KR102023985B1 - Method for producing graft copolymer and thermoplastic resin composition containing the same - Google Patents
Method for producing graft copolymer and thermoplastic resin composition containing the same Download PDFInfo
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- KR102023985B1 KR102023985B1 KR1020160011520A KR20160011520A KR102023985B1 KR 102023985 B1 KR102023985 B1 KR 102023985B1 KR 1020160011520 A KR1020160011520 A KR 1020160011520A KR 20160011520 A KR20160011520 A KR 20160011520A KR 102023985 B1 KR102023985 B1 KR 102023985B1
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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
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
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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
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
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- 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
- C08L51/06—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 homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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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
- C08J2300/00—Characterised by the use of unspecified polymers
- C08J2300/22—Thermoplastic resins
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Abstract
The present disclosure relates to a method for preparing a graft copolymer, and a thermoplastic resin composition prepared therefrom, and more particularly, based on 100 parts by weight of the total monomers used for preparing the graft copolymer, based on (a) alkyl acrylate type. Preparing a seed latex by polymerizing 5 to 20 parts by weight of a monomer including 0.5 to 5.0 parts by weight of a nonionic emulsifier having a cloud point of 73 to 83 ° C; (b) preparing a core by polymerizing 20 to 70 parts by weight of an alkyl acrylate monomer in the presence of the prepared seed latex; (c) aging the prepared core at a cloud point of or higher than the nonionic emulsifier of step (a), but not exceeding a maximum of 85 ° C. to enlarge the large diameter core; And (d) polymerizing 20 to 75 parts by weight of at least one monomer selected from the group consisting of a vinyl monomer, a vinyl cyan monomer and an alkyl (meth) acrylate monomer in the presence of the large diameter core to prepare a graft shell. It relates to a method for producing a graft copolymer comprising;
According to the present invention, while producing a large diameter graft copolymer in a short time, there is an effect of providing a method for producing a graft copolymer and the like which is remarkably improved in weather resistance, pigment colorability and impact resistance.
Description
The present invention relates to a method for producing a graft copolymer, and a thermoplastic resin composition comprising the graft copolymer, and more particularly, to prepare a large-diameter graft copolymer in a short time, and at the same time weather resistance, pigment colorability and impact resistance It provides a method for producing a significantly improved graft copolymer, and relates to a thermoplastic resin composition comprising the graft copolymer.
ABS resin is an acrylonitrile-butadiene-styrene terpolymer and has excellent impact resistance, rigidity, chemical resistance and processability, and is widely used in various fields such as electric / electronic, construction, and automobile. However, since ABS resin uses butadiene polymer as rubber, there is a problem in that it is not suitable as an outdoor material because of poor weather resistance.
In general, in order to obtain a thermoplastic resin having excellent physical properties and excellent weatherability and aging resistance, there should be no ethylenically unsaturated polymer in the graft copolymer. Acrylonitrile-styrene-acrylate (ASA) resins are crosslinked alkyl acrylate rubber polymers that do not contain ethylenically unsaturated polymers, so they are excellent in weatherability and aging resistance. It is used in many ways.
As a method for preparing the ASA polymer having excellent weather resistance and aging resistance, German Patent No. 1,260,135 uses a cross-linked acrylate large diameter latex having an average particle diameter of 150 to 800 nm and a narrow particle size distribution as a core. According to the German patent, the ASA polymer including the large diameter polyacrylate latex has the advantage that the notch impact strength is improved, the hardness is high, and the shrinkage is reduced, compared to the ASA polymer prepared using the small diameter polyacrylate latex, but the small diameter graph Compared with the ASA polymer using the copolymer, there is a problem that coloring is difficult and manufacturing time is long.
In addition, U. S. Patent No. 4,224, 419 relates to a thermoplastic resin composition having high weather resistance and high impact resistance, which is easy to color, and is a crosslinked acrylate polymer having an average particle diameter of about 50 to 150 nm and a graft shell with styrene and acryl. First graft copolymer made of nitrile; A crosslinked acrylate polymer having an average particle diameter of about 200 to 500 nm as a core and a second graft copolymer comprising styrene and acrylonitrile as a graft shell; And a hard resin including a copolymer of acrylonitrile and styrene or α-methylstyrene. The weight ratio of the core in the first graft copolymer and the second graft copolymer is 90: 1 to 35:65. And the sum of the cores is about 10 to 35% by weight in the thermoplastic resin composition.
In addition, European Patent Nos. 534,212 and US Pat. No. 5,932,655 prepare large-diameter graft copolymers and small-diameter graft copolymers, respectively, and use the seed component as a hard component having a glass transition temperature higher than room temperature, thereby improving colorability and impact resistance. The method to make it are disclosed. Specifically, European Patent No. 534,212 uses hard seeds only for small diameter graft copolymers, and US Patent No. 5,932,655 uses hard polystyrene seeds for both large diameter and small diameter graft copolymers.
The prior art as described above has a somewhat improved weather resistance, mechanical properties and colorability, but insufficient level, the large diameter graft copolymer used to improve the colorability has a problem that the production time is long, the productivity is lowered.
In order to solve the problems of the prior art as described above, it is an object of the present invention to provide a method for producing a graft copolymer with a significant improvement in weather resistance, pigment colorability and impact resistance while producing a large diameter graft copolymer in a short time.
In addition, an object of the present invention is to provide a thermoplastic resin composition comprising a graft copolymer produced by the above method.
The above and other objects of the present disclosure can be achieved by the present disclosure described below.
In order to achieve the above object, the present disclosure is based on 100 parts by weight of the total monomers used in the graft copolymer preparation, (a) 5 to 20 parts by weight of the alkyl acrylate monomer 73 to 83 cloud point (cloud point) Preparing a seed latex by polymerization including 0.5 to 5.0 parts by weight of a nonionic emulsifier, (b) preparing a core by polymerizing 20 to 70 parts by weight of an alkyl acrylate monomer in the presence of the prepared seed latex; (c) aging the prepared core at a cloud point of or higher than the nonionic emulsifier of step (a), but not exceeding a maximum of 85 ° C. to enlarge the core to a large diameter core; And (d) polymerizing 20 to 75 parts by weight of at least one monomer selected from the group consisting of an aromatic vinyl monomer, a vinyl cyan monomer and an alkyl (meth) acrylate monomer in the presence of the large diameter core to prepare a graft shell; It provides a method for producing a graft copolymer comprising a.
In addition, the present disclosure provides a thermoplastic resin composition comprising a graft copolymer prepared by the above method.
According to the present disclosure, a large diameter graft copolymer can be prepared in a short time, and the thermoplastic resin prepared from the large diameter graft copolymer has an effect of remarkably improving weather resistance, pigment colorability, and impact resistance.
Hereinafter, the present description will be described in detail.
The present description is based on 100 parts by weight of the total monomers used to prepare the graft copolymer, (a) 0.5 to 5.0 nonionic emulsifiers having a cloud point of 73 to 83 ℃ to 5 to 20 parts by weight of alkyl acrylate monomers Preparing a seed latex by polymerization, including parts by weight; (b) preparing a core by polymerizing 20 to 70 parts by weight of an alkyl acrylate monomer in the presence of the prepared seed latex; (c) aging the prepared core at a cloud point of or higher than the nonionic emulsifier of step (a), but not exceeding a maximum of 85 ° C. to enlarge the large diameter core; And (d) polymerizing 20 to 75 parts by weight of at least one monomer selected from the group consisting of an aromatic vinyl monomer, a vinyl cyan monomer and an alkyl (meth) acrylate monomer in the presence of the large diameter core to prepare a graft shell; The graft copolymer prepared while preparing a large diameter graft copolymer in a short time by the method of manufacturing a graft copolymer comprising a has the effect of remarkably improving weather resistance, pigment colorability and impact resistance.
The term "cloud point", unless otherwise specified, tends to increase solubility generally with ionic emulsifiers as the temperature rises, whereas nonionic emulsifiers decrease solubility and have a temperature range of ± 0.1 Hydrating crystals precipitate at 占 폚 and change to a cloudy state like cloud, which refers to the temperature at which such a state occurs.
The nonionic emulsifier having a cloud point of 73 to 83 ° C. is not particularly limited as long as it is a nonionic emulsifier used for preparing a conventional graft copolymer. Examples thereof include ethoxylated alcohols, ethoxylated alkyl phenols, and fatty acids. At least one selected from the group consisting of ester-based and nitrogen-based nonionics, in which case the production time of the graft copolymer is shortened, and the weathering, pigment coloring and impact resistance of the manufactured graft copolymer are excellent. .
Seed latex of the step (a) may be an average particle diameter of 5 to 50nm, 10 to 45nm, or 15 to 40nm, for example, there is an effect that is easy to manufacture a large diameter core within this range and the impact strength is improved. .
In the step (a), the alkyl acrylate monomer may be, for example, 5 to 20 parts by weight, 7 to 19 parts by weight, or 10 to 17 parts by weight, and has excellent effects on physical properties and colorability within this range.
In the step (b), the temperature at the time of the core polymerization can be polymerized in a range not exceeding the cloud point of the nonionic emulsifier, for example, but not exceeding 85 ° C., and the stability of the latex is excellent within this range.
In the step (b), the alkyl acrylate monomer may be, for example, 20 to 70 parts by weight, 26 to 65 parts by weight, or 30 to 60 parts by weight, and both impact strength and tensile strength are excellent in this range. .
In the step (b), the alkyl acrylate monomer may be polymerized by, for example, batch administration or continuous administration to seed latex.
Aging in step (c) may be, for example, 30 to 90 minutes, or 40 to 80 minutes, and within this range, the particles of the core are effectively enlarged to large diameters.
In step (c), the solubility of the nonionic emulsifier is reduced by aging at or above the cloud point of the nonionic emulsifier of step (a), but not exceeding 85 ° C., thereby losing the role of the emulsifier, thereby losing the role of the emulsifier. There is an effect that the micro-agglomeration occurs and enlarges. When (c) exceeds 85 ° C., there is a problem that the stability of the latex is lowered.
In the step (c), the large-diameter core may have, for example, an average particle diameter of 200 to 700 nm, 250 to 650 nm, or 300 to 600 nm, and has excellent colorability within this range.
The large-diameter core of step (c) is, for example, 50 to 95% by weight or 70 to 80% by weight of the gel content, within this range has an excellent balance of physical properties, glossiness and combustibility.
The steps (a) and (b) may further include one or more selected from the group consisting of diene monomers, aromatic vinyl monomers, alkyl (meth) acrylate monomers, and vinyl cyan monomers. .
The alkyl acrylate monomer may be, for example, an alkyl acrylate having 2 to 8 carbon atoms in the alkyl group, and as another example, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethyl Hexyl acrylate, hexyl methacrylate and 2-ethylhexyl methacrylate may be one or more selected from the group consisting of, preferably n-butyl acrylate can be used.
The diene monomer is for example one selected from the group consisting of 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-pentadiene and isoprene It may be abnormal.
The aromatic vinyl monomer may be at least one selected from the group consisting of styrene, α-methylstyrene, o-ethylstyrene, p-ethylstyrene, and vinyltoluene.
The alkyl (meth) acrylate monomer may be, for example, an alkyl (meth) acrylate having 2 to 8 carbon atoms in the alkyl group, preferably ethyl acrylate, ethyl methacrylate, methyl acrylate, methyl methacrylate. It may be at least one selected from the group consisting of, butyl acrylate, butyl methacrylate, propyl acrylate, propyl methacrylate, and 2-ethylhexyl acrylate.
The vinyl cyan monomer may be at least one selected from the group consisting of, for example, acrylonitrile, methacrylonitrile, and ethacrylonitrile.
Step (a) is a specific example of 0.1 to 3 parts by weight of anionic emulsifier, 0.01 to 0.5 parts by weight of crosslinking agent, 0.01 to 0.5 parts by weight of grafting agent, polymerization initiator based on 100 parts by weight of the total monomers used in the graft copolymer production. The polymerization may be performed by including 0.01 to 1.5 parts by weight and 0.01 to 1.0 parts by weight of the electrolyte.
Step (b) is a specific example of 0.1 to 5.0 parts by weight of anionic emulsifier, 0.05 to 0.5 parts by weight of crosslinking agent, 0.03 to 0.3 parts by weight of grafting agent and polymerization initiator based on 100 parts by weight of the total monomers used to prepare the graft copolymer. It may be a step of polymerization including 0.02 to 1.5 parts by weight.
Step (d) includes 0.5 to 3.0 parts by weight of anionic emulsifier, 0.02 to 1.5 parts by weight of polymerization initiator, and 0.01 to 0.5 parts by weight of molecular weight modifier based on 100 parts by weight of the total monomers used to prepare the graft copolymer. It may be a step of polymerizing.
The anionic emulsifier in the (a), (b) and (d) step has the effect of increasing the stability of the latex and increase the particle size within the above range.
The anionic emulsifier may be, for example, fatty acid soap system such as oleic acid, stearic acid, lauric acid, sodium or potassium salt of mixed fatty acid, rosin acid soap system such as abietin acid salt, or a mixture thereof.
In step (a), (b) and (d), the polymerization initiator is, for example, a water-soluble initiator such as sodium persulfate, potassium persulfate, ammonium persulfate, cumene hydroperoxide, diisopropyl benzene hydroperoxide, azobis At least one selected from the group consisting of oil-soluble initiators such as isobutylnitrile, tertiary butyl hydroperoxide, paramethane hydroperoxide and benzoyl peroxide and an oxidation-reducing agent can be used.
In the step (a), the electrolyte is, for example, KCl, NaCl, KHCO 3 , NaHCO 3 , K 2 CO 3 , Na 2 CO 3 , KHSO 3 , NaHSO 3 , Na 2 S 2 O 7 , K 4 P 2 O 7 , It may be at least one selected from the group consisting of K 3 PO 4 , Na 3 PO 4 , K 2 HPO 4 and Na 2 HPO 4 .
The step (a) and (b) may be polymerized further including a crosslinking agent, a grafting agent or both.
The crosslinking agent is, for example, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, neo At least one selected from the group consisting of pentyl glycol dimethacrylate, trimethylolpropane trimethacrylate and trimethylol methane triacrylate.
The grafting agent is used in the graft polymerization reaction, which is a polymerization reaction in which a straight chain polymer is used as a stem and other kinds of polymers are bound together as if they are branched, for example, allyl methacrylate (AMA) and triallyl isocyanur. It may be at least one selected from the group consisting of latex (TAIC), triallylamine (TAA) and diallylamine (DAA).
In the step (d), the molecular weight modifier is used to adjust the molecular weight of the graft polymer, and may be, for example, mercaptans, specifically, α-methylstyrene dimer, t-dodecyl mercaptan, n-dodecyl mercaptan It may be at least one selected from the group consisting of, and octyl mercaptan.
The graft copolymer may be prepared as a graft copolymer powder through agglomeration, aging, dehydration and washing.
The aggregation may be performed using a flocculant, and for example, sulfuric acid, MgSO 4 , CaCl 2, and Al 2 (SO 4 ) 3 may be one or more selected from the group consisting of.
In addition, the present invention provides a thermoplastic resin composition comprising 10 to 90% by weight of the graft copolymer and 10 to 90% by weight of the hard matrix resin prepared by the above production method.
The hard matrix resin may be, for example, a resin having a glass transition temperature of 60 ° C. or higher or 60 to 200 ° C.
As another example, the hard matrix resin may include a polymer polymerized including at least one monomer selected from the group consisting of an aromatic vinyl compound, a vinyl cyan compound, and methyl methacrylate; Polymers polymerized from monomers having polar functional groups such as polyols, polycarboxylic acids, vinyl chlorides, and polyamines; Or a mixture thereof.
As a specific example, the hard matrix resin may be polymethyl methacrylate, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, acrylonitrile-ethylene-propylene-diene-styrene copolymer, polycarbonate, poly With butylene terephthalate, polyethylene terephthalate, polyvinyl chloride, polystyrene, methyl methacrylate-styrene copolymer, acrylonitrile-styrene-methyl methacrylate copolymer, polyacetal resin, polyphenylene ether and polyamide resin It may be at least one selected from the group consisting of.
The thermoplastic resin composition may include at least one selected from the group consisting of dyes, pigments, oxidative stabilizers, ultraviolet stabilizers, reinforcing agents, fillers, flame retardants, foaming agents, lubricants, and plasticizers, in which the graft copolymer and the hard matrix resin total 100 weight. 0.1 to 10 parts by weight, 1.0 to 5 parts by weight, or 1.5 to 3 parts by weight may be further included.
EXAMPLE
Example One
Seed latex manufacturers
10 parts by weight of butyl acrylate, 5 parts by weight of styrene, 0.02 parts by weight of ethylene glycol dimethacrylate, allyl methacrylate, based on 100 parts by weight of the total monomers used to prepare the graft copolymer in a nitrogen-substituted polymerization reactor (autoclave). Rate 0.04 parts by weight, polyoxyethylene lauryl ether (nonionic emulsifier, cloud point 77 ~ 79 ℃), 2.0 parts by weight, 0.5 parts by weight of potassium laurate salt, 0.1 parts by weight of sodium chloride (NaCl), and 70 parts by weight of distilled water After the batch was administered and the reaction temperature was raised to 70 ° C., 0.05 parts by weight of sodium persulfate was dosed to react to obtain a seed latex having an average particle diameter of 30 nm.
Core manufacturing
40 parts by weight of butyl acrylate, 1.0 parts by weight of potassium laurate salt, 0.2 parts by weight of ethylene glycol dimethacrylate, allyl methacrylate, in the presence of the seed latex, based on 100 parts by weight of the total monomers used to prepare the graft copolymer. A mixture of 0.3 parts by weight and 50 parts by weight of distilled water was continuously administered at 70 ° C. for 3 hours, and then heated to 80 ° C. and aged for 1 hour to obtain a large diameter core.
In this case, the large diameter core had an average particle diameter of 470 nm and a gel content of 80 wt%.
Graft Shell manufacturer
30 parts by weight of styrene, 15 parts by weight of acrylonitrile, 1.3 parts by weight of potassium laurate salt, and 0.01 parts by weight of tertiary dodecyl mercaptan based on 100 parts by weight of the total monomers used to prepare the graft copolymer. , The mixture of 0.2 parts by weight of sodium persulfate and 50 parts by weight of distilled water was continuously administered at 75 ° C. for 2 hours, and then further reacted for 1 hour. After cooling the reactor internal temperature to 60 ° C., the polymerization was terminated. To prepare a copolymer.
The graft copolymer prepared above was agglomerated at 85 ° C. using an aqueous calcium chloride solution, then aged at 95 ° C., dehydrated and washed, and dried for 30 minutes with hot air at 90 ° C. to obtain final graft copolymer particles. .
Preparation of Thermoplastic Resin Composition
40 parts by weight of the prepared graft copolymer particles, 60 parts by weight of styrene-acrylonitrile copolymer (92HR, LG Chem.) As a hard matrix, 1 part by weight of lubricant, 0.5 parts by weight of antioxidant and 0.5 parts by weight of UV stabilizer And mixed. The mixture was prepared in pellet form using a 40 pie compression kneader at a cylinder temperature of 220 ° C., and injected into the pellet to prepare a physical specimen.
In addition, 40 parts by weight of the graft copolymer particles prepared above, 60 parts by weight of styrene-acrylonitrile copolymer (92HR, LGChem.) As a hard matrix, 1 part by weight of lubricant, 0.5 parts by weight of antioxidant, 0.5 parts by weight of UV stabilizer And 1 part by weight of carbon black were mixed. The mixture was then prepared in pellet form using a 40 pie kneader at a cylinder temperature of 220 ° C., and injected into the pellet to prepare a pigment complexation measurement specimen.
Example 2
A graft copolymer was prepared in the same manner as in Example 1, except that 1.0 parts by weight of polyoxyethylene lauryl ether was used in preparing the seed latex in Example 1. At this time, the average particle diameter of the large diameter core was 400nm and the gel content was 71% by weight.
Example 3
In Example 1, the core was manufactured in the same manner as in Example 1, except that the temperature was increased to 80 ° C. during the polymerization of the core instead of the reactor internal temperature. At this time, the average particle diameter of the large diameter core was 340nm and the gel content was 75% by weight.
Example 4
A seed latex was prepared in Example 1, except that polyoxyethylene lauryl ether, a nonionic emulsifier, was used in an amount of 4.0 parts by weight. At this time, the average particle diameter of the large diameter core was 460nm and the gel content was 77% by weight.
Comparative example One
The seed latex was prepared in the same manner as in Example 1, except that the polyoxyethylene lauryl ether was not used in the preparation of the seed latex in Example 1, followed by preparing a core to prepare a graft copolymer. At this time, the average particle diameter of the large diameter core was 430nm and the gel content was 74% by weight.
Comparative example 2
Cores were prepared in the same manner as in Example 1 except that the reactor internal temperature was increased to 75 ° C. after the core was manufactured in Example 1, wherein the average diameter of the large-diameter core was 100 nm and the gel content was 70 wt%.
Comparative example 3
In Example 1, the seed latex was prepared in the same manner as in Example 1, except that 2.0 parts by weight of the polyoxyethylene lauryl ether was added after preparing the seed latex without using the polyoxyethylene lauryl ether. At this time, the average particle diameter of the large-diameter core was 320 nm and the gel content was 70% by weight.
Comparative example 4
In Example 1, the seed latex was prepared in the same manner as in Example 1, except that 2.0 parts by weight of polyoxyethylene lauryl ether was added after preparing the core without using polyoxyethylene lauryl ether. At this time, the average particle diameter of the large diameter core was 450nm and the gel content was 70% by weight.
Comparative example 5
In Example 1, except that 0.3 parts by weight of polyoxyethylene lauryl ether was used to prepare the seed latex, the preparation was performed in the same manner as in Example 1. At this time, the average particle diameter of the large diameter core was 230nm and the gel content was 69% by weight.
Comparative example 6
After preparing the core in Example 1 was prepared in the same manner as in Example 1 except that the temperature inside the reactor was raised to 86 ℃. At this time, the stability of the emulsifier was lowered and latex could not be prepared.
[Test Example]
The properties of the specimens prepared in Examples 1 to 4 and Comparative Examples 1 to 5 were measured by the following method, and the results are shown in Table 1 below.
* Average particle size: The average particle diameter was measured using an intensity Gaussian distribution (Nicomp 370HPL) by dynamic laser light scattering.
Gel content: The rubber latex is coagulated with dilute acid or metal salt, washed, dried in a vacuum oven at 60 ° C. for 24 hours, and then the resulting rubber mass is chopped with scissors, and then 1 g of rubber sections is added to 100 g of toluene. After storing for 48 hours at room temperature in the dark, separated into a sol and gel, the gel content was measured according to the following formula (1).
[Equation 1]
Gel content (% by weight) = [weight of insolubles (gel) / weight of sample] × 100
* Seed preparation time: measured based on exothermic peak time.
Izod impact strength (1/4 "notched at 23 ° C., -20 ° C .; kgf · cm / cm): Measured according to ASTM D256.
Pigment coloring: The L value of the colorimetric measurement specimen was measured using a color difference meter. At this time, the lower the L value, the lower the brightness is to give a dark black color means that the pigment colorability is good.
* Weather resistance: 83 ℃ water spray cycle on waterometer (Weatherometer, Ci35A, ATLAS Co., Ltd.) for 18 hours / 120 minutes, leaving the resin for 2,000 hours, then discoloration degree (△ E) Was measured. At this time, the degree of discoloration (ΔE) is the arithmetic mean value of the Hunter Lab (Hunter Lab) value before and after the 2,000 hours weathering test, the closer to 0 means better weatherability.
Manufacture time
Impact strength
Coloring
As shown in Table 1, Examples 1 to 4 according to the present invention was able to produce a large diameter graft copolymer in a short time compared to Comparative Examples 1 to 5, and at the same time excellent in Izod impact strength, pigment colorability and weather resistance Could confirm. However, when the nonionic emulsifier according to the present disclosure is not used as in Comparative Example 1, impact strength and weather resistance were decreased, and the seed production time was increased. In addition, Comparative Example 2, in which the core was aged at a temperature lower than the cloud point of the nonionic emulsifier, had a short seed production time but a very small average particle diameter, a sharp drop in impact strength, and a nonionic emulsifier in the seed. 3 and 4 also increased seed preparation time and reduced weather resistance. Comparative Example 5 using a small amount of the nonionic emulsifier was increased seed production time and the impact strength was very low, Comparative Example 6 was unable to measure the physical properties because the latex was not manufactured due to the stability of the nonionic emulsifier.
Claims (10)
(a) preparing a seed latex by polymerizing 5 to 20 parts by weight of an alkyl acrylate monomer with 0.5 to 5.0 parts by weight of a nonionic emulsifier having a cloud point of 73 to 83 ° C;
(b) polymerizing 20 to 70 parts by weight of an alkyl acrylate monomer in the presence of the prepared seed latex to prepare a core;
(c) aging the prepared core at a cloud point of or higher than the nonionic emulsifier of step (a), but not exceeding a maximum of 85 ° C. to enlarge the large diameter core; And
(d) polymerizing 20 to 75 parts by weight of at least one monomer selected from the group consisting of an aromatic vinyl monomer, a vinyl cyan monomer and an alkyl (meth) acrylate monomer in the presence of the large diameter core to prepare a graft shell;
Including,
The graft characterized in that the nonionic emulsifier having a cloud point of 73 to 83 ° C. is at least one selected from the group consisting of ethoxylated alcohols, ethoxylated alkylpetols, fatty acid esters and nitrogen-based nonionics. Method of Preparation of Copolymer.
Seed latex in step (a) is a method for producing a graft copolymer, characterized in that the average particle diameter of 5 to 50nm.
In the step (c), the large-diameter core has an average particle diameter of 200 to 700 nm and a gel content of 50 to 95 wt%.
In the steps (a) and (b), the alkyl acrylate monomer is used as the diene monomer, the aromatic vinyl monomer, the alkyl (meth) acrylate monomer and the vinyl cyan monomer alone or in the alkyl acrylate monomer. Method for producing a graft copolymer, characterized in that it comprises one or more selected from the group consisting of.
The method of producing a graft copolymer, characterized in that the polymerization at the core polymerization temperature in the step (b) at a cloud point or higher than the nonionic emulsifier, but not exceeding a maximum of 85 ℃.
Step (a) and (b) is an alkyl acrylate monomer, a crosslinking agent; Or a crosslinking agent and a grafting agent.
The hard matrix resin is polymethyl methacrylate, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, acrylonitrile-ethylene-propylene-diene-styrene copolymer, polycarbonate, polybutylene tere From phthalate, polyethylene terephthalate, polyvinyl chloride, polystyrene, methyl methacrylate-styrene copolymer, acrylonitrile-styrene-methyl methacrylate copolymer, polyacetal resin, polyphenylene ether and polyamide resin The thermoplastic resin composition, characterized in that at least one selected.
The thermoplastic resin composition further comprises one or more selected from the group consisting of dyes, pigments, oxidative stabilizers, ultraviolet stabilizers, reinforcing agents, fillers, flame retardants, foaming agents, lubricants and plasticizers.
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| FR2619570B1 (en) * | 1987-08-20 | 1992-02-14 | Charbonnages Ste Chimique | PROCESS FOR THE MANUFACTURE OF AN IMPACT RESISTANT THERMOPLASTIC RESIN, COMPRISING A STEP OF TRANSFER OF THE PARTICLES OF A REINFORCING LATEX IN THE MATRIX MONOMERS, BY FORMING INTERPOLYMER COMPLEXES DESTABILIZING THE LATEX |
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| KR100787338B1 (en) * | 2005-08-12 | 2007-12-18 | 주식회사 엘지화학 | Method for preparing graft copolymer |
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