KR20170011520A - Impact strength modifiers, method for preparing the same, and polylactic acid/polycarbonate resin composition - Google Patents
Impact strength modifiers, method for preparing the same, and polylactic acid/polycarbonate resin composition Download PDFInfo
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Abstract
The present invention relates to a methacrylate-butadiene-styrene-based impact modifier comprising an alkoxysilane, a process for producing the same, and a polylactic acid-polycarbonate resin mixed composition comprising the same. And a composite graft shell coated on the surface of the rubber polymer core, wherein the composite graft shell comprises a compound selected from the group consisting of a (meth) acrylic acid alkyl ester compound, an aromatic vinyl compound, and an unsaturated epoxy compound, Butadiene-styrene type impact modifier, a method for producing the same, and a polylactic acid-polycarbonate resin mixed composition comprising the methacrylate-butadiene-styrene type impact modifier, and a shell obtained by graft-polymerizing an alkoxysilane compound.
Description
The present invention relates to an impact modifier capable of enhancing compatibility between a polycarbonate resin and a poly (lactic acid) resin, a process for producing the same, and a poly (lactic acid-polycarbonate) resin composition containing the same.
In general, polycarbonate resins are widely used as interior and exterior materials throughout the industry in recent years because of their excellent impact resistance, electrical properties, and heat resistance. For example, it is widely used as an electronic product requiring impact resistance and flame retardancy, or as an interior and exterior material for automobiles.
However, the polycarbonate resin has a problem in that processability, chemical resistance, moisture resistance and low temperature impact resistance are deteriorated depending on the environment. In addition, since the polycarbonate resin produces waste polymers after use, the problem of environmental pollution resulting therefrom is emerging as a social problem.
Accordingly, attention has been paid to a polycarbonate resin composition which is not deteriorated in impact resistance even under the conditions of moist heat resistance. Further, as the necessity of environmentally friendly polymer materials is required, researches on biodegradable polymers have been conducted.
As biodegradable polymers, many aliphatic polyester polymers having excellent processability and easy control of decomposition properties have been studied. Among them, polylactic acid (PLA) resins have been proposed. The poly (lactic acid) resin market has a global market size of 150,000 tons, and its application range has been extended to areas where general plastics such as food packaging materials, containers, and electronic cases have been used.
The existing poly (lactic acid) resin is easily broken in the case of thin film molded articles because of lack of moldability, mechanical strength and heat resistance, and resistance to temperature is low, and when the external temperature rises above 60 ° C, .
In order to improve the physical properties such as deterioration of properties, studies for improving physical properties such as heat resistance and impact strength through blending with existing engineering plastics have been continued. In general, it is known that when the poly (lactic acid) resin is effectively dispersed in the polycarbonate resin, the most efficient efficiency is obtained.
However, due to the low miscibility between the poly (lactic acid) resin and the polycarbonate resin, the blending itself suffers from many difficulties. Therefore, it is urgent to develop a method for improving the compatibility of the polycarbonate resin and the poly (lactic acid) resin in order to solve this problem.
SUMMARY OF THE INVENTION The present invention has been made in order to solve the problems of the prior art,
More specifically, it is an object of the present invention to provide an alkoxysilane-containing methacrylate-butadiene-styrene impact modifier capable of improving the impact strength of a polycarbonate resin while serving as a compatibilizer capable of enhancing compatibility between a polycarbonate resin and a poly .
It is still another object of the present invention to provide a method for producing the alkoxysilane-containing methacrylate-butadiene-styrene type impact modifier.
It is also an object of the present invention to provide a polylactic acid-polycarbonate resin mixed composition comprising the alkoxysilane-containing methacrylate-butadiene-styrene type impact modifier.
In order to solve the above problems,
In one embodiment of the present invention
Butadiene-based rubber polymer core; And
And a composite graft shell coated on the surface of the rubber polymer core,
The composite grafted shell may contain an alkoxysilane-containing methacrylic compound having at least one compound selected from the group consisting of a (meth) acrylic acid alkyl ester compound, an aromatic vinyl compound, and an unsaturated epoxy compound and a shell obtained by graft polymerizing an alkoxysilane compound Butadiene-styrene type impact modifier.
In an embodiment of the present invention,
(a) preparing a butadiene-based rubber polymer core by emulsion polymerization;
(b) adding at least one compound selected from the group consisting of a (meth) acrylic acid alkyl ester compound, an aromatic vinyl compound, and an unsaturated epoxy compound and an alkoxysilane compound in the presence of the prepared core to perform graft polymerization, - obtaining a graft copolymer having a composite shell structure, and a process for producing an alkoxysilane-containing methyl methacrylate-butadiene-styrene type impact modifier.
In an embodiment of the present invention,
100 parts by weight of a base resin consisting of 50 to 90% by weight of a polylactic acid resin and 10 to 50% by weight of a polycarbonate resin; And
And 5 to 20 parts by weight of the alkoxysilane-containing methyl methacrylate-butadiene-styrene type impact modifier.
As described above, according to the present invention, incorporation of an alkoxysilane-containing methyl methacrylate-butadiene-styrene type impact modifier enhances compatibility of a polycarbonate resin with a poly lactic acid resin, A polylactic acid-polycarbonate resin composition having a low temperature impact strength, an anti-wet heat shock resistance, a mechanical strength and a heat resistance remarkably improved even when the rubber is used in a smaller amount than the conventional methyl methacrylate-butadiene-styrene impact reinforcement .
Hereinafter, the present invention will be described in detail in order to facilitate understanding of the present invention.
The terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms and the inventor may appropriately define the concept of the term in order to best describe its invention It should be construed as meaning and concept consistent with the technical idea of the present invention.
In the present invention, by mixing a polylactic acid resin as a biodegradable resin with a polycarbonate resin, the limit of mechanical strength and heat resistance, which is a disadvantage of polylactic acid resin, can be compensated. In particular, by using an impact modifier containing an alkoxysilane compound as an impact modifier , A polylactic acid-polycarbonate resin mixed composition improved in heat resistance and mechanical strength by increasing the compatibility of the polycarbonate resin and the polylactic acid resin can be provided. In addition, even though the butadiene rubber is used in a smaller amount than the conventional methyl methacrylate-butadiene-styrene type impact reinforcement due to the action of the silicone rubber in the polybutadiene rubber, the polybutylene terephthalate is remarkably improved in low temperature impact strength, - polycarbonate resin mixed composition.
Alkoxy Silane contain Methacrylate -Butadiene-styrene series Impact modifier
Specifically, in one embodiment of the present invention
Butadiene-based rubber polymer core (A); And
And a composite graft shell (B) coated on the surface of the rubber polymer core,
Wherein the composite grafted shell comprises a shell obtained by graft polymerizing an alkoxysilane compound with at least one compound selected from the group consisting of an alkyl (meth) acrylate compound, an aromatic vinyl compound, and an unsaturated epoxy compound, Silane-containing methacrylate-butadiene-styrene-based impact modifier.
More specifically, in one embodiment of the present invention
20 to 60% by weight of a butadiene-based rubber polymer core;
A methacrylate-butadiene-styrene-based impact modifier comprising 40 to 80% by weight of a composite graft shell coated on the surface of the rubber polymer core.
Core (A)
At this time, in the impact modifier of the present invention, the average particle size of the butadiene rubber polymer core is preferably 150 to 200 nm. If the core particle diameter is less than 150 nm, the shell may be too thin and thick to be dispersed. If the core particle diameter is more than 200 nm, the number of particles of impact reinforcement particles may be decreased, which may lower the impact strength of the polycarbonate at low temperature.
In addition, in the impact modifier of the present invention, the content of the rubber polymer constituting the core is preferably 20 to 60% by weight. If the content of the rubber polymer is less than 20% by weight, the impact reinforcing effect is insignificant. When the content of the rubber polymer is more than 60% by weight, the content of the graft compound forming the shell is decreased and the grafting rate can not be sufficiently increased. The safety is deteriorated.
complex Graft Shell (B)
It is important to uniformly form a shell on the surface of the core so that the rubber polymer can be dispersed well. If the shell is formed to be too thick at 80 wt% or more, impact from the outside can not be transmitted to the core, .
Specifically, in the methacrylate-butadiene-styrene type impact modifier of the present invention, the ratio of the particle diameter of the core: composite graft shell is preferably 5: 5 to 7: 3.
At this time, in the impact modifier of the present invention, the (meth) acrylic acid alkyl ester compound constituting the shell may be at least one selected from the group consisting of methyl methacrylate, n-butyl methacrylate, benzyl methacrylate, lauryl methacrylate and stearyl methacrylate , And most preferably, at least one selected from the group consisting of methyl methacrylate.
Further, in the impact modifier of the present invention, the aromatic vinyl compound forming the shell is a component that suppresses scattering of light generated by a difference in refractive index and maintains transparency, and representative examples thereof include styrene, , o-ethylstyrene, p-ethylstyrene, and vinyltoluene.
In addition, in the impact modifier of the present invention, the unsaturated epoxy compound constituting the shell serves as a compatibilizer which is compatible with the epoxy resin in the molecule and the hydroxy (-OH) at the terminal of the poly (lactic acid) resin through chemical reaction Examples of the component to be used include epoxy alkyl acrylate, allyl glycidyl ester, aryl glycidyl ester, glycidyl methacrylate, glycidyl acrylate, 3,4-epoxy-1-butene, vinyl Glycidyl ether, glycidyl itaconate, and mixtures thereof, and most preferably at least one selected from the group consisting of glycidyl methacrylate.
Also, in the impact modifier of the present invention, the alkoxysilane compound constituting the shell includes a silane-based compound containing one or two or more alkoxy groups, and typical examples thereof include vinylmethyldimethoxysilane, vinyltrimethoxysilane, trie Methacryloxypropyltrimethoxysilane, or a mixture of two or more of them.
Further, with respect to 100 parts by weight of the impact modifier of the present invention,
Wherein the composite grafted shell comprises 10 to 25 parts by weight of a (meth) acrylic acid alkyl ester compound; 3 to 7 parts by weight of an aromatic vinyl compound, 1 to 10 parts by weight of an unsaturated epoxy compound, And 5 to 20 parts by weight of an alkoxysilane compound, specifically 15 to 24 parts by weight of a (meth) acrylic acid alkyl ester compound; 4 to 6 parts by weight of an aromatic vinyl compound; 1 to 10 parts by weight of an unsaturated epoxy compound; And 5 to 10 parts by weight of an alkoxysilane compound.
When the amount of the (meth) acrylic acid alkyl ester compound is less than 10 parts by weight, miscibility is poor and there is a problem in dispersibility. When the amount is more than 25 parts by weight, the polyethylene glycol-based proportion decreases and the impact strength is lowered.
Particularly, when the content of the unsaturated epoxy compound is less than 1 part by weight, there is a disadvantage in that the compatibility of the polycarbonate resin with the polylactic acid resin is insufficient. When the content of the unsaturated epoxy compound exceeds 10 parts by weight, compatibility with the polycarbonate is poor, The effect of improving the usability of the lactic acid resin is not sufficient, and the polycarbonate is not well dispersed, and the impact strength is lowered.
In addition, when the alkoxysilane compound is contained in an amount exceeding 20 parts by weight, the stability of the impact modifier may be deteriorated.
Accordingly, when the content of the (meth) acrylic acid alkyl ester compound, the aromatic vinyl compound, the unsaturated epoxy compound, and the alkoxysilane compound is within the above range, the composite grafted shell does not cause condensation reaction of methacrylic acid Gel formation can be prevented, and transparency can be maintained. In addition, when used as an impact modifier in the production of a polylactic acid-polycarbonate resin mixed composition, it is possible to improve the compatibility between the polylactic acid resin and the polycarbonate resin, and to improve the physical properties such as improving the low temperature impact strength, which is a weak point of the existing polycarbonate .
More specifically, in the case of the impact modifier of the present invention, the epoxy group of the unsaturated epoxy compound contained in the composite graft shell can impart compatibility between the poly lactic acid resin and the polycarbonate resin. That is, the epoxy group of the unsaturated epoxy compound and the hydroxyl group (-OH) at the terminal of the polylactic acid resin are chemically bonded to each other while the methacrylate-butadiene-styrene type impact modifier is well dispersed in the polycarbonate resin to serve as a compatibilizer .
Further, the alkoxysilane compound contained in the impact modifier is a component capable of further improving the efficiency of the butadiene rubber, and the alkoxy group is converted into a hydroxyl group (-OH) by moisture (H 2 O) during the graft polymerization reaction (Si-O-Si) bonds to the shell through a condensation reaction, and can act as a silicone rubber. As a result, an effect of improving the low-temperature impact strength of the resin composition can be imparted.
Impact modifier Manufacturing method
In an embodiment of the present invention,
(a) preparing a butadiene-based rubber polymer core by emulsion polymerization;
(b) graft polymerization is carried out by sequentially adding an alkoxysilane compound, an alkyl (meth) acrylate compound, an aromatic vinyl compound, and an unsaturated epoxy compound in the presence of the prepared core to obtain a core- Graft copolymer having an alkoxysilane-containing methyl methacrylate-butadiene-styrene type impact modifier. The present invention also provides a method for producing an alkoxysilane-containing methyl methacrylate-butadiene-styrene type impact modifier.
The impact modifier of the present invention may be prepared by separating the polymer and water by adding salt, heat, and acid (sulfuric acid aqueous solution) while stirring the prepared impact modifier with the antioxidant, if necessary after completion of the polymerization reaction, And a reaction termination step of producing a powder.
Specifically, in the method for producing the impact modifier of the present invention, the step (a) of producing the butadiene rubber polymer core comprises the steps of: preparing a butadiene compound, an emulsifier, a polymerization initiator, ethylenediaminetetra sodium acetate, ferrous sulfate, The polymerization reaction can be carried out.
Specifically, the step of preparing the butadiene rubber polymer core (a) is formed into an emulsion by emulsion polymerization,
(a ') 30 to 70 parts by weight of a butadiene compound, 70 to 120 parts by weight of ion exchanged water, 0.1 to 1.5 parts by weight of an emulsifier, 0.1 to 1.5 parts by weight of a polymerization initiator, and 0.5 to 2 parts by weight of an electrolyte, Lt; 0 > C to prepare a first polymerization reaction product;
(a ") 0.1 to 1 part by weight of an emulsifier is added to the first polymerization reaction, and then 15 to 35 parts by weight of the remainder in 100 parts by weight of the butadiene monomer is added and reacted at 50 to 85 ° C to obtain a second polymerization reaction product And
(a '' ') adding 15 to 35 parts by weight of the remainder in 100 parts by weight of the butadiene-based monomer to the second polymerization reaction, and reacting at 60 to 90 ° C.
At this time, the butadiene compound is not limited thereto, but 1,3-butadiene is preferably used.
The emulsifier preferably contains about 0.5 to 3 parts by weight based on 100 parts by weight of the butadiene compound. When the amount of the emulsifier is less than the above range, an excessive amount of solidification product is generated during polymerization, Gas may be generated in the appearance of the molded article, which is not preferable.
Examples of the emulsifier include alkyl aryl sulfonates, alkaline methyl alkyl sulfonates, sulfonated alkyl esters, fatty acid soaps, and alkali salts of rosin acid, potassium oleate, and the like.
In addition, the polymerization initiator preferably includes about 0.5 to 3 parts by weight based on 100 parts by weight of the butadiene compound. Typical examples thereof include t-butyl hydroperoxide (TBHP), cumene hydroperoxide, diisopropylbenzene hydroperoxide Peroxides such as sodium peroxodisulfate and roper oxide and oxidation-reduction catalysts such as sodium formaldehyde sulfoxylate, ethylenediaminetetra sodium acetate, ferrous sulfate, sodium pyrophosphate and dextrose can be used.
It is preferable that pure water having a metal ion concentration of 2 ppm or less through the ion exchanger is used as the ion-exchanged water. The use amount of the ion exchange water is preferably at most 75 parts by weight. If the amount of the ion-exchanged water to be used is less than the above range, it is difficult to adjust the reaction heat during the polymerization reaction. If the amount exceeds the above range, excessive use of the ion-exchanged water results in a low slurry content.
The emulsion polymerization process for preparing the butadiene rubber polymer core (a) is preferably carried out at a temperature within a range of about 40 to 65 ° C, more preferably at a temperature of 50 to 60 ° C.
In the method for producing an impact modifier according to the present invention, the (b) graft polymerization reaction may be an emulsifier in the butadiene rubber polymer core, and more specifically, an alkoxysilane compound and an alkyl (meth) A compound, and an unsaturated epoxy compound and a polymerization initiator, followed by reacting.
Specifically, the graft polymerization reaction (b) may be carried out by swelling an alkoxysilane compound on the butadiene-based latex polymer core, and then adding a (meth) acrylic acid alkyl ester compound, an aromatic vinyl compound and an unsaturated epoxy compound And then adding the first monomer emulsion continuously to perform polymerization reaction. In this case, the alkoxysilane compound can be first grafted onto the butadiene-based latex polymer core, thereby maximizing the effect produced by the alkoxysilane compound.
At this time, the emulsifier preferably includes about 0.1 to 0.5 parts by weight based on 100 parts by weight of the butadiene rubber polymer, and is selected from various kinds well known in emulsion polymerization techniques, However, potassium oleate or the like can be preferably used.
The polymerization initiator preferably includes about 0.1 to 0.3 parts by weight based on 100 parts by weight of the butadiene rubber polymer. The same polymerization initiator as used for polymerizing the rubber polymer core may be used, but t-butyl hydroperoxide Is preferably used.
The second emulsion graft polymerization reaction is preferably carried out at a temperature within a range of about 40 to 65 ° C, more preferably at a temperature of 50 to 60 ° C.
In the present invention, the inputting process of the compounds in each step is performed in parallel with the temporary input method and the continuous input method. For example, the core polymerization step for preparing the rubber polymer core can increase the processability by reacting the reaction compound with a continuous feed method without making it a pre-emulsion. In addition, the shell polymerization step may be carried out in such a manner that the alkoxysilane compound is firstly subjected to a polymerization reaction for about one hour by continuous feeding, and then the (meth) acrylic acid alkyl ester compound, the aromatic vinyl compound and the unsaturated epoxy compound are converted into a preemulsion, It can be grafted by continuously injecting it for about several hours.
As a result of the polymerization according to the method of the present invention, 100 parts by weight of the impact modifier equivalent to the sum of the charged compounds was obtained.
Poly lactic acid -Polycarbonate resin mixed composition
In an embodiment of the present invention,
100 parts by weight of a base resin consisting of 50 to 90% by weight of a polylactic acid resin and 10 to 50% by weight of a polycarbonate resin; And
And 5 to 20 parts by weight of the alkoxysilane-containing methyl methacrylate-butadiene-styrene type impact modifier.
Specifically, the polylactic acid-polycarbonate resin mixed composition may contain
100 parts by weight of a base resin comprising 60 to 80% by weight of a polylactic acid resin and 20 to 40% by weight of a polycarbonate resin; And
And 5 to 15 parts by weight of the alkoxysilane-containing methyl methacrylate-butadiene-styrene type impact modifier.
Since the dispersion efficiency of the methyl methacrylate-butadiene-styrene type impact modifier in the polylactic acid resin is low when the conventional poly (lactic acid) resin composition is prepared, the content of the poly (lactic acid) resin: methyl methacrylate-butadiene- styrene type impact modifier is 75 : 25 showed the highest impact strength.
However, in the present invention, by blending a polycarbonate resin with a poly (lactic acid) resin and then injecting the alkoxysilane-containing methyl methacrylate-butadiene-styrene type impact modifier of the present invention into the core made of a rubber- With the synergistic effect of the silicone rubber by the alkoxysilane compound, a better impact efficiency can be obtained even by using a small amount of 20 parts by weight or less.
At this time, the efficiency of the impact reinforcing material varies depending on the content of the unsaturated epoxy compound contained in the impact modifier, and if it is within the above range, the optimum effect can be realized.
The poly (lactic acid) resin is preferably selected from the group consisting of L-isomers, D-isomers, L, D-isomers, and combinations thereof. The weight average molecular weight of the poly (lactic acid) resin is preferably 80,000 to 300,000 g / mol.
The polycarbonate resin is preferably a resin having a weight average molecular weight of 10,000 to 35,000 g / mol.
The polycarbonate / polybutylene blend may be prepared by extrusion at 250 ° C.
The resin composition may contain other additives such as a flame retardant, a lubricant, an antioxidant, a light stabilizer, a reaction catalyst, a releasing agent, a pigment, an antistatic agent, a conductivity imparting agent, an EMI shielding agent, An antistatic agent, an antistatic agent, an inorganic filler, a glass fiber, an anti-friction wear-resistant agent, and a coupling agent.
A method of melt-kneading and processing the polylactic acid resin, the polycarbonate resin, the impact modifier, and other additives is not particularly limited, but specific examples thereof include a twin-screw extruder, a uniaxial extruder, a roll mill, Kneaded using one of conventional compounding machines such as a stirrer, a stirrer, a stirrer, a stirrer, a stirrer, a stirrer, a stirrer, a stirrer, a stirrer, a stirrer, a stirrer, a bar mixer and the like.
Hereinafter, the present invention will be described in more detail with reference to Examples and Experimental Examples. However, the following examples and experimental examples are provided to illustrate the present invention and are not intended to limit the scope of the present invention.
Example
(Examples 1 to 3)
(a) a step of producing a butadiene-based rubber polymer
At this time, the weight% of the compounds shown in the following Table 1 is based on 100 wt% of the whole mixture used for the preparation of rubber latex, and the weight parts are based on 100 wt% of the whole mixture.
80 parts by weight of ion-exchanged water, 70 parts by weight of 1,3-butadiene, 0.95 parts by weight of potassium oleate, 0.1 parts by weight of sodium formaldehyde sulfoxylate, 0.05 parts by weight of diisopropylbenzene hydroperoxide 0.05 parts by weight, , 0.11 part by weight of ethylenediaminetetra sodium acetate and 0.19 part by weight of ferrous sulfate, and the reaction was carried out at a reaction temperature of 70 캜 until the polymerization conversion rate reached 60%. 15 parts by weight of butadiene and 0.65 parts by weight of potassium oleate were added After the temperature was raised to 80 ° C, the reaction was terminated at a polymerization conversion of 95%. The time required for the polymerization was 23 hours, and the average particle size of the prepared butadiene-based latex polymer core was 190 nm.
(b) Composite graft shell manufacture
The butadiene-based latex polymer core (solid content) prepared in the above step (a) was introduced into a closed reactor at a content ratio shown in the following Table 1, and the temperature was raised to 60 DEG C with nitrogen filling. The reactor was charged with vinylmethyldimethoxy Silane was added thereto, and the mixture was stirred for about 30 minutes.
In a separate mixer, 0.3 parts by weight of potassium methyl oleate, 0.05 part by weight of t-butyl hydroperoxide, 0.1 part by weight of sodium formaldehyde sulfoxylate, 0.1 part by weight of methyl methacrylate, styrene, glycidyl methacrylate, 0.02 part by weight of ethylenediaminetetra sodium acetate, 0.001 part by weight of ferrous sulfate, and 20 parts by weight of ion exchanged water were mixed to prepare a monomer emulsion.
The prepared monomer emulsion was continuously added to the reactor containing the alkoxysilane swapped butadiene-based latex polymer core over 2.5 hours, and then 0.02 part by weight of t-butyl hydroperoxide was added after 30 minutes, And the reaction was terminated at a polymerization conversion rate of 98% to prepare a methyl methacrylate-butadiene-styrene type latex resin having a core-shell structure.
The prepared graft copolymer on the latex was solidified with hydrochloric acid to separate the polymer and water, followed by dehydration and drying to obtain an alkoxysilane-containing methyl methacrylate-butadiene-styrene type impact modifier powder.
(c) Preparation of Poly (lactic acid) -Polycarbonate resin mixed composition
The polylactic acid resin and the polycarbonate resin at the content ratios shown in Table 1 were mixed with the impact modifier powder prepared at the step (b), and melt-kneaded at 250 ° C using an extruder to obtain pellets. The obtained pellets were subjected to T-die extrusion at a die temperature of 220 占 폚 to obtain a sheet having a thickness of 0.5 mm.
(Comparative Example 1)
A sheet was prepared in the same manner as in Example 1, except that only 100 wt% of polylactic acid resin was used without containing an impact modifier and a polycarbonate resin.
(Comparative Example 2)
A sheet was prepared in the same manner as in Example 2 except that the polycarbonate resin was not used and only 100% by weight of the polylactic acid resin and 10% by weight of the impact modifier were used.
(Comparative Example 3)
A sheet was produced in the same manner as in Example 1 except that the impact modifier was not included.
(Comparative Example 4)
A sheet was prepared in the same manner as in Example 1 except that glycidyl methacrylate was not used but a graft copolymer was prepared by using 25 wt% of methyl methacrylate.
(Comparative Example 5)
A sheet was prepared in the same manner as in Example 2 except that 5% by weight of an impact modifier was used.
(Comparative Example 6)
A sheet was prepared in the same manner as in Example 2 except that 20% by weight of the impact modifier was used.
(Comparative Example 7)
A sheet was prepared in the same manner as in Example 1 except that a graft copolymer was prepared using 5% by weight of methyl methacrylate and 20% by weight of glycidyl methacrylate.
Experimental Example
The physical properties of the polylactic acid-polycarbonate resin mixed compositions obtained in Examples 1 to 3 and Comparative Examples 1 to 7 were evaluated, and the results are shown in Table 1 below.
* Evaluation of Izod Impact Strength: According to the ASTM D-256 test method, 1/8 "(room temperature), 1/8" (-30 ° C), 1/4 " And the results are summarized in Table 1 below.
As can be seen from Table 1, the specimens of the examples prepared using the polyacetic acid-polycarbonate resin composition using the impact modifier of the present invention had higher impact strength than the specimens prepared in the comparative examples.
Claims (20)
And a composite graft shell coated on the surface of the rubber polymer core,
Wherein the composite grafted shell comprises a shell obtained by graft-polymerizing an alkoxysilane compound with at least one compound selected from the group consisting of a (meth) acrylic acid alkyl ester compound, an aromatic vinyl compound, and an unsaturated epoxy compound Alkoxysilane-containing methacrylate-butadiene-styrene type impact modifier.
Wherein the (meth) acrylic acid alkyl ester compound is at least one or more selected from the group consisting of methyl methacrylate, n-butyl methacrylate, benzyl methacrylate, lauryl methacrylate and stearyl methacrylate. Silane-containing methacrylate-butadiene-styrene type impact modifier.
Wherein the aromatic vinyl compound is at least one selected from the group consisting of styrene,? -Methylstyrene, o-ethylstyrene, p-ethylstyrene, and vinyltoluene.
The unsaturated epoxy compound may be at least one selected from the group consisting of epoxy alkyl acrylates, allyl glycidyl esters, aryl glycidyl esters, glycidyl methacrylate, glycidyl acrylate, 3,4-epoxy-1-butene, vinyl glycidyl An alkoxysilane-containing methacrylate-butadiene-styrene-based impact modifier, which is at least one selected from the group consisting of an ether, glycidyl itaconate, and mixtures thereof.
The alkoxysilane-containing methacrylate-butadiene-styrene impact modifier is characterized in that the unsaturated epoxy compound is glycidyl methacrylate.
Wherein the alkoxysilane compound is a single substance selected from the group consisting of vinylmethyldimethoxysilane, vinyltrimethoxysilane, triethoxyvinylsilane and gamma-methacryloxypropyltrimethoxysilane, or a mixture of two or more thereof. Silane-containing methacrylate-butadiene-styrene type impact modifier.
The methacrylate-butadiene-styrene type impact modifier
20 to 60% by weight of a butadiene-based rubber polymer core;
And 40 to 80 wt% of a composite grafted shell coated on the surface of the rubber polymer core. The alkoxysilane-containing methacrylate-butadiene-styrene type impact modifier.
The composite grafted shell
5 to 20 parts by weight of an alkoxysilane compound,
10 to 25 parts by weight of a (meth) acrylic acid alkyl ester compound,
3 to 7 parts by weight of an aromatic vinyl compound, and
1 to 10 parts by weight of an unsaturated epoxy compound.
The composite grafted shell
5 to 10 parts by weight of an alkoxysilane compound,
15 to 24 parts by weight of a (meth) acrylic acid alkyl ester compound,
4 to 6 parts by weight of an aromatic vinyl compound, and
An alkoxysilane-containing methacrylate-butadiene-styrene type impact modifier comprising 1 to 10 parts by weight of an unsaturated epoxy compound.
Wherein the butadiene rubber polymer core has a particle diameter of 150 to 200 nm. The alkoxysilane-containing methacrylate-butadiene-styrene-based impact modifier.
Wherein the core: composite grafted shell has a particle size ratio of 5: 5 to 7: 3. The alkoxysilane-containing methacrylate-butadiene-styrene type impact modifier.
(b) graft polymerization is carried out by adding an alkoxysilane compound, a (meth) acrylic acid alkyl ester compound, an aromatic vinyl compound, and an unsaturated epoxy compound in the presence of the prepared core to obtain a graft copolymer having a core- To obtain an alkoxysilane-containing methyl methacrylate-butadiene-styrene type impact modifier.
The step of (a) preparing the butadiene rubber polymer core comprises
(a ') 30 to 70 parts by weight of a butadiene compound, 70 to 120 parts by weight of ion exchanged water, 0.1 to 1.5 parts by weight of an emulsifier, 0.1 to 1.5 parts by weight of a polymerization initiator, and 0.5 to 2 parts by weight of an electrolyte, Lt; 0 > C to prepare a first polymerization reaction product;
(a ") 0.1 to 1 part by weight of an emulsifier is added to the first polymerization reaction, and then 15 to 35 parts by weight of the remainder in 100 parts by weight of the butadiene monomer is added and reacted at 50 to 85 ° C to obtain a second polymerization reaction product And
(a ''') adding 15 parts by weight to 35 parts by weight of the remainder in 100 parts by weight of the butadiene-based monomer to the second polymerization reaction, and reacting at 60 to 90 ° C. Methyl methacrylate-butadiene-styrene type impact modifier.
Wherein the butadiene compound is 1,3-butadiene. The method for producing an alkoxysilane-containing methyl methacrylate-butadiene-styrene type impact modifier according to claim 1,
The method for producing an alkoxysilane-containing methyl methacrylate-butadiene-styrene type impact modifier according to claim 1, wherein the (b) graft polymerization is carried out at 40 to 65 ° C.
And 5 to 20 parts by weight of an alkoxysilane-containing methyl methacrylate-butadiene-styrene type impact modifier according to claim 1. [Claim 5] The polylactic acid-polycarbonate resin composition according to claim 1,
100 parts by weight of a base resin consisting of 50 to 90% by weight of a polylactic acid resin and 10 to 50% by weight of a polycarbonate resin; And
And 5 to 15 parts by weight of an alkoxysilane-containing methyl methacrylate-butadiene-styrene type impact modifier.
Wherein the polycarbonate resin has a weight average molecular weight of 10,000 to 35,000 g / mol.
Wherein the poly (lactic acid) resin is selected from the group consisting of L-isomer, D-isomer, L, D-isomer, and combinations thereof.
Wherein the poly (lactic acid) resin has a weight average molecular weight of 80,000 to 300,000 g / mol.
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| KR20200011905A (en) * | 2018-07-25 | 2020-02-04 | 주식회사 엘지화학 | Adhesive composition |
| KR20200011910A (en) * | 2018-07-25 | 2020-02-04 | 주식회사 엘지화학 | Adhesive composition |
| KR20200078065A (en) * | 2018-12-21 | 2020-07-01 | 주식회사 엘지화학 | Method for preparing graft copolymer powder |
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