CN116808947A - Synthesis process and equipment of polyether ester polyol - Google Patents
Synthesis process and equipment of polyether ester polyol Download PDFInfo
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- CN116808947A CN116808947A CN202310808221.0A CN202310808221A CN116808947A CN 116808947 A CN116808947 A CN 116808947A CN 202310808221 A CN202310808221 A CN 202310808221A CN 116808947 A CN116808947 A CN 116808947A
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- kettle
- esterification
- reaction
- polycondensation
- polyether
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- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 97
- 229920000570 polyether Polymers 0.000 title claims abstract description 97
- 229920005862 polyol Polymers 0.000 title claims abstract description 77
- -1 ester polyol Chemical class 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 40
- 230000008569 process Effects 0.000 title claims abstract description 32
- 230000015572 biosynthetic process Effects 0.000 title claims description 18
- 238000003786 synthesis reaction Methods 0.000 title claims description 18
- 238000005886 esterification reaction Methods 0.000 claims abstract description 114
- 230000032050 esterification Effects 0.000 claims abstract description 100
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 81
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 68
- 238000005809 transesterification reaction Methods 0.000 claims abstract description 59
- 125000003118 aryl group Chemical group 0.000 claims abstract description 56
- 239000002253 acid Substances 0.000 claims abstract description 51
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 150000003077 polyols Chemical class 0.000 claims abstract description 24
- 150000002148 esters Chemical group 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 9
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims description 86
- 239000003054 catalyst Substances 0.000 claims description 51
- 229920000728 polyester Polymers 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000010009 beating Methods 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- 229910052787 antimony Inorganic materials 0.000 claims description 7
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 7
- 150000008064 anhydrides Chemical class 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 150000004703 alkoxides Chemical class 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 150000007942 carboxylates Chemical class 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 229910052732 germanium Inorganic materials 0.000 claims description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 3
- 150000004820 halides Chemical class 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 3
- 150000002910 rare earth metals Chemical class 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 239000011135 tin Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 27
- 229920002334 Spandex Polymers 0.000 abstract description 24
- 239000004759 spandex Substances 0.000 abstract description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 20
- 238000004519 manufacturing process Methods 0.000 abstract description 12
- 229920000909 polytetrahydrofuran Polymers 0.000 abstract description 10
- 125000004185 ester group Chemical group 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 39
- 239000002002 slurry Substances 0.000 description 17
- 238000003860 storage Methods 0.000 description 14
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 10
- 150000002009 diols Chemical class 0.000 description 10
- 239000010409 thin film Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000002202 Polyethylene glycol Substances 0.000 description 8
- 229920001223 polyethylene glycol Polymers 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000004537 pulping Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 150000003384 small molecules Chemical class 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
- 210000004177 elastic tissue Anatomy 0.000 description 4
- 239000010408 film Substances 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
- 239000000178 monomer Substances 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 229920001451 polypropylene glycol Polymers 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 150000007519 polyprotic acids Polymers 0.000 description 3
- 229920003226 polyurethane urea Polymers 0.000 description 3
- 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 3
- 238000009987 spinning Methods 0.000 description 3
- 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 3
- 239000004970 Chain extender Substances 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 150000001412 amines Chemical group 0.000 description 2
- WSXIMVDZMNWNRF-UHFFFAOYSA-N antimony;ethane-1,2-diol Chemical compound [Sb].OCCO WSXIMVDZMNWNRF-UHFFFAOYSA-N 0.000 description 2
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 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 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920005906 polyester polyol Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 229920006306 polyurethane fiber Polymers 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- LJPCNSSTRWGCMZ-UHFFFAOYSA-N 3-methyloxolane Chemical compound CC1CCOC1 LJPCNSSTRWGCMZ-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- 101100298222 Caenorhabditis elegans pot-1 gene Proteins 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- ABMFBCRYHDZLRD-UHFFFAOYSA-N naphthalene-1,4-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1 ABMFBCRYHDZLRD-UHFFFAOYSA-N 0.000 description 1
- KHARCSTZAGNHOT-UHFFFAOYSA-N naphthalene-2,3-dicarboxylic acid Chemical compound C1=CC=C2C=C(C(O)=O)C(C(=O)O)=CC2=C1 KHARCSTZAGNHOT-UHFFFAOYSA-N 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920002523 polyethylene Glycol 1000 Polymers 0.000 description 1
- 238000010094 polymer processing Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
-
- 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
- B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
- B01J3/04—Pressure vessels, e.g. autoclaves
-
- 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
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention provides a process and equipment for synthesizing polyether ester polyol, which sequentially and continuously pass through equipment such as an ester exchange esterification kettle, a deep esterification kettle, a polycondensation kettle, a filter, a heat exchanger and the like, wherein raw materials containing aromatic groups and polyether glycol raw materials are subjected to corresponding preliminary ester exchange/esterification reaction, deep esterification reaction and polycondensation reaction step by step, and the polyether ester polyol with a specific structure is obtained after filtration and heat exchange. According to the invention, the esterification or transesterification reaction of the aromatic dibasic acid or the aromatic dibasic acid ester-containing substance and the polyether polyol with a specific feeding ratio is divided into three stages under different conditions, so that the reaction is more complete, the reaction efficiency is improved, the production of the polyether ester polyol for spandex can be industrially carried out on a large scale, and the prepared polyether ester polyol is used as a substitute of polytetrahydrofuran ether glycol, so that the production cost of the spandex can be remarkably reduced.
Description
Technical Field
The invention relates to the technical field of polymer processing, in particular to a synthesis process and equipment of polyether ester polyol.
Background
Spandex is an elastic fiber which is the most widely used at present, and is a block copolymer of soft segments and hard segments, wherein the soft segments are generally composed of soft segments, and the soft segments are generally obtained by reacting polyols such as polyether, polyester, hydroxyl-terminated polybutadiene and the like with polyisocyanates for connecting the polyols; the hard segment is composed of segments with excellent crystallization performance, and is generally obtained by reacting polyisocyanate with small molecular polyol and small molecular amine chain extender. The main raw materials of the dry-method polyether type spandex are polytetrahydrofuran ether glycol, diphenylmethane diisocyanate and chain-extended amines, a polyurethane urea solution is prepared through a two-step polymerization reaction, then necessary additives are added to prepare a polyurethane urea spinning solution, and the polyurethane urea spinning solution is prepared through channel spinning. According to the method, polytetrahydrofuran ether glycol is adopted as a soft chain segment, the performance of the prepared spandex fiber is relatively balanced, the elastic elongation is relatively high, the tensile modulus of the spandex fiber can basically meet the daily clothing requirements, but the polytetrahydrofuran ether glycol as a raw material of the soft chain segment is relatively high in price, and the production cost of the spandex fiber is increased.
The inventor finds that the block structure with rigid aromatic groups and polyether groups with a certain length is used as a soft chain segment of spandex in long-term research and development work, and the block structure can ensure the tensile modulus of the spandex and simultaneously has higher elastic elongation. The inventors therefore conceived that polyether ester polyols having the above structure can be substituted for polytetrahydrofuran ether glycol as a soft segment raw material of spandex. In the prior art, a large-scale industrialized preparation method of the polyether ester polyol is not available, and the application of the polyether ester polyol in the spandex industry is limited.
Disclosure of Invention
In order to solve the technical problems, the invention provides a synthesis process and equipment for mass industrialized production of polyether ester polyol suitable for producing spandex. The specific scheme is as follows:
the utility model provides a polyether ester polyol synthesis equipment, its characterized in that, including the transesterification esterification kettle that sets gradually, degree of depth esterification kettle and polycondensation kettle, wherein, the discharge gate of transesterification esterification kettle passes through material pipeline with the feed inlet of degree of depth esterification kettle and links to each other, and the discharge gate of degree of depth esterification kettle passes through material pipeline with the feed inlet of polycondensation kettle and links to each other, transesterification esterification kettle and degree of depth esterification kettle link to each other with the rectifying column, degree of depth esterification kettle, polycondensation kettle link to each other with vacuum system, be provided with the catalyst jar between degree of depth esterification kettle and the polycondensation kettle, the catalyst jar passes through material pipeline and links to each other with the polycondensation kettle, and the material pipeline that extends from the polycondensation kettle discharge gate loops through filter and heat exchanger.
Optionally, the feeding end of the transesterification esterification kettle is also connected with a polyester feeding device.
Optionally, the feeding end of the transesterification esterification kettle is connected with a pulping tank and a slurry tank, and the pulping tank is positioned in front of the slurry tank.
Optionally, the reflux port of the rectifying tower is connected with the feed end of the transesterification esterification kettle.
Optionally, an evaporator is further arranged between the filter and the heat exchanger, and the evaporator is connected with a vacuum system.
Optionally, a first pump is arranged between the deep esterification kettle and the polycondensation kettle, a second pump is arranged between the catalyst tank and the polycondensation kettle, a third pump is arranged between the polycondensation kettle and the filter, and a fourth pump is arranged before the heat exchanger.
Optionally, the discharge end of the heat exchanger is connected to a product storage tank.
Optionally, a second evaporator is arranged between the deep esterification kettle and the polycondensation kettle.
A process for synthesizing a polyetherester polyol according to claim 1, comprising the steps of:
step 1): one or more of aromatic dibasic acid, aromatic dibasic acid ester, aromatic dibasic anhydride and polyester containing aromatic dibasic acid polyol ester structure are continuously added into a transesterification esterification kettle to carry out esterification reaction and/or transesterification reaction under the protection of inert gas, wherein the polymerization degree of the polyether glycol is 2-20, preferably 3-10, the molecular weight is 100-1000, preferably 300-100, more preferably 600-900, the molar ratio of the polyether glycol to the aromatic ring group is 1.05-2, and the reaction temperature is 220-290 ℃, preferably 240-270 ℃. The reaction time is 1-72 hours, the absolute pressure is 60KPa-400KPa, the acid value of the reacted material is less than 50mgKOH/g, or the esterification rate is controlled to be 80-99%, preferably 90-99%;
step 2): continuously transferring the material obtained in the step 1) into a deep esterification kettle, wherein the temperature in the deep esterification kettle is 220-290 ℃, preferably 240-270 ℃, the absolute pressure during reaction is less than 80KPa, preferably less than 60KPa, and performing further esterification reaction to ensure that the acid value of the material is less than 10mgKOH/g, or controlling the esterification rate to be 90-99.9%, preferably 95-99.8%;
and 3) fully mixing the material obtained in the step 2) with a catalyst continuously added in a catalyst tank through a material conveying pipeline connected with a polycondensation kettle, continuously transferring the mixture into the polycondensation kettle together, wherein the temperature in the polycondensation kettle is 220-290 ℃, preferably 240-270 ℃, and performing transesterification polycondensation reaction under the absolute pressure of less than 20KPa to ensure that the acid value of the product is less than 0.8mgKOH/g, preferably less than 0.5mgKOH/g, or controlling the esterification rate to be more than 99%, preferably more than 99.9%.
Absolute pressure as used herein refers to the pressure measured with absolute vacuum as zero.
Optionally, in step 1) and step 2), the water and the small molecular low-boiling-point substances generated by the reaction are separated by a rectifying tower and then discharged from the top of the tower.
Optionally, in step 3), the catalyst is one or more of oxides, alkoxides, carboxylates and halides of tin, zinc, magnesium, calcium, copper, antimony, titanium, gallium, germanium and rare earth metals. Optionally, the method further comprises the steps of:
continuously transferring the product obtained in the step 3) to an evaporator through a filter, and separating small molecular products in the product.
Optionally, the method further comprises the steps of:
and 3) enabling the product obtained in the step 3) to pass through a heat exchanger to reduce the temperature of the product to the process requirement temperature.
The beneficial effects are that:
according to the synthesis process and the equipment for the polyether ester polyol, the esterification or transesterification reaction of the aromatic dibasic acid or the aromatic dibasic acid ester-containing substance and the polyether polyol with a specific feeding ratio is divided into three stages under different conditions, so that the reaction is more complete, the reaction efficiency is improved, the production of the polyether ester polyol for spandex can be continuously carried out in a large-scale industrialized manner, and the prepared polyether ester polyol can be used as a substitute of polytetrahydrofuran ether glycol, and the production cost of the spandex can be remarkably reduced.
Drawings
FIG. 1 is an overall schematic diagram of a polyetherester polyol synthesis apparatus according to the present invention
The reference numerals are as follows:
1. beating tank 2, slurry storage tank 3, polyester feeding device 4, transesterification esterification kettle 5, rectifying tower 6, deep esterification kettle 7, first pump 8, catalyst tank 9, second pump 10, polycondensation kettle 11, third pump 12, filter 13, thin film evaporator 14, fourth pump 15, heat exchanger 16, product storage tank 17, vacuum system
Detailed Description
The spandex is the most widely used elastic fiber at present, and the conventional spandex generally adopts polytetrahydrofuran ether glycol as a soft segment raw material, but the polytetrahydrofuran ether glycol has higher price, so that the production cost of the spandex is raised. The inventor finds that polyether ester polyol with aromatic group-polyether block structure prepared by reacting aromatic dibasic acid with specific polyether can be used as a soft segment of spandex, can also meet the requirements of mechanical parameters such as elastic recovery performance, elastic modulus and the like of the spandex, and has more cost advantage. The polyether ester polyol with the structure is only prepared in a small scale in a laboratory at present, and equipment and a process for large-scale continuous production of the polyether ester polyol are not available, so that the application of the polyether ester polyol in the spandex industry is limited. Therefore, the invention provides a continuous synthesis process and equipment of polyether ester polyol, which can realize industrial production of the polyether ester polyol with the structure.
The apparatus and process are described in detail below with reference to examples, which are illustrative of some, but not all, of the embodiments of the invention. In the interest of clarity and conciseness, not all features of an actual implementation are described in this specification. The following "first" and "second" are only for distinguishing between the same named components at different locations and not for indicating the sequential location or start-up sequence before each other. In order to avoid obscuring the invention in unnecessary detail, only the device structures and method steps closely related to the solution according to the present invention are described in the drawings and description. Hereinafter, the aromatic group includes an aromatic ring and an aromatic heterocyclic ring.
Unlike other types of polyetherester polyols, the polyetherester polyols described in the present invention are polyetherester polyols suitable for the production of spandex, which have the following characteristics:
the polyetherester polyol comprises repeating units and capped alcoholic hydroxyl groups as described by the formula:
wherein R is 1 Is at least one of an aromatic ring or an aromatic heterocyclic ring, and R 1 The mass content in the repeating unit of formula (1) is 4.5% -44%; r is R 2 At least one of saturated alkane groups with 2-5 carbon atoms; x is 2-20;
the mass percentage of the repeating units shown in the formula (1) in the polyether ester polyol is more than 75 percent;
the average functionality of the end capping alcohol hydroxyl groups is 1.95-2.00;
the polyetherester polyols have a number average molecular weight of from 800 to 5000.
The polyether ester polyol with the characteristics has a linear chain structure as a whole, wherein polyether is bondedThe structure is arranged at intervals with the aromatic ring, so as to improve the plastic deformation resistance of the polyurethane elastic fiber; the introduction of aromatic or heteroaromatic rings also gives polyurethane elastic fibers with higher modulus. In addition to the above-described structure of the repeating unit, some other structure may be added to the polyether ester polyol for differential modification, but in the present invention, it is preferable that the mass ratio of the repeating unit of formula (1) in the polyether ester polyol is more than 95%, i.e., the polyether ester polyol is constituted of only the repeating unit of formula (1) and the terminal hydroxyl group as much as possible. The polyether ester polyol should have a hydroxyl functionality of the capped alcohol of less than 2 and as close to 2 as possible to ensure that, when used as a spandex starting material, it reacts with the diisocyanate and the chain extender to form linear polyurethane molecules. The polyetherester polyols may have a molecular weight of from 1000 to 5000, preferably from 1000 to 3500, more preferably from 1400 to 2500, most preferably from 1500 to 2300. The larger the number average molecular weight of the polyether ester polyol, the larger the viscosity thereof, and it is difficult to conduct continuous operation on an industrial scale. However, polyether ester polyols have too low a molecular weight, and when the molecular weight requirements of polyurethane prepolymers are consistent, more diisocyanate is required to participate in the synthesis, resulting in a higher urethane group content in the prepolymer, and thus the interaction-enhanced viscosity between prepolymer molecules is also increased. Moreover, the short length of the soft segments in the polyurethane formed at this time can affect the recovery properties of the final polyurethane fiber. In a preferred embodiment, the polyetherester polyols of the present invention are used in a polyester polyol composition at 90℃and shear rate 1S -1 The viscosity at lower may be less than 500 poise, preferably less than 200 poise. The polyether ester polyol of the present invention may have a melting point below 80 c, preferably in a liquid state at normal temperature, so that it is prevented from solidifying during storage or transportation to ensure industrial continuous operation. Otherwise, the alloy needs to be melted by heating, so that the energy consumption is increased.
In order to obtain the polyether ester polyol with the characteristics, the invention provides a preparation method of the polyether ester polyol, which comprises the steps of carrying out condensation reaction or transesterification reaction on aromatic dibasic acid, esterified product or anhydride thereof and polyether glycol. In the process of the present invention, the aromatic diacid, its ester or its anhydride provides R to the polyetherester 1 Aromatic rings or aromatics in (B)Heterocyclic structures, polyether diols provide polyether structures for polyetherester diols.
In particular, for the synthetic polyetherester polyols to meet the above-described characteristic requirements, the aromatic diacid may be selected from one or more of terephthalic acid, isophthalic acid, phthalic acid, diphthalic acid, 1, 4-naphthalenedicarboxylic acid, 2, 6-naphthalenedicarboxylic acid, 2, 3-naphthalenedicarboxylic acid, 2, 5-furandicarboxylic acid, terephthaloic acid, isophthalic acid, and phthalic acid. In one embodiment, the esters thereof may be obtained by reacting an aromatic diacid with a monohydric alcohol having a boiling point below 150 ℃ such as methanol, ethanol, n-butanol, n-hexanol and the like small molecule alcohols, whereby they may be easily removed by distillation in a subsequent esterification reaction or transesterification reaction; the small molecule alcohol is preferably methanol or ethanol. Moreover, the transesterification reaction between the above-mentioned esters and polyether glycol can be performed under milder reaction conditions than that of aromatic dibasic acids, which is advantageous in production process design. In addition, polyesters containing aromatic groups can also be used as R 1 Structural source, and polyether glycol. The aromatic diacid suitable for the invention can be derived from recycled plastics, thereby realizing waste recycling, reducing the production cost of polyurethane fibers and meeting the current requirements of green economy. Hereinafter, for convenience of description, the above-mentioned aromatic dibasic acid, its ester or its anhydride, and the aromatic group-containing polyester are collectively referred to as an aromatic group raw material.
Accordingly, in the process of the present invention, the polyether diol as a raw material has a polymerization degree of preferably 2 to 20, more preferably 3 to 10; suitable polyether diols may have a number average molecular weight of from 100 to 1000, preferably from 300 to 1000, more preferably from 600 to 900. In fact, the structure of polyether segments spaced from aromatic rings makes the resulting polyetherester polyols suitable for the preparation of spandex only if the degree of polymerization and number average molecular weight of the polyether diol are within the above-mentioned ranges. If the molecular weight of the polyether glycol is too low, the viscosity of the prepared polyether ester polyol is too high, the continuous process is not facilitated, and if the molecular weight of the polyether glycol is too high, the elastic modulus of spandex is difficult to meet the requirement. Polyether glycol can be synthesized through ring-opening polymerization of epoxy monomers or polycondensation of small molecular glycol; either as a homopolymer synthesized from a single monomer or as a copolymer synthesized from two or more monomers. By way of example, polyether diols suitable for use in the present invention may be polyethylene glycol, polypropylene glycol, polytrimethylene ether glycol, polytetrahydrofuran ether glycol, or copolymer diols obtained by reacting tetrahydrofuran with monomers such as ethylene oxide, propylene oxide, 2-methyltetrahydrofuran, or 3-methyltetrahydrofuran. From the synthetic flow, the synthetic route of polyethylene glycol and polypropylene glycol is relatively short, the production cost is low, and the product price is low, so that the polyethylene glycol or polypropylene glycol is preferably used as the polyether glycol raw material. In addition, the polytetrahydrofuran can be used as raw materials by adding part of polyethylene glycol and polypropylene glycol, thereby having the functions of reducing cost and regulating the performance of the product.
In order to obtain a polyetherester polyol having a molecular weight in the range of 1000 to 5000, the molecular weight of the polyetherester polyol can be controlled by adjusting the molar ratio R of polyetherdiol to aromatic groups in the raw material. The molar ratio R should be in the range of 1.05 to 2, preferably 1.1 to 1.6, and too small a molar ratio R will result in too large a molecular weight of the resulting polyetherester polyol and too large a molar ratio R will result in too small a molecular weight of the resulting polyetherester polyol.
The equipment for synthesizing the polyether ester polyol is described below by way of examples.
Example 1
This example relates to a polyether ester polyol synthesizing apparatus, as shown in fig. 1, comprising a beating tank 1, a slurry storage tank 2, a transesterification esterification kettle 4, a deep esterification kettle 6, a polycondensation kettle 10, a filter 12, a thin film evaporator 13, a heat exchanger 15, and a product storage tank 16, which are connected in this order by material conveying pipes. The transesterification reaction vessel 4 is also connected to a polyester feeder 3 for adding polyester particles to the transesterification reaction vessel 4. The transesterification esterification reactor 4 and the deep esterification reactor 6 are respectively connected with the rectification column 5, and can be connected with the same rectification column or different rectification columns, in this embodiment, both are connected with the same rectification column 5, and a reflux pipe of polyether component separated by the rectification column 5 is connected with a feed inlet of the transesterification esterification reactor 4. The feed inlet of the polycondensation reactor 10 is also connected with a catalyst tank 8, and the polycondensation reactor 10 and the thin film evaporator 13 are both connected with a vacuum system 17. A first pump 7 is arranged between the deep esterification kettle 6 and the polycondensation kettle, a second pump 9 is arranged between the catalyst tank 8 and the polycondensation kettle 10, a third pump 11 is arranged between the polycondensation kettle 10 and the filter 12, and a fourth pump 14 is arranged between the thin film evaporator 13 and the heat exchanger 15. Optionally, a second thin film evaporator can be added between the deep esterification kettle 6 and the polycondensation kettle 10.
The working procedure of the polyether ester polyol synthesis apparatus of this example is as follows:
aromatic group-containing raw materials such as aromatic polybasic acid, aromatic polybasic acid ester or acid anhydride and polyether glycol raw materials are uniformly mixed in a beating tank 1, the mixture is conveyed to a slurry storage tank 2 through a material conveying pipeline, the mixed materials in the slurry storage tank 2 are conveyed to a transesterification esterification kettle 4 through the material conveying pipeline, meanwhile, crushed aromatic polyester materials such as polyethylene terephthalate (PET), polypropylene terephthalate (PPT), polybutylene terephthalate (PBT), polybutylene terephthalate-adipate (PBAT) and the like can be added to a polyester feeding device 3, other raw material components can be jointly beaten into slurry, and the polyester is granular, so that the polyester needs to be added by the polyester feeding device 3 alone. The aromatic polyester material can adopt the recycled material after washing and sorting, so that the whole process is more in line with the concept of environmental protection and regeneration. The beating tank 1, the slurry storage tank 2 and the polyester feeding device 3 are used as feeding devices of the equipment, and the molar ratio of the polyether glycol raw material to the aromatic group (namely the aromatic group in the polyester, the aromatic polybasic acid ester or the anhydride in the raw material) in the three materials is controlled to be 1.05-2, preferably 1.1-1.6, so as to control the molecular weight of the polyether ester polyol prepared by the target to meet the requirements. In FIG. 1A shows the aromatic group raw material, polyether glycol raw material, catalyst and the like fed into the beating tank 1.
In the transesterification esterification kettle 4, the reaction temperature is kept at 220-290 ℃, and the color of the product is easily darkened at an excessively high temperature, so that the reaction temperature is preferably 240-270 ℃, the absolute pressure during the reaction is 60KPa-400KPa, and inert gases such as nitrogen, carbon dioxide and the like are filled for protection. In the transesterification esterification reactor 4, the polyether diol raw material and the aromatic group raw material undergo preliminary esterification reaction or transesterification reaction, and the reaction at this stage is mainly the esterification reaction of an aromatic dibasic acid with the polyether diol or the transesterification reaction of an ester of an aromatic dibasic acid, an acid anhydride with the polyether diol, and the conditions of both reactions are similar, so that the aromatic group raw material entering the transesterification esterification reactor 4 may be one or more of an aromatic dibasic acid, an ester or acid anhydride thereof, and an aromatic group-containing polyester. The reaction in the transesterification esterification vessel 4 is preliminary reaction, the polyether glycol raw material and the aromatic group raw material are subjected to esterification and/or transesterification reaction preliminarily for 1-72 hours, the purpose of the transesterification esterification vessel 4 is to react most of the raw materials under milder conditions, the esterification rate of the materials is controlled to 80-98%, preferably 90-96% by the transesterification esterification vessel 4, the esterification rate can be estimated by measuring the acid value of the materials in real time, for the reaction of the present invention, the acid value of the materials is less than 50mgKOH/g, which is considered to satisfy the above-mentioned esterification rate requirement, and the acid value can be determined by the method in the determination of acid value in HG T2708-1995 polyester polyol. In addition, the temperature in the reaction kettle is also higher than the boiling point of the micromolecule low-boiling-point substances obtained by the reaction and lower than the boiling point of polyether glycol, the micromolecule low-boiling-point substances such as water or micromolecule glycol generated in the reaction enter the rectifying tower 5 through a pipeline at the top of the transesterification esterification kettle 4, the by-products B which do not participate in the reaction any more such as the low-boiling-point water and the micromolecule low-boiling-point substances are discharged from the rectifying tower 5 through the separation of the rectifying tower 5, and the useful polyether glycol collected at the bottom of the tower returns to the transesterification esterification kettle 4 to continuously participate in the reaction, so that the waste of effective components is avoided, and the reaction efficiency is improved. In addition, the water and the small molecular low-boiling-point substances discharged from the rectifying tower 5 can be further separated, the water is separated and discharged, valuable small molecules can be further recovered, and the economic benefit is improved.
The materials obtained by the reaction in the transesterification esterification kettle 4 are continuously transferred into a deep esterification kettle 6 for further esterification or transesterification reaction, the reaction temperature in the deep esterification kettle 6 is controlled at 220-290 ℃, preferably 240-270 ℃, and the absolute pressure during the reaction is less than 80KPa, preferably less than 60KPa. In the deep esterification kettle 6, the reaction kettle is vacuumized, so that the escape of low-boiling-point water and small-molecular low-boiling-point matters to the rectifying tower 5 is further accelerated, and the reaction is further promoted. In the deep esterification reactor 6, the esterification rate is controlled to be 90 to 99.9%, preferably 95 to 99.8%.
The material obtained by the deep esterification reactor 6 is continuously transferred to a polycondensation reactor 10 by a first pump 7, and simultaneously, the catalyst in a catalyst tank 8 is continuously transferred to the polycondensation reactor by a second pump 9 to carry out transesterification polycondensation reaction. In the material transfer process, the material is preferably continuously transferred to the polycondensation reactor 10 together after being fully mixed with the catalyst continuously added in the catalyst tank 8 through a material transfer pipe connected to the polycondensation reactor 10. In the polycondensation reactor 10, the main reaction process is the stage in which the aromatic-polyether glycol ester structure formed by the previous reaction further reacts with polyether glycol to grow the product chain. The temperature of the polycondensation process is controlled at 220-290 ℃, preferably 240-270 ℃, the absolute pressure during the reaction is less than 20KPa, preferably less than 10KPa, the polycondensation kettle 10 is connected with the vacuum system 17, under the action of a catalyst and high vacuum degree, the escape of byproducts such as water, small molecular low-boiling substances and the like can be accelerated, the molecular structure of the material is easier to remove water and small molecules, the further molecular weight increase reaction of the product can be promoted to be more complete, and the target molecular weight is reached. After passing through the polycondensation kettle, the esterification rate of the material is controlled to be more than 99%, preferably more than 99.9%, and the acid value of the product prepared at the time is controlled to be less than 0.8mgKOH/g, preferably less than 0.5mgKOH/g. Optionally, a second evaporator can be arranged between the deep esterification kettle 6 and the polycondensation kettle 10, after the material comes out from the deep esterification kettle 6, water and small molecular alcohol in the material can be removed through the second thin film evaporator, so that the reverse reaction of polyether ester in the subsequent reaction can be avoided, and the reduction of the catalytic activity of the catalyst caused by hydrolysis in the subsequent reaction can be avoided after the water in the material is reduced.
The catalyst added into the polycondensation reactor 10 may be oxides, alkoxides, carboxylates, halides, or other corresponding organic compounds of metals such as tin, zinc, magnesium, calcium, copper, antimony, titanium, gallium, germanium, rare earth, or one or more of the above. In addition to the catalyst addition by means of the catalyst tank 8 before the polycondensation reactor 10, the catalyst can also be added in a beating tank or in a polyester-feeding device at the beginning of the process. Specifically, the catalyst is preferably titanium series catalyst, such as tetraisopropyl titanate, tetrabutyl titanate and the like, and the catalyst of the type easily turns yellow and deepens the color of the product, so the catalyst is not suitable to be added before esterification, and the catalyst continuous adding device consisting of the catalyst tank 8 and the second pump 9 is additionally arranged after deep esterification and before polycondensation in the process, so that the process parameters can be controlled more flexibly in production, the product quality is more stable, and the yellowing of the prepared product is avoided. In the preparation process of polyether ester, common catalysts include antimony catalysts and titanium catalysts, wherein the antimony catalysts such as antimony trioxide and ethylene glycol antimony have large addition amount and light color, and can be added into a pulping tank 1 together with raw materials, but antimony is generally regarded as heavy metal and is not friendly to human bodies and environment; the titanium catalyst is more environment-friendly and the addition amount is small, but the titanium catalyst is easy to cause the materials to turn yellow, so the titanium catalyst is preferably added into the polycondensation kettle 10 through a catalyst continuous adding device consisting of a catalyst tank 8 and a second pump 9, and the influence of the yellowing of the materials is reduced while the environment is protected. However, in a specific embodiment, the apparatus of the present invention may also add antimony-based catalyst to the beater tank 1.
The material obtained in the polycondensation reactor 10 is continuously transferred to an evaporation device after impurities are removed by a third pump 11 through a filter 12, and by-products such as small molecules in the material are evaporated and separated. The evaporation equipment in this embodiment is a thin film evaporator 13, other types of short-process evaporators can be adopted, the thin film evaporator 13 is connected with a vacuum system 17 through an air extraction pipeline, and moisture and redundant micromolecular products in the materials can be separated in a mode of vacuumizing, introducing inert gases such as nitrogen and carbon dioxide into the materials, and the purity of the products is improved.
The material passing through the thin film evaporator 13 passes through the heat exchanger 15 under the action of the fourth pump 14, and after the product temperature is reduced to the process requirement temperature, is continuously transferred to the product storage tank 16, or enters the next process.
In the process, each esterification kettle can adopt an annular plug flow mode or a multi-layer tower structure and the like so as to ensure that materials have enough residence time in the reactor to fully react, and simultaneously ensure that the materials are continuously conveyed and are beneficial to volatilizing and separating small molecules.
After the materials are put into the synthesis equipment, polyether ester polyol with aromatic group-polyether block structure can be prepared, and the number average molecular weight of the polyether ester polyol is 1000-5000, preferably 1000-3500, more preferably 1200-2500, most preferably 1500-2300; the acid value of the product is controlled to be 0.8mgKOH/g or less, preferably 0.5mgKOH/g or less, more preferably 0.3mgKOH/g or less.
The polyether ester polyol synthesis process provided by the present invention is described below by way of specific examples.
Example 2
Polyethylene glycol PEG600 (number average molecular weight 600) was added to terephthalic acid at a weight ratio of 17:3 (i.e. the molar ratio R is 1.58) are put into a beating kettle 1, mixed and stored in a slurry storage tank 2, the slurry is continuously added into a transesterification esterification kettle 4, and the reaction is carried out at the temperature of 240 ℃. When the acid value of the material in the transesterification esterification kettle 4 is less than 40KOHmg/g, the material is continuously transferred into the deep esterification kettle 6, the esterification reaction is further carried out under the condition that the absolute pressure in the kettle is 50KPa at 270 ℃, when the acid value of the material in the kettle is less than 5KOHmg/g, the material in the deep esterification kettle 6 is continuously transferred into the polycondensation kettle 10 through a pump 7, meanwhile, the ethylene glycol solution of the catalyst tetrabutyl titanate in the catalyst tank 8 is also continuously transferred into the polycondensation kettle 10 through a second pump 9, the transesterification polycondensation reaction is carried out under the condition that the absolute pressure in the kettle is 1.5KPa at 270 ℃, and when the esterification rate is more than 99.9 percent and the acid value is about 0.5mgKOH/g, the material in the polycondensation kettle 10 is continuously transferred into a film evaporator 13 through a filter 12 through a pump 11, and small molecular products in the material are separated. The material is continuously transferred by a pump 14 through a heat exchanger 15 to a product tank 16. The polyether ester polyol in product tank 16 was tested to have an acid number of 0.42mgKOH/g, a number average molecular weight of 1820, an average functionality of 1.98, a viscosity at 90℃of 28 poise at 1S-1, and a liquid at ambient temperature.
Example 3
Polyethylene glycol PEG600 (number average molecular weight 600) was added to terephthalic acid at a weight ratio of 17:3.5 The raw materials (i.e., the molar ratio R is 1.35) were charged into the beating pot 1, mixed and stored in the slurry tank 2, and the slurry was continuously fed into the transesterification esterification pot 4 to carry out the reaction at 255 ℃. When the acid value of the material in the transesterification esterification kettle 4 is less than 40KOHmg/g, the material is continuously transferred into the deep esterification kettle 6, the esterification reaction is further carried out under the condition that the absolute pressure in the deep esterification kettle is 50KPa at 255 ℃, when the acid value of the material in the kettle is less than 5KOHmg/g, the material in the deep esterification kettle 6 is continuously transferred into the polycondensation kettle 10 through a pump 7, meanwhile, the ethylene glycol solution of the catalyst tetraisopropyl titanate in the catalyst tank 8 is also continuously transferred into the polycondensation kettle 10 through a pump 9, the transesterification polycondensation reaction is carried out under the condition that the absolute pressure in the kettle is 2KPa at 255 ℃, and when the esterification rate is more than 99.9 percent and the acid value is about 0.5mgKOH/g, the material in the polycondensation kettle 10 is continuously transferred into a film evaporator 13 through a filter 12 through a pump 11, and small molecular products in the material are separated. The material is continuously transferred by a pump 14 through a heat exchanger 15 to a product tank 16. The polyether ester polyol in product tank 16 was tested to have an acid number of 0.5mgKOH/g, a number average molecular weight of 2750, an average functionality of 1.99, a viscosity at 90℃of 29 poise at 1S-1, and a liquid at ordinary temperature.
Example 4
Under the protection of nitrogen, the raw materials of poly (1, 3-propylene glycol) PPG950 (with the number average molecular weight of 950) and terephthalic acid with the weight ratio of 9:1 (namely, the mol ratio R is 1.57) are put into a pulping kettle 1, are stored in a slurry storage tank 2 after being mixed, are continuously added into a transesterification esterification kettle 4, and simultaneously, polyester reclaimed materials are continuously added into the transesterification esterification kettle 4, so that the mol ratio R of total polyether glycol to aromatic groups is 1.4. The reaction was carried out at a temperature of 265 ℃. When the acid value of the material in the transesterification esterification kettle 4 is less than 30KOHmg/g, the material is continuously transferred into the deep esterification kettle 6, the esterification reaction is further carried out under the condition that the absolute pressure in the kettle is 50KPa at the temperature of 265 ℃, when the acid value of the material in the kettle is less than 5KOHmg/g, the material in the deep esterification kettle 6 is continuously transferred into the polycondensation kettle 10 through a pump 7, meanwhile, the ethylene glycol solution of the catalyst tetraisopropyl titanate in the catalyst tank 8 is also continuously transferred into the polycondensation kettle 10 through a pump 9, the transesterification polycondensation reaction is carried out under the condition that the absolute pressure in the kettle is 1.5KPa at the temperature of 265 ℃, and when the esterification rate is more than 99.9 percent and the acid value is about 0.5mgKOH/g, the material in the polycondensation kettle 10 is continuously transferred into a film evaporator 13 through a filter 12 through a pump 11, and small molecular products in the material are separated. The material is continuously transferred by a pump 14 through a heat exchanger 15 to a product tank 16. The polyether ester polyol in the product tank 16 was tested to have an acid value of 0.35mgKOH/g, a number average molecular weight of 3620, an average functionality of 1.99, a viscosity at 90℃of 1S-1 of 5 poise, and a liquid at ordinary temperature.
Example 5
Under the protection of nitrogen, polyethylene glycol PEG1000 (with the number average molecular weight of 1000) and 2, 6-naphthalene dicarboxylic acid are added into a pulping kettle 1 together with catalyst ethylene glycol antimony in a weight ratio of 19:3 (namely, the molar ratio R is 1.3), the mixture is stored in a slurry storage tank 2, and the slurry is continuously added into a transesterification esterification kettle 4 for reaction at the temperature of 275 ℃. When the acid value of the material in the transesterification esterification kettle 4 is less than 50KOHmg/g, the material is continuously transferred into a deep esterification kettle 6, the esterification reaction is further carried out under the condition that the absolute pressure in the kettle is 40KPa at the temperature of 275 ℃, when the acid value of the material in the kettle is less than 5KOHmg/g, the material in the deep esterification kettle 6 is continuously transferred into a polycondensation kettle 10 through a pump 7, the transesterification polycondensation reaction is carried out under the condition that the absolute pressure in the kettle is 1KPa at the temperature of 275 ℃, and when the esterification rate is more than 99.9 percent and the acid value is about 0.5mgKOH/g, the material in the polycondensation kettle 10 is continuously transferred into a thin film evaporator 13 through a filter 12 by a pump 11, and small molecular products in the material are separated. The material is continuously transferred by a pump 14 through a heat exchanger 15 to a product tank 16. The polyether ester polyol in product tank 16 was tested to have an acid number of 0.48mgKOH/g, a number average molecular weight of 3320, an average functionality of 1.99, a viscosity at 90℃of 1S-1 of 8 poise, and a melting point of 32.8 ℃.
Example 6
Polyethylene glycol PEG600 (number average molecular weight 600) was added to terephthalic acid at a weight ratio of 5:1 (i.e. molar ratio of 1.38) and the catalyst antimony trioxide are put into a pulping kettle 1, mixed and stored in a slurry storage tank 2, the slurry is continuously added into a transesterification esterification kettle 4, and simultaneously polyester reclaimed materials are continuously added into the transesterification esterification kettle 4, so that the molar ratio R of total polyether glycol to aromatic groups is 1.2. The reaction was carried out at a temperature of 265 ℃. When the acid value of the material in the transesterification esterification kettle 4 is less than 40KOHmg/g, the material is continuously transferred into a deep esterification kettle 6, the esterification reaction is further carried out under the condition that the absolute pressure in the kettle is 50KPa at the temperature of 265 ℃, when the acid value of the material in the kettle is less than 4KOHmg/g, the material in 6 is continuously transferred into a polycondensation kettle 10 through a pump 7, the transesterification polycondensation reaction is carried out under the condition that the absolute pressure in the kettle is 1KPa at the temperature of 265 ℃, and when the esterification rate is more than 99.9 percent and the acid value is about 0.5mgKOH/g, the material in 10 is continuously transferred into a film evaporator 13 through a filter 12 by a pump 11, and small molecular products in the material are separated. The material is continuously transferred by a pump 14 through a heat exchanger 15 to a product tank 16. The polyether ester polyol in the product tank 16 was tested to have an acid value of 0.32mgKOH/g, a number average molecular weight of 4600, an average functionality of 1.97, a viscosity at 90℃of 1S-1 of 60 poise, and a liquid at ordinary temperature.
Claims (9)
1. The utility model provides a polyether ester polyol synthesis equipment, its characterized in that, including the transesterification esterification kettle that sets gradually, degree of depth esterification kettle and polycondensation kettle, wherein, the discharge gate of transesterification esterification kettle passes through material pipeline with the feed inlet of degree of depth esterification kettle and links to each other, and the discharge gate of degree of depth esterification kettle passes through material pipeline with the feed inlet of polycondensation kettle and links to each other, transesterification esterification kettle and degree of depth esterification kettle link to each other with the rectifying column, degree of depth esterification kettle, polycondensation kettle link to each other with vacuum system, be provided with the catalyst jar between degree of depth esterification kettle and the polycondensation kettle, the catalyst jar passes through material pipeline and links to each other with the polycondensation kettle, and the material pipeline that extends from the polycondensation kettle discharge gate loops through filter and heat exchanger.
2. The polyether ester polyol synthesis apparatus according to claim 1, wherein the transesterification esterification vessel is further connected at its feed end to a polyester feeding device.
3. A process for synthesizing polyether ester polyol according to the polyol synthesizing apparatus of claim 1, comprising the steps of:
step 1): under the protection of inert gas, one or more of aromatic dibasic acid, aromatic dibasic acid ester, aromatic dibasic anhydride and polyester containing aromatic dibasic acid polyol ester structure are continuously added into a transesterification esterification kettle to carry out transesterification reaction and/or esterification reaction with polyether glycol, wherein the polymerization degree of the polyether glycol is 2-20, the molecular weight is 100-1000, the molar ratio of the polyether glycol to aromatic ring groups is 1.05-2, the reaction temperature is 220-290 ℃, the reaction time is 1-72 hours, the absolute pressure during the reaction is 60KPa-400KPa, and the acid value of the material is less than 50mgKOH/g;
step 2): continuously transferring the material obtained in the step 1) into a deep esterification kettle, wherein the temperature in the deep esterification kettle is 220-290 ℃, and the absolute pressure during reaction is less than 80KPa, and performing further esterification reaction to ensure that the acid value of the material is less than 10mgKOH/g;
and 3) fully mixing the material obtained in the step 2) with a catalyst continuously added in a catalyst tank through a material conveying pipeline connected with a polycondensation kettle, continuously transferring the mixture into the polycondensation kettle together, and carrying out transesterification polycondensation reaction at the temperature of 220-290 ℃ and the absolute pressure of less than 10KPa in the polycondensation kettle so that the acid value of the product is less than 0.8mgKOH/g, preferably less than 0.5mgKOH/g.
4. The process for synthesizing polyether ester polyol according to claim 3, wherein in the step 1) and the step 2), the water and the small molecular low boiling substances generated by the reaction are separated by a rectifying tower and then discharged from the top of the tower.
5. The process for synthesizing polyether ester polyol according to claim 3, wherein in the step 3), the catalyst is one or more of tin, zinc, magnesium, calcium, copper, antimony, titanium, gallium, germanium, oxide, alkoxide, carboxylate and halide of rare earth metal.
6. The process for the synthesis of polyether ester polyols according to claim 5, wherein the catalyst is added in a beating tank or a polyester feeding device at the beginning of the process, instead of through a catalyst tank before the polycondensation reactor.
7. A process for the synthesis of polyetherester polyols according to claim 3, further comprising the steps of:
continuously transferring the product obtained in the step 3) to an evaporator through a filter, and separating small molecular products in the product.
8. A process for the synthesis of polyetherester polyols according to claim 3, further comprising the steps of:
and 3) enabling the product obtained in the step 3) to pass through a heat exchanger to reduce the temperature of the product to the process requirement temperature.
9. A process for the synthesis of polyetherester polyols according to claim 3, wherein the molar ratio of polyether glycol to aromatic ring groups in step 1) is from 1.1 to 1.6.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2024164834A1 (en) * | 2023-02-09 | 2024-08-15 | 郑州中远氨纶工程技术有限公司 | Polyether ester polyol, preparation method therefor, and method for preparing polyurethane elastomer by using polyether ester polyol |
| WO2024164835A1 (en) * | 2023-02-09 | 2024-08-15 | 郑州中远氨纶工程技术有限公司 | Polyether ester polyol, preparation method therefor, and method for using same to prepare polyurethane elastomer |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024164834A1 (en) * | 2023-02-09 | 2024-08-15 | 郑州中远氨纶工程技术有限公司 | Polyether ester polyol, preparation method therefor, and method for preparing polyurethane elastomer by using polyether ester polyol |
| WO2024164835A1 (en) * | 2023-02-09 | 2024-08-15 | 郑州中远氨纶工程技术有限公司 | Polyether ester polyol, preparation method therefor, and method for using same to prepare polyurethane elastomer |
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