WO2014157346A1 - 塩素化塩化ビニル系樹脂の製造方法及び製造装置 - Google Patents
塩素化塩化ビニル系樹脂の製造方法及び製造装置 Download PDFInfo
- Publication number
- WO2014157346A1 WO2014157346A1 PCT/JP2014/058560 JP2014058560W WO2014157346A1 WO 2014157346 A1 WO2014157346 A1 WO 2014157346A1 JP 2014058560 W JP2014058560 W JP 2014058560W WO 2014157346 A1 WO2014157346 A1 WO 2014157346A1
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- Prior art keywords
- vinyl chloride
- tank
- chloride resin
- chlorinated vinyl
- suspension
- Prior art date
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- 239000011347 resin Substances 0.000 title claims abstract description 290
- 229920005989 resin Polymers 0.000 title claims abstract description 290
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical class ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims abstract description 268
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 65
- 239000000460 chlorine Substances 0.000 claims abstract description 110
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 110
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 109
- 239000000725 suspension Substances 0.000 claims abstract description 103
- 239000007788 liquid Substances 0.000 claims description 22
- 230000001678 irradiating effect Effects 0.000 claims description 20
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 8
- 239000012071 phase Substances 0.000 claims description 8
- 229920002554 vinyl polymer Polymers 0.000 claims description 5
- 150000001805 chlorine compounds Chemical class 0.000 claims description 2
- 239000007792 gaseous phase Substances 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 abstract 1
- 238000005660 chlorination reaction Methods 0.000 description 73
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 39
- 239000007900 aqueous suspension Substances 0.000 description 38
- 230000000052 comparative effect Effects 0.000 description 31
- 239000011521 glass Substances 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 23
- 230000035484 reaction time Effects 0.000 description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 19
- 238000000034 method Methods 0.000 description 19
- 239000002002 slurry Substances 0.000 description 19
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 16
- 229910052751 metal Inorganic materials 0.000 description 16
- 239000002184 metal Substances 0.000 description 16
- 238000003756 stirring Methods 0.000 description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 15
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 15
- 229910052753 mercury Inorganic materials 0.000 description 15
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 239000002245 particle Substances 0.000 description 11
- 238000003856 thermoforming Methods 0.000 description 11
- 238000000295 emission spectrum Methods 0.000 description 10
- 239000003381 stabilizer Substances 0.000 description 10
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- 238000004040 coloring Methods 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- 239000005297 pyrex Substances 0.000 description 7
- 230000003068 static effect Effects 0.000 description 7
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000000314 lubricant Substances 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- -1 for example Substances 0.000 description 5
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- 235000021355 Stearic acid Nutrition 0.000 description 3
- 239000012736 aqueous medium Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000004926 polymethyl methacrylate Substances 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- 229910002704 AlGaN Inorganic materials 0.000 description 1
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- 241000270295 Serpentes Species 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 150000001804 chlorine Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002455 scale inhibitor Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- NMOALOSNPWTWRH-UHFFFAOYSA-N tert-butyl 7,7-dimethyloctaneperoxoate Chemical compound CC(C)(C)CCCCCC(=O)OOC(C)(C)C NMOALOSNPWTWRH-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 230000002463 transducing effect Effects 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
- B01J19/121—Coherent waves, e.g. laser beams
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
- B01J19/122—Incoherent waves
- B01J19/123—Ultraviolet light
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
- B01J19/122—Incoherent waves
- B01J19/127—Sunlight; Visible light
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
-
- 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
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/18—Suspension polymerisation
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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
- C08F8/00—Chemical modification by after-treatment
- C08F8/18—Introducing halogen atoms or halogen-containing groups
- C08F8/20—Halogenation
- C08F8/22—Halogenation by reaction with free halogens
-
- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
-
- 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
- C08L27/22—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 modified by chemical after-treatment
- C08L27/24—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 modified by chemical after-treatment halogenated
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
- C08L91/06—Waxes
- C08L91/08—Mineral waxes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J2219/0873—Materials to be treated
- B01J2219/0881—Two or more materials
- B01J2219/0884—Gas-liquid
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J2219/12—Processes employing electromagnetic waves
- B01J2219/1203—Incoherent waves
Definitions
- the present invention relates to a method and an apparatus for producing a chlorinated vinyl chloride resin, and more particularly to a method and an apparatus for producing a chlorinated vinyl chloride resin using a photochlorination method.
- the heat resistance temperature of the chlorinated vinyl chloride resin becomes higher than the heat resistance temperature of the vinyl chloride resin due to chlorination. Therefore, chlorinated vinyl chloride resins are used in various fields such as heat resistant pipes, heat resistant industrial plates, heat resistant films and heat resistant sheets.
- a chlorinated vinyl chloride resin is produced by chlorinating a vinyl chloride resin while supplying chlorine to an aqueous suspension obtained by suspending vinyl chloride resin particles in an aqueous medium. It is common. Usually, when chlorination is performed by a photochlorination method, ultraviolet irradiation with a mercury lamp is performed to generate chlorine radicals (Patent Document 1).
- chlorine is infiltrated into the granular material by a step of dissolving chlorine in an aqueous suspension of the polyolefin granular material under conditions where radicals are not generated, and then chlorinated by heating or / and light irradiation.
- Patent Document 2 A method of obtaining chlorinated polyolefin particles in the same reaction tank by repeating these two steps alternately has been reported.
- a chlorination reaction is performed by inserting a mercury lamp 102 protected by a glass tube 101 into an aqueous suspension 105 of vinyl chloride resin.
- the present inventors diligently studied. As a result, after separating a chlorine introduction tank for introducing chlorine and a tank for performing photochlorination reaction by ultraviolet irradiation, the chlorine introduction tank By increasing the internal pressure, the amount of chlorine dissolved in the suspension can be increased, and as a result, the production efficiency of the chlorinated vinyl chloride resin can be improved, and the present invention is completed. It came. That is, the present invention includes the following inventions.
- a step of introducing chlorine into the suspension of the vinyl chloride resin, the suspension into which the chlorine has been introduced is transferred from the first tank to the second tank, and the second tank And irradiating the suspension with ultraviolet light.
- the tank 2 is an apparatus for producing a chlorinated vinyl chloride resin, which includes a light source for irradiating the suspension with ultraviolet rays.
- the amount of dissolved chlorine in the suspension of the vinyl chloride resin is improved.
- the reaction efficiency at the time of producing a vinyl-based resin is improved.
- a to B representing a numerical range is “A or more (including A and greater than A) and B or less (including B and less than B)”, “%”. Means “% by mass”, and “part” means “part by mass”.
- the method for producing a chlorinated vinyl chloride resin according to the present invention includes (i) introducing chlorine into a suspension of the vinyl chloride resin in the first tank. And (ii) transferring the suspension into which the chlorine has been introduced from the first tank to the second tank, and irradiating the suspension with ultraviolet rays in the second tank; Other specific processes, conditions, materials, facilities, etc. are not particularly limited.
- the production method according to the present invention includes a tank for supplying chlorine to a suspension of vinyl chloride resin, and a photochlorination reaction by irradiating ultraviolet light to the suspension of vinyl chloride resin containing chlorine. It is characterized in that it is separated from the tank that performs. With this configuration, the internal pressure of the first tank for introducing chlorine can be increased. For this reason, the amount of chlorine dissolved in the suspension of the vinyl chloride resin is improved, and for example, the reaction efficiency when producing a chlorinated chlorine vinyl resin is improved.
- the manufacturing method according to the present invention since heat is generated during the photochlorination reaction, it was necessary to remove heat from the tank in the conventional manufacturing method in which chlorine introduction and light irradiation were simultaneously performed.
- the first tank for introducing chlorine and the second tank for photochlorination reaction are separated from each other. It is not necessary to remove heat from the tank, and the equipment cost related to heat removal can be reduced.
- a heat removal method of the suspension other than removing the heat from the first tank a method of removing heat or cooling with a pipe can be mentioned.
- the heat removal or cooling method in the pipe is not particularly limited, but for example, a method using a pipe provided with a cooling jacket or “cooling” of the pipe can be used.
- an ultraviolet light source can be used, and is not particularly limited.
- at least one light source selected from the group consisting of mercury lamp, ultraviolet LED, organic EL, inorganic EL, and ultraviolet laser More preferably, at least one light source selected from the group consisting of an ultraviolet LED, an organic EL, an inorganic EL, and an ultraviolet laser is preferably used.
- the present invention also includes a first tank for introducing chlorine into the suspension of the vinyl chloride resin and a second tank for introducing the suspension from the first tank and chlorinating. And the second tank has at least one light source selected from the group consisting of an ultraviolet LED, an organic EL, an inorganic EL, and an ultraviolet laser for irradiating the suspension with ultraviolet rays.
- An apparatus for manufacturing a chlorinated vinyl chloride resin provided is also included (hereinafter simply referred to as a manufacturing apparatus according to the present invention).
- the manufacturing apparatus according to the present invention can implement the manufacturing method according to the present invention.
- an example in which an ultraviolet LED is used as a light source is given as an example.
- the light source is not limited to this.
- a chlorinated vinyl chloride resin production apparatus 11 that can be used in the production method according to the present invention includes a chlorine introduction part 1 for introducing chlorine gas, and a suspension 12 of vinyl chloride resin. From the first tank 2 for introducing chlorine into the slurry, the slurry extraction part 3 for transferring the suspension into which chlorine has been introduced from the first tank 2 to the second tank 6, and from the first tank 2 The pressure reducing valve 4 for reducing the pressure of the taken-out suspension, the second tank 6 for irradiating the suspension with ultraviolet rays and performing the photochlorination reaction, the first from the second tank 6.
- a slurry circulation line 7 for circulating the suspension to the tank 2 for circulating the suspension to the tank 2
- a chlorine introduction part 8 for introducing chlorine gas to the suspension taken out from the second tank 6, and the suspension into the second
- a slurry circulation pump 5 for transferring from the tank 6 to the first tank 2 and a stirrer for stirring the suspension 12 in the first tank 2.
- the first tank 2 may be any pressure-resistant container that can be sealed, and various reaction containers can be used without any particular limitation, and the specific configuration is not limited.
- a tank for producing a known chlorinated vinyl chloride resin can be suitably used.
- a suspension 12 in which a vinyl chloride resin is dispersed is placed in the first tank 2, and is stirred by the stirring unit 9 disposed in the first tank 2.
- Chlorine gas is supplied from the chlorine inlet 1 to the stirred suspension 12.
- the stirring unit 9 disposed in the first tank 2 is not particularly limited, and a stirring blade or the like can be used.
- the stirring blade may be an axial flow type such as a propeller blade, or a wide flow type such as a paddle blade or a turbine blade.
- the manufacturing apparatus 11 includes a pressurizing unit (pressurizing means) for pressurizing the first tank 2.
- a pressurizing unit pressurizing means
- the inside of the 1st tank 2 can be pressurized.
- the chlorine introduction part 1 functions as a pressurizing part. That is, when the chlorine introduction part 1 introduces chlorine gas into the first tank 2, the pressure inside the first tank 2 increases.
- the pressure in the first tank 2 is not particularly limited, and examples thereof include 0.02 to 2.00 MPa. Further, it is preferably 0.04 to 2.00 MPa, preferably 0.05 to 2.00 MPa, more preferably 0.06 to 1.50 MPa, and 0.08 to 1.20 MPa. More preferably it is. In addition, it is more preferably 0.10 to 1.00 MPa, and particularly preferably 0.12 to 0.50 MPa. If it is in the said range, the reaction efficiency of chlorination can be improved.
- the suspension 12 supplied with chlorine is taken out from the slurry extraction section 3 provided at the bottom of the first tank 2 and passes through the pressure reducing valve 4 for reducing the pressure of the suspension 12. , Transferred to the second tank 6.
- the pressure reducing valve 4 various general pressure reducing valves can be used and are not particularly limited.
- the suspension 12 introduced into the second tank 6 is irradiated with ultraviolet rays and chlorinated by a photochlorination reaction. Thereafter, the suspension 12 derived from the second tank 6 is returned to the first tank 2 via the slurry circulation line 7 and the slurry circulation pump 5. At this time, chlorine in the suspension is consumed in the second tank 6 by the photochlorination reaction. For this reason, it is preferable to supply chlorine gas from the chlorine introduction part 8 (2nd chlorine introduction means) with respect to the suspension taken out from the 2nd tank 6.
- the chlorine introduction part 8 introduces chlorine gas into the suspension before the suspension taken out from the second tank 6 is returned to the first tank 2.
- the chlorine introduction unit 8 prevents the inside of the slurry circulation line 7 from becoming negative pressure with respect to the suspension taken out from the second tank 6, in other words, the inside of the slurry circulation line 7 exceeds the negative pressure. It is preferable to supply chlorine gas so that
- this manufacturing apparatus 11 is provided with the circulation part (circulation means) which circulates the suspension irradiated with the ultraviolet-ray in the 2nd tank 6 to the 1st tank 2, and manufacture which concerns on this invention
- the circulation portion (circulation means) include the slurry circulation pump 5 and the slurry circulation line 7. According to this configuration, since supply of chlorine and chlorination by ultraviolet irradiation can be repeated, production can be easily performed.
- the slurry circulation pump 5 is not particularly limited as long as it can circulate a stable and constant amount of the suspension to the first tank 2, and is preferably a gear pump or a snake pump, for example.
- the pump material for example, ceramic, titanium palladium, or the like can be used.
- the pump material is preferably a material that satisfies wet chlorine and hydrogen chloride.
- the manufacturing apparatus 11 may include a jacket portion 10 that covers the first tank 2.
- the jacket portion 10 that covers the first tank 2 has a function of controlling the internal temperature of the first tank 2.
- a jacket for cooling the internal temperature of the reactor can be exemplified.
- the internal temperature of the first tank 2 can be controlled by balancing the amount of heat removal and the amount of heat generated by the cooling jacket.
- second tank 6 although only one second tank 6 is shown in FIG. 1, the number of installation is not particularly limited, and a plurality of second tanks 6 may be provided. When a plurality of second tanks 6 are provided, they may be installed in series or in parallel. However, in consideration of reaction efficiency, it is preferable to install them in parallel.
- the circulation part preferably introduces the suspension 12 to the gas phase part of the first tank 2 or the vicinity of the gas-liquid interface.
- the suspension 12 may be circulated to any location within the range of the purpose.
- the second tank 6 includes a transparent pipe for circulating the suspension 12 and a light source for irradiating the transparent pipe with ultraviolet rays.
- the number of transparent pipes may be one or more, and the number is not particularly limited.
- Various transparent pipes can also be used for the size and shape of the diameter.
- any transparent pipe can be used as long as it transmits ultraviolet light and can withstand the manufacturing conditions (chlorine resistance, acid resistance, etc.) of the chlorinated vinyl chloride resin.
- glass piping is preferable.
- the light source is not particularly limited as long as the light source is disposed so as to be able to irradiate ultraviolet rays with respect to the suspension of the vinyl chloride resin circulating in the transparent pipe.
- the suspension of the vinyl chloride resin circulating in the transparent pipe is irradiated with ultraviolet rays for chlorination. It can be carried out.
- the second tank 6 includes an ultraviolet irradiation panel 20 including a plurality of ultraviolet LED elements 21 and a transparent pipe 22 through which the vinyl chloride resin suspension 12 is circulated.
- an ultraviolet irradiation panel 20 including a plurality of ultraviolet LED elements 21 and a transparent pipe 22 through which the vinyl chloride resin suspension 12 is circulated.
- FIG. 4 Although only one ultraviolet irradiation panel 20 is shown in FIG. 4, it is preferable to install another ultraviolet irradiation panel 20 so as to face the transparent pipe 22.
- FIG. 4 the illustration of the ultraviolet irradiation panel 20 on the front side is omitted for convenience of explanation (the same applies to FIGS. 5 and 6).
- the transparent pipe 22 has an S shape with two bent portions in order to achieve longer-time ultraviolet irradiation.
- the suspension 12 flows from the slurry inlet 23 of the transparent pipe 22 and is irradiated with ultraviolet rays from the ultraviolet irradiation panel 20 while flowing through the transparent pipe 22. Thereafter, it exits from the second tank 6 through the slurry outlet 24.
- the transparent pipe provided in the second tank 6 there may be mentioned one provided with a static mixer inside the pipe.
- a static mixer By providing a static mixer inside the transparent pipe, it is possible to chlorinate by irradiating ultraviolet rays while mixing a suspension of the vinyl chloride resin circulating inside the pipe, so that the reaction efficiency can be further increased.
- the specific configuration of the static mixer is not particularly limited, and those installed in various pipes can be used.
- the second tank 6 ′ includes an ultraviolet irradiation panel 20 including a plurality of ultraviolet LED elements 21 and a transparent pipe 25 through which a suspension of vinyl chloride resin is circulated.
- the transparent pipe 25 is provided with a static mixer inside. As shown in FIG. 5, according to the transparent pipe 25 provided with the static mixer, the suspension 12 flowing from the slurry inlet 23 can be irradiated with ultraviolet rays while being stirred, so that the chlorination reaction can be performed efficiently.
- interposed in FIG. 5 may be sufficient.
- a metal pipe that circulates a suspension of vinyl chloride resin and further has a transparent window, a light source that irradiates the transparent window with ultraviolet light May be provided.
- the number of metal pipes may be one or more, and the number is not particularly limited. Also, various metal pipes can be used for the material, the size and shape of the diameter, and the like.
- the size and shape of the transparent window are not particularly limited as long as they can be irradiated with ultraviolet rays.
- the material of the transparent window is not limited, but any material can be used as long as it transmits ultraviolet light and can withstand the manufacturing conditions (chlorine resistance, acid resistance, etc.) of the chlorinated vinyl chloride resin. Although it can do and is not specifically limited, For example, what is formed with glass is preferable.
- the light source is not particularly limited as long as the light source is disposed so as to be able to irradiate ultraviolet rays through a transparent window with respect to the suspension of the vinyl chloride resin circulating in the metal pipe. .
- UV light is passed through the transparent window to the suspension of the vinyl chloride resin flowing through the metal pipe. Chlorination can be performed by irradiation.
- the second tank 6 has an ultraviolet irradiation panel 20 including a plurality of ultraviolet LED elements 21, and a suspension of vinyl chloride resin.
- the metal piping 26 which distribute
- the metal pipe 26 includes a transparent window 27 for ultraviolet irradiation. As shown in FIG. 6, according to the metal pipe 26 having the transparent window 27, the suspension 12 flowing from the slurry inlet 23 can be irradiated with ultraviolet rays through the transparent window 27. The reaction can be performed.
- FIG. 6 according to the metal pipe 26 having the transparent window 27, the suspension 12 flowing from the slurry inlet 23 can be irradiated with ultraviolet rays through the transparent window 27. The reaction can be performed.
- the transparent window 27 of the metal pipe 26 and the ultraviolet irradiation panel 20 are not opposed to each other, but this is for convenience of explanation, and in fact, the transparent window 27 of the metal pipe 26 and the ultraviolet irradiation panel. 20 is installed facing. Further, a plurality of ultraviolet irradiation panels 20 may be installed so that the transparent window 27 can be irradiated with ultraviolet rays effectively.
- a static mixer may be provided inside the metal pipe 26.
- the ultraviolet rays can be irradiated while stirring the suspension in the metal pipe 26, the chlorination reaction can be performed efficiently.
- a light source for irradiating ultraviolet rays is externally installed (outside the tank).
- the ultraviolet LED can be easily cooled. Become. Furthermore, it is easy to perform maintenance such as maintenance and inspection of the ultraviolet LED, and the equipment can be used for a long time.
- the light source is not particularly limited as long as it can irradiate ultraviolet rays, but the present inventors use at least one light source selected from the group consisting of ultraviolet LED, organic EL, inorganic EL, and ultraviolet laser, Preferably, by using ultraviolet LEDs to irradiate the vinyl chloride resin and chlorine with ultraviolet rays, and chlorinating the vinyl chloride resin, the initial coloration of the obtained chlorinated vinyl chloride resin during thermoforming can be suppressed and / or Alternatively, the inventors have found that an improvement in thermal stability is achieved, and have completed a preferred embodiment of the present invention.
- At least one light source selected from the group consisting of ultraviolet LED, organic EL, inorganic EL and ultraviolet laser is used.
- the total power consumption in the step of chlorinating the vinyl chloride resin is reduced, and the production cost is reduced, which is preferable.
- at least one light source selected from the group consisting of an ultraviolet LED, an organic EL, an inorganic EL, and an ultraviolet laser in particular, an ultraviolet LED suppresses a decrease in luminous intensity due to long-term use compared to a mercury lamp.
- At least one light source selected from the group consisting of an ultraviolet LED, an organic EL, an inorganic EL, and an ultraviolet laser is preferable because the reaction time is shorter than that of a mercury lamp when the total power consumption is the same.
- the total power consumption is calculated by the following formula 1 when the current value of the light source is I (A), the voltage value of the light source is V (V), and the chlorination reaction time is t (h). To do.
- the ultraviolet LED is not particularly limited as long as the LED can irradiate ultraviolet rays.
- a semiconductor light emitting element using a nitride semiconductor material such as AlN, AlGaN, or AlInGaN for a light emitting layer or a semiconductor light emitting element using a diamond thin film for a light emitting layer is used.
- an ultraviolet LED having a single peak wavelength is used.
- the peak wavelength of the ultraviolet rays irradiated by the ultraviolet LED can be adjusted by the ratio of each composition of the light emitting layer.
- the peak wavelength of the ultraviolet light becomes shorter as the Al content increases.
- a light source such as an organic EL, an inorganic EL, an ultraviolet laser, or the like that can irradiate the ultraviolet light can be used for the ultraviolet irradiation.
- ultraviolet LED it is preferable to use ultraviolet LED as a light source.
- Light sources such as organic EL, inorganic EL, and ultraviolet laser are also preferably irradiated with ultraviolet rays having the same peak wavelength and / or wavelength range as the ultraviolet rays emitted by the ultraviolet LED.
- the peak wavelength and wavelength range of the ultraviolet rays irradiated by the ultraviolet LED are as described later.
- the peak wavelength of the ultraviolet light emitted by the ultraviolet LED is preferably 290 nm to 400 nm from the viewpoint of suppressing initial coloring during heat molding and improving the thermal stability.
- the wavelength range of the ultraviolet rays irradiated by the ultraviolet LED is preferably 260 nm to 430 nm.
- an ultraviolet LED that emits ultraviolet rays having a wavelength range of 300 nm to 430 nm and a peak wavelength of 350 nm to 400 nm.
- the chlorination reaction efficiency is determined by the total amount of light and / or the reaction time required. Can be evaluated. The smaller the total amount of light required, the higher the chlorination reaction efficiency. Moreover, the shorter the reaction time, the higher the chlorination reaction efficiency. In the present invention, the “total light amount” is measured and calculated as follows. A vinyl chloride resin that is present in the reactor when a chlorination reaction is carried out by attaching a sensor (TOPCON, product number “UD-36”) to the light intensity meter (TOPCON, product number “UVR-2”).
- the number of ultraviolet LEDs used for chlorination of vinyl chloride resin may be one or more.
- ultraviolet LEDs having the same peak wavelength of irradiated ultraviolet light may be used in combination, or ultraviolet LEDs having different peak wavelengths of irradiated ultraviolet light may be used in combination. May be.
- ultraviolet LED refers to both an ultraviolet LED element and an ultraviolet LED light source device having a plurality of ultraviolet LED elements.
- the suspension of the vinyl chloride resin can be obtained by suspending the vinyl chloride resin in an aqueous medium.
- aqueous medium water can be used as an aqueous medium, and a vinyl chloride resin and water can be mixed to obtain an aqueous suspension of the vinyl chloride resin.
- the vinyl chloride resin used as a raw material for the chlorinated vinyl chloride resin is a vinyl chloride monomer homopolymer or a copolymer of a vinyl chloride monomer and another copolymerizable monomer. Can be used.
- Other copolymerizable monomers are not particularly limited, and examples thereof include ethylene, propylene, vinyl acetate, allyl chloride, allyl glycidyl ether, acrylic acid ester, vinyl ether and the like.
- a dispersant and an oil-soluble polymerization initiator are used.
- a polymerization regulator, a chain transfer agent, a pH regulator, an antistatic agent, a crosslinking agent, a stabilizer, a filler, an antioxidant, a scale inhibitor, and the like may be further used.
- the dispersing agent for example, partially saponified polyvinyl acetate, methylcellulose, hydroxypropylmethylcellulose and the like are used.
- the oil-soluble polymerization initiator include lauroyl peroxide, di-2-ethylhexyl peroxyneodecanoate, t-butylperoxyneodecanoate, ⁇ , ⁇ ′-azobis-2,4-dimethylvaleronitrile. Etc. are used.
- the vinyl chloride resin is not particularly limited, but the average particle size is preferably 0.1 to 350 ⁇ m, more preferably 80 to 200 ⁇ m. In the present invention, the average particle size of the vinyl chloride resin is measured according to JIS K0069.
- the ultraviolet light is irradiated by the light source provided in the second tank, and the start of the ultraviolet irradiation starts the chlorination reaction of the vinyl chloride resin.
- the vinyl chloride resin in the aqueous suspension is chlorinated until the desired chlorine content is reached.
- the chlorination reaction is stopped by terminating the irradiation with ultraviolet rays.
- unreacted chlorine in the chlorinated vinyl chloride resin is purged with nitrogen, etc., and chlorinated chloride is used with warm water at a temperature lower than Tg (glass transition temperature) of the chlorinated vinyl chloride resin. Residual hydrochloric acid in the vinyl resin is removed. Thereafter, a chlorinated vinyl chloride resin is obtained through dehydration and drying processes.
- the concentration of the vinyl chloride resin in the aqueous suspension is preferably 10% by weight to 40% by weight. More preferably, it is from 35% by weight to 35% by weight.
- chlorine When supplying chlorine to the first tank, chlorine may be gaseous or liquid, but is preferably gaseous from the viewpoint of ease of handling.
- the chlorine supply method is not particularly limited as long as it can supply chlorine into the aqueous suspension.
- the chlorine supply method includes a method of charging chlorine in an initial batch before the start of the chlorination reaction, a method of intermittently supplying chlorine during the chlorination reaction, a method of supplying chlorine continuously during the chlorination reaction, etc. is there.
- the chlorination reaction is started by starting ultraviolet irradiation, and is ended by ending ultraviolet irradiation.
- the maximum reaction temperature during the chlorination reaction is not particularly limited, but is preferably 90 ° C. or lower, more preferably 88 ° C. or lower, and further preferably 86 ° C. or lower.
- the minimum reaction temperature during the chlorination reaction is preferably more than 0 ° C. from the viewpoint of facilitating the flow of the aqueous suspension with the stirring blade.
- the minimum reaction temperature is preferably 30 ° C. or higher, more preferably 50 ° C. or higher, from the viewpoint of shortening the reaction time.
- At least one light source selected from the group consisting of an ultraviolet LED, an organic EL, an inorganic EL, and an ultraviolet laser is applied to the suspension of the vinyl chloride resin into which chlorine is introduced in the second tank.
- the chlorinated vinyl chloride resin obtained by irradiating with ultraviolet rays and chlorinating the vinyl chloride resin achieves at least one of suppression of initial coloring during heat molding and improvement of thermal stability.
- the chlorinated vinyl chloride resin has suppressed initial coloring during heat molding and improved thermal stability.
- initial coloring during thermoforming of a chlorinated vinyl chloride resin is evaluated by measuring a yellow index according to JIS K7373 using a sample prepared by thermoforming a chlorinated vinyl chloride resin. To do. It means that the lower the yellow index value, the more the initial coloration at the time of heat forming is suppressed, that is, the better the initial colorability at the time of heat forming.
- the thermal stability of the chlorinated vinyl chloride resin is determined by using a sample (sheet) prepared using the chlorinated vinyl chloride resin and heating it in an oven at 200 ° C., that is, the sheet becomes black. Evaluation is made by measuring the time until the L value (lightness) is 20 or less. The longer the time until blackening, the higher the thermal stability.
- the heat resistance of the chlorinated vinyl chloride resin is evaluated by measuring the Vicat softening point by the B50 method according to JIS K7206. Higher Vicat softening point means higher heat resistance.
- the present invention includes the following inventions.
- a step of introducing chlorine into the suspension of the vinyl chloride resin, and the suspension into which the chlorine has been introduced is transferred from the first tank to the second tank. And a step of irradiating the suspension with ultraviolet rays in the tank of No. 2, and a method for producing a chlorinated vinyl chloride resin.
- the step of irradiating the suspension with ultraviolet rays is performed using at least one light source selected from the group consisting of ultraviolet LEDs, organic EL, inorganic EL, and ultraviolet lasers.
- the second tank is an apparatus for producing a chlorinated vinyl chloride resin comprising a light source for irradiating the suspension with ultraviolet rays.
- the circulating means introduces the suspension to the gas phase portion of the first tank or the vicinity of the gas-liquid interface of the chlorinated vinyl chloride resin according to (11) or (12) Manufacturing equipment.
- the chlorinated vinyl chloride system according to any one of (8) to (13), wherein the light source is at least one light source selected from the group consisting of an ultraviolet LED, an organic EL, an inorganic EL, and an ultraviolet laser. Resin manufacturing equipment.
- UV-LED light source unit manufactured by Sentec Co., Ltd., model number “OX223”
- the ultraviolet LED light source device 100 has three ultraviolet LED elements 110 (manufactured by Nichia Corporation, product number “NC4U133”, forward current 500 mA, forward voltage 14.9 V) having a peak wavelength of 365 nm.
- the emission spectrum of the ultraviolet LED element used in Reference Example 1 is as shown in FIG.
- the ultraviolet light emitted from the ultraviolet LED element 110 has a wavelength range of 350 nm to 392 nm, one peak, and a peak wavelength of 365 nm.
- the wavelength range means a range of wavelengths having a relative emission intensity of 2% or more with respect to the relative emission intensity of the peak wavelength in the emission spectrum.
- the ultraviolet LED light source device 100 is placed on an aluminum support 200 having a length of 20 mm, a width of 20 mm, and a height of 300 mm, and then a transparent glass cylindrical container 300 having an inner diameter of 75 mm, a height of 400 mm, and a thickness of 2.5 mm. (PYREX (registered trademark)).
- an ultraviolet LED light source device 100 placed in a cylindrical container 300 and a reactor 600 (capacity 3 L, capacity 3.6 mm) made of a transparent glass container having a thickness of 3.6 mm. PYREX (registered trademark)).
- the ultraviolet LED light source device 100 disposed in the water bath 500 is opposed to the reactor 600, and three ultraviolet LED elements 110 are arranged in a row in the height direction at equal intervals of 15 mm. Is arranged in. At this time, the distance A between the reactor 600 and the ultraviolet LED element 110 was 80 mm.
- the water bath 500 is provided with a heat source (not shown) for maintaining the hot water 400 at a predetermined temperature.
- the inside of the reactor 600 was vacuum degassed and purged with nitrogen. Thereafter, chlorine gas was blown into the aqueous suspension 700 of the vinyl chloride resin. At the same time, while stirring the aqueous suspension 700 of the vinyl chloride resin with the turbine blade 610, the ultraviolet LED element 110 was irradiated with ultraviolet rays to the aqueous suspension 700 of the vinyl chloride resin to start the chlorination reaction. . When chlorine gas was blown in, care was taken not to depressurize the reactor 600. During the chlorination reaction, the temperature of the hot water 400 in the water bath 500 was maintained at 60 ° C.
- the chlorine content of the chlorinated vinyl chloride resin was calculated from the neutralization titration value of hydrochloric acid by-produced in the chlorination reaction (the same applies to the following values).
- the reaction time of the chlorination reaction which is the time required for the chlorine content of the chlorinated vinyl chloride resin to reach 66.3%, that is, the time from the start of ultraviolet irradiation to the end of irradiation was 96 minutes.
- Comparative Example 1 Reference example except that one UV LED light source device 100 supported by the support 200 was used instead of one 100 W high-pressure mercury lamp (manufactured by Toshiba Lighting & Technology Corp., current value 1.3 A, voltage value 100 V). In the same manner as in Example 1, a chlorinated vinyl chloride resin was obtained.
- the reaction time of the chlorination reaction which is the time required for the chlorine content of the chlorinated vinyl chloride resin to reach 66.3%, that is, the time from the start of ultraviolet irradiation to the end of irradiation is 120 For minutes.
- the initial coloration, thermal stability measurement and evaluation at the time of thermoforming the chlorinated vinyl chloride resins obtained in Reference Example 1 and Comparative Example 1 were performed as follows. Moreover, the heat resistance was measured and evaluated by measuring and evaluating the Vicat softening point as follows.
- the pressure is adjusted in the range of 3 MPa to 5 MPa at 200 ° C. for 10 minutes.
- a plate having a thickness of 5 mm was produced by pressing.
- the yellow index (hereinafter also referred to as “YI”) of the obtained plate was measured in accordance with JIS-K7373 using a color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., product number “ZE-2000”).
- ⁇ Thermal stability 10 parts by weight of methyl methacrylate / butadiene / styrene (MBS) resin (manufactured by Kaneka Corporation, product number “Kane Ace (registered trademark) B31”), 100 parts by weight of chlorinated vinyl chloride resin, liquid tin stabilizer 1 part by weight (manufactured by Nitto Kasei Co., Ltd., product number “TVS # 8831”), 1 part by weight of powdered tin stabilizer (manufactured by Nitto Kasei Co., Ltd., product number “TVS # 8813”), stearic acid as a lubricant 1 part by weight (product number “Lunac (registered trademark) S-90V” manufactured by Kao Corporation) and 0.3 part by weight of polyethylene wax (part number “Hiwax220MP” manufactured by Mitsui Chemicals, Inc.) are mixed, and 8 inches.
- a roll was kneaded at
- the obtained sheet was cut into a length of 3 cm and a width of 5 cm, heated in an oven at 200 ° C., and the time until the sheet turned black was measured.
- Blackening means that the L value of the sheet is 20 or less.
- the L value was measured using a color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., product number “ZE-2000”).
- the pressure is adjusted in the range of 3 MPa to 5 MPa at 200 ° C. for 10 minutes.
- a plate having a thickness of 5 mm was produced by pressing.
- the Vicat softening point (Vicat softening point) of the chlorinated vinyl chloride resin was measured according to JIS-K7206. However, the load was 5 kg, and the temperature elevation rate was 50 ° C./h (B50 method).
- the chlorinated vinyl chloride resin obtained in Reference Example 1 has a lower YI than the chlorinated vinyl chloride resin obtained in Comparative Example 1, so that it can be measured at the time of heat molding. The initial colorability was good, and the time required for blackening was long, so the thermal stability was also good.
- the chlorinated vinyl chloride resin obtained in Reference Example 1 had a higher Vicat softening point than the chlorinated vinyl chloride resin obtained in Comparative Example 1, and therefore had good heat resistance.
- the reference example 1 in which the ultraviolet ray was irradiated using the ultraviolet LED was used in comparison with the comparative example 1 in which the ultraviolet ray was irradiated using the mercury lamp.
- the total power consumption required for the chlorination reaction is remarkably small, which has an energy saving effect and the cost is reduced.
- a UV-LED light source unit manufactured by Sentec Co., Ltd., model number “OX224” was prepared as the ultraviolet LED light source device 100a.
- the ultraviolet LED light source device 100a has 12 ultraviolet LED elements 110a (manufactured by Nichia Corporation, product number “NC4U133”, forward current 500 mA, forward voltage 14.9 V) that irradiates ultraviolet rays having a peak wavelength of 365 nm. ing.
- the emission spectrum of the ultraviolet LED element used in Reference Example 2 is as shown in FIG.
- a transparent glass cylindrical container 300a (PYREX (registered trademark) having an inner diameter of 74 mm, a height of 600 mm, and a thickness of 7 mm is provided. )) Inserted in.
- one UV LED light source device 100a placed in a cylindrical container 300a was placed in a jacketed reactor 600a (capacity 100L).
- the ultraviolet LED light source device 100a has a distance between the center of the cylindrical reactor 600a and the center of the cylindrical container 300a in the top view, that is, the length of B represented by a one-dot chain line in FIG. It arrange
- the 12 ultraviolet LED elements 110a are arranged in a line in the height direction at equal intervals of 15 mm.
- the ultraviolet LED element 110a disposed at the lowest position was at a position where the distance from the bottom surface of the reactor 600a was 132 mm.
- the ultraviolet LED element 110a was arrange
- the reactor 600a is charged with 45 kg of pure water, a K value of 57.1, an average particle size of 125 ⁇ m, and an apparent density of 0.496 g / ml, a vinyl chloride resin (manufactured by Kaneka Corporation). 5 kg was charged and the reactor 600a was sealed with a lid 620a. Then, an aqueous suspension 700a of vinyl chloride resin, which is a mixed liquid of pure water and vinyl chloride resin, was stirred at a rotational speed of 590 rpm using a turbine blade 610a (diameter 180 mm) of the reactor 600a.
- the inside of the reactor 600a was vacuum degassed and purged with nitrogen, and then vacuum degassed again. Next, chlorine gas was blown into the aqueous suspension 700a of the vinyl chloride resin.
- the UV suspension from the ultraviolet LED element 110a was applied to the aqueous suspension 700a of the vinyl chloride resin to start the chlorination reaction.
- the temperature in the reactor 600a is raised to 50 ° C. in 25 minutes after the start of nitrogen substitution, cooled to 40 ° C. in 15 minutes from the start of the chlorination reaction (start of ultraviolet irradiation), and during the subsequent chlorination reaction ( During UV irradiation, the temperature was maintained at 40 ° C.
- the reaction time of the chlorination reaction which is the time required for the chlorine content of the chlorinated vinyl chloride resin to reach 64.4%, that is, the time from the start of ultraviolet irradiation to the end of irradiation, 234 minutes.
- MVS methyl methacrylate / butadiene / styrene
- the pressure was adjusted to a range of 3 MPa to 5 MPa at 190 ° C.
- the plate was pressed for 5 minutes to produce a 5 mm thick plate.
- the obtained plate was measured for YI according to JIS-K7373 using a color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., product number “ZE-2000”).
- MVS methyl methacrylate / butadiene / styrene
- ⁇ Vicat softening point> 5 parts by weight of methyl methacrylate / butadiene / styrene (MBS) resin manufactured by Kaneka Corporation, product number “Kane Ace (registered trademark) B11A”), 100 parts by weight of chlorinated vinyl chloride resin, liquid tin stabilizer 3 parts by weight (manufactured by Nitto Kasei Co., Ltd., product number “N2000C”), 1 part by weight of PMMA resin (manufactured by Kaneka Corp., product number “Kane Ace (registered trademark) PA-20”), composite lubricant (Kawaken Fine Chemical Co., Ltd.) 1 part by weight of a product number “VLTN-4”) was blended and kneaded for 3 minutes at 180 ° C.
- MVS methyl methacrylate / butadiene / styrene
- the pressure was adjusted to a range of 3 MPa to 5 MPa at 200 ° C.
- the plate was pressed for 5 minutes to produce a 5 mm thick plate.
- the Vicat softening point of the chlorinated vinyl chloride resin was measured in accordance with JIS-K7206. However, the load was 5 kg, and the temperature elevation rate was 50 ° C./h (B50 method).
- YI of the chlorinated vinyl chloride resin obtained in Reference Example 2 is 77.6, the time required for blackening is 80 minutes, and the Vicat softening point is 98.6 ° C. Met.
- the YI of the chlorinated vinyl chloride resin obtained in Comparative Example 2 was 87.1, the time required for blackening was 70 minutes, and the Vicat softening point was 97.2 ° C.
- the chlorinated vinyl chloride resin obtained in Reference Example 2 has a lower YI than the chlorinated vinyl chloride resin obtained in Comparative Example 2, so that the initial value during thermoforming The colorability was good, and the heat stability was also good because the time required for blackening was long. Further, the chlorinated vinyl chloride resin obtained in Reference Example 2 had a higher Vicat softening point than the chlorinated vinyl chloride resin obtained in Comparative Example 2, and therefore had good heat resistance.
- the reference example 2 in which ultraviolet rays were irradiated using an ultraviolet LED was compared with the comparative example 2 in which ultraviolet rays were irradiated using a mercury lamp. The total power consumption required for this is significantly less, which has the effect of energy saving and reduced costs.
- a UV-LED light source unit (manufactured by Sentec Co., Ltd., model number “OX558”) was prepared as the ultraviolet LED light source device 100b.
- the ultraviolet LED light source device 100b has three ultraviolet LED elements 110b (manufactured by Nichia Corporation, product number “NC4U133A”, forward current 500 mA, forward voltage 14.9 V) having a peak wavelength of 365 nm.
- the emission spectrum of the ultraviolet LED element used in Reference Example 3 is as shown in FIG. As shown in FIG. 9, the ultraviolet light irradiated by the ultraviolet LED element 110b has a wavelength range of 350 nm to 392 nm, one peak, and a peak wavelength of 365 nm.
- the ultraviolet LED light source device 100b was inserted into a transparent glass cylindrical container 300b (PYREX (registered trademark)) having an inner diameter of 25 mm, a height of 360 mm, and a thickness of 2.5 mm.
- a transparent glass cylindrical container 300b PYREX (registered trademark) having an inner diameter of 25 mm, a height of 360 mm, and a thickness of 2.5 mm.
- a reactor 600b (capacity 10L, PYREX (registered trademark)), which is a transparent glass container, is placed in a water bath 500a containing warm water 400a of 25 ° C., and a cylindrical container 300b.
- One UV LED light source device 100b placed in the reactor was placed in the reactor 600b.
- the three ultraviolet LED elements 110b were arranged in a line in the height direction at equal intervals of 15 mm.
- the ultraviolet LED element 110b disposed at the lowest position was at a position 90 mm from the bottom surface of the reactor 600b.
- the ultraviolet LED element 110b was arrange
- the water bath 500a is provided with a heat source (not shown) for maintaining the hot water 400a at a predetermined temperature.
- the chlorine content of the chlorinated vinyl chloride resin reached 67.1%
- the ultraviolet irradiation by the ultraviolet LED element 110b was terminated, and the chlorination reaction was terminated.
- the reaction time of the chlorination reaction that is, the time required for the chlorine content of the chlorinated vinyl chloride resin to reach 67.1%, that is, the time from the start of irradiation to the end of irradiation was 120 minutes. .
- the remaining hydrochloric acid was removed by washing with water, and then the chlorinated vinyl chloride resin was dried. Thereby, a chlorinated vinyl chloride resin was obtained.
- Reference Example 4 Chlorinated vinyl chloride in the same manner as in Reference Example 3 except that one UV-LED light source unit (manufactured by Sentec Co., Ltd., model number “OX559”) was used instead of the ultraviolet LED light source device 100b. A system resin was obtained.
- the ultraviolet LED light source device has three ultraviolet LED elements (manufactured by Nichia Corporation, product number “NC4U134A”, forward current 500 mA, forward voltage 14.8 V) having a peak wavelength of 385 nm.
- the emission spectrum of the ultraviolet LED used in Reference Example 4 is as shown in FIG.
- the ultraviolet light emitted from the ultraviolet LED element has a wavelength range of 355 nm to 415 nm, one peak, and a peak wavelength of 385 nm.
- the wavelength range means a range of wavelengths having a relative emission intensity of 2% or more with respect to the relative emission intensity of the peak wavelength in the emission spectrum.
- reaction time of the chlorination reaction which is the time required for the chlorine content of the chlorinated vinyl chloride resin to reach 67.2%, that is, the time from the start of ultraviolet irradiation to the end of irradiation, It was 135 minutes.
- the reaction time of the chlorination reaction which is the time required for the chlorine content of the chlorinated vinyl chloride resin to reach 67.1%, that is, the time from the start of ultraviolet irradiation to the end of irradiation, 93 minutes.
- the YI of the chlorinated vinyl chloride resin obtained in Reference Example 3 was 91.1, the time required for blackening was 60 minutes, and the Vicat softening point was 117.8 ° C.
- the YI of the chlorinated vinyl chloride resin obtained in Reference Example 4 was 93.3, the time required for blackening was 50 minutes, and the Vicat softening point was 115.2 ° C.
- the YI of the chlorinated vinyl chloride resin obtained in Comparative Example 3 was 132.3, the time required for blackening was 20 minutes, and the Vicat softening point was 114.3 ° C.
- the total light amount in Reference Example 3, Reference Example 4 and Comparative Example 3 was measured and calculated as follows.
- the light quantity per unit area of the ultraviolet rays emitted from the light source was measured at the position where the distance between the light source and the light source was closest.
- the irradiation area where the ultraviolet rays irradiated from the light source hit the chlorinated vinyl resin was measured at the position where the distance between the vinyl chloride resin present in the reactor and the light source was the shortest when the chlorination reaction was performed.
- a value obtained by multiplying the value of the irradiation area obtained by the above measurement with the value of the light amount per unit area was defined as the total light amount.
- the amount of light per unit area and the irradiation area were measured in an air atmosphere and with the reactor inside empty. The results are shown in Table 3 below.
- the chlorinated vinyl chloride resin obtained in Reference Example 3 and Reference Example 4 has a lower YI value than the chlorinated vinyl chloride resin obtained in Comparative Example 3.
- the initial colorability at the time of heat molding was good, and since the time required for blackening was long, the thermal stability was also good.
- the chlorinated vinyl chloride resins obtained in Reference Example 3 and Reference Example 4 had a higher Vicat softening point than the chlorinated vinyl chloride resins obtained in Comparative Example 3, and thus had good heat resistance. .
- Reference Example 3 using an ultraviolet LED that irradiates ultraviolet light with a peak wavelength of 365 nm is used in Reference Example 4 that uses an ultraviolet LED that irradiates ultraviolet light with a peak wavelength of 385 nm.
- a chlorinated vinyl chloride resin with improved initial colorability and thermal stability during heat molding was obtained.
- UV light having a peak wavelength of 365 nm is applied to Reference Example 4 using an UV LED that emits UV light having a peak wavelength of 385 nm. It was found that Reference Example 3 using an ultraviolet LED requires less total light, has a shorter reaction time, and has a higher reaction efficiency.
- the ultraviolet LED light source device 100b was inserted into a transparent glass cylindrical container 300 (PYREX (registered trademark)) having an inner diameter of 75 mm, a height of 400 mm, and a thickness of 2.5 mm.
- the LED light source device 100b is surrounded by aluminum foil for the purpose of collecting light, and the front surface of the ultraviolet LED element 110b is cut out to 50 mm in length and 50 mm in width so that light does not leak from other than that portion.
- an ultraviolet LED light source device 100b placed in a cylindrical container 300, and a reactor 600b (capacity 10L, which is a transparent glass container). , PYREX (registered trademark)).
- the ultraviolet LED light source device 100b disposed in the water bath 500a is opposed to the reactor 600b, and three ultraviolet LED elements 110b are arranged in a row in the height direction at equal intervals of 15 mm. Arranged. At this time, the distance A between the reactor 600b and the ultraviolet LED element 110b was 60 mm.
- the water bath 500a is provided with a heat source (not shown) for maintaining the hot water 400a at a predetermined temperature.
- the reaction time of the chlorination reaction which is the time required for the chlorine content of the chlorinated vinyl chloride resin to reach 67.2%, that is, the time from the start of irradiation to the end of irradiation was 309 minutes. .
- the remaining hydrochloric acid was removed by washing with water, and then the chlorinated vinyl chloride resin was dried. Thereby, a chlorinated vinyl chloride resin was obtained.
- reaction time of the chlorination reaction which is the time required for the chlorine content of the chlorinated vinyl chloride resin to reach 67.2%, that is, the time from the start of ultraviolet irradiation to the end of irradiation, It was 300 minutes.
- Reference Example 5 using an ultraviolet LED that emits ultraviolet light having a peak wavelength of 365 nm is used in Reference Example 5 that uses an ultraviolet LED that emits ultraviolet light having a peak wavelength of 385 nm.
- a chlorinated vinyl chloride resin having better initial colorability during thermoforming was obtained.
- ultraviolet light having a peak wavelength of 365 nm is applied to Reference Example 6 using an ultraviolet LED that emits ultraviolet light having a peak wavelength of 385 nm. It was found that the reaction time of Reference Example 5 using an ultraviolet LED was almost the same, but the required total light amount was almost half and the reaction efficiency was high.
- Example 1 ⁇ Production of chlorinated vinyl chloride resin> (Example 1) As shown in FIG. 17, a PVC pipe 800a for circulating an aqueous suspension was connected to an aqueous suspension outlet provided at the bottom of a jacketed reactor 600c, and a transparent glass tube 810 was disposed at the tip of 800a. Further, a pressure reducing valve 4 is provided in front of the transparent glass tube 810, and the slurry is decompressed before entering the transparent glass tube 810.
- a PVC pipe 800b for circulating an aqueous suspension, a pump 900 for circulating an aqueous suspension, and a PVC pipe 800c for circulating an aqueous suspension are further connected in this order.
- the outlet part of the pipe 800c was connected to the gas phase part of the jacketed reactor 600c.
- the jacketed reactor 600c is provided with a lid 620c.
- FIG. 18 shows an enlarged view of the transparent glass tube 810 and the light source for irradiating ultraviolet rays in the apparatus of FIG.
- a UV-LED light source unit manufactured by Sentec Co., Ltd.
- 100c is disposed as a light source for irradiating ultraviolet rays at a position 15 mm from the surface of the transparent glass tube 810 (hereinafter referred to as “ultraviolet LED light source device”). 100c ").
- the ultraviolet LED light source device 100c includes twelve ultraviolet LED elements 110c (manufactured by Nichia Corporation, product number “NC4U133A”, forward current 500 mA, forward voltage 14.9 V) with a peak wavelength of 365 nm at 15 mm intervals in the vertical direction. As shown in FIG. 18, the ultraviolet light is disposed so as to be applied to the aqueous suspension flowing in the transparent glass pipe 810. In FIG. 18, only three ultraviolet LED elements 110c of the ultraviolet LED light source device 100c are shown because of space.
- the emission spectrum of the ultraviolet LED element 110c used in Example 1 is as shown in FIG.
- the ultraviolet light emitted from the ultraviolet LED element 110c has a wavelength range of 350 nm to 392 nm, one peak, and a peak wavelength of 365 nm.
- the wavelength range means a range of wavelengths having a relative emission intensity of 2% or more with respect to the relative emission intensity of the peak wavelength in the emission spectrum.
- a vinyl chloride resin (Kaneka Co., Ltd.) having 35 kg of pure water, a K value of 66.4, an average particle size of 200 ⁇ m, and an apparent density of 0.557 g / ml. 15 kg), a lid 620c was installed, and the jacketed reactor 600c was sealed.
- An aqueous suspension 700c of vinyl chloride resin which is a mixed liquid of pure water and vinyl chloride resin, was stirred at a rotational speed of 590 rpm using a turbine blade 610c (diameter 180 mm) of the reactor 600c.
- the aqueous suspension 700c was circulated in the apparatus using the aqueous suspension circulation pump 900.
- the inside of the reactor 600c with jacket was vacuum degassed and purged with nitrogen, and then vacuum degassed again.
- chlorine gas was blown into an aqueous suspension 700c of the vinyl chloride resin through a chlorine introduction portion (not shown).
- ultraviolet light was irradiated from the ultraviolet LED element 110c while stirring the aqueous suspension 700c of the vinyl chloride resin with the turbine blade 610c.
- the ultraviolet ray is irradiated to the aqueous suspension 700c of the vinyl chloride resin through the transparent glass pipe 810, and the chlorination reaction is started.
- the inside of the jacketed reactor 600c was pressurized to 0.02 MPa by introduction of chlorine gas from the start of chlorination reaction (start of UV irradiation), and thereafter maintained at 0.06 MPa during the chlorination reaction (during UV irradiation).
- the temperature in the reactor 600c is raised to 50 ° C. in 25 minutes after the start of nitrogen substitution, and is heated up to 85 ° C. in 100 minutes from the start of chlorination reaction (start of ultraviolet irradiation). (During UV irradiation) was maintained at 85 ° C.
- the time required for the chlorine content of the chlorinated vinyl chloride resin to reach 67.1% was defined as the reaction time of the chlorination reaction. This time, that is, the time from the start of irradiation with ultraviolet rays to the end of irradiation, was 137 minutes. Then, after unreacted chlorine in the chlorinated vinyl chloride resin was purged with nitrogen gas, the remaining hydrochloric acid was removed by washing with water to dry the chlorinated vinyl chloride resin. Thereby, a chlorinated vinyl chloride resin was obtained.
- Example 2 A chlorinated vinyl chloride resin was obtained in the same manner as in Example 1 except that the pressure inside the jacketed reactor 600c during the chlorination reaction was 0.1 MPa.
- the time required for the chlorine content of the chlorinated vinyl chloride resin to reach 67.1% (the reaction time of the chlorination reaction, that is, the time from the start of irradiation to the end of irradiation) is the same hereinafter. ) For 128 minutes.
- Example 3 A chlorinated vinyl chloride resin was obtained in the same manner as in Example 1 except that the pressure inside the jacketed reactor 600c during the chlorination reaction was changed to 0.12 MPa. In this example, the time required for the chlorine content of the chlorinated vinyl chloride resin to reach 67.1% was 123 minutes.
- Example 4 A chlorinated vinyl chloride resin was obtained in the same manner as in Example 1 except that the pressure inside the jacketed reactor 600c during the chlorination reaction was 0.14 MPa. In this example, the time required for the chlorine content of the chlorinated vinyl chloride resin to reach 67.1% was 125 minutes.
- Example 5 A chlorinated vinyl chloride resin was obtained in the same manner as in Example 1 except that the pressure inside the jacketed reactor 600c during the chlorination reaction was changed to 0.02 MPa. In this example, the time required for the chlorine content of the chlorinated vinyl chloride resin to reach 67.1% was 144 minutes.
- Comparative Example 4 As a comparative example, one glass cylindrical container was placed in a reactor with a jacket, and an attempt was made to produce a chlorinated vinyl chloride resin. An ultraviolet light source similar to the ultraviolet LED light source device 100c was provided in the glass cylindrical container. In the same manner as in Example 1, water and vinyl chloride resin were charged into this reactor, and the reactor was sealed with a lid. Then, an aqueous suspension of vinyl chloride resin, which is a mixed liquid of pure water and vinyl chloride resin, was stirred at a rotational speed of 590 rpm using a turbine blade (diameter: 180 mm) of the reactor.
- Comparative Example 4 when the ultraviolet LED light source device was put into a glass cylindrical container and inserted into the reactor, the cylindrical container of the light source could not withstand the pressure inside the reactor and was damaged. have done. As shown in Comparative Example 5, when the pressure inside the reactor (0.01 MPa) that can withstand the cylindrical container of the light source was used, the reaction time for chlorination was long.
- Example 6 The raw material vinyl chloride resin used was changed to a vinyl chloride resin (manufactured by Kaneka Corporation) having a K value of 58.4, an average particle diameter of 150 ⁇ m, and an apparent density of 0.574 g / ml, A chlorinated vinyl chloride resin was obtained in the same manner as in Example 1 except that the pressure inside the jacketed reactor 600c during the chlorination reaction was 0.04 MPa. In this example, the time required for the chlorine content of the chlorinated vinyl chloride resin to reach 67.1% was 140 minutes.
- Example 7 A chlorinated vinyl chloride resin was obtained in the same manner as in Example 6 except that the pressure inside the jacketed reactor 600c during the chlorination reaction was changed to 0.06 MPa. In this example, the time required for the chlorine content of the chlorinated vinyl chloride resin to reach 67.1% was 135 minutes.
- Example 8 A chlorinated vinyl chloride resin was obtained in the same manner as in Example 6 except that the pressure inside the jacketed reactor 600c during the chlorination reaction was 0.08 MPa. In this example, the time required for the chlorine content of the chlorinated vinyl chloride resin to reach 67.1% was 128 minutes.
- Example 9 A chlorinated vinyl chloride resin was obtained in the same manner as in Example 6 except that the pressure inside the jacketed reactor 600c during the chlorination reaction was set to 0.02 MPa. In this example, the time required for the chlorine content of the chlorinated vinyl chloride resin to reach 67.1% was 153 minutes.
- reaction time of the reference example and the reaction time of the example of the present application are different in the vinyl chloride resin of the material used, and in addition, the reach of the chlorination content is different (in the reference example, the reach of the chlorine content is different) Therefore, it is not possible to make a general comparison. For this reason, the effect of the present invention can be understood by comparing Examples 1 to 5 and Comparative Examples 4 and 5 that have the same conditions such as the material and the degree of achievement of chlorination content.
- the chlorinated vinyl chloride resin obtained by the present invention has excellent characteristics such as high mechanical strength, weather resistance, chemical resistance and the like of vinyl chloride resin, and is further superior in heat resistance than vinyl chloride resin. It can be used in various industrial fields.
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Abstract
Description
紫外線LEDとしては、紫外線を照射することができるLEDであればよく、特に限定されない。例えば、紫外線LEDには、AlN、AlGaN、AlInGaNなどの窒化物半導体材料を発光層に用いた半導体発光素子、又は、ダイヤモンド薄膜を発光層に用いた半導体発光素子などが用いられる。好ましくは、ピーク波長が1つの紫外線LEDを用いる。また、紫外線LEDの照射する紫外線のピーク波長は、発光層の各組成の割合により調整することができる。例えば、紫外線LEDの発光層に窒化物半導体材料が用いられる場合、Alの含有量が増えるにしたがって、紫外線のピーク波長が短くなる。紫外線の照射には、紫外線LEDの他に、紫外線を照射できる有機EL、無機EL、紫外線レーザーなどの光源を用いることができる。中でも、光源としては、紫外線LEDを用いることが好ましい。有機EL、無機EL、紫外線レーザーなどの光源も、紫外線LEDが照射する紫外線と同様のピーク波長及び/又は波長範囲の紫外線を照射することが好ましい。紫外線LEDが照射する紫外線のピーク波長や波長範囲については、後述のとおりである。
ここで、水銀灯(水銀ランプ)を光源として用いる替わりに、紫外線LED、有機EL、無機EL及び紫外線レーザーからなる群より選択される少なくとも1種の光源、具体的には紫外線LEDを光源として用いた場合の効果、即ち、光源として紫外線LEDを用いた場合の効果を、参考例として示す。下記参考例及び比較例において、「部」及び「%」は、特に断りが無い限り、重量基準である。
<塩素化塩化ビニル系樹脂の作製>
図8に示すように、紫外線LED光源装置100として、UV-LED光源ユニット(株式会社センテック製、型番「OX223」)を準備した。紫外線LED光源装置100は、ピーク波長が365nmである紫外線LED素子110(日亜化学工業株式会社製、品番「NC4U133」、順電流500mA、順電圧14.9V)を3個有している。
支持体200で支持された1台の紫外線LED光源装置100に替えて、100Wの高圧水銀灯(東芝ライテック株式会社製、電流値1.3A、電圧値100V)を1灯用いた以外は、参考例1と同様にして、塩素化塩化ビニル系樹脂を得た。
塩素化塩化ビニル系樹脂100重量部に対して、メチルメタクリレート・ブタジエン・スチレン(MBS)樹脂(株式会社カネカ製、品番「カネエース(登録商標)B31」)を10重量部、液状の錫系安定剤(日東化成株式会社製、品番「TVS#8831」)を1重量部、粉末状の錫系安定剤(日東化成株式会社製、品番「TVS#8813」)を1重量部、滑剤であるステアリン酸(花王株式会社製、品番「ルナック(登録商標)S-90V」)を1重量部、及びポリエチレンワックス(三井化学株式会社製、品番「Hiwax220MP」)を0.3重量部配合した後、8インチロールにて、195℃で5分間混練し、厚さ0.6mmのシートを作製した。
塩素化塩化ビニル系樹脂100重量部に対して、メチルメタクリレート・ブタジエン・スチレン(MBS)樹脂(株式会社カネカ製、品番「カネエース(登録商標)B31」)を10重量部、液状の錫系安定剤(日東化成株式会社製、品番「TVS#8831」)を1重量部、粉末状の錫系安定剤(日東化成株式会社製、品番「TVS#8813」)を1重量部、滑剤であるステアリン酸(花王株式会社製、品番「ルナック(登録商標)S-90V」)を1重量部、及びポリエチレンワックス(三井化学株式会社製、品番「Hiwax220MP」)を0.3重量部配合した後、8インチロールにて、195℃で5分間混練し、厚さ0.6mmのシートを作製した。
塩素化塩化ビニル系樹脂100重量部に対して、メチルメタクリレート・ブタジエン・スチレン(MBS)樹脂(株式会社カネカ製、品番「カネエース(登録商標)B31」)を10重量部、液状の錫系安定剤(日東化成株式会社製、品番「TVS#8831」)を1重量部、粉末状の錫系安定剤(日東化成株式会社製、品番「TVS#8813」)を1重量部、滑剤であるステアリン酸(花王株式会社製、品番「ルナック(登録商標)S-90V」)を1重量部、及びポリエチレンワックス(三井化学株式会社製、品番「Hiwax220MP」)を0.3重量部配合した後、8インチロールにて、195℃で5分間混練し、厚さ0.6mmのシートを作製した。
<塩素化塩化ビニル系樹脂の作製>
図10に示すように、紫外線LED光源装置100aとして、UV-LED光源ユニット(株式会社センテック製、型番「OX224」)を準備した。紫外線LED光源装置100aは、ピーク波長が365nmである紫外線を照射する紫外線LED素子110a(日亜化学工業株式会社製、品番「NC4U133」、順電流500mA、順電圧14.9V)を12個有している。尚、参考例2で用いた紫外線LED素子の発光スペクトルは、図9に示す通りである。
支持体200aに支持された1台の紫外線LED光源装置100aに代えて、100Wの高圧水銀灯(サンエナジー株式会社製、品番「SEH1002J01」、順電流1.1±0.1A、順電圧110±10V)を1灯用いた以外は、参考例2と同様にして、塩素化塩化ビニル系樹脂を得た。
塩素化塩化ビニル系樹脂100重量部に対して、メチルメタクリレート・ブタジエン・スチレン(MBS)樹脂(株式会社カネカ製、品番「カネエース(登録商標)B11A」)を5重量部、液状の錫系安定剤(日東化成株式会社製、品番「N2000C」)を3重量部、PMMA樹脂(株式会社カネカ製、品番「カネエース(登録商標)PA-20」)を1重量部、複合滑剤(川研ファインケミカル株式会社製、品番「VLTN―4」)を1重量部配合して、8インチロールにて、180℃で3分間混練し、厚さ0.6mmのシートを作製した。
塩素化塩化ビニル系樹脂100重量部に対して、メチルメタクリレート・ブタジエン・スチレン(MBS)樹脂(株式会社カネカ製、品番「カネエース(登録商標)B11A」)を5重量部、液状の錫系安定剤(日東化成株式会社製、品番「N2000C」)を3重量部、PMMA樹脂(株式会社カネカ製、品番「カネエース(登録商標)PA-20」)を1重量部、複合滑剤(川研ファインケミカル株式会社製、品番「VLTN―4」)を1重量部配合して、8インチロールにて、180℃で3分間混練し、厚さ0.6mmのシートを作製した。得られたシートを縦3cm、横3.5cmに切り取り、200℃のオーブンにて加熱し、シートが黒化するまでの時間を測定した。黒化とは、シートのL値が20以下であることをいう。L値は色差計(日本電色工業株式会社製、品番「ZE-2000」)を使用して測定した。
塩素化塩化ビニル系樹脂100重量部に対して、メチルメタクリレート・ブタジエン・スチレン(MBS)樹脂(株式会社カネカ製、品番「カネエース(登録商標)B11A」)を5重量部、液状の錫系安定剤(日東化成株式会社製、品番「N2000C」)を3重量部、PMMA樹脂(株式会社カネカ製、品番「カネエース(登録商標)PA-20」)を1重量部、複合滑剤(川研ファインケミカル株式会社製、品番「VLTN―4」)を1重量部配合して、8インチロールにて、180℃で3分間混練し、厚さ0.6mmのシートを作製した。得られたシートを15枚重ね合わせたものを、鋼板にクロームメッキを施して鏡面仕上げされたフェロ板間に挟んだ後、200℃の条件で、圧力を3MPa~5MPaの範囲に調整して10分間プレスし、厚さ5mmの板を作製した。得られた板を用い、JIS-K7206に従って、塩素化塩化ビニル系樹脂のビカット軟化点の測定を行った。但し、荷重を5kgとし、昇温速度は50℃/h(B50法)とした。
<塩素化塩化ビニル系樹脂の作製>
図13に示すように、紫外線LED光源装置100bとして、UV-LED光源ユニット(株式会社センテック製、型番「OX558」)を準備した。紫外線LED光源装置100bは、ピーク波長が365nmである紫外線LED素子110b(日亜化学工業株式会社製、品番「NC4U133A」、順電流500mA、順電圧14.9V)を3個有している。
紫外線LED光源装置100bに代えて、紫外線LED光源装置としてUV-LED光源ユニット(株式会社センテック製、型番「OX559」)を1灯用いた以外は、参考例3と同様にして、塩素化塩化ビニル系樹脂を得た。紫外線LED光源装置は、ピーク波長が385nmである紫外線LED素子(日亜化学工業株式会社製、品番「NC4U134A」、順電流500mA、順電圧14.8V)を3個有している。
紫外線LED光源装置100bに代えて、100Wの高圧水銀灯(東芝ライテック株式会社製、順電流1.3A、順電圧100V)を1灯用いた以外は、参考例3と同様にして、塩素化塩化ビニル系樹脂を得た。
<塩素化塩化ビニル系樹脂の作製>
参考例3と同様に、紫外線LED光源装置100bを用いた。
紫外線LED光源装置として、参考例4と同様の紫外線LED光源装置を1灯用いた以外は、参考例5と同様にして、塩素化塩化ビニル系樹脂を得た。
<塩素化塩化ビニル系樹脂の作製>
(実施例1)
図17に示すように、ジャケット付き反応器600cの底部に設けた水性懸濁液出口に水性懸濁液循環用PVC製配管800aを接続し、800aの先には透明ガラス管810を配置した。また、透明ガラス管810の前には、減圧弁4が設けられており、透明ガラス管810に入る前に、スラリーが減圧される。さらにその先には水性懸濁液循環用PVC製配管800b、水性懸濁液循環用ポンプ900、さらに水性懸濁液循環用PVC製配管800cの順で接続し、水性懸濁液循環用PVC製配管800cの出口部分を、ジャケット付き反応器600c気相部へ接続した。なお、ジャケット付き反応器600cには、蓋620cが設けられている。
塩素化反応中のジャケット付き反応器600c内部の圧力を0.1MPaとした以外は、実施例1と同様にして、塩素化塩化ビニル系樹脂を得た。本実施例において、塩素化塩化ビニル系樹脂の塩素含有量が67.1%に達するまでに要した時間(塩素化反応の反応時間、すなわち紫外線の照射開始から照射終了までの時間、以下同じ。)は、128分間であった。
塩素化反応中のジャケット付き反応器600c内部の圧力を0.12MPaとした以外は、実施例1と同様にして、塩素化塩化ビニル系樹脂を得た。本実施例において、塩素化塩化ビニル系樹脂の塩素含有量が67.1%に達するまでに要した時間は、123分間であった。
塩素化反応中のジャケット付き反応器600c内部の圧力を0.14MPaとした以外は、実施例1と同様にして、塩素化塩化ビニル系樹脂を得た。本実施例において、塩素化塩化ビニル系樹脂の塩素含有量が67.1%に達するまでに要した時間は、125分間であった。
塩素化反応中のジャケット付き反応器600c内部の圧力を0.02MPaとした以外は、実施例1と同様にして、塩素化塩化ビニル系樹脂を得た。本実施例において、塩素化塩化ビニル系樹脂の塩素含有量が67.1%に達するまでに要した時間は、144分間であった。
比較例として、ガラス製の円筒状容器をジャケット付き反応器中に1台配置し、塩素化塩化ビニル系樹脂の製造を試みた。ガラス製の円筒状容器内には、紫外線LED光源装置100cと同様の紫外線光源を設けた。この反応器へ実施例1と同様に水、塩化ビニル系樹脂を仕込み、蓋をして反応器内を密閉した。そして、純水と塩化ビニル系樹脂との混合液である塩化ビニル系樹脂の水性懸濁液を、反応器のタービン翼(直径180mm)を用いて、回転数590rpmで攪拌した。
塩素化反応中のジャケット付き反応器600c内部の圧力を0.01MPaとした以外は、比較例4と同様にして、塩素化塩化ビニル系樹脂を得た。本比較例において、塩素化塩化ビニル系樹脂の塩素含有量が67.1%に達するまでに要した時間は、155分間であった。
用いた原料塩化ビニル系樹脂をK値が58.4であり、平均粒子径が150μmであり、見かけ密度が0.574g/mlである塩化ビニル系樹脂(株式会社カネカ製)に変更したこと、及び塩素化反応中のジャケット付き反応器600c内部の圧力を0.04MPaとしたこと以外は、実施例1と同様にして、塩素化塩化ビニル系樹脂を得た。本実施例において、塩素化塩化ビニル系樹脂の塩素含有量が67.1%に達するまでに要した時間は、140分間であった。
塩素化反応中のジャケット付き反応器600c内部の圧力を0.06MPaとした以外は、実施例6と同様にして、塩素化塩化ビニル系樹脂を得た。本実施例において、塩素化塩化ビニル系樹脂の塩素含有量が67.1%に達するまでに要した時間は、135分間であった。
塩素化反応中のジャケット付き反応器600c内部の圧力を0.08MPaとした以外は、実施例6と同様にして、塩素化塩化ビニル系樹脂を得た。本実施例において、塩素化塩化ビニル系樹脂の塩素含有量が67.1%に達するまでに要した時間は、128分間であった。
塩素化反応中のジャケット付き反応器600c内部の圧力を0.02MPaとした以外は、実施例6と同様にして、塩素化塩化ビニル系樹脂を得た。本実施例において、塩素化塩化ビニル系樹脂の塩素含有量が67.1%に達するまでに要した時間は、153分間であった。
2:第1の槽
6,6’,6”:第2の槽
7:スラリー循環ライン7
11:塩素化塩化ビニル系樹脂の製造装置
12:塩化ビニル系樹脂の懸濁液
20:紫外線照射パネル
21:紫外線LED素子
22:透明配管
25:スタティックミキサーを備える透明配管
26:金属配管
27:透明窓
Claims (14)
- 第1の槽において、塩化ビニル系樹脂の懸濁液に塩素を導入する工程と、
前記塩素が導入された懸濁液を第1の槽から第2の槽へ移送し、当該第2の槽において、前記懸濁液に対して紫外線を照射する工程と、を有することを特徴とする塩素化塩化ビニル系樹脂の製造方法。 - 前記第1の槽内は、加圧されていることを特徴とする請求項1に記載の塩素化塩化ビニル系樹脂の製造方法。
- 前記第1の槽内の圧力は、0.02~2MPaであることを特徴とする請求項2に記載の塩素化塩化ビニル系樹脂の製造方法。
- 前記第2の槽において紫外線照射された懸濁液を、前記第1の槽へ循環させることを特徴とする請求項1~3のいずれか1項に記載の塩素化塩化ビニル系樹脂の製造方法。
- さらに、前記第2の槽から取り出された懸濁液に塩素を導入する工程を含むことを特徴とする請求項4に記載の塩素化塩化ビニル系樹脂の製造方法。
- 前記第2の槽から第1の槽へ循環させるとき、前記懸濁液を、前記第1の槽の気相部又は気液界面近傍へ導入することを特徴とする請求項4又は5に記載の塩素化塩化ビニル系樹脂の製造方法。
- 前記懸濁液に対して紫外線を照射する工程は、紫外線LED、有機EL、無機EL及び紫外線レーザーからなる群より選択される少なくとも1種の光源を用いて行われることを特徴とする請求項1~6のいずれか1項に記載の塩素化塩化ビニル系樹脂の製造方法。
- 塩化ビニル系樹脂の懸濁液に塩素を導入するための第1の槽と、
前記第1の槽から懸濁液を導入し、塩素化するための第2の槽と、を備え、
前記第2の槽は、前記懸濁液に対して紫外線を照射するための光源を備えることを特徴とする塩素化塩化ビニル系樹脂の製造装置。 - 前記第1の槽を加圧するための加圧手段を備えることを特徴とする請求項8に記載の塩素化塩化ビニル系樹脂の製造装置。
- 前記第1の槽内の圧力は、0.02~2MPaに設定されていることを特徴とする請求項9に記載の塩素化塩化ビニル系樹脂の製造装置。
- 前記第2の槽において紫外線照射された懸濁液を、前記第1の槽へ循環させる循環手段を備えることを特徴とする請求項8~10のいずれか1項に記載の塩素化塩化ビニル系樹脂の製造装置。
- 前記第2の槽から取り出された懸濁液に塩素を導入する第2の塩素導入手段を備えることを特徴とする請求項11に記載の塩素化塩化ビニル系樹脂の製造装置。
- 前記循環手段は、前記懸濁液を前記第1の槽の気相部又は気液界面近傍へ導入するものであることを特徴とする請求項11又は12に記載の塩素化塩化ビニル系樹脂の製造装置。
- 前記光源は、紫外線LED、有機EL、無機EL及び紫外線レーザーからなる群より選択される少なくとも1種の光源であることを特徴とする請求項8~13のいずれか1項に記載の塩素化塩化ビニル系樹脂の製造装置。
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2016075567A1 (en) * | 2014-11-11 | 2016-05-19 | Reliance Industries Limited | Preparation of chlorinated polyvinyl chloride |
WO2016075591A1 (en) * | 2014-11-11 | 2016-05-19 | Reliance Industries Limited | Apparatus and process for chlorination of polyvinyl chloride |
JP2017075298A (ja) * | 2015-07-29 | 2017-04-20 | リライアンス、インダストリーズ、リミテッドReliance Industries Limited | ポリマーの塩化プロセス |
CN111939864A (zh) * | 2020-10-16 | 2020-11-17 | 山东颐工化学有限公司 | 一种mbs树脂的制备装置及工艺 |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10370463B2 (en) * | 2014-07-22 | 2019-08-06 | Reliance Industries Limited | Process for manufacturing chlorinated polyvinylchloride |
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KR102684209B1 (ko) * | 2018-12-19 | 2024-07-10 | 한화솔루션 주식회사 | 염소화 폴리염화비닐 수지의 제조 방법 |
KR20210086152A (ko) * | 2019-12-31 | 2021-07-08 | 한화솔루션 주식회사 | 염소화 폴리염화비닐의 제조 방법 |
CN112029137A (zh) * | 2020-09-09 | 2020-12-04 | 金川集团股份有限公司 | 一种氯化专用pvc树脂的制备方法 |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5215638B1 (ja) * | 1965-01-15 | 1977-05-02 | ||
JPS63145305A (ja) * | 1986-12-08 | 1988-06-17 | Tokuyama Sekisui Kogyo Kk | 塩素化塩化ビニル系樹脂の製造方法 |
JPH06100618A (ja) | 1992-09-18 | 1994-04-12 | Sekisui Chem Co Ltd | 塩素化ポリオレフィンの製造方法 |
JPH10279627A (ja) | 1997-04-09 | 1998-10-20 | Tokuyama Sekisui Ind Corp | 塩素化塩化ビニル系樹脂の製造方法 |
JP2002275213A (ja) * | 2001-01-15 | 2002-09-25 | Kanegafuchi Chem Ind Co Ltd | 塩素化塩化ビニル系樹脂の製造方法および装置 |
JP2003183320A (ja) * | 2001-12-18 | 2003-07-03 | Kanegafuchi Chem Ind Co Ltd | 塩素化塩化ビニル系樹脂の製造方法および装置 |
JP2003277436A (ja) * | 2002-03-26 | 2003-10-02 | Kanegafuchi Chem Ind Co Ltd | 塩素化塩化ビニル系樹脂の製造方法および装置 |
JP2008038129A (ja) * | 2006-01-26 | 2008-02-21 | Kaneka Corp | 塩素化塩化ビニル系樹脂の製造方法 |
WO2013069542A1 (ja) * | 2011-11-07 | 2013-05-16 | 株式会社カネカ | 塩素化塩化ビニル系樹脂の製造方法 |
Family Cites Families (27)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2291574A (en) * | 1938-08-12 | 1942-07-28 | Jasco Inc | Method for the chlorination of polymeric compounds |
NL293563A (ja) * | 1958-01-08 | |||
DE1544752B2 (de) * | 1964-01-10 | 1974-05-30 | Dynamit Nobel Ag, 5210 Troisdorf | Verfahren zur Herstellung von geformten Gebilden aus thermoplastischen Massen auf der Basis von nachchloriertem Polyvinylchlorid |
GB1131318A (en) * | 1965-11-20 | 1968-10-23 | Shinetsu Chem Ind Co | Heat stabilized polyvinyl chloride compositions |
US4006126A (en) * | 1966-02-16 | 1977-02-01 | Montecatini Edison S.P.A. | Process for the chlorination of vinyl polymers |
US3862264A (en) * | 1969-08-30 | 1975-01-21 | Yosuhiro Nojima | Chlorinated polyvinyl chloride composition |
US3725359A (en) * | 1970-12-23 | 1973-04-03 | Stauffer Chemical Co | Fire retardant resin compositions of post-chlorinated vinyl halide-bis(hydrocarbyl) vinylphosphonate copolymers |
US3862066A (en) * | 1971-05-26 | 1975-01-21 | Universal Pvc Resins | Method for making rigid vinyl chloride polymer compounds |
JPS5148795B2 (ja) * | 1974-05-18 | 1976-12-22 | ||
JPS5215638A (en) | 1975-07-23 | 1977-02-05 | Hitachi Cable | Tension controller |
US4412898A (en) * | 1980-08-26 | 1983-11-01 | The B.F. Goodrich Company | Process for chlorination of PVC in water without use of swelling agents |
JPH0241523B2 (ja) | 1980-08-26 | 1990-09-18 | ||
US4459387A (en) * | 1981-01-26 | 1984-07-10 | The B. F. Goodrich Company | Chlorination of poly(vinyl chloride) in liquid chlorine, and chlorinated poly(vinyl chloride) composition |
US4350798A (en) * | 1981-01-26 | 1982-09-21 | The B. F. Goodrich Company | Chlorination of poly(vinyl chloride) in liquid chlorine, and chlorinated poly(vinyl chloride) composition |
JPS58145704A (ja) * | 1982-02-25 | 1983-08-30 | Toyo Ink Mfg Co Ltd | 塩素化樹脂の製造方法 |
US4448658A (en) * | 1982-08-25 | 1984-05-15 | The B. F. Goodrich Company | Use of high-intensity rapidly-pulsating actinic radiation in the chlorination of polyvinyl chloride resin |
JP3176504B2 (ja) * | 1994-03-29 | 2001-06-18 | 徳山積水工業株式会社 | 塩素化塩化ビニル系樹脂の製造方法 |
JP2000344830A (ja) * | 1999-06-01 | 2000-12-12 | Tokuyama Sekisui Ind Corp | 塩素化塩化ビニル系樹脂の製造方法 |
WO2002055565A1 (fr) * | 2001-01-15 | 2002-07-18 | Kaneka Corporation | Procede et appareil pour produire une resine chloree de chlorure de vinyle |
CN1401672A (zh) * | 2002-09-05 | 2003-03-12 | 刘旭思 | 氯化聚氯乙烯的水相悬浮紫外光制备方法 |
US7345114B2 (en) | 2006-01-26 | 2008-03-18 | Kaneka Corporation | Method for producing chlorinated vinyl chloride resin |
WO2008135810A2 (en) * | 2007-05-03 | 2008-11-13 | Freescale Semiconductor, Inc. | Method and apparatus for designing an integrated circuit |
CN101981007A (zh) * | 2008-03-31 | 2011-02-23 | 住友精化株式会社 | 纯化吡啶的方法和制造氯化吡啶的方法 |
DE102009020527A1 (de) * | 2009-05-08 | 2010-11-11 | Ehrfeld Mikrotechnik Bts Gmbh | Vorrichtung zur Durchführung photochemischer Prozesse |
CN101831021B (zh) * | 2010-05-10 | 2011-08-31 | 河北科技大学 | 一种气固相法制备氯化聚氯乙烯的装置及其方法 |
CN102936302A (zh) * | 2011-08-15 | 2013-02-20 | 沈阳欧陆科技发展有限公司 | 一种氯化聚氯乙烯树脂的制备方法 |
CN102786610A (zh) * | 2012-07-10 | 2012-11-21 | 苏州宝津塑业有限公司 | 一种气固相法合成氯化聚氯乙烯树脂的方法 |
-
2014
- 2014-03-26 WO PCT/JP2014/058560 patent/WO2014157346A1/ja active Application Filing
- 2014-03-26 KR KR1020157000843A patent/KR101581890B1/ko active IP Right Grant
- 2014-03-26 US US14/411,818 patent/US9399687B2/en active Active
- 2014-03-26 EP EP14774645.7A patent/EP2980106B1/en active Active
- 2014-03-26 CN CN201480001706.8A patent/CN104395359B/zh active Active
- 2014-03-26 JP JP2014540679A patent/JP5690027B1/ja active Active
- 2014-03-27 TW TW103111520A patent/TWI490245B/zh active
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5215638B1 (ja) * | 1965-01-15 | 1977-05-02 | ||
JPS63145305A (ja) * | 1986-12-08 | 1988-06-17 | Tokuyama Sekisui Kogyo Kk | 塩素化塩化ビニル系樹脂の製造方法 |
JPH06100618A (ja) | 1992-09-18 | 1994-04-12 | Sekisui Chem Co Ltd | 塩素化ポリオレフィンの製造方法 |
JPH10279627A (ja) | 1997-04-09 | 1998-10-20 | Tokuyama Sekisui Ind Corp | 塩素化塩化ビニル系樹脂の製造方法 |
JP2002275213A (ja) * | 2001-01-15 | 2002-09-25 | Kanegafuchi Chem Ind Co Ltd | 塩素化塩化ビニル系樹脂の製造方法および装置 |
JP2003183320A (ja) * | 2001-12-18 | 2003-07-03 | Kanegafuchi Chem Ind Co Ltd | 塩素化塩化ビニル系樹脂の製造方法および装置 |
JP2003277436A (ja) * | 2002-03-26 | 2003-10-02 | Kanegafuchi Chem Ind Co Ltd | 塩素化塩化ビニル系樹脂の製造方法および装置 |
JP2008038129A (ja) * | 2006-01-26 | 2008-02-21 | Kaneka Corp | 塩素化塩化ビニル系樹脂の製造方法 |
WO2013069542A1 (ja) * | 2011-11-07 | 2013-05-16 | 株式会社カネカ | 塩素化塩化ビニル系樹脂の製造方法 |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2016075567A1 (en) * | 2014-11-11 | 2016-05-19 | Reliance Industries Limited | Preparation of chlorinated polyvinyl chloride |
WO2016075591A1 (en) * | 2014-11-11 | 2016-05-19 | Reliance Industries Limited | Apparatus and process for chlorination of polyvinyl chloride |
JP2017075298A (ja) * | 2015-07-29 | 2017-04-20 | リライアンス、インダストリーズ、リミテッドReliance Industries Limited | ポリマーの塩化プロセス |
CN111939864A (zh) * | 2020-10-16 | 2020-11-17 | 山东颐工化学有限公司 | 一种mbs树脂的制备装置及工艺 |
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EP2980106A4 (en) | 2017-01-11 |
TWI490245B (zh) | 2015-07-01 |
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