KR20160118707A - Impact strength modifier for polyester resin and thermoplastic polyester resin composition containing the same - Google Patents
Impact strength modifier for polyester resin and thermoplastic polyester resin composition containing the same Download PDFInfo
- Publication number
- KR20160118707A KR20160118707A KR1020150047241A KR20150047241A KR20160118707A KR 20160118707 A KR20160118707 A KR 20160118707A KR 1020150047241 A KR1020150047241 A KR 1020150047241A KR 20150047241 A KR20150047241 A KR 20150047241A KR 20160118707 A KR20160118707 A KR 20160118707A
- Authority
- KR
- South Korea
- Prior art keywords
- weight
- parts
- polyester resin
- ethylene glycol
- compound
- Prior art date
Links
Classifications
-
- 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
- C08K5/01—Hydrocarbons
-
- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
-
- 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
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/009—Additives being defined by their hardness
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
Abstract
Description
The present invention relates to an impact modifier for polyester resins and a thermoplastic polyester resin composition using the same, and more particularly, to an impact modifier having a core-shell structure improved in impact reinforcing effect by synthesis using a phosphate emulsifier, To a thermoplastic polyester resin composition having improved transparency and impact strength.
Generally, thermoplastic polyester resins such as polybutylene terephthalate and polybutylene terephthalate are excellent in chemical resistance such as solvent resistance, acid resistance and alkali resistance, heat resistance, transparency, and mechanical properties, Is widely used not only for industrial materials such as automobiles, electric and electronic parts, but also in packaging materials such as bottles and the like. Particularly in recent years, extrusion applications such as sheet, film, profile extrusion and the like have been studied taking advantage of transparency and surface property.
However, when such a thermoplastic polyester resin is to be used in industrial materials as described above, in addition to flame retardancy and rigidity, impact strength and toughness are additionally required. Since the polyester resin is a crystalline polymer, It has a disadvantage that the impact resistance is poor. Particularly, since the impact resistance is further lowered at a low temperature, the use of the resin as an industrial material is limited. Moreover, since the polyester resin generally has a large temperature dependence of the melt viscosity, the melt viscosity is low in the melt processing such as injection molding and extrusion molding, which is performed in a temperature range higher than the melting point, which is disadvantageous.
A method for improving the physical properties of a polyester resin by adding various kinds of impact modifiers has been known as a method for overcoming such problems.
As a method for improving the impact resistance of a polyester resin, there has been proposed a method of adding an? -Olefin-based copolymer as an impact modifier to a thermoplastic polyester resin. In this case, although a relatively excellent impact resistance is exhibited, a thermoplastic polyester resin the compatibility between the? -olefin-based copolymer becomes poor, resulting in a problem that the physical properties of the molded article are deteriorated when used for a long period of time.
Alternatively, a butadiene-based copolymer was added to the epoxy compound to improve the impact resistance and moldability, but the heat resistance was poor and the moldability was poor. In addition, there has been proposed a method of mixing a copolymer made of a monomer such as an? -Olefin-based,?,? -Unsaturated glycidyl ester, etc. However, the molded product obtained by this method exhibits good impact resistance near room temperature, There has been a problem that the impact resistance is significantly lowered at a low temperature atmosphere of 40 캜.
Thus, in order to improve the impact resistance and toughness of conventional polyester resins, additives such as impact modifiers have been used to mix, but the differences in physical properties have not been overcome.
Recently, a method of blending an impact modifier comprising a copolymer having compatibility with these resins, that is, a thermoplastic graft copolymer, has been proposed in order to improve the moldability of the thermoplastic polyester resin. However, even in such a case, the impact strength is improved, but the other properties are degraded.
That is, Patent Documents 1 and 2 disclose a method of increasing the impact strength of a polyester resin composition by adding a core-shell type polymer having a butadiene-based core to a thermoplastic polyester resin as an impact modifier However, in this case, there is a problem that the transparency of the polyester resin composition is impaired. Patent Documents 3 to 5 disclose a method of using a rubber latex having a multi-layered structure in a graft copolymer in order to improve the impact strength of a polychlorinated resin. However, this also causes a problem that resin transparency is lowered due to a difference in refractive index Respectively.
Thus, it is necessary to develop a thermoplastic polyester resin composition which hardly changes in physical properties such as transparency when the impact strength is improved.
Disclosure of Invention Technical Problem [8] The present invention has been conceived to solve the problems of the prior art, and provides a method of manufacturing an impact modifier having a core-shell structure having improved compatibility with a polyester resin by synthesis using a phosphate emulsifier.
In addition, the present invention provides an impact modifier having a core-shell structure produced according to the above method.
The present invention also provides a thermoplastic polyester resin composition improved in transparency and impact strength by containing a poly (ethylene glycol) compound together with an impact modifier of the core-shell structure.
In order to solve the above problems,
In one embodiment of the present invention
5 to 30 parts by weight of a conjugated diene monomer, 70 to 95 parts by weight of an ethylenically unsaturated aromatic compound and 70 to 95 parts by weight of a poly (ethylene glycol) compound to form a seed;
70 to 95 parts by weight of a conjugated diene monomer, 5 to 30 parts by weight of an ethylenically unsaturated aromatic compound, 0.1 to 1 part by weight of a poly (ethylene glycol) compound and 1 to 2 parts by weight of a phosphate emulsifier in the presence of 1 to 20 parts by weight of the seed, Polymerizing to produce a core; And
20 to 80 parts by weight of an ethylenically unsaturated aromatic compound, 20 to 80 parts by weight of an acrylate compound, 1 to 2 parts by weight of a poly (ethylene glycol) compound and 1 to 2 parts by weight of a phosphate emulsifier in the presence of 40 to 70 parts by weight of the core To form 30 to 60 parts by weight of a shell. The present invention also provides a method for producing an impact modifier of a core-shell structure.
In addition, the present invention provides an impact modifier having a core-shell structure prepared from the above method.
Further, in the present invention, 50 to 95% by weight of a thermoplastic polyester resin; And
A thermoplastic polyester resin composition comprising 5 to 50% by weight of the impact modifier of the present invention.
According to the present invention, it is possible to synthesize an impact modifier having a core-shell structure having improved compatibility with a polyester resin by using a phosphate-based emulsifier. In addition, by including a poly (ethylene glycol) A thermoplastic polyester resin composition can be produced.
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.
The present inventors have studied a polyester resin composition comprising a thermoplastic polyester resin and an impact modifier for a thermoplastic polyester resin, and have included a core-shell structure impact modifier prepared by multistage graft polymerization of a phosphate emulsifier and a polyethylene monomer , It is confirmed that a thermoplastic polyester resin composition having improved transparency and impact strength can be produced with improved compatibility with a polyester resin, and the present invention has been completed on the basis thereof.
Specifically, in one embodiment of the present invention
5 to 30 parts by weight of a conjugated diene monomer, 70 to 95 parts by weight of an ethylenically unsaturated aromatic compound and 70 to 95 parts by weight of a poly (ethylene glycol) compound to form a seed;
70 to 95 parts by weight of a conjugated diene monomer, 5 to 30 parts by weight of an ethylenically unsaturated aromatic compound, 0.1 to 1 part by weight of a poly (ethylene glycol) compound and 1 to 2 parts by weight of a phosphate emulsifier in the presence of 1 to 20 parts by weight of the seed, Polymerizing to produce a core; And
20 to 80 parts by weight of an ethylenically unsaturated aromatic compound, 20 to 80 parts by weight of an acrylate compound, 1 to 2 parts by weight of a poly (ethylene glycol) compound and 1 to 2 parts by weight of a phosphate emulsifier in the presence of 40 to 70 parts by weight of the core To form 30 to 60 parts by weight of a shell. The present invention further provides a method for producing an impact modifier of a core-shell structure.
In the method of the present invention, the conjugated diene monomer is a component which imparts a role of absorbing impact from the outside to improve impact resistance, and is not particularly limited. For example, 1,3-butadiene, isoprene, And at least one selected from the group consisting of chloroprene. Specifically, it may be 1,3-butadiene.
The ethylenically unsaturated aromatic compound is a component that suppresses scattering of light generated by the difference in refractive index and maintains transparency by making the refractive index of the rubber latex equal to that of the thermoplastic polyester resin, and examples thereof include styrene, alpha At least one member selected from the group consisting of methylstyrene, isopropylphenylnaphthalene, vinylnaphthalene, alkylstyrene substituted with C 1 to C 3 alkyl groups, and halogen-substituted styrene.
The poly (ethylene glycol) compound is a component added to increase the size of the rubber polymer and improve the transparency. Typical examples thereof include poly (ethylene glycol) n acrylate, poly (ethylene glycol) n methacrylate PEGMA), and poly (ethylene glycol) n diacrylate, wherein n is an integer from 3 to 14, wherein the number average molecular weight of the poly (ethylene glycol) Mn) is preferably 300 to 10,000.
The amount of the poly (ethylene glycol) compound used is preferably 0.1 to 1 part by weight. When the amount of the poly (ethylene glycol) compound is less than 0.1 part by weight, the impact resistance of the impact modifier is deteriorated. There is a problem of deterioration.
In addition, the amount of the poly (ethylene glycol) compound used in the production of the shell is preferably 1 to 2 parts by weight. If the amount is less than 1 part by weight, the impact resistance of the impact modifier is deteriorated. If the amount is more than 2 parts by weight, the transparency is lowered.
The poly (ethyleneglycol) compound is a compound having an intermolecular stretch between a polyester resin and a graft chain outside the methyl methacrylate-butadiene-styrene graft copolymer (hereinafter referred to as MBS graft copolymer) the entanglement structure can be improved to dramatically improve the compatibility, thereby absorbing the external impact and improving the impact strength.
In addition, in the method of the present invention, the amount of the seed is preferably 1 to 20 parts by weight at the time of producing the core, and if it is less than 1 part by weight, the impact resistance of the impact modifier is deteriorated. There is a problem that transparency is lowered.
Further, in the method of the present invention, the phosphate emulsifier may include a compound represented by the following formula (1).
[Chemical Formula 1]
In this formula,
R is a branched or linear alkyl group having from 12 to 14 carbon atoms,
n is an integer of 4 to 8, and m is an integer of 1 to 2.
When R is not an alkyl having 12 to 14 carbon atoms, the chain of the hydrophobic group is insufficient and the emulsification function is weak. When the number of carbon atoms is too large, the viscosity is too high to use, and when the number of n is out of 4 to 8, . m is an integer of 1, 2, more preferably 1.
Specifically, in the above formula, R may be alkyl having 12 to 13 carbon atoms, n may be an integer of 5 to 7, and m may be 1. In another example, R may be alkyl of 12 carbon atoms, n may be 6, and m may be 1.
The phosphate emulsifier is a sodium salt of polyoxyethylene alkyl ether phosphate, and representative examples thereof include polyoxyethylene-9-lauryl ether, polyoxyethylene-9-stearyl ether, polyoxyethylene-8-stearyl ether, poly Oxyethylene-4-lauryl ether, polyoxyethylene-35-lauryl ether, and polyoxyethylene-23-lauryl ether.
Further, di (hexaoxyethylene lauryl ether) phosphate may be further used as the phosphate emulsifier.
In the method of the present invention, the amount of the phosphate emulsifier used is preferably 1 to 2 parts by weight, and if the amount is less than 1 part by weight, the impact modifier of the impact modifier may deteriorate. There is a problem that transparency is lowered.
In the method of the present invention, the seed forming step, the core forming step and the shell forming step may be such that polymerization is performed under different temperature conditions, respectively. Specifically, the seed forming step may be performed under a temperature condition of 60 ° C. to 72 ° C., and the core forming step may be performed under a temperature condition of 72 ° C. to 85 ° C., To < RTI ID = 0.0 > 85 C. < / RTI > That is, the present invention can perform the reaction while gradually increasing the temperature condition as the polymerization proceeds.
In addition, in the method of the present invention, the core preferably comprises 40 to 70 parts by weight of the core in forming the core-shell structure. When the amount is less than 40 parts by weight, the effect of improving the impact strength is insignificant, There is a problem that the dispersibility and the mechanical properties are deteriorated due to the lack of compatibility with the rubber latex and the thermoplastic polyester resin. Therefore, the impact modifier containing the core within this range is excellent in impact reinforcing effect, compatibility and dispersibility for the thermoplastic polyester resin and the like.
In the method of the present invention, the core-shell forming step is characterized in that it is produced by multi-stage graft copolymerization of a conjugated diene monomer, an ethylenically unsaturated aromatic compound and optionally a crosslinking agent, if necessary.
The crosslinking agent controls the degree of crosslinking of the rubber latex core and is preferably selected from the group consisting of divinylbenzene, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3-butylene glycol Dimethacrylate, aryl methacrylate, 1,3-butylene glycol diacrylate, and the like.
The crosslinking agent is preferably used in an amount of 5 parts by weight or less, more preferably 2 parts by weight or less, based on 100 parts by weight of the total monomers (including a crosslinking agent) used in the production of the impact modifier. Impact reinforcing effect of manufactured impact modifier is excellent.
The shell according to the method of the present invention may further comprise, in the presence of the core, 20 to 80 parts by weight of an ethylenically unsaturated aromatic compound, 20 to 80 parts by weight of an acrylate compound, 1 to 2 parts by weight of a poly (ethylene glycol) , And 1 to 2 parts by weight of a phosphate emulsifier is graft-emulsion-polymerized.
At this time, the acrylate monomer added to form the shell is not particularly limited, but is selected from the group consisting of hydroxyethyl methacrylate, ethylene glycol methacrylate, ethylene glycol acrylate, and ethylene glycol diacrylate It may be more than one species.
When the amount of the shell is less than 30 parts by weight, the compatibility is poor and the workability is poor. When the shell amount is more than 60 parts by weight, the impact strength is lowered.
In addition, in the method of the present invention, an ion exchange resin, a catalyst, a polymerization initiator, a heat stabilizer, an activator, and the like may be optionally added.
At this time, examples of the catalyst include sodium formaldehyde sulfoxylate and the like.
The polymerization initiator may be a water-soluble initiator of sodium persulfate, potassium persulfate or ammonium persulfate; Initiators of availability of cumene hydroperoxide, diisopropylbenzene hydroperoxide, azobisisobutylnitrile, tert-butyl hydroperoxide, paramethane hydroperoxide or benzoyl peroxide; Or a redox-based polymerization initiator in which an oxidation-reduction agent is combined, may be used.
Examples of the thermal stabilizer include N-methylhydroxyamine sulfate, N-ethylhydroxyamine sulfate, hydrochloride, diethylamine, tetraethylene, tetrapentylimine, diphenylamine, bis (p- Diamine tetra sodium acetate and the like can be used.
As the activating agent, for example, sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, ferrous sulfate, dextrose, sodium pyrophosphate or sodium sulfite may be used.
In an embodiment of the present invention,
50 to 95% by weight of a thermoplastic polyester resin; And
There is provided a thermoplastic polyester resin composition comprising 5 to 50% by weight of an impact modifier for a thermoplastic polyester resin produced by the method of the present invention.
At this time, the difference between the refractive index of the thermoplastic polyester resin and the refractive index of the impact modifier for thermoplastic polyester resin may be 0.005 or less.
In addition, the thermoplastic polyester resin composition may further include at least one member selected from the group consisting of process oil, lubricating oil, antioxidant, heat stabilizer, activator, and pigment.
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
Example 1
[Production of thermoplastic graft copolymer]
A methyl methacrylate-butadiene-styrene (MBS) graft copolymer was prepared as a thermoplastic graft polymer in the following manner. Here, parts by weight of the following compounds are expressed based on 100 parts by weight of the final graft copolymer.
(Core: manufactured by rubber latex)
(R: alkyl of 12 carbon atoms, n: 6, m: 1) as an emulsifier was added to a 120 L high-pressure polymerization vessel equipped with a stirrer, to which 150 parts by weight of ion exchanged water, 0.4 part by weight of sodium sulfate as an additive, 1.0 part by weight, polyethylene glycol methacrylate 0.5 part by weight, ethylenediaminetetra sodium acetate 0.0047 part by weight, ferrous sulfate 0.003 part by weight, sodium formaldehyde sulfoxylate 0.02 part by weight, and diisopropylbenzene hydroperoxide 0.1 part by weight The part was initially charged.
60 parts by weight of butadiene, 40 parts by weight of styrene, and 0.1 part by weight of divinylbenzene were charged and polymerized at 40 DEG C for 10 hours to obtain a styrene-butadiene rubber latex having a particle size of 1200 ANGSTROM, and its final polymerization conversion rate was 98%.
(Shell: preparation of thermoplastic graft copolymer)
45 parts by weight (solid content) of the obtained rubber latex was charged into a closed reactor, and then nitrogen was charged at 60 DEG C. Then, 0.0094 part by weight of ethylenediaminetetra sodium acetate, 0.006 part by weight of ferrous sulfate, 1.0 part by weight of a sodium salt of polyoxyethylene alkyl ether phosphate (R: alkyl having 12 carbon atoms, n: 6, m: 1) and 1.0 part by weight of polyethylene glycol methacrylate as an emulsifier were added, 5 parts by weight of hydroxyethyl methacrylate and 0.05 part by weight of t-butyl hydroperoxide were added to 50 parts by weight of ion-exchanged water, and the mixture was added to the polymer for 60 minutes, followed by polymerization at 60 DEG C for 2 hours . Polymerization was carried out in the same manner as above, and 100 parts by weight of the same amount of the added latex monomer was obtained. The particle diameter of the finally obtained thermoplastic graft copolymer was 1500 Å.
(Production of Thermoplastic Graft Copolymer Powder)
0.5 part by weight of an antioxidant (Irganox-245) and 0.5 part by weight of sulfuric acid were added to the prepared reaction solution of the graft copolymer, and the copolymer and water were separated at 70 ° C. and then dehydrated and dried to obtain an MBS graft copolymer powder Respectively.
[Production of thermoplastic polyester resin composition sheet]
80% by weight of the thermoplastic polyester resin and 20% by weight of the MBS graft copolymer prepared by the above method were mixed and melted and kneaded at 250 캜 using an extruder to obtain pellets. The obtained pellets were subjected to T-die extrusion at a die temperature of 220 DEG C to obtain a sheet having a thickness of 0.5 mm.
The refractive index, transparency and impact strength of the obtained graft copolymer and thermoplastic resin were measured, and the results are shown in Table 1 below.
Example 2
As shown in the following Table 1, except that 1.5 parts by weight of poly (ethylene glycol) methacrylate was used in the preparation of the thermoplastic graft copolymer for forming the shell, the rubber latex, A thermoplastic graft copolymer and a thermoplastic resin were prepared. The refractive index, transparency and impact strength of the obtained graft copolymer and thermoplastic resin were measured, and the results are shown in Table 1 below.
Example 3
As shown in the following Table 1, except that 0.5 part by weight of poly (ethylene glycol) methacrylate, which is a poly (ethylene glycol) compound, was used in the preparation of the thermoplastic graft copolymer, Graft copolymer and a thermoplastic resin were prepared. The refractive index, transparency and impact strength of the obtained graft copolymer and thermoplastic resin were measured, and the results are shown in Table 1 below.
Example 4
As shown in the following Table 1, a thermoplastic graft copolymer and a thermoplastic resin were prepared in the same manner as in Example 1, except that 1.5 parts by weight of a phosphate emulsifier was contained in the core. The refractive index, transparency and impact strength of the obtained graft copolymer and thermoplastic resin were measured, and the results are shown in Table 1 below.
Example 5
As shown in the following Table 1, a thermoplastic graft copolymer and a thermoplastic resin were prepared in the same manner as in Example 1, except that 1.5 parts by weight of a phosphate emulsifier was used in the preparation of the thermoplastic graft copolymer. The refractive index, transparency and impact strength of the obtained graft copolymer and thermoplastic resin were measured, and the results are shown in Table 1 below.
Example 6
As shown in the following Table 1, in the same manner as in Example 1 except that 0.7 parts by weight of poly (ethylene glycol) methacrylate was added during the preparation of the core, and the particle size of the graft copolymer was increased to 1600 ANGSTROM A thermoplastic graft copolymer and a thermoplastic resin were prepared. The refractive index, transparency and impact strength of the obtained graft copolymer and thermoplastic resin were measured, and the results are shown in Table 1 below.
Comparative Example 1
As shown in the following Table 1, instead of using both the poly (ethylene glycol) compound and the phosphate emulsifier in the production of the core and the graft copolymer, 1.5 parts by weight of potassium oleate was used as an emulsifier in the production of the core, A thermoplastic graft copolymer and a thermoplastic resin were prepared in the same manner as in Example 1, except that 1.0 part by weight of potassium oleate was used in preparing the copolymer. The refractive index, transparency and impact strength of the obtained graft copolymer and thermoplastic resin were measured, and the results are shown in Table 1 below.
Comparative Example 2
As shown in the following Table 1, a thermoplastic graft copolymer and a thermoplastic resin were prepared in the same manner as in Comparative Example 1, except that 1.0 part by weight of potassium oleate was used in the production of the core. The refractive index, transparency and impact strength of the obtained graft copolymer and thermoplastic resin were measured, and the results are shown in Table 1 below.
Comparative Example 3
As shown in the following Table 1, 1.5 parts by weight of a poly (ethylene glycol) compound and 1.0 part by weight of a phosphate emulsifier were used in the production of the core, and the poly (ethylene glycol) compound and the phosphate emulsifier were added at 2.5 The thermoplastic graft copolymer and the thermoplastic resin were prepared in the same manner as in Example 1, except that the weight parts were used. The refractive index, transparency and impact strength of the obtained graft copolymer and thermoplastic resin were measured, and the results are shown in Table 1 below.
Comparative Example 4
As shown in the following Table 1, the poly (ethylene glycol) compound and the phosphate emulsifier were included in the preparation of the graft copolymer, while the poly (ethylene glycol) compound was not included in the production of the core and 1.0 part by weight of the phosphate emulsifier was included. A thermoplastic graft copolymer and a thermoplastic resin were prepared in the same manner as in Comparative Example 1, except that 1.0 part by weight of potassium oleate was used as an emulsifier. The refractive index, transparency and impact strength of the obtained graft copolymer and thermoplastic resin were measured, and the results are shown in Table 1 below.
Comparative Example 5
As shown in the following Table 1, 0.5 parts by weight of a poly (ethylene glycol) compound and 1.5 parts by weight of potassium oleate as an emulsifying agent were not included in the preparation of the core, and the phosphate emulsifier was included in the preparation of the graft copolymer A thermoplastic graft copolymer and a thermoplastic resin were prepared in the same manner as in Comparative Example 1, except that 1.0 part by weight of a poly (ethylene glycol) compound and 1.0 part by weight of potassium oleate as an emulsifier were used. The refractive index, transparency and impact strength of the obtained graft copolymer and thermoplastic resin were measured, and the results are shown in Table 1 below.
Comparative Example 6
Except that potassium oleate and poly (ethylene glycol) compounds were not included in the preparation of the core and graft copolymer as shown in the following Table 1, and 1.0 part by weight of a phosphate emulsifier was used. To prepare a thermoplastic graft copolymer and a thermoplastic resin. The refractive index, transparency and impact strength of the obtained graft copolymer and thermoplastic resin were measured, and the results are shown in Table 1 below.
Experimental Example
The transparency and impact resistance of the thermoplastic polyester resin composition prepared in Examples 1 to 6 and Comparative Examples 1 to 6, the content and refractive index of the thermoplastic graft copolymer used in the resin composition, and the content of rubber latex were respectively measured The results are shown in Table 1 below.
* Refractive Index: The refractive index was measured at 25 ° C using an Abbe Refractometer.
Evaluation of Impact Strength: The sheets prepared in Examples and Comparative Examples were cut to prepare specimens having a thickness of 0.5 mm and a size of 10 cm x 14 cm. After aging at 25 ° C for 2 hours, the circular saw blade was rotated and the saw blade was rotated at a speed of 15 mm / The specimen was measured at 50% cracking rpm.
* Evaluation of transparency: The sheets prepared in the above Examples and Comparative Examples were made into specimens having a thickness of 3 mm for measurement of transparency according to the ASTM D1003 standard at 130 캜 using a hot press, and haze values were measured using a haze meter .
As shown in Table 1, in the case of the thermoplastic resins of Examples 1 to 6 including a core-shell structure impact modifier made of a phosphate emulsifier and a poly (ethylene glycol) compound, Comparative Examples 1 to 6 In comparison, it can be seen that it has improved to have much better impact strength with excellent transparency.
Specifically, when Example 1 and Comparative Examples 1 and 2 were compared, when a phosphate emulsifier and a poly (ethylene glycol) compound were used, Comparative Example 1 was small in size and had good transparency but poor impact strength, It was confirmed that the impact strength was improved but the transparency was decreased. In Example 1, both the transparency and the impact strength were found to be satisfied.
In addition, in Comparative Example 3, when a large amount of a poly (ethylene glycol) compound was added, it was found that the transparency was reduced although the size was increased and the impact strength was improved. In addition, in Comparative Example 6, when only the phosphate emulsifier is applied, the effect of improving the transparency and improving the impact strength is not significant.
Claims (16)
70 to 95 parts by weight of a conjugated diene monomer, 5 to 30 parts by weight of an ethylenically unsaturated aromatic compound, 0.1 to 1 part by weight of a poly (ethylene glycol) compound and 1 to 2 parts by weight of a phosphate emulsifier in the presence of 1 to 20 parts by weight of the seed, Polymerizing to produce a core; And
20 to 80 parts by weight of an ethylenically unsaturated aromatic compound, 20 to 80 parts by weight of an acrylate compound, 1 to 2 parts by weight of a poly (ethylene glycol) compound and 1 to 2 parts by weight of a phosphate emulsifier in the presence of 40 to 70 parts by weight of the core To form 30 to 60 parts by weight of the shell. ≪ Desc / Clms Page number 20 >
Wherein the conjugated diene monomer is at least one selected from the group consisting of 1,3-butadiene, isoprene, and chloroprene.
The ethylenically unsaturated aromatic compound is selected from the group consisting of styrene, alpha methyl styrene, isopropyl phenyl naphthalene, vinyl naphthalene, C 1 Wherein at least one selected from the group consisting of alkyl styren substituted with an alkyl group of C 3 is substituted with halogen substituted styrenes.
Wherein the poly (ethylene glycol) compound is selected from the group consisting of poly (ethylene glycol) n acrylate, poly (ethylene glycol) n methacrylate, and poly (ethylene glycol) n diacrylate (n is an integer from 3 to 14) Wherein the core-shell structure is at least one selected from the group consisting of polypropylene and polypropylene.
Wherein the poly (ethylene glycol) compound has a number average molecular weight (Mn) of 300 to 10,000.
Wherein the phosphate emulsifier is represented by the following formula (1).
[Chemical Formula 1]
In this formula,
R is a branched or linear alkyl group having from 12 to 14 carbon atoms,
n is an integer of 4 to 8, and m is an integer of 1 to 2.
Wherein R is an alkyl group having 12 to 13 carbon atoms,
n is an integer of 5 to 7, and m is 1. < Desc / Clms Page number 36 >
The phosphate-based emulsifier is selected from the group consisting of polyoxyethylene-9-lauryl ether, polyoxyethylene-9-stearyl ether, polyoxyethylene-8-stearyl ether, polyoxyethylene- And at least one group selected from the group consisting of polyoxyethylene-lauryl ether and polyoxyethylene-23-lauryl ether.
Wherein the phosphate emulsifier is a di (hexaoxyethylene lauryl ether) phosphate compound.
Wherein the acrylate compound is at least one selected from the group consisting of hydroxyethyl methacrylate, ethylene glycol methacrylate, ethylene glycol acrylate, and ethylene glycol diacrylate. .
Wherein the seed forming step is performed under a temperature condition of 60 ° C to 72 ° C.
Wherein the core forming step is performed at a temperature of 72 캜 to 85 캜.
A thermoplastic polyester resin composition comprising 5 to 50% by weight of an impact modifier for thermoplastic polyester resin according to claim 13.
Wherein the refractive index of the thermoplastic polyester resin and the refractive index difference of the impact modifier for thermoplastic polyester resin are 0.005 or less.
Wherein the thermoplastic polyester resin composition further comprises at least one additive selected from the group consisting of process oil, lubricating oil, antioxidant, heat stabilizer, activator and pigment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020150047241A KR101757039B1 (en) | 2015-04-03 | 2015-04-03 | Impact strength modifier for polyester resin and thermoplastic polyester resin composition containing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020150047241A KR101757039B1 (en) | 2015-04-03 | 2015-04-03 | Impact strength modifier for polyester resin and thermoplastic polyester resin composition containing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20160118707A true KR20160118707A (en) | 2016-10-12 |
| KR101757039B1 KR101757039B1 (en) | 2017-07-11 |
Family
ID=57173870
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020150047241A KR101757039B1 (en) | 2015-04-03 | 2015-04-03 | Impact strength modifier for polyester resin and thermoplastic polyester resin composition containing the same |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR101757039B1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190034783A (en) * | 2017-09-25 | 2019-04-03 | 주식회사 엘지화학 | Copolymer composition, method for preparing the same and thermoplastic resin composition comprising the same |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4117034A (en) | 1975-08-11 | 1978-09-26 | Borg-Warner Corporation | Amorphous polyester graft polymer alloys |
| US4180494A (en) | 1977-08-15 | 1979-12-25 | Rohm And Haas Company | Thermoplastic polyesters |
| KR20020060011A (en) | 2001-01-09 | 2002-07-16 | 노기호 | Method for preparing rubber latex for methylmethacrylate-butadiene- styrene resin |
| KR20030018671A (en) | 2001-08-30 | 2003-03-06 | 주식회사 엘지화학 | Method for preparing methylmethacrylate-butadiene-styrene resin |
| KR20070021894A (en) | 2005-08-19 | 2007-02-23 | 주식회사 엘지화학 | Impact strength modifiers for polyvinyl chloride and preparation method thereof |
-
2015
- 2015-04-03 KR KR1020150047241A patent/KR101757039B1/en active IP Right Grant
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4117034A (en) | 1975-08-11 | 1978-09-26 | Borg-Warner Corporation | Amorphous polyester graft polymer alloys |
| US4180494A (en) | 1977-08-15 | 1979-12-25 | Rohm And Haas Company | Thermoplastic polyesters |
| KR20020060011A (en) | 2001-01-09 | 2002-07-16 | 노기호 | Method for preparing rubber latex for methylmethacrylate-butadiene- styrene resin |
| KR20030018671A (en) | 2001-08-30 | 2003-03-06 | 주식회사 엘지화학 | Method for preparing methylmethacrylate-butadiene-styrene resin |
| KR20070021894A (en) | 2005-08-19 | 2007-02-23 | 주식회사 엘지화학 | Impact strength modifiers for polyvinyl chloride and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190034783A (en) * | 2017-09-25 | 2019-04-03 | 주식회사 엘지화학 | Copolymer composition, method for preparing the same and thermoplastic resin composition comprising the same |
Also Published As
| Publication number | Publication date |
|---|---|
| KR101757039B1 (en) | 2017-07-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101692106B1 (en) | Acrylic impact modifier with core-shell structure and composition of acrylic resin comprising thereof | |
| EP3584264B1 (en) | Method for preparing asa-based graft copolymer, method for preparing thermoplastic resin composition comprising same, and method for manufacturing molded product | |
| JP2014530957A (en) | Alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound copolymer having improved low-temperature impact strength and polycarbonate composition containing the same | |
| CN104136530B (en) | Transparent abs resin composition having superior shock resistance, scratch resistance, and transparency | |
| JP2008528756A (en) | Impact reinforcing agent for PVC resin and method for producing the same | |
| KR101799637B1 (en) | Graft copoymer and polycarbonate and san blend resin composition comprising the same | |
| EP3882285A1 (en) | Acrylic graft copolymer, method for producing same, and thermoplastic resin composition containing same | |
| KR102168348B1 (en) | MBS impact modifier, polyvinyl chloride resin composition comprising the same | |
| KR102024138B1 (en) | Impact strength modifiers, method for preparing the same, and polylactic acid/polycarbonate resin composition | |
| KR101651736B1 (en) | Method for preparing weather resistance reinforced acrylate based resin using them | |
| KR101827613B1 (en) | Rubber-modified vinyl-based graft copolymer and thermoplastic resin composition comprising the same | |
| KR101757039B1 (en) | Impact strength modifier for polyester resin and thermoplastic polyester resin composition containing the same | |
| CN111065682B (en) | Matrix copolymer, graft copolymer and thermoplastic resin composition | |
| KR101489558B1 (en) | Rubber reinforced thermoplastic transparent resin composition and thermoplastic high transparent resin | |
| KR102316287B1 (en) | Core-shell copolymer, method for preparing the copolymer and resin composition comprising the copolymer | |
| KR101656919B1 (en) | Composition for rubber reinforced graft copolymer, rubber reinforced graft copolymer, and rubber reinforced thermoplastic high transparent resin comprising the same | |
| KR101716927B1 (en) | Method for preparing rubber reinforced thermoplastic high transparent resin | |
| KR20100113841A (en) | Impact strength modifiers for thermoplastic polyester and thermoplastic resin composition containing the same | |
| KR102244956B1 (en) | Method for preparing graft copolymer | |
| US20060122324A1 (en) | Amorphous polyester resin composition | |
| KR100994055B1 (en) | Impact Strength Modifiers For Thermoplastic Polyester And Thermoplastic Polyester Resin Composition Containing The Same | |
| KR102009313B1 (en) | Graft copolymer, method for preparing the copolymer and thermoplastic resin composition comprising the copolymer | |
| KR20150030847A (en) | Acrylate-conjugated diene-aromatic vinyl-based copolymer and poly(lactic acid) resin composition comprising the same | |
| KR20130082221A (en) | Transparent thermoplastic resin and method of preparing the same | |
| KR20170038334A (en) | MBS based impact modifier, preparation method thereof, and polylactic acid composition comprising the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E902 | Notification of reason for refusal | ||
| E701 | Decision to grant or registration of patent right | ||
| GRNT | Written decision to grant |