KR20050095504A - Highly functional resin recycled polyester and polyamide hybrid waste and its manufacturing method - Google Patents
Highly functional resin recycled polyester and polyamide hybrid waste and its manufacturing method Download PDFInfo
- Publication number
- KR20050095504A KR20050095504A KR1020040020944A KR20040020944A KR20050095504A KR 20050095504 A KR20050095504 A KR 20050095504A KR 1020040020944 A KR1020040020944 A KR 1020040020944A KR 20040020944 A KR20040020944 A KR 20040020944A KR 20050095504 A KR20050095504 A KR 20050095504A
- Authority
- KR
- South Korea
- Prior art keywords
- polyester
- acid
- amide
- resin
- weight
- Prior art date
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- 229920006149 polyester-amide block copolymer Polymers 0.000 title claims abstract description 176
- 229920005989 resin Polymers 0.000 title claims abstract description 117
- 239000011347 resin Substances 0.000 title claims abstract description 117
- 239000002699 waste material Substances 0.000 title claims abstract description 44
- 239000004952 Polyamide Substances 0.000 title claims abstract description 32
- 229920002647 polyamide Polymers 0.000 title claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 238000000034 method Methods 0.000 claims abstract description 73
- 229920000642 polymer Polymers 0.000 claims abstract description 69
- 239000002253 acid Substances 0.000 claims abstract description 53
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 52
- -1 polyethylene terephthalate Polymers 0.000 claims abstract description 18
- 239000011230 binding agent Substances 0.000 claims abstract description 17
- 150000007514 bases Chemical class 0.000 claims abstract description 15
- 238000000576 coating method Methods 0.000 claims abstract description 13
- 239000003822 epoxy resin Substances 0.000 claims abstract description 13
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 13
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 12
- 239000011248 coating agent Substances 0.000 claims abstract description 11
- 239000003607 modifier Substances 0.000 claims abstract description 11
- 239000000976 ink Substances 0.000 claims abstract description 9
- 239000000853 adhesive Substances 0.000 claims abstract description 8
- 230000001070 adhesive effect Effects 0.000 claims abstract description 8
- 239000010419 fine particle Substances 0.000 claims abstract description 8
- 239000000843 powder Substances 0.000 claims abstract description 8
- 239000011342 resin composition Substances 0.000 claims abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 229920003002 synthetic resin Polymers 0.000 claims abstract description 8
- 239000000057 synthetic resin Substances 0.000 claims abstract description 8
- 239000003623 enhancer Substances 0.000 claims abstract description 7
- 239000003094 microcapsule Substances 0.000 claims abstract description 7
- 239000003973 paint Substances 0.000 claims abstract description 7
- 230000007935 neutral effect Effects 0.000 claims abstract description 6
- 238000007639 printing Methods 0.000 claims abstract description 6
- 238000012545 processing Methods 0.000 claims abstract description 6
- 238000004065 wastewater treatment Methods 0.000 claims abstract description 6
- 239000004831 Hot glue Substances 0.000 claims abstract description 5
- 239000003463 adsorbent Substances 0.000 claims abstract description 5
- 239000004568 cement Substances 0.000 claims abstract description 5
- 238000004078 waterproofing Methods 0.000 claims abstract description 5
- 239000002270 dispersing agent Substances 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 53
- 239000010812 mixed waste Substances 0.000 claims description 50
- 239000000243 solution Substances 0.000 claims description 41
- 239000000047 product Substances 0.000 claims description 39
- 150000005846 sugar alcohols Polymers 0.000 claims description 39
- 238000004064 recycling Methods 0.000 claims description 37
- 239000002904 solvent Substances 0.000 claims description 37
- 150000007519 polyprotic acids Polymers 0.000 claims description 29
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 27
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 27
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 25
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 25
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 24
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 23
- 239000000194 fatty acid Substances 0.000 claims description 23
- 229930195729 fatty acid Natural products 0.000 claims description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 21
- 239000007787 solid Substances 0.000 claims description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 18
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 16
- 229920000728 polyester Polymers 0.000 claims description 16
- 150000004665 fatty acids Chemical class 0.000 claims description 15
- 239000012046 mixed solvent Substances 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 229920000180 alkyd Polymers 0.000 claims description 12
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 10
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 10
- 238000006068 polycondensation reaction Methods 0.000 claims description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 9
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 claims description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000001361 adipic acid Substances 0.000 claims description 8
- 235000011037 adipic acid Nutrition 0.000 claims description 8
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 8
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 claims description 8
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 claims description 8
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 8
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 8
- 239000003208 petroleum Substances 0.000 claims description 8
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims description 7
- 239000000908 ammonium hydroxide Substances 0.000 claims description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 6
- 239000000835 fiber Substances 0.000 claims description 6
- 235000011187 glycerol Nutrition 0.000 claims description 6
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 claims description 6
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims description 6
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 claims description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 5
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 5
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 5
- 150000001408 amides Chemical class 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 239000000539 dimer Substances 0.000 claims description 5
- 239000001530 fumaric acid Substances 0.000 claims description 5
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 5
- 238000005809 transesterification reaction Methods 0.000 claims description 5
- 239000002023 wood Substances 0.000 claims description 5
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 4
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 claims description 4
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 4
- 229940035437 1,3-propanediol Drugs 0.000 claims description 4
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 4
- 240000000972 Agathis dammara Species 0.000 claims description 4
- 239000004859 Copal Substances 0.000 claims description 4
- 229920002871 Dammar gum Polymers 0.000 claims description 4
- 241000782205 Guibourtia conjugata Species 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 claims description 3
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- 239000000376 reactant Substances 0.000 claims description 2
- LLHSEQCZSNZLRI-UHFFFAOYSA-M sodium;3,5-bis(methoxycarbonyl)benzenesulfonate Chemical compound [Na+].COC(=O)C1=CC(C(=O)OC)=CC(S([O-])(=O)=O)=C1 LLHSEQCZSNZLRI-UHFFFAOYSA-M 0.000 claims description 2
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- 239000004848 polyfunctional curative Substances 0.000 claims 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 claims 2
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- XHCGTVHIQUXPRM-SSIREWOPSA-N (2s)-n-[(2r,4s,7r)-7-acetamido-2-amino-4-[[(2s)-2-amino-6-[(5-amino-1h-1,2,4-triazol-3-yl)amino]hexanoyl]-[(2s)-2-[[(2r)-2-amino-6-[(5-amino-1h-1,2,4-triazol-3-yl)amino]hexanoyl]amino]-4-methylpentanoyl]carbamoyl]-1-(4-chlorophenyl)-8-naphthalen-2-yl-3,6- Chemical compound C([C@@H](N)C(=O)N[C@@H](CC(C)C)C(=O)N(C(=O)[C@@H](N)CCCCNC=1N=C(N)NN=1)C(=O)[C@@](CC(=O)[C@@H](CC=1C=C2C=CC=CC2=CC=1)NC(C)=O)(N(C(=O)[C@H](CO)NC(=O)[C@H](N)CC=1C=NC=CC=1)C(=O)[C@H]1N(CCC1)C(=O)[C@@H](N)CCCCNC(C)C)C(=O)[C@H](N)CC=1C=CC(Cl)=CC=1)CCCNC1=NNC(N)=N1 XHCGTVHIQUXPRM-SSIREWOPSA-N 0.000 description 1
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- HTXMGVTWXZBZNC-UHFFFAOYSA-N 3,5-bis(methoxycarbonyl)benzenesulfonic acid Chemical compound COC(=O)C1=CC(C(=O)OC)=CC(S(O)(=O)=O)=C1 HTXMGVTWXZBZNC-UHFFFAOYSA-N 0.000 description 1
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 1
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- OBMUNMYYDDBZAC-UHFFFAOYSA-N [Co].C(C)CCCCCC Chemical compound [Co].C(C)CCCCCC OBMUNMYYDDBZAC-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
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- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 108700022499 azaline Proteins 0.000 description 1
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- 229910052799 carbon Inorganic materials 0.000 description 1
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- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003937 drug carrier Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000009503 electrostatic coating Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 239000001788 mono and diglycerides of fatty acids Substances 0.000 description 1
- 235000019960 monoglycerides of fatty acid Nutrition 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 238000005406 washing Methods 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
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
- C08J11/18—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material
- C08J11/22—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds
- C08J11/24—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds containing hydroxyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/44—Polyester-amides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/12—Polyester-amides
-
- 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
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/12—Polyester-amides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/20—Recycled plastic
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
본 발명은 폴리에틸렌 테레프탈레이트를 포함하는 폴리에스텔 및 폴리아미드가 서로 분리할 수 없는 형태로 이루어진 폴리에스텔과 폴리아미드 혼성폐기물(이하 혼성폐기물이라 한다.)을 재활용하여 산가 1∼150mgKOH/g, 중량평균분자량 3,000∼50,000, 연화점 10∼150℃의 중합체를 괴상상태 또는 상용성, 용해성, 분산성이 좋은 액상의 폴리에스텔-아미드 수지 조성물 및 산가 20mgKOH/g 이상의 중합체는 염기성 화합물로 중화염을 만들어 수용성 폴리에스텔-아미드 수지 조성물을 제조하여 합성수지 미립자, 마이크로캡슐, 흡착제, 전자사진용 중합법 토너 결착제, 섬유 가공제, 제지 사이즈제 및 지력증강제, 폐수처리제, 분산제, 시멘트혼화제, 잉크젯 잉크 결착제, 에폭시 수지 경화제 및 개질제, 수분산 에폭시수지 경화제 및 개질제로 사용하고 산가 10mgKOH/g 이하의 괴상 또는 용액상 폴리에스텔-아미드 수지조성물은 인쇄잉크, 도료, 분체도료, 접착제, 핫멜트접착제, 분쇄법 토너의 결착제, 방수제, 불포화 폴리에스텔-아미드수지, 폴리우레탄수지 등의 산업상 유용한 재료로 활용될 수 있다.The present invention recycles polyester and polyamide hybrid wastes (hereinafter referred to as hybrid wastes) in which polyester and polyamide including polyethylene terephthalate are inseparable from each other, and has an acid value of 1 to 150 mg KOH / g, weight average. The polymer having a molecular weight of 3,000 to 50,000 and a softening point of 10 to 150 ° C. in a bulk state, or in a liquid polyester-amide resin composition having good compatibility, solubility, and dispersibility, and a polymer having an acid value of 20 mg KOH / g or higher form a neutral salt with a basic compound to form a water-soluble poly Preparation of ester-amide resin composition, synthetic resin fine particles, microcapsules, adsorbents, electrophotographic polymerization toner binders, textile processing agents, paper size agents and strength enhancers, wastewater treatment agents, dispersants, cement admixtures, inkjet ink binders, epoxy Used as resin curing agent and modifier, water-disperse epoxy resin curing agent and modifier, acid value 10mgKOH / g The bulk or solution polyester-amide resin composition below is an industrially useful material such as printing ink, paint, powder coating, adhesive, hot melt adhesive, binder of grinding method toner, waterproofing agent, unsaturated polyester-amide resin, polyurethane resin, etc. It can be used as.
Description
본 발명은 폴리에스텔 및 폴리아미드가 혼성되어 분리하기 불가능한 폴리에스텔과 폴리아미드 혼방섬유폐기물, 폐플라스틱 맥주병, 폐복합성형품 등의 폴리에스텔과 폴리아미드 혼성폐기물(이하 혼성 폐기물이라 한다)을 재활용하여 신소재용 폴리에스텔-아미드 수지조성물을 제조하는 방법에 관한 것이다. 근래 PET와 나일론으로 대표되는 폴리에스텔 및 폴리아미드가 플라스틱 소재로 섬유, PET병, 필름, 사출성형재로 광법위하게 사용되어 이들의 제조과정 및 사용 후에 발생되는 폐기물이 환경문제로 대두될 만큼 다량이나 이들을 재활용하는 양이 극히 제한적이고 또한 단순한 물리적으로만 열용융 처리하여 변형품을 만드는 기술수준이어서 재생품의 품질이 만족스럽지 못하여 재활용하는 양이 극히 제한적이었다. 특히 플라스틱 맥주병과 복합성형품은 폴리에스텔과 폴리아미드 혼성품임으로 전혀 재활용되지 않아 이들의 처리에 큰 문제가 되고 있으며 이를 해결할 방법이 간절히 요구되고 있는 실정이다. 더구나 고기능성 소재를 얻기 위한 연구 및 제조는 지금까지 이루어지지 않았다.The present invention recycles polyester and polyamide mixed waste (hereinafter referred to as hybrid waste) such as polyester and polyamide mixed fiber waste, waste plastic beer bottles, and waste composite molded products, which are incompatible with polyester and polyamide. A method for producing a polyester-amide resin composition for use. Recently, polyester and polyamide, represented by PET and nylon, are widely used as plastic materials for fibers, PET bottles, films, and injection molding materials, so that the wastes generated during the manufacturing process and their use are emerging as environmental problems. However, the amount of recycling them is extremely limited and the quality of the recycled products is extremely unsatisfactory because the quality of the regenerated products is not satisfactory because it is a technical level of making the transformed products by heat melting only simple physically. In particular, plastic beer bottles and composite molded products are mixed with polyester and polyamide, and thus are not recycled at all, which is a serious problem in their treatment, and there is an urgent need for a method to solve them. Moreover, research and manufacture to obtain high functional materials have not been made so far.
본 발명자들은 종래 기술의 제반 문제점을 해소하기 위하여 예의 연구한 결과 혼성폐기물을 물리적으로 분쇄한 후 해중합하고 축중합 반응을 일으켜서 괴상또는 액상의 원하는 물성의 중합체를 얻음으로서 고기능성과 고부가가치를 갖는 산업상 유용한 제품으로 탄생시킬 수 있다는 결론에 도달하여 본 발명을 완성하여 폴리에스텔-아미드수지 조성물을 제조하는 방법을 제공함에 그 목적이 있다.The present inventors have studied diligently to solve all the problems of the prior art, and as a result of physically pulverizing the mixed waste, depolymerizing and condensation-polymerizing the reaction to obtain a polymer having a desired physical property of a bulk or a liquid, it has a high functionality and high added value. It is an object to provide a method for producing a polyester-amide resin composition by completing the present invention to the conclusion that it can be produced as a useful product.
상기 기술적 과제를 달성하기 위하여 본 발명은 (1) 고체수지를 이용한 해중합 양태, (2) 다가알콜을 이용한 해중합 양태, (3) 다가알콜과 고체수지를 함께 이용한 해중합 양태, (4) 올리고머를 이용한 해중합 양태, (5) 지방산의 모노글리세리드 및 지방산의 모노알콜라이드를 이용한 해중합 양태로 개시되며In order to achieve the above technical problem, the present invention provides a method for (1) depolymerization using solid resin, (2) depolymerization using polyhydric alcohol, (3) depolymerization using polyhydric alcohol and solid resin, and (4) oligomer. Depolymerization embodiment, (5) a depolymerization embodiment using monoglyceride of fatty acid and monoalcohol of fatty acid,
상기 기술적 과제를 달성하기 위하여 제1 양태에서 본 발명은In order to achieve the above technical problem, the present invention provides a
(a) 혼성 폐기물을 고체 수지로 해중합하고 다염기산을 가하여 부가 반응시키는 단계(a) depolymerizing the hybrid waste into a solid resin and adding a polybasic acid for addition reaction
(b) 상기 해중합 생성물을 다가알콜과 중축합 반응시켜 산가 1∼150mgKOH/g의 폴리에스테르-아미드 중합체를 얻는 단계; 및(b) polycondensing the depolymerization product with a polyhydric alcohol to obtain a polyester-amide polymer having an acid value of 1 to 150 mgKOH / g; And
(c) 상기 폴리에스테르-아미드 중합체의 산가가 20mgKOH/g 이상인 경우에는 상기 폴리에스테르-아미드 중합체를 괴상 또는 용액 상태로 회수하고, 산가가 20mgKOH/g 이하인 경우에는 괴상 상태로 회수하는 단계를 포함하는 혼성폐기물의 재활용 방법을 제공한다. (c) recovering the polyester-amide polymer in a bulk or solution state when the acid value of the polyester-amide polymer is 20 mgKOH / g or more, and recovering it in a bulk state when the acid value is 20 mgKOH / g or less. Provides a method for recycling mixed waste.
상기 기술적 과제를 달성하기 위하여 제2 양태에서 본 발명은,In order to achieve the above technical problem, the present invention provides a second aspect,
(a) 혼성폐기물을 다가알콜과 반응시켜 해중합하고 폴리에스테르-아미드 해중합 생성물을 얻는 단계(a) reacting hybrid waste with polyhydric alcohol to depolymerize to obtain a polyester-amide depolymerization product
(b) 상기 해중합 생성물을 다염기산과 반응시킨 후, 다시 그 반응 생성물을 다가알콜과 중축합시켜 사슬말단에 2∼3개의 카르복실기를 갖는 산가 1∼150mgKOH/g의 폴리에스테르-아미드 중합체를 얻는 단계 및(b) reacting the depolymerization product with a polybasic acid, and then polycondensing the reaction product with a polyhydric alcohol to obtain a polyester-amide polymer having an acid value of 1 to 150 mgKOH / g having 2 to 3 carboxyl groups at the chain end;
(c) 상기 폴리에스테르-아미드 중합체를 염기성 화합물과 반응시켜 얻은 중화염 형태의 폴리에스테르-아미드 중합체를 물, 친수성 용매 또는 이들의 혼합용매에 분산시켜 수용성 및 수분산 폴리에스테르 용액을 얻는 단계를 포함하는 혼성폐기물의 재활용 방법을 제공한다.(c) dispersing the polyester-amide polymer in neutral salt form obtained by reacting the polyester-amide polymer with a basic compound in water, a hydrophilic solvent or a mixed solvent thereof to obtain a water-soluble and water-dispersible polyester solution. It provides a method of recycling mixed waste.
상기 기술적 과제를 달성하기 위하여 제3 양태에서 본 발명은,In order to achieve the above technical problem, the present invention provides a third aspect,
(a) 혼성폐기물을 다가알콜과 반응시켜 해중합하고 해중합 안정화 고형수지로 안정화된 폴리에스테르-아미드 해중합 생성물을 얻는 단계(a) reacting the mixed waste with polyhydric alcohol to depolymerize and obtain a polyester-amide depolymerization product stabilized with depolymerization stabilized solid resin
(b) 상기 해중합 생성물을 다염기산, DMSSIP(디메틸 5-술포이소프탈레이트 소디움솔트) 또는 이들의 혼합물과 중축합 반응시킨 후 다시 산가조절용 다가알콜을 첨가하여 폴리에스테르-아미드 중합체를 얻는 단계 및(b) polycondensation of the depolymerization product with polybasic acid, DMSSIP (dimethyl 5-sulfoisophthalate sodium salt) or a mixture thereof, and then adding a polyhydric alcohol for acid value adjustment to obtain a polyester-amide polymer; and
(c) 상기 폴리에스테르-아미드 중합체를 물에 용해시킨 수용액 상태, 친수성 유기 용매에 용해시킨 유기 용액 상태, 또는 괴상 상태로 회수하는 단계를 포함하는 혼성폐기물의 재활용 방법을 제공한다.(c) recovering the mixed waste comprising the step of recovering the polyester-amide polymer in an aqueous solution state dissolved in water, an organic solution state dissolved in a hydrophilic organic solvent, or a bulk state.
상기 기술적 과제를 달성하기 위하여 제4 양태에서 본 발명은, In order to achieve the above technical problem, the present invention provides a fourth aspect,
(a) 다가알콜과 DMSSIP를 포함하는 방향족 디카복실산의 설폰산 알카리금속염과 반응시켜 폴리에스테르 올리고머를 제조하는 단계;(a) reacting with a sulfonic acid alkali metal salt of an aromatic dicarboxylic acid including polyhydric alcohol and DMSSIP to prepare a polyester oligomer;
(b) 상기 폴리에스테르 올리고머를 혼성 폐기물와 반응시켜 상기 혼성 폐기물을 해중합시키고, 이어서 에스테르 교환반응을 동반하는 중축합에 의하여 폴리에스테르-아미드 중합체를 얻는 단계;(b) reacting the polyester oligomer with a hybrid waste to depolymerize the hybrid waste and then obtaining a polyester-amide polymer by polycondensation with a transesterification reaction;
(c) 상기 폴리에스테르-아미드 중합체를 물에 용해시킨 수용액 상태, 친수성 용매에 용해시킨 유기 용액 상태, 또는 괴상 상태로 회수하는 단계를 포함하는 혼성폐기물의 재활용 방법을 제공한다.(c) recovering the mixed waste comprising the steps of recovering the polyester-amide polymer in an aqueous solution state dissolved in water, an organic solution state dissolved in a hydrophilic solvent, or a bulk state.
상기 기술적 과제를 달성하기 위하여 제 5 양태에서 본 발명은The present invention in a fifth aspect to achieve the above technical problem
(a) 유지(Oil＆Fat)를 글리세린을 포함하는 다가알콜과 에스텔 교환 반응시켜 지방산의 모노글리세리드 및 지방산의 모노알콜라이드를 제조한 후 혼합폐기물을 가하여 해중합 시키는 단계;(A) esterification of the oil and fat (Oil & Fat) with a polyhydric alcohol containing glycerin to prepare a monoglyceride of fatty acids and monoalcohol of fatty acids, followed by depolymerization by adding mixed waste;
(b) 상기 해중합 조성물에 다염기산과 다가알콜을 가하여 축중합시켜 폴리에스텔 아미드 중합체를 포함하는 유지변성 알키드수지를 제조하는 단계;(b) adding polybasic acid and polyhydric alcohol to the depolymerization composition to condensate to prepare an oil-modified alkyd resin comprising a polyester amide polymer;
(c) 상기 폴리에스텔 아미드 중합체를 포함하는 유지변성 알키드 수지를 솔벤트나프사 및 키시렌 등 유기 용매에 용해시킨 유기용액 상태로 회수하는 단계를 포함하는 혼성 폐기물을 재활용하는 방법을 제공한다.(c) recovering the hybrid waste comprising recovering the oil-modified alkyd resin including the polyester amide polymer in an organic solution dissolved in an organic solvent such as solvent naphtha and xylene.
본 발명에 따른 혼성폐기물의 재활용 방법에 따르면, 혼성폐기물을 재활용 하여 액상 또는 고상의 상용성, 용해성, 분산성이 좋은 폴리에스테르-아미드 수지를 용이하게 얻을 수 있다. 상세하게는, 본 발명의 재활용 방법에 의하여 얻은 폴리에스테르-아미드 수지는 상용성 및 분산성이 우수하고 용해성 및 접착성이 우수하다. 따라서 본 발명에 의하여 재활용된 폴리에스텔-아미드 수지는 합성수지 미립자, 마이크로 캡슐, 흡착제, 전자사진용 중합법 토너 결착제, 섬유가공제, 제지 사이즈제 및 지력증강제, 폐수처리제, 시멘트혼화제, 잉크젯 잉크 결착제, 에폭시 수지 경화제 및 개질제, 수분산 에폭시수지 경화제 및 개질제, 인쇄잉크, 도료, 분체도료, 접착제, 핫멜트 접착제, 분쇄법 토너의 결착제, 방수제, 가교경화형 불포화폴리에스텔-아미드 수지, 폴리우레탄 수지등의 산업상 유용한 재료로 이용될 수 있다.According to the method for recycling mixed waste according to the present invention, it is possible to easily obtain a polyester-amide resin having good compatibility, solubility, and dispersibility in a liquid or solid phase by recycling the mixed waste. In detail, the polyester-amide resin obtained by the recycling method of the present invention is excellent in compatibility and dispersibility and excellent in solubility and adhesion. Therefore, the polyester-amide resin recycled according to the present invention is a synthetic resin fine particles, microcapsules, adsorbents, electrophotographic polymerization toner binder, fiber processing agent, paper size agent and strength enhancer, wastewater treatment agent, cement admixture, inkjet ink binder Agent, epoxy resin curing agent and modifier, water dispersion epoxy resin curing agent and modifier, printing ink, paint, powder coating, adhesive, hot melt adhesive, binder of grinding method toner, waterproofing agent, crosslinking curing type unsaturated polyester-amide resin, polyurethane resin It can be used as industrially useful materials such as.
이어서, 본 발명의 각 양태에 따른 혼성폐기물의 재활용방법에 대하여 상세하게 설명한다.Next, the recycling method of the mixed waste which concerns on each aspect of this invention is demonstrated in detail.
먼저, 본 발명의 제1 양태에 따른 혼성폐기물의 재활용방법에 대하여 설명한다.First, the recycling method of the mixed waste according to the first aspect of the present invention will be described.
본 발명의 제1 양태에 따른 혼성폐기물의 재활용 방법은,Recycling method of the mixed waste according to the first aspect of the present invention,
(a) 혼성폐기물을 해중합 시키는 단계(a) depolymerizing hybrid waste
(b) 상기 해중합 생성물을 다가알콜과 중축합 반응시켜 산가 1∼150mgKOH/g의 폴리에스테르-아미드 중합체를 얻는 단계 및(b) polycondensing the depolymerization product with a polyhydric alcohol to obtain a polyester-amide polymer having an acid value of 1 to 150 mg KOH / g; and
(c) 상기 폴리에스테르-아미드 중합체의 산가가 20mgKOH/g 이상인 경우에는 상기 폴리에스테르-아미드 중합체를 괴상 또는 용액 상태로 회수하고, 산가가 20mgKOH/g 이하인 경우에는 괴상 상태로 회수하는 단계를 포함한다.(c) recovering the polyester-amide polymer in a bulk or solution state when the acid value of the polyester-amide polymer is 20 mgKOH / g or more, and recovering it in a bulk state when the acid value is 20 mgKOH / g or less. .
상기 (a) 단계는 수거된 혼성폐기물을 해중합시키는 단계이다. 즉, 혼성폐기물을 물리적으로 분쇄한 후 질소가스와 같은 불활성 가스 분위기중에서 용융시킨 후, 고체수지 용해제와 반응시켜 1차 해중합시킨다. 상기 고체수지 용해제 분자구조내의 아비에틴산 (Abietic acid), 피마릭산 (Pimaric acid), 복합수지산 등의 공액 결합과 같은 반응성 관능기를 갖는 성분들이 혼성폐기물중의 에스테르 결합 및 아미드 결합과 반응하여 주쇄를 절단하여 혼성폐기물을 해중합시켜 그의 분자량을 저하시킨다. 본 발명에서 사용될 수 있는 고체수지 용해제의 구체적인 예는 검 로진, 우드 로진, 탈로진, 수첨로진, 말레인화 로진, 로진 에스테르, 피넨 수지, 디펜텐 수지, C5계 석유수지, C9계 석유수지, 대비(dammar)수지, 코팔(copal) 수지, DCPD수지, 수첨 DCPD수지, 말레인화 스티렌수지, 또는 이들의 혼합물을 들 수 있으나, 이에 한정되는 것은 아니다.Step (a) is a step of depolymerizing the collected mixed waste. That is, the mixed waste is physically pulverized and then melted in an inert gas atmosphere such as nitrogen gas, and then reacted with the solid resin solubilizer to primary depolymerization. Components having a reactive functional group such as conjugated bonds such as abietic acid, pimaric acid, complex resin acid, etc. in the molecular structure of the solid resin solubilizer react with ester bonds and amide bonds in the hybrid waste. The main chain is cleaved to depolymerize the hybrid waste to lower its molecular weight. Specific examples of solid resin solubilizers that can be used in the present invention include gum rosin, wood rosin, deloginate, hydrogenated rosin, maleated rosin, rosin ester, pinene resin, dipentene resin, C5 petroleum resin, C9 petroleum resin, It may include, but is not limited to, dammar resins, copal resins, DCPD resins, hydrogenated DCPD resins, maleated styrene resins, or mixtures thereof.
상기 고체수지 용해제 대 상기 혼성폐기물의 혼합비는 중량비를 기준으로 1:10 ∼ 10:1인 것이 바람직하다. 상기 혼합비가 1:10 미만이면 해중합 불량의 문제점이 있고, 10:1을 초과하면 내열성 및 기계적 물성 불량의 문제점이 있다.The mixing ratio of the solid resin solubilizer to the mixed waste is preferably 1:10 to 10: 1 based on the weight ratio. If the mixing ratio is less than 1:10, there is a problem of poor depolymerization, and if it exceeds 10: 1, there is a problem of poor heat resistance and mechanical properties.
이어서, 고유점도 조절 및 분자량 조절을 위하여 상기 해중합 생성물을 다염기산과 반응시켜 2차 해중합 및 부가반응(Diels-Alder Reaction)을 더욱 일으킨다. 본 발명에서 사용될 수 있는 다염기산의 구체적인 예는 무수프탈산, 이소프탈산, 테레프탈산, 아디픽산, 아제라인산, 세바신산, 무수테트라하이드로프탈산, 무수말레인산, 푸말산, 이타콘산, 트리멜리트산, 무수트리멜리트산, 무수피로멜리트산, 숙신산, 사이클로헥산디카복실산, 나프탈렌 디카복실산, 다이머산, C6∼C25지방산, 또는 이들의 혼합물을 포함하지만, 이에 한정되는 것은 아니다. Subsequently, the depolymerization product is reacted with polybasic acid to further induce secondary depolymerization and dies-alder reaction for controlling intrinsic viscosity and molecular weight. Specific examples of the polybasic acid which can be used in the present invention include phthalic anhydride, isophthalic acid, terephthalic acid, adipic acid, azeline acid, sebacic acid, tetrahydrophthalic anhydride, maleic anhydride, fumaric acid, itaconic acid, trimellitic acid, and trimellitic anhydride. , Pyromellitic anhydride, succinic acid, cyclohexanedicarboxylic acid, naphthalene dicarboxylic acid, dimer acid, C6 to C25 fatty acid, or mixtures thereof, but is not limited thereto.
상기 다염기산은 상기 1차 해중합 생성물의 중량을 기준으로 1∼70중량% 사용되는 것이 바람직하다. 상기 사용량이 1중량% 미만이면 고융점 중합체 생성으로 개질불량의 문제점이 있고, 70중량%를 초과하면 다량의 다가알콜의 소요에 의한 경제성의 문제점이 있다.The polybasic acid is preferably used 1 to 70% by weight based on the weight of the first depolymerization product. If the amount is less than 1% by weight, there is a problem of poor reforming due to the production of high melting point polymer, and if it exceeds 70% by weight, there is a problem of economics due to the requirement of a large amount of polyhydric alcohol.
상기 (b) 단계는 이전 (a) 단계의 해중합 생성물을 다가알콜과 중축합 반응시켜 산가를 조절하고 분자량을 증가시키는 단계이다.Step (b) is a step of polycondensation reaction of the depolymerization product of step (a) with polyhydric alcohol to adjust the acid value and increase the molecular weight.
본 발명에서 사용될 수 있는 다가알콜의 구체예는 에틸렌글리콜, 프로필렌 글리콜, 1, 3-프로판디올, 1,4-부탄디올, 1,6-헥산디올, 네오펜틸 글리콜, 디에틸렌 글리콜, 디프로필렌 글리콜, 폴리에틸렌 글리콜, 비스페놀 A의 알킬렌옥사이드 부가물, 트리메틸올 프로판, 글리세린, 펜타에리쓰리톨, 지방산의 모노글리세리드 및 지방산의 모노다가알콜라이드 또는 이들의 혼합물을 포함하지만, 이에 한정되는 것은 아니다.Specific examples of polyhydric alcohols that can be used in the present invention include ethylene glycol, propylene glycol, 1, 3-propanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, Polyethylene glycols, alkylene oxide adducts of bisphenol A, trimethylol propane, glycerin, pentaerythritol, monoglycerides of fatty acids and monopolyhydralcolides of fatty acids, or mixtures thereof.
다가 알콜의 사용량은 상기 (a) 단계의 해중합 생성물의 중량을 기준으로 1∼70중량%인 것이 바람직하다. 1중량% 미만이면 고융점 중합체 생성으로 개질불량의 문제점이 있고, 70 중량%를 초과하면 고분자량 중합체가 생성되어 수용성 또는 수분산성 불량의 문제점이 있다.The amount of the polyhydric alcohol is preferably 1 to 70% by weight based on the weight of the depolymerization product of step (a). If it is less than 1% by weight, there is a problem of poor modification due to the production of a high melting point polymer, and if it exceeds 70% by weight, a high molecular weight polymer is generated, thereby causing a problem of poor water solubility or water dispersibility.
이때 얻어진 폴리에스테르-아미드 중합체의 산가는 1∼150mgKOH/g으로 조절되는 것이 수용성 및 수분산성의 측면에서 바람직하다. 산가가 1mgKOH/g 미만이면 수용성 및 수분산성 불량의 문제점이 있고, 산가가 150mgKOH/g를 초과하면 접착성, 화학적 물성, 전기적 물성의 문제점이 있다. The acid value of the polyester-amide polymer obtained at this time is preferably adjusted to 1 to 150 mgKOH / g from the viewpoint of water solubility and water dispersibility. If the acid value is less than 1mgKOH / g, there is a problem of poor water solubility and water dispersibility, and if the acid value exceeds 150mgKOH / g, there are problems of adhesion, chemical properties, and electrical properties.
상기 (a), (b) 단계의 반응은 모두 용융상태의 괴상에서 진행되는데, 반응물 전체의 중량을 기준으로 0.05∼0.5중량%의 DBTO과 같은 반응촉매의 존재하에서 진행되는 것이 반응속도를 촉진하는 측면에서 바람직하다. 또한 상기 (a), (b) 단계는 200∼250℃의 온도범위에서 실시되는 것이 바람직하다. 반응온도가 200℃ 미만이면 반응속도 지연 및 저분자량 중합체 생성의 문제점이 있고, 250℃를 초과하면 산화 반응 및 고분자량 중합체 생성의 문제점이 있다.The reactions of steps (a) and (b) all proceed in a molten mass, which is carried out in the presence of a reaction catalyst such as 0.05 to 0.5% by weight of DBTO based on the total weight of the reactants. It is preferable in terms of. In addition, the steps (a), (b) is preferably carried out in a temperature range of 200 ~ 250 ℃. If the reaction temperature is less than 200 ℃ there is a problem of the reaction rate delay and low molecular weight polymer production, if it exceeds 250 ℃ there is a problem of the oxidation reaction and high molecular weight polymer production.
상기 (b) 단계에서 얻어진 폴리에스테르-아미드 중합체는 중량 평균분자량이 3,000∼50,000이고, 연화점이 10∼150℃이 되도록 조절되는 것이 접착성, 기계적 물성의 측면에서 바람직하다.The polyester-amide polymer obtained in step (b) has a weight average molecular weight of 3,000 to 50,000 and a softening point of 10 to 150 ° C. is preferably adjusted in terms of adhesiveness and mechanical properties.
이렇게 하여 얻어진 폴리에스테르-아미드 중합제의 산가가 20mgKOH/g 이상인 경우에는 상기 폴리에스테르-아미드 중합체를 괴상으로 회수할 수 있을 뿐만 아니라 용도에 맞는 충분할 수용성을 얻을 수 있으므로 수용액, 친수성 유기용매 또는 이들의 혼합용매에 용해시킨 용액 상태로도 회수할 수 있다. 반대로, 상기 폴리에스테르-아미드 중합체의 산가가 20mgKON/g 이하인 경우에는 충분한 수용성을 얻을 수 없으므로 수용액 상태로는 회수할 수 없고 용도에 따라 고체 상태로 사용하거나 용매에 용해시켜 사용하기 위하여 괴상 상태로 회수하는 것이 바람직하다.In the case where the acid value of the polyester-amide polymerizer thus obtained is 20 mgKOH / g or more, the polyester-amide polymer can be recovered not only in bulk but also sufficient water solubility can be obtained for the intended use, so that an aqueous solution, a hydrophilic organic solvent or It can collect | recover also in the solution state dissolved in the mixed solvent. On the contrary, when the acid value of the polyester-amide polymer is 20 mgKON / g or less, sufficient water solubility cannot be obtained, so that it cannot be recovered in an aqueous state, and can be recovered in a solid state or used in a solid state or dissolved in a solvent depending on the purpose. It is desirable to.
(c) 단계에서 폴리에스테르-아미드 중합체를 용액 상태로 회수하는 경우에는 바람직하게는 다음과 같은 단계에 의하여 용액화 될 수 있다.In the case of recovering the polyester-amide polymer in solution in step (c), it may be preferably liquefied by the following steps.
즉, 먼저 (b) 단계에서 얻어진 산가 20mgKOH/g 이상의 폴리에스테르-아미드 중합체를 염기성 화합물과 반응시켜 중화염 형태의 폴리에스테르-아미드 중합체를 얻는다. 중화 프로세스에서 폴리에스테르-아미드 중합체 내에 존재하는 카르복실기는 해당 중화염 구조로 전환되어 수용성이 증가된다. 본 발명에서 사용될 수 있는 염기성 화합물의 구체예는 수산화나트륨, 수산화칼륨, 수산화암모늄, 수산화 리튬, 유기 아민 또는 이들의 혼합물을 포함하지만, 이에 한정되는 것은 아니다. 상기 염기성 화합물의 사용량은 상기 폴리에스테르-아미드 중합체의 중량을 기준으로 3∼30중량% 인 것이 바람직하다. 염기성 화합물의 사용량이 3중량% 미만이면 수용성 또는 수분산성 불량의 문제점이 있고, 30중량%를 초과하면 접착성, 화학적 물성, 전기적 물성의 문제점이 있다.That is, first, the polyester-amide polymer having an acid value of 20 mg KOH / g or more obtained in step (b) is reacted with a basic compound to obtain a polyester-amide polymer in a neutral salt form. In the neutralization process, the carboxyl groups present in the polyester-amide polymer are converted to the corresponding neutral salt structure to increase water solubility. Specific examples of basic compounds that can be used in the present invention include, but are not limited to, sodium hydroxide, potassium hydroxide, ammonium hydroxide, lithium hydroxide, organic amines or mixtures thereof. It is preferable that the usage-amount of the said basic compound is 3-30 weight% based on the weight of the said polyester-amide polymer. If the amount of the basic compound is less than 3% by weight, there is a problem of poor water solubility or water dispersibility, and if it exceeds 30% by weight, there is a problem of adhesiveness, chemical properties, and electrical properties.
상기 중화된 폴리에스테르-아미드 중합체를 물, 친수성 용매 또는 이들의 혼합용매에 용해시키면 폴리에스테르 수용액 또는 폴리에스테르 유기용액을 얻을 수 있다. 본 발명에서 사용될 수 있는 친수성 용매의 구체예는 알콜류, 에테르류, 아세톤, 디아세톤알콜, 디메틸포름아미드, 디메틸아세트아미드, 테트라하이드로푸란, 에틸셀솔브, 프로필셀솔브, 부틸셀솔브, N-메틸-2-피롤리돈 또는 이들의 혼합물을 포함하지만, 이에 한정되는 것은 아니다.When the neutralized polyester-amide polymer is dissolved in water, a hydrophilic solvent or a mixed solvent thereof, an aqueous polyester solution or a polyester organic solution can be obtained. Specific examples of hydrophilic solvents that can be used in the present invention include alcohols, ethers, acetone, diacetone alcohol, dimethylformamide, dimethylacetamide, tetrahydrofuran, ethyl cell solve, propyl cell solve, butyl cell solve, N-methyl 2-pyrrolidone or mixtures thereof, but is not limited thereto.
상기 물, 친수성 용매 또는 이들의 혼합용매는, 상기 중화된 폴리에스테르-아미드 중합체의 중량을 기준으로 1∼10배 사용되는 것이 바람직하다. 용매의 사용량이 1배 미만이면 작업성의 문제점이 있고, 10배를 초과하면 용액이 과다하게 희석되어 접착성, 효율성의 문제점이 있다.The water, the hydrophilic solvent or a mixed solvent thereof is preferably used 1 to 10 times based on the weight of the neutralized polyester-amide polymer. If the amount of the solvent is less than 1 times, there is a problem of workability, if more than 10 times the solution is excessively diluted, there is a problem of adhesion, efficiency.
이어서, 본 발명의 제2 양태에 따른 혼성폐기물의 재활용방법에 대하여 설명한다. Next, a method for recycling the mixed waste according to the second aspect of the present invention will be described.
먼저, 혼성폐기물을 다가알콜과 반응시켜 해중합한다. 상기 다가 알코올의 히드록실기는 혼성폐기물중의 에스테르 결합과 반응하여 주쇄를 절단하여 혼성폐기물을 해중합시켜 그의 분자량을 저하시킨다. 본 발명의 제2 양태에서 사용될 수 있는 다가알콜의 구체예는 에틸렌글리콜, 프로필렌글리콜, 1,3-프로판디올, 1,4-부탄디올, 1,6-헥산디올, 네오펜틸 글리콜, 디에틸렌 글리콜, 디프로필렌 글리콜, 폴리에틸렌 글리콜, 비스페놀 A의 알킬렌옥사이드 부가물, 트리메틸올 프로판, 글리세린, 펜타에리쓰리톨, 지방산모노글리세리드 및 지방산모노다가알콜라이드 또는 이들의 혼합물을 포함하나, 이에 한정되는 것은 아니다.First, the hybrid waste is depolymerized by reacting with polyhydric alcohol. The hydroxyl group of the polyhydric alcohol reacts with the ester bond in the hybrid waste to break the main chain to depolymerize the hybrid waste to lower its molecular weight. Specific examples of the polyhydric alcohols that may be used in the second aspect of the present invention include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, Dipropylene glycol, polyethylene glycol, alkylene oxide adducts of bisphenol A, trimethylol propane, glycerin, pentaerythritol, fatty acid monoglycerides and fatty acid monopolyalcolides or mixtures thereof.
이어서, 상기 해중합 생성물을 다염기산과 반응시킨 후, 다시 그 반응 생성물을 다가알콜과 중축합시켜 사슬말단에 2∼3개의 카르복실기를 갖는 산가 1∼150mgKOH/g의 폴리에스테르-아미드 중합체를 얻는다.Subsequently, the depolymerization product is reacted with a polybasic acid, and then the reaction product is polycondensed with a polyhydric alcohol, thereby obtaining a polyester-amide polymer having an acid value of 1 to 150 mgKOH / g having 2 to 3 carboxyl groups at the chain end.
본 발명의 제2 양태의 재활용 방법에서 사용될 수 있는 다염기산의 구체예는 무수프탈산, 이소프탈산, 테레프탈산, 아디픽산, 아제라인산, 세바신산, 무수테트라하이드로프탈산, 무수말레인산, 푸말산, 이타콘산, 트리멜리트산, 무수트리멜리트산, 무수피로멜리트산, 숙신산, 사이클로헥산디카복실산, 나프탈렌 디카복실산, 다이머산, C6∼C25지방산 또는 이들의 혼합물을 포함하지만, 이에 한정되는 것은 아니다. 상기 다염기산은, 이전 단계의 해중합 생성물의 중량을 기준으로 1∼50중량% 사용되는 것이 바람직하다. 상기 사용량이 1중량% 미만이면 고융점 중합체 생성으로 개질불량의 문제점이 있고, 50중량%를 초과하면 다량의 다가알콜의 소요에 의한 경제성의 문제점이 있다. Specific examples of the polybasic acid that can be used in the recycling method of the second aspect of the present invention include phthalic anhydride, isophthalic acid, terephthalic acid, adipic acid, azaline acid, sebacic acid, tetrahydrophthalic anhydride, maleic anhydride, fumaric acid, itaconic acid, triacid Mellitic acid, trimellitic anhydride, pyromellitic anhydride, succinic acid, cyclohexanedicarboxylic acid, naphthalene dicarboxylic acid, dimer acid, C6 to C25 fatty acid, or mixtures thereof, are not limited thereto. The polybasic acid, preferably 1 to 50% by weight based on the weight of the depolymerization product of the previous step. If the amount is less than 1% by weight, there is a problem of poor modification due to the production of high melting point polymer, and if it exceeds 50% by weight, there is a problem of economics due to the requirement of a large amount of polyhydric alcohol.
이어서, 상기 폴리에스테르-아미드 중합체를 염기성 화합물과 반응시켜 물 또는 친수성 유기용매에 대한 용해성이 증가된 중화염 형태의 폴리에스테르-아미드 중합체를 얻는다. 본 발명의 제2 양태의 재활용 방법에서 사용될 수 있는 염기성 화합물의 구체예는 수산화나트륨, 수산화칼륨, 수산화암모늄, 수산화 리튬, 유기 아민 또는 이들의 혼합물을 포함하지만, 이에 한정되는 것은 아니다. 상기 염기성 화합물은 상기 폴리에스테르-아미드 중합체의 중량을 기준으로 1∼30중량% 사용되는 것이 바람직하다. 1중량% 미만이면 물 또는 친수성 유기용매와 물의 혼합용매에 대한 용해성이 불충분한 문제점이 있고 30중량%를 초과하면 접착성 불량 및 화학적 물성, 전기적 물성의 문제점이 있다.The polyester-amide polymer is then reacted with a basic compound to obtain a polyester-amide polymer in neutral salt form with increased solubility in water or hydrophilic organic solvents. Specific examples of basic compounds that can be used in the recycling method of the second aspect of the present invention include, but are not limited to, sodium hydroxide, potassium hydroxide, ammonium hydroxide, lithium hydroxide, organic amines or mixtures thereof. The basic compound is preferably used 1 to 30% by weight based on the weight of the polyester-amide polymer. If it is less than 1% by weight, there is a problem of insufficient solubility in water or a mixed solvent of hydrophilic organic solvent and water, and if it exceeds 30% by weight, there is a problem in poor adhesion, chemical properties, and electrical properties.
이어서, 상기 중화염 형태의 폴리에스테르-아미드 중합체를 물, 친수성용매 또는 이들의 혼합용매에 분산시킴으로써 최종적으로 혼성폐기물을 수용성 및 수분산 폴리에스테르-아미드 용액의 형태로 회수할 수 있다. 본 발명의 제2 양태에 따른 재활용 방법에서 사용될 수 있는 친수성 용매의 구체예는 알콜류, 아세톤, 디아세톤알콜, 디메틸포름아미드, 디메틸아세트아미드, 에틸셀솔브, 프로필셀솔브, 부틸셀솔브, 테트라하이드로푸란, N-메틸-2-피롤리돈 또는 이들의 혼합물을 포함하지만, 이에 한정되는 것은 아니다.Subsequently, the mixed waste can be finally recovered in the form of a water-soluble and water-dispersible polyester-amide solution by dispersing the polyester-amide polymer in the neutralized salt form in water, a hydrophilic solvent or a mixed solvent thereof. Specific examples of hydrophilic solvents that can be used in the recycling method according to the second aspect of the present invention include alcohols, acetone, diacetone alcohol, dimethylformamide, dimethylacetamide, ethylcellsolve, propylcellsolve, butylcellsolve, tetrahydro Furan, N-methyl-2-pyrrolidone or mixtures thereof, but is not limited thereto.
상기 친수성 용매의 사용량은 상기 중화염 형태의 폴리에스테르-아미드 중합체의 중량을 기준으로 1∼100중량% 인 것이 바람직하다. 상기 용매의 사용량이 1중량% 미만이면 용해불량의 문제점이 있고, 100중량%를 초과하면 환경 및 경제성의 문제점이 있다. 또한 본 발명의 제 2양태의 응용으로 혼성폐기물을 해중합시켜 얻은 생성물에 다염기산과 다가알콜을 반응시켜 산가 1∼10mgKOH/g, 히드록실가 5∼200mgKOH/g인 폴리에스텔아미드 폴리올을 만들고 여기에 디이소시아네이트를 가하여 반응시켜 폴리우레탄 수지를 얻고 또한 폴리에스텔 아미드 중합체에 중합금지제가 함유된 에틸렌성 비닐단량체를 가하여 용해시켜 가교경화형 불포화 폴리에스텔 아미드 수지를 얻을 수 있다.The amount of the hydrophilic solvent is preferably 1 to 100% by weight based on the weight of the polyester-amide polymer in the neutralized salt form. If the amount of the solvent is less than 1% by weight, there is a problem of dissolution, and if the amount of the solvent exceeds 100% by weight, there is a problem of environmental and economical efficiency. In addition, according to the second aspect of the present invention, a polybasic acid and a polyalcohol are reacted with a product obtained by depolymerization of a mixed waste to produce a polyesteramide polyol having an acid value of 1 to 10 mgKOH / g and a hydroxyl value of 5 to 200 mgKOH / g. Isocyanate may be added to react to obtain a polyurethane resin, and an ethylenic vinyl monomer containing a polymerization inhibitor may be added to and dissolved in the polyester amide polymer to obtain a crosslinkable unsaturated polyester amide resin.
이어서, 본 발명의 제3 양태에 따른 혼성폐기물의 재활용방법에 대하여 설명한다.Next, a method for recycling the mixed waste according to the third aspect of the present invention will be described.
먼저, 상기 제2 양태의 재활용 방법에서 설명한 방법과 동일한 방법에 따라 혼성폐기물을 다가알콜과 반응시켜 해중합하고 폴리에스테르-아미드 해중합 생성물을 얻는다.First, the hybrid waste is reacted with polyhydric alcohol according to the same method as described in the recycling method of the second aspect to depolymerize to obtain a polyester-amide depolymerization product.
이어서 위의 해중합된 폴리에스테르-아미드 해중합 생성물을 해중합 안정화 고형수지와 반응시켜 에스테르 교환 반응 으로부터 안정화된 폴리에스테르-아미드 해중합 생성물을 얻는다. 해중합 안정화 고형수지는 중합도 조절 특성 때문에 폴리에스테르-아미드 해중합 생성물을 가역반응으로부터 안정화시킬 수 있다. 본 발명의 제2 태양에서 사용될 수 있는 해중합 안정화 고형수지의 구체예는, 검 로진, 우드 로진, 탈로진, 수첨로진, 말레인화 로진, 로진 에스테르, 피넨 수지, 디펜텐 수지, C5계 석유수지, C9계 석유수지, 대머(dammar)수지, 코팔(copal) 수지, DCPD수지, 수첨 DCPD수지, 말레인화스티렌수지 또는 이들의 혼합물을 포함하지만, 이에 한정되는 것은 아니다. 해중합 안정화 고형수지의 사용량은 해중합 생성물의 중량을 기준으로 1∼100중량% 인 것이 바람직하다. 상기 사용량이 1중량% 미만이면 고유점도 및 중합도 조절의 문제점이 있고, 상기 사용량이 100 중량%를 초과하면 내열성 및 기계적 성질의 문제점이 있다.The above depolymerized polyester-amide depolymerization product is then reacted with a depolymerization stabilized solid resin to obtain a stabilized polyester-amide depolymerization product from the transesterification reaction. Depolymerization stabilized solid resins can stabilize polyester-amide depolymerization products from reversible reactions due to polymerization degree control properties. Specific examples of the depolymerized stabilized solid resin that can be used in the second aspect of the present invention include gum rosin, wood rosin, thalose rosin, hydrogenated rosin, maleated rosin, rosin ester, pinene resin, dipentene resin, C5 petroleum resin , C9 type petroleum resin, dammar resin, copal resin, DCPD resin, hydrogenated DCPD resin, maleic styrene resin or mixtures thereof, but is not limited thereto. The amount of the depolymerized stabilized solid resin is preferably 1 to 100% by weight based on the weight of the depolymerized product. If the amount is less than 1% by weight, there is a problem of intrinsic viscosity and polymerization degree control, and if the amount is more than 100% by weight, there is a problem of heat resistance and mechanical properties.
이어서, 상기 해중합 생성물을 다염기산, DMSIP(디메틸 5-술포이소프탈레이트의 소디움솔트) 또는 이들의 혼합물과 중축합 반응시킨다. 이때 사용될 수 있는 다염기산의 구체예 및 그 사용량은 제2 양태의 경우와 동일하다. DMSIP는 수용성 또는 수분산성 촉진을 위하여 사용되는데, DMSIP가 다염기산과 혼합되어 사용되는 경우, DMSIP는 다염기산의 중량을 기준으로 1∼30 중량% 혼합되는 것이 바람직하다. DMSIP의 사용량이 1 중량% 미만이면 DMSIP 사용효과를 실질적으로 얻을 수 없고, DMSIP의 사용량이 30중량%를 초과하면 내수성 및 화학적 물성, 전기적 물성의 문제점이 있다.The depolymerization product is then polycondensed with polybasic acid, DMSIP (sodium salt of dimethyl 5-sulfoisophthalate) or mixtures thereof. Specific examples of the polybasic acid which can be used at this time and the amount of use thereof are the same as in the second embodiment. DMSIP is used to promote water solubility or water dispersibility. When DMSIP is used in combination with polybasic acid, DMSIP is preferably mixed in an amount of 1 to 30% by weight based on the weight of the polybasic acid. If the amount of DMSIP is less than 1% by weight, the effect of using DMSIP cannot be substantially obtained. If the amount of DMSIP is more than 30% by weight, there is a problem in water resistance, chemical properties, and electrical properties.
계속해서, 상기 결과물에 산가조절용 다가알콜을 첨가하여 더욱 중축합반응시킴으로써 폴리에스테르-아미드 중합체를 얻는다. 이때 사용될 수 있는 다가알콜의 구체예는 제2 양태의 경우와 동일하다.Subsequently, an acid value-controlled polyhydric alcohol is added to the resultant to further polycondensate to obtain a polyester-amide polymer. Specific examples of the polyhydric alcohol that may be used at this time are the same as those of the second embodiment.
이어서, 상기 폴리에스테르-아미드 중합체를 물, 친수성 유기용매 또는 이들의 혼합용매에 용해시킴으로써 수용액 상태, 친수성 유기용매에 용해된 유기 용액 상태, 또는 괴상 상태로 회수한다. 이때 사용될 수 있는 친수성 유기용매의 구체예 및 사용량은 제2 양태의 재활용방법의 경우와 동일하다. 이어서, 본 발명의 제4 양태에 따른 혼성폐기물의 재활용방법에 대하여 설명한다.Subsequently, the polyester-amide polymer is dissolved in water, a hydrophilic organic solvent or a mixed solvent thereof, and recovered in an aqueous solution state, in an organic solution state dissolved in a hydrophilic organic solvent, or in a bulk state. At this time, the specific examples and the amount of the hydrophilic organic solvent that can be used are the same as in the recycling method of the second aspect. Next, a method for recycling the mixed waste according to the fourth aspect of the present invention will be described.
먼저, DMSIP를 포함하는 방향족 디카르복실산의 설폰산 알카리금속염 잔기가 함유된 폴리에스테르 올리고머를 제조한다. 이 폴리에스테르 올리고머는 통상적인 폴리에스테르 제조방법인 에스테르 교환반응법 또는 직접 에스테르화법을 통하여 제조될 수 있다. 생성된 폴리에스테르-아미드 중합체의 물 또는 친수성 용매와 물의 혼합용매에 대한 용해성을 증가시키기 위하여 DMSIP를 포함하는 방향족 디카르복실산의 설폰산 알카리금속염이 혼합되어 사용된다. 이때, 방향족디카르복실산의 설폰산 알카리금속염의 사용량은 다 염기산의 중량을 기준으로 1∼30중량% 혼합되는 것이 바람직하다. 상기 사용량이 1 중량% 미만이면 방향족 디카르복실산의 설폰산 알카리금속염 첨가효과를 실질적으로 얻을 수 없고, 30 중량%를 초과하면 얻어지는 폴리에스테르-아미드의 열적 및 기계적 물성이 실용적 목적에 불충분한 문제점이 있다.First, polyester oligomers containing sulfonic acid alkali metal salt residues of aromatic dicarboxylic acids comprising DMSIP are prepared. This polyester oligomer may be prepared through a transesterification method or a direct esterification method which is a conventional polyester production method. In order to increase the solubility of the resulting polyester-amide polymer in water or a mixed solvent of hydrophilic solvent and water, sulfonic acid alkali metal salts of aromatic dicarboxylic acids including DMSIP are used in combination. At this time, it is preferable that the usage-amount of the sulfonic-acid alkali metal salt of aromatic dicarboxylic acid is mixed with 1-30 weight% based on the weight of polybasic acid. If the amount is less than 1% by weight, the effect of adding sulfonic acid alkali metal salt of aromatic dicarboxylic acid may not be substantially obtained. If the amount is more than 30% by weight, thermal and mechanical properties of the obtained polyester-amide are insufficient for practical purposes. There is this.
이어서, 상기 방향족 디카르복실산의 설폰산 알카리 금속염 잔기가 함유된 폴리에스테르 올리고머를 혼성폐기물과 반응시켜 상기 혼성폐기물을 해중합시킨다. 반응을 계속 진행시키면 에스테르 교환반응을 동반하는 중축합에 의하여 물 또는 친수성 용매와 물의 혼합 용매에 대한 용해성이 증가된 폴리에스테르-아미드 중합체를 얻을 수 있다.The polyester oligomer containing the sulfonic acid alkali metal salt residue of the aromatic dicarboxylic acid is then reacted with the hybrid waste to depolymerize the hybrid waste. By continuing the reaction, it is possible to obtain a polyester-amide polymer having increased solubility in water or a mixed solvent of water and a hydrophilic solvent by polycondensation accompanied by a transesterification reaction.
마지막으로, 상기 폴리에스테르-아미드 중합체를 물, 친수성용매 또는 이들의 혼합용매에 용해시킨 수용액 또는 친수성 유기 용액으로 회수한다. 이때 사용될 수 있는 친수성 용매의 구체예 및 그 사용량은 제2 양태에 따른 재활용방법과 동일하다. 한편, 중축합 반응이 완료된 후, 상기 폴리에스테르-아미드 중합체를 그대로 괴상 상태로도 회수할 수 있는 것은 물론이다. Finally, the polyester-amide polymer is recovered in an aqueous solution or a hydrophilic organic solution dissolved in water, a hydrophilic solvent or a mixed solvent thereof. At this time, the specific examples of the hydrophilic solvent that can be used and the amount thereof are the same as the recycling method according to the second aspect. On the other hand, after the polycondensation reaction is completed, it is a matter of course that the polyester-amide polymer can be recovered in the form of a bulk as it is.
이어서 본 발명의 제 5양태에 따른 혼성 폐기물의 재활용 방법에 대하여 설명한다.Next, a recycling method of the mixed waste according to the fifth aspect of the present invention will be described.
먼저 유지(Oil＆Fat)를 글리세린을 포함하는 다가알콜과 에스텔 교환 반응을 시켜 지방산의 모노글리세리드 또는 지방산의 모노다가알콜라이드를 제조한다. 생성된 지방산의 모노글리세리드 또는 지방산의 모노다가알콜라이드에 혼성 폐기물을 가하여 반응시켜 해중합 생성물을 얻는다. 이어서 상기 해중합 생성물에 다염기산을 가하여 중축합 시킨후 다가알콜을 가하여 산가조절을 하며 더욱 중축합 반응을 계속하여 폴리에스텔-아미드 중합체를 포함하는 유지변성 알키드 수지를 얻고 솔벤트나프사, 키시렌등 유기용제에 용해시켜 유지변성 알키드 수지 유기용액을 제조한다. 이때 사용될 수 있는 다염기산과 다가알콜의 구체예는 제2의 양태와 동일하다.First, fats and oils (Oil & Fat) are subjected to an ester exchange reaction with a polyhydric alcohol containing glycerin to prepare a monoglyceride of a fatty acid or a monopolyhydric alcohol of a fatty acid. A hybrid waste is added to the monoglyceride of the produced fatty acid or monohydric alcohol of the fatty acid to react to obtain a depolymerized product. Subsequently, polybasic acid is added to the depolymerized product to polycondensate, and then polyhydric alcohol is added to control acid value, and the polycondensation reaction is further performed to obtain an oil-modified alkyd resin containing a polyester-amide polymer, and an organic solvent such as solvent naphtha and xylene. It is dissolved in to prepare an organic solution of oil-modified alkyd resin. Specific examples of the polybasic acid and the polyhydric alcohol that can be used at this time are the same as in the second embodiment.
지금까지 설명한 본 발명의 제1 내지 제5 양태에 따른 혼성폐기물의 재활용 방법에 따르면, 괴상 또는 용액 상태의 폴리에스테르-아미드 수지를 얻을 수 있다. 이렇게 하여 얻어진 폴리에스테르-아미드 수지는 일정하중 압출세관식 레오미터로 측정한 결과 유출개시온도(Tfb)가 10∼110℃, 유출종료온도(Tend)가 110∼165℃이었고, 유리전이온도(Tg)는 10∼85℃ 이었다. 또한 사슬말단에 카르복실기를 2∼3개 가지므로 반응성과 분산성이 좋다. 따라서, 본 발명에 의하여 재활용된 폴리에스테르-아미드 수지는 합성수지 미립자, 마이크로 캡슐, 흡착제, 전자사진용 중합법 토너 결착제, 섬유가공제, 제지 사이즈제 및 지력증강제, 폐수처리제, 시멘트혼화제, 잉크젯 잉크 결착제, 에폭시 수지 경화제 및 개질제, 수분산 에폭시수지 경화제 및 개질제 등으로 유용하게 사용될 수 있다.According to the recycling method of the mixed waste according to the first to fifth embodiments of the present invention described above, a polyester-amide resin in a bulk or solution state can be obtained. The polyester-amide resin thus obtained was measured by a constant load extruded tubular rheometer and the outflow start temperature (Tfb) was 10 to 110 ° C, the outflow end temperature (Tend) was 110 to 165 ° C, and the glass transition temperature (Tg). ) Was 10 to 85 ° C. Moreover, since it has 2-3 carboxyl groups at the chain end, reactivity and dispersibility are good. Therefore, the polyester-amide resin recycled according to the present invention is a synthetic resin fine particles, microcapsules, adsorbents, electrophotographic polymerization toner binder, fiber processing agent, paper size agent and strength enhancer, wastewater treatment agent, cement admixture, inkjet ink It can be usefully used as a binder, an epoxy resin curing agent and modifier, a water-dispersible epoxy resin curing agent and a modifier.
이하에서는 본 발명에 따라 혼성폐기물로부터 재생된 폴리에스테르를 결착제로서 이용하여 정전하 현상용 토너를 제조하는 방법을 설명한다. 즉, 본 발명에 의해 재생된 폴리에스테르-아미드 수지에 착색제, 전하조절제 및 이형제를 첨가한 조성물을 이용하면 통상적인 중합법 또는 분쇄법에 의하여 정전하 현상용 토너를 제조할 수 있다.Hereinafter, a method for producing a toner for developing electrostatic charge using polyester recycled from mixed waste according to the present invention as a binder will be described. That is, by using a composition in which a colorant, a charge control agent and a release agent are added to the polyester-amide resin recycled by the present invention, a toner for electrostatic development can be produced by a conventional polymerization method or a pulverization method.
본 발명의 수용성 폴리에스텔-아미드 수지 조성물은 분산성, 상용성, 용해성이 좋아서 약물, 향료, 금속분말 등을 코어물질로 택하여 표면에 쉘을 형성 할 수 있으므로 이들과 혼합하여 현탁촉진제가 포함된 수중에 투입하여 현탁처리시켜 여과하고 수세건조하여 입자경이 1㎛∼10㎛ 합성수지 미립자를 제조하여 화장품, 약물담체, 전자재료로 사용할 수 있다.Since the water-soluble polyester-amide resin composition of the present invention has a good dispersibility, compatibility, and solubility, the drug, perfume, metal powder, etc. can be selected as a core material to form a shell on the surface thereof. It can be put into water, suspended, filtered, washed with water and dried to prepare synthetic resin fine particles of 1㎛ ~ 10㎛, which can be used as cosmetics, drug carriers and electronic materials.
본 발명의 수용성 폴리에스텔-아미드 조성물은 상용성, 용해성, 분산성, 접착성이 우수하므로 합성섬유 원사와 직물의 사이즈제 및 가공제로 사용할 수 있다.Since the water-soluble polyester-amide composition of the present invention has excellent compatibility, solubility, dispersibility, and adhesion, it can be used as a sizing agent and processing agent for synthetic fiber yarns and fabrics.
본 발명의 수용성 폴리에스텔-아미드 조성물은 펄프셀루로즈와 반응성, 접착성, 응집성이 우수하므로 제지사이즈제 및 지력증강제로 사용 할 수 있다.The water-soluble polyester-amide composition of the present invention is excellent in reactivity, adhesiveness, and cohesiveness with pulp cellulose, so that it can be used as a paper size agent and an intelligence enhancer.
본 발명의 수용성 폴리에스텔-아미드 조성물은 폐수중의 오니와 반응성, 응집성이 우수하므로 폐수처리제로 사용할 수 있다.The water-soluble polyester-amide composition of the present invention can be used as a wastewater treatment agent because it is excellent in reactivity and cohesiveness with sludge in wastewater.
본 발명의 수용성 폴리에스텔-아미드 조성물은 함유된 아미드가 에폭시 수지와 반응성이 풍부하고 접착성, 가소성, 용해성이 우수하여 경화제 및 개질제로 사용할 수 있다.The water-soluble polyester-amide composition of the present invention can be used as a curing agent and a modifier because the amide contained is rich in reactivity with the epoxy resin and excellent in adhesiveness, plasticity, and solubility.
본 발명에 따라 혼성폐기물로부터 재생된 폴리에스테르-아미드를 이용하면 에폭시 수지를 경화제로 하는 분체도료 조성물을 제조할 수 있다. 본 발명의 재활용방법에 의하여 재생된 폴리에스테르-아미드는 사슬말단에 카르복실기를 2∼3개 갖고 있으므로 반응성이 좋고 분산성이 좋다. 또한 블록킹 방지제를 소량첨가해도 저장 안정성이 우수하며, 저연화점 수지이므로 180℃이하에서 10분 정도의 짧은 시간에 경화 반응이 가능하다. 따라서, 본 발명의 방법에 따라 재생된 폴리에스테르-아미드를 금속용 가열경화형 도료로서 이용하면 도막의 경화온도를 낮출 수 있으므로 고광택, 내열성, 내약품성 등이 우수한 도료 도막을 얻을 수 있다.By using the polyester-amide regenerated from the mixed waste according to the present invention, it is possible to prepare a powder coating composition using an epoxy resin as a curing agent. The polyester-amide regenerated by the recycling method of the present invention has 2-3 carboxyl groups at the chain end, so that the reactivity is good and the dispersibility is good. In addition, even if a small amount of the antiblocking agent is added, the storage stability is excellent, and since it is a low softening point resin, the curing reaction is possible in a short time of about 10 minutes at 180 ° C or less. Therefore, when the polyester-amide regenerated according to the method of the present invention is used as a heat-curable coating material for metal, the curing temperature of the coating film can be lowered, so that a coating film excellent in high gloss, heat resistance, chemical resistance and the like can be obtained.
본 발명에 따라 혼성폐기물로부터 재생된 폴리에스테르-아미드를 이용하면 유변성 알키드 바니쉬 도료 및 인쇄잉크를 제조할 수 있다.The use of polyester-amides recycled from hybrid wastes in accordance with the present invention makes it possible to produce rheological alkyd varnish paints and printing inks.
본 발명에 따라 얻어진 폴리에스테르-아미드에 지방산 및 건성유를 첨가하고 반응시켜 얻은 유변성 알키드 바니쉬 도료는 지방족 탄화수소계 용제 또는 방향족 탄화수소계 용제에 용해성이 우수하며, 이를 이용하여 얻은 도료도막은 광택성, 내수성, 내후성이 우수하고 강고하다. 또한, 본 발명에서 얻어진 폴리에스테르-아미드에 착색제 및 첨가제를 첨가하여 제조한 그라비아 잉크는 케톤 용제 및 방향족 탄화수소계 용제의 혼합용제에 대한 용해성이 좋아서 속건성, 부착성, 내마모성, 견뢰성이 우수한 인쇄화면을 얻을 수 있다.The rheological alkyd varnish paint obtained by adding and reacting a fatty acid and a dry oil to the polyester-amide obtained according to the present invention has excellent solubility in aliphatic hydrocarbon solvents or aromatic hydrocarbon solvents. Excellent water resistance and weather resistance In addition, the gravure ink prepared by adding a colorant and an additive to the polyester-amide obtained in the present invention has good solubility in a mixed solvent of a ketone solvent and an aromatic hydrocarbon solvent, and is excellent in fast drying, adhesion, abrasion resistance, and fastness. Can be obtained.
본 발명에 따라 혼성폐기물로부터 재생된 폴리에스테르-아미드를 이용하면 접착제를 제조할 수도 있다.Adhesives can also be prepared using polyester-amides recycled from hybrid waste in accordance with the present invention.
본 발명에 따라 재생한 폴리에스테르-아미드를 베이스 수지로 사용한 핫멜트 접착제는 저연화점, 저용융 점도, 부착성, 내수성, 내약품성, 가속성, 상용성이 우수하므로 종이, 보드류, 가죽, 직물, 목재, 플라스틱, 알루미늄과 같은 금속 등에 우수한 초기 접착성 및 강고한 접착력을 얻을 수 있다. 또한, 본 발명에 따라 재생한 폴리에스테르-아미드를 베이스 수지로 하여 유기용제에 용해시켜 얻은 액상 접착제도 또한 상기 기재를 접착하는 데 유용하게 사용될 수 있었다.Hot melt adhesive using the polyester-amide regenerated according to the present invention as a base resin is excellent in low softening point, low melt viscosity, adhesion, water resistance, chemical resistance, acceleration, compatibility, paper, boards, leather, textiles, wood, Excellent initial adhesion and firm adhesion can be obtained for metals such as plastic and aluminum. In addition, a liquid adhesive obtained by dissolving the polyester-amide regenerated according to the present invention as a base resin in an organic solvent could also be usefully used to adhere the substrate.
이하 실시예를 참조하여 본 발명에 따른 혼성폐기물의 재활용방법을 더욱 상세하게 설명하는데, 이는 예시를 위한 것으로서 본 발명의 범위가 이에 의하여 한정되지 않는 것은 물론이다.Hereinafter, a method for recycling mixed waste according to the present invention will be described in more detail with reference to the following examples, which are intended to illustrate the scope of the present invention.
〈실시예 1〉<Example 1>
교반기, 환류냉각기, 분리기, 온도계, 질소주입구를 구비한 반응기에 혼성폐기물을 분쇄한 칩 400g, 검로진 200g, DBTO 0.3g을 넣고 질소 가스를 주입하면서 250℃로 가열하였다. 혼성폐기물이 점차로 용융되기 시작하면, 교반을 시작하고 이 온도에서 2시간 동안 유지하였다. 내용물이 투명해지면, 내용물을 150℃로 냉각한 후, 무수말레인산 120g을 가하였다. 개환 반응의 발생열이 더 이상 발생하지 않으면, 반응물을 재가열하여 235℃에서 3시간 반응시켰다. 이 해중합 생성물의 산가는 110mgKOH/g이었다.Into a reactor equipped with a stirrer, a reflux condenser, a separator, a thermometer, and a nitrogen inlet, 400 g of mixed waste chips, 200 g of gum rosin, and 0.3 g of DBTO were added and heated to 250 ° C. while injecting nitrogen gas. When the mixed waste began to melt gradually, stirring was started and maintained at this temperature for 2 hours. When the contents became clear, the contents were cooled to 150 ° C and 120 g of maleic anhydride was added thereto. When the heat of the ring-opening reaction no longer occurred, the reaction was reheated and reacted at 235 ° C. for 3 hours. The acid value of this depolymerization product was 110 mgKOH / g.
여기에 비스페놀 A의 에틸렌 옥사이드 부가물 200g을 가하고 250℃에서 5시간 동안 탈수하면서 축중합을 한 후 산가 55mgKOH/g에 도달하면 반응생성물을 냉각하였다. 이어서, 상기 반응생성물에 수산화나트륨 50g, 증류수 1500g을 가하여 85℃에서 30분간 교반하여 폴리에스테르-아미드 수지 수용액을 제조하였다. 상기 폴리에스테르-아미드는 산가 39mgKOH/g, 중량평균 분자량 11,500, 연화점 75℃, PH 8.1이었다. 200 g of ethylene oxide adduct of bisphenol A was added thereto, and after condensation polymerization while dehydrating at 250 ° C. for 5 hours, the reaction product was cooled when the acid value reached 55 mgKOH / g. Subsequently, 50 g of sodium hydroxide and 1500 g of distilled water were added to the reaction product, followed by stirring at 85 ° C. for 30 minutes to prepare an aqueous polyester-amide resin solution. The polyester-amide had an acid value of 39 mgKOH / g, a weight average molecular weight of 11,500, a softening point of 75 ° C, and a PH of 8.1.
상기 폴리에스테르-아미드 수지를 중합토너 결착제로 사용하여 중합법으로 토너를 다음과 같이 제조해 본 결과 물성이 좋고 정착성이 우수한 토너를 제조할 수 있었다.When the toner was prepared by the polymerization method using the polyester-amide resin as the polymerized toner binder as follows, it was possible to prepare a toner having good physical properties and excellent fixability.
상기 폴리에스테르-아미드 수지 수용액 100g, 카본블랙(PRINTEX 150T) 3g, 전하제어제(BONTRON S-34) 0.1g, 및 이형제 1g을 혼합하고 분산시킨 후, 이 분산액을 강산성 수용액 중에 투입하여 입자를 생성시켜서 여과하여 얻은 입자를 수세하고 건조하였다. 이 입자 100g에 외첨제 1g을 첨가하고 혼합하여 토너 입자를 제조하였다.100 g of the polyester-amide resin solution, 3 g of carbon black (PRINTEX 150T), 0.1 g of charge control agent (BONTRON S-34), and 1 g of a releasing agent were mixed and dispersed, and the dispersion was added to a strong acid aqueous solution to form particles. The particles obtained by filtration were washed with water and dried. Toner particles were prepared by adding 1 g of external additive to 100 g of these particles and mixing them.
이 토너 입자를 프린터 카트리지에 충진하고 프린팅을 시행하였다. 화상을 형성시킨 결과 선명한 화상과 정착성이 우수한 화상을 얻을 수 있었다.The toner particles were filled in a printer cartridge and printed. As a result of forming the image, a clear image and an image excellent in fixability were obtained.
〈실시예 2〉<Example 2>
혼성폐기물칩 400g, 수첨 로진 200g, DBTO 0.3g, 무수트리멜리트산 150g, 네오펜틸 글리콜 200g을 반응기에 투입한 것을 제외하고는, 실시예 1과 동일한 방법으로 폴리에스테르-아미드 수지 수용액을 제조하였다. 얻어진 폴리에스테르-아미드 수지 수용액의 폴리에스테르-아미드의 산가는 30mgKOH/g이었고, 중량평균 분자량은 11,000,연화점 91℃, PH 8.5이었다.A polyester-amide resin aqueous solution was prepared in the same manner as in Example 1, except that 400 g of mixed waste chip, 200 g of hydrogenated rosin, 0.3 g of DBTO, 150 g of trimellitic anhydride, and 200 g of neopentyl glycol were added to the reactor. The acid value of the polyester-amide of the obtained polyester-amide resin aqueous solution was 30 mgKOH / g, and the weight average molecular weight was 11,000, softening point 91 degreeC, and PH 8.5.
상기 수용성 폴리에스테르-아미드 수지를 중합토너 결착제로 사용하여 다음과 같이 중합법으로 토너를 제조한 결과 물성이 좋고 정착성이 우수한 토너를 제조할 수 있었다.The toner was prepared by the polymerization method using the water-soluble polyester-amide resin as the polymerized toner binder, and thus a toner having good physical properties and excellent fixability could be prepared.
상기 폴리에스테르-아미드 수지 수용액 100g, 시아닌블루 3g, 전하제어제 (BONTRON S-34) 0.1g, 및 이형제 1g을 혼합하고 분산시킨 후, 〈실시예1〉과 동일하게 입자를 생성시켜서 여과하여 얻은 입자를 수세하고 건조하였다. 얻어진 입자 100g에 외첨제 1g을 첨가하고 혼합하여 청색 토너 입자를 제조하였다.100 g of the polyester-amide resin aqueous solution, 3 g of cyanine blue, 0.1 g of a charge control agent (BONTRON S-34), and 1 g of a release agent were mixed and dispersed, and particles were produced and filtered in the same manner as in <Example 1>. The particles were washed with water and dried. 1 g of external additive was added to 100 g of the obtained particles and mixed to prepare blue toner particles.
이 토너 입자를 프린터 카트리지에 충진하고 프린팅을 시행하였다. 화상을 형성시킨 결과 선명한 화상과 정착성이 우수한 화상을 얻을 수가 있었다.The toner particles were filled in a printer cartridge and printed. As a result of forming the image, a clear image and an image excellent in fixability were obtained.
〈실시예 3〉<Example 3>
혼성 폐기물칩 400g, 디에틸렌 글리콜 100g, DBTO 0.3g을 넣고 질소 기류중에서 235℃로 가열하여 3시간동안 해중합 시킨후 내용물이 투명해지면 푸말산 150g을 넣고 220℃로 승온시켜 6시간동안 중축합 반응을 시켜서 폴리에스테르-아미드 수지 수용액을 제조하였다. 중화제로 수산화칼륨 55g을 사용하였다. 얻어진 폴리에스테르-아미드수지 수용액의 폴리에스테르-아미드의 산가는 28mgKOH/g이고 중량평균 분자량은 11,500, 연화점은 100℃, PH 7.9이었다.400 g of mixed waste chips, 100 g of diethylene glycol, and 0.3 g of DBTO were added, heated to 235 ° C. in a nitrogen stream, and depolymerized for 3 hours. When the contents became clear, 150 g of fumaric acid was added and the temperature was raised to 220 ° C. for 6 hours. To prepare a polyester-amide resin aqueous solution. 55 g of potassium hydroxide was used as a neutralizing agent. The acid value of the polyester-amide of the obtained polyester-amide resin aqueous solution was 28 mgKOH / g, the weight average molecular weight was 11,500 and the softening point was 100 degreeC and PH 7.9.
상기 수지용액 100중량부 자외선 차단제 10중량부를 혼합하여 잘 분산시켜서 현탁촉진제 2중량부가 함유된 500중량부의 수중에 투입하여 현탁시켜 입자를 만들고 여과하여 얻은 입자를 수세하고 건조하여 합성 수지미립자를 만들어 화장품에 사용하는 체적 평균 입경에 5㎛ 합성수지 미립자를 제조할 수 있었다.100 parts by weight of the resin solution, 10 parts by weight of the sunscreen is mixed and dispersed well, and added into 500 parts by weight of water containing 2 parts by weight of the suspension accelerator to suspend the particles to make the particles obtained by washing and filtering the synthetic resin particles to make cosmetics 5 micrometers synthetic resin microparticles | fine-particles could be manufactured in the volume average particle diameter used for the process.
〈실시예 4〉<Example 4>
혼성폐기물칩 400g, 에틸렌 글리콜 100g, DBTO 0.3g, 무수트리멜리트산150g을 사용한 것을 제외하고는 실시예 3과 동일한 방법에 의하여 폴리에스테르-아미드 수지 수용액을 제조하였다. Aqueous polyester-amide resin solution was prepared in the same manner as in Example 3 except that 400 g of mixed waste chip, 100 g of ethylene glycol, 0.3 g of DBTO, and 150 g of trimellitic anhydride were used.
다만, 중화제로서 수산화나트륨 50g은 수산화암모늄 50g으로 대체되었다.However, 50 g of sodium hydroxide was replaced by 50 g of ammonium hydroxide as a neutralizing agent.
이렇게 하여 얻어진 폴리에스테르-아미드 수지는 산가 45mgKOH/g, 중량평균 분자량은 12,500, 연화점 105℃, 및 PH 7.7이었다.The polyester-amide resin thus obtained had an acid value of 45 mgKOH / g, a weight average molecular weight of 12,500, a softening point of 105 ° C, and a PH of 7.7.
수지용액 100중량부, 향료 5중량부, 자외선 차단제 3중량부, 아크릴에멀젼 50중량부를 혼합해서 강산성 수중에 현탁시켜 마이크로캡슐을 얻고 여과하여 수세, 건조시켜 향료 및 자외선 차단제가 코어에 잘 보호된 화장품용 마이크로캡슐을 제조할 수 있었다.100 parts by weight of resin solution, 5 parts by weight of fragrance, 3 parts by weight of sunscreen, 50 parts by weight of acrylic emulsion are suspended in strong acidic water to obtain microcapsules, filtered and washed with water and dried to protect perfume and sunscreen well on the core. Microcapsules could be prepared.
〈실시예 5〉<Example 5>
혼성폐기물칩 400g, 프로필렌 글리콜 100g, DBTO 0.3g, 아디픽산 50g, 무수말레인산 100g을 사용한 것을 제외하고는 실시예 3과 동일한 방법에 의하여 폴리에스테르-아미드 수지 수용액을 제조하였다.Aqueous polyester-amide resin solution was prepared in the same manner as in Example 3, except that 400 g of mixed waste chip, 100 g of propylene glycol, 0.3 g of DBTO, 50 g of adipic acid, and 100 g of maleic anhydride were used.
다만, 중화제로서 수산화나트륨 30g 및 트리에틸아민 35g이 사용되었다. 이렇게하여 얻어진 폴리에스테르-아미드 수지는 산가 50mgKOH/g, 중량평균 분자량은 11,700, 및 PH 7.5이었다.However, 30 g of sodium hydroxide and 35 g of triethylamine were used as neutralizing agents. The polyester-amide resin thus obtained had an acid value of 50 mgKOH / g, a weight average molecular weight of 11,700, and a PH of 7.5.
수지용액 100g, 아크릴 에멀젼 50중량부, 도전성 분말 200g, 이형제 3g을 혼합하여 강산성 수중에 현탁시켜 도전성 미립자를 얻고 여과, 수세, 건조시켜 분산성, 전기도전성이 우수한 전자 재료를 제조할 수 있었다.100 g of a resin solution, 50 parts by weight of an acrylic emulsion, 200 g of conductive powder, and 3 g of a releasing agent were mixed, suspended in strong acidic water to obtain conductive fine particles, and filtered, washed with water and dried to prepare an electronic material having excellent dispersibility and electrical conductivity.
〈실시예 6〉<Example 6>
혼성폐기물칩 400g, 에틸렌글리콜 100g, 수첨로진 100g, OBTO 0.3g, DMSSIP100g, 무스트리메리트산 150g, 트리메틸롤프로판 80g을 반응기에 사입하고 실시예 3과 동일한 방법으로 실시하고 중화제로 수산화암모늄 50g 대체하고 . 상기 수용성 폴리에스텔-아미드 수지 산가는 30mgKOH/g이고 중량평균 분자량은 12,500, PH 7.1이다400 g of mixed waste chips, 100 g of ethylene glycol, 100 g of hydrogenated rosin, 0.3 g of OBTO, 100 g of DMSSIP, 150 g of mutrimeric acid, and 80 g of trimethylolpropane were introduced into the reactor and carried out in the same manner as in Example 3, replacing 50 g of ammonium hydroxide as a neutralizing agent. and . The acid value of the water-soluble polyester-amide resin is 30 mgKOH / g, the weight average molecular weight is 12,500, PH 7.1
수지용액 100중량부, 유연제 5중량부, 실리콘 1중량부를 혼합하고 증류수 200중량부를 가하고 폴리에스텔 원사와 직물를 침적시켜 건조시켜 시험한 결과 우수한 부착성과 사이징 효과를 나타냈다.100 parts by weight of the resin solution, 5 parts by weight of a softener, and 1 part by weight of silicone were mixed, and 200 parts by weight of distilled water were added, and polyester yarns and fabrics were deposited and dried to be tested. The results showed excellent adhesion and sizing effect.
〈실시예 7〉<Example 7>
혼성폐기물칩 350g, 네오펜틸 글리콜 100g, 말레인화 검로진 250g, DBTO 0.3g, 아디픽산 100g을 사용한 것을 제외하고는 실시예 3과 동일한 방법에 의하여 폴리에스테르-아미드 수지를 제조하고 트리에틸렌테트라민 150g을 가하여 수용화시켜 폴리에스테르-아미드 수용액을 제조하였다.A polyester-amide resin was prepared in the same manner as in Example 3, except that 350 g of mixed waste chip, 100 g of neopentyl glycol, 250 g of maleated gumrozin, 0.3 g of DBTO, and 100 g of adipic acid were used, and 150 g of triethylenetetramine was prepared. The solution was added thereto to prepare a polyester-amide aqueous solution.
이렇게 하여 얻어진 폴리에스테르-아미드 수지 수용액의 폴리에스테르-아미드의 산가는 45mgKOH/g, 중량평균 분자량은 11,200, 연화점은 79℃, 및 PH 8.5이었다.The acid value of the polyester-amide of the obtained polyester-amide resin aqueous solution was 45 mgKOH / g, the weight average molecular weight was 11,200, the softening point was 79 degreeC, and PH 8.5.
수지용액 10중량부, 산화전분 2g, 증류수 200중량부를 혼합하여 제지용 사이즈제 및 지력 증강제를 제조하여 파일럿제지기를 사용하여 초지하고 건조시켜 종이를 만들어 보니 사이징 효과와 지질이 우수하였다.10 parts by weight of a resin solution, 2 g of starch oxide, and 200 parts by weight of distilled water were mixed to prepare a paper size agent and a paper strength enhancer, and papermaking was carried out using a pilot paper machine and dried to make paper.
〈실시예 8〉<Example 8>
혼성폐기물칩 350g, 네오펜틸 글리콜 100g, 디사이클로펜타디엔 레진 250g, DBTO 0.3g, 무수말레인산 150g을 사용한 것을 제외하고는 실시예3과 동일한 방법에 의하여 폴리에스테르-아미드 수지 수용액을 제조하였다.A polyester-amide resin aqueous solution was prepared in the same manner as in Example 3, except that 350 g of mixed waste chip, 100 g of neopentyl glycol, 250 g of dicyclopentadiene resin, 0.3 g of DBTO, and 150 g of maleic anhydride were used.
다만, 중화제로서 수산화 암모늄30g, 트리에틸아민 50g을 사용하였다. 이렇게 하여 얻어진 폴리에스테르-아미드 수지 수용액의 폴리에스테르-아미드는 산가 80mgKOH/g, 중량평균 분자량은 11,900, 연화점 90℃, 및 PH 7.9이었다 수지용액 10중량부, 증류수 200중량부를 혼합 희석하여 세차장에서 배출되는 폐수 1000중량부에 넣으며 강하게 교반하여 정치한 결과 오니가 프록을 형성하며 침전되고 상등액이 수도수처럼 맑아졌다.However, 30 g of ammonium hydroxide and 50 g of triethylamine were used as neutralizing agents. The polyester-amide of the aqueous solution of polyester-amide resin thus obtained had an acid value of 80 mgKOH / g, a weight average molecular weight of 11,900, a softening point of 90 ° C., and a pH of 7.9. 10 parts by weight of the resin solution and 200 parts by weight of distilled water were mixed and diluted in a car wash. The mixture was added to 1000 parts by weight of wastewater, and stirred with a strong mixture. As a result, sludge formed as a floc, and the supernatant liquid became clear as tap water.
〈실시예 9〉<Example 9>
혼성폐기물칩 350g, 디에틸렌글리콜 100g, DBTO 0.3g, 다이머산 100g, 아디픽산 100g을 사입하고 실시예 3과 동일한 방법으로 실시하고 이소프로필알콜 100g을 넣고 트리에틸렌테트라민 100g을 가하여 수용성 폴리에스텔-아미드수지를 제조하였다.A mixed waste chip 350g, diethylene glycol 100g, DBTO 0.3g, dimer acid 100g, adipic acid was added in the same manner as in Example 3, 100g isopropyl alcohol and 100g triethylenetetramine were added to the water-soluble polyester- An amide resin was prepared.
상기 수용성 폴리에스텔-아미드 수지는 산가 70, 중량평균 분자량은 11,000, PH 7.1이다.The water-soluble polyester-amide resin has an acid value of 70, a weight average molecular weight of 11,000, and a PH of 7.1.
수지용액 100중량부, 수분산에폭시수지(국도화학KEM-134-60) 300중량부, 경화촉진제 10중량부, 실리콘 오일 1중량부를 혼합하여 교반하여 바니시를 제조하여 유리시편에 도포하여 도막을 형성시킨 결과 접착성이 좋고 광택이 우수한 강견한 도막이 생성되었다.100 parts by weight of a resin solution, 300 parts by weight of an epoxy resin (Kukdo Chemical KEM-134-60), 10 parts by weight of a curing accelerator, and 1 part by weight of a silicone oil were mixed and stirred to prepare a varnish, which was then coated on a glass specimen to form a coating film. As a result, a strong coating film having good adhesion and gloss was produced.
〈실시예 10〉<Example 10>
혼성폐기물칩 400g, 네오펜틸글리콜 70g, 디사이클로펜타디엔 레진 200g, DBTO 0.3g, 이소프탈산 100g및 비스페놀A의 에틸렌옥사이드 부가물 120g을 사용한 것을 제외하고는 실시예 3과 동일한 방법에 의하여 폴리에스테르-아미드 수지를 제조하였다.Polyester- by the same method as in Example 3, except that 400 g of mixed waste chip, 70 g of neopentyl glycol, 200 g of dicyclopentadiene resin, 0.3 g of DBTO, 100 g of isophthalic acid, and 120 g of ethylene oxide adduct of bisphenol A were used. An amide resin was prepared.
다만, 중화 및 수용화 단계는 생략하고 괴상의 폴리에스테르-아미드 수지로 회수하였다. 상기 괴상의 폴리에스테르-아미드 수지는 산가가 7mgKOH/g이었고, 중량평균 분자량은 19,000, 연화점은 120℃이었다However, the neutralization and solubilization step was omitted and recovered as a bulk polyester-amide resin. The bulk polyester-amide resin had an acid value of 7 mgKOH / g, a weight average molecular weight of 19,000, and a softening point of 120 ° C.
괴상수지 100중량부, 샤닌브루 7중량부,전하제 1중량부, 이형제 3중량부를 혼합하여 니다에 넣고 150℃로 가열하여 혼련시킨후 조분쇄하고 젯트밀로 미분쇄하고 분급하여 입자경 8㎛의 전자사진용 청색토너를 제조하여 카트리지에 넣고 삼성전자 레이저 프린터 4300i에 장착하여 인쇄하니 화상이 선명한 청색인쇄물을 얻었다.100 parts by weight of the bulk resin, 7 parts by weight of Shanin brew, 1 part by weight of charge agent, and 3 parts by weight of release agent are mixed, mixed by heating at 150 ° C., finely pulverized, finely pulverized and classified by a jet mill, and having an electron having a particle diameter of 8 μm. A blue toner for photographs was prepared, placed in a cartridge, and mounted on a Samsung laser printer 4300i to print, thereby obtaining a clear blue print.
〈실시예 11〉<Example 11>
혼성폐기물칩 500g, 디에틸렌글리콜 100g, DBTO 0.3g, 무수말레인산 100g, 및 펜타에리쓰리톨 100g을 사용한 것을 제외하고는 실시예 3과 동일한 방법에 의하여 폴리에스테르-아미드 수지를 제조하였다.A polyester-amide resin was prepared in the same manner as in Example 3, except that 500 g of mixed waste chip, 100 g of diethylene glycol, 0.3 g of DBTO, 100 g of maleic anhydride, and 100 g of pentaerythritol were used.
다만, 중화 및 수용화 단계는 생략하고 괴상의 폴리에스테르-아미드 수지로 회수하였다. 상기 괴상의 폴리에스테르수지는 산가가 5mgKOH/g이었고, 중량평균 분자량은 27,000, 연화점은 140℃이었다.However, the neutralization and solubilization step was omitted and recovered as a bulk polyester-amide resin. The bulk polyester resin had an acid value of 5 mgKOH / g, a weight average molecular weight of 27,000, and a softening point of 140 ° C.
괴상수지 100중량부, 카본FW-200 5중량부, 에폭시수지 50중량부, 경화촉진제 1중량부, 흐름조정제 1중량부, 왁스 2중량부를 혼합하여 니다에 넣고 150℃로 가열하여 혼련시켜서 냉각하여 조분쇄, 미분쇄하고 분급하여 입자경 50㎛분체도료를 제조하였다. 갈바니아 처리된 철제 시편에 정전도장하여 실험용 오븐에서 180℃ 30분동안 가열 경화시키니 부착력과 내굴곡성, 광택이 우수한 도편을 얻을 수 있었다.100 parts by weight of the bulk resin, 5 parts by weight of carbon FW-200, 50 parts by weight of epoxy resin, 1 part by weight of curing accelerator, 1 part by weight of flow regulator, and 2 parts by weight of wax are added to a mixture, heated to 150 ° C., kneaded and cooled. Coarsely pulverized, finely pulverized and classified to prepare a powder coating having a particle size of 50 μm. Electrostatic coating on galvanized iron specimens was carried out by heat curing at 180 ° C. for 30 minutes in an experimental oven, thereby obtaining a coating having excellent adhesion, bending resistance, and gloss.
〈실시예 12〉<Example 12>
반응기에 혼성폐기물칩 500g, 지방산모노글리세리드 500g, DBTO 0.3g을 넣고 질소기류중에 230℃로 가열하여 3시간 동안 해중합 시킨후 내용물이 투명해 지는 시점에서 검로진 100g을 넣고 내용물이 점도가 낮아지고 투명해지면 무수프탈산 100g을 넣고 235℃에서 3시간동안 키시렌용제환류중에서 반응시켜서 유변성알키드수지를 제조하고 솔벤트나프사 1100g을 가하고 희석하여 건조제를 첨가하여 도료용알키드 수지바니스를 제조하였다. 이 바니스는 고광택, 내수성, 내후성이 우수한 도막을 얻을 수 있다.500 g of mixed waste chips, 500 g of fatty acid monoglycerides, and 0.3 g of DBTO were added to the reactor, heated to 230 ° C. in nitrogen stream, depolymerized for 3 hours, and when the contents became transparent, 100 g of gum rosin was added. When the solution was dissolved, 100 g of phthalic anhydride was added and reacted at 235 ° C. for 3 hours under reflux of a xylene solvent to prepare a rheology alkyd resin, and 1100 g of solvent naphtha was added thereto, followed by dilution to add a drying agent to prepare an alkyd resin varnish for coatings. This varnish can obtain a coating film excellent in high gloss, water resistance and weather resistance.
〈실시예 13〉<Example 13>
혼성 폐기물칩 500g, 트리메틸올프로핀 200g, DBTO 0.5g을 넣고 질소기류중에 235℃로 가열하여 반응 시킨후 PTMEG 150g, 아디픽산 100g을 가하여 220℃에서 3시간동안 반응시킨후 95℃이하로 냉각하여 초산에틸 100g을 가하고 50℃이하에서 DBTDL 0.5g을 가하고 톨리렌디이소시아네이트 200g을 2시간에 걸쳐 50℃를 유지하면서 적가한 후 95℃로 승온하여 3시간동안 더 반응시킨후 냉각하여 초산에틸 200g을 가하여 희석시켜서 폴리우레탄수지유기 용액을 얻었다. 상기 폴리우레탄수지유기용액 100g, 초산에틸 10g, 경화촉진제 2g을 혼합하여 우레탄접착제를 만들어 합성섬유직물에도 양면을 접합시킨 접착면을 내수성, 접착성, 탄성이 우수한 접착면을 얻을 수 있었다.500 g of mixed waste chips, 200 g of trimethylolpropine and 0.5 g of DBTO were added and reacted by heating to 235 ° C. in a nitrogen stream. Then, 150 g of PTMEG and 100 g of adipic acid were added and reacted at 220 ° C. for 3 hours, followed by cooling below 95 ° C. 100 g of ethyl acetate was added, 0.5 g of DBTDL was added at 50 ° C. or lower, and 200 g of tolylene diisocyanate was added dropwise while maintaining 50 ° C. over 2 hours. The temperature was raised to 95 ° C., further reacted for 3 hours, and then cooled and 200 g of ethyl acetate was added. It diluted, and obtained the polyurethane resin organic solution. The polyurethane resin organic solution 100g, ethyl acetate 10g, the curing accelerator 2g was mixed to make a urethane adhesive to obtain a bonding surface excellent in water resistance, adhesiveness, elasticity of the adhesive surface bonded to both sides to a synthetic fiber fabric.
〈실시예 14〉<Example 14>
혼성폐기물칩 400g, 프로필렌글리콜 200g, DBTO 0.5g을 넣고 질소기류 중에서 230℃로 가열하여 3시간 반응시킨후 160℃로 감온하여 무수말레인산 250g, 무수프탈산 100g, 플로필렌글리콜 150g을 가하여 220℃로 유지하면서 7시간동안 중축합 반응을 시켜 중합금지제 하이드로퀴논 0.2g을 가하여 냉각시켜 불포화 폴리에스테르 수지를 얻는다.400 g of mixed waste chips, 200 g of propylene glycol, 0.5 g of DBTO were added, and heated to 230 ° C. in a nitrogen stream for 3 hours to react. The polycondensation reaction was carried out for 7 hours while adding 0.2 g of hydroquinone, a polymerization inhibitor, followed by cooling to obtain an unsaturated polyester resin.
상기 불포화 폴리에스테르 수지 100g을 스티렌모노머 50g(하이드로퀴논 0.1g함유)에 용해시켜서 코발트옥테이트 1g, MEK퍼옥사이드 1g을 혼합하여 가교경화형 불포화 폴리에스텔-아미드 수지 용액을 얻어 유리섬유시편에 도포하여 SMC성형품을 만들어 폴리에틸렌 필름에 싸서 상온에서 48시간 보관한 후 SMC를 가열성형하여 유리섬유성형판을 얻은 결과 핀홀이 없고 강견한 광택이 균일하게 양호한 성형판을 얻을 수가 있었다.100 g of the unsaturated polyester resin was dissolved in 50 g of styrene monomer (containing 0.1 g of hydroquinone), 1 g of cobalt octane and 1 g of MEK peroxide were mixed to obtain a cross-linked unsaturated polyester-amide resin solution and applied to a glass fiber specimen to apply SMC. After forming a molded article, wrapped in a polyethylene film, and stored at room temperature for 48 hours, SMC was heated and obtained as a glass fiber molded plate.
상기한 바와 같이, 본 발명의 혼성폐기물의 재활용 방법에 따라 제조된 폴리에스테르-아미드 중합체는 착색제를 포함하는 첨가제와의 상용성과 분산성이 우수하고 매체와의 부착성이 우수할 뿐만 아니라 수용화가 가능하다. As described above, the polyester-amide polymer prepared according to the recycling method of the mixed waste of the present invention is excellent in compatibility and dispersibility with the additive including the colorant, and excellent in adhesion to the medium, and can be solubilized. Do.
이렇게 하여 혼성폐기물로부터 제조된 폴리에스테르-아미드 중합체 수용액은 합성수지 미립자, 마이크로캡슐, 흡착제, 전자사진용 중합법 토너 결착제, 섬유 가공제, 제지 사이즈제 및 지력증강제, 폐수처리제, 분산제, 시멘트혼화제, 잉크젯 잉크 결착제, 에폭시 수지 경화제 및 개질제, 수분산 에폭시수지 경화제 및 개질제 등의 산업상 유용한 재료로 활용될 수 있고 괴상 또는 유기 용액상 폴리에스텔-아미드 수지는 분쇄법 토너의 결착제, 인쇄잉크, 도료, 분체도료, 접착제, 핫멜트 접착제, 방수제, 가교경화형 불포화 폴리에스텔-아미드 수지, 폴리우레탄 수지 등의 산업상 유용한 재료로 활용될 수 있다.Thus, the aqueous polyester-amide polymer prepared from the mixed waste is composed of synthetic resin fine particles, microcapsules, adsorbents, electrophotographic polymerization toner binders, fiber processing agents, paper size agents and strength enhancers, wastewater treatment agents, dispersants, cement admixtures, It can be used as industrially useful materials such as inkjet ink binders, epoxy resin curing agents and modifiers, water-dispersible epoxy resin curing agents and modifiers, and bulk or organic solution polyester-amide resins can be used as binders, printing inks, Paints, powder coatings, adhesives, hot melt adhesives, waterproofing agents, cross-linking unsaturated polyester-amide resins, polyurethane resins and the like can be utilized as industrially useful materials.
Claims (39)
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR20040020944A KR101160352B1 (en) | 2004-03-26 | 2004-03-26 | Highly functional resin recycled polyester and polyamide hybrid waste and its manufacturing method |
| PCT/KR2005/000851 WO2005092963A1 (en) | 2004-03-26 | 2005-03-24 | Recycled method for a wasted polymer which is mixed polyester polyamide and reclaimed materials thereof |
| CNB2005800169517A CN100497451C (en) | 2004-03-26 | 2005-03-24 | Recycled method for a wasted polymer which is mixed polyester and polyamide and reclaimed materials thereof |
| US10/599,339 US7511081B2 (en) | 2004-03-26 | 2005-03-24 | Recycled method for a wasted polymer which is mixed polyester polyamide and reclaimed materials thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR20040020944A KR101160352B1 (en) | 2004-03-26 | 2004-03-26 | Highly functional resin recycled polyester and polyamide hybrid waste and its manufacturing method |
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| KR20050095504A true KR20050095504A (en) | 2005-09-29 |
| KR101160352B1 KR101160352B1 (en) | 2012-06-26 |
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| CN (1) | CN100497451C (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008111726A1 (en) * | 2007-03-12 | 2008-09-18 | Jung Hun Woo | Polyester resin composition for toner and toner containing the same |
| KR101013814B1 (en) * | 2010-05-06 | 2011-02-14 | 주식회사 길종합건축사사무소 | The method of manufacturing painting composite used in concrete floor type |
| US8030364B2 (en) | 2004-10-11 | 2011-10-04 | Do Gyun Kim | Polyols and polyurethanes, polyurethaneforms using the same |
| CN114181430A (en) * | 2021-11-29 | 2022-03-15 | 江苏志成新材料科技有限公司 | Process system for chemically regenerating waste polyester and waste polyamide into PBAT |
| CN114466885A (en) * | 2019-08-08 | 2022-05-10 | 伊士曼化工公司 | Process for recovering sulfopolyesters |
| CN115807335A (en) * | 2021-09-13 | 2023-03-17 | 南亚塑胶工业股份有限公司 | Method for recycling polyester fabric |
| CN116082646A (en) * | 2023-01-03 | 2023-05-09 | 万华化学集团股份有限公司 | Dynamic cross-linked polyether amide elastomer and preparation method thereof |
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| CN113248705B (en) * | 2021-04-30 | 2022-03-04 | 东华大学 | Alcoholysis regeneration method and application of waste polyester-polyamide 6 blended textile |
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Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1538544A (en) * | 1976-06-23 | 1979-01-24 | British Industrial Plastics | Resins |
| JP2846278B2 (en) * | 1996-02-19 | 1999-01-13 | 和歌山県 | Recycling of cured unsaturated polyester resin waste |
| KR100765744B1 (en) * | 2001-12-15 | 2007-10-15 | 김도균 | Method for producing polymer for toner, ink and coating agent by recycling waste polyester |
-
2004
- 2004-03-26 KR KR20040020944A patent/KR101160352B1/en active IP Right Grant
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- 2005-03-24 CN CNB2005800169517A patent/CN100497451C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8030364B2 (en) | 2004-10-11 | 2011-10-04 | Do Gyun Kim | Polyols and polyurethanes, polyurethaneforms using the same |
| WO2008111726A1 (en) * | 2007-03-12 | 2008-09-18 | Jung Hun Woo | Polyester resin composition for toner and toner containing the same |
| KR101013814B1 (en) * | 2010-05-06 | 2011-02-14 | 주식회사 길종합건축사사무소 | The method of manufacturing painting composite used in concrete floor type |
| CN114466885A (en) * | 2019-08-08 | 2022-05-10 | 伊士曼化工公司 | Process for recovering sulfopolyesters |
| CN115807335A (en) * | 2021-09-13 | 2023-03-17 | 南亚塑胶工业股份有限公司 | Method for recycling polyester fabric |
| CN114181430A (en) * | 2021-11-29 | 2022-03-15 | 江苏志成新材料科技有限公司 | Process system for chemically regenerating waste polyester and waste polyamide into PBAT |
| CN116082646A (en) * | 2023-01-03 | 2023-05-09 | 万华化学集团股份有限公司 | Dynamic cross-linked polyether amide elastomer and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100497451C (en) | 2009-06-10 |
| KR101160352B1 (en) | 2012-06-26 |
| CN1957027A (en) | 2007-05-02 |
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