KR100657739B1 - High Impact, High Gloss Weatherable Resin Composition And Method For Preparing The Same - Google Patents

Abstract

The present invention relates to a high gloss high impact weather resistant resin having a bimodal particle size distribution and a method for producing the same, wherein the method for preparing a weather resistant resin includes an ethylene propylene-based rubber polymer (EPR, EPDM), styrene and acryl in an organic solvent. A pre-graft polymerization step of graft polymerizing a predetermined amount of the mixed solution in which the nitrile monomer is dissolved using a polymerization initiator; And the present graft polymerization step of graft polymerization by further adding the remaining amount of the mixed solution to the pre-graft polymer. The weather resistant resin (AES resin) according to the present invention has excellent impact strength and gloss. have.

Thermoplastic, AES resin, bulk polymerization, bimodal, ethylene propylene rubber, EPR, EPDM

Description

Weathering resin having high impact and high gloss and its manufacturing method {High Impact, High Gloss Weatherable Resin Composition And Method For Preparing The Same}

The present invention relates to a weather resistant resin (AES resin) having excellent impact resistance and gloss, and a method for manufacturing the same, and more particularly, to a constant ethylene propylene rubber polymer (EPR, EPDM) and styrene-based and acrylonitrile-based monomers. The present invention relates to a weatherproof resin having excellent impact resistance and gloss, in which rubbery particles are formed in a bimodal form by producing a resin by performing a pre-graft reaction using a low temperature initiator to vary the graft ratio of a rubber phase, and a method of manufacturing the same.

Weather resistant resin is a thermoplastic resin having excellent moldability, weather resistance and impact resistance obtained by graft copolymerization of styrene-based and acrylonitrile-based monomers in the presence of a rubber polymer, and is suitable for various fields such as home appliances, office equipment parts, automobile parts, and outdoor facilities. Is being applied.

The mechanical properties and gloss of such weatherable resins are influenced by the size, composition and content of rubber particles in the resin. For example, when the rubber content in the resin is low or the rubber particles are small, tensile strength and gloss are improved, but elongation and impact strength are improved. There is a disadvantage in that it decreases, and if the rubber content in the resin is increased, the impact strength can be improved, but the gloss is deteriorated. However, since the requirement of the practical impact strength of the weather-resistant resin is high, the resin is manufactured by increasing the rubber content, and thus has the disadvantages of decreasing the gloss property and increasing the manufacturing cost. Therefore, in order to solve this problem, the rubber particles dispersed in the resin in the form of a bi-modal to reduce the average rubber particle size in favor of the gloss properties, while improving the efficiency of the rubber particles to produce a weather-resistant resin that improved the impact strength The results are usually not satisfactory.

On the other hand, patents related to weathering resin production are as follows.

U.S. Patent No. 4814388 discloses a method for preparing an AES resin by copolymerizing styrene and acrylonitrile by solution polymerization under ethylene propylene rubber having a specific polydispersity index (PDI) and toluene as a reaction medium to ethylene propylene diene rubber. In addition, US Patent No. 3984496 introduces a method for preparing AES resin by solution polymerization using various reaction media. Since the resin composition thus prepared has excellent mechanical properties but an excessive amount of solvent is used, since chain transfer to the solvent is inevitable, the molecular weight of the polymer is lower than that of other polymerization methods and the polymerization rate is also slow. In addition, the process of recovering the solvent is complicated and the production cost is higher than that of the conventional bulk polymerization.

In the preparation of AES resin, U.S. Pat.No. 5,067,78 has prepared a resin having excellent mechanical properties, colorability, appearance, and transparency by adding methyl methacrylate and hydrogenated butadiene to the polymerization solution. Three kinds of rubbers, such as butene copolymer or ethylene octene copolymer rubber, ethylene propylene rubber or ethylene propylene diene rubber, and hydrogenated butadiene, were used to prepare AES resin having excellent weather resistance, chemical resistance, and molding appearance, but still have mechanical properties and weather resistance. The balance with the appearance of molding is not satisfactory.

Patents related to bimodal resin production are as follows.

U.S. Patent Nos. 4,153,645 and 4,334,039 produce bimodal resins using various types of butadiene-based rubbers, but these resins have excellent mechanical properties but have disadvantages of reduced gloss.

European Patent Publication No. 048,389 has excellent impact strength and gloss with bimodal distribution particles by forming core-shell and salami forms using styrene butadiene block copolymer and butadiene-based rubber. Although the resin is manufactured, the manufacturing cost is high.

U.S. Patent No. 4,146,589 discloses a method for preparing bimodal styrene resin by bulk polymerization, the method of which is as follows. It consists of three reaction zones, two of which produce polymers with small rubbery particle sizes (0.5-1.0 μm) and large polymers (2-3 μm), respectively. Although a bimodal styrene-based resin was prepared by mixing a polymer and performing a polymerization reaction, the present invention has a disadvantage in that the process is complicated and the production cost is high because separate polymerization should be performed in three regions.

In U.S. Patent Nos. 5,491,195 and 4,254,236, the rubber phase of the rubber solution introduced into the first reactor becomes small particles and the rubber phase into the second reactor becomes large particles by dividing the rubber solution into the first reactor and the second reactor. To prepare a bimodal form of the polymer.

In US Patent Nos. 6,444,752 and 5,708,081, bimodal resins were prepared using butadiene-based rubbers having high viscosity solution viscosity and butadiene-based rubbers having low viscosity solution viscosity.

Star-branched rubber in U.S. Patent Nos. 5,191,023, 4,587,294 and 4,639,494, European Patent Nos. 277,687, and Japanese Patent Publication Nos. 59-232140 and 59-179611 The resins were prepared using US Pat. Nos. 6,441,090 and 6,350,813, Japanese Patent Publication Nos. 5-194,676, 5-247,149 and 6-166,729 and European Patent Publication No. 160,974. A bimodal resin was prepared using butadiene rubber and linear butadiene rubber.

However, there is a problem that all of the above is not balanced to a satisfactory level of gloss and mechanical properties, there was a limit to apply to the manufacture of weatherable resin.

In order to solve the above problems, the present invention uses a polymerization initiator to perform a predetermined graft reaction with a predetermined weight part of the styrene monomer and the acrylonitrile monomer by ethylene propylene rubber (EPR, EPDM) An object of the present invention is to provide a weather resistant resin (AES resin) having excellent impact strength and gloss produced by one continuous process, and a method of manufacturing the same.

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 provides a weather resistant resin comprising two kinds of ethylene propylene rubber particles having an average particle diameter of 0.3 to 0.8 탆 and 1 to 5 탆, respectively. to provide.

In addition, in the production method of weathering resin, A) 10 to 90% by weight relative to the total amount of ethylene propylene-based rubber polymers (EPR, EPRM) in the presence of a polymerization initiator, 5 to 30% by weight of the total amount of the styrene monomer, A pre-graft-polymerization step of performing graft polymerization of a mixed solution in which 5-30% by weight of the total amount of the acrylonitrile monomer is dissolved in 0-100% by weight of the total amount of the organic solvent; And B) the present graft polymerization step of graft polymerization by further adding a mixed solution consisting of the balance of the components to the graft polymer produced in step A). Provide a method.

The ethylene propylene-based rubber polymer is 5 to 15 parts by weight based on the total amount of monomers, the sum of the input amount of the styrene-based monomer and acrylonitrile-based monomer is added to 45 to 95 parts by weight based on the total amount, the styrene-based monomer and acrylonitrile-based The ratio of the monomer is 7: 3 to 9: 1 and the organic solvent may be administered 0 to 40 parts by weight based on the total amount.                     

The pre-graft polymerization step is carried out for 1 to 3 hours at a temperature of 50 to 100 ℃, this graft polymerization step is carried out in a reactor of a continuous polymerization apparatus of 100 to 180 ℃ temperature in which two or more stirred reactors are connected in series Can be.

In the graft polymerization step, 10 to 30 parts by weight of the styrene monomer and acrylonitrile monomer and 0.01 to 1.0 part by weight of the organic peroxide polymerization initiator may be further added based on the total amount of monomers.

The ethylene propylene rubber has a weight average molecular weight of 150,000 to 400,000, and is ethylene-propylene rubber (EPR) or ethylene-propylene-diene rubber (EPDM), of which ethylene The content is 45 to 80% by weight, the propylene content is 20 to 55%, the diene monomer is one or more selected from the group consisting of ethylene norbornene (ENB), dicyclopentadiene (DCPE) and hexadiene (HD) 0 to 13% by weight may be contained.

The styrene monomers include styrene, α-methyl styrene, o-methyl styrene, p-methyl styrene, m-methyl styrene, ethyl styrene, I-butyl styrene, t-butyl styrene and alkyl styrenes having equivalent properties; And o-bromo styrene, p-bromo styrene, m-bromo styrene, o-chloro styrene, p-chloro styrene, m-chloro styrene, and halogenated styrenes having equivalent properties. Can be.

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

The polymerization initiator is 3,5,5-trimethylhexanoyl peroxide, lauroyl peroxide, dibenzoyl peroxide and diacryl peroxides having the same properties; 1,1-dimethyl-3-hydroxybutyl peroxyneodecanoate, α-cumyl peroxyneodecanoate, α-cumyl peroxyneheptanoate, t-amyl peroxyneodecanoate t-amyl Peroxypivalate, t-butyl peroxypivalate, 2,5-dimethyl-2,5-di- (2-ethylhexanoyl peroxy) hexane, t-amyl peroxy-2-ethylhexanoate, t Butyl peroxy-2-ethylhexanoate and peroxyesters having the same properties; and at least one selected from the group consisting of:

The pre-graft polymerization step and the present graft polymerization step may be carried out by a polymerization method selected from the group consisting of continuous block polymerization, batch batch polymerization, solution polymerization and block-suspension polymerization.

Hereinafter, the present invention will be described in detail.

The present invention In a continuous process for producing a weather-resistant resin produced by a method comprising graft polymerization of a styrene monomer and an acrylonitrile monomer in the presence of an ethylene propylene rubber polymer, it has a bimodal particle distribution and has excellent impact strength and gloss. In order to produce a weather resistant resin, the weather resistant resin according to the present invention is excellent in impact resistance and gloss, and is suitable for molding an injection molded article having a thin thickness for a housing application.

5 to 15 parts by weight of the ethylene propylene-based rubber polymer used in the present invention, the styrene monomer and acrylonitrile monomer is preferably 85 to 95 parts by weight, the styrene monomer and acrylonitrile monomer 10 to 30 parts by weight of the present graft polymerization step may be added.

The organic solvent used in the present invention may be any of styrene monomer, acrylonitrile monomer, ethylene propylene rubber polymer, and an organic solvent capable of forming a solution with styrene and acrylonitrile copolymer. In particular, benzene, Ethyl benzene, toluene, xylene and the like are preferred.

Since the ethylene propylene rubber polymer, styrene monomer and acrylonitrile monomer can be liquefied only, the organic solvent may not be added, but 0 to 40 parts by weight is preferably added to adjust the viscosity of the solution.

The organic peroxide polymerization initiator used in the present invention is preferably added to 0.01 to 1.0 parts by weight based on the total amount.

Hereinafter, the manufacturing steps of the present invention will be described in detail.

I) 10 to 90% by weight of the total amount of the ethylene propylene rubber polymer is dissolved in 5 to 30% by weight of the total amount of the styrene monomer and acrylonitrile monomer and 0 to 100% by weight of the total amount of the organic solvent. Preparing a solution;

Ⅱ) mixing the polymerization initiator with the mixed solution of step I) and then performing pre-graft-polymerization at a reactor temperature of 50 to 100 ° C. for 1 to 3 hours;

Ⅲ) 10 to 90% by weight relative to the total amount of the ethylene propylene rubber polymer in the graft polymer of step II), 70 to 95% by weight relative to the total amount of the styrene monomer and acrylonitrile monomer and the total amount of the organic solvent Preparing a mixed solution of raw materials by adding 0 to 100% of the total amount;

Ⅳ) graft polymerization by mixing the mixed solution of step III) into a first reactor of a continuous polymerization apparatus in which two or more stirring reactors are connected in series while maintaining the temperature of the reactor at 100 to 180 ° C;

V) a polymerization step of continuously introducing two or more series-connected copolymers of step IV) into a reactor to obtain a final polymer;

Ⅵ) optionally adding 10 to 30 parts by weight of the styrene monomer and acrylonitrile monomer of step I) and 0.01 to 1.0 parts by weight of the organic peroxide polymerization initiator in the polymer production step of step III), IV) or V) Increasing the yield;

Iii) devolatilizing and pelletizing the final copolymer of step V) or VI);

To prepare a weather-resistant resin by a method comprising a.

In the above steps I) and III), the ethylene propylene rubber polymer has a 5% styrene solution viscosity of 30 to 200cp at 25 ° C. If the styrene solution viscosity is out of the above range, the impact strength and gloss are not balanced.

Styrene-based monomers to be introduced in the present invention are alkyl styrenes such as styrene, α-methyl styrene, o-methyl styrene, p-methyl styrene, m-methyl styrene, ethyl styrene, I-butyl styrene, t-butyl styrene; halogenated styrenes such as o-bromo styrene, p-bromo styrene, m-bromo styrene, o-chloro styrene, p-chloro styrene, m-chloro styrene; and the like. And styrene is preferably used.

In addition, the acrylonitrile-based monomer may be used in combination of one or more selected from the group consisting of acrylonitrile, methacrylonitrile and ethacrylonitrile, preferably acrylonitrile. Nitrile is used.

In the step IV), when the monomer mixed solution is continuously introduced into a continuous polymerization apparatus in which two or more stirring reactors are connected in series, the temperature of the first reactor is preferably 100 to 180 ° C, more preferably 100 to 150 ° C.

The polymerization temperature in the step II) is preferably 50 to 100 ° C, since the one hour half-life temperature of the polymerization initiator to be introduced is 50 to 100 ° C. If the polymerization temperature is lower than 50 ℃ the efficiency of the graft reaction of the monomer to the rubber polymer is lowered, if it exceeds 100 ℃ it is not preferable because the control of step III) becomes difficult. More preferably, it is 70-90 degreeC.

Diacryl peroxides such as 3,5,5-trimethylhexanoyl peroxide, lauroyl peroxide, dibenzoyl peroxide, etc. as the polymerization initiator; 1,1-dimethyl-3-hydroxybutyl peroxyneodecanoate, α-cumyl peroxyneodecanoate, α-cumyl peroxyneheptanoate, t-amyl peroxyneodecanoate t-amyl Peroxypivalate, t-butyl peroxypivalate, 2,5-dimethyl-2,5-di- (2-ethylhexanoyl peroxy) hexane, t-amyl peroxy-2-ethylhexanoate, t Peroxy esters, such as butyl peroxy-2-ethylhexanoate, can be selected from one or more kinds.

In the production method of the present invention, a weather resistant resin can be prepared by adding a lubricating agent, a solvent, a plasticizer, an antioxidant, or an ultraviolet absorber used in a conventional polymer polymerization.

As the manufacturing process used in the present invention, continuous or batch bulk polymerization, solution polymerization or block-suspension polymerization is possible, and continuous bulk polymerization or solution polymerization is preferable in that there is no problem of productivity and quality uniformity and water pollution. .

The particle size of the rubber particles in the weatherable resin according to the present invention is 0.3 to 0.8㎛ in the rubber phase after the pre-grafting polymerization step of step II) due to the difference in the degree of graft of the monomer and the ethylene propylene rubber polymer, rubber not In the case of the phase is formed to 1 to 5㎛ to prepare a bimodal weathering resin.

Hereinafter, the present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited to the examples.

Example 1

10.0 parts by weight of ethylene propylene rubber polymer (25 ° C., 5% styrene solution viscosity 170 cps), 46.0 parts of styrene, 14.0 parts by weight of acrylonitrile and 30.0 parts by weight of toluene were used as the composition of the final raw material mixed solution.

T-butyl peroxy pival was prepared by dissolving 90% by weight of the total amount of ethylene propylene-based rubber polymer in 20% by weight of the total amount of styrene and acrylonitrile and 100% by weight of the total amount of toluene. 0.01 parts by weight of the rate was added and pre-grafted for 3 hours at a reactor temperature of 75 ° C.

Thereafter, the remaining rubber polymer, styrene and acrylonitrile were mixed, and four stirred reactors were introduced into a continuous polymerization apparatus connected in series to continuously carry out the graft polymerization.

The temperature at the inlet of the polymerization apparatus was 125 ° C and the temperature at the outlet was 150 ° C. The final polymerization mixture solution was sent to a devolatilization tank to remove unreacted monomer and solvent at 230 ° C. and 20 torr, and then pelletized to obtain a final weather resistant resin. After injection molding the resin obtained as described above and measured the physical properties in the following manner is shown in Table 1.

◎ Particle shape: Observation was performed using a transmission electron microscope (TEM, Jeol JEM-1010). The samples were treated with osmium tetroxide and then made into ultra-tear cut specimens using a microtome.

? Average particle size of rubber particles: 0.5 g of styrene-based rubber modified resin was dissolved in 100 mL of methylethylkenone, and the average particle diameter of the rubber particles was measured using a Coulter counter (Beckman Coulter, LS230).

Izod Impact: Measured by ASTM D256 method.

◎ Tensile strength and elongation: It was measured by ASTM D638 method.

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

Example 2

It was carried out in the same composition and method as in Example 1, except that the ethylene propylene-based rubber polymer in the composition before pre-grafting polymerization was prepared by adding 70% by weight to the total amount.

Example 3

It was carried out in the same composition and method as in Example 1, except that the ethylene propylene-based rubber polymer in the composition before pre-graft polymerization was prepared by adding 50% by weight to the total amount.

Comparative Example 1

It was carried out in the same composition and method as in Example 1, except that the polymerization mixture solution was prepared by feeding the reactor 1 to the reactor without prior graft polymerization.

Comparative Example 2

It was carried out in the same composition and method as in Example 1, except that the ethylene propylene-based rubber polymer in the composition before pre-grafting polymerization was prepared by adding 100% by weight to the total amount.

division Example Comparative example One 2 3 One 2 Rubber particle distribution form (bimodal: ○, unimodal: X) ○ ○ ○ X X Rubber particle average particle diameter Small particles 0.7 0.6 0.4 - 0.9 Large particles 2.2 2.9 4.3 5.7 - Impact strength (kgcm / cm) (1/4 ") 31 24 21 14 20 (1/8 ") 38 31 27 21 27 Polish(%) 94 87 81 77 93 Tensile Strength (kg / ㎠) 421 403 379 356 417 % Elongation 24 28 37 21 11

As can be seen in Table 1, the resins of Examples 1 to 3 according to the present invention have a bimodal form having two kinds of rubbery particles having an average particle diameter of 0.3 to 0.8 µm and 1 to 5 µm, respectively. In comparison with the resins of Comparative Examples 1 and 2 of the uni-modal form manufactured by the conventional method, the impact strength and elongation are excellent, and the gloss and tensile strength can be confirmed.

As described above, the weather resistant resin according to the present invention is a useful invention in which the rubber particles in the resin have a bimodal form, and thus have excellent impact strength and gloss.                     

While the invention has been described in detail above with reference to the described embodiments, it will be apparent to those skilled in the art that various modifications and variations are possible within the scope and spirit of the invention, and such modifications and variations fall within the scope of the appended claims. It is also natural.

Claims (10)

In weather resistant resin, A weather resistant resin comprising two kinds of ethylene propylene-based rubbery particles having an average particle diameter of 0.3 to 0.8 mu m and 1 to 5 mu m, respectively. In the manufacturing method of weather resistant resin, A) 10 to 90% by weight of the total amount of the ethylene propylene rubber polymer, 5 to 30% by weight of the total amount of the styrene monomer, and 5 to 30% by weight of the total amount of the acrylonitrile monomer in the presence of the polymerization initiator. Pre-graft polymerization step of graft polymerization of the mixed solution dissolved in 0 to 100% by weight based on the total amount of the organic solvent; And B) the graft polymerization step of graft polymerization by further adding a mixed solution consisting of the remaining amount of the components to the graft polymer produced in step A); Method for producing a weather-resistant resin of claim 1 characterized in that comprises a. The method of claim 2, The ethylene propylene-based rubber polymer is 5 to 15 parts by weight based on the total amount of monomers, the sum of the input amount of the styrene-based monomer and acrylonitrile-based monomer is added to 45 to 95 parts by weight based on the total amount, the styrene-based monomer and acrylonitrile-based The ratio of the monomer is composed of 7: 3 to 9: 1 and the organic solvent is a method for producing a weather resistant resin, characterized in that 0 to 40 parts by weight based on the total amount. The method of claim 2, The pre-graft polymerization step is carried out for 1 to 3 hours at a temperature of 50 to 100 ℃, this graft polymerization step is carried out in a reactor of a continuous polymerization apparatus of 100 to 180 ℃ temperature in which two or more stirred reactors are connected in series Method for producing a weather-resistant resin, characterized in that. The method of claim 2, 10 to 30 parts by weight of the styrene-based monomers and acrylonitrile-based monomers and 0.01 to 1.0 parts by weight of the organic peroxide polymerization initiator in the present graft polymerization step, further comprising a method of producing a weather resistant resin. The method of claim 2, The ethylene propylene-based rubber is an ethylene-propylene rubber (ethylene-propylene rubber, EPR) or ethylene-propylene-diene rubber (EPDM) having a weight average molecular weight of 150,000 to 400,000, of which ethylene content 45-80% silver, propylene content 20-55%, the diene monomer is at least one selected from the group consisting of ethylene norbornene (ENB), dicyclopentadiene (DCPE) and hexadiene (HD) 0-13 weight% of this is contained, The manufacturing method of the weather resistant resin characterized by the above-mentioned. The method of claim 2, The styrene monomers include styrene, α-methyl styrene, o-methyl styrene, p-methyl styrene, m-methyl styrene, ethyl styrene, I-butyl styrene, t-butyl styrene and alkyl styrenes having equivalent properties; At least one member selected from the group consisting of o-bromo styrene, p-bromo styrene, m-bromo styrene, o-chloro styrene, p-chloro styrene, m-chloro styrene, and halogenated styrene having equivalent properties. Method for producing a weather resistant resin, characterized in that. The method of claim 2, The acrylonitrile-based monomer is acrylonitrile (acrylonitrile), methacrylonitrile (methacrylonitrile) and ethacrylonitrile (ethacrylonitrile) method for producing a weatherproof resin, characterized in that at least one selected from the group consisting of. The method of claim 2, The polymerization initiator is 3,5,5-trimethylhexanoyl peroxide, lauroyl peroxide, dibenzoyl peroxide and diacryl peroxides having the same properties; 1,1-dimethyl-3-hydroxybutyl peroxyneodecanoate, α-cumyl peroxyneodecanoate, α-cumyl peroxyneheptanoate, t-amyl peroxyneodecanoate t-amyl Peroxypivalate, t-butyl peroxypivalate, 2,5-dimethyl-2,5-di- (2-ethylhexanoyl peroxy) hexane, t-amyl peroxy-2-ethylhexanoate, t Butyl peroxy-2-ethylhexanoate and peroxy esters having the same properties; at least one member selected from the group consisting of a method for producing a weather resistant resin. The method of claim 2, The pre-graft polymerization step and the present graft polymerization step is a method for producing a weather-resistant resin, characterized in that carried out by a polymerization method selected from the group consisting of continuous block polymerization, batch block polymerization, solution polymerization and block-suspension polymerization.