CN106916286A - The semi continuous preparation method of Biodegradable polyester resin - Google Patents
The semi continuous preparation method of Biodegradable polyester resin Download PDFInfo
- Publication number
- CN106916286A CN106916286A CN201611048310.6A CN201611048310A CN106916286A CN 106916286 A CN106916286 A CN 106916286A CN 201611048310 A CN201611048310 A CN 201611048310A CN 106916286 A CN106916286 A CN 106916286A
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- CN
- China
- Prior art keywords
- polyester resin
- biodegradable polyester
- continuous preparation
- semi continuous
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229920005989 resin Polymers 0.000 title claims abstract description 37
- 239000011347 resin Substances 0.000 title claims abstract description 37
- 229920000229 biodegradable polyester Polymers 0.000 title claims abstract description 34
- 239000004622 biodegradable polyester Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 71
- 239000000047 product Substances 0.000 claims abstract description 56
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- 238000005886 esterification reaction Methods 0.000 claims abstract description 32
- 150000001991 dicarboxylic acids Chemical class 0.000 claims abstract description 27
- 230000032050 esterification Effects 0.000 claims abstract description 24
- 239000004970 Chain extender Substances 0.000 claims abstract description 20
- 150000001298 alcohols Chemical class 0.000 claims abstract description 20
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 11
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 11
- 125000003118 aryl group Chemical group 0.000 claims abstract description 6
- 239000003381 stabilizer Substances 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 230000003068 static effect Effects 0.000 claims description 9
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 6
- 239000000155 melt Substances 0.000 claims description 4
- 238000003860 storage Methods 0.000 claims description 4
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 3
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 3
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 claims description 3
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 claims description 3
- QOPBTFMUVTXWFF-UHFFFAOYSA-N tripropyl phosphite Chemical compound CCCOP(OCCC)OCCC QOPBTFMUVTXWFF-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical compound OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 claims description 2
- NCPXQVVMIXIKTN-UHFFFAOYSA-N trisodium;phosphite Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])[O-] NCPXQVVMIXIKTN-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 42
- 238000006116 polymerization reaction Methods 0.000 abstract description 8
- 229920001896 polybutyrate Polymers 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 14
- 238000012643 polycondensation polymerization Methods 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000002253 acid Substances 0.000 description 13
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 12
- 230000000704 physical effect Effects 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 9
- 229920001225 polyester resin Polymers 0.000 description 9
- 239000004645 polyester resin Substances 0.000 description 9
- -1 2- ethyl Chemical group 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 6
- 238000007711 solidification Methods 0.000 description 6
- 230000008023 solidification Effects 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 239000001361 adipic acid Substances 0.000 description 5
- 235000011037 adipic acid Nutrition 0.000 description 5
- 239000006085 branching agent Substances 0.000 description 5
- 239000012467 final product Substances 0.000 description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 4
- 238000010923 batch production Methods 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 238000010924 continuous production Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- WHBMMWSBFZVSSR-UHFFFAOYSA-N 3-hydroxybutyric acid Chemical compound CC(O)CC(O)=O WHBMMWSBFZVSSR-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- PWLXTFFHCFWCGG-UHFFFAOYSA-N Heneicosanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCCCCCC(O)=O PWLXTFFHCFWCGG-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 2
- 229920000704 biodegradable plastic Polymers 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- DGXRZJSPDXZJFG-UHFFFAOYSA-N docosanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCCCCCCC(O)=O DGXRZJSPDXZJFG-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- DIVDFFZHCJEHGG-UHFFFAOYSA-N oxidopamine Chemical compound NCCC1=CC(O)=C(O)C=C1O DIVDFFZHCJEHGG-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 2
- RLJWTAURUFQFJP-UHFFFAOYSA-N propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)O.CC(C)O.CC(C)O RLJWTAURUFQFJP-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N tetraisopropyl titanate Substances CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical class CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 description 1
- BUYHVRZQBLVJOO-UHFFFAOYSA-N 2-ethyl-2,4-dimethylhexane-1,3-diol Chemical class CCC(C)C(O)C(C)(CC)CO BUYHVRZQBLVJOO-UHFFFAOYSA-N 0.000 description 1
- UJMZZAZBRIPOHZ-UHFFFAOYSA-N 2-ethylhexan-1-ol;titanium Chemical group [Ti].CCCCC(CC)CO UJMZZAZBRIPOHZ-UHFFFAOYSA-N 0.000 description 1
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- WSQZNZLOZXSBHA-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione Chemical compound O=C1OCCCCOC(=O)C2=CC=C1C=C2 WSQZNZLOZXSBHA-UHFFFAOYSA-N 0.000 description 1
- XJMMNTGIMDZPMU-UHFFFAOYSA-N 3-methylglutaric acid Chemical class OC(=O)CC(C)CC(O)=O XJMMNTGIMDZPMU-UHFFFAOYSA-N 0.000 description 1
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- 241000195493 Cryptophyta Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
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- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
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- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical group CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
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- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical class OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 230000000505 pernicious effect Effects 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 229920002961 polybutylene succinate Polymers 0.000 description 1
- 239000004631 polybutylene succinate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical class OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- AFCAKJKUYFLYFK-UHFFFAOYSA-N tetrabutyltin Chemical compound CCCC[Sn](CCCC)(CCCC)CCCC AFCAKJKUYFLYFK-UHFFFAOYSA-N 0.000 description 1
- CRHIAMBJMSSNNM-UHFFFAOYSA-N tetraphenylstannane Chemical compound C1=CC=CC=C1[Sn](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 CRHIAMBJMSSNNM-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 229960000314 zinc acetate Drugs 0.000 description 1
Classifications
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/785—Preparation processes characterised by the apparatus used
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The present invention provides a kind of semi continuous preparation method of Biodegradable polyester resin, including：(I) step, at least one dihydroxylic alcohols and catalyst at least one dicarboxylic acids, the aliphatic dihydroxy alcohol in aliphatic dicarboxylic acid and aromatic dicarboxylic acid are put into the first batch reactor carries out esterification by dicarboxylic acids and dihydroxylic alcohols；(II) step, is transplanted on the second batch reactor, so as to carry out polycondensation reaction by the esterification reaction product obtained from (I) step；(III) step, is transplanted on the polycondensation product of the molten condition obtained from (II) step surge tank and is stored；And (IV) step, the polycondensation product and chain extender in surge tank are supplied to flow reactor, so as to carry out chain extending reaction.Biodegradable polyester resin preparation method of the invention is used and uses batch polymerization processes and the semi continuous preparation method of continous way chain extending reaction technique, it is thus possible to eliminate the problem occurred in the case where each technique is used alone.
Description
Technical field
The present invention relates to a kind of semi continuous preparation method of Biodegradable polyester resin, in more detail, it is related to one kind
And with batch polymerization processes and the semi continuous preparation method of the Biodegradable polyester resin of continous way chain extending reaction technique.
Background technology
Plastics are efficiently used plastics due to high functionality and durability etc. in real life.But, it is conventional
, in landfill, it is low to there is the speed being decomposed by the microorganisms, and pernicious gas is discharged during burning for plastics, the reason for as environmental pollution etc.
Problem, thus carried out the exploitation of biodegradable plastic.
In this biodegradable plastic, attracted tremendous attention with Biodegradable polyester resin.So-called biological degradability
Polyester resin, refer to can the microorganism present in such as bacterium, algae, the nature of mould be broken down into water and carbon dioxide
Or the polymer of water and biogas.This Biodegradable polyester resin is prompted to be ring caused by being prevented from by filling or burning
The powerful solution of border pollution.
In general, disclosure satisfy that the high-viscosity polyester resin article of commercial physical property, it is necessary in high temperature in order to obtain
Reactor in be detained for a long time.Now, due to the result of reversible reaction, while viscosity rises, decomposition reaction also increases
It is many, so as to be had undesirable effect to physical property.
Accordingly, as the method for obtaining high-viscosity polyester resin, the method for utilizing in the past is, by using interval
The esterification of formula technique and polycondensation reaction, after making low viscous polyester prepolyer, are granulated and are solidified
And dry, then in other reactor, in the case of dry particle is carried out into remelted and chain extender reaction, so that
Carry out high viscosity.But, according to the method, solidification, it is dry and remelted during consume many energy, but also may
There is thus caused physical property reduction problem.
As the method for solving this problem, (0-2012- of Korean Patent Laid the of patent document 1
No. 0101387) describe the continuous preparation side of the polyester mixture for being carried out continuously esterif iotacation step, condensation polymerization step and chain extension step
Method.
According to the patent document 1, the polyester polymers of the molten condition by condensation polymerization step will not be granulated,
Solidification and dry, and can be with molten condition directly with chain extender reaction and carry out high viscosity, it is thus possible to solve
In formula of having a rest technique occur solidification, drying and it is remelted during highly energy-consuming transitivity reduction problem.But, just using continuous
For the preparation method of the Biodegradable polyester resin of formula technique, the problem for existing is when varietal change is produced, in cleaning
The operations such as reactor aspect has difficulties.
Therefore, in the urgent need to the new biodegradation of the problem to the batch process and continuous process can be eliminated
The research of property preparation method of polyester resin.
[prior art literature]
[patent document]
The A of (patent document 0001) KR 1020120101387
The content of the invention
The technical problem to be solved
The present invention is intended to provide a kind of semi continuous preparation method of Biodegradable polyester resin, imports and has used interval
Semi continuous (semi-continuous type) preparation method of formula polymerization technique and continous way chain extending reaction technique, so as to
Enough eliminate the problem of each technique.
Technical scheme
In order to solve problem as described above, the present invention provides a kind of semi continuous of Biodegradable polyester resin and prepares
Method, including：(I) step, by least one dicarboxylic acids, aliphatic dihydroxy alcohol in aliphatic dicarboxylic acid and aromatic dicarboxylic acid
In at least one dihydroxylic alcohols and catalyst put into the first batch reactor, so as to by the dicarboxylic acids and the dihydroxylic alcohols
Carry out esterification；(II) step, the second intermittent reaction is transplanted on by the esterification reaction product obtained from (I) step
Device, so as to carry out polycondensation reaction；(III) step, the polycondensation product transfer of the molten condition that will be obtained from (II) step
Stored to surge tank；And (IV) step, by the polycondensation product and chain extender in the surge tank supplied to continuously
Formula reactor, so as to carry out chain extending reaction.
It is preferred that after terminating esterification in (I) step, in first batch reactor, relative to described
Dicarboxylic acids 1mol, by 0.01mmol~0.5mmol scopes put into stabilizer, the stabilizer can include be selected from by phosphorous acid,
Phosphonous acid (phosphonous acid), Trimethyl phosphite, triethyl phosphite, tripropyl phosphite, triphenyl phosphite,
At least one compound in the group of sodium phosphite and sodium hypophosphite composition.
The melt index (MI) of the polycondensation product obtained from (II) step can be 30g/10min~100g/
10min。
It is preferred that (III) step is performed under the covering (blanket) of nitrogen, and in (III) step, can be by institute
State polycondensation product and be cooled to 180 DEG C~200 DEG C temperature.
It is preferred that between (III) step and (IV) step, in the polycondensation product, relative to described
Dicarboxylic acids 1mol, stabilizer is put into by 0.05mmol~2.0mmol scopes, therefore, in (IV) step, will can throw
Enter the polycondensation product that has the stabilizer and perform institute in the case of the chain extender puts into the flow reactor
State chain extending reaction.
It is preferred that (IV) step is performed 20 minutes~50 minutes at 190 DEG C~200 DEG C, what is now used is described continuous
Formula reactor can be selected from the group being made up of extruder, tandem (list) reactor and static mixer (static mixer)
In one kind.
Also, it is preferred that the content of the chain extender is 0.01 weight portion relative to the weight portion of the polycondensation product 100
~5 weight portions.
Beneficial effect
Biodegradable polyester resin preparation method of the invention, consolidating without product after polycondensation reaction
Change, dry and remelted process, therefore, will not occur because of the transitivity reduction problem that consumed energy caused by the process.Therefore, according to
Biodegradable polyester resin prepared by the present invention shows excellent colourity and acid number, is prepared such as by the polyester resin
The mechanical properties of the end article of film or monofilament etc. can also be improved.
In addition, Biodegradable polyester resin preparation method of the invention is used and has used batch process and continuous
The semi continuous preparation method of formula technique, thus compared with situation about only being produced with existing continuous process, work as production
During varietal change, it can be ensured that to operation easiness such as the washing and cleaning operations of reactor.
Brief description of the drawings
Fig. 1 be medelling show the semi continuous of Biodegradable polyester resin according to an embodiment of the invention
The figure of preparation technology.
<Reference>
1：First batch reactor 2：Second batch reactor
3：Surge tank 31,33：High-pressure piston pump
32：Gear pump 4：Premixer
5：Main blender
PI：Pressure indicator
TI：Temperature indicator
Specific embodiment
The present invention relates to a kind of semi continuous preparation method of Biodegradable polyester resin.
Reference picture 1, the semi continuous preparation method to Biodegradable polyester resin of the invention is examined or check, institute
Stating preparation method includes：(I) step, by least one dicarboxylic acids, aliphatic in aliphatic dicarboxylic acid and aromatic dicarboxylic acid
At least one dihydroxylic alcohols and catalyst in dihydroxylic alcohols are put into the first batch reactor, so as to by the dicarboxylic acids and described
Dihydroxylic alcohols carries out esterification；(II) step, the second batch (-type) is transplanted on by the esterification reaction product obtained from (I) step
Reactor, so as to carry out polycondensation reaction；(III) step, the polycondensation product of the molten condition that will be obtained from (II) step
Surge tank is transplanted on to be stored；And (IV) step, the polycondensation product and chain extender in the surge tank are supplied to
Flow reactor, so as to carry out chain extending reaction.
With reference to the accompanying drawings, the half of Biodegradable polyester resin according to an embodiment of the invention is illustrated by step
Continuous preparation method.
(I) esterif iotacation step
The step is to put into the dicarboxylic acids to the first batch reactor 1 dicarboxylic acids, dihydroxylic alcohols and catalyst
The step of esterification being carried out with the dihydroxylic alcohols.
The dicarboxylic acids used in the present invention can include substituted or non-substituted C4~C10Aliphatic dicarboxylic acid and
Substituted or non-substituted C8~C20Aromatic dicarboxylic acid at least one dicarboxylic acids.The dicarboxylic acids can for example include fat
At least one dicarboxylic acids in fat race dicarboxylic acids and aromatic dicarboxylic acid, the aliphatic dicarboxylic acid include malonic acid, succinic acid,
Glutaric acid, 2- methylglutaric acids, 3- methylglutaric acids, adipic acid, pimelic acid, azelaic acid, decanedioic acid, heneicosanedioic acid, 12
Docosandioic acid, tridecandioic acid, tetracosandioic acid, fumaric acid, 2,2- dimethylated pentanedioic acids, suberic acid, maleic acid, itaconic acid or it
Combination aliphatic dicarboxylic acid；The aromatic dicarboxylic acid include terephthalic acid (TPA), M-phthalic acid, 2,6- naphthoic acids,
1,5- naphthoic acids or combinations thereof.
The dihydroxylic alcohols can include substituted or non-substituted C2~C10Aliphatic dihydroxy alcohol at least one binary
Alcohol.The dihydroxylic alcohols can for example include comprising ethylene glycol, 1,2- propane diols, 1,3- propane diols, 1,2- butanediols, 1,4- fourths two
Alcohol, 1,5- pentanediols, 1,6-HD, 2,4- dimethyl -2- ethyl -1,3- hexylene glycols, 2,2- dimethyl -1,3- propane diols,
2- ethyl -2- butyl -1,3- propane diols, 2- ethyl -2- isobutyl group -1,3- propane diols, 2,2,4- trimethyls -1,6-HD or
At least one dihydroxylic alcohols in the aliphatic dihydroxy alcohol of combinations thereof.
The content of the dihydroxylic alcohols, relative to 1 mole of the dicarboxylic acids, can be 1~2 mole.The dicarboxylic acids and described
Dihydroxylic alcohols, in polymerization prepared by the semi continuous for the Biodegradable polyester resin, in ratio stoichiometrically
In the case of being reacted, can be by 1:1 mol ratio is reacted.That is, the usage amount of described dihydroxylic alcohols is to the dicarboxylic acids
Usage amount can be 1:1 (mol ratio), but in order to promote to react, improve yield, compared with the usage amount of the dicarboxylic acids, institute
The usage amount for stating dihydroxylic alcohols can be excessive.
The catalyst is used to perform the effect for promoting the esterification and the polycondensation reaction, the throwing of the catalyst
Enter amount relative to the dicarboxylic acids 1mol, preferably 0.1~0.4mmol.If the content of the catalyst be the scope with
It is interior, then polymerisation can occur with excellent reaction efficiency, the Biodegradable polyester resin for being prevented from thus preparing
The physical property such as colourity reduction problem.
The catalyst can be included containing selected from by titanium (Ti), tin (Sn), antimony (Sb), cerium (Ce), germanium (Ge), zinc
(Zn), at least one gold in the group of cobalt (Co), manganese (Mn), iron (Fe), aluminium (Al), magnesium (Mg), calcium (Ca) and strontium (Sr) composition
The metallic compound of category.The catalyst for example can include being selected from by calcium acetate, manganese acetate, magnesium acetate, zinc acetate, monobutyl
Tin oxide, Dibutyltin oxide, dibutyl tin dichloride, only son's hydroxyl tin oxide (monobutyl hydroxyl tin
Oxide), tin octylate, tetrabutyltin, tetraphenyltin, metatitanic acid triethyl (triethyl titanate), the propyl ester of acetyl metatitanic acid three
(acetyl tripropyl titanate), tetramethoxy titanate ester (tetramethyl titanate), metatitanic acid orthocarbonate
(tetrapropyl titanate), tetraisopropyl titanate (tetraisopropyl titanate), tetra-n-butyl titanate
(tetra (n-butyl) titanate) and four (2- ethylhexyls) titanate esters (tetra (2-ethylhexyl) titanate) group
Into group in a kind of metallic compound.
In addition, in the esterification, can also include being selected from by glycerine, pentaerythrite and trimethylolpropane group
Into group at least one branching agent.The content of the branching agent, relative to the dicarboxylic acids 1mol, can be 0.001mol
~0.05mol, if the content of the branching agent is within the scope, in the situation of the gelation for preventing polyester resin
Under, the polyester resin of the desired degree of polymerization can also be obtained.
After terminating esterification in the esterif iotacation step, in first batch reactor 1, relative to described two
Carboxylic acid 1mol, can put into stabilizer by 0.01mmol~0.5mmol scopes.The stabilizer is used to perform the reduction catalysis
The active effect of agent, not only suppresses because of back reaction caused by catalyst or side reaction, and can improve described later by polycondensation
The product obtained in step high temperature storing stabilization in the molten state.
The stabilizer can be the phosphorus compound for including phosphorous (P), for example, can include being selected from by phosphorous acid, sub- phosphine
Sour (phosphonous acid), Trimethyl phosphite, triethyl phosphite, tripropyl phosphite, triphenyl phosphite, phosphorous
At least one phosphorus compound in the group of sour sodium and sodium hypophosphite composition.
The esterification can be carried out 60 minutes~300 minutes at 160 DEG C~240 DEG C.The knot of the esterification
Beam time point can measure the water of subsidiary generation in the reaction or the amount of alcohol to determine.For example, distinguishing when as the dicarboxylic acids
Using adipic acid and dimethyl terephthalate (DMT) 0.6mol and 0.4mol, BDO 1.3mol is used as the dihydroxylic alcohols
When, it is assumed that the adipic acid and all amounts of dimethyl terephthalate (DMT) for being used react with BDO, then, if subsidiary
Generating the maximum 1.2mol water for producing that can attach can attach more than the 95% of the 0.8mol methyl alcohol for producing with maximum, i.e.
Water 1.14mol and more than methyl alcohol 0.76mol are incidentally generated, then can terminate the esterification.
In the esterification, in order to increase reaction speed by mobile chemical balance, can be by subsidiary generation
Water, alcohol and/or unreacted dihydroxylic alcohols are discharged to outside reaction system by means of evaporation or distillation.
By means of esterification as described above, esterification reaction product (oligomer) of the generation with ester bond.
(II) condensation polymerization step
The step is that the esterification reaction product (oligomer) is transplanted on into the second batch reactor 2 and to carry out polycondensation anti-
The step of answering.
The polycondensation reaction can carry out 40 minutes~300 at 220 DEG C~260 DEG C with 2 supports (torr) pressure below
Minute.Like this, the polycondensation reaction is carried out under vacuo, such that it is able in removal unreacting material (unreacted monomer and low
Polymers) and it is subsidiary produce water/butanediol in the case of, obtain the polycondensation product of HMW.
Melt index (the melting index of the polycondensation product obtained from the step:MI) can be 30g/10min
~100g/10min.When the melt index is less than 30g/10min, exists and gelation and workability occur in chain extending reaction
The worry of decline, conversely, when more than 100g/10min, the extension holdup time being may require that in chain extension step, reaction temperature is raised
The follow up measures such as degree, increase mixing speed.In the present invention, melt index is represented and uses 2160g's at 190 DEG C to polymer
When loading 10 minutes, the polymer weight (g) being forced out by extruding viscosimeter hole (0.0825 inch of diameter), and according to
ASTM D1238 are measured.
(III) storing step
The step is that the polycondensation product of the molten condition obtained from the condensation polymerization step is transplanted on into surge tank 3 to carry out
The step of storage, be the centre for connecting the condensation polymerization step using batch process and the chain extension step using continuous process
Step.
So-called intermittence type polymerization method, it is meant that by reactant in the early stage all added to reactor, after the completion of polymerization, will
The method that the polymer of completion is reclaimed as final product.That is, in esterif iotacation step of the invention, reactant of esterification is existed
Initial stage, all input, to the first batch reactor 1, after the completion of esterification, was returned product as final product
Receive, in condensation polymerization step, the final product reclaimed in the esterif iotacation step is all put into the second intermittent reaction in the early stage
Device 2, after the completion of polycondensation reaction, final product is recovered as by product quickly.
It was in the past to be dried after being solidified into the shapes such as particle using the final product obtained in the condensation polymerization step, and
The dry particle is carried out into remelted method in chain extension step, so as to be prepared into the biology with desired viscosity
Degradability polyester resin.But, according to this conventional method, solidification, drying in particle and it is remelted when produce consumption big
Energy, the problem that physical property is also reduced.
Therefore, used following methods in the present invention, methods described as will not by with batch (-type) by esterif iotacation step
And the product of the molten condition of condensation polymerization step is solidified, but according to the facts it is transplanted on anti-for chain extension by surge tank 3
The flow reactor 4,5 answered.
Specifically, the surge tank 3 is to produce the polycondensation reaction spued quickly from second batch reactor 2
Thing, in the space that input is stored to before being used for the flow reactor 4,5 of chain extending reaction, the contracting in the surge tank 3
Polybutadiene reaction product is continuously supplied to flow reactor 4,5.In order to successfully carry out this continuous production, preferably described
Terminate in second batch reactor 2 before next batch (-type) polycondensation reaction terminates, by the product in the surge tank 3
Supplied to the flow reactor 4,5.
The storing step of this polycondensation product can be performed under the covering (blanket) of nitrogen, at this point it is possible to press down
System because with air in oxygen and contact with moisture caused by the polycondensation product physical property reduce problem.
In the storing step, the polycondensation product can be cooled to 180~200 DEG C of temperature.When the polycondensation
When product is cooled to the temperature range, can maximize will produce after being spued from surge tank 3 in the polycondensation reaction
The effect of the stabilizer put into thing, thus be preferred.Used as the effect of the stabilizer, Ke Yiyou suppresses because of the contracting
Residual catalyst present in polybutadiene reaction product and the such as pyrolysis, oxidation reaction in subsequent technique that may occur
And the side reaction such as hydrolysis, and improve the heat endurance of polycondensation product under molten condition and ensure that high temperature storage is steady
It is qualitative etc..
The stabilizer can be between (III) storing step and (IV) chain extension step described later, additional input to institute
Polycondensation product is stated, preferred input amount can be 0.05mmol~2.0mmol relative to the dicarboxylic acids 1mol.Specifically
Ground, the polycondensation product from surge tank 3 discharge after, as shown in figure 1, can by high-pressure piston pump 31, gear pump 32 and
High-pressure piston pump 33 and put into flow reactor 4,5, it is preferable that the stabilizer can be by positioned at the front end of gear pump 32
High-pressure piston pump 31 and put into the polycondensation product.
(IV) chain extension step
The step is to put into flow reactor 4,5 polycondensation product and chain extender in the surge tank 3
The step of carrying out chain extending reaction.
As previously described, the polycondensation product in the surge tank 3 can put into process and put into even through stabilizer
Continuous formula reactor 4,5, therefore, chain extending reaction according to the present invention can will put into the polycondensation reaction of the stabilizer
Product and the chain extender put into in the case of the flow reactor 4 and perform.Specifically, as shown in figure 1, can pass through
Positioned at the high-pressure piston pump 33 of the rear end of gear pump 32, chain extender is put into the polycondensation product put into it is anti-to continous way
Device 4 is answered to perform.
In addition, the chain extender can be simultaneously put into the flow reactor 4 with the polycondensation product
Reacted under situation.Chain extender timing input can be adjusted according to circumstances and suitably.
The content of the chain extender is preferably 0.01 weight portion~5 weight relative to the weight portion of the polycondensation product 100
Amount part, but when the content of the stabilizer increases, it is also possible to correspondingly increase the content of chain extender.As the chain extension
Agent, it is possible to use polyvalent isocyanate compound.For example, as polyvalent isocyanate compound, it is possible to use selected from by 2,4-
Toluene di-isocyanate(TDI), 2,6- toluene di-isocyanate(TDI)s, '-diphenylmethane diisocyanate, xylylene diisocyanate, 1,5-
One or more of group of naphthalene diisocyanate, hexamethylene diisocyanate and triphenylmethane triisocyanate composition.
It is preferred that the chain extension step is performed 20 minutes~50 minutes at 190 DEG C~200 DEG C, when in the temperature and time
In the range of when performing chain extending reaction, the Biodegradable polyester with the desired viscosity for meeting commercial physical property can be prepared
Resin, thus be preferred.
The flow reactor used in this chain extension step can be selected from by extruder, tandem (list)
One kind in the group of reactor and static mixer (static mixer) composition.
As described above, in the present invention, by importing and batch polymerization processes and continous way chain extending reaction technique have been used
Semi continuous (semi-continuous type) preparation method so that the solidification once required without conventional batch process
And remelted process, just can prepare Biodegradable polyester resin such that it is able to be substantially reduced because solidification, it is dry and remelted
Energy-output ratio caused by process, and can solve the problem that the thus physical property such as caused colourity and acid number reduction problem.
Embodiment is set forth below, the present invention is described in more detail, but simultaneously non-invention is defined in these embodiments.
Embodiment 1
<Step of esterification>
By 1,4- butanediols 11.45kg (127.05mol), adipic acid 17.68kg (120.98mol), tetra-n-butyl titanate
After 5.5g (0.016mol) inputs to the first batch reactor 1, warming while stirring, after the water for flowing out 4,300ml, will be interior
Portion's temperature increases to 215 DEG C.As a result, obtaining as the adipic acid dihydroxy butyl ester (Bis of esterification reaction product
Hydroxybutyl Adipate,BHBA).Then, generation have first batch reactor 1 of the BHBA in put into Isosorbide-5-Nitrae-
Butanediol 18.29kg (202.95mol), dimethyl terephthalate (DMT) 19.22kg (98.97mol), the glycerine as branching agent
55.5g (0.60mol), as the tetra-n-butyl titanate 5.5g (0.016mol) of polymerization catalyst after, warming while stirring, stream
After going out the methyl alcohol of 8,000ml, the inside reactor temperature is increased to 215 DEG C.As a result, obtaining final esterification instead
Answer product.
Then, put into as the phosphorous acid of stabilizer in the esterification reaction product in first batch reactor 1
3.0g (0.037mol), stirs 10 minutes, after preparing reaction solution, by the reaction solution transfer in first batch reactor 1
To the second batch reactor 2.
<Polycondensation steps>
In the case of the reaction solution of second batch reactor 2 being transplanted on using double helix with blade stirring,
After internally temperature reaches 220 DEG C, then implement decompression 30 minutes, pressure is reached 5 supports.Then, by the reaction solution at 225 DEG C
At a temperature of in the case of stir, by the pressure 20 minutes in second batch reactor 2, pressure is reached 2
Support, is warming up to 240 DEG C, by terminating polycondensation reaction after 4 hours.As a result, obtaining polycondensation product (hereinafter referred to as
“Base-PBAT”)。
Then, the decompression inside second batch reactor 2 is released, is implemented to pressurize with nitrogen, the polycondensation is anti-
Product is answered to be transplanted on surge tank (high temperature storage tank) 3.
<Storing step and chain extension step>
The polycondensation product that the molten condition of the surge tank 3 will be transplanted on is rapidly cooled to 190 DEG C and stores.
Then, in order to continuously produce, before next batch (-type) polycondensation reaction is terminated in second batch reactor 2, by institute
The polycondensation product stated in surge tank 3 was supplied to static mixer by the way that gear pump 32 is continuous with the speed of 6.6kg/ hours
(combination (SMX and Helical type combination) of ternary engineering company, SMX and screw type) 4,5.
Now, by the high-pressure piston pump 31 positioned at the front end of the gear pump 32, using as the phosphorous acid of stabilizer with 1g/
The speed of hour is put into the polycondensation product, then, in the polycondensation product for having passed through the gear pump 32, is led to
Cross hexa-methylene of the high-pressure piston pump 33 for being located at the rear end of the gear pump 32 using the speed input of 60g/ hours as chain extender
After diisocyanate (HDI), the polycondensation reaction product for including the stabilizer and chain extender is supplied to the static mixer 4,5
Thing.
The static mixer is made up of premixer 4 and main blender 5, and the polycondensation product and chain extender are pre-
In blender 4, it is pre-mixed at 190 DEG C 1.5 minutes, then, in main blender 5, is told after being detained 25 minutes at 195 DEG C
Go out.As a result, being finally obtained polyadipate/butylene terephthalate (poly (butylene adipate-co-
terephthalate):PBAT) resin (hereinafter referred to as " Final-PBAT ").
Then, by the Final-PBAT spued from the static mixer in water in cool down after, using line material cutter
(Strand cutter) is granulated, and is made Final-PBAT chips.
Embodiment 2
<Step of esterification>
Using 1,4- butanediols 20.73kg (230.02mol), succinic acid 23.62kg (200.17mol) and as branching agent
After glycerine 20g (0.22mol) inputs to the first batch reactor 1, warming while stirring, after outflow 7,200ml water, will be interior
Portion's temperature increases to 205 DEG C.Then, put into first batch reactor 1 as polymerization catalyst metatitanic acid four just
Butyl ester 16g (0.047mol) and as the phosphorous acid 6.0g (0.073mol) of stabilizer after, stirring 10 minutes and be prepared for reaction
Liquid.Then, the reaction solution in first batch reactor 1 is transplanted on the second batch reactor 2.
<Condensation polymerization step>
The condensation polymerization step of the reaction solution of second batch reactor 2 is transplanted on identical with the embodiment 1
Method carry out.As a result, obtain polycondensation product (hereinafter referred to as " Base-PBS "), and by its with the implementation
The identical method of example 1 is transplanted on surge tank 3.
<Storing step and chain extension step>
Be transplanted on the surge tank 3 the polycondensation product " storing step and chain extension step " with the implementation
The identical method of example 1 is carried out.As a result, poly butylene succinate (poly (butylene are finally obtained
succinate):PBS) resin (hereinafter referred to as " Final-PBS ") and Final-PBS chips.
Comparative example 1
<Step of esterification>
In " step of esterification " the identical method with the embodiment 1, prepared in the first batch reactor 1 anti-
Liquid is answered, the reaction solution is transplanted on the second batch reactor 2.
<Condensation polymerization step>
To be transplanted on second batch reactor 2 the reaction solution condensation polymerization step with the phase of the embodiment 1
Same method is carried out, but is not to be warming up to 240 DEG C and by terminating polycondensation reaction after 4 hours, but is warming up to 240 DEG C and is passed through
Terminate polycondensation reaction after 5 hours.As a result, obtaining polycondensation product (hereinafter referred to as " Base-PBAT ").
After polycondensation reaction terminates, by nitrogen pressurize will the Base-PBAT that be spued from the second batch reactor 2 in water
After cooling, granulated using line material cutter (strand cutter), be prepared for Base-PBAT chips (chip).
The Base-PBAT chips are dried extremely by dehumidifying heat pump (modern electrical mechanical industry company, HDD-050)
Below moisture 100ppm.
<Chain extension step>
By by the Base-PBAT chips 10kg, hexamethylene diisocyanate (HDI) 0.01kg of drying process and
Phosphorous acid 0.002kg mixes 1 minute in super blender, using double screw extruder (prosperous P＆R companies product, L/D:36/
1, diameter：24.2mm), reaction extrusion process is implemented at 150 DEG C, is then entered in water-filling after cooling, using line material cutter
(strand cutter) is granulated, and is prepared into chip (chip).Cut as a result, being finally obtained Final-PBAT
Bits.
Comparative example 2
<Step of esterification>
In " step of esterification " the identical method with the embodiment 2, prepared in the first batch reactor 1 anti-
Liquid is answered, the reaction solution is transplanted on the second batch reactor 2.
<Condensation polymerization step>
The condensation polymerization step of the reaction solution of second batch reactor 2 is transplanted on identical with the comparative example 1
Method carry out.As a result, obtaining polycondensation product (hereinafter referred to as " Base-PBS ").
After polycondensation reaction terminates, by nitrogen pressurize will the Base-PBAT that be spued from the second batch reactor 2 in water
After cooling, granulated using line material cutter (strand cutter), be prepared for Base-PBAT chips (chip).
The Base-PBS chips are dried extremely by dehumidifying heat pump (modern electrical mechanical industry company, HDD-050)
Below moisture 100ppm.
<Chain extension step>
By by the Base-PBS chips 10kg of drying process and hexamethylene diisocyanate (HDI) 0.025kg
And phosphorous acid 0.002kg mixes 1 minute in super blender, using double screw extruder (prosperous P＆R companies product, L/D:
36/1, diameter：24.2mm), reaction extrusion process is implemented at 150 DEG C, after then being cooled down in water, using line material cutter
(strand cutter) is granulated, and is prepared into chip (chip).As a result, obtaining Final-PBS chips.
Evaluation method
The Base-PBAT chips and Final- prepared according to the embodiment 1 and comparative example 1 are measured according to following method
PBAT chips, the melt index (MI) of the Base-PBS chips prepared according to embodiment 2 and comparative example 2 and Final-PBS chips,
Colourity and acid number, its result is shown in table 1 below.Now, the Base-PBAT chips of the embodiment 1 are using as polycondensation
After the Base-PBAT of product is cooled down in water, granulated using line material cutter (strand cutter) and prepared
, the Base-PBS chips of embodiment 2 are that the Base-PBS as polycondensation product is granulated in the same way
And prepare.Then, described each chip is dried by dehumidifying heat pump (modern electrical mechanical industry company, HDD-050)
To below moisture 100ppm.
On the other hand, in table 1 below, the Base of embodiment 1 and comparative example 1 represents Base-PBAT chips, and Final is represented
Final-PBAT chips, in embodiment 2 and comparative example 2, Base represents Base-PBS chips, and Final represents that Final-PBS cuts
Bits.
1. melt index (MI)
Measured when the load 10 minutes of 2160g is used polymer at 190 DEG C, by squeezing according to ASTM D1238
The weight (g) of the polymer for going out viscosimeter hole (0.0825 inch of diameter) and being forced out, its value is shown in table 1 below.
2. colour measurement
Using Konica Minolta (Konica Minolta) colour difference meter, in CIE-L*a*b* (CIE 1976) chromaticity coordinates
Measure L*, a* and b*." L* " value, " a* " value and " b* " value are the colors identified in CIE-L*a*b* (CIE1976) chromaticity coordinates
The index of tune." L* " value represents brightness, and the numerical value is bigger, then brighter." a* " value represents red degree, and the numerical value is bigger, then red
Colourity is higher." b* " value represents yellow degree, and the numerical value is bigger, then it represents that yellow chromaticity is higher.Now, L* values are bigger, then it represents that
Color is brighter, and b* values are smaller, then it represents that closer to the color of white, thus it is excellent to be evaluated as colourity.
3. acid number measurement
By the Base-PBAT chips, Final-PBAT chips, Base-PBS chips and Final-PBS chips about 0.5g
It is additional to add ethanol 20ml after making solution, to use 0.1N KOH after chloroform (Chloroform) 30ml is dissolved at 25 DEG C
Ethanol solution is titrated, and measures the acid number of each resin.
4. crystallization temperature (Tc)
Using differential scanning calorimeter (DSC) (TA instrument companies, Q2000), measured with 10 DEG C/min programming rates.
[table 1]
If examining or check the table 1, can confirm that the Final-PBAT chips prepared according to embodiment 1 compared to according to comparing
Final-PBAT chips prepared by example 1, colourity and acid number are excellent, and the Final-PBS chips according to the preparation of embodiment 2 are compared to root
According to Final-PBS chips prepared by comparative example 2, colourity and acid number are excellent.In addition, the biology prepared according to the embodiment 1 and 2
Degradability polyester resin shows that crystallization temperature (Tc) is low compared to the Biodegradable polyester resin prepared according to comparative example 1 and 2,
Now, when processing film is carried out, because crystallization is slow, with less there is the effect of orientation, thus can improve
The longitudinal direction (MD) of film and the laterally homogeneity of (TD) physical property.
5. film evaluation of physical property
The Final-PBAT chips prepared according to the embodiment 1 and comparative example 1 are put into single screw rod blown film respectively and is squeezed
Go out machine (bull wheel machinery, L/D:28:1, mode diameter：45mm, cylinder temperature：190 DEG C), it is shaped to film.30 μ are obtained as a result
The film of m thickness.
In ASTM D-638 methods, measured using universal tensile testing machine (Instron Corporation, UTM-4484) each thin
Tensile strength on the longitudinal direction (MD) of film and laterally (TD), in ASTM D-1922 methods, using tear tester (Thwing-
Albert instrument companies, ProTearTM) measure Elmendorf (Elmendorf) tearability of longitudinal direction (MD).
[table 2]
If examining or check the table 2, it has been confirmed that using embodiment 1 Final-PBAT prepare film compared to utilization
Film prepared by the Final-PBAT of comparative example 1, shows tensile strength and tearing strength high.
6. monofilament evaluation of physical property
The Final-PBS chips prepared according to the embodiment 2 and comparative example 2 are utilized respectively melt spinning device (GNS
Company, JSM-65) it is prepared into monofilament.Now, draw ratio is 6.8 times.The monofilament obtained using mode so makes 20 examinations
Piece, a diameter of 0.404mm of each test piece.
It is described each with the measurement of ASTM D-2256 methods using universal tensile testing machine (Instron Corporation, UTM-4484)
The tension load (kgf) of monofilament, tensile strength and extensibility are measured in ASTM D-638 methods.Now, the tension load
The maximum load before fracture when applying to load to monofilament along its length is represented, is the value not maked corrections to the value of thickness.
Tension load, tensile strength and extensibility described in table 3 below are directed to the measured value of 20 monofilament test pieces
Average value, in the physical measurement, the interval between holding rod (grip) is 400mm, and test speed is entered with 300mm/min
Row measurement.
And, in table 3 below, " difference " represents the length of elongation maximum monofilament when being broken in 20 monofilament test pieces
Degree subtracts the value after the length of the minimum monofilament of elongation.
[table 3]
| Tension load (kgf) | Extensibility (%) | Difference (mm) | ||
| Embodiment 2 | 6.35 | 4,960 | 26 | Δ13 |
| Comparative example 2 | 5.80 | 4,500 | 28 | Δ30 |
If examining or check the table 3, can confirm that the monofilament that is prepared using the Final-PBS chips of embodiment 2 compared to
The monofilament prepared using the Final-PBS of comparative example 2 shows tension load and tensile strength high, can confirm that and shows
Low extensibility.In addition, for monofilament prepared by the Final-PBS chips using embodiment 2, " difference " value is smaller, by
The degree that this extends before understanding fracture is homogeneous.
Embodiment disclosed in the above present invention is not intended to limit technological thought of the invention but for illustrating this hair
Bright technological thought.Interest field of the invention should explain by claims of the present invention, with its equal category in
All technological thoughts should be interpreted to be contained in interest field of the invention.
Claims (11)
1. the semi continuous preparation method of a kind of Biodegradable polyester resin, including：
(I) step, by least one dicarboxylic acids, the aliphatic dihydroxy alcohol in aliphatic dicarboxylic acid and aromatic dicarboxylic acid extremely
A kind of few dihydroxylic alcohols and catalyst are put into the first batch reactor, so as to the dicarboxylic acids and the dihydroxylic alcohols are carried out into ester
Change reaction；
(II) step, is transplanted on the second batch reactor, so as to carry out by the esterification reaction product obtained from (I) step
Polycondensation reaction；
(III) step, is transplanted on the polycondensation product of the molten condition obtained from (II) step surge tank and is deposited
Storage；And
(IV) step, is supplied to flow reactor, so as to carry out by the polycondensation product and chain extender in the surge tank
Chain extending reaction.
2. the semi continuous preparation method of Biodegradable polyester resin according to claim 1, it is characterised in that
After terminating esterification in (I) step, in first batch reactor, relative to the dicarboxylic acids
1mol, stabilizer is put into by 0.01mmol~0.5mmol scopes.
3. the semi continuous preparation method of Biodegradable polyester resin according to claim 2, it is characterised in that
The stabilizer include be selected from by phosphorous acid, phosphonous acid, Trimethyl phosphite, triethyl phosphite, tripropyl phosphite,
At least one compound in the group of triphenyl phosphite, sodium phosphite and sodium hypophosphite composition.
4. the semi continuous preparation method of Biodegradable polyester resin according to claim 1, it is characterised in that
The melt index of the polycondensation product obtained from (II) step is 30g/10min~100g/10min.
5. the semi continuous preparation method of Biodegradable polyester resin according to claim 1, it is characterised in that
(III) step is performed under the covering of nitrogen.
6. the semi continuous preparation method of Biodegradable polyester resin according to claim 1, it is characterised in that
In (III) step, the polycondensation product is cooled to 180 DEG C~200 DEG C temperature.
7. the semi continuous preparation method of Biodegradable polyester resin according to claim 1, it is characterised in that
Between (III) step and (IV) step, in the polycondensation product, relative to the dicarboxylic acids
1mol, stabilizer is put into by 0.05mmol~2.0mmol scopes.
8. the semi continuous preparation method of Biodegradable polyester resin according to claim 7, it is characterised in that
In (IV) step, input there is into the continuous input of the polycondensation product and the chain extender of the stabilizer extremely
The chain extending reaction is performed in the case of the flow reactor.
9. the semi continuous preparation method of Biodegradable polyester resin according to claim 1, it is characterised in that
(IV) step is performed 20 minutes~50 minutes at 190 DEG C~200 DEG C.
10. the semi continuous preparation method of Biodegradable polyester resin according to claim 1, it is characterised in that
The flow reactor is selected from the one kind in the group being made up of extruder, tandem reactor and static mixer.
The semi continuous preparation method of 11. Biodegradable polyester resins according to claim 1, it is characterised in that
The content of the chain extender is 0.01 weight portion~5 weight portion relative to the weight portion of the polycondensation product 100.
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| KR101989045B1 (en) * | 2017-12-28 | 2019-06-13 | (주) 티엘씨 코리아 | Biodegradable resin composition having excellent weather resistance and storage stability and the method of manufacturing the same |
| WO2020226199A1 (en) * | 2019-05-07 | 2020-11-12 | Tlc Korea Co., Ltd. | Biodegradable resin composition having excellent weather resistance and storage stability and production method thereof |
| WO2021141236A1 (en) * | 2020-01-09 | 2021-07-15 | 주식회사 안코바이오플라스틱스 | Biodegradable resin composition having improved mechanical properties, moldability, and weather resistance, and preparation method therefor |
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| KR100226009B1 (en) * | 1997-04-25 | 1999-10-15 | 구광시 | Semi-continuous process for preparing polyester having buffer reactor |
| KR100430627B1 (en) * | 2001-07-10 | 2004-05-10 | 주식회사 코오롱 | A process of preparing the alkali extractable polyester |
| BRPI0911045B8 (en) * | 2008-04-15 | 2020-03-10 | Basf Se | process for the continuous production of a biodegradable polyester, biodegradable polyester, biodegradable polyester blend, and use of polyesters. |
| BR112012008514A2 (en) | 2009-10-15 | 2016-04-05 | Basf Se | process for continuous production of polyester blends |
| JP2013144754A (en) | 2012-01-16 | 2013-07-25 | Toray Ind Inc | Method for producing copolyester |
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