[1][Mutual citations and related applications;
[2]This application is all the information described in the literature of 09.02.2016 chair Korea Patent Application Korea Patent Application claims the benefit, and those of the priority based on the No. 10-2016-0113346 which is incorporated as a part hereof.
[3][Technology]
[4]The present invention by controlling the foam level that occurs during the polymerization reaction to an appropriate value the surface properties are excellent vinyl-based method for producing a vinyl chloride polymer capable of producing a polymer, a vinyl-based polymer and a vinyl-based the chloride chloride prepared in this chloride It relates to an apparatus for manufacturing a vinyl chloride polymer capable of producing a polymer.
[5]
BACKGROUND
[6]
Vinyl chloride-based polymer is a polymer containing vinyl chloride and 50% or more, cost-effective and easier to control hardness, a range of applications and is applicable to most of the processing unit. Besides, there are widely used in many fields it is possible to provide a molded article excellent physical and chemical properties, such as mechanical strength, weather resistance, and chemical resistance.
[7]
These vinyl chloride polymers may be prepared by various polymerization methods, and is mainly produced through suspension polymerization and emulsion polymerization. The suspension polymerization is a method for producing a vinyl chloride polymer by using water, a vinyl chloride monomer, suspension stabilizer, the polymerization initiator or the like having a particle size of less than 150 ㎛.
[8]
[9]
Polymerization for producing a vinyl chloride polymer has been to maintain a constant temperature by installing a jacket for heating and cooling to the outside the polymerization reactor in order to control the heat generated during the exothermic reaction. However, the polymerization reactor is enlarged according As there is a limit in controlling the heat generated during the reaction alone jacket to install a reflux condenser to the polymerization reactor the upper heat control for increased productivity.
[10]
However, heat removal by the reflux condenser has to be accompanied by the vaporization of the reaction, there arises the necessity foam (foam) by evaporation. This form is the surface to generate the scale in the cause of this there is, the polymer particles mixed in the form into the reflux condenser, the reflux condenser of the scale formation and not only cause a problem of lowering the heat removing ability fish eyes (fish-eye) occurs, there is not a bad property issues.
[11]
In order to solve this problem, the Republic of Korea Patent Publication 2013-0025515 discloses a level within the foam polymerization reactor through the overhead reflux non-condensable gas exhaust process and at the same time control the upper temperature to the polymerization temperature of the polymerization reactor equipped with a condenser to the polymerization reactor there is a process for the production of vinyl chloride-based polymer is disclosed that the height is adjusted to meet the 70% or less. However, in this case, when the non-condensable gas to an excessive exhaust back flow is to form the reflux condenser, this generates the scale as a result, a problem of fish eye generation.
[12]
Thus, the development of a method that can adjust the form of the polymerization to occur at an appropriate level is needed to produce a superior vinyl chloride polymer surface properties.
[13]
Detailed Description of the Invention
SUMMARY
[14]
An object of the present invention is to provide a method for producing vinyl chloride polymers that can be produced with excellent vinyl chloride polymer surface properties by controlling the foam level that occurs during the polymerization reaction to an appropriate value.
[15]
Another object of the invention is that the surface properties produced from the method for producing the vinyl-based polymer to excellent chloride.
[16]
A further object of the present invention is to provide an apparatus for manufacturing a vinyl chloride polymer capable of producing a vinyl chloride polymer in the above.
[17]
Problem solving means
[18]
In order to solve the above problems, the present invention comprises In the reaction containing the polymerization initiator, a suspension stabilizer and the vinyl chloride monomer in a polymerization reactor equipped with a reflux condenser on the top of the column and the suspension polymerization and the suspension polymerization is It is to perform while controlling such that in the form level polymerization reactor is kept below 10%, the foam level that represents the ratio of the thickness of the foam occupying raised above reaction outermost surface in the full-height distance from the surface within the reaction outermost polymerization reactor to a polymerization reactor, the top of the column will, the foam level is provided a method for preparing a vinyl chloride-based polymer to adjust by putting a defoaming agent.
[19]
[20]
In addition, the present invention provides a vinyl chloride-based polymer prepared from the method of manufacturing the above.
[21]
[22]
In addition, the present invention is a polymerization reactor; The reflux condenser was provided at the polymerization reactor, the top of the column; The foam detector is provided to the polymerization reactor separate from the top of the column reflux condenser; And it provides a device for manufacturing a vinyl chloride polymer containing the anti-foaming agent having the fill stream to an intermediate point in the polymerization reactor, the height direction.
[23]
Effects of the Invention
[24]
Method of producing a vinyl chloride polymer according to the present invention while maintaining the level of foam generated during the polymerization reaction to an appropriate value by proceeding the polymerization reaction less surface properties, such as fish eyes occurs producing the excellent transparency vinyl polymer Chloride can.
[25]
Vinyl chloride polymer according to the present invention, the surface properties being manufactured through the manufacturing method of the above, for example, low fish-eye generation amount can be excellent in transparency and Haze.
[26]
Accordingly, the production process and the vinyl chloride-based polymer prepared through which the vinyl chloride polymer according to the invention may be useful in industries that require the vinyl chloride polymer.
[27]
Brief Description of the Drawings
[28]
Following figures attached to this specification is intended to illustrate preferred embodiments of the present invention, the components which serve to further understand the teachings of the present invention with the content of the above-described invention, the invention is only to details set forth in those figures It is limited not to be construed.
[29]
1 is a schematic illustration of a device for manufacturing a vinyl chloride polymer according to one embodiment of the present invention.
[30]
[31]
Reference Numerals
[32]
100: apparatus for manufacturing a vinyl chloride polymer
[33]
10: polymerization reactor,
[34]
20: reflux condenser
[35]
30: Form detector
[36]
40: In line anti-foaming agent
[37]
50: Stirrers
[38]
T: defoamer reservoir
[39]
S: the outermost surface reactants
[40]
C: reaction
[41]
Best Mode for Carrying Out the Invention
[42]
Hereinafter, the present invention will be described in more detail to aid the understanding of the present invention.
[43]
The terms or words used in the specification and claims are general and not be construed as limited to the dictionary meanings are not, the inventor can adequately define terms to describe his own invention in the best way on the basis of the principle that the interpreted based on the meanings and concepts corresponding to technical aspects of the present invention.
[44]
[45]
The invention the surface properties, by proceeding polymerization reaction, while maintaining the foam level of the generated during the polymerization reaction in the suspension polymerization using a reflux condenser in an appropriate value, such as fish less child generation to transparency and producing a superior vinyl polymer Chloride number of vinyl chloride polymer provides a process for the preparation of that.
[46]
Method of producing a vinyl chloride polymer according to one embodiment of the present invention In the reaction containing the polymerization initiator, a suspension stabilizer and the vinyl chloride monomer in a polymerization reactor equipped with a reflux condenser on the top of the column, and the step of suspension polymerization (Step A ) and wherein the suspension polymerization is to perform while controlling such that in the form level polymerization reactor maintained at less than 10%, the foam level is above the reaction outermost surface in the full-height distance from the surface within the reaction outermost polymerization reactor to a polymerization reactor, the top of the column a will represent the ratio of the thickness of the generated foam, the foam level is characterized by regulating the input of anti-foaming agent.
[47]
[48]
Specifically, the reaction of the step A comprises a polymerization initiator, a suspension stabilizer and the vinyl chloride monomer in a polymerization reactor equipped with a step for producing a vinyl chloride polymer by polymerizing vinyl chloride monomer, a reflux condenser on the top of the column input and it may perform the combined suspension.
[49]
[50]
In one embodiment of the present invention, the vinyl chloride-based monomers may be one, which means, or means a mixture of vinyl chloride monomer and this is copolymerized vinyl monomer of pure vinyl chloride monomer. That is, vinyl chloride polymer, according to one embodiment of the present invention can be not only a polymer consisting of a vinyl chloride monomer and the vinyl chloride monomer as the main component include a copolymer of the vinyl chloride monomer and a copolymerizable vinyl monomer. In this case, the vinyl chloride-based monomer when a mixture of vinyl monomers are vinyl monomers, and this copolymer chloride as possible is used in the My chloride with a vinyl-based polymer chloride prepared therefrom appropriately controlled by the weight ratio to be at least 50% It may be.
[51]
As the vinyl chloride monomer and a copolymerizable vinyl monomer is not particularly limited, for example, olefins (olefin) compounds, such as ethylene, propylene and butene; Vinyl esters (vinyl ester) such as vinyl acetate and vinyl propionate, vinyl stearate and the like; Unsaturated nitriles such as acrylonitrile; Vinyl methyl ether, vinyl ethyl ether, vinyl octyl ether, vinyl lauryl ether, vinyl alkyl ether and the like; Halogenated vinylidene (vinylidene) acids, such as vinylidene chloride; Acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, maleic anhydride, itaconic anhydride, etc. of the unsaturated acids and anhydrides of these acids; Unsaturated fatty acid esters such as methyl acrylate, ethyl acrylate, maleic acid monomethyl maleate, dimethyl maleate, butyl benzyl; Di, and the like cross-linking monomer such as diallyl phthalate, the vinyl monomers may be used alone or as a mixture of two or more.
[52]
[53]
The suspension stabilizing agent is an additive which acts to stabilize the reaction product of the polymerization of the vinyl chloride polymer was uniform and produced a stable particle, but are not particularly limited and the vinyl chloride-based monomer based on 100 parts by weight 0.03 parts by weight to 5 parts by weight It may be used for parts. If, when the suspension stabilizer used is less than 0.03 parts by weight, it is the particle size of the final vinyl polymer chloride produced by the excessively increased, and the potential for Miguel ring particles to a molded article produced by using a vinyl-based polymer wherein the chloride , it may occur due to an increase of finally the vinyl-based polymer microparticles in chloride prepared in the initial coloring property degradation of the produced molded article using the vinyl chloride-based polymer, when used in excess of 5 parts by weight.
[54]
The suspension stabilizer may be the intended one kind or a mixture of two selected from the group consisting of vinyl alcohol resin, cellulose and unsaturated organic acid polymer, specifically, the suspension stabilizer is polyvinyl alcohol-based resin and the cellulose can be mixed mixture have. At this time, the mixing ratio of the vinyl alcohol-based resin and the cellulose can be mixed with properly adjusted, as desired is not particularly limited but, for example, vinyl alcohol-based resin and the cellulose is from 5 to 9: mixing in a weight ratio of from 1 to 7 It may be. In addition, the vinyl alcohol-based resin is hydrated may be also is in the 50 weight% of a second polyvinyl alcohol 90 weight% or less, the first polyvinyl alcohol with moisture content of 30% to 50% by weight blend mixture. In this case, the first poly (vinyl alcohol) and a second polyvinyl alcohol is not particularly limited, for example, 2 to 1: may be mixed in a weight ratio of 1 to 2.
[55]
Further, the cellulose or the like is not particularly limited, methyl cellulose, hydroxyethyl cellulose or hydroxypropyl methyl cellulose, and may be any one of these or a mixture of two or more. May be these, hydroxypropyl methylcellulose, specifically, a 2% aqueous solution viscosity of 10 cps to 20,000 cps in the content of groups in hydroxypropyl molecule from 3% to 20% by weight, 23 ± 5 ℃ It may be.
[56]
Further, the unsaturated organic acid polymer may be an acrylic acid polymer, methacrylic acid polymer, itaconic acid polymer, fumaric acid polymer, maleic acid polymer, and the like, or acid polymer, any one or a mixture of two or more of them.
[57]
[58]
The polymerization initiator relative to the vinyl chloride monomer to 100 parts by weight used in the polymerization can be used as part of 0.02 part by weight to 0.2 parts by weight, and the like. If the content of the polymerization initiator is 0.02 parts by weight of less than if prolongs the polymerization time, and the possibility that the conversion of a vinyl chloride polymer low deterioration in productivity, the polymerization initiator is not completely consumed in the polymerization process, when it exceeds 0.2 parts by weight not final manufacturing a vinyl chloride-based polymer to remain in the physical properties of the polymer, in particular, there is a possibility to degrade the thermal stability.
[59]
The polymerization initiator is not particularly limited, for example peroxide compounds such as dicumyl peroxide, diphenhydramine tilpeo peroxide, di -3,5,5- trimethyl hexanoyl peroxide or dilauryl peroxide; Diisopropyl peroxydicarbonate, peroxydicarbonate-based compounds, such as di -sec- butyl peroxydicarbonate or di-2-ethylhexyl peroxydicarbonate; t- butyl peroxypivalate, 1,1,3,3-tetramethylbutyl peroxyneodecanoate or t- butyl peroxy neo having peroxy ester compounds such as decanoate; Azo compounds such as azobis-nitrile 2,4-dimethylvaleronitrile; Hydroperoxide-based compound such as t- butyl hydroperoxide; Or potassium persulfate, and the like sulfated compounds such as ammonium persulfate, there is any one or a mixture of two or more of them may be used.
[60]
[61]
The suspension polymerization may be to perform control so as to keep the foam level in the polymerization reactor up to 10%, as described above. At this point, the foam level may be to adjust by putting a defoaming agent.
[62]
The term "foam level (foam level)" in the present invention indicates the degree of occurrence of foam produced during the polymerization reaction, the foam thickness of the raised above reaction is an outermost surface (the top) in the total height from the reaction outermost surface to the polymerization reactor, the top of the column It may be a means occupying ratio. That is, the foam level may be indicated by the height by the thickness of the foam occupying formed on the outermost surface reactants to the overall height of the reaction product from the outermost surface to the polymerization reactor, the top of the column at 100% in percentage. For example, when the total height of 100 cm from the outermost surface reactants to the polymerization reactor, the top of the column, the foam thickness of the reactant formed on the outermost surface of 20 cm has the foam level may be equal to 20%. Here, the reaction product is a liquid of any substance used in the polymerization reaction present in addition may be one that contains all the additives used, and thus the polymerization reactor, as desired in addition to the polymerization initiator, a suspension stabilizer and the vinyl monomer chloride above It may be an indication of the mixture.
[63]
More specifically, the suspension polymerization can be to do with controlling the foam level by introducing the anti-foaming agent so that the foam level inside the polymerization reactor maintained at less than 10%. More specifically, it may be to control the foam level by introducing the anti-foaming agent to be kept below 8%. Here, in the above form, the level of 10% point can be the point with the thickness of the foam thickness has occurred in the reaction is an outermost surface corresponding from within the reaction outermost surface of the polymerization reactor to 10% of the height of the assumption height of 100% of the polymerization reactor up to the top of the column have.
[64]
[65]
In addition, the foam level may be measured through the foam detector (foam detector).
[66]
The foam detector is separated from the reflux condenser to the polymerization reactor, the top of the column is provided separately, and in part, may be inserted into the above polymerization reactor column top, the bottom of the insert form the detector is turned anti-foaming agent to the polymerization reactor, the height direction of the line compared to It may be positioned at the top. In addition, the bottom of the form, a detector may be positioned under the touch reaction outermost surface or outermost surface. At this time, if the bottom of the form detectors positioned under the outermost surface reactants may be positioned at the top than it is turned while the bottom of the anti-foaming agent in the form detectors contained in the reaction line.
[67]
[68]
On the other hand, the form detectors according to one embodiment of the present invention may be in non-contact form, the detector, in such a non-contact form, the detector, but can use the conventionally known in the art depending on what purpose is not particularly limited and, for example, radar a sensor or the like can be used.
[69]
[70]
That is, the suspension polymerization according to one embodiment of the present invention is continuously detected by a form-level occurring within the polymerization reactor during the polymerization reaction by a form, the detector, foam level by injecting the anti-foaming agent when the foam level is reached in more than a predetermined value a it may be to remain below 10%.
[71]
[72]
The defoaming agent may be added to a level of 3% or less in a form at least 10% point, specifically, may be to form the input to the level of 8% or less than 5% of the time. If, when the input to the anti-foaming agent at the time the foam level is less than 3% being reduced in fish eyes amount produced vinyl polymer chloride and surface properties like are improved surface properties as compared geoe that the amount of one anti-foaming agent increases the degree of insignificant, and rather may result in a problem that the transparency and Haze by using a large amount of anti-foaming agent degradation. On the other hand, if the input to the anti-foaming agent at the time that the foam level in excess of 10% has a surface characteristic can be reduced by the amount in fish eyes produced vinyl chloride polymer significantly increased. In number and input method of the defoaming agent has no particular restrictions foam level measured by the foam detector could be to the batch input or form level each time it reaches the predetermined value added continuously until lowered to less than a certain value. In addition, the amount of dosage of the anti-foaming agent can be used to specifically not limited to appropriate adjustment in the amount that allows the purposes foam level but the amount of anti-foaming agent used is 0.1 parts by weight or less than the vinyl monomer 100 chloride parts by weight It may be used to. If the anti-foaming agent is a vinyl monomer to 100 parts by weight compared to 0.1 when used in an amount exceeding part, the form removed, and generation suppression fish eyes amount of the vinyl-based polymer chloride prepared's effect to the increase is reduced, the effect of chloride It is but may be, becomes the color of the vinyl chloride polymer suspended may cause a problem that transparency and Haze deteriorated.
[73]
[74]
In addition, the anti-foaming agent may be added to the anti-foaming agent through the fill stream provided to the polymerization reactor, the anti-foaming agent added line can be located at the mid-point in the overall height of the polymerization reactor from the bottom to the top of the column.
[75]
The term "bottom" used in the present invention is showing the bottom or base of the polymerization reactor, the "overhead" may be an indication of the uppermost or top portion of the polymerization reactor.
[76]
Specifically, the anti-foaming agent is a total distance from a bottom of the polymerization reactor through a defoamer input line which is located at an intermediate point in the whole height of the column top may be one which added into the polymerization reactor, in which the intermediate point is from the bottom of the polymerization reactor up to the top of the column It may be positioned at the 4/7 point to 5/7 from the bottom in the height. More specifically, the anti-foaming agent may be one input line which is located below the outermost surface of it while in a polymerization reactor which is located at an intermediate point during the overall height from a bottom of the polymerization reactor up to the top of the column reaction (top). Thus, anti-foaming agent injected it can be easily mixed with the polymerization reaction in the reactor even with the use of a small amount of defoaming agent can be improved foam removal and foam generation inhibitory effect.
[77]
[78]
Anti-foaming agent used in the suspension polymerization according to one embodiment of the invention, but can use the conventionally known in the art, it is not particularly limited, for example, polysiloxanes, dimethylpolysiloxane, di-phenyl silicone oils such as polysiloxanes; Aliphatic or aromatic alcohol of carbon number 10 to 30 and the like; Surface active agents such as a low degree of saponification of the polyvinyl alcohol; And polyester, and the like oxyalkylene glycols.
[79]
[80]
On the other hand, the suspension polymerization according to one embodiment of the present invention, conditions such as the polymerization temperature, other than those that do, while maintaining within the foam level polymerization reactor in the above-mentioned range is intended to perform properly adjusted, as desired it is not particularly limited can.
[81]
For example, the suspension polymerization can be performed at a temperature range of 30 ℃ to 70 ℃, the temperature may be suitably adjusted according to the degree of polymerization desired in the above-mentioned range. For example, the higher the desired degree of polymerization that the temperature may be lowered, it is an object The degree of polymerization is low, the temperature that may be as high.
[82]
Further, the suspension polymerization is the reactive species by putting billing may terminate the polymerization, and the termination point is 6 kg / cm pressure in the polymerization reactor 2 to 8 kg / cm 2, the time of exceeding (or a 85% polymerization conversion rate ) it may be the point.
[83]
The payment may be a reactive species not particularly limited, for example, a phenol compound, an amine compound, a nitrile compound, a sulfur compound. Specifically, the reactive species billing is triethylene glycol-bis -3- (3-t- butyl-4-hydroxy-5-methylphenyl) propionate, hydroquinone, p- methoxyphenol, t- butyl hydroxy hydroxy anisole, n- octadecyl-3- (4-hydroxy-3,5-di -t- butyl-phenyl) propionate, 2,5-di -t- butyl-hydroquinone, 4,4'- butylidenebis (3-methyl -6-t- butylphenol), t- butyl catechol, 4,4'-thiobis (6-t- butyl -m- cresol), phenol compounds, such as tocopherol, N, N '- diphenyl -p- phenylenediamine, 4,4'-bis (dimethyl benzyl) diphenyl amine compounds such as amine, 2-nitro-phenyl carbonyl nitro hydroxide (2-phenyl nitronylnitroxide), 3- imidazoline nitro hydroxide (3-imidazoline nitroxide), 4- hydroxy-2,2 ', 6,6'-tetramethyl-piperidine-1-oxyl (4-hydroxy-2,2', 6,6'- nitrile compounds, such as tetramethyl-piperidine-1-oxyl), dodecyl mercaptan, 1,2-may be at least one member selected from sulfur compounds, such as phenyl-2-thiol.
[84]
[85]
Further, the suspension polymerization can be used a solvent, the solvent may be deionized water. In this case, the solvent may also be used with appropriate adjustment according to the size of the amount and the polymerization of vinyl chloride monomer in a polymerization reactor is used, for example, be used more than 70 parts by weight based on the vinyl chloride monomer to 100 parts by weight.
[86]
[87]
In addition, the suspension polymerization may be further added an additive, such as the base material a polymerization adjusting agent as needed in addition to the active ingredient, a chain transfer agent, pH adjusting agent, an antioxidant, a crosslinking agent, an antistatic agent, a scale inhibitor, surfactant, the additive the type and the content may be used in an industry known conventional type, and the sugar content is not particularly limited. The additive may be added at any point in the suspension polymerization of seconds, polymerization during or after the polymerization, may be added at once or added continuously.
[88]
[89]
Production process according to the present invention may further comprise the step of drying after the step A, the drying may be carried out by commonly known methods in the art and is not particularly limited.
[90]
[91]
In addition, the present invention provides a vinyl chloride-based polymer prepared from the method of manufacturing the above.
[92]
Vinyl chloride polymer according to one embodiment of the present invention can have a good transparency by being manufactured through the manufacturing method of the above. Specifically, a vinyl-based polymer wherein the chloride may be one and the transparency is 84 to 85, the Haze is 6.5 to 7.0.
[93]
Also, the vinyl chloride-based polymer may have excellent surface properties, specifically, to the vinyl chloride-based polymer is fish-eye generation amount is less than 10, more specifically, it may be 5 or less.
[94]
[95]
Here, the transparency and Haze is a tin-based stabilizer 3 parts by weight of a lubricant 0.3 parts by weight into a 160 ℃ roll vinyl-based polymer to 100 parts by weight of the chloride of the above-] After the fabrication of the kneaded mill for 4 minutes 0.05 mm thick sheet, Haze-gard plus instrument (BYK-Gardner 社) is a value measured by using a, and the remaining materials except the vinyl chloride polymer is the transparency and Haze is expressed from a vinyl chloride polymer as the additive is added in order to facilitate sheet manufacture It will cost.
[96]
In addition, the fish eye generation by using added to the vinyl-based polymer to 100 parts by weight of chloride, dioctyl phthalate 45 parts by weight, stearic acid, barium, 0.1 part by weight of tin based stabilizer, 0.2 part by weight and 0.1 parts by weight of carbon black and 6 inches rolreul of 140 ℃ then a solution of 6 minutes kneading, and then a sheet of 0.3 mm thick, 100 cm 2 were measured to be within the area of white transparent particles.
[97]
[98]
Furthermore, the present invention provides an apparatus for producing a vinyl chloride polymer capable of producing a vinyl chloride polymer.
[99]
The apparatus for manufacturing a vinyl chloride-based polymer is a polymerization reactor according to an embodiment of the present invention; The reflux condenser was provided at the polymerization reactor, the top of the column; It is to the polymerization reactor separate from the overhead reflux condenser, a form provided with a separate detector; And it characterized in that it comprises an anti-foaming agent having the fill stream to an intermediate point in the polymerization reactor, the height direction.
[100]
The apparatus for manufacturing a vinyl chloride-based polymer can be used to carry out the production method of the aforementioned vinyl chloride-based polymer.
[101]
[102]
Hereinafter will be described a production apparatus of the vinyl chloride-based polymer according to an embodiment of the present invention with reference to Fig.
[103]
1 is a schematic illustration of a device for manufacturing a vinyl chloride polymer according to one embodiment of the present invention.
[104]
As shown in Fig. 1, the manufacturing apparatus 100 of the vinyl chloride polymer is a polymerization reactor (10); Reflux condenser (20); Form the detector 30; And it may include an anti-foaming agent In line 40. The reflux condenser 20 and form the detector 30 may be, which is provided separated from each other at a top of the polymerization reactor 10, the anti-foaming agent added line 40 is intermediate the height direction of the polymerization reactor (10) It may be one that is provided with a branch. Here, inside of the polymerization reactor 10 may be in which the agitator 50 is mounted.
[105]
The antifoaming agent In line 40 the polymerization reactor (10) and that for introducing an anti-foaming agent into the polymerization reactor 10 in the anti-foaming agent reservoir (T), which is provided separately, in the height direction of the polymerization reactor 10 4/7 to be one which is located on the 5/7 points, and, specifically, may be positioned at a lower point than the outermost surface (S) in the reaction (C) a polymerization reactor (10).
[106]
In addition, the form detectors 30 a polymerization reactor (10) intended to detect within the foam level, and are part can be inserted into the above polymerization reactor 10, the top of the column, the inserted form the detector 30, the bottom may be located in the upper polymerization reactor 10. in contrast anti-foaming agent line (40) in the height direction. Specifically, the bottom of the form detectors 30 are either in contact with the polymerization reactor 10 within the reaction product (C) an outermost surface (S) may be located below the outermost surface. That is, the bottom of the form detectors 30 may be positioned at the top compared to the polymerization reactor 10 within the reaction product in contact with an outermost surface (S), or while immersed in the reaction In the defoaming agent line (40).
[107]
[108]
And more specifically than that of the present invention by the following Examples and Experimental Examples. However, the following Examples and Experimental Examples are not limited the scope of the invention to these are for illustrating the invention.
[109]
[110]
Example 1
[111]
Also by using a production apparatus shown in Figure 1 was prepared a vinyl chloride polymer (100).
[112]
Specifically, deionized water, 390 kg, moisture content is 78.5% polyvinyl alcohol 150 g, moisture content is 40.7% polyvinyl alcohol 100 g, hydroxypropyl the reflux condenser (20) inside the polymerization reactor 10 is provided with a methyl cellulose 30 g batch added to the polymerization reactor 10 and charged into the di-2-ethylhexyl peroxydicarbonate 30 g, 120 g to Kano carbonate t- butylperoxy neo then added the vinyl chloride monomer to 300 kg while maintaining 57 ℃ advances the suspension polymerization reaction, when the foam level sensing to form the detector 30 reaches the 5%, anti-foaming agents in line 40, an anti-foaming agent added LDC-120A (Dow corning Co.) through the the polymerization was continued. At this time, the anti-foaming agent was such that the foam level is the amount added to the form level throughout the polymerization reaction that the 0.01 parts by weight to 100 parts by weight of vinyl chloride monomer over each time it reaches the 5% maintain more than 5%. Polymerization reactor 10, the pressure inside kg 6.3 / cm 2 -piperidin-1-oxyl 15 g, triethylene glycol-4-hydroxy-2,2,6,6-tetramethyl-you when you reach bis 3 - by (3-t- butyl-4-hydroxy-5-methylphenyl) propionate 60 g of carbonate to stop the reaction were charged into a polymerization reactor 10 and remove the unreacted monomers and the polymer slurry from the polymerization reactor 10 It was recovered. Drying the recovered polymer slurry to the fluid bed dryer to give a vinyl chloride polymer.
[113]
[114]
Example 2
[115]
And is a vinyl chloride polymer through the same procedure as in Example 1 except that the antifoaming agent who committed an amount corresponding to 0.01 parts by weight to 100 parts by weight of vinyl chloride monomer over each time it reaches the foam level is 3% detected as a foam detector It was obtained.
[116]
[117]
Example 3
[118]
And is a vinyl chloride polymer through the same procedure as in Example 1 except that the antifoaming agent who committed an amount corresponding to 0.01 parts by weight to 100 parts by weight of vinyl chloride monomer over each time it reaches the foam level is 10% detected as a foam detector It was obtained.
[119]
[120]
Comparative Example 1
[121]
By using a manufacturing device that is not provided with a anti-foaming agent fill stream to prepare a vinyl chloride polymer were combined suspension.
[122]
Specifically, the inner volume of 1 m provided with a reflux condenser 3 deionized water 390 kg, hydrated polyvinyl alcohol 150 is 78.5% g, moisture content is 40.7% polyvinyl alcohol 100 g, hydroxypropylmethyl the polymerization reactor cellulose 30 g batch added to the polymerization reactor and maintaining a 57 ℃ charged into the di-2-ethylhexyl peroxydicarbonate 30 g, t- butyl peroxy neo to Kano carbonate 120 g was charged into the vinyl monomer chloride 300 kg while the suspension was allowed to proceed polymerization. The polymerization reactor internal pressure of kg 6.3 / cm 2 at the time of reaching the 4-hydroxy-2,2,6,6-tetramethyl-piperidine-1-oxyl 15 g, triethylene glycol-bis 3- (3 in the -t- butyl-4-hydroxy-5-methylphenyl) propionate 60 g into a polymerization reactor (10) to terminate the reaction and was collected by removing the unreacted monomers and the polymer slurry from the polymerization reactor (10). Drying the recovered polymer slurry to the fluid bed dryer to give a vinyl chloride polymer.
[123]
[124]
Comparative Example 2
[125]
Example 1 to obtain a vinyl chloride polymer by the same method, except that the input with the anti-foaming agent and a polymerization initiator pre-polymerization initiator. In this case, the antifoaming agent was used in Example 1 in the same amount.
[126]
[127]
Comparative Example 3
[128]
Anti-foaming agent with a reflux condenser operating at the same time and subsequently to obtain a vinyl chloride polymer by the same method as in Example 2 except that the input. Here, the reflux condenser operating point may be a time of beginning to form a generation, may be a foam level is about 1% of the time. At this time, the anti-foaming agent was continuously added for 5 minutes, 0.01 parts by weight of a 5-minute interval.
[129]
[130]
Comparative Example 4
[131]
And vinyl chloride by the same method as in Example 3 except that the anti-foaming agent who committed an amount corresponding to 0.01 parts by weight to 100 parts by weight of vinyl chloride monomer over each time it reaches the foam level in the time of 15% detection with foam detector a polymer was obtained. In this case, the antifoaming agent was used in Example 3 in the same amount.
[132]
[133]
Comparative Example 5
[134]
And vinyl chloride by the same method as in Example 3 except that the anti-foaming agent who committed an amount corresponding to 0.01 parts by weight to 100 parts by weight of vinyl chloride monomer over each time it reaches the foam level in the time of 30% detection with foam detector a polymer was obtained.
[135]
[136]
Comparative Example 6
[137]
And vinyl chloride by the same method as in Example 3 except that the anti-foaming agent who committed an amount corresponding to 0.01 parts by weight to 100 parts by weight of vinyl chloride monomer over each time it reaches the foam level in the time of 70% detection with foam detector a polymer was obtained.
[138]
[139]
Comparative Example 7
[140]
And is a vinyl chloride polymer by the same method as in Example 3 except that the amount corresponding to the anti-foaming agent in 0.02 part by weight to 100 parts by weight of vinyl chloride monomer over each time it reaches the point in time at least one form, the level is 30% detected as a foam detector input It was obtained.
[141]
[142]
Comparative Example 8
[143]
Polymerization reactor (10) was obtained a vinyl chloride polymer by the same method as example 1 except that input through the top of the column a defoaming agent. In this case, the antifoaming agent was used as an anti-foaming agent used in Example 1 and the same amount.
[144]
[145]
Experimental Example 1
[146]
To the Examples 1 to 3 and Comparative Example 1 to Comparative A Comparative Analysis of the surface characteristics of the vinyl polymer chloride prepared in Example 8 was measured for average particle size, fish eyes (fish-eye) generation and transparency and Haze . The results are shown in Table 1.
[147]
1) Average particle diameter
[148]
The average particle size according to ASTM D1705 were determined to confirm that the average particle diameter of each of the vinyl chloride polymer.
[149]
[150]
2) Fish Eye generation
[151]
The addition of each vinyl chloride polymer 100 parts by weight of dioctyl phthalate (DOP), 45 parts by weight of stearic acid, barium, 0.1 part by weight of a tin-based stabilizer (MT800, Songwon Industrial Co.), 0.2 part by weight, 0.1 parts by weight of carbon black, and 6 inches of 140 ℃ after the mixture kneaded using a roll 6 minutes, to prepare each sheet having a thickness of 0.3 mm. In each sheet 100 cm 2 was measured to be within the area of white transparent particles.
[152]
[153]
3) Transparency and Haze
[154]
Each of the vinyl chloride polymer tin-based stabilizer (MT800, Songwon Industrial Co.) to 100 parts by weight 3 parts by weight of a lubricant (SL63, LG Chemical), 0.3 parts by weight adding portion, and a roll-mill at 160 ℃ 4 minutes to use (roll-mill) after the kneading was prepared for each sheet of 0.05 mm thickness. Each sheet using a Haze-gard plus (BYK-Gardner 社) was measured for transparency and Haze. Transparency indicates a higher value Great, Haze indicates a more excellent value is low.
[155]
TABLE 1
division Anti-foaming agent total amount (parts by weight) The maximum level of the polymerization form (%) Average particle size (㎛) Fish Eye emissions (more) transparency Haze
Example 1 0.05 5 135 5 84.5 6.87
Example 2 0.09 3 133 4 84.6 6.79
Example 3 0.03 10 135 5 84.5 6.8
Comparative Example 1 - 89 135 59 85.1 6.63
Comparative Example 2 0.05 36 154 23 84.5 7.02
Comparative Example 3 0.4 1 137 7 81.4 10.20
Comparative Example 4 0.03 15 138 10 82.7 9.2
Comparative Example 5 0.01 30 131 11 84.8 6.58
Comparative Example 6 0.01 70 135 18 84.7 6.71
Comparative Example 7 0.04 30 135 12 82.5 9.27
Comparative Example 8 0.05 19 133 14 83.2 8.39

[156]
[157]
As shown in Table 1, while showing the embodiments 1 to 3 excellent transparency and Haze Overall Vinyl chloride polymer is prepared in Comparative Example 1 to compare the vinyl chloride polymer of Example 8 according to the invention the fish-eye generation significantly at the same time it was confirmed that a decrease.
[158]
Specifically, the equivalent of the vinyl chloride polymer of the embodiment is manufactured while maintaining the foam level in accordance with the invention Examples 1 to 3 are compared to the vinyl polymer chloride of Comparative Example 1 (no added anti-foaming agents) manufactured without controlling the foam level indicating the transparency and Haze Fish Eye emissions were drastically reduced to a level of 1.12 to 1.15. In the case of the comparative vinyl chloride polymer of Example 2 prepared by introducing the anti-foaming agent is foam level in the polymerization reactor with the reactants in the polymerization before the start without commitment to maintain a certain level, the same amount as compared with the vinyl chloride polymer of Example 1 Despite the use of anti-foaming agent, and transparency and Haze has increased, but the Fish Eye emissions significantly to 5.7 times the level of similarity.
[159]
Also, the vinyl chloride polymer of Comparative Example 3 produced while maintaining a certain level present a form level in the present invention is less than the embodiment even though 2 Use of the vinyl chloride polymer and the anti-foaming agent more than four times, and the transparency and Haze decreases was fish eye generation amount is increased to 1.75 times, the vinyl chloride polymer of Comparative example 4 produced while maintaining the foam level to a level of more than a certain level, as compared to the vinyl chloride polymer of example 3, in spite of using the same amount of anti-foaming agent the transparency and Haze is reduced fish eye generation was significantly increased in the double level.
[160]
In addition, a comparative vinyl chloride polymer of Example 8, without commitment to a polymerization reactor, the mid-point input prepared by the top of the column, as provided an antifoaming agent in the present invention, though using the same amount of anti-foaming agent as compared to the vinyl chloride polymer of Example 1 Despite increased transparency and Haze in a Fish Eye or three times higher than the amount it falls.

Claims

[Claim 1]A polymerization initiator in a polymerization reactor equipped with a top with a reflux condenser, a suspension stabilizer and added the reaction containing the vinyl chloride monomer, and including the step of suspension polymerization and the suspension polymerization is maintained within the foam level, the polymerization reactor to less than 10% is to perform while controlling such that, the foam levels were the foam thickness of the raised above reaction is the outermost surface in the full-height distance from the surface within the reaction outermost polymerization reactor to a polymerization reactor, the top of the column indicating the occupied ratio, wherein the foam level is controlled by introducing an anti-foaming agent a method for producing a vinyl chloride-based polymer to.
[Claim 2]
The method according to claim 1, wherein the defoamer is a method for producing a vinyl chloride-based polymer to form the input to the level of not more than 10% time of more than 3%.
[Claim 3]
The method according to claim 1, wherein the defoaming agent is an anti-foaming agent will be introduced through the input line, the input line is a defoaming agent The method of producing a vinyl chloride polymer to which is located in the mid-point of the polymerization reactor in the height direction comprising a polymerization reactor.
[Claim 4]
The method according to claim 3, wherein the anti-foaming agent In line method of producing a vinyl chloride polymer to position the whole of 4/7 to 5/7 of the height from the bottom spot in the bottom of the polymerization reactor up to the top of the column.
[Claim 5]
The method according to claim 1, wherein the foam level is an exemplary measurement through the foam detector, the foam detector is provided separate from the reflux condenser to the polymerization reactor, the top of the column separately, part of the form, the detector is to inserted into the above polymerization reactor overhead a method for producing a vinyl chloride polymer.
[Claim 6]
A polymerization reactor; The reflux condenser was provided at the polymerization reactor, the top of the column; It is to the polymerization reactor separate from the overhead reflux condenser, a form provided with a separate detector; And an anti-foaming agent fill stream chloride production apparatus of the vinyl-based polymer containing having a mid-point of the polymerization reactor in the height direction.
[Claim 7]
According to claim 6, wherein said anti-foaming agent added line is a vinyl chloride-based apparatus for manufacturing a polymer to position the whole of 4/7 to 5/7 of the height from the bottom point of the polymerization reactor bottom to the top of the column.
[Claim 8]
The method according to claim 6, wherein the vinyl-based polymer chloride to a portion of the form, the detector will be inserted into the polymerization reactor, the top of the column, the bottom of the form, the detector is inserted in the inner position to the upper than the point at which the anti-foaming agent In line position of the production apparatus.