KR101777922B1 - Graft copolymer, thermoplastic resin composition and article produced therefrom - Google Patents
Graft copolymer, thermoplastic resin composition and article produced therefrom Download PDFInfo
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- KR101777922B1 KR101777922B1 KR1020150157190A KR20150157190A KR101777922B1 KR 101777922 B1 KR101777922 B1 KR 101777922B1 KR 1020150157190 A KR1020150157190 A KR 1020150157190A KR 20150157190 A KR20150157190 A KR 20150157190A KR 101777922 B1 KR101777922 B1 KR 101777922B1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
- C08F279/04—Vinyl aromatic monomers and nitriles as the only monomers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
Abstract
TECHNICAL FIELD The present invention relates to a graft copolymer, a thermoplastic resin composition containing the same, and a molded article produced therefrom, and more particularly to a rubber composition comprising 60 to 70% by weight of a rubbery polymer; From 30 to 40% by weight of at least one selected from the group consisting of aromatic vinyl compounds, vinyl cyan compounds and (meth) acrylic acid alkyl ester compounds; And 0.001 to 1 part by weight of myrcene based on 100 parts by weight of the total of the rubbery polymer and the compound; and a thermoplastic resin composition containing the same, and a molded article .
According to the present invention, there is provided a graft copolymer excellent in mechanical properties, thermal stability and gloss characteristics, which has high grafting ratio even at a high rubber content, excellent in polymerization stability, excellent in powder characteristics, And a molded article produced from the composition.
Description
TECHNICAL FIELD The present invention relates to a graft copolymer, a thermoplastic resin composition containing the same, and a molded article produced therefrom. More particularly, the present invention relates to a graft copolymer which has a high graft ratio even at a high rubber content and has excellent polymerization stability, The present invention relates to a graft copolymer having both excellent mechanical properties, thermal stability and gloss characteristics, a thermoplastic resin composition containing the same, and a molded article produced therefrom.
In general, the graft copolymer, particularly an acrylonitrile-butadiene-styrene copolymer, an MBS resin, an acrylate-styrene-acrylonitrile copolymer, and the like, However, in order to reduce the cost and improve the quality of the resin, it is necessary to increase the specific gravity of the rubbery polymer or to minimize the reaction time There are many ways to do this.
However, when the rubber content is increased, the formation of the graft copolymer is not smooth and not only the impact strength, gloss and thermal stability of the polymerized graft copolymer are lowered, but also the graft copolymer In the case of the copolymer, the block is formed during storage or loading in large quantities, and the amount of the graft copolymer can not be kept constant during the transfer and extrusion process, thereby causing a quality deviation of the final product.
In addition, when the reaction time is shortened, the particle diameter becomes small and the amount of the coagulated product becomes large. In addition, the increase of the reaction pressure due to the excessive heat of reaction may cause safety problems in the field factory.
In order to solve the problems of the prior art as described above, it is an object of the present invention to provide a rubber composition which has high grafting ratio even at a high rubber content and thus has excellent polymerization stability and powder characteristics, An excellent graft copolymer, a thermoplastic resin composition containing the same, and a molded article produced therefrom.
These 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 rubber composition comprising 60 to 70% by weight of a rubbery polymer; From 30 to 40% by weight of at least one selected from the group consisting of aromatic vinyl compounds, vinyl cyan compounds and (meth) acrylic acid alkyl ester compounds; And 0.001 to 1 part by weight of myrcene based on 100 parts by weight of the total of the rubbery polymer and the compound.
The present invention also provides a thermoplastic resin composition comprising the graft copolymer of the present invention.
Further, the present invention provides a molded article produced from the thermoplastic resin composition of the present invention.
As described above, according to the present invention, since the grafting ratio is high even in a high rubber content, it has excellent polymerization stability, and also has high drying productivity because of excellent powder properties such as excellent caking property, low water content and fine powder content. A thermoplastic resin composition containing the graft copolymer, and a molded article produced therefrom, all of which are excellent in mechanical properties, thermal stability and gloss characteristics.
Hereinafter, the present invention will be described in detail.
The graft copolymer of the present invention comprises 60 to 70% by weight of a rubbery polymer; From 30 to 40% by weight of at least one selected from the group consisting of aromatic vinyl compounds, vinyl cyan compounds and (meth) acrylic acid alkyl ester compounds; And 0.001 to 1 part by weight of myrcene based on 100 parts by weight of the total of the rubbery polymer and the compound.
If the content of the rubbery polymer is less than 60% by weight, the yield tends to be poor, resulting in poor economical efficiency. When the content of the rubbery polymer is more than 70% by weight, grafting is difficult to achieve.
The rubbery polymer may preferably be 65 to 70% by weight.
For example, the rubbery polymer may have an average particle diameter of 2,500 to 4,000 Å, a gel content of 80 to 99% by weight, and a glass transition temperature of 0 ° C. or less. The graft ratio and the powder property This has an excellent effect.
As another example, the rubbery polymer may have an average particle size of 3,000 to 3,500 Å, a gel content of 80 to 95% by weight, and a glass transition temperature of 0 to -80 ° C. The graft copolymer The graft ratio and the powder characteristics of the powder are excellent.
The rubbery polymer may be, for example, a conjugated diene rubber in which a conjugated diene monomer is polymerized.
The conjugated diene-based monomer may be, for example, 1,3-butadiene, isoprene, chloroprene, or the like.
The rubbery polymer can be produced, for example, by polymerizing the conjugated diene monomer at a predetermined temperature for a predetermined time using an emulsifier, a polymerization initiator, an electrolyte, a molecular weight regulator and ion-exchange water.
The polymerization initiator, the electrolyte, the molecular weight regulator, the ion-exchanged water, the polymerization temperature and the polymerization time are not particularly limited as far as they are usually applicable to the production of the rubbery polymer, and can be appropriately selected if necessary.
The aromatic vinyl compound may be at least one selected from the group consisting of styrene,? -Methylstyrene, m-methylstyrene, p-methylstyrene, p-tert-butylstyrene, and the like.
The aromatic vinyl compound may be, for example, 15 to 35% by weight, 15 to 30% by weight, or 20 to 30% by weight based on the total weight of the rubbery polymer and the compound. Within this range, polymerization stability, And excellent physical properties, thermal stability and gloss characteristics.
The vinyl cyan compound may be at least one selected from the group consisting of acrylonitrile, methanitrrolonitrile, ethyl acrylonitrile, isopropyl acrylonitrile, and the like.
The vinyl cyan compound may be, for example, 3 to 20% by weight, 5 to 15% by weight, or 5 to 10% by weight based on the total weight of the rubbery polymer and the compound. Within this range, polymerization stability, And excellent physical properties, thermal stability and gloss characteristics.
The (meth) acrylic acid alkyl ester compound may be, for example, at least one selected from the group consisting of a methacrylic acid alkyl ester compound and an acrylic acid alkyl ester compound, and further examples thereof include methyl methacrylate, ethyl methacrylate, Propyl methacrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, and the like.
The (meth) acrylic acid alkyl ester compound may be, for example, 0 to 5% by weight or 0.1 to 5% by weight based on the total weight of the rubbery polymer and the compound. Within this range, polymerization stability, dry productivity, Thermal stability and gloss characteristics are excellent.
The myrcene may be used in an amount of 0.015 to 0.5 parts by weight, 0.1 to 0.4 parts by weight, or 0.15 to 0.35 parts by weight, and the effect of grafting and gloss is excellent within this range.
The graft copolymer may have a graft rate of 35 to 45%, or 37 to 40%, for example. Within this range, economical efficiency and product properties are all excellent.
The graft copolymer may for example have a fine powder content of less than 70 microns of less than 5.0 wt.%, 4.6 wt.% Or 4.3 to 4.6 wt.%, And an effect of having good caking properties within this range have.
For example, the graft copolymer may have a moisture content (100 ° C) of 30% by weight or less, 29% by weight or 29% by weight or less and a powder property within the above range, This has an excellent effect.
The graft copolymer may have a caking property (decay rate) of 80% or more, 87% or 87% or 92%, and the transfer and quantitative loading of the powder within this range is stable.
The graft copolymer may be a graft-polymerized copolymer including a reactive emulsifier.
The reactive emulsifier is not particularly limited as long as it is a reactive emulsifier used in the production of a graft copolymer, and may be selected and used as needed.
The thermoplastic resin composition of the present invention may be a graft copolymer of the present invention; And an aromatic vinyl compound-vinyl cyan compound copolymer.
The graft copolymer may be, for example, 20 to 40% by weight or 20 to 30% by weight, and the aromatic vinyl compound-vinyl cyanide copolymer may be 60 to 80% by weight or 70 to 80% by weight, for example. There is an effect of excellent mechanical properties, gloss characteristics, surface characteristics and heat resistance within the range.
The aromatic vinyl compound-vinyl cyanide copolymer may have a weight average molecular weight of 80,000 to 150,000 g / mol, 90,000 to 130,000 g / mol, or 100,000 to 120,000 g / mol, for example. Graft copolymers And excellent in gloss, surface characteristics, and processability.
The aromatic vinyl compound-vinyl cyan compound copolymer may include 20 to 35% by weight or 25 to 30% by weight of a vinyl cyan compound.
The thermoplastic resin composition may further include at least one selected from the group consisting of an antioxidant, a lubricant, and a heat stabilizer.
The antioxidant may be added in an amount of 0.05 to 5 parts by weight, 0.05 to 2 parts by weight, or 0.1 to 1 part by weight based on 100 parts by weight of the total of the graft copolymer and the aromatic vinyl compound-vinyl cyan compound copolymer , The effect of preventing oxidation is maximized without affecting other physical properties within this range.
The antioxidant may be added to the latex after the graft copolymer is polymerized before or after aggregation. In this case, the antioxidant effect is maximized without affecting other physical properties.
The lubricant may be added in an amount of 0.1 to 5 parts by weight, 0.5 to 2 parts by weight, or 0.5 to 1.5 parts by weight based on 100 parts by weight of the total of the graft copolymer and the aromatic vinyl compound-vinyl cyan compound copolymer, Within this range, there is an effect that the workability is maximized without affecting other physical properties.
The heat stabilizer may be added in an amount of 0.01 to 2 parts by weight, 0.05 to 1 part by weight, or 0.05 to 0.5 part by weight based on 100 parts by weight of the total of the graft copolymer and the aromatic vinyl compound-vinyl cyan compound copolymer , There is an effect that the thermal stability is maximized without affecting other physical properties within this range.
The thermoplastic resin composition may have, for example, a total rubber content of 10 to 30% by weight, 15 to 25% by weight, or 15 to 20% by weight, and within this range, mechanical properties such as impact strength, There is an effect of excellent heat resistance.
The process for producing the graft copolymer of the present invention comprises: 60 to 70% by weight of a rubbery polymer; 30 to 40% by weight of at least one member selected from the group consisting of aromatic vinyl monomers, vinyl cyan monomers and (meth) acrylic acid alkyl ester monomers; And 0.001 to 1 part by weight of myrcene based on 100 parts by weight of the sum of the rubbery polymer and the monomer.
The graft polymerization may be carried out by further including a reactive emulsifier.
The above-mentioned myrcene can be added together with the rubbery polymer before the initiation of polymerization, or it can be continuously added by mixing with the monomer, and in this case, the effect of grafting and gloss is excellent.
The myrcene may be added in an amount of 0.015 to 0.5 part by weight, 0.1 to 0.4 part by weight, or 0.15 to 0.35 part by weight, for example. Within this range, the effect of grafting and gloss is excellent.
The graft polymerization can be, for example, a polymerization conversion rate of 95% or more, 98% or more, or 98 to 99%. Within this range, polymerization stability and productivity are excellent.
The polymerization conversion rate can be measured by calculating the total solid content (TSC) after measuring 1.5 g of the prepared latex by drying for 15 minutes in a 150 ° C hot air drier for 15 minutes and then using the following equation (I).
[Mathematical Formula I]
For example, the graft copolymer may be prepared by agglomerating, aging, dehydrating and drying the graft copolymer latex prepared by the graft polymerization to prepare a graft copolymer powder.
The method of agglomeration, aging, dehydration and drying is not particularly limited as long as it is a method applied in graft polymerization.
In the coagulation, for example, the antioxidant may be added to the latex. In this case, the antioxidant effect is maximized without deteriorating other physical properties.
The process for producing a thermoplastic resin composition according to the present invention is a process for producing a thermoplastic resin composition by melt kneading and extruding a graft copolymer powder prepared by the method for producing a graft copolymer of the present invention and an aromatic vinyl compound-vinyl cyanide copolymer And a control unit.
The melt kneading and extruding method is not particularly limited in the case of a method usually applied in graft polymerization.
In the melt-kneading or melt-kneading, for example, the graft copolymer powder and the aromatic vinyl compound-vinyl cyanide copolymer may be added with a lubricant, a heat stabilizer or both of them. In this case, And / or to improve thermal stability.
The molded article of the present invention is characterized by being produced from the thermoplastic resin composition of the present invention.
The molded article may be, for example, an injection molded article or a blow molded molded article, and may be, for example, a refrigerator part, a refrigerator body, or a refrigerator housing.
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 One
<Large diameter Rubbery Preparation of polymer >
60 parts by weight of ion-exchanged water, 75 parts by weight of 1,3-butadiene as a monomer, 1 part by weight of potassium rosinate as an emulsifier, 0.8 parts by weight of fatty acid soap, 1.5 parts by weight of potassium carbonate as an electrolyte, 0.3 parts by weight of tertiary dodecylmercaptan (TDDM) as a molecular weight regulator and 0.3 part by weight of potassium persulfate (K 2 S 2 O 8 ) as initiators were added at a time when the polymerization conversion rate was 30 to 40% at a reaction temperature of 72 ° C 25 parts by weight of 1,3-butadiene and 0.15 part by weight of potassium persulfate were added to the mixture, and the mixture was reacted until the polymerization conversion was 60% at 70 ° C. After the temperature was raised to 80 ° C, the polymerization conversion was 95% And a gel content of 85%.
The analysis method of the rubbery polymer latex is as follows.
Gel content: The rubber latex was solidified using a dilute acid or metal salt, washed, dried in a vacuum oven at 60 ° C for 24 hours, and then the resulting rubber mass was finely cut with scissors. One gram of the rubber piece was placed in 100 g of toluene After storing in a dark room at room temperature for 48 hours, the gel was separated into a gel and a gel, and the gel content was measured by the following equation (1).
[Equation 1]
Gel content (%) = weight of insoluble matter (gel) / sample weight * 100
B) Particle size and particle size distribution: Measured using a dynamic laser light skating method using a Nicomp 370HPL instrument (Nicomp, USA).
& Lt ; Preparation of graft copolymer >
65 parts by weight (based on solid content) of the rubbery polymer latex was charged into a reactor purged with nitrogen, and 9 parts by weight of acrylonitrile, 26 parts by weight of styrene, 0.25 parts by weight of myrcene, 10 parts by weight of ion- , 0.12 parts by weight of t-butyl hydroperoxide, 0.3 parts by weight (based on solid content, 28% aqueous solution) of a reactive emulsifier Alkenyl C16-18 succinate potassium slat (ELOPLA AS200) and 0.1 part by weight of an alkali salt of rosin acid, And 0.3 part by weight of mercaptan was added to the emulsion continuously at 70 캜 for 1 hour. At this time, 0.054 parts by weight of dextrose, 0.004 parts by weight of sodium pyrophosphate and 0.002 parts by weight of ferrous sulfate were continuously added.
After the addition of the monomer emulsion, 0.05 part by weight of dextrose, 0.03 part by weight of sodium pyrophosphate, 0.001 part by weight of ferrous sulfate and 0.05 part by weight of t-butyl hydroperoxide were fed into the reactor, Lt; 0 > C for 1 hour, and then the reaction was terminated. The graft copolymer latex thus obtained had a polymerization conversion rate of 98.5%, a grafting rate of 38% and a formed coagulated content of 0.03%.
A method of analyzing the latex of the graft copolymer is as follows.
A) Solidification water content: solid solidification component which is an index of polymerization stability is calculated by the following equation (2).
&Quot; (2) "
Solid solid content (%) = {weight (g) of formed solidified product in the reaction tank / weight (g) of total rubber and monomer) x 100
When the solid solid content is 0.7% or more, the latex stability is extremely low and it is difficult to obtain a graft polymer suitable for the present invention due to a large amount of solidification product.
Graft ratio: The graft polymer latex is solidified, washed and dried to obtain a powdery form. 2 g of this powder is added to 300 ml of acetone and stirred for 24 hours. After separating the solution using an ultracentrifuge, the separated acetone solution is dropped into methanol to obtain a non-grafted portion, and the weight is measured by drying at 60 to 120 ° C. From these weights, the graft rate is calculated according to the following equation (3).
&Quot; (3) "
Graft rate (%) = weight of grafted monomer (g) / rubber weight (g) x 100
At this time, when the graft rate is 25% or less, the gloss is lowered, which is not preferable.
≪ Preparation of rubber-reinforced resin composition >
After the completion of the reaction the graft rubber latex having an average particle size In 0.9㎛ antioxidants (winstay-L / IR1076 = 0.8 / 0.2) 0.5 parts by weight of the emulsion, while it maintains the coagulation bath to 85 ℃ H 2 SO 4 ( 10% aqueous solution), followed by primary agglomeration and secondary aging at 97 DEG C, followed by dehydration and drying to obtain a powdery graft polymer. To 25 parts by weight of this powdery graft copolymer were added 75 parts by weight of a styrene-acrylonitrile (SAN) copolymer having a weight average molecular weight of 110,000 g / mol and an acrylonitrile content of 27% by weight, 1.0 part by weight of a lubricant and 0.1 part by weight of a heat stabilizer 0.1 By weight, and extruded and injection-molded to prepare a specimen having a final rubber content of 16.5% by weight.
Example 2
< Graft Preparation of Copolymer >
In the preparation of the graft copolymer of Example 1, 0.25 part by weight of myrcene was prepared in the same manner as the preparation of the graft copolymer of Example 1 except that the rubbery polymer was added at the time of charging. The polymerization conversion of the obtained polymer was 98.7%, the grafting rate was 39.5%, and the content of the resulting coagulated product was 0.03% by weight.
≪ Preparation of rubber-reinforced resin composition >
Extrusion and injection were carried out in the same manner as in the preparation of the rubber-reinforced resin composition of Example 1 to prepare specimens.
Example 3
& Lt ; Preparation of graft copolymer >
In the preparation of the graft copolymer of Example 1, 70 parts by weight of the large-diameter rubbery latex and 0.35 part by weight of myrcene were charged in a reactor substituted with nitrogen, and 7.5 parts by weight of acrylonitrile, 22.5 parts by weight , 10 parts by weight of ion-exchanged water, 0.12 parts by weight of t-butyl hydroperoxide, 0.3 parts by weight of a reactive emulsifier Alkenyl C16-18 succinate potassium slat (ELOPLA AS200) (aqueous solution of 28% solids) And 0.3 part by weight of tertiary dodecyl mercaptan were continuously added to the emulsion at 70 캜 for 1 hour. At this time, 0.054 parts by weight of dextrose, 0.004 parts by weight of sodium pyrophosphate and 0.002 parts by weight of ferrous sulfate were continuously added.
After the addition of the monomer emulsion, 0.05 part by weight of dextrose, 0.03 part by weight of sodium pyrophosphate, 0.001 part by weight of ferrous sulfate and 0.05 part by weight of t-butyl hydroperoxide were fed into the reactor, Lt; 0 > C for 1 hour, and then the reaction was terminated.
The polymerization conversion of the obtained polymer was 98.3%, the grafting rate was 37.0%, and the content of formed coagulated matter was 0.02%.
≪ Preparation of rubber-reinforced resin composition >
Extrusion and injection were carried out in the same manner as in the preparation of the rubber-reinforced resin composition of Example 1 to prepare specimens.
Example 4
A rubber-reinforced resin composition specimen was prepared in the same manner as in Example 1, except that 0.15 part by weight of myrcene was added in Example 1.
Example 5
A rubber-reinforced resin composition specimen was prepared in the same manner as in Example 1, except that 0.6 parts by weight of myrcene was added in Example 1.
Comparative Example One
& Lt ; Preparation of graft copolymer >
The graft copolymer of Example 1 was prepared in the same manner as the preparation of the graft copolymer of Example 1 except that no myrcene was added. The polymerization conversion of the obtained polymer was 97.0%, the grafting rate was 33.0%, and the content of formed coagulated matter was 0.05%.
≪ Preparation of rubber-reinforced resin composition >
Extrusion and injection were carried out in the same manner as in the preparation of the rubber-reinforced resin composition of Example 1 to prepare specimens.
Comparative Example 2
& Lt ; Preparation of graft copolymer >
The same procedure as in the preparation of the graft copolymer of Example 3 was conducted except that myrcene was not added in the preparation of the graft copolymer of Example 1 above. The polymerization conversion of the obtained polymer was 97.5%, the grafting rate was 28%, and the content of formed coagulated matter was 0.03%.
≪ Preparation of rubber-reinforced resin composition >
Extrusion and injection were carried out in the same manner as in the preparation of the rubber-reinforced resin composition of Example 1 to prepare specimens.
Comparative Example 3
A rubber-reinforced resin composition specimen was prepared in the same manner as in Example 1, except that 1.2 parts by weight of myrcene was added in Example 1.
[Test Example]
The properties of the graft copolymer powder and rubber-reinforced resin composition specimens prepared in Examples 1 to 5 and Comparative Examples 1 to 3 were measured by the following methods, and the results are shown in Table 1 below.
< Graft Copolymer Powder Characteristics>
A) Water content (%): The prepared graft copolymer powder was dehydrated at 2000 rpm, dried at 80 to 120 캜, and then measured using the following equation (4).
&Quot; (4) "
Water content = (Weight of latex resin powder before drying - Weight (g) of latex resin powder after drying) / Weight (g) of latex resin powder before drying X 100
(B) Content of fine powder (%): 70 ㎛ - 400 ㎛ size using standard netting Content of powder less than 70 ㎛ in the powdery powder
Fine content (%) = weight of powder less than 70 μm (g) / weight of whole measured powder (g) X 100
Caking (Cracking Rate (%)): 20 kg of powder was subjected to 40 kg of load and 30 minutes of standard cake, vibration was applied for 1 minute on 20 mesh vibration screen, And it is advantageous for the dosing.
Decay rate (%) = amount of powder left on screen (g) / weight of powder used for making cake (g) X 100
≪ Properties of rubber-reinforced resin composition >
A) Izod impact strength (㎏ · cm / ㎝): Measured by the ASTM 256 method with the thickness of the specimen being 1 / 4˝.
B) Surface gloss: measured by the ASTM D528 method at an angle of 45 °.
C) Residence gloss: The pellets obtained from the extruder were placed in an injection machine and held at 270 ° C for 15 minutes to obtain glossy specimens. The specimens were extruded without staying at 200 ° C and measured for 45 ° gloss. Respectively. The smaller the measured value, the better the staying gloss.
D) Residual discoloration (ΔE): L, a, and b values of the specimen obtained before and after retention were obtained on a glossy specimen obtained by the same method as that used for measuring the residence gloss, according to the following equation And the degree of discoloration of the stain was obtained.
&Quot; (5) "
As shown in Table 1 above, the rubber-reinforced resin compositions (Examples 1 to 5) prepared according to the present invention had a graft copolymer having an excellent graft ratio as well as myrcene even under a high rubber polymer content And it was confirmed that the water content and the fine powder content of the powder were low and the caking property was excellent and the polymer productivity and the mechanical properties were excellent.
However, as in Comparative Examples 1 and 2, when the myrcene was not added, it was confirmed that the graft ratio of the graft copolymer was low, the moisture content and the fine powder content of the powder were high, and the caking property was poor.
When the amount of myrcene added was greater than that of the present invention as in Comparative Example 3, the graft ratio of the graft copolymer was high, but it was difficult to keep the process constant due to the high coagulum content. It was confirmed that the impact strength, whiteness, gloss, staying luster and staining discoloration were all poor.
Claims (19)
Graft copolymer.
Wherein the rubbery polymer has an average particle diameter of 2500 to 4000 Å, a gel content of 80 to 99% by weight, and a glass transition temperature of 0 ° C. or less
Graft copolymer.
Wherein the rubbery polymer is a conjugated diene-based rubber
Graft copolymer.
Wherein the graft copolymer has a graft ratio of 35% or more
Graft copolymer.
Characterized in that the graft copolymer has a fineness content of less than < RTI ID = 0.0 > 70 < / RTI &
Graft copolymer.
The graft copolymer is characterized in that the caking property is 80% or more
Graft copolymer.
Wherein the graft copolymer is graft-polymerized, further comprising a reactive emulsifier
Graft copolymer.
Thermoplastic resin composition.
Wherein the graft copolymer is 20 to 40 wt%, and the aromatic vinyl compound-vinyl cyanide copolymer is 60 to 80 wt%
Thermoplastic resin composition.
Wherein the aromatic vinyl compound-vinyl cyanide copolymer has a weight average molecular weight of 80,000 to 150,000 g / mol
Thermoplastic resin composition.
Wherein the thermoplastic resin composition further comprises at least one member selected from the group consisting of an antioxidant, a lubricant, and a heat stabilizer
Thermoplastic resin composition.
Wherein the thermoplastic resin composition has a total rubber content of 10 to 30% by weight
Thermoplastic resin composition.
Graft copolymer.
Wherein the graft polymerization is carried out by further comprising a reactive emulsifier
Graft copolymer.
The myrcene may be added together with the rubbery polymer thus prepared, or may be continuously mixed with the monomer mixture
Graft copolymer.
The graft polymerization is characterized in that the polymerization conversion ratio is 98% or more
Graft copolymer.
Shaped article.
Wherein the molded article is a refrigerator component, a refrigerator body or a refrigerator housing
Shaped article.
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|---|---|---|---|---|
| JP2001261755A (en) * | 2000-03-15 | 2001-09-26 | Mitsubishi Rayon Co Ltd | Graft copolymer and thermoplastic resin composition comprising the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2001261755A (en) * | 2000-03-15 | 2001-09-26 | Mitsubishi Rayon Co Ltd | Graft copolymer and thermoplastic resin composition comprising the same |
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