[1]Mutual citations and related applications
[2]
This application claims the benefit of priority based on the date of September 23, Korea Patent Application No. 10-2016-0122459, 2016, and all information disclosed in the literature of the Korea patent application are included as part of the specification.
[3]
[4]
Art
[5]
The present invention relates to a process for the preparation of vinyl chloride polymers, the present invention relates to a vinyl chloride polymer prepared therefrom.
[6]
BACKGROUND
[7]
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.
[8]
On the other hand in preparing a vinyl chloride polymer of a low degree of polymerization, it is usual to proceed with the polymerization at a high temperature and high pressure compared to the condition for producing a vinyl chloride polymer with a high polymerization degree. However, it is difficult to safely producing a vinyl chloride polymer of a low degree of polymerization, such as the design pressure of the polymerization reactor limitation reasons.
[9]
Thus mercaptan through a series chain chain transfer agent, but a method for adjusting the degree of polymerization, in the case of producing a vinyl chloride polymer by bulk polymerization, the dispersion of the chain transfer agent injected, because polymerization proceeds in the absence of the characteristics of water in the bulk polymerization conditions apart has the disadvantage that the polymer obtained has a intended to achieve a degree of polymerization is difficult or broad molecular weight distribution.
[10]
Thus, in preparing a vinyl chloride polymer of a low degree of polymerization, the manufacture of a low polydispersity index narrow molecular weight distribution while maintaining a safe operating conditions, a situation that is required for producing a polymer having a degree of polymerization of the target technology.
[11]
Detailed Description of the Invention
SUMMARY
[12]
The present invention is a relatively uniform molecular weight distribution thereby to be made in view of solving the problems of the prior art, improving the dispersibility by introducing a chain transfer agent of mercaptans based on a particular conversion rate during particle nucleation in the polymerisation process of vinyl yeomhoe polymer of yet intended to provide a a method for producing a vinyl chloride polymer having a target degree of polymerization, the production cost is low, the operating conditions eumyeonseodo a method of making a stable vinyl chloride polymer.
[13]
Problem solving means
[14]
In accordance with one embodiment of the present invention for solving the above problems, the prepolymerization step the invention by the addition of mercapto tangye chain transfer agent in the monomer composition containing the vinyl chloride monomer and a pre-polymerization initiator to form a particle core; And a vinyl chloride monomer and the polymerization step for producing a polymer by mixing the nucleus particles and the addition of the polymerization initiator; provides a vinyl chloride-based polymer production process comprising a.
[15]
Effects of the Invention
[16]
According to the present invention, by administration of a chain transfer agent to a specific conversion rate of the prepolymerization reaction at the former stage of the preliminary polymerization step of the polymerization, the molecular weight distribution is uniform and is low in dispersion index at the same time, the small number average molecular weight due to the attainment of a low degree of polymerization to provide a vinyl chloride polymer, and it is possible to provide a manufacturing method that can ensure the safety of the process in an efficient application of the chain transfer agent eumyeonseodo the production costs low by using a bulk polymerization.
[17]
Best Mode for Carrying Out the Invention
[18]
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.
[19]
[20]
Example
[21]
Example 1
[22]
Volume 0.2 m high vacuum deaerated 3 from the input to the vinyl chloride monomer 135 kg of a pre-polymerization reactor and the reaction initiator, di-2-ethylhexyl peroxy dicarbonate and then a 80 g In the stirring maintained 12 K / G the boosted to thereby prepare a particle nucleus. At this time, when the conversion rate of the prepolymerization reaction reached 8% 2-mercaptoethanol Murray When the 60 g added, and the conversion rate of the pre-polymerization reached 10% was terminated prepolymerization reaction.
[23]
0.5 m 3 In the vinyl chloride monomer of 75 kg to the polymerization reactor and the particles after transferring the nuclear 1,1,3,3-tetramethylbutyl peroxy neodecanoate reaction initiator prepared in the prepolymerization reactor 170 in g added to a stirred state is maintained and polymerization was 180 minutes at a pressure of 7.5 K / g. After polymerization is complete, when the agitation is to recover the state residual unreacted vinyl chloride monomer in a vacuum for 30 minutes at the holding finally obtaining a vinyl chloride polymer.
[24]
[25]
Example 2
[26]
The 2-mercaptoethanol in the preliminary polymerization reactor 45 g except that the polymerization be conducted as one input to a 8.0 K / G, to prepare a vinyl chloride polymer in the same manner as in Example 1.
[27]
[28]
Example 3
[29]
The 2-mercaptoethanol in the preliminary polymerization reactor 75 g except that the polymerization be conducted as one input to a 8.0 K / G, to prepare a vinyl chloride polymer in the same manner as in Example 1.
[30]
[31]
Example 4
[32]
Except that 2-mercaptoethanol to the prepolymerization reactor to the input when the conversion of the pre-polymerization reaction reaches 3%, the vinyl chloride polymer was prepared in the same manner as in Example 1.
[33]
[34]
Example 5
[35]
Except the prepolymerization reactor to which 2-mercaptoethanol instead of In a 3-mercapto-1,2-propanediol to prepare a vinyl chloride polymer in the same manner as in Example 1.
[36]
[37]
Comparative Example 1
[38]
Except that no 2-mercaptoethanol added to the prepolymerisation reactor, a vinyl chloride polymer was prepared in the same manner as in Example 1.
[39]
[40]
Comparative Example 2
[41]
Except that the polymerization reaction that did not supply the 2-mercaptoethanol in the prepolymerisation reactor will be subjected to 8.0K / G, to prepare a vinyl chloride polymer in the same manner as in Example 1.
[42]
[43]
Comparative Example 3
[44]
Except that 2-mercaptoethanol to the prepolymerization reactor to a conversion rate when the input reaches 2%, the vinyl chloride polymer was prepared in the same manner as in Example 1.
[45]
[46]
Comparative Example 4
[47]
In one except that when the conversion rate of 2-mercaptoethanol in the prepolymerization reactor is reached in the 10% to prepare a vinyl chloride polymer in the same manner as in Example 1.
[48]
Comparative Example 5
[49]
2-mercaptoethanol Murray except that the input at the same time as the start of the polymerization reaction without administration of the pre-polymerization, the vinyl chloride polymers were produced in the same manner as in Example 1.
[50]
[51]
Comparative Example 6
[52]
The 2-mercaptoethanol in the preliminary polymerization reactor 10 g except that the polymerization be conducted as one input to a 8.0 K / G, to prepare a vinyl chloride polymer in the same manner as in Example 1.
[53]
[54]
Comparative Example 7
[55]
The 2-mercaptoethanol in the pre-polymerization reactor 150 g except that the polymerization be conducted as one input to a 8.0 K / G, to prepare a vinyl chloride polymer in the same manner as in Example 1.
[56]
[57]
Experimental Example
[58]
Using the Examples 1 to 5 and Comparative Examples 1 to a vinyl chloride resin, 0.02 g of 20 mL THF completely the filtered solution by the pore size 0.45 ㎛ or less filter Waters Corporation GPC (Gel Permeation Chromatography) was dissolved in Preparation 7 , and deriving a weight average molecular weight (Mw) and number average molecular weight was measured (Mn), calculating the Mw / Mn ratio of the polydispersity index (PDI).
[59]
[60]
TABLE 1
The weight average molecular weight Mw The number average molecular weight Mn The number average degree of polymerization Polydispersity index PDI
Example 1 114,209 50,313 805 2.27
Example 2 113,400 50,625 810 2.24
Example 3 99,329 43,375 694 2.29
Example 4 111,639 50,063 801 2.23
Example 5 114,570 50,250 804 2.28
Comparative Example 1 140,250 63,750 1020 2.20
Comparative Example 2 131,909 59,688 955 2.21
Comparative Example 3 ND ND ND ND
Comparative Example 4 130,334 55,938 895 2.33
Comparative Example 5 133,818 57,188 915 2.34
Comparative Example 6 131,218 59,375 950 2.21
Comparative Example 7 ND ND ND ND

[61]
* ND: inability to measure
[62]
In the above case, as shown in Table 1, by the process according to the invention, mercapto carried out by administration of tangye chain transfer agent in the conversion of 3 to 8% by the time of the preliminary polymerization in Example 1 to 5, and a polydispersity index of about 2.3 or less and a molecular weight distribution can see that it is in uniform, it can be seen that the molecular weight distribution uniformity and at the same time, a number average molecular weight of 55,000 or less of a low polymerization degree vinyl chloride polymer can be produced.
[63]
On the other hand, yieoteuna same conditions In the Comparative Examples 1 and 2 did not receive a mercapto tangye chain transfer agent, the molecular weight distribution may determine a vision relatively uniform pieces or be compared with the embodiments the average molecular weight is extremely large, the prepolymerization for a comparison of example 3 administered prior to the conversion rate of the reaction is 3%, the polymerization reaction decreases in a competitive reaction of the preliminary polymerization reaction and radical reaction of the chain transfer agent being to check that it has not the reaction progress made so not even measure have. Further, the mercapto administered tangye chain transfer agent at the time the conversion of the pre-polymerization passed to 8%, or, after the preliminary polymerization reaction is complete when the comparison of administration of a chain transfer agent in the polymerization reaction Examples 4 and 5, the polydispersity index is 2.3 the measurement is greater is greater than it was confirmed that it can not achieve the uniformity of the molecular weight distribution to be obtained by administration of a chain transfer agent.
[64]
In addition, mercapto and found that tangye chain batching the transfer agent is too low dose Example 6 is not obtained the effect to be obtained that the number average molecular weight as in the Comparative Example 2 through a significantly appear larger chain transfer agent, for example, so comparing a overdose 7, it was confirmed that no polymerization proceeds normally, due to the predominance of radical reaction as in Comparative example 3.
[65]
Through this, it can be seen that tangye mercaptosilane chain transfer agent can be produced by administering to a point-in-time of the conversion of the pre-polymerization, the vinyl chloride polymer is a fairly uniform molecular weight distribution The molecular weight eumyeonseodo lower the degree of polymerization is less.
[66]
Mode for the Invention
[67]
Hereinafter, the present invention will be described in more detail to aid the understanding of the present invention.
[68]
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.
[69]
[70]
Process for the production of vinyl chloride-based polymer of the present invention, by adding a mercapto tangye chain transfer agent in the monomer composition containing the vinyl chloride monomer and the polymerization initiator, pre-pre-polymerized to form a particle core; And a mixture of vinyl monomers, and the particle nucleus chloride and addition of the polymerization initiator, the polymerization step for producing the polymer; and a.
[71]
[72]
Preliminary polymerization
[73]
According to one embodiment of the invention, can be carried out by separating the polymerization reaction in the production of vinyl chloride polymers in two steps, after performing the step of generating a particle nucleus in the preliminary polymerization step, the polymer in the main polymerization step is a vinyl chloride-based polymer can be prepared by following the process of manufacture.
[74]
According to one embodiment of the invention, mercapto after which the pre-polymerisation step is to form a monomer composition by administering the vinyl chloride monomer and a pre-polymerization initiator to the pre-polymerisation reactor pre-formed, pre-polymerization is performed a period of time tangye chain It may be performed by administering the transfer agent. The prepolymerization reaction may be completed to form the grain nuclei by administration of a chain transfer agent to complete the reaction at constant conversion time.
[75]
[76]
(Reaction Conditions)
[77]
To the end time of the preliminary polymerization is because it is not particularly limited, and the reaction of forming the old grain nuclei to form a polymer, there may be a limitation for the reaction should not proceed excessively, the conversion rate in order to satisfy this requirement it may be desirable to complete the reaction in about 10% to about 15% of the time.
[78]
Moreover, the reaction conditions of the preliminary polymerization reaction pressure may be applied in the range of 11 to 13 K / G, the temperature may preferably be applied at 65 to 75 ℃. And it may require continuous stirring during which the pre-polymerisation reaction proceeds, the stirring is conducted when it is recommended that a high speed is possible.
[79]
[80]
(Tangye mercaptosilane chain transfer agent)
[81]
According to one embodiment of the invention, by administering the pre-polymerization of the mercapto tangye chain prepolymerization step the transfer agent, it is possible to suppress the growth of the polymer. Tangye the mercaptosilane chain transfer agent is administered to the monomer composition and cause the reaction to go through a radical chain transfer agent, the radical reaction proceeds with the growth of the polymer reaction, the two reactions may occur competitively.
[82]
By two of the reaction occurs competitively as described above, while the growth reaction of the polymer may have the effect that some suppressed, the control of the polymerization degree of the vinyl chloride polymer easier accordingly, and as a result, the molecular weight distribution uniformity of the low molecular weight a vinyl chloride polymer can be produced.
[83]
According to one embodiment of the invention, may be a mercapto tangye chain transfer agent is an important factor, such as input control point or input in order to function effectively in the polymerization reaction, it can also be important that any material which is introduced.
[84]
Tangye the mercaptosilane chain transfer agent is a compound containing a mercapto group represented by "-SH" is to be not particularly limited but, preferably may be a compound represented by the general formula (1).
[85]
Formula 1
[86]
[87]
In the formula 1, wherein R1 and R2 are the same or different, each independently, hydrogen or an alkyl group having 1 to 20 carbon atoms, when R1 and R2 are different from hydrogen, either one of R1 and R2 is -OH, -COOH, or -COOR comprises a (wherein, R is an alkyl group having 1 to 5 carbon atoms), and a is C 1 -C 30 alkylene group or a C2 to containing the alkylene group, one or more hydroxy groups having 1 to 30 carbon atoms 30 is a heteroalkylene group, the hetero alkylene group containing at least one hetero element selected from the group consisting of N, O and S, wherein X is -OH, -COOH, or -COOR (wherein, R is an alkyl group having 1 to 5 carbon atoms )to be.
[88]
Tangye the mercaptosilane chain transfer agent, and essentially as a mercapto group, may further include one or more other functional groups, preferably a hydroxy group represented by -OH, a carboxyl group represented by -COOH, ester groups represented by -COOR are applied Do.
[89]
More specifically, the mercapto tangye chain transfer agent is a compound that satisfies the above-mentioned formula (I), 2-mercaptoethanol, 3-mercapto-1,2-propanediol, methyl mercapto tode decanoate, dimethyl-9-mercapto-octahydro decyl -1,18- video benzoate, or may be applied to the mixtures thereof.
[90]
Further, the mercapto tangye chain transfer agent may be as well as the type, importance is turned on when and amount, the mercapto tangye chain transfer agent may be administered at the time between from when the conversion rate is 3% of the pre-polymerization to 8% point can. When administering a mercapto tangye chain transfer agent at this point, to the dispersion of the chain transfer agent can be obtained excellent effects that the optimum.
[91]
If the pre-input, even though the conversion of the pre-polymerization was short of 3% has been conducted as a radical transfer reaction by a chain transfer agent predominantly before they progress micheo the growth reaction of the polymer, so the growth of the polymer are placed into disadvantage in a competitive reaction polymerization cause progress of the reaction is not abnormal, and if the conversion rate is input to the chain transfer agent in excess of 8% has been actively carried out a growth reaction of the polymer is difficult to properly control the degree of polymerization, whereby the molecular weight distribution is non-uniform, or the molecular weight this is a big possibility that the vinyl chloride-based polymer is prepared which results appears.
[92]
At this time, the conversion of 3 to 8% if the input frequency or input method may not have a significant effect on the vinyl-based polymer chloride is produced, therefore, to mubang be applied to any method including dividing input, batch input and a continuous input can. However, it can exert the best effect of the batch input at any one time the conversion of 3 to 8%.
[93]
Tangye the mercaptosilane chain transfer agent may be added in an amount of 0.01 to 0.1 parts by weight of vinyl chloride monomer pre-polymerization step of 100 parts by weight of the preparation. Mercapto tangye chain transfer agent is about 0.01 when administered as part by weight of less than there may not effectively suppress the growth reaction of the polymer and about 0.1 if the excess of the growth of the polymer predominantly due to the furnace of a radical transfer reaction by a chain transfer agent is It may be poorly made.
[94]
The action of the chain transfer agent like mercapto tangye is because, rather than occurring only in the preliminary polymerization, the product of the prepolymerization reaction are all transferred to the main polymerization and the polymerization reaction proceeds, can continue to take place in the polymerization reaction.
[95]
In the case of using the mercapto tangye chain transfer agent as described above, due to the action of the chain transfer agent as above, and a step of high-temperature and high-pressure conditions are indispensable for not be necessary in preparing a vinyl chloride polymer of a low degree of polymerization, this has the advantage that the process can be operated more reliably.
[96]
[97]
Polymerization reaction
[98]
According to one embodiment of the invention, it can be transferred to the polymerization reactor nuclear particles formed through the preliminary polymerization in advance is provided, wherein the polymerization reactor has a generally may be a vinyl chloride monomer is introduced. Administration of the particle core and the vinyl chloride-based monomer is mixed polymerization initiator present is a vinyl chloride polymer of a low degree of polymerization can be prepared by proceeding after the end of the main polymerization reaction started and a certain time reaction.
[99]
[100]
(Reaction Conditions)
[101]
According to one embodiment of the invention, at which to end the present polymerisation are not particularly limited, it is common that as this reaction to form a polymer end after the reaction is progressed sufficiently, unlike the pre-polymerized, and thus the conversion rate it is common to terminate the reaction at greater than about 70% of the time.
[102]
The pressure in the reaction conditions of the present polymerization reaction may be applied in the range of 7.0 to 8.0 K / G, the temperature may preferably be applied at 50 to 60 ℃. During which the present polymerization reaction proceeds may require continuous agitation.
[103]
[104]
Common matters in the preliminary polymerization and the main polymerization reaction
[105]
(Reactor)
[106]
According to one embodiment of the present invention, may have mutually different reactors to be applied in each of the polymerization reaction and the preliminary polymerization, the reactor is applied as will that can be used to produce a low polymerization degree vinyl chloride polymer, the prepolymerization the reactor and the volume of the polymerization reactor is that the volume of the polymerization reactor in an about 25: 75 to 40: 60 may be larger.
[107]
[108]
(Vinyl chloride monomer)
[109]
According to one embodiment of the present invention, the vinyl chloride-based monomer may be a mixture of the pure vinyl chloride monomer alone or a vinyl chloride monomer and the vinyl chloride monomer and a copolymerizable vinyl monomer. As the vinyl chloride monomer Chemistry copolymerizable vinyl monomer is not particularly limited, a vinyl ester such as ethylene, propylene, -olefins such as butene (olefin) compounds, vinyl acetate and vinyl propionate, stearate, vinyl (vinyl ester) flow, unsaturated nitriles such as acrylonitrile, vinyl methyl ether, vinyl ethyl ether, vinyl octyl ether, vinyl laurate carbonyl ethers such as vinyl alkyl ethers, halogenated vinylidene (vinylidene) acids, acrylic acid, methacrylic acid, such as vinyl chloride, vinylidene acid, itaconic acid, maleic acid, fumaric acid, maleic anhydride, itaconic anhydride, such as the unsaturated fatty acid and unsaturated fatty acid ester (ester) acids, such as their fatty acid anhydride, acrylic esters such as methyl acrylate, ethyl maleate, monomethyl maleate, dimethyl maleate, butyl benzyl , di, and the like cross-linking monomer such as diallyl phthalate, a vinyl-based monomers It may be mixed alone or in combination of two or more.
[110]
Since the vinyl chloride-based monomer as described above is to pre-polymerization and can be administered both to the polymerization reaction, is typically a vinyl chloride-based monomer administration in the prepolymerization reaction transferred to the polymerization reactor the reaction is continued, at a dose is the case of the pre-polymerization reaction may be larger than that in the main polymerization reaction. In general, the dosage of the vinyl chloride monomer in the polymerization reaction and the dose of the vinyl chloride monomer in the preliminary polymerization may be from about 55:45 to about 75:25 by weight.
[111]
[112]
(Polymerization initiator)
[113]
According to one embodiment of the invention, the polymerization initiator may be used is the polymerization initiator, and pre-polymerization initiator, the two initiators may also be the same and may be different from each other. Preliminary polymerization initiator and the polymerization initiator are, each independently, for example, t- butyl peroxy ester, cumyl peroxy ester, cumyl peroxyneodecanoate, 1,1,3,3-tetramethylbutyl peroxy neo decanoate, t- hexyl peroxyneodecanoate, t- butyl peroxyneodecanoate, t- hexyl peroxypivalate, t- butyl peroxypivalate, di -sec- butyl peroxy dicarbonate, to the di-2-ethoxyethyl peroxy dicarbonate, di-2-ethylhexyl peroxy dicarbonate, isobutyryl peroxide, 3,5,5-trimethyl hexanoyl peroxide, lauryl peroxide, or mixtures thereof It can be applied.
[114]
The pre-polymerization initiator, but are not limited thereto, may be added 0.01 to 1 part by weight of vinyl chloride monomer to 100 parts by weight of the preparation is administered in the pre-polymerization, it is possible to configure the monomer composition with the vinyl chloride monomer. In the time of the preliminary polymerization initiator it may be added after all if the case is introduced into the reactor with a vinyl chloride monomer or the vinyl chloride monomer both injected.
[115]
Wherein the polymerization initiator may be administered from 0.1 to 2 parts by weight of vinyl monomer than 100 parts by weight of chloride but are not to be, to be administered in addition during the polymerization so limited. Above may be the smaller the impact input point on the reaction of the polymerization initiator, when the particle nucleus transferred from the pre-polymerization reactor, or after the transfer is completed, or added together with the vinyl chloride monomer, or a particle nuclear transfer, and at any time, it may be administered before the reaction begins, such as after the closing of the vinyl chloride monomer is completed.
[116]
[117]
(Bulk polymerization)
[118]
According to one embodiment of the invention, the prepolymerization and the polymerization it can be made in accordance with the bulk polymerization. In general, mass polymerization does not include water in the reaction, so when administered in accordance with a chain transfer agent, there has been a problem is not due to the absence of water the chain transfer agent is dispersed smoothly. For this reason, there was the preparation of the vinyl chloride polymers of low polymerization degree and a difficulty in applying a chain transfer agent which can be added to progress the reaction to break the stable high temperature and high pressure reaction.
[119]
However, in accordance with one embodiment of the present invention, it is possible to solve the above problems by appropriately controlling the input timing of tangye mercaptosilane chain transfer agent, there is an advantage to maximize the input due to the effect of the chain transfer agent.
[120]
Details relating to the input of the chain transfer agent, so the foregoing, detailed description will be omitted.
[121]
Production process through the mass polymerization can remove the reactivity of the polymerization initiator added to the polymerization inhibitor remaining in the polymerization end. The polymerization inhibitor may be selected from conventionally known in the art and is not particularly limited. However, I pray hydroquinone, butylated hydroxytoluene, monomethyl ether hydroquinone, quaternary-butylcatechol, diphenylamine, triisopropoxide in propanol amine, triethanolamine and the like. The amount of the polymerization inhibitor may be used appropriately adjusted according to the amount of the polymerization initiator which remains, can usually be used as part of 0.001 to 0.1 parts by weight based on 100 parts by weight of vinyl chloride monomer.
[122]
In addition, the manufacturing method through the bulk polymerization according to the present invention may further include additives such as chain transfer agent in addition to the active ingredient which may be used by mixing the reaction medium with the vinyl chloride monomer, wherein the base material.
[123]
The reaction medium is a common organic solvent can be used without particular limitation. For example, the reaction medium and the like, benzene, toluene, xylene aromatic compound and methyl ethyl ketone, acetone, n- hexane, such as alkylene, chloroform, cyclohexane can be used. The chain transfer agent is not particularly limited, for example n- butyl mercaptan, n- octylmercapto mercaptan, n- dodecyl mercaptan silmeo, t- dodecyl mercaptan, and the like silmeo.
[124]
[125]
Vinyl chloride-based polymer
[126]
According to one embodiment of the invention, the vinyl chloride-based polymer produced through the production method of the above appears low average molecular weight is the degree of polymerization can be reduced by the molecular weight distribution is uniform it may have a small polydispersity index.
[127]
According to one embodiment of the present invention, the vinyl-based polymer chloride, generally it can be used in applications such as rigid sheet or fitting, if this is the number average molecular weight when used for the same purpose exceeds 55,000 problem that workability is lowered that may occur.
[128]
On the other hand, production cost is however possible to produce a number average molecular weight of 55,000 or less vinyl chloride polymer through a low bulk polymerization, by applying a bulk polymerization to apply the vinyl chloride polymer in the hard sheet or the use of fittings such as in order to reduce the average molecular weight of less than 55,000, there is a problem to be common and, accompanied by the risk of the process that requires a high temperature and a high risk of high-pressure reaction conditions.
[129]
In addition, the number may be employed a method for producing an average molecular weight low vinyl chloride polymer through the input of the chain transfer agent. However, in the case of bulk polymerization do not have a medium such as water does not easily dispersed in the chain transfer agent target number average molecular weight there is a problem that is difficult to obtain a polymer, or polydispersity index is high, the molecular weight distribution is produced is wide vinyl chloride polymer.
[130]
However, according to the production method of the present invention, as described above, the safety of the process through the efficient use of the chain transfer agent, it is possible to secure the economical efficiency of the product, the vinyl chloride-based polymer suitable for applied to a rigid sheet or fittings It can be prepared.
[131]
In accordance with one embodiment of the present invention, the vinyl-based polymer chloride is by employing the above-described method for manufacturing a) a number average molecular weight of 55,000 or less, b) a degree of polymerization of 890 or less, c) it has a dispersion index be 2.3 or less.
[132]
The above vinyl chloride-based polymer has a number average molecular weight may preferably be 37,000 to 55,000.
[133]
The vinyl chloride-based polymer is an average polymerization degree may preferably be from 600 to 890.
[134]
Also, the vinyl chloride polymer is a mercapto tangye chain transfer agent may be included in more than 500 ppm. Tangye the mercaptosilane chain transfer agent may or may not be removed even if some residual water, after the reaction, and to affect in to become a vinyl chloride polymer application.

WE CLAIM

[Claim 1]
The prepolymerization step by the addition of mercapto tangye chain transfer agent in the monomer composition containing the vinyl chloride monomer and a pre-polymerization initiator to form a particle core; And a vinyl-based monomer and the polymerization step for producing a polymer by the addition of the particle nuclei by the mixture and the polymerization initiator chloride; vinyl chloride-based polymer production method comprising a.
[Claim 2]
The method of claim 1, wherein the mercapto tangye chain transfer agent to method for producing a vinyl-based polymer chloride is represented by the following Formula 1: [Formula 1] and in the formula (I), R1 and R2 are the same or different, each independently , is hydrogen or an alkyl group having 1 to 20 carbon atoms, when R1 and R2 are different from hydrogen, either one of R1 and R2 is -OH, -COOH, or -COOR (wherein, R is an alkyl group having 1 to 5) will a chemical bond, a is a group containing 1 to 30 carbon atoms and the alkylene group, a heteroalkylene group having a carbon number of 1 1 the more hydroxy groups are bonded to 30 alkylene group or a C2 to C30 group, the hetero alkylene group selected from the group consisting of N, O and S above, and one or more heteroatoms including the element X is -OH, -COOH, or -COOR (wherein, R is an alkyl group having 1 to 5 carbon atoms).
[Claim 3]
The method of claim 2 wherein the mercapto tangye chain transfer agent 2-mercaptoethanol, 3-mercapto-1,2-propanediol, methyl mercapto tode decanoate, and 9-mercapto-dimethyl octadecyl -1,18- a vinyl chloride-based polymer production method comprises at least one selected from the group consisting of audio benzoate.
[Claim 4]
The method of claim 1 wherein said chain transfer agent is mercapto tangye the vinyl chloride-based polymer production method will be administered at the time of the conversion of the pre-polymerization of 3 to 8%.
[Claim 5]
The method of claim 1 wherein said chain transfer agent is mercapto tangye the vinyl chloride-based polymer production method will be added in an amount of 0.01 to 0.1 parts by weight vinyl monomer of 100 parts by weight of the chloride prepared in the prepolymerization step.
[Claim 6]
2. The method of claim 1, wherein the polymerization of vinyl chloride-based polymer production method is performed as a bulk polymerization method.
[Claim 7]
The method of claim 1, wherein the volume ratio of the reactor of the reactor and wherein the polymerization of the preliminary polymerization is 25: 75 to 40:60 in that the vinyl chloride-based polymer production method.
[Claim 8]
a) a number average molecular weight of 55,000 or less, b) number average degree of polymerization of 890 or less, c) a polydispersity index of 2.3 or less vinyl chloride polymer.
[Claim 9]
The method of claim 8, wherein the vinyl chloride-based polymer wherein the vinyl chloride polymer is a number average molecular weight of 37,000 to 55,000.
[Claim 10]
The method of claim 8, wherein the vinyl chloride-based polymer wherein the vinyl chloride polymer is having a degree of polymerization of from 600 to 890.
[Claim 11]
9. The method of claim 8 wherein the vinyl chloride-based polymer is a mercapto-vinyl chloride-based polymer that contains a tangye chain transfer agent to less than 500 ppm.