CN116836372A - Polyester and process for producing the same - Google Patents
Polyester and process for producing the same Download PDFInfo
- Publication number
- CN116836372A CN116836372A CN202210298180.0A CN202210298180A CN116836372A CN 116836372 A CN116836372 A CN 116836372A CN 202210298180 A CN202210298180 A CN 202210298180A CN 116836372 A CN116836372 A CN 116836372A
- Authority
- CN
- China
- Prior art keywords
- polyester
- diethylene glycol
- alkali metal
- acetate
- less
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920000728 polyester Polymers 0.000 title claims abstract description 79
- 238000000034 method Methods 0.000 title claims description 11
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims abstract description 118
- SLGGJMDAZSEJNG-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethanol;terephthalic acid Chemical compound OCCOCCO.OC(=O)C1=CC=C(C(O)=O)C=C1 SLGGJMDAZSEJNG-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 19
- 239000002685 polymerization catalyst Substances 0.000 claims abstract description 9
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 8
- 239000000155 melt Substances 0.000 claims abstract description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 25
- -1 alkali metal acetate Chemical class 0.000 claims description 22
- 150000003863 ammonium salts Chemical class 0.000 claims description 20
- 238000002844 melting Methods 0.000 claims description 17
- 230000008018 melting Effects 0.000 claims description 17
- 150000001339 alkali metal compounds Chemical class 0.000 claims description 12
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 12
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 6
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 4
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 4
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 235000011056 potassium acetate Nutrition 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 abstract description 4
- 238000004321 preservation Methods 0.000 abstract description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 10
- 150000007514 bases Chemical class 0.000 description 9
- 238000005886 esterification reaction Methods 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- 239000012760 heat stabilizer Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002667 nucleating agent Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 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
- WBSRIXCTCFFHEF-UHFFFAOYSA-N (3,5-ditert-butyl-4-hydroxyphenyl)methyl-ethoxyphosphinic acid Chemical compound CCOP(O)(=O)CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 WBSRIXCTCFFHEF-UHFFFAOYSA-N 0.000 description 1
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- IHLDFUILQQSDCQ-UHFFFAOYSA-L C(C)(=O)[O-].[Ge+2].C(C)(=O)[O-] Chemical compound C(C)(=O)[O-].[Ge+2].C(C)(=O)[O-] IHLDFUILQQSDCQ-UHFFFAOYSA-L 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 159000000007 calcium salts Chemical group 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 description 1
- ONIHPYYWNBVMID-UHFFFAOYSA-N diethyl benzene-1,4-dicarboxylate Chemical compound CCOC(=O)C1=CC=C(C(=O)OCC)C=C1 ONIHPYYWNBVMID-UHFFFAOYSA-N 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000000835 fiber Substances 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
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229960005336 magnesium citrate Drugs 0.000 description 1
- 239000004337 magnesium citrate Substances 0.000 description 1
- 235000002538 magnesium citrate Nutrition 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- GGUBFICZYGKNTD-UHFFFAOYSA-N triethyl phosphonoacetate Chemical compound CCOC(=O)CP(=O)(OCC)OCC GGUBFICZYGKNTD-UHFFFAOYSA-N 0.000 description 1
- PLSARIKBYIPYPF-UHFFFAOYSA-H trimagnesium dicitrate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O PLSARIKBYIPYPF-UHFFFAOYSA-H 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—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
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/83—Alkali metals, alkaline earth metals, beryllium, magnesium, copper, silver, gold, zinc, cadmium, mercury, manganese, or compounds thereof
-
- 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
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
- C08G63/86—Germanium, antimony, or compounds thereof
- C08G63/866—Antimony or compounds thereof
Abstract
The invention discloses a polyester and a preparation method thereof, wherein the content of diethylene glycol in the polyester is below 0.8wt%, diethylene glycol terephthalate is added into a melt polycondensation kettle to be melted at 110-250 ℃ in a heat preservation way, a polymerization catalyst is added after all the diethylene glycol terephthalate is melted, then the mixture is vacuumized, the temperature is raised to start the polymerization reaction, and the mixture is discharged after the polymerization reaction is finished. The resulting polyester articles have better dimensional stability due to the lower diethylene glycol content in the polyesters of the invention.
Description
Technical Field
The invention relates to polyester and a preparation method thereof, in particular to polyester with low diethylene glycol content and a preparation method thereof, wherein the polyester takes diethyl terephthalate as a raw material.
Background
Polyester (PET) is one of the most commonly used polymers at present, has excellent mechanical properties, abrasion resistance and creep resistance, and is widely used in the fields of textile, packaging, engineering plastics and the like. With the high-speed development of the automobile industry, the polyester tire meridian starts to gradually replace the steel tire meridian, and the application field of the polyester tire meridian is further widened. However, there are side reactions that produce diethylene glycol (DEG) during polyester production, such that DEG levels in polyester materials are typically between 1 and 2%. With increasing DEG content in the polyester, the dimensional stability, mechanical properties and thermal stability of the product are reduced. Currently polyester tire meridians are used only for the production of tires for small vehicles, and to be used for tires for large vehicles, it is necessary to further reduce the DEG content in the polyester. Therefore, how to reduce the DEG content in polyesters is a technical problem to be solved.
Chinese patent CN108299628A discloses a method for reducing diethylene glycol in PET products, which adopts potassium salt, water and ethylene glycol with preset mass ratio to prepare additive solution, and adds the additive solution into a slurry preparation tank or an esterification reactor, and the diethylene glycol content in the final PET product is reduced by inhibiting the generation of diethylene glycol in the reaction process by potassium ions. The higher the amount of potassium salt added, the less diethylene glycol the PET product contains. However, too high an amount of potassium salt may affect not only the reactivity of the polymerization reaction but also the color tone of the polyester.
Disclosure of Invention
In view of the above problems, the present invention aims to provide a polyester having a lower diethylene glycol content and a better dimensional stability of the product, and a process for producing the same.
The technical scheme of the invention is as follows:
polyester, obtained by polycondensation of diethylene glycol terephthalate. The diethylene glycol content in the polyester is 0.8wt% or less, preferably 0.5wt% or less, more preferably 0.3wt% or less.
The polyester preferably contains 300ppm or less of alkali metal element and/or 3000ppm or less of organic ammonium salt.
The organic ammonium salt is preferably one or more of tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide and tetrabutyl ammonium hydroxide.
The invention also discloses a preparation method of the polyester, which is mainly characterized in that the diethylene glycol terephthalate is added into a melt polycondensation kettle, and is subjected to heat preservation and melting at 110-250 ℃, a polymerization catalyst is added after the diethylene glycol terephthalate is completely melted, then the polymerization reaction is started by vacuumizing, and the polyester is obtained by spitting out after the polymerization reaction is finished.
The alkali metal acetate, inorganic alkali metal compound and/or organic ammonium salt are preferably added at any stage of the above polymerization process.
Preferably, the alkali metal acetate, the inorganic alkali metal compound and/or the organic ammonium salt are added at a temperature of 200 ℃ or lower in the melt polycondensation reaction vessel.
The alkali metal acetate is preferably one or more of lithium acetate, sodium acetate and potassium acetate; the inorganic alkali metal compound is preferably one or more of lithium carbonate, potassium carbonate and cesium carbonate; the organic ammonium salt is preferably one or more of tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide and tetrabutyl ammonium hydroxide.
The total addition amount of the alkali metal acetate and the inorganic alkali metal compound is preferably 300ppm or less in terms of metal element relative to the polyester; the amount of the organic ammonium salt to be added is preferably 3000ppm or less with respect to the polyester.
The polyester obtained by polymerizing the polyethylene terephthalate serving as the raw material has extremely low diethylene glycol content, and the dimensional stability of the polyester is obviously improved.
Detailed Description
Generally, the diethylene glycol content of the polyester is above 1.0wt%, which results in poor dimensional stability of the polyester product. In the prior art, the reduction of the diethylene glycol content of polyesters is generally achieved by adding basic compounds during the polymerization. However, the minimum diethylene glycol content of the polyester obtained by this method is only about 0.8wt%, and the inhibition effect on diethylene glycol production is a bottleneck, i.e., the diethylene glycol production tends to gradually decrease with increasing addition of the alkaline compound in the initial stage, but the decrease is gradually decreased to 0. This is because the production of diethylene glycol is promoted by the high temperature during the polymerization of the polyester, the carboxyl groups in the aromatic dibasic acid, and the like. In addition, since the amount of the basic compound to be added is also greatly limited in view of the adverse effect of the basic compound on the polyester reaction, the polyester obtained by this method is difficult to further develop and use in the field where a lower diethylene glycol content is required.
The invention provides a polyester with diethylene glycol terephthalate as a raw material, wherein the diethylene glycol content can be reduced to below 0.8 wt%. In order to obtain more excellent dimensional stability of the polyester, the diethylene glycol content in the polyester is preferably 0.5wt% or less, more preferably 0.3wt% or less.
In a preferred embodiment, the polyester contains alkali metal elements and/or organic ammonium salts. The alkali metal element is derived from an alkali metal acetate and/or an inorganic alkali metal compound. Alkali metal acetates, inorganic alkali metal compounds and organic ammonium salts can be effective in further reducing the diethylene glycol content of the polyester.
The content of alkali metal element in the polyester is preferably 300ppm or less, and the content of organic ammonium salt is preferably 3000ppm or less.
The organic ammonium salt is preferably one or more of tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide and tetrabutyl ammonium hydroxide.
The invention also discloses a preparation method of the polyester, which mainly comprises the steps of adding the diethylene glycol terephthalate into a melt polycondensation kettle for heat preservation and melting, adding a polymerization catalyst after all the diethylene glycol terephthalate is melted, then starting vacuumizing and heating to start polymerization reaction, and spitting the diethylene glycol terephthalate after the diethylene glycol terephthalate reaches a set viscosity.
Since the melting point of diethylene glycol terephthalate is very low, it can be melted at a low temperature, and from the viewpoint of suppressing diethylene glycol formation, the lower the melting temperature is, the better; however, the temperature should not be too low in view of the flowability of the diethylene glycol terephthalate after melting. Thus, in combination, the melting temperature range of the present invention is selected to be 110 to 250℃and preferably 150 to 220 ℃.
By the above method, a polyester having a diethylene glycol content of 0.8wt% or less can be basically obtained. In order to further reduce the diethylene glycol content, alkali metal acetate, inorganic alkali metal salt and/or organic ammonium salt of the basic compound may be added at any stage, but when the temperature in the system is too high, DEG is generated in advance in the system by adding the basic compound, so that the addition temperature of the basic compound is preferably 200℃or less, more preferably 180℃or less.
The alkali metal acetate is preferably one or more of lithium acetate, sodium acetate and potassium acetate; the inorganic alkali metal compound is preferably lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium hydroxide, potassium hydroxide, sodium hydroxide, cesium hydroxide or the like, and one or more of lithium carbonate, sodium carbonate, cesium carbonate is more preferable. When the addition amount of the alkali metal acetate and the inorganic alkali metal salt is too large, side reactions in the system are increased, the color tone of the polyester is deteriorated, and the use of the polyester is affected. Therefore, the total addition amount of the alkali metal acetate and the inorganic alkali metal salt is preferably 300ppm or less in terms of metal element relative to the polyester.
The organic ammonium salt is preferably one or more of tetramethylammonium hydroxide, tetraethylammonium hydroxide and tetrabutylammonium hydroxide, and the addition amount thereof is preferably 3000ppm or less with respect to the polyester. When the organic ammonium salt is added in an excessive amount, foreign matters are generated in the polyester, and the spinning pressure is increased and yarn floating/breakage frequently occurs in the subsequent spinning process.
The polymerization catalyst may be an antimony catalyst, a titanium catalyst, a germanium catalyst, or an aluminum catalyst, specifically, antimony trioxide, antimony glycol, antimony acetate, germanium oxide, germanium acetate, tetrabutyl titanate, tetraisopropyl titanate, titanium glycol, aluminum glycol, TYZOR < beta > -ACtivate ™, TYZOR < beta > -ACtivate ™, 436, TOYOBO GS Catalyst, etc.
To meet various use or functional requirements, heat stabilizers, nucleating agents, and the like may also be added during polymerization. The heat stabilizer may be phosphoric acid, trimethyl phosphate, triethyl phosphate, triphenyl phosphate, triethyl phosphonoacetate, triphenyl phosphite, etc. The nucleating agent is selected from calcium salt or magnesium salt, wherein calcium acetate, calcium bis (3, 5-di-tert-butyl-4-hydroxybenzyl phosphonic acid monoethyl ester), magnesium acetate and magnesium citrate are preferred.
The diethylene glycol content in the polyester prepared by taking the diethylene glycol terephthalate as the raw material can reach below 0.8wt%, and the dimensional stability of the polyester product is higher than that of a common polyester product. Has wide application in the field of industrial fiber application.
The invention will now be described in more detail by way of examples. The physical properties of the examples were measured by the following methods.
(1) Test of diethylene glycol
0.5g of sample is weighed, added with 2ml of ethanolamine and 10mg of adipic acid for heating and dissolving, 10ml of methanol is added after dissolving, and the mixture is cooled until the amine salt is separated out and is crushed by shaking in an ultrasonic cleaner. 15g of TPA was added for neutralization, and the mixture was filtered to obtain a sample. A2 μm sample was taken by syringe, injected into LC for testing, and the diethylene glycol content was determined by internal standard method.
(2) Content of basic metallic element
The alkali metal content of the polymer was analyzed by ICP-MS.
(3) Content of organic ammonium salt
The nitrogen content in the polymer was analyzed by combustion.
Example 1
Adding diethylene glycol terephthalate into a melting kettle, heating to 110 ℃, preserving heat and melting, sequentially adding heat stabilizer phosphoric acid, a polymerization catalyst of antimonous oxide and 100ppm lithium acetate (calculated by metal elements), starting vacuumizing and heating after the addition, starting the polymerization reaction, and discharging after the set viscosity is reached. The DEG content in the final polyester was 0.3wt%.
Examples 2 to 8
The melting temperature of the diethylene glycol terephthalate was changed to polymerize the diethylene glycol terephthalate. Specific physical properties are shown in Table 1.
Examples 9 to 14
The addition temperature of the basic compound was changed. Specific physical properties are shown in Table 2.
Examples 15 to 22
The amount of the alkaline compound to be added was changed. Specific physical properties are shown in Table 3.
Examples 23 to 28
The type of the basic compound is changed. The specific physical properties are shown in Table 4.
Example 29
No basic compound was added. The specific physical properties are shown in Table 4.
Examples 30 to 34
An inorganic alkali metal compound is added. The specific physical properties are shown in Table 5.
Comparative example 1
Adding terephthalic acid and ethylene glycol into an esterification kettle for esterification reaction, transferring into a polymerization kettle after the esterification reaction is finished, adding heat stabilizer phosphoric acid and a polymerization catalyst antimonous oxide, then starting the polymerization reaction by vacuumizing and heating from 250 ℃, and spitting out after the set viscosity is reached.
Due to the use of the usual polyester preparation method, the DEG content in the polyester reaches 1.5wt%.
Comparative example 2
Adding terephthalic acid and ethylene glycol into an esterification kettle for esterification reaction, transferring into a polymerization kettle after the esterification reaction is finished, adding 100ppm of heat stabilizer phosphoric acid, a polymerization catalyst antimony trioxide and an alkaline compound lithium acetate (calculated by lithium element), starting vacuumizing and heating from 250 ℃ to start the polymerization reaction, and spitting out after the set viscosity is reached.
Although alkali metal acetate is added to suppress DEG production, the requirement of extremely low DEG content in the final polyester is not met due to the polyester raw material.
Comparative example 3
Adding diethylene glycol terephthalate into a melting kettle, heating to 260 ℃, preserving heat and melting, sequentially adding heat stabilizer phosphoric acid and polymerization catalyst antimonous oxide, starting vacuumizing and heating after the addition is finished, starting the polymerization reaction, and spitting out after the set viscosity is reached.
Since the melting temperature of the diethylene glycol terephthalate is too high, the DEG content in the final polyester is relatively high even if alkali metal acetate is added to suppress DEG generation.
Comparative example 4
The diethylene glycol terephthalate is added into a melting kettle, and the temperature is raised to 100 ℃ to keep the temperature for melting, so that the diethylene glycol terephthalate cannot be polymerized because the diethylene glycol terephthalate is not melted below the melting point of the raw materials.
Claims (10)
1. Polyester obtained by polycondensation of diethylene glycol terephthalate, characterized in that: the diethylene glycol content in the polyester is 0.8wt% or less.
2. The polyester according to claim 1, wherein: the polyester contains less than 300ppm of alkali metal elements and/or less than 3000ppm of organic ammonium salts.
3. The polyester according to claim 2, wherein: the organic ammonium salt is one or more of tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide and tetrabutyl ammonium hydroxide.
4. The polyester according to claim 1 or 2, characterized in that: the diethylene glycol content in the polyester is 0.5wt% or less.
5. The polyester according to claim 4, wherein: the diethylene glycol content in the polyester is below 0.3wt%.
6. The process for producing the polyester according to claim 1, wherein: adding diethylene glycol terephthalate into a melt polycondensation kettle, keeping the temperature at 110-250 ℃ for melting, adding a polymerization catalyst after all melting, then starting vacuumizing and heating to start polymerization reaction, and discharging after the polymerization reaction is finished to obtain polyester.
7. The process for producing a polyester according to claim 6, wherein: alkali metal acetate, inorganic alkali metal compound and/or organic ammonium salt are added at any stage of the polymerization process.
8. The method for producing a polyester according to claim 7, wherein: adding alkali metal acetate, inorganic alkali metal compound and/or organic ammonium salt when the temperature in the melt polycondensation kettle is below 200 ℃.
9. The process for producing a polyester according to claim 7 or 8, wherein: the alkali metal acetate is one or more of lithium acetate, sodium acetate and potassium acetate; the inorganic alkali metal compound is one or more of lithium carbonate, potassium carbonate and cesium carbonate; the organic ammonium salt is one or more of tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide and tetrabutyl ammonium hydroxide.
10. The method for producing a polyester according to claim 7, wherein: the total addition amount of the alkali metal acetate and the inorganic alkali metal compound is 300ppm or less in terms of metal element relative to the polyester; the organic ammonium salt is added in an amount of 3000ppm or less relative to the polyester.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210298180.0A CN116836372A (en) | 2022-03-25 | 2022-03-25 | Polyester and process for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210298180.0A CN116836372A (en) | 2022-03-25 | 2022-03-25 | Polyester and process for producing the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116836372A true CN116836372A (en) | 2023-10-03 |
Family
ID=88162174
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210298180.0A Pending CN116836372A (en) | 2022-03-25 | 2022-03-25 | Polyester and process for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116836372A (en) |
-
2022
- 2022-03-25 CN CN202210298180.0A patent/CN116836372A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6506853B2 (en) | Copolymer comprising isophthalic acid | |
| CA2255561C (en) | Method of catalyst deactivation in continuous polyethylene terephthalate production | |
| US6020421A (en) | Polyester composition and method for producing the same | |
| US5874517A (en) | Method to reduce regenerated acetaldehyde in pet resin | |
| JPWO2005075539A1 (en) | Polyester polymerization catalyst, polyester produced using the same, and method for producing polyester | |
| TW200303879A (en) | Polyester resin, catalyst for the production of polyester, process for the production of polyester resin by using the catalyst, and hollow shaped container made from the polyester resin | |
| JP2002322258A (en) | Polyester and method for producing the same and polyester film | |
| US10072118B2 (en) | Polycyclohexylenedimethylene terephthalate resin having enhanced crystallization speed and method for preparing same | |
| US5898060A (en) | Copolyester for molding a bottle | |
| TWI424000B (en) | Process for producing polybutylene terephthalate | |
| CN116836372A (en) | Polyester and process for producing the same | |
| WO2017183550A1 (en) | Polybutylene terephthalate resin | |
| WO2021172215A1 (en) | Method for producing polyester and polyester produced by said method | |
| KR20230008065A (en) | Co-polyester resins, molded articles, heat-shrinkable films and fibers | |
| US20070225469A1 (en) | Polyester Resin and Process for Production Thereof | |
| JP7435842B1 (en) | Chemically recycled polyethylene terephthalate resin and molded products thereof | |
| JP6673952B2 (en) | Stabilizer for polyester resin production, method for producing the same, method for producing polyester resin using the stabilizer, and polyester resin produced thereby | |
| JP3374544B2 (en) | Method for producing polyester copolymer | |
| JPH04309521A (en) | Polyethylene terephthalate for molding bottle | |
| JP3770792B2 (en) | Method for producing polyester resin and polyester resin obtained therefrom | |
| KR20230081450A (en) | Method for Preparing Chemically Recycled PET | |
| WO2023063218A1 (en) | Copolyester resin, molded article, heat-shrinkable film, and fiber | |
| TW202108657A (en) | Method for producing polyester resin | |
| JP2009526115A (en) | Polyester solid phase polymerization catalyst for low acetaldehyde generating resin | |
| JP2007100105A (en) | Polyester and method for producing the same and polyester film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication |