CN115353614A - Composite catalyst, preparation method thereof and application thereof in antimony-free polyester synthesis - Google Patents
Composite catalyst, preparation method thereof and application thereof in antimony-free polyester synthesis Download PDFInfo
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- CN115353614A CN115353614A CN202211047983.5A CN202211047983A CN115353614A CN 115353614 A CN115353614 A CN 115353614A CN 202211047983 A CN202211047983 A CN 202211047983A CN 115353614 A CN115353614 A CN 115353614A
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- titanium
- zinc
- composite catalyst
- antimony
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- 239000003054 catalyst Substances 0.000 title claims abstract description 115
- 229920000728 polyester Polymers 0.000 title claims abstract description 45
- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 230000015572 biosynthetic process Effects 0.000 title abstract description 7
- 238000003786 synthesis reaction Methods 0.000 title abstract description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000010936 titanium Substances 0.000 claims abstract description 41
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 39
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000011701 zinc Substances 0.000 claims abstract description 37
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 37
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000227 grinding Methods 0.000 claims abstract description 21
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 17
- 239000006185 dispersion Substances 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 239000011787 zinc oxide Substances 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 239000002270 dispersing agent Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 59
- 238000000034 method Methods 0.000 claims description 22
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 21
- 239000002245 particle Substances 0.000 claims description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- -1 sodium dodecyl propane sulfonate Chemical compound 0.000 claims description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 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 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 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 claims description 4
- 238000005886 esterification reaction Methods 0.000 claims description 4
- 229920002401 polyacrylamide Polymers 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 4
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 4
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 4
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 4
- DLINORNFHVEIFE-UHFFFAOYSA-N hydrogen peroxide;zinc Chemical compound [Zn].OO DLINORNFHVEIFE-UHFFFAOYSA-N 0.000 claims description 3
- 229940105296 zinc peroxide Drugs 0.000 claims description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 2
- KRXBVZUTZPDWQI-UHFFFAOYSA-N ethane-1,2-diol;titanium Chemical compound [Ti].OCCO KRXBVZUTZPDWQI-UHFFFAOYSA-N 0.000 claims description 2
- ITNVWQNWHXEMNS-UHFFFAOYSA-N methanolate;titanium(4+) Chemical compound [Ti+4].[O-]C.[O-]C.[O-]C.[O-]C ITNVWQNWHXEMNS-UHFFFAOYSA-N 0.000 claims description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 2
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 239000002253 acid Substances 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000010924 continuous production Methods 0.000 abstract description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 14
- 238000006116 polymerization reaction Methods 0.000 description 13
- 230000008569 process Effects 0.000 description 13
- 239000000463 material Substances 0.000 description 12
- 229910052787 antimony Inorganic materials 0.000 description 10
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 10
- 238000012545 processing Methods 0.000 description 10
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 8
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 238000004537 pulping Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- BUZZDKUKPQGUGX-UHFFFAOYSA-N [Ti+4].[Zn+2] Chemical compound [Ti+4].[Zn+2] BUZZDKUKPQGUGX-UHFFFAOYSA-N 0.000 description 2
- FAWGZAFXDJGWBB-UHFFFAOYSA-N antimony(3+) Chemical compound [Sb+3] FAWGZAFXDJGWBB-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical group 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 1
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- WSXIMVDZMNWNRF-UHFFFAOYSA-N antimony;ethane-1,2-diol Chemical compound [Sb].OCCO WSXIMVDZMNWNRF-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 238000004383 yellowing 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
- C08G63/78—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
- C08G63/02—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
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses a composite catalyst and a preparation method thereof and application thereof in antimony-free polyester synthesis, wherein the preparation method comprises the following steps: s1, mixing zinc oxide, a dispersing agent and a first solvent according to a certain proportion, adding the mixture into a high-speed dispersion machine for pre-dispersion, then adding a first pH regulator to regulate the pH, and pouring the mixture into a grinding machine for grinding to obtain a nano-scale zinc catalyst solution; s2, adjusting the pH value of the second solvent through a second pH regulator, and then adding a titanium catalyst to prepare a titanium catalyst solution; and S3, mixing the nano-scale zinc catalyst solution and the titanium catalyst solution to obtain the composite catalyst, wherein the composite catalyst can be used for preparing antimony-free polyester. The composite catalyst has good catalytic activity, is stable in a high-temperature and high-acid environment, is beneficial to reducing the use amount of zinc and titanium catalysts, can ensure that the polycondensation time meets the continuous production requirement without adding a cocatalyst, and can ensure that the prepared polyester has good color value without adding a toner.
Description
Technical Field
The invention belongs to the field of catalysts for polyester synthesis, and particularly relates to a composite catalyst, a preparation method thereof and application thereof in antimony-free polyester synthesis.
Background
Products of synthetic polyester have very wide application in production and life, but in the polycondensation process of polyester, antimony (Sb) catalysts are often used, the catalysts have high catalytic activity, are easy to use and have excellent performance, but antimony element has the problems of harming human health and polluting environment, and the latest European regulations also start to limit the antimony content of textiles, so that antimony-free polyester gradually becomes a development trend.
The titanium catalyst is an environment-friendly catalyst which is expected to replace antimony catalysts, wherein the dihydric alcohol compound of titanium is accepted by various large research institutions at home and abroad due to the stable annular chelating structure of the dihydric alcohol compound of titanium, but the catalyst is often poor in hydrolysis resistance, unstable in chemical combination structure and low in solubility in ethylene glycol, and the prepared polyester is still poor in hue and has the problem of yellowing of polyester. Chinese patent CN103539928B discloses a titanium-based polyester catalyst and a method for producing semi-dull polyester, wherein a reaction product of a titanium compound, a dihydric alcohol and at least one metal salt compound selected from group ii a, group V ii B and group ii B of the periodic table of elements, at least one aliphatic organic acid and at least one phosphate ester compound is used as the titanium-based polyester catalyst, and the self-made homogeneous liquid catalyst is used in the patent, so that the problems of poor hydrolysis resistance, low solubility in ethylene glycol and color difference of the prepared semi-dull polyester chip are solved, but the catalyst prepared in the patent requires a system pH value of 4.5-6.5, and the polyester production process is in a strong acid and high temperature environment, and similar homogeneous catalysts are difficult to stably exist in the environment, are easy to generate unfavorable conditions such as decomposition and inactivation of the catalyst, and are difficult to stably produce the polyester.
The present invention has been made to solve the above-mentioned problems occurring in the prior art.
Disclosure of Invention
Aiming at the technical problems, the invention provides a composite catalyst, a preparation method thereof and application thereof in antimony-free polyester synthesis.
The technical scheme of the invention is as follows:
the invention provides a preparation method of a composite catalyst, which comprises the following steps:
s1, mixing zinc oxide, a dispersing agent and a first solvent according to a certain proportion, adding the mixture into a high-speed dispersion machine for pre-dispersion, then adding a first pH regulator to regulate the pH, and pouring the mixture into a grinding machine for grinding to obtain a nano-scale zinc catalyst solution;
s2, adjusting the pH of the second solvent through a second pH regulator, and then adding a titanium catalyst to prepare a titanium catalyst solution;
and S3, mixing the nano-scale zinc catalyst solution and the titanium catalyst solution to obtain the composite catalyst.
Preferably, the zinc oxide is zinc oxide or zinc peroxide, and the mass of the zinc element accounts for 5-30% of the total mass of the zinc catalyst solution;
the dispersant is one or more of polyethylene glycol, polyacrylamide, sodium dodecyl propane sulfonate and sodium hexametaphosphate, and the mass of the dispersant accounts for 1-25% of the total mass of the zinc oxide.
Preferably, in the step S1, the pre-dispersion rotating speed is 2500-4500 r/min, and the pre-dispersion time is 5-30 min;
the grinding speed of the grinder is 2000-3000 r/min, and the grinding time is 1-48 h;
the particle size after grinding is in the range of 10-1000 nm.
Preferably, the titanium catalyst is one or more of titanate, ethylene glycol titanium, potassium fluotitanate and nano titanium dioxide, and the mass of the titanium catalyst accounts for 0.1-5% of the total mass of the titanium catalyst solution.
Preferably, the titanate-based catalyst is one or more of tetramethyl titanate, tetraethyl titanate, tetraethylhexyl titanate, tetrapropyl titanate, tetraisopropyl titanate, tetrabutyl titanate, and tetraisooctyl titanate.
Preferably, the first solvent is one or more of deionized water, ethylene glycol, propylene glycol, butylene glycol and ethanol;
the first pH regulator is one or more of hydrochloric acid, sulfuric acid and phosphoric acid, and the pH regulating range is 2-5;
the second solvent is one or more of deionized water, ethylene glycol, propylene glycol, butanediol and ethanol;
the second pH regulator is one or more of hydrochloric acid, sulfuric acid and phosphoric acid, and the pH regulating range is 2-5.
Preferably, the mass ratio of the zinc element to the titanium element in the composite catalyst is 2-20: 1, and further preferably 5-15: 1.
The invention also provides a composite catalyst prepared by the preparation method.
The invention also provides a synthesis method of the antimony-free polyester, which takes dicarboxylic acid and dihydric alcohol as raw materials, carries out esterification reaction at the reaction temperature of 200-270 ℃ and the reaction pressure of 0-0.5 MPa in the presence of a composite catalyst, and then carries out polycondensation reaction under the vacuum condition that the reaction temperature is 250-300 ℃ and the reaction pressure is less than 150Pa to obtain the antimony-free polyester.
Preferably, based on the mass of the antimony-free polyester, the addition amount of the zinc element in the composite catalyst is 10-100 ppm, and the addition amount of the titanium element in the composite catalyst is 0.5-10 ppm;
the polycondensation reaction time is 50-200 min.
The invention has the beneficial effects that:
(1) The invention can replace antimony catalyst to prepare antimony-free polyester, the invention compounds nanometer zinc catalyst solution and titanium catalyst solution, the compound catalyst obtained is stable under the high-temperature and high-acid environment, and the invention has solved the problem that zinc catalyst is apt to yellow polyester, the consumption of the compound catalyst is reduced greatly too;
(2) The composite catalyst prepared by the invention has good catalytic activity, can ensure that the polycondensation time meets the continuous production requirement without adding a cocatalyst, and can ensure that the prepared polyester has good color value without adding a toner;
(3) PET polymerization is divided into two parts of ester exchange condensation and end group condensation, the defect is that one part is not available, a zinc catalyst has high activity on the ester exchange condensation, the activity on the end group condensation is lower, the reaction speed is determined by the end group condensation speed, a large addition amount is needed when the catalyst is used alone, a titanium catalyst has high activity on the zinc catalyst and the titanium catalyst, the use amount of the zinc catalyst and the titanium catalyst is reduced by using a composite catalyst, and the processing thermal degradation rate is low.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the description is intended to be exemplary only, and is not intended to limit the scope of the present invention. Moreover, in the following description, descriptions of well-known structures and techniques are omitted so as to not unnecessarily obscure the concepts of the present invention.
Example 1
(1) Mixing 10g of zinc oxide, 1g of polyethylene glycol, 0.5g of polyacrylamide and 90g of deionized water, pre-dispersing by using a high-speed dispersion machine, adjusting the pH to 2.8 by using 1% (mass fraction, the same below) of dilute hydrochloric acid in the dispersed solution, pouring the solution into a grinder for grinding at the grinding speed of 2000r/min for 30 hours to obtain a zinc catalyst solution, testing the particle size by using a laser particle sizer, wherein D50 is 100nm;
(2) Adjusting the pH of ethylene glycol to 2.8 by using 1% dilute sulfuric acid, weighing 99g of the ethylene glycol solution with the pH adjusted, adding 1g of tetrabutyl titanate, and uniformly stirring to obtain a titanium catalyst solution;
(3) Mixing 12.5g of zinc catalyst solution and 71.4g of titanium catalyst solution to prepare a composite catalyst;
(4) 1660g of PTA (purified terephthalic acid), 868g of EG (ethylene glycol) and 8g of composite catalyst (based on the mass of the generated polyester, wherein the addition of zinc element is 50ppm, and the addition of titanium element is 5 ppm) are added into a polymerization kettle for pulping, after nitrogen in a device is replaced, the temperature is raised to 220-260 ℃ for esterification reaction, the esterification pressure is 0-0.3MPa, after water in a fractionating column is discharged to 360g, the temperature is raised to 270-280 ℃ for polycondensation reaction, the polycondensation pressure is 100-150Pa, the polycondensation time is 130min, after the stirring power reaches a preset value, nitrogen is used for breaking vacuum for discharging, and the materials are granulated after water cooling.
The indexes of the antimony-free polyester prepared in the example 1 are as follows according to GB/T14190-2017 test: intrinsic viscosity 0.685dl/g, terminal carboxyl group 18mol/t, melting point 258.2 ℃, L value 88.5, a value-0.8 and b value 1.2.
The chips were extruded from a twin-screw extruder at temperatures (in ℃ C.) in the respective zones as shown in Table 1 below:
TABLE 1
| A region | Two zones | Three zones | Four zones | Five zones | Six zones | Seven regions |
| 230 | 255 | 275 | 275 | 275 | 274 | 273 |
The indexes of the processed material are as follows: the intrinsic viscosity was 0.656dl/g, the rate of decrease was 4.2%, and the terminal carboxyl groups were 33mol/t.
Example 2
(1) Mixing 20g of zinc oxide, 2.5g of sodium hexametaphosphate and 80g of ethylene glycol, pre-dispersing by using a high-speed dispersion machine, adjusting the pH to 2.3 by using 1% dilute hydrochloric acid in the dispersed solution, pouring the mixture into a grinder for grinding at the rotation speed of 3000r/min for 12h to obtain a zinc catalyst solution, and testing the particle size by using a laser particle sizer, wherein the D50 is 200nm;
(2) Adjusting the pH of ethylene glycol to 2.3 by using 1% dilute hydrochloric acid, weighing 97g of ethylene glycol solution after adjusting the pH, adding 3g of tetraisopropyl titanate, and uniformly stirring to obtain a titanium catalyst solution;
(3) 5.9g of zinc catalyst solution and 37g of titanium catalyst solution are mixed to prepare a composite catalyst;
(4) 1660g of PTA, 868g of EG and 3.5g of composite catalyst (based on the mass of the generated polyester, wherein the adding amount of zinc element is 40ppm and the adding amount of titanium element is 8 ppm) are added into a polymerization kettle for pulping, polymerization is carried out by the same process as in example 1, the polycondensation time is 110min, and then nitrogen is used for vacuum breaking discharge, and the materials are cooled by water and then cut into particles.
The antimony-free polyester prepared in example 2 has the following indexes according to GB/T14190-2017: intrinsic viscosity 0.681dl/g, terminal carboxyl group 15mol/t, melting point 257 ℃, L value 86.5, a value-1, b value 2.1.
The same process as in example 1 was used for the processing, and the indices of the processed material were: the intrinsic viscosity is 0.650dl/g, the reduction rate is 4.6 percent, and the terminal carboxyl groups are 30mol/t.
Example 3
(1) Mixing 15g of zinc peroxide, 2g of polyethylene glycol and 85g of deionized water, and then pre-dispersing by using a high-speed dispersion machine, wherein the pre-dispersion speed is 3500r/min, the dispersion time is 10min, adjusting the pH value to 4.2 by using 1% dilute sulfuric acid in the dispersed solution, pouring the solution into a grinding machine for grinding, wherein the grinding speed is 2000r/min, the grinding time is 6h, so that a zinc catalyst solution is obtained, testing the particle size by using a laser particle size analyzer, and the D50 is 400nm;
(2) Adjusting the pH of water to 4.2 by using 1% dilute sulfuric acid, weighing 98g of ethylene glycol solution after adjusting the pH, adding 2g of ditetraethanolamine diisopropyl titanate, and uniformly stirring to obtain a titanium catalyst solution;
(3) Mixing 11.9g of zinc catalyst solution and 38.8g of titanium catalyst solution to prepare a composite catalyst;
(4) 1660g of PTA, 868g of EG and 5g of composite catalyst (based on the mass of the generated polyester, wherein the adding amount of zinc element is 61ppm and the adding amount of titanium element is 4 ppm) are added into a polymerization kettle for pulping, the polymerization is carried out by the same process as the example 1, the polycondensation time is 155min, and then nitrogen is used for vacuum breaking discharge, and the materials are cooled by water and then cut into particles.
The indexes of the antimony-free polyester prepared in the example 3 are as follows according to GB/T14190-2017: intrinsic viscosity 0.677dl/g, terminal carboxyl group 22mol/t, melting point 257.2 ℃, L value 86.8, a value-0.9, b value 1.9.
The same process as in example 1 was used for the processing, and the indices of the processed material were: the intrinsic viscosity is 0.648dl/g, the reduction rate is 4.3 percent, and the terminal carboxyl is 35mol/t.
Example 4
(1) Mixing 25g of zinc oxide, 2.5g of sodium hexametaphosphate, 2.5g of polyacrylamide and 75g of propylene glycol, pre-dispersing by using a high-speed dispersion machine, adjusting the pH to 3.1 by using 1% dilute phosphoric acid in the dispersed solution, pouring the solution into a grinding machine for grinding at the rotating speed of 4500r/min for 48 hours to obtain a zinc catalyst solution, testing the particle size by using a laser particle sizer, wherein D50 is 60nm;
(2) Adjusting the pH of propylene glycol to 3.1 by using 1% diluted phosphoric acid, weighing 95g of propylene glycol solution with the pH adjusted, adding 5g of titanium glycol, and uniformly stirring to obtain a titanium catalyst solution;
(3) Mixing 8.2g of zinc catalyst solution and 10g of titanium catalyst solution to prepare a composite catalyst;
(4) 1660g of PTA, 868g of EG and 1.7g of composite catalyst (based on the mass of the generated polyester, wherein the adding amount of zinc element is 80ppm and the adding amount of titanium element is 7 ppm) are added into a polymerization kettle for pulping, polymerization is carried out by the same process as in example 1, the polycondensation time is 110min, and then nitrogen is used for vacuum breaking discharge, and the materials are cooled by water and then cut into particles.
The indexes of the antimony-free polyester prepared in the example 4 are as follows according to GB/T14190-2017: intrinsic viscosity 0.683dl/g, terminal carboxyl groups 23mol/t, melting point 258.1 ℃, L value 86.8, a value-1.1, b value 1.6.
The same process as in example 1 was used for the processing, and the indices of the processed material were: the intrinsic viscosity is 0.645dl/g, the reduction rate is 5.6 percent, and the terminal carboxyl groups are 36mol/t.
Comparative example 1
1660g of PTA, 868g of EG and 0.74g of ethylene glycol antimony (based on the mass of the polyester produced, the addition amount of antimony element is 220 ppm) are taken and added into a polymerization kettle for pulping, polymerization is carried out by the same process as in example 1, the polycondensation time is 150min, and then vacuum breaking by using nitrogen is used for discharging, and the materials are cooled by water and then cut into granules.
According to GB/T14190-2017, the indexes of the polyester prepared in the comparative example 1 are as follows: intrinsic viscosity 0.681dl/g, terminal carboxyl group 22mol/t, melting point 258.5 ℃, L value 85.2, a value-1.4, b value 1.5.
The same process as in example 1 was used for the processing, and the indices of the processed material were: the intrinsic viscosity was 0.647dl/g, the rate of decrease was 5.0%, and the terminal carboxyl group content was 38mol/t.
Comparative example 2
1660g of PTA, 868g of EG and 0.2g of tetrabutyl titanate (the addition of titanium element is 15ppm based on the mass of the polyester produced) are added into a polymerization kettle for pulping, polymerization is carried out by the same process as in example 1 for 90min of polycondensation time, and then vacuum breaking by using nitrogen is used for discharging, and the materials are cooled by water and then cut into particles.
According to GB/T14190-2017 test, the indexes of the polyester prepared in the comparative example 2 are as follows: intrinsic viscosity 0.685dl/g, terminal carboxyl group 13mol/t, melting point 257.7 ℃, L value 86.2, a value-0.6 and b value 7.9.
The same process as in example 1 was used for the processing, and the indices of the processed material were: the intrinsic viscosity was 0.630dl/g, the rate of decrease was 8.0%, and the terminal carboxyl group content was 31mol/t.
The indices of the examples and comparative examples are summarized in Table 2 below.
TABLE 2
| Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 | Comparative example 2 | |
| Catalytic system | Zinc: titanium (IV) | Zinc: titanium (Ti) | Zinc: titanium (IV) | Zinc: titanium (Ti) | Antimony (Sb) | Titanium (IV) |
| The particle size of the zinc catalyst is D50nm | 100 | 200 | 400 | 60 | / | / |
| In ppm amount | 50:5 | 40:8 | 61:4 | 80:7 | 220 | 15 |
| Polycondensation time min | 130 | 110 | 155 | 110 | 150 | 90 |
| Intrinsic viscosity dl/g | 0.685 | 0.681 | 0.677 | 0.683 | 0.681 | 0.685 |
| Terminal carboxyl group mol/t | 18 | 15 | 22 | 23 | 22 | 13 |
| Melting Point C | 258.2 | 257 | 257.2 | 258.1 | 258.5 | 257.7 |
| L | 88.5 | 86.50 | 86.80 | 86.80 | 85.2 | 86.2 |
| a | -0.8 | -1 | -0.9 | -1.1 | -1.4 | -0.6 |
| b | 1.2 | 2.10 | 1.90 | 1.60 | 1.5 | 7.9 |
| Intrinsic viscosity dl/g after processing | 0.656 | 0.65 | 0.648 | 0.645 | 0.647 | 0.63 |
| Rate of decline | 4.2％ | 4.6％ | 4.3％ | 5.6％ | 5.0％ | 8.0％ |
| Mol/t of carboxyl group at the end of processing | 33 | 30 | 35 | 36 | 38 | 31 |
The invention grinds the zinc catalyst and compounds the zinc catalyst with the titanium catalyst solution, the obtained composite catalyst is stable in a high-temperature and high-acid environment, compared with the conventional antimony-based polyester, the composite catalyst can be used for producing antimony-free polyester, and the problem that the conventional polyester pollutes the environment by using a heavy metal antimony catalyst is solved. As can be seen from Table 2, under the same synthesis process, compared with comparative example 1 corresponding to the antimony-based catalyst, the polycondensation time in examples 1-4 is close to or less than 150min, and the addition amount of the catalyst additive is much less than that of the catalyst in comparative example 1, which shows that the catalytic activity of the composite catalyst of the present invention is higher than that of the antimony catalyst.
By using the method, the reaction rate is equivalent to the conventional reaction rate, the indexes of the product such as viscosity, terminal carboxyl, melting point and the like are consistent with the conventional reaction rate, and the method has the amplification capability of continuous polymerization production; the invention does not need to add toner even if the polyester has good color value, the color value of the corresponding product of the example is good, the L value is higher than that of the comparative example 1 (the conventional antimony system), the b value is equivalent to or lower than that of the comparative example 1 and is obviously lower than that of the comparative example 2 (the titanium system); the heat stability in the processing process of the invention is good, and the processing viscosity reduction rate is equivalent to or lower than that of comparative example 1 and is obviously lower than that of comparative example 2.
It is to be understood that the above-described embodiments of the present invention are merely illustrative of or explaining the principles of the invention and are not to be construed as limiting the invention. Therefore, any modification, equivalent replacement, improvement and the like made without departing from the spirit and scope of the present invention should be included in the protection scope of the present invention. Further, it is intended that the appended claims cover all such variations and modifications as fall within the scope and boundaries of the appended claims or the equivalents of such scope and boundaries.
Claims (10)
1. The preparation method of the composite catalyst is characterized by comprising the following steps:
s1, mixing zinc oxide, a dispersing agent and a first solvent according to a certain proportion, adding the mixture into a high-speed dispersion machine for pre-dispersion, then adding a first pH regulator to regulate the pH, and pouring the mixture into a grinding machine for grinding to obtain a nano-scale zinc catalyst solution;
s2, adjusting the pH of the second solvent through a second pH regulator, and then adding a titanium catalyst to prepare a titanium catalyst solution;
and S3, mixing the nano-scale zinc catalyst solution and the titanium catalyst solution to obtain the composite catalyst.
2. The preparation method of the composite catalyst according to claim 1, wherein the zinc oxide is zinc oxide or zinc peroxide, and the mass of the zinc element accounts for 5-30% of the total mass of the zinc catalyst solution;
the dispersant is one or more of polyethylene glycol, polyacrylamide, sodium dodecyl propane sulfonate and sodium hexametaphosphate, and the mass of the dispersant accounts for 1-25% of the total mass of the zinc oxide.
3. The preparation method of the composite catalyst according to claim 1, wherein in the step S1, the pre-dispersion rotation speed is 2500 to 4500r/min, and the pre-dispersion time is 5 to 30min;
the grinding speed of the grinder is 2000-3000 r/min, and the grinding time is 1-48 h;
the particle size after grinding is in the range of 10-1000 nm.
4. The method for preparing the composite catalyst according to claim 1, wherein the titanium catalyst is one or more of titanates, ethylene glycol titanium, potassium fluotitanate and nano titanium dioxide, and the mass of the titanium catalyst accounts for 0.1-5% of the total mass of the titanium catalyst solution.
5. The method of claim 4, wherein the titanate-based catalyst is one or more of tetramethyl titanate, tetraethyl titanate, tetraethylhexyl titanate, tetrapropyl titanate, tetraisopropyl titanate, tetrabutyl titanate, and tetraisooctyl titanate.
6. The method for preparing the composite catalyst according to claim 1, wherein the first solvent is one or more of deionized water, ethylene glycol, propylene glycol, butylene glycol and ethanol;
the first pH regulator is one or more of hydrochloric acid, sulfuric acid and phosphoric acid, and the pH regulating range is 2-5;
the second solvent is one or more of deionized water, ethylene glycol, propylene glycol, butanediol and ethanol;
the second pH regulator is one or more of hydrochloric acid, sulfuric acid and phosphoric acid, and the pH regulating range is 2-5.
7. The method for preparing the composite catalyst according to claim 1, wherein the mass ratio of the zinc element to the titanium element in the composite catalyst is 2-20: 1.
8. A composite catalyst, which is prepared by the preparation method according to any one of claims 1 to 7.
9. A method for synthesizing antimony-free polyester is characterized in that dicarboxylic acid and dihydric alcohol are used as raw materials, esterification reaction is carried out at the reaction temperature of 200-270 ℃ and the reaction pressure of 0-0.5 MPa in the presence of the composite catalyst of claim 8, and then polycondensation reaction is carried out at the reaction temperature of 250-300 ℃ and the reaction pressure of less than 150Pa under the vacuum condition, so as to obtain the antimony-free polyester.
10. The method for synthesizing antimony-free polyester according to claim 9, wherein the amount of zinc added in the composite catalyst is 10-100 ppm and the amount of titanium added is 0.5-10 ppm based on the mass of the antimony-free polyester;
the polycondensation reaction time is 50-200 min.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003119269A (en) * | 2001-10-05 | 2003-04-23 | Mitsubishi Chemicals Corp | Catalyst for manufacturing polyester, method for producing polyester resin, and polyethylene terephthalate |
| CN101126006A (en) * | 2007-06-29 | 2008-02-20 | 上海天洋热熔胶有限公司 | Method for preparing polyester thermosol |
| US20080064797A1 (en) * | 2004-05-05 | 2008-03-13 | Zahir Bashir | Process For The Production Of Polyethylene Terephthalate Copolyester, Copolyester Obtained Thereby And Its Use And Catalyst Useful In The Process |
| CN101525429A (en) * | 2009-03-30 | 2009-09-09 | 东华大学 | Binary composite catalyst for preparing biodegradable copolyester |
| CN103289069A (en) * | 2013-06-06 | 2013-09-11 | 东华大学 | Aluminum-titanium composite catalyst for polyester polycondensation and preparation method of same |
| KR20130142468A (en) * | 2012-06-19 | 2013-12-30 | 롯데케미칼 주식회사 | Catalyst composition for preparing polyesters, and method for preparing polyesters using the same |
| CN105350107A (en) * | 2015-10-22 | 2016-02-24 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of light-colored PET polyester conductive fiber based on conductive zinc oxide |
| CN110433790A (en) * | 2019-08-30 | 2019-11-12 | 山东天纳元新材料科技有限公司 | Catalyst and the preparation method and application thereof for polyester of degrading |
-
2022
- 2022-08-30 CN CN202211047983.5A patent/CN115353614A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003119269A (en) * | 2001-10-05 | 2003-04-23 | Mitsubishi Chemicals Corp | Catalyst for manufacturing polyester, method for producing polyester resin, and polyethylene terephthalate |
| US20080064797A1 (en) * | 2004-05-05 | 2008-03-13 | Zahir Bashir | Process For The Production Of Polyethylene Terephthalate Copolyester, Copolyester Obtained Thereby And Its Use And Catalyst Useful In The Process |
| CN101126006A (en) * | 2007-06-29 | 2008-02-20 | 上海天洋热熔胶有限公司 | Method for preparing polyester thermosol |
| CN101525429A (en) * | 2009-03-30 | 2009-09-09 | 东华大学 | Binary composite catalyst for preparing biodegradable copolyester |
| KR20130142468A (en) * | 2012-06-19 | 2013-12-30 | 롯데케미칼 주식회사 | Catalyst composition for preparing polyesters, and method for preparing polyesters using the same |
| CN103289069A (en) * | 2013-06-06 | 2013-09-11 | 东华大学 | Aluminum-titanium composite catalyst for polyester polycondensation and preparation method of same |
| CN105350107A (en) * | 2015-10-22 | 2016-02-24 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of light-colored PET polyester conductive fiber based on conductive zinc oxide |
| CN110433790A (en) * | 2019-08-30 | 2019-11-12 | 山东天纳元新材料科技有限公司 | Catalyst and the preparation method and application thereof for polyester of degrading |
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