KR20150034979A - Heat-resistant san resin composition, heat-resistant san resin, method for preparing the resin and heat-resistant abs resin composition containing the same - Google Patents

Abstract

The present invention relates to a heat-resistant SAN resin composition, a heat-resistant SAN resin, a manufacturing method thereof and a heat-resistant ABS resin composition including the same. In the present invention, provided are a SAN resin composition with good heat resistance and productivity, which contributes to improvement of heat resistance when being applied to the ABS resin and thus can be used in products which need a high heat resistance, a heat-resistant SAN resin, a manufacturing method thereof and a heat-resistant ABS resin composition including the same.

Description

TECHNICAL FIELD [0001] The present invention relates to a heat-resistant SAN resin composition, a heat-resistant SAN resin, a process for producing the same, and a heat-resistant ABS resin composition containing the same. BACKGROUND ART [0002]

The present invention relates to a heat-resistant SAN resin composition, a heat-resistant SAN resin, a method for producing the same, and a heat-resistant ABS resin composition containing the same. More particularly, the present invention relates to a heat- Heat-resistant SAN resin, a process for producing the same, and a heat-resistant ABS resin composition containing the same.

Styrene-acrylonitrile (SAN) resin, which is a copolymer resin made by polymerizing styrene (SM) and acrylonitrile (AN), is excellent in transparency, chemical resistance and rigidity and is used in electric and electronic, household, Widely used.

In addition, the SAN resin has excellent processability and impact resistance, but the SAN resin has a thermal deformation temperature of 90 to 100 占 폚, has a low heat resistance, and thus has limited application to products requiring high heat resistance.

In order to impart high heat resistance, a method of introducing α-methylstyrene (AMS) monomer into the SAN resin is generally used. However, the lower depolymerization temperature of AMS and the higher polymerization temperature cause more oligomer production, Therefore, unlike general SAN polymerization, it is necessary to keep the polymerization temperature low, thereby causing a problem of lowering the polymerization rate.

In order to solve such a problem, a method of lengthening the reaction residence time or introducing an initiator in an excessive amount is used. However, problems such as a decrease in productivity, a poor color of the final product, .

In order to solve the problems of the prior art as described above, the present invention relates to a SAN resin composition, a heat-resistant SAN resin, a method for producing the same, and a heat-resistant ABS resin composition containing the same, which are excellent in heat resistance and productivity and contribute to improvement in heat resistance when applied to ABS resins And to provide the above objects.

(Ii) 25 to 35 wt% of an acrylonitrile monomer; and (iii) a styrene-based monomer (a) from 0 to 10 wt% of a monomer mixture, excluding 90 wt% of a-methylstyrene monomer; (b) 2 to 10% by weight of an organic solvent; (c) an organic peroxide having a lipid-soluble functional group and having a half-life of 1 hour to 100 to 120 ° C; And (d) an organic peroxide having a lipid-soluble functional group and a half-life of 1 hour at 70 to 90 ° C,

Wherein the organic peroxide (c) is 0.01 to 0.1 parts by weight and the organic peroxide (d) is 0.05 to 0.2 parts by weight based on 100 parts by weight of the total of the monomer mixture and the organic solvent. .

(Ii) 25 to 35 wt% of an acrylonitrile monomer; and (iii) a styrene-based monomer (excluding a-methylstyrene monomer). ) 0 to 10 wt% of a monomer mixture 90 to 98 wt%; (b) 2 to 10% by weight of an organic solvent; (C) 0.01 to 0.1 parts by weight of an organic peroxide having a fat-soluble functional group and a half-life of 1 hour to 100 to 120 ° C, based on 100 parts by weight of the monomer mixture (a) and the organic solvent; And (d) 0.05 to 0.2 parts by weight of an organic peroxide having a fat-soluble functional group and a half-life of 1 hour at 70 to 90 ° C, and heating at 80 to 100 ° C for 3 to 5 hours and at 100 to 120 ° C for 1 to 3 hours And a step of polymerizing the resin.

The present invention also provides a process for producing a styrene-based copolymer, which comprises the steps of obtaining 60 to 75 wt% of an alpha -methylstyrene monomer, 25 to 35 wt% of an acrylonitrile monomer, and 0 to 10 wt.%, a weight average molecular weight of 90,000 to 130,000 g / mol, and a glass transition temperature (Tg) of 122 to 130 DEG C.

Further, the present invention includes an ABS resin and a SAN resin,

The SAN resin comprises 60 to 75 wt% of an alpha -methylstyrene monomer, 25 to 35 wt% of an acrylonitrile monomer, and 0 to 10 wt% of a styrene monomer (excluding an alpha -methylstyrene monomer) (90 to 130,000 g / mol) and a glass transition temperature (Tg) of 122 to 130 ° C.

According to the present invention, it is possible to provide a SAN resin composition, a heat-resistant SAN resin, a method for producing the SAN resin composition, and a heat-resistant ABS resin composition containing the same, which are excellent in heat resistance and productivity and can contribute to improvement in heat resistance when applied to ABS resins.

Hereinafter, the present invention will be described in detail.

The heat-resistant SAN resin composition of the present invention is a heat-resistant SAN resin composition comprising (a) 60 to 75 wt% of an α-methylstyrene monomer, 25 to 35 wt% of an acrylonitrile monomer, and (iii) From 0 to 10 wt% of a monomer mixture (excluding styrene monomer) from 90 to 98 wt%; (b) 2 to 10% by weight of an organic solvent; (c) an organic peroxide having a lipid-soluble functional group and having a half-life of 1 hour to 100 to 120 ° C; And (d) an organic peroxide having a lipid-soluble functional group and a half-life of 1 hour at 70 to 90 ° C,

The organic peroxide (c) is 0.01 to 0.1 parts by weight based on 100 parts by weight of the monomer mixture and the organic solvent, and the organic peroxide (d) is 0.05 to 0.2 parts by weight.

As used herein, the term " 1 hour half-life "refers to the temperature at which the active oxygen of the initiator is halved in 1 hour, unless otherwise specified.

The lipid-soluble functional group contains, for example, from 1 to 4 functional groups and can act as an initiator and simultaneously fulfills the productivity and heat resistance of the SAN resin within the reaction conditions.

The functional group is, for example, a peroxide group, and in this case, productivity and SAN resin heat resistance are excellent.

Specifically, the organic peroxide having (c) a fat-soluble functional group and a half-life of 1 hour at 100 to 120 ° C is 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, Butyl peroxyisopropyl monocarbonate, and butyl peroxyisopropyl monocarbonate.

The organic peroxide having a fat-soluble functional group (d) and a half-life of 1 hour at 70 to 90 ° C is lauroyl peroxide, 2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) -Butylperoxy-2-ethylhexanoate. ≪ / RTI >

The content of the (c) organic peroxide having a fat-soluble functional group and a half-life of 1 hour at 100 to 120 ° C is 0.01 to 0.1 parts by weight or 0.04 to 0.06 parts by weight, for example, and the strength and productivity It has excellent effect.

The content of the organic peroxide having (d) the fat-soluble functional group and a half-life of 1 hour at 70 to 90 ° C is, for example, 0.05 to 0.2 parts by weight, or 0.1 to 0.12 parts by weight, and the strength and productivity It has excellent effect.

Examples of the acrylonitrile-based monomer include acrylonitrile, methacrylonitrile, and ethacrylonitrile.

Examples of the styrenic monomer (excluding the? -Methylstyrene monomer) include styrene, p-bromostyrene, p-methylstyrene, p-chlorostyrene, Bromostyrene, and the like.

The content of? -Methylstyrene is, for example, from 65 to 75% by weight or from 68 to 71% by weight. Within this range, the heat resistance is excellent and the conversion does not decrease.

The content of the acrylonitrile monomer is, for example, from 25 to 32% by weight, or from 28 to 31% by weight. Within this range, there is an effect of excellent polymerization conversions, strength, heat resistance and resistance to environmental stress cracking.

The content of the styrene-based monomer (excluding the? -Methylstyrene monomer) is, for example, from 0 to 10% by weight, or from 0.1 to 5% by weight. Within this range, an appropriate polymerization rate is maintained and an excellent heat resistance is obtained.

A method for producing a heat-resistant SAN resin using the above-described heat-resistant SAN resin composition can be carried out, for example, in the following manner:

(ii) acrylonitrile monomer, and (iii) 0 to 10 wt% of styrene monomer (excluding? -methylstyrene monomer), based on 100 parts by weight of (a) % To 90% by weight of the monomer mixture; (b) 2 to 10% by weight of an organic solvent; (C) 0.01 to 0.1 parts by weight of an organic peroxide having a fat-soluble functional group and a half-life of 1 hour to 100 to 120 ° C, based on 100 parts by weight of the monomer mixture (a) and the organic solvent; And (d) 0.05 to 0.2 parts by weight of an organic peroxide having a fat-soluble functional group and a half-life of 1 hour at 70 to 90 ° C, and heating at 80 to 100 ° C for 3 to 5 hours and at 100 to 120 ° C for 1 to 3 hours .

The organic solvent may be added in an amount of from 2 to 10% by weight, from 2 to 8% by weight, or from 4 to 6% by weight, and the viscosity of the organic solvent may be controlled within the above range. The hydrocarbon solvent is not particularly limited when it is a solvent that can be used when the SAN resin is produced by bulk polymerization.

The polymerization may be, for example, bulk continuous polymerization. Specifically, the polymerization is carried out at 85 to 95 ° C, or 88 to 92 ° C, and then the polymerization is carried out at 105 to 115 ° C or 108 to 112 ° C, respectively, which can provide excellent polymerization conversion and heat resistance.

The polymerization has a polymerization conversion rate of 50% or more, or 55% or more. Within this range, the process is easy and the productivity is excellent.

The method of manufacturing the heat-resistant SAN resin according to the present invention may include, for example, volatilizing and removing unreacted monomers and solvent at 30 Torr or less, or 10 to 30 Torr after the polymerization. In this case, have.

The step of volatilizing and removing the unreacted monomer and the solvent is performed at 200 to 250 ° C or 210 to 230 ° C, for example.

The heat-resistant SAN resin obtained according to the above-mentioned method is, for example, 60 to 75 wt% of an alpha -methylstyrene monomer, 25 to 35 wt% of an acrylonitrile monomer, and 0 to 10 wt% of a styrenic monomer (excluding an alpha -methylstyrene monomer) wt%, a weight average molecular weight of 90,000 to 130,000 g / mol, and a glass transition temperature (Tg) of 122 to 130 ° C.

The weight average molecular weight of the SAN resin is, for example, 100,000 to 120,000 g / mol, or 105,000 to 117,000 g / mol, and the chemical resistance and strength are excellent in this range.

The SAN resin has a glass transition temperature (Tg) of 123 占 폚 to 130 占 폚 or 125 占 폚 to 130 占 폚, for example.

Further, the heat-resistant ABS resin composition comprising the heat-resistant SAN resin and the ABS resin can be provided.

The heat-resistant ABS resin composition may comprise 10 to 40% by weight of an ABS resin and 60 to 90% by weight of a heat-resistant SAN resin.

The ABS resin is not particularly limited when it is a copolymer comprising an acrylonitrile monomer, a conjugated diene compound and an aromatic vinyl compound.

The ABS resin may be, for example, a graft copolymer obtained by graft-polymerizing an acrylonitrile-based monomer and an aromatic vinyl compound in a conjugated diene rubber.

The heat resistant ABS resin composition may further include an antioxidant, for example.

The antioxidant may be, for example, a hindered phenol-based antioxidant, a phosphorus-based antioxidant or a mixture thereof, and in this case, it has an excellent weather resistance and heat resistance.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention within the scope and spirit of the following claims, Such variations and modifications are intended to be within the scope of the appended claims.

[Example]

Example  One

<Heat resistance SAN  From the resin composition, SAN  Preparation of Resin>

As shown in the following Table 1, 95 parts by weight of a monomer mixture of 70% by weight of? -Methylstyrene (AMS) and 30% by weight of acrylonitrile (AN) and 5 parts by weight of toluene were mixed as Example 1 to prepare a mixed solution Respectively.

(C) 1, 1-bis (t-butylperoxy) -3,3,5-trimethylphenol as an organic peroxide having a fat-soluble functional group and a half-life of 1 hour at 100 to 120 ° C, 0.05 part by weight of cyclohexane, and (d) 0.1 part by weight of lauroyl peroxide as a peroxide having a fat-soluble functional group and having a half-life of 70 to 90 DEG C for 1 hour, to prepare a polymerization solution. series The reactor was continuously charged and bulk-polymerized for 4 hours, and then a series of 110 ° C And the mixture was continuously subjected to bulk polymerization for 2 hours. Unreacted monomers and solvent were removed at 230 ° C in a volatilizer at a vacuum degree of 30 Torr, and pelletized SAN resin was prepared through a die and a pelletizer .

Example  2 to 4, Comparative Example  1 to 3

The same steps as in Example 1 were repeated except that the component content and the polymerization temperature in Example 1 were changed as shown in the following Table 1 to prepare a SAN resin in a pellet state.

The properties of the physical specimens prepared in Examples 1 to 4 and Comparative Examples 1 to 3 were measured by the following methods, and the results are shown in Table 1 below.

[ Test Example ]

Glass Transition Temperature ( Tg ): Measured using DSC of TA Corporation.

Weight average molecular weight ( Mw ): Measured by GPC (Waters Breeze) relative to a standard PS (Standard polystyrene) sample.

division Example Comparative Example One 2 3 4 One 2 3 polymerization
solution
Furtherance (a) AMS (wt%) 70 70 75 70 70 70 75 AN (wt%) 30 30 25 30 30 30 25 (b) Toluene (parts by weight) 5 5 5 5 5 5 5 (c) peroxide (parts by weight) 0.05 0.05 0.05 0.04 - 0.15 0.1 (d) Peroxide (parts by weight) 0.1 0.1 0.1 0.12 0.15 - 0.05 Reaction temperature (캜) (RE1 / RE2) 90/110 90/110 90/110 90/110 90 110 110 Heat resistance
SAN
Properties Conversion Rate (%) 54 58 56 57 41 59 53 Mw (g / mol) 113,0000 117,0000 105,0000 115,0000 125,0000 101,0000 96,0000 Tg (占 폚) 123.3 124 125.2 123 125 120 121.2

As shown in Table 1, according to Examples 1 to 4 of the present invention, excellent conversion rates, Mw, and Tg were confirmed.

On the other hand, according to Comparative Example 1 in which the peroxide (c) was not added, although the Mw and the Tg were all excellent, the conversion was less than 50%, which was not preferable from the productivity standpoint. According to Comparative Example 2 applied to the range, the conversion ratio, Mw, was improved but the Tg was insufficient. In Comparative Example 3 where the peroxide (c, d) was used but the temperature range was not suitable, the Mw was remarkably reduced and the Tg was also low The results were confirmed.

<Add Experimental Example  1 to 7>

< ABS  Resin (powder)>

LG ABS DP (styrene: acrylonitrile = 75: 25, butadiene content = 60%) was used.

<Heat resistance ABS  Preparation of resin composition &gt;

To 73 parts by weight of the heat-resistant SAN resin prepared in each of Examples 1 to 4 and Comparative Examples 1 to 3, 27 parts by weight of the ABS resin (powder) was mixed and 0.2 part by weight of the antioxidant Iganox 1076 was added. (28Φ) to prepare a heat-resistant ABS resin composition in the form of pellets, and the pellets were injected to prepare a physical specimen.

[ Test Example ]

The properties of the physical specimens prepared in Examples 1 to 4 and Comparative Examples 1 to 3 were measured by the following methods, and the results are shown in Table 2 below.

Impact strength (1/4 ", kg / cm): measured according to ASTM D256 method (Izod Impact).

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

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

* ESCR (Environmental Stress Cracking Resistance, s) Time of cracking was measured by using a Zig of 1% strain and buried in a thinner in the specimen.

No. used Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Impact strength 18 17.5 15 17.5 20 14.3 13 Heat distortion temperature 101.7 102.4 103 101.6 102.8 95 96.5 Color (b) 15.7 15.6 15.1 15.7 17.5 15 14 ESCR 100 98 83 98 110 78 70

As shown in Table 2, the heat-resistant ABS resin compositions to which Examples 1 to 4 of the present invention were applied had the properties of the heat-resistant SAN resin composition in which the c) organic peroxide (corresponding to the high temperature initiator) However, as shown in Table 1, it was not good in terms of productivity such as conversion rate.

In addition, the heat-resistant ABS resin compositions to which Examples 1 to 4 of the present invention were applied exhibited remarkably improved heat resistance and strength in comparison with heat-resistant SAN resin compositions which did not use the organic peroxide (corresponding to the low-temperature initiator) .

In addition, the strength and heat resistance of the cured silicone resin composition of Comparative Example 3 were improved compared to the heat-resistant SAN resin composition of c) organic peroxide (corresponding to high temperature initiator) and d) organic peroxide (corresponding to low temperature initiator) .

In particular, it was confirmed that the heat-resistant ABS resin compositions (Examples 1 to 4) of the present invention were superior in heat resistance to the heat-resistant ABS resin compositions (Comparative Examples 2 and 3) to which the heat-resistant SAN resin having a low glass transition temperature was applied.

Claims (13)

(ii) acrylonitrile monomer, and (iii) 0 to 10 wt% of styrene monomer (excluding? -methylstyrene monomer), based on 100 parts by weight of (a) % To 90% by weight of the monomer mixture; (b) 2 to 10% by weight of an organic solvent; (c) an organic peroxide having a lipid-soluble functional group and having a half-life of 1 hour to 100 to 120 ° C; And (d) an organic peroxide having a lipid-soluble functional group and a half-life of 1 hour at 70 to 90 ° C,
Wherein the organic peroxide (c) is 0.01 to 0.1 parts by weight and the organic peroxide (d) is 0.05 to 0.2 parts by weight based on 100 parts by weight of the total of the monomer mixture and the organic solvent. . The method according to claim 1,
Wherein the fat-soluble functional group contains from 1 to 4 peroxide groups. The method according to claim 1,
The organic peroxide having a fat-soluble functional group (c) and a half-life of 1 hour at 100 to 120 ° C is 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (Tert-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, Oxy-isopropyl monocarbonate, and mixtures thereof. The method according to claim 1,
The organic peroxide having a (d) lipophilic functional group and a half-life of 1 hour at 70 to 90 ° C is lauroyl peroxide, 2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) Butyl peroxy-2-ethylhexanoate. (ii) acrylonitrile monomer, and (iii) 0 to 10 wt% of styrene monomer (excluding? -methylstyrene monomer), based on 100 parts by weight of (a) % To 90% by weight of the monomer mixture; (b) 2 to 10% by weight of an organic solvent; (C) 0.01 to 0.1 parts by weight of an organic peroxide having a fat-soluble functional group and a half-life of 1 hour to 100 to 120 ° C, based on 100 parts by weight of the monomer mixture (a) and the organic solvent; And (d) 0.05 to 0.2 parts by weight of an organic peroxide having a fat-soluble functional group and a half-life of 1 hour at 70 to 90 ° C, and heating at 80 to 100 ° C for 3 to 5 hours and at 100 to 120 ° C for 1 to 3 hours Wherein the heat-resistant SAN resin is a thermosetting resin. 6. The method of claim 5,
Wherein the polymerization has a polymerization conversion of 50 to 65%. 6. The method of claim 5,
Wherein the polymerization is bulk continuous polymerization. 6. The method of claim 5,
Wherein the heat-resistant SAN resin is produced by volatilizing and removing unreacted monomers and a solvent at 25 Torr or less after the polymerization. 9. The method of claim 8,
Wherein the step of volatilizing and removing the unreacted monomer and the solvent is carried out at 200 to 250 ° C at 30 torr and at a reduced pressure of 0 torr. 9. A process for the preparation of a polyurethane foam obtained by the process of any one of claims 5 to 9 and comprising 60 to 75 wt% of an alpha -methylstyrene monomer, 25 to 35 wt% of an acrylonitrile monomer, and a styrene- ) 0 to 10 wt%, a weight average molecular weight of 90,000 to 130,000 g / mol, and a glass transition temperature (Tg) of 122 to 130 DEG C. ABS resin and SAN resin,
Wherein the SAN resin comprises 60 to 75 wt% of an alpha -methylstyrene monomer, 25 to 35 wt% of an acrylonitrile monomer, and 0 to 10 wt% of a styrene monomer (excluding an alpha -methylstyrene monomer) Heat resistant ABS resin composition. 12. The method of claim 11,
Wherein the heat-resistant ABS resin composition comprises 10 to 40% by weight of an ABS resin and 60 to 90% by weight of a heat-resistant SAN resin. 12. The method of claim 11,
The heat-resistant ABS resin composition comprises a hindered phenol-based antioxidant, a phosphorus-based antioxidant, and a mixture thereof.