WO2008088138A1 - The restoring method of waste polyvinyl chloride - Google Patents
The restoring method of waste polyvinyl chloride Download PDFInfo
- Publication number
- WO2008088138A1 WO2008088138A1 PCT/KR2007/006960 KR2007006960W WO2008088138A1 WO 2008088138 A1 WO2008088138 A1 WO 2008088138A1 KR 2007006960 W KR2007006960 W KR 2007006960W WO 2008088138 A1 WO2008088138 A1 WO 2008088138A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polyvinyl chloride
- waste
- soft
- hard
- weight
- Prior art date
Links
- 229920000915 polyvinyl chloride Polymers 0.000 title claims abstract description 166
- 239000004800 polyvinyl chloride Substances 0.000 title claims abstract description 164
- 239000002699 waste material Substances 0.000 title claims abstract description 102
- 238000000034 method Methods 0.000 title claims abstract description 26
- 239000000203 mixture Substances 0.000 claims abstract description 45
- 239000004014 plasticizer Substances 0.000 claims abstract description 31
- 238000004064 recycling Methods 0.000 claims abstract description 26
- 239000000654 additive Substances 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 238000000227 grinding Methods 0.000 claims abstract description 12
- 239000003381 stabilizer Substances 0.000 claims description 20
- 239000004609 Impact Modifier Substances 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 12
- 239000000049 pigment Substances 0.000 claims description 12
- 239000003063 flame retardant Substances 0.000 claims description 11
- 239000000945 filler Substances 0.000 claims description 10
- 239000000314 lubricant Substances 0.000 claims description 9
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 8
- 239000010409 thin film Substances 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 3
- 230000003028 elevating effect Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 230000006872 improvement Effects 0.000 abstract description 6
- 239000000047 product Substances 0.000 description 26
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 7
- 229920003023 plastic Polymers 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 239000000326 ultraviolet stabilizing agent Substances 0.000 description 6
- 238000007792 addition Methods 0.000 description 5
- 238000007796 conventional method Methods 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 229920001519 homopolymer Polymers 0.000 description 4
- 238000012856 packing Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 3
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000010292 electrical insulation Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000003017 thermal stabilizer Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- ZVFDTKUVRCTHQE-UHFFFAOYSA-N Diisodecyl phthalate Chemical compound CC(C)CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC(C)C ZVFDTKUVRCTHQE-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- OCWMFVJKFWXKNZ-UHFFFAOYSA-L lead(2+);oxygen(2-);sulfate Chemical compound [O-2].[O-2].[O-2].[Pb+2].[Pb+2].[Pb+2].[Pb+2].[O-]S([O-])(=O)=O OCWMFVJKFWXKNZ-UHFFFAOYSA-L 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229940088417 precipitated calcium carbonate Drugs 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- 239000004808 2-ethylhexylester Substances 0.000 description 1
- 229940122930 Alkalising agent Drugs 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- KRADHMIOFJQKEZ-UHFFFAOYSA-N Tri-2-ethylhexyl trimellitate Chemical compound CCCCC(CC)COC(=O)C1=CC=C(C(=O)OCC(CC)CCCC)C(C(=O)OCC(CC)CCCC)=C1 KRADHMIOFJQKEZ-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 229920001617 Vinyon Polymers 0.000 description 1
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- UQLDLKMNUJERMK-UHFFFAOYSA-L di(octadecanoyloxy)lead Chemical compound [Pb+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O UQLDLKMNUJERMK-UHFFFAOYSA-L 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000194 fatty acid Chemical class 0.000 description 1
- 229930195729 fatty acid Chemical class 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- UMKARVFXJJITLN-UHFFFAOYSA-N lead;phosphorous acid Chemical compound [Pb].OP(O)O UMKARVFXJJITLN-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical class CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000005498 phthalate group Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- JNXDCMUUZNIWPQ-UHFFFAOYSA-N trioctyl benzene-1,2,4-tricarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C(C(=O)OCCCCCCCC)=C1 JNXDCMUUZNIWPQ-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/06—Recovery or working-up of waste materials of polymers without chemical reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
- B29B17/04—Disintegrating plastics, e.g. by milling
- B29B17/0404—Disintegrating plastics, e.g. by milling to powder
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use 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; Derivatives of such polymers
- C08J2327/02—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/04—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08J2327/06—Homopolymers or copolymers of vinyl chloride
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Definitions
- the present invention relates to a method for recycling waste polyvinyl chloride.
- polyvinyl chloride(PVC) (also known as a "polyvinyl resin”) refers to a vinyl chloride homopolymer or a 50% or more of a vinyl chloride-containing copolymer.
- Vinyl chloride homopolymers vary in characteristics depending upon their molecular weights.
- Polyvinyl chloride is polymerized using peroxide and azo-catalysts. The polymerization is also carried out by exposure to light or alpha-ray irradiation. The polymerization may be divided into emulsion- and suspension-polymerization. During the polymerization, the polymerization heat is distributed by dispersing vinyl chloride in water.
- polyvinyl chloride thus prepared are varied depending upon reaction conditions. Due to considerably bad crys- tallinity, polyvinyl chloride is decomposed by light and heat, thus turning yellow or brown and showing deteriorated gaseous properties. For this reason, one or more stabilizers are generally combined with polyvinyl chloride. At ambient temperature, polyvinyl chloride is stable against all of acids, alkalis and oxidizing agents and is insoluble in solvents such as acetone, alcohol and benzene. For this reason, it is difficult to bond polyvinyl chloride during processing. Polyvinyl chloride is well soluble in a solvent such as tetrahydrofuran and cyclohexanone.
- Polyvinyl chloride is relatively hard and readily breakable. However, with the addition of a plasticizer such as dioctyl phthalate, it is possible to impart elasticity to polyvinyl chloride. Maximum and minimum use temperatures of polyvinyl chloride are 6O 0 C and -2O 0 C, respectively. In spite of the addition of a cold-resistant plasticizer, polyvinyl chloride is softened at the minimum use temperature. Vinyl chloride is copolymerized with another compound such as styrene, vinyl acetate, methyl acetate or vinylidene chloride. Vinyl chloride copolymers are processed at a lower temperature and are thus more flexible, as compared to vinyl chloride homopolymers. Owing to improvement in quality of vinyl chloride homopolymers and development of processing techniques, chloride copolymers are now rarely used except in specific applications.
- a plasticizer such as dioctyl phthalate
- Polyvinyl chloride is combined with various ingredients, thermal-processed and then manufactured into a final product.
- Polyvinyl chloride products are mostly plasticizer-containing soft products in the form of sheets or films for packing or agricultural purposes. Compared to polyethylene products, polyvinyl chloride products are less cold-resistant and less expansible, but have superior transparency and high strength. Extrusion-molding is used to manufacture sheathings for electrical cables, tubes, hoses, etc. The most important application for hard polyvinyl chloride products is production of sewer pipes by extrusion molding. Examples of synthetic fibers that use polyvinyl chloride as a major ingredient include teviron, environ, and the like. There are several polyvinyl chloride copolymers e.g. Abisco vinyon (American viscose corp.). Polyvinyl chloride copolymers have absorbency, but do have elasticity. In addition, polyvinyl chloride copolymers exhibit superior chemical resistance, but show poor heat resistance.
- polyvinyl chloride used in various forms is a thermoplastic material which is deformed by heat.
- Polyvinyl chloride is economical in that the wasted products after use are recyclable by application of suitable heating and addition of a plasticizer.
- waste polyvinyl chloride is collected and impurities are removed from the waste polyvinyl chloride.
- the resulting waste polyvinyl chloride is ground to a size of 10 to 15 mm and then mixed in a mixer. During mixing, frictional heat generated by rotation of the mixer elevates the temperature of the mixture to 100-150 0 C.
- the conventional method for recycling waste polyvinyl chloride includes stirring at a constant elevated temperature. Accordingly, the method involves a problem in that the only one type of products is recycled according to the type of soft-, hard- or soft- hard blend products.
- plasticizers and stabilizers in order to impart cold resistance, heat resistance, flame-retardancy, high tensile strength and expendability to sheathings for electrical cables or other soft products, it is preferable to use a variety of plasticizers and stabilizers.
- soft products contain 50 or more parts by weight of a plasticizer, it is impossible to add plasticizers and stabilizers to the soft products.
- hard products contain a small amount (i.e., 0 to 15 parts by weight) of plasticizer, they cannot readily absorb the plasticizer due to their small surface areas during grinding, thus making it difficult to provide products. For these reasons, the products thus obtained do not exhibit satisfactory properties e.g.
- waste polyvinyl chloride is separately recycled according to the desired type of soft-, hard- or soft-hard blend products, thus disadvantageously involving further collection/separation costs.
- waste polyvinyl chloride is separately recycled according to the type of soft-, hard or soft-hard blend products. Accordingly, products formed with the combination of soft-, hard- and soft-hard blend cannot be recycled, and are discarded or disposed as waste fuels, thus disadvantageously causing resource dissipation and environmental pollution. Disclosure of Invention Technical Problem
- the present invention has been made in view of the above-mentioned problems of in the prior art and it is one aspect of the present invention to provide a method for recycling waste polyvinyl chloride, comprising pretreating soft-, hard- and soft-hard blend polyvinyl chloride waste, grinding the waste polyvinyl chloride, and mixing the resulting waste polyvinyl chloride with plasticizers and additives to impart desired properties such as cold resistance, heat resistance, flame retardancy, high tensile strength and extensibility to the waste polyvinyl chloride, so that waste polyvinyl chloride can be recycled into high-quality polyvinyl chloride products and improvement in recycling efficiency and production efficiency can thus be realized.
- Technical Solution comprising pretreating soft-, hard- and soft-hard blend polyvinyl chloride waste, grinding the waste polyvinyl chloride, and mixing the resulting waste polyvinyl chloride with plasticizers and additives to impart desired properties such as cold resistance, heat resistance, flame retardancy, high tensile strength and extensibility to the
- a method for recycling waste polyvinyl chloride comprising: pretreating waste polyvinyl chloride by grinding a total of 100 parts by weight of soft-, hard- and soft-hard blend polyvinyl chloride waste; placing 80 parts by weight of the pretreated hard- and soft-hard blend polyvinyl chloride waste in a mixer; mixing the hard- and soft-hard blend polyvinyl chloride waste with the mixer, simultaneously, adding 15 to 30 parts by weight of a heat-resistant plasticizer to the polyvinyl chloride waste at a temperature of 70 to 8O 0 C attained through frictional heat generated by the mixing; adding, to the resulting mixture, additives, i.e., 15 to 30 parts by weight of a filler, 1 part by weight of a pigment, 5 to 13 parts by weight of an impact modifier, 3.5 parts by weight of a stabilizer, 0.5 parts by weight of a lubricant and 20 parts by weight of a
- the method for recycling waste polyvinyl chloride according to the present invention comprises pretreating a combination of soft-, hard- and soft-hard blend polyvinyl chloride waste, grinding the waste polyvinyl chloride, and mixing the resulting waste polyvinyl chloride with plasticizers and additives to impart improved properties such as cold resistance, heat resistance, flame retardancy, tensile strength and extensibility to the waste polyvinyl chloride, so that waste polyvinyl chloride can be recycled into high-quality polyvinyl chloride products and improvement in recycling efficiency and production efficiency can thus be realized.
- the pretreating varies depending upon the type of polyvinyl chloride. Specifically, the hard polyvinyl chloride waste is sequentially ground several times from large particles to small particles, hard polyvinyl chloride waste in the form of a thin film is ground into relatively large particles and then ground to small particles through elevation in temperature, and soft-hard blend polyvinyl chloride products are sequentially ground and then extruded. That is to say, the pretreating is carried out according to the shape and type of desired polyvinyl chloride products to provide improved recycling efficiency.
- the pretreated polyvinyl chloride waste is mixed in a mixer, heated through frictional heat generated by the mixing, a filler, a pigment, an impact modifier, a stabilizer, a lubricant and a flame-retardant are added thereto, the mixer temperature is re-elevated, and the polyvinyl chloride incorporated with the additives is prepared through an extruder.
- the waste polyvinyl chloride with improved properties such as cold resistance, heat resistance, flame retardancy, tensile strength and extensibility can be recycled, and improved- quality, highly functional products can thus be mass-produced. Accordingly, it is possible to improve recycling efficiency of polyvinyl chloride, reduce environmental contamination and increase resource reuse efficiency.
- soft polyvinyl chloride waste is mixed with the pretreated mixture of hard- and soft-hard blend polyvinyl chloride waste, so that the pigment employed in the step of adding the filler, the pigment, the impact modifier, the stabilizer, the lubricant and the flame-retardant, for the purpose of modifying the inherent various colors of the polyvinyl chloride waste, can render the desired color. Furthermore, the impact modifier prevents deterioration of heat resistance due to the addition of soft polyvinyl chloride waste. Accordingly, with the present invention, it is possible to provide high quality recycled polyvinyl chloride that renders the desired color and exhibits improved heat resistance and flame-retardancy.
- FIG. 1 is a flow chart illustrating a method for recycling polyvinyl chloride according to the present invention. Best Mode for Carrying Out the Invention
- the present invention is directed to a method for recycling waste polyvinyl chloride comprising: pretreating waste polyvinyl chloride by grinding a total of 100 parts by weight of soft-, hard- and soft-hard blend polyvinyl chloride waste; placing 80 parts by weight of the pretreated hard- and soft-hard blend polyvinyl chloride waste in a mixer; mixing the hard- and soft-hard blend polyvinyl chloride waste with the mixer, simultaneously, adding 15 to 30 parts by weight of a heat- resistant plasticizer to the polyvinyl chloride waste at a temperature of 70 to 8O 0 C attained through frictional heat generated by the mixing; adding, to the resulting mixture, additives, i.e., 15 to 30 parts by weight of a filler, 1 part by weight of a pigment, 5 to 13 parts by weight of an impact modifier, 3.5 parts by weight of a stabilizer, 0.5 parts by weight of a lubricant and 20 parts by weight of a flame- retardant, while the mixer temperature is elevated
- the pretreatment step may include grinding the polyvinyl chloride waste several times with several grinders to enable a gradual decrease in size and thereby to grind the hard-poly vinyl chloride waste to a size of 2 mm or less.
- the polyvinyl chloride waste in the form of a thin film is ground to a size of 10 mm or less and is then placed in a mixer such that the size of the thin-film polyvinyl chloride waste is varied to 2 mm or less by heat when elevating in temperature.
- the soft-hard blend polyvinyl chloride waste is extruded in an extruder and then placed in the mixer to recycle the polyvinyl chloride waste without causing separation of soft- and hard polyvinyl chloride.
- the waste polyvinyl chloride is obtained by collecting: soft-polyvinyl chloride that contains large quantities of plasticizer in order to be suitable for use in sheets or films for packing or agricultural purposes or sheathings for electrical cables and thus has superior softness; hard-poly vinyl chloride having the strength required for profile or pipe applications; hard-poly vinyl chloride in the form of thin films or cloths for use in decorative sheets, hard-packing materials and pattern packing materials; and soft-hard blend polyvinyl chloride that exhibits both the flexibility of soft-polyvinyl chloride and the strength of hard-polyvinyl chloride, for use in washing machine hoses, sewer pipes and hoses for agricultural purposes.
- Polyvinyl chloride is transparent and self-extinguishing and exhibits excellent solvent-resistance and superior electrical insulation.
- polyvinyl chloride has drawbacks of poor thermal stability, poor processibility, low heat deflection temperature and low impact strength.
- the heat-resistant plasticizer is added to adjust the processibility and flowability of highly hard polyvinyl chloride to a desired level.
- Examples of heat-resistant plasticizers for general purposes that have been used to impart softness to polyvinyl chloride include phthalates such as dioctyl phthalate (DOP) and diisononyl phthalate (DINP).
- DOP dioctyl phthalate
- DINP diisononyl phthalate
- TOTM triisodecyl trimelliatate
- DIDP diisodecyl phthalate
- di(2-methyhlhexyl) aipate may be preferably used to improve cold-resistance.
- Suitable pigments include organic pigments such as carbon black (C) and titanium dioxide. Pigments vary in color and particle size depending upon the synthesis method thereof and can render colors according to users' demands.
- Suitable fillers are precipitated calcium carbonate (PCC) and ground calcium carbonate (GCC) which are classified according to preparation methods thereof. Fillers serve to regulate weight feeling and physical properties of polyvinyl chloride and adjust processibility and prices thereof.
- a representative filler is calcium carbonate (CaCO 3 ).
- Suitable stabilizers are divided into thermal stabilizers and ultraviolet stabilizers.
- thermal stabilizers When heating at 140 to 18O 0 C in the extrusion process of polyvinyl chloride, thermal stabilizers are decomposed at a temperature not more than a softening point to generate a chlorine gas.
- the chlorine gas causes polymeric chains of polyvinyl chloride to be successively and continuously degraded.
- resin stabilizers are added to prevent the successive degradation.
- Representative stabilizers are tribasic lead sulfate (TLS), dibasic lead phosphite (DLP), lead stearate (Pb-St), tin stabilizers and calcium- zinc stabilizers. According to application, the stabilizers may be used in a combination.
- Energy sources to induce chemical reaction may include heat as well as light. Ul- traviolet rays at a wavelength less than 3,40OA have sufficient energy to decompose molecules. Plastics are decomposed by ultraviolet light with a wavelength of 3,000 to
- Ultraviolet stabilizers refer to additives that block or absorb ultraviolet rays and thereby protect plastics. Ultraviolet stabilizers are mostly included in highly-transparent outdoor plastics. Ultraviolet stabilizers are one type of optical stabilizers and serve to solve the decomposition by polyolefin. Ultraviolet stabilizers are also known as UV agents in the art and incorporated with stabilizers.
- the stabilizer used herein preferably takes the form of a combination of 3 parts by weight of a thermal stabilizer and 0.5 parts by weight of an ultraviolet stabilizer.
- Lubricants decrease a processing temperature and reduce processing time, thus causing improvement in flowability and appearance of polyvinyl chloride.
- the most commonly used lubricants are metal salts of stearic acid and fatty acid.
- Impact modifiers are insoluble fibrous substances which are added to plastics for the purpose of improving cleavage strength, tensile strength, compressive strength, bending strength and impact strength of the plastics. Generally, impact modifiers also yield improved dimensional stability and resistance against heat deflection. As such, impact modifiers are easy to process and have a variety of applications. Impact modifiers are used in order to solve drawbacks in view of impact resistance, processibility, and heat resistance of polyvinyl chloride.
- the impact modifier used herein preferably comprises 35% chloride-containing chloride polyethylene (CPE).
- Flame retardants refer to additives that inhibit combustion of readily combustible plastics via physical and chemical enhancement thereof.
- Pure polyvinyl chloride is in the form of a transparent, readily breakable glass, and undergoes successive thermal decomposition and is thus difficult to process.
- pure polyvinyl chloride has electrical insulation property and is self-extinguishing, i.e., flame retardancy.
- a stabilizer to retard and inhibit a series of pyrolysis and a plasticizer to improve flowability of bonds between non-flowable molecules are added thereto, thereby causing a significant decrease in flame retandancy of the pure polyvinyl chloride.
- Representative flame retardants are antimony trioxide (Sb O ), aluminum hydroxide (AL(OH) ) and brome-based flame retardants such as decabrom.
- waste polyvinyl chloride is pretreated by grinding and mixing a total of 100 parts by weight of a soft-, hard- and soft-hard blend polyvinyl chloride waste (Sl).
- the step Sl includes grinding waste hard-poly vinyl chloride several times with several grinders in order to enable a gradual decrease in size and thereby to grind the waste hard-polyvinyl chloride to a size of 2 mm or less.
- the waste polyvinyl chloride in the form of a thin-film with the particle size of 10 mm or less is placed in a mixer and then heated.
- the thin-film waste polyvinyl chloride is ground to a size of 2 mm or less by heating.
- the waste soft-hard blend polyvinyl chloride is extruded in an extruder and then placed in the mixer to recycle the waste polyvinyl chloride without causing separation of soft- and hard polyvinyl chlorides.
- the heat-resistant plasticizer serves to improve heat-resistance, weatherability, electric insulating property and cold-resistance and thereby to enhance functions of the recycled polyvinyl chloride.
- the heat-resistant plasticizer may be used alone or in any combination thereof, if desired.
- additives i.e., 15 to 30 parts by weight of a filler, 1 part by weight of a pigment, 5 to 13 parts by weight of an impact modifier, 3.5 parts by weight of a stabilizer, 0.5 parts by weight of a lubricant and 20 parts by weight of a flame-retardant at an elevated temperature of 140 to 15O 0 C (S4).
- the additives include the filler to regulate weight feeling and physical properties, the pigment to render various colors and adjust particle size, the impact modifier to improve impact resistance, a stabilizer to improve thermal stability and stability against ultraviolet rays, the lubricant to improve processability and the flame- retardant to inhibit combustion.
- the waste soft polyvinyl chloride is incorporated in the additive- containing polyvinyl chloride, such that the pigment can render the desired color.
- the polyvinyl chloride waste is ground to a small particle size to perform the pretreatment, the polyvinyl chloride waste is mixed in the mixer, while being heated by the frictional heat generated during the mixing, desired additives and heat-resistant plasticizers are added to the heated mixer to improve tensile strength, heat resistance, weatherability, electrical insulation and flame-retardancy, and the resulting mixture is extrusion-recycled.
- highly functional polyvinyl chloride is prepared by recycling waste polyvinyl chloride. As a result, it is possible to reuse resources, increase productivity and significantly reduce production costs.
- waste polyvinyl chloride can be recycled into high-quality polyvinyl chloride by pretreating a combination of soft-, hard- and soft-hard blend polyvinyl chloride waste, grinding the waste polyvinyl chloride, and mixing the resulting waste polyvinyl chloride with plasticizers and additives to impart improved properties such as cold resistance, heat resistance, flame retardancy, tensile strength and extensibility to the waste polyvinyl chloride.
- plasticizers and additives to impart improved properties such as cold resistance, heat resistance, flame retardancy, tensile strength and extensibility
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WO2022243043A1 (fr) * | 2021-05-20 | 2022-11-24 | IFP Energies Nouvelles | Procede d'extraction et de transformation par transesterification de phtalates contenus dans des plastiques pvc |
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KR101275023B1 (ko) * | 2013-02-01 | 2013-06-17 | 케이엘건설 주식회사 | 폐 pvc 자재를 포함하는 난연 pvc졸 조성물 및 그 제조방법, 이를 이용한 난연 pvc 방수 시트 |
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KR102046264B1 (ko) | 2018-11-27 | 2019-11-19 | 노우준 | 재생 폴리염화비닐 컴파운드 조성물 및 이의 제조방법 |
KR102211439B1 (ko) * | 2019-07-29 | 2021-02-03 | (주)디피아이 | 폐 pvc를 재활용한 테이프 제조 방법 |
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JPH06297459A (ja) * | 1992-09-24 | 1994-10-25 | Masakazu Abe | 廃農業用塩化ビニルの再生方法並にその装置 |
JPH0892412A (ja) * | 1994-09-22 | 1996-04-09 | Toshiba Corp | プラスチックの再資源化方法 |
JPH09123169A (ja) * | 1995-11-07 | 1997-05-13 | Ain Eng Kk | ペットボトルを原料とする熱可塑性樹脂合成体及びその製造方法、並びに前記熱可塑性樹脂合成体を用いた熱可塑性樹脂成形品及びその製造方法 |
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JP2006037084A (ja) * | 2004-06-21 | 2006-02-09 | Taketoshi Kito | 塩化ビニル重合体含有廃棄物の再生方法 |
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JPH06279614A (ja) * | 1993-03-27 | 1994-10-04 | Masakazu Abe | 廃電線の再資源化方法およびその再資源化装置 |
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JPH06297459A (ja) * | 1992-09-24 | 1994-10-25 | Masakazu Abe | 廃農業用塩化ビニルの再生方法並にその装置 |
JPH0892412A (ja) * | 1994-09-22 | 1996-04-09 | Toshiba Corp | プラスチックの再資源化方法 |
JPH09123169A (ja) * | 1995-11-07 | 1997-05-13 | Ain Eng Kk | ペットボトルを原料とする熱可塑性樹脂合成体及びその製造方法、並びに前記熱可塑性樹脂合成体を用いた熱可塑性樹脂成形品及びその製造方法 |
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WO2022243043A1 (fr) * | 2021-05-20 | 2022-11-24 | IFP Energies Nouvelles | Procede d'extraction et de transformation par transesterification de phtalates contenus dans des plastiques pvc |
FR3123070A1 (fr) * | 2021-05-20 | 2022-11-25 | IFP Energies Nouvelles | Procede d’extraction et de transformation par transesterification de phtalates contenus dans des plastiques pvc |
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