WO2018056611A1 - Method for preparing vinyl chloride-based polymer, vinyl chloride-based polymer, and vinyl chloride-based polymer composition - Google Patents

Method for preparing vinyl chloride-based polymer, vinyl chloride-based polymer, and vinyl chloride-based polymer composition Download PDF

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Publication number
WO2018056611A1
WO2018056611A1 PCT/KR2017/009713 KR2017009713W WO2018056611A1 WO 2018056611 A1 WO2018056611 A1 WO 2018056611A1 KR 2017009713 W KR2017009713 W KR 2017009713W WO 2018056611 A1 WO2018056611 A1 WO 2018056611A1
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Prior art keywords
vinyl chloride
phosphite
based polymer
polymer
producing
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PCT/KR2017/009713
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French (fr)
Korean (ko)
Inventor
안성용
김건지
이세웅
하현규
신성재
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주식회사 엘지화학
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Priority claimed from KR1020170112014A external-priority patent/KR102105041B1/en
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to EP17853325.3A priority Critical patent/EP3357942B1/en
Priority to US15/774,961 priority patent/US10696760B2/en
Priority to CN201780004330.XA priority patent/CN108290978B/en
Publication of WO2018056611A1 publication Critical patent/WO2018056611A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F14/02—Monomers containing chlorine
    • C08F14/04—Monomers containing two carbon atoms
    • C08F14/06—Vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/02—Polymerisation in bulk
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride

Definitions

  • the present invention relates to a vinyl chloride-based polymer production method, a vinyl chloride-based polymer and a vinyl chloride-based polymer composition, a method of preparing a vinyl chloride-based polymer in which phosphite is added during polymerization to improve thermal stability and transparency, vinyl chloride It is to provide a polymer and a vinyl chloride polymer composition.
  • Vinyl chloride-based polymers are the most commonly used synthetic resin among thermoplastic resins.
  • Polymerization methods of the vinyl chloride polymer include suspension polymerization, emulsion polymerization and bulk polymerization.
  • the bulk polymerization does not use water and a dispersing agent (emulsifier) and polymerizes only the vinyl chloride monomer, the initiator, and the reaction additive as necessary.
  • the bulk polymerization has a merit that the apparatus is simple, the reaction is fast, and does not undergo the purification process such as distillation, extraction, so that the yield is high, the polymer of high purity can be obtained, and the polymer can be handled as it is.
  • the bulk polymerization has a disadvantage in that it is difficult to control the temperature due to the strong heat generation during the polymerization process.
  • the bulk polymerization has no material capable of absorbing and removing the heat of polymerization other than the vinyl chloride monomer, and the viscosity of the polymer increases as the polymerization proceeds, so that it is difficult to spread the reaction heat by conduction or convection. Accordingly, in the case of the vinyl chloride polymer prepared by the bulk polymerization, heat may be damaged due to the reaction heat generated during the bulk polymerization process or an unexpectedly generated exotherm, and thus, it is very important to secure the thermal stability of the vinyl chloride polymer. .
  • An object of the present invention is to provide a method for preparing a vinyl chloride-based polymer using a phosphite which can perform both a heat stabilizer and an antioxidant.
  • the present invention is the first step of the bulk polymerization of the vinyl chloride monomer in the presence of the initiator; And a second step of obtaining a vinyl chloride polymer after completing the bulk polymerization, and providing a phosphite in the first step.
  • the present invention also provides a vinyl chloride polymer, characterized in that the phosphite is dispersed in a matrix of the vinyl chloride polymer.
  • the present invention is a vinyl chloride polymer; It provides a vinyl chloride polymer composition comprising at least one selected from the group consisting of stabilizers, processing aids, impact modifiers and lubricants.
  • the method of preparing the vinyl chloride polymer of the present invention by adding phosphite in the polymerization process, thermal damage of the vinyl chloride polymer may be minimized due to unexpected heat generation during the bulk polymerization process, which is difficult to control the temperature.
  • the phosphite can suppress side reactions of the initiator that may occur during the bulk polymerization process. Accordingly, it is possible to minimize the coloring of the vinyl chloride-based polymer caused by the side reaction to improve transparency, and to prevent a decrease in the bulk polymerization rate.
  • the vinyl chloride polymer of the present invention and the vinyl chloride polymer composition including the same may improve both thermal stability and transparency.
  • the vinyl chloride polymer may mean that phosphite is dispersed in a matrix of the vinyl chloride polymer.
  • the vinyl chloride polymer and the phosphite are not chemically bonded, but may mean that the phosphite is uniformly dispersed and immobilized between the matrix of the vinyl chloride polymer, that is, the three-dimensional network structure. have.
  • the method for preparing a vinyl chloride polymer according to the first embodiment of the present invention may include a first step of bulk polymerizing a vinyl chloride monomer in the presence of an initiator, and phosphite may be added in the first step. .
  • the first step specifically includes a first-first step of mass-polymerizing the first vinyl chloride monomer and forming particle nuclei in the presence of the first initiator; And in the presence of a second initiator, may include a step 1-2 of the second bulk polymerization of the particle nucleus, the first vinyl chloride monomer and the second vinyl chloride monomer unreacted in the step 1-1. .
  • the first and second initiators may be the same as or different from each other, and each independently dicumyl peroxide, dipentyl peroxide, di (3,5,5-trismethylhexanoyl) per Diacyl peroxides such as oxide (di (3,5,5-trimethylhexanoyl) peroxide) and dilauuroyl peroxide; Diisopropyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, di (2-ethylhexyl) peroxydicarbonate, etc.
  • Peroxycarbonates t-butylperoxy neodecanoate, t-butylperoxy neoheptanoate, t-amyl peroxy neodecanoate, cumyl Cumyl peroxy neodecanoate, cumyl peroxy neoheptanoate, 1,1,3,3-tetramethylbutyl peroxynedecanoate (1,1,3,3 peroxy esters such as -tetramethylbutyl peroxy neodecanoate); Azo compounds, such as azobis-2,4-dimethylvaleronitrile (azobis-2,4-dimethylvaleronitrile); It may be at least one selected from the group consisting of sulfates such as potassium persulfate and ammonium persulfate.
  • sulfates such as potassium persulfate and ammonium persulfate.
  • the first or second vinyl chloride monomer may be the same as or different from each other, and each independently may be a pure vinyl chloride monomer, a vinyl monomer copolymerizable with the pure vinyl chloride monomer and copolymerized with the pure vinyl chloride monomer. It may be a mixed monomer comprising a.
  • the mixed monomer may include 1 to 50 parts by weight of the vinyl monomer based on 100 parts by weight of the vinyl chloride monomer.
  • the vinyl monomers include olefin compounds such as ethylene and propylene; Vinyl esters such as vinyl acetate and vinyl propionate; Unsaturated nitriles such as acrylonitrile; Vinyl alkyl ethers such as vinyl methyl ether and vinyl ethyl ether; Unsaturated fatty acids such as acrylic acid, methacrylic acid, itaconic acid and maleic acid; And it may be at least one selected from the group consisting of anhydrides of these fatty acids.
  • the first initiator may be included in an amount of 0.01 to 0.2 parts by weight, specifically 0.03 to 0.15 parts by weight, and more specifically 0.05 to 0.1 parts by weight based on 100 parts by weight of the first vinyl chloride monomer. When the above range is satisfied, the stability of the process during polymerization is excellent.
  • the second initiator is 0.03 to 0.6 parts by weight, specifically, based on 100 parts by weight of the total amount of the particle nucleus, the unreacted first vinyl chloride monomer and the second vinyl chloride monomer in step 1-1. 0.05 to 0.4 parts by weight, more specifically 0.08 to 0.3 parts by weight may be included. When the above range is satisfied, the stability of the process during polymerization is excellent.
  • the first bulk polymerization may be performed at a temperature of 60 to 80 ° C. and a pressure of 9 to 14 kg / cm 2 G. If the above conditions are satisfied, the particle nucleus can be formed from the first vinyl chloride monomer. When the polymerization conversion rate is 10% to 15%, the first bulk polymerization may be terminated.
  • the second bulk polymerization may be performed at a temperature of 50 to 70 ° C. and a pressure of 7 to 12 kg / cm 2 G. If the above conditions are satisfied, the particle nucleus can be grown to form a vinyl chloride polymer.
  • the phosphite may be added in any one of the first step and the second step, it can be added in both the first step and the second step.
  • the phosphite may be added before the first block polymerization is performed, and the phosphite may be added during the first block polymerization.
  • the phosphite may be added before the second block polymerization is performed, during the second block polymerization, or after the second block polymerization is completed.
  • the phosphite may be added before the first bulk polymerization is performed, and in the first-second step, the phosphite is added before the second bulk polymerization is performed. can do.
  • the phosphite may be added while stirring is maintained, and the phosphite may be added and then stirred.
  • the phosphite When the phosphite is added in the above-described step, it is possible to prevent thermal damage of the vinyl chloride-based polymer, which may occur due to unexpected heat generation during the bulk polymerization process, which is difficult to control the temperature.
  • the phosphite may suppress side reactions due to initiators that may occur in the first and second bulk polymerization processes. As a result, it is possible to minimize coloring caused by the side reactions, thereby improving transparency of the vinyl chloride polymer as a final product.
  • the mass polymerization rate can be kept constant without lowering.
  • since a processed product using a vinyl chloride polymer is processed at a high temperature, it is very important to secure transparency and thermal stability.
  • the phosphite is included in the polymerization process of the vinyl chloride-based polymer, it can be dispersed to reach the matrix of the vinyl chloride-based polymer. Accordingly, the transparency and thermal stability of the processed product using the composition containing the vinyl chloride-based polymer including the phosphite according to the production method of the present invention rather than the processed product prepared using the composition containing the vinyl chloride-based polymer and phosphite. It can be much better.
  • the phosphite may be a compound represented by Formula 1 below.
  • L 1 to L 3 are each independently the same as or different from each other, and are a direct bond, an alkylene group of C1 to C20, or an arylene group of C6 to C20,
  • R 1 to R 3 are each independently the same or different and are a substituted or unsubstituted C1 to C20 straight or branched chain alkyl group or a substituted or unsubstituted C6 to C20 aryl group.
  • 'direct bond' means that O and R 1 to R 3 are directly bonded without L 1 to L 3 .
  • the phosphite satisfying Formula 1 may be at least one selected from the group consisting of compounds shown in Table 1 below.
  • Trisethyl phosphite 2 Trisisopropyl phosphite 3 Trisisodecyl phosphite 4 Trisdodecyl phosphite 5 Phenyl-diisodecyl phosphite 6 Diphenyl-isodecyl phosphite 7 Trisphenyl phosphite 8 Phenyl-bis (4-nonylphenyl) phosphite 9 Tris (4-octylphenyl) phosphite 10 Tris [(4-1-phenylethyl) phenyl] phosphite
  • the phosphite may be added in an amount of 0.001 to 1 part by weight, specifically 0.003 to 0.1 part by weight, based on 100 parts by weight of the total of the first and second vinyl chloride monomers. If the above range is satisfied, thermal damage of the vinyl chloride polymer may be minimized, which may occur due to the exotherm generated unexpectedly during the bulk polymerization process. Since it is possible to suppress side reactions caused by the first and second initiators that may occur in the first and second bulk polymerization processes, it is possible to minimize the coloration generated by the side reactions, thereby improving transparency of the final product vinyl chloride polymer. Can be improved. In addition, since the side reaction of the initiator is suppressed, the mass polymerization rate can be kept constant without lowering.
  • the phosphite may be added in a solution mixed with a solvent.
  • the phosphite may be included in an amount of 0.1 to 5% by weight, specifically 0.5 to 2% by weight, based on the total weight of the solution.
  • the phosphite can be more uniformly dispersed in the first and second vinyl chloride monomers, thereby improving the thermal stability and transparency of the vinyl chloride polymer as a final product.
  • the phosphite may be added to at least one selected from the group consisting of the first vinyl chloride monomer and the second vinyl chloride monomer by spray spraying or spraying through a nozzle.
  • after the addition of the phosphite may be stirred to disperse one or more selected from the group consisting of the first vinyl chloride monomer and the second vinyl chloride monomer.
  • the solvent may be an alcohol solvent which is easily volatilized during the bulk polymerization process and does not burden the polymerization, and the alcohol solvent may be methanol, ethanol, isopropanol, 1-methoxypropanol, butanol, ethylhexyl alcohol, and terpineol It may be at least one selected from the group consisting of.
  • the method for preparing a vinyl chloride polymer according to the first embodiment of the present invention may include a second step of obtaining a vinyl chloride polymer after completing the bulk polymerization.
  • the bulk polymerization may be completed, and a reaction terminator may be added to complete the bulk polymerization.
  • the reaction terminator is a substance which terminates the reaction by losing the function of the second initiator, and may be at least one selected from the group consisting of a phenol compound, an amine compound, a nitrile compound, and a sulfur compound.
  • the phenolic compound is triethylene glycol-bis-3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate (triethylene glycol-bis-3- (3-t-butyl-4-hydroxy- 5-methylphenylpropionate), hydroquinone, p-methoxy phenol, t-butyl-4-hydroxyanisole, n-octadecyl- 3- (4-hydroxy-3,5-di-t-butylphenyl) propionate (n-octadecyl-3- (4-hydroxy-3,5-di-t-butylphenyl) propionate), 2,5 2,5-di-t-butyl hydroquione, 4,4'-butylidene bis (3-methyl-6
  • 4,4-bis (dimethylbenzyl) diphenyl (4,4-bis (dimethylb) enzyl) diphenyl) may be at least one selected from the group consisting of 4-hydroxy-2,2,6,6-tetramethyl-piperidine-1-oxyl (4-Hydroxy-2, 2,6,6-tetramethyl piperidine 1-oxyl)
  • the sulfur compounds are dodecyl mercaptan and 1,2-biphenyl-2-thiol. It may be at least one selected from the group consisting of.
  • additives such as antioxidants may be added as necessary.
  • the antioxidant may be added for the purpose of making the color of the vinyl chloride polymer white.
  • the vinyl chloride polymer according to the second embodiment of the present invention is prepared according to the method for producing a vinyl chloride polymer according to the first embodiment, includes a vinyl chloride polymer and a phosphite salt, and the phosphite salt is It may be dispersed in a matrix of the vinyl chloride polymer. Specifically, the phosphite may be integrated into a vinyl chloride polymer matrix, that is, uniformly dispersed and immobilized between three-dimensional network structures.
  • the phosphite may be included in an amount of 0.001 to 2% by weight, specifically 0.008 to 1% by weight, and more specifically 0.005 to 0.1% by weight, based on the total weight of the vinyl chloride polymer.
  • the phosphite is hardly lost in the manufacturing process of the vinyl chloride polymer, and specifically, 90% or more of the phosphite added in the manufacturing method of the vinyl chloride polymer may be included in the polymer. Accordingly, the total weight of the vinyl chloride polymer may be included in the above-described range.
  • the phosphite may provide a vinyl chloride polymer having excellent thermal stability and transparency without degrading the performance of the vinyl chloride polymer without loss in the manufacturing process of the vinyl chloride polymer.
  • the vinyl chloride polymer composition according to the third embodiment of the present invention may include one or two or more selected from the group consisting of the vinyl chloride polymer and a stabilizer, a processing aid, an impact modifier, and a lubricant.
  • the stabilizer is a material that prevents coloring and decomposition by increasing stability to heat, and may be a metal-based stabilizer or an organic acid metal salt stabilizer.
  • the metal stabilizer may be one or two selected from the group consisting of lead stabilizers, (organic) tin stabilizers, cadmium stabilizers, and barium stabilizers.
  • the organic acid metal salt may be a metal salt of carboxylic acid, organophosphoric acid or phenols.
  • the carboxylic acid is capric acid, caprylic acid, pelagonic acid, 2-ethylhexyl acid, capric acid, neodecanoic acid, undecylenic acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, 12- Hydroxystearic acid, chlorostearic acid, 12-ketostearic acid, phenylstearic acid, ricinolic acid, linoleic acid, linolenic acid, oleic acid, arachnic acid, behenic acid, ercaic acid, brasidic acid, pseudoacid, resin fatty acid, palm oil fatty acid, tung oil fatty acid, 1 selected from the group consisting of soybean oil fatty acid, cottonseed oil fatty acid, benzoic acid, pt-butylbenzoic acid, ethylbenzoic acid, isopropylbenzoic acid, toluic acid, xyly
  • the organic phosphoric acid is monooctyl phosphoric acid, dioctyl phosphoric acid, monododecyl phosphoric acid, didodecyl phosphoric acid, monooctadecyl phosphoric acid, dioctadecyl phosphoric acid, mono (nonylphenyl) phosphoric acid, di (nonylphenyl) phosphoric acid, phosphonic acid nonylphenyl It may be one kind or two or more kinds selected from the group consisting of esters, phosphonic acid nonylphenyl esters, and phosphonic acid stearyl esters.
  • the phenols may be one or more selected from the group consisting of phenol, cresol, ethylphenol, cyclohexylphenol, nonylphenol and dodecylphenol.
  • the metal salt may be neutral salt, acid salt, basic salt or overbased complex.
  • the processing aid is a substance that promotes gelation of the vinyl chloride polymer, the homopolymer or copolymer of alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, butyl methacrylate; Copolymers of the above alkyl methacrylate with alkyl acrylates such as methyl acrylate, ethyl acrylate and butyl acrylate; Copolymers of the above alkyl methacrylates with aromatic vinyl compounds such as styrene, ⁇ -methylstyrene, and vinyltoluene; And copolymers of alkyl methacrylate with vinyl cyan compounds such as acrylonitrile and methacrylonitrile.
  • the processing aid may be used alone or in combination of two or more thereof.
  • the impact modifier is a material that reinforces the impact resistance by imparting elasticity to the vinyl chloride polymer, MBS (Methyl Methacrylate-Butadiene Styrene) polymer, chlorinated polyethylene copolymer, ethylene vinyl acetate polymer, acrylic polymer and butadiene polymer It may be one or more selected from the group consisting of.
  • MBS Metal Methacrylate-Butadiene Styrene
  • the lubricant is a substance that improves the processability and interfacial properties of the vinyl chloride polymer, hydrocarbon lubricants such as low molecular wax, paraffin wax, polyethylene wax, chlorinated hydrocarbon, fluorocarbon; Natural wax-based lubricants such as carnauba wax and candelilla wax; Fatty acid lubricants such as higher fatty acids such as lauric acid, stearic acid and behenic acid, or oxy fatty acids such as hydroxystearic acid; Aliphatic amide lubricants such as aliphatic amide compounds such as stearylamide, laurylamide, and oleylamide or alkylenebisaliphatic amides such as methylenebisstearylamide and ethylenebisstearylamide; Fatty acid monohydric alcohol ester compounds, such as stearyl stearate, butyl stearate, and distearyl phthalate, or glycerin tris stearate, sorbitan tri
  • Example 1-1 Example 1-2, Comparative example 1-1 and Comparative example 1-2
  • the vinyl chloride monomer was polymerized in the following manner using a polymerization apparatus including the same.
  • the total amount of particle nuclei in the polymerization reactor, the total amount of unreacted vinyl chloride monomer in the first bulk polymerization, 80 kg of additional vinyl chloride monomer, and 1,1,3,3-tetramethyl butyl peroxy neo as an initiator were 200 g of decanoate was added sequentially and stirred. While maintaining the agitation, the polymerization was initiated under the temperature and pressure shown in Table 2 below and the second bulk polymerization was carried out for the time shown in Table 2. When the polymerization conversion rate shown in Table 2 was reached, 200 g of butylated hydroxytoluene was sequentially added to the phosphate solution and antioxidant as shown in Table 3, and then residual unreacted in vacuo while stirring was maintained. After recovering the monomer, a vinyl chloride polymer was obtained.
  • Example 1-1 Trisphenyl phosphite One ethanol 99 One
  • Example 1-2 Tris Dodecyl Phosphite One ethanol 99 10 Comparative Example 1-1 - - - - - - Comparative Example 1-2 - - - - - -
  • Example 1-3 Example 1-4
  • the vinyl chloride monomer was polymerized in the following manner using a polymerization apparatus including the same.
  • the total amount of particle nuclei in the polymerization reactor, the total amount of unreacted vinyl chloride monomer in the first bulk polymerization, 80 kg of additional vinyl chloride monomer, and 1,1,3,3-tetramethyl butyl peroxy neo as an initiator were 200 g of decanoate was added sequentially and stirred.
  • the second mass polymerization was carried out for the time shown in Table 4 under a temperature of 52 ° C. and a pressure of 7.5 kg / cm 2 G while maintaining the stirring. At this time, the polymerization conversion rate was 55%. 200 g of butylated hydroxy toluene was added as an antioxidant, and the vinyl chloride polymer was obtained after recovering the residual unreacted monomer in vacuo while stirring was maintained.
  • Example 1-3 180 Phenyl-bis (4-nonylphenyl) phosphite One ethanol 99 One Example 1-4 200 Tris (4-octylphenyl) phosphite One ethanol 99 3
  • a polymerization apparatus including a polymerization reactor of 1 m 3, a reflux condenser connected to the polymerization reactor to remove the temperature of the polymerization reaction, and a vinyl chloride recovery pipe connected to the reflux condenser and discharging the unreacted vinyl chloride monomer.
  • the vinyl chloride monomer was polymerized in the following manner.
  • the first polymer slurry was recovered, and a stripping process and a dehydration process were performed to separate the unreacted vinyl chloride monomer and water to obtain a second polymer slurry.
  • the second polymer slurry was hot-air dried at 60 ° C. in a fluidized bed dryer to separate residual water and to obtain a vinyl chloride polymer in powder form through a screening facility.
  • the content of phosphite in the obtained vinyl chloride polymer was measured, but could not be measured because the phosphite was already hydrolyzed.
  • Example 2-1 to 2-4 Comparative example 2-1 to Comparative example 2-4
  • Example 2-1 Example 1-1 - - Example 2-2
  • Example 1-2 - - Example 2-3 Example 1-3 - - Example 2-4
  • Example 1-4 - - Comparative Example 2-1 Comparative Example 1-1 - - Comparative Example 2-2
  • Comparative Example 1-2 - - Comparative Example 2-3 Comparative Example 1-1 Trisphenyl phosphite
  • the preliminary sheet was cut and overlapped 10 sheets, put into a 3 mm thick mold and compressed, preheated at 185 ° C. for 2 minutes, heated at 185 ° C. for 3 minutes at a pressure of 10 kg / cm 2, and 15 kg / cm 2.
  • the sheet was cooled to 2 minutes at a pressure of 185 ° C. to produce a sheet having a thickness of 3 mm.
  • Example 3-1 Example 1-1 - - Example 3-2
  • Example 1-2 - - Example 3-3 Example 1-3 - - Example 3-4
  • Example 1-4 - - Comparative Example 3-1 Comparative Example 1-1 - - Comparative Example 3-2
  • Comparative Example 1-2 - - Comparative Example 3-3 Comparative Example 1-1 Trisphenyl phosphite
  • Haze Defined as the percentage of light that passes through the sample relative to the initial fired beam, the more the light passes through the sample, the smaller the value of turbidity, which means better transparency.
  • Example 2-1 6.6 86.5
  • Example 2-2 7.0 85.5
  • Example 2-4 7.1 85.0 Comparative Example 2-1 10.5 77.6 Comparative Example 2-2 10.7 77.1 Comparative Example 2-3 8.5 83.0 Comparative Example 2-4 10.6 76.4
  • the sheets of Examples 2-1 to 2-4 had turbidity of 6.6% to 7.1% and transmittance of 85.0% to 86.5%.
  • the sheets of Comparative Examples 2-1 and 2-2 had turbidity of 10.5% and 10.7% and transmittance of 77.6% and 77.1%, the sheets of Examples 2-1 to 2-4 were more transparent than the sheets of Examples 2-1 to 2-4. I could see this falling. It can be seen that the sheets of Comparative Example 2-3 are inferior in turbidity and permeability as compared with the sheets of Examples 2-1 to 2-4.
  • the sheet of Comparative Example 2-3 has transparency because the phosphite is not dispersed in the matrix of the vinyl chloride-based polymer even though the content of the phosphite in the sheet is similar to the sheet made of the vinyl chloride-based polymer of the present invention. It was found that the degradation. Since the sheet of the comparative example 2-4 was the same as using the vinyl chloride polymer type polymer which did not add the phosphite, it turned out that suspension and permeability are inferior.
  • thermal stability of the sheets of Examples 3-1 to 3-4 and Comparative Examples 3-1 to 3-4 was measured using NR-3000 (manufacturer: Nippon Denshoku). ) was measured and the results are shown in Table 8. In general, the thermal stability can be evaluated from the whiteness value, and the higher the whiteness value, the better the thermal stability.
  • Example 3-1 32.90 Example 3-2 32.45
  • Example 3-3 32.10 Example 3-4 31.80 Comparative Example 3-1 23.50 Comparative Example 3-2 23.00 Comparative Example 3-3 28.30 Comparative Example 3-4 28.00
  • the sheets of Examples 3-1 to 3-4 had excellent thermal stability because the whiteness values were 31.80 to 32.90.
  • the sheets of Comparative Examples 3-1 and 3-2 have whiteness values of 23.5 and 23, so that the thermal stability was lower than those of Examples 3-1 to 3-4. It can be seen that the sheet of Comparative Example 3-3 has a lower whiteness than the sheets of Examples 3-1 to 3-4.
  • the sheet of Comparative Example 3-3 is thermally stable because the phosphite is not dispersed in the matrix of the vinyl chloride-based polymer even though the content of the phosphite in the sheet is similar to the sheet made of the vinyl chloride-based polymer of the present invention. It turned out that this falls. Since the sheet

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Abstract

The present invention relates to a method for preparing a vinyl chloride-based polymer, to a vinyl chloride-based polymer, and to a vinyl chloride-based polymer composition comprising same, the method comprising: a first step of bulk polymerizing a vinyl chloride-based monomer under the presence of an initiator; and a second step of obtaining a vinyl chloride-based polymer after completing the bulk polymerization, wherein a phosphite is input in the first step.

Description

염화비닐계 중합체의 제조방법, 염화비닐계 중합체 및 염화비닐계 중합체 조성물Method for preparing vinyl chloride polymer, vinyl chloride polymer and vinyl chloride polymer composition
[관련출원과의 상호인용][Citations with Related Applications]
본 발명은 2016.09.26에 출원된 한국 특허 출원 제10-2016-0123388호 및 2017.09.01에 출원된 한국 특허 출원 제10-2017-0112014호에 기초한 우선권의 이익을 주장하며, 해당 한국 특허 출원의 문헌에 개시된 모든 내용을 본 명세서의 일부로서 포함한다.The present invention claims the benefit of priority based on Korean Patent Application No. 10-2016-0123388 filed on September 26, 2016 and Korean Patent Application No. 10-2017-0112014 filed on September 1, 2017, All content disclosed in the literature is included as part of this specification.
[기술분야][Technical Field]
본 발명은 염화비닐계 중합체의 제조방법, 염화비닐계 중합체 및 염화비닐계 중합체 조성물에 관한 것으로서, 아인산염을 중합 과정에서 투입시켜 열안정성 및 투명성을 개선시킨 염화비닐계 중합체의 제조방법, 염화비닐계 중합체 및 염화비닐계 중합체 조성물을 제공하는 것이다. The present invention relates to a vinyl chloride-based polymer production method, a vinyl chloride-based polymer and a vinyl chloride-based polymer composition, a method of preparing a vinyl chloride-based polymer in which phosphite is added during polymerization to improve thermal stability and transparency, vinyl chloride It is to provide a polymer and a vinyl chloride polymer composition.
염화비닐계 중합체는 열가소성 수지 중 가장 많이 사용되는 합성 수지이다. 염화비닐계 중합체의 중합방식에는 현탁 중합, 유화 중합 및 괴상 중합이 있다. 이 중 괴상 중합은 물과 분산제(유화제)를 사용하지 않고 염화비닐계 단량체, 개시제 그리고 필요에 따라 반응 첨가제만을 공급하고 중합한다. 괴상 중합은 장치가 간단하고, 반응이 빠르며, 증류, 추출 등의 정제과정을 거치지 않으므로 수득률이 높고, 고순도의 중합체를 얻을 수 있으며, 중합체를 그대로 취급할 수 있는 장점이 있다. Vinyl chloride-based polymers are the most commonly used synthetic resin among thermoplastic resins. Polymerization methods of the vinyl chloride polymer include suspension polymerization, emulsion polymerization and bulk polymerization. Among these, the bulk polymerization does not use water and a dispersing agent (emulsifier) and polymerizes only the vinyl chloride monomer, the initiator, and the reaction additive as necessary. The bulk polymerization has a merit that the apparatus is simple, the reaction is fast, and does not undergo the purification process such as distillation, extraction, so that the yield is high, the polymer of high purity can be obtained, and the polymer can be handled as it is.
하지만 괴상 중합은 중합 과정에서 발열이 강하여 온도조절이 어렵다는 단점이 있다. 그리고, 괴상 중합은 염화비닐계 단량체 이외에 중합 열을 흡수해 제거해 줄 수 있는 물질이 없고, 중합의 진행에 따라 중합 물질의 점도도 증가하므로 전도 또는 대류에 의해 반응열 확산이 어렵다는 단점이 있다. 이에 따라 괴상 중합에 의해 제조된 염화비닐계 중합체의 경우, 괴상 중합 과정에서 발생하는 반응열 또는 예기치 못하게 발생하는 발열로 인해 열손상될 수 있으므로, 염화비닐계 중합체의 열안정성을 확보하는 것이 매우 중요하다.However, the bulk polymerization has a disadvantage in that it is difficult to control the temperature due to the strong heat generation during the polymerization process. In addition, there is a disadvantage that the bulk polymerization has no material capable of absorbing and removing the heat of polymerization other than the vinyl chloride monomer, and the viscosity of the polymer increases as the polymerization proceeds, so that it is difficult to spread the reaction heat by conduction or convection. Accordingly, in the case of the vinyl chloride polymer prepared by the bulk polymerization, heat may be damaged due to the reaction heat generated during the bulk polymerization process or an unexpectedly generated exotherm, and thus, it is very important to secure the thermal stability of the vinyl chloride polymer. .
본 발명의 목적은 열안정제와 항산화제 역할을 모두 수행할 수 있는 아인산염을 이용한 염화비닐계 중합체의 제조방법을 제공하는 것이다.An object of the present invention is to provide a method for preparing a vinyl chloride-based polymer using a phosphite which can perform both a heat stabilizer and an antioxidant.
또한, 본 발명의 목적은 열안정성 및 투명성이 모두 우수한 염화비닐계 중합체 및 염화비닐계 중합체 조성물을 제공하는 것이다.It is also an object of the present invention to provide a vinyl chloride polymer and a vinyl chloride polymer composition excellent in both thermal stability and transparency.
상술한 과제를 해결하기 위하여, 본 발명은 개시제 존재 하에, 염화비닐계 단량체를 괴상 중합시키는 제1 단계; 및 상기 괴상 중합을 완료한 후 염화비닐계 중합체를 수득하는 제2 단계를 포함하고, 상기 제1 단계에서 아인산염을 투입하는 것을 특징으로 하는 염화비닐계 중합체의 제조방법을 제공한다.In order to solve the above problems, the present invention is the first step of the bulk polymerization of the vinyl chloride monomer in the presence of the initiator; And a second step of obtaining a vinyl chloride polymer after completing the bulk polymerization, and providing a phosphite in the first step.
또한, 본 발명은 염화비닐계 중합체의 매트릭스 내에 아인산염이 분산된 것을 특징으로 하는 염화비닐계 중합체를 제공한다.The present invention also provides a vinyl chloride polymer, characterized in that the phosphite is dispersed in a matrix of the vinyl chloride polymer.
또한, 본 발명은 상기 염화비닐계 중합체; 안정제, 가공조제, 충격보강제 및 활제로 이루어진 군에서 선택되는 1종 이상을 포함하는 것을 특징으로 하는 염화비닐계 중합체 조성물을 제공한다.In addition, the present invention is a vinyl chloride polymer; It provides a vinyl chloride polymer composition comprising at least one selected from the group consisting of stabilizers, processing aids, impact modifiers and lubricants.
본 발명의 염화비닐계 중합체의 제조방법은 중합 과정에서 아인산염을 첨가함으로써 온도조절이 어려운 괴상 중합 과정에서 예기치 못하게 발생하는 발열로 인해 발생할 수 있는 염화비닐계 중합체의 열손상을 최소화할 수 있다. 또한, 괴상 중합 과정 중에 발생할 수 있는 개시제의 부반응을 아인산염이 억제시킬 수 있다. 이에 따라 상기 부반응으로 야기되는 염화비닐계 중합체의 착색을 최소화하여 투명성을 향상시킬 수 있고, 괴상 중합 속도의 저하를 방지할 수 있다. In the method of preparing the vinyl chloride polymer of the present invention, by adding phosphite in the polymerization process, thermal damage of the vinyl chloride polymer may be minimized due to unexpected heat generation during the bulk polymerization process, which is difficult to control the temperature. In addition, the phosphite can suppress side reactions of the initiator that may occur during the bulk polymerization process. Accordingly, it is possible to minimize the coloring of the vinyl chloride-based polymer caused by the side reaction to improve transparency, and to prevent a decrease in the bulk polymerization rate.
또한, 본 발명의 염화비닐계 중합체와 이를 포함하는 염화비닐계 중합체 조성물은 열안정성 및 투명성이 모두 향상될 수 있다.In addition, the vinyl chloride polymer of the present invention and the vinyl chloride polymer composition including the same may improve both thermal stability and transparency.
이하, 본 발명에 대한 이해를 돕기 위하여 보다 상세하게 설명한다.Hereinafter, the present invention will be described in more detail to aid in understanding the present invention.
본 명세서 및 청구범위에 사용된 용어나 단어는 통상적이거나 사전적인 의미로 한정해서 해석되어서는 아니 되며, 발명자는 그 자신의 발명을 가장 최선의 방법으로 설명하기 위해 용어의 개념을 적절하게 정의할 수 있다는 원칙에 입각하여 본 발명의 기술적 사상에 부합하는 의미와 개념으로 해석되어야만 한다.The terms or words used in this specification and claims are not to be construed as limiting in their usual or dictionary meanings, and the inventors may appropriately define the concept of terms in order to best explain their invention in the best way possible. It should be interpreted as meaning and concept corresponding to the technical idea of the present invention based on the principle that the present invention.
본 발명에서 염화비닐계 중합체는 염화비닐계 중합체의 매트릭스 내에 아인산염이 분산된 것을 의미할 수 있다. 구체적으로는 상기 염화비닐계 중합체와 상기 아인산염이 화학 결합되어 있지는 않지만, 상기 염화비닐계 중합체의 매트릭스, 즉 3차원 네트워크 구조 사이에 상기 아인산염이 균일하게 분산 및 고정화되어 일체화된 것을 의미할 수 있다.In the present invention, the vinyl chloride polymer may mean that phosphite is dispersed in a matrix of the vinyl chloride polymer. Specifically, the vinyl chloride polymer and the phosphite are not chemically bonded, but may mean that the phosphite is uniformly dispersed and immobilized between the matrix of the vinyl chloride polymer, that is, the three-dimensional network structure. have.
본 발명의 제1 실시예에 따른 염화비닐계 중합체의 제조방법은 개시제 존재 하에, 염화비닐계 단량체를 괴상 중합시키는 제1 단계를 포함할 수 있고, 상기 제1 단계에서 아인산염을 투입할 수 있다.The method for preparing a vinyl chloride polymer according to the first embodiment of the present invention may include a first step of bulk polymerizing a vinyl chloride monomer in the presence of an initiator, and phosphite may be added in the first step. .
상기 제1 단계는 구체적으로 제1 개시제 존재 하에, 제1 염화비닐계 단량체를 제1 괴상 중합시키고 입자핵을 형성하는 제1-1 단계; 및 제2 개시제 존재 하에, 상기 입자핵, 상기 제1-1 단계에서 미반응된 제1 염화비닐계 단량체 및 제2 염화비닐계 단량체를 제2 괴상 중합시키는 제1-2 단계를 포함할 수 있다.Specifically, the first step specifically includes a first-first step of mass-polymerizing the first vinyl chloride monomer and forming particle nuclei in the presence of the first initiator; And in the presence of a second initiator, may include a step 1-2 of the second bulk polymerization of the particle nucleus, the first vinyl chloride monomer and the second vinyl chloride monomer unreacted in the step 1-1. .
상기 제1 및 제2 개시제는 서로 같거나 다를 수 있고, 각각 독립적으로 디큐밀 퍼옥사이드(dicumyl peroxide), 디펜틸 퍼옥사이드(dipentyl peroxide), 디(3,5,5-트리스메틸헥사노일)퍼옥사이드(di(3,5,5-trimethylhexanoyl)peroxide), 디라우로일 퍼옥사이드(dilauroyl peroxide) 등의 디아실퍼옥사이드류; 디이소프로필 퍼옥시다카보네이트(diisopropyl peroxydicarbonate), 디-sec-부틸퍼옥시디카보네이트(di-sec-butyl peroxydicarbonate), 디(2-에틸헥실)퍼옥시 디카보네이트(di(2-ethylhexyl)peroxydicarbonate) 등의 퍼옥시카보네이트류; t-부틸퍼옥시 네오데카노에이트(t-butylperoxy neodecanoate), t-부틸퍼옥시 네오헵타노에이트(t-butylperoxy neoheptanoate), t-아밀 퍼옥시 네오데카노에이트(t-amyl peroxy neodecanoate), 큐밀 퍼옥시네오데카노에이트(cumyl peroxy neodecanoate), 큐밀 퍼옥시네오헵타노에이트(cumyl peroxy neoheptanoate), 1,1,3,3-테트라메틸부틸 퍼옥시네오데카노에이트(1,1,3,3-tetramethylbutyl peroxy neodecanoate) 등의 퍼옥시 에스테르; 아조비스-2,4-디메틸발레로니트릴(azobis-2,4-dimethylvaleronitrile) 등의 아조 화합물; 포타슘 퍼설페이트(potassium persulfate), 암모늄 퍼설페이트(ammonium persulfate) 등의 설페이트류로 이루어진 군에서 선택되는 1종 이상일 수 있다.The first and second initiators may be the same as or different from each other, and each independently dicumyl peroxide, dipentyl peroxide, di (3,5,5-trismethylhexanoyl) per Diacyl peroxides such as oxide (di (3,5,5-trimethylhexanoyl) peroxide) and dilauuroyl peroxide; Diisopropyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, di (2-ethylhexyl) peroxydicarbonate, etc. Peroxycarbonates; t-butylperoxy neodecanoate, t-butylperoxy neoheptanoate, t-amyl peroxy neodecanoate, cumyl Cumyl peroxy neodecanoate, cumyl peroxy neoheptanoate, 1,1,3,3-tetramethylbutyl peroxynedecanoate (1,1,3,3 peroxy esters such as -tetramethylbutyl peroxy neodecanoate); Azo compounds, such as azobis-2,4-dimethylvaleronitrile (azobis-2,4-dimethylvaleronitrile); It may be at least one selected from the group consisting of sulfates such as potassium persulfate and ammonium persulfate.
상기 제1 또는 제2 염화비닐계 단량체는 서로 같거나 다를 수 있고, 각각 독립적으로 순수 염화비닐 단량체일 수 있고, 상기 순수 염화비닐 단량체를 주체로 하고 상기 순수 염화비닐 단량체와 공중합이 가능한 비닐계 단량체를 포함하는 혼합 단량체일 수 있다. 상기 혼합 단량체는 상기 염화비닐 단량체 100중량부를 기준으로 상기 비닐계 단량체가 1 내지 50중량부로 포함될 수 있다. 상기 비닐계 단량체는 에틸렌, 프로필렌 등의 올레핀 화합물; 초산비닐, 프로피온산 비닐 등의 비닐 에스테르류; 아크릴로니트릴 등의 불포화 니트릴류; 비닐메틸 에테르, 비닐에틸 에테르 등의 비닐알킬 에테르류; 아크릴산, 메타크릴산, 이타콘산, 말레인산 등의 불포화 지방산; 및 이들 지방산의 무수물로 이루어진 군에서 선택되는 1종 이상일 수 있다.The first or second vinyl chloride monomer may be the same as or different from each other, and each independently may be a pure vinyl chloride monomer, a vinyl monomer copolymerizable with the pure vinyl chloride monomer and copolymerized with the pure vinyl chloride monomer. It may be a mixed monomer comprising a. The mixed monomer may include 1 to 50 parts by weight of the vinyl monomer based on 100 parts by weight of the vinyl chloride monomer. The vinyl monomers include olefin compounds such as ethylene and propylene; Vinyl esters such as vinyl acetate and vinyl propionate; Unsaturated nitriles such as acrylonitrile; Vinyl alkyl ethers such as vinyl methyl ether and vinyl ethyl ether; Unsaturated fatty acids such as acrylic acid, methacrylic acid, itaconic acid and maleic acid; And it may be at least one selected from the group consisting of anhydrides of these fatty acids.
상기 제1 개시제는 상기 제1 염화비닐계 단량체 100중량부에 대하여, 0.01 내지 0.2중량부, 구체적으로는 0.03 내지 0.15중량부, 보다 구체적으로는 0.05 내지 0.1중량부로 포함될 수 있다. 상술한 범위를 만족하면 중합 시 공정의 안정성이 우수해진다.The first initiator may be included in an amount of 0.01 to 0.2 parts by weight, specifically 0.03 to 0.15 parts by weight, and more specifically 0.05 to 0.1 parts by weight based on 100 parts by weight of the first vinyl chloride monomer. When the above range is satisfied, the stability of the process during polymerization is excellent.
상기 제2 개시제는 상기 입자핵, 상기 제1-1 단계에서 미반응된 제1 염화비닐계 단량체 및 상기 제2 염화비닐계 단량체의 총합 100중량부에 대하여, 0.03 내지 0.6중량부, 구체적으로는 0.05 내지 0.4중량부, 보다 구체적으로는 0.08 내지 0.3중량부로 포함될 수 있다. 상술한 범위를 만족하면 중합 시 공정의 안정성이 우수해진다. The second initiator is 0.03 to 0.6 parts by weight, specifically, based on 100 parts by weight of the total amount of the particle nucleus, the unreacted first vinyl chloride monomer and the second vinyl chloride monomer in step 1-1. 0.05 to 0.4 parts by weight, more specifically 0.08 to 0.3 parts by weight may be included. When the above range is satisfied, the stability of the process during polymerization is excellent.
상기 제1 괴상 중합은 60 내지 80℃의 온도, 9 내지 14㎏/㎠ G의 압력 하에서 수행될 수 있다. 상술한 조건을 만족하면, 상기 제1 염화비닐계 단량체로부터 상기 입자핵을 형성할 수 있다. 중합 전환율이 10% 내지 15%일 때, 상기 제1 괴상 중합을 종료할 수 있다.The first bulk polymerization may be performed at a temperature of 60 to 80 ° C. and a pressure of 9 to 14 kg / cm 2 G. If the above conditions are satisfied, the particle nucleus can be formed from the first vinyl chloride monomer. When the polymerization conversion rate is 10% to 15%, the first bulk polymerization may be terminated.
상기 제2 괴상 중합은 50 내지 70℃의 온도, 7 내지 12㎏/㎠ G의 압력 하에서 수행될 수 있다. 상술한 조건을 만족하면, 상기 입자핵을 성장시켜 염화비닐계 중합체를 형성할 수 있다.The second bulk polymerization may be performed at a temperature of 50 to 70 ° C. and a pressure of 7 to 12 kg / cm 2 G. If the above conditions are satisfied, the particle nucleus can be grown to form a vinyl chloride polymer.
한편, 상기 아인산염은 상기 제1 단계 및 상기 제2 단계 중 어느 하나의 단계에서 투입할 수 있고, 상기 제1 단계 및 상기 제2 단계에서 모두 투입할 수 있다. 구체적으로는 상기 제1-1 단계에서는 상기 제1 괴상 중합이 수행되기 전에 상기 아인산염을 투입할 수 있고, 상기 제1 괴상 중합 중에 상기 아인산염을 투입할 수 있다. 상기 제1-2 단계에서는 상기 제2 괴상 중합이 수행되기 전, 상기 제2 괴상 중합 중, 또는 상기 제2 괴상 중합이 완료된 후에 상기 아인산염을 투입할 수 있다. 보다 구체적으로는 상기 제1-1 단계에서는 상기 제1 괴상 중합이 수행되기 전에 상기 아인산염을 투입할 수 있고, 상기 제1-2 단계에서는 상기 제2 괴상 중합이 수행되기 전에 상기 아인산염을 투입할 수 있다. 상기 아인산염은 교반이 유지되는 상태에서 투입할 수 있고, 상기 아인산염을 투입한 후 교반을 수행할 수 있다.On the other hand, the phosphite may be added in any one of the first step and the second step, it can be added in both the first step and the second step. Specifically, in the first-first step, the phosphite may be added before the first block polymerization is performed, and the phosphite may be added during the first block polymerization. In the step 1-2, the phosphite may be added before the second block polymerization is performed, during the second block polymerization, or after the second block polymerization is completed. More specifically, in the first-first step, the phosphite may be added before the first bulk polymerization is performed, and in the first-second step, the phosphite is added before the second bulk polymerization is performed. can do. The phosphite may be added while stirring is maintained, and the phosphite may be added and then stirred.
상기 아인산염을 상술한 단계에서 투입하면, 온도조절이 어려운 괴상 중합 과정에서 예기치 못하게 발생하는 발열로 인해 발생할 수 있는 염화비닐계 중합체의 열손상을 방지할 수 있다. 또한 상기 아인산염은 상기 제1 및 제2 괴상 중합 과정에서 발생할 수 있는 개시제로 인한 부반응을 억제시킬 수 있다. 이로 인해 상기 부반응으로 발생되는 착색을 최소화할 수 있어 최종 생산품인 염화비닐계 중합체의 투명성을 향상시킬 수 있다. 또한 괴상 중합 속도가 저하되지 않고 일정하게 유지될 수 있다. 또한, 염화비닐계 중합체를 이용한 가공품은 고온에서 가공이 수행되므로, 투명성 및 열안정성을 확보하는 것이 매우 중요하다. 상기 아인산염이 상기 염화비닐계 중합체의 중합 과정에서 포함된다면, 상기 염화비닐계 중합체의 매트릭스까지 도달하여 분산될 수 있다. 이에 따라 상기 염화비닐계 중합체와 아인산염을 포함하는 조성물을 이용하여 제조한 가공품보다 본 발명의 제조방법을 따른 상기 아인산염을 포함한 염화비닐계 중합체를 포함하는 조성물을 이용한 가공품의 투명성 및 열안정성이 훨씬 우수할 수 있다. When the phosphite is added in the above-described step, it is possible to prevent thermal damage of the vinyl chloride-based polymer, which may occur due to unexpected heat generation during the bulk polymerization process, which is difficult to control the temperature. In addition, the phosphite may suppress side reactions due to initiators that may occur in the first and second bulk polymerization processes. As a result, it is possible to minimize coloring caused by the side reactions, thereby improving transparency of the vinyl chloride polymer as a final product. In addition, the mass polymerization rate can be kept constant without lowering. In addition, since a processed product using a vinyl chloride polymer is processed at a high temperature, it is very important to secure transparency and thermal stability. If the phosphite is included in the polymerization process of the vinyl chloride-based polymer, it can be dispersed to reach the matrix of the vinyl chloride-based polymer. Accordingly, the transparency and thermal stability of the processed product using the composition containing the vinyl chloride-based polymer including the phosphite according to the production method of the present invention rather than the processed product prepared using the composition containing the vinyl chloride-based polymer and phosphite. It can be much better.
상기 아인산염은 하기 화학식 1로 표시되는 화합물일 수 있다.The phosphite may be a compound represented by Formula 1 below.
<화학식 1><Formula 1>
Figure PCTKR2017009713-appb-I000001
Figure PCTKR2017009713-appb-I000001
상기 화학식 1에 있어서,In Chemical Formula 1,
L1 내지 L3는 각각 독립적으로, 서로 같거나 다르고, 직접 결합, C1 내지 C20의 알킬렌기 또는 C6 내지 C20의 아릴렌기이고,L 1 to L 3 are each independently the same as or different from each other, and are a direct bond, an alkylene group of C1 to C20, or an arylene group of C6 to C20,
R1 내지 R3는 각각 독립적으로, 서로 같거나 다르고, 치환 또는 비치환된 C1 내지 C20의 직쇄 또는 분지쇄 알킬기 또는 치환 또는 비치환된 C6 내지 C20의 아릴기이다.R 1 to R 3 are each independently the same or different and are a substituted or unsubstituted C1 to C20 straight or branched chain alkyl group or a substituted or unsubstituted C6 to C20 aryl group.
여기서, ‘직접결합’은 L1 내지 L3이 없이 O와 R1 내지 R3가 직접 결합된 것을 의미한다.Here, 'direct bond' means that O and R 1 to R 3 are directly bonded without L 1 to L 3 .
상기 화학식 1을 만족하는 아인산염은 하기 표 1에 기재된 화합물로 이루어진 군에서 선택되는 1종 이상일 수 있다.The phosphite satisfying Formula 1 may be at least one selected from the group consisting of compounds shown in Table 1 below.
화학명Chemical name 화학식Chemical formula
1One 트리스에틸 포스파이트Trisethyl phosphite
Figure PCTKR2017009713-appb-I000002
Figure PCTKR2017009713-appb-I000002
22 트리스이소프로필 포스파이트Trisisopropyl phosphite
Figure PCTKR2017009713-appb-I000003
Figure PCTKR2017009713-appb-I000003
33 트리스이소데실 포스파이트Trisisodecyl phosphite
Figure PCTKR2017009713-appb-I000004
Figure PCTKR2017009713-appb-I000004
44 트리스도데실 포스파이트Trisdodecyl phosphite
Figure PCTKR2017009713-appb-I000005
Figure PCTKR2017009713-appb-I000005
55 페닐-디이소데실 포스파이트Phenyl-diisodecyl phosphite
Figure PCTKR2017009713-appb-I000006
Figure PCTKR2017009713-appb-I000006
66 디페닐-이소데실 포스파이트Diphenyl-isodecyl phosphite
Figure PCTKR2017009713-appb-I000007
Figure PCTKR2017009713-appb-I000007
77 트리스페닐 포스파이트Trisphenyl phosphite
Figure PCTKR2017009713-appb-I000008
Figure PCTKR2017009713-appb-I000008
88 페닐-비스(4-노닐페닐)포스파이트Phenyl-bis (4-nonylphenyl) phosphite
Figure PCTKR2017009713-appb-I000009
Figure PCTKR2017009713-appb-I000009
99 트리스(4-옥틸페닐)포스파이트Tris (4-octylphenyl) phosphite
Figure PCTKR2017009713-appb-I000010
Figure PCTKR2017009713-appb-I000010
1010 트리스[(4-1-페닐에틸)페닐]포스파이트Tris [(4-1-phenylethyl) phenyl] phosphite
Figure PCTKR2017009713-appb-I000011
Figure PCTKR2017009713-appb-I000011
상기 아인산염은 상기 제1 및 제2 염화비닐계 단량체의 총 합 100 중량부에 대하여, 0.001 내지 1 중량부, 구체적으로는 0.003 내지 0.1 중량부로 투입할 수 있다. 상술한 범위를 만족하면, 괴상 중합 과정에서 예기치 못하게 발생하는 발열로 인해 발생할 수 있는 염화비닐계 중합체의 열손상을 최소화할 수 있다. 상기 제1 및 제2 괴상 중합 과정에서 발생할 수 있는 상기 제1 및 제2 개시제로 인한 부반응을 억제시킬 수 있으므로, 상기 부반응으로 발생되는 착색을 최소화할 수 있어 최종 생산품인 염화비닐계 중합체의 투명성을 향상시킬 수 있다. 또한 상기 개시제의 부반응을 억제하므로 괴상 중합 속도가 저하되지 않고 일정하게 유지될 수 있다.The phosphite may be added in an amount of 0.001 to 1 part by weight, specifically 0.003 to 0.1 part by weight, based on 100 parts by weight of the total of the first and second vinyl chloride monomers. If the above range is satisfied, thermal damage of the vinyl chloride polymer may be minimized, which may occur due to the exotherm generated unexpectedly during the bulk polymerization process. Since it is possible to suppress side reactions caused by the first and second initiators that may occur in the first and second bulk polymerization processes, it is possible to minimize the coloration generated by the side reactions, thereby improving transparency of the final product vinyl chloride polymer. Can be improved. In addition, since the side reaction of the initiator is suppressed, the mass polymerization rate can be kept constant without lowering.
상기 아인산염은 용매에 혼합된 용액 상태로 투입할 수 있다. 또한, 용액 총 중량에 대하여, 상기 아인산염을 0.1 내지 5 중량%, 구체적으로는 0.5 내지 2 중량%로 포함할 수 있다. 상술한 상태 및 함량으로 투입하면, 상기 제1 및 제2 염화비닐계 단량체에 보다 균일하게 상기 아인산염을 분산시킬 수 있으므로, 최종 생산품인 염화비닐계 중합체의 열안정성 및 투명성을 보다 향상시킬 수 있다. 상기 아인산염은 상기 제1 염화비닐계 단량체 및 제2 염화비닐계 단량체로 이루어진 군에서 선택되는 1종 이상에 스프레이 분사방식 또는 노즐을 통한 분사 방식으로 투입될 수 있다. 또한 상기 아인산염의 투입 후 교반을 하여 상기 제1 염화비닐계 단량체 및 제2 염화비닐계 단량체로 이루어진 군에서 선택되는 1종 이상에 분산시킬 수 있다.The phosphite may be added in a solution mixed with a solvent. In addition, the phosphite may be included in an amount of 0.1 to 5% by weight, specifically 0.5 to 2% by weight, based on the total weight of the solution. When added in the above-described state and content, the phosphite can be more uniformly dispersed in the first and second vinyl chloride monomers, thereby improving the thermal stability and transparency of the vinyl chloride polymer as a final product. . The phosphite may be added to at least one selected from the group consisting of the first vinyl chloride monomer and the second vinyl chloride monomer by spray spraying or spraying through a nozzle. In addition, after the addition of the phosphite may be stirred to disperse one or more selected from the group consisting of the first vinyl chloride monomer and the second vinyl chloride monomer.
상기 용매는 괴상 중합 과정에서 용이하게 휘발되어 중합에 부담을 주지 않는 알코올류 용매일 수 있고, 상기 알코올류 용매는 메탄올, 에탄올, 이소프로판올, 1-메톡시프로판올, 부탄올, 에틸헥실 알코올 및 테르피네올로 이루어진 군에서 선택되는 1종 이상일 수 있다.The solvent may be an alcohol solvent which is easily volatilized during the bulk polymerization process and does not burden the polymerization, and the alcohol solvent may be methanol, ethanol, isopropanol, 1-methoxypropanol, butanol, ethylhexyl alcohol, and terpineol It may be at least one selected from the group consisting of.
본 발명의 제1 실시예에 따른 염화비닐계 중합체의 제조방법은 상기 괴상 중합을 완료한 후 염화비닐계 중합체를 수득하는 제2 단계를 포함할 수 있다.The method for preparing a vinyl chloride polymer according to the first embodiment of the present invention may include a second step of obtaining a vinyl chloride polymer after completing the bulk polymerization.
상기 제2 단계에서는 괴상 중합 전환율이 50 내지 70%에 도달하면, 상기 괴상 중합을 완료할 수 있고, 상기 괴상 중합을 완료시키기 위하여 반응 종결제를 투입할 수 있다. In the second step, when the bulk polymerization conversion reaches 50 to 70%, the bulk polymerization may be completed, and a reaction terminator may be added to complete the bulk polymerization.
상기 반응종결제는 상기 제2 개시제의 기능을 상실시킴으로써 반응을 종결시키는 물질로서, 페놀 화합물, 아민 화합물, 니트릴 화합물 및 황 화합물로 이루어진 군에서 선택되는 1종 이상일 수 있다. 상기 페놀 화합물은 트리스에틸렌 글리콜-비스-3-(3-t-부틸-4-히드록시-5-메틸페닐)프로피오네이트(triethylene glycol-bis-3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionate), 하이드로퀴논(hydroquinone), p-메톡시 페놀(p-methoxy phenol), t-부틸-4-하이드록시아니솔(t-butyl-4-hydroxyanisole), n-옥타데실-3-(4-히드록시-3,5-디-t-부틸페닐)프로피오네이트(n-octadecyl-3-(4-hydroxy-3,5-di-t-butylphenyl)propionate), 2,5-디-t-부틸 하이드로퀴논(2,5-di-t-butyl hydroquione), 4,4'-부틸리덴 비스(3-메틸-6-t-부틸 페놀)(4,4'-butylidene bis(3-methyl-t-butyl phenol), t-부틸 카테콜(t-butyl catechol), 4,4-티오비스(6-t-부틸-m-크레졸)(4,4-thiobis(6-t-butyl-m-cresol)), 및 토코페롤(tocopherol)로 이루어진 군에서 선택되는 1종 이상일 수 있다. 상기 아민 화합물은 N,N-디페닐-p-페닐렌디아민(N,N-diphenyl-p-phenylenediamine) 및 4,4-비스(디메틸벤질)디페닐(4,4-bis(dimethylbenzyl)diphenyl)로 이루어진 군에서 선택되는 1종 이상일 수 있다. 상기 니트릴 화합물은 4-하이드록시-2,2,6,6-테트라메틸-피페리딘-1-옥실(4-Hydroxy-2,2,6,6-tetramethyl piperidine 1-oxyl)일 수 있다. 상기 황 화합물은 도데실 메르캅탄(dodecyl mercaptan) 및 1,2-비페닐-2-티올(1,2-biphenyl-2-thiol)로 이루어진 군에서 선택되는 1종 이상일 수 있다.The reaction terminator is a substance which terminates the reaction by losing the function of the second initiator, and may be at least one selected from the group consisting of a phenol compound, an amine compound, a nitrile compound, and a sulfur compound. The phenolic compound is triethylene glycol-bis-3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate (triethylene glycol-bis-3- (3-t-butyl-4-hydroxy- 5-methylphenylpropionate), hydroquinone, p-methoxy phenol, t-butyl-4-hydroxyanisole, n-octadecyl- 3- (4-hydroxy-3,5-di-t-butylphenyl) propionate (n-octadecyl-3- (4-hydroxy-3,5-di-t-butylphenyl) propionate), 2,5 2,5-di-t-butyl hydroquione, 4,4'-butylidene bis (3-methyl-6-t-butyl phenol) (4,4'-butylidene bis (3-methyl-t-butyl phenol), t-butyl catechol, 4,4-thiobis (6-t-butyl-m-cresol) (4,4-thiobis (6-t -butyl-m-cresol)), and tocopherol may be at least one selected from the group consisting of N, N-diphenyl-p-phenylenediamine (N, N-diphenyl-p). -phenylenediamine) and 4,4-bis (dimethylbenzyl) diphenyl (4,4-bis (dimethylb) enzyl) diphenyl) may be at least one selected from the group consisting of 4-hydroxy-2,2,6,6-tetramethyl-piperidine-1-oxyl (4-Hydroxy-2, 2,6,6-tetramethyl piperidine 1-oxyl) The sulfur compounds are dodecyl mercaptan and 1,2-biphenyl-2-thiol. It may be at least one selected from the group consisting of.
상기 반응종결제 투입시 필요에 따라 항산화제 등의 첨가제를 투입할 수 있다. 상기 항산화제는 염화비닐계 중합체의 색을 백색으로 만들 목적으로 첨가되는 것일 수 있다.When the reaction terminator is added, additives such as antioxidants may be added as necessary. The antioxidant may be added for the purpose of making the color of the vinyl chloride polymer white.
본 발명의 제2 실시예에 따른 염화비닐계 중합체는, 상기 제1 실시예에 따른 염화비닐계 중합체의 제조방법에 따라 제조되고, 염화비닐계 중합체와 아인산염을 포함하고, 상기 아인산염이 상기 염화비닐계 중합체의 매트릭스 내에 분산된 것일 수 있다. 구체적으로는 상기 아인산염이 염화비닐계 중합체 매트릭스, 즉 3차원 네트워크 구조 사이에 균일하게 분산 및 고정화되어 일체화된 것일 수 있다.The vinyl chloride polymer according to the second embodiment of the present invention is prepared according to the method for producing a vinyl chloride polymer according to the first embodiment, includes a vinyl chloride polymer and a phosphite salt, and the phosphite salt is It may be dispersed in a matrix of the vinyl chloride polymer. Specifically, the phosphite may be integrated into a vinyl chloride polymer matrix, that is, uniformly dispersed and immobilized between three-dimensional network structures.
상기 아인산염은 염화비닐계 중합체 총 중량에 대하여, 0.001 내지 2 중량%, 구체적으로는 0.008 내지 1중량%, 보다 구체적으로는 0.005 내지 0.1 중량%로 포함될 수 있다. 상기 아인산염은 상기 염화비닐계 중합체의 제조공정에서 거의 손실되지 않고, 구체적으로는 상기 염화비닐계 중합체의 제조 방법 중 투입된 아인산염의 90% 이상이 중합체 내에 포함될 수 있다. 이에 따라 상기 염화비닐계 중합체 총 중량에 대하여, 상술한 범위로 포함될 수 있는 것이다. 상술한 범위를 만족하면, 상기 아인산염은 염화비닐계 중합체의 제조공정에서 손실 없이 염화비닐계 중합체의 성능은 저하시키지 않으면서 열안정성과 투명성이 모두 우수한 염화비닐계 중합체를 제공할 수 있다.The phosphite may be included in an amount of 0.001 to 2% by weight, specifically 0.008 to 1% by weight, and more specifically 0.005 to 0.1% by weight, based on the total weight of the vinyl chloride polymer. The phosphite is hardly lost in the manufacturing process of the vinyl chloride polymer, and specifically, 90% or more of the phosphite added in the manufacturing method of the vinyl chloride polymer may be included in the polymer. Accordingly, the total weight of the vinyl chloride polymer may be included in the above-described range. When the above-mentioned range is satisfied, the phosphite may provide a vinyl chloride polymer having excellent thermal stability and transparency without degrading the performance of the vinyl chloride polymer without loss in the manufacturing process of the vinyl chloride polymer.
본 발명의 제3 실시예에 따른 염화비닐계 중합체 조성물은 상기 염화비닐계 중합체와 안정제, 가공조제, 충격보강제 및 활제로 이루어진 군에서 선택되는 1종 또는 2종 이상을 포함할 수 있다.The vinyl chloride polymer composition according to the third embodiment of the present invention may include one or two or more selected from the group consisting of the vinyl chloride polymer and a stabilizer, a processing aid, an impact modifier, and a lubricant.
상기 안정제는 열에 대한 안정성을 높임으로써 착색 및 분해를 방지하는 물질로서, 금속계 안정제 또는 유기산 금속염 안정제일 수 있다. 상기 금속계 안정제는 납계 안정제, (유기)주석계 안정제, 카드뮴계 안정제 및 바륨계 안정제로 이루어진 군에서 선택되는 1종 또는 2종일 수 있다. 상기 유기산 금속염은 카르복실산, 유기인산 또는 페놀류의 금속염일 수 있다. 상기 카르복실산은 카프론산, 카프릴산, 펠라르곤산, 2-에틸헥실산, 카프린산, 네오데칸산, 운데실렌산, 라우린산, 미리스틴산, 팔미틴산, 스테아린산, 이소스테아린산, 12-히드록시스테아린산, 클로로스테아린산, 12-케토스테아린산, 페닐스테아린산, 리시놀산, 리놀산, 리놀렌산, 올레인산, 아라킨산, 베헨산, 에르카산, 브라시드산, 유사산, 수지 지방산, 야자유 지방산, 동유 지방산, 대두유 지방산, 면실유 지방산, 벤조산, p-t-부틸벤조산, 에틸벤조산, 이소프로필벤조산, 톨루일산, 자일릴산, 살리실산, 5-t-옥틸살리실산, 나프텐산 및 시클로헥사카르복실산으로 이루어진 군에서 선택되는 1종 또는 2종 이상일 수 있다. 상기 유기인산은 모노옥틸인산, 디옥틸인산, 모노도데실인산, 디도데실인산, 모노옥타데실인산, 디옥타데실인산, 모노(노닐페닐)인산, 디(노닐페닐)인산, 포스폰산노닐페닐에스테르 및 포스폰산노닐페닐에스테르, 포스폰산스테아릴에스테르로 이루어진 군에서 선택되는 1종 또는 2종 이상일 수 있다. 상기 페놀류는 페놀, 크레졸, 에틸페놀, 시클로헥실페놀, 노닐페놀 및 도데실페놀로 이루어진 군에서 선택되는 1종 이상일 수 있다. 상기 금속염은 중성염, 산성염, 염기성염 또는 과염기성 착체일 수 있다.The stabilizer is a material that prevents coloring and decomposition by increasing stability to heat, and may be a metal-based stabilizer or an organic acid metal salt stabilizer. The metal stabilizer may be one or two selected from the group consisting of lead stabilizers, (organic) tin stabilizers, cadmium stabilizers, and barium stabilizers. The organic acid metal salt may be a metal salt of carboxylic acid, organophosphoric acid or phenols. The carboxylic acid is capric acid, caprylic acid, pelagonic acid, 2-ethylhexyl acid, capric acid, neodecanoic acid, undecylenic acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, 12- Hydroxystearic acid, chlorostearic acid, 12-ketostearic acid, phenylstearic acid, ricinolic acid, linoleic acid, linolenic acid, oleic acid, arachnic acid, behenic acid, ercaic acid, brasidic acid, pseudoacid, resin fatty acid, palm oil fatty acid, tung oil fatty acid, 1 selected from the group consisting of soybean oil fatty acid, cottonseed oil fatty acid, benzoic acid, pt-butylbenzoic acid, ethylbenzoic acid, isopropylbenzoic acid, toluic acid, xylyl acid, salicylic acid, 5-t-octylsalicylic acid, naphthenic acid and cyclohexacarboxylic acid Species or two or more kinds. The organic phosphoric acid is monooctyl phosphoric acid, dioctyl phosphoric acid, monododecyl phosphoric acid, didodecyl phosphoric acid, monooctadecyl phosphoric acid, dioctadecyl phosphoric acid, mono (nonylphenyl) phosphoric acid, di (nonylphenyl) phosphoric acid, phosphonic acid nonylphenyl It may be one kind or two or more kinds selected from the group consisting of esters, phosphonic acid nonylphenyl esters, and phosphonic acid stearyl esters. The phenols may be one or more selected from the group consisting of phenol, cresol, ethylphenol, cyclohexylphenol, nonylphenol and dodecylphenol. The metal salt may be neutral salt, acid salt, basic salt or overbased complex.
상기 가공조제는 염화비닐계 중합체의 겔화를 촉진하는 물질로서, 메틸메타크릴레이트, 에틸메타크릴레이트, 부틸메타크릴레이트 등의 알킬메타크릴레이트의 단독 중합체 또는 공중합체; 상기 알킬메타크릴레이트와 메틸아크릴레이트, 에틸아크릴레이트, 부틸아크릴레이트 등의 알킬아크릴레이트와의 공중합체; 상기 알킬메타크릴레이트와 스티렌, α-메틸스티렌, 비닐톨루엔 등의 방향족 비닐화합물과의 공중합체; 알킬메타크릴레이트와, 아크릴로니트릴, 메타크릴로니트릴 등의 비닐시안 화합물 등과의 공중합체 등을 들 수 있다. 상기 가공조제는 1종 또는 2종 이상 혼합하여 이용할 수 있다.The processing aid is a substance that promotes gelation of the vinyl chloride polymer, the homopolymer or copolymer of alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, butyl methacrylate; Copolymers of the above alkyl methacrylate with alkyl acrylates such as methyl acrylate, ethyl acrylate and butyl acrylate; Copolymers of the above alkyl methacrylates with aromatic vinyl compounds such as styrene, α-methylstyrene, and vinyltoluene; And copolymers of alkyl methacrylate with vinyl cyan compounds such as acrylonitrile and methacrylonitrile. The processing aid may be used alone or in combination of two or more thereof.
상기 충격보강제는 염화비닐계 중합체에 탄성을 부여하여 내충격성을 보강하는 물질로서, MBS(Methyl Methacrylate-Butadiene Styrene)계 중합체, 염소화폴리에틸렌계 공중합체, 에틸렌비닐아세테이트계 중합체, 아크릴계 중합체 및 부타디엔계 중합체로 이루어진 군으로부터 선택되는 1종 이상일 수 있다.The impact modifier is a material that reinforces the impact resistance by imparting elasticity to the vinyl chloride polymer, MBS (Methyl Methacrylate-Butadiene Styrene) polymer, chlorinated polyethylene copolymer, ethylene vinyl acetate polymer, acrylic polymer and butadiene polymer It may be one or more selected from the group consisting of.
상기 활제는 염화비닐계 중합체의 가공성 및 계면성을 향상시키는 물질로서, 저분자 왁스, 파라핀 왁스, 폴리에틸렌 왁스, 염소화 탄화수소, 플루오로카본 등의 탄화수소계 활제; 카르나우바 왁스, 칸데릴라 왁스 등의 천연 왁스계 활제; 라우린산, 스테아린산, 베헤닌산 등의 고급 지방산, 또는 히드록시스테아린산과 같은 옥시 지방산 등의 지방산계 활제; 스테아릴아미드, 라우릴아미드, 올레일아미드 등의 지방족아미드 화합물 또는 메틸렌비스스테아릴아미드, 에틸렌비스스테아릴아미드와 같은 알킬렌비스지방족아미드 등의 지방족아미드계 활제; 스테아릴스테아레이트, 부틸스테아레이트, 디스테아릴프탈레이트 등의 지방산 1가 알코올 에스테르 화합물, 또는, 글리세린트리스스테아레이트, 솔비탄트리스스테아레이트, 펜타에리스리톨테트라스테아레이트, 디펜타에리스리톨헥사스테아레이트, 폴리글리세린폴리리시노레이트, 경화 피마자유 등의 지방산 다가 알코올 에스테르 화합물, 또는, 디펜타에리스리톨의 아디프산·스테아린산 에스테르와 같은 1가 지방산, 및 다염기성 유기산과 다가 알코올의 복합 에스테르 화합물 등의 지방산 알코올 에스테르계 활제; 스테아릴알코올, 라우릴알코올, 팔미틸알코올 등의 지방족 알코올계 활제; 금속 비누류; 부분 비누화몬탄산 에스테르 등의 몬탄산계 활제; 아크릴계 활제; 및 실리콘 오일 등을 들 수 있다. 상기 활제는 1종 또는 2종 이상을 혼합하여 이용할 수 있다.The lubricant is a substance that improves the processability and interfacial properties of the vinyl chloride polymer, hydrocarbon lubricants such as low molecular wax, paraffin wax, polyethylene wax, chlorinated hydrocarbon, fluorocarbon; Natural wax-based lubricants such as carnauba wax and candelilla wax; Fatty acid lubricants such as higher fatty acids such as lauric acid, stearic acid and behenic acid, or oxy fatty acids such as hydroxystearic acid; Aliphatic amide lubricants such as aliphatic amide compounds such as stearylamide, laurylamide, and oleylamide or alkylenebisaliphatic amides such as methylenebisstearylamide and ethylenebisstearylamide; Fatty acid monohydric alcohol ester compounds, such as stearyl stearate, butyl stearate, and distearyl phthalate, or glycerin tris stearate, sorbitan tris stearate, pentaerythritol tetrastearate, dipentaerythritol hexastearate, and polyglycerol Fatty acid alcohol esters, such as fatty acid polyhydric alcohol ester compounds, such as polylisinorate and hardened castor oil, or monohydric fatty acids, such as adipic acid stearic acid ester of dipentaerythritol, and a complex ester compound of polybasic organic acid and a polyhydric alcohol System lubricants; Aliphatic alcohol lubricants such as stearyl alcohol, lauryl alcohol and palmityl alcohol; Metal soaps; Montan acid type lubricants, such as a partially saponified montan acid ester; Acrylic lubricants; And silicone oils. The said lubricant can be used 1 type or in mixture of 2 or more types.
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시하나, 상기 실시예는 본 기재를 예시하는 것일 뿐 본 기재의 범주 및 기술사상 범위 내에서 다양한 변경 및 수정이 가능함은 당업자에게 있어서 명백한 것이며, 이러한 변형 및 수정이 첨부된 특허청구범위에 속하는 것은 당연한 것이다.Hereinafter, preferred embodiments are provided to aid in understanding the present invention, but the above embodiments are merely illustrative of the present disclosure, and it is apparent to those skilled in the art that various changes and modifications can be made within the scope and spirit of the present disclosure. It is natural that such variations and modifications fall within the scope of the appended claims.
<< 염화비닐계Vinyl chloride 중합체의 제조> Preparation of Polymer>
실시예Example 1-1,  1-1, 실시예Example 1-2,  1-2, 비교예Comparative example 1-1 및  1-1 and 비교예Comparative example 1-2 1-2
0.2㎥의 예비 중합 반응기, 0.5㎥의 중합 반응기, 상기 중합 반응기와 연결되고 중합반응의 온도를 제열하는 환류 응축기 및 상기 환류 응축기와 연결되고 미반응 염화비닐계 단량체를 배출하는 염화비닐 회수배관을 포함하는 중합장치를 이용하여 염화비닐계 단량체를 하기와 같은 방법으로 중합하였다.A preliminary polymerization reactor of 0.2m 3, a polymerization reactor of 0.5m 3, a reflux condenser connected to the polymerization reactor to heat the temperature of the polymerization reaction, and a vinyl chloride recovery pipe connected to the reflux condenser and discharging the unreacted vinyl chloride monomer The vinyl chloride monomer was polymerized in the following manner using a polymerization apparatus including the same.
고 진공으로 탈기한 예비 중합 반응기에 염화비닐 단량체 140㎏ 및 개시제로 t-부틸퍼옥시네오데카노네이트 85g을 순차적으로 투입하고 교반하였다. 상기 교반을 유지하면서 상기 예비 중합 반응기의 압력을 12㎏/㎠ G까지 승압하여 75℃에서 제1 괴상 중합을 수행하여 입자핵을 제조하였다. 이때 상기 제1 괴상 중합의 중합 전환율이 10%였다. 140 kg of vinyl chloride monomer and 85 g of t-butylperoxy neodecanoate were sequentially added to the prepolymerization reactor degassed by high vacuum, followed by stirring. While maintaining the stirring, the pressure of the prepolymerization reactor was elevated to 12 kg / cm 2 G to carry out the first bulk polymerization at 75 ° C., thereby preparing particle nuclei. At this time, the polymerization conversion rate of the first bulk polymerization was 10%.
이어서, 상기 중합 반응기에 상기 입자핵 전량, 상기 제1 괴상 중합에서 미반응된 염화비닐 단량체 전량, 추가의 염화비닐 단량체 80㎏, 및 개시제로 1,1,3,3-테트라메틸 부틸 퍼옥시 네오데카노에이트 200g을 순차적으로 투입하고 교반하였다. 상기 교반을 유지하면서 하기 표 2에 기재된 온도 및 압력 하에서 중합을 개시하였고 표 2에 기재된 시간 동안 제2 괴상 중합을 수행하였다. 하기 표 2에 기재된 중합 전환율이 되었을 때 하기 표 3에 기재된 아인산염 용액 및 항산화제로 부틸레이티드 하이드록시 톨루엔(Butylated hydroxytoluene) 200g을 순차적으로 투입한 후, 교반이 유지된 상태에서 진공으로 잔류 미반응 단량체를 회수한 후 염화비닐계 중합체를 수득하였다.Subsequently, the total amount of particle nuclei in the polymerization reactor, the total amount of unreacted vinyl chloride monomer in the first bulk polymerization, 80 kg of additional vinyl chloride monomer, and 1,1,3,3-tetramethyl butyl peroxy neo as an initiator were 200 g of decanoate was added sequentially and stirred. While maintaining the agitation, the polymerization was initiated under the temperature and pressure shown in Table 2 below and the second bulk polymerization was carried out for the time shown in Table 2. When the polymerization conversion rate shown in Table 2 was reached, 200 g of butylated hydroxytoluene was sequentially added to the phosphate solution and antioxidant as shown in Table 3, and then residual unreacted in vacuo while stirring was maintained. After recovering the monomer, a vinyl chloride polymer was obtained.
구분division 중합온도(℃)Polymerization temperature (℃) 중합압력(㎏/㎠ G)Polymerization pressure (㎏ / ㎠ G) 중합전환율(%)Polymerization Conversion Rate (%) 중합시간(분)Polymerization time (minutes)
실시예 1-1Example 1-1 5252 7.57.5 5555 180180
실시예 1-2Example 1-2 6060 9.09.0 6060 200200
비교예 1-1Comparative Example 1-1 5252 7.57.5 5555 180180
비교예 1-2Comparative Example 1-2 9090 9.09.0 6060 200200
구분division 아인산염Phosphate 용매menstruum 총량(㎏)Total amount (㎏)
종류Kinds 함량(중량%)Content (% by weight) 종류Kinds 함량(중량%)Content (% by weight)
실시예 1-1Example 1-1 트리스페닐 포스파이트Trisphenyl phosphite 1One 에탄올ethanol 9999 1One
실시예 1-2Example 1-2 트리스 도데실 포스파이트Tris Dodecyl Phosphite 1One 에탄올ethanol 9999 1010
비교예 1-1Comparative Example 1-1 -- -- -- -- --
비교예 1-2Comparative Example 1-2 -- -- -- -- --
실시예Example 1-3 및  1-3 and 실시예Example 1-4 1-4
0.2㎥의 예비 중합 반응기, 0.5㎥의 중합 반응기, 상기 중합 반응기와 연결되고 중합반응의 온도를 제열하는 환류 응축기 및 상기 환류 응축기와 연결되고 미반응 염화비닐계 단량체를 배출하는 염화비닐 회수배관을 포함하는 중합장치를 이용하여 염화비닐계 단량체를 하기와 같은 방법으로 중합하였다.A preliminary polymerization reactor of 0.2m 3, a polymerization reactor of 0.5m 3, a reflux condenser connected to the polymerization reactor to heat the temperature of the polymerization reaction, and a vinyl chloride recovery pipe connected to the reflux condenser and discharging the unreacted vinyl chloride monomer The vinyl chloride monomer was polymerized in the following manner using a polymerization apparatus including the same.
고 진공으로 탈기한 예비 중합 반응기에 염화비닐 단량체 140㎏, 개시제로 t-부틸퍼옥시네오데카노네이트를 85g와 하기 표 4에 기재된 용액을 순차적으로 투입하고 교반하였다. 상기 교반을 유지하면서 상기 예비 중합 반응기의 압력을 12㎏/㎠ G까지 승압하여 75℃에서 제1 괴상 중합을 수행하여 입자핵을 제조하였다. 이때 상기 제1 괴상 중합의 중합 전환율이 10%였다. Into the prepolymerization reactor degassed in high vacuum, 140 g of a vinyl chloride monomer and 85 g of t-butylperoxy neodecanoate as an initiator were sequentially added and stirred. While maintaining the stirring, the pressure of the prepolymerization reactor was elevated to 12 kg / cm 2 G to carry out the first bulk polymerization at 75 ° C., thereby preparing particle nuclei. At this time, the polymerization conversion rate of the first bulk polymerization was 10%.
이어서, 상기 중합 반응기에 상기 입자핵 전량, 상기 제1 괴상 중합에서 미반응된 염화비닐 단량체 전량, 추가의 염화비닐 단량체 80㎏, 및 개시제로 1,1,3,3-테트라메틸 부틸 퍼옥시 네오데카노에이트 200g을 순차적으로 투입하고 교반하였다. 상기 교반을 유지하면서 52℃의 온도, 7.5㎏/㎠ G의 압력 하에서 표 4에 기재된 시간 동안 제2 괴상 중합하였다. 이때 중합 전환율은 55%였다. 항산화제로 부틸레이티드 하이드록시 톨루엔을 200g을 투입한 후, 교반이 유지된 상태에서 진공으로 잔류 미반응 단량체를 회수한 후 염화비닐계 중합체를 수득하였다.Subsequently, the total amount of particle nuclei in the polymerization reactor, the total amount of unreacted vinyl chloride monomer in the first bulk polymerization, 80 kg of additional vinyl chloride monomer, and 1,1,3,3-tetramethyl butyl peroxy neo as an initiator were 200 g of decanoate was added sequentially and stirred. The second mass polymerization was carried out for the time shown in Table 4 under a temperature of 52 ° C. and a pressure of 7.5 kg / cm 2 G while maintaining the stirring. At this time, the polymerization conversion rate was 55%. 200 g of butylated hydroxy toluene was added as an antioxidant, and the vinyl chloride polymer was obtained after recovering the residual unreacted monomer in vacuo while stirring was maintained.
구분division 중합시간(분)Polymerization time (minutes) 아인산염Phosphate 용매menstruum 총량(㎏)Total amount (㎏)
종류Kinds 함량(중량%)Content (% by weight) 종류Kinds 함량(중량%)Content (% by weight)
실시예1-3Example 1-3 180180 페닐- 비스(4-노닐페닐)포스파이트Phenyl-bis (4-nonylphenyl) phosphite 1One 에탄올ethanol 9999 1One
실시예1-4Example 1-4 200200 트리스(4-옥틸페닐)포스파이트Tris (4-octylphenyl) phosphite 1One 에탄올ethanol 9999 33
비교예Comparative example 1-3 1-3
1㎥의 중합 반응기, 상기 중합 반응기와 연결되고 중합반응의 온도를 제열하는 환류 응축기 및 상기 환류 응축기와 연결되고 미반응 염화비닐계 단량체를 배출하는 염화비닐 회수배관을 포함하는 중합장치를 이용하여 염화비닐계 단량체를 하기와 같은 방법으로 중합하였다.By using a polymerization apparatus including a polymerization reactor of 1 m 3, a reflux condenser connected to the polymerization reactor to remove the temperature of the polymerization reaction, and a vinyl chloride recovery pipe connected to the reflux condenser and discharging the unreacted vinyl chloride monomer. The vinyl chloride monomer was polymerized in the following manner.
우선, 상기 중합 반응기에 탈이온수 390㎏를 투입하고, 분산제로 폴리비닐알코올(수화도: 78.5%) 150g, 폴리비닐알코올(수화도: 40.7%) 100g 및 하이드록시프로필메틸셀룰로오스 30g을 일괄 투입하였다. 이어서, 염화비닐계 단량체 300㎏를 투입하고, 개시제로 디-2-에틸 헥실 퍼옥시디카보네이트 30g 및 t-부틸퍼옥시 네오데카보네이트 120g을 투입하였다. 상기 중합 반응기의 내부 온도를 57℃로 유지하면서 중합을 수행하였다. 상기 중합율이 60%에 이르면, 1중량%의 트리페닐포스페이트를 포함하는 용액(용매: 에탄올) 30㎏를 펌프로 압입하였다. 상기 중합 반응기의 내부 압력이 6.3㎏/㎠에 도달한 시점에 반응종결제로 4-하이드록시-2,2,6,6-테트라 메틸-피페리딘-1-옥실 15g, 항산화제로 트리에틸렌 글리콜-비스-3-(3-t-부틸-4-하이드록시-5-메틸페닐)프로피오네이트 60g를 순차적으로 투입한 후, 미반응 단량체를 회수하고 반응을 종결시켜 제1 중합체 슬러리를 수득하였다. 이어서, 상기 제1 중합체 슬러리를 회수하고, 탈거 공정 및 탈수 공정을 수행하여 미반응 염화비닐계 단량체와 수분을 분리하여 제2 중합체 슬러리를 수득하였다. 상기 제2 중합체 슬러리를 유동층 건조기에서 60℃에서 열풍 건조하여 잔여 수분을 분리하고 선별시설을 거쳐 분말형태의 염화비닐계 중합체를 수득하였다. 상기 수득된 염화비닐계 중합체 내 아인산염의 함량을 측정하였지만, 아인산염이 이미 가수분해되었으므로 측정할 수 없었다. First, 390 kg of deionized water was added to the polymerization reactor, and 150 g of polyvinyl alcohol (degree of hydration: 78.5%), 100 g of polyvinyl alcohol (degree of hydration: 40.7%), and 30 g of hydroxypropylmethylcellulose were added as a dispersant. . Subsequently, 300 kg of a vinyl chloride monomer was added, and 30 g of di-2-ethylhexyl peroxydicarbonate and 120 g of t-butylperoxy neodecarbonate were added as an initiator. The polymerization was carried out while maintaining the internal temperature of the polymerization reactor at 57 ℃. When the polymerization rate reached 60%, 30 kg of a solution (solvent: ethanol) containing 1% by weight of triphenylphosphate was press-fitted with a pump. When the internal pressure of the polymerization reactor reached 6.3 kg / cm 2, 15 g of 4-hydroxy-2,2,6,6-tetra methyl-piperidine-1-oxyl as a terminator and triethylene glycol- as an antioxidant After sequentially adding 60 g of bis-3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate, unreacted monomer was recovered and the reaction was terminated to obtain a first polymer slurry. Subsequently, the first polymer slurry was recovered, and a stripping process and a dehydration process were performed to separate the unreacted vinyl chloride monomer and water to obtain a second polymer slurry. The second polymer slurry was hot-air dried at 60 ° C. in a fluidized bed dryer to separate residual water and to obtain a vinyl chloride polymer in powder form through a screening facility. The content of phosphite in the obtained vinyl chloride polymer was measured, but could not be measured because the phosphite was already hydrolyzed.
<시트의 제조><Manufacture of Sheet>
실시예Example 2-1 내지 2-4,  2-1 to 2-4, 비교예Comparative example 2-1 내지  2-1 to 비교예Comparative example 2-4  2-4
하기 표 5에 기재된 염화비닐계 중합체 100중량부, 주석계 안정제로 모노, 디메틸 틴 메르캅티드 복합체(Mono, Dimethyl tin mercaptide complex) 2중량부, 가공조제로 아크릴 및 메틸 메타크릴레이트 복합체(Acryl and Methyl Methacrylate(MMA) complex) 1중량부, 충격보강제로 메틸 메타크릴레이트 및 부타디엔 복합체(Methyl Methacrylate(MMA) and Butadiene complex) 5중량부, 활제로 지방산 에스테르 및 왁스 복합체(Fatty acid ester and wax complex) 0.5중량부 및 하기 표 5에 기재된 첨가제로 배합하고, 롤밀을 이용하여 185℃에서 3분 동안 혼련한 후 두께가 0.5㎜인 예비 시트를 수득하였다. 상기 시트를 절단하고 10장 겹치게 하고, 압축한 후 두께가 6㎜인 시트를 제작하였다.100 parts by weight of the vinyl chloride polymer shown in Table 5, 2 parts by weight of mono, dimethyl tin mercaptide complex (Mono, Dimethyl tin mercaptide complex) as a tin stabilizer, acryl and methyl methacrylate complex (Acryl and Methyl Methacrylate (MMA) complex, 1 part by weight, Methyl Methacrylate (MMA) and Butadiene complex as an impact modifier, 5 parts by weight, Fatty acid ester and wax complex 0.5 parts by weight and the additives described in Table 5 below were mixed and kneaded at 185 ° C. for 3 minutes using a roll mill to obtain a preliminary sheet having a thickness of 0.5 mm. The sheets were cut, stacked 10 sheets, and compressed to prepare a sheet having a thickness of 6 mm.
구분division 염화비닐계 중합체Vinyl chloride polymer 첨가제additive
종류Kinds 함량(중량부)Content (parts by weight)
실시예 2-1Example 2-1 실시예 1-1Example 1-1 -- --
실시예 2-2Example 2-2 실시예 1-2Example 1-2 -- --
실시예 2-3Example 2-3 실시예 1-3Example 1-3 -- --
실시예 2-4Example 2-4 실시예 1-4Example 1-4 -- --
비교예 2-1Comparative Example 2-1 비교예 1-1Comparative Example 1-1 -- --
비교예 2-2Comparative Example 2-2 비교예 1-2Comparative Example 1-2 -- --
비교예 2-3Comparative Example 2-3 비교예 1-1Comparative Example 1-1 트리스페닐 포스파이트Trisphenyl phosphite 1One
비교예 2-4Comparative Example 2-4 비교예 1-3Comparative Example 1-3 -- --
실시예Example 3-1 내지 3-4,  3-1 to 3-4, 비교예Comparative example 3-1 내지  3-1 to 비교예Comparative example 3-4  3-4
하기 표 6에 기재된 염화비닐계 중합체 100중량부, 주석계 안정제로 모노, 디메틸 틴 메르캅티드 복합체(Mono, Dimethyl tin mercaptide complex) 4중량부, 가공조제로 아크릴 및 메틸 메타크릴레이트 복합체(Acryl and Methyl Methacrylate(MMA) complex) 1중량부, 충격보강제로 메틸 메타크릴레이트 및 부타디엔 복합체(Methyl Methacrylate(MMA) and Butadiene complex) 6중량부, 활제로 지방산 에스테르 및 왁스 복합체(Fatty acid ester and wax complex) 0.5중량부, 및 하기 표 6에 기재된 첨가제로 배합하고, 롤밀을 이용하여 185에서 3분간 혼련한 후 두께가 0.5㎜ 두께인 예비 시트를 수득하였다. 상기 예비 시트를 절단하고 10장 겹치게 하고, 3㎜ 두께의 틀에 넣어 압축하고, 185℃에서 2분 동안 예열하고, 10㎏/㎠의 압력으로 185℃에서 3분 동안 가열하고, 15㎏/㎠의 압력, 185℃에서 2분 동안 냉각하여 두께가 3㎜인 시트를 제작하였다.100 parts by weight of the vinyl chloride polymer shown in Table 6, 4 parts by weight of mono, dimethyl tin mercaptide complex (Mono, Dimethyl tin mercaptide complex) as a tin stabilizer, acryl and methyl methacrylate complex (Acryl and 1 part by weight of Methyl Methacrylate (MMA) complex, 6 parts by weight of Methyl Methacrylate (MMA) and Butadiene complex as impact modifier, Fatty acid ester and wax complex as lubricant 0.5 parts by weight and the additives shown in Table 6 below were mixed and kneaded at 185 for 3 minutes using a roll mill to obtain a preliminary sheet having a thickness of 0.5 mm. The preliminary sheet was cut and overlapped 10 sheets, put into a 3 mm thick mold and compressed, preheated at 185 ° C. for 2 minutes, heated at 185 ° C. for 3 minutes at a pressure of 10 kg / cm 2, and 15 kg / cm 2. The sheet was cooled to 2 minutes at a pressure of 185 ° C. to produce a sheet having a thickness of 3 mm.
구분division 염화비닐계 중합체Vinyl chloride polymer 첨가제additive
종류Kinds 함량(중량부)Content (parts by weight)
실시예 3-1Example 3-1 실시예 1-1Example 1-1 -- --
실시예 3-2Example 3-2 실시예 1-2Example 1-2 -- --
실시예 3-3Example 3-3 실시예 1-3Example 1-3 -- --
실시예 3-4Example 3-4 실시예 1-4Example 1-4 -- --
비교예 3-1Comparative Example 3-1 비교예 1-1Comparative Example 1-1 -- --
비교예 3-2Comparative Example 3-2 비교예 1-2Comparative Example 1-2 -- --
비교예 3-3Comparative Example 3-3 비교예 1-1Comparative Example 1-1 트리스페닐 포스파이트Trisphenyl phosphite 1One
비교예 3-4Comparative Example 3-4 비교예 1-3Comparative Example 1-3 -- --
실험예Experimental Example 1 One
<혼탁도 및 <Turbidity and 투과도의Transmittance 측정> Measurement>
실시예 2-1 내지 실시예 2-4, 비교예 2-1 내지 비교예 2-4의 시트의 혼탁도(haze)와 투과도(transmission)를 BYK-Gardner(모델명: Haze-gard plus)을 이용하여 측정하였고, 그 결과를 표 7에 나타내었다.The haze and transmission of the sheets of Examples 2-1 to 2-4 and Comparative Examples 2-1 to 2-4 were obtained using BYK-Gardner (Model: Haze-gard plus). It was measured by, and the results are shown in Table 7.
혼탁도(Haze): 초기 발사되는 빔(beam)에 대하여 시료를 통과한 빛의 백분율로 정의되며, 빛이 시료를 많이 통과할수록 혼탁도의 수치는 작아지며 이는 투명성이 좋아진다는 것을 의미함 Haze: Defined as the percentage of light that passes through the sample relative to the initial fired beam, the more the light passes through the sample, the smaller the value of turbidity, which means better transparency.
투과도(Transmission): 혼탁도와 반비례하는 관계임 Transmission: Inversely related to turbidity
구분division 혼탁도(%)Turbidity (%) 투과도(%)Permeability (%)
실시예 2-1Example 2-1 6.66.6 86.586.5
실시예 2-2Example 2-2 7.07.0 85.585.5
실시예 2-3Example 2-3 6.86.8 85.985.9
실시예 2-4Example 2-4 7.17.1 85.085.0
비교예 2-1Comparative Example 2-1 10.510.5 77.677.6
비교예 2-2Comparative Example 2-2 10.710.7 77.177.1
비교예 2-3Comparative Example 2-3 8.58.5 83.083.0
비교예 2-4Comparative Example 2-4 10.610.6 76.476.4
표 7을 참조하면, 실시예 2-1 내지 실시예 2-4의 시트는 혼탁도가 6.6% 내지 7.1%이고, 투과도가 85.0% 내지 86.5%이므로, 투명성이 뛰어난 것을 알 수 있었다. Referring to Table 7, the sheets of Examples 2-1 to 2-4 had turbidity of 6.6% to 7.1% and transmittance of 85.0% to 86.5%.
하지만, 비교예 2-1 및 비교예 2-2의 시트는 혼탁도가 10.5% 및 10.7%이고, 투과도가 77.6% 및 77.1%이므로, 실시예 2-1 내지 실시예 2-4의 시트보다 투명성이 떨어지는 것을 알 수 있었다. 비교예 2-3의 시트는 실시예 2-1 내지 실시예 2-4의 시트에 비하여 혼탁도 및 투과도가 떨어지는 것을 알 수 있다. 비교예 2-3의 시트는, 시트 내 아인산염의 함량이 본 발명의 염화비닐계 중합체로 제조된 시트와 유사할지라도, 염화비닐계 중합체의 매트릭스 내에 아인산염이 분산된 것이 아니므로, 투명성이 저하되는 것을 알 수 있었다. 비교예 2-4의 시트는 아인산염을 투입하지 않은 염화비닐 중합계 중합체를 이용한 것과 마찬가지므로, 현탁도 및 투과도가 떨어지는 것을 알 수 있었다. However, since the sheets of Comparative Examples 2-1 and 2-2 had turbidity of 10.5% and 10.7% and transmittance of 77.6% and 77.1%, the sheets of Examples 2-1 to 2-4 were more transparent than the sheets of Examples 2-1 to 2-4. I could see this falling. It can be seen that the sheets of Comparative Example 2-3 are inferior in turbidity and permeability as compared with the sheets of Examples 2-1 to 2-4. The sheet of Comparative Example 2-3 has transparency because the phosphite is not dispersed in the matrix of the vinyl chloride-based polymer even though the content of the phosphite in the sheet is similar to the sheet made of the vinyl chloride-based polymer of the present invention. It was found that the degradation. Since the sheet of the comparative example 2-4 was the same as using the vinyl chloride polymer type polymer which did not add the phosphite, it turned out that suspension and permeability are inferior.
실험예Experimental Example 2 2
<< 열안정성Thermal stability 평가의 측정> Measurement of Evaluation>
실시예 3-1 내지 실시예 3-4, 비교예 3-1 내지 비교예 3-4의 시트의 열안정성을 NR-3000(제조사: 니폰 덴소쿠(Nippon Denshoku)사)를 이용하여 백색도(W.I) 값을 측정하였고, 그 결과를 표 8에 나타내었다. 일반적으로, 백색도 값으로부터 열안정성을 평가할 수 있으며, 백색도 값이 높을수록 열안정성이 우수한 것이다.The thermal stability of the sheets of Examples 3-1 to 3-4 and Comparative Examples 3-1 to 3-4 was measured using NR-3000 (manufacturer: Nippon Denshoku). ) Was measured and the results are shown in Table 8. In general, the thermal stability can be evaluated from the whiteness value, and the higher the whiteness value, the better the thermal stability.
구분division 백색도Whiteness
실시예 3-1Example 3-1 32.9032.90
실시예 3-2Example 3-2 32.4532.45
실시예 3-3Example 3-3 32.1032.10
실시예 3-4Example 3-4 31.8031.80
비교예 3-1Comparative Example 3-1 23.5023.50
비교예 3-2Comparative Example 3-2 23.0023.00
비교예 3-3Comparative Example 3-3 28.3028.30
비교예 3-4Comparative Example 3-4 28.0028.00
표 8을 참조하면, 실시예 3-1 내지 실시예 3-4의 시트는 백색도 값이 31.80 내지 32.90므로 열안정성이 뛰어난 것을 알 수 있었다. 반면, 비교예 3-1 및 비교예 3-2의 시트는 백색도 값이 23.5 및 23이므로 실시예 3-1 내지 실시예 3-4의 시트보다 열안정성이 떨어지는 것을 알 수 있었다. 비교예 3-3의 시트는 실시예 3-1 내지 실시예 3-4의 시트에 비하여 백색도가 떨어지는 것을 알 수 있다. Referring to Table 8, it was found that the sheets of Examples 3-1 to 3-4 had excellent thermal stability because the whiteness values were 31.80 to 32.90. On the other hand, the sheets of Comparative Examples 3-1 and 3-2 have whiteness values of 23.5 and 23, so that the thermal stability was lower than those of Examples 3-1 to 3-4. It can be seen that the sheet of Comparative Example 3-3 has a lower whiteness than the sheets of Examples 3-1 to 3-4.
비교예 3-3의 시트는, 시트 내 아인산염의 함량이 본 발명의 염화비닐계 중합체로 제조된 시트와 유사할지라도, 염화비닐계 중합체의 매트릭스 내에 아인산염이 분산된 것이 아니므로, 열안정성이 저하되는 것을 알 수 있었다. 비교예 3-4의 시트는 아인산염을 투입하지 않은 염화비닐 중합계 중합체를 이용한 것과 마찬가지므로, 백색도가 떨어지는 것을 알 수 있었다. 비교예 3-4의 시트가 비교예 3-1 및 3-2의 시트 대비 백색도가 우수하지만, 이는 중합 방법의 차이로 인한 것일 뿐 유의미한 차이는 아니었다.The sheet of Comparative Example 3-3 is thermally stable because the phosphite is not dispersed in the matrix of the vinyl chloride-based polymer even though the content of the phosphite in the sheet is similar to the sheet made of the vinyl chloride-based polymer of the present invention. It turned out that this falls. Since the sheet | seat of the comparative example 3-4 is the same as using the vinyl chloride polymer type polymer which does not add the phosphite, it turned out that whiteness falls. Although the sheets of Comparative Examples 3-4 were superior in whiteness than the sheets of Comparative Examples 3-1 and 3-2, this was due to the difference in polymerization method and was not a significant difference.

Claims (13)

  1. 개시제 존재 하에, 염화비닐계 단량체를 괴상 중합시키는 제1 단계; 및A first step of bulk polymerizing the vinyl chloride monomer in the presence of an initiator; And
    상기 괴상 중합을 완료한 후 염화비닐계 중합체를 수득하는 제2 단계를 포함하고,Comprising a second step of obtaining a vinyl chloride-based polymer after the bulk polymerization is completed,
    상기 제1 단계에서 아인산염을 투입하는 것을 특징으로 하는 염화비닐계 중합체의 제조방법.Method of producing a vinyl chloride-based polymer, characterized in that the phosphite is added in the first step.
  2. 청구항 1에 있어서,The method according to claim 1,
    상기 제1 단계는The first step is
    제1 개시제 존재 하에, 제1 염화비닐계 단량체를 제1 괴상 중합시키고 입자핵을 형성하는 제1-1 단계; 및A first-first step of mass-polymerizing the first vinyl chloride monomer in the presence of the first initiator and forming particle nuclei; And
    제2 개시제 존재 하에, 상기 입자핵, 상기 제1-1 단계에서 미반응된 제1 염화비닐계 단량체 및 제2 염화비닐계 단량체를 제2 괴상 중합시키는 제1-2 단계를 포함하고,In the presence of a second initiator, the first and second stages of the second bulk polymerization of the particle nucleus, the first vinyl chloride monomer and the second vinyl chloride monomer unreacted in the step 1-1,
    상기 제1-1 단계 및 상기 제1-2 단계 중 하나 이상의 단계에서 상기 아인산염을 투입하는 것을 특징으로 하는 염화비닐계 중합체의 제조방법.Method of producing a vinyl chloride-based polymer, characterized in that the phosphite is added in at least one of steps 1-1 and 1-2.
  3. 청구항 2에 있어서,The method according to claim 2,
    상기 제1 괴상 중합은 60 내지 80℃의 온도, 9 내지 14㎏/㎠ G의 압력 하에서 수행되는 것을 특징으로 하는 염화비닐계 중합체의 제조방법.The first bulk polymerization is a method of producing a vinyl chloride-based polymer, characterized in that carried out under a temperature of 60 to 80 ℃, pressure of 9 to 14kg / ㎠ G.
  4. 청구항 2에 있어서,The method according to claim 2,
    상기 제2 괴상중합은 50 내지 70℃의 온도, 7 내지 12㎏/㎠ G의 압력 하에서 수행되는 것을 특징으로 하는 염화비닐계 중합체의 제조방법.The second bulk polymerization is a method of producing a vinyl chloride-based polymer, characterized in that carried out under a temperature of 50 to 70 ℃, pressure of 7 to 12kg / ㎠ G.
  5. 청구항 1에 있어서,The method according to claim 1,
    상기 아인산염은 하기 화학식 1로 표시되는 화합물인 것을 특징으로 하는 염화비닐계 중합체의 제조방법:The phosphite is a method of producing a vinyl chloride-based polymer, characterized in that the compound represented by the formula (1):
    <화학식 1><Formula 1>
    Figure PCTKR2017009713-appb-I000012
    Figure PCTKR2017009713-appb-I000012
    상기 화학식 1에 있어서,In Chemical Formula 1,
    L1 내지 L3는 각각 독립적으로, 서로 같거나 다르고, 직접 결합, C1 내지 C20의 알킬렌기 또는 C6 내지 C20의 아릴렌기이고,L 1 to L 3 are each independently the same as or different from each other, and are a direct bond, an alkylene group of C1 to C20, or an arylene group of C6 to C20,
    R1 내지 R3는 각각 독립적으로, 서로 같거나 다르고, 치환 또는 비치환된 C1 내지 C20의 직쇄 또는 분지쇄 알킬기 또는 치환 또는 비치환된 C6 내지 C20의 아릴기이다.R 1 to R 3 are each independently the same or different and are a substituted or unsubstituted C1 to C20 straight or branched chain alkyl group or a substituted or unsubstituted C6 to C20 aryl group.
  6. 청구항 5에 있어서,The method according to claim 5,
    상기 아인산염은 트리스에틸 포스파이트, 트리스이소프로필 포스파이트, 트리스이소데실 포스파이트, 트리스도데실 포스파이트, 페닐-디이소데실 포스파이트, 디페닐-이소데실 포스파이트, 트리스페닐 포스파이트, 페닐-비스(4-노닐페닐)포스파이트, 트리스(4-옥틸페닐) 포스파이트 및 트리스((4-1-페닐에틸)페닐) 포스파이트로 이루어진 군에서 선택되는 1종 또는 2종 이상인 것을 특징으로 하는 염화비닐계 중합체의 제조방법.The phosphites are trisethyl phosphite, trisisopropyl phosphite, trisisodecyl phosphite, trisdodecyl phosphite, phenyl-diisodecyl phosphite, diphenyl-isodecyl phosphite, trisphenyl phosphite, phenyl- Bis (4-nonylphenyl) phosphite, tris (4-octylphenyl) phosphite and tris ((4-1-phenylethyl) phenyl) phosphite; Method for producing vinyl chloride polymer.
  7. 청구항 1에 있어서,The method according to claim 1,
    상기 아인산염은 상기 염화비닐계 단량체 100 중량부에 대하여, 0.001 내지 1 중량부로 투입되는 것을 특징으로 하는 염화비닐계 중합체의 제조방법.The phosphite is prepared from 0.001 to 1 part by weight based on 100 parts by weight of the vinyl chloride monomer.
  8. 청구항 1에 있어서,The method according to claim 1,
    상기 아인산염을 용매에 혼합된 용액 상태로 투입하는 것을 특징으로 하는 염화비닐계 중합체의 제조방법.Method for producing a vinyl chloride-based polymer, characterized in that the phosphite is added in a solution state mixed in a solvent.
  9. 청구항 1에 있어서,The method according to claim 1,
    상기 염화비닐계 중합체는 상기 염화비닐계 중합체의 매트릭스 내에 상기 아인산염이 분산된 것을 특징으로 하는 염화비닐계 중합체의 제조방법.The vinyl chloride polymer is a method of producing a vinyl chloride polymer, characterized in that the phosphite is dispersed in a matrix of the vinyl chloride polymer.
  10. 청구항 9에 있어서,The method according to claim 9,
    상기 염화비닐계 중합체는 상기 염화비닐계 중합체의 3차원 네트워크 구조 사이에 상기 아인산염이 분산 및 고정화된 것을 특징으로 하는 염화비닐계 중합체의 제조방법.The vinyl chloride-based polymer is a method of producing a vinyl chloride-based polymer, characterized in that the phosphite is dispersed and immobilized between the three-dimensional network structure of the vinyl chloride-based polymer.
  11. 염화비닐계 중합체의 매트릭스 내에 아인산염이 분산된 것을 특징으로 하는 염화비닐계 중합체.A vinyl chloride-based polymer, wherein a phosphite is dispersed in a matrix of the vinyl chloride-based polymer.
  12. 청구항 11에 있어서,The method according to claim 11,
    상기 아인산염이 상기 염화비닐계 중합체 총 중량에 대하여, 0.001 내지 2 중량%로 포함되는 것을 특징으로 하는 염화비닐계 중합체.Vinyl chloride-based polymer, characterized in that the phosphite is contained in 0.001 to 2% by weight based on the total weight of the vinyl chloride-based polymer.
  13. 청구항 11에 따른 염화비닐계 중합체; 및A vinyl chloride polymer according to claim 11; And
    안정제, 가공조제, 충격보강제 및 활제로 이루어진 군에서 선택되는 1종 이상을 포함하는 것을 특징으로 하는 염화비닐계 중합체 조성물.A vinyl chloride polymer composition comprising at least one selected from the group consisting of stabilizers, processing aids, impact modifiers, and lubricants.
PCT/KR2017/009713 2016-09-26 2017-09-05 Method for preparing vinyl chloride-based polymer, vinyl chloride-based polymer, and vinyl chloride-based polymer composition WO2018056611A1 (en)

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