase, causing a large phase separation, not only the workability is lowered but also the physical properties of the blend is lowered, there is a problem that can not fully exhibit the advantages of each mixed resin.

In order to compensate for these disadvantages, a method of using a block copolymer of blended resins as a compatibilizer has been introduced.

While the block copolymer has the advantage of making the dispersed phase of the blend small or increasing the compatibility, there is a problem in that it does not provide a strong adhesive force to the interface of the dispersed phase and the continuous phase of the mixed dissimilar resin, and is not easy to manufacture. There have been a number of problems such as a manufacturing apparatus and a lot of costs can not be consumed.

In this regard, U.S. Patent Nos. 4,174,358, 3,668,274, 3,972,961, etc., are polyolefin resins having functional groups such as maleic anhydride, carboxyl groups or epoxy groups in the molecule as reactive compatibilizers for incompatible interpolymer blends or The use of an elastomer introduces a technique that solves the shortcomings seen in the above block copolymers.

Copolymer resins and elastomers having such functional groups have many advantages in terms of productivity, such as low manufacturing costs and simplified manufacturing equipment and equipment.

In addition, the commercialization method using the resin and the elastomer not only reduce the interfacial tension due to the chemical reaction between components during blending to form a small and uniform dispersibility, but also chemical bonding between the components compared to the method using a block copolymer Since it has the advantage that can give a strong adhesion between the interfaces by the recent research to actively use it has been actively conducted.

However, as described above, the functional groups such as maleic anhydride, carboxyl group or epoxy group which are composed of copolymer resin and elastomer which are used as reactive compatibilizer for incompatible polymer blend and are involved in chemical reaction during blending, may be used when blending with amine groups of polyamide resin. Although the reaction occurs excellently, it is difficult to effectively react with the hydroxyl group, the carboxyl group, and the like of other resins, and thus has been limited in many applications as a reactive compatibilizer.

The present invention is to solve the above problems, and to form an isocyanate group in a thermoplastic polymer molecule such as a thermoplastic resin or an elastomer, when used as a reactive compatibilizer, as well as the amine group of the counterpart resin blended with these thermoplastic polymers, as well as hydroxy and carboxyl groups. It can be used for most non-commercial blends regardless of the type of resin to be blended, because it rapidly reacts chemically with most functional groups.The chemical reaction gives lowering of interfacial tension and strong adhesion of the interface. It is an object of the present invention to provide a method for producing a thermoplastic polymer having an isocyanate group capable of maximizing.

In order to achieve the above object, the present invention provides a thermoplastic polymer comprising a compound having a structure represented by the following formula (1) in a molecule.

In Formula 1, A is a monovalent radical derived from an unsaturated compound having a hydroxy group, a carboxyl group, an amine group, an amide group, a urethane group, a urea group, and the like, and D is an aliphatic or Divalent radicals derived from cyclic aliphatic or aromatic compounds constituting the aromatic diisocyanate compound (hereinafter the same).

Examples of the compound containing A include hydroxyethyl acrylate, hydroxyethyl methacrylate, acrylic acid, methacrylic acid, acrylamide, and the like. Examples of the cyclic aliphatic or aromatic diisocyanate compound containing D include toluene diisocyanate. , Isophorone diisocyanate, 4,4'- dicyclohexyl methane diisocyanate, diphenyl diisocyanate, xylene diisocyanate, tetramethyl xylene diisocyanate, etc. are mentioned.

It is possible to form the compound of Formula 1 according to the present invention in a thermoplastic polymer polymer molecule such as a thermoplastic resin or an elastomer by conventional graft copolymerization.

That is, graft copolymerization may be performed by adding a polymerization initiator such as a compound of Formula 1 and a peroxide in the process of dissolving the thermoplastic resin or the elastomer in an organic solvent or extruding at a high temperature of about 220 ° C.

In order to produce a compound having the structure of Formula 1 for producing a thermoplastic resin and an elastomer having an isocyanate group of the present invention, in the present invention, a cyclic aliphatic or aromatic diisocyanate compound of Formula 2, an amine group, and a hydroxyl group It is obtained by reacting a compound (A in Chemical Formula 1) selected from unsaturated compounds having the same and the like in a molar ratio of 1: 1.

(D in Chemical Formula 2 is as defined in Chemical Formula 1)

Thermoplastic resins or elastomers in which the compound of Formula 1 is constituted in a molecule include polyolefin resins such as polyethylene, polypropylene, polystyrene, copolymers thereof, ethylene-propylene-diene terpolymer, and the like.

When the thermoplastic polymer having an isocyanate group of the present invention prepared in the method described above is mixed at a ratio of 5 to 900% (w / w) of the amount of heterogeneous incompatible resins mixed therewith, effective commercialization can be achieved. The blends thus produced can be used extensively throughout the industry, from food packaging and packaging films requiring gas barriers to automotive parts such as gasoline fuel tanks and the electronics industry, as well as polyolefin resins and engineering. When extruded resin etc., when used as an adhesive resin of an interface, it can give very excellent adhesive force.

Hereinafter, the present invention will be described in more detail with reference to Examples, Comparative Examples, and Experimental Examples.

[Elastomer Production Example 1 Having an Isocyanate Group (hereinafter referred to as Production Example 1)]

After mixing 17.5 kg of toluene diisocyanate and 11.6 kg of hydroxymethyl acrylate and reacting for 4 hours while maintaining a temperature of 50 ± 1 ° C. under a nitrogen atmosphere, a compound having the structure of Formula 3 was synthesized.

1 kg of the compound of Formula 3, 20 kg of an ethylene-propylene-diene terpolymer copolymer having a number average molecular weight of 20,500, and 0.2 kg of dicumyl peroxide were mixed to maintain a temperature of 220 ± 2 ° C. in an extruder and then extruded. Elastomer composed of propylene-diene terpolymer prepared as polymer base chain and C = C double bond of Formula 3 is radical by dicumyl peroxide to react with base chain to form the compound of formula 3 It was.

[Production example 2 of thermoplastic resin having isocyanate group (hereinafter referred to as production example 2)]

After mixing 22.2 kg of isophorone diisocyanate and 13.0 kg of hydroxyethyl methacrylate and reacting for 4 hours while maintaining a temperature of 50 ± 1 ° C. under a nitrogen atmosphere, a compound having the structure of Chemical Formula 4 was synthesized.

1 kg of the compound of Formula 4, 20 kg of low density polyethylene resin having a number average molecular weight of 23,500, and 0.2 kg of dicumyl peroxide are mixed and extruded by maintaining the temperature at 220 ± 2 ° C. in an extruder, thereby polymerizing the ethylene-propylene-diene 3 copolymer The C = C double bond of the formula (4) as a base chain was made into a radical by dicumyl peroxide to react with the basic chain to prepare a low density polyethylene composed of the compound of formula (4).

[Example 3 of thermoplastic resin having an isocyanate group (hereinafter referred to as Production Example 3)]

After mixing 22.2 kg of isophorone diisocyanate and 13.0 kg of hydroxyethyl methacrylate and reacting for 4 hours while maintaining a temperature of 50 ± 1 ° C. under a nitrogen atmosphere, a compound having the structure of Chemical Formula 4 was synthesized. By mixing 1 kg of the compound of 4, 20 kg of high density polyethylene resin having a number average molecular weight of 26,000, and 0.2 kg of dicumyl peroxide, the extruder was maintained at a temperature of 220 ± 2 ° C. to extrude the ethylene-propylene-diene terpolymer to the polymer base chain. The C = C double bond of Chemical Formula 4 became a radical by dicumyl peroxide and reacted with the basic chain to prepare a low density polyethylene having a compound of Chemical Formula 4 in a branched form.

Blend Preparation Example 1

Ethylene-propylene-diene terpolymer having an isocyanate group prepared in Preparation Example 1: a mixture obtained by mixing ethylene-propylene-diene terpolymer in 1: 1% (w / w) with nylon having a number average molecular weight of 17,500 6 resin was mixed with 1: 9% (w / w) to prepare a blend, which was extruded while maintaining a temperature of 250 ± 2 ° C. in an extruder, cooled and solidified, and cut into chips.

Blend Preparation Example 2

Low density polyethylene resin having an isocyanate group prepared in Preparation Example 2: a mixture of low density polyethylene resin in a ratio of 1: 1% (w / w) and polyethylene terephthalate resin having a number average molecular weight of 22,500, respectively 2: 8% (w / w) and 8: 2% (w / w) were mixed to prepare a blend, which was extruded in an extruder while maintaining a temperature of 290 ± 2 ℃, cooled, solidified and cut into chips. .

Blend Preparation Example 3

Low density polyethylene resin having an isocyanate group prepared in Preparation Example 2: a mixture of a low density polyethylene resin 1: 1% (w / w) and a polycarbonate resin having a number average molecular weight of 19,000 and 2: 8% ( w / w) and 8: 2% (w / w) to prepare a blend, which was then extruded while maintaining a temperature of 250 ± 2 ° C. in an extruder, cooled and solidified and cut into chips.

Blend Preparation Example 4

The high-density polyethylene resin having an isocyanate group prepared in Preparation Example 3: a mixture of high density polyethylene resin in a ratio of 1: 1% (w / w), polyacetal resin having a number average molecular weight of 21,000, and 2: 8% ( w / w) and 8: 2% (w / w) to prepare a blend, which was extruded while maintaining a temperature of 220 ± 2 ° C. in an extruder, cooled and solidified and cut into chips.

Blend Preparation Example 5

A high density polyethylene resin having an isocyanate group prepared in Preparation Example 3; a mixture of high density polyethylene resin mixed at 1: 1% (w / w), a high density polyethylene resin having a melt index of 3.5 and a vinyl alcohol mole fraction of 68% To a blend of 2: 8% (w / w) and 8: 2% (w / w), respectively, and then extruded, cooled, and solidified in an extruder at a temperature of 220 ± 2 ° C. The chip was cut into chips.

[Comparative Example 1 for Blend Preparation]

After blending the ethylene-propylene-diene terpolymer with a nylon 6 resin having a number average molecular weight of 17,500 at 1: 9% (w / w), a blend was prepared and maintained at a temperature of 250 ± 2 ° C. in an extruder. Extruded in one state, cooled and solidified and cut into chips.

Blend Preparation Comparative Example 2

A low density polyethylene resin and a polyethylene terephthalate resin having a number average molecular weight of 22,500 were mixed at 2: 8% (w / w) and 8: 2% (w / w), respectively, to prepare a blend, which was then 290 in an extruder. Extrusion, cooling, and solidification were carried out while maintaining a temperature of ± 2 ° C, and cut into chips.

Blend Preparation Comparative Example 3

A low density polyethylene resin and a polycarbonate resin having a number average molecular weight of 19,000 were mixed at 2: 8% (w / w) and 8: 2% (w / w), respectively, to prepare a blend, which was then 250 ±. Extrusion, cooling, and solidification were carried out while maintaining a temperature of 2 ° C, and cut into chips.

Blend Preparation Comparative Example 4

A high density polyethylene resin and a polyacetal resin having a number average molecular weight of 21,000 were mixed at 2: 8% (w / w) and 8: 2% (w / w), respectively, to prepare a blend, and then 220 ± Extrusion, cooling, and solidification were carried out while maintaining a temperature of 2 ° C, and cut into chips.

Blend Preparation Comparative Example 5

A blend was prepared by mixing a high density polyethylene resin and a high density polyethylene resin having a melt index of 3.5 and a vinyl alcohol mole fraction of 68% at 2: 8% (w / w) and 8: 2% (w / w), respectively. Then, this was extruded while maintaining the temperature of 220 ± 2 ℃ in an extruder, cooled, solidified and cut into chips.

Experimental Example 1

After blending the blended water chips prepared in Examples 1 to 5 and Blend Preparation Comparative Examples 1 to 5 with crushed by liquid nitrogen, the fracture surface was observed with a differential scanning electron microscope to detect 1,000 of the dispersed phases formed in the blend. The average size of the dogs is shown in Table 1.

As shown in Table 1, blends prepared by blending the thermoplastic polymer having the isocyanate group of the present invention in Examples 1 to 5, while the average size of the dispersed phase appeared to be very small as 0.2 to 1.3㎛, blend preparation comparison In the case of 1 to 5, 7.3 to 15.2 μm, the average size of which was shown to be up to 76 times larger than that of the blend manufacturing example. As a polyamide resin, not only nylon 6 having an amine group but also a heteropolymer resin having a hydroxy group or a carboxyl group When blending the liver, it can be seen that when the thermoplastic polymer having the isocyanate group of the present invention is added, the interfacial tension between the dispersed phase and the continuous phase can be effectively reduced to exhibit excellent commercialization effects.

Experimental Example 2

[Tensile strength measurement test]

The blend water chips prepared from the blend preparation examples 1 to 5 and blend preparation comparison examples 1 to 5 were dried under reduced pressure at a temperature of 80 ° C. for 48 hours, and then injection molded into dumbbell-shaped specimens as defined in the tensile strength measurement test method of ASTM D638. After measuring the strength at break while stretching at a rate of 1.68 cm / min, the same test was repeated 10 times the average value is shown in Table 2 below.

[Impact strength test]

The blend water chips prepared from the blend preparation examples 1 to 5 and the blend preparation examples 1 to 5 were dried under reduced pressure at a temperature of 80 ° C. for 48 hours, and then the width × vertical × thickness as defined in the impact strength measurement test method of ASTM D256. After forming a specimen of 63.5 × 12.7 × 6.4mm, form a V-shaped groove of 2.5mm depth at the middle point of the specimen and measure the impact strength with an Izod impact tester. It is shown in Table 2 below.

As shown in Table 2, blends prepared by blending thermoplastic polymers having isocyanate groups of the present invention Examples 1 to 5 in the tensile strength as compared to blends of Comparative Preparation Examples 1 to 5 at the lowest 151% 217% was found to be high, and the impact strength was found to be markedly increased from 138% to 450%.

In the present invention, by forming an isocyanate group in the thermoplastic resin and the elastomer molecule, it is possible to exhibit an excellent commercial effect when used as a compatibilizer in blending between incompatible polymers, to form a small and uniform dispersed phase, and to have a tensile strength and an impact strength incompatible polymer. It can show significantly increased physical properties compared to blends of liver, shows excellent reactivity for most functional groups when blending dissimilar resins, and can be used without limitation in the polymer to be blended, and also as an adhesive resin in coextrusion of thermoplastic resins. It is a useful invention to provide thermoplastic polymers having isocyanate groups that can be used well.

Claims (3)

In a graft copolymer comprising a polyolefin or a polyolefin copolymer as a basic polymer, a cyclic aliphatic or aromatic diisocyanate compound represented by the following formula (2) and an unsaturated compound having an amine group, a hydroxyl group, or a carboxyl group in a molecule thereof in a molar ratio of 1: 1. After the reaction to prepare a compound of formula 1, [Formula 1]

In Formula 1, A is a monovalent radical derived from an unsaturated compound having a hydroxy group, a carboxyl group, an amine group, an amide group, a urethane group, a urea group, and the like, and D is an aliphatic or Divalent radicals derived from cyclic aliphatic or aromatic compounds that form an aromatic diisocyanate compound. [Formula 2]

(D in Chemical Formula 2 is as defined in Chemical Formula 1) A method for producing a thermoplastic polymer having an isocyanate group, characterized in that the compound of Formula 1 copolymerizes a polyolefin or a polyolefin copolymer by a conventional graft copolymerization. The method according to claim 1, wherein the compound comprising A is hydroxyethyl acrylate, hydroxyethyl methacrylate, acrylic acid, methacrylic acid or acrylamide. The cyclic aliphatic or aromatic diisocyanate compound according to claim 1 or 2, wherein the cyclic aliphatic or aromatic diisocyanate compound includes toluene diisocyanate, isophorone diisocyanate, 4,4'-dihexyhexyl methane diisocyanate, diphenyl diisocyanate, A method for producing a thermoplastic polymer having an isocyanate group, characterized in that xylene diisocyanate or tetramethyl xylene diisocyanate.