Method for producing graft polymer and graft polymer powder

Abstract

A method for producing a graft polymer and a graft polymer powder may be provided. The production method comprises: forming a first solution comprising a graft polymer of a polyolefin and an acid anhydride; cooling the first solution to a first temperature and then maintaining the same at the first temperature to form a second solution; cooling the second solution to a second temperature or cooling the same and then maintaining the same at the second temperature to form a third solution; solid-liquid separating the third solution to obtain a first graft polymer; and washing and drying the first graft polymer to obtain a second graft polymer, wherein the first graft polymer may be washed at least twice, or a nucleating agent may be added to at least one of the first to third solutions and homogenized. The span value of a second graft polymer powder and the graft polymer powder may be 1 to 20.

Description

Method for manufacturing graft polymer and graft polymer powder

[0001] The embodiments of the present application relate to a method for manufacturing a graft polymer and a graft polymer powder.

[0002] Polyolefins are widely used in various industrial fields, including label films, food packaging, everyday products, and textiles. However, since polyolefins are non-polar polymers, properties such as surface energy, adhesion, compatibility, and water resistance required for specific applications may not be sufficiently achieved. Accordingly, research is being conducted to improve these properties by introducing polar groups into polyolefins.

[0003] For example, a graft reaction is used to bond acid anhydride compounds to polyolefin chains. Techniques for grafting polar compounds, such as maleic anhydride, onto polyolefins include methods for inducing a graft reaction by mixing polyolefin, maleic anhydride, and a radical reaction initiator together in a mixing facility such as an extruder or mixer, or methods for performing the graft reaction by introducing the reactants into a reactor.

[0004] While graft manufacturing technology using mixing equipment offers a simple process and high processability, controlling the dispersion and reaction of initiators and polar compounds can be difficult. Additionally, unreacted polar compounds or initiators may remain.

[0005] Meanwhile, a method of performing a graft reaction by adding a polar compound to a solution of polyolefin dissolved in an organic solvent requires a large amount of solvent during manufacturing, which may result in limitations in terms of process safety and working environment, and may increase costs. For example, organic solvents with a boiling point of 100°C or higher, such as toluene, xylene, or monochlorobenzene (MCB), may be used to dissolve the polyolefin. After the graft reaction is completed, an antisolvent process using water and / or a polar organic solvent (e.g., methyl isobutyl ketone) may be applied to remove unreacted reactants and to recover and purify the grafted polyolefin, and the product may be separated through precipitation or crystallization during this process.

[0006] However, the above antisolvent process requires a large amount of solvent and involves additional solvent recovery and drying processes, which can complicate the overall manufacturing process; as mentioned above, process safety and workability are low, and costs may increase.

[0007] For example, when maleic anhydride is grafted onto a polyolefin, under high temperature conditions, some of the maleic anhydride may be hydrolyzed and converted into maleic acid, or the maleic acid may be isomerized into fumaric acid. The maleic acid or fumaric acid may remain in the grafted polymer as a byproduct, which may lead to changes in the color of the final product, reduced thermal stability, or reduced adhesive performance. For example, in fields requiring appearance quality and adhesive properties, such as packaging materials or label films, the presence of the aforementioned impurities can act as a factor that undermines product reliability.

[0008] One objective of the present disclosure is to provide a method for manufacturing a graft polymer in which the handling properties of the material are improved, the uniformity of quality is improved, and the impurity content is reduced.

[0009] One objective of the present disclosure is to provide a graft polymer powder with improved material handling, improved quality uniformity, and reduced impurity content.

[0010] A method for preparing a graft polymer according to embodiments of the present disclosure comprises: grafting a polyolefin and an acid anhydride in a solvent to form a first solution comprising a graft polymer of said polyolefin and said acid anhydride; cooling the first solution to a first temperature of 70°C to 90°C and maintaining it at the first temperature to form a second solution; cooling the second solution to a second temperature of 35°C to 60°C or cooling it and maintaining it at the second temperature to form a third solution; separating the solid and liquid of the third solution to obtain a first graft polymer; and washing and drying the first graft polymer to obtain a second graft polymer, wherein the first graft polymer is washed two or more times; or a nucleating agent is added to at least one of the first to third solutions and homogenized, and the span value of the obtained second graft polymer may be 1 to 20.

[0011] In one embodiment, the span value can be calculated by the following Equation 1.

[0012] [Equation 1]

[0013] Span value = (D 90 -D 10 ) / D 50

[0014] D in Equation 1 above 10 , D 50 and D 90 represents the particle size at the 10%, 50%, and 90% points, respectively, based on the cumulative volume distribution measured by laser diffraction particle size analysis for the second graft polymer.

[0015] In one embodiment, the intermediate particle size (D of the obtained second graft polymer 50) can be 10 μm to 625 μm.

[0016] In one embodiment, D of the obtained second graft polymer 10 It can be 0.01 μm to 50 μm.

[0017] In one embodiment, D of the obtained second graft polymer 90 It can be 100 μm to 2000 μm.

[0018] In one embodiment, the first graft polymer can be washed 2 to 5 times.

[0019] In one embodiment, the first graft polymer can be washed using acetone.

[0020] In one embodiment, each washing may include immersing in 100 to 1,000 parts by weight of acetone based on 100 parts by weight of the first graft polymer.

[0021] In one embodiment, the nucleating agent is a polymer of the same type as the graft polymer of the polyolefin and the acid anhydride, and has an intermediate particle size (D) of 10 μm to 300 μm. 50 Can have ).

[0022] In one embodiment, the total amount of the nucleating agent added may be 0.01 to 10 parts by weight per 100 parts by weight of the polyolefin provided to the graft reaction.

[0023] In one embodiment, a first solution can be cooled to a first temperature at a cooling rate of -6 ℃ / hr to -60 ℃ / hr and then maintained at the first temperature to form a second solution.

[0024] In one embodiment, a second solution can be formed by cooling a first solution to a first temperature and maintaining it at the first temperature for at least one minute.

[0025] In one embodiment, a third solution can be formed by cooling the second solution to a second temperature at a cooling rate of -6 ℃ / hr to -100 ℃ / hr, or by maintaining it at the second temperature after cooling.

[0026] In one embodiment, a third solution can be formed by cooling the second solution to a second temperature and maintaining it at the second temperature for 1 minute to 5 hours.

[0027] In one embodiment, the acid anhydride may include maleic anhydride (MA).

[0028] In one embodiment, after the formation of the third solution and before solid-liquid separation, it may further include cooling to a third temperature of 10°C to 30°C, or maintaining at the third temperature after cooling.

[0029] In one embodiment, the second temperature may be 50°C to 60°C.

[0030] The graft polymer powder according to the embodiments of the present disclosure is a polymer powder in which an acid anhydride is grafted onto a polyolefin and may have a span value of 1 to 20.

[0031] In one embodiment, the median particle size (D) of the graft polymer powder 50 ) can be 10 μm to 625 μm.

[0032] According to the method for manufacturing a graft polymer according to the embodiments of the present disclosure, the span value of the graft polymer powder being manufactured is appropriately controlled, thereby improving the handling properties of the material and the uniformity of quality. In addition, by crystallizing the polymer through a cooling process, the content of impurities can be reduced to almost nothing or effectively reduced.

[0033]

[0034] The method for manufacturing a graft polymer and the graft polymer powder according to the embodiments of the present disclosure can be applied to various technical fields, such as food packaging materials, medical packaging materials, and sheets or films for electrical and electronic products.

[0035] FIG. 1 is a schematic process flow diagram of a method for manufacturing a graft polymer according to one embodiment.

[0036] Figure 2 is a graph showing the temperature change over time in a method for manufacturing a graft polymer according to one embodiment.

[0037] Figure 3 is a graph showing the change in temperature over time in a method for manufacturing a graft polymer according to another embodiment.

[0038] Figure 4 is a graph of the cumulative volume particle size distribution obtained from the particle size analysis results of the graft polymer powder prepared in each example.

[0039] Figure 5 is a graph of the cumulative volume particle size distribution obtained from the particle size analysis results of the graft polymer powder prepared in each comparative example.

[0040] Hereinafter, embodiments of the present disclosure will be described in more detail with reference to the attached drawings. In this case, the same reference numerals are used for identical components in the drawings, and redundant descriptions of identical components are omitted. The embodiments disclosed in the attached drawings are exemplary and should be understood to include all modifications, equivalents, and substitutions that fall within the spirit and scope of the present invention.

[0041] In this specification, terms such as "first," "second," etc. are used as relative concepts to distinguish different components and do not specify an absolute order.

[0042]

[0043] Method for manufacturing graft polymers

[0044] FIG. 1 is a schematic process flow diagram of a method for manufacturing a graft polymer according to one embodiment.

[0045] FIG. 2 is a graph showing the change in temperature over time in a method for manufacturing a graft polymer according to one embodiment, and FIG. 3 is a graph showing the change in temperature over time in a method for manufacturing a graft polymer according to another embodiment. The temperatures and times described in FIG. 2 and FIG. 3 are merely examples for explaining one embodiment, and the method for manufacturing a graft polymer of the present disclosure is not limited thereto.

[0046] A method for preparing a graft polymer according to embodiments of the present disclosure may include: grafting a polyolefin and an acid anhydride in a solvent to form a first solution comprising a graft polymer of the polyolefin and the acid anhydride (step S10); cooling the first solution to a first temperature of 70°C to 90°C and maintaining it at the first temperature to form a second solution (step S20); cooling the second solution to a second temperature of 35°C to 60°C or cooling it and maintaining it at the second temperature to form a third solution (step S30); separating the solid from the liquid of the third solution to obtain a first graft polymer (step S40); and washing and drying the first graft polymer to obtain a second graft polymer (step S50).

[0047] In the above method for manufacturing the graft polymer, the first graft polymer may be washed two or more times; or a nucleating agent may be added to at least one of the first to third solutions and homogenized.

[0048] The span value of the second graft polymer obtained by the above method for manufacturing the graft polymer may be 1 to 20. Accordingly, the handling properties of the second graft polymer are improved, and the uniformity of quality may be improved.

[0049] If the above span value is too small, the cohesive force between particles increases, reducing powder fluidity and increasing scattering during the conveying process, which may lead to equipment contamination and deterioration of the working environment. Furthermore, during the mixing process for subsequent processes such as forming into sheets or films and / or extrusion, a discrepancy in the mixing ratio relative to the actual input amount may occur, resulting in uneven quality of the final product. Additionally, powder may remain inside the equipment without being sufficiently discharged or washed away.

[0050] If the above span value is too large, separation by particle size may occur during storage and transport, or non-uniform filling may occur in subsequent processes such as mixing and extrusion, which may lead to non-uniform quality.

[0051] In addition, according to the method for manufacturing the graft polymer described above, the graft polymer dissolved in the first solution is precipitated and / or crystallized by a cooling process without using an anti-solvent, so reflux at high temperatures is not required, costs are reduced, and process time can be shortened. For example, the use of expensive toxic solvents such as methyl isobutyl ketone can be excluded.

[0052] For example, among acid anhydrides, maleic anhydride can be converted to maleic acid at temperatures higher than 60°C under conditions where moisture is present, and can be isomerized into fumaric acid at temperatures around 100°C. Since the maleic acid and fumaric acid have low solubility in organic solvents, they cannot be sufficiently removed by a washing process using a solvent such as methyl isobutyl ketone and may remain in the resulting polymer. Consequently, there may be limitations in applying the polymer to fields with strict regulations on residues, such as packaging products related to food and pharmaceuticals.

[0053] According to the above method for manufacturing the graft polymer, a reflux process at high temperature is not required, so maleic anhydride may not exist in the form of maleic acid or fumaric acid, or may exist in extremely small amounts. Accordingly, it can be washed with a ketone-based solvent that has a low boiling point and low toxicity, such as acetone, and unreacted maleic anhydride can be easily removed by acetone, etc., so that no impurities remain in the second graft polymer or the amount of impurities can be effectively reduced.

[0054] In this specification, the term "graft reaction" refers to a reaction in which an acid anhydride is bonded to the main chain or side chain of a polyolefin to form a graft structure, and may include, for example, a polymerization reaction, a ring-opening reaction, a radical reaction, or a combination thereof.

[0055] For example, the graft reaction of the polyolefin and the acid anhydride can be carried out as follows.

[0056] The above polyolefin and the above acid anhydride can be dissolved or dispersed in the solvent.

[0057] The above solvent may be an organic solvent, for example, an organic solvent with a boiling point higher than the reaction temperature of 130°C to 200°C. The above organic solvent may include, for example, p-xylene, decalin, tetralin, mineral oil, toluene, or dichlorobenzene.

[0058] For example, a radical initiator may be further added to the solvent in which the polyolefin and the acid anhydride are dissolved. The radical initiator may be a peroxide-based initiator or an azo-based initiator as a non-limiting example.

[0059] The above peroxide-based initiator may include, for example, dicumyl peroxide, benzoyl peroxide, di-tert-butyl peroxide, t-butyl peroxybenzoate, lauroyl peroxide, etc.

[0060] The above azo-based initiator may include, for example, AIBN (azobisisobutyronitrile), AIBA (2,2'-azobis(2-methylpropionamidine) dihydrochloride), V-70 (2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile)), V-65 (2,2'-azobis(2,4-dimethylvaleronitrile)), etc.

[0061] For example, 0.1 to 50 parts by weight of the acid anhydride can be reacted with 100 parts by weight of the polyolefin.

[0062] For example, the radical initiator can be mixed in an amount of 0.1 to 50 parts by weight with respect to 100 parts by weight of the total polyolefin and acid anhydride. For example, the radical initiator can be mixed in an amount of 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.

[0063] For example, a total of 100 parts by weight of the polyolefin and the acid anhydride can be dissolved in 200 to 500 parts by weight of the solvent.

[0064] The graft reaction can be performed by increasing the temperature of the solvent in which the polyolefin and the acid anhydride are dissolved to a reaction temperature of 130°C to 200°C, for example, 135°C to 150°C. The reaction time may be, for example, 30 minutes to 10 hours, but is not limited thereto.

[0065] The graft reaction described above can be carried out, for example, inside a reactor.

[0066] The polyolefin, the acid anhydride, the solvent, and the radical initiator can be introduced into the reactor simultaneously, sequentially, or in any order to be mixed.

[0067] As a non-limiting example, the reactor may be a conventional batch reactor equipped with a stirring device and a heating device, and may be a reactor having a sealed structure so as to be operated in a nitrogen atmosphere or an inert gas atmosphere as needed.

[0068] The above reactor may be, for example, a stainless steel reactor equipped with a jacket, a glass-lined reactor, or a stirred reactor equipped with an internal impeller capable of high-shear mixing.

[0069] The reactor may include, for example, an overhead agitator, an anchor agitator, a paddle agitator, or a rotor-stator agitator for uniform mixing of the reaction mixture, and the stirring speed may be set to a range of, for example, about 30 rpm to about 3,000 rpm depending on the size of the reactor, the shape of the agitator, etc.

[0070] In one embodiment, the span value can be calculated by the following Equation 1.

[0071] [Equation 1]

[0072] Span value = (D 90 -D10 ) / D 50

[0073] D in Equation 1 above 10 , D 50 and D 90 represents the particle size at the 10%, 50%, and 90% points, respectively, based on the cumulative volume distribution measured by laser diffraction particle size analysis for the second graft polymer.

[0074] The above laser diffraction particle size analysis can be performed, for example, under test conditions according to ASTM E3340 of ASTM International and / or test conditions according to ISO 13320 of the International Organization for Standardization.

[0075] For example, the above cumulative volume distribution can be measured using a laser diffraction particle size analyzer, and the measurement mode may be a wet dispersion method or a dry dispersion method.

[0076] For example, the above cumulative volume distribution can be analyzed by applying a Mie scattering model or a Fraunhofer scattering model after dispersing it in a non-reactive dispersion medium containing p-xylene using a wet dispersion module.

[0077] In one embodiment, the span value may be 1.5 to 20, 1.9 to 19, 2 to 19, 2 to 10, 2 to 6, 2 to 5.5, or 2 to 5.

[0078] In one embodiment, the intermediate particle size (D of the obtained second graft polymer 50 ) can be 10 μm to 625 μm, and, for example, 20 μm to 500 μm, 20 μm to 450 μm, or 70 μm to 400 μm.

[0079] In one embodiment, D of the obtained second graft polymer 10 It can be 0.01 μm to 50 μm, and, for example, 1 μm to 50 μm or 1 μm to 45 μm.

[0080] In one embodiment, D of the obtained second graft polymer 90 It can be 100 μm to 2000 μm, for example, 100 μm to 1000 μm, 200 μm to 1000 μm, or 200 μm to 900 μm.

[0081] In one embodiment, the first graft polymer can be washed 2 to 5 times, for example, 3 to 5 times.

[0082] If the first graft polymer is washed too lightly, particles that are excessively small or large in size may not be sufficiently removed, and residual impurities and residual volatile organic compounds may not be sufficiently removed. Conversely, if the first graft polymer is washed too heavily, the amount of first graft polymer powder lost during the washing process may increase relatively, and the generation of fine particles may be promoted.

[0083] In one embodiment, the first graft polymer can be washed using acetone. Since acetone has a low boiling point of about 56°C and relatively low toxicity, it can be easily removed by refluxing under temperature conditions below 80°C. In addition, since acetone is used alone and no solvent capable of forming hydrogen bonds, such as water, is used, the ring structure of maleic anhydride can be suppressed from opening by a hydration reaction during the washing process. Accordingly, maleic acid or fumaric acid modified from residual maleic anhydride may remain in the obtained second graft polymer in a trace amount of 12,600 ppm or less, or may not remain substantially at all. For example, the residual amount of maleic acid may be 8,700 ppm or less, 400 ppm or less, 300 ppm or less, or 235 ppm or less, and the lower limit is not particularly limited, but a smaller amount may be preferable. For example, the residual amount of the above fumaric acid may be 415 ppm or less, 413 ppm or less, or 0 ppm.

[0084] Furthermore, since the ring structure of maleic anhydride grafted onto the polyolefin is not opened by the hydration reaction, a graft polymer can be manufactured while maintaining the ring structure of maleic anhydride, thereby possessing excellent adhesive properties. In contrast, if the ring structure of maleic anhydride is opened by the hydration reaction, thermal stability is reduced, making it susceptible to degradation such as decarboxylation or other chemical modifications.

[0085] According to the method for manufacturing a graft polymer according to one embodiment, the occurrence of yellowing caused by degradation as described above can be suppressed or reduced.

[0086] In one embodiment, each washing may include immersing 100 parts by weight of the first graft polymer in 100 to 1000 parts by weight of acetone. For example, each washing may be performed by immersing 100 parts by weight of the first graft polymer in 100 to 900 parts by weight, 100 to 800 parts by weight, 100 to 700 parts by weight, 100 to 600 parts by weight, 100 to 500 parts by weight, 100 to 400 parts by weight, or 100 to 300 parts by weight of acetone.

[0087] For example, washing three or more times may mean repeating the process of immersing 100 parts by weight of the first graft polymer in 100 to 1000 parts by weight of acetone three or more times.

[0088] In one embodiment, each washing process may be repeated, and a drying process may be performed once after all washing processes are completed. For example, drying may be performed once after two or more washes.

[0089] In one embodiment, filtration may be further performed between washing and drying.

[0090] In one embodiment, after two or more washes, filtration and drying may each be performed once.

[0091] In one embodiment, washing and drying may be repeated as one cycle, and the cycle may be repeated two or more times or three or more times.

[0092] In one embodiment, washing, filtration, and drying may be repeated as one cycle, and said cycle may be repeated two or more times or three or more times.

[0093] As a non-limiting example, the filtration may be performed by a filter press, a notch filter, a vacuum filtration device (e.g., a filter connected to a Buechner funnel and a vacuum flask or vacuum device), or a cartridge filter.

[0094] In one embodiment, the drying may be performed at a temperature of 57°C to 80°C, for example, at a temperature of 57°C or higher and less than 80°C.

[0095] The above drying time may be 30 minutes to 12 hours, but is not particularly limited as long as it is sufficient to remove the solvent used for washing.

[0096] In one embodiment, the nucleating agent is a polymer of the same type as the graft polymer of the polyolefin and the acid anhydride, and has an intermediate particle size (D) of 10 μm to 300 μm. 50 Can have ).

[0097] Accordingly, the span value of the obtained second graft polymer can be controlled as described above, and the purity of the polyolefin resin can be prevented from decreasing. That is, the incorporation of impurities into the polyolefin resin can be suppressed.

[0098] In one embodiment, the nucleating agent has an intermediate particle size (D) of 10 μm to 300 μm. 50 It can have ), for example, an intermediate particle size (D) of 100 μm to 200 μm. 50 Can have ).

[0099] In one embodiment, the second graft polymer obtained by the above manufacturing method may be used as the nucleating agent. By using the second graft polymer as the nucleating agent instead of using a heterogeneous material as such, the purity and uniformity of the quality of the graft polymer can be further improved.

[0100] In one embodiment, the nucleating agent can be added to the first solution and homogenized.

[0101] In one embodiment, the nucleating agent can be added to the second solution and homogenized.

[0102] In one embodiment, the nucleating agent can be added to the third solution and homogenized.

[0103] In one embodiment, the nucleating agent can be added to the first solution and the second solution and homogenized.

[0104] In one embodiment, the nucleating agent can be added to the first solution and the third solution and homogenized.

[0105] In one embodiment, the nucleating agent can be added to the second solution and the third solution and homogenized.

[0106] In one embodiment, the nucleating agent can be added to the first to third solutions and homogenized.

[0107] In one embodiment, the first solution may be cooled to a first temperature, the nucleating agent may be added, and the solution may be maintained at the first temperature to form a second solution. For example, the second solution may be formed by maintaining at the first temperature and stirring.

[0108] In one embodiment, the nucleating agent may be introduced while maintaining the first solution at the first temperature after cooling it to the first temperature. For example, the nucleating agent may be introduced at any point while maintaining the first temperature.

[0109] In one embodiment, a second solution can be formed by maintaining and stirring a solution cooled to a first temperature at the first temperature.

[0110] In one embodiment, the second solution may be cooled to a second temperature, the nucleating agent may be added, and the solution may be maintained at the second temperature to form a third solution. For example, the third solution may be formed by maintaining and stirring at the second temperature.

[0111] In one embodiment, the nucleating agent may be introduced while maintaining the second solution at the second temperature after cooling it to the second temperature. For example, the nucleating agent may be introduced at any point while maintaining it at the second temperature. In one embodiment, the solution cooled to the second temperature may be maintained at the second temperature and stirred to form a third solution.

[0112] In one embodiment, stirring can be performed while forming the first solution.

[0113] In one embodiment, stirring can be performed while forming the second solution.

[0114] In one embodiment, stirring can be performed while forming the third solution.

[0115] In one embodiment, the total amount of the nucleating agent added may be 0.01 to 10 parts by weight per 100 parts by weight of the polyolefin provided to the graft reaction, and for example, 0.01 to 7 parts by weight, 0.01 to 5 parts by weight, 0.01 to 4 parts by weight, 0.01 to 3 parts by weight, 0.01 to 1 part by weight, or 0.01 to 0.7 parts by weight.

[0116] The total amount of the nucleating agent added above may mean the sum of the amounts of the nucleating agent added to at least one of the first to third solutions.

[0117] For example, the amount of each nucleating agent added to any one or more of the first solution, the second solution, and the third solution is sufficient if the total sum satisfies the range described above, and the ratio of addition to each solution is not particularly limited.

[0118] In one embodiment, after the formation of the first solution and before cooling, the nucleating agent may be added to the first solution and homogenized. For example, the amount of the nucleating agent added to the first solution may be 1% to 100% of the total amount of the nucleating agent added.

[0119] In one embodiment, after the formation of the second solution and before cooling, the nucleating agent may be added to the second solution and homogenized. For example, the amount of the nucleating agent added to the second solution may be 1% to 100% of the total amount of the nucleating agent added.

[0120] In one embodiment, after the formation of the third solution and before solid-liquid separation, the nucleating agent may be added to the third solution and homogenized. For example, the amount of the nucleating agent added to the third solution may be 0.1% to 30% of the total amount of the nucleating agent added.

[0121] As a non-limiting example, the homogenization may be performed using a high-speed stirrer, a rotor-stator type homogenizer, a propeller type overhead stirrer, or an ultrasonic homogenizer. During the homogenization, the rotational speed of the impeller or rotor may be 20 rpm to 10,000 rpm. The homogenization may be performed for 1 minute to 1 hour. As a non-limiting example, the output of the ultrasonic homogenizer may be about 50 W to about 300 W, the amplitude may be about 30% to 80%, and the ultrasonic irradiation time may be performed for 5 minutes to 30 minutes.

[0122] In one embodiment, in step S20, the first solution may be cooled to a first temperature at a cooling rate of -6 ℃ / hr to -60 ℃ / hr and then maintained at the first temperature to form a second solution. For example, the cooling rate of the first solution may be -6 ℃ / hr to -50 ℃ / hr, -10 ℃ / hr to -50 ℃ / hr, or -10 ℃ / hr to -45 ℃ / hr. Accordingly, the span value and median particle size (D) of the second graft polymer obtained 50 ) can be controlled together to suppress excessive increase in cohesive force between particles and reduce the occurrence of flying debris.

[0123] In one embodiment, a second solution can be formed by cooling a first solution to a first temperature and maintaining it at the first temperature for at least one minute.

[0124] In one embodiment, a second solution can be formed by cooling a first solution to a first temperature and maintaining it at the first temperature for 5 minutes to 5 hours.

[0125] In one embodiment, a second solution can be formed by cooling the first solution to a first temperature and then maintaining it at the first temperature for 5 minutes to 4 hours, 10 minutes to 5 hours, 15 minutes to 5 hours, 20 minutes to 5 hours, 30 minutes to 4 hours, or 30 minutes to 3 hours.

[0126] Accordingly, the span value of the second graft polymer obtained can be controlled more precisely.

[0127] In one embodiment, in step S30, the second solution may be cooled to a second temperature at a cooling rate of -6 ℃ / hr to -100 ℃ / hr, or maintained at the second temperature after cooling to form a third solution. For example, the cooling rate of the second solution may be -10 ℃ / hr to -90 ℃ / hr, -10 ℃ / hr to -85 ℃ / hr, -10 ℃ / hr to -80 ℃ / hr, or -10 ℃ / hr to -70 ℃ / hr. Accordingly, the span value and median particle size (D) of the second graft polymer obtained 50 ) can be controlled together to suppress or reduce the separation phenomenon by particle size.

[0128] In one embodiment, a third solution can be formed by cooling the second solution to a second temperature and maintaining it at the second temperature for 1 minute to 5 hours.

[0129] In one embodiment, a third solution can be formed by cooling the second solution to a second temperature and maintaining it at the second temperature for 5 minutes to 5 hours.

[0130] In one embodiment, a third solution can be formed by cooling the second solution to a second temperature and then maintaining it at the second temperature for 10 minutes to 5 hours, 15 minutes to 5 hours, 20 minutes to 5 hours, 30 minutes to 4 hours, or 30 minutes to 3 hours.

[0131] Accordingly, the span value of the second graft polymer obtained can be controlled more stably.

[0132] In one embodiment, the acid anhydride may include maleic anhydride (MA). The acid anhydride may include the maleic anhydride in an amount of 90% or more by weight, 95% or more by weight, 99% or more by weight, or 99% to 100% by weight based on the total weight of the acid anhydride.

[0133] In one embodiment, the acid anhydride may be maleic anhydride. Accordingly, the graft polymer may have a structure in which maleic anhydride is grafted onto a polyolefin.

[0134] In one embodiment, the polyolefin may be polypropylene. Accordingly, the graft polymer may be a polypropylene-maleic anhydride graft polymer.

[0135] In one embodiment, after the formation of the third solution and before solid-liquid separation, the step of further cooling to a third temperature of 10°C to 30°C or maintaining at the third temperature after cooling may be further included.

[0136] In one embodiment, the second temperature may be 50°C to 60°C.

[0137] For example, the second solution may be cooled to a second temperature of 50°C to 60°C, or maintained at the second temperature after cooling to form a third solution, and then the third solution may be cooled to a third temperature of 20°C to 30°C, or maintained at the third temperature for 5 minutes to 3 hours after cooling, and then the third solution may be separated into solid and liquid phases.

[0138] In one embodiment, while cooling the third solution to a third temperature of 10°C to 30°C, the cooling rate may be -6°C / hr to -120°C / hr. For example, the cooling rate of the third solution may be -6°C / hr to -110°C / hr, -10°C / hr to -100°C / hr, or -15°C / hr to -110°C / hr.

[0139] For example, the above solid-liquid separation can be performed using a filtration method that filters out solids using a filter, a centrifugation method that settles solids and separates the supernatant by centrifugation, or a sedimentation and decantation method that allows solids to settle by gravity sedimentation and then removes the upper liquid phase.

[0140] In one embodiment, the solid-liquid separation may be performed by filtration, centrifugation, or sedimentation and decantation.

[0141] In one embodiment, the total content of unreacted maleic anhydride, maleic acid, and fumaric acid remaining without being grafted onto the obtained second graft polymer may be 120,000 ppm or less, 60,000 ppm or less, 50,000 ppm or less, 40,000 ppm or less, and, for example, 0 ppm to 120,000 ppm, 0 ppm to 60,000 ppm, 0 ppm to 50,000 ppm, 0 ppm to 40,000 ppm, or 0 ppm to 20,000 ppm.

[0142] Accordingly, residual impurities in the second graft polymer are suppressed or reduced, thereby improving appearance quality, adhesive properties, and product reliability.

[0143]

[0144] Grafted Polymer Powder

[0145] The graft polymer powder according to the embodiments of the present disclosure is a polymer powder in which an acid anhydride is grafted onto a polyolefin and may have a span value of 1 to 20.

[0146] The above-described graft polymer powder can be manufactured by the method for manufacturing the graft polymer described above, and can be manufactured as a second graft polymer.

[0147] In one embodiment, the span value can be calculated by the following Equation 1.

[0148] [Equation 1]

[0149] Span value = (D 90 -D 10 ) / D 50

[0150] In the above Equation 1, D10, D50, and D90 represent the particle sizes at the 10%, 50%, and 90% points, respectively, based on the cumulative volume distribution measured by laser diffraction particle size analysis for the second graft polymer.

[0151] The above laser diffraction particle size analysis can be performed, for example, under test conditions according to ASTM E3340 of ASTM International and / or test conditions according to ISO 13320 of the International Organization for Standardization.

[0152] In one embodiment, the span value may be 1.5 to 20, 1.9 to 19, 2 to 19, 2 to 10, 2 to 6, 2 to 5.5, or 2 to 5.

[0153] In one embodiment, the median particle size (D) of the graft polymer powder 50 ) can be 10 μm to 625 μm, and, for example, 20 μm to 500 μm, 20 μm to 450 μm, or 70 μm to 400 μm.

[0154] In one embodiment, D of the graft polymer powder 10 It can be 0.01 μm to 50 μm, and, for example, 1 μm to 50 μm or 1 μm to 45 μm.

[0155] In one embodiment, D of the graft polymer powder 90 It can be 100 μm to 2000 μm, for example, 100 μm to 1000 μm, 200 μm to 1000 μm, or 200 μm to 900 μm.

[0156] In one embodiment, the total content of unreacted maleic anhydride, maleic acid, and fumaric acid remaining without being grafted into the graft polymer powder may be 120,000 ppm or less, 60,000 ppm or less, 50,000 ppm or less, 40,000 ppm or less, and, for example, 0 ppm to 120,000 ppm, 0 ppm to 60,000 ppm, 0 ppm to 50,000 ppm, 0 ppm to 40,000 ppm, or 0 ppm to 20,000 ppm.

[0157] Accordingly, the residue of impurities in the graft polymer powder is suppressed or reduced, thereby improving appearance quality, adhesive properties, and product reliability.

[0158] In one embodiment, the acid anhydride may be maleic anhydride (MA). Accordingly, the graft polymer may have a structure in which maleic anhydride is grafted onto the polyolefin.

[0159] In one embodiment, the polyolefin may be polypropylene. Accordingly, the graft polymer powder may be a graft polymer powder of polypropylene-maleic anhydride.

[0160]

[0161] In the following, embodiments of the present disclosure are further described with reference to specific experimental examples. The embodiments and comparative examples included in the experimental examples are merely illustrative of the present disclosure and do not limit the appended claims.

[0162]

[0163] Examples and Comparative Examples

[0164]

[0165] Example 1

[0166] (1) Graft polymerization reaction

[0167] 900 L of monochlorobenzene (MCB), 300 kg of polypropylene (INEOS, 100-GA35), and 44.1 kg of maleic anhydride were sequentially introduced into a 3,000 L capacity glass-lined reactor (inner diameter: 1.6 m, height: 2.0 m) equipped with a 3-curved blade turbine under nitrogen atmosphere and room temperature conditions.

[0168] Afterwards, the internal temperature of the reactor was raised to about 133°C and heated refluxed for 3 hours and 30 minutes, and then maintained at about 133°C for about 30 minutes to prepare reaction solution A in which the reactants were dissolved.

[0169] Subsequently, while maintaining the reactor temperature at approximately 130°C, reaction solution B, in which 14.1 kg of the radical initiator Luperox 26 was dissolved in 68 L of MCB, was slowly introduced into the reactor over a period of approximately 2 hours. At this time, a graft reaction was carried out for 2 hours at a temperature of approximately 130°C while maintaining a stirring speed of 500 rpm to prepare a first solution containing the graft polymer of the polypropylene and the maleic anhydride.

[0170]

[0171] (2) Cooling

[0172] The prepared first solution was cooled from approximately 130 ℃ to approximately 90 ℃ over a period of approximately 2 hours. During this cooling rate, the rate was -20 ℃ / hr. Subsequently, the second solution was obtained by maintaining the temperature at approximately 90 ℃ for approximately 1 hour while stirring.

[0173] Subsequently, the temperature inside the reactor was cooled to approximately 60°C over a period of about 2 hours. At this time, the cooling rate was -15°C / hr. Then, the temperature was maintained at approximately 60°C for about 3 hours while stirring to obtain a third solution in the form of a slurry.

[0174] Afterwards, the third solution was cooled to a temperature of about 30 ℃ for about 2 hours. At this time, the cooling rate was -15 ℃ / hr. Subsequently, the temperature of the third solution was maintained at about 30 ℃ for about 1 hour while stirring.

[0175]

[0176] (3) High-value separation

[0177] Subsequently, a third solution at approximately 30°C was transferred to a Nutsche filter facility with a capacity of 2,500 L, and a solid-liquid separation process by vacuum filtration was performed to obtain a first graft polymer containing MCB.

[0178]

[0179] (4) Washing and drying

[0180] Subsequently, 300 L (100 parts by weight) of acetone was slowly added to 100 parts by weight of the first graft polymer over a period of about 15 minutes to immerse and wash, and vacuum filtration was performed while maintaining the stirring speed of the notch filter at 25 rpm. This immersion, washing, and filtration process was repeated a total of 5 times, and each immersion and washing was performed using 100 parts by weight of acetone for every 100 parts by weight of the first graft polymer.

[0181] Afterwards, the temperature of the filter cake in the notch filter was raised to about 60°C and maintained for about 6 hours to remove residual volatile organic compounds.

[0182] From this, a second graft polymer was obtained with a solid content of 99% or more after drying.

[0183] Subsequently, 0.36 kg of the second graft polymer and the antioxidant Irganox-1076 were introduced into a rotary vacuum drying device under reduced pressure conditions of 40 torr and a temperature of about 60 ℃, and mixed and dried for about 12 hours.

[0184] From this, about 290 kg of the second graft polymer (hereinafter referred to as the graft polymer prepared according to Example 1) was obtained in a yield of about 97%.

[0185]

[0186] Example 2

[0187] (4) A second graft polymer was prepared by the same method as in Example 1, except that the immersion, washing, and filtration were repeated a total of four times in the washing and drying process. From this, about 281 kg of the second graft polymer (hereinafter referred to as the graft polymer prepared according to Example 2) was obtained with a yield of about 94%.

[0188]

[0189] Example 3

[0190] (4) A second graft polymer was prepared by the same method as in Example 1, except that the immersion, washing, and filtration processes were repeated a total of three times in the washing and drying process. From this, about 293 kg of the second graft polymer (hereinafter referred to as the graft polymer prepared according to Example 3) was obtained with a yield of about 98%.

[0191]

[0192] Example 4

[0193] (4) A second graft polymer was prepared by the same method as in Example 2, except that in the washing and drying process, each immersion and washing was performed using 300 parts by weight of acetone per 100 parts by weight of the first graft polymer. From this, about 287 kg of the second graft polymer (hereinafter referred to as the graft polymer prepared according to Example 4) was obtained with a yield of about 96%.

[0194]

[0195] Example 5

[0196] (4) A second graft polymer was prepared by the same method as in Example 3, except that the immersion and washing processes in the washing and drying process were performed using 300 parts by weight of acetone per 100 parts by weight of the first graft polymer. From this, about 280 kg of the second graft polymer (hereinafter referred to as the graft polymer prepared according to Example 5) was obtained with a yield of about 94%.

[0197]

[0198] Example 6

[0199] (2) The first solution prepared in the cooling process was cooled from about 130°C to about 90°C over about 2 hours, and maintained at about 90°C for about 1 hour while stirring to obtain the second solution.

[0200] While maintaining the mixture at a temperature of about 90°C for about 1 hour while stirring, (1) 0.075 parts by weight (0.225 kg) of the second graft polymer prepared in Example 1 was introduced into the reactor as a nucleating agent based on 100 parts by weight (300 kg) of the polypropylene introduced into the reactor in the graft polymerization reaction process.

[0201] A second graft polymer was prepared by the same method as in Example 1, except for the addition of the nucleating agent described above. From this, about 290 kg of the second graft polymer (hereinafter referred to as the graft polymer prepared according to Example 6) was obtained in a yield of about 97%.

[0202]

[0203] Example 7

[0204] (2) The first solution prepared in the cooling process was cooled from about 130°C to about 90°C over about 2 hours, and the second solution was obtained by maintaining it at about 90°C while stirring for about 1 hour.

[0205] While maintaining the mixture at a temperature of about 90°C for about 1 hour while stirring, (1) 0.225 parts by weight (0.675 kg) of the second graft polymer prepared in Example 1 was added as a nucleating agent based on 100 parts by weight (300 kg) of the polypropylene introduced into the reactor in the graft polymerization reaction process.

[0206] A second graft polymer was prepared by the same method as in Example 1, except for the addition of the nucleating agent described above. From this, about 284 kg of the second graft polymer (hereinafter referred to as the graft polymer prepared according to Example 7) was obtained in a yield of about 95%.

[0207]

[0208] Example 8

[0209] (2) The first solution prepared in the cooling process was cooled from about 130°C to about 90°C over about 2 hours, and the second solution was obtained by maintaining it at about 90°C while stirring for about 1 hour.

[0210] While maintaining the mixture at a temperature of about 90°C for about 1 hour while stirring, 1.0 part (3.0 kg) of the second graft polymer prepared in Example 1 was added as a nucleating agent based on 100 parts (300 kg) of the polypropylene introduced into the reactor in the graft polymerization reaction process (1).

[0211] A second graft polymer was prepared by the same method as in Example 1, except for the addition of the nucleating agent described above. From this, about 290 kg of the second graft polymer (hereinafter referred to as the graft polymer prepared according to Example 8) was obtained in a yield of about 98%.

[0212]

[0213] Example 9

[0214] (4) A second graft polymer was prepared by the same method as in Example 6, except that the immersion, washing, and filtration processes were performed only once in the washing and drying process. From this, about 291 kg of the second graft polymer (hereinafter referred to as the graft polymer prepared according to Example 9) was obtained with a yield of about 97%.

[0215]

[0216] Example 10

[0217] (2) A second graft polymer was prepared by the same method as in Example 1, except that the first solution prepared in the cooling process was cooled from about 130 ℃ to about 90 ℃ over about 30 minutes. The cooling rate of the first solution was -80 ℃ / hr.

[0218] From this, about 258 kg of the second graft polymer (hereinafter referred to as the graft polymer prepared according to Example 10) was obtained in a yield of about 86%.

[0219]

[0220] Example 11

[0221] (2) The first solution prepared in the cooling process was cooled from approximately 130 ℃ to approximately 90 ℃ over a period of approximately 2 hours. The cooling rate was -20 ℃ / hr. Subsequently, the second solution was obtained by maintaining the temperature at approximately 90 ℃ for approximately 1 hour while stirring.

[0222] Afterward, the temperature inside the reactor was cooled to approximately 60 ℃ over a period of about 15 minutes. At this time, the cooling rate was -120 ℃ / hr.

[0223] A second graft polymer was prepared by the same method as in Example 1, except that the cooling rate of the second solution was changed as described above. From this, about 228 kg of the second graft polymer (hereinafter referred to as the graft polymer prepared according to Example 11) was obtained in a yield of about 76%.

[0224]

[0225] Example 12

[0226] (2) During the cooling process, the third solution in the form of a slurry was maintained at a temperature of about 60°C for about 3 hours while stirring, and then the third solution maintained at a temperature of about 60°C was used in the (3) solid-liquid separation process without further cooling, except that the second graft polymer was prepared by the same method as in Example 1. From this, about 287 kg of the second graft polymer (hereinafter referred to as the graft polymer prepared according to Example 12) was obtained with a yield of about 96%.

[0227]

[0228] Comparative Example 1

[0229] (1) Graft polymerization reaction

[0230] 900 L of monochlorobenzene (MCB), 300 kg of polypropylene (INEOS, 100-GA35), and 44.1 kg of maleic anhydride were sequentially introduced into a 3,000 L capacity glass-lined reactor (inner diameter: 1.6 m, height: 2.0 m) equipped with a 3-curved blade turbine under nitrogen atmosphere and room temperature conditions.

[0231] Afterwards, the internal temperature of the reactor was raised to about 133°C and heated refluxed for 3 hours and 30 minutes, and then maintained at about 133°C for about 30 minutes to prepare reaction solution A in which the reactants were dissolved.

[0232] Subsequently, while maintaining the reactor temperature at approximately 130°C, reaction solution B, in which 14.1 kg of the radical initiator Luperox 26 was dissolved in 68 L of MCB, was slowly introduced into the reactor over a period of approximately 2 hours. At this time, a graft reaction was carried out for 2 hours at a temperature of approximately 130°C while maintaining a stirring speed of 500 rpm to prepare a first solution containing the graft polymer of the polypropylene and the maleic anhydride.

[0233]

[0234] (2) Solvent removal by precipitation induction and azeotropic reflux

[0235] In the above reactor, the first solution was stirred while cooling from about 130°C to about 90°C, and 3,000 kg of distilled water was added. During this process, as the solubility of the graft polymer formed by the above graft polymerization reaction decreased in the solution into which distilled water was added, the graft polymer precipitated and a slurry-state solution was formed.

[0236] Afterwards, reflux was performed at a temperature of about 90°C to remove MCB, the solvent used in the graft polymerization reaction described above, by azeotropic reflux for more than 20 hours, and the removal rate of MCB was about 98%.

[0237] Afterward, the reaction was allowed to stand to induce phase separation, and then approximately 1,500 kg of the aqueous phase formed in the upper layer was removed.

[0238]

[0239] (3) Washing and solid-liquid separation

[0240] (1) Subsequently, 700 parts by weight of methyl isobutyl ketone (MIBK) were added to the reactor based on 100 parts by weight of polypropylene added to the reactor in the graft polymerization reaction process.

[0241] Afterwards, the mixed solvent of organic solvent and distilled water was removed by simple distillation for more than 5 hours while maintaining a temperature of about 90 ℃, and the removal rate of the mixed solvent was about 97%.

[0242] Afterwards, (1) 100 parts by weight (300 kg) of MIBK solution was added to the reactor based on 100 parts by weight of polypropylene added to the reactor in the graft polymerization reaction process, and transferred to a Nutsche filter facility with a capacity of 2,500 L.

[0243] Subsequently, a solid-liquid separation process by vacuum filtration was performed a total of three times to obtain a graft polymer.

[0244]

[0245] (4) Drying process

[0246] Subsequently, the graft polymer was introduced into a rotary vacuum drying device, and 0.36 kg of the antioxidant Irganox-1076 was administered under reduced pressure conditions of 40 torr and a temperature of about 80 ℃, followed by mixing and drying for about 12 hours.

[0247] From this, about 281 kg of graft polymer according to Comparative Example 1 (graft polymer corresponding to the second graft polymer) was obtained with a yield of about 94%.

[0248]

[0249] Comparative Example 2

[0250] (2) A second graft polymer was prepared by the same method as in Example 1, except that the temperature holding period in the cooling process was completely excluded and the third solution was prepared by natural cooling from about 130 ℃ to about 23 ℃ over 15 hours. From this, about 287 kg of the second graft polymer (hereinafter referred to as the graft polymer prepared according to Comparative Example 2) was obtained with a yield of about 96%. The cooling rate was about -7 ℃ / hr.

[0251]

[0252] Comparative Example 3

[0253] (2) A second graft polymer was prepared by the same method as Comparative Example 2, except that a third solution was prepared by cooling from about 130 ℃ to about 30 ℃ at a cooling rate of -10 ℃ / hr during the cooling process. From this, about 185 kg of the second graft polymer (hereinafter referred to as the graft polymer prepared according to Comparative Example 3) was obtained in a yield of about 62%.

[0254]

[0255] Comparative Example 4

[0256] (2) A second graft polymer was prepared by the same method as Comparative Example 2, except that a third solution was prepared by cooling from about 130 ℃ to about 30 ℃ at a cooling rate of -30 ℃ / hr during the cooling process. From this, about 161 kg of the second graft polymer (hereinafter referred to as the graft polymer prepared according to Comparative Example 4) was obtained in a yield of about 54%.

[0257]

[0258] Comparative Example 5

[0259] (2) A second graft polymer was prepared by the same method as Comparative Example 2, except that a third solution was prepared by cooling from about 130 ℃ to about 30 ℃ at a cooling rate of -50 ℃ / hr during the cooling process. From this, about 147 kg of the second graft polymer (hereinafter referred to as the graft polymer prepared according to Comparative Example 5) was obtained in a yield of about 49%.

[0260]

[0261] Comparative Example 6

[0262] (4) A second graft polymer was prepared by the same method as in Example 1, except that the immersion, washing, and filtration processes were performed only once in the washing and drying process. From this, about 276 kg of the second graft polymer (hereinafter referred to as the graft polymer prepared according to Comparative Example 6) was obtained with a yield of about 92%.

[0263]

[0264] Experimental Example

[0265] The physical properties of each graft polymer prepared according to the above-described examples and comparative examples were evaluated as follows.

[0266]

[0267] Experimental Example 1: Particle Size Analysis

[0268] The particle size analysis of the manufactured graft polymer was performed according to the ISO 13320 test method. The graft polymer was fed into a laser diffraction particle size analyzer (Malvern, Mastersizer 3000) and particle size analysis was performed.

[0269] The analysis conditions were as follows.

[0270] - Measurement mode: Dry dispersion method

[0271] - Particle size: Non-spherical

[0272] - Temperature: Room temperature

[0273] - Refractive index: n = approx. 1.49

[0274] - Density (g / cm³) 3 ): Approx. 0.95

[0275]

[0276] Calculation of span value

[0277] D obtained 10 , D 50 and D 90 The span value was calculated by substituting it into Equation 1 below.

[0278] [Equation 1]

[0279] Span value = (D 90 -D 10 ) / D 50

[0280]

[0281] The cumulative volume particle size distribution graph obtained from the particle size analysis of the graft polymer powder prepared in the examples is shown in Figure 4.

[0282] The cumulative volume particle size distribution graph obtained from the particle size analysis of the graft polymer powders prepared in the comparative examples is shown in Figure 5.

[0283]

[0284] Experimental Example 2: Content of impurities

[0285] The respective contents of unreacted maleic anhydride, maleic acid, and fumaric acid included as impurities in the manufactured graft polymer were evaluated as follows.

[0286]

[0287] (1) Preparation of samples for HPLC analysis and HPLC content analysis

[0288] 1.00 g of the prepared graft polymer powder was placed in a 20 mL vial, and 10 mL of acetonitrile was added as a solvent. Subsequently, the vial was placed in an ultrasonic bath, and ultrasonic treatment was performed for about 10 minutes to extract maleic anhydride, maleic acid, and fumaric acid into the solvent. The output of the ultrasonic bath was about 300 W, and the frequency was about 40 kHz.

[0289] The extracted solution was filtered through a 0.45 µm PTFE syringe filter and used as a sample for HPLC analysis.

[0290] HPLC analysis was performed using high-performance liquid chromatography (HPLC, Agilent 1100), and the analysis conditions were as follows.

[0291] - Detector: UV detector (wavelength 210 nm)

[0292] - Column: C18 reversed-phase column (e.g., 4.6 mm × 250 mm, 5 µm)

[0293] - Mobile phase: Water (A) / Acetonitrile (B), isocratic conditions

[0294] - Flow rate: 1.0 mL / min

[0295] - Injection volume: 10 µl

[0296] - Column temperature: 40 ℃

[0297]

[0298] (2) 1 Sample preparation for H NMR analysis and 1 H NMR content analysis

[0299] Take approximately 100 mg of the prepared graft polymer powder into a 20 mL clear vial. 1 10 mL of CDCl3(Sigma) was added as an H NMR solvent. Subsequently, the solution in the vial was thoroughly stirred using a magnetic stirrer.

[0300] Subsequently, about 10 mg to 20 mg of toluene was added to the above vial as an internal standard substance to prepare a sample for NMR analysis.

[0301] After transferring the above sample to an NMR tube, it was measured using a Bruker 500 MHz NMR analyzer, and through this, the content of unreacted maleic anhydride, maleic acid, and fumaric acid included as impurities in the second graft polymer was quantitatively evaluated.

[0302]

[0303] (3) TD-GC sample preparation for VOC analysis and VOC content analysis

[0304] Approximately 150 mg of the prepared graft polymer was placed in a 2 mL vial for GC analysis, and the volatile organic compound (VOC) content was evaluated using thermal desorption-gas chromatography (TD-GC) analysis.

[0305] The analysis conditions were as follows.

[0306] - TD conditions: 130 ℃, 20 min

[0307] - TD-GC Column: DB-5ms (60 m × 0.25 mm × 0.25 µm)

[0308] - GC Oven Conditions: Maintain at 40 ℃ for 5 minutes, then heat to 300 ℃ at a heating rate of 10 ℃ / min, and maintain at 300 ℃ for 20 minutes, i.e., 40 ℃(5 min) → 10 ℃ / min → 300 ℃(20 min)

[0309] - GC flow rate: 0.8 mL / min

[0310] - Split ratio: 50:1

[0311] - MSD Transfer Line Temperature: 250 ℃

[0312]

[0313] Experimental Example 3: Yield of obtained graft polymer and graft efficiency

[0314] After sufficiently mixing and homogenizing the graft polymer obtained according to the example or comparative example, i.e., the prepared graft polymer, a representative sample was taken.

[0315] To minimize the influence of residual solvent, the sample was further dried under reduced pressure conditions of about 35 torr and a temperature of 80 ℃ before being used for analysis.

[0316]

[0317] (1) Yield of graft polymer

[0318] The yield of the graft polymer was calculated based on the amount of polyolefin input provided to the graft reaction according to the following Equation 2.

[0319] [Equation 2]

[0320] Yield (%) of graft polymer = (Wp / Wr) × 100

[0321] In Equation 2, Wr represents the mass (kg) of the polyolefin, i.e., polypropylene, provided for the graft reaction, and Wp represents the mass (kg) of the graft polymer produced.

[0322] Each of the above masses was measured using a precision balance. The above-mentioned prepared graft polymer refers to the obtained second graft polymer or a corresponding polymer.

[0323] The yield of the above-mentioned graft polymer may refer to the mass-based yield of the polymer solid recovered after the graft reaction.

[0324]

[0325] (2) Graft efficiency

[0326] The graft efficiency was calculated based on the content of maleic anhydride grafted onto the manufactured graft polymer. The content of the maleic anhydride was calculated using the acid number.

[0327] About 1.0 g of the prepared graft polymer was taken and placed into a 500 mL flask, and then 200 mL of xylene was added. Subsequently, the internal temperature of the reaction mixture was heated to about 140 °C to completely dissolve the graft polymer and prepare a graft polymer solution. After cooling the solution, about 0.5 g of bromothymol blue indicator was added and dissolved while maintaining the temperature at about 90 °C. Subsequently, titration was performed using a standard solution of potassium hydroxide (KOH) (0.05 N) dissolved in ethanol.

[0328] The acid number was calculated according to Equation 3 below using the volume of KOH solution consumed in the titration.

[0329] [Equation 3]

[0330] Acid value (mg KOH / g) = (V Х N Х 56.1) / W

[0331] In Equation 3, V represents the volume (mL) of the KOH standard solution consumed in the titration, N represents the normal concentration (N) of the KOH standard solution, and W represents the mass (g) of the graft polymer sample.

[0332] The above acid value may refer to a value reflecting the acidity of the maleic acid group formed by the hydrolysis of the maleic anhydride introduced into the graft polymer.

[0333] The content (A) of maleic anhydride actually introduced into the graft polymer from the calculated acid value was calculated according to the following Equation 4.

[0334] [Equation 4]

[0335] Actual introduced content of maleic anhydride (A, wt%) = (Acid value × 98) / (2 × 561)

[0336] In Equation 4, 98 represents the molecular weight (g / mol) of maleic anhydride, 2 represents the number of acid groups per molecule of maleic groups derived from maleic anhydride, and 561 represents the unit conversion factor for converting the acid value (mg KOH / g) into a weight percentage.

[0337] Meanwhile, the theoretical maximum introduction content (wt%) of the maleic anhydride when assuming that the entire amount of maleic anhydride introduced into the above graft reaction is grafted was calculated according to Equation 5 below.

[0338] [Equation 5]

[0339] A0={Wm / (Wr+Wm)}×100

[0340] In Equation 5, Wr is the mass (kg) of the polyolefin, i.e., polypropylene, provided for the graft reaction, and Wm is the mass (kg) of the maleic anhydride provided for the graft reaction.

[0341] The graft efficiency was calculated according to the following Equation 6 using the actual introduction content (A) of the maleic anhydride and the theoretical maximum introduction content (A0) of the maleic anhydride.

[0342] [Equation 6]

[0343] Graft Efficiency (%) = (A / A0) × 100

[0344] In Equation 6, A represents the actual introduction content (wt%) of maleic anhydride actually introduced into the graft polymer, and A0 represents the theoretical maximum introduction content (wt%) calculated from the maleic anhydride introduced into the graft reaction.

[0345]

[0346] (3) Quantitative analysis of residual impurities

[0347] The content of unreacted maleic anhydride and / or its modified products (maleic acid, fumaric acid, etc.) remaining in the graft polymer without being grafted was quantified and evaluated.

[0348] About 1.0 g of the above graft polymer sample was taken and placed in a 50 mL vial, and 20 mL of acetonitrile (ACN) was added. Then, the residual low molecular weight components were extracted by stirring at about 25 ℃ for about 1 hour.

[0349] The extract obtained therefrom was centrifuged (3000 rpm, 10 min), and the supernatant was filtered through a 0.45 μm PTFE (polytetrafluoroethylene) filter and used as a sample for HPLC analysis.

[0350] The HPLC conditions were as follows.

[0351] - Column: C18 reverse-phase column (e.g., 4.6 mm x 150 mm, 5 µm)

[0352] - Mobile phase: Water / acetonitrile mixed solvent

[0353] - Flow rate: Approx. 1.0 mL / min

[0354] - Injection volume: Approx. 15 µl

[0355] - Detection: UV range of approximately 210 nm

[0356] Standard solutions were prepared for maleic anhydride (MA), maleic acid, and fumaric acid, respectively, and calibration curves were constructed using the concentration-peak area relationship.

[0357] After quantifying the concentration of each component in the extract of the graft polymer sample, the content (ppm) of each component was calculated by converting it to the sample mass.

[0358]

[0359] Cooling Process Cleaning Process Nucleating Agent Input Section 1 Cooling to approximately 90°C Section 2 Cooling to approximately 60°C Section 3 Cooling to approximately 30°C Cleaning Acetone Content (parts by weight) Example 1 - 20°C / hr - 15°C / hr - 15°C / hr 5 times 100X Example 2 - 20°C / hr - 15°C / hr - 15°C / hr 4 times 100X Example 3 - 20°C / hr - 15°C / hr - 15°C / hr 3 times 100X Example 4 - 20°C / hr - 15°C / hr - 15°C / hr 4 times 300X Example 5 - 20°C / hr - 15°C / hr - 15°C / hr 3 times 300X Example 6 - 20°C / hr - 15°C / hr - 15 ℃ / hr 5 times 100 ○ Example 7 - 20 ℃ / hr - 15 ℃ / hr - 15 ℃ / hr 5 times 100 ○ Example 8 - 20 ℃ / hr - 15 ℃ / hr - 15 ℃ / hr 5 times 100 ○ Example 9 - 20 ℃ / hr - 15 ℃ / hr - 15 ℃ / hr 1 time 100 ○ Example 10 - 80 ℃ / hr - 15 ℃ / hr - 15 ℃ / hr 5 times 100 ○ Example 11 - 20 ℃ / hr - 120 ℃ / hr - 15 ℃ / hr 5 times 100 ○ Example 12 - 20 ℃ / hr - 15 ℃ / hr - 5 times 100 - Comparative Example 1: Using precipitation by solvent exchange instead of cooling Comparative Example 2: Continuous cooling without a temperature maintenance section, - 7 ℃ / hr 5 times 100°C - Comparative Example 3: Continuous cooling without temperature holding interval, -10 ℃ / hr 5 times 100°C - Comparative Example 4: Continuous cooling without temperature holding interval, -30 ℃ / hr 5 times 100°C - Comparative Example 5: Continuous cooling without temperature holding interval, -50 ℃ / hr 5 times 100°C - Comparative Example 6: 20 ℃ / hr -15 ℃ / hr -15 ℃ / hr 1 time 100°C

[0360]

[0361] D 10 (㎛)D 50 (㎛)D 90(㎛) Span Value Example 1 15.06 7.026 5.3 3.74 Example 2 14.129 0.36 40.5 1.60 Example 3 12.835 1.79 36.5 2.04 Example 4 20.026 1.08 42.03.15 Example 5 26.029 6.09 51.03.13 Example 6 28.515 5.56 90.5 4.26 Example 7 32.618 9.35 73.02.86 Example 8 15.53 7.47 24.818.99 Example 9 28.56 20.512 12.8 1.91 Example 10 12.65 2.125 4.64.64 Example 11 13.54 1.72 01.94.52 Example 12 17.56 5.32 81.74.05 Comparative Example 1 12.01 51.05 95.03.86 Comparative Example 2 11.52 2.072 8.032.52 Comparative Example 3 18.22 5.68 00.03 0.54 Comparative Example 4 15.62 8.89 50.03 2.44 Comparative Example 5 19.32 6.28 30.03 0.94 Comparative Example 6 23.45 17.01 425.02.71

[0362]

[0363] Obtained Graft Polymer Residual Impurity Content (ppm) VOC (ppm) Yield (%) Graft Efficiency (%) Maleic Anhydride Maleic Acid Fumaric Acid Example 1 973.201082784-770 Example 2 943.15156454073-3096 Example 3 983.23307198656-5243 Example 4 963.28433392-929 Example 5 943.19271235-1049 Example 6 973.22271235-231 Example 7 953.10413235-283 Example 8 983.26357273-368 Example 9 973.139863412510-1 66000 Example 10863.101203962-953 Example 11763.101025820-863 Example 12963.17985821832 Comparative Example 1943.2439973699413380 Comparative Example 2963.11856235-480 Comparative Example 3623.23916362-500 Comparative Example 4543.21513491-780 Comparative Example 5493.111063298-1020 Comparative Example 6543.4810120015600-183000

[0364]

[0365] According to the method for manufacturing graft polymers according to the examples, the span values ​​of the manufactured graft polymers were all formed within the range of 1 to 20. In addition, in Examples 1 to 8, 9 and 10, the content of impurities remaining in the graft polymers was maintained at a relatively low level.

[0366] Meanwhile, in the case of Example 8, it was confirmed that the span value tended to increase relatively as the amount of nucleating agent added increased. In addition, in Examples 10 and 11, the cooling rate increased, and solid graft polymers were formed in the upper layer, such as on the surface of the graft polymer solution inside the impeller and the reactor. As a result, the graft polymer slurry solution could not be formed smoothly, and the process stability and yield were relatively lower compared to other examples.

[0367] However, according to the manufacturing methods of Comparative Examples 2 to 5, the span values ​​of the obtained graft polymers all significantly exceeded 20. In this case, there is a high possibility that separation by particle size will occur during storage or transport, and non-uniform filling may be induced in subsequent processes such as mixing and extrusion, which may lead to non-uniform quality of the final product.

[0368]

[0369] In addition, according to the method for manufacturing graft polymers according to the examples, the yield of the obtained graft polymer was improved to 94% or higher, and the graft efficiency was also maintained at a high level. Furthermore, in the method according to the examples, the content of residual impurities in the graft polymer was kept low.

[0370] However, in the manufacturing methods according to Comparative Examples 1 and 6, the content of impurities remaining in the obtained graft polymer was relatively high, and in particular, in the manufacturing methods according to Comparative Examples 3 to 5, the yield of the obtained graft polymer was significantly reduced to 62% or less.

Claims

1. A step of grafting a polyolefin and an acid anhydride in a solvent to form a first solution comprising a graft polymer of the polyolefin and the acid anhydride; A step of cooling a first solution to a first temperature of 70°C to 90°C and then maintaining it at the first temperature to form a second solution; A step of forming a third solution by cooling the second solution to a second temperature of 35°C to 60°C, or maintaining it at the second temperature after cooling; A step of obtaining a first graft polymer by separating the solid and liquid of the third solution; and The method includes the step of washing and drying the first graft polymer to obtain a second graft polymer, Wash the first graft polymer two or more times; or A nucleating agent is added to at least one of the first to third solutions and homogenized, and A method for manufacturing a graft polymer, wherein the span value of the second graft polymer obtained is 1 to 20.

2. A method for manufacturing a graft polymer according to claim 1, wherein the span value is calculated by the following formula 1: [Equation 1] Span value = (D 90 -D 10 ) / D 50 D in Equation 1 above 10 , D 50 and D 90 represents the particle size at the 10%, 50%, and 90% points, respectively, based on the cumulative volume distribution measured by laser diffraction particle size analysis for the second graft polymer.

3. In paragraph 2, the median particle size (D) of the obtained second graft polymer 50 A method for manufacturing a graft polymer, wherein ) is 10 μm to 625 μm.

4. In paragraph 2, D of the obtained second graft polymer 10 A method for manufacturing a graft polymer having a thickness of 0.01 μm to 50 μm.

5. In claim 1, D of the obtained second graft polymer 90 A method for manufacturing a graft polymer having a thickness of 100 μm to 2000 μm.

6. A method for manufacturing a graft polymer according to claim 1, wherein the first graft polymer is washed 2 to 5 times.

7. A method for manufacturing a graft polymer according to claim 1, wherein the first graft polymer is washed using acetone.

8. A method for manufacturing a graft polymer according to claim 7, wherein each washing is performed by immersing in 100 to 1,000 parts by weight of acetone based on 100 parts by weight of the first graft polymer.

9. In claim 1, the nucleating agent is a polymer of the same type as the graft polymer of the polyolefin and the acid anhydride, and has an intermediate particle size (D) of 10 μm to 300 μm. 50 A method for manufacturing a graft polymer having ).

10. A method for manufacturing a graft polymer according to claim 1, wherein the total amount of the nucleating agent added is 0.01 to 10 parts by weight per 100 parts by weight of the polyolefin provided to the graft reaction.

11. A method for manufacturing a graft polymer according to claim 1, wherein the first solution is cooled to a first temperature at a cooling rate of -6 ℃ / hr to -60 ℃ / hr and then maintained at the first temperature to form a second solution.

12. A method for manufacturing a graft polymer according to claim 11, wherein the first solution is cooled to a first temperature and then maintained at the first temperature for at least one minute to form a second solution.

13. A method for manufacturing a graft polymer according to claim 1, wherein the second solution is cooled to a second temperature at a cooling rate of -6 ℃ / hr to -100 ℃ / hr, or maintained at the second temperature after cooling to form a third solution.

14. A method for manufacturing a graft polymer according to claim 13, wherein the second solution is cooled to a second temperature and then maintained at the second temperature for 1 minute to 5 hours to form a third solution.

15. A method for manufacturing a graft polymer according to claim 1, wherein the acid anhydride comprises maleic anhydride (MA).

16. A method for manufacturing a graft polymer according to claim 1, further comprising the step of cooling to a third temperature of 10°C to 30°C after the formation of the third solution and before solid-liquid separation, or maintaining at the third temperature after cooling.

17. A method for manufacturing a graft polymer according to claim 16, wherein the second temperature is 50°C to 60°C.

18. A polymer powder in which an acid anhydride is grafted onto a polyolefin, and the grafted polymer powder has a span value of 1 to 20.

19. In paragraph 18, the median particle size (D) of the graft polymer powder 50 ) is a graft polymer powder with a particle size of 10 μm to 625 μm.

Images