CN114367257B - Polyester resin and preparation method and synthesis device thereof - Google Patents
Polyester resin and preparation method and synthesis device thereof Download PDFInfo
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- CN114367257B CN114367257B CN202111348745.3A CN202111348745A CN114367257B CN 114367257 B CN114367257 B CN 114367257B CN 202111348745 A CN202111348745 A CN 202111348745A CN 114367257 B CN114367257 B CN 114367257B
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- polyester resin
- reaction
- reaction kettle
- falling film
- liquid distributor
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- 229920001225 polyester resin Polymers 0.000 title claims abstract description 100
- 239000004645 polyester resin Substances 0.000 title claims abstract description 100
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 39
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 210
- 239000007788 liquid Substances 0.000 claims abstract description 110
- 239000011552 falling film Substances 0.000 claims abstract description 85
- 239000000463 material Substances 0.000 claims abstract description 19
- 238000009826 distribution Methods 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 25
- 238000006068 polycondensation reaction Methods 0.000 claims description 22
- 238000000576 coating method Methods 0.000 claims description 20
- 239000000843 powder Substances 0.000 claims description 19
- 238000005886 esterification reaction Methods 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 238000001723 curing Methods 0.000 claims description 13
- 230000002194 synthesizing effect Effects 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 150000007519 polyprotic acids Polymers 0.000 claims description 11
- 239000011248 coating agent Substances 0.000 claims description 10
- 230000032050 esterification Effects 0.000 claims description 9
- 239000000155 melt Substances 0.000 claims description 8
- 229920005862 polyol Polymers 0.000 claims description 8
- 150000003077 polyols Chemical class 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 238000009833 condensation Methods 0.000 claims description 6
- 230000005494 condensation Effects 0.000 claims description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 4
- 239000001361 adipic acid Substances 0.000 claims description 4
- 230000009477 glass transition Effects 0.000 claims description 4
- 150000005846 sugar alcohols Polymers 0.000 claims description 4
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 3
- 239000010408 film Substances 0.000 abstract description 13
- 239000006227 byproduct Substances 0.000 abstract description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 26
- 239000000047 product Substances 0.000 description 26
- 229920000728 polyester Polymers 0.000 description 14
- 229920005989 resin Polymers 0.000 description 13
- 239000011347 resin Substances 0.000 description 13
- 230000008569 process Effects 0.000 description 11
- 238000001816 cooling Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 230000001276 controlling effect Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-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
- 238000012360 testing method Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 239000012752 auxiliary agent Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000010924 continuous production Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000009434 installation Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- -1 titanium phosphorus compound Chemical class 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- 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
- 238000005265 energy consumption Methods 0.000 description 2
- 239000003623 enhancer Substances 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
- 238000009413 insulation Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000010907 mechanical stirring Methods 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
- 239000004408 titanium dioxide 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
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 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
- 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
- 229920001688 coating polymer Polymers 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007590 electrostatic spraying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 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
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000013035 low temperature curing Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000002861 polymer material Substances 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
- 239000000376 reactant Substances 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
- 238000010189 synthetic method Methods 0.000 description 1
- 229920001059 synthetic polymer 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
- 239000001038 titanium pigment Substances 0.000 description 1
- CMSYDJVRTHCWFP-UHFFFAOYSA-N triphenylphosphane;hydrobromide Chemical compound Br.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 CMSYDJVRTHCWFP-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
Classifications
-
- 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
-
- 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
Landscapes
- 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, a preparation method thereof and a synthesis device thereof. According to the polyester resin synthesis device, 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, efficient devolatilization is achieved, and devolatilization is carried out in the reaction kettle and the falling film reaction tank at the same time, so that micromolecule byproducts in a polyester resin synthesis system can be efficiently removed, forward progress of a polyester resin synthesis reaction is promoted, the polymerization degree is improved, and polydisperse polyester resin with higher viscosity or wider 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 a polyester resin, a preparation method thereof and a synthesis device.
Background
Alcohol and water in the polyester synthetic raw material for powder coating are mutually soluble in any proportion, the boiling point is close to that of the polyester synthetic raw material and difficult to separate, so that the function of the synthetic equipment needs to be focused on the separation of the polyester synthetic raw material from the esterified water and the loss of low-boiling-point alcohol is prevented in the initial stage of the synthetic reaction; after the esterification reaction, vacuum polycondensation is usually required, and the function of synthesis equipment is required to pay attention to enhancing stirring and improving the mass transfer effect so as to remove trace moisture in the system and improve the relative molecular mass of the product; in the final stage of production, an auxiliary agent is generally required to be added in a cooling way, and the equipment is required to have a better dispersing function in the stage; therefore, the requirements of equipment structures and performances at each stage of synthesis are different, and in the field of general PET polyesters, large-scale production lines are designed into multi-kettle continuous production processes, and mainly represent five-kettle process flow represented by Ji Ma and three-kettle process flow represented by DuPont. The product produced by the continuous method has more stable performance, and the reaction kettles with different structures can be designed according to different requirements on equipment functions in different reaction stages. However, continuous process reaction equipment is not suitable for small-batch and customized products, and domestic powder coatings mostly adopt a small-batch and customized sales mode, and the performance requirements of the powder coatings of different batches on polyester resins are relatively large in difference. 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 intermittent reaction kettle has the advantages of flexible operation, easy adaptation to different operation conditions and product varieties, suitability for small-batch, multi-variety and long-reaction-time product production; however, the whole production process of the existing polyester resin is completed in the same intermittent reaction kettle, the structure of the reaction kettle cannot be changed according to the requirements of different stages of esterification and polycondensation on equipment, the heat and mass transfer effect is poor, and the domestic production requirements of the coating cannot be met.
The polyester resin is mainly subjected to esterification reaction in the initial stage of synthesis, has a small equilibrium constant, and needs to remove water generated by the raw materials and the reaction so as to promote the forward movement of the equilibrium. When polyester is produced by a common intermittent reaction kettle, the polyester resin melt in the polycondensation stage contains low-content micromolecule reactants and product water which are difficult to completely remove, so that the reaction degree can not be improved any more, and therefore, when high-viscosity polyester is produced, even if measures such as long-time vacuumizing, 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 process equipment cost is greatly increased.
The synthetic polymers all have a certain molecular weight distribution, i.e. have a polydispersity. The molecular weight distribution can be represented by a distribution index d. The molecular weight distribution index refers to the ratio of the weight average molecular weight Mw to the number average molecular weight Mn, i.e. d=mw/Mn. If d=1.02-1.1 then it means monodisperse and if d=1.5-3.0 then it means polydisperse. The molecular weight distribution index of the polyester synthesized by the batch reactor is generally between 1.1 and 1.5. It is generally believed that certain aspects of the performance will be more pronounced with a relatively narrow molecular weight distribution range for the coating polymer, but certain special applications may require a broader synthetic molecular weight distribution and better overall performance, where conventional batch reactors are difficult to meet.
CN103772674a discloses a synthetic method of polyester resin, wherein the esterification reaction is carried out in a first-stage reaction kettle, the polycondensation reaction is carried out in a second-stage reaction kettle, different functional requirements can be realized by designing a reaction kettle with a differential structure, and the production efficiency is improved. The technical schemes of CN111701553A and the like can improve the devolatilization efficiency to produce high-viscosity polyester, but can only be used as a final polymerization reaction kettle of a continuous production line. It is difficult for a single batch reactor in the prior art to meet the above technical requirements at the same time.
Disclosure of Invention
In order to overcome the problems of the prior art, an object of the present invention is to provide a device for synthesizing a polyester resin.
The second object of the present invention is to provide a polyester resin.
The third object of the present invention is to provide a method for producing a polyester resin.
The fourth object of the present invention is to provide a powder coating.
In order to achieve the above 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 the second liquid distributor is connected with the reaction kettle. The polyester resin synthesizing device can synthesize polydisperse polyester resin with wider molecular weight distribution index which is difficult to synthesize by a common intermittent reaction kettle according to the needs by arranging the first liquid distributor and the falling film reaction tank so as to realize specific performance requirements.
Preferably, the polyester resin synthesizing device is a batch synthesizing device.
Preferably, the first liquid distributor is connected with an outlet of the reaction kettle.
Preferably, the second liquid distributor is connected to the 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 the 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, wherein 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 a first liquid distributor is sleeved on the stirring shaft.
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 polyalcohol; 43-60% of polybasic acid; 5-15% of acidolysis agent; 0.01 to 0.1 percent of catalyst; and 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 percentage of the polyol is 35-40%; further preferably, the mass percentage of the polyol is 35-38%.
Preferably, the polyol is at least one of neopentyl glycol, 2-butyl-2-ethyl-1, 3-propanediol, 1, 4-cyclohexanedimethanol, trimethylolpropane, 1, 6-hexanediol.
Preferably, the mass percentage of the polybasic acid is 45-55%; further preferably, the mass percentage of the polybasic acid is 50-55%.
Preferably, the polybasic acid is at least one selected from terephthalic acid, isophthalic acid, 1, 4-cyclohexanedicarboxylic acid and 1, 6-adipic acid.
Preferably, the mass percentage of neopentyl glycol in the polyol is 75-100%, the mass percentage of trimethylolpropane is 0-3%, and the mass percentage of trimethylolpropane is not 0%.
Preferably, the sum of the mass percent of 1, 6-hexanediol in the polyol and the mass percent of 1, 6-adipic acid in the polyacid is 0-3%, and not 0%.
Preferably, the acidolysis agent accounts for 5-12% by mass; further preferably, the acidolysis agent accounts for 7 to 10 mass percent.
Preferably, the acidolysis agent is at least one of isophthalic acid, 1, 4-cyclohexanedicarboxylic acid and 1, 6-adipic acid.
Preferably, the mass percentage of the catalyst is 0.05-0.1%; further preferably, the mass percentage of the catalyst is 0.05-0.08%.
Preferably, the catalyst is at least one of tin-based catalyst, germanium-based catalyst and 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 compound.
Preferably, the mass percentage of the curing accelerator is 0.1-1.5%; further preferably, the mass percentage of the curing accelerator is 0.3-1%; still more preferably, the curing accelerator is 0.4 to 0.9 mass%.
Preferably, the curing accelerator is at least one of triphenylphosphine bromide and triphenylphosphine.
Preferably, the raw materials for preparing the polyester resin also comprise an antioxidant.
Preferably, the mass percentage of the antioxidant is 0.05-2%; further preferably, the antioxidant accounts for 0.05 to 1 percent of the total mass of the composition.
Preferably, the antioxidant is at least one selected from triphenyl phosphite, antioxidant 168, antioxidant 1010 and antioxidant 1076. Antioxidant 168 is tris (2, 4-di-tert-butylphenyl) phosphite; the antioxidant 1010 is pentaerythritol tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ]; antioxidant 1076 is beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) stearyl propionate.
Preferably, the polyester resin meets at least one of the following conditions:
(1) An acid value of 25-45mgKOH/g;
(2) A hydroxyl value of less than 3mgKOH/g;
(3) The glass transition temperature is 60-70 ℃;
(4) The melt viscosity at 200 ℃ is 4500-7500mPa.s;
(5) Number average molecular weight 2500-6500;
(6) The molecular weight distribution index is 1.5-2.5.
A third aspect of the present invention provides a method for producing a polyester resin according to the second aspect of the present invention, using the polyester resin synthesis apparatus according to the first aspect of the present invention, the method comprising the steps of:
s1: esterification: mixing polyol, polybasic acid and a catalyst in a reaction kettle for reaction, and obtaining an esterification product after the mixed reaction reaches a clear point;
s2: acidolysis: reacting the esterified product with an acidolysis agent;
s3: polycondensation: circulating the product in the step S2 between the reaction kettle and the falling film reaction tank;
s4: and (3) mixing the product in the step (S3) with a curing accelerator, and circulating the mixture between a reaction kettle and a falling film reaction tank to obtain the polyester resin.
Preferably, in the step S1, the esterification reaction is performed under an anaerobic condition.
Preferably, the step S1 further includes an automatic cleaning step for the reaction kettle; the automatic cleaning step is accomplished by circulating the reaction mixture between the reactor and the falling film reactor. The automatic cleaning step is to prevent coking in the reaction tank.
Preferably, in the step S2, the acidolysis step is performed under anaerobic conditions.
Preferably, in the step S3, the polycondensation step is performed under vacuum conditions; further preferably, step S2 is specifically: after acidolysis reaction is completed, the reaction kettle and the falling film reaction tank are vacuumized, so that materials circulate between the reaction kettle and the falling film reaction tank. A thin liquid film is formed in the reaction kettle and the falling film reaction tank at the same time, so that the aim of quick devolatilization is fulfilled.
Preferably, the step S4 further includes a cooling step, where the cooling step is located before the step of mixing the product in the step S3 with the curing accelerator.
Preferably, in the step S1, a step of vacuumizing is further included; vacuum is pumped in the esterification reaction to improve the esterification reaction degree.
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, a gloss enhancer.
Preferably, the filler is at least one selected from titanium dioxide and barium sulfate.
The beneficial effects of the invention are as follows: according to the polyester resin synthesis device, materials circulate between the reaction kettle and the falling film reaction tank, high-efficiency devolatilization is realized through the first liquid distributor and the second liquid distributor, and devolatilization is performed in the reaction kettle and the falling film reaction tank at the same time, so that small molecular byproducts in a polyester resin synthesis system can be efficiently removed, forward progress of a polyester resin synthesis reaction is promoted, the polymerization degree is improved, and polydisperse polyester resin with higher viscosity or wider molecular weight distribution index can be synthesized.
Drawings
FIG. 1 is a schematic view showing a structure of a polyester resin synthesizing apparatus according to one embodiment of the present invention.
Reference numerals:
the device comprises a rectifying system 1, a driving motor 2, a first liquid distributor 3, a heat insulation 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 conveying pump 14 and a condenser 15.
Detailed Description
Specific embodiments of the present invention will be described in further detail below with reference to the drawings and examples, but the practice and protection of the present invention are not limited thereto. It should be noted that the following processes, unless specifically described otherwise, are all realized or understood by those skilled in the art with reference to the present technology. The reagents or apparatus used were not manufacturer-specific and were considered conventional products commercially available. In the description of the present invention, it should be understood that the terms "center," "longitudinal," "lateral," "width," "thickness," "upper," "lower," "front," "rear," "left," "right," "face," "bottom," and the like indicate or are based on the orientation or positional relationship shown in the drawings, merely to facilitate description of the present invention and simplify the description, and do not indicate or imply that the devices or elements referred to must have a specific orientation, be configured and operated in a specific orientation, and thus should not be construed as limiting the present invention.
In the description of the present invention, a number means one or more, a number means two or more, and greater than, less than, exceeding, etc. are understood to not include the present number, and above, below, within, etc. are understood to include the present number.
A polyester resin synthesizing apparatus according to an embodiment of the invention is described below with reference to FIG. 1.
As shown in the structural schematic diagram of the polyester resin synthesis device in fig. 1, the polyester resin synthesis device according to the embodiment of the invention comprises a reaction kettle 5 and a falling film reaction tank 10, wherein a first liquid distributor 3 is arranged in the reaction kettle 5, an inlet of the first liquid distributor 3 is connected with an outlet of the falling film reaction tank 10, a second liquid distributor 11 is arranged in the falling film reaction tank 10, and an inlet of the second liquid distributor 11 is connected with 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 the upper and lower heads 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 installation position of the second liquid distributor 11 is the connection part of the upper end socket of the falling film reaction tank 10 and the cylinder, and the second liquid distributor 11 is horizontally installed. In some embodiments, the inlet of the second liquid distributor 11 is connected to the outlet of the reaction kettle 5 through a pipe, and a first melt pump 7 is provided on the pipe connecting the second liquid distributor 11 to the reaction kettle 5, and the melt is conveyed by the first melt pump 7. Specifically, the method comprises the following steps: 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 connecting the falling film reaction tank 10 with the first liquid distributor 3 according to the requirement for melt conveying. In some embodiments, a stirring device is arranged in the reaction kettle 5, the stirring device comprises a stirring shaft 6, the first liquid distributor 3 is arranged outside the stirring shaft 6, the stirring shaft 6 is not contacted with the first liquid distributor 3, the first liquid distributor 3 does not rotate along with the stirring shaft 6 in the rotation process of the stirring shaft 6, and the first liquid distributor 3 is fixed in the reaction kettle 5. Specifically, the stirring device comprises a stirring shaft 6, stirring paddles and a driving motor 2, wherein the driving motor 2 is arranged at the top of the reaction kettle 5, the driving motor 2 is connected with the stirring shaft 6, the stirring shaft 6 is inserted into the reaction kettle 5 and connected with the stirring paddles, and a first liquid distributor 3 is sleeved outside the stirring shaft 6. 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 circular ring shape, the inner diameter of the circular ring is larger than the diameter of the stirring shaft 6 of the reaction kettle 5, and the outer diameter is smaller than the inner diameter of the reaction kettle 5. The stirring shaft 6 of the reaction kettle 5 penetrates through the inner hole of the first liquid distributor 3 to connect the driving motor 2 with the stirring paddle. The installation position of the first liquid distributor 3 is the joint of the upper end socket of the reaction kettle 5 and the cylinder body, and the first liquid distributor is horizontally installed.
In some embodiments of the present invention, the inlet of the first liquid distributor 3 is connected to the outlet of the reaction vessel 5 and the outlet of the falling film reaction vessel 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 connected with the outlet of the reaction kettle 5 of the first liquid distributor 3, a second melt pump 9 is arranged on a pipeline connected with the outlet of the falling film reaction tank 10 of the first liquid distributor 3, and liquid is conveyed through the first melt pump 7 and the second melt pump 9.
In some embodiments of the present invention, the inlet of the second liquid distributor 11 is connected to the outlet of the reaction vessel 5 and the outlet of the falling film reaction vessel 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 connected with the outlet of the reaction kettle 5 of the second liquid distributor 11, a second melt pump 9 is arranged on a pipeline connected with the outlet of the falling film reaction tank 10 of the second liquid distributor 11, and liquid is conveyed through the first melt pump 7 and the second melt pump 9.
In some embodiments of the present invention, the inlet of the first liquid distributor 3 is connected with the outlet of the falling film reaction tank 10 and the outlet of the reaction kettle 5 through the second three-way valve 12, the pipeline for communicating the first liquid distributor 3 with the reaction kettle 5 is further provided with the first three-way valve 8, the first three-way valve 8 is communicated with the second liquid distributor 11 through the pipeline, the first three-way valve 8 is communicated with the second three-way valve 12, the pipeline for communicating the first liquid distributor 3 with the falling film reaction tank 10 is provided with the second melt pump 9, the pipeline for communicating the first liquid distributor 3 with the reaction kettle 5 is provided with the first melt pump 7, and materials in the reaction kettle 5 and the falling film reaction tank 10 can be circulated through the first melt pump 7 and the second melt pump 9. The specific circulation process is as follows: the materials in the reaction kettle 5 are conveyed to the first three-way valve 8 through the first melt pump 7, the materials can be controlled to flow to the second liquid distributor 11 or the first liquid distributor 3 by controlling the first three-way valve 8, the materials in the falling film reaction tank 10 are conveyed to the second three-way valve 12 through the second melt pump 9, and the materials can be controlled to flow to the first liquid distributor 3 or the second liquid distributor 11 by controlling the second three-way valve 12.
In some embodiments of the invention, the first liquid distributor 3 or the second liquid distributor 11 is a pressure type porous tube distributor, a pore flow distributor or an overflow trough distributor. In some embodiments, the first liquid distributor 3 or the second liquid distributor 11 is a hole flow distributor or an overflow trough distributor, and further, the material of the first liquid distributor 3 or the second liquid distributor 11 is stainless steel, specifically, the material of the first liquid distributor 3 or the second liquid distributor 11 is 06Cr19Ni10 stainless steel or 0Cr17Ni12Mo2 stainless steel. Further, the first liquid distributor 3 or the second liquid distributor 11 may be a disk Kong Liuxing liquid distributor made of 0Cr17Ni12Mo2 stainless steel. In some embodiments, the first liquid distributor 3 is a pressure type porous tubular distributor with a circular ring shape or a pore flow distributor with a circular ring shape; further, the first liquid distributor 3 is a disk Kong Liuxing liquid distributor in the shape of a circular ring.
In some embodiments of the present invention, the reaction vessel 5 is connected to the rectification system 1, and the rectification system 1 is connected to the condensation reflux system. In some specific embodiments, the rectification system 1 may be a rectification column, and the condensation reflux system includes a condenser 15 and a delivery pump 14, where the condenser 15 is connected to the rectification column, the condenser 15 is connected to the delivery pump 14, and the delivery pump 14 is connected to the rectification column through a pipe.
In some embodiments of the invention, the reaction vessel 5 or falling film reaction vessel 10 is connected to a vacuum system 13. The inside of the reaction vessel 5 or the falling film reaction tank 10 may be vacuumed by the vacuum system 13, so that the polyester polycondensation stage is completed in a vacuum state.
In the vacuum polycondensation stage of polyester synthesis, the falling film reaction tank 10 has small volume and no mechanical stirring and other parts, can form higher vacuum degree, and 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 dead weight pressure, and uniformly distributed through the second liquid distributor 11 to form film-shaped falling, so that a larger devolatilization area is provided, and the gasification removal of small molecules is facilitated. In the polyester synthesis vacuum polycondensation stage, the reaction kettle 5 is simultaneously vacuumized, part of reaction materials form a film-shaped liquid film through a second liquid distributor 11 in a falling film reaction tank 10, after falling to the bottom of the falling film reaction tank 10, the film-shaped liquid film is pumped through a second melt pump 9 or passes through a second three-way valve 12 of a closed pipeline through the bottom of the falling film reaction tank 10 by means of dead weight pressure, part or all of resin melt returns to the second liquid distributor 11 in the falling film reaction tank 10 to form a film again for devolatilization, and in addition, part of resin melt enters a first liquid distributor 3 in the reaction kettle 5 to be uniformly distributed and then form a film-shaped falling, so that the devolatilization area is further increased, and the devolatilization efficiency is improved.
In some embodiments of the invention, all melt transfer lines of the polyester resin synthesis apparatus are equipped with a self-temperature control heat tracing band or heating system to prevent the resin melt from clogging the lines after cooling within the lines.
In some embodiments of the invention, the reaction kettle 5 is externally sleeved with a thermal insulation sleeve 4.
In some embodiments of the present invention, the batch polyester resin synthesis apparatus for polyester resin 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, etc. 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 socket and the lower end socket are standard end sockets, a circular overflow trough type liquid distributor is arranged in the reactor, and the reactor is made of 0Cr17Ni12Mo2 stainless steel. The falling film reaction tank 10 is arranged at the horizontal position of the reaction kettle 5, 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 communication 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 overflow trough type liquid distributor with a circular ring shape is horizontally arranged at the upper part in the reaction kettle 5, and is made of 0Cr17Ni12Mo2 stainless steel. All melt conveying pipelines are provided with self-temperature-control heat tracing belts.
The polyester resin synthesis device performs devolatilization in the reaction kettle 5 and the falling film tank at the same time, the falling film tank has no mechanical stirring, a thinner liquid film and higher vacuum degree can be formed, and compared with the prior art, the polyester resin synthesis device synthesizes polyester with the same viscosity, can greatly shorten the vacuum polycondensation time, can effectively reduce the production process cost of the polyester resin, improve the utilization rate of equipment and reduce the energy consumption. In addition, the intermittent polyester resin synthesizing device can customize polyester resin according to the production requirement of the paint, can save equipment investment and equipment installation space compared with a continuous synthesizing device, does not need to design a plurality of reaction kettles 5 to be connected in series according to a multi-kettle process flow, and simplifies equipment and process flow. The resin melt with different proportions is regulated to return to the second liquid distributor 11 in the falling film reaction tank 10 by controlling the opening and closing proportion of the second three-way valve 12 on the connecting pipeline of the outlet of the falling film reaction tank 10 and the first liquid distributor 3 in the reaction tank 5, and can be linked with the first melt pump 7 and the first three-way valve 8 at the bottom of the reaction tank 5 to control the resin melt in the reaction tank 5 with the same quality to enter the falling film reaction tank 10 so as to form a continuous and stable liquid film.
The present invention will be described in further detail with reference to specific examples. The raw materials, reagents or apparatus used hereinafter are commercially available from conventional sources unless otherwise specified.
Polyester resins of examples 1 to 3 and comparative examples 1 to 2 and process for producing the same
Polyester resins of examples 1 to 3 and comparative examples 1 to 2 were synthesized according to the formulations shown 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 (the units of the following components are kg unless otherwise noted)
The preparation procedure of the polyester resin in example 1:
1) Adding polyalcohol into a reaction kettle 5 of the polyester resin intermittent polyester resin synthesis device according to the proportion of the embodiment 1 in the table 1, heating and heating until materials are melted, adding polybasic acid and a catalyst, gradually heating to 245 ℃ under the protection of nitrogen to perform esterification reaction, opening a first melt pump 7 and a first three-way valve 8 on a connecting pipeline of the reaction kettle 5 and a falling film reaction tank 10 after the reaction reaches a clear point (namely the raw materials are completely reacted and dissolved), circulating the materials for 10min, and continuously preserving heat until the acid value reaches 17-23mgKOH/g to obtain an esterification product;
2) Under the protection of nitrogen, adding an acidolysis agent into the esterified product to carry out acidolysis reaction for 3 hours at 240 ℃ to obtain an acidolysis product, wherein the acid value of the acidolysis product reaches 20-30 mgKOH/g;
3) Vacuumizing the reaction kettle 5, carrying out polycondensation reaction on acidolysis products for 0.5h under the vacuum degree of-0.095 MPa, vacuumizing the falling film reaction tank 10, starting the first melt pump 7 and the first three-way valve 8 to enable resin in the reaction kettle 5 to enter the second liquid distributor 11 in the falling film reaction tank 10 to form a liquid film, and controlling the pipeline second three-way valve 12 to enable all resin melt out of the falling film reaction tank 10 to return to the first liquid distributor 3 in the reaction kettle 5 for film formation and devolatilization again. Continuously carrying out vacuum polycondensation for 2h, wherein the acid value is lower than 10mgKOH/g, the melt viscosity is 26000-30000mPa.s at 200 ℃, and cooling to 210 ℃ and discharging to obtain the polyester resin.
Preparation procedure of polyester resin of example 2:
1) The same operation as in example 1 is carried out, the material is added according to the proportion of example 2 in Table 1, and the acid value of the esterification product is 7-13 mgKOH/g;
2) The same procedure as in example 1 is carried out, wherein the acid value of the acidolysis product reaches 43-47 mgKOH/g;
3) Vacuumizing the reaction kettle 5, carrying out polycondensation reaction on acidolysis products for 0.5h under the vacuum degree of-0.095 MPa, vacuumizing the falling film reaction tank 10, starting the first melt pump 7 to enable resin in the reaction kettle 5 to enter the second liquid distributor 11 in the falling film reaction tank 10 to form a liquid film, controlling the second three-way valve 12 to enable 10% of the resin melt out of the falling film reaction tank 10 to return to the first liquid distributor 3 in the reaction kettle 5, and enabling 90% of the 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, wherein the acid value is 30-36mgKOH/g, and the melt viscosity is 4000-5000mPa.s at 200 DEG C
4) And 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 connecting pipeline of the reaction kettle 5 and the falling film reaction tank 10, circulating the materials for 30min, and discharging to obtain the polyester resin.
Preparation procedure of polyester resin in example 3:
1) The same procedure as in example 1 was conducted, except that the acid value of the esterified product was 7 to 13mgKOH/g;
2) The same operation as in example 2 is carried out, and the acid value of the acidolysis product reaches 55-65 mgKOH/g;
3) The same procedure as in example 2 was followed except that the polyester resin had an acid value of 40 to 46mgKOH/g and a melt viscosity at 200℃of 4500 to 5500 Pa.s.
4) The procedure is as in example 2.
The preparation procedure of the polyester resin in comparative example 1:
1) Adding polyalcohol into a polyester resin conventional batch reaction kettle (such as a reaction kettle which is optionally used in CN110935408A, and has a volume of 3000L) according to the proportion of comparative example 1 in table 1, heating to raise the temperature until materials melt, adding polybasic acid and a catalyst, gradually raising the temperature to 245 ℃ under the protection of nitrogen to perform esterification reaction, and preserving the temperature until the acid value reaches 17-23mgKOH/g to obtain an esterified product;
2) The same procedure as in example 1, polyester resin preparation step 2);
3) Vacuumizing, carrying out polycondensation reaction on acidolysis products for 3 hours 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 2 hours, so that the acid value and the viscosity of the polyester resin are not greatly changed.
The preparation procedure of the polyester resin in comparative example 2:
1) Operating the same comparative example 1, feeding according to the proportion of comparative example 2 in Table 1, and obtaining 7-13 mgKOH/g of esterified product;
2) The same procedure as in example 2, polyester resin preparation step 2);
3) Vacuumizing, and performing polycondensation reaction on acidolysis products for 4 hours under the vacuum degree of-0.095 MPa, wherein the acid value is 30-36mgKOH/g, and the melt viscosity is 4000-5000mPa.s at 200 DEG C
4) Cooling to 200 ℃, adding an auxiliary agent, stirring for 30min, and discharging to obtain the polyester resin.
Performance test of powder coatings made from the polyester resins of examples 2, 3 and comparative example 2:
the polyester resins of examples 2, 3 and comparative example 2 of the present invention were weighed and mixed with curing agent TGIC, leveling agent GLP588, titanium pigment, barium sulfate, benzoin and gloss enhancer 701, respectively, in the proportions shown in Table 2 below (unless otherwise specified, the component units in Table 2 were g), melt-extruded by a screw extruder, tableted, crushed, and then crushed and sieved to obtain powder coatings of examples 4 to 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 polyester resins in examples 1 to 3 and comparative examples 1 to 2:
the properties of examples 1 to 3 and comparative examples 1 to 2 were tested, wherein the acid value was tested according to GB/T6743-2008; hydroxyl number was tested according to GB/T12008.3-2009; viscosity was tested according to astm d 4287; number average molecular weight and molecular weight distribution were tested according to GB/T21864-2008 and glass transition temperature was tested according to GB/T19466.2; the reactivity was tested according to Q/QTCL1-2014, i.e.the gelation time of the resin with equivalent curing agent at 180 ℃. The performance test data of the polyester resins in examples 1 to 3 and comparative examples 1 to 2 are recorded in the following table 3.
TABLE 3 Properties of the polyester resins in examples 1 to 3 and comparative examples 1 to 2
From the properties of the polyester resins in table 3 and the synthetic processes by the polyester resins in comparative examples 1 to 3 and comparative examples 1 to 2, 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 that in comparative example 1. As can be seen from comparative example 1 and comparative example 1: the intermittent polyester resin synthesis device in the embodiment of the invention can be used for synthesizing high-viscosity polyester resin during synthesis, and can be used for performing film formation and devolatilization twice between the reaction kettle 5 and the falling film reaction tank 10, and forming high vacuum degree in the falling film reaction tank 10, so that micromolecular byproducts in the reaction can be effectively removed, the polycondensation reaction balance can be moved forward, the reaction range degree can be improved, the vacuum polycondensation time can be shortened, and the energy consumption can be reduced. As can be seen from comparative examples 2 and 2, the batch type polyester resin synthesizing apparatus according to the embodiment of the present invention can synthesize a polyester resin having a wide molecular weight distribution, and can satisfy the demand of a part of the coating materials for a polyester resin having a wide molecular weight distribution.
Performance test of powder coatings in examples 4 to 5 and comparative example 3:
the powder coatings of examples 4, 5 and 3 according to the present invention were respectively applied to the surface-treated iron plates by electrostatic spraying, cured at 130 c 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 of which are recorded 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) Impact testing was performed according to GB/T1732-1993;
(3) Bending tests were carried out according to GB/T6742-2007;
(4) 1000h xenon lamp aging test 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 is used for synthesizing high-viscosity polyester, the flow proportion of liquid is controlled by adjusting the second three-way valve 12 at the bottom of the falling film reaction tank 10, the polyester resin melt after film formation and devolatilization of the resin melt through the second liquid distributor 11 in the falling film reaction tank 10 is controlled to return to the second liquid distributor 11 in the falling film reaction tank 10 again, and the residual resin melt enters the first liquid distributor 3 in the reaction tank 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 tank, has higher glass transition temperature when being applied to low-temperature curing powder coating, has higher leveling property and weather resistance, and has better performance than that of the conventional intermittent reaction tank.
While the embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various changes may be made without departing from the spirit of the present invention within the knowledge of those skilled in the art. Furthermore, embodiments of the invention and features of the embodiments may be combined with each other without conflict.
Claims (9)
1. A polyester resin synthesizing device, characterized in that: the reactor comprises a reaction kettle and a falling film reaction tank, wherein a first liquid distributor is arranged in the reaction kettle, an inlet of the first liquid distributor is connected with an outlet of the falling film reaction tank, a second liquid distributor is arranged in the falling film reaction tank, and an inlet of the second liquid distributor is connected with an outlet of the reaction kettle.
2. The polyester resin synthesis apparatus according to claim 1, wherein: the inlet of the first liquid distributor is connected with the outlet of the reaction kettle; and an inlet of the second liquid distributor is connected with an outlet of the falling film reaction tank.
3. The polyester resin synthesis apparatus according to claim 1 or 2, wherein: the reaction kettle is internally provided with a stirring device, the stirring device comprises a stirring shaft, and the first liquid distributor is arranged outside the stirring shaft.
4. The polyester resin synthesis 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 synthesis 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 type distributor, a hole flow distributor or an overflow trough type distributor.
6. The polyester resin synthesis 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 in that: the material is prepared from the following components in percentage by mass: 33-40% of polyalcohol; 43-60% of polybasic acid; 5-15% of acidolysis agent; 0.01 to 0.1 percent of catalyst; 0.05-2% of curing accelerator, wherein the polybasic acid is at least one selected from terephthalic acid, isophthalic acid, 1, 4-cyclohexanedicarboxylic acid and 1, 6-adipic acid; the polyester resin meets the following conditions:
(1) An acid value of 25-45mgKOH/g;
(2) A hydroxyl value of less than 3mgKOH/g;
(3) The glass transition temperature is 60-70 ℃;
(4) The melt viscosity at 200 ℃ is 4500-7500mPa.s;
(5) Number average molecular weight 2500-6500;
(6) A molecular weight distribution index of 1.5 to 2.5;
the method for producing the polyester resin using the polyester resin synthesis apparatus according to any one of claims 1 to 6, comprising the steps of:
s1: esterification: mixing polyol, polybasic acid and a catalyst in a reaction kettle for reaction, and after the mixed reaction reaches a clear point, circulating a reaction mixture between the reaction kettle and a falling film reaction tank, stopping circulation, and continuing the reaction to obtain an esterification product;
s2: acidolysis: reacting the esterified product with an acidolysis agent;
s3: polycondensation: circulating the product in the step S2 between the reaction kettle and the falling film reaction tank;
s4: and (3) mixing the product in the step (S3) with a curing accelerator, and then circulating the mixture between a reaction kettle and a falling film reaction tank to obtain the polyester resin.
8. The method for producing a polyester resin according to claim 7, wherein: use of the polyester resin synthesis apparatus according to any one of claims 1 to 6, the method comprising the steps of:
s1: esterification: mixing polyol, polybasic acid and a catalyst in a reaction kettle for reaction, and after the mixed reaction reaches a clear point, circulating a reaction mixture between the reaction kettle and a falling film reaction tank, stopping circulation, and continuing the reaction to obtain an esterification product;
s2: acidolysis: reacting the esterified product with an acidolysis agent;
s3: polycondensation: circulating the product in the step S2 between the reaction kettle and the falling film reaction tank;
s4: and (3) mixing the product in the step (S3) with a curing accelerator, and then circulating the mixture between a reaction kettle and a falling film reaction tank to obtain the polyester resin.
9. A powder coating, characterized by: comprising the polyester resin of claim 7.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007127786A2 (en) * | 2006-04-28 | 2007-11-08 | Wellman, Inc. | Methods for making polyester resins in falling film melt polycondensation reactors |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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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