KR101005635B1 - Polycarbonate/acrylonitrile-butadiene-styrene blend resin and method of preparing the same - Google Patents

Abstract

The present invention relates to a polycarbonate / acrylonitrile-butadiene-styrene blend resin (PC / ABS) and a method for preparing the same, and more particularly to an acrylonitrile-applied to a polycarbonate / acrylonitrile-butadiene-styrene blend resin. In preparing the butadiene-styrene (ABS) resin, a polycarbonate / acrylonitrile- characterized in that a molecular weight modifier is added to the graft reactor in an uninfused or minimal amount, followed by a large amount into a phase inversion reactor and subsequent reactors. Butadiene-styrene blend resin (PC / ABS) and its preparation method.

The polycarbonate / acrylonitrile-butadiene-styrene blend resin (PC / ABS) prepared according to the present invention not only has excellent molding processability but also has excellent effects such as low temperature impact strength, heat aging resistance and gloss.

Polycarbonate / acrylonitrile-butadiene-styrene blend resin (PC / ABS), molecular weight modifier, continuous bulk polymerization, acrylonitrile-butadiene-styrene (ABS) resin

Description

POLYCARBONATE / ACRYLONITRILE-BUTADIENE-STYRENE BLEND RESIN AND METHOD OF PREPARING THE SAME} Polycarbonate / Acrylonitrile-Butadiene-Styrene Blend Resin (PS / AS)

The present invention relates to a polycarbonate / acrylonitrile-butadiene-styrene blend resin (PC / ABS) and a method for preparing the same, and more particularly to an acrylonitrile-applied to a polycarbonate / acrylonitrile-butadiene-styrene blend resin. The present invention relates to a polycarbonate / acrylonitrile-butadiene-styrene blend resin (PC / ABS) characterized by a method of introducing a molecular weight modifier in the production of butadiene-styrene (ABS) resins and a method for preparing the same.

A method of blending with acrylonitrile-butadiene-styrene (ABS) resin is widely used to improve molding processability of polycarbonate (PC) resins having excellent heat resistance and impact resistance but poor molding processability.

Due to the increase in size and thickness of the processed products to which the PC / ABS blend resin is applied, and the expansion of the range of use, it is possible to further improve the molding processability without deteriorating the main physical properties such as heat resistance and impact resistance, and at the same time, additional requirements such as low temperature impact strength and heat aging characteristics. The need for resins with improved physical properties also continues to increase.

In order to achieve the above object, a method of using an ABS resin produced by a continuous bulk polymerization method alone or in combination instead of the conventional emulsion polymerization type ABS resin has been proposed. That is, attempts to improve the physical properties of the PC / ABS blend resin by adjusting the molecular weight and composition of the matrix, the type and content of the rubber used, the rubber particle diameter, etc. in the manufacture of ABS resin has been somewhat incomplete.

First of all, in order to improve the molding processability of the PC / ABS blend resin, the molecular weight of the ABS resin matrix is preferably lower within a certain limit, so that a lot of molecular weight regulators are used. Increasing the rubber particle diameter, the gloss and the low-temperature impact strength decreases.

In addition, when styrene-butadiene-based rubber (SBR), which is advantageous for controlling the rubber particle size, is mainly used to solve the problem of glossiness, there is a problem that the low-temperature impact strength is reduced compared to the case where the butadiene-based rubber (BR) is mainly used.

In order to solve the problems of the prior art as described above, the present invention is to provide a polycarbonate / acrylonitrile-butadiene-styrene blend resin (PC / ABS) excellent in molding processability and low temperature impact strength, heat aging characteristics and gloss The purpose.

Another object of the present invention is to provide a method for producing a polycarbonate / acrylonitrile-butadiene-styrene blend resin (PC / ABS) having excellent molding processability, low temperature impact strength, heat aging resistance, and gloss.

The above and other objects of the present invention can be achieved by the present invention described below.

In order to achieve the above object,

In the process for producing acrylonitrile-butadiene-styrene resin applied to polycarbonate / acrylonitrile-butadiene-styrene blend resin (PC / ABS) by continuous bulk polymerization method,

a) preparing a mixed solution of styrene monomer and acrylonitrile monomer by adding 5 to 10% by weight of the total of styrene monomer and acrylonitrile monomer in the reaction solvent;

b) preparing a polymerization solution by dissolving butadiene rubber in a mixed solution of the styrene monomer and the acrylonitrile monomer;

c) polymerizing the prepared polymerization solution, initiator, and 0 to 0.01 parts by weight of a molecular weight regulator into a grafting reactor based on 100 parts by weight of a total of styrene-based monomers and acrylonitrile-based monomers;

d) adding 90 to 95% by weight of the styrene-based monomer and the acrylonitrile-based monomer and a molecular weight regulator into the phase inversion reactor including the reactant of step c) to proceed with the polymerization;

e) preparing a acrylonitrile-butadiene-styrene resin by adding a molecular weight modifier to a subsequent reactor including the reactant of step d) and further polymerizing to a temperature of 130 to 160 ° C; And

f) mixing 20 to 50% by weight of the acrylonitrile-butadiene-styrene resin prepared above with 50 to 80% by weight of polycarbonate to prepare a polycarbonate / acrylonitrile-butadiene-styrene blend resin.

The total content of the molecular weight regulators added in step d) and e) is 0.01 to 1 part by weight based on 100 parts by weight of the total of styrene monomer and acrylonitrile monomer.

Provided are methods for preparing polycarbonate / acrylonitrile-butadiene-styrene blend resins (PC / ABS).

Also provided is a polycarbonate / acrylonitrile-butadiene-styrene blend resin (PC / ABS) prepared according to the above.

The polycarbonate / acrylonitrile-butadiene-styrene blend resin (PC / ABS) manufactured according to the present invention has excellent molding processability, low temperature impact strength, heat aging characteristics, and gloss, without deteriorating basic physical properties.

Hereinafter, the present invention will be described in detail.

The present invention relates to a process for producing acrylonitrile-butadiene-styrene (ABS) resin by continuous bulk polymerization method applied to polycarbonate / acrylonitrile-butadiene-styrene blend resin (PC / ABS). By introducing a graft reactor that can be dissolved in a portion of the monomer and control the graft reaction, the graft reactor is introduced into the graft reactor without the addition of a molecular weight regulator or only a minimum amount to ensure a sufficient graft rate, and then a large amount from the phase inversion reactor ABS resin is prepared by lowering the molecular weight by adding a molecular weight regulator.

When the ABS resin thus prepared is applied to the PC / ABS blend resin, it is possible to obtain a resin having excellent molding processability and excellent low temperature impact strength, gloss, and heat aging characteristics.

Specifically, the ABS resin applied to the PC / ABS blend resin of the present invention is prepared by the following method.

First, a mixed solution of a styrene monomer and an acrylonitrile monomer is prepared by adding 5 to 10% by weight of the total of the styrene monomer and the acrylonitrile monomer in the reaction solvent. Thereafter, butadiene-based rubber is dissolved in the mixed solution to prepare a polymerization solution, and the polymerization solution and the initiator are polymerized while being introduced into the graft reactor. The polymerized polymer in the graft reactor is then further polymerized in a phase inversion reactor. At this time, 90 to 95% by weight of the total of the styrene-based monomer and acrylonitrile-based monomer and the molecular weight regulator are added to the polymerization proceeds together. The polymerized polymer in the phase inversion reactor is added to the molecular weight regulator in the subsequent reactor and further polymerized to a temperature of 130 to 160 ℃ to produce an acrylonitrile-butadiene-styrene resin. At this time, the molecular weight regulator is added to the phase inversion reactor and subsequent reactors in an amount of 0.01 to 1 parts by weight based on 100 parts by weight of the total of the styrene monomer and acrylonitrile monomer. Thereafter, the preparation of the polycarbonate / acrylonitrile-butadiene-styrene blend (PC / ABS) resin of the present invention is completed by mixing 20 to 50 wt% of the prepared ABS resin and 50 to 80 wt% of the polycarbonate.

The polymerization process in the present invention is based on bulk polymerization.

The reaction solvent used in the production of the present invention may be one or more selected from the group consisting of toluene, ethylbenzene and xylene, preferably ethylbenzene.

The content of the reaction solvent is preferably 10 to 45 parts by weight based on 100 parts by weight of the total of styrene monomer and acrylonitrile monomer. If it is less than 10 parts by weight, it is difficult to control the high viscosity, and if it exceeds 45 parts by weight, the shape of the rubber particles produced during the polymerization process may not be effectively controlled.

The styrenic monomers used in the preparation of the present invention are selected from the group consisting of styrene, a-methylstyrene, p-bromostyrene, p-methylstyrene, p-chlorostyrene and o-bromostyrene. Can be used.

In addition, the acrylonitrile-based monomer may be used at least one selected from the group consisting of acrylonitrile, methacrylonitrile and ethacrylonitrile.

The amount of the styrene-based monomer and acrylonitrile-based monomer introduced into the initial graft reactor is preferably 5 to 10% by weight of the total amount of the total styrene-based monomer and acrylonitrile-based monomer, and then the amount to be added to the phase inversion reactor It is preferable that it is 90 to 95 weight%. When the amount of the monomer mixture added to the graft reactor is less than 5% by weight, the rubber and graft reactions do not occur smoothly, and when the amount of the monomer mixture exceeds 10% by weight, the effective graft reaction cannot be controlled and the mechanical properties and gloss of the final resin deteriorate. Occurs.

The butadiene-based rubber used in the preparation of the present invention may be used butadiene, styrene-butadiene rubber or a mixture thereof.

The initiator used in the preparation of the present invention is t-butylperoxy-2-ethylhexanoate, 1,1-bis (t-butylperoxy) -3,3,5-trimethyl cyclohexane, 1,1- Bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) -2-methyl cyclohexane and 2,2-bis (4,4-di-t-butylperoxy cyclohexyl) One or more organic peroxides selected from the group consisting of propane can be used.

The amount of the initiator is preferably 0.002 to 0.05 parts by weight based on 100 parts by weight of the total of styrene monomer and acrylonitrile monomer. If it is less than 0.002 parts by weight, the polymerization of the graft reactor is impossible to proceed, so that the balance of physical properties of the entire resin does not come out. If it exceeds 0.05 parts by weight, excessive viscosity rise may be disadvantageous and dangerous in the process, and the resin properties may be degraded. The molecular weight modifier used in the preparation of the present invention may be a thiol-based compound which is t-dodecyl mercaptan or n-octyl mercaptan.

The molecular weight modifier is preferably added to the phase inversion reactor 0.01 to 0.1 parts by weight based on 100 parts by weight of the total of the styrene monomer and acrylonitrile monomer. If it is less than 0.01 parts by weight, it is difficult to control the molecular weight even if a large amount of molecular weight regulator is added to the reactor, and if it exceeds 0.1 parts by weight, a decrease in gloss and low temperature impact strength occurs due to an increase in rubber particle size. In addition, in the reactor after the phase inversion reactor, it is preferable that 0.1 to 1.0 parts by weight of the molecular weight regulator is added to 100 parts by weight of the total of the styrene monomer and the acrylonitrile monomer.

On the other hand, even if the molecular weight modifier is not added to the graft reactor at all or is preferably added only a very small amount. If more than 0.01% by weight, the graft ratio is reduced and there is a problem that the gloss and low-temperature impact strength decreases due to the increase in the rubber particle diameter

The ABS resin prepared according to the present invention preferably has a graft ratio of 95% or more.

Moreover, it is preferable that average rubber particle diameter is 0.5-1 micrometer.

By adjusting the molecular weight modifier according to the content and the timing of the input as described above, it is possible to manufacture an ABS resin with a lower molecular weight while ensuring a sufficient graft rate, PC resin by applying such ABS resin to PC / ABS blend resin It is possible to obtain a resin having excellent molding processability while maintaining basic physical properties, and excellent in all low temperature impact strength, gloss and heat aging characteristics.

Hereinafter, preferred examples are provided to help understanding of the present invention, but the following examples are merely to illustrate the present invention, and the scope of the present invention is not limited to the following examples.

[Example]

Example  One

After dissolving 20.5% by weight of rubber (BR / SBR = 50/50) in a mixed solution of 73.7% by weight of ethylbenzene and 4.7% by weight of styrene and 1.2% by weight of acrylonitrile, t-butylperoxy-2-ethylhexa was used as an initiator. The polymerization solution was prepared by adding 0.02% by weight of noate. The polymerization solution was polymerized at 5.7 L / hr in a 26 L graft reactor at a temperature of 95 DEG C. In a second phase inversion reactor, 80 wt% of styrene, 20 wt% of acrylonitrile and 0.1 wt% of t-dodecylmercaptan The mixed solution was polymerized at 110 ° C. with 6.3 L / hr, and 10% t-dodecyl mercaptan ethylbenzene solution was charged with 0.24 L / hr in the third reactor, and the third and fourth reactors were 135/150 ° C. respectively. When the polymerization conversion was 80%, the unreacted monomer and the reaction solvent were removed at a temperature of 230 ° C. in a volatilizer to prepare an ABS resin in pellet form. 70 wt% of polycarbonate resin and 30 wt% of the ABS resin prepared above were blended using an extruder having a temperature of 260 ° C., followed by injection to measure physical properties of the PC / ABS blend resin, and the results are shown in Table 1 below.

Example  2

Dissolve 19.5% by weight of rubber (BR / SBR = 50/50) in a mixed solution of 69.9% by weight of ethylbenzene and 8.4% by weight of styrene and 2.2% by weight of acrylonitrile, and then use t-butylperoxy-2-ethylhexa as an initiator. The polymerization solution was prepared by adding 0.02% by weight of noate. The polymerization solution was introduced into a 26 L graft reactor at 6.0 L / hr, and 6.0 L / hr of a mixed solution of 80 wt% styrene, 20 wt% acrylonitrile and 0.1 wt% t-dodecylmercaptan in a second phase inversion reactor. Except that the ABS resin was prepared in the same manner as in Example 1, but also measured the physical properties of the PC / ABS blend resin prepared in the same manner, and the results are shown in Table 1.

Comparative example  One

After dissolving 9.75% by weight of rubber (BR / SBR = 50/50) in a mixed solution of 35% by weight of ethylbenzene, 44.2% by weight of styrene and 11.05% by weight of acrylonitrile, t-butylperoxy-2-ethylhexa as an initiator A polymerization solution was prepared by adding 0.02% by weight of noate and 0.05% by weight of t-dodecylmercaptan. The polymerization solution was introduced into a 26 L phase inversion reactor at 12 L / hr and polymerized at a temperature of 110 ° C., and 10% t-dodecylmercaptan ethylbenzene solution was charged at 0.24 L / hr in a second reactor, and the second and third reactors were used. The temperature was polymerized at 135/150 ° C., respectively, to prepare ABS resin in pellet form in the same manner as in Example 1. The physical properties of the PC / ABS blend resin prepared also in the same manner was measured, and the results are shown in Table 1.

Comparative example  2

When preparing the polymerization solution in Comparative Example 1, the same as in Comparative Example 1 except that t- dodecylmer captan is not added and 2% t-dodecylmercaptan ethylbenzene solution is added at 0.24 L / hr to the second reactor. ABS resin was prepared by the method. The physical properties of the PC / ABS blend resin also prepared in the same manner was measured, and the results are shown in Table 1.

Comparative example  3

After dissolving 20.5% by weight of rubber (BR / SBR = 50/50) in a mixed solution of 73.7% by weight of ethylbenzene and 4.7% by weight of styrene and 1.2% by weight of acrylonitrile, t-butylperoxy-2-ethylhexa was used as an initiator. A polymerization solution was prepared by adding 0.02% by weight of noate and 0.05% by weight of t-dodecylmercaptan. The polymerization solution was introduced into a 26 L graft reactor at 5.7 l / hr, followed by polymerization at a temperature of 95 ° C., and a mixed solution of 80 wt% of styrene and 20 wt% of acrylonitrile was added at 6.3 l / hr in a second phase inversion reactor. And polymerization at 110 ° C., 10% t-dodecylmercaptan ethylbenzene solution was charged at 0.24 L / hr in a third reactor, and the third and fourth reactors were polymerized at 135/150 ° C., respectively. ABS resin in pellet form was prepared by the method. The physical properties of the PC / ABS blend resin also prepared in the same manner was measured, and the results are shown in Table 1.

[Test Example]

* Graft rate: A certain amount (X) of ABS resin is introduced into acetone and vibrated for 24 hours with a vibrator to dissolve the free resin. The solution is centrifuged at 14,000 rpm for 1 hour using a centrifuge to obtain insolubles. The insoluble content thus obtained is dried at 140 ° C. for 2 hours using a vacuum dryer to obtain an insoluble content (Y). The graft ratio was calculated by the following formula.

Graft Rate (%) = [(Y-XR) / XR] * 100 (R: Rubber fraction in certain amount (X) of ABS resin)

* Average rubber particle size: 0.5 g of the prepared ABS resin was dissolved in 100 ml of methylethylkenone, and the average particle diameter of the rubber particles was measured using a Coulter counter (LS230, Beckman Coulter, Inc.).

* Fluidity (A): It measured on 220 degreeC x 10 kg conditions based on ASTMD12138 method.

* Fluidity (B): It measured on 250 degreeC x 2.16 kg conditions based on ASTMD12138 method.

Impact strength: measured according to ASTM D256 method.

* Tensile strength and elongation: It was measured according to ASTM D638 method.

* Glossiness: An injection test piece having a thickness of 3 mm was produced and measured according to ASTM 1003.

TABLE 1

Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 ABS resin
Properties Graft Rate (%) 98 105 76 85 73 Average rubber particle size (㎛) 0.92 0.85 1.47 1.04 1.30 Fluidity (A)
(g / 10 min) 43.4 45.6 47.7 13.9 44.5 PC / ABS blend resin properties Liquidity (B)
(g / 10 min) 5.0 5.3 5.2 4.3 4.9 Izod impact strength (23 ℃, kgm / cm 59 57 46 50 41 Izod impact strength (-40 ℃, kgm / cm 27 24 15 20 13 Tensile Strength (kg / cm ² ) 575 585 515 530 520 % Elongation 190 170 180 100 150 Glossiness (45 °%) 100 102 73 90 69 PC / ABS Blend Resin Heat Aging Measurement (120 ℃, / 300hrs) Tensile strength reduction rate (%) 15 10 30 25 35 % Elongation 60 55 35 25 35 Izod impact strength (23 ℃, kgm / cm 45 42 27 32 24

Through Table 1, Examples 1 and 2 in which the molecular weight modifier was added to the graft reactor in a large amount into the phase inversion reactor and subsequent reactors according to the present invention, Comparative Example 3, the monomer was added in a large amount to the graft reactor The physical properties of ABS resin and PC / ABS blend resin were compared with those of Comparative Example 1 in which the molecular weight regulator was added from the first polymerization and Comparative Example 2 in which only a small amount was added under an environment in which it was not divided and not passed through the graft reactor. It can be confirmed that excellent. In particular, it can be seen that the heat-aging characteristics of the PC / ABS blend resin are greatly improved.

Although described in detail above with reference to the specific embodiments of the present invention, it will be apparent to those skilled in the art that various changes and modifications can be made within the scope and spirit of the present invention, and such modifications and modifications belong to the appended claims. It is also natural.

Claims (10)

In the method for producing a polycarbonate / acrylonitrile-butadiene-styrene blend resin (PC / ABS) by a continuous bulk polymerization method, a) preparing a mixed solution of styrene monomer and acrylonitrile monomer by adding 5 to 10% by weight of the total of styrene monomer and acrylonitrile monomer in the reaction solvent; b) preparing a polymerization solution by dissolving butadiene rubber in a mixed solution of the styrene monomer and the acrylonitrile monomer; c) polymerizing the prepared polymerization solution, and the initiator while introducing into the grafting reactor; d) to 90 to 95% by weight of the total amount of the styrene-based monomer and acrylonitrile-based monomer and the molecular weight regulator in the phase inversion reactor including the reactant of step c), wherein the styrene-based monomer and acrylonitrile Adding 0.01 to 0.1 parts by weight based on 100 parts by weight of the total monomers and proceeding with polymerization; e) Injecting a molecular weight regulator into the reactor after the reaction comprising the step of d), wherein the molecular weight regulator is added to 0.1 to 1.0 parts by weight based on 100 parts by weight of the total of the styrene monomer and acrylonitrile monomer and 130 to 130 Further polymerizing to a temperature of 160 ° C. to produce an acrylonitrile-butadiene-styrene resin having an average rubber particle size of 0.5 to 1 μm; And f) preparing a polycarbonate / acrylonitrile-butadiene-styrene blend resin by mixing 20 to 50% by weight of the acrylonitrile-butadiene-styrene resin prepared above with 50 to 80% by weight of polycarbonate. By Process for preparing polycarbonate / acrylonitrile-butadiene-styrene blend resin (PC / ABS). The method of claim 1, The reaction solvent is at least one selected from the group consisting of toluene, ethylbenzene and xylene Process for preparing polycarbonate / acrylonitrile-butadiene-styrene blend resin (PC / ABS). The method of claim 1, The styrene monomer is selected from the group consisting of styrene, a-methyl styrene, p-bromostyrene, p-methyl styrene, p-chlorostyrene and o-bromostyrene Process for preparing polycarbonate / acrylonitrile-butadiene-styrene blend resin (PC / ABS). The method of claim 1, The acrylonitrile-based monomer is characterized in that at least one selected from the group consisting of acrylonitrile, methacrylonitrile and ethacrylonitrile Process for preparing polycarbonate / acrylonitrile-butadiene-styrene blend resin (PC / ABS). The method of claim 1, The butadiene-based rubber is characterized in that the butadiene, styrene-butadiene rubber or a mixture thereof Process for preparing polycarbonate / acrylonitrile-butadiene-styrene blend resin (PC / ABS). The method of claim 1, The initiator is t-butylperoxy-2-ethylhexanoate, 1,1-bis (t-butylperoxy) -3,3,5-trimethyl cyclohexane, 1,1-bis (t-butylperoxy 1) cyclohexane, 1,1-bis (t-butylperoxy) -2-methyl cyclohexane and 2,2-bis (4,4-di-t-butylperoxy cyclohexyl) propane Characterized in that the organic peroxide selected above Process for preparing polycarbonate / acrylonitrile-butadiene-styrene blend resin (PC / ABS). The method of claim 1, The molecular weight modifier is a thiol-based compound which is t-dodecyl mercaptan or n-octyl mercaptan Process for preparing polycarbonate / acrylonitrile-butadiene-styrene blend resin (PC / ABS). The method of claim 1, The prepared acrylonitrile-butadiene-styrene (ABS) resin is characterized in that the graft rate is 95% or more Process for preparing polycarbonate / acrylonitrile-butadiene-styrene blend resin (PC / ABS). delete Polycarbonate / acrylonitrile-butadiene-styrene blend resin (PC / ABS) prepared according to claim 1.