[1][Mutual citations and related applications;
[2]
This application is all the information described in the literature of 04.25.2016 chair Korea Patent Application Korea Patent Application claims the benefit, and those of the priority based on the No. 10-2016-0049960 which is incorporated as a part hereof.
[3]
[4]
[Technology]
[5]
The present invention relates to a production method and hence the vinyl chloride polymer prepared in accordance with the vinyl chloride polymer to improve the melt processability of the high polymerization degree vinyl chloride polymer.
[6]
BACKGROUND
[7]
Vinyl chloride-based polymer is a copolymer comprising a homopolymer or vinyl chloride of 50% or more of vinyl chloride, 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. However, and because of the vinyl chloride-based polymer has a low moldability as such impart workability by suitably adding various additives such as a plasticizer.
[8]
A method of prior art as a method for improving the processability of vinyl chloride polymer, improve the processability of vinyl chloride polymer itself by using a dispersion stabilizer such as a vinyl chloride-based polymer during the polymerization of polyvinyl alcohol has been proposed. However, according to the method of bulk specific gravity of vinyl chloride polymer it is increased, but the melt characteristics of the polymer there is a problem to be lowered.
[9]
In response, as a method for improving the melting property with processability of vinyl chloride polymer, a method for controlling the polymerization degree distribution characteristic by changing the temperature during polymerization of the vinyl chloride polymer it has been proposed. However, such, according to the above method has a high bulk density can be workability manufacturing an improved vinyl chloride-based polymer, but, being the polymerization reaction time is reduced productivity becomes longer, and a vinyl chloride-based monomer according to the change of polymerization temperature due to side reactions between the reactants and additives has a problem that the water grade properties of the polymer itself, such as increase in coloring property, mechanical properties decrease degradation.
[10]
As another method for improving the processability of vinyl chloride polymer, there is generally used a method using a plasticizer along with the manufacture of vinyl chloride-based polymer of the molded article. However, this way when using the plasticizer, in the case of a phthalate-based plasticizer which plasticizer is a plastic is and is a problem that gradually decrease, in particular, mainly depending on the occurred the stickiness of the surface by moving the surface of the product, and further over time during combustion a large amount of smoke, and also represents a fairly flexible in high temperatures, has the disadvantage of requiring a high energy during processing.
[11]
In particular, a vinyl chloride-based polymer having a high polymerization degree, there is a problem that melting time is lengthened significantly decreased productivity in processing a molded article. In order to improve this, if increasing the processing temperature of the color change occurs due to the structural characteristics of the vinyl chloride polymer. In addition if the plasticizer during processing can be processed at low temperature, but there is a limit to the amount used, because the possibility that the physical properties of the processed molded article decreases.
[12]
The high to produce a degree of polymerization of the vinyl chloride polymer with high polymerization productivity of the development process for the production of vinyl chloride-based polymer which has excellent melt processability is desired accordingly.
Detailed Description of the Invention
SUMMARY
[13]
An object of the present invention is to solve the above problems and to provide a high degree of polymerization method of the vinyl chloride vinyl chloride polymer to improve the melt processability of the polymer.
[14]
Another object of the present invention is to provide a vinyl chloride resin containing a vinyl chloride-based polymer and it is prepared according to the method for producing the composition.
[15]
Problem solving means
[16]
In order to solve the above problems, according to one embodiment of the present invention includes the step of suspension polymerizing a vinyl chloride monomer, a pressure relative to the equilibrium pressure at the input after the polymerization reactor the polymerization temperature of the vinyl chloride-based monomer change is 0.5kg / cm 2 to 1.5kg / cm 2 provides a method for producing a vinyl chloride-based polymer added to the aromatic hydrocarbon compound containing a reactive functional group and a hydroxy group containing a double bond between the carbon in the point .
[17]
According to another embodiment of the present invention, is prepared by the above method, the degree of polymerization is provided a vinyl chloride polymer of 1300 to 3000.
[18]
According to another embodiment of the present invention, there is provided a vinyl chloride resin composition comprising a vinyl chloride polymer prepared by the above method.
[19]
Effects of the Invention
[20]
Process for the production of vinyl chloride-based polymer according to the present invention, it is possible by the addition of additives to improve the melt processability of vinyl chloride polymer in the suspension polymerization end, improve the melt processability of the vinyl chloride polymer to be produced.
[21]
Best Mode for Carrying Out the Invention
[22]
Hereinafter, the present invention will be described in more detail to aid the understanding of the present invention.
[23]
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.
[24]
[25]
For general preparation of vinyl chloride polymers by suspension polymerization, the earlier point conversion (critical conversion), the while the pressure is maintained constant by maintaining the equilibrium of the liquid and gas phase, after a certain conversion has a vinyl chloride monomer in the gas phase falling pressure phenomena will occur after consumption. In the present invention, it can be introduced by the additives to improve the melt processability of the vinyl chloride polymers produced by the polymerization reaction at the time of pressure decrease to a certain level, significantly improves the melt processability of the vinyl chloride polymer. As a result, it is possible to increase productivity in the manufacture of processed molded article using the same.
[26]
[27]
Specifically, the production method of the vinyl chloride polymer according to one embodiment of the invention, the vinyl chloride-based monomer, and a comprising the step of suspension polymerization, the equilibrium pressure at the after injection of the chlorinated vinyl monomer polymerization reactor polymerization temperature as the pressure change based on 0.5kg / cm for 2 to 1.5kg / cm 2 to the time point of the aromatic hydrocarbon-based compound containing a reactive functional group and a hydroxy group containing a double bond between the carbon is added.
[28]
[29]
In the production method of the vinyl chloride polymer, according to one embodiment of the present invention, the aromatic hydrocarbon compound is present as a dispersion in the vinyl chloride polymer is prepared form, the hydroxy group in the aromatic hydrocarbon-based compound include vinyl polymers chloride as the radical reaction due to the stability of the radical resonance structure according to the benzene ring it can be to complete a polymerization reaction of a vinyl chloride polymer.
[30]
[31]
The aromatic hydrocarbon compound can be specifically cross-carbon double bond include a reactive functional group and a hydroxyl group, optionally as part of a carbon number of 6 to 20 further comprising a single alkoxy or polycyclic aromatic hydrocarbon compound comprising. At this time, the alkoxy group may date alkoxy having 1 to 10 carbon atoms, may be located at the hydroxy group and the meta-position (meta-position).
[32]
More specifically, to have the aromatic hydrocarbon compound may be a compound of the formula:
[33]
Formula 1
[34]
[35]
In the formula 1,
[36]
R is an alkyl group may be a group having 1 to 10 carbon atoms, more specifically, more than the alkyl group having 1 to 6 carbon atoms, and specifically may be a straight chain alkyl group having 1 to 3 carbon atoms,
[37]
Y is a carbon-reactive functional groups as containing a double bond between carbon atoms, vinyl group, allyl group, isopropenyl pen group, 2-butenyl group, or may be an alkenyl of 2 to 10 carbon atoms, such as Al 3-butenyl group, more specifically as it is more alkenyl groups, having 2 to 6 carbon atoms and particularly, may be an allyl 3 carbon atoms.
[38]
More specifically, the aromatic hydrocarbon-based compound is more eugenol (4-allyl-2-methoxy phenol), or isopropyl, and the like eugenol, a mixture of either or both of them may be used. Most specifically, the above aromatic hydrocarbon compound yuge play.
[39]
[40]
Eugenol serves to be added in the manufacture of a processing composition containing a conventional vinyl chloride polymer workability improves. However, it resulted in a case to be used during processing of the vinyl chloride polymer, a sufficient melt processability in order to obtain the improvement effect, and must be added in excess, and its distinctive odor due to deterioration of the working environment as in the prior art. In addition, when input with the initial stage of polymerization, the monomer of the vinyl chloride polymer, to act as a polymerization inhibitor to inhibit the polymerization reaction, the polymerization degree is to be obtained with low vinyl chloride polymer.
[41]
In the suspension polymerization according to the present invention for end stage, specifically, the polymerization reaction equilibrium pressure is the pressure change on the basis of 0.5kg / cm on board a polymerization temperature of 2 to 1.5kg / cm 2 In the above-mentioned aromatic hydrocarbon-based compound in a view manner, can be produced at the same time having a high polymerization degree of 1,300 to 3,000 melt processability is improved vinyl chloride polymer. At this time, the polymerization temperature may be 40 ℃ to 60 ℃, more specifically 47 to 52 ℃ ℃. If out of the range of a change in pressure, a high polymerization degree can not be obtained and the effect of improving melt processability at the same time. More specifically, the pressure changes based on the equilibrium pressure of the in-flight polymerization polymerization temperature is 0.8kg / cm 2 to 1.2kg / cm 2 can be added to the aromatic hydrocarbon compound in the above point.
[42]
[43]
Further, the above aromatic hydrocarbon compound can be introduced as part of 0.005 to 0.1 parts by weight relative to the vinyl chloride monomer to 100 parts by weight. If the amount of the aromatic hydrocarbon-based compound is less than 0.005 parts by weight, and if the excess of the degree of polymerization and melt processability improving effect is insignificant, and also 0.1 weight according to the input mimihayeo the increase in improved contrast dose effect inefficient, and produced vinyl chloride there is a possibility to degrade the physical properties of the polymer. More specifically, the above aromatic hydrocarbon compound can be added from 0.01 to 0.1 parts by weight based on 100 parts by weight of vinyl chloride monomer.
[44]
[45]
On the other hand, in the production method of the vinyl chloride polymer, according to an embodiment of the invention, the suspension polymerization solvent and a polymerization initiator, and optionally a dispersing agent, such as at least one additive is added to vinyl chloride monomer in the filled polymerisation reactor by the reaction it can be carried out.
[46]
Here, the "filled polymerisation reactor" will represent a state in which a vinyl-based monomer added prior to solvent and a polymerization initiator into the polymerization reactor, the chloride, and optionally, are added the additives of the dispersing agent and the like.
[47]
In the present invention, "polymerization initiator I" means before In the vinyl chloride-based monomer in said reactor filling.
[48]
[49]
Chloride, which is produced by the method for producing the vinyl-based polymer chloride in accordance with one embodiment of the present invention, the vinyl polymer is a polymer made purely as a vinyl chloride monomer, as well as the vinyl chloride monomer as the main component is copolymerized with the vinyl chloride monomer vinyl It may be a copolymer of a monomer. At this time, when the vinyl chloride-based polymer is a copolymer of vinyl chloride monomer and a vinyl monomer is vinyl chloride in the copolymer it may be one that contains more than 50%.
[50]
Accordingly, the suspension polymerization and the vinyl chloride-based monomer used in the vinyl chloride may be a single material; Or it may be a vinyl chloride, and mixtures of said vinyl chloride copolymer and a vinyl-based monomer. Olefins (olefin) compounds, such as the vinyl-based monomer is not particularly limited, 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; Methyl acrylate, ethyl acrylate, maleic acid monomethyl, maleic acid dimethyl, and the unsaturated fatty acid esters such as maleic acid benzyl butyl (ester) and the like; D may be made of a cross-linking monomer such as diallyl phthalate, and any one or a mixture of two or more of them may be used.
[51]
[52]
In addition, the solvent may be a de-ionized water, the amount of the solvent may be appropriately adjusted depending on the amount of monomers used and the polymerization reactor size, for example, relative to 100 parts by weight of vinyl chloride-based monomer used in the suspension polymerization 70 can be used as parts by weight or more.
[53]
[54]
In the polymerization initiator it may be used as part of 0.02 part by weight to 0.2 parts by weight per 100 parts by weight of the vinyl chloride-based monomer used in the polymerization. If, when used in which the polymerization initiator is less than 0.02 parts by weight, it prolongs the polymerization time, and the possibility that the conversion of a vinyl chloride polymer low decrease in productivity, in the polymerization process, when used in excess of 0.2 wt. the polymerization initiator is to remain in the final production of vinyl chloride polymer slurry does not completely consumed in a danger of lowering the thermal stability. More specifically, the polymerization initiator may be used as part of 0.04 to 0.12 parts by weight to 100 parts by weight of a vinyl chloride-based monomers prepared.
[55]
The polymerization initiators include specifically, 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 or the like, and sulfated compounds such as ammonium persulfate, there is any one or a mixture of two or more of them may be used.
[56]
[57]
Further, the suspension polymerization is more specifically 40 ℃ to 60 ℃, may be carried out at a temperature ranging from 47 to 52 ℃ ℃. In addition, conventional polymerization of vinyl chloride polymer may be to maintain the range of temperature change is 0.1 ℃ to 0.2 ℃ during the suspension polymerization, since the exothermic reaction, heat removal process is optionally further carried out through the reactor jacket and the R / CN . Accordingly, the production method of the vinyl chloride polymer according to one embodiment of the present invention may further include a heat removing step to keep the polymerization temperature of suspension polymerization.
[58]
When keeping the temperature of a certain level in the polymerization temperature range as described above, be a polymerization reaction, it is possible to prevent the foam generation and suppressing the re-polymerization and scale generated, and the decomposition of the polymerization initiator in the reaction end of the residual sexual derived superior water after reaction characteristics, i.e. that there is a vinyl chloride-based polymer having a degree of polymerization and improved melt processability can be prepared.
[59]
[60]
In addition, additives such as the suspension polymerization if necessary in addition to the above-described active ingredients (also known as a protective colloid preparation), a dispersing agent, polymerization regulator, chain transfer agent, pH adjusting agent, an antioxidant, a crosslinking agent, an antistatic agent, a scale inhibitor or a surfactant to be further added, and the type and amount of the additives may be used in the industry is known a 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.
[61]
[62]
In some embodiments, the dispersing agent is to act so as to be stabilized during the polymerization reaction was uniform and the resulting particles are stable, and can be added at the beginning of the suspension polymerization. The dispersant may be mentioned specifically, vinyl alcohol resin, cellulose and unsaturated organic acid polymer or the like, may be used any one or a mixture of two or more of them.
[63]
[64]
Further, as a dispersing agent in the polyvinyl alcohol-based resin it may be used to specifically, the moisture content is 30% by weight to 90% by weight, more specifically, moisture content exceeds 50% by weight of 90 wt% or less, the first polyvinyl alcohol and , sign language may be used a mixture of the second polyvinyl alcohol is 30 to 50% by weight. At this time, the first and second mixing ratio of the polyvinyl alcohol is from 2: 1 to 1: 2, more specifically 5: can be a 3: 4 to 2.
[65]
Further, as a dispersing agent in the cellulose, and the like, and specifically it includes methyl cellulose, hydroxyethyl cellulose, or hydroxypropylmethyl cellulose, the one or a mixture of two or more of them may be used. May be hydroxypropylmethylcellulose Of these, more specifically, a 2% aqueous solution viscosity at the content of hydroxypropyl groups in the molecule 3% to 20% by weight, 23 ± 5 ℃ be of 10cps to 20,000cps can.
[66]
Further, as a dispersing agent in the above-mentioned unsaturated organic acid polymer it may be mentioned specifically, acrylic acid polymer, methacrylic acid polymer, itaconic acid polymer, fumaric acid polymer, maleic acid polymer, or acid polymer or the like, there is one or a mixture of two or more of these may be used .
[67]
More specifically, the available dispersing agent for the suspension polymerization may be one which comprises a mixture of vinyl alcohol-based resin and a cellulose-based resin, and more specifically, of the vinyl alcohol-based resin and a cellulose-based resin 5: 1 to 7:07 It may be one comprising a mixture of (by weight).
[68]
[69]
The dispersing agent may be used as part of 0.005 part by weight to 5 parts by weight based on 100 parts by weight of a vinyl chloride-based monomer used in the production of vinyl chloride polymer. Concerns the amount of the dispersant of 0.005 parts by weight of less than if the initial coloring property degrades due to an increase of the fine particles to the particle size of the vinyl chloride polymer is too increased and the risk occur Fish eye (fish-eye), addition exceeding 5 parts by weight a. Considering that the remarkable improvement in the polymerization efficiency and the physical properties of the vinyl chloride polymer effect of the use of the dispersing agent, the dispersing agent may be used as part of 0.005 part by weight to 2.5 parts by weight based on 100 parts by weight of vinyl chloride monomer.
[70]
[71]
In addition, the antioxidants that serve to stop the polymerization reaction and a radical of a vinyl chloride polymer, the suspension polymerization end, and to be more specific, it can be added at the same time as the above-mentioned aromatic hydrocarbon-based compound. In the present invention, the polymerization conversion can measure the amount of vinyl chloride monomer to be recovered after the completion of the reaction by the flow meter, and calculating therefrom. The polymerization conversion ratio includes a margin of error of ± 2% during measurement, and the polymerization conversion rate of 0% is meant to include a polymerization starting time or before the start.
[72]
[73]
The antioxidant as long as it is commonly used in the manufacture of vinyl chloride polymers does not especially limited, specific examples include triethylene glycol-bis - [3- (3-t- butyl-5-methyl-4-hydroxyphenyl ) propionate], hydroquinone, p- methoxyphenol, t- butyl hydroxy anisole, n- octadecyl-3- (4-hydroxy-3,5-di -t- butyl) propionate, 2,5-di -t- butyl-hydroquinone, 4,4-butylidenebis (3-methyl -6-t- butylphenol), t- butyl catechol, 4,4-thio-bis (6-t- butyl -m- cresol), tocopherol, non dihydro obtain fringing phenolic compounds, such as lactic acid (non dihydro guaretic acid); N, N- diphenyl -p- amine compounds such as phenylenediamine, 4,4-bis (dimethylbenzyl) diphenylamine; Dodecyl mercaptan, 1,3-and the like sulfur compounds, such as phenyl-2-thiol, there is any one or a mixture of two or more of them may be used.
[74]
[75]
The antioxidant may be used as part of 0.01 part by weight to 1 part by weight based on 100 parts by weight of a vinyl chloride-based monomer used in the production of vinyl chloride polymer. When When the content of the antioxidant is less than 0.01 parts by weight it is that the particle size of the vinyl chloride polymer is too increased and the risk occur Fish eye, and more than 1 parts by weight due to the increase of the fine particles may cause lowering of the initial coloring. Considering that the remarkable improvement in the polymerization efficiency and the physical properties of the vinyl chloride polymer effect of the use of the dispersing agent, the antioxidant may be used as part of 0.05 part by weight to 1 part by weight based on 100 parts by weight of vinyl chloride monomer.
[76]
[77]
Vinyl chloride polymer produced according to the method above-mentioned manufacturing By this the reactor pressure during the aromatic hydrocarbon compound to the suspension polymerization reaction containing a hydroxy group with a reactive functional group containing a double bond between carbon change it added as desired within the range and it can exhibit excellent melt processability with a high polymerization degree. As a result, it is possible to increase productivity in the manufacture of processed molded article using the same.
[78]
[79]
Thus, according to another embodiment of the present invention, the vinyl chloride-based polymer produced by the process wherein the manufacture is provided.
[80]
The vinyl chloride polymer may be a pure polymer, as well as made of a vinyl chloride monomer and the vinyl chloride monomer as a main component also include copolymers of the vinyl chloride monomer and a copolymerizable vinyl monomer. At this time, when the vinyl chloride-based polymer is a copolymer of vinyl chloride monomer and a vinyl monomer is vinyl chloride in the copolymer it may be one that contains more than 50%. In this case, the vinyl monomer wherein the vinyl chloride monomer and a copolymerizable are the same as previously described.
[81]
[82]
Also, the vinyl chloride-based polymer may be those having a degree of polymerization of 1300 to 3000. Degree of polymerization according to the present invention has an average degree of polymerization was measured by JIS K6721-77.
[83]
[84]
According to further another embodiment of the present invention, the vinyl chloride-based, which a vinyl chloride-based polymer produced by the process the resin composition and the molded article prepared by using this are provided.
[85]
[86]
Specifically, the vinyl chloride-based resin composition is a vinyl-based polymer to 100 parts by weight of plasticizer, 30 parts by weight to 120 parts by weight with respect to the chloride prepared in accordance with the manufacturing method described above, one which more specifically, further comprising 35 parts by weight to 100 parts by weight number, and it may further include a dispersion diluent, a stabilizer, a lubricant, one or more additives such as a viscosity controlling agent, and a foaming agent, as needed.
[87]
The vinyl chloride resin composition by including a vinyl chloride polymer having excellent melt processability is produced by the above production process, exhibits a reduced melting time and melt the load and, as a result, can exhibit excellent workability. The result is to improve the production rate in the manufacture of a molded article using the same, may be particularly useful in the manufacture of heat-resistant electric wire covering, gasket.
[88]
[89]
And to more specifically explain 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.
[90]
Example 1
[91]
Reflux condenser, and a stirrer having an inner volume of 1m 3 as de-ionized water 140 parts by weight of a dispersing agent as a polymerization solvent to a polymerization reactor of stainless hydroxypropylmethylcellulose 0.005 parts by weight, as a polymerization initiator, t- butylperoxy-neodecanoate (BND ) 0.088 inside the stirring after the addition parts by weight were added degassed with a vacuum pump, and 100 parts by weight of vinyl chloride monomer. The reaction was carried out while maintaining the polymerization reactor temperature to 52 ℃ during the reaction the whole process, the equilibrium pressure over 1.0kg / cm in the polymerization polymerization reaction, while checking the in-flight cabin pressure polymerization temperature 2 oxidation at the time that the change in as inhibitors of triethylene glycol-bis - [3- (3-t- butyl-5-methyl-4-hydroxyphenyl) propionate carbonate was added 0.05 part by weight and 0.05 parts by weight of eugenol, and to terminate the polymerization. After the completion of the reaction, respectively the non-reacted monomers and the resin slurry was recovered from the polymerization reactor, and by drying the recovered resin slurry in a fluid bed dryer to give a vinyl chloride polymer.
[92]
[93]
Example 2
[94]
By performing eugenol one The same method as in Example 1, except that the input amount of 0.1 parts by weight to prepare a vinyl chloride polymer.
[95]
[96]
Example 3
[97]
While the polymerization temperature was maintained at 47 ℃ carry out the reaction, and further to and are carried out in the same manner as Example 1, except that the In 0.05 part by weight of eugenol was prepared a vinyl chloride polymer.
[98]
[99]
Example 4
[100]
By performing eugenol one The same method as in Example 3 except that the input amount of 0.1 parts by weight to prepare a vinyl chloride polymer.
[101]
[102]
Comparative Example 1
[103]
To and is carried out in the same manner as in Example 1, except that no use of eugenol was prepared a vinyl chloride polymer.
[104]
[105]
Comparative Example 2
[106]
And it is carried out by the same method as in Example 3 except that no use of eugenol was prepared a vinyl chloride polymer.
[107]
[108]
Comparative Example 3
[109]
Eugenol 0.1, except that the input at the same time as the parts by weight of a dispersing agent and a polymerization initiator before the initiator was carried out in the same manner as in Example 1.
[110]
However, yuge not play a role similar to the antioxidant and the polymerization reaction is not proceeding did not give a vinyl chloride polymer.
[111]
[112]
Comparative Example 4
[113]
Polymerization equilibrium pressure than 0.1kg / cm on board the polymerization temperature 2 addition of antioxidants and yuge at the time that a change in play with the exception that to stop polymerization and the vinyl chloride is carried out in the same manner as in Example 1 -based polymer was produced.
[114]
[115]
Comparative Example 5
[116]
Polymerization equilibrium pressure than 3.0kg / cm on board the polymerization temperature 2 addition of antioxidants and yuge at the time that a change in play with the exception that to stop polymerization and the vinyl chloride is carried out in the same manner as in Example 1 -based polymer was produced.
[117]
[118]
Preparation Example 1
[119]
A vinyl-based polymer to 100 parts by weight of each chloride prepared in Example 1, dioctyl phthalate (DOP), 35 parts by weight of an organic tin compound (MT-800, Songwon Industrial Co., Ltd.) as a heat stabilizer, 2 parts by weight of a lubricant as a plasticizer ( after addition SONGSTAB SL-29, Songwon industrial Co., Ltd.) 1 part by weight was prepared by mixing a vinyl chloride, a thermoplastic resin composition.
[120]
[121]
Preparation Examples 2 to 4 and Comparative Preparation Examples 1 to 5
[122]
The above Examples 2 to 4 and Comparative Examples 1 except for the vinyl chloride polymer prepared by the use of respectively 5 and are carried out in the same manner as in Preparation Example 1, a vinyl chloride-based thermoplastic resin composition was prepared.
[123]
[124]
Experimental Example
[125]
The Examples 1-4, and Comparative Example 1, the average degree of polymerization of the vinyl chloride polymer prepared in 1-5, and the melting time and the load of the molten thermoplastic resin composition containing the vinyl chloride-based polymer was measured, respectively. The results are shown in Table 1.
[126]
(1) The average degree of polymerization
[127]
It was measured by JIS K6721-77.
[128]
(2) melting time (fusion time) and melting load measurement
[129]
In Example 1-4, and Comparative Examples 1 to 140 ℃ using Bradender plastograph for a thermoplastic resin composition comprising a vinyl chloride polymer prepared in 5, the conditions of 30rpm to measure the melting time and melt-load respectively. The shorter the melting time indicates that the melting properties can be excellent.
[130]
TABLE 1
Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4
Eugenol amount (parts by weight) 0.05 0.1 0.05 0.1 0 0 0.1 0.05
In time △1.0kg/cm2 △1.0kg/cm2 △1.0kg/cm2 △1.0kg/cm2 - - Before the start of polymerization △0.1kg/cm2
The average degree of polymerization 1300 1300 1700 1700 1300 1700 ND 1300
Melting time (sec) 274 255 518 495 304 576 ND 268
Melting load (Nm) 26.2 26.5 26.3 26.1 27.9 27.3 ND 26.3

[131]
In Table 1 ND means hayeoteum polymerization is not measured because the physical properties take place.
[132]
The experimental results, in the case of a thermoplastic resin composition comprising the Examples 1 to 4 vinyl chloride polymer of one In the polymerization end eugenol, regardless of the amount of the polymerization degree and eugenol of vinyl chloride polymer in Comparative Example 1 and compared to the second the melting time is shortened, the lower melting load. In particular embodiments in comparison 1 and 2, but further shortening the melt time as the amount of eugenol increased melt load was substantially the same level. In addition, it exhibited the same results as in Examples 1 and 2 than in Examples 3 and 4 having a high polymerization degree.
[133]
The pressure change is 0.1kg / cm 2 in the case of comparing the completion of the reaction by the addition of the eugenol in the time Example 4. The physical properties of the produced vinyl chloride polymer is yieoteuna Example 1 and the same level, polymerization time compared to the vinyl chloride polymer the production rate decreases were inefficient in terms of productivity. The pressure change is 3.0kg / cm 2 is in a lowered compared to terminate the reaction of eugenol was added at the time also in the case of Example 5, the polymerization time of the production rate compared to the vinyl chloride polymer was less efficient in terms of productivity.
[134]
This results from the same experiment on the basis of the equilibrium pressure is the pressure change 0.5kg / cm in the polymerization reactor during the polymerization The polymerization temperature of vinyl chloride polymer 2 to 1.5kg / cm 2 by the addition of eugenol to the point that melting time is shortened the molten low load it can be seen that advantageous than that of the workpiece forming.

Claims

[Claim 1]Comprising the step of suspension polymerizing a vinyl chloride-based monomer, it added after the polymerization reaction equilibrium pressure is the pressure change on the basis of 0.5kg / cm on board the polymerization temperature of the vinyl chloride monomer 2 to 1.5kg / cm 2 in a view , the carbon between the method for producing a vinyl chloride-based polymer added to the aromatic hydrocarbon compound containing a reactive functional group and a hydroxy group containing a double bond.
[Claim 2]
The method according to claim 1, wherein the aromatic hydrocarbon-based compound comprises a reactive functional group and a hydroxy group containing a double bond between carbon, or a monocyclic or polycyclic aromatic hydrocarbon compounds having 6 to 20 further comprising an alkoxy group having 1 to 10 carbon atoms the method of producing a vinyl chloride-based polymer will.
[Claim 3]
The method according to claim 2, wherein the aromatic hydrocarbon-based compound is A method for producing a vinyl-based polymer chloride comprises a compound of formula 1: [Formula 1] In Chemical Formula 1, R is an alkyl group having 1 to 10, Y is an alkenyl group having 2 to 10 carbon atoms.
[Claim 4]
The method according to claim 2, the method of producing a vinyl chloride polymer to the aromatic hydrocarbon-based compounds include eugenol.
[Claim 5]
The method according to claim 1, wherein the aromatic hydrocarbon compound is A method for producing a vinyl chloride polymer that is added 0.005 part by weight to 0.1 parts by weight based on 100 parts by weight of vinyl chloride monomer.
[Claim 6]
The method according to claim 1, wherein the suspension polymerization is a method for producing a vinyl chloride-based polymer is performed in a solvent in the presence of a polymerization initiator and a dispersing agent.
[Claim 7]
The method according to claim 1, wherein the polymerization temperature is in the method for producing a vinyl chloride-based polymer to the 40 ℃ to 60 ℃.
[Claim 8]
Is manufactured by the manufacturing method according to claim 1, wherein the vinyl chloride-based polymer a degree of polymerization of 1300 to 3000.
[Claim 9]
Vinyl chloride-based resin composition comprising a vinyl chloride polymer according to claim 8.
[Claim 10]
The method according to claim 9, wherein the vinyl chloride-based resin composition with respect to the vinyl chloride-based polymer comprising 100 parts by weight of a plasticizer, 30 parts by weight to 120 parts by weight.