WO2018056611A1 - Procédé de préparation de polymère à base de chlorure de vinyle, polymère à base de chlorure de vinyle et composition de polymère à base de chlorure de vinyle - Google Patents

Procédé de préparation de polymère à base de chlorure de vinyle, polymère à base de chlorure de vinyle et composition de polymère à base de chlorure de vinyle Download PDF

Info

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
Authority
WO
WIPO (PCT)
Prior art keywords
vinyl chloride
phosphite
based polymer
polymer
producing
Prior art date
Application number
PCT/KR2017/009713
Other languages
English (en)
Korean (ko)
Inventor
안성용
김건지
이세웅
하현규
신성재
Original Assignee
주식회사 엘지화학
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from KR1020170112014A external-priority patent/KR102105041B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to US15/774,961 priority Critical patent/US10696760B2/en
Priority to EP17853325.3A priority patent/EP3357942B1/fr
Priority to CN201780004330.XA priority patent/CN108290978B/zh
Publication of WO2018056611A1 publication Critical patent/WO2018056611A1/fr

Links

Classifications

    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

La présente invention concerne un procédé de préparation d'un polymère à base de chlorure de vinyle, un polymère à base de chlorure de vinyle, et une composition de polymère à base de chlorure de vinyle le comprenant, le procédé comprenant: une première étape de polymérisation en masse d'un monomère à base de chlorure de vinyle en présence d'un amorceur; et une seconde étape consistant à obtenir un polymère à base de chlorure de vinyle après achèvement de la polymérisation en masse, un phosphite étant introduit à la première étape.
PCT/KR2017/009713 2016-09-26 2017-09-05 Procédé de préparation de polymère à base de chlorure de vinyle, polymère à base de chlorure de vinyle et composition de polymère à base de chlorure de vinyle WO2018056611A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US15/774,961 US10696760B2 (en) 2016-09-26 2017-09-05 Method of preparing vinyl chloride-based polymer, vinyl chloride-based polymer, and vinyl chloride-based polymer composition
EP17853325.3A EP3357942B1 (fr) 2016-09-26 2017-09-05 Procédé de préparation de polymère à base de chlorure de vinyle, polymère à base de chlorure de vinyle et composition de polymère à base de chlorure de vinyle
CN201780004330.XA CN108290978B (zh) 2016-09-26 2017-09-05 氯乙烯基聚合物的制备方法、氯乙烯基聚合物和氯乙烯基聚合物组合物

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR10-2016-0123388 2016-09-26
KR20160123388 2016-09-26
KR10-2017-0112014 2017-09-01
KR1020170112014A KR102105041B1 (ko) 2016-09-26 2017-09-01 염화비닐계 중합체의 제조방법, 염화비닐계 중합체 및 염화비닐계 중합체 조성물

Publications (1)

Publication Number Publication Date
WO2018056611A1 true WO2018056611A1 (fr) 2018-03-29

Family

ID=61690504

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2017/009713 WO2018056611A1 (fr) 2016-09-26 2017-09-05 Procédé de préparation de polymère à base de chlorure de vinyle, polymère à base de chlorure de vinyle et composition de polymère à base de chlorure de vinyle

Country Status (1)

Country Link
WO (1) WO2018056611A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115260349A (zh) * 2022-07-06 2022-11-01 新疆中泰化学托克逊能化有限公司 一种本体法pvc医用片材专用料及其制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5153589A (en) * 1974-11-06 1976-05-12 Shinetsu Chemical Co Harogenkabiniruno kaijojugoho
JPS5278985A (en) * 1975-12-26 1977-07-02 Tokuyama Soda Co Ltd Polymerization of vinyl chloride polymers
JPH06199911A (ja) * 1992-12-28 1994-07-19 Shin Etsu Chem Co Ltd 塩化ビニル系重合体の製造方法
KR20100023340A (ko) * 2008-08-21 2010-03-04 주식회사 엘지화학 분산성이 향상된 염화비닐계 수지 중합체의 제조방법
KR20160061126A (ko) * 2014-11-21 2016-05-31 주식회사 엘지화학 염화비닐계 중합체 및 이의 제조방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5153589A (en) * 1974-11-06 1976-05-12 Shinetsu Chemical Co Harogenkabiniruno kaijojugoho
JPS5278985A (en) * 1975-12-26 1977-07-02 Tokuyama Soda Co Ltd Polymerization of vinyl chloride polymers
JPH06199911A (ja) * 1992-12-28 1994-07-19 Shin Etsu Chem Co Ltd 塩化ビニル系重合体の製造方法
KR20100023340A (ko) * 2008-08-21 2010-03-04 주식회사 엘지화학 분산성이 향상된 염화비닐계 수지 중합체의 제조방법
KR20160061126A (ko) * 2014-11-21 2016-05-31 주식회사 엘지화학 염화비닐계 중합체 및 이의 제조방법

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115260349A (zh) * 2022-07-06 2022-11-01 新疆中泰化学托克逊能化有限公司 一种本体法pvc医用片材专用料及其制备方法

Similar Documents

Publication Publication Date Title
KR102105041B1 (ko) 염화비닐계 중합체의 제조방법, 염화비닐계 중합체 및 염화비닐계 중합체 조성물
WO2018056610A1 (fr) Procédé de préparation d'un composite polymère à base de chlorure de vinyle, composite polymère à base de chlorure de vinyle, et composition composite polymère à base de chlorure de vinyle
WO2016047955A1 (fr) Polymère à base de chlorure de vinyle et son procédé de fabrication
WO2015080367A1 (fr) Procédé pour la préparation de résine à base de chlorure de vinyle
WO2018056611A1 (fr) Procédé de préparation de polymère à base de chlorure de vinyle, polymère à base de chlorure de vinyle et composition de polymère à base de chlorure de vinyle
WO2023200200A1 (fr) Composition de billes polymères et procédé de fabrication de billes polymères l'utilisant
KR20220009686A (ko) 염화비닐계 중합체의 제조방법
KR20210136868A (ko) 염화비닐계 중합체 복합체의 제조방법, 염화비닐계 중합체 복합체 및 이를 포함하는 염화비닐계 중합체 복합체 조성물
KR101606240B1 (ko) 난연성 열가소성 공중합체, 그 제조방법 및 이를 포함하는 성형품
WO2022005118A1 (fr) Procédé de production d'un composite polymère à base de chlorure de vinyle
WO2018044017A1 (fr) Procédé de préparation d'un polymère à base de chlorure de vinyle et dispositif pour préparer un polymère à base de chlorure de vinyle
WO2021256867A1 (fr) Procédé de production d'un composite polymère à base de chlorure de vinyle
WO2021225394A1 (fr) Procédé de préparation de composite polymère de chlorure de vinyle, composite polymère de chlorure de vinyle et composition de composite polymère de chlorure de vinyle comprenant celui-ci
WO2018056668A1 (fr) Procédé de préparation d'un polymère à base de chlorure de vinyle
KR20220009687A (ko) 염화비닐계 중합체의 제조방법
WO2017188594A1 (fr) Procédé de préparation d'un polymère à base de chlorure de vinyle, et polymère à base de chlorure de vinyle obtenu selon ce procédé
WO2016047954A1 (fr) Polymère à base de chlorure de vinyle et son procédé de production
WO2017061829A1 (fr) Polymère à base de chlorure de vinyle et son procédé de préparation
WO2015034209A1 (fr) Procédé de préparation d'une résine à base d'acrylate renforcée, résistante aux intempéries
WO2022065784A1 (fr) Procédé de préparation d'un polymère à base de chlorure de vinyle
WO2022014989A1 (fr) Procédé de préparation d'un polymère de chlorure de vinyle
WO2017222213A1 (fr) Procédé de production d'un polymère à base de chlorure de vinyle
KR102065160B1 (ko) 염화비닐계 수지 플라스티졸, 이의 제조방법 및 이로부터 제조된 염화비닐계 수지 성형품
WO2023277530A1 (fr) Procédé de préparation d'un polymère à base de chlorure de vinyle et polymère à base de chlorure de vinyle préparé par ce procédé
WO2016089000A1 (fr) Procédé de préparation de résine thermoplastique

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 2017853325

Country of ref document: EP

NENP Non-entry into the national phase

Ref country code: DE