KR100921209B1 - Impact Reinforcing Copolymer, Method of Preparing Thereof, and Thermoplastic Resin Composition Using the Same - Google Patents

Abstract

The method of manufacturing the impact reinforcing copolymer according to the present invention comprises a first step of preparing a first graft polymer by graft polymerizing a diene rubber and an aromatic vinyl monomer; A second step of preparing a second graft polymer by adding and polymerizing an epoxide compound to the first graft polymer; And a third step of graft polymerization by adding and polymerizing an alkyl (meth) acrylate alone or a mixture of an alkyl (meth) acrylate and an epoxide compound to the second graft polymer. In addition, the present invention provides a thermoplastic resin composition comprising the impact reinforcing copolymer.

Methyl methacrylate-butadiene-styrene, impact reinforcing copolymer, epoxide compound, crystalline resin

Description

Impact Reinforcing Copolymer, Manufacturing Method and Thermoplastic Resin Composition Using the Same {Impact Reinforcing Copolymer, Method of Preparing Thereof, and Thermoplastic Resin Composition Using the Same}

Field of invention

The present invention relates to an impact reinforcing copolymer, a preparation method thereof, and an impact resistant thermoplastic resin composition containing the same. More specifically, in the graft polymerization of the diene rubber, the aromatic vinyl monomer and the alkyl (meth) acrylate, the impact reinforcement effect is further improved by introducing the epoxide compound into the second step to copolymerize. A copolymer for and a thermoplastic resin composition using the same.

Background of the Invention

Techniques for graft copolymerizing aromatic vinyl monomers and ester monomers on polybutadiene rubber to reinforce the impact resistance, weather resistance and workability of a resin composition containing polyvinyl chloride as a main component are well known.

As an impact modifier of such polyvinyl chloride resin, a methyl methacrylate-butadiene-styrene (hereinafter referred to as "MBS") impact modifier, an acrylonitrile-butadiene-styrene (hereinafter referred to as "ABS") impact modifier, a halogenated polyethylene ( Hereinafter, "CPE") impact modifiers and acrylate impact modifiers have been generally used.

However, the impact modifiers developed so far are effective for the impact reinforcement effect of polyvinyl chloride resin, but the impact reinforcement effect is satisfactory in other resins such as polycarbonate, polyethyl terephthalate, nylon and polybutyl terephthalate. There was no.

Japanese Unexamined Patent Publication Nos. 52-68706, 55-179501, 57-122445 and U.S. Patent No. 6,331,580 disclose methods of increasing impact resistance and the like by MBS-based impact modifiers. The MBS-based impact modifier prepared by the above patents is a two-stage multistage emulsion polymerization, and is composed of graft polymerized monomers such as aromatic vinyl and alkyl methacrylate on a diene rubber to form a shell. . However, since the MBS-based impact modifier mentioned in the patent was prepared for the purpose of improving the impact of the polyvinyl chloride resin, when applied to polycarbonate, polyethyl terephthalate, nylon and polybutyl terephthalate, the impact reinforcing effect Has the problem of falling.

Korean Patent Publication No. 2000-22759 discloses a method of preparing an impact modifier by polymerizing an aromatic vinyl compound to rubber constituting the core, then polymerizing an alkyl acrylate to form an intermediate layer, and then polymerizing an acrylic acid alkyl ester monomer. Is doing. However, the impact modifiers prepared above have the advantage of increasing the practical impact of the polyvinyl chloride resin, the applicability to resins other than polyvinyl chloride has not been proved.

In addition, WO 02/34806 discloses a method of improving the impact reinforcement of polyvinyl chloride by copolymerizing a hard part with an impact modifier using divinylbenzene as a crosslinking agent. However, the impact modifier prepared in the patent may improve the impact reinforcement performance with polyvinyl chloride, but divinylbenzene used as a crosslinking agent induces the production of an grafted crosslinked polymer, thereby making polycarbonate and polyethyl terephthalate When applied to resins such as nylon and polybutyl terephthalate, impact reinforcing performance may be degraded.

In order to solve this problem, the present inventors graft polymerized diene rubber, aromatic vinyl monomer, and alkyl (meth) acrylate, thereby copolymerizing the epoxide compound to the intermediate layer and the hard part, thereby improving chemical affinity. By increasing the impact reinforcing effect of polyvinyl chloride to the maximum, the impact reinforcing copolymer having improved the impact reinforcing effect of other thermoplastic resins such as polycarbonate, polyethyl terephthalate, polyamide and polybutyl terephthalate has been developed.

An object of the present invention is to provide a novel method for producing a diene rubber-aromatic vinyl compound-alkyl (meth) acrylate-based impact modifier.

Another object of the present invention is to improve the impact reinforcement performance of not only polyvinyl chloride resins, but also all thermoplastic resins such as amorphous resins such as polycarbonate and polyamide, and crystalline resins such as polyethyl terephthalate, nylon and polybutyl terephthalate. To provide an impact modifier that can be made.

Still another object of the present invention is to provide a thermoplastic resin composition having excellent impact resistance and mechanical properties by applying the impact modifier in an appropriate amount.

The object of the present invention can be achieved by the present invention described below. Hereinafter, the content of the present invention will be described in detail.

Summary of the Invention

Method for producing a impact reinforcing copolymer of the thermoplastic resin of the present invention comprises a first step of graft polymerization of a diene rubber and an aromatic vinyl monomer to prepare a first graft polymer; A second step of preparing a second graft polymer by adding and polymerizing an epoxide compound to the first graft polymer; And a third step of graft polymerizing the alkyl (meth) acrylate alone or a mixture of the alkyl (meth) acrylate and the epoxide compound to the second graft polymer. In addition, the present invention includes a thermoplastic resin composition consisting of 70 to 99% by weight of the thermoplastic resin and 1 to 30% by weight of the impact reinforcing copolymer.

Hereinafter, the content of the present invention will be described in detail below.

Detailed Description of the Invention

First stage

The first graft polymer is prepared by graft polymerization of the diene rubber and the aromatic vinyl monomer.

In one embodiment of the present invention, the diene rubber and the aromatic vinyl monomer are polymerized by adding an emulsifier, a polymerization initiator, and a graft agent.

In another embodiment, general additives such as deionized water, an emulsifier, a reducing agent, an oxidizing agent, an electrolyte, and the like are added to the diene rubber, and the reaction temperature is raised to about 50 to 80 ° C, preferably 60 to 75 ° C, and then the aromatic vinyl monomer, After the polymerization initiator and the graft agent are injected, the polymerization is carried out for 1 to 4 hours to polymerize the conversion to 85 to 97%.

The diene rubber may be polybutadiene, polyisoprene, polychloroprene, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer and the like, these may be used alone or in combination of two or more. Among these are polybutadiene and butadiene-styrene copolymers. The diene rubber preferably has an average particle diameter of 0.1 to 1 mu m, preferably 0.1 to 0.8 mu m. In the present invention, the diene rubber is used in 60 to 80 parts by weight, preferably 70 to 80 parts by weight of the total monomer content.

As the aromatic vinyl monomer, styrene, α-ethylstyrene, α-methylstyrene, or the like may be used, but is not limited thereto. These can be used individually or in mixture of 2 or more types. Among these, preferably styrene. In the present invention, the aromatic vinyl monomer is used in an amount of 5 to 25 parts by weight, preferably 6.5 to 20 parts by weight, more preferably 8 to 15 parts by weight. When used within the above range, it is advantageous in terms of impact reinforcement performance or other processing stability, productivity.

The emulsifier may include potassium stearate, sodium dodecyl sulfate, sodium dodecylbenzene sulfate, potassium oleate sulfate, potassium oleate, rosin acid salts, fatty acid salts, and the like, but is not limited thereto. The emulsifier is used in 0.5 to 3 parts by weight based on 100 parts by weight of the impact reinforcing copolymer.

As the graft agent used in the present invention, divinylbenzene, trivinylbenzene, trialkyl isocyanurate may be used, and two or more polymerizable doubles in one molecule such as allyl methacrylate, ethylene glycol dimethacrylate, etc. Methacrylic monomers having a bond may be used. The graft agent used in the present invention is preferably used at 0.1 to 5 parts by weight based on 100 parts by weight of the impact reinforcing copolymer.

The polymerization initiator that can be used in the present invention is not particularly limited, and benzoyl peroxide, cumene hydroperoxide, azobisisobutylonitrile (AIBN), and the like, but are not necessarily limited thereto.

Additives such as reducing agents, oxidizing agents, electrolytes, and the like may be used in general, and the type and content may be easily carried out by those skilled in the art.

2nd step

An epoxide compound is added to the first graft polymer prepared in the first step and polymerized to prepare a second graft polymer.

Alkenepoxide, cyclodiene epoxide, glycidyl alkyl methacrylate may be used as the epoxide compound, and these may be used alone or in combination of two or more thereof.

As the alkene epoxide, dipentene dioxide, 1,2,7,8-diepoxyoctane, dodecatriene dioxide and mixtures thereof may be used. The cyclodiene epoxide is bi-cycloheptadiene diepoxide, vinyl cyclodioxide, vinyl cyclopenta diene dioxide, butene cyclopentene dioxide, bi-cyclopentadiene diepoxide, bis (c, 4 epoxycyclohexylmethyl) Adipates and mixtures thereof can be used. As the glycidyl alkyl methacrylate, 1,4-butanediol diglycidyl ether, bisglycidyl ether bisphenol-A, glycidyl methacrylate, triglycidyl isocyanurate and mixtures thereof may be used. have.

In the present invention, the epoxide compound is preferably added to 1 to 10 parts by weight, preferably 1.5 to 5 parts by weight of the total monomer content in the second step. If it is added in excess of 10 parts by weight, since the epoxide compound is crosslinkable, the prepared impact modifier may lower the appearance of the matrix resin. In addition, when less than 1 part by weight, the impact reinforcing effect is insignificant.

The addition of the epoxide compound may be added at a time, or continuously for 10 minutes to 180 minutes, preferably 20 minutes to 60 minutes.

In the second step of the present invention can be polymerized by adding a polymerization initiator with the epoxide compound. The polymerization initiator used in the second step is not particularly limited, and the same polymerization initiator used in the first step may be used.

In the second step, the polymerization temperature is performed at about 50 to 80 ° C., preferably at 60 to 75 ° C., and the polymerization is performed for about 10 to 120 minutes.

3rd step

An alkyl (meth) acrylate is added to the second graft polymer prepared in the second step to perform graft polymerization.

In one embodiment of the present invention, an alkyl (meth) acrylate may be added to the second graft polymer together with an initiator to perform graft polymerization.

In another embodiment of the present invention, the second graft polymer may be grafted by adding an epoxide compound together with an alkyl (meth) acrylate. In this case, the alkyl (meth) acrylate and the epoxide compound may be mixed in advance and added together with the initiator.

As the alkyl (meth) acrylate, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate Etc., and these may be used alone or as a mixture of two or more thereof. In the present invention, the alkyl (meth) acrylate is added to 5 to 20 parts by weight, preferably 7 to 20 parts by weight, more preferably 10 to 20 parts by weight of the total monomer content.

The epoxide compound may be used alkene epoxide, cyclodiene epoxide, glycidyl alkyl methacrylate and the like, these may be used alone or in combination of two or more.

As the alkene epoxide, dipentene dioxide, 1,2,7,8-diepoxyoctane, dodecatriene dioxide and mixtures thereof may be used. The cyclodiene epoxide is bi-cycloheptadiene diepoxide, vinyl cyclodioxide, vinyl cyclopentadiene dioxide, butene cyclopentene dioxide, bi-cyclopentadiene diepoxide, bis (c, 4 epoxycyclohexylmethyl) Adipates and mixtures thereof can be used. As the glycidyl alkyl methacrylate, 1,4-butanediol diglycidyl ether, bisglycidyl ether bisphenol-A, glycidyl methacrylate, triglycidyl isocyanurate and mixtures thereof may be used. have.

In one embodiment of the present invention, the epoxide compound introduced in the third step may be the same as the epoxide compound used in the second step.

In another embodiment of the present invention, the epoxide compound introduced in the third step may be different from the epoxide compound used in the second step.

In the third step, the epoxide compound is added in 2 parts by weight or less of the total monomer content, preferably 1 part by weight or less, more preferably 0.7 parts by weight or less.

In one embodiment of the present invention, the epoxide compound is added at 0.1 to 2 parts by weight of the total monomer content in the third step. In another embodiment, the epoxide compound is added at 0.3 to 1 part by weight of the total monomer content. If it is added in excess of 2 parts by weight, the impact modifier prepared may reduce the appearance of the matrix resin because the epoxide compound is crosslinkable.

The alkyl (meth) acrylate or the mixture of the epoxide compound and the alkyl (meth) acrylate may be added at a time, or continuously for 30 minutes to 180 minutes, preferably 70 minutes to 150 minutes.

In the third step of the present invention can be polymerized by adding a polymerization initiator with the alkyl (meth) acrylate. The polymerization initiator used in the third step is not particularly limited, and the same polymerization initiator used in the first and second steps may be used.

In the third step, the polymerization temperature is performed at about 50 to 80 ° C., preferably 60 to 75 ° C., and the polymerization is performed for about 30 to 120 minutes.

In the present invention The method may further include solidifying and drying the copolymer obtained in the third step. In addition, after the antioxidant is added to the copolymer obtained in the third step, if necessary, it can be solidified. The solidification and drying method can be easily carried out by those skilled in the art.

The final product passed through the solidification and drying steps is in the form of a white powder.

The present invention provides a thermoplastic resin composition using the impact reinforcing copolymer prepared above. The thermoplastic resin composition including the impact reinforcing copolymer of the present invention exhibits an excellent impact reinforcing effect.

The thermoplastic resin composition is prepared by blending a thermoplastic resin and the impact reinforcing copolymer prepared above in a conventional manner.

In one embodiment, the thermoplastic resin composition includes (A) 70 to 99 wt% of the thermoplastic resin and (B) 1 to 30 wt% of the impact reinforcing copolymer. When used in less than 1% by weight, the impact reinforcing effect may be insignificant. If it exceeds 30% by weight, the impact reinforcing effect may be lowered and the characteristics of the original thermoplastic resin may be lost.

The thermoplastic resin (A) which can be used as a matrix in the present invention can be applied to all thermoplastic resins including polybutyl terephthalate, polyethyl terephthalate, polycarbonate, vinyl chloride resin, polyamide and the like. These thermoplastic resins can be used individually or in mixture of 2 or more types.

The thermoplastic resin composition comprising the impact reinforcing copolymer of the present invention may further include general additives such as flame retardant aids, lubricants, mold release agents, nucleating agents, antistatic agents, stabilizers, reinforcing agents and the like, in addition to the above components. .

The invention can be better understood by the following examples, which are intended for the purpose of illustration of the invention and are not intended to limit the scope of protection defined by the appended claims.

Example

Example 1

First stage

75 parts by weight of a butadiene rubbery polymer latex mixture having a gel content of 80% and an average particle diameter of 0.3 μm (hereinafter, all parts by weight are based on solids), 150 parts by weight of deionized water, 0.3 parts by weight of potassium stearylate as an emulsifier, sodium naphthalene sulfonate and electrolyte 0.02 parts by weight of potassium hydroxide, 0.2 parts by weight of sodium chelated pyrophosphate, 0.01 parts by weight of ferrous sulfate initiator, and 0.3 parts by weight of reducing agent glucose were introduced into the reactor, and the temperature was raised to 70 ° C. 0.17 parts by weight of the polymerization initiator cumenehydroperoxide, 10.5 parts by weight of styrene and 0.19 parts by weight of arylmethacrylate were injected with stirring the reactor for 30 minutes, and polymerization was carried out at this temperature for 2 hours to reach a conversion rate of 96%.

2nd step

After the polymerization in the first step is completed, 0.05 parts by weight of cumene hydroperoxide and 2 parts by weight of glycidyl methacrylate are added for 30 minutes at 70 ° C. and maintained for 30 minutes.

3rd step

After the completion of the polymerization in the second step, a mixture of 0.2 parts by weight of cumene hydroperoxide, 12 parts by weight of methyl methacrylate and 0.5 parts by weight of glycidyl methacrylate at 70 ° C. was continuously added for 2 hours and aged for 1 hour. After the polymerization was completed, a polymer latex having a conversion rate of 99% was obtained.

To 100 parts by weight of the polymer latex of the third step, 0.5 parts by weight of methyl butylated methylphenol and 150 parts by weight of calcium chloride 2% aqueous solution were added to solidify at 65 ° C., washed and dried to obtain MBS white powder. .

Examples 2-6

As described in Table 1 was prepared in the same manner as in Example 1 except for changing the composition of each component.

Comparative Example 1

11.5 parts by weight of styrene was added in the first step, the second step was not performed, and the same procedure as in Example 1 was carried out except that 13.5 parts by weight of methyl methacrylate was used in the third step.

Comparative Example  2

The same procedure as in Example 1 was carried out except that butyl acrylate was added instead of the epoxide compound in the second and third steps.

TABLE 1

The physical properties of the MBS powders prepared as described above were evaluated in the following manner, and the measurement results are shown in Table 2.

1) Izod impact strength (kgfcm / cm)

5 parts by weight of the above-mentioned impact modifier, 3.0 parts by weight of dibutyl maleade and 1.0 parts by weight of butyl stearate were added to 100 parts by weight of polybutyl terephthalate to extrude and inject to prepare an 1/8 "IZOD impact specimen. The impact strength was measured by ASTM D256 method at -30 ° C, and repeated 5 times in a method of maintaining the same specimen for 1 hour at 20 ° C and 60 ° C respectively, and then the impact strength according to the change of the ambient temperature of the resin was measured. Measured.

2) Elongation (%): A specimen of 3.2 mm in width and 13 mm in length was prepared in the same manner as in the Izod measurement specimen preparation method and measured by Instron.

TABLE 2

From the results of Table 2, in the case of Examples 1 to 7 where the epoxide compound was added in the second step, compared with Comparative Examples 1 to 2 without adding the epoxide compound in the second step, an excellent impact strength improvement effect It can be seen that.

The present invention has the effect of providing an impact reinforcing copolymer exhibiting an excellent impact strength improving effect that can be used in amorphous or crystalline thermoplastic resins, a method for producing the same, and an impact resistant thermoplastic resin composition using the same.

Simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

Claims (13)

Graft polymerization of a diene rubber and an aromatic vinyl monomer to prepare a first graft polymer; A second step of preparing a second graft polymer by adding and polymerizing an epoxide compound to the first graft polymer; And A third step of adding and polymerizing an alkyl (meth) acrylate to the second graft polymer; Method for producing a impact reinforcing copolymer, characterized in that comprises a. The method of claim 1, wherein the first graft polymer is polymerized by adding an emulsifier, a polymerization initiator, and a graft agent to a diene rubber and an aromatic vinyl monomer. The method of claim 2, wherein the emulsifier is selected from the group consisting of potassium stearate, sodium dodecyl sulfate, sodium dodecylbenzene sulfate, potassium oleate sulfate, potassium oleate, rosin acid salts, fatty acid salts and mixtures thereof; The polymerization initiator is selected from the group consisting of benzoyl peroxide, cumene hydroperoxide, azobisisobutylonitrile and mixtures thereof; The graft agent of the impact reinforcing copolymer, characterized in that selected from the group consisting of divinylbenzene, trivinylbenzene, trialkyl isocyanurate, allyl methacrylate, ethylene glycol dimethacrylate and mixtures thereof Manufacturing method. The method of claim 1, wherein the diene rubber is selected from the group consisting of polybutadiene, polyisoprene, polychloroprene, butadiene-styrene copolymers, butadiene-acrylonitrile copolymers and mixtures thereof; The aromatic vinyl monomer is selected from the group consisting of styrene, α-ethylstyrene, α-methylstyrene and mixtures thereof; The alkyl (meth) acrylate is methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate and Method for producing an impact reinforcing copolymer, characterized in that selected from the group consisting of a mixture thereof. The method of claim 1, wherein the epoxide compound is prepared from the group consisting of alkene epoxide, cyclodiene epoxide, glycidyl alkyl methacrylate and mixtures thereof. Way. 6. The compound of claim 5, wherein the alkene epoxide is dipentene dioxide, 1,2,7,8-diepoxyoctane, dodecatrioxide, and mixtures thereof; Cyclodiene epoxides are bi-cycloheptadiene diepoxide, vinyl cyclodioxide, vinylcyclopentadiene dioxide, butenecyclopentene dioxide, bi-cyclopentadiene diepoxide, bis (c, 4 epoxycyclohexylmethyl) adiene Pates and mixtures thereof; Glycidylalkyl methacrylate is 1,4-butanediol diglycidyl ether, bisglycidyl ether bisphenol-A, glycidyl methacrylate, triglycidyl isocyanurate and mixtures thereof Method of producing an impact reinforcing copolymer. [Claim 2] The method of claim 1, wherein in the third step, an epoxide compound is added together with an alkyl (meth) acrylate to polymerize the impact reinforcing copolymer. According to claim 1, wherein the diene rubber is 60 to 80 parts by weight, the aromatic vinyl monomer is 5 to 25 parts by weight, the alkyl (meth) acrylate 5 to 20 parts by weight, the epoxide compound is 1 to 10 parts by weight in the second step, 0.1 to 2 parts by weight in the third step of the manufacturing method of the impact reinforcing copolymer. The method of claim 1, wherein the polymerization initiator is added with the epoxide compound in the second and third steps. The method of claim 1, further comprising the step of solidifying and drying the copolymer obtained in the third step. It is prepared by the method of any one of claims 1 to 10, An impact reinforcing copolymer comprising 60 to 80 parts by weight of a diene rubber, 5 to 25 parts by weight of an aromatic vinyl monomer, 5 to 20 parts by weight of an alkyl (meth) acrylate, and 1 to 12 parts by weight of an epoxide compound. (A) 70 to 99% by weight of the thermoplastic resin; And (B) 1 to 30% by weight of the impact reinforcing copolymer of claim 11; Thermoplastic resin composition comprising a. The thermoplastic resin composition according to claim 12, wherein the thermoplastic resin (A) is selected from the group consisting of polybutyl terephthalate, polyethylene terephthalate, polycarbonate, vinyl chloride resin, polyamide, and mixtures thereof. .