Title of Invention: Thermoplastic resin composition
technical field
[One]
[Citation with related applications]
[2]
The present invention claims the benefit of priority based on Korean Patent Application No. 10-2020-0060730, filed on May 21, 2020, and Korean Patent Application No. 10-2021-0041215, filed on March 30, 2021, , all contents disclosed in the literature of the corresponding Korean patent application are incorporated as a part of this specification.
[3]
[Technical field]
[4]
The present invention relates to a thermoplastic resin composition, and to a thermoplastic resin composition having excellent transparency, impact resistance, processability, chemical resistance and resistance to gamma rays.
[5]
background
[6]
Recently, along with environmental problems, there have been many changes in the material industry. In particular, for materials used for medical or food containers, many efforts are being made to replace polyvinyl chloride, polycarbonate, and the like, which were previously used due to problems such as environmental hormones and disposal. In particular, it is necessary to develop new materials in the field of medical transparent materials used for syringes and tube connectors that store and store liquid inside.
[7]
On the other hand, polycarbonate, polymethyl methacrylate, polystyrene, polyacrylonitrile-styrene, etc. are generally used as transparent resins. However, although polycarbonate has excellent impact strength and transparency, it is difficult to make complex products due to poor processability and has poor chemical resistance. And, the use is increasingly limited due to bisphenol A used in the manufacture of polycarbonate. In addition, polymethyl methacrylate has excellent optical properties, but is not excellent in impact resistance and chemical resistance. Also, polystyrene and polyacrylonitrile-styrene are not excellent in impact resistance and chemical resistance. In addition, the diene-based graft polymer is excellent while balancing impact resistance and processability, but is not excellent in transparency.
[8]
Therefore, the development of medical materials excellent in transparency, impact resistance, chemical resistance and processability is required.
[9]
DETAILED DESCRIPTION OF THE INVENTION
technical challenge
[10]
The problem to be solved by the present invention is that transparency, impact resistance and processability are balanced, and chemical resistance and resistance to gamma rays can be improved by reducing the amount of (meth)acrylate-based monomer, and manufacturing costs can be reduced. To provide a thermoplastic resin composition. Another object of the present invention is to provide a thermoplastic resin composition that can be used for medical purposes.
[11]
means of solving the problem
[12]
In order to solve the above problems, the present invention provides a rubbery polymer comprising a first styrene-based monomer unit and a diene-based monomer unit in a weight ratio of 10:90 to 35:65 and having an average particle diameter of 250 to 450 nm; (meth)acrylate-based monomer units; and a second styrene-based monomer unit, wherein the weight ratio of the (meth)acrylate-based monomer unit to the second styrene-based monomer unit is 2 or less, and the thermoplastic resin composition has a weight average molecular weight of 130,000 to 250,000 g/mol. provides
[13]
Effects of the Invention
[14]
The thermoplastic resin composition of the present invention has excellent transparency, impact resistance, processability, chemical resistance, and resistance to gamma rays, and can reduce the amount of (meth)acrylate-based monomer used, thereby reducing manufacturing costs. It can also be used as a medical material.
[15]
Modes for carrying out the invention
[16]
Hereinafter, the present invention will be described in detail to help the understanding of the present invention.
[17]
The terms or words used in the present specification and claims are not to be construed as being limited to their ordinary or dictionary meanings, and the inventor may properly define the concept of the term in order to best describe his invention. Based on the principle that there is, it should be interpreted as meaning and concept consistent with the technical idea of ​​the present invention.
[18]
[19]
In the present invention, the average particle size may be measured using a dynamic light scattering method, and in detail, may be measured using a Nicomp 380 equipment manufactured by Particle Sizing Systems. In the present invention, the average particle diameter may mean an arithmetic average particle diameter in the particle size distribution measured by the dynamic light scattering method, that is, the average particle diameter of scattering intensity (Intensity Distribution).
[20]
In the present invention, the average particle diameter may be measured with a transmission electron microscope (TEM).
[21]
[22]
In the present invention, the refractive index refers to the absolute refractive index of a material, and the refractive index can be recognized as the ratio of the speed of electromagnetic radiation in free space to the speed of radiation in the material. In this case, the radiation may be visible light having a wavelength of 450 nm to 680 nm, specifically, visible light having a wavelength of 589.3 nm. The refractive index can be measured by a known method, that is, an Abbe refractometer.
[23]
In the present invention, the graft copolymer and the non-graft copolymer are sliced ​​to a thickness of 0.2 mm, and then measured with an Abbe refractometer at 25° C. using visible light having a wavelength of 589.3 nm.
[24]
[25]
In the present invention, the weight of the rubber polymer, the diene-based monomer unit, the (meth)acrylate-based monomer unit, the first styrene-based monomer unit, and the second styrene-based monomer unit included in the thermoplastic resin composition is measured by infrared spectroscopy (Infrared Spectroscopy). can do. In this case, a Nicolet TM iS20 FTIR Spectrometer (model name, manufacturer: Thermo Scientific) may be used as an infrared spectroscopy measuring device .
[26]
[27]
In the present invention, the impact reinforcing region of the thermoplastic resin composition may mean a region composed of a rubbery polymer and a monomer unit grafted with the rubbery polymer. It may refer to a region composed of a non-grafted monomer unit and a monomer unit included in the non-grafted copolymer.
[28]
[29]
In the present invention, the weight average molecular weight of the thermoplastic resin composition or graft copolymer is obtained by dissolving the thermoplastic resin composition or graft copolymer in acetone, centrifuging to separate the supernatant from the precipitate, drying the supernatant, and then dissolving in tetrahydrofuran. By filtering, it can be obtained relative to a standard polystyrene sample by gel permeation chromatography.
[30]
Specifically, 1 g of the thermoplastic resin composition or graft copolymer powder was dissolved in 50 g of acetone with stirring for 24 hours, and then put into a centrifugal separator (trade name: SUPRA 30 K, manufacturer: Hanil Science Industrial), 16,000 rpm, -10 The supernatant and the precipitate are separated by centrifugation under the condition of ℃ for 4 hours, and the supernatant can be dried with a hot air dryer at 50 ℃ for 12 hours. The obtained dried material is dissolved in tetrahydrofuran at a concentration of 1 wt%, filtered through a 1 μm filter, and can be measured as a relative value with respect to a standard polystyrene sample through gel permeation chromatography.
[31]
Meanwhile, an Agilent 1200 series system may be used for measuring gel permeation chromatography, and measurement conditions may be as follows.
[32]
Refractive index detector (RI): Agilent G1362 RID
[33]
RI temperature: 35 ℃
[34]
Data processing: Agilent ChemStation S/W
[35]
Solvent: tetrahydrofuran
[36]
Column temperature: 40 °C
[37]
Flow rate: 0.3 ml/min
[38]
Sample concentration: 2.0 mg/ml
[39]
Injection volume: 10 μl
[40]
Column model: 1 × PLgel 10 μm MiniMix-B (250 × 4.6 mm)
[41]
+ 1 × PLgel 10 μm MiniMix-B (250 × 4.6 mm)
[42]
+ 1 × PLgel 10 μm MiniMix-B Guard (50 × 4.6 mm)
[43]
Standard sample: polystyrene
[44]
[45]
In the present invention, the weight average molecular weight of the non-graft copolymer can be measured as a relative value with respect to a standard polystyrene sample using tetrahydrofuran as an eluent and gel permeation chromatography.
[46]
[47]
In the present invention, the first styrenic monomer unit may mean a styrenic monomer unit included in the rubbery polymer, and the second styrenic monomer unit is included in the thermoplastic resin composition, but is not included in the rubbery polymer. can mean
[48]
[49]
In the present invention, the first and second styrenic monomer units may be units derived from styrenic monomers, respectively. The styrene-based monomer may be at least one selected from the group consisting of styrene, α-methyl styrene, α-ethyl styrene, and p-methyl styrene, among which styrene is preferable.
[50]
[51]
In the present invention, the (meth)acrylonitrile-based monomer unit may be a unit derived from a (meth)acrylonitrile-based monomer. The (meth) acrylonitrile-based monomer may be a C 1 to C 10 alkyl (meth) acrylate-based monomer, and the C 1 to C 10 alkyl (meth) acrylate-based monomer is methyl (meth) acrylate, Ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, heptyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate and decyl (meth)acrylic It may be one or more selected from the group consisting of methyl methacrylate, among which methyl methacrylate is preferable.
[52]
[53]
In the present invention, the acrylonitrile-based monomer unit may be a unit derived from an acrylonitrile-based monomer. The acrylonitrile-based monomer may be at least one selected from the group consisting of acrylonitrile, methacrylonitrile, phenylacrylonitrile and α-chloroacrylonitrile, among which acrylonitrile is preferable.
[54]
[55]
In the present invention, the diene-based monomer unit may be a unit derived from the diene-based monomer. The diene-based monomer unit may be at least one selected from the group consisting of 1,3-butadiene, isoprene, chloroprene and piperylene, of which 1,3-butadiene is preferable.
[56]
[57]
Thermoplastic resin composition
[58]
The thermoplastic resin composition according to an embodiment of the present invention comprises: a rubbery polymer comprising the first styrene-based monomer unit and the diene-based monomer unit in a weight ratio of 10:90 to 35:65 and having an average particle diameter of 250 to 450 nm; (meth)acrylate-based monomer units; and a second styrene-based monomer unit, wherein the weight ratio of the (meth)acrylate-based monomer unit to the second styrene-based monomer unit is 2 or less, and the weight average molecular weight is 130,000 to 250,000 g/mol.
[59]
[60]
The present inventors control the composition and average particle diameter of the rubbery polymer, control the weight ratio of the second styrene-based monomer unit and the (meth)acrylate-based monomer unit included in the thermoplastic resin composition, and control the weight average molecular weight, transparency, It was found that a thermoplastic resin composition having excellent impact resistance, processability, chemical resistance and resistance to gamma rays was prepared, and thus the present invention was completed.
[61]
[62]
Hereinafter, the present invention will be described in detail.
[63]
[64]
When the rubbery polymer includes only diene-based monomer units, in order to avoid or minimize a difference in refractive index between the impact reinforcing region and the matrix region of the thermoplastic resin composition, an excess of (meth)acrylate-based monomer units must be included in the matrix region. However, the (meth)acrylate-based monomer unit causes a decrease in the chemical resistance of the thermoplastic resin composition, and a high unit cost of the monomer increases the manufacturing cost. In addition, the rubbery polymer cannot be prepared by using the styrenic monomer alone. On the other hand, the rubbery polymer according to the present invention can increase the refractive index of the rubbery polymer by including the first styrenic monomer unit as well as the diene-based monomer unit, and thus the (meth)acrylate-based monomer unit is included in a small amount in the matrix region. it is possible to do Therefore, the thermoplastic resin composition according to the present invention can minimize the decrease in chemical resistance and increase in manufacturing cost caused by the (meth)acrylate-based monomer unit.
[65]
[66]
According to an embodiment of the present invention, the rubbery polymer includes the first styrene-based monomer unit and the diene-based monomer unit in a weight ratio of 10:90 to 35:65, preferably 15:85 to 30:70 by weight. can be included as When the above-mentioned conditions are satisfied, impact resistance can be improved and refractive index can be increased, so that the amount of (meth)acrylate-based monomer unit used can be reduced, and chemical resistance due to (meth)acrylate-based monomer unit is lowered and The increase in manufacturing cost can be minimized. However, when the content of the first styrenic monomer unit is less than the above-described range, chemical resistance and resistance to gamma rays are remarkably reduced. In addition, when the content of the first styrenic monomer unit exceeds the above-described range, transparency and impact resistance are remarkably deteriorated.
[67]
Since the rubbery polymer includes the diene-based monomer unit and the first styrene-based monomer in the above weight ratio, the refractive index may be higher than that of the rubbery polymer made of only the diene-based monomer. As a specific example, the rubber polymer may have a refractive index of 1.5230 to 1.5420, preferably 1.5300 to 1.5400.
[68]
[69]
In addition, the rubbery polymer included in the thermoplastic resin composition according to an embodiment of the present invention may have an average particle diameter of 250 to 450 nm, preferably 300 to 350 nm. If the thermoplastic resin composition according to an embodiment of the present invention includes a rubbery polymer that is less than the above-mentioned range, processability and impact resistance may be significantly reduced. In addition, if the average particle diameter includes the rubbery polymer exceeding the above-mentioned range, the surface gloss properties may be deteriorated. In addition, when the rubber polymer is produced by emulsion polymerization, it is not preferable because the latex stability of the rubber polymer is significantly lowered.
[70]
[71]
In the thermoplastic resin composition according to an embodiment of the present invention, a weight ratio of the (meth)acrylate-based monomer unit to the second styrene-based monomer unit may be 2 or less, preferably 0.8 to 2. When the weight ratio of the (meth)acrylate-based monomer unit to the second styrene-based monomer unit exceeds 2, it means that the (meth)acrylate-based monomer unit is included in excess, and the second styrene-based monomer unit is included in an excess amount. When the weight ratio of the (meth) acrylate-based monomer unit to the monomer unit exceeds 2, the chemical resistance of the thermoplastic resin composition is remarkably reduced, and the manufacturing cost increases according to the input of an excess (meth) acrylate monomer. cause In addition, when the weight ratio of the (meth)acrylate-based monomer unit to the second styrene-based monomer unit is less than 0.8, impact resistance is reduced.
[72]
[73]
The thermoplastic resin composition according to an embodiment of the present invention may have a weight average molecular weight of 130,000 to 250,000 g/mol, preferably 140,000 to 210,000 g/mol. The weight average molecular weight refers to the weight average molecular weight of the thermoplastic resin composition including the graft copolymer and the non-graft copolymer described below, that is, the thermoplastic resin composition itself including the impact reinforcing region and the matrix region, and the thermoplastic resin When the weight average molecular weight of the composition is less than the above-mentioned range, the chemical resistance of the thermoplastic resin composition is lowered, and when it exceeds the above-mentioned range, the processability of the thermoplastic resin composition is lowered.
[74]
[75]
On the other hand, the thermoplastic resin composition according to an embodiment of the present invention is 20.00 to 40.00% by weight of the rubbery polymer; 23.00 to 51.00 wt% of the (meth)acrylate-based monomer unit; and 18.00 to 41.00 wt% of the second styrenic monomer unit. Preferably, 27.00 to 37.00% by weight of the rubbery polymer; 27.00 to 45.00 wt% of the (meth)acrylate-based monomer unit; and 22.00 to 37.00 wt% of the second styrenic monomer unit. When the above-described conditions are satisfied, a thermoplastic resin composition having improved impact resistance, chemical resistance and processability may be prepared.
[76]
The thermoplastic resin composition according to an embodiment of the present invention may further include an acrylonitrile-based monomer unit to further improve chemical resistance. The acrylonitrile-based monomer unit may be included in an amount of 3.00 to 12.00 wt%, preferably 5.00 to 10.00 wt%, in order to minimize yellowing while improving chemical resistance.
[77]
[78]
Meanwhile, the thermoplastic resin composition according to an embodiment of the present invention may include a graft copolymer and a non-graft copolymer.
[79]
The graft copolymer may have a refractive index of 1.5230 to 1.5420, preferably 1.5300 to 1.5400. When the above-described range is satisfied, the refractive index of the above-described rubbery polymer is identical to or similar to that of the above-described rubbery polymer, so that the transparency of the graft copolymer can be further improved.
[80]
The difference in refractive index between the graft copolymer and the non-graft copolymer may be 0.0100 or less, preferably 0. When the above conditions are satisfied, the thermoplastic resin composition may become more transparent.
[81]
The weight ratio of the graft copolymer and the non-graft copolymer may be 40:60 to 80:20, preferably 50:50 to 70:30. When the above-described range is satisfied, workability may be further improved without lowering impact resistance.
[82]
[83]
The graft copolymer includes a first styrenic monomer unit and a diene-based monomer unit and includes a rubbery polymer having an average particle diameter of 250 to 450 nm, a (meth)acrylate-based monomer unit grafted to the rubbery polymer, and the rubbery polymer A second styrenic monomer unit grafted to the polymer may be included.
[84]
The rubbery polymer included in the thermoplastic resin composition according to an embodiment of the present invention and the rubbery polymer included in the graft copolymer may be the same.
[85]
The graft copolymer may also include a (meth)acrylate-based monomer unit and a second styrene-based monomer unit that are not grafted to the rubbery polymer.
[86]
Meanwhile, the transparency of the graft copolymer may be determined by the refractive index of the rubber polymer and a shell including the monomer unit grafted to the rubber polymer. And, the refractive index of the shell can be adjusted by the mixing ratio of the monomer units. That is, the refractive indices of the rubbery polymer and the shell should be similar and preferably match. Accordingly, the difference between the refractive index of the rubber polymer included in the graft copolymer and the refractive index of the monomer unit grafted to the rubber polymer may be 0.0100 or less, preferably 0. When the above conditions are satisfied, the thermoplastic resin composition may become more transparent.
[87]
The graft copolymer may include 30.00 to 65.00 weight percent of the rubbery polymer, preferably 35.00 to 60.00 weight percent. When the above-described range is satisfied, the impact resistance is excellent, and grafting occurs sufficiently during the preparation of the graft copolymer, so that the graft copolymer can realize excellent transparency.
[88]
The rubbery polymer may include the first styrene-based monomer unit and the diene-based monomer unit in a weight ratio of 10:90 to 35:65, preferably 15:85 to 30:70 by weight. When the above-mentioned conditions are satisfied, impact resistance can be improved and refractive index can be increased, so that the amount of (meth)acrylate-based monomer unit used can be reduced, and chemical resistance due to (meth)acrylate-based monomer unit is lowered and The increase in manufacturing cost can be minimized. However, when the content of the first styrenic monomer unit is less than the above-described range, chemical resistance and resistance to gamma rays are remarkably reduced. In addition, when the content of the first styrenic monomer unit exceeds the above-described range, transparency and impact resistance are remarkably deteriorated.
[89]
The graft copolymer may include the (meth)acrylate-based monomer unit in an amount of 11.00 to 46.00 wt%, preferably 15.00 to 40.00 wt%. When the above-mentioned range is satisfied, the graft copolymer can implement excellent transparency.
[90]
The graft copolymer may include the second styrenic monomer unit in an amount of 10.00 to 36.00 wt%, preferably 15.00 to 30.00 wt%. When the above-mentioned range is satisfied, the graft copolymer can implement excellent processability.
[91]
The graft copolymer may further include an acrylonitrile-based monomer unit to further improve chemical resistance. The acrylonitrile-based monomer unit may be included in an amount of 9.00 wt% or less, preferably 1.00 to 9.00 wt%, in order to minimize yellowing while improving chemical resistance.
[92]
The graft copolymer may have a weight average molecular weight of 70,000 to 250,000 g/mol, preferably 100,000 to 200,000 g/mol. When the above-described range is satisfied, the chemical resistance and processability of the thermoplastic resin composition may be further improved.
[93]
[94]
In the graft copolymer, it is preferable to use emulsion polymerization to prepare a rubbery polymer under the above-described conditions.
[95]
[96]
The non-graft copolymer may include a non-graft copolymer including a (meth)acrylate-based monomer unit and a second styrene-based monomer unit.
[97]
The non-graft copolymer may include the (meth)acrylate-based monomer unit in an amount of 45.00 to 70.00 wt%, preferably 50.00 to 65.00 wt%. When the above-described range is satisfied, a thermoplastic resin composition having improved transparency may be prepared.
[98]
The non-graft copolymer may include the second styrenic monomer unit in an amount of 30.00 to 55.00 wt%, preferably 35.00 to 50.00 wt%. When the above conditions are satisfied, a thermoplastic resin composition with improved processability can be manufactured.
[99]
The non-graft copolymer may further include an acrylonitrile-based monomer unit to further improve chemical resistance. The acrylonitrile-based monomer unit may be included in an amount of 15.00 wt% or less, preferably 5.00 to 15.00 wt%, in order to minimize yellowing while improving chemical resistance.
[100]
The non-graft copolymer may have a weight average molecular weight of 140,000 to 250,000 g/mol, preferably 160,000 to 230,000 g/mol. When the above-described range is satisfied, the chemical resistance and processability of the thermoplastic resin composition may be further improved.
[101]
[102]
Hereinafter, embodiments of the present invention will be described in detail so that those of ordinary skill in the art can easily carry out the present invention. However, the present invention may be embodied in various different forms and is not limited to the embodiments described herein.
[103]
[104]
Preparation Example 1: Preparation of graft copolymer powder A-1
[105]
A styrene/butadiene rubbery polymer latex having an average particle diameter of 350 nm and a refractive index of 1.5380 was prepared by emulsion polymerization of a monomer mixture composed of 30% by weight of styrene and 70% by weight of 1,3-butadiene.
[106]
21.20 parts by weight of methyl methacrylate, 20.80 parts by weight of styrene, 3.00 parts by weight of acrylonitrile, 100 parts by weight of ion-exchanged water, 1.0 parts by weight of sodium oleate, 0.05 parts by weight of t-dodecyl mercaptan, 0.05 parts by weight of ethylenediaminetetraacetic acid Part, sodium formaldehyde sulfoxylate 0.1 parts by weight, ferrous sulfate 0.001 parts by weight, and cumene hydroperoxide 0.2 parts by weight were uniformly mixed to prepare a mixed solution.
[107]
After raising the temperature of the reactor in which 55.00 parts by weight of the styrene/butadiene rubbery polymer latex exists to 75° C., the mixture solution was continuously introduced for 5 hours to perform polymerization. After the continuous input was completed, the reactor was heated to 80 °C, aged for 1 hour, and then polymerization was terminated to obtain a graft copolymer latex.
[108]
The graft copolymer latex was aggregated with calcium chloride, washed, dehydrated and dried to obtain a graft copolymer powder A-1 having a refractive index of 1.5380 and a weight average molecular weight of 150,000 g/mol.
[109]
[110]
Preparation Example 2: Preparation of graft copolymer powder A-2
[111]
A styrene/butadiene rubbery polymer latex having an average particle diameter of 300 nm and a refractive index of 1.5230 was prepared by emulsion polymerization of a monomer mixture composed of 10% by weight of styrene and 90% by weight of 1,3-butadiene.
[112]
28.44 parts by weight of methyl methacrylate, 14.56 parts by weight of styrene, 7.00 parts by weight of acrylonitrile, 100 parts by weight of ion-exchanged water, 1.0 parts by weight of sodium oleate, 0.07 parts by weight of t-dodecyl mercaptan, 0.05 parts by weight of ethylenediaminetetraacetic acid Parts, sodium formaldehyde sulfoxylate 0.10 parts by weight, ferrous sulfate 0.001 parts by weight, and cumene hydroperoxide 0.2 parts by weight were uniformly mixed to prepare a mixed solution.
[113]
After raising the temperature of the reactor in which 50.00 parts by weight of the styrene/butadiene rubbery polymer latex exists to 75° C., the mixture solution was continuously introduced for 5 hours and polymerization was carried out. After the continuous input was completed, the reactor was heated to 80 °C, aged for 1 hour, and then polymerization was terminated to obtain a graft copolymer latex.
[114]
The graft copolymer latex was aggregated with calcium chloride, washed, dehydrated and dried to obtain a graft copolymer powder A-2 having a refractive index of 1.523 and a weight average molecular weight of 150,000 g/mol.
[115]
[116]
Preparation Example 3: Preparation of graft copolymer powder A-3
[117]
A styrene/butadiene rubbery polymer latex having an average particle diameter of 300 nm and a refractive index of 1.5268 was prepared by emulsion polymerization of a monomer mixture composed of 15% by weight of styrene and 85% by weight of 1,3-butadiene.
[118]
26.58 parts by weight of methyl methacrylate, 16.42 parts by weight of styrene, 7.00 parts by weight of acrylonitrile, 100 parts by weight of ion-exchanged water, 1.0 parts by weight of sodium oleate, 0.05 parts by weight of t-dodecyl mercaptan, 0.05 parts by weight of ethylenediaminetetraacetic acid Parts, sodium formaldehyde sulfoxylate 0.10 parts by weight, ferrous sulfate 0.001 parts by weight, and cumene hydroperoxide 0.2 parts by weight were uniformly mixed to prepare a mixed solution.
[119]
After raising the temperature of the reactor in which 50.00 parts by weight of the styrene/butadiene rubbery polymer latex exists to 75° C., the mixture solution was continuously introduced for 5 hours and polymerization was carried out. After the continuous input was completed, the reactor was heated to 80 °C, aged for 1 hour, and then polymerization was terminated to obtain a graft copolymer latex.
[120]
The graft copolymer latex was aggregated with calcium chloride, washed, dehydrated and dried to obtain a graft copolymer powder A-3 having a refractive index of 1.5268 and a weight average molecular weight of 170,000 g/mol.
[121]
[122]
Preparation Example 4: Preparation of graft copolymer powder A-4
[123]
A styrene/butadiene rubbery polymer latex having an average particle diameter of 300 nm and a refractive index of 1.5330 was prepared by emulsion polymerization of a monomer mixture composed of 23 wt% of styrene and 77 wt% of 1,3-butadiene.
[124]
24.90 parts by weight of methyl methacrylate, 20.10 parts by weight of styrene, 5.00 parts by weight of acrylonitrile, 100 parts by weight of ion-exchanged water, 1.0 parts by weight of sodium oleate, 0.10 parts by weight of t-dodecyl mercaptan, 0.050 parts by weight of ethylenediaminetetraacetic acid Parts, sodium formaldehyde sulfoxylate 0.100 parts by weight, ferrous sulfate 0.001 parts by weight, and cumene hydroperoxide 0.2 parts by weight were uniformly mixed to prepare a mixed solution.
[125]
After raising the temperature of the reactor in which 50.00 parts by weight of the styrene/butadiene rubbery polymer latex (based on solid content) was present to 75° C., the mixture solution was continuously introduced for 5 hours to perform polymerization. After the continuous input was completed, the reactor was heated to 80 °C, aged for 1 hour, and then polymerization was terminated to obtain a graft copolymer latex.
[126]
The graft copolymer latex was aggregated with calcium chloride, washed, dehydrated and dried to obtain a graft copolymer powder A-4 having a refractive index of 1.5330 and a weight average molecular weight of 130,000 g/mol.
[127]
[128]
Preparation Example 5: Preparation of graft copolymer powder A-5
[129]
A styrene/butadiene rubbery polymer latex having an average particle diameter of 300 nm and a refractive index of 1.5379 was prepared by emulsion polymerization of a monomer mixture composed of 30% by weight of styrene and 70% by weight of 1,3-butadiene.
[130]
21.00 parts by weight of methyl methacrylate, 22.00 parts by weight of styrene, 7.00 parts by weight of acrylonitrile, 100 parts by weight of ion-exchanged water, 1.0 parts by weight of sodium oleate, 0.1 parts by weight of t-dodecyl mercaptan, 0.05 parts by weight of ethylenediaminetetraacetic acid Part, sodium formaldehyde sulfoxylate 0.1 parts by weight, ferrous sulfate 0.001 parts by weight, and cumene hydroperoxide 0.2 parts by weight were uniformly mixed to prepare a mixed solution.
[131]
After raising the temperature of the reactor in which 50.00 parts by weight of the styrene/butadiene rubbery polymer latex exists to 75° C., the mixture solution was continuously introduced for 5 hours and polymerization was carried out. After the continuous input was completed, the reactor was heated to 80 °C, aged for 1 hour, and then polymerization was terminated to obtain a graft copolymer latex.
[132]
The graft copolymer latex was aggregated with calcium chloride, washed, dehydrated and dried to obtain a graft copolymer powder A-5 having a refractive index of 1.5379 and a weight average molecular weight of 150,000 g/mol.
[133]
[134]
Preparation Example 6: Preparation of graft copolymer powder A-6
[135]
A styrene/butadiene rubbery polymer latex having an average particle diameter of 300 nm and a refractive index of 1.5416 was prepared by emulsion polymerization of a monomer mixture composed of 35 wt% of styrene and 65 wt% of 1,3-butadiene.
[136]
20.58 parts by weight of methyl methacrylate, 24.42 parts by weight of styrene, 5.00 parts by weight of acrylonitrile, 100 parts by weight of ion-exchanged water, 1.0 parts by weight of sodium oleate, 0.03 parts by weight of t-dodecyl mercaptan, 0.05 parts by weight of ethylenediaminetetraacetic acid Part, sodium formaldehyde sulfoxylate 0.1 parts by weight, ferrous sulfate 0.001 parts by weight, and cumene hydroperoxide 0.2 parts by weight were uniformly mixed to prepare a mixed solution.
[137]
After raising the temperature of the reactor in which 50.00 parts by weight of the styrene/butadiene rubbery polymer latex exists to 75° C., the mixture solution was continuously introduced for 5 hours and polymerization was carried out. After the continuous input was completed, the reactor was heated to 80 °C, aged for 1 hour, and then polymerization was terminated to obtain a graft copolymer latex.
[138]
The graft copolymer latex was aggregated with calcium chloride, washed, dehydrated and dried to obtain a graft copolymer powder A-6 having a refractive index of 1.5416 and a weight average molecular weight of 190,000 g/mol.
[139]
[140]
Preparation Example 7: Preparation of graft copolymer powder A-7
[141]
A styrene/butadiene rubbery polymer latex having an average particle diameter of 300 nm and a refractive index of 1.5200 was prepared by emulsion polymerization of a monomer mixture composed of 6 wt% of styrene and 94 wt% of 1,3-butadiene.
[142]
31.37 parts by weight of methyl methacrylate, 13.63 parts by weight of styrene, 5.00 parts by weight of acrylonitrile, 100 parts by weight of ion-exchanged water, 1.0 parts by weight of sodium oleate, 0.10 parts by weight of t-dodecyl mercaptan, 0.05 parts by weight of ethylenediaminetetraacetic acid Part, sodium formaldehyde sulfoxylate 0.1 parts by weight, ferrous sulfate 0.001 parts by weight, and cumene hydroperoxide 0.2 parts by weight were uniformly mixed to prepare a mixed solution.
[143]
After raising the temperature of the reactor in which 50.00 parts by weight of the styrene/butadiene rubbery polymer latex exists to 75° C., the mixture solution was continuously introduced for 5 hours and polymerization was carried out. After the continuous input was completed, the reactor was heated to 80 °C, aged for 1 hour, and then polymerization was terminated to obtain a graft copolymer latex.
[144]
The graft copolymer latex was aggregated with calcium chloride, washed, dehydrated and dried to obtain a graft copolymer powder A-7 having a refractive index of 1.52 and a weight average molecular weight of 130,000 g/mol.
[145]
[146]
Preparation Example 8: Preparation of graft copolymer powder A-8
[147]
A styrene/butadiene rubbery polymer latex having an average particle diameter of 300 nm and a refractive index of 1.5454 was prepared by emulsion polymerization of a monomer mixture composed of 40 wt% of styrene and 60 wt% of 1,3-butadiene.
[148]
18.72 parts by weight of methyl methacrylate, 26.28 parts by weight of styrene, 5.00 parts by weight of acrylonitrile, 100 parts by weight of ion-exchanged water, 1.0 parts by weight of sodium oleate, 0.10 parts by weight of t-dodecyl mercaptan, 0.05 parts by weight of ethylenediaminetetraacetic acid Part, sodium formaldehyde sulfoxylate 0.1 parts by weight, ferrous sulfate 0.001 parts by weight, and cumene hydroperoxide 0.2 parts by weight were uniformly mixed to prepare a mixed solution.
[149]
After raising the temperature of the reactor in which 50.00 parts by weight of the styrene/butadiene rubbery polymer latex exists to 75° C., the mixture solution was continuously introduced for 5 hours and polymerization was carried out. After the continuous input was completed, the reactor was heated to 80 °C, aged for 1 hour, and then polymerization was terminated to obtain a graft copolymer latex.
[150]
The graft copolymer latex was aggregated with calcium chloride, washed, dehydrated and dried to obtain a graft copolymer powder A-8 having a refractive index of 1.5454 and a weight average molecular weight of 130,000 g/mol.
[151]
[152]
Preparation Example 9: Preparation of graft copolymer powder A-9
[153]
1,3-butadiene was emulsion-polymerized to prepare a butadiene rubbery polymer latex having an average particle diameter of 300 nm and a refractive index of 1.5160.
[154]
24.90 parts by weight of methyl methacrylate, 20.10 parts by weight of styrene, 5.00 parts by weight of acrylonitrile, 100 parts by weight of ion-exchanged water, 1.0 parts by weight of sodium oleate, 0.10 parts by weight of t-dodecyl mercaptan, 0.05 parts by weight of ethylenediaminetetraacetic acid Part, sodium formaldehyde sulfoxylate 0.1 parts by weight, ferrous sulfate 0.001 parts by weight, and cumene hydroperoxide 0.2 parts by weight were uniformly mixed to prepare a mixed solution.
[155]
After raising the temperature of the reactor in which 50.00 parts by weight of the butadiene rubbery polymer latex exists to 75° C., the mixture solution was continuously introduced for 5 hours and polymerization was performed. After the continuous input was completed, the reactor was heated to 80 °C, aged for 1 hour, and then polymerization was terminated to obtain a graft copolymer latex.
[156]
The graft copolymer latex was aggregated with calcium chloride, washed, dehydrated and dried to obtain a graft copolymer powder A-9 having a refractive index of 1.5454 and a weight average molecular weight of 130,000 g/mol. Since the graft copolymer powder A-9 became opaque due to the difference in refractive index between the butadiene rubbery polymer and the rigid copolymer grafted thereto, the refractive index was not measured.
[157]
[158]
Preparation Example 10: Preparation of graft copolymer powder A-10
[159]
A styrene/butadiene rubbery polymer latex having an average particle diameter of 100 nm and a refractive index of 1.5330 was prepared by emulsion polymerization of a monomer mixture composed of 23 wt% of styrene and 77 wt% of 1,3-butadiene.
[160]
24.90 parts by weight of methyl methacrylate, 20.10 parts by weight of styrene, 5.00 parts by weight of acrylonitrile, 100 parts by weight of ion-exchanged water, 1.0 parts by weight of sodium oleate, 0.10 parts by weight of t-dodecyl mercaptan, 0.05 parts by weight of ethylenediaminetetraacetic acid Part, sodium formaldehyde sulfoxylate 0.1 parts by weight, ferrous sulfate 0.001 parts by weight, and cumene hydroperoxide 0.2 parts by weight were uniformly mixed to prepare a mixed solution.
[161]
After raising the temperature of the reactor in which 50.00 parts by weight of the styrene/butadiene rubbery polymer latex exists to 75° C., the mixture solution was continuously introduced for 5 hours and polymerization was carried out. After the continuous input was completed, the reactor was heated to 80 °C, aged for 1 hour, and then polymerization was terminated to obtain a graft copolymer latex.
[162]
The graft copolymer latex was aggregated with calcium chloride, washed, dehydrated and dried to obtain a graft copolymer powder A-10 having a refractive index of 1.5330 and a weight average molecular weight of 100,000 g/mol.
[163]
[164]
Preparation Example 11: Preparation of graft copolymer powder A-11
[165]
A styrene/butadiene rubbery polymer latex having an average particle diameter of 350 nm and a refractive index of 1.5380 was prepared by emulsion polymerization of a monomer mixture composed of 30% by weight of styrene and 70% by weight of 1,3-butadiene.
[166]
21.20 parts by weight of methyl methacrylate, 20.80 parts by weight of styrene, 3.00 parts by weight of acrylonitrile, 100 parts by weight of ion-exchanged water, 1.0 parts by weight of sodium oleate, 0.20 parts by weight of t-dodecyl mercaptan, 0.3 parts by weight of ethylenediaminetetraacetic acid Part, sodium formaldehyde sulfoxylate 0.1 parts by weight, ferrous sulfate 0.001 parts by weight, and cumene hydroperoxide 0.2 parts by weight were uniformly mixed to prepare a mixed solution.
[167]
After raising the temperature of the reactor in which 55.00 parts by weight of the styrene/butadiene rubbery polymer latex exists to 75° C., the mixture solution was continuously introduced for 5 hours to perform polymerization. After the continuous input was completed, the reactor was heated to 80 °C, aged for 1 hour, and then polymerization was terminated to obtain a graft copolymer latex.
[168]
The graft copolymer latex was aggregated with calcium chloride, washed, dehydrated and dried to obtain a graft copolymer powder A-11 having a refractive index of 1.5380 and a weight average molecular weight of 80,000 g/mol.
[169]
[170]
Preparation Example 12: Preparation of graft copolymer powder A-12
[171]
A styrene/butadiene rubbery polymer latex having an average particle diameter of 300 nm and a refractive index of 1.5230 was prepared by emulsion polymerization of a monomer mixture composed of 10% by weight of styrene and 90% by weight of 1,3-butadiene.
[172]
33.00 parts by weight of methyl methacrylate, 16.00 parts by weight of styrene, 1.00 parts by weight of acrylonitrile, 100 parts by weight of ion-exchanged water, 1.0 parts by weight of sodium oleate, 0.15 parts by weight of t-dodecyl mercaptan, 0.05 parts by weight of ethylenediaminetetraacetic acid Part, sodium formaldehyde sulfoxylate 0.1 parts by weight, ferrous sulfate 0.001 parts by weight, and cumene hydroperoxide 0.2 parts by weight were uniformly mixed to prepare a mixed solution.
[173]
After raising the temperature of the reactor in which 50.00 parts by weight of the styrene/butadiene rubbery polymer latex exists to 75° C., the mixture solution was continuously introduced for 5 hours and polymerization was carried out. After the continuous input was completed, the reactor was heated to 80 °C, aged for 1 hour, and then polymerization was terminated to obtain a graft copolymer latex.
[174]
The graft copolymer latex was aggregated with calcium chloride, washed, dehydrated and dried to obtain a graft copolymer powder A-12 having a refractive index of 1.5230 and a weight average molecular weight of 130,000 g/mol.
[175]
[176]
Preparation Example 13: Preparation of graft copolymer powder A-13
[177]
1,3-butadiene was emulsion-polymerized to prepare a butadiene rubbery polymer latex having an average particle diameter of 300 nm and a refractive index of 1.5160.
[178]
35.00 parts by weight of methyl methacrylate, 12.00 parts by weight of styrene, 3.00 parts by weight of acrylonitrile, 100 parts by weight of ion-exchanged water, 1.0 parts by weight of sodium oleate, 0.5 parts by weight of t-dodecyl mercaptan, 0.05 parts by weight of ethylenediaminetetraacetic acid Part, sodium formaldehyde sulfoxylate 0.1 parts by weight, ferrous sulfate 0.001 parts by weight, and cumene hydroperoxide 0.2 parts by weight were uniformly mixed to prepare a mixed solution.
[179]
After raising the temperature of the reactor in which 50.00 parts by weight of the butadiene rubbery polymer latex exists to 75° C., the mixture solution was continuously introduced for 5 hours and polymerization was performed. After the continuous input was completed, the reactor was heated to 80 °C, aged for 1 hour, and then polymerization was terminated to obtain a graft copolymer latex.
[180]
The graft copolymer latex was aggregated with calcium chloride, washed, dehydrated and dried to obtain a graft copolymer powder A-13 having a refractive index of 1.5160 and a weight average molecular weight of 100,000 g/mol.
[181]
[182]
Preparation 14: Preparation of non-grafted copolymer pellets B-1
[183]
A mixed solution containing 44.10 parts by weight of methyl methacrylate, 44.90 parts by weight of styrene, 11.00 parts by weight of acrylonitrile, 30 parts by weight of toluene, and 0.05 parts by weight of n-octyl mercaptan was continuously added to the reactor so that the average polymerization time was 3 hours. did. At this time, the polymerization temperature was maintained at 148 ℃. The polymerization solution continuously discharged from the reactor is heated in a preheating tank, the unreacted monomer and solvent are volatilized in the volatilization tank, and the temperature of the polymer is maintained at 210 ° C. Using a polymer transfer pump extrusion processor, the refractive index is 1.5380 and a weight average molecular weight of 200,000 g/mol to prepare non-grafted copolymer pellets B-1.
[184]
[185]
Preparation 15: Preparation of non-grafted copolymer pellets B-2
[186]
A mixed solution containing 60.52 parts by weight of methyl methacrylate, 30.48 parts by weight of styrene, 9.00 parts by weight of acrylonitrile, 30 parts by weight of toluene, and 0.06 parts by weight of n-octyl mercaptan was continuously added to the reactor so that the average polymerization time was 3 hours. did. At this time, the polymerization temperature was maintained at 148 ℃. The polymerization solution continuously discharged from the reactor is heated in a preheating tank, the unreacted monomer and solvent are volatilized in the volatilization tank, and the temperature of the polymer is maintained at 210 ° C. Using a polymer transfer pump extrusion processor, the refractive index is 1.5230 and a weight average molecular weight of 190,000 g/mol to prepare non-grafted copolymer pellets B-2.
[187]
[188]
Preparation 16: Preparation of non-grafted copolymer pellets B-3
[189]
A mixed solution containing 56.72 parts by weight of methyl methacrylate, 34.28 parts by weight of styrene, 9.00 parts by weight of acrylonitrile, 30 parts by weight of toluene, and 0.06 parts by weight of n-octyl mercaptan was continuously added to the reactor so that the average polymerization time was 3 hours. did. At this time, the polymerization temperature was maintained at 148 ℃. The polymerization solution continuously discharged from the reactor is heated in a preheating tank, the unreacted monomer and solvent are volatilized in the volatilization tank, and the temperature of the polymer is maintained at 210 ° C. Using a polymer transfer pump extrusion processor, the refractive index is 1.5268 and a weight average molecular weight of 190,000 g/mol to prepare non-grafted copolymer pellets B-3.
[190]
[191]
Preparation Example 17: Preparation of non-grafted copolymer pellets B-4
[192]
A mixed solution containing 52.00 parts by weight of methyl methacrylate, 39.00 parts by weight of styrene, 9.00 parts by weight of acrylonitrile, 30 parts by weight of toluene, and 0.06 parts by weight of n-octyl mercaptan was continuously added to the reactor so that the average polymerization time was 3 hours. did. At this time, the polymerization temperature was maintained at 148 ℃. The polymerization solution continuously discharged from the reactor is heated in a preheating tank, the unreacted monomer and solvent are volatilized in the volatilization tank, and the temperature of the polymer is maintained at 210 ° C. Using a polymer transfer pump extrusion processor, the refractive index is 1.5315 and a weight average molecular weight of 190,000 g/mol to prepare non-grafted copolymer pellets B-4.
[193]
[194]
Preparation 18: Preparation of non-grafted copolymer pellets B-5
[195]
A mixed solution containing 45.62 parts by weight of methyl methacrylate, 45.38 parts by weight of styrene, 9.00 parts by weight of acrylonitrile, 30 parts by weight of toluene, and 0.06 parts by weight of n-octyl mercaptan was continuously added to the reactor so that the average polymerization time was 3 hours. did. At this time, the polymerization temperature was maintained at 148 ℃. The polymerization solution continuously discharged from the reactor is heated in a preheating tank, the unreacted monomer and solvent are volatilized in the volatilization tank, and the temperature of the polymer is maintained at 210 ° C. Using a polymer transfer pump extrusion processor, the refractive index is 1.5379 and a weight average molecular weight of 190,000 g/mol to prepare non-grafted copolymer pellets B-5.
[196]
[197]
Preparation 19: Preparation of non-grafted copolymer pellets B-6
[198]
A mixed solution containing 41.92 parts by weight of methyl methacrylate, 49.08 parts by weight of styrene, 9.00 parts by weight of acrylonitrile, 30 parts by weight of toluene, and 0.06 parts by weight of n-octyl mercaptan was continuously added to the reactor so that the average polymerization time was 3 hours. did. At this time, the polymerization temperature was maintained at 148 ℃. The polymerization solution continuously discharged from the reactor is heated in a preheating tank, the unreacted monomer and solvent are volatilized in the volatilization tank, and the temperature of the polymer is maintained at 210 ° C. Using a polymer transfer pump extrusion processor, the refractive index is 1.5416 and a weight average molecular weight of 190,000 g/mol to prepare non-grafted copolymer pellets B-6.
[199]
[200]
Preparation 20: Preparation of non-grafted copolymer pellets B-7
[201]
A mixed solution containing 63.52 parts by weight of methyl methacrylate, 27.48 parts by weight of styrene, 9.00 parts by weight of acrylonitrile, 30 parts by weight of toluene, and 0.06 parts by weight of n-octyl mercaptan was continuously added to the reactor so that the average polymerization time was 3 hours. did. At this time, the polymerization temperature was maintained at 148 ℃. The polymerization solution continuously discharged from the reactor is heated in a preheating tank, the unreacted monomer and solvent are volatilized in the volatilization tank, and the temperature of the polymer is maintained at 210 ° C. Using a polymer transfer pump extrusion processor, the refractive index is 1.5200 and a weight average molecular weight of 190,000 g/mol to prepare non-grafted copolymer pellets B-7.
[202]
[203]
Preparation 21: Preparation of non-grafted copolymer pellets B-8
[204]
A mixed solution containing 38.12 parts by weight of methyl methacrylate, 52.88 parts by weight of styrene, 9.00 parts by weight of acrylonitrile, 30 parts by weight of toluene, and 0.06 parts by weight of n-octyl mercaptan was continuously added to the reactor so that the average polymerization time was 3 hours. did. At this time, the polymerization temperature was maintained at 148 ℃. The polymerization solution continuously discharged from the reactor is heated in a preheating tank, the unreacted monomer and solvent are volatilized in the volatilization tank, and the temperature of the polymer is maintained at 210 ° C. Using a polymer transfer pump extrusion processor, the refractive index is 1.5454 and a weight average molecular weight of 190,000 g/mol to prepare non-grafted copolymer pellets B-8.
[205]
[206]
Preparation 22: Preparation of non-grafted copolymer pellets B-9
[207]
A mixed solution containing 56.72 parts by weight of methyl methacrylate, 34.28 parts by weight of styrene, 9.00 parts by weight of acrylonitrile, 30 parts by weight of toluene, and 0.01 parts by weight of n-octyl mercaptan was continuously added to the reactor so that the average polymerization time was 3 hours. did. At this time, the polymerization temperature was maintained at 148 ℃. The polymerization solution continuously discharged from the reactor is heated in a preheating tank, the unreacted monomer and solvent are volatilized in the volatilization tank, and the temperature of the polymer is maintained at 210 ° C. Using a polymer transfer pump extrusion processor, the refractive index is 1.5268 and the weight average molecular weight was 350,000 g/mol to prepare non-graft copolymer pellets B-9.
[208]
[209]
Preparation 23: Preparation of non-grafted copolymer pellets B-10
[210]
A mixed solution containing 44.10 parts by weight of methyl methacrylate, 44.90 parts by weight of styrene, 11.00 parts by weight of acrylonitrile, 30 parts by weight of toluene, and 0.3 parts by weight of n-octyl mercaptan was continuously added to the reactor so that the average polymerization time was 3 hours. did. At this time, the polymerization temperature was maintained at 148 ℃. The polymerization solution continuously discharged from the reactor is heated in a preheating tank, the unreacted monomer and solvent are volatilized in the volatilization tank, and the temperature of the polymer is maintained at 210 ° C. Using a polymer transfer pump extrusion processor, the refractive index is 1.5380 and a weight average molecular weight of 90,000 g/mol to prepare non-grafted copolymer pellets B-10.
[211]
[212]
Preparation 24: Preparation of non-grafted copolymer pellets B-11
[213]
A mixed solution containing 63.50 parts by weight of methyl methacrylate, 31.50 parts by weight of styrene, 5.00 parts by weight of acrylonitrile, 30 parts by weight of toluene, and 0.08 parts by weight of n-octyl mercaptan was continuously added to the reactor so that the average polymerization time was 3 hours. did. At this time, the polymerization temperature was maintained at 148 ℃. The polymerization solution continuously discharged from the reactor is heated in a preheating tank, the unreacted monomer and solvent are volatilized in the volatilization tank, and the temperature of the polymer is maintained at 210 ° C. Using a polymer transfer pump extrusion processor, the refractive index is 1.5230 and a weight average molecular weight of 190,000 g/mol to prepare non-grafted copolymer pellets B-11.
[214]
[215]
Preparation 25: Preparation of non-grafted copolymer pellets B-12
[216]
A mixed solution containing 70.40 parts by weight of methyl methacrylate, 24.60 parts by weight of styrene, 5.00 parts by weight of acrylonitrile, 30 parts by weight of toluene, and 0.1 parts by weight of n-octyl mercaptan was continuously added to the reactor so that the average polymerization time was 3 hours. did. At this time, the polymerization temperature was maintained at 148 ℃. The polymerization solution continuously discharged from the reactor is heated in a preheating tank, the unreacted monomer and solvent are volatilized in the volatilization tank, and the temperature of the polymer is maintained at 210 ° C. Using a polymer transfer pump extrusion processor, the refractive index is 1.5160 and the weight average molecular weight was 150,000 g/mol to prepare non-graft copolymer pellets B-12.
[217]
[218]
Examples and Comparative Examples
[219]
A thermoplastic resin composition was prepared by uniformly mixing the graft copolymer powder and the non-graft copolymer pellet at the content shown in Tables 1 to 3 below.
[220]
[221]
Experimental Example 1
[222]
The physical properties of the thermoplastic resin compositions of Examples and Comparative Examples were measured by the following method, and the results are shown in Tables 1 to 3.
[223]
[224]
1) Weight average molecular weight (g/mol): 1 g of the thermoplastic resin composition was dissolved in 50 g of acetone with stirring for 24 hours, and then put into a centrifugal separator (trade name: SUPRA 30 K, manufacturer: Hanil Science Industrial) at 16,000 rpm, The supernatant and the precipitate were separated by centrifugation under -10 °C conditions for 4 hours, and the supernatant was dried with a hot air dryer at 50 °C for 12 hours. The obtained dried material was dissolved in tetrahydrofuran at a concentration of 1 wt%, filtered through a 1 μm filter, and measured as a relative value with respect to a standard polystyrene sample through gel permeation chromatography.
[225]
Meanwhile, when measuring gel permeation chromatography, an Agilent 1200 series system was used, and measurement conditions were as follows.
[226]
Refractive index detector (RI): Agilent G1362 RID
[227]
RI temperature: 35 ℃
[228]
Data processing: Agilent ChemStation S/W
[229]
Solvent: tetrahydrofuran
[230]
Column temperature: 40 °C
[231]
Flow rate: 0.3 ml/min
[232]
Sample concentration: 2.0 mg/ml
[233]
Injection volume: 10 μl
[234]
Column model: 1 × PLgel 10 μm MiniMix-B (250 × 4.6 mm)
[235]
+ 1 × PLgel 10 μm MiniMix-B (250 × 4.6 mm)
[236]
+ 1 × PLgel 10 μm MiniMix-B Guard (50 × 4.6 mm)
[237]
Standard sample: polystyrene
[238]
[239]
2) Methyl methacrylate unit/second styrene unit (MMA unit/ST unit): methyl methacrylate unit and rubbery polymer in the thermoplastic resin composition by infrared spectroscopy using a Nicolet TM iS20 FTIR Spectrometer (model name, manufacturer: Thermo Scientific) After deriving the weight of the styrene unit not included in , the weight ratio of the methyl methacrylate unit to the styrene unit was calculated.
[240]
[241]
Experimental Example 2
[242]
After uniformly mixing 100 parts by weight of the thermoplastic resin composition of Examples and Comparative Examples, 0.3 parts by weight of lubricant, and 0.2 parts by weight of antioxidant, pellets were prepared using a twin-screw extrusion kneader having a cylinder temperature of 220°C. The physical properties of the pellets were measured by the following method, and the results are shown in Tables 1 to 3.
[243]
[244]
1) Melt flow index (g/10 min): It was measured under the conditions of 220 °C and 10 kg in accordance with ASTM D1238.
[245]
[246]
Experimental Example 3
[247]
Specimens were prepared by injecting the pellets prepared in Experimental Example 2, and physical properties were measured by the following method, and the results are shown in Tables 1 to 3 below.
[248]
[249]
1) Haze value (%): The transparency of the specimen (thickness: 1/8 inch) was measured according to ASTM D1003.
[250]
2) Notched Izod impact strength (kgf·cm/cm, 1/4 inch): It was measured at 23° C. according to ASTM D256.
[251]
3) Chemical resistance: A specimen fixed to a jig with a jig strain of 0.5% was dipped in 70% isopropyl alcohol and examined for 10 minutes. If there was no change, OK, and if cracks occurred, it was recorded as NG.
[252]
4) Gamma-ray discoloration: L, a, and b values ​​of a 3 mm thick specimen were measured according to ASTM D2244. Then, after irradiating a 3 mm thick specimen with gamma rays and storing it for 21 days, L, a, and b values ​​were measured according to ASTM D2244.
[253]

[254]
In the above formula, L 1 , a 1 and b 1 are the values ​​measured in the CIE LAB color coordinate system after storing the specimen irradiated with gamma rays for 21 days, and L 2 , a 2 and b 2 are the values ​​of gamma rays. The values ​​of L, a, and b of the unirradiated specimen are measured using the CIE LAB color coordinate system.
[255]
[256]
[Table 1]
division Example
One 2 3 4 5 6
graft
copolymer powder Content (parts by weight) 65 60 60 60 60 60
type A-1 A-2 A-3 A-4 A-5 A-6
refractive index 1.5380 1.5230 1.5268 1.5330 1.5379 1.5416
weight average molecular weight 150,000 150,000 170,000 130,000 150,000 190,000
rubbery polymer ST (wt%) 30 10 15 23 30 35
BD (wt%) 70 90 85 77 70 65
average particle size 350 300 300 300 300 300
refractive index 1.5380 1.5230 1.5268 1.5330 1.5379 1.5416
Gummy polymers and monomers
(parts by weight) rubbery polymer 55.00 50.00 50.00 50.00 50.00 50.00
MMA 21.20 28.44 26.58 24.90 21.00 20.58
ST 20.80 14.56 16.42 20.10 22.00 24.42
AN 3.00 7.00 7.00 5.00 7.00 5.00
ungrafted
copolymer Content (parts by weight) 35 40 40 40 40 40
type B-1 B-2 B-3 B-4 B-5 B-6
refractive index 1.5380 1.5230 1.5268 1.5315 1.5379 1.5416
weight average molecular weight 200,000 190,000 190,000 190,000 190,000 190,000
Monomer
(parts by weight) MMA 44.10 60.52 56.72 52.00 45.62 41.92
ST 44.90 30.48 34.28 39.00 45.38 49.08
AN 11.00 9.00 9.00 9.00 9.00 9.00
Thermoplastic resin composition MMA unit/ST unit about 1.00 about 1.97 about 1.64 about 1.29 about 0.98 about 0.84
weight average molecular weight 180,000 170,000 180,000 170,000 170,000 190,000
flow index 2.5 2.5 2.3 3.0 2.8 3.0
haze 2.4 2.0 2.1 2.1 2.2 2.3
impact strength 24 25 23 20 18 15
chemical resistance OK OK OK OK OK OK
gamma ray discoloration 1.5 2.7 2.4 2.1 1.8 1.7
ST: styrene, BD: 1,3-butadiene, MMA: methyl methacrylate, AN: acrylonitrile
[257]
[Table 2]
division Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5
graft
copolymer powder Content (parts by weight) 60 60 60 60 60
type A-7 A-8 A-3 A-9 A-10
refractive index 1.5200 1.5454 1.5268 Measurable 1.5330
weight average molecular weight 130,000 130,000 170,000 130,000 100,000
rubbery polymer ST (wt%) 6 40 15 0 23
BD (wt%) 94 60 85 100 77
average particle size 300 300 300 300 100
refractive index 1.5200 1.5454 1.5268 1.5160 1.5330
Gummy polymers and monomers
(parts by weight) rubbery polymer 50.00 50.00 50.00 50.00 50.00
MMA 31.37 18.72 26.58 24.90 24.90
ST 13.63 26.28 16.42 20.10 20.10
AN 5.00 5.00 7.00 5.00 5.00
ungrafted
copolymer Content (parts by weight) 40 40 40 40 40
type B-7 B-8 B-9 B-4 B-4
refractive index 1.5200 1.5454 1.5268 1.5315 1.5315
weight average molecular weight 190,000 190,000 350,000 190,000 190,000
Monomer
(parts by weight) MMA 63.52 38.12 56.72 52.00 52.00
ST 27.48 52.88 34.28 39.00 39.00
AN 9.00 9.00 9.00 9.00 9.00
Thermoplastic resin composition MMA unit/ST unit Approx. 2.31 about 0.71 about 1.64 about 1.29 about 1.29
weight average molecular weight 160,000 160,000 270,000 170,000 165,000
flow index 2.2 3.5 - 3.0 2.4
haze 2.0 5.1 - >50 1.7
impact strength 27 8 - 21 6
chemical resistance NG OK - OK OK
gamma ray discoloration 4.7 1.3 - 1.9 2.2
ST: styrene, BD: 1,3-butadiene, MMA: methyl methacrylate, AN: acrylonitrile
[258]
[Table 3]
division Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9
graft
copolymer powder Content (parts by weight) 65 60 60 60
type A-11 A-11 A-12 A-13
refractive index 1.5380 1.5380 1.5230 1.5160
weight average molecular weight 80,000 80,000 130,000 100,000
rubbery polymer ST (wt%) 30 30 10 0
BD (wt%) 70 70 90 100
average particle size 350 350 300 300
refractive index 1.5380 1.5380 1.5230 1.5160
Gummy polymers and monomers
(parts by weight) rubbery polymer 55.00 55.00 50.00 50.00
MMA 21.20 21.20 33.00 35.00
ST 20.80 20.80 16.00 12.00
AN 3.00 3.00 1.00 3.00
ungrafted
copolymer Content (parts by weight) 35 40 40 40
type B-10 B-10 B-11 B-12
refractive index 1.5380 1.5380 1.5230 1.5160
weight average molecular weight 90,000 90,000 190,000 150,000
Monomer
(parts by weight) MMA 44.10 44.10 63.50 70.40
ST 44.90 44.90 31.50 24.60
AN 11.00 11.00 5.00 5.00
Thermoplastic resin composition MMA unit/ST unit about 1.00 about 1.00 about 2.04 Approx. 2.88
weight average molecular weight 85,000 85,000 170,000 130,000
flow index 11.4 13.1 3.0 2.7
haze 2.3 2.3 2.9 2.1
impact strength 29 27 25 27
chemical resistance NG NG NG NG
gamma ray discoloration 1.6 1.8 3.3 5.3
ST: styrene, BD: 1,3-butadiene, MMA: methyl methacrylate, AN: acrylonitrile
[259]
Referring to Tables 1 to 3, Examples 1 to 6 using a styrene/butadiene rubber polymer prepared by polymerizing 10 to 35% by weight of styrene and 65 to 90% by weight of 1,3-butadiene are, Transparency, impact resistance, chemical resistance and resistance to gamma rays were all excellent. However, Comparative Example 1 using a styrene/butadiene rubber polymer prepared by polymerizing 6% by weight of styrene and 94% by weight of 1,3-butadiene has significantly higher chemical resistance and resistance to gamma rays compared to Examples 1 to 6 was lowered
[260]
In Comparative Example 2 using a styrene/butadiene rubber polymer prepared by polymerizing 40 wt% of styrene and 60 wt% of 1,3-butadiene, the transparency and impact resistance were significantly lowered compared to Examples 1 to 6.
[261]
On the other hand, Comparative Example 3, in which the weight average molecular weight of the thermoplastic resin composition was 270,000 g/mol, was not molded during injection processing because the weight average molecular weight was too high. For this reason, it was not possible to evaluate the physical properties.
[262]
In Comparative Example 4 containing a butadiene rubbery polymer having an average particle diameter of 300 nm, transparency was remarkably deteriorated.
[263]
In Comparative Example 5 using a styrene/butadiene rubbery polymer having an average particle diameter of 100 nm, the impact resistance was significantly lowered.
[264]
Chemical resistance of Comparative Examples 6 and 7, in which the weight average molecular weight of the thermoplastic resin composition was 85,000 g/mol, was significantly reduced.
[265]
In Comparative Example 8, in which the weight ratio of the (meth)acrylate-based monomer unit to the second styrene-based monomer unit was about 2.04, transparency, chemical resistance, and resistance to gamma rays were significantly reduced.
[266]
Comparative Example 9, in which the weight ratio of the (meth)acrylate-based monomer unit to the second styrene-based monomer unit was about 2.88, contained an excessive amount of methyl methacrylate unit, so that the chemical resistance was reduced, and the expensive raw material methyl methacrylic Since the rate was used in excess, the manufacturing cost increased. In addition, the resistance to gamma rays was significantly reduced.
Claims
[Claim 1]
a rubbery polymer comprising the first styrene-based monomer unit and the diene-based monomer unit in a weight ratio of 10:90 to 35:65 and having an average particle diameter of 250 to 450 nm; (meth)acrylate-based monomer units; and a second styrenic monomer unit, wherein the weight ratio of the (meth)acrylate-based monomer unit to the second styrene-based monomer unit is 2 or less, and the thermoplastic resin composition has a weight average molecular weight of 130,000 to 250,000 g/mol. .
[Claim 2]
The thermoplastic resin composition of claim 1, wherein the weight ratio of the (meth)acrylate-based monomer unit to the second styrene-based monomer unit is 0.80 to 2.00.
[Claim 3]
The thermoplastic resin composition of claim 1, wherein the thermoplastic resin composition has a weight average molecular weight of 140,000 to 210,000 g/mol.
[Claim 4]
The method according to claim 1, wherein the thermoplastic resin composition comprises 20.00 to 40.00 wt% of the rubbery polymer; 23.00 to 51.00 wt% of the (meth)acrylate-based monomer unit; and 18.00 to 41.00 wt% of the second styrenic monomer unit.
[Claim 5]
The thermoplastic resin composition of claim 1, wherein the thermoplastic resin composition comprises an acrylonitrile-based monomer unit.
[Claim 6]
The thermoplastic resin composition of claim 5, wherein the thermoplastic resin composition comprises 3.00 to 12.00 wt% of the acrylonitrile-based monomer unit.
[Claim 7]
The method according to claim 1, wherein the thermoplastic resin composition comprises a first styrenic monomer unit and a diene-based monomer unit in a weight ratio of 10:90 to 35:65 and an average particle diameter of 250 to 450 nm, a rubbery polymer, the rubber polymer a graft copolymer comprising a (meth)acrylate-based monomer unit and a second styrene-based monomer unit grafted to the rubbery polymer; and a (meth) acrylate-based monomer unit and a non-grafted copolymer including a second styrene-based monomer unit.
[Claim 8]
The thermoplastic resin composition of claim 7, wherein the graft copolymer has a refractive index of 1.5230 to 1.5420.
[Claim 9]
The thermoplastic resin composition of claim 7, wherein the graft copolymer has a weight average molecular weight of 70,000 to 250,000 g/mol.
[Claim 10]
The thermoplastic resin composition of claim 7, wherein the non-grafted copolymer has a weight average molecular weight of 140,000 to 250,000 g/mol.