KR20190060499A - Preparation method of matt thermoplastic resin and matt thermoplastic resin prepared thereby - Google Patents

Abstract

The present invention relates to: a method for manufacturing a matt thermoplastic resin using conjugated diene-based rubber having a viscosity of 150 to 300 cp and controlling an injection timing of a molecular weight regulator, and thus it is possible to manufacture the matt thermoplastic resin having excellent low glossiness and extrusion processability, and containing rubber particles of a large particle diameter; and the matt thermoplastic resin manufactured from the same.

Description

TECHNICAL FIELD [0001] The present invention relates to a method for producing a matte thermoplastic resin and a matte thermoplastic resin prepared therefrom. BACKGROUND ART < RTI ID = 0.0 >

The present invention relates to a process for producing a non-heat-resistant thermoplastic resin which is excellent in low-glossiness and extrusion-processability and which comprises rubber particles having a large particle size, and a non-heat-resistant thermoplastic resin produced therefrom.

In recent years, development of thermoplastic resins having excellent physical properties including heat resistance, impact resistance, and the like have been demanded due to the necessity of light weight of automobiles and the increase in use of complicated large parts of electric devices and electronic devices. In particular, the use of information technology equipment components, such as automotive interiors and computers and other electronic equipment cases, tends to have a non-glossy or low-gloss characteristic for aesthetic reasons as well as to eliminate expensive coating and painting steps. In addition, we are interested in eco-friendly materials. Accordingly, there is a growing need for material development to meet the above requirements.

BACKGROUND ART Conventionally, a propylene resin has been widely used as a material for an automobile interior material. Propylene resins are known to exhibit less shine than some thermoplastic resins. However, the propylene resin is lacking in properties such as stiffness and scratch resistance, and a method of improving the properties by adding a filler and other additives to compensate for the insufficient properties has been proposed. However, It is insufficient to be used so that there is a limitation in use.

In addition, a high impact polystyrene resin produced by mixing polybutadiene and polystyrene has been developed by adding a quencher to a resin having low gloss characteristics. However, like the propylene resin, the low gloss, heat resistance, There is a problem that characteristics such as impact resistance are not balanced.

On the other hand, acrylonitrile-butadiene-styrene (ABS) resin, methylmethacrylate-butadiene-styrene (MBS) resin, acrylate-butadiene- Styrene-acrylonitrile (ASA) resin and acrylic impact modifier (AIM) resin are widely used as modifiers for various plastics because of their excellent properties such as impact resistance, rigidity and fluidity.

Especially, ABS resin has excellent dimensional stability, processability and chemical resistance, and is widely used as a material for monitor housings, game machine housings, home appliances, office equipment, automobile lamp housings and the like. Recently, many researches have been made to use ABS resin having excellent impact resistance, chemical resistance and workability by imparting heat resistance and low gloss to automotive interior materials.

For example, there has been proposed a method in which an ABS resin is modified and used as large-diameter rubber particles of 1 占 퐉 or larger. However, the resin produced by this method has a problem of insufficient low-gloss effect and poor impact strength and heat resistance. As another method, there has been proposed a method of adding a matting filler having a particle size of 5 mu m or more to an ABS resin. However, the produced resin shows excellent moldability, but has insufficient low-glossiness, There is a problem that arises. Further, a low-gloss filler is added in order to exhibit low-gloss characteristics, which must also be added in a large amount in order to exhibit a low-gloss characteristic, thereby lowering impact strength and increasing production costs.

Therefore, it is necessary to develop a resin containing rubber particles having a large particle diameter as well as being excellent in extrusion processability while having low glossiness.

US 4,808,661 A

SUMMARY OF THE INVENTION The present invention has been made in order to solve the problems of the prior art described above, and it is an object of the present invention to provide a method for producing a non-light thermoplastic resin which is excellent in low glossiness and extrusion processability and contains rubber particles of a large particle size.

Another object of the present invention is to provide a matt thermoplastic resin produced by the above production method.

In order to solve the above problems, the present invention provides a process for preparing a polymer solution, comprising the steps of: 1) introducing a conjugated diene rubber having a viscosity of 150 cp to 300 cp into a mixed solution containing a reaction solvent, an aromatic vinyl compound and a vinyl cyanide compound, Producing; 2) a first polymerization step of polymerizing the polymerization solution while continuously introducing the polymerization solution into the first reactor; 3) a second polymerization step in which the polymerization product obtained in the first polymerization step is introduced into the second reactor and polymerized by feeding a molecular weight modifier of 150 ppm to 700 ppm based on the weight of the polymerized product to the front end of the second reactor; And 4) devolatilizing the obtained polymerization product. The present invention also provides a method for producing a non-light thermoplastic resin.

In addition, the present invention is characterized in that the weight average particle size of the rubber particles produced by the above-mentioned production method is 17 탆 to 25 탆, and the spiral flow measured according to ASTM D3123 (150 3 캜) cm and a weight average molecular weight (Mw) of 180,000 g / mol to 280,000 g / mol.

The method for producing a non-light thermoplastic resin according to an embodiment of the present invention can produce a non-light thermoplastic resin having excellent low glossiness and extrusion processability and containing rubber particles having a large particle size by controlling the injection timing of the molecular weight modifier.

BRIEF DESCRIPTION OF THE DRAWINGS The accompanying drawings, which are incorporated in and constitute a part of the specification, illustrate exemplary embodiments of the invention and, together with the description of the invention, It should not be construed as limited.
FIG. 1 illustrates an exemplary process system capable of carrying out the process for producing a matt thermoplastic resin according to an embodiment of the present invention.

Hereinafter, the present invention will be described in detail in order to facilitate understanding of the present invention.

The terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms and the inventor may appropriately define the concept of the term in order to best describe its invention It should be construed as meaning and concept consistent with the technical idea of the present invention.

The method for producing a matte thermoplastic resin of the present invention comprises the steps of (1) adding a conjugated diene rubber having a viscosity of 150 cp to 300 cp to a mixed solution containing a reaction solvent, an aromatic vinyl compound and a vinyl cyan compound to prepare a polymerization solution step; 2) a first polymerization step of polymerizing the polymerization solution while continuously introducing the polymerization solution into the first reactor; 3) a second polymerization step in which the polymerization product obtained in the first polymerization step is introduced into the second reactor and polymerized by feeding a molecular weight modifier of 150 ppm to 700 ppm based on the weight of the polymerized product to the front end of the second reactor; And 4) devolatilizing the obtained polymerization product.

1) adding a conjugated diene rubber having a viscosity of 150 cp to 300 cp to a mixed solution containing a reaction solvent, an aromatic vinyl compound and a vinyl cyan compound to prepare a polymerization solution

The step 1 is a step for preparing a polymerization solution for polymerization, and a conjugated diene rubber having a viscosity of 150 cp to 300 cp is added to a mixed solution containing a reaction solvent, an aromatic vinyl compound and a vinyl cyanide compound, Dispersing, and dissolving them.

The polymerization solution contains 10 to 30% by weight of a reaction solvent; From 35% to 65% by weight of an aromatic vinyl compound; 15% by weight to 40% by weight of a vinyl cyanide compound; And 5 wt% to 15 wt% of a conjugated diene rubber, specifically, 22 wt% to 28 wt% of a reaction solvent; From 45% to 50% by weight of an aromatic vinyl compound; 18% by weight to 35% by weight of a vinyl cyan compound; And 5% to 10% by weight of conjugated diene rubber.

When the polymerization solution contains the reaction solvent, the aromatic vinyl compound, the vinyl cyanide compound and the conjugated diene rubber within the above-mentioned range, it is possible to produce a matt thermoplastic resin having excellent low glossiness and extrusion processability and containing rubber particles having a large particle diameter can do.

When the reaction solvent is contained in an amount less than the above range, the viscosity of the polymerization solution may be too high to control, and when the reaction solvent is contained in excess of the above range, it is difficult to effectively control the shape of the rubber particles produced during the polymerization reaction .

If the content of the aromatic vinyl compound is less than the above range, the viscosity may increase and the process stability may be deteriorated. If the aromatic vinyl compound is contained in the range exceeding the above range, the mechanical strength and chemical resistance of the final resin are deteriorated .

If the amount of the vinyl cyanide compound is less than the above range, the mechanical strength and chemical resistance of the final resin may be deteriorated. If the vinyl cyanide compound is contained in the range exceeding the above range, Can be degraded.

When the conjugated diene rubber is contained in an amount outside the above range, the viscosity of the conjugated diene rubber may deviate from the viscosity range of 150 cp to 300 cp as described above. Thus, the rubber particles in the thermo- The adjustment of the average particle diameter may be difficult, and as a result, properties such as low-gloss characteristics and other impact resistance may be deteriorated.

The reaction solvent may be at least one member selected from the group consisting of ethylbenzene, toluene, xylene, methyl ethyl ketone, and methyl isobutyl ketone, and specifically may be ethylbenzene.

The aromatic vinyl compound may be at least one member selected from the group consisting of styrene,? -Methylstyrene, p-bromostyrene, p-methylstyrene, p-chlorostyrene and o-bromostyrene, .

The vinyl cyan compound may be at least one kind selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, phenyl acrylonitrile and? -Chloroacrylonitrile, and specifically, May be acrylonitrile.

The conjugated diene rubber may be a conjugated diene compound homopolymer or a copolymer of a conjugated diene compound and an ethylenically unsaturated compound, and the conjugated diene compound may be 1,3-butadiene, 2-ethyl-1,3- Butadiene, isoprene, chloroprene, and 1,3-pentadiene. Also, the ethylenically unsaturated compound may include an ethylenically unsaturated nitrile compound, an ethylenic unsaturated acid compound, or a mixture thereof, and examples thereof include acrylonitrile, methacrylonitrile,? -Chloronitrile, styrene, alkylstyrene, vinylnaphthalene , Chloroethyl vinyl ether, (meth) acrylamide, dibutyl maleate, dibutyl fumarate, diethyl maleate, and the like.

More specifically, the conjugated diene rubber may be at least one selected from the group consisting of a butadiene homopolymer, an isoprene homopolymer, a butadiene-styrene copolymer, a butadiene-acrylonitrile copolymer, and an isobutylene-isoprene copolymer . More specifically, the conjugated diene rubber may be a butadiene homopolymer.

The conjugated diene rubber may have a viscosity of 150 cp to 300 cp, and the conjugated diene rubber may have a viscosity of 170 cp to 250 cp. When the viscosity of the conjugated diene rubber is out of the above viscosity range, it may be difficult to control the average particle diameter of the rubber particles in the final produced matt thermoplastic resin, and as a result, properties such as low glossiness and other impact resistance may be deteriorated have. The viscosity of the conjugated diene rubber is a value obtained by dissolving the conjugated diene rubber at a concentration of 5% in styrene and measuring the number of revolutions at 10 rpm using a # 3 spindle using a Brookfield DV type viscometer.

In one example of the present invention, the above step 1) is not particularly limited, but a reaction solvent, an aromatic vinyl compound and a vinyl cyanide compound are added to a rubber dissolving tank having a temperature condition of 50 DEG C or less, specifically 40 DEG C to 50 DEG C To prepare a mixed solution, adding the conjugated diene rubber to the mixed solution, and dispersing and dissolving the mixture.

The polymerization solution may contain 0.01 to 0.04 part by weight of a polymerization initiator based on 100 parts by weight of the polymerization solution, and the polymerization initiator may be added together when the conjugated diene rubber is added.

The polymerization initiator may be at least one selected from the group consisting of t-butylperoxy-2-ethylhexanoate, azobisisobutyronitrile, benzoyl peroxide, cumyl peroxide and t-butyl peroxide, 1,1- Cyclohexane, and the like.

2) a first polymerization step of polymerizing the polymerization solution while continuously introducing the polymerization solution into the first reactor

In the step 2), a first polymerization step is carried out in which a polymerization reaction is carried out using a polymerization solution, and the first polymerization step may be carried out by continuous bulk polymerization.

The first polymerization step may be carried out by continuous bulk polymerization at a temperature range of, for example, 100 DEG C to 120 DEG C for 1.5 to 2.5 hours. The time in the first polymerization step may be controlled according to the flow rate of the polymerization solution introduced into the first reactor and may be the time of residence of the polymerization solution in the first polymerization reactor in which the first polymerization step is performed.

3) a second polymerization step in which the polymerization product obtained in the first polymerization step is introduced into a second reactor and a polymerization initiator is added to the front end of the second reactor in an amount of 150 ppm to 700 ppm based on the weight of the polymer,

In the step 3), the polymerization product obtained in the first polymerization step is introduced into the second reactor, and a molecular weight regulator of 150 ppm to 700 ppm based on the weight of the polymer is fed to the front end of the second reactor, The polymerization product obtained in the polymerization step can be swelled to produce rubber particles of a large diameter, and a more excellent non-heat-resistant thermoplastic resin can exhibit more excellent matte properties.

When the content of the vinyl cyanide compound in the polymerization solution is high, the weight average molecular weight (Mw) of the non-heat-resistant thermoplastic resin to be polymerized may increase rapidly. By feeding the molecular weight modifier to the front end of the second reactor, It is possible to prepare a non-heat-resistant thermoplastic resin which can control the weight average molecular weight (Mw) of the resin and is excellent in workability which can be judged by the extrudability and the spiral flow value.

The molecular weight regulator is added only in the second polymerization step of step 3), and the first polymerization step of 2) may be performed without the molecular weight regulator being added. The first polymerization step is carried out in a state in which the molecular weight regulator is not added and then the polymerization is carried out by introducing the molecular weight regulator at the front end of the second polymerization step so that rubber particles of larger diameter can be produced, The matte property can be further excellent.

The molecular weight regulator may be added in an amount of 150 ppm to 700 ppm based on the total weight of the polymerization solution, specifically, 200 ppm to 500 ppm. When the amount of the molecular weight modifier is in the above range, the final matt thermoplastic resin to be prepared may be adjusted to have an appropriate weight average molecular weight (Mw). If the amount of the molecular weight control agent is too small, the weight average molecular weight (Mw) of the final matt thermoplastic resin to be produced may be excessively increased and the extrusion processability may be deteriorated. If the amount of the molecular weight adjusting agent is excessive, The weight average molecular weight (Mw) of the thermoplastic resin becomes excessively small, and mechanical properties such as melt strength may be deteriorated.

The molecular weight regulator may be selected from the group consisting of n-dodecyl mercaptan, n-amyl mercaptan, t-butyl mercaptan, t-dodecyl mercaptan, n-hexyl mercaptan, n-octyl mercaptan and n-nonyl mercaptan , And specifically may be t-dodecylmercaptan.

The second polymerization step may be performed at a higher polymerization temperature than the first polymerization step. In an embodiment of the present invention, the second polymerization step may be performed by continuous bulk polymerization at a temperature ranging from 125 캜 to 140 캜. have.

The molecular weight regulator may be added in an amount of 150 ppm to 700 ppm with respect to the flow rate of the polymerization solution introduced into the reactor, specifically, 200 ppm to 500 ppm. Wherein the ppm is by weight.

The molecular weight modifier may be added to the reactor in the form of a solution of a molecular weight modifier dissolved in a solvent, and the solvent may be any of those mentioned above as the reaction solvent. When the molecular weight modifier is added in the form of a molecular weight modifier solution, the flow rate of the molecular weight modifier solution may be 0.045 kg / hr to 0.3 kg / hr, specifically 0.06 kg / hr to 0.21 kg / hr, more specifically 0.15 kg / hr.

In the production method according to an example of the present invention, the first polymerization step and the second polymerization step may be performed by continuous bulk polymerization in this manner.

In the production process according to an example of the present invention, the polymerization step may be additionally carried out in addition to the first polymerization step and the second polymerization step, and the entire polymerization reaction may be carried out by continuous bulk polymerization comprising a total of 2 to 10 polymerization steps . Specifically, the manufacturing method according to an exemplary embodiment of the present invention may further include a third polymerization step and a fourth polymerization step in addition to the first polymerization step and the second polymerization step, and the first to fourth polymerization steps Can be carried out by continuous bulk polymerization.

For example, the production method according to one example of the present invention may further comprise: 3-1) a third polymerization step of charging the polymerization product obtained in the second polymerization step into a third reactor and polymerizing, The step, the second polymerization step and the third polymerization step may be carried out by continuous bulk polymerization. Specifically, the third polymerization step may be performed by continuous bulk polymerization at a temperature ranging from 140 ° C to 150 ° C.

In addition, the production method according to an example of the present invention may include, for example, 3-2) a fourth polymerization step of charging the polymerization product obtained in the third polymerization step into a fourth reactor and polymerizing, The first polymerization step, the second polymerization step, the third polymerization step and the fourth polymerization step may be carried out by continuous bulk polymerization. Specifically, the fourth polymerization step may be performed by continuous bulk polymerization at a temperature ranging from 150 ° C to 160 ° C.

In the production method according to an example of the present invention, the polymerization reaction may be performed while sequentially passing through the first polymerization step, the second polymerization step, the third polymerization step and the fourth polymerization step, and in the first polymerization step, The polymerization temperature can be increased as the polymerization proceeds. That is, the polymerization temperature in the second polymerization step may be relatively higher than the polymerization temperature in the first polymerization step, and the polymerization temperature in the third polymerization step may be relatively higher than the polymerization temperature in the second polymerization step, The polymerization temperature in the fourth polymerization step may be relatively higher than in the third polymerization step.

4) Step of devolatilizing the obtained polymerization product

In the step 4), the unreacted monomers and the reaction solvent may be removed from the polymerization product obtained through the above steps, and the polymerization product may be devolatilized to obtain the desired matt thermoplastic resin.

The devolatilization may be performed at a temperature of 230 ° C to 250 ° C and a pressure of 30 Torr or less. Specifically, it can be carried out under a pressure of 10 torr to 30 torr. The production method according to an embodiment of the present invention can reduce the content of volatile organic compounds in the matt thermoplastic resin finally produced by performing the devolatilization under the above conditions.

Hereinafter, the manufacturing method according to an embodiment of the present invention will be described with reference to FIG.

Figure 1 illustrates an exemplary process system capable of performing the manufacturing method according to one embodiment of the present invention.

The process system 100 according to an embodiment of the present invention includes a rubber melting tank 10 capable of producing a polymerization solution, a polymerization tank 20 capable of performing a polymerization reaction, and a devolatilizer The first polymerization reactor 21, the second polymerization reactor 22, the third polymerization reactor 23 and the fourth polymerization reactor 24 are continuous ≪ / RTI >

Specifically, the step 1) may be performed in the rubber melting tank 10. A polymerization solution can be prepared by adding a reaction solvent, an aromatic vinyl compound and a vinyl cyanide compound to a rubber dissolving tank 10 to prepare a mixed solution, adding the conjugated diene rubber and, if necessary, a polymerization initiator, have. At this time, the rubber melting tank 10 may include a stirrer inside.

The steps 2) and 3) may be performed in the polymerization tank 20 in which the first polymerization reactor 21 and the second polymerization reactor 22 are continuously arranged, and the steps 3-1) and 3-2) May be carried out in the third polymerization reactor 23 and the fourth polymerization reactor 24 which are continuously arranged in the polymerization tank 20. The polymerization solution may be transferred from the rubber melting tank 10 to the first polymerization reactor 21 and polymerized at a temperature ranging from 100 ° C to 120 ° C for 1.5 to 2.5 hours to perform the first polymerization step. At this time, the polymerization solution may be transferred into the first polymerization reactor 21 at a flow rate of 10 L / hr to 20 L / hr, and the retention time in the first polymerization reactor may be 1.5 to 2.5 hours Lt; / RTI > At this time, the residence time in the first polymerization reactor may indicate the polymerization time in the first polymerization reactor. The polymerization product obtained in the first polymerization step may be transferred to the second polymerization reactor 22 and polymerized in the temperature range of 125 캜 to 140 캜 to carry out the second polymerization step. At this time, a molecular weight regulator of 150 ppm to 700 ppm, based on the total weight of the polymerization solution, is added to the front end of the second polymerization reactor separately from the polymerization product obtained in the first polymerization step, Can be polymerized. In this case, the molecular weight modifier may be added to the front end of the second polymerization reactor 22 in the form of a solution of a molecular weight modifier dissolved in a solvent. As the solvent, the above-mentioned reaction solvents may be used. When the molecular weight modifier is added in the form of a molecular weight modifier solution, the flow rate of the molecular weight modifier solution may be 0.045 kg / hr to 0.3 kg / hr, specifically 0.06 kg / hr to 0.21 kg / hr, more specifically 0.15 kg / hr.

Thereafter, the polymerization product obtained in the second polymerization step is further transferred to the third polymerization reactor 23 and polymerized in the temperature range of 140 ° C to 150 ° C to carry out the third polymerization step, and additionally, the polymerization product obtained in the third polymerization step The polymerization product may be transferred to the fourth polymerization reactor 24 and polymerized at a temperature ranging from 150 캜 to 160 캜 to prepare a polymerization product.

The step 4) may be performed in the devolatilizing tank 30. The polymerized product is transferred from the fourth polymerization reactor (24) to the devolatilizing tank (30) and devolatilized under a temperature range of 230 ° C to 250 ° C and a pressure of 30 torr or less to obtain a matt thermoplastic resin.

Further, the present invention provides a matt thermoplastic resin produced by the above-mentioned production method.

A matte thermoplastic resin according to an exemplary embodiment of the present invention has a spiral flow of 10 cm to 16 cm measured according to ASTM D3123 (150 占 폚) with a weight average rubber particle size of 17 占 퐉 to 25 占 퐉 , And a weight average molecular weight (Mw) of 150,000 g / mol to 280,000 g / mol, and specifically, a weight average rubber particle size of 18 μm to 23 μm, measured according to ASTM D3123 (150 ± 3 ° C.) One may have a spiral flow of 11 cm to 16 cm and a weight average molecular weight (Mw) of 180,000 g / mol to 250,000 g / mol. The non-heat-resistant thermoplastic resin according to one embodiment of the present invention is excellent in low-glossiness, excellent impact resistance, and excellent extrusion processability by satisfying the above physical properties.

The non-heat-resistant thermoplastic resin according to an exemplary embodiment of the present invention may have a tensile strength of 200 kgf / cm ² to 300 kgf / cm ² measured at 100 ° C, specifically, 220 kgf / cm ² to 290 kgf / cm ² . The melt strength was measured according to ASTM D638 using a universal testing machine (Model 4466, Instron) at a crosshead speed of 500 mm / min in a high temperature (100 ° C) And the point at which the resin is cut is measured.

The glossless thermoplastic resin according to an exemplary embodiment of the present invention may have a gloss value of 45 or less as measured by a gloss meter of 12 or less, specifically 3 to 12, more specifically 6 to 11.

In the present invention, the weight average molecular weight (Mw) is determined by dissolving the resin in a tetrahydrofuran (THF) solution at a concentration of 0.25% and measuring the relative value with respect to a standard polystyrene sample using gel permeation chromatography (GPC, Waters Breeze) It is.

Specifically, the non-light thermoplastic resin according to an example of the present invention may be an acrylonitrile-butadiene-styrene (ABS) terpolymer resin.

Hereinafter, the present invention will be described in more detail with reference to Examples and Experimental Examples. However, the following examples and experimental examples are provided for illustrating the present invention, and the scope of the present invention is not limited thereto.

Example 1

A mixed solution was prepared by adding 25% by weight of ethylbenzene, 47.6% by weight of styrene and 20.4% by weight of acrylonitrile to a rubber dissolving tank at 50 ° C, and 170 cp of a butadiene rubber (Asaprene 730AX, manufactured by Asahi-Kasei) , And 0.025 part by weight of t-butylperoxy-2-ethylhexanoate as an initiator was added based on 100 parts by weight of the above-mentioned components to prepare a polymerization solution. The polymerization solution was polymerized by continuous bulk polymerization. At this time, the polymerization reaction was carried out in a two-stage polymerization reactor system including a first polymerization reactor and a second polymerization reactor except for the third polymerization reactor and the fourth polymerization reactor in the multistage polymerization reactor system as shown in Fig.

Specifically, the polymerization solution was continuously fed into the first polymerization reactor at a rate of 16 L / hr and polymerized at a temperature of 105 캜. The first polymerized product polymerized in the first polymerization reactor was fed to the front end of the second polymerization reactor At a flow rate of 16 L / hr, while a solution in which 5 parts by weight of a molecular weight regulator (t-dodecyl mercaptan) was dissolved in ethylbenzene was fed at a flow rate of 0.15 kg / hr, Respectively. The polymerization product obtained through the polymerization reaction was transferred to a devolatilizing vessel and the unreacted monomers and the reaction solvent were recovered and removed at a temperature of 230 ° C to obtain a pellet-shaped thermoplastic resin, a mild acrylonitrile-butadiene-styrene resin .

Examples 2 to 6 and Comparative Examples 1 to 3

Except that the viscosity of the butadiene rubber, the amount of acrylonitrile used, and the amount of t-dodecyl mercaptan (TDDM) were changed, as shown in Table 1 below, Acrylonitrile-butadiene-styrene resin.

Polymerization solution Viscosity of butadiene rubber (cps) Amount of acrylonitrile used (% by weight) Addition amount of TDDM
(ppm) Example 1 170 20.4 500 Example 2 250 23.8 300 Example 3 250 17 400 Example 4 250 20.4 200 Example 5 170 23.8 300 Example 6 250 20.4 500 Comparative Example 1 40 20.4 500 Comparative Example 2 170 13.6 100 Comparative Example 3 250 20.4 800

Experimental Example

In order to comparatively analyze the physical properties of the resins prepared in Examples 1 to 6 and Comparative Examples 1 to 3, the following analyzes were carried out for each resin. The results are shown in Table 1 below.

1) Measurement of average particle size (RPS, rubber particle size) of rubber particles

The average particle diameters of the rubber particles (dispersed phase) in the resin prepared in each of Examples 1 to 6 and Comparative Examples 1 to 3 were measured and compared and analyzed.

The average particle diameter was measured by dissolving 0.5 g of each resin in 100 mL of methyl ethyl ketone and then using a Coulter counter (LS 230, BECKMAN COULTER).

2) Measurement of gloss

Resins prepared in each of Examples 1 to 6 and Comparative Examples 1 to 3 were measured at a 45 ° angle using a gloss meter.

3) Measurement of weight average molecular weight (Mw)

The resin prepared in each of Examples 1 to 6 and Comparative Examples 1 to 3 was dissolved in a tetrahydrofuran (THF) solution at a concentration of 0.25%, and the resin was dissolved in a standard polystyrene sample using gel permeation chromatography (GPC, Waters Breeze) As the relative value.

4) Spiral flow

The resin prepared in each of Examples 1 to 6 and Comparative Examples 1 to 3 was measured according to ASTM D3123 (300, mold temperature 80, capillary thickness 1.5 mm, holding pressure 2000 bar).

5) Melt strength

The melt strength was measured according to ASTM D638 using a universal testing machine (Model 4466, Instron) at a crosshead speed of 500 mm / min in a high temperature (100 ° C) And the point at which the resin is cut is measured.

RPS
(탆) Gross Mw
(g / mol) Spiral fluidity
(cm) Melt strength
(kgf / cm ² ) Example 1 18 10.4 190,000 15.5 250 Example 2 22.3 8.2 220,000 12.2 268 Example 3 21.0 9.7 210,000 13.1 263 Example 4 21.8 8.7 250,000 11.2 281 Example 5 18.5 10.3 225,000 11.9 271 Example 6 21.5 9.1 185,000 15.8 247 Comparative Example 1 4.3 43.0 185,000 16.1 245 Comparative Example 2 16.0 13 300,000 6.5 310 Comparative Example 3 20.8 9.9 120,000 28.6 135

As shown in Table 1, the matte acrylonitrile-butadiene-styrene type resins of Examples 1 to 6 had a large rubber particle size, had excellent matt characteristics, had an appropriate weight average molecular weight, It can be confirmed that the extrusion processability and the melt strength appear uniformly.

The acrylonitrile-butadiene-styrene resin of Comparative Example 1 had a low viscosity of the butadiene rubber used in the polymerization, and the prepared acrylonitrile-butadiene-styrene resin had a rubber particle size that was too small and had poor matte properties .

The acrylonitrile-butadiene-styrene type resin of Comparative Example 2 had a low TDDM content and had an excessively large weight average molecular weight of the acrylonitrile-butadiene-styrene type resin produced, poor extrusion strength, .

In the acrylonitrile-butadiene-styrene resin of Comparative Example 3, the weight average molecular weight of the acrylonitrile-butadiene-styrene resin was too low and the melt strength was poor because of the high content of TDDM used.

100: Process system 10: Rubber melting tank
20: Polymerization tank 21: First polymerization reactor
22: Second polymerization reactor 23: Third polymerization reactor
24: fourth polymerization reactor 30: devolatilizing tank

Claims (16)

1) adding a conjugated diene rubber having a viscosity of 150 cp to 300 cp to a mixed solution containing a reaction solvent, an aromatic vinyl compound and a vinyl cyan compound to prepare a polymerization solution;
2) a first polymerization step of polymerizing the polymerization solution while continuously introducing the polymerization solution into the first reactor;
3) a second polymerization step in which the polymerization product obtained in the first polymerization step is introduced into the second reactor and a polymerization initiator of 150 ppm to 700 ppm based on the total weight of the polymerization solution is added to the front end of the second reactor to polymerize step; And
4) A step of devolatilizing the obtained polymerization product.
The method according to claim 1,
The polymerization solution contains 10 to 30% by weight of a reaction solvent;
From 35% to 65% by weight of an aromatic vinyl compound;
15% by weight to 40% by weight of a vinyl cyanide compound; And
And 5 to 15% by weight of a conjugated diene-based rubber.
The method according to claim 1,
Wherein the first polymerization step is performed by continuous bulk polymerization in a temperature range of 100 占 폚 to 120 占 폚 for 1.5 hours to 2.5 hours.
The method according to claim 1,
Wherein the first polymerization step is performed in a state where no molecular weight regulator is added.
The method according to claim 1,
Wherein the second polymerization step is performed at a higher polymerization temperature than the first polymerization step.
The method according to claim 1,
Wherein the second polymerization step is carried out by continuous bulk polymerization in a temperature range of 125 占 폚 to 140 占 폚.
The method according to claim 1,
Wherein the first polymerization step and the second polymerization step are performed by continuous bulk polymerization.
The method according to claim 1,
3-1) a third polymerization step in which the polymerization product obtained in the second polymerization step is introduced into a third reactor and polymerized,
Wherein the first polymerization step, the second polymerization step and the third polymerization step are carried out by continuous bulk polymerization.
9. The method of claim 8,
Wherein the third polymerization step is carried out by continuous bulk polymerization in a temperature range of 140 캜 to 150 캜.
9. The method of claim 8,
In addition, 3-2) a fourth polymerization step of introducing the polymerization product obtained in the third polymerization step into a fourth reactor and polymerizing,
Wherein the first polymerization step, the second polymerization step, the third polymerization step and the fourth polymerization step are carried out by continuous bulk polymerization.
11. The method of claim 10,
Wherein the fourth polymerization step is performed by continuous bulk polymerization in a temperature range of from 150 캜 to 160 캜.
The method according to claim 1,
The molecular weight regulator may be selected from the group consisting of n-dodecyl mercaptan, n-amyl mercaptan, t-butyl mercaptan, t-dodecyl mercaptan, n-hexyl mercaptan, n-octyl mercaptan and n-nonyl mercaptan Wherein the thermoplastic resin is a thermoplastic resin.
The method according to claim 1,
Wherein the matt thermoplastic resin obtained after the step of devolatilizing has a weight average rubber particle size of from 17 mu m to 25 mu m.
A weight average rubber particle size of 17 mu m to 25 mu m,
The spiral flow measured according to ASTM D3123 (150 占 3 占 폚) is 10 cm to 16 cm,
A matt thermoplastic resin produced by the process of claim 1 having a weight average molecular weight (Mw) of 150,000 g / mol to 280,000 g / mol.
15. The method of claim 14,
Wherein said non-heat-resistant thermoplastic resin has a tensile strength of 200 kgf / cm ² to 300 kgf / cm ² measured at 100 ° C.
15. The method of claim 14,
Wherein said non-heat-resistant thermoplastic resin has a gross value at 45 DEG measured by a gloss meter of 12 or less.

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