CN117887054A - Titanium catalyst and preparation method and application thereof - Google Patents
Titanium catalyst and preparation method and application thereof Download PDFInfo
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- CN117887054A CN117887054A CN202410068104.XA CN202410068104A CN117887054A CN 117887054 A CN117887054 A CN 117887054A CN 202410068104 A CN202410068104 A CN 202410068104A CN 117887054 A CN117887054 A CN 117887054A
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 170
- 239000010936 titanium Substances 0.000 title claims abstract description 167
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 163
- 239000003054 catalyst Substances 0.000 title claims abstract description 130
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 148
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 65
- 229940061720 alpha hydroxy acid Drugs 0.000 claims abstract description 55
- 150000001280 alpha hydroxy acids Chemical class 0.000 claims abstract description 55
- 239000011574 phosphorus Substances 0.000 claims abstract description 25
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 25
- 229920000728 polyester Polymers 0.000 claims abstract description 24
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 20
- -1 phosphorus compound Chemical class 0.000 claims abstract description 19
- 239000011541 reaction mixture Substances 0.000 claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 150000003609 titanium compounds Chemical class 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 165
- 238000006243 chemical reaction Methods 0.000 claims description 56
- 235000015165 citric acid Nutrition 0.000 claims description 55
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 31
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 14
- 239000012295 chemical reaction liquid Substances 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 10
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 5
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 239000004310 lactic acid Substances 0.000 claims description 5
- 235000014655 lactic acid Nutrition 0.000 claims description 5
- 239000001630 malic acid Substances 0.000 claims description 5
- 235000011090 malic acid Nutrition 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims 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 claims description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 claims 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims 1
- 229940043375 1,5-pentanediol Drugs 0.000 claims 1
- 229940051250 hexylene glycol Drugs 0.000 claims 1
- WCVRQHFDJLLWFE-UHFFFAOYSA-N pentane-1,2-diol Chemical compound CCCC(O)CO WCVRQHFDJLLWFE-UHFFFAOYSA-N 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 13
- 239000002253 acid Substances 0.000 abstract description 9
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 116
- 239000000243 solution Substances 0.000 description 58
- 230000007062 hydrolysis Effects 0.000 description 20
- 238000006460 hydrolysis reaction Methods 0.000 description 20
- 239000000203 mixture Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 11
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 8
- 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 8
- 238000012360 testing method Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 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
- 239000000047 product Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 230000003068 static effect Effects 0.000 description 5
- 238000004448 titration Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000005886 esterification reaction Methods 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 239000011877 solvent mixture Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- GRWIABMEEKERFV-UHFFFAOYSA-N methanol;oxolane Chemical compound OC.C1CCOC1 GRWIABMEEKERFV-UHFFFAOYSA-N 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- VVLUUGNZSQRYFP-UHFFFAOYSA-N butane-1,4-diol;hexanedioic acid;terephthalic acid Chemical compound OCCCCO.OC(=O)CCCCC(O)=O.OC(=O)C1=CC=C(C(O)=O)C=C1 VVLUUGNZSQRYFP-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- UQLDLKMNUJERMK-UHFFFAOYSA-L di(octadecanoyloxy)lead Chemical compound [Pb+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O UQLDLKMNUJERMK-UHFFFAOYSA-L 0.000 description 1
- UVCJGUGAGLDPAA-UHFFFAOYSA-N ensulizole Chemical compound N1C2=CC(S(=O)(=O)O)=CC=C2N=C1C1=CC=CC=C1 UVCJGUGAGLDPAA-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 229920009537 polybutylene succinate adipate Polymers 0.000 description 1
- 229920001896 polybutyrate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Abstract
The present disclosure provides a titanium catalyst, a preparation method and applications thereof, and belongs to the technical field of catalysts. The titanium-based catalyst of the present disclosure comprises the reaction product and/or mixture of: titanium compound, alpha-hydroxy acid, dihydric alcohol, tetrahydrofuran and phosphorus compound, wherein the mass concentration of tetrahydrofuran is 50-500ppm; the molar ratio of the alpha-hydroxy acid to the titanium is 1-3:1, the molar ratio of the dihydric alcohol to the titanium is 0.5-3:1, and the molar ratio of the phosphorus to the titanium in the phosphorus compound is 0-1:1. According to the method, the hydrolyzability of the titanium catalyst is avoided by adding tetrahydrofuran, and the catalytic efficiency of the titanium catalyst is improved; when the method is applied to the preparation of polyester, the polyester with low acid value and high whiteness of color value can be obtained.
Description
Technical Field
The present disclosure relates to the technical field of catalysts, and in particular to a titanium catalyst, a preparation method and applications thereof.
Background
In the polyester preparation process, the catalyst has very important influence on the quality of products such as hue, stability, viscosity and the like. The titanium catalyst has the characteristics of high catalytic activity and no harm to human bodies and environment, and is the object of controversial research and application in the polyester industry, wherein the titanium catalyst is mainly an organic titanate catalyst, but water generated in the esterification reaction process can hydrolyze and deactivate part of titanate, so that the catalyst dosage is increased or the reaction temperature is increased for shortening the reaction time, but three new difficult problems 1: the side reaction is aggravated, and the tetrahydrofuran and carboxyl end group contents of the side reaction products are increased; 2: the catalyst hydrolysate is deposited inside the equipment to cause the problems of reduced heat transfer efficiency, even blockage and the like; 3: the polyester polymerization reaction is a reversible reaction, and the residual catalyst accelerates the hydrolysis of the polymer.
Wu Miaojiang A five-membered chelate ring tri-ligand complex formed by citric acid and titanium ions is synthesized by adjusting the PH value by tetrabutyl titanate in citric acid aqueous solution through NaOH. The titanium catalyst has good hydrolysis resistance, can be kept stable in BDO aqueous solution at 230 ℃ and has no white precipitate. However, for polyester synthesis, the defect of introducing NaOH impurities exists, and partial titanate hydrolysis side reaction exists in the catalyst synthesis process, so that the conversion rate is uncontrollable.
In the prior art, although titanium catalysts are studied, it is difficult to control the quality of titanium catalyst products, and therefore, further catalysts which can ensure the quality of products and have high activity are required.
Disclosure of Invention
The purpose of the present disclosure is to overcome the shortcomings of the prior art, and provide a titanium catalyst, a preparation method and an application thereof, wherein the titanium catalyst has good hydrolysis resistance, high catalytic efficiency and low cost; the polyester product obtained by using the titanium catalyst has low acid value, high color value whiteness and excellent ageing resistance.
In order to achieve the above purpose, the technical scheme adopted by the present disclosure is as follows: a titanium-based catalyst comprising the reaction product and/or mixture of: titanium compound, alpha-hydroxy acid, dihydric alcohol, tetrahydrofuran and phosphorus compound, wherein the mass concentration of tetrahydrofuran is 50-500ppm; the molar ratio of alpha-hydroxy acid to titanium is 1-3:1, the molar ratio of dihydric alcohol to titanium is 0.5-3:1, and the molar ratio of phosphorus to titanium in the phosphorus compound is 0-1:1.
According to the method, the hydrolyzability of the titanium catalyst is avoided by adding tetrahydrofuran, and the catalytic efficiency of the titanium catalyst is improved; when the method is applied to the preparation of polyester, the polyester with low acid value and high whiteness of color value can be obtained.
In the present application, the tetrahydrofuran may be present at a mass concentration of 50ppm, 70ppm, 90ppm, 100ppm, 120ppm, 150ppm, 180ppm, 200ppm, 230ppm, 250ppm, 280ppm, 300ppm, 320ppm, 350ppm, 380ppm, 400ppm, 450ppm, 480ppm, 500ppm, but the present application is not limited thereto, and is preferably 100 to 300ppm.
The inventors of the present application have surprisingly found that controlling the tetrahydrofuran content to be in the range of 50ppm to 500ppm can optimize the catalytic efficiency of the hydrolysis-resistant catalyst with the active site in a reasonable range. Too high can lead to too few catalytic sites of the synthesized hydrolysis-resistant catalyst, the catalytic efficiency is reduced, too low can lead to too many catalytic sites of the synthesized hydrolysis-resistant catalyst, and the catalytic efficiency is also affected.
In the titanium-based catalyst, the mass concentration of tetrahydrofuran is obtained by testing the following method:
preparation of THF standard curve: preparing THF methanol solutions with the concentrations of 0.010g/L, 0.1g/L, 1.0g/L, 5.0g/L, 10.0g/L, 20.0g/L, 50.0g/L and 100.0g/L, respectively testing the peak areas of THF in the THF methanol solutions with different concentrations by a static headspace method, and preparing a THF standard curve by taking the peak areas of THF as an ordinate and the concentration of THF as an abscissa;
determination of THF in titanium-based catalysts: accurately weighing about 1.2000g of titanium catalyst, adding the titanium catalyst into a static headspace test bottle, testing the peak area of THF in the titanium catalyst by a static headspace method, and calculating the mass concentration of THF in the titanium catalyst according to the THF standard curve;
the static headspace test conditions are as follows:
temperature: heating box: 105 ℃, quantitative loop: 135 ℃, transmission line: 165 ℃;
time: sample bottle balancing: 120 minutes, sample duration: 0.09 min, GC cycle: 30 minutes;
the instrument model and parameters used for the static headspace are as follows:
Agilent Technologies 7697Headspace Sampler；
Agilent Technologies 7890AGC System；
chromatographic column: j & W122-7032: 250 ℃ C: 30m x 250 mu m x 0.25 mu m;
and (3) sample injection: front SS sample inlet N2; sample preparation: front detector FID.
In one embodiment, the molar ratio of alpha-hydroxy acid to titanium may be 1:1, 1.2:1, 1.5:1, 1.8:1, 2:1, 2.3:1, 2.5:1, 2.8:1, 3:1, the present application is not limited thereto, preferably the molar ratio of alpha-hydroxy acid to titanium is 1-2.5:1.
The molar ratio of the alpha-hydroxy acid to the titanium affects the performance of the titanium catalyst, and if the content of the alpha-hydroxy acid is too small, on one hand, the complexation effect is poor, hydrolysis resistance is not achieved, and the catalyst cost is high, and on the other hand, the content of the alpha-hydroxy acid is too large, the complexation is excessive, and the catalytic efficiency is reduced.
In this application, the molar ratio of glycol to titanium may be 0.5:1, 0.8:1, 1:1, 1.5:1, 1.8:1, 2:1, 2.2:1, 2.5:1, 2.7:1, 3:1, but is not limited to the recited values, as other non-recited values are equally applicable within the scope of this application.
In the present application, the molar ratio of phosphorus to titanium in the phosphorus compound may be 0:1, 0.2:1, 0.5:1, 0.7:1, 1:1, but is not limited to the recited values, and other non-recited values are equally applicable within the scope of the present application.
In the application, the titanium catalyst can form a stable complex structure by adjusting the mole ratio of the phosphorus compound to the titanium compound, so that the hydrolysis resistance and the catalytic effect of the titanium catalyst are improved; too low a content of the phosphorus compound may affect hydrolysis resistance of the hydrolysis-resistant catalyst, and too high a content of the phosphorus compound may result in a decrease in catalyst activity.
In one embodiment, the titanium compound is a titanium compound having Ti (OR) 4 A compound of the formula wherein R is selected from the group consisting of C1-C10 linear alkyl, C1-C10 branched alkyl, or C1-C10 aryl; preferably selected from C1-C6 linear alkyl groups or C1-C6 branched alkyl groups, such as butyl, isopropyl. Specific examples of the titanium compound include n-butyl titanate and isopropyl titanate.
In one embodiment, the alpha-hydroxy acid is at least one of citric acid, lactic acid, malic acid;
the alpha-hydroxy acid is chelated with titanium atoms in the titanium compound, so that the solubility of the titanium compound in dihydric alcohol is improved, and in addition, the chelation can effectively inhibit the hydrolysis of titanate, so that the hydrolysis resistance and the catalytic efficiency of the titanium catalyst are improved.
In the application, the dihydric alcohol is at least one of ethylene glycol, propylene glycol, butanediol, pentanediol and hexanediol; 1, 4-butanediol is preferred.
In one embodiment, the phosphorus compound is at least one of phosphoric acid, phosphorous acid, hypophosphorous acid, phosphate salts, phosphate esters. Specific examples of the phosphate ester include triphenyl phosphate and triethyl phosphate.
In a second aspect, a method for preparing the titanium-based catalyst is provided, comprising the steps of:
preparing an alpha-hydroxy acid solution: uniformly mixing alpha-hydroxy acid, dihydric alcohol and tetrahydrofuran to obtain alpha-hydroxy acid solution;
preparation of titanium-based catalyst: and (3) carrying out a first reaction on dihydric alcohol, a titanium compound and a phosphorus compound under the conditions of vacuum and 70-90 ℃ until no bubbles are generated in the first reaction liquid, then adding an alpha-hydroxy acid solution for a second reaction, and vacuumizing after the second reaction is finished, wherein the obtained solution is the titanium catalyst.
In the application, the boiling point of tetrahydrofuran is low, and after the second reaction is finished, vacuumizing can be carried out, so that most tetrahydrofuran can be removed, and the contents of titanium compounds, alpha-hydroxy acid, butanediol and phosphorus compounds are not influenced; the tetrahydrofuran content in the titanium catalyst is adjusted by controlling the vacuumizing time and/or the vacuumizing degree.
The reaction can be effectively controlled by two steps, the loss of raw materials is reduced, the efficient hydrolysis-resistant catalyst is obtained, dihydric alcohol is 1, 4-butanediol, titanium compound is n-butyl titanate, alpha-hydroxy acid is citric acid, and the reaction principle of the titanium catalyst is as follows:
in one embodiment, the alpha-hydroxy acid solution is prepared with a molar ratio of (2-3:): (0.04-0.06): (0.8-1.2) of alpha-hydroxy acid, glycol and tetrahydrofuran.
In one embodiment, the molar ratio of glycol to titanium in the preparation of the titanium-based catalyst is in the range of 0.44 to 2.96:1 and the molar ratio of phosphorus to titanium in the phosphorus compound is in the range of 0 to 1:1.
In one embodiment, the vacuum pressure of the first and second reactions is each independently 650-900Pa.
In one embodiment, the vacuum pressure of the vacuumized air is 650-900Pa, and the time is 30-60min.
In one embodiment, the alpha-hydroxy acid solution is added dropwise.
In one embodiment, the α -hydroxy acid solution is added dropwise over 30 minutes.
In one embodiment, both the first reaction and the second reaction are carried out under stirring.
In a third aspect, the application of the titanium catalyst in polyester synthesis, in particular in PBAT, PBSeT, PBST, PBS, PBSA, PBT and other polyester synthesis is provided
In one embodiment, the titanium-based catalyst may be used in a polycondensation reaction of a polyol (e.g., a glycol) and a polyacid (e.g., a diacid), and may be particularly used in a polycondensation reaction of terephthalic acid (PTA) and Butanediol (BDO).
In one embodiment, the titanium-based catalyst is used in an amount of 10 to 70ppm based on the weight of the polyester, wherein the titanium-based catalyst is used in an amount based on the weight of titanium element therein.
Wherein the weight of the polyester refers to the theoretical amount of the dibasic acid and the dibasic alcohol produced at present, and the titanium-based catalyst is used in an amount of 10ppm, 20ppm, 30ppm, 40ppm, 50ppm, 60ppm or 70ppm based on the weight of the polyester.
In the above technical solutions, the application is not particularly limited, and the person skilled in the art can apply the catalyst composition according to the existing technical conditions of the process, for example, but not limited to, the application of the catalyst composition in the preparation of poly (terephthalic acid-adipic acid-butylene glycol).
Compared with the prior art, the beneficial effects of the present disclosure are:
(1) The titanium catalyst with good hydrolysis resistance, good catalytic effect and low cost is prepared by adding tetrahydrofuran; the titanium catalyst is a liquid catalyst, and is convenient to dose and add when being used for preparing polyester.
(2) The titanium catalyst is used for preparing polyester, and the obtained polyester has low acid value, high color value whiteness and excellent ageing resistance.
Detailed Description
For a better understanding of the objects, technical solutions and advantages of the present disclosure, the present disclosure will be further described with reference to specific examples and comparative examples, which are intended to be in detail, not to be limiting of the present disclosure. All other embodiments, which can be made by one of ordinary skill in the art without making any inventive effort, are intended to be within the scope of the present disclosure. The experimental reagents and apparatus to which the present disclosure is directed are common reagents and apparatus unless otherwise indicated.
Example 1
The present example provides a titanium-based catalyst comprising the reaction product and/or mixture of: n-butyl titanate, citric acid, 1, 4-butanediol and tetrahydrofuran, wherein the mass concentration of the tetrahydrofuran is 299ppm, the molar ratio of the citric acid to the titanium is 2:1, and the molar ratio of the 1, 4-butanediol to the titanium is 2:1.
The embodiment provides a titanium catalyst, and the preparation method comprises the following steps:
(1) Uniformly mixing 0.2mol of citric acid, 0.005mol of 1, 4-butanediol and 0.1mol of tetrahydrofuran, and adding the mixture into a constant pressure funnel to obtain an alpha-hydroxy acid solution;
(2) Adding 0.195mol of 1, 4-butanediol and 0.1mol of n-butyl titanate into a 250mL three-neck flask with a stirrer and a thermometer, performing a first reaction under the conditions of 680Pa and 80 ℃ of vacuum pressure until no bubbles are generated in the first reaction liquid, then dropwise adding the alpha-hydroxy acid solution in the step (1) for a second reaction under the conditions of 680Pa of vacuum pressure within 30min, vacuumizing under the conditions of 680Pa of vacuum pressure after the second reaction is finished, and vacuumizing for 40 min to obtain the solution, namely the titanium catalyst.
Example 2
The present example provides a titanium-based catalyst comprising the reaction product and/or mixture of: the titanium alloy comprises n-butyl titanate, malic acid, 1, 4-butanediol and tetrahydrofuran, wherein the mass concentration of the tetrahydrofuran is 308ppm, the molar ratio of the malic acid to the titanium is 2:1, and the molar ratio of the 1, 4-butanediol to the titanium is 1:1.
The embodiment provides a titanium catalyst, and the preparation method comprises the following steps:
(1) Uniformly mixing 0.2mol of malic acid, 0.005mol of 1, 4-butanediol and 0.1mol of tetrahydrofuran, and adding the mixture into a constant pressure funnel to obtain an alpha-hydroxy acid solution;
(2) Adding 0.095mol of 1, 4-butanediol and 0.1mol of n-butyl titanate into a 250mL three-neck flask with a stirrer and a thermometer, carrying out a first reaction under the conditions of vacuum pressure of 765Pa and 70 ℃ until no bubbles are generated in the first reaction liquid, then dropwise adding the alpha-hydroxy acid solution in the step (1) under the conditions of vacuum pressure of 765Pa within 30min for carrying out a second reaction, and vacuumizing under the conditions of vacuum pressure of 765Pa for 42 min after the second reaction is finished, wherein the obtained solution is the titanium catalyst.
Example 3
The present example provides a titanium-based catalyst comprising the reaction product and/or mixture of: n-butyl titanate, lactic acid, 1, 4-butanediol and tetrahydrofuran, wherein the mass concentration of the tetrahydrofuran is 305ppm, the molar ratio of lactic acid to titanium is 2:1, and the molar ratio of 1, 4-butanediol to titanium is 3:1.
The embodiment provides a titanium catalyst, and the preparation method comprises the following steps:
(1) Uniformly mixing 0.2mol of lactic acid, 0.005mol of 1, 4-butanediol and 0.1mol of tetrahydrofuran, and adding the mixture into a constant pressure funnel to obtain an alpha-hydroxy acid solution;
(2) Adding 0.295mol of 1, 4-butanediol and 0.1mol of n-butyl titanate into a 250mL three-neck flask with a stirrer and a thermometer, carrying out a first reaction under the conditions that the vacuum pressure is 880Pa and the temperature is 90 ℃, reacting until no bubble is generated in the first reaction liquid, then dropwise adding the alpha-hydroxy acid solution in the step (1) for a second reaction under the conditions that the vacuum pressure is 880Pa within 30min, vacuumizing under the conditions that the vacuum pressure is 880Pa after the second reaction is finished, and vacuumizing for 44 minutes, wherein the obtained solution is the titanium catalyst.
Example 4
The present example provides a titanium-based catalyst comprising the reaction product and/or mixture of: n-butyl titanate, citric acid, 1, 4-butanediol and tetrahydrofuran, wherein the mass concentration of the tetrahydrofuran is 295ppm, the molar ratio of the citric acid to the titanium is 1:1, and the molar ratio of the 1, 4-butanediol to the titanium is 2:1.
This example provides a titanium-based catalyst, the preparation method of which differs from that of example 1 only in that: the content of the citric acid is adjusted according to the different contents of the citric acid, so that the molar ratio of the citric acid to the titanium is 1:1.
Example 5
The present example provides a titanium-based catalyst comprising the reaction product and/or mixture of: n-butyl titanate, citric acid, 1, 4-butanediol and tetrahydrofuran, wherein the mass concentration of the tetrahydrofuran is 298ppm, the molar ratio of the citric acid to the titanium is 2.5:1, and the molar ratio of the 1, 4-butanediol to the titanium is 2:1.
This example provides a titanium-based catalyst, the preparation method of which differs from that of example 1 only in that: the content of the citric acid is adjusted according to the different contents of the citric acid, so that the molar ratio of the citric acid to the titanium is 2.5:1.
Example 6
The present example provides a titanium-based catalyst comprising the reaction product and/or mixture of: n-butyl titanate, citric acid, 1, 4-butanediol and tetrahydrofuran, wherein the mass concentration of the tetrahydrofuran is 297ppm, the molar ratio of the citric acid to the titanium is 3:1, and the molar ratio of the 1, 4-butanediol to the titanium is 2:1.
This example provides a titanium-based catalyst, the preparation method of which differs from that of example 1 only in that: the content of the citric acid is adjusted according to the different contents of the citric acid, so that the molar ratio of the citric acid to the titanium is 3:1.
Example 7
The present example provides a titanium-based catalyst comprising the reaction product and/or mixture of: n-butyl titanate, citric acid, 1, 4-butanediol and tetrahydrofuran, wherein the mass concentration of the tetrahydrofuran is 301ppm, the molar ratio of the citric acid to the titanium is 4:1, and the molar ratio of the 1, 4-butanediol to the titanium is 2:1.
This example provides a titanium-based catalyst, the preparation method of which differs from that of example 1 only in that: the content of the citric acid is adjusted according to the different contents of the citric acid, so that the molar ratio of the citric acid to the titanium is 4:1.
Example 8
The present example provides a titanium-based catalyst comprising the reaction product and/or mixture of: n-butyl titanate, citric acid, 1, 4-butanediol, tetrahydrofuran and triphenyl phosphate, wherein the mass concentration of the tetrahydrofuran is 300ppm, the molar ratio of the citric acid to the titanium is 2:1, the molar ratio of the 1, 4-butanediol to the titanium is 2:1, and the molar ratio of the phosphorus to the titanium in the triphenyl phosphate is 0.1:1.
The embodiment provides a titanium catalyst, and the preparation method comprises the following steps:
(1) Uniformly mixing 0.2mol of citric acid, 0.005mol of 1, 4-butanediol and 0.1mol of tetrahydrofuran, and adding the mixture into a constant pressure funnel to obtain an alpha-hydroxy acid solution;
(2) Adding 0.195mol of 1, 4-butanediol, 0.1mol of n-butyl titanate and 0.01mol of triphenyl phosphate into a 250mL three-neck flask with a stirrer and a thermometer, performing a first reaction under the conditions that the vacuum pressure is 680Pa and the temperature is 80 ℃ until no bubbles are generated in the first reaction liquid, then dropwise adding the alpha-hydroxy acid solution in the step (1) under the conditions that the vacuum pressure is 680Pa for a second reaction within 30min, and vacuumizing for 40 min under the conditions that the vacuum pressure is 680Pa after the second reaction is finished, wherein the obtained solution is the titanium catalyst.
Example 9
The present example provides a titanium-based catalyst comprising the reaction product and/or mixture of: n-butyl titanate, citric acid, 1, 4-butanediol, tetrahydrofuran and triphenyl phosphate, wherein the mass concentration of the tetrahydrofuran is 304ppm; the molar ratio of citric acid to titanium is 2:1, the molar ratio of 1, 4-butanediol to titanium is 2:1, and the molar ratio of phosphorus to titanium in triphenyl phosphate is 0.2:1.
The embodiment provides a titanium catalyst, and the preparation method comprises the following steps:
(1) 0.2mol of citric acid is added into 0.005mol of 1, 4-butanediol and 0.1mol of tetrahydrofuran, and after being dissolved, the mixture is added into a constant pressure funnel to obtain alpha-hydroxy acid solution;
(2) Adding 0.195mol of 1, 4-butanediol, 0.1mol of n-butyl titanate and 0.02mol of triphenyl phosphate into a 250mL three-neck flask with a stirrer and a thermometer, carrying out a first reaction under the conditions of 700Pa and 80 ℃ of vacuum pressure until no bubbles are generated in the first reaction liquid, then dropwise adding the alpha-hydroxy acid solution in the step (1) under the conditions of 700Pa of vacuum pressure for a second reaction within 30min, and vacuumizing under the conditions of 700Pa of vacuum pressure for 40 min after the second reaction is finished, wherein the obtained solution is the titanium catalyst.
Example 10
The present example provides a titanium-based catalyst comprising the reaction product and/or mixture of: n-butyl titanate, citric acid, 1, 4-butanediol, tetrahydrofuran and phosphoric acid, wherein the mass concentration of the tetrahydrofuran is 299ppm; the molar ratio of citric acid to titanium is 2:1, the molar ratio of 1, 4-butanediol to titanium is 2:1, and the molar ratio of phosphorus to titanium in phosphoric acid is 1:1.
The embodiment provides a titanium catalyst, and the preparation method comprises the following steps:
(1) 0.2mol of citric acid is added into 0.005mol of 1, 4-butanediol and 0.1mol of tetrahydrofuran, and after being dissolved, the mixture is added into a constant pressure funnel to obtain alpha-hydroxy acid solution;
(2) Adding 0.195mol of 1, 4-butanediol, 0.1mol of n-butyl titanate and 0.1mol of phosphoric acid into a 250mL three-neck flask with a stirrer and a thermometer, carrying out a first reaction under the conditions of 670Pa vacuum pressure and 80 ℃ until no bubble is generated in the first reaction liquid, then dropwise adding the alpha-hydroxy acid solution in the step (1) for a second reaction within 30min under the conditions of 670Pa vacuum pressure, and vacuumizing under the conditions of 670Pa vacuum pressure for 40 min vacuum pressure after the second reaction is finished, wherein the obtained solution is the titanium catalyst.
Example 11
The titanium-based catalyst of the present embodiment comprises a reaction product and/or mixture of: n-butyl titanate, citric acid, 1, 4-butanediol and tetrahydrofuran, wherein the mass concentration of the tetrahydrofuran is 106ppm; the molar ratio of citric acid to titanium was 2:1 and the molar ratio of 1, 4-butanediol to titanium was 2:1.
The implementation provides a titanium catalyst, and the preparation method comprises the following steps:
(1) Uniformly mixing 0.2mol of citric acid, 0.005mol of butanediol and 0.1mol of tetrahydrofuran, and adding the mixture into a constant pressure funnel to obtain an alpha-hydroxy acid solution;
(2) Adding 0.195mol of 1, 4-butanediol and 0.1mol of n-butyl titanate into a 250mL three-neck flask with a stirrer and a thermometer, carrying out a first reaction under the conditions that the vacuum pressure is 690Pa and the temperature is 80 ℃, reacting until no bubble is generated in the first reaction liquid, then dropwise adding the alpha-hydroxy acid solution in the step (1) under the conditions that the vacuum pressure is 690Pa within 30min for carrying out a second reaction, vacuumizing under the conditions that the vacuum pressure is 690Pa after the second reaction is finished, and vacuumizing for 50 minutes, wherein the obtained solution is the titanium catalyst.
Example 12
The present example provides a titanium-based catalyst comprising the reaction product and/or mixture of: n-butyl titanate, citric acid, 1, 4-butanediol and tetrahydrofuran, wherein the mass concentration of the tetrahydrofuran is 407ppm; the molar ratio of citric acid to titanium was 2:1 and the molar ratio of 1, 4-butanediol to titanium was 2:1.
The implementation provides a titanium catalyst, and the preparation method comprises the following steps:
(1) Uniformly mixing 0.2mol of citric acid, 0.005mol of 1, 4-butanediol and 0.1mol of tetrahydrofuran, and adding the mixture into a constant pressure funnel to obtain an alpha-hydroxy acid solution;
(2) Adding 0.195mol of 1, 4-butanediol and 0.1mol of n-butyl titanate into a 250mL three-neck flask with a stirrer and a thermometer, carrying out a first reaction under the conditions of 705Pa and 80 ℃ of vacuum pressure until no bubbles are generated in the first reaction liquid, then dropwise adding the alpha-hydroxy acid solution in the step (1) under the conditions of 705Pa of vacuum pressure within 30min for carrying out a second reaction, vacuumizing under the conditions of 705Pa of vacuum pressure after the second reaction is finished, and vacuumizing for 35 min to obtain a solution which is the titanium catalyst.
Example 13
The titanium-based catalyst of the present embodiment comprises a reaction product and/or mixture of: n-butyl titanate, citric acid, 1, 4-butanediol and tetrahydrofuran, wherein the mass concentration of the tetrahydrofuran is 496ppm; the molar ratio of citric acid to titanium was 2:1 and the molar ratio of 1, 4-butanediol to titanium was 2:1.
The implementation provides a titanium catalyst, and the preparation method comprises the following steps:
(1) Uniformly mixing 0.2mol of citric acid, 0.005mol of 1, 4-butanediol and 0.1mol of tetrahydrofuran, and adding the mixture into a constant pressure funnel to obtain an alpha-hydroxy acid solution;
(2) Adding 0.195mol of 1, 4-butanediol and 0.1mol of n-butyl titanate into a 250mL three-neck flask with a stirrer and a thermometer, performing a first reaction under the conditions of 710Pa and 80 ℃ of vacuum pressure until no bubbles are generated in the first reaction liquid, then dropwise adding the alpha-hydroxy acid solution in the step (1) under the conditions of 710Pa of vacuum pressure within 30min for performing a second reaction, vacuumizing under the conditions of 710Pa of vacuum pressure after the second reaction is finished, and vacuumizing for 30min to obtain the solution, namely the titanium catalyst.
Example 14
The titanium-based catalyst of the present embodiment comprises a reaction product and/or mixture of: n-butyl titanate, citric acid, 1, 4-butanediol and tetrahydrofuran, wherein the mass concentration of the tetrahydrofuran is 52ppm; the molar ratio of citric acid to titanium was 2:1 and the molar ratio of 1, 4-butanediol to titanium was 2:1.
The implementation provides a titanium catalyst, and the preparation method comprises the following steps:
(1) Uniformly mixing 0.2mol of citric acid, 0.005mol of 1, 4-butanediol and 0.1mol of tetrahydrofuran, and adding the mixture into a constant pressure funnel to obtain an alpha-hydroxy acid solution;
(2) Adding 0.195mol of 1, 4-butanediol and 0.1mol of n-butyl titanate into a 250mL three-neck flask with a stirrer and a thermometer, carrying out a first reaction under the conditions of 650Pa and 80 ℃ of vacuum pressure until no bubbles are generated in a first reaction liquid, then dropwise adding the alpha-hydroxy acid solution in the step (1) under the conditions of 650Pa of vacuum pressure within 30min for carrying out a second reaction, vacuumizing under the conditions of 650Pa of vacuum pressure for 60min after the second reaction is finished, and obtaining a solution which is the titanium catalyst
Comparative example 1
This comparative example provides a titanium-based catalyst comprising the reaction product and/or mixture of: n-butyl titanate, citric acid and 1, 4-butanediol, wherein the molar ratio of the citric acid to the titanium is 2:1, and the molar ratio of the 1, 4-butanediol to the titanium is 2:1.
The comparative example provides a titanium-based catalyst, the preparation method of which comprises the following steps:
(1) Adding 0.2mol of citric acid into 0.005mol of 1, 4-butanediol, dissolving, and adding into a constant pressure funnel to obtain an alpha-hydroxy acid solution;
(2) Adding 0.195mol of 1, 4-butanediol and 0.1mol of n-butyl titanate into a 250mL three-neck flask with a stirrer and a thermometer, carrying out a first reaction under the conditions of 680Pa and 80 ℃ of vacuum pressure until no bubbles are generated in the first reaction liquid, then dropwise adding the alpha-hydroxy acid solution in the step (1) for a second reaction under the conditions of 680Pa of vacuum pressure within 30min, vacuumizing under the conditions of 680Pa of vacuum pressure after the second reaction is finished, and vacuumizing for 40 min to obtain the solution, namely the titanium catalyst.
Comparative example 2
The titanium-based catalyst of this comparative example comprises the reaction product and/or mixture of: n-butyl titanate, citric acid, 1, 4-butanediol and tetrahydrofuran, wherein the mass concentration of the tetrahydrofuran is 610ppm; the molar ratio of citric acid to titanium was 2:1 and the molar ratio of 1, 4-butanediol to titanium was 2:1.
The comparison provides a titanium catalyst, the preparation method of which comprises the following steps:
(1) Uniformly mixing 0.2mol of citric acid, 0.005mol of 1, 4-butanediol and 0.1mol of tetrahydrofuran, and adding the mixture into a constant pressure funnel to obtain an alpha-hydroxy acid solution;
(2) Adding 0.195mol of 1, 4-butanediol and 0.1mol of n-butyl titanate into a 250mL three-neck flask with a stirrer and a thermometer, performing a first reaction under the conditions of 750Pa and 80 ℃ of vacuum pressure until no bubbles are generated in the first reaction liquid, then dropwise adding the alpha-hydroxy acid solution in the step (1) under the conditions of 750Pa of vacuum pressure within 30min for performing a second reaction, vacuumizing under the conditions of 750Pa of vacuum pressure after the second reaction is finished, and vacuumizing for 25 min to obtain the solution, namely the titanium catalyst.
The titanium-based catalysts obtained in examples 1 to 14 and comparative examples 1 to 2 were used for producing polyesters, and the production method thereof was as follows:
2.5g of terephthalic acid, 2.5g of adipic acid, 5g of 1, 4-butanediol and the catalyst (the weight of titanium atoms is 50ppm based on the amount of the produced polyester) are mixed to prepare slurry, the slurry is added into a polymerization kettle for esterification reaction, the esterification temperature is 190-230 ℃, the pressure is normal pressure, and water produced by the reaction is discharged through a rectification device. And (3) reducing the pressure to normal pressure after the esterification is finished, adding triphenyl phosphate (the weight of P atoms is 20ppm based on the amount of the generated polyester), vacuumizing and reducing the pressure to a system pressure lower than 200Pa, gradually heating to 240-250 ℃, stopping the reaction after the system reaction reaches 150min, and extruding, cooling and granulating the product from the bottom of the polymerization kettle for performance test.
In the present invention, the hydrolysis resistance of the catalyst, the intrinsic viscosity of the polyester, the acid value, the whiteness of the color value, etc. are tested by the following methods:
hydrolysis resistance: the catalysts obtained in examples 1-14 and comparative examples 1-2 were prepared into BDO solutions with a certain titanium (Ti) concentration (calculated as Ti element) of 0.5% and different water contents by taking 4 sample bottles of 20mL, and the hydrolysis conditions of the catalyst after the preparation and after a period of time were observed for 4 samples of BDO solutions with water mass fractions of 0.5%,2%,4% and 6%, respectively. The hydrolysis resistance of the catalyst was evaluated according to the time at which white precipitate appeared.
Intrinsic viscosity: the sample concentration was 5mg/ml as determined in a phenol/o-dichlorobenzene solution in a weight ratio of 1:1 in a constant temperature water bath at 25.+ -. 0.05 ℃ according to GB/T17931-1999.
Acid value: the acid number AN (mg KOH/g) of the samples was determined in accordance with DIN EN 12634, month 10 1998. The solvent mixture used included 1 volume of dimethyl sulfoxide, 8 volumes of isopropanol, and 7 volumes of toluene, the solvent mixture volume being 150ml. The samples were pre-titrated according to DIN EN 12634 to determine the appropriate sample quality and to ensure that the volume of spent titrant was 2-3ml. The samples were added to the solvent mixture and heated to 70-85 ℃ to dissolve all the samples into a clear solution, maintaining the solution temperature at 65-75 ℃ during titration to avoid sample precipitation. If appropriate, tetrabutylammonium hydroxide is used as the titration solution, and the use of highly toxic tetramethylammonium hydroxide is avoided. At the same time, to avoid the absorption of CO in the air by the solvent mixture 2 Therefore, the volume of the blank solvent consumption titration solution is influenced, when the volume of the blank solvent consumption titration solution is tested, the blank solvent is subjected to pretreatment according to the same process of sample testing operation, such as heating treatment of the blank solvent for the same time and temperature, and then titration of the blank solvent is carried out.
Color value: the whiteness index of aliphatic polyester particles having a particle size of 1.2 to 5.4g/100 particles, measured in parallel three times, was measured using a Minolta CM-5 spectrophotometer according to ASTM E313-73, thereby determining the average value. The glass cuvette (from Minolta) was filled with the particulate material to be analyzed (filling height at least 3 cm). The granular material was compacted using pressure from the Minolta instrument head.
The test results are shown in table 1 below.
TABLE 1
As can be seen from table 1, the titanium-based catalyst prepared in the examples of the present disclosure has excellent hydrolysis resistance.
Comparative examples 1, 4-7 show that when the molar ratio of titanium compound to alpha-hydroxy acid is 1:1-2.5; the acid value of the polyester is lower.
As is clear from comparative examples 1, 11 to 14 and comparative examples 1 to 2, the mass concentration of tetrahydrofuran in the titanium-based catalyst affects the performance of the titanium-based catalyst, and when the mass concentration of tetrahydrofuran is 50 to 500ppm, the performance of the obtained titanium-based catalyst is better; when tetrahydrofuran is not contained in the titanium-based catalyst or the mass concentration of tetrahydrofuran is out of the range of the present application, the performance of the obtained titanium-based catalyst is significantly lowered.
Finally, it should be noted that the above embodiments illustrate the technical solution of the present disclosure and not limit the scope of the present disclosure, and although the present disclosure has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present disclosure may be modified or equally substituted without departing from the spirit and scope of the technical solution of the present disclosure.
Claims (10)
1. A titanium-based catalyst, characterized by comprising the reaction product and/or mixture of: the titanium compound, alpha-hydroxy acid, dihydric alcohol, tetrahydrofuran and phosphorus compound, wherein the mass concentration of the tetrahydrofuran is 50-500ppm, the molar ratio of the alpha-hydroxy acid to the titanium is 1-3:1, the molar ratio of the dihydric alcohol to the titanium is 0.5-3:1, and the molar ratio of the phosphorus to the titanium in the phosphorus compound is 0-1:1.
2. The titanium-based catalyst according to claim 1, wherein the molar ratio of the α -hydroxy acid to titanium is 1-2.5:1.
3. The titanium-based catalyst according to claim 1, wherein the titanium compound is a catalyst having Ti (OR) 4 A compound of the formula wherein R is selected from C1-a linear alkyl group of C10, a branched alkyl group of C1-C10 or an aryl group of C1-C10; preferably, the titanium compound is at least one of n-butyl titanate and isopropyl titanate.
4. The titanium-based catalyst according to claim 1, wherein the α -hydroxy acid is at least one of citric acid, lactic acid, and malic acid; and/or the dihydric alcohol is at least one of ethylene glycol, propylene glycol, butylene glycol, pentylene glycol and hexylene glycol.
5. The titanium-based catalyst according to claim 1, wherein the phosphorus compound is at least one of phosphoric acid, phosphorous acid, hypophosphorous acid, a phosphate salt and a phosphate ester.
6. The method for producing a titanium-based catalyst according to any one of claims 1 to 5, comprising the steps of:
preparing an alpha-hydroxy acid solution: uniformly mixing alpha-hydroxy acid, dihydric alcohol and tetrahydrofuran to obtain alpha-hydroxy acid solution;
preparation of titanium-based catalyst: and (3) carrying out a first reaction on dihydric alcohol, a titanium compound and a phosphorus compound under the conditions of vacuum and 70-90 ℃ until no bubbles are generated in the first reaction liquid, then adding an alpha-hydroxy acid solution for a second reaction, and vacuumizing after the second reaction is finished, wherein the obtained solution is the titanium catalyst.
7. The method according to claim 6, wherein the molar ratio of the alpha-hydroxy acid, the dihydric alcohol and the tetrahydrofuran is (2-3) to (0.04-0.06) to (0.8-1.2).
And/or preparing the titanium catalyst, wherein the molar ratio of the dihydric alcohol to the titanium is 0.44-2.96:1, and the molar ratio of the phosphorus to the titanium in the phosphorus compound is 0-1:1.
8. The method of claim 6, wherein the vacuum pressure of the first reaction and the second reaction are each independently 650Pa to 900Pa.
9. Use of the titanium-based catalyst according to any one of claims 1 to 5 in the synthesis of polyesters.
10. The use according to claim 9, wherein the catalyst is used in an amount of 10 to 70ppm based on the weight of the polyester, wherein the catalyst is used in an amount based on the weight of the titanium element therein.
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