[1][Mutual citations and related applications;
[2]This application claims the benefit of priority based on party 06.21.2016 Korea Patent Application No. 10-2016-0077236 29.05.2017 and Now Korea Patent Application No. 10-2017-0066099, all described in the literature of the Korea Patent Application content of which is incorporated as a part hereof.
[3][Technology]
[4]The present invention relates to that, more specifically, the production method of the vinyl chloride polymer to improve the melt processability relates to a process for the preparation of vinyl chloride polymer.
[5]
BACKGROUND
[6]
Vinyl chloride-based polymer is a polymer containing repeating units derived from vinyl chloride monomer (Vinyl Chloride Monomer, VCM) at least 50% by weight, and inexpensive and easy hardness adjustment, application and is applicable to most of the processing device the diverse. 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. In particular, for the light is used as a pipe (pipe), the chassis (sash), etc., for soft is used as such packaging wraps (wrapping vinyl), a film (film), the sheet (sheet). In addition, high degree of polymerization for vinyl chloride polymers such as coated and special gaskets (gasket) of the high-strength and heat-resistant electric wire according to the physical property may be used.
[7]
However, the high degree of polymerization for the vinyl chloride polymer, the melt processability is lowered compared to the hard or soft vinyl chloride-based polymer is used as a general purpose product, there is a disadvantage that the productivity in processing a molded article falls.
[8]
Thus, if the up-regulation of the working temperature to improve the melt processability, and due to the structural characteristics of the vinyl chloride polymer is a problem that color fading has occurred. Further, a case to inject the plasticizer during processing, one can be processed Although even at low temperatures, due to the plasticizer is left in the work piece greatly affects the physical properties of the work piece, limited in its usage.
[9]
Therefore, a situation that is constantly required in the relevant industry, efforts to improve the melt processability of the high polymerization degree vinyl chloride polymer.
[10]
Detailed Description of the Invention
SUMMARY
[11]
The invention do not have to have affected the basic polymerization properties of that, such as the polymerization time and the degree of polymerization by putting the chain control agent (activated chain regulator) activating the initial stage of polymerization of a vinyl chloride polymer made in view of solving the problems of the prior art even, an object of the present invention to provide a vinyl chloride-based polymer production process to improve the melt processability.
[12]
Problem solving means
[13]
Step (S1), which, according to one embodiment of the present invention for solving the above problems, the present invention is preparing a mixture of a mixture of a first protective colloid (protective colloid) Preparation and chain control agent (chain regulator); Preparing a second protective colloid preparation comprising a chain control agent activated by stirring the mixture prepared in the above (S1) step (S2); And in the presence of a second protective colloid preparation prepared in (S2) step, a step (S3) of polymerizing the added vinyl chloride monomer and a polymerization initiator, and the mixture was stirred at (S2) step is 70 rpm to about 100 rpm 10-minute stirring speed to provide a vinyl chloride-based polymer production method is carried out for 40 minutes.
[14]
Effects of the Invention
[15]
The protective colloid additive In the initial stage of polymerization, according to the present invention, pre-stirred for chain control agent, by charging together with the activated state, having a polymerization time and the degree of polymerization, such as basic polymerization properties is even, a large particle size without affecting the distribution of the , side chain has the effect that to prepare a vinyl chloride polymer containing the (side chain), provides a method of producing during the processing of the resulting vinyl chloride polymer, the melt processability is the significant improvement in the vinyl chloride-based polymer.
[16]
Best Mode for Carrying Out the Invention
[17]
Hereinafter, the present invention will be described in more detail to aid the understanding of the present invention.
[18]
The terms or words used in the description and claims of the present invention is general and not be construed as limited to the dictionary meanings are not, the inventor accordingly the concept of a term to describe his own invention in the best way on the basis of the principle that can be defined, which must be interpreted based on the meanings and concepts corresponding to technical aspects of the present invention.
[19]
[20]
Vinyl chloride-based polymer production process of the present invention according to that using the characteristic of increasing the polymerization efficiency in a short time to improve the activity of the chain control agent, in one embodiment, the first protective colloid (protective colloid) Preparation and chain control agent (chain regulator ) is to prepare a mixed mixture (S1); Preparing a second protective colloid preparation comprising a chain control agent activated by stirring the mixture prepared in the above (S1) step (S2); And in the presence of a second protective colloid preparation prepared in (S2) step, a step (S3) of polymerizing the added vinyl chloride monomer and a polymerization initiator, and the mixture was stirred at (S2) step is 70 rpm to about 100 rpm in may be conducted for 10 to 40 minutes with agitation speed.
[21]
Polymerization of the present invention may be a means for suspension polymerization (suspension polymerization) unless otherwise defined.
[22]
The activity enhancing properties of the chain control agent according to the invention compared with when the power is applied to be expressed through the stirring with the first protective colloid preparation, the in each, one without agitation and a protective colloid prepared separately chloride, having a high polymerization degree be the polymerization of the vinyl-based polymer and, while the mechanical properties of the vinyl chloride polymer is held, is further improved melt processability of this, there is an effect that productivity is significantly improved. That is, in the case of pre-stirring the chain modifier, and a first protective colloid preparation, via a chain reaction such as a transesterification reaction between the ester functional group of the chain control agent in the first protective colloid alcohol of preparation functional chain control and I to be activated, this through, and further improve the only chain melt processability improved and the dispersibility improvement over the first protective colloids prepared through the modulators each effect, to enable the polymerization of the vinyl chloride polymer with a high polymerization degree, as described above, the vinyl chloride polymer while a high degree of polymerization of the can exhibit a synergistic effect the melt-processability and productivity are significantly improved.
[23]
According to one embodiment of the invention the first protective colloid preparation may mean a hydrophilic colloid (hydrophilic colloid) is used in order to reduce the instability of the electrolyte of the vinyl monomer chloride few colloidal (hydrophobic colloid), for example Water can be dissolved in the first dispersion stability to the (aqueous phase), it may be a specific example of the water-soluble polymer.
[24]
The first protective colloid preparation of the present invention may be a polyvinyl alcohol as an example, the specific examples, the polyvinyl alcohol may have a number average degree of polymerization may be from 1,000 to 3,500, 1,100 to 3,300, or 1,200 to 3,100, another example number may be an average degree of polymerization of 1,250 to 1,320, 1,650 to 1,750 or 2,900 to 3,100 polyvinyl alcohol first mixed or more kinds, excellent is the range protection during suspension polymerization colloid action in effect, that the activation is easy effect of chain control agent have.
[25]
As another example, the polyvinyl alcohol is moisture content that may be 60 mol% to 90 mol%, 65 mol% to 89 mol%, or 72 mol% to 88 mol%, polyvinyl having a high degree of hydration in the range alcohol primary when it is used as a first protective colloid preparation for the dispersants role, excellent protection during suspension polymerization colloidal action and effect, there is one enable easy effect of chain control agent, wherein the polyvinyl alcohol is in the range of the moisture content different sign language may be also mixed two or more kinds selected from the group consisting of polyvinyl alcohol having a specific example, the sign language as a first embodiment of the present invention is 72 mol%, polyvinyl alcohol and moisture content is 88 mol% but it can use a mixture of polyvinyl alcohol, but is not limited thereto.
[26]
According to one embodiment of the invention, the first protecting the content of the colloidal preparation is in the range of 0.01 parts by weight to 1 part by weight per 100 parts by weight of the vinyl chloride monomer, 0.02 part by weight to 0.5 parts by weight or 0.03 parts by weight to 0.1 parts by weight may be used, this range is then in the stability of the polymerization process in the solid, and the polymerization is excellent in productivity and the residual monomers recovered easily effect.
[27]
The chain control agent of the present invention is to improve the polymerization degree of vinyl chloride polymer, diallyl phthalate, allyl methacrylate, diallyl maleate, triallyl isocyanurate, pentaerythritol triallyl ether, ethyl glycol dimethyl acrylate, diallyl maleate may be at least one selected from the group consisting of light (having 6 to 30 carbon atoms, or carbon atoms, an aryl group of 10 to 30), and divinylbenzene, may be a phthalate specifically allyl di, the while if the number average degree of polymerization is 1,000 or higher production of vinyl chloride-based polymer available, there is excellent in melt processability effect.
[28]
According to one embodiment of the invention, the amount of the chain control agent is from 0.01 part by weight to 0.5 parts by weight per 100 parts by weight of the vinyl chloride monomer, 0.05 part by weight to 0.05 parts by weight or 0.08 parts by weight to 0.2 parts by weight can Buil and, the basic physical properties of the polymerization, such as the range and yet the production of vinyl chloride polymers of the degree of polymerization be within a polymerization time and the degree of polymerization does not affect the quality, it is excellent in melt processability effect.
[29]
According to one embodiment of the present invention, the stirring in (S2) step may be performed for 10 to 40 minutes, 15 minutes to 30 minutes, or 10 minutes to 20 minutes, a second protective colloid within the range in the preparation has an effect, the activity of the chain control agent is significantly improved.
[30]
According to one embodiment of the invention, when the stirring in (S2) step can be carried out by 70 rpm to about 100 rpm, 80 rpm to 100 rpm, or 90 rpm to 100 rpm, and stirred at these conditions the in the second protective colloidal preparation it has the effect that the activity of the chain control agent significantly improved.
[31]
Specifically, according to one embodiment of the present invention, the stirring in (S2) step may be performed for 10 to 40 minutes with a stirring speed of 70 rpm to 100 rpm, as described above, more specifically, 90 10 minutes by a stirring speed of rpm to 100 rpm to be carried out for 20 minutes.
[32]
More specifically, according to one embodiment of the present invention stirred at said (S2) step is for 40 minutes with agitation speed of 70 rpm, for 10 minutes with a stirring rate of 20 minutes or 100 rpm as the stirring rate of 90 rpm embodiment can be.
[33]
[34]
The vinyl chloride-based monomer of the present invention, vinyl chloride monomer (VCM) can be meant to include both a single or a vinyl chloride monomer and a copolymerizable vinyl-based monomers, vinyl-based monomers wherein the copolymer is an olefin such as ethylene, propylene compound; Vinyl esters, unsaturated nitriles such as acrylonitrile, acrylic acids such as vinyl acetate and vinyl propionate; Vinyl methyl ether, vinyl alkyl ethers such as vinyl ethyl ether; And acrylic acid, methacrylic acid, itaconic acid, unsaturated acids and anhydrides of these acids such as maleic acid; be at least one selected from the group consisting of and, if it contains copolymerized vinyl-based monomer other than the vinyl chloride monomer alone or vinyl chloride based on the polymer, and the content of repeating units derived from vinyl chloride monomer (VCM) it is at least 50% by weight.
[35]
[36]
The polymerization initiator of the present invention as long as they can be used in the polymerization of vinyl chloride-based polymer is not particularly limited, for example α, α'- bis (decanoyl neo-butylperoxy) diisopropylbenzene, cumene peroxyneodecanoate , di -n- propyl peroxy dicarbonate, diisopropyl peroxy dicarbonate, 1,1,3,3-tetramethylbutyl peroxyneodecanoate, bis (4-t- butylcyclohexyl) peroxy di carbonate, 1-cyclohexyl-1-methylethyl peroxyneodecanoate, di-2-ethoxyethyl peroxy dicarbonate, di-2-ethylhexyl peroxy dicarbonate, t- hexyl peroxyneodecanoate , dimethoxy-butylperoxy dicarbonate, bis (3-methyl-3-methoxybutyl) peroxy dicarbonate, t- butyl peroxyneodecanoate, t- hexyl peroxypivalate, such as peroxides; And 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis the group consisting of azo compounds such as (isobutyronitrile), dimethyl 2.2'- azobis (isobutyrate) It may be at least one selected from the.
[37]
According to one embodiment of the invention, the polymerization initiator with respect with respect to 100 parts by weight of the vinyl chloride monomer 0.01 parts by weight to 0.5 parts by weight, 0.05 parts by weight to 0.05 parts by weight or 0.05 parts by weight to 0.1 parts by weight can Buil and , the stability of the process at the time of polymerization in this range has an excellent effect.
[38]
[39]
According to one embodiment of the invention, the polymerization of the (S3) step has the effect that the third can be carried out in a protective colloid preparation further comprises, possible in this case, further enhance the protection during a suspension polymerization a colloidal action and effect . The third protective colloid prepared is cellulose-based compound, polyethylene glycol, starch, dextrin, water-soluble for example, polyvinylpyrrolidone, Polystyrol -b- polyethylene oxide-block copolymer, and poly (ethylene oxide) -b- methacrylate-block may be at least one selected from the group consisting of a copolymer, preferably a cellulose-based compound may be a water-soluble, the water-soluble cellulose-based compound may be a hydroxyalkyl cellulose for example concrete. In this case, the alkyl group may be a linear or branched alkyl group having 1 to 10 carbon atoms, or 1 to 5.
[40]
[41]
According to one embodiment of the invention, the (S3) the polymerization of the step may be carried out at 48 ℃ to 62 ℃, 50 ℃ to 60 ℃, or 50 ℃ to 58 ℃, the chain control agent is added to the polymerization as an example It can be adjusted according to the content of, and, if the content of chain control agent may be increased by increasing the polymerization degree the polymerization temperature. Specific examples, in the case of In the present invention of Examples 1 to 3 with 0.08 parts by weight of a chain modifier, such as a, it is possible to carry out polymerization at 54 ℃, if added 0.1 parts by weight of a chain regulator, to carry out polymerization at 56 ℃ and can, when added 0.13 parts by weight of a chain regulator, but can be subjected to polymerization at 58 ℃, but is not limited thereto. In this way, there is the excellent effect process stability during the polymerization when the polymerization temperature to increase even as the amount of chain control agent increases.
[42]
[43]
Further, prepared in the above (S2) step of the present invention, the second protective colloidal preparation, according to the vinyl-based polymer production process chloride of the present invention, the polymerization which is converted to polymer to be added above in (S3) step, i.e., before the onset of polymerization it is preferred in terms of maximizing the efficiency. After that, the start of polymerization not before start of polymerization as in the present invention the polymerization medium additional protective colloid preparation or separate chain control agent is added to the degree of polymerization is difficult to control and is not get a high degree of polymerization of the vinyl chloride polymers to aim.
[44]
[45]
One embodiment the vinyl polymer chloride prepared in accordance with embodiments of the present invention, including the derived chain control agent functional group, and the number average degree of polymerization of 1,300 to 3,000, and the average particle diameter is 100 ㎛ to 200 ㎛, the particle size distribution of 1.8 to 2.5 days can.
[46]
The number average degree of polymerization is to mean the average number of repeating units in the polymer chain, the number may be calculated from the ratio of the average molecular weight for the molecular weight of the repeating units, to 1,300 for example 3,000, 1,300 to 2,500, or 1,300 to 2,000 one may be, may be a specific example 1,300 to 1,700.
[47]
The average particle size may be different according to the number-average degree of polymerization of the vinyl chloride polymer for example, and specific examples 140 ㎛ to 200 ㎛ If the average polymerization degree of the number of vinyl chloride polymer 1,300, 140 ㎛ to 160 ㎛, or 140 ㎛ to be 150 ㎛, and also when another example of the average degree of polymerisation is the number of vinyl chloride polymer 17 may be a 100 ㎛ to 140 ㎛, 120 ㎛ to 140 ㎛, or 120 ㎛ to 130 ㎛, high polymerization degree within the range mechanical properties of the vinyl chloride polymer is maintained, yet, there is an effect the melt processability in processing is remarkably improved.
[48]
The particle size distribution may be different according to the number-average degree of polymerization of the vinyl chloride polymer as an example, in the case specific examples of the average degree of polymerisation is the number of vinyl chloride polymer 1,300 2.1 to 2.5, 2.1 to 2.3, or 2.1 to number and one 2.2 , and when another example of the average degree of polymerisation is the number of vinyl chloride polymer 17 may be from 1.8 to 2.1, 1.9 to 2.1, or 1.9 to 2.0, the mechanical properties of a high polymerization degree vinyl polymer chloride within this range while maintaining and processing is effective in melt processability is remarkably improved.
[49]
The average particle size and particle size distribution by using the optical laser method particle measuring instrument, the sample unit (sample unit) of powder (powder) is measured from the angle of light size is diffracted depending on the size of the particles as they pass through the cell (cell) It may be a value the average particle diameter and particle size distribution.
[50]
[51]
And to more specifically explain the present invention by the following examples. However, the Examples are not limited the scope of the invention to these are for illustrating the invention.
[52]
[53]
Example
[54]
Example 1
[55]
Moisture content is 88 mol% polyvinyl alcohol 0.05 parts by weight and the moisture content is mixed by introducing 72 mol% of poly (vinyl alcohol) 0.02 parts by weight diallyl the prepared stirrer phthalate 0.08 part by weight of allyl di and stirred for 20 minutes with 90 rpm the phthalate is activated mixture was prepared.
[56]
Reflux condenser and a stirrer was attached to the inner volume of 1 m 3 in a stainless polymerization reactor, the mixture and the polymerization can be 140 parts by weight of hydroxypropyl methyl cellulose 0.005 weight parts of In, and subsequently to the polymerization reactor, t- butyl peroxy neo the polymerization in the decanoate 0.088 after adding parts by weight, after degassing the interior and at the same time stirred by a vacuum pump, and the polymerization temperature 54 ℃ to input 100 parts by weight vinyl chloride monomer (VCM) parts and to achieve a number-average degree of polymerization of 1,300 were used . Then, the pressure in the polymerization reactor, kg 1.0 / cm 2 , the polymerization was stopped at this point occurs a change in the. Here, as an antioxidant triethylene glycol-bis- [3- (3-t- butyl-5-methyl-4-hydroxyphenyl) propionate 0.05 part by weight and additives eugenol (4-allyl-2- It was added methoxy-phenol), 0.05 parts by weight, and then recovering the unreacted monomer, the polymer slurry was recovered from the polymerization reactor. Then, the thus obtained polymer slurry was dried using a conventional fluidized bed dryer can be a final average degree of polymerization of 1,300, and a gel content of 1.35% by weight, and the average particle diameter of 141 ㎛, vinyl polymers chloride has a particle size distribution between 2.1 and 2.2 It was obtained.
[57]
The gel content after the resultant vinyl chloride polymer sample 0.2 g in was dissolved in 50 ℃ in THF 20 ml for 24 hours, using a centrifuge (6,000 rpm, 20 minutes) separating the gel, and 80 ℃ 1 time Drying by measuring the weight, it was calculated by the following formula.
[58]
* Gel content (% by weight) = (centrifugal separation and then dried weight / sample weight) x 100
[59]
The average particle size and particle size distribution by using the optical laser method particle measuring instrument, the sample unit (sample unit) of powder (powder) is measured from the angle of light size is diffracted depending on the size of the particles as they pass through the cell (cell) the average particle diameter and particle size distribution values ​​are shown in the error range.
[60]
[61]
Example 2
[62]
And In the diallyl phthalate amount of 0.1 parts by weight, and the number was performed by the average degree of polymerization and the above embodiment except that subjected to polymerization at a polymerization temperature of 56 ℃ to achieve the 1,300 Example 1 in the same manner, the final number average polymerization degree of 1,300, the gel content of 1.37% by weight, and the average particle diameter of 141 ㎛, the particle size distribution to give a vinyl chloride polymer 2.1 to 2.2.
[63]
[64]
Example 3
[65]
D. In a diallyl phthalate parts of 0.13 wt., And the number was performed in the same manner as in Example 1, except that in order to achieve an average polymerization degree of 1,300 subjected to polymerization at a polymerization temperature of 58 ℃, and finally a number average degree of polymerization of 1,300, the gel content of 2.32% by weight, and the average particle diameter of 142 ㎛, the particle size distribution to give a vinyl chloride polymer 2.1 to 2.2.
[66]
[67]
Example 4
[68]
In a diallyl phthalate parts of 0.04 wt., And the number was performed in the same manner as in Example 1, except that in order to achieve an average polymerization degree of 1,700 subjected to polymerization at a polymerization temperature of 50 ℃, and finally a number average degree of polymerization of 1,700, the gel content of 1.21% by weight, and the average particle diameter of 121 ㎛, the particle size distribution to give a vinyl chloride polymer, from 1.9 to 2.0.
[69]
[70]
Example 5
[71]
In a diallyl phthalate parts of 0.06 wt., And the number was performed in the same manner as in Example 1, except that in order to achieve an average polymerization degree of 1,300 subjected to polymerization at a polymerization temperature of 51 ℃, and finally a number average degree of polymerization of 1,700, the gel content of 1.26% by weight, and the average particle diameter of 121 ㎛, the particle size distribution to give a vinyl chloride polymer, from 1.9 to 2.0.
[72]
[73]
Example 6
[74]
And In the diallyl phthalate amount of 0.1 parts by weight, and the number was performed by the average degree of polymerization and the above embodiment except that subjected to polymerization at a polymerization temperature of 53 ℃ to achieve the 1,700 Example 1 in the same manner, the final number average polymerization degree of 1,700, the gel content of 1.32% by weight, and the average particle diameter of 122 ㎛, the particle size distribution to give a vinyl chloride polymer, from 1.9 to 2.0.
[75]
[76]
Example 7
[77]
And In the diallyl phthalate portion 0.2, and the number was performed by the average degree of polymerization and the above embodiment except that subjected to polymerization at a polymerization temperature of 55 ℃ to achieve the 1,700 Example 1 in the same manner, the final number average polymerization degree of 1,700, the gel content of 4.78% by weight, and the average particle diameter of 122 ㎛, the particle size distribution to give a vinyl chloride polymer, from 1.9 to 2.0.
[78]
[79]
Example 8
[80]
The moisture content is stirred for 88 mol% of poly (vinyl alcohol) 0.05 parts by weight and the moisture content is mixed by introducing 72 mol% of poly (vinyl alcohol) 0.02 parts by weight diallyl the prepared stirrer phthalate 0.1 parts by weight, 10 minutes to 70 rpm D and preparing a mixture of a diallyl phthalate activated, the number was performed by the average degree of polymerization and the above embodiment except that subjected to polymerization at a polymerization temperature of 56 ℃ to achieve the 1,300 example 1 in the same manner, the final number average polymerization degree of 1,300, the gel content of 1.37% by weight, and the average particle diameter of 146 ㎛, the particle size distribution to give a vinyl chloride polymer 2.1 to 2.2.
[81]
[82]
Example 9
[83]
The moisture content is stirred for 88 mol% of poly (vinyl alcohol) 0.05 parts by weight and the moisture content is mixed by introducing 72 mol% of poly (vinyl alcohol) 0.02 parts by weight diallyl the prepared stirrer phthalate 0.1 parts by weight, with 70 rpm 40 bun di and preparing a mixture of a diallyl phthalate activated, the number was performed by the average degree of polymerization and the above embodiment except that subjected to polymerization at a polymerization temperature of 56 ℃ to achieve the 1,300 example 1 in the same manner, the final number average polymerization degree of 1,300, the gel content of 1.37% by weight, and the average particle diameter of 145 ㎛, the particle size distribution to give a vinyl chloride polymer 2.1 to 2.2.
[84]
[85]
Example 10
[86]
The moisture content is stirred for 88 mol% of poly (vinyl alcohol) 0.05 parts by weight and the moisture content is mixed by introducing 72 mol% of poly (vinyl alcohol) 0.02 parts by weight diallyl the prepared stirrer phthalate 0.1 parts by weight, and 10 minutes at 100 rpm D. and preparing a mixture of a diallyl phthalate activated, the number was performed by the average degree of polymerization and the above embodiment except that subjected to polymerization at a polymerization temperature of 56 ℃ to achieve the 1,300 example 1 in the same manner, the final number average polymerization degree of 1,300, the gel content of 1.37% by weight, and the average particle diameter of 142 ㎛, the particle size distribution to give a vinyl chloride polymer 2.1 to 2.2.
[87]
[88]
Example 11
[89]
The moisture content is stirred for 88 mol% of poly (vinyl alcohol) 0.05 parts by weight and the moisture content is mixed by introducing 72 mol% of poly (vinyl alcohol) 0.02 parts by weight diallyl the prepared stirrer phthalate 0.1 parts by weight, to 100 rpm 40 bun di and preparing a mixture of a diallyl phthalate activated, the number was performed by the average degree of polymerization and the above embodiment except that subjected to polymerization at a polymerization temperature of 56 ℃ to achieve the 1,300 example 1 in the same manner, the final number average polymerization degree of 1,300, the gel content of 1.37% by weight, and the average particle diameter of 141 ㎛, the particle size distribution to give a vinyl chloride polymer 2.1 to 2.2.
[90]
[91]
Comparative Example 1
[92]
D does not supply the diallyl phthalate, the number was performed in the same manner as in Example 1, except that in order to achieve an average polymerization degree of 1,300 subjected to polymerization at a polymerization temperature of 52 ℃, and finally a number average degree of polymerization is 1,300, the gel content this is a 1.18% by weight, and the average particle diameter of 150 ㎛, the particle size distribution to give a vinyl chloride polymer 2.1 to 2.2.
[93]
[94]
Comparative Example 2
[95]
D does not supply the diallyl phthalate, the number was performed in the same manner as in Example 1, except that in order to achieve an average polymerization degree of 1,700 subjected to polymerization at a polymerization temperature of 47.5 ℃, and finally a number average degree of polymerization is 1,700, the gel content the 1.06% by weight and an average particle diameter of 130 ㎛, the particle size distribution to give a vinyl chloride polymer from 1.9 to 2.0.
[96]
[97]
Comparative Example 3
[98]
The reflux condenser and internal volume 1m equipped with a stirrer 3 of a stainless polymerization reactor, 0.05 polyvinylalcohol diallyl phthalate is also a sign language instead of the activated mixture of 88 mol% parts by weight of a moisture content of 72 mole% of poly (vinyl alcohol) 0.02 parts by weight of diethylene was conducted in the same manner as in example 1, except that carried by each input diallyl phthalate 0.008 parts by weight, and finally the number average degree of polymerization of 1,280, and a gel content of 1.38% by weight and a mean particle diameter 141 ㎛, and the particle size distribution to give a vinyl chloride polymer, 2.1 to 2.2.
[99]
[100]
Comparative Example 4
[101]
The reflux condenser and a stirrer was attached to the inner volume of 1 m 3 in a stainless polymerization reactor, which polyvinyl diallyl phthalate is from 0.05 polyvinyl alcohol hydration rather than the activated mixture is also 88 mol% parts by weight of a moisture content of 72 mol% alcohol 0.02 parts by weight of diallyl phthalate 0.04 wt was carried parts in the same manner and is as in the above example 4 except that the input, respectively, and finally a number average degree of polymerization of 1,680, and a gel content of 1.22% by weight and a mean particle diameter 121 ㎛, and the particle size distribution to give a vinyl chloride polymer, from 1.9 to 2.0.
[102]
[103]
Comparative Example 5
[104]
The moisture content is stirred for 88 mol% of poly (vinyl alcohol) 0.05 parts by weight and the moisture content is mixed by introducing 72 mol% of poly (vinyl alcohol) 0.02 parts by weight diallyl the prepared stirrer phthalate 0.1 parts by weight, 5 minutes at 70 rpm D It was and is carried out as example 8, except that to prepare a mixture with a diallyl phthalate activation, and finally a number average degree of polymerization of 1,260, and a gel content of 1.37% by weight and a 148 ㎛ average particle size and particle size distribution It is to give a vinyl chloride polymer, 2.1 to 2.2.
[105]
[106]
Comparative Example 6
[107]
The moisture content is stirred for 88 mol% of poly (vinyl alcohol) 0.05 parts by weight and the moisture content is mixed by introducing 72 mol% of poly (vinyl alcohol) 0.02 parts by weight diallyl the prepared stirrer phthalate 0.1 parts by weight, 50 minutes to 70 rpm D It was and is carried out as example 8, except that to prepare a mixture with a diallyl phthalate activation, and finally a number average degree of polymerization of 1,290, and a gel content of 1.37% by weight and a 145 ㎛ average particle size and particle size distribution It is to give a vinyl chloride polymer, 2.1 to 2.2.
[108]
[109]
Comparative Example 7
[110]
The moisture content is stirred for 88 mol% of poly (vinyl alcohol) 0.05 parts by weight and the moisture content is mixed by introducing 72 mol% of poly (vinyl alcohol) 0.02 parts by weight diallyl the prepared stirrer phthalate 0.1 parts by weight, 5 minutes at 100 rpm D. It was and is carried out as example 8, except that to prepare a mixture with a diallyl phthalate activation, and finally a number average degree of polymerization of 1,280, and a gel content of 1.37% by weight and a 144 ㎛ average particle size and particle size distribution It is to give a vinyl chloride polymer, 2.1 to 2.2.
[111]
[112]
Comparative Example 8
[113]
The moisture content is stirred for 88 mol% of poly (vinyl alcohol) 0.05 parts by weight and the moisture content is mixed by introducing 72 mol% of poly (vinyl alcohol) 0.02 parts by weight diallyl the prepared stirrer phthalate 0.1 parts by weight, 50 minutes at 100 rpm D. It was and is carried out as example 8, except that to prepare a mixture with a diallyl phthalate activation, and finally a number average degree of polymerization of 1,290, and a gel content of 1.37% by weight and a 141 ㎛ average particle size and particle size distribution It is to give a vinyl chloride polymer, 2.1 to 2.2.
[114]
[115]
Comparative Example 9
[116]
The moisture content is stirred for 88 mol% of poly (vinyl alcohol) 0.05 parts by weight and the moisture content is mixed by introducing 72 mol% of poly (vinyl alcohol) 0.02 parts by weight diallyl the prepared stirrer phthalate 0.1 parts by weight, with 60 rpm 10 bun di It was and is carried out as example 8, except that to prepare a mixture with a diallyl phthalate activation, and finally a number average degree of polymerization of 1,250, and a gel content of 1.37% by weight and a 150 ㎛ average particle size and particle size distribution It is to give a vinyl chloride polymer, 2.1 to 2.2.
[117]
[118]
Comparative Example 10
[119]
The moisture content is stirred for 88 mol% of poly (vinyl alcohol) 0.05 parts by weight and the moisture content is mixed by introducing 72 mol% of poly (vinyl alcohol) 0.02 parts by weight diallyl the prepared stirrer phthalate 0.1 parts by weight for 10 minutes to 110 rpm D. It was and is carried out as example 8, except that to prepare a mixture with a diallyl phthalate activation, and finally a number average degree of polymerization of 1,290, and a gel content of 1.37% by weight and a 142 ㎛ average particle size and particle size distribution It is to give a vinyl chloride polymer, 2.1 to 2.2.
[120]
[121]
Experimental Example
[122]
The Examples 1 to 11 and Comparative Examples 1 to the vinyl-based analysis comparing the melt processability of the polymer chloride prepared in 10, wherein the manufacturing the vinyl-based polymer to 100 parts by weight of chloride, the plasticizer 35 parts by weight of an organic tin-based stabilizer, 2 parts by weight portion and the lubricant 1 weight uniformly mixing portion, Brabender (brabender plastograph, Brabender Gmbh & Co KG) using the process under the conditions of 140 ℃ and 30 rpm, melting time of plastic processed chloride-based polymer, melt-load, to measure the plasticizer absorption and apparent specific gravity of the results are shown in Table 1 below.
[123]
1) Melting Time (seconds) and the melting load (Nm)
[124]
Melting time and melt load was described in each of the check process when, melting time and melt the load using the Brabender. At this time, the melting time denotes the time it takes for each vinyl chloride polymer and a plasticizer to be fully molten form are mixed together, melt-load represents the torque (torque) when the completely melted state.
[125]
[126]
2) plasticizer absorption (CPA,% by weight)
[127]
Plasticizer absorptivity is blocking the hole in the glass tube bottom with cotton, and then weighed to the processing of vinyl chloride-based polymer 1 g placed in the tube, DOP (dioctyl phthalate) was added to 2 g. It was then centrifuged for 30 minutes, and 4,800 rpm after mounting the tube on a centrifuge to calculate the weight of the polymer to be increased is shown as a percentage.
[128]
[129]
3) bulk density (BD)
[130]
The apparent specific gravity to match the test sample funnel (funnel) filled with poured sample is a rear, for a funnel bottom and the measuring cup (measuring cup) not to get on the walls of the funnel by hitting the upper part of the funnel as a bar in the middle button of the funnel (button) to open up to free fall into the cup for the measurement of the measurement sample, flattened to the surface of the measurement sample is ADD filled with the above-mentioned measuring cup bar after Nu calculated by measuring the weight of the test sample containing the above-mentioned measuring cup It was.
[131]
TABLE 1
[132]
[133]
In Table 1, the melting time, the melting load and plasticizer absorption rate the smaller the value, the apparent specific gravity will exhibit superior characteristics the higher the value. Further, it is known that usually be according to the average degree of polymerization exhibits a large difference in the melting time and melting rate characteristics, the number average degree of polymerization is relatively increased melting time, and the load compared to the low melting polymer a number-average degree of polymerization for high polymers. Accordingly, the number average degree of polymerization of high polymer is relatively number average degree of polymerization is in the figures is simply a larger difference than the difference represented by the case showing a melting time, and the molten polymer compared to low-load reduction.
[134]
As it is shown in Table 1, and the case of the invention of Examples 1 to 11 produced by a production method according to Comparative Examples 1 to 10, the plasticizer absorptivity decreases compared to make sure that not only hayeoteul increase in apparent specific gravity is excellent in melt processability .
[135]
[136]
Evaluation of the effect of the use of a chain regulator
[137]
Specifically, in the case of Examples 1 to 3 and Examples 8 to 11, and has a same number of average degree of polymerization and average particle size, was Comparative Example 1, the plasticizer absorptivity decreases compared not put a chain regulator, and increases the apparent specific gravity, performed for example, 4 to 7 has decreased, the same number-average degree of polymerization and Comparative example 2 compared to the plasticizer absorption and has a mean particle size, are not added to the chain control agent, and increases the apparent specific gravity. From this, the inner polymer particles filled but projected to increase the melting time and melt the load, this prediction and it was confirmed that, unlike Examples 1 to 11 all of Comparative Examples 1 and is improved both melting time and melt the load is compared to the second.
[138]
This is because the polymer particles containing the side chains (side chain) other than the polymer particles in pure parallel chain from the input of the chain control agent is generated, and these particles are compared with the polymer particles formed of only parallel chain, a relatively large friction occurs between the particles and, while the smaller particles melt first, thus to rapidly melt the large polymer particles, the results showing a processing-rescue improve the melting property.
[139]
[140]
Evaluation of the effect with and without stirring process applied
[141]
In the case of Comparative Examples 3 and 4, but it did not achieve an average polymerization degree can be desired, it was confirmed that not good productivity thereto. Furthermore, Comparative Examples 3 and 4 are each of Examples 1 and 4 were increased compared to the plasticizer absorption and reduce the apparent specific gravity, number average degree of polymerization is low, even though the less was increased melting time and melt the load. This comparison by Examples 3 and 4 was confirmed that the melt processability of Examples 1 and 4 significantly decreased compared to. On the other hand, the Comparative Examples 3 and 4 is not added to the polymerization before the chain modifier, and a first protective colloid is prepared by pre-stirred in a mixture with each input separately, except that the polymerization was prepared in the same conditions as in Example 1 and 4 will be.
[142]
[143]
Evaluation of the effects of the stirring speed and time control
[144]
On the other hand, in the case of Comparative Examples 5 to 10, chain regulators, and the first was not even though used for the polymerization, a protective colloid to prepare a mixture in advance stirred to achieve a number-average degree of polymerization desired, Examples 8 to 11, compared to the plasticizer absorptivity, the apparent specific gravity, melting time and melting rate characteristics were not good. Here, the Comparative Examples 5 to 10, but used by putting a mixture in advance stirred for chain control agent in the first protective colloid preparation, except that manufactured under the conditions out of the stirring speed or stirring time presenting the mixture in the present invention and it is manufactured by the same conditions as in examples 8 to 11 respectively.
[145]
Specifically, Comparative Examples 5 and 9 and Comparative Examples 7 and 10, respectively, in Example 8 and Example 10, against increased plasticizer absorption and decreased apparent specific gravity, number-average degree of polymerization is even and each melting time 121% of even low and it was increased by 122% and 118% of the level and the 103% level.
[146]
On the other hand, in Comparative Examples 6 and 8, Examples 9 and 11 compared to melting time, the melting load, eoteuna the plasticizer absorption and bulk density show a similar level numerically, Comparative Example 6 and the number of the Example 9. The average polymerization degree of 8 for the case of and given that less than 11, it can be seen that the melting time and melt load examples 9 and 11, up against.
[147]
[148]
The above results, the first protective colloid preparation affecting a distributed degree of the number average degree of polymerization of the chain control agent as julppun affect the productivity of the polymer, according to the present invention with the results shown to affect melt processability, through which method can be found that it is possible to prepare the first protective colloid and prepared in advance by stirring the vinyl chloride-based polymer is melt processible even improved without adversely affecting the productivity by using the polymerase chain control agents.
[149]
Further, the stirring conditions at the time of the stirring (stirring speed and stirring time) is found to be important elements for improving the melt processability while maintaining the excellent productivity of the polymer.
[150]
Specifically, the results of agitation can speed fails to evenly (less than 70 rpm) chain control agent dispersion, if not enough, if excessively high (greater than 100 rpm) and over-differentiating the chain control agent particles in the stirred foam (foam) by generating it indicates that may act as an element to prevent the dispersion.
[151]
Further, that the stirring If the time is not enough (less than 10 minutes) may be chain control agents not be properly dispersed, whereas if the 40-minute exceeded, the degree of desired effect increase may be insignificant, and lost productivity rather due to a time increase occurs It represents.

Claims

[Claim 1]A first protective colloid (protective colloid) Preparation and chain control agent (chain regulator) is to prepare a mixed mixture (S1); the second protective colloid comprising a chain control agent activated by stirring the mixture prepared in the above (S1) phase preparing a preparation (S2); And in the presence of a second protective colloid preparation prepared in (S2) step, a step (S3) of polymerizing the added vinyl chloride monomer and a polymerization initiator, and the mixture was stirred at (S2) step is 70 rpm to about 100 rpm the stirring speed of 10 to 40 minutes the vinyl chloride-based polymer production method will be carried out for.
[Claim 2]
The method of claim 1, wherein the first protective colloid is a polyvinyl alcohol prepared a vinyl chloride-based polymer production method.
[Claim 3]
Claim 2 wherein the polyvinyl alcohol has a number average degree of polymerization of 1,000 to 3,500 a vinyl chloride-based polymer production method a.
[Claim 4]
Claim 2 wherein the polyvinyl alcohol hydration method is also 60 mol% to 90 mol% of vinyl chloride-based polymer production in.
[Claim 5]
The method of claim 4, wherein the polyvinyl alcohol is a poly 2-vinyl chloride-based polymer production method more mixtures selected from the group consisting of polyvinyl alcohol having a different moisture content within the range of the moisture content.
[Claim 6]
In the first protective colloid content of the preparation is in the range of 0.01 parts to 1 parts by weight of vinyl chloride-based polymer production method based on 100 parts by weight of the vinyl chloride-based monomer of claim 1.
[Claim 7]
The method of claim 1, wherein the chain control agent is diallyl phthalate, allyl methacrylate and pentaerythritol method for producing at least one member vinyl chloride polymer selected from the group consisting of triallyl ether.
[Claim 8]
The method of claim 1, wherein the content is 0.01 parts by weight to 0.5 parts by weight of vinyl chloride-based polymer production method based on 100 parts by weight of the vinyl chloride-based monomer of the chain control agent.
[Claim 9]
2. The method of claim 1, wherein (S2) is stirred in step a vinyl chloride-based polymer production method that is carried out for 10 minutes to 20 minutes with a stirring speed of 90 rpm to 100 rpm.
[Claim 10]
The method of claim 1, wherein the polymerization of the (S3) is phase method of producing a vinyl chloride polymer to be performed by further comprising a third protective colloid preparation.
[Claim 11]
11. The method of claim 10, wherein the third protective colloid to prepare a water-soluble cellulose-based compound, a vinyl chloride-based polymer production method.
[Claim 12]
The method of claim 1, wherein the (S3) of the polymerization step, the vinyl chloride-based polymer production method will be carried out at 48 ℃ to 62 ℃.