CN114367257A - Polyester resin and preparation method and synthesis device thereof - Google Patents
Polyester resin and preparation method and synthesis device thereof Download PDFInfo
- Publication number
- CN114367257A CN114367257A CN202111348745.3A CN202111348745A CN114367257A CN 114367257 A CN114367257 A CN 114367257A CN 202111348745 A CN202111348745 A CN 202111348745A CN 114367257 A CN114367257 A CN 114367257A
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- Prior art keywords
- polyester resin
- liquid distributor
- reaction
- reaction kettle
- falling film
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- 239000004645 polyester resin Substances 0.000 title claims abstract description 104
- 229920001225 polyester resin Polymers 0.000 title claims abstract description 104
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 36
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 189
- 239000007788 liquid Substances 0.000 claims abstract description 113
- 239000011552 falling film Substances 0.000 claims abstract description 80
- 239000010408 film Substances 0.000 claims abstract description 20
- 238000009826 distribution Methods 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 23
- 238000000576 coating method Methods 0.000 claims description 22
- 238000005886 esterification reaction Methods 0.000 claims description 21
- 238000006068 polycondensation reaction Methods 0.000 claims description 21
- 239000000843 powder Substances 0.000 claims description 19
- 239000002253 acid Substances 0.000 claims description 16
- 230000002194 synthesizing effect Effects 0.000 claims description 16
- 230000032050 esterification Effects 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 239000011248 coating agent Substances 0.000 claims description 12
- 238000001723 curing Methods 0.000 claims description 11
- 239000000155 melt Substances 0.000 claims description 11
- 150000007519 polyprotic acids Polymers 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 150000005846 sugar alcohols Polymers 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 6
- 238000005903 acid hydrolysis reaction Methods 0.000 claims description 5
- 238000009833 condensation Methods 0.000 claims description 5
- 230000005494 condensation Effects 0.000 claims description 5
- 230000009477 glass transition Effects 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 229920005862 polyol Polymers 0.000 claims description 3
- 150000003077 polyols Chemical class 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 2
- 239000003973 paint Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 18
- 239000006227 byproduct Substances 0.000 abstract description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 25
- 229920000728 polyester Polymers 0.000 description 12
- 229920005989 resin Polymers 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- 230000008569 process Effects 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 230000001276 controlling effect Effects 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 2
- 229960002130 benzoin Drugs 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 2
- -1 polyethylene terephthalate Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 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 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 1
- NGCDGPPKVSZGRR-UHFFFAOYSA-J 1,4,6,9-tetraoxa-5-stannaspiro[4.4]nonane-2,3,7,8-tetrone Chemical compound [Sn+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O NGCDGPPKVSZGRR-UHFFFAOYSA-J 0.000 description 1
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 description 1
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- FQYHHEJETOLDHR-UHFFFAOYSA-K butyl(chloro)tin(2+);dihydroxide Chemical compound CCCC[Sn](O)(O)Cl FQYHHEJETOLDHR-UHFFFAOYSA-K 0.000 description 1
- BVFSYZFXJYAPQJ-UHFFFAOYSA-N butyl(oxo)tin Chemical compound CCCC[Sn]=O BVFSYZFXJYAPQJ-UHFFFAOYSA-N 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007590 electrostatic spraying Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- JHYNXXDQQHTCHJ-UHFFFAOYSA-M ethyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1 JHYNXXDQQHTCHJ-UHFFFAOYSA-M 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 229940119177 germanium dioxide Drugs 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000013035 low temperature curing Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 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 1
- 238000005086 pumping Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 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 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- ADDWXBZCQABCGO-UHFFFAOYSA-N titanium(iii) phosphide Chemical compound [Ti]#P ADDWXBZCQABCGO-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/009—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping in combination with chemical reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/24—Stationary reactors without moving elements inside
- B01J19/2475—Membrane reactors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/08—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles
- B01J8/10—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles moved by stirrers or by rotary drums or rotary receptacles or endless belts
-
- 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
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
-
- 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
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/199—Acids or hydroxy compounds containing cycloaliphatic rings
-
- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/03—Powdery paints
-
- 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
- C08G2150/00—Compositions for coatings
- C08G2150/20—Compositions for powder coatings
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses a polyester resin and a preparation method and a synthesis device thereof, wherein the synthesis device of the polyester resin comprises a reaction kettle and a falling film reaction tank, a first liquid distributor is arranged in the reaction kettle and is connected with the falling film reaction tank, a second liquid distributor is arranged in the falling film reaction tank and is connected with the reaction kettle. The polyester resin synthesis device provided by the invention has the advantages that materials circulate between the reaction kettle and the falling film reaction tank, liquid distribution is carried out through the first liquid distributor and the second liquid distributor, a liquid film is formed, high-efficiency devolatilization is realized, devolatilization is carried out in the reaction kettle and the falling film reaction tank simultaneously, small molecular byproducts in a polyester resin synthesis system can be removed efficiently, forward progress of polyester resin synthesis reaction is promoted, the degree of polymerization is improved, and polydisperse polyester resin with high viscosity or wide molecular weight distribution index can be synthesized.
Description
Technical Field
The invention belongs to the technical field of high polymer material synthesis, and particularly relates to polyester resin, a preparation method and a synthesis device thereof.
Background
In the polyester synthetic raw materials for the powder coating, alcohol and water can be mutually dissolved in any proportion, the boiling points are close, and the alcohol and the water are difficult to separate, so that the function of the synthetic equipment needs to pay attention to the separation of the alcohol and the esterified water and the loss of the low-boiling-point alcohol at the initial stage of the synthetic reaction; after esterification reaction, vacuum polycondensation is usually required, the function of the synthesis equipment needs to pay attention to enhancing stirring to improve the mass transfer effect, remove trace water in the system and improve the relative molecular mass of the product; in the final stage of production, the temperature is usually reduced and the addition of the auxiliary agent is needed, and equipment with a good dispersing function is needed in the final stage; therefore, the requirements of each stage of synthesis on the structure and the performance of equipment are different, and in the field of general PET (polyethylene terephthalate) polyester, a large-scale production line is designed into a multi-kettle continuous production process which mainly represents a five-kettle process flow represented by Gima and a three-kettle process flow represented by DuPont. The product produced by the continuous method has more stable performance, and reaction kettles with different structures can be designed according to different requirements of different reaction stages on the functions of equipment. However, the continuous reaction equipment is not suitable for small-batch and customized products, domestic powder coatings mostly adopt small-batch and customized sales modes, and the performance requirements of different batches of powder coatings on polyester resin are greatly different. In order to meet the diversified performance requirements of the powder coating on the polyester resin, the polyester resin for the powder coating is produced by adopting an intermittent reaction kettle. The batch type reaction kettle has the advantages of flexible operation, easy adaptation to different operation conditions and product varieties, and suitability for the production of products with small batch, multiple varieties and longer reaction time; however, the whole production process of the existing polyester resin is completed in the same batch type reaction kettle, the structure of the reaction kettle can not be changed according to the requirements of different stages of esterification and polycondensation reaction on equipment, the heat and mass transfer effect is poor, and the domestic coating production requirements can not be met.
The initial stage of polyester resin synthesis is mainly esterification reaction, the equilibrium constant is small, and water in raw materials and generated in the reaction needs to be removed to promote the forward shift of the equilibrium. When the common batch type reaction kettle produces polyester, the polyester resin melt contains low-content micromolecular reactants and product water which are difficult to completely remove in the polycondensation stage, namely the reaction degree can not be improved any more, so that when the high-viscosity polyester is produced, even if measures such as vacuumizing for a long time, increasing the vacuum degree of a secondary vacuum system and the like are adopted, the molecular weight or viscosity improving effect is limited, and the cost of process equipment is greatly increased.
The synthetic polymers all have a certain molecular weight distribution, i.e. have polydispersity. The molecular weight distribution can be expressed by the distribution index d. The molecular weight distribution index is the ratio of the weight average molecular weight Mw to the number average molecular weight Mn, i.e. d ═ Mw/Mn. If d is 1.02 to 1.1, monodisperse is meant, and if d is 1.5 to 3.0, polydisperse is meant. Typically, batch reactor synthesized polyesters have molecular weight distribution indices between 1.1 and 1.5. It is generally believed that certain properties will be more pronounced when the molecular weight distribution range of the polymeric resin for coating is relatively narrow, but in some special applications, it may be desirable to synthesize a polymer having a wider molecular weight distribution and better overall properties, which is difficult to meet with conventional batch reactors.
CN103772674A discloses a method for synthesizing polyester resin, wherein esterification reaction is carried out in a first-stage reaction kettle, polycondensation reaction is carried out in a second-stage reaction kettle, different functional requirements can be realized by designing reaction kettles with differentiated structures, and production efficiency is improved. CN111701553A and other technical schemes can improve devolatilization efficiency to produce high-viscosity polyester, but can only be used as a final polymerization reaction kettle of a continuous production line. The single batch type reaction kettle in the prior art is difficult to simultaneously meet the technical requirements.
Disclosure of Invention
In order to overcome the problems of the prior art, the invention provides a device for synthesizing polyester resin.
The second object of the present invention is to provide a polyester resin.
The invention also aims to provide a preparation method of the polyester resin.
The fourth purpose of the invention is to provide a powder coating.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention provides a polyester resin synthesis device, which comprises a reaction kettle and a falling film reaction tank, wherein a first liquid distributor is arranged in the reaction kettle and is connected with the falling film reaction tank, a second liquid distributor is arranged in the falling film reaction tank and is connected with the reaction kettle. The polyester resin synthesis device provided by the invention can synthesize the polydisperse polyester resin with wider molecular weight distribution index, which is difficult to synthesize by a common batch reaction kettle, according to needs by arranging the first liquid distributor and the falling film reaction tank so as to realize the specific performance requirements.
Preferably, the polyester resin synthesis apparatus is a batch synthesis apparatus.
Preferably, the first liquid distributor is connected with an outlet of the reaction kettle.
Preferably, the second liquid distributor is connected to an outlet of the falling film reaction tank.
Preferably, a stirring device is arranged in the reaction kettle and comprises a stirring shaft, and the first liquid distributor is arranged outside the stirring shaft.
Preferably, the reaction kettle is connected with a rectification system, and the rectification system is connected with a condensation reflux system.
Preferably, the first liquid distributor and the second liquid distributor are each independently a pressure-type porous tubular distributor, a pore flow distributor, or an overflow trough distributor.
Preferably, the reaction kettle and the falling film reaction tank are respectively connected with a vacuum system.
Preferably, a second three-way valve is arranged between the first liquid distributor and the falling film reaction tank; and a first three-way valve is arranged between the reaction kettle and the second liquid distributor and is connected with a second three-way valve.
Preferably, a second melt pump is arranged between the second three-way valve and the falling film reaction tank.
Preferably, a first melt pump is arranged between the reaction kettle and the first three-way valve.
Preferably, the stirring device comprises a stirring shaft, a stirring paddle and a driving motor, the driving motor is arranged at the top of the reaction kettle, the driving motor is connected with the stirring shaft, the stirring shaft is inserted into the reaction kettle and connected with the stirring paddle, and the stirring shaft is sleeved with a first liquid distributor.
Preferably, the condensation reflux system comprises a condenser and a delivery pump, wherein the condenser is connected with the rectification column, the condenser is connected with the delivery pump, and the delivery pump is connected with the rectification column through a pipeline.
The second aspect of the invention provides a polyester resin, which is prepared from the following components in percentage by mass: 33-40% of polyhydric alcohol; 43-60% of polybasic acid; 5-15% of an acidolysis agent; 0.01-0.1% of a catalyst; 0.05-2% of curing accelerator, wherein the polyester resin is prepared by adopting the polyester resin synthesis device provided by the first aspect of the invention.
Preferably, the mass percent of the polyhydric alcohol is 35-40%; more preferably, the mass percent of the polyhydric alcohol is 35-38%.
Preferably, the polyhydric alcohol is at least one of neopentyl glycol, 2-butyl-2-ethyl-1, 3-propanediol, 1, 4-cyclohexanedimethanol, trimethylolpropane and 1, 6-hexanediol.
Preferably, the mass percent of the polybasic acid is 45-55%; more preferably, the mass percent of the polybasic acid is 50-55%.
Preferably, the polybasic acid is selected from at least one of terephthalic acid, isophthalic acid, 1, 4-cyclohexanedicarboxylic acid, 1, 6-adipic acid.
Preferably, the polyol comprises 75-100% by mass of neopentyl glycol, 0-3% by mass of trimethylolpropane, and not 0% by mass of trimethylolpropane.
Preferably, the sum of the mass percent of 1, 6-hexanediol in the polyhydric alcohol and the mass percent of 1, 6-adipic acid in the polybasic acid is 0-3% and is not 0%.
Preferably, the mass percent of the acidolysis agent is 5-12%; more preferably, the mass percent of the acidolysis agent is 7-10%.
Preferably, the acidolysis agent is at least one of isophthalic acid, 1, 4-cyclohexanedicarboxylic acid and 1, 6-adipic acid.
Preferably, the mass percent of the catalyst is 0.05-0.1%; more preferably, the mass percentage of the catalyst is 0.05-0.08%.
Preferably, the catalyst is at least one of a tin-based catalyst, a germanium-based catalyst and a titanium-based catalyst; further preferably, the catalyst is at least one of monobutyl tin oxide, tin oxalate, monobutyl dihydroxy tin chloride, germanium dioxide, tetrabutyl titanate, tetraisopropyl titanate, active titanium dioxide and organic titanium-phosphorus complex.
Preferably, the mass percent of the curing accelerator is 0.1-1.5%; further preferably, the mass percent of the curing accelerator is 0.3-1%; more preferably, the mass percentage of the curing accelerator is 0.4-0.9%.
Preferably, the curing accelerator is at least one of triphenyl ethyl phosphonium bromide and triphenyl phosphine.
Preferably, the preparation raw materials of the polyester resin also comprise an antioxidant.
Preferably, the mass percent of the antioxidant is 0.05-2%; more preferably, the mass percentage of the antioxidant is 0.05-1%.
Preferably, the antioxidant is at least one selected from triphenyl phosphite, antioxidant 168, antioxidant 1010 and antioxidant 1076. The antioxidant 168 is tris (2, 4-di-tert-butylphenyl) phosphite; the antioxidant 1010 is tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester; the antioxidant 1076 is octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate.
Preferably, the polyester resin meets at least one of the following conditions:
(1) the acid value is 25-45 mgKOH/g;
(2) the hydroxyl value is less than 3 mgKOH/g;
(3) the glass transition temperature is 60-70 ℃;
(4) the melt viscosity at 200 ℃ is 4500-;
(5) number average molecular weight of 2500-;
(6) the molecular weight distribution index is 1.5-2.5.
The third aspect of the present invention provides a method for producing a polyester resin provided by the second aspect of the present invention, using the polyester resin synthesizing apparatus provided by the first aspect of the present invention, the method comprising the steps of:
s1: esterification: mixing and reacting polyol, polybasic acid and a catalyst in a reaction kettle, and obtaining an esterification product after the mixed reaction reaches a clear point;
s2: acid hydrolysis: reacting the esterification product with an acidolysis agent;
s3: polycondensation: circulating the product of step S2 between the reaction kettle and the falling film reaction tank;
s4: mixing the product of the step S3 with a curing accelerator, and circulating the mixture between a reaction kettle and a falling film reaction tank to prepare the polyester resin.
Preferably, in step S1, the esterification reaction is performed under oxygen-free conditions.
Preferably, the step S1 further includes a step of automatically cleaning the reaction kettle; the self-cleaning step is accomplished by circulating the reaction mixture between the reaction kettle and the falling film reaction tank. The automatic cleaning step is to prevent coking in the reaction tank.
Preferably, in step S2, the acid hydrolysis step is performed under oxygen-free conditions.
Preferably, in the step S3, the polycondensation step is performed under vacuum conditions; further preferably, step S2 is embodied as: and after the acidolysis reaction is finished, vacuumizing the reaction kettle and the falling film reaction tank to ensure that the materials circulate between the reaction kettle and the falling film reaction tank. Thin-layer liquid films are formed in the reaction kettle and the falling film reaction tank simultaneously, so that the aim of quickly devolatilizing is fulfilled.
Preferably, the step S4 further includes a cooling step, and the cooling step is before the step of mixing the product obtained in the step S3 with the solidification promoter.
Preferably, in step S1, a step of vacuumizing is further included; the degree of esterification can be improved by vacuumizing during the esterification reaction.
In a fourth aspect, the present invention provides a powder coating comprising the polyester resin provided in the second aspect of the present invention.
Preferably, the powder coating further comprises at least one of a curing agent, a leveling agent, a pigment, a filler, benzoin and a brightener.
Preferably, the filler is selected from at least one of titanium dioxide and barium sulfate.
The invention has the beneficial effects that: the polyester resin synthesis device provided by the invention realizes high-efficiency devolatilization through the first liquid distributor and the second liquid distributor by the circulation of materials between the reaction kettle and the falling film reaction tank, and devolatilization is simultaneously carried out in the reaction kettle and the falling film reaction tank, so that small molecular byproducts in a polyester resin synthesis system can be efficiently removed, the forward progress of a polyester resin synthesis reaction is promoted, the degree of polymerization is improved, and the polydisperse polyester resin with higher viscosity or wider molecular weight distribution index can be synthesized.
Drawings
Fig. 1 is a schematic structural view of a polyester resin synthesizing apparatus according to one embodiment of the present invention.
Reference numerals:
the system comprises a rectification system 1, a driving motor 2, a first liquid distributor 3, a heat preservation sleeve 4, a reaction kettle 5, a stirring shaft 6, a first melt pump 7, a first three-way valve 8, a second melt pump 9, a falling film reaction tank 10, a second liquid distributor 11, a second three-way valve 12, a vacuum system 13, a delivery pump 14 and a condenser 15.
Detailed Description
The following detailed description of specific embodiments of the present invention is provided in connection with the accompanying drawings and examples, but the present invention is not limited thereto. It is to be noted that the following processes, if not described in particular detail, are all realizable or understandable by those skilled in the art with reference to the prior art. The reagents or apparatus used are not indicated to the manufacturer, and are regarded as conventional products available commercially. In the description of the present invention, it is to be understood that the terms "central", "longitudinal", "lateral", "width", "thickness", "upper", "lower", "front", "rear", "left", "right", "face", "bottom", and the like, indicate orientations or positional relationships based on those shown in the drawings, and are only for convenience of description and simplicity of description, and do not indicate or imply that the referenced devices or elements must have a particular orientation, be constructed and operated in a particular orientation, and thus, are not to be construed as limiting the present invention.
In the description of the present invention, the meaning of a plurality of means is one or more, the meaning of a plurality of means is two or more, and larger, smaller, larger, etc. are understood as excluding the number, and larger, smaller, inner, etc. are understood as including the number.
A polyester resin synthesizing apparatus according to an embodiment of the invention is described below with reference to fig. 1.
As shown in fig. 1, a schematic structural diagram of a polyester resin synthesizing apparatus according to an embodiment of the present invention includes a reaction kettle 5 and a falling film reactor 10, wherein a first liquid distributor 3 is disposed in the reaction kettle 5, an inlet of the first liquid distributor 3 is connected to an outlet of the falling film reactor 10, a second liquid distributor 11 is disposed in the falling film reactor 10, and an inlet of the second liquid distributor 11 is connected to an outlet of the reaction kettle 5.
In some embodiments of the invention, the polyester resin synthesis apparatus is a batch synthesis apparatus.
In some embodiments of the present invention, the falling film reactor 10 is a vertical cylindrical reactor, and both the upper head and the lower head of the falling film reactor 10 are standard heads. In some embodiments, a circular second liquid distributor 11 is installed inside the falling film reaction tank 10, the diameter of the second liquid distributor 11 is smaller than the inner diameter of the falling film reaction tank 10, the second liquid distributor 11 is installed at the joint of the upper head and the barrel body of the falling film reaction tank 10, and the second liquid distributor 11 is installed horizontally. In some embodiments, the inlet of the second liquid distributor 11 is connected with the outlet of the reaction vessel 5 through a pipeline, and a first melt pump 7 is arranged on the pipeline connecting the second liquid distributor 11 with the reaction vessel 5, and the melt is conveyed through the first melt pump 7. Specifically speaking: the length-diameter ratio of the falling film reaction tank 10 is 1.5-3.5, and the volume ratio of the falling film reaction tank 10 to the reaction kettle 5 is (0.01-0.1): 1.
in some embodiments of the invention, the bottom of the falling film reaction tank 10 is connected with the inlet of the first liquid distributor 3 in the reaction kettle 5 through a closed pipeline, and a second melt pump 9 is arranged on the pipeline of the falling film reaction tank 10 connected with the first liquid distributor 3 for melt conveying according to requirements. In some embodiments, a stirring device is disposed in the reaction kettle 5, the stirring device includes a stirring shaft 6, the first liquid distributor 3 is disposed outside the stirring shaft 6, the stirring shaft 6 is not in contact with the first liquid distributor 3, the first liquid distributor 3 does not rotate along with the stirring shaft 6 during rotation of the stirring shaft 6, and the first liquid distributor 3 is fixed in the reaction kettle 5. Particularly, agitating unit includes (mixing) shaft 6, stirring rake and driving motor 2, and driving motor 2 sets up at 5 tops of reation kettle, and driving motor 2 is connected with (mixing) shaft 6, and stirring shaft 6 inserts and is connected with the stirring rake in reation kettle 5, and 6 outside covers of (mixing) shaft have first liquid distributor 3. In order to further improve the vacuum polycondensation efficiency, the outlet of the falling film reaction tank 10 is connected with the first liquid distributor 3 in the reaction kettle 5, the first liquid distributor 3 in the reaction kettle 5 is in a ring shape, the inner diameter of the ring is larger than the diameter of the stirring shaft 6 of the reaction kettle 5, and the outer diameter of the ring is smaller than the inner diameter of the reaction kettle 5. A stirring shaft 6 of the reaction kettle 5 penetrates through an inner hole of the first liquid distributor 3 to be connected with the driving motor 2 and the stirring paddle. The first liquid distributor 3 is horizontally arranged at the joint of the upper end enclosure of the reaction kettle 5 and the cylinder.
In some embodiments of the invention, the inlet of the first liquid distributor 3 is connected with the outlet of the reaction kettle 5 and the outlet of the falling film reaction tank 10 respectively; further, the first liquid distributor 3 is connected with the outlet of the reaction kettle 5 and the outlet of the falling film reaction tank 10 through a second three-way valve 12; furthermore, a first melt pump 7 is arranged on a pipeline of the first liquid distributor 3 connected with an outlet of the reaction kettle 5, a second melt pump 9 is arranged on a pipeline of the first liquid distributor 3 connected with an outlet of the falling film reaction tank 10, and liquid is conveyed through the first melt pump 7 and the second melt pump 9.
In some embodiments of the invention, the inlet of the second liquid distributor 11 is connected with the outlet of the reaction kettle 5 and the outlet of the falling film reaction tank 10 respectively; further, the second liquid distributor 11 is connected with the outlet of the reaction kettle 5 and the outlet of the falling film reaction tank 10 through the first three-way valve 8; furthermore, a first melt pump 7 is arranged on a pipeline of the second liquid distributor 11 connected with an outlet of the reaction kettle 5, a second melt pump 9 is arranged on a pipeline of the second liquid distributor 11 connected with an outlet of the falling film reaction tank 10, and liquid is conveyed through the first melt pump 7 and the second melt pump 9.
In some embodiments of the present invention, an inlet of the first liquid distributor 3 is connected to an outlet of the falling film reactor 10 and an outlet of the reactor 5 through a second three-way valve 12, a first three-way valve 8 is further disposed on a pipeline through which the first liquid distributor 3 communicates with the reactor 5, the first three-way valve 8 communicates with the second liquid distributor 11 through a pipeline, the first three-way valve 8 communicates with the second three-way valve 12, a second melt pump 9 is disposed on a pipeline through which the first liquid distributor 3 communicates with the falling film reactor 10, a first melt pump 7 is disposed on a pipeline through which the first liquid distributor 3 communicates with the reactor 5, and materials in the reactor 5 and the falling film reactor 10 can be circulated through the first melt pump 7 and the second melt pump 9. The specific cycle process is as follows: the material in reation kettle 5 is carried to first three-way valve 8 through first melt pump 7, can control the material through controlling first three-way valve 8 and flow to second liquid distributor 11 or first liquid distributor 3, and the material in falling film retort 10 passes through second melt pump 9 and carries to second three-way valve 12, can realize controlling the material through controlling second three-way valve 12 and flow to first liquid distributor 3 or second liquid distributor 11.
In some embodiments of the invention, the first liquid distributor 3 or the second liquid distributor 11 is a pressure-type perforated pipe distributor, a pore flow distributor or an overflow launder distributor. In some embodiments, the first liquid distributor 3 or the second liquid distributor 11 is an orifice flow distributor or an overflow trough distributor, and further, the first liquid distributor 3 or the second liquid distributor 11 is made of stainless steel, specifically, the first liquid distributor 3 or the second liquid distributor 11 is made of 06Cr19Ni10 stainless steel or 0Cr17Ni12Mo2 stainless steel. More specifically, the first liquid distributor 3 or the second liquid distributor 11 may be a disc-type hole flow type liquid distributor made of 0Cr17Ni12Mo2 stainless steel. In some embodiments, the first liquid distributor 3 is selected from a pressure-type porous tubular distributor in the shape of a circular ring or a pore flow distributor in the shape of a circular ring; further, the first liquid distributor 3 is a disc-hole flow type liquid distributor in a circular ring shape.
In some embodiments of the present invention, reaction vessel 5 is connected to rectification system 1, and rectification system 1 is connected to a condensate reflux system. In some specific embodiments, the rectification system 1 can be a rectification column, the reflux condensation system includes a condenser 15 and a transfer pump 14, the condenser 15 is connected to the rectification column, the condenser 15 is connected to the transfer pump 14, and the transfer pump 14 is connected to the rectification column through a pipeline.
In some embodiments of the invention, the reaction vessel 5 or the falling film reaction tank 10 is connected to a vacuum system 13. The polyester polycondensation stage can be completed under vacuum by forming a vacuum in the reaction vessel 5 or the falling film reactor 10 by means of the vacuum system 13.
In the vacuum polycondensation stage of polyester synthesis, the falling film reaction tank 10 is small in volume and does not have mechanical stirring and other parts, high vacuum degree can be formed, reaction materials are pumped from the bottom of the reaction kettle 5 through the first melt pump 7 or enter the second liquid distributor 11 of the falling film reaction tank 10 through a closed pipeline by means of self-weight pressure, and are uniformly distributed through the second liquid distributor 11 to form a film shape to fall, so that a large devolatilization area is provided, and gasification and removal of small molecules are facilitated. In the vacuum polycondensation stage of polyester synthesis, vacuum pumping is simultaneously carried out in the reaction kettle 5, part of reaction materials form a film-shaped liquid film through a second liquid distributor 11 in the falling film reaction tank 10, the film-shaped liquid film falls to the bottom of the falling film reaction tank 10 and then is pumped by a second melt pump 9 or passes through the bottom of the falling film reaction tank 10 by means of self-weight pressure through a second three-way valve 12 of a closed pipeline, part or all of resin melt returns to the second liquid distributor 11 in the falling film reaction tank 10 to carry out film forming and devolatilization again, and the other part of resin melt enters a first liquid distributor 3 in the reaction kettle 5 to be uniformly distributed to form a film shape and fall, so that the devolatilization area is further increased, and the devolatilization efficiency is improved.
In some embodiments of the invention, a temperature self-regulating heat tracing band or heating system is provided on all melt conveying pipes of the polyester resin synthesis plant to prevent the resin melt from cooling in the pipes and blocking the pipes.
In some embodiments of the present invention, the reaction vessel 5 is externally covered with a thermal insulation cover 4.
In some embodiments of the present invention, the polyester resin batch type polyester resin synthesizing apparatus of the present invention comprises a reaction kettle 5, a stirring device, a rectification system 1, a condensation reflux system, a vacuum system 13, a falling film reaction tank 10, and the like. The volume of the reaction kettle 5 is 3000L, the falling film reaction tank 10 is a vertical cylindrical reactor, the length-diameter ratio is 2, the volume is 300L, the upper end enclosure and the lower end enclosure are both standard end enclosures, a circular overflow trough type liquid distributor is arranged in the reaction kettle, and the material is 0Cr17Ni12Mo2 stainless steel. The falling film reaction tank 10 is arranged at the horizontal position of the reaction kettle 5 and is connected with the lowest point of the bottom of the reaction kettle 5 through a closed pipeline, and a first melt pump 7 and a second melt pump 9 are arranged on the pipeline connecting the reaction kettle 5 and the falling film reaction tank 10 for melt conveying. A communicating pipeline is arranged between the outlet of the falling film reaction tank 10 and the inlet of the second liquid distributor 11 and is controlled by a second three-way valve 12. An annular overflow trough type liquid distributor made of 0Cr17Ni12Mo2 stainless steel is horizontally arranged at the upper part in the reaction kettle 5. All melt conveying pipelines are provided with a temperature self-control heat tracing band.
The polyester resin synthesis device simultaneously devolatilizes in the reaction kettle 5 and the falling film tank, the falling film tank is not mechanically stirred, a thinner liquid film and a higher vacuum degree can be formed, compared with the prior art, the polyester resin synthesis device synthesizes polyester with the same viscosity, the vacuum polycondensation time can be greatly shortened, the production process cost of polyester resin can be effectively reduced, the utilization rate of equipment is improved, and the energy consumption is reduced. In addition, the intermittent polyester resin synthesis device can customize polyester resin according to the production requirement of the coating, and compared with a continuous synthesis device, the intermittent polyester resin synthesis device can save equipment investment and equipment installation space, a plurality of reaction kettles 5 do not need to be designed to be connected in series according to a multi-kettle process flow, and equipment and the process flow are simplified. By controlling the on-off proportion of a second three-way valve 12 on a connecting pipeline between an outlet of the falling film reaction tank 10 and the first liquid distributor 3 in the reaction kettle 5, resin melts with different proportions are regulated to return to a second liquid distributor 11 in the falling film reaction tank 10 and can be linked with a first melt pump 7 and a first three-way valve 8 at the bottom of the reaction kettle 5, the resin melts with the same quality in the reaction kettle 5 are controlled to enter the falling film reaction tank 10, and a continuous and stable liquid film is formed.
The present invention will be described in further detail with reference to specific examples. The starting materials, reagents or apparatus used below are commercially available in a usual manner unless otherwise specified.
Polyester resins of examples 1 to 3 and comparative examples 1 to 2 and methods for producing the same
The polyester resins of examples 1 to 3 and comparative examples 1 to 2 were synthesized according to the formulations in the following Table 1.
Table 1 shows the components of the polyester resins of examples 1 to 3 and comparative examples 1 to 2 (unless otherwise noted, the units of the following components are all in kg)
Procedure for preparation of polyester resin in example 1:
1) adding polyhydric alcohol into a reaction kettle 5 of a polyester resin batch type polyester resin synthesis device in an embodiment of the invention according to the proportion of the embodiment 1 in the table 1, heating until the materials are melted, then adding polybasic acid and a catalyst, gradually heating to 245 ℃ under the protection of nitrogen to perform esterification reaction, starting a first melt pump 7 and a first three-way valve 8 on a pipeline connecting the reaction kettle 5 and a falling film reaction tank 10 after the reaction reaches a clear point (namely all raw materials are dissolved in the reaction), circulating the materials for 10min, and continuously keeping the temperature until the acid value reaches 17-23mgKOH/g to obtain an esterification product;
2) adding an acidolysis agent into the esterification product under the protection of nitrogen, and carrying out acidolysis reaction for 3h at 240 ℃ to obtain an acidolysis product, wherein the acid value reaches 20-30 mgKOH/g;
3) vacuumizing a reaction kettle 5, performing polycondensation reaction on acidolysis products for 0.5h under the vacuum degree of-0.095 MPa, vacuumizing a film falling reaction tank 10, starting a first melt pump 7 and a first three-way valve 8 to enable resin in the reaction kettle 5 to enter a second liquid distributor 11 in the falling film reaction tank 10 to form a liquid film, and controlling a pipeline second three-way valve 12 to enable all resin melts discharged from the falling film reaction tank 10 to return to the first liquid distributor 3 in the reaction kettle 5 to form a film again and devolatilize. Continuing vacuum polycondensation for 2h, wherein the acid value is lower than 10mgKOH/g, the melt viscosity is 26000-30000mPa.s at 200 ℃, cooling to 210 ℃, and discharging to obtain the polyester resin.
Procedure for preparation of the polyester resin of example 2:
1) the operation is the same as that of example 1, the materials are fed according to the proportion of example 2 in the table 1, and the acid value of the esterification product is 7-13 mgKOH/g;
2) the operation is the same as that of the example 1, and the acid hydrolysis product acid value reaches 43-47 mgKOH/g;
3) vacuumizing a reaction kettle 5, performing polycondensation reaction on acidolysis products for 0.5h under the vacuum degree of-0.095 MPa, vacuumizing a film falling reaction tank 10, starting a first melt pump 7 to enable resin of the reaction kettle 5 to enter a second liquid distributor 11 in the falling film reaction tank 10 to form a liquid film, controlling a second three-way valve 12 to enable 10% of resin melt out of the falling film reaction tank 10 to return to a first liquid distributor 3 in the reaction kettle 5, and enabling 90% of resin melt to continuously enter the second liquid distributor 11 in the falling film reaction tank 10 to form a film again for devolatilization. Continuing vacuum polycondensation for 1h, the acid value is 30-36mgKOH/g, the melt viscosity at 200 ℃ is 4000-
4) Cooling to 200 ℃, adding an auxiliary agent, starting a first melt pump 7, a second melt pump 9, a first three-way valve 8 and a second three-way valve 12 on a pipeline connecting the reaction kettle 5 and the falling film reaction tank 10, circulating the materials for 30min, and discharging to obtain the polyester resin.
Procedure for preparation of polyester resin in example 3:
1) the operation is the same as that of example 1, and the acid value of the esterification product is 7-13 mgKOH/g;
2) the operation is the same as that of the example 2, and the acid hydrolysis product acid value reaches 55-65 mgKOH/g;
3) the procedure is as in example 2, the polyester resin has an acid value of 40-46mgKOH/g and a melt viscosity of 4500-5500mPa.s at 200 ℃.
4) The procedure is as in example 2.
Procedure for preparation of polyester resin in comparative example 1:
1) adding polyalcohol into a conventional intermittent reaction kettle (3000L in volume, such as a reaction kettle disclosed in CN110935408A embodiment) of polyester resin according to the proportion of comparative example 1 in Table 1, heating until the material is melted, adding polyacid and a catalyst, gradually heating to 245 ℃ under the protection of nitrogen to perform esterification reaction, and keeping the temperature until the acid value reaches 17-23mgKOH/g to obtain an esterified product;
2) the procedure was the same as in example 1, preparation step 2) of the polyester resin;
3) vacuumizing, performing polycondensation reaction on the acidolysis product for 3h under the vacuum degree of-0.095 MPa, wherein the acid value is 17-23mgKOH/g, the melt viscosity at 200 ℃ is 6500-9500mPa.s, and continuously vacuumizing for 2h, and the acid value and the viscosity of the polyester resin are not changed greatly.
Procedure for preparation of polyester resin in comparative example 2:
1) the operation is the same as that of the comparative example 1, the materials are fed according to the proportion of the comparative example 2 in the table 1, and the esterification product is 7-13 mgKOH/g, so that the esterification product is obtained;
2) the procedure was the same as in example 2, preparation step 2) of the polyester resin;
3) vacuumizing, and performing polycondensation reaction on the acidolysis product for 4 hours under the vacuum degree of-0.095 MPa, wherein the acid value is 30-36mgKOH/g, and the melt viscosity is 4000-
4) Cooling to 200 ℃, adding the auxiliary agent, stirring for 30min, and discharging to obtain the polyester resin.
Performance testing of powder coatings made from the polyester resins of examples 2, 3 and comparative example 2:
the polyester resins of examples 2 and 3 and comparative example 2 of the present invention are respectively weighed and mixed with curing agent TGIC, leveling agent GLP588, titanium dioxide, barium sulfate, benzoin and brightener 701 according to the proportion of the following table 2 (note: if no special description is provided, the component units in the table 2 are g), the mixture is melted and extruded by a screw extruder, tabletted and crushed, and then the tabletted materials are crushed and sieved to obtain the powder coatings of examples 4-5 and comparative example 3, wherein: example 4 used the polyester resin of example 2, example 5 used the polyester data of example 3, and comparative example 3 used the polyester resin of comparative example 2.
TABLE 2 Components of powder coatings in examples 4-5 and comparative example 3
Performance testing
Performance test of the polyester resins in examples 1 to 3 and comparative examples 1 to 2:
the performances of examples 1-3 and comparative examples 1-2 were tested, wherein the acid value was tested according to GB/T6743-; hydroxyl number was tested according to GB/T12008.3-2009; viscosity was tested according to astm d 4287; the number average molecular weight and the molecular weight distribution are tested according to GB/T21864-2008, and the glass transition temperature is tested according to GB/T19466.2; reactivity was tested according to Q/QTCL1-2014, i.e., the gelation time for the resin to react with an equivalent curing agent at 180 ℃. The performance test data of the polyester resins of examples 1 to 3 and comparative examples 1 to 2 are recorded in the following Table 3.
TABLE 3 Properties of polyester resins in examples 1 to 3 and comparative examples 1 to 2
As can be seen by comparing the synthetic processes of the polyester resins in examples 1 to 3 and comparative examples 1 to 2 with the properties of the polyester resins in Table 3, the polyester resin in example 1 has a higher molecular weight, a high viscosity and a high Tg, a narrower molecular weight distribution, and a shorter vacuum polycondensation time than those in comparative example 1. As can be seen by comparing example 1 with comparative example 1: when the polyester resin is synthesized, the intermittent polyester resin synthesis device in the embodiment of the invention can be used for synthesizing high-viscosity polyester resin, film formation and devolatilization are carried out twice between the reaction kettle 5 and the falling film reaction tank 10, and high vacuum degree is formed in the falling film reaction tank 10, so that micromolecule byproducts in the reaction can be effectively removed, the polycondensation reaction is balanced and moved in the positive direction, the reaction degree is improved, the vacuum polycondensation time is shortened, and the energy consumption is reduced. It can be seen from the comparison between example 2 and comparative example 2 that the batch type polyester resin synthesizing apparatus in the embodiment of the present invention can synthesize polyester resin with wide molecular weight distribution, and can meet the requirement of partial coating on polyester resin with wide molecular weight distribution.
Performance testing of the powder coatings in examples 4-5 and comparative example 3:
the powder coatings of example 4, example 5 and comparative example 3 according to the present invention were respectively sprayed on the surface-treated iron plates by electrostatic spraying, cured at 130 ℃ for 15min to obtain 60 to 80 μm powder coatings, and then the powder coatings formed on the iron plates were subjected to the following performance tests, the test results being reported in table 4, wherein:
(1) powder flow was tested according to Q/QTCL 1-2014;
(1) gloss was tested according to GB/T9754-2007;
(2) the impact test was tested according to GB/T1732-1993;
(3) the bending test was tested according to GB/T6742-2007;
(4) the 1000h xenon lamp aging test is carried out according to GB/T1865-2009;
TABLE 4 Properties of the powder coatings in examples 4-5 and comparative example 3
As can be seen from Table 4: when the intermittent polyester resin synthesis device in the embodiment of the invention is used for synthesizing high-viscosity polyester, the liquid flow proportion is controlled by adjusting the second three-way valve 12 at the bottom of the falling film reaction tank 10, the polyester resin melt which is formed into a film through the second liquid distributor 11 in the falling film reaction tank 10 and is devolatilized is controlled to return to the second liquid distributor 11 in the falling film reaction tank 10 again, the rest of the resin melt enters the first liquid distributor 3 in the reaction kettle 5, so that the difference between the molecular weights of the polyester resin is increased, the synthesized polyester resin has higher molecular weight distribution which is difficult to reach by a conventional reaction kettle, and when the intermittent polyester resin synthesis device is applied to low-temperature curing powder coating, the synthesized polyester resin has higher glass transition temperature, higher leveling property and weather resistance, and more excellent performance than the conventional intermittent reaction kettle.
The embodiments of the present invention have been described in detail, but the present invention is not limited to the embodiments, and various changes can be made without departing from the gist of the present invention within the knowledge of those skilled in the art. Furthermore, the embodiments of the present invention and the features of the embodiments may be combined with each other without conflict.
Claims (10)
1. A polyester resin synthesis device is characterized in that: including reation kettle and falling liquid film retort, be equipped with first liquid distributor in the reation kettle, first liquid distributor is connected with the falling liquid film retort, is equipped with second liquid distributor in the falling liquid film retort, and second liquid distributor is connected with reation kettle.
2. The polyester resin synthesizing apparatus according to claim 1, wherein: the first liquid distributor is connected with an outlet of the reaction kettle; and the second liquid distributor is connected with an outlet of the falling film reaction tank.
3. The polyester resin synthesizing apparatus according to claim 1 or 2, wherein: a stirring device is arranged in the reaction kettle and comprises a stirring shaft, and the first liquid distributor is arranged outside the stirring shaft.
4. The polyester resin synthesizing apparatus according to claim 1 or 2, wherein: the reaction kettle is connected with a rectification system, and the rectification system is connected with a condensation reflux system.
5. The polyester resin synthesizing apparatus according to claim 1 or 2, wherein: the first liquid distributor and the second liquid distributor are respectively and independently a pressure type porous pipe distributor, a pore flow distributor or an overflow groove type distributor.
6. The polyester resin synthesizing apparatus according to claim 1, wherein: the reaction kettle and the falling film reaction tank are respectively connected with a vacuum system.
7. A polyester resin characterized by: the paint is prepared from the following components in percentage by mass: 33-40% of polyhydric alcohol; 43-60% of polybasic acid; 5-15% of an acidolysis agent; 0.01-0.1% of a catalyst; 0.05-2% of curing accelerator, wherein the polyester resin is prepared by adopting the polyester resin synthesizing device as defined in any one of claims 1-6.
8. The polyester resin according to claim 7, wherein: the polyester resin satisfies at least one of the following conditions:
(1) the acid value is 25-45 mgKOH/g;
(2) the hydroxyl value is less than 3 mgKOH/g;
(3) the glass transition temperature is 60-70 ℃;
(4) the melt viscosity at 200 ℃ is 4500-;
(5) number average molecular weight of 2500-;
(6) the molecular weight distribution index is 1.5-2.5.
9. The method for preparing a polyester resin according to claim 7 or 8, wherein: the polyester resin synthesis apparatus according to any one of claims 1 to 6, wherein the method comprises the steps of:
s1: esterification: mixing polyol, polybasic acid and a catalyst in a reaction kettle for reaction, and when the mixed reaction reaches a clear point, circulating the reaction mixture between the reaction kettle and a falling film reaction tank, stopping circulation, and continuing the reaction to obtain an esterification product;
s2: acid hydrolysis: reacting the esterification product with an acidolysis agent;
s3: polycondensation: circulating the product of step S2 between the reaction kettle and the falling film reaction tank;
s4: and (3) mixing the product obtained in the step S3 with a curing accelerator, and circulating the mixture between the reaction kettle and the falling film reaction tank to obtain the polyester resin.
10. A powder coating characterized by: comprising the polyester resin according to claim 7 or 8.
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| US20090093600A1 (en) * | 2006-04-28 | 2009-04-09 | Wellman, Inc. | Methods for Making Polyester Resins in Falling Film Melt Polycondensation Reactors |
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| CN212492943U (en) * | 2020-06-12 | 2021-02-09 | 湖南聚仁化工新材料科技有限公司 | Polyester polyol reaction kettle |
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| US20090093600A1 (en) * | 2006-04-28 | 2009-04-09 | Wellman, Inc. | Methods for Making Polyester Resins in Falling Film Melt Polycondensation Reactors |
| CN105771868A (en) * | 2016-04-22 | 2016-07-20 | 扬州惠通化工技术有限公司 | Esterification and polymerization double-kettle apparatus |
| CN106633018A (en) * | 2016-12-30 | 2017-05-10 | 上海聚友化工有限公司 | Continuous production process and continuous production device for polyester polyol |
| CN107254240A (en) * | 2017-04-20 | 2017-10-17 | 浙江传化天松新材料有限公司 | A kind of high decorative surface of curable epoxide, enhanced water resistance polyester resin for powder coating and preparation method thereof |
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