KR20150143196A - Manufacture apparatus of polybutadiene latex particles and Manufacturing of polybutadiene latex particles by continuous process using the same - Google Patents

Abstract

The present invention relates to a polybutadiene latex particle production apparatus, and a continuous process-type polybutadiene latex particle production method using the same. The production apparatus of the present invention comprises: a first tube for injecting acid; and a second tube including a first injection hole for injecting a polybutadiene polymerization solution, and a second injection hole for injecting air.

Description

TECHNICAL FIELD The present invention relates to a polybutadiene latex particle producing apparatus and a continuous process polybutadiene latex particle producing apparatus using the same,

The present invention relates to a device for producing polybutadiene latex particles and a process for producing continuous process polybutadiene latex particles using the same.

Polybutadiene latex (PBL) prepared from 1,3-butadiene is typically used as a raw material for forming rubber particles, which are a major component of ABS (Acrylonitrile-Butadiene-Styrene) resin .

In particular, ABS-based resins are excellent in properties such as impact resistance, chemical resistance and molding processability, and are widely used in office equipment, electric / electronic parts, automobile interior materials and the like. In order to secure the impact resistance of ABS, securing the physical properties of the rubbery latex is largely an important factor of the particle size and the gel content generated by the internal crosslinking. Generally, in order to secure effective impact resistance, It is known that latex is advantageous and rubber latex having a lower gel content than rubber latex having a high gel content is advantageous.

On the other hand, the surface of the polybutadiene latex produced through polymerization has a negative charge as a whole and is stably dispersed by the repulsive force between the particles. However, when such particles are agglomerated to form large diameter particles, excellent physical properties desired can be achieved. In the conventional method of agglomerating polymer latex particles, a method of destabilizing polymer latex by using an acid and inducing agglomeration is typical .

In order to solve this problem, it is necessary to add a low concentration of acid to the solution, but the concentration of the acid to be added is too high to prevent the formation of a coagulated product, namely, a coagulated product in which the added acid is excessively agglomerated at the diffusion interface inside the polymer latex. The effect of increasing the particle size is reduced. Particularly, when an acid having a certain concentration or more is added to the batch type flocculation reactor, excess coagulated solidification is often formed around the stirrer. Therefore, there is a need for a new technique capable of producing large-diameter polybutadiene latex particles in a short time while inducing coagulation by neutralizing the surface of particles using an acid.

US registered patent US 4,480,078 Korean Patent Publication No. KR 2013-0065295

The production of polymer latex particles by the prior art has the disadvantage that a large amount of solidification product is generated. This is because the excess coagulated solidification, called so-called coagulation, is formed at the inner diffusion interface to obtain a stable and uniform particle size rubber latex There is a problem that it is difficult.

Accordingly, the present invention can provide a manufacturing apparatus capable of producing stable polybutadiene latex particles having a stable particle size.

It is another object of the present invention to provide a process for producing polybutadiene latex particles which can prevent the production of excessively agglomerated coagulated product by using the production apparatus according to the present invention.

It is another object of the present invention to provide a production method for producing stable and uniformly sized polybutadiene latex particles by preventing the formation of excessively agglomerated coagulated material.

In order to achieve the above object, And a second tube including a first injection port for injecting the polybutadiene polymerization solution and a second injection port for air injection, wherein a part of the first tube is inserted into the closed one end of the second tube, And the first injection port is formed at a position where the polybutadiene polymerization solution can be injected into the lumen, and the second injection port is formed at a position where the first tube is inserted A first agglomeration reaction part is formed in the second tube between the distal end of the first tube and the second injection port and a second agglutination reaction part is formed in the second tube behind the second injection port, A latex particle production apparatus is provided.

According to another aspect of the present invention, there is provided a process for producing polybutadiene latex particles using the production apparatus according to the present invention, comprising the steps of: (a) injecting a polybutadiene polymerization solution and an acid into a first inlet and a first tube, ; And (b) injecting air into the second inlet port to perform a secondary agglomeration reaction with the primary aggregation reactant. The present invention also provides a process for producing continuous process polybutadiene latex particles.

According to a preferred embodiment of the present invention, the flow rate of the acid injected into the first tube and the polybutadiene polymerization solution injected into the first injection port may be 1: 4 to 8.

The average particle size of the polybutadiene latex particles prepared by the process of the present invention may be 230 to 330 nm.

The present invention can provide a method for producing polybutadiene latex particles in which the particle size is stably uniform using the production apparatus according to the present invention.

In addition, the production method of the present invention can prevent the production of excessively agglomerated coagulated material when the polybutadiene latex particles are produced.

Therefore, economical and stable quality for mass production can be ensured, and the manufacturing process time can be remarkably reduced, and the TSC (total solid content), that is, the yield of polybutadiene latex particles as the solid in the present invention .

1 is a block diagram of an apparatus for producing polybutadiene latex particles according to an embodiment of the present invention.
2 is a configuration diagram of an apparatus for producing a polybutadiene latex particle according to a comparative example of the present invention.

Hereinafter, the present invention will be described in detail. The following detailed description is merely an example of the present invention, and therefore, the present invention is not limited thereto.

The production of polymer latex particles by the prior art has the disadvantage that a large amount of solidification product is generated. This is because the excess coagulated solidification, called so-called coagulation, is formed at the inner diffusion interface to obtain a stable and uniform particle size rubber latex There is a problem that it is difficult.

Accordingly, the present inventors have found that the above problems can be solved by air injection using the production apparatus according to the present invention, and the present invention has been completed.

That is, the present invention provides a method of manufacturing a semiconductor device, And a second tube including a first injection port for injecting the polybutadiene polymerization solution and a second injection port for air injection, wherein a part of the first tube is inserted into the closed one end of the second tube, And the first injection port is formed at a position where the polybutadiene polymerization solution can be injected into the lumen, and the second injection port is formed at a position where the first tube is inserted A first agglomeration reaction part is formed in the second tube between the distal end of the first tube and the second injection port and a second agglutination reaction part is formed in the second tube behind the second injection port, A latex particle production apparatus is provided.

First, an apparatus for producing polybutadiene latex particles provided by the present invention will be described.

FIG. 1 is a schematic view showing a manufacturing apparatus according to a preferred embodiment of the present invention, and the manufacturing apparatus may be a tubular reactor which is a continuous insertion structure.

1, a first tube 1 for acid injection and a second tube 2 including a first injection port 4 for injecting a polybutadiene polymerization solution and a second injection port 5 for air injection, And the first tube 1 is inserted in the second tube 2 in the longitudinal direction. That is, a part of the first tube is inserted into the closed end of the second tube 2 to form a lumen 3 between the first tube 1 and the second tube 2, The first injection port 4 is formed at a position where the polybutadiene polymerization solution can be injected into the lumen 3 and the second injection port 5 is formed at a position where the first tube is not inserted . The tube means a space in the second tube formed by inserting the first tube into the second tube.

A polybutadiene polymerization solution and a first agglomeration reaction part (6) of acid are formed in the second tube between the distal end of the first tube and the second injection port. In the second tube at the rear of the second injection port, And a second aggregation reaction unit 7 for the tea aggregation reaction product.

In the first agglomeration reaction part 6, the primary agglomeration reaction of the acid injected into the first tube 1 and the polybutadiene polymerization solution injected into the first injection port 4 takes place, and in the second agglomeration reaction part, The reaction product is mixed with the air injected from the second inlet (5) to cause a secondary agglomeration reaction. The primary agglomeration reaction may include a primary agglomeration reaction product and / or an unreacted polybutadiene polymerization solution and an acid have.

That is, the first tube is inserted into the second tube so as to extend to the interface of the first flocculation reaction part (6), whereby the first flocculation reaction is carried out in the first flocculation reaction part and the second flocculation reaction is carried out in the second flocculation reaction part It happens.

This is because, in the conventional tubular reactor, the fluids introduced are immediately mixed to produce an overflowing coagulated product. However, in the present invention, by using the manufacturing apparatus which is a tubular reactor having a continuous insertion structure in which the first tube is extended and inserted into the second tube, the flow of the fluid is transmitted through the first flocculation reaction unit 6 and the second flocculation reaction unit 7 ) So that each coagulation reaction was continuously performed. Therefore, excessive coagulated solidification is not produced as compared with the conventional process because it is stably and uniformly mixed.

More specifically, the diameter of the first tube is smaller than the diameter of the second tube, and the first tube 1 can be inserted into the second tube 2 in the tube-in-tube manner .

The first injection port 4 may be formed at one end of the second tube 2 in a T shape in a direction perpendicular to the first acid injection tube 1. The second injection port 5 may also be formed at one end of the second tube 2 in a direction perpendicular to the first acid injection tube 1 and may have a first inlet 4, (5) may be formed in parallel at regular intervals, and the first injection port may be formed in front of the second injection port.

On the other hand, the shorter the interval between the first inlet 4 and the second inlet 5, the greater the effect that the acid and polybutadiene polymerization solution are mixed by air injection as soon as they meet. On the contrary, the wider the gap between the first inlet 4 and the second inlet 5, the greater the possibility that the acid and the polybutadiene polymerization solution will over-agglomerate before being brought into contact with the air to be injected to produce a solidified product. Therefore, in the primary agglomerate 6, air must be injected in a state in which the acid and the polybutadiene polymerization solution are in a parallel flow, and the air is injected into the first inlet 4 and the second inlet 5 It is efficient to shorten the interval to minimize the primary agglomerate 6.

In order to allow each injected material to flow in the same direction to the areas of the first flocculation reaction part 6 and the second flocculation reaction part 7 and to prevent the flow in the reverse direction, And a pressure control means for controlling the pressure inside the second tube.

According to another aspect of the present invention, there is provided a process for producing polybutadiene latex particles using the production apparatus according to the present invention, comprising the steps of: (a) injecting a polybutadiene polymerization solution and an acid into a first inlet and a first tube, ; And (b) injecting air into the second inlet port to cause a second agglomeration reaction with the one aggregation reaction product. The present invention also provides a process for producing continuous process polybutadiene latex particles.

The present invention can prevent the formation of excess agglomerate in the process of preparing polybutadiene latex particles by co-injection with air at the same time while adding an acid at a certain concentration or higher to the polybutadiene polymerization solution according to the present invention. In addition, it is possible to stably produce large-diameter polybutadiene latex particles having small diameters and various sizes.

First, the step (a) of injecting the polybutadiene-polymerized solution and the acid into the first inlet and the first tube, respectively, for primary agglomeration reaction will be described.

The polybutadiene polymerization solution is a solution containing polybutadiene latex (PBL) particles (hereinafter referred to as solid content) and a solvent. In this step, the polybutadiene polymerization solution injected into the tubular reactor according to the present invention is mixed with the acid, And the primary aggregation reaction is caused by inducing aggregation.

According to a preferred embodiment of the present invention, the polybutadiene polymerization solution injected into the primary agglomeration reaction may have a solid content of 30 to 50% by weight, preferably 35 to 45% by weight, Water, and water. The water may be ordinary water, preferably DI water.

The acid injected into the first tube 1 may be one selected from the group consisting of sulfuric acid, hydrochloric acid, maleic acid, itaconic acid, acetic acid, and mixtures thereof. Preferably, acetic acid corresponding to a weak acid whose flow rate is controlled is injected do.

According to a preferred embodiment of the present invention, the total flow rate of the injected polybutadiene polymerization solution and acid may be 1 to 50 L / hr, preferably 10 to 30 L / hr. If the total flow rate is less than 1 L / hr, there may be a problem that sufficient agglomeration can not be caused by the acid, and if the total flow rate exceeds 50 L / hr, there may be a problem that the solidified material over- . In addition, at a flow rate deviating from the above range, the uniformity of the particles is decreased, so that the standard deviation of the particle size can be relatively large.

The flow rate ratio of the acid injected into the first tube and the polybutadiene polymerization solution injected into the first injection port may be 1: 4 to 8, preferably 1: 4 to 5, If the flow rate is higher than the above range, excess aggregate is generated. If the flow rate of the acid is lower than the above range, generation of large diameter particles is difficult.

Therefore, desired large-diameter polybutadiene particles can be produced while lowering the occurrence of the over-agglomerated coagulated matter at the above flow rate ratio.

It is preferable that the flow rate ratio of the injected acid and polybutadiene polymerization solution is 1: 4 to 8 and the total flow rate simultaneously satisfies 1 to 50 L / hr. If the flow rate is out of the total flow rate range, The excessively agglomerated particles may be generated and the inside of the tubular reactor may be clogged.

Meanwhile, even if the acid and polybutadiene polymerization solution are mixed at the above-mentioned flow ratio, if the concentration of the acid is higher than a certain concentration and the continuous flocculation reaction takes place, the flocculated coagulum is formed. That is, if the step (b) is not performed, the mixing effect of the reactants is relatively lowered, and the coagulated solidification material is piled up in the reactor, resulting in clogging, which makes it difficult to operate the continuous process for a long time.

Next, the step of injecting air into the second inlet (b) and performing a secondary agglomeration reaction with the primary agglomeration reaction will be described.

 The present invention also relates to a process for reducing aggregation of polybutadiene latex particles which have not sufficiently aggregated in step (a) and / or lowering the occurrence of excessively agglomerated coagulation, And / or the unreacted polybutadiene polymerization solution and the acid are mixed with the air injected into the second injection port to cause a secondary agglomeration reaction in the second agglomeration reaction part.

Particularly, the air injected in the step (b) is a method which can prevent the excessive aggregation and can perform the mixing of the acid and the polymerization solution of the polybutadiene most efficiently.

For example, if a structure such as a static mixer is mounted in a tubular reactor artificially instead of an air injection system, or if the structure of the tubular reactor itself is changed, a mixing effect can be enhanced, but a large amount of excessively agglomerated solidification product is produced .

According to a preferred embodiment of the present invention, the flow rate of the air injected into the second injection port may be 50 to 1000 cc / min, preferably 100 to 500 cc / min, , It is similar to the case where no air is injected, and when exceeding 1000 cc / min, excessively injecting air may cause excessive aggregation of particles, so the flow rate in the above range is preferable.

On the other hand, when the polybutadiene latex particles are prepared without air injection, the particle size is about 280 nm at maximum. Generally, in the case of polybutadiene latex particles through a continuous process, particles of 200 to 250 nm are easy to produce. Uneasy. The fact that the particle size is made small due to no air injection does not mean that there are too few particles that overflow. This is because, when the polybutadiene polymerization solution grows through the agglomeration process, it becomes a particle of 300 nm in the latter half of 200 nm, and at the same time, it excessively agglomerates without stopping the growth. Further, when the flow rate of the acid to be injected or the total flow rate of the injected acid to increase the polybutadiene latex particles is increased to a value exceeding the critical value, there is a problem that excessive coagulated solidification product is produced.

However, in the present invention, this is solved by injecting air.

That is, when the polybutadiene latex particles are produced, the increase of the shear stress in the tube when air is injected is minimized, whereby the primary aggregation reaction product and / or unreacted polybutadiene polymerization solution and the acid are mixed with air mixing effect is stably increased to cause a secondary agglomeration reaction. As a result, polybutadiene latex particles having a diameter of 300 nm or more can be stably produced. As a result, when the polybutadiene latex particle having a large diameter of 300 nm is produced by air injection, the particles excessively aggregated are sharply reduced. This is because the air injection method is a method of mixing with minimizing shear stress. The shear stress means the resistance generated between the fluid and the inner wall of the tube. The larger the shear stress value of the fluid, the greater the amount of the coagulum produced. The shear stress increases as the flow rate increases. The larger the area, the higher the viscosity.

In addition, since the production of excessively agglomerated polybutadiene latex particles is low depending on the amount of the acid and polybutadiene polymerization solution injected than in the prior art, even if the solvent of the acid and polybutadiene polymerization solution is reduced, the polybutadiene latex particles The content is high. Therefore, economical efficiency and stable quality can be secured.

Therefore, according to a preferred embodiment of the present invention, the average particle size of the polybutadiene latex particles produced by the production method of the present invention may be 230 to 330 nm, and the size of the polybutadiene latex particles may be determined by the flow rate of the injected acid It is possible to control the particle size generated by controlling.

In addition, the standard deviation of the size of the polybutadiene latex particles produced by the production method of the present invention may be 33% or less, preferably 20% or less, which is conventionally a standard deviation of 34% It can be seen that it is possible to produce polybutadiene latex particles of uniform size in the present invention in contrast to the difficulty of manufacturing particles.

As a result, the polybutadiene latex particles produced by the production method according to the present invention can produce polybutadiene latex particles having a uniform size and a large diameter.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the embodiments of the present invention described below are illustrative only and the scope of the present invention is not limited to these embodiments. The scope of the present invention is indicated in the claims, and moreover, includes all changes within the meaning and range of equivalency of the claims. In the following Examples and Comparative Examples, "%" and "part" representing the content are based on weight unless otherwise specified.

Example  One

Polybutadiene latex particles were prepared by using the apparatus for producing polybutadiene latex particles according to the present invention shown in FIG.

5 wt% of acetic acid was injected into the first tube 1 of the manufacturing apparatus and a polybutadiene polymerization solution (PBL) having a solid content of 40 wt% was injected into the first injection port 4 of the second tube 2 at a flow rate ratio 5% by mass: a polybutadiene polymerization solution having a solid content of 40% by weight) was 1: 7.5, and the total flow rate of the polymerization solution of acetic acid and polybutadiene was 20 L / hr. Then, 200 cc / min of air was injected into the second injection port of the second tube (2).

Example  2

Except that the flow rate ratio of the polybutadiene polymerization solution having 5% by weight of acetic acid and the solid content of 40% by weight was 1: 6.

Example  3

Except that the flow rate ratio of the polybutadiene polymerization solution having 5% by weight of acetic acid and 40% by weight of the solid content was 1: 5.

Example  4

Except that the flow rate ratio of the polybutadiene polymerization solution having 5% by weight of acetic acid and the solid content of 40% by weight was 1: 4.5.

Example  5

Except that the flow rate ratio of the polybutadiene polymerization solution having 5% by weight of acetic acid and the solid content of 40% by weight was 1: 4.

Comparative Example  One

Polybutadiene latex particles were prepared using the polybutadiene latex particle production apparatus shown in FIG. 2 below.

5 wt% of acetic acid was injected into the first tube 1 of the production apparatus and a polybutadiene polymerization solution (PBL) having a solid content of 40 wt% was injected into the first injection port 4 of the second tube 2 at a flow rate ratio of 1: 4.5 and a total flow rate of 20 L / hr.

Comparative Example  2

Except that the flow rate ratio of the polybutadiene polymerization solution having 5% by weight of acetic acid and the solid content of 40% by weight was 1: 4.

Comparative Example  3

3 was prepared in the same manner as in Comparative Example 2, except that a tubular reactor composed of a T union as shown in Fig. 3 was used instead of the continuous insertion structure.

Experimental Example

The polybutadiene latex particles prepared according to Examples 1 to 5 and Comparative Examples 1 to 3 were analyzed for particle size using a particle size analyzer (NICOMP AW380), and the results are shown in Table 1 below.

division Acetic acid: PBL Average particle size (nm) Standard Deviation (%) Example 1 1: 7.5 233 31 Example 2 1: 6 256 21 Example 3 1: 5 286 15 Example 4 1: 4.5 301 19 Example 5 1: 4 322 21 Comparative Example 1 1: 4.5 261 38.8 Comparative Example 2 1: 4 274 34.9 Comparative Example 3 1: 4 202 31.3

Results of measurement With reference to Table 1, it can be seen that the particles of the polybutadiene latex particles prepared in Examples 1 to 5 and Comparative Examples 1 to 3 were large and uniform in size.

Specifically, it can be seen that the average particle size and standard deviation of the prepared polybutadiene latexes of Examples 1 to 5 are smaller than those of Comparative Examples 1 to 3, so that the prepared average particle size was stably and uniformly produced.

Particularly, Example 4 and Comparative Example 1, Example 5 and Comparative Example 2 were produced at the flow rate ratio of the same acetic acid: polybutadiene polymerization solution, but Examples 4 and 5 were the sizes of polybutadiene latex particles prepared from Comparative Examples 1 and 2, respectively Is 40 to 50 nm, it can be seen that the production method of the present invention is superior to the conventional production method.

Comparing Comparative Example 1 and Comparative Example 3, it was found that the average particle size of Comparative Example 3 was smaller than that of Comparative Example 2 by 72 nm even in the same flow rate ratio of the same acetic acid: polybutadiene polymerization solution, and in Comparative Example 3, The operation could not be performed for a long time.

As a result of Comparative Examples 1 and 2 and Comparative Example 3, it was also found that the embodiment of Embodiment 1 is more efficient even when air is injected into the T-tubular reactor after mixing the two solutions.

That is, it can be seen that the tubular reactor of the continuous insertion structure of the present invention has superior performance to that of the conventional T union tubular reactor. In addition, when polybutadiene latex particles are produced by injecting air into a tubular reactor having a continuous insertion structure including the air injection structure of the present invention, the mixing effect can be stably maintained while minimizing an increase in shear stress in the tube The polybutadiene latex particles of uniform size can be produced. And polybutadiene latex particles of 300 nm or more can be prepared.

1: first tube 2: second tube
3: lumen 4: first inlet
5: second inlet 6: first flocculation reactor
7: Second aggregation reaction unit

Claims (12)

A first tube for injecting acid; And
And a second tube including a first injection port for injecting the polybutadiene polymerization solution and a second injection port for air injection,
Wherein a portion of the first tube is inserted into a closed end of the second tube to form a lumen between the first tube and the second tube,
Wherein the first injection port is formed at a position where the polybutadiene polymerization solution can be injected into the formed lumen, the second injection port is formed at a position where the first tube is not inserted,
Wherein a first agglutination reaction part is formed inside the second tube between the distal end of the first tube and the second injection port and a second agglutination reaction part is formed inside the second tube behind the second injection port. . The method according to claim 1,
Wherein the first injection port is formed at one end of the second tube in a direction perpendicular to the first tube. The method according to claim 1,
Wherein the second injection port is formed at one end of the second tube in a direction perpendicular to the first tube. The method according to claim 1,
The manufacturing apparatus further includes a pressure control means for controlling the internal pressure, and the polybutadiene polymerization solution injected into the manufacturing apparatus by the pressure control means, the acid and the air are mixed while being flowed in the same direction and reacted Wherein the polybutadiene latex particles have an average particle size of from 1 to 10 nm. A process for producing polybutadiene latex particles using the production apparatus according to claim 1,
(a) injecting a polybutadiene polymerization solution and an acid into a first inlet and a first tube, respectively, so as to perform a primary agglomeration reaction; And
(b) injecting air into the second inlet port to cause a second flocculation reaction with the one flocculation reactant. The method of claim 5,
Wherein the acid is any one selected from the group consisting of sulfuric acid, hydrochloric acid, maleic acid, itaconic acid, acetic acid, and mixtures thereof. The method of claim 5,
Wherein the polybutadiene polymerization solution injected into the first inlet comprises polybutadiene latex (PBL) particles having a solid content,
Wherein the solid polybutadiene latex (PBL) particles are contained in an amount of 30 to 50% by weight. The method of claim 5,
Wherein the total amount of polybutadiene polymer solution and acid to be injected is 1 to 50 L / hr per hour. The method of claim 5,
Wherein the flow rate of the acid injected into the first tube and the polybutadiene polymerization solution injected into the first injection port is 1: 4 to 8. The method of claim 5,
Wherein the flow rate of the air injected into the second injection port is 50 to 1000 cc / min. The method of claim 5,
Wherein the average particle size of the polybutadiene latex particles is from 230 to 330 nm. The method of claim 5,
Wherein the standard deviation of the particle size of the polybutadiene latex is 33% or less.

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