KR101554825B1 - Apparatus for preparing of polymer latex resin powder and method for preparing of polymer latex resin powder using thereof - Google Patents

Abstract

The present invention relates to an apparatus for producing a polymer latex resin powder comprising a single reactor in which a stirrer having hexagonal paddles fixed on three sides is arranged in a screw shape and simultaneously performs agglomeration and aging, and a method for producing polymer latex resin powder using the same The present invention relates to a polymer latex resin powder produced by a production method. As a result, the production apparatus can increase the shearing force applied to the polymer latex slurry by the paddles fixed to the respective agitators to the maximum, and thus the polymer latex slurry having a high viscosity can be effectively transported, It is possible to produce a powder having a uniform particle size distribution while lowering the inclusion water content.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymer latex resin powder and a method for preparing the polymer latex resin powder using the polymer latex resin powder,

The present invention relates to an apparatus for producing a polymer latex resin powder, which comprises an integrated reactor in which a stirrer having hexagonal paddles fixed on three sides is arranged in a screw shape and simultaneously performs agglomeration and aging, a method for producing polymer latex resin powder using the same, The present invention relates to a polymer latex resin powder produced by a production method.

Polymeric materials formed by emulsion polymerization are processed and processed into powder in order to reduce the volume, various usability, and ease of handling. In order to obtain a polymer substance as a powder, it is required to coagulate, dehydrate and dry a polymer substance (latex) formed by emulsion polymerization.

Emulsion Polymerization Polymer latex agglomerates are stabilized by emulsifying agents. Each latex particle is chemically attacked by using various flocculants or by strong mechanical shear force to break its stability by mechanical force. Chemical method using coagulant breaks stability by using different coagulant depending on kinds of emulsifier used to ensure stability of latex. When breaking stability by using mechanical force, repulsive force between emulsifier by strong shear force So that latex particles and particles are aggregated.

Rapid coagulation has been proposed as a method for preparing the polymer latex as a powder. The rapid aggregation rapidly injects an aqueous solution of flocculant such as inorganic salt and acid to break the stability of the emulsifier, thereby rapidly aggregating the polymer in the latex. The aggregation of latex polymer particles is referred to as agglomeration, and the aggregation of polymer particles is referred to as slurry. Since they are physically weakly bonded, they are easily broken off by external shear by a stirrer or the like. ). Thus, the agglomerated slurry is subjected to an aging process, which is a process of heating the slurry to strengthen the binding force by interpenetrating the chains. The aged slurry is subjected to dehydration and drying to finally obtain a powdery phase.

In the case of rapeseed coagulation using an excessive amount of the flocculant as described above, the stability of the latex breaks down very quickly, so that the process of entangling the polymer latex particles occurs very quickly and disorderly. This disordered aggregation causes a problem that the apparent specific gravity is lowered and the particle size distribution of the final particles becomes very wide.

The apparatus for manufacturing a polymer latex resin powder according to the related art generally comprises a latex storage tank, an agglomeration tank, a first aging tank, a second aging tank, a polymer slurry tank, a dehydrator and a dryer.

In order to increase the dewatering and drying efficiency, the conventional powder manufacturing apparatus has a problem that it is difficult to agitate the slurry having a high viscosity, And therefore it is possible to apply the slurry to a slurry having a low solids content.

In order to solve the above problems, there has been proposed a multi-stage continuous agglomeration and aging process. However, the process has the advantage of effectively aging the polymer latex slurry having a low solid content, but is applicable to a slurry having a high solid content And the efficiency of the process is somewhat deteriorated because it has to go through several steps.

Also, a slow coagulation process has been proposed which improves the powder properties of the resulting final particles by controlling the coagulation rate through the partial introduction of the coagulant. This is because the coagulation occurs in the second well region where the energy barrier exists, so that the coagulation speed is slow and the particles can be rearranged, so that spherical particles can be produced by regular filling. However, the total amount of flocculant used is similar to that of rapid flocculation. Therefore, it is impossible to prevent the generation of waste water due to excessive flocculant. In the case of the first flocculating tank, a small amount of coagulant is added to the flocculant, There is a disadvantage that it has a high water content as a result.

Another method is shear coagulation in which slurry is produced by applying shear force with strong mechanical force to aggregate particles of latex and latex. The polymer latex slurry is prepared by applying a shear stress by high-speed rotation of 4,000 rpm or more without using a flocculant. However, in the case of the emulsion polymer latex which is stabilized by the use of emulsifier, residual emulsifier remains in the recovered powder, which adversely affects thermal stability and color during processing.

Therefore, it is possible to manufacture a polymer latex resin powder which can improve the drying efficiency by lowering the water content of the polymer latex slurry and reduce the amount of the coagulant to be used, and thereby to provide a polymer latex resin powder excellent in color and powder properties, and a method for producing polymer latex resin powder using the same Is still required.

Accordingly, the present inventors have found that a polymer latex slurry can be obtained from an emulsion polymerization latex which can lower the water content of a polymer latex slurry and produce a powder having a uniform particle size distribution and improve the color and thermal stability of the polymer resin obtained by extruding and extruding the powder. In studying a manufacturing apparatus capable of efficiently producing powders, there has been proposed a manufacturing method in which an agitator in which at least one hexagonal paddle having three sides is fixed is arranged in the form of a screw, and an integral reactor capable of coagulation and aging together The polymer latex resin powder was found to have a uniform particle size distribution, a low moisture content and excellent thermal stability, thereby completing the present invention.

An object of the present invention is to provide a polymer latex resin powder having uniform particle size distribution, low water content, and excellent powder properties with respect to thermal stability and color after processing, in which an agitator having at least one hexagonal paddle And the stirrer is arranged on the rotating shaft in a screw shape so that the paddles fixed to the stirrer are at an angle with the adjacent paddles. The present invention also provides an apparatus for manufacturing the polymer latex resin powder.

Another object of the present invention is to provide a method for producing a polymer latex resin powder using the above production apparatus.

Another object of the present invention is to provide a polymer latex resin powder produced by the above-mentioned production method.

In order to solve the above problems, the present invention includes an integrated reactor including an agglomeration tank and an aging tank; The reactor comprises: a rotating shaft extending along a central axis in the longitudinal direction of the reactor; And at least one stirrer mounted on an outer surface of the rotating shaft, to which at least one paddle is fixed; The paddles are hexagonal paddles consisting of three surfaces: a conveying surface a, a conveying opposite surface b and a front surface c; Wherein the agitator is arranged in a screw shape on the rotating shaft so as to form a constant angle between adjacent left paddles and right paddles based on a longitudinal axis of the rotating shaft.

The present invention also provides a process for producing a polymer latex resin powder using the above production apparatus, wherein the polymer latex slurry containing the polymer latex and the coagulant is introduced into an integrated reactor to simultaneously carry out the agglomeration step and the aging step do.

In addition, the present invention provides a polymer latex resin powder produced by the above-mentioned production method.

The apparatus for producing a polymer latex resin powder according to the present invention, which comprises an integrated reactor in which stirrers on which three-plane paddles are fixed are arranged in the form of a screw, is characterized in that the shear force applied to the polymer latex slurry by the paddles fixed to the respective stirrers It is possible to increase the decomposition efficiency even in the polymer latex slurry having a high viscosity and to minimize the impurity content in the polymer latex slurry by allowing the residues trapped in the inside to escape through the water phase as much as possible have.

Further, when the polymer latex slurry passes between the barrel pin and the paddles fixed to the agitator, a strong shearing force can be applied to the polymer latex slurry so that the polymer latex and the flocculant can be more uniformly mixed, and the agitator The polymer latex slurry can be strongly agitated while effectively transferring the polymer latex slurry having a high viscosity without further water supply by arranging the slurry in a screw shape so as to form a constant angle between adjacent paddles fixed to each of the agitators, thereby lowering the inclusion water content of the polymer latex slurry It is effective.

Accordingly, the drying process can be shortened, operation cost can be reduced, and the polymer latex powder having a uniform particle size distribution can be produced. Thus, the color and thermal stability of the polymer resin obtained by extruding and injecting the powder can be improved have.

1 schematically shows a conventional apparatus for producing a polymer latex resin powder.
FIG. 2 is a cross-sectional view of an integral reactor including a rotary shaft equipped with a stirrer to which hexagonal paddles constituted by three surfaces according to an embodiment of the present invention are fixed.
Figure 3 shows a schematic view of a hexagonal paddle according to an embodiment of the invention.
FIG. 4 is a schematic view showing that a stirrer in which a hexagonal paddle according to an embodiment of the present invention is fixed is mounted on a rotary shaft in the form of a screw.

Hereinafter, the present invention will be described in detail in order to facilitate understanding of the present invention.

The terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms and the inventor may appropriately define the concept of the term in order to best describe its invention It should be construed as meaning and concept consistent with the technical idea of the present invention.

The present invention provides an apparatus for producing a polymer latex resin powder comprising a stirrer having at least one hexagonal paddle having three or more surfaces fixed.

The apparatus for producing a polymer latex resin powder according to the present invention comprises an integrated reactor including an aggregation tank and an aging tank; The reactor comprises: a rotating shaft extending along a central axis in the longitudinal direction of the reactor; And at least one stirrer mounted on an outer surface of the rotating shaft, to which at least one paddle is fixed; The paddles are hexagonal paddles consisting of three surfaces: a conveying surface a, a conveying opposite surface b and a front surface c; And the agitator is arranged in a screw shape on the rotary shaft so as to form a constant angle between the adjacent left paddle and the right paddle based on the vertical axis of the rotary shaft.

Hereinafter, an apparatus for producing a conventional polymer latex powder will be described with reference to FIG.

1, the apparatus includes a latex storage tank 1, an aggregation tank 2, a first aging tank 3, a second aging tank 4, a polymer slurry tank 5, a dehydrator 6, And a dryer (7). The polymer powder can be produced by the following procedure.

First, the polymer latex stored in the latex storage tank 1 is added to the flocculation tank 2 through the polymer latex injection line 11, and an aqueous solution of flocculant such as an inorganic salt or acid is introduced into the polymer latex And adding additional water to the water supply line 14 while adding steam to the flocculation tank 2 through the steam supply line 12. [ The added aqueous flocculant solution breaks the electrostatic stabilization by the emulsifier to aggregate the polymer particles in the latex, and through this aggregation process, the polymer latex slurry is obtained. The agglomerated polymer latex slurry is transferred to the first aging tank 3 and supplied with steam through the steam supply line 12 to moor for 30 to 60 minutes at a high temperature. After completion of the first aging process, it is transferred to the second aging tank (4), and water and residues are removed through press aging and transferred to the polymer slurry tank (5). The finally obtained slurry is dehydrated in a dehydrator 6, dried in a dryer 7, and finally a final polymer powder 15 can be obtained.

The above production apparatus has a problem that it is difficult to agitate the slurry having a high viscosity and the slurry is not smoothly conveyed and the efficiency of processing into powder is low. Therefore, a slurry having a high solid content is used in order to increase the dewatering and drying efficiency It is difficult to apply the slurry to a slurry having a low solid content.

Accordingly, the apparatus for producing a polymer latex resin powder of the present invention includes an integrated reactor including a latex tank, an agglomeration tank and an aging tank, a reaction tube arranged outside the reactor, a dehydrator and a dryer to improve the above problems , And the integrated reactor includes at least one stirrer in which at least one hexagonal paddle composed of three surfaces arranged in a screw shape on a rotary shaft is fixed.

Hereinafter, an apparatus for producing a polymer latex resin powder according to the present invention will be described in detail with reference to FIG.

FIG. 2 is a cross-sectional view of an integrated reactor constituting an apparatus for producing a polymer latex resin powder according to a preferred embodiment of the present invention.

As shown in FIG. 2, the integrated reactor 200 includes a rotation axis 220 extending along a central axis in the reactor longitudinal direction; And at least one stirrer (230) mounted on an outer surface of the rotating shaft, to which at least one paddle (231a, 231b) is fixed; The paddles 231a and 231b are hexagonal paddles consisting of three surfaces: a conveying surface a, a conveying opposite surface b and a front surface c; The stirrer 230 may be arranged in a screw shape on the rotary shaft so as to form a predetermined angle between the adjacent left paddle and the right paddle with respect to the longitudinal axis of the rotary shaft 220.

The integrated reactor 200 may include a polymer latex injection line 214, a flocculant injection line 212, and a steam injection line 213.

The manufacturing apparatus according to an embodiment of the present invention may include at least one barrel pin 211a and 211b protruding upward or downward in the reactor 200 from the inner wall of the reaction tube 210 outside the reactor 200 ).

In the present invention, the barrel fins 211a and 211b are not particularly limited, and any shape such as circular, triangular, oblique, elliptical, rhombic, and square shapes may be used.

The hexagonal paddles 231a and 231b of the present invention constituted by the three surfaces of the conveying surface a, the conveying opposite surface b and the front surface c fixed to the stirrer 230 are arranged in the order of the conveying surface a, the conveying opposite surface b and the front surface c May range from 1: 4 to 1: 1 to 8, but may be from 1: 3: 1: 1 to 5. And most preferably 1: 2: 1: 3. If the ratio is within the above range, the shear force applied to the polymer latex slurry can be maximized without interrupting the flow of the polymer latex slurry There is an advantage of improving the engaging force. The paddles 231a and 231b are specifically shown in FIG.

The number of stirrers 230 mounted on the outer surface of the rotary shaft 220 may be 1 to 200, but it may be adjusted within the range. For example, the number of the stirrers 230 may be 1 to 100, and may be adjusted to 1 to 20 as necessary. When the number of agitators in the above range is installed, the shear force applied to the polymer latex slurry can be maximized, so that the decomposition efficiency can be increased even in the polymer latex slurry having a high viscosity. In addition, There is an effect that can let go out.

The number of paddles 231a and 231b fixed to each of the agitators 230 may be 1 to 6, but 1 to 4 may be preferable. Most preferably 2 to 4, but is not limited thereto.

The stirrer in which the paddles of the present invention are fixed may be mounted on the rotary shaft in the number of the ranges described above, but the present invention is not limited thereto and the number of the stirrers may be suitably set according to the length L of the reactor of the present invention.

Further, the stirrer to which the paddle according to the present invention is fixed is preferably mounted on the outer surface of the rotating shaft 220 in a screw shape.

Specifically, the stirrer mounted on the outer surface of the rotary shaft of the present invention is configured such that the paddles fixed to each of the stirrers have a predetermined angle between the left paddle and the right paddle, It is preferable to mount it on the rotating shaft. At this time, it is preferable to arrange the agitator sequentially in the direction opposite to the rotating direction of the rotating shaft during the reaction process.

The angle between the left paddle and the right paddle adjacent to each other may be between 2.5 and 45, and preferably between 2.5 and 30. Most preferably from 2.5 to 15 and when the paddles are arranged at an angle within the range, a high shear force can be applied when the polymer latex slurry passes between the barrel pin and the paddle, thereby making the polymer latex and flocculant more uniform The polymer latex slurry can be effectively stirred while strongly dispersing the polymer latex slurry having a high viscosity by arranging the pellets in the shape of a screw so that the inclusion water content of the polymer latex slurry can be lowered.

Hereinafter, a method of mounting the stirrer on which the paddle according to the present invention is fixed to the rotating shaft will be described in detail with reference to FIG.

FIG. 4 is a schematic view of a rotating shaft equipped with a stirrer to which paddles are fixed according to a preferred embodiment of the present invention.

As shown in FIG. 4, each of the stirrers 310, 320, 330, 340 and 350 to which the paddles 311, 321, 331, 341 and 351 are fixed is connected to one end And the other end (for example, the right side). At this time, the mounting of each of the stirrers 310, 320, 330, 340 and 350 is performed in the opposite direction 302 of the rotating direction 301 of the rotating shaft 300 during the reaction process, The paddles 311, 321, 331, 341, and 351 fixed to the paddles 340 and 350 are arranged and mounted so as to have a predetermined angle between adjacent paddles. The angle may be between 2.5 and 45 as mentioned above, preferably between 2.5 and 30 degrees. Most preferably from 2.5 [deg.] To 15 [deg.].

In the integrated reactor of the present invention having the above structure, a stirrer having at least one hexagonal paddle composed of three sides fixed is mounted on a rotating shaft, and when the stirrer is mounted, each paddle fixed to each stirrer is adjacent The stirrer is arranged on the rotary shaft in the longitudinal direction of the rotary shaft (for example, from the left end to the right end) while rotating in the opposite direction of rotation in the reaction process so as to form a constant angle between the paddles. In the integrated reactor of the present invention, the polymer latex slurry is easily transported by the rotation of the stirrer in which the paddles are fixed in the screw shape on the outer surface of the rotating shaft and the paddles are fixed during the reaction, It is possible to maximize the grinding efficiency during the agglomeration by applying a strong shearing force to the polymer latex slurry. In addition, by decomposing the polymer latex slurry that has gathered with a strong shearing force, the residues can be efficiently discharged into the polymer latex slurry by water phase.

Accordingly, the apparatus for producing a polymer latex resin powder including the integrated reactor of the present invention can provide a strong agitating force so that the polymer latex and the coagulant can be more uniformly and rapidly mixed and agglomerated, and the polymer latex slurry having a high viscosity A strong shearing force can be provided while effectively transferring the powder, and powder having a more uniform particle size distribution while having a low water content can be effectively produced.

The method for producing a polymer latex resin powder using the apparatus for producing a polymer latex resin powder according to the present invention is characterized in that a polymer latex slurry containing a polymer latex and a flocculant is put into an integrated reactor to substantially simultaneously perform an agglomeration step and an aging step .

It is preferable that the production method further includes a dehydration and drying step after the agglomeration step and the aging step.

The polymer latex of the present invention preferably has a solid content of 10% by weight to 90% by weight. In the present invention, the polymer latex may be a graft copolymer of a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound.

The graft copolymer can be prepared by polymerizing a monomer mixture of an aromatic vinyl compound and a vinyl cyan compound with a conjugated diene compound.

The conjugated diene compound may be at least one selected from the group consisting of a butadiene rubber, an ethylene-propylene-diene monomer rubber (EPDM), an ethylene propylene rubber (EPR), a halobutyl rubber, a butyl rubber, a styrene-isoprene- ), And it may be at least one selected from the group consisting of butadiene rubber.

The aromatic vinyl compound may be styrene, alpha methyl styrene, alpha ethyl styrene, para methyl styrene, vinyl toluene or derivatives thereof, preferably styrene.

The vinyl cyan compound may be acrylonitrile, methacrylonitrile, ethacrylonitrile or a derivative thereof, preferably acrylonitrile.

The flocculant may be contained in an amount of 0.5 to 5 parts by weight, preferably 0.5 to 3 parts by weight, based on 100 parts by weight of the polymer latex. Most preferably 0.5 to 2 parts by weight. The flocculant of the present invention is not particularly limited, but a water-soluble inorganic acid such as sulfuric acid, phosphoric acid, hydrochloric acid, or an inorganic salt such as a sulfate can be used.

The retention time of the polymer latex slurry in the agglomeration step and the aging step may be 0.5 to 30 minutes, preferably 0.5 to 10 minutes. Most preferably 0.5 to 5 minutes. This is because, in contrast to the conventional agglomeration and aging processes, which require a long residence time of 30 minutes to 1 hour, in the present invention, a stirrer in which hexagonal paddles composed of three sides are fixed is placed between adjacent paddles The polymer latex, the coagulant and the steam can be efficiently mixed by arranging the polymer latexes at a certain angle and mounting them on the rotating shaft, so that polymer latex slurry having excellent powder characteristics can be produced with only a short residence time. During the residence time, the agglomeration period is completed within a few seconds to one minute, and aging proceeds as soon as the agglomeration is finished during the residence time, and the polymer latex slurry is continued until the polymer latex slurry is discharged to the outside.

The solid content of the polymer latex slurry of the present invention produced by the above process may vary depending on the solid content of the polymer latex, but may be preferably 25 wt% to 60 wt%. If the solid content is less than 25% by weight, the flowability of the polymer latex slurry may be too high to ensure the retention time of the polymer latex slurry. If the content of the latex slurry exceeds 60% by weight, The polymer latex slurry may clog the inside of the apparatus and the operation may become impossible.

The present invention also provides a polymer latex resin powder produced by the above-mentioned production method. The powder of the present invention comprises a polymer latex resin comprising an integral reactor capable of simultaneously performing agglomeration and aging, wherein the agglomerator comprises a rotating shaft on which a stirrer having hexagonal paddles composed of the three sides according to the present invention is mounted in a screw- By using the powder production apparatus, it is possible to have a more uniform particle size distribution and a low moisture content. The powder prepared according to the present invention preferably has a water content of 21.5% to 24.9%. In addition, the powder of the present invention may contain 2.9 wt% to 3.9 wt% fine particles in the polymer latex resin powder.

Hereinafter, the present invention will be described in more detail with reference to the following examples and experimental examples. However, the following examples and experimental examples are provided for illustrating the present invention, and the scope of the present invention is not limited thereto.

Manufacturing example : Polymer latex (vinyl cyanide compound - Conjugated diene series  Compound - aromatic vinyl compound Graft  Copolymer)

a) Preparation of polybutadiene rubber latex (core)

Nitrogen ion exchange water with respect to 100 parts by weight of 1,3-butadiene in the substituted polymerization reactor 110 parts by weight of rosin acid potassium salt 1.2 parts by weight of oleic acid potassium salt, 1.5 parts by weight, 0.1 part by weight of sodium carbonate (Na ₂ NO ₃₎ as the electrolyte , 0.5 part by weight of potassium hydrogencarbonate (KHCO ₃ ) and 0.3 part by weight of tertiary dodecyl mercaptan (TDDM) at a room temperature, and 0.3 part by weight of potassium persulfate as an initiator. The reaction temperature was continuously raised to 65 ° C for 17 hours, and the reaction was terminated to prepare a conjugated diene rubber latex. The obtained rubber latex had a gel content of 85% and a swelling index of 12, and had an average particle size of 950 Å and a refractive index of 1.518. Here, A is a unit of length mainly used to express the wavelength of electromagnetic radiation, and 1 A equals 0.1 nm.

b) Production of polymer latex (vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer)

The graft copolymer was prepared in a ratio of 50% by weight of the polybutadiene rubber latex prepared in a), 34% by weight of methyl methacrylate, 13% by weight of styrene and 3% by weight of acrylonitrile. First, 85 parts by weight of ion-exchanged water and 0.2 parts by weight of sodium oleate were added to a polymerization reactor purged with nitrogen at a total pressure of 50 parts by weight per 100 parts by weight of the polybutadiene rubber latex and the graft copolymer latex and monomers. Then, 80 parts by weight of ion-exchanged water, 0.4 part by weight of an alkylaryl sulfonate salt, and 3 parts by weight of an alkylaryl sulfonate salt were added to 100 parts by weight of the total of the methacrylate, styrene and acrylonitrile and the graft copolymer latex and the monomer, A mixed solution of 0.7 part by weight of dodecyl mercaptan, 0.048 part by weight of sodium pyrophosphate, 0.012 part by weight of dextrose, 0.001 part by weight of ferrous sulfate, and 0.1 part by weight of diisopropylbenzene hydroperoxide was continuously administered for 5 hours, The temperature was raised to 80 DEG C and the reaction was terminated by aging for 1 hour. After completion of the polymerization, the polymerization conversion was 99.5% and the solid solid content was 0.1%. An antioxidant and a stabilizer were administered thereto to obtain a polymer latex. The total solids content was 38%.

Example  One

The polymer latex (acrylonitrile-butadiene-styrene-methacrylate copolymer) prepared in the above Preparation Example was applied to three surfaces of the transfer surface (a), the transfer surface (b) and the transfer surface (c) (CaCl ₂ ) diluted as a coagulant was added in an amount of 1.0 part by weight based on 100 parts by weight of the total polymer latex content, and the mixture was stirred at a constant flow rate of 12 kg / hr in a reactor equipped with an agitator . The coagulation process was carried out without adding any additional liquid water while directly applying steam. At this time, the ratio of the conveying surface (a), the conveying surface (b), and the front surface (c) of the hexagonal paddles composed of three sides was 2: 1: 1, and the arrangement angle of each stirrer was 5 ° , And a total of 200 stirrers were mounted on the rotating shaft.

The residence time of the integral reactor was 1.5 minutes, and agglomeration and aging temperature were 90 ° C. At this time, the mechanical force was averaged 40 N · m inside, and aged by mechanical force. The aging period started as soon as the agglomeration was finished and continued until the polymer latex slurry was discharged to the outside. The agglomerated polymer latex slurry exits through the agitator and moves to the slurry storage tank. The agglomerated and aged polymer latex slurry was recovered as a polymer resin powder through dehydration and drying processes.

Example  2

The polymer resin powder was prepared in the same manner as in Example 1 except that the ratio of the transfer surface (a), the transfer surface (b) and the shear surface (c) of the hexagonal paddles was 2: 1: 2.

Example  3

The polymer resin powder was prepared in the same manner as in Example 1 except that the ratio of the transfer surface (a), the transfer surface (b) and the shear surface (c) of the hexagonal paddles was 2.3: 1: 3.

Example  4

The polymer resin powder was prepared in the same manner as in Example 1 except that the ratio of the transfer surface (a), the transfer surface (b) and the shear surface (c) of the hexagonal paddles was 1: 1: 1.

Example  5

The same as Example 1, except that the ratio of the conveying surface (a), the conveying opposite surface (b) and the shearing surface (c) of the hexagonal paddles was 2: 1: 2 and the angle of arrangement of each stirrer was 2.5 °. Polymer resin powders were prepared.

Example  6

The same as in Example 1, except that the ratio of the conveying surface (a), conveying opposite surface (b) and shearing surface (c) of the hexagonal paddles was 2: 1: 2 and the angle of arrangement of each stirrer was 7.5 °. Polymer resin powders were prepared.

Example  7

The same as in Example 1, except that the ratio of the conveying surface (a), the conveying opposite surface (b) and the shearing surface (c) of the hexagonal paddles was 2: 1: 2 and the angle of arrangement of each stirrer was 10 °. Polymer resin powders were prepared.

Example  8

The same as in Example 1, except that the ratio of the conveying surface (a), the conveying opposite surface (b) and the shearing surface (c) of the hexagonal paddles was 2: 1: 2, Polymer resin powders were prepared.

Example  9

The same as Example 1, except that the ratio of the conveying surface (a), the conveying opposite surface (b), and the front surface (c) of the hexagonal paddles was 2: 1: 2 and the angle of arrangement of the stirrers was 20 °. Polymer resin powders were prepared.

Example  10

The same as Example 1, except that the ratio of the conveying surface (a), the conveying opposite surface (b) and the front surface (c) of the hexagonal paddles was 2: 1: 2 and the angle of arrangement of each stirrer was 30 °. Polymer resin powders were prepared.

Example  11

The same as Example 1, except that the ratio of the conveying surface (a), the conveying opposite surface (b) and the shearing surface (c) of the hexagonal paddles was 2: 1: 2 and the angle of arrangement of each stirrer was 45 °. Polymer resin powders were prepared.

Comparative Example  One

The polymer latex (acrylonitrile-butadiene-styrene-methacrylate copolymer) prepared in the above Production Example was introduced into the first agglomeration tank of the reactor as shown in FIG. 1 at a flow rate of 12 kg / hr, diluted with a flocculant 3.0 parts by weight of calcium chloride (CaCl ₂ ) was added to 100 parts by weight of the entire polymer latex. The solid content of the polymer latex slurry was adjusted to 19% by agitation while direct addition of steam at a flow rate of 12 kg / hr. At this time, the flocculation temperature was 94 ° C., and the residence time of the reactor in the flocculation tank was 30 minutes on average. When the flocculation was over, the flocculation tank was moved to the first aging tank. In the aging tank, the temperature was elevated to 98 캜 while steam was added without addition of water, and aged. In this case, the average residence time was 60 minutes. After the first aging process, the second aging tank was moved to the second aging tank. In the second aging process, the temperature was raised to the transition temperature of the polymer latex through pressure aging, And the residue was removed. At this time, the average temperature was 130 ° C and the average pressure was 1.6 kgf / cm ² . After agglomeration and aging, the polymer latex slurry agglomerated was moved to a slurry storage tank and recovered as a polymer latex resin powder through dehydration and drying fixation.

Comparative Example  2

The polymer latex resin powder was prepared in the same manner as in Comparative Example 1, except that the coagulation temperature was 92 ° C.

Comparative Example  3

Polymer latex resin powder was prepared in the same manner as in Comparative Example 1, except that the secondary aging temperature was 120 캜 and the pressure was 1.4 kgf / cm ² .

Comparative Example  4

The polymer latex resin powder was prepared in the same manner as in Example 1 except that the transfer surface (a) and the transfer surface (b) were rectangular pellets having a ratio of 2: 1.

Comparative Example  5

The polymer latex resin powder was prepared in the same manner as in Example 1, except that the transfer surface (a) and the transfer surface (b) were rectangular paddles having a ratio of 2: 1 and the angle of arrangement of the stirrer was 0 ° Respectively.

Comparative Example  6

Polymer latex resin powder was prepared in the same manner as in Example 1 except that the transfer surface (a) and the transfer surface (b) were square pellets having a ratio of 1: 1.

Comparative Example  7

The same as Example 1, except that the ratio of the conveying surface (a), conveying opposite surface (b) and shearing surface (c) of the hexagonal paddles was 2: 1: 2 and the angle of arrangement of each stirrer was 0 °. Polymer resin powders were prepared.

Comparative Example  8

The same as Example 1, except that the ratio of the conveying surface (a), conveying opposite surface (b) and shearing surface (c) of the hexagonal paddles was 2: 1: 2 and the angle of arrangement of each stirrer was 60 °. Polymer resin powders were prepared.

Comparative Example  9

The same as Example 1, except that the ratio of the conveying surface (a), conveying opposite surface (b) and shearing surface (c) of the hexagonal paddles was 2: 1: 2 and the angle of arrangement of each stirrer was 90 °. Polymer resin powders were prepared.

Experimental Example

For comparison and analysis of water content, particle size distribution, apparent specific gravity, resin color and thermal stability of the polymer latex resin powders prepared in the above Examples and Comparative Examples, the properties of each polymer latex resin powder were measured by the following methods. The results of each measurement are shown in Tables 1 and 2 below. Table 1 shows the results of comparative analysis on the presence or absence of hexagonal paddles having three sides composed of the conveying surface (a), the conveying opposite surface (b) and the front surface (c) The results of the comparative analysis according to the angular difference between the hexagonal paddles are shown.

1) Moisture content

Using a moisture meter (METTLER / TOLEDO HR83-P), the weight change was measured after complete drying at 150 ° C.

2) Particle size distribution

The particle diameter was measured using a wicker, and the content of large particles (coarse) of 1400 탆 or more was measured.

3) Apparent Specific Gravity

It was measured according to ASTM D1985.

4) Color of powder

Each of the polymer latex resin powders prepared in Examples and Comparative Examples was mixed with SAN resin at a ratio of 25:75, and then 2.0 parts by weight of solid magnesium stearate was mixed and pelletized at 200 ° C using a twin screw extruder. The pellet was again injected at 220 ° C to prepare a physical specimen. The b values of the prepared specimens were measured using a colorimeter (Color Quest UU, Hunter Lab Co.). The b value may have positive and negative values based on 0, and a value larger than 0 means yellow, and a value smaller than 0 means a blue value.

5) Thermal stability

OIT (Oxidative Induction Time) was measured using Differential Scanning Calorimetry (DSC). The measurement was carried out while introducing 50 ml / min of oxygen at 190 占 폚. OIT means the time taken for oxidation to take place under an isothermal condition while oxygen is added. The larger the OIT, the better the thermal stability.

Table 1 below shows the polymer latex resin particles prepared using the apparatus for producing a polymer latex resin powder including the integral reactor in which each of the stirrers on which the hexagonal paddles constituting the three sides of the present invention are fixed is arranged at an angle of 5 degrees between adjacent paddles. Polymer latex resin powders (Comparative Examples 1 to 3) prepared by using a polymer latex resin powder production apparatus comprising a resin powder (Examples 1 to 4) and a paddle-free integral reactor, Manufactured by using a polymer latex resin powder production apparatus comprising a polymer latex resin powder (Comparative Example 4 and Comparative Example 5) produced by using a polymer latex resin powder production apparatus including an integrated reactor and an integral reactor having square paddles (Comparative Example 6) of the polymer latex resin powder will be.

division Paddle face ratio Agitator arrangement angle Slurry solids (%) Moisture content (%) Powder characteristics Thermal stability color The transfer surface (a) Reverse transfer surface (b) The front section (c) Course (% by weight) Fine (% by weight) Apparent specific gravity
(g / ml) Example 1 2 One One 5 38 23.89 10.1 3.1 0.34 35.2 1.63 Example 2 2 One 2 5 38 23.01 8.7 2.8 0.36 37.5 1.55 Example 3 2.3 One 3 5 38 23.25 8.6 3 0.36 35.5 1.59 Example 4 One One One 5 38 24.71 9.2 3.9 0.35 33.2 1.71 Comparative Example 1 - - - - 19 30.82 17.9 5.8 0.30 23.5 2.26 Comparative Example 2 - - - - 19 31.69 16.8 6.2 0.29 22.7 2.38 Comparative Example 3 - - - - 19 32.74 17.6 5.6 0.30 21.4 2.52 Comparative Example 4 2 One - 5 38 26.95 13.3 4.8 0.32 29.5 1.90 Comparative Example 5 2 One - 0 38 27.5 13.7 4.6 0.32 29.2 1.92 Comparative Example 6 One One - 5 38 28.73 14.3 5.1 0.32 28.6 2.01

As shown in Table 1, the polymer latex resin powders of Comparative Examples 1 to 3 prepared in an integrated reactor without paddle and the polymers of Comparative Examples 4 to 6 prepared in an integrated reactor having rectangular or square paddles It was confirmed that the polymer latex resin powders of Examples 1 to 4 prepared in the integral reactor having the hexagonal paddles of the present invention as compared with the latex resin powders showed a decrease in the content of the course and fine particles as a whole and that the apparent specific gravity was increased Respectively. This is because the polymer latex slurry gives a strong shear force when passing between the hexagonal paddle and the barrel pin to give a greater force to the polymer latex slurry particles during agglomeration and aging to provide an excellent agglomeration force so that the polymer latex slurry having a uniform particle size distribution It can be manufactured.

In addition, compared with the polymer latex resin powders of Comparative Examples 1 to 6, in which the polymer latex resin powders of Examples 1 to 4 prepared in the integral reactor having hexagonal paddles of the present invention had a water content of 26.95% to 32.74% The moisture content was reduced from 23.01% to 24.71%, and the thermal stability and the color of the processed resin were also improved.

Therefore, the apparatus for producing a polymer latex resin powder including an integrated reactor having paddles according to the present invention can arrange the agitators so as to have a certain angle between adjacent paddles fixed to each agitator, thereby transferring the polymer latex slurry even under a high viscosity, It is possible to reduce the water content because no additional moisture is required, and it is possible to improve the color and thermal stability of the polymer resin after the extrusion and injection processes because of having a uniform particle size distribution.

The following Table 2 shows the results obtained by using a polymer latex resin powder manufacturing apparatus comprising an integrated reactor in which each of the stirrers having hexagonal paddles with three sides of the present invention fixed thereon was arranged at an angle of 2.5 to 45 degrees between adjacent paddles The polymer latex resin powders (Example 2, Examples 5 to 11) and polymer pellets were prepared by using a polymer latex resin powder production apparatus comprising an integral reactor arranged at 0 °, 60 ° or 90 ° between adjacent paddles (Comparative example 7 to comparative example 9) were compared with each other.

division Paddle face ratio Agitator arrangement angle Slurry solids (%) Moisture content (%) Powder characteristics Thermal stability color The transfer surface (a) Reverse transfer surface (b) The front section (c) Course (% by weight) Fine (% by weight) Apparent specific gravity
(g / ml) Example 2 2 One 2 5 38 23.01 8.7 2.8 0.36 37.5 1.55 Example 5 2 One 2 2.5 38 23.75 8.8 3.0 0.36 35 1.61 Example 6 2 One 2 7.5 38 22.9 9.1 3.2 0.36 36.8 1.57 Example 7 2 One 2 10 38 22.81 9.5 3.5 0.36 36.3 1.58 Example 8 2 One 2 15 38 21.98 9.4 3.5 0.36 38.2 1.51 Example 9 2 One 2 20 38 22.16 9.2 3.1 0.36 37.8 1.54 Example 10 2 One 2 30 38 23.37 9.6 3.6 0.36 37 1.55 Example 11 2 One 2 45 38 24.81 10.2 3.8 0.35 33.7 1.75 Comparative Example 7 2 One 2 0 38 26.29 13.5 5.2 0.33 29.1 1.91 Comparative Example 8 2 One 2 60 38 26.95 13.3 4.5 0.33 30.1 1.92 Comparative Example 9 2 One 2 90 38 27.34 13.8 4.8 0.33 29.8 1.95

As shown in Table 2 above, when arranging the stirrer in which the hexagonal paddles are fixed, the paddles fixed to the first stirrer and the paddles fixed to the second stirrer (i.e., adjacent paddles) 45 °), the polymer latex slurry having a high viscosity can be smoothly transferred to uniformly mix the polymer latex with the coagulant and the steam, so that the water content can be decreased and the powder having a uniform particle size can be obtained (Examples 2 to 11). ≪ tb > < TABLE > In addition, the thermal stability of the dried particles and the hue of the processed resin were also excellent.

On the other hand, when the stirrer in which the hexagonal paddles were fixed was arranged so as to have no angle between the paddles (0 °, Comparative Example 7), when the paddles were arranged to form an angle of 60 ° (Comparative Example 8) (Comparative Example 9) exhibited the same level of properties as those of the polymer latex resin powders of Comparative Examples 4 to 6 prepared in an integral reactor including a rectangular or square paddle.

Therefore, the apparatus for producing a polymer latex resin powder of the present invention comprises a single reactor in which each stirrer is arranged in the form of a screw so as to form an angle of 2.5 ° to 45 ° between adjacent paddles, thereby providing a uniform particle size distribution A powder having a moisture content can be produced.

1, 214: Polymer latex injection line 13, 212: Coagulant injection line
12, 213: Stept injection line 14: Water injection line
1: latex storage tank 2: coagulation tank
3: first ripening tank 4: second ripening tank
5: Polymer slurry tank 6: Dehydrator
7: dryer 15: final polymer powder
200: integral reactor 210: reaction tube
220, 300: rotation axis 211a, 211b: barrel pin
230, 310, 320, 330, 340, 350:
231a, 231b, 311, 321, 331, 341, 351: hexagonal paddles
301: direction in which the rotation axis rotates 302: direction in which the rotation axis is rotated

Claims (18)

An integrated reactor including an agglomeration tank and an aging tank, and a reaction tube arranged outside the reactor;
The reactor comprises: a rotating shaft extending along a central axis in the longitudinal direction of the reactor; And
And at least one stirrer mounted on an outer surface of the rotating shaft and having at least one paddle fixed thereto;
The paddles are hexagonal paddles consisting of three surfaces: a conveying surface a, a conveying opposite surface b and a front surface c;
Wherein the agitator is mounted on the rotating shaft in a screw shape so as to have a predetermined angle between adjacent left paddles and right paddles with respect to the longitudinal axis of the rotating shaft.
The method according to claim 1,
Wherein the manufacturing apparatus comprises at least one barrel fin protruding from the inner wall of the reactor outside the reactor in the upper or lower direction of the reactor.
The method according to claim 1,
Wherein the apparatus comprises a latex tank, a dehydrator or a dryer.
The method according to claim 1,
Wherein the integrated reactor includes a polymer latex injection line, a flocculant injection line, and a steam injection line.
The method according to claim 1,
Wherein the number of the agitators is 1 to 200. 2. The apparatus for producing a polymer latex resin powder according to claim 1,
The method according to claim 1,
Wherein each of the agitators comprises one to six paddles.
The method according to claim 1,
Wherein the transfer surface (a), the transfer opposite surface (b), and the front surface (c) have a ratio of 1: 4: 1: 1 to 8.
The method according to claim 1,
Wherein the predetermined angle between the left paddle and the right paddle adjacent to the axis of rotation is in the range of 2.5 to 45 degrees.
Wherein the polymer latex slurry containing the polymer latex and the coagulant is introduced into an integrated reactor to simultaneously carry out the agglomeration step and the aging step. The method for producing the polymer latex resin powder according to claim 1,
The method of claim 9,
Wherein the preparation method further comprises a dehydration and drying step after the agglomeration step and the aging step.
The method of claim 9,
Wherein the coagulant is contained in an amount of 0.5 to 5 parts by weight based on 100 parts by weight of the polymer latex.
The method of claim 9,
Wherein the polymer latex slurry resides in the agglomeration step and the aging step for 0.5 to 30 minutes.
10. The method of claim 9,
Wherein the solid content of the polymer latex slurry is 25 wt% to 60 wt%.
The method of claim 9,
Wherein the solid content of the polymer latex is 10 wt% to 90 wt%.
The method of claim 9,
Wherein the polymer latex is a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer.
The polymer latex resin powder produced by the method of claim 9.
18. The method of claim 16,
Wherein the powder has a water content of 21.5% to 24.9%.
18. The method of claim 16,
Wherein the powder has a fine particle content of 2.8 wt% to 3.9 wt% in the polymer latex resin powder.

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