KR20200077958A - Method of preparing heat resistant abs resin - Google Patents

Abstract

The present invention relates to a method for preparing a heat-resistant ABC resin and, more particularly, to a method for preparing a heat-resistant ABS resin with excellent thermal stability and mechanical properties while showing a very excellent effect of reducing a smell. The method comprises a step of polymerizing a polymerization solution, which mixes: 0.01 to 1 part by weight of an initiator and 0.01 to 1 part by weight of an α-alkylstyrene multimer as a molecular weight control agent in 100 parts by weight of a mixed solution containing 20 to 70 wt% of an aromatic vinyl compound; 5 to 35 wt% of a vinylcyan compound; 1 to 20 wt% of a maleimide-based compound; 1 to 20 wt% of a conjugated diene polymer; 1 to 30 wt% of an aromatic rubbery copolymer; and 10 to 40 wt% of a reaction solvent, in which the step of polymerizing is performed with thiol-free.

Description

Manufacturing method of heat-resistant ABS resin {METHOD OF PREPARING HEAT RESISTANT ABS RESIN}

The present invention relates to a method of manufacturing a heat-resistant ABS resin, and more particularly, to a method of manufacturing a heat-resistant ABS resin having excellent thermal stability and mechanical properties while having excellent odor improvement effect.

ABS (Acrylonitrile-Butadiene-Styrene) resin has excellent chemical resistance, stiffness, and processability, and is widely used in electrical and electronic, household, and office supplies.

However, the ABS resin is not high in heat resistance, and thus has limitations in application to automobile interior products requiring high heat resistance.

In addition, not only heat resistance but also odor are considered important in automobile interior products. To remove TVOC (Total Volatile Organic Compounds), which is one of the main causes of this odor, deodorant or foam beads are applied to ABS resin. In this case, TVOC is reduced to improve odor, but mechanical properties such as impact strength The problem of decreasing together occurs.

Accordingly, there is a need to develop an ABS resin that does not have a plastic odor (chemical odor) without applying a deodorant or foam beads, and has excellent thermal stability and does not degrade mechanical properties such as impact strength.

Korean Registered Patent No. 10-0409071

In order to solve the problems of the prior art as described above, an object of the present invention is to provide a method for manufacturing a heat-resistant ABS resin having excellent mechanical properties such as impact strength while having no plastic odor and excellent thermal stability.

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, the present invention is an aromatic vinyl compound 20 to 70% by weight, vinyl cyan compound 5 to 35% by weight, maleimide-based compound 1 to 20% by weight, conjugated diene polymer 1 to 20% by weight, aromatic rubber Polymerization by mixing 1 to 30 parts by weight of the copolymer and 10 to 40 parts by weight of the reaction solvent to 100 parts by weight of the initiator, 0.01 to 1 part by weight of the initiator and 0.01 to 1 part by weight of the α-alkylstyrene multimer as a molecular weight modifier; Including the step of polymerizing the solution, the polymerization step provides a method for producing a heat-resistant ABS resin, characterized in that thiol-free (Thiol-free).

According to the present invention, there is an effect of providing a method for manufacturing a heat-resistant ABS resin having excellent odor improvement effect and excellent thermal stability and mechanical properties.

Hereinafter, a method of manufacturing the heat-resistant ABS resin of the present description will be described in detail.

The present inventors prepared an aromatic vinyl compound, a vinyl cyan compound, a conjugated diene polymer, an aromatic rubber copolymer, a maleimide-based compound, and an α-alkylstyrene multimer in a specific content with a molecular weight modifier, to deodorize or foam beads. As the odor characteristics were improved without application, the thermal stability and mechanical properties were also excellent, confirming that it was particularly suitable for automobile interior materials, and based on this, further research was conducted to complete the present invention.

The method for producing the heat-resistant ABS resin of the present invention includes 20 to 70% by weight of an aromatic vinyl compound, 5 to 35% by weight of a vinyl cyan compound, 1 to 20% by weight of a maleimide compound, 1 to 20% by weight of a conjugated diene polymer, and an aromatic rubbery copolymer Polymerization solution comprising: 1 to 30 parts by weight of the mixture and 10 to 40 parts by weight of the reaction solvent; 100 to 1 part by weight of the initiator; 0.01 to 1 part by weight of the initiator and 0.01 to 1 part by weight of the α-alkylstyrene multimer as a molecular weight regulator; Including the step of polymerizing, the polymerization step is characterized in that it is thiol-free (Thiol-free), in which case the odor characteristics are improved without applying a deodorant or a foamed bead and the thermal stability is excellent while the impact strength is the same. It has excellent mechanical properties.

The aromatic vinyl compound of the present disclosure may be, for example, one or more selected from the group consisting of styrene, α-methylstyrene, o-ethylstyrene, p-ethylstyrene, and vinyltoluene. Mechanical properties such as strength and impact strength also have excellent effects.

The aromatic vinyl compound may be, for example, 20 to 70% by weight, or 30 to 60% by weight with respect to 100% by weight of the mixed solution, preferably 40 to 60% by weight, fluidity within this range is appropriate The odor is improved and has excellent heat resistance and mechanical properties.

The vinyl cyan compound of the present disclosure may be, for example, one or more selected from the group consisting of acrylonitrile, methacrylonitrile, and ethacrylonitrile, and in this case, has excellent effects such as impact resistance and processability.

The vinyl cyan compound may be, for example, 5 to 35% by weight, 5 to 25% by weight, or 5 to 20% by weight based on 100% by weight of the mixed solution, and preferably 7 to 15% by weight, in this range There are few residual monomers within, and there is an effect of excellent mechanical properties such as impact strength and tensile strength.

Maleimide compounds of the present disclosure are, for example, N-phenylmaleimide, 　maleimide, 　N-methylmaleimide, 　N-ethylmaleimide, 　N-propylmaleimide, 　N-isopropyl　maleimide, 　N-butylmaleimide, N-isobutylmaleimide,　Nt-butylmaleimide,　N-cyclo　hexylmaleimide,　N-chlorophenylmaleimide,　N-methylphenylmaleimide,　N-bromo phenylmaleimide,　N-naphthylmaleimide,　N -Lauryl maleimide, 　N-hydroxy　phenyl maleimide, 　N-methoxyphenylmaleimide, 　N-carboxyphenylmaleimide, 　N-nitro　phenylmaleimide and 　N-benzyl maleimide It may be, preferably, N-phenylmaleimide, and in this case, it has excellent heat resistance as well as improved odor characteristics and excellent mechanical properties.

The maleimide-based compound may be, for example, 1 to 20% by weight, 1 to 10% by weight, or 1 to 8% by weight relative to 100% by weight of the mixed solution, and preferably 2 to 5% by weight, which Residual monomer and TVOC are reduced within the range, and there is an effect of excellent heat resistance.

The maleimide-based compound preferably has a glass transition temperature (Tg) in the polymer state of 100 to 150°C, 110 to 120°C, or 113 to 117°C, and within this range, odor is improved and heat resistance and mechanical properties are improved. Has an excellent effect.

The glass transition temperature in this substrate is measured by DSC (Differential Scanning Calorimeter) according to ASTM D3418.

The maleimide-based compound may have, for example, a weight average molecular weight of 130,000 to 210,000 g/mol, 150,000 to 190,000 g/mol, or 160,000 to 180,000 g/mol, and has excellent mechanical properties within this range.

The conjugated diene polymer of the present disclosure may be, for example, a polymer including a conjugated diene compound having a structure in which double bonds and single bonds are arranged one over another, and does not contain an aromatic vinyl compound. It can be distinguished from the copolymer, and preferably may be a butadiene polymer (BR), in which case it has excellent mechanical properties, processability, and the like.

The conjugated diene polymer may be, for example, 1 to 20% by weight, 1 to 10% by weight, or 1 to 7% by weight relative to 100% by weight of the mixed solution, and preferably 1 to 5% by weight, in this range Residual monomers are reduced and the processability and mechanical properties are improved.

The conjugated diene polymer may have, for example, a volume average particle diameter of 1 to 4 μm, 1.5 to 3 μm, 1.7 to 2.5 μm, 1.8 to 2.3 μm, or 1.9 to 2.2 μm, improving mechanical properties and processability within this range. It has an effect.

In the present description, the volume average particle diameter is measured using a LS 13 320 manufactured by Beckman coulter through a laser diffraction method.

The conjugated diene polymer may have, for example, a gel content of 50 to 85% by weight, 50 to 75% by weight, or 50 to 65% by weight, and within this range, mechanical strength and transparency are excellent, but fluidity is adequate, and processability is excellent. It works.

The conjugated diene polymer may have, for example, a swelling index of 3 to 8, or 4 to 6, and has excellent effects in physical properties such as impact resistance and transparency within this range.

The gel content and swelling index of the conjugated diene polymer in this substrate are, for example, coagulated diene polymer using dilute acid or metal salt, washed, dried in a vacuum oven at 60° C. for 24 hours, and the obtained rubber mass is finely cut with scissors. Thereafter, 1 g of the rubber section was put in 100 g of toluene, stored in a dark room at room temperature for 48 hours, and then separated into sol and gel, and calculated through Equation 1 or Equation 2.

[Equation 1]

Gel content (% by weight) = (weight of insoluble matter (gel) / weight of sample) X 100

[Equation 2]

Swelling index = weight of swollen gel / weight of gel

The aromatic rubber-based copolymer of the present disclosure may be, for example, a copolymer of a conjugated diene compound and an aromatic vinyl compound, and in this case, has excellent effects in mechanical properties, processability, and the like.

The conjugated diene compound contained in the aromatic rubber copolymer is, for example, 1,3-butadiene, 2-methyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 2,3-dimethyl-1,3- It may be one or more selected from the group consisting of butadiene, 1,3-pentadiene and 3-butyl-1,3-octadiene.

The conjugated diene compound contained in the aromatic rubbery copolymer is, for example, 100% by weight of the aromatic rubbery copolymer, that is, 60 to 99% by weight, or 70 to 90% by weight relative to 100% by weight of the total content of the conjugated diene compound and the aromatic vinyl compound. It is possible to improve the workability and mechanical properties within this range.

The aromatic vinyl compound contained in the aromatic rubber copolymer may be, for example, one or more selected from the group consisting of styrene, α-methylstyrene, o-ethylstyrene, p-ethylstyrene, and vinyltoluene.

The aromatic vinyl compound contained in the aromatic rubbery copolymer may be, for example, 1 to 40% by weight, or 10 to 30% by weight relative to 100% by weight of the aromatic rubbery copolymer, and improves processability and mechanical properties within this range. It works.

The aromatic rubber-based copolymer may be styrene-butadiene rubber (SBR) as a specific example, and has excellent mechanical properties, processability, and the like.

The aromatic rubber copolymer may be, for example, 1 to 30% by weight, 1 to 15% by weight, or 1 to 10% by weight relative to 100% by weight of the mixed solution, preferably 3 to 8% by weight, and If it is less than the range, mechanical properties such as impact strength and tensile strength are deteriorated, and if it is more than the above range, fluidity is reduced and processing becomes difficult.

The weight ratio of the conjugated diene polymer and the aromatic rubbery copolymer may be, for example, 1:1 to 1:7, or 1:1 to 1:5, preferably 1:1 to 1:3, and this range There is an effect that the fluidity is appropriate within, so that processing is easy and mechanical properties are improved.

The reaction solvent of the present disclosure may be, for example, one or more selected from the group consisting of ethylbenzene, toluene, methyl ethyl ketone, and xylene, and in this case, it is easy to control viscosity and has an effect of suppressing a decrease in polymerization conversion rate.

The reaction solvent may be, for example, 10 to 40% by weight, or 15 to 35% by weight with respect to 100% by weight of the mixed solution, preferably 15 to 25% by weight, and the viscosity is excessively increased within this range It has the effect of reducing or decreasing the conversion rate and molecular weight.

The molecular weight modifier of the present disclosure may be, for example, an α-alkylstyrene multimer, preferably an α-alkylstyrene multimer having 1 to 3 carbon atoms in the alkyl group, in which case the odor is improved without deteriorating mechanical properties. There is.

The α-alkylstyrene multimer may be, for example, one or more multimers selected from the group consisting of α-methylstyrene and α-ethylstyrene, in which case the odor is very excellent in improving the effect while the mechanical properties are deteriorated. It does not work.

The multimer may be, for example, one or more selected from the group consisting of a dimer, a trimer, and a tetramer, and in this case, the odor improvement effect is very excellent.

The α-alkylstyrene multimer may be an α-methylstyrene dimer as a preferred example, and in this case, the odor is improved without deteriorating mechanical properties, and thus there is an effect suitable for application to automobile interior materials.

The molecular weight modifier may be, for example, 0.01 to 1 part by weight, or 0.01 to 0.06 part by weight, based on 100 parts by weight of the mixed solution, and preferably 0.02 to 0.04 part by weight, improving odor problems and mechanical properties within this range. There is an effect of not lowering the silver, and if it is less than the above range, the stability of the heat-resistant ABS resin of the present substrate is lowered, and when it is above the above range, the polymerization rate is reduced to lower the productivity.

The polymerization step may be, for example, thiol-free, and in this case, the odor improving effect is very excellent without deteriorating mechanical properties.

“Thiol-free” as used herein means that the thiol compound is not intentionally included in the polymerization step of the present description.

The initiator of the present disclosure is, for example, t-butylperoxy-2-ethylhexanoate, tert-Butylperoxy-2-ethylhexanoate, benzoyl peroxide, t-butylperoxyisobutyrate, 1,1-bis(t-butylperoxy)cyclohexane, 2,2-bis(4,4-di-t-butylperoxycyclohexane)propane (2, 2-bis(4,4-di-t-butylperoxy cyclohexane)propane, t-hexyl peroxy isopropyl monocarbonate, t-butylperoxylaurate, t- T-butyl peroxy isopropylmonocarbonate, t-butyl peroxy 2-ethylhexylmonocarbonate, t-hexyl peroxybenzoate, t-butyl Peroxyacetate (t-butyl peroxyacetate), 2,2-bis(t-butyl peroxy)butane, t-butyl peroxybenzoate, Dicumyl peroxide, 2,5-dimethyl-2,5-bis(t-butyl peroxy)hexane, t- 1 type selected from the group consisting of t-butyl cumyl peroxide, di-t-butyl peroxide and di-t-amyl peroxide It may be the above, preferably t-butylperoxy-2-ethylhexanoate (tert-Butylperoxy-2-ethylhexanoate), in this case, the polymerization reaction to facilitate the present invention The purpose of the effect is well revealed.

The polymerization step may be, for example, a foamed bead-free, and in this case, there is an effect of improving odor without deteriorating mechanical properties.

As used herein, the term "foamed bead free" means that the foamed beads were not intentionally added in the polymerization step of the present description.

The method of manufacturing the heat-resistant ABS resin includes, for example, primary polymerization of the polymerization solution in a reactor at 90 to 110° C.; After the first polymerization step, the second polymerization in a reactor of 120 to 140 ℃; And tertiary polymerization in a reactor at 145 to 170° C. after the secondary polymerization step. In this case, the odor is improved, thermal stability is excellent, and mechanical properties such as impact strength are excellent.

The primary, secondary and tertiary polymerization may be, for example, solution polymerization, preferably continuous solution polymerization, in which case the odor is improved and heat stability is excellent, but heat resistance ABS with excellent mechanical properties such as impact strength It is easy to manufacture.

The primary, secondary and tertiary polymerization are preferably polymerized by injecting a mixed solution into each reactor at a constant rate per unit time.

The primary, secondary and tertiary reactors, respectively, may have an input rate of a polymerization solution of 10 to 18 L/hr, or 12 to 16 L/hr, and the polymerization conversion rate rises within this range, resulting in a reaction. It has the effect of becoming easy.

The reactor may be, for example, one or more selected from the group consisting of a continuous stirred tank reactor (CSTR), a tubular reactor (plug flow reactor), and a multi-stage reactor.

The manufacturing method of the heat-resistant ABS resin may include, for example, a step of removing unreacted monomers and solvents under a high temperature vacuum in a devolatilization tank after a third polymerization step, and then extruding them to produce pellets, in which case the residual monomer content in the resin This has the effect of improving the low thermal stability.

The high temperature vacuum in the devolatilization tank may be, for example, 25 Torr or less, or 10 to 25 Torr. In this case, the residual monomer content in the resin is low and thermal stability is improved.

The temperature of the devolatilization tank may be, for example, 200 to 250°C, or 220 to 240°C, and it is easy to remove unreacted monomers and reaction solvents within the above range.

The method of manufacturing the heat-resistant ABS resin is preferably thiol-free even in the post-treatment step after the polymerization step, and in this case, the odor improvement effect is very excellent without deteriorating mechanical properties.

The heat-resistant ABS resin produced by the above-described manufacturing method is, for example, using a UTM (manufacturer; Instron, model name; 4466) as a test device according to ASTM D638, and pulling the cross head speed to 200 mm/min. After that, the tensile strength measured at the point where the 1T specimen is cut may be 450 kgf/cm ² or more, 450 to 1,000 kgf/cm ² , or 480 to 700 kgf/cm ² , and excellent mechanical properties within this range There is.

The heat-resistant ABS resin, for example, may be 15 to 50%, 19 to 40%, or 22 to 30% of tensile elongation measured according to standard measurement ASTM D638 using a 1/8" specimen, within this range. It has excellent mechanical properties.

The heat-resistant ABS resin, for example, using a 1/8" specimen according to ASTM D790, the flexural strength measured under a span 50 mm condition is 700 to 1,500 kgf/cm ² , 800 to 1,000 kgf/cm ² , or It may be 800 to 900 kgf/cm ² , and has excellent mechanical properties within this range.

The heat-resistant ABS resin has a flexural modulus of 20,000 MPa or more, 20,000 to 40,000 MPa, or 23,500 to 25,000 MPa, measured using an all-purpose material tester (manufactured by Zwick's Z020) as a flexural specimen having a thickness of 4.0 mm according to ISO 178 as an example. It may be, there is an effect excellent in mechanical properties within this range.

The heat-resistant ABS resin, for example, has an Izod impact strength (1/4", 23°C) measured in accordance with ASTM D256 of 10 kg·cm/cm or more, 10 to 30 kg·cm/cm, or 12 to 20 kg· cm/cm, and the Izod impact strength (1/8", 23°C) may be 15 kg·cm/cm or more, 15-30 kg·cm/cm, or 18-25 kg·cm/cm, Within this range, mechanical properties are excellent.

The heat-resistant ABS resin may have, for example, a heat strain temperature measured under 18.6 kgf stress using a specimen having a thickness of 6.4 mm, and may be 90°C or higher, 90 to 150°C, or 93 to 110°C, and thermal stability within this range. It has an excellent effect.

The heat-resistant ABS resin may have, for example, a residual monomer content of 1,000 ppm or less, 100 to 1,000 ppm, or 500 to 1,000 ppm, preferably 800 to 950 ppm, and an excellent odor improvement effect within this range. There is.

The heat-resistant ABS resin is, for example, based on the Volvo Car Corporation measurement method (VCS 1027) by heating for 5 hours at 120 °C to convert all hydrocarbons detected per g to acetone content, TVOC (Total Volatile Organic Compounds) It may be 60 µg/g or less, 10 to 60 µg/g, or 20 to 55 µg/g, and has an excellent effect of improving odor within this range.

The heat-resistant ABS resin has, for example, a melt index (220° C., 10 kg) measured according to ASTM D1238 (220° C., 10 kg) of 1 to 20 g/10min, 1 to 15 g/10min, or 4 to 12 g. It may be /10min, and within this range, fluidity is appropriate, and thus there is an effect of excellent workability and formability.

The heat-resistant ABS resin may be, for example, a heat-resistant ABS resin for automobile interior materials. In this case, the odor characteristics are improved, and mechanical properties such as impact strength and thermal stability are excellent, thereby improving durability.

Hereinafter, a preferred embodiment is provided to help the understanding of the present invention, but the following examples are merely illustrative of the present invention, and it is apparent to those skilled in the art that various changes and modifications are possible within the scope and technical scope of the present invention. It is no wonder that such variations and modifications fall within the scope of the appended claims.

[Example]

Example 1

20.0% by weight of ethylbenzene (EB), 55.0% by weight of styrene (SM), 13.8% by weight of acrylonitrile (AN) and 2.5% by weight of N-phenylmaleimide (PMI), butadiene rubber ( Butadiene Rubber) 8.7% by weight (BR:SBR = 3:7) was added to dissolve well to prepare a mixed solution, and then 100 parts by weight of the mixed solution was used as an initiator, t-butylperoxy-2-ethylhexanoate (tert- A polymerization solution was prepared by adding 0.03 parts by weight of butylperoxy-2-ethylhexanoate and 0.04 parts by weight of AMSD (α-methylstyrene dimer), a molecular weight regulator. The prepared polymerization solution was first polymerized in the first reactor (26 L) at 105°C, and secondly polymerized in the second reactor (16 L) at 135°C after the first polymerization, and third at 150°C after the second polymerization. Third polymerization was carried out in a reactor (16 L). At this time, the rate of adding the polymerization solution to the three reactors was 12 L/hr. After the tertiary polymerization, an unreacted monomer and a reaction solvent were recovered and removed in a volatilization tank at 250° C. to 25 Torr or less, and then extruded to prepare pellet resin in the form of pellets.

Example 2

It was carried out in the same manner as in Example 1, except that 0.02 parts by weight of AMSD was used in Example 1 instead of 0.04 parts by weight.

Example 3

It was carried out in the same manner as in Example 1, except that 0.06 parts by weight of AMSD was used in Example 1 instead of 0.04 parts by weight.

Comparative Example 1

It was carried out in the same manner as in Example 1, except that in Example 1, 0.02 parts by weight of TSDDM instead of 0.04 parts by weight of AMSD was used.

Comparative Example 2

After adding 2 parts by weight of expanded beads (F-36D from Matsumoto Yushi-Seiyaku, Japan) to the ABS resin in the form of pellets prepared in the same manner as in Comparative Example 1, the resin was pelletized by extruding in an extruder (28Ø) at 240°C. Was prepared.

Comparative Example 3

In Example 1, except for using 0.04 parts by weight of AMSD, 0.01 parts by weight of TDDM and 0.02 parts by weight of AMSD were performed in the same manner as in Example 1.

[Test Example]

The properties of the ABS resins prepared in Examples 1 to 3 and Comparative Examples 1 to 3 were measured by the following method, and the results are shown in Table 2 below.

* Tensile strength (kgf/cm ² ): 1T specimen after pulling the cross head speed to 200 mm/min using UTM (manufacturer; Instron, model name; 4466), a test device according to ASTM D638 The cut point was measured and the tensile strength was calculated as follows:

Tensile strength (kgf/cm ² ) = load value (kgf) / thickness (cm) X width (cm)

* Tensile elongation (%): Measured according to standard measurement ASTM D638 using a 1/8" specimen.

* Flexural strength (kgf/cm ² ): Flexural strength was measured under a span of 50 mm using a 1/8" specimen according to ASTM D790.

* Flexural modulus (MPa): According to ISO 178, it was measured using a universal tester (made by Zwick, manufactured by Zwick) as a flexural specimen having a thickness of 4.0 mm.

* Izod impact strength (1/4", 23°C) (kg·cm/cm): Measured according to ASTM D256.

* Izod impact strength (1/8", 23 °C) (kg·cm/cm): Measured according to ASTM D256.

* Vicat (℃): Measured according to ASTM D1525.

* Heat Deflection Temperature (HDT) (℃): Measured under 18.6 kgf stress using a specimen with a thickness of 6.4 mm according to ASTM D648.

* Residual monomer content (ppm): measured based on gel chromatography (GPC).

* TVOC (Total Volatile Organic Compound) (µg/g): Based on the Volvo Car Corporation measurement method (VCS1027), it was heated at 120° C. for 5 hours to measure the value of all hydrocarbons detected per 1 g in terms of acetone. .

* Melt Index (MI) (g/10min): measured according to ASTM D1238 (220 ℃, 10 kg).

* Odor Rating: As an evaluation method according to the odor intensity according to the VDA 270 measurement method, 11 types of STD solution are prepared by adding n-Butyl Alcohol to Pure Water as shown in Table 1 below, and a measurement sample based on the odor intensity (injection specimen) The odor grade was determined by comparing the mixture after being kept in an oven at 80° C. for 2 hours. For reference, in order to use it for automobile interior materials, it should be less than 3.5 grade.

Odor Level
(class) Addition amount of n-Butyl Alcohol
(ml/l) Distinction Remarks 1.0 0 Good









Bad Not aware
↓
Minor perception
↓
Intense recognition
↓
Stinging nose
↓
↓
↓
Unbearable 1.5 0.2 2.0 0.6 2.5 1.2 3.0 2.4 3.5 3.6 4.0 6.0 4.5 9.0 5.0 18.0 5.5 22.7 6.0 100% B-OH

Remark Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 TDDM (parts by weight) - - - 0.02 0.02 0.01 AMSD (parts by weight) 0.04 0.02 0.06 - - 0.02 Foam Bead Application X X X X ○ X Heat-resistant ABS resin properties Odor class (class) 3~3.5 3~3.5 3~3.5 4~4.5 4 3~3.5 Residual monomer (ppm) 896 911 956 927 932 270 TVOC (µg/g) 53.2 54.4 57.9 56.3 56.6 19.4 MI (g/10min) 7.3 4.7 10.1 7.4 7.9 6.0 Vicat (℃) 106.6 106.3 106.2 106.5 106.4 107.3 HDT (℃) 94.1 93.2 93.3 93.8 93.2 94.6 Tensile strength (kgf/cm ² ) 493 480 485 489 486 473 Tensile Elongation (%) 23.1 22.2 19.8 19.4 21.5 12.6 Flexural strength (kgf/cm ² ) 833 800 812 818 823 780 Flexural modulus (MPa) 23,882 24,212 24,021 24,011 23,985 25,155 Impact strength (1/4")
(kg·cm/cm) 12.4 13.6 11.7 12.6 12.8 9.8 Impact strength (1/8")
(kg·cm/cm) 18.0 18.3 17.2 17.8 18.1 12.4

As shown in Table 2, it was confirmed that the thiol-free ABS resins of Examples 1 to 3 of the present invention have improved odor, reduced residual monomers and TVOC, and excellent both thermal stability and mechanical properties.

On the other hand, in Comparative Example 1 using TDDM other than the molecular weight modifier AMSD of the present invention, it was found that the odor was not very good, and thus it was difficult to apply to automobile interior materials, and the mechanical properties were also deteriorated compared to Examples.

In addition, when using a thiol-based molecular weight modifier TDDM and simultaneously applying a foamed bead (Comparative Example 2), it was confirmed that the odor was improved, but mechanical properties were significantly reduced.

In addition, when the thiol-based molecular weight modifier was used together with the molecular weight modifier used in the Examples of the present invention (Comparative Example 3), it was confirmed that the odor was not improved and residual monomer was present in excess.

Furthermore, although not described in Table 2, when the resin was prepared in the same manner as in the Example of the present invention, except that the molecular weight modifier AMSD of the present invention was used in an amount of less than 0.01 part by weight, the melt index was extremely reduced to 2 g/10min. Due to poor flowability, the workability was greatly reduced.

In addition, when the resin was prepared in the same manner as in the embodiment of the present invention, except that the molecular weight modifier AMSD of the present invention was used in excess of 1 part by weight, there was a problem that the melting index of the heat-resistant ABS resin was exceeded.

Claims (11)

Aromatic vinyl compound 20 to 70 wt%, vinyl cyan compound 5 to 35 wt%, maleimide compound 1 to 20 wt%, conjugated diene polymer 1 to 20 wt%, aromatic rubbery copolymer 1 to 30 wt%, and reaction solvent 10 It comprises a step of polymerizing a polymerization solution of a mixture of 0.01 to 1 part by weight of the initiator and 0.01 to 1 part by weight of the α-alkylstyrene multimer as a molecular weight modifier, 100 parts by weight of the mixed solution containing 40% by weight,
The polymerization step is characterized in that the thiol-free (Thiol-free)
Method of manufacturing heat-resistant ABS resin.
According to claim 1,
The maleimide compound is N-phenylmaleimide, maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-isopropyl maleimide, N-butylmaleimide, N-iso Butylmaleimide, Nt-butylmaleimide, N-cyclo hexylmaleimide, N-chlorophenylmaleimide, N-methylphenylmaleimide, N-bromo phenyl maleimide, N-naphthylmaleimide, N-lauryl Maleimide, N-hydroxy phenylmaleimide, N-methoxyphenylmaleimide, N-carboxyphenylmaleimide, N-nitro phenylmaleimide, and N-benzylmaleimide.
Method of manufacturing heat-resistant ABS resin.
According to claim 1,
The aromatic rubber polymer is a copolymer of a conjugated diene compound and an aromatic vinyl compound.
Method of manufacturing heat-resistant ABS resin.
According to claim 1,
It characterized in that the weight ratio of the conjugated diene polymer and the aromatic rubber copolymer is 1:1 to 1:7
Method of manufacturing heat-resistant ABS resin.
According to claim 1,
The reaction solvent is characterized in that at least one selected from the group consisting of ethylbenzene, toluene, methyl ethyl ketone and xylene
Method of manufacturing heat-resistant ABS resin.
According to claim 1,
The α-alkylstyrene multimer is characterized by being at least one multimer selected from the group consisting of α-methylstyrene and α-ethylstyrene.
Method of manufacturing heat-resistant ABS resin.
The method of claim 6,
The multimer is characterized in that it is at least one member selected from the group consisting of dimers, trimers and tetramers.
Method of manufacturing heat-resistant ABS resin.
According to claim 1,
The method of manufacturing the heat-resistant ABS resin comprises the steps of first polymerizing the polymerization solution in a reactor at 90 to 110°C; After the first polymerization step, the second polymerization in a reactor of 120 to 140 ℃; And after the second polymerization step of the third polymerization in a reactor of 145 to 170 ℃; characterized in that it comprises a
Method of manufacturing heat-resistant ABS resin.
According to claim 1,
The method of manufacturing the heat-resistant ABS resin is characterized in that it comprises removing the unreacted monomers and solvents under a high temperature vacuum in a devolatilization tank after the third polymerization step and then extruding them to produce pellets.
Method of manufacturing heat-resistant ABS resin.
According to claim 1,
The polymerization step is characterized in that the foamed beads (Bead) free
Method of manufacturing heat-resistant ABS resin.
According to claim 1,
The heat-resistant ABS resin is characterized in that the melt index (220 ℃, 10 kg) measured in accordance with ASTM D1238 is 1 to 20 g/10min
Method of manufacturing heat-resistant ABS resin.