KR101738739B1 - Method for producing heat-resistant san resin and heat-resistant resin composition containing the same - Google Patents

Abstract

The present invention relates to a method for producing a heat-resistant SAN resin and a heat-resistant resin containing the same, and more particularly to a heat-resistant resin comprising 100 parts by weight of a monomer containing 60 to 85% by weight of alpha-methylstyrene and 15 to 40% by weight of a vinyl cyan monomer; And 0.01 to 0.2 parts by weight of a chain extender, wherein the weight average molecular weight is 85,000 to 120,000 g / mol, and a heat-resistant SAN resin and an ABS resin prepared by the above- Resistant resin composition.
According to the present invention, a heat-resistant SAN resin having a high molecular weight can be produced with improved productivity, and the heat-resistant resin containing the heat-resistant SAN resin and the ABS resin obtained above is excellent in environmental stress cracking resistance.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a heat-resistant SAN resin and a heat-

More particularly, the present invention relates to a method for producing a heat-resistant SAN resin, and more specifically, a heat-resistant SAN resin having a high molecular weight while improving productivity is produced, and the heat- ≪ / RTI >

The styrene-acrylonitrile (SAN) resin obtained by polymerizing styrene (SM), an aromatic hydrocarbon, and acrylonitrile (AN), an unsaturated nitrile, is excellent in transparency, chemical resistance and rigidity, However, since the heat distortion temperature is in the range of 100 to 105 캜, it is difficult to apply the heat resistance to a product requiring high heat resistance.

In order to improve the heat resistance of the SAN resin, alpha-methylstyrene (AMS) monomer is introduced. When the polymerization temperature is increased due to the depolymerization temperature at which AMS is low, oligomer production increases and heat resistance is lowered. Lower. However, if the polymerization temperature is lowered, the polymerization rate is lowered. In order to solve this problem, if the reaction residence time is prolonged or the initiator is used in excess, the productivity lowers, the color of the final product is poor, the polymerization conversion rate lowers, There is a problem that a lot of defects are generated when the product is molded.

Korea Patent Publication No. 2010-0077568 (Published on July 8, 2010)

In order to solve the problems of the prior art as described above, the present invention aims to provide a method for producing a heat-resistant SAN resin having a high molecular weight while improving productivity.

It is another object of the present invention to provide a heat-resistant resin composition comprising a heat-resistant SAN resin and an ABS resin produced by the above production method.

These and other objects of the present disclosure can be achieved by all of the present invention described below.

In order to achieve the above object, the present invention relates to a composition comprising 100 parts by weight of a monomer comprising 60 to 75% by weight of alpha-methylstyrene and 25 to 40% by weight of a vinyl cyan monomer; And 0.01 to 0.15 parts by weight of a chain extender, wherein the weight average molecular weight is 85,000 to 120,000 g / mol, and a process for producing the same.

Further, the present invention provides a heat-resistant resin composition comprising 60 to 80% by weight of a heat-resistant SAN resin produced by the above-described production method and 20 to 40% by weight of an ABS resin.

As described above, according to the present invention, there is provided a method of manufacturing a heat-resistant SAN resin having a high molecular weight, while improving productivity, and a heat-resistant resin composition comprising a heat-resistant SAN resin and an ABS resin produced by the above- The effect is excellent.

Hereinafter, the present invention will be described in detail.

The present disclosure includes 100 parts by weight of a monomer comprising 60 to 85% by weight of alpha-methylstyrene and 15 to 40% by weight of a vinyl cyan monomer; And 0.01 to 0.2 parts by weight of a chain extender, and having a weight average molecular weight of 85,000 to 120,000 g / mol, the present invention has the effect of producing a resin having a high molecular weight while improving productivity .

As another example, the alpha-methylstyrene content is 63 to 80% by weight or 67 to 75% by weight, and the heat resistance is excellent within the above range.

The vinyl cyan monomer may be at least one selected from the group consisting of acrylonitrile, methacrylonitrile, and ethacrylonitrile.

As another example, the chain extender is 0.02 to 0.17 part by weight or 0.03 to 0.13 part by weight, and the weight average molecular weight is increased while the production amount is increased within the above range.

The chain extender may be selected from the group consisting of divinylbenzene, trivinylbenzene, trialkylisocyanurate, diethylene glycol dimethacrylate, diethylene glycol divinyl ether, and triethylpropane triacrylate. Or more, and is preferably divinylbenzene.

As another example, the weight-average molecular weight of the heat-resistant SAN resin is 88,000 to 117,000 g / mol or 91,000 to 113,000 g / mol, and the impact strength and heat distortion temperature are elevated within the above range and the workability is excellent.

The polymerization may include at least one selected from the group consisting of toluene, ethylbenzene, xylene, methyl ethyl ketone and xylene as a reaction solvent, and preferably toluene.

The reaction solvent is used in an amount of 0 to 10 parts by weight, 1 to 8 parts by weight, or 2 to 7 parts by weight based on 100 parts by weight of the monomer, and the effect of dissolving the monomer within the above range is excellent.

The polymerization may include, for example, 0.2 to 0.3 parts by weight, 0.22 to 0.28 parts by weight, or 0.24 to 0.26 parts by weight of the initiator, and the molecular weight is increased within the above range.

Examples of the initiator include 1,1-bis (t-butylperoxy) cyclohexane, t-butylperoxy-2-ethylhexanoate, benzoyl peroxide benzoyl peroxide, t-butylperoxyisobutyrate, 2,2-bis (4,4-di-t-butylperoxycyclohexane) di-t-butylperoxy cyclohexane) propane, t-hexyl peroxy isopropyl monocarbonate, t-butylperoxylaurate, t-butyl peroxyisopropyl monocarbonate t-butyl peroxy isopropyl monocarbonate, t-butyl peroxy 2-ethylhexyl monocarbonate, t-hexyl peroxybenzoate, t-butyl peroxyacetate, t -butyl peroxyacetate, 2,2-bis (t-butyl peroxy) butane, t-butyl peroxybenzoate, Oxa Dicumylperoxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, t-butyl cumyl peroxide May be at least one selected from the group consisting of t-butyl cumyl peroxide, di-t-butyl peroxide, and di-t-amyl peroxide. have.

The polymerization may be, for example, bulk polymerization, preferably continuous bulk polymerization.

The polymerization is effected at 105 to 120 deg. C, 107 to 115 deg. C, or 109 to 113 deg. C, for example. Within the above range, polymerization conversion rises and the production amount increases when the heat resistant SAN resin is produced.

The present invention provides a heat-resistant resin composition comprising 60 to 80% by weight of a heat-resistant SAN resin produced by the above-described production method and 20 to 40% by weight of an ABS resin.

The ABS resin is, for example, a vinyl cyan compound-conjugated diene compound-vinyl aromatic compound copolymer.

The vinyl cyan compound-conjugated diene compound-vinyl aromatic compound copolymer includes, for example, 30 to 70% by weight of a conjugated diene compound, 5 to 40% by weight of a vinyl cyan compound, and 20 to 65% by weight of a vinyl aromatic compound.

Examples of the conjugated diene compound include one selected from the group consisting of 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-pentadiene and isoprene Or more.

The vinyl aromatic compound is at least one selected from the group consisting of styrene,? -Methylstyrene, o-ethylstyrene, p-ethylstyrene, and vinyltoluene.

The vinyl cyanide compound is at least one selected from the group consisting of acrylonitrile, methacrylonitrile, and ethacrylonitrile.

The heat-resistant resin composition may further include, for example, a hindered phenol-based antioxidant, a phosphorus-based antioxidant, or both.

The heat resistant resin composition is ESCR (Environmental Stress Cracking Resistance) which measures the time during which a crack is generated by using a zig of 1% strain and a thinner is buried in the center of the specimen. , 40 seconds or more, 45 seconds or more, or 40 to 69 seconds, and the environmental stress cracking resistance is excellent within the above range.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the present invention. Such variations and modifications are intended to be within the scope of the appended claims.

[Example]

Example 1

Manufacture of heat-resistant SAN resin

100 parts by weight of a monomer mixture composed of 71% by weight of alpha-methylstyrene and 29% by weight of acrylonitrile was mixed with 0.2 part by weight of 1,1-bis (t-butylperoxy) cyclohexane as an initiator, And 0.05 part by weight of vinylbenzene were added thereto to prepare a polymerization solution. The polymerization solution was continuously fed into a series of reactors at a feeding rate of 9 Kg / hr at 109 캜 by continuous polymerization to polymerize the mixture at a temperature of 200 The unreacted monomers and the solvent were removed from the volatilization vessel at 250 DEG C and a vacuum degree of 21.4 Torr, and the pelletized resin was prepared and the physical properties thereof were measured.

Examples 2 to 8 and Comparative Examples 1 to 6

A pelletized resin was prepared in the same manner as in Example 1, except that the feed amount, polymerization temperature, feed rate and vacuum degree of the following Table 1 were used in Example 1.

Examples 9 to 16 and Comparative Examples 7 to 12

Preparation of heat-resistant resin composition

73% by weight of the heat-resistant SAN resin prepared in Examples 1 to 8 and Comparative Examples 1 to 6 and 15% by weight of ABS powder (60% by weight butadiene content, 30% by weight styrene content and 10% by weight acrylonitrile content, ), And 0.2 part by weight of Iganox 1076 as an antioxidant was added thereto. The resulting mixture was poured into an extruder (28Φ) at 240 DEG C to prepare a resin in the form of pellets, followed by injection and measurement of physical properties.

 [Test Example]

The properties of the heat-resistant SAN resin prepared in Examples 1 to 8 and Comparative Examples 1 to 6 and the heat-resistant resin compositions prepared in Examples 9 to 16 and Comparative Examples 7 to 12 were measured by the following methods, Are shown in Tables 2 to 3 below.

Glass Transition Temperature (Tg, ° C): Measured using a Pyris 6 DSC from Perkin Elmer.

* Weight average molecular weight (Mw, g / mol): measured relative to standard PS (Standard polystyrene) samples via GPC (Waters Breeze).

Impact strength (1/4 ", kgf · cm / cm): Measured according to ASTM D256 method (Izod Impact strength).

Heat distortion temperature (HDT, 占 폚): Measured according to ASTM D648.

Color (Color b): The yellow index of the sample was measured using a Hunter Lab colorimeter.

Residual Oligomer Content (ppm): Analyzed by Gel Chromatograph.

* ESCR: The time of occurrence of the crack was measured by using a zig of 1% strain to thinner the specimen.

division AMS
(weight%) AN
(weight%) Initiator
(Parts by weight) Chain extender
(Parts by weight) Polymerization temperature
(° C) Feed rate (kg / hr) Vacuum degree
(torr) Example 1 71 29 0.2 0.05 109 9 21.4 Example 2 71 29 0.25 0.05 107 10 23.5 Example 3 71 29 0.25 0.05 107 9 19.6 Example 4 71 29 0.25 0.05 107 8 19.8 Example 5 71 29 0.3 0.1 107 8 23.3 Example 6 71 29 0.3 0.1 107 10 17.2 Example 7 71 29 0.25 0.1 107 8 19.5 Example 8 71 29 0.25 0.1 107 10 20.5 Comparative Example 1 71 29 0.25 0 105 8 14.7 Comparative Example 2 71 29 0.25 0 107 8 19.8 Comparative Example 3 71 29 0.25 0 109 8 20.5 Comparative Example 4 71 29 0.2 0 105 8 20.4 Comparative Example 5 71 29 0.2 0 107 9 20.5 Comparative Example 6 71 29 0.2 0 109 9 21.5

division Heat Resistance SAN resin properties polymerization
Conversion Rate (%) output
(Kg / hr) Tg (占 폚) Mw
(g / mol) Residual monomer content
(ppm) Example 1 57.44 5.17 125.0 93,937 1,433 Example 2 56.50 5.35 124.9 88,689 1,691 Example 3 56.78 5.11 125.6 91,812 1,313 Example 4 65.13 5.21 125.8 97,023 1,015 Example 5 57.13 5.17 125.3 93,612 1,233 Example 6 62.30 6.13 124.2 104,401 1,138 Example 7 72.63 5.91 126.4 112,782 1,139 Example 8 60.60 6.06 125.9 108,504 1,026 Comparative Example 1 57.63 4.81 126.3 83,144 1,064 Comparative Example 2 65.75 4.96 125.3 83,980 1,131 Comparative Example 3 62.88 5.03 125.7 82,338 1,052 Comparative Example 4 61.50 4.92 125.9 81,650 1,276 Comparative Example 5 61.78 5.16 125 80,076 1,394 Comparative Example 6 57.78 5.2 125.2 79,809 1,423

division Heat Resistant Properties Impact Strength (1/4 ") Heat deformation temperature (캜) color
(color b) ESCR
(sec.) Example 9 10.9 101.8 17.4 45 Example 10 11.0 101.9 17.7 47 Example 11 11.3 102.3 16.8 47 Example 12 12.1 102.6 17.9 46 Example 13 10.4 101.7 18.1 40 Example 14 11.2 102.4 17.1 47 Example 15 11.7 102.5 15.8 69 Example 16 11.4 102.5 17.5 69 Comparative Example 7 11.8 102.9 15.8 28 Comparative Example 8 11.3 102.5 17.3 33 Comparative Example 9 11.6 103.2 17.7 36 Comparative Example 10 12.7 101.8 16.2 34 Comparative Example 11 11.5 101.4 17.4 30 Comparative Example 12 11.8 101.8 17.0 34

As shown in Tables 1 to 3, the heat-resistant SAN resins of Examples 1 to 8 produced by the production method of the present invention had a decrease in the residual monomer content while the polymerization conversion rate and the production amount were improved, and the glass transition temperature and weight average The effect of increasing the molecular weight was confirmed.

On the other hand, Comparative Examples 1 to 6, which did not use a chain extender, had a lowered weight average molecular weight and an increased residual monomer content.

EXAMPLES 9 to 16, which are heat-resistant resins made of heat-resistant SAN and ABS resins produced by the manufacturing method of the present invention, exhibited better color than Comparative Examples 7 to 12, particularly ESCR (environmental stress cracking resistance) 12, respectively.

Claims (12)

100 parts by weight of a monomer comprising 60 to 85% by weight of alpha-methylstyrene and 15 to 40% by weight of a vinyl cyan monomer; And 0.01 to 0.20 parts by weight of a chain extender selected from the group consisting of divinylbenzene and trivinylbenzene, and having a weight average molecular weight of 85,000 to 120,000 g / mol. Gt;
The method according to claim 1,
Wherein the polymerization is bulk polymerization.
The method according to claim 1,
Wherein said polymerization further comprises at least one selected from the group consisting of toluene, ethylbenzene, xylene, methyl ethyl ketone and xylene as a reaction solvent.
delete The method according to claim 1,
Wherein the polymerization comprises 0.2 to 0.3 parts by weight of an initiator.
6. The method of claim 5,
The initiator may be selected from the group consisting of 1,1-bis (t-butylperoxy) cyclohexane, t-butylperoxy-2-ethylhexanoate, benzoyl peroxide, t-butylperoxyisobutyrate, 2,2-bis (4,4-di-t-butylperoxycyclohexane) t-butylperoxy cyclohexane) propane, t-hexyl peroxy isopropyl monocarbonate, t-butylperoxylaurate, t-butylperoxyisopropyl monocarbonate (t butyl peroxy isopropyl monocarbonate, t-butyl peroxy 2-ethylhexyl monocarbonate, t-hexyl peroxybenzoate, t-butyl peroxide, peroxyacetate, 2,2-bis (t-butyl peroxy) butane, t-butyl peroxybenzoate, dicumyl peroxide dicum 2,5-dimethyl-2,5-bis (t-butyl peroxy) hexane, t-butyl cumyl peroxide t-butyl cumyl peroxide, di-t-butyl peroxide, and di-t-amyl peroxide. Of the heat-resistant SAN resin.
The method according to claim 1,
Wherein the polymerization is carried out at 105 to 120 占 폚.
The method according to claim 1,
Wherein the vinyl cyan monomer is at least one selected from the group consisting of acrylonitrile, methacrylonitrile, and ethacrylonitrile.
60 to 85% by weight of alpha-methylstyrene and 15 to 40% by weight of a vinyl cyan monomer, and 100 to 80% by weight of a monomer containing 50 to 80% by weight of a heat resistant SAN resin and 20 to 40% ; And 0.01 to 0.20 parts by weight of a chain extender selected from the group consisting of divinylbenzene and trivinylbenzene; and a weight average molecular weight of 85,000 to 120,000 g / mol.
10. The method of claim 9,
Wherein the heat-resistant resin composition further comprises a hindered phenol-based antioxidant.
10. The method of claim 9,
The heat-resistant resin composition has ESCR (Environmental Stress Cracking Resistance) of 40 to 69 seconds for measuring the time during which a thinner is buried in a specimen by using a 1% strain zig Resistant resin composition.
11. The method of claim 10,
Wherein the hindered phenol-based antioxidant is Iganox 1076.