CN114479038A - Titanium catalyst and preparation method and application thereof - Google Patents
Titanium catalyst and preparation method and application thereof Download PDFInfo
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- CN114479038A CN114479038A CN202011144752.7A CN202011144752A CN114479038A CN 114479038 A CN114479038 A CN 114479038A CN 202011144752 A CN202011144752 A CN 202011144752A CN 114479038 A CN114479038 A CN 114479038A
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- titanium
- compound
- ammonium
- alkaline earth
- alkali metal
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 239000003054 catalyst Substances 0.000 title claims abstract description 97
- 239000010936 titanium Substances 0.000 title claims abstract description 82
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229920000728 polyester Polymers 0.000 claims abstract description 56
- 150000003609 titanium compounds Chemical class 0.000 claims abstract description 45
- 150000003868 ammonium compounds Chemical class 0.000 claims abstract description 30
- 150000001339 alkali metal compounds Chemical class 0.000 claims abstract description 29
- 150000001341 alkaline earth metal compounds Chemical class 0.000 claims abstract description 26
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 21
- -1 ammonium ions Chemical class 0.000 claims abstract description 20
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 19
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 19
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 18
- 239000002245 particle Substances 0.000 claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000012798 spherical particle Substances 0.000 claims abstract description 7
- 229920000139 polyethylene terephthalate Polymers 0.000 claims abstract description 6
- 239000005020 polyethylene terephthalate Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 129
- 238000003756 stirring Methods 0.000 claims description 29
- 238000010438 heat treatment Methods 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 15
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 12
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 11
- 150000007942 carboxylates Chemical class 0.000 claims description 9
- 239000001099 ammonium carbonate Substances 0.000 claims description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- 239000011591 potassium Substances 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 claims description 6
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 5
- 150000002009 diols Chemical class 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 4
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 4
- 239000000908 ammonium hydroxide Substances 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 3
- YSRSBDQINUMTIF-SNVBAGLBSA-N (2r)-decane-1,2-diol Chemical compound CCCCCCCC[C@@H](O)CO YSRSBDQINUMTIF-SNVBAGLBSA-N 0.000 claims description 3
- 229940043375 1,5-pentanediol Drugs 0.000 claims description 3
- RWLALWYNXFYRGW-UHFFFAOYSA-N 2-Ethyl-1,3-hexanediol Chemical compound CCCC(O)C(CC)CO RWLALWYNXFYRGW-UHFFFAOYSA-N 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- 150000001242 acetic acid derivatives Chemical class 0.000 claims description 3
- 229940097037 decylene glycol Drugs 0.000 claims description 3
- 229960005082 etohexadiol Drugs 0.000 claims description 3
- 229940051250 hexylene glycol Drugs 0.000 claims description 3
- 150000004679 hydroxides Chemical class 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- WCVRQHFDJLLWFE-UHFFFAOYSA-N pentane-1,2-diol Chemical compound CCCC(O)CO WCVRQHFDJLLWFE-UHFFFAOYSA-N 0.000 claims description 3
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims 1
- INSRQEMEVAMETL-UHFFFAOYSA-N decane-1,1-diol Chemical compound CCCCCCCCCC(O)O INSRQEMEVAMETL-UHFFFAOYSA-N 0.000 claims 1
- WDZVNNYQBQRJRX-UHFFFAOYSA-K gold(iii) hydroxide Chemical class O[Au](O)O WDZVNNYQBQRJRX-UHFFFAOYSA-K 0.000 claims 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 claims 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 claims 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 claims 1
- 239000012535 impurity Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- 229920005989 resin Polymers 0.000 abstract description 4
- 239000011347 resin Substances 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 83
- 238000006243 chemical reaction Methods 0.000 description 44
- 238000006116 polymerization reaction Methods 0.000 description 32
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 31
- 239000000843 powder Substances 0.000 description 31
- 239000007787 solid Substances 0.000 description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 29
- 238000005886 esterification reaction Methods 0.000 description 28
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 28
- 238000012360 testing method Methods 0.000 description 26
- 239000000047 product Substances 0.000 description 16
- 239000002002 slurry Substances 0.000 description 15
- 238000001816 cooling Methods 0.000 description 14
- 238000001035 drying Methods 0.000 description 14
- 230000032050 esterification Effects 0.000 description 14
- 238000011056 performance test Methods 0.000 description 14
- 125000004437 phosphorous atom Chemical group 0.000 description 14
- 239000002244 precipitate Substances 0.000 description 14
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 14
- 229940097364 magnesium acetate tetrahydrate Drugs 0.000 description 13
- XKPKPGCRSHFTKM-UHFFFAOYSA-L magnesium;diacetate;tetrahydrate Chemical compound O.O.O.O.[Mg+2].CC([O-])=O.CC([O-])=O XKPKPGCRSHFTKM-UHFFFAOYSA-L 0.000 description 13
- 238000001914 filtration Methods 0.000 description 12
- 238000005406 washing Methods 0.000 description 12
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 11
- 229940040526 anhydrous sodium acetate Drugs 0.000 description 11
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 229910052787 antimony Inorganic materials 0.000 description 5
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 229910052732 germanium Inorganic materials 0.000 description 4
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 4
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 3
- 239000001639 calcium acetate Substances 0.000 description 3
- 235000011092 calcium acetate Nutrition 0.000 description 3
- 229960005147 calcium acetate Drugs 0.000 description 3
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 2
- 239000005695 Ammonium acetate Substances 0.000 description 2
- 229940043376 ammonium acetate Drugs 0.000 description 2
- 235000019257 ammonium acetate Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 2
- 229940069446 magnesium acetate Drugs 0.000 description 2
- 239000011654 magnesium acetate Substances 0.000 description 2
- 235000011285 magnesium acetate Nutrition 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- SXSVTGQIXJXKJR-UHFFFAOYSA-N [Mg].[Ti] Chemical compound [Mg].[Ti] SXSVTGQIXJXKJR-UHFFFAOYSA-N 0.000 description 1
- 159000000021 acetate salts Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
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
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, 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
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 titanium catalyst and a preparation method and application thereof, wherein the catalyst contains (1) titanium element, (2) alkaline earth metal element, (3) alkali metal element and/or ammonium ions, and the catalyst is spherical particles of 50-500 nm. The preparation method comprises the following steps: mixing the titanium compound (1), the alkaline earth metal compound (2), the alkali metal compound and/or the ammonium compound (3) and the dihydric alcohol (4), and reacting to obtain the titanium catalyst. By adopting the technical scheme of the invention, the obtained titanium polyester catalyst has small particle size, and has the advantages of high activity, good hue, low particle impurity content and the like when being used for preparing polyethylene terephthalate resin.
Description
Technical Field
The invention belongs to the field of catalysts, and particularly relates to a titanium catalyst, in particular to a titanium catalyst for polyester.
Background
Polyethylene terephthalate (PET) is a thermoplastic polyester obtained by polycondensation of Purified Terephthalic Acid (PTA) and Ethylene Glycol (EG). The resin has the characteristics of excellent mechanical properties (high strength, rigidity, toughness, impact resistance and the like), electrical properties, good dimensional stability and the like, so that the resin is widely applied to the fields of various polyester fibers, packaging, electronic and electric appliances, medical sanitation, buildings, automobiles, machinery and the like.
In the polyester preparation process, the catalyst has very important influence on the quality of products such as hue, stability, viscosity and the like. At present, most of the research at home and abroad uses antimony, germanium, titanium and other series catalysts. Wherein, the antimony catalyst is the most commonly used and occupies more than 90 percent of the polyester catalyst market. However, antimony is a heavy metal, and may adversely affect human bodies and the environment during use, so that the application thereof is increasingly restricted. The germanium catalyst has mild performance and less side reaction, and the obtained polyester has remarkable transparency, but the germanium resource is less, the price is high, and the germanium catalyst is only suitable for high-grade polyester products.
In recent years, titanium catalysts, which are the most promising environmentally friendly catalysts to replace antimony catalysts, have the characteristics of high catalytic activity and no harm to human bodies and the environment, and have been the subject of controversial research and application in the polyester industry. However, since titanium has many side reactions, a polyester obtained by using only titanium as a catalyst tends to have problems such as yellow hue and poor thermal stability. Therefore, in the development of titanium-based catalysts, other metal promoters such as alkali metals, alkaline earth metals, aluminum, silicon, zirconium, manganese, rare earth, etc. are commonly used in combination. For example, patent [ US 6667383] proposes that a polyester resin having excellent properties is prepared by sequentially adding ethylene glycol solutions of titanium, magnesium and phosphorus compounds to a polymerization vessel at the polycondensation stage. However, the method of adding titanium catalyst in batches requires modification of equipment, additional catalyst adding equipment and corresponding investment when the titanium catalyst is used in the antimony polyester device. Chinese patent CN102127215A developed a liquid titanium-based catalyst comprising an organic chelated titanium complex, a magnesium compound and a phosphorus compound. However, this technique uses organic acid ligands, which can be polymerized into the backbone as new impurities during the polymerization process or can be released into the recycle glycol by vacuum, thereby affecting the quality of the polyester and recycle glycol. Chinese patent CN101389688A reports a solid titanium catalyst using magnesium hydroxide as the inner coating layer and titanic acid as the outer layer. However, this technique has a problem that the catalyst preparation step is complicated. If the process needs to be carried out in advance through steps of hydrolysis, filtration, washing and the like to prepare magnesium hydroxide water slurry, and then the steps are further repeated to attach titanic acid and the solid titanium catalyst is obtained after drying. Patent US 2006/0084784 Al discloses a titanium magnesium ethylene glycol hexagonal crystal compound as a titanium catalyst. However, the authors found that the titanium magnesium glycol compound is susceptible to the formation of large (on the order of tens of microns) crystals during the preparation process, and that the crystal material may become or induce the formation of large particulate impurities that affect the quality of the polyester.
In order to solve the problems, the invention effectively reduces the particle size of the titanium-magnesium glycol compound by adding a small amount of alkali metal or ammonium ions in the process of preparing the titanium-magnesium glycol compound, wherein the particle size is about 0.1-0.3 mu m. The polyester obtained by using the catalyst has better quality, and meanwhile, no large particles exist in the slices, so that better technical effects are obtained.
Disclosure of Invention
One of the technical problems to be solved by the invention is the particle impurity problem in the polyester chip caused by the oversize of the titanium catalyst (or titanium magnesium glycol crystal compound) in the prior art. The titanium polyester catalyst is solid powder type, has the size of 50-500 nm, and has the characteristics of high activity, good polyester color phase, low particle impurity content and the like when being used for polyester catalysis.
An object of the present invention is to provide a titanium-based catalyst containing (1) a titanium element, (2) an alkaline earth metal element, and (3) an alkali metal element and/or ammonium ion, wherein the catalyst is in the form of spherical particles of 50 to 500nm, preferably 100 to 300 nm.
Wherein the catalyst is in the form of spherical particles of nanometer scale. During the drying process, the spherical nanoparticles are agglomerated to form a micron-shaped agglomerate, as shown in fig. 1. However, this is a common phenomenon during nanoparticle drying and does not affect the performance of the catalyst, as can be seen from the polymerization data.
In a preferred embodiment, the molar ratio of the alkali metal element and/or ammonium ion to the titanium element in the titanium-based catalyst is (0.1 to 1):1, preferably (0.1 to 0.8): 1.
In a preferred embodiment, the molar ratio of the alkaline earth metal element to the titanium element is (0.5-10):1, preferably (0.6-8): 1.
In a preferred embodiment, the titanium-based catalyst comprises: (1) a titanium compound, (2) an alkaline earth metal compound, (3) an alkali metal compound and/or an ammonium compound, and (4) optionally a dihydric alcohol.
In a preferred embodiment, the titanium compound is a titanium compound having Ti (OR)4A compound of formula (la) wherein R is selected from C1～C10Straight chain alkyl group of (1), C1～C10Branched alkyl or C1～C10Aryl group of (1).
In a further preferred embodiment, the titanium compound is selected from C1～C6Straight chain alkyl or C1～C6Branched alkyl groups such as butyl, isopropyl.
In a preferred embodiment, the alkaline earth metal compound is selected from the group consisting of carbonates, bicarbonates or C of alkaline earth metals2～C4At least one of the carboxylates, preferably an acetate of an alkaline earth metal.
In a further preferred embodiment, the alkaline earth metal compound is selected from magnesium acetate and/or calcium acetate.
In a preferred embodiment, the alkali metal compound and/or ammonium compound is selected from the group consisting of salts or bases of alkali metals and/or ammonium.
In a further preferred embodiment, the alkali metal compound is selected from the group consisting of hydroxides, carbonates, bicarbonates and C of alkali metals2～C4At least one carboxylate, wherein the alkali metal is at least one selected from lithium, sodium and potassium; the ammonium compound is selected from the group consisting of ammonium hydroxide, carbonate, bicarbonate or C2～C4A carboxylate salt.
In a further preferred embodiment, the alkali metal compound and/or ammonium compound is selected from acetates of at least one of lithium, sodium, potassium, ammonium.
Among them, the inventors have found, after a lot of experiments, that the particle size of the catalyst can be effectively controlled by introducing an appropriate amount of alkali metal and/or ammonium in the preparation process of the titanium-magnesium glycol compound, and the obtained solid catalyst can reduce the content of impurity particles in the polyester while maintaining the good performance of the catalyst when used for polymerization.
In a preferred embodiment, the diol is selected from at least one of ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, octylene glycol, and decylene glycol.
In a further preferred embodiment, the glycol is ethylene glycol.
In a preferred embodiment, the molar ratio of the alkaline earth metal compound to the titanium compound is (0.5-10):1, wherein the molar amount of the titanium compound is based on the molar amount of the titanium element therein and the alkaline earth metal compound is based on the molecular molar amount thereof.
In a further preferred embodiment, the molar ratio of the alkaline earth metal compound to the titanium compound is (0.6-8):1, wherein the molar amount of the titanium compound is based on the molar amount of the titanium element therein and the molar amount of the alkaline earth metal compound is based on the molar amount of the alkaline earth metal element therein.
Wherein the molar ratio of the alkaline earth metal compound to the titanium compound may be 0.6:1, 0.8:1, 1:1, 1.5:1, 2:1, 3:1, 4:1, 5:1, 6:1, 8: 1.
After a lot of experiments, the inventor finds that the content of alkaline earth metal directly affects the color of polyester, and specifically, when the content of alkaline earth metal is too high or too low, the content of alkaline earth metal leads to a higher b value, and when the content of alkaline earth metal is higher, the content of alkaline earth metal leads to a lower L value.
In a preferred embodiment, the molar ratio of the alkali metal compound and/or ammonium compound to the titanium compound is (0.1-1):1, wherein the molar amount of the titanium compound is based on the molar amount of the titanium element therein, and the alkali metal compound and/or ammonium compound is based on the molecular molar amount thereof.
In a further preferred embodiment, the molar ratio of the alkali metal compound and/or ammonium compound to the titanium compound is (0.1-0.8):1, wherein the molar amount of the titanium compound is based on the molar amount of the titanium element therein and the alkali metal compound and/or ammonium compound is based on the molar amount of the alkali metal element and/or ammonium therein.
Wherein the molar ratio of the alkali metal compound and/or the ammonium compound to the titanium compound may be 0.1:1, 0.2:1, 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 1: 1.
In a preferred embodiment, the molar ratio of the dihydric alcohol to the titanium compound is (1-100): 1.
In a further preferred embodiment, the molar ratio of the diol to the titanium compound is (2-80): 1.
Another object of the present invention is to provide a method for preparing the titanium-based catalyst, which comprises: mixing (1) a titanium compound, (2) an alkaline earth metal compound, (3) an alkali metal compound and/or an ammonium compound with (4) dihydric alcohol, and reacting to obtain the titanium catalyst.
In a preferred embodiment, the preparation method comprises the following steps:
step 1, mixing the dihydric alcohol and the titanium compound to obtain a mixed solution I;
step 2, adding the alkaline earth metal compound and the alkali metal compound and/or the ammonium compound into the mixed solution I to obtain a mixed solution II;
and 3, heating and stirring the mixed solution II to obtain the titanium catalyst.
In a preferred embodiment, in step 1, the titanium compound is dropped into the ethylene glycol, and after completion of the dropping, the mixture is stirred to obtain a first white turbid mixed solution.
In a further preferred embodiment, in step 1, the molar ratio of the diol to the titanium compound is (1-100): 1, preferably (2-80): 1.
In a preferred embodiment, in step 1, the diol is at least one selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, octylene glycol, and decylene glycol, preferably ethylene glycol.
In a preferred embodiment, in step 1, the titanium compound is a compound having Ti (OR)4A compound of formula (la) wherein R is selected from C1～C10Straight chain alkyl group of (1), C1～C10Branched alkyl or C1～C10Preferably, the titanium compound is selected from C1～C6Straight chain alkyl or C1～C6Branched alkyl groups such as butyl, isopropyl.
In a preferred embodiment, in step 2, the mixture is stirred to obtain the second mixed solution.
In a preferred embodiment, in step 2, the alkaline earth metal compound is selected from the group consisting of alkaline earth metal carbonates, bicarbonates or C2～C4At least one of carboxylate salts.
In a further preferred embodiment, in step 2, the alkaline earth metal compound is selected from acetates of alkaline earth metals, preferably from magnesium acetate and/or calcium acetate.
In a preferred embodiment, in step 2, the alkali metal compound and/or ammonium compound is selected from the group consisting of salts or bases of alkali metals and/or ammonium.
In a further preferred embodiment, in step 2, the alkali metal compound is selected from the group consisting of hydroxides, carbonates, bicarbonates and C of alkali metals2～C4At least one carboxylate, wherein the alkali metal is at least one selected from lithium, sodium and potassium; the ammonium compound is selected from the group consisting of ammonium hydroxide, carbonate, bicarbonate or C2～C4A carboxylate salt.
In a further preferred embodiment, in step 2, the alkali metal compound and/or ammonium compound is selected from at least one acetate salt of lithium, sodium, potassium, ammonium.
In a preferred embodiment, in step 2, the molar ratio of the alkaline earth metal compound to the titanium compound is (0.5-10) to 1, preferably (0.6-8) to 1; wherein the molar amount of the titanium compound is based on the molar amount of the titanium element therein, and the molar amount of the alkaline earth metal compound is based on the molecular molar amount thereof.
In a preferred embodiment, in step 2, the molar ratio of the alkali metal compound and/or ammonium compound to the titanium compound is (0.1-1):1, preferably (0.1-0.8):1, wherein the molar amount of the titanium compound is based on the molar amount of the titanium element therein and the alkali metal compound and/or ammonium compound is based on the molecular molar amount thereof.
In a preferred embodiment, in step 3, the temperature is raised to 50-200 ℃ and the stirring is carried out for 0.2-24 h.
In a further preferred embodiment, in step 3, the temperature is raised to 80-150 ℃ and stirring is carried out for 1-10 h.
In a preferred embodiment, the titanium-based catalyst is obtained by post-treatment after the reaction of step 3.
In a more preferred embodiment, the titanium-based catalyst is obtained by filtering, washing and drying after the reaction in step 3.
The use of an organic chelating agent such as hydroxycarboxylic acid is not involved in the preparation of the titanium-based catalyst of the present invention. The organic chelating agent adopted in the prior art is usually a micromolecule without benzene ring, has low decomposition temperature, is easy to polymerize into the polyester main chain, and further reduces the thermal stability of the polyester.
The third object of the present invention is to provide a titanium-based catalyst obtained by the second object of the present invention. Spherical particles with the particle size of 50-500 nm, preferably 100-300 nm
The fourth object of the present invention is to provide the use of the titanium-based catalyst for polyester production, which is one of the objects of the present invention or three of the objects of the present invention. Preferably in the preparation of polyethylene terephthalate.
The endpoints of the ranges and any values disclosed in the present application are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein. In the following, various technical solutions can in principle be combined with each other to obtain new technical solutions, which should also be regarded as specifically disclosed herein.
Compared with the prior art, the invention has the following beneficial effects: by adopting the technical scheme of the invention, the obtained titanium polyester catalyst has the advantages of small particle size, high activity, good hue, low particle impurity content and the like when being used for preparing polyethylene terephthalate resin, and particularly, the obtained polyester has higher intrinsic viscosity, high L value and low b value, and better technical effect is obtained.
Drawings
FIG. 1 shows the morphology of the catalyst powder obtained in example 1;
FIG. 2 shows the morphology of the catalyst powder obtained in comparative example 3.
Detailed Description
While the present invention will be described in detail with reference to the following examples, it should be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the present invention.
It is to be further understood that the various features described in the following detailed description may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention can be made, as long as the technical solution formed by the combination does not depart from the idea of the present invention, and the technical solution formed by the combination is part of the original disclosure of the present specification, and also falls into the protection scope of the present invention.
The raw materials used in the examples and comparative examples are disclosed in the prior art if not particularly limited, and may be, for example, directly purchased or prepared according to the preparation methods disclosed in the prior art.
In the present invention, the intrinsic viscosity, hue, etc. of the polyester are measured by the following methods:
(1) intrinsic viscosity: the phenol-tetrachloroethane mixture is used as a solvent, and is measured by an Ubbelohde viscometer at the temperature of 25 ℃.
(2) Hue: the pellet samples were measured for Hunter L value (lightness), a value (red-green hue) and b value (yellow-blue hue) using a color-view automatic color difference meter of BYK Gardner after being treated at 135 ℃ for 1 hour. Wherein, the higher the L value, the larger the brightness; when the value of b is high, the polyester chip is yellowish. For the present invention, a high L value and a low b value are desired.
(3) Agglomeration of particles: randomly taking 5 slices from the specimen, each slice being cut with a microtome to 5-8 slices with a thickness of 20 μm, so that the total mass of the slices reaches 3-5mg, to an accuracy of 0.1mg, placing the slices on clean glass slides and wetting them well with oil by means of a microscope, covering the slides with cover slips, placing under a microscope for observation, and counting agglomerated particles with a size greater than or equal to 5 μm (measured as the longest part of the particle).
[ example 1 ]
In a 100mL three-necked flask equipped with a stirrer, a condenser and a thermometer, 40g of ethylene glycol was charged, 2.84g of tetraisopropyl titanate was slowly dropped into the three-necked flask, and the mixture was stirred for several hours to obtain a white turbid solution. And then adding 2.14g of magnesium acetate tetrahydrate and 0.16g of anhydrous sodium acetate into the solution, stirring for about 0.5h to obtain a clear and transparent solution, and heating to 80 ℃. Stirring for about 3 hours gave a white precipitate. And filtering the solution, washing the solution with water, and drying the solution to obtain a solid powder type titanium catalyst, wherein the content of titanium in the solid powder is 20.3 wt% by ICP test. The powder microstructure is shown in FIG. 1.
500g of terephthalic acid, 316g of ethylene glycol, the catalyst (based on the amount of polyester formed, the weight of titanium atoms is 5ppm) and trimethyl phosphate (based on the amount of polyester formed, the weight of phosphorus atoms is 20ppm) were mixed to prepare a slurry, which was added to a polymerization vessel to carry out an esterification reaction at a temperature of 230 ℃ and 250 ℃ and a pressure of 0.25MPa, and the water produced by the reaction was discharged through a rectifying apparatus. And after the esterification is finished, reducing the pressure to normal pressure, vacuumizing and reducing the pressure until the system pressure is lower than 130Pa, simultaneously gradually heating to 280 ℃, stopping the reaction when the system reaction reaches 150min, and then extruding, cooling and granulating the product from the bottom of the polymerization kettle for performance test.
The test results are shown in Table 1.
[ example 2 ]
In a 100mL three-necked flask equipped with a stirrer, a condenser and a thermometer, 40g of ethylene glycol was charged, 2.84g of tetraisopropyl titanate was slowly dropped into the three-necked flask, and the mixture was stirred for several hours to obtain a white turbid solution. Adding 1.07g of magnesium acetate tetrahydrate and 0.16g of anhydrous sodium acetate into the solution, stirring for about 0.5h to obtain a clear and transparent solution, and heating to 80 ℃. Stirring for about 3 hours gave a white precipitate. And filtering the solution, washing the solution with water, and drying the solution to obtain a solid powder type titanium catalyst, wherein the content of titanium in the solid powder is 22.5 wt% by ICP test.
500g of terephthalic acid, 316g of ethylene glycol, the catalyst (5 ppm by weight of titanium atom based on the amount of polyester produced), and trimethyl phosphate (20 ppm by weight of phosphorus atom based on the amount of polyester produced) were mixed to prepare a slurry, which was fed into a polymerization vessel to conduct an esterification reaction at a temperature of 230 ℃ and 250 ℃ and a pressure of 0.25MPa, and the water produced by the reaction was discharged through a rectification apparatus. And after the esterification is finished, reducing the pressure to normal pressure, vacuumizing and reducing the pressure until the system pressure is lower than 130Pa, simultaneously gradually heating to 280 ℃, stopping the reaction when the system reaction reaches 150min, and then extruding, cooling and granulating the product from the bottom of the polymerization kettle for performance test.
The test results are shown in Table 1.
[ example 3]
In a 100mL three-necked flask equipped with a stirrer, a condenser and a thermometer, 40g of ethylene glycol was charged, 2.84g of tetraisopropyl titanate was slowly dropped into the three-necked flask, and the mixture was stirred for several hours to obtain a white turbid solution. And then adding 5.35g of magnesium acetate tetrahydrate and 0.16g of anhydrous sodium acetate into the solution, stirring for about 0.5h to obtain a clear and transparent solution, and heating to 80 ℃. Stirring for about 3 hours gave a white precipitate. And filtering the solution, washing the solution with water, and drying the solution to obtain a solid powder type titanium catalyst, wherein the content of titanium in the solid powder is 18.2 wt% by ICP test.
500g of terephthalic acid, 316g of ethylene glycol, the catalyst (based on the amount of polyester formed, the weight of titanium atoms is 5ppm) and trimethyl phosphate (based on the amount of polyester formed, the weight of phosphorus atoms is 20ppm) were mixed to prepare a slurry, which was added to a polymerization vessel to carry out an esterification reaction at a temperature of 230 ℃ and 250 ℃ and a pressure of 0.25MPa, and the water produced by the reaction was discharged through a rectifying apparatus. And after the esterification is finished, reducing the pressure to normal pressure, vacuumizing and reducing the pressure until the system pressure is lower than 130Pa, simultaneously gradually heating to 280 ℃, stopping the reaction when the system reaction reaches 150min, and then extruding, cooling and granulating the product from the bottom of the polymerization kettle for performance test.
The test results are shown in Table 1.
[ example 4 ]
In a 100mL three-necked flask equipped with a stirrer, a condenser and a thermometer, 40g of ethylene glycol was charged, 2.84g of tetraisopropyl titanate was slowly dropped into the three-necked flask, and the mixture was stirred for several hours to obtain a white turbid solution. And then 10.7g of magnesium acetate tetrahydrate and 0.16g of anhydrous sodium acetate are added into the solution, the solution is stirred for about 0.5h to obtain a clear and transparent solution, and the temperature is raised to 80 ℃. Stirring for about 3 hours gave a white precipitate. And filtering the solution, washing the solution with water, and drying the solution to obtain a solid powder type titanium catalyst, wherein the content of titanium in the solid powder is 16.1 wt% by ICP test.
500g of terephthalic acid, 316g of ethylene glycol, the catalyst (based on the amount of polyester formed, the weight of titanium atoms is 5ppm) and trimethyl phosphate (based on the amount of polyester formed, the weight of phosphorus atoms is 20ppm) were mixed to prepare a slurry, which was added to a polymerization vessel to carry out an esterification reaction at a temperature of 230 ℃ and 250 ℃ and a pressure of 0.25MPa, and the water produced by the reaction was discharged through a rectifying apparatus. And after the esterification is finished, reducing the pressure to normal pressure, vacuumizing and reducing the pressure until the system pressure is lower than 130Pa, simultaneously gradually heating to 280 ℃, stopping the reaction when the system reaction reaches 150min, and then extruding, cooling and granulating the product from the bottom of the polymerization kettle for performance test.
The test results are shown in Table 1.
[ example 5 ]
In a 100mL three-necked flask equipped with a stirrer, a condenser and a thermometer, 40g of ethylene glycol was charged, 2.84g of tetraisopropyl titanate was slowly dropped into the three-necked flask, and the mixture was stirred for several hours to obtain a white turbid solution. And then adding 17.12g of magnesium acetate tetrahydrate and 0.16g of anhydrous sodium acetate into the solution, stirring for about 0.5h to obtain a clear and transparent solution, and heating to 80 ℃. Stirring for about 3 hours gave a white precipitate. The solution was filtered, washed with water, and dried to obtain a solid powder type titanium catalyst, and the titanium content in the solid powder was 14.6 wt% by ICP test.
500g of terephthalic acid, 316g of ethylene glycol, the catalyst (based on the amount of polyester formed, the weight of titanium atoms is 5ppm) and trimethyl phosphate (based on the amount of polyester formed, the weight of phosphorus atoms is 20ppm) were mixed to prepare a slurry, which was added to a polymerization vessel to carry out an esterification reaction at a temperature of 230 ℃ and 250 ℃ and a pressure of 0.25MPa, and the water produced by the reaction was discharged through a rectifying apparatus. And after the esterification is finished, reducing the pressure to normal pressure, vacuumizing and reducing the pressure until the system pressure is lower than 130Pa, simultaneously gradually heating to 280 ℃, stopping the reaction when the system reaction reaches 150min, and then extruding, cooling and granulating the product from the bottom of the polymerization kettle for performance test.
The test results are shown in Table 1.
[ example 6 ]
In a 100mL three-necked flask equipped with a stirrer, a condenser and a thermometer, 40g of ethylene glycol was charged, 2.84g of tetraisopropyl titanate was slowly dropped into the three-necked flask, and the mixture was stirred for several hours to obtain a white turbid solution. And adding 1.58g of anhydrous calcium acetate and 0.16g of anhydrous sodium acetate into the solution, stirring for about 0.5h to obtain a clear and transparent solution, and heating to 80 ℃. Stirring for about 3 hours gave a white precipitate. And filtering the solution, washing the solution with water, and drying the solution to obtain a solid powder type titanium catalyst, wherein the content of titanium in the solid powder is 20.5 wt% by ICP test.
500g of terephthalic acid, 316g of ethylene glycol, the catalyst (based on the amount of polyester formed, the weight of titanium atoms is 5ppm) and trimethyl phosphate (based on the amount of polyester formed, the weight of phosphorus atoms is 20ppm) were mixed to prepare a slurry, which was added to a polymerization vessel to carry out an esterification reaction at a temperature of 230 ℃ and 250 ℃ and a pressure of 0.25MPa, and the water produced by the reaction was discharged through a rectifying apparatus. And after the esterification is finished, reducing the pressure to normal pressure, vacuumizing and reducing the pressure until the system pressure is lower than 130Pa, simultaneously gradually heating to 280 ℃, stopping the reaction when the system reaction reaches 150min, and then extruding, cooling and granulating the product from the bottom of the polymerization kettle for performance test.
The test results are shown in Table 1.
[ example 7 ]
In a 100mL three-necked flask equipped with a stirrer, a condenser and a thermometer, 40g of ethylene glycol was charged, 2.84g of tetraisopropyl titanate was slowly dropped into the three-necked flask, and the mixture was stirred for several hours to obtain a white turbid solution. And then adding 2.14g of magnesium acetate tetrahydrate and 0.19g of potassium acetate into the solution, stirring for about 0.5h to obtain a clear and transparent solution, and heating to 80 ℃. Stirring for about 3 hours gave a white precipitate. And filtering the solution, washing the solution with water, and drying the solution to obtain a solid powder type titanium catalyst, wherein the content of titanium in the solid powder is 20.2 wt% by ICP test.
500g of terephthalic acid, 316g of ethylene glycol, the catalyst (based on the amount of polyester formed, the weight of titanium atoms is 5ppm) and trimethyl phosphate (based on the amount of polyester formed, the weight of phosphorus atoms is 20ppm) were mixed to prepare a slurry, which was added to a polymerization vessel to carry out an esterification reaction at a temperature of 230 ℃ and 250 ℃ and a pressure of 0.25MPa, and the water produced by the reaction was discharged through a rectifying apparatus. And after the esterification is finished, reducing the pressure to normal pressure, vacuumizing and reducing the pressure until the system pressure is lower than 130Pa, simultaneously gradually heating to 280 ℃, stopping the reaction when the system reaction reaches 150min, and then extruding, cooling and granulating the product from the bottom of the polymerization kettle for performance test.
The test results are shown in Table 1.
[ example 8 ]
In a 100mL three-necked flask equipped with a stirrer, a condenser and a thermometer, 40g of ethylene glycol was charged, 2.84g of tetraisopropyl titanate was slowly dropped into the three-necked flask, and the mixture was stirred for several hours to obtain a white turbid solution. And then adding 2.14g of magnesium acetate tetrahydrate and 0.15g of ammonium acetate into the solution, stirring for about 0.5h to obtain a clear and transparent solution, and heating to 80 ℃. Stirring for about 3 hours gave a white precipitate. And filtering the solution, washing the solution with water, and drying the solution to obtain a solid powder type titanium catalyst, wherein the content of titanium in the solid powder is 20.4 wt% by ICP test.
500g of terephthalic acid, 316g of ethylene glycol, the catalyst (based on the amount of polyester formed, the weight of titanium atoms is 5ppm) and trimethyl phosphate (based on the amount of polyester formed, the weight of phosphorus atoms is 20ppm) were mixed to prepare a slurry, which was added to a polymerization vessel to carry out an esterification reaction at a temperature of 230 ℃ and 250 ℃ and a pressure of 0.25MPa, and the water produced by the reaction was discharged through a rectifying apparatus. And after the esterification is finished, reducing the pressure to normal pressure, vacuumizing and reducing the pressure until the system pressure is lower than 130Pa, simultaneously gradually heating to 280 ℃, stopping the reaction when the system reaction reaches 150min, and then extruding, cooling and granulating the product from the bottom of the polymerization kettle for performance test.
The test results are shown in Table 1.
[ example 9 ]
40g of ethylene glycol was put into a 100mL three-necked flask equipped with a stirrer, a condenser and a thermometer, 2.84g of tetraisopropyl titanate was slowly dropped into the three-necked flask, and stirred for several hours to obtain a white turbid solution. And then adding 2.14g of magnesium acetate tetrahydrate and 0.32g of anhydrous sodium acetate into the solution, stirring for about 0.5h to obtain a clear and transparent solution, and heating to 80 ℃. Stirring for about 3 hours gave a white precipitate. And filtering the solution, washing the solution with water, and drying the solution to obtain a solid powder type titanium catalyst, wherein the content of titanium in the solid powder is 20.1 wt% by ICP test.
500g of terephthalic acid, 316g of ethylene glycol, the catalyst (based on the amount of polyester formed, the weight of titanium atoms is 5ppm) and trimethyl phosphate (based on the amount of polyester formed, the weight of phosphorus atoms is 20ppm) were mixed to prepare a slurry, which was added to a polymerization vessel to carry out an esterification reaction at a temperature of 230 ℃ and 250 ℃ and a pressure of 0.25MPa, and the water produced by the reaction was discharged through a rectifying apparatus. And after the esterification is finished, reducing the pressure to normal pressure, vacuumizing and reducing the pressure until the system pressure is lower than 130Pa, simultaneously gradually heating to 280 ℃, stopping the reaction when the system reaction reaches 150min, and then extruding, cooling and granulating the product from the bottom of the polymerization kettle for performance test. The test results are shown in Table 1.
[ example 10 ]
In a 100mL three-necked flask equipped with a stirrer, a condenser and a thermometer, 40g of ethylene glycol was charged, 2.84g of tetraisopropyl titanate was slowly dropped into the three-necked flask, and the mixture was stirred for several hours to obtain a white turbid solution. And then adding 2.14g of magnesium acetate tetrahydrate and 0.48g of anhydrous sodium acetate into the solution, stirring for about 0.5h to obtain a clear and transparent solution, and heating to 80 ℃. Stirring for about 3 hours gave a white precipitate. The solution was filtered, washed with water, and dried to obtain a solid powder type titanium catalyst having a titanium content of 19.8 wt% as measured by ICP.
500g of terephthalic acid, 316g of ethylene glycol, the catalyst (based on the amount of polyester formed, the weight of titanium atoms is 5ppm) and trimethyl phosphate (based on the amount of polyester formed, the weight of phosphorus atoms is 20ppm) were mixed to prepare a slurry, which was added to a polymerization vessel to carry out an esterification reaction at a temperature of 230 ℃ and 250 ℃ and a pressure of 0.25MPa, and the water produced by the reaction was discharged through a rectifying apparatus. And after the esterification is finished, reducing the pressure to normal pressure, vacuumizing and reducing the pressure until the system pressure is lower than 130Pa, simultaneously gradually heating to 280 ℃, stopping the reaction when the system reaction reaches 150min, and then extruding, cooling and granulating the product from the bottom of the polymerization kettle for performance test. The test results are shown in Table 1.
Comparative example 1
In a 100mL three-necked flask equipped with a stirrer, a condenser and a thermometer, 40g of ethylene glycol was charged, 2.84g of tetraisopropyl titanate was slowly dropped into the three-necked flask, and the mixture was stirred for several hours to obtain a white turbid solution. And then 0.43g of magnesium acetate tetrahydrate and 0.16g of anhydrous sodium acetate are added into the solution, the mixture is stirred for about 0.5h to obtain a clear and transparent solution, and the temperature is raised to 80 ℃. Stirring for about 3 hours gave a white precipitate. The solution was filtered, washed with water, and dried to obtain a solid powder type titanium catalyst, and the titanium content in the solid powder was 23.0 wt% by ICP test.
500g of terephthalic acid, 316g of ethylene glycol, the catalyst (based on the amount of polyester formed, the weight of titanium atoms is 5ppm) and trimethyl phosphate (based on the amount of polyester formed, the weight of phosphorus atoms is 20ppm) were mixed to prepare a slurry, which was added to a polymerization vessel to carry out an esterification reaction at a temperature of 230 ℃ and 250 ℃ and a pressure of 0.25MPa, and the water produced by the reaction was discharged through a rectifying apparatus. And after the esterification is finished, reducing the pressure to normal pressure, vacuumizing and reducing the pressure until the system pressure is lower than 130Pa, simultaneously gradually heating to 280 ℃, stopping the reaction when the system reaction reaches 150min, and then extruding, cooling and granulating the product from the bottom of the polymerization kettle for performance test.
The test results are shown in Table 1.
Comparative example 2
In a 100mL three-necked flask equipped with a stirrer, a condenser and a thermometer, 40g of ethylene glycol was charged, 2.84g of tetraisopropyl titanate was slowly dropped into the three-necked flask, and the mixture was stirred for several hours to obtain a white turbid solution. And then 32.2g of magnesium acetate tetrahydrate and 0.16g of anhydrous sodium acetate are added into the solution, the mixture is stirred for about 0.5h to obtain a semitransparent solution, and the temperature is raised to 80 ℃. Stirring for about 3 hours gave a white precipitate. And filtering the solution, washing the solution with water, and drying the solution to obtain a solid powder type titanium catalyst, wherein the content of titanium in the solid powder is 12.1 wt% by ICP test.
500g of terephthalic acid, 316g of ethylene glycol, the catalyst (based on the amount of polyester formed, the weight of titanium atoms is 5ppm) and trimethyl phosphate (based on the amount of polyester formed, the weight of phosphorus atoms is 20ppm) were mixed to prepare a slurry, which was added to a polymerization vessel to carry out an esterification reaction at a temperature of 230 ℃ and 250 ℃ and a pressure of 0.25MPa, and the water produced by the reaction was discharged through a rectifying apparatus. And after the esterification is finished, reducing the pressure to normal pressure, vacuumizing and reducing the pressure until the system pressure is lower than 130Pa, simultaneously gradually heating to 280 ℃, stopping the reaction when the system reaction reaches 150min, and then extruding, cooling and granulating the product from the bottom of the polymerization kettle for performance test.
The test results are shown in Table 1.
Comparative example 3
In a 100mL three-necked flask equipped with a stirrer, a condenser and a thermometer, 40g of ethylene glycol was charged, 2.84g of tetraisopropyl titanate was slowly dropped into the three-necked flask, and the mixture was stirred for several hours to obtain a white turbid solution. And then adding 2.14g of magnesium acetate tetrahydrate into the solution, stirring for about 0.5h to obtain a clear and transparent solution, and heating to 80 ℃. Stirring for about 3 hours gave a white precipitate. And filtering the solution, washing the solution with water, and drying the solution to obtain a solid powder type titanium catalyst, wherein the content of titanium in the solid powder is 20.5 wt% by ICP test. The powder micro-morphology is shown in fig. 2.
500g of terephthalic acid, 316g of ethylene glycol, the catalyst (based on the amount of polyester formed, the weight of titanium atoms is 5ppm) and trimethyl phosphate (based on the amount of polyester formed, the weight of phosphorus atoms is 20ppm) were mixed to prepare a slurry, which was added to a polymerization vessel to carry out an esterification reaction at a temperature of 230 ℃ and 250 ℃ and a pressure of 0.25MPa, and the water produced by the reaction was discharged through a rectifying apparatus. And after the esterification is finished, reducing the pressure to normal pressure, vacuumizing and reducing the pressure until the system pressure is lower than 130Pa, simultaneously gradually heating to 280 ℃, stopping the reaction when the system reaction reaches 150min, and then extruding, cooling and granulating the product from the bottom of the polymerization kettle for performance test.
The test results are shown in Table 1.
Comparative example 4
In a 100mL three-necked flask equipped with a stirrer, a condenser and a thermometer, 40g of ethylene glycol was charged, 2.84g of tetraisopropyl titanate was slowly dropped into the three-necked flask, and the mixture was stirred for several hours to obtain a white turbid solution. And then adding 2.14g of magnesium acetate tetrahydrate and 1.64g of anhydrous sodium acetate into the solution, stirring for about 0.5h to obtain a clear and transparent solution, and heating to 80 ℃. Stirring for about 3 hours gave a white precipitate. The solution was filtered, washed with water, and dried to obtain a solid powder type titanium catalyst having a titanium content of 19.2 wt% as measured by ICP.
500g of terephthalic acid, 316g of ethylene glycol, the catalyst (based on the amount of polyester formed, the weight of titanium atoms is 5ppm) and trimethyl phosphate (based on the amount of polyester formed, the weight of phosphorus atoms is 20ppm) were mixed to prepare a slurry, which was added to a polymerization vessel to carry out an esterification reaction at a temperature of 230 ℃ and 250 ℃ and a pressure of 0.25MPa, and the water produced by the reaction was discharged through a rectifying apparatus. And after the esterification is finished, reducing the pressure to normal pressure, vacuumizing and reducing the pressure until the system pressure is lower than 130Pa, simultaneously gradually heating to 280 ℃, stopping the reaction when the system reaction reaches 150min, and then extruding, cooling and granulating the product from the bottom of the polymerization kettle for performance test.
The test results are shown in Table 1.
Comparative example 5
Example 8 was repeated except that ammonium acetate was used in an amount of 1.5 g.
TABLE 1
The invention has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to be construed in a limiting sense. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, which fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (14)
1. A titanium catalyst contains (1) titanium element, (2) alkaline earth metal element, (3) alkali metal element and/or ammonium ion, wherein the catalyst is spherical particles of 50-500 nm.
2. The titanium-based catalyst according to claim 1,
the catalyst is spherical particles with the particle size of 100-300 nm; and/or
In the titanium-based catalyst, the molar ratio of the alkali metal element and/or ammonium ion to the titanium element is (0.1-1) to 1, preferably (0.1-0.8) to 1; and/or
In the titanium-based catalyst, the molar ratio of the alkaline earth metal element to the titanium element is (0.5 to 10):1, preferably (0.6 to 8): 1.
3. The titanium-based catalyst according to claim 1, characterized in that the titanium-based catalyst comprises: (1) a titanium compound, (2) an alkaline earth metal compound, (3) an alkali metal compound and/or an ammonium compound, and (4) optionally a dihydric alcohol.
4. The titanium-based catalyst according to claim 1,
the titanium compound is Ti (OR)4A compound of formula (la) wherein R is selected from C1～C10Straight chain alkyl group of (1), C1～C10Branched alkyl or C1～C10Preferably, the titanium compound is selected from C1～C6Straight chain alkyl or C1～C6A branched alkyl group of (a); and/or
The alkaline earth metal compound is selected from the group consisting of alkaline earth metal carbonates, bicarbonates or C2～C4At least one of the carboxylates, preferably an acetate of an alkaline earth metal; and/or
The molar ratio of the alkaline earth metal compound to the titanium compound is (0.5-10):1, preferably (0.6-8):1, wherein the molar amount of the titanium compound is based on the molar amount of the titanium element therein, and the molar amount of the alkaline earth metal compound is based on the molar amount of the alkaline earth metal element therein.
5. The titanium-based catalyst according to claim 1, wherein said alkali metal compound and/or ammonium compound is selected from the group consisting of salts or bases of alkali metals and/or ammonium;
preferably, the alkali metal compound is selected from the group consisting of hydroxides, carbonates, bicarbonates and C of alkali metals2～C4At least one of carboxylate, wherein the alkali metal is selected from at least one of lithium, sodium, potassium; the ammonium compound is selected from the group consisting of ammonium hydroxide, carbonate, bicarbonate or C2～C4A carboxylate;
more preferably, the alkali metal compound and/or ammonium compound is selected from acetates of at least one of lithium, sodium, potassium, ammonium.
6. The titanium-based catalyst according to any one of claims 1 to 5, wherein the molar ratio of the alkali metal compound and/or the ammonium compound to the titanium compound is (0.1-1):1, preferably (0.1-0.8):1, wherein the molar amount of the titanium compound is based on the molar amount of the titanium element and the molar amount of the alkali metal compound and/or the ammonium compound is based on the molar amount of the alkali metal element and/or the ammonium element.
7. The titanium-based catalyst according to claim 6, wherein said diol is at least one selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, octylene glycol, and decylene glycol; preferably, the molar ratio of the dihydric alcohol to the titanium compound is (1-100): 1, preferably (2-80): 1.
8. A method for preparing the titanium-based catalyst according to any one of claims 1 to 7, comprising: mixing the titanium compound (1), the alkaline earth metal compound (2), the alkali metal compound and/or the ammonium compound (3) and the dihydric alcohol (4), and reacting to obtain the titanium catalyst.
9. The method according to claim 8,
the titanium compound is Ti (OR)4A compound of formula (la) wherein R is selected from C1～C10Straight chain alkyl group of (1), C1～C10Branched alkyl or C1～C10Preferably, the titanium compound is selected from C1～C6Straight chain alkyl or C1～C6A branched alkyl group of (a); and/or
The alkaline earth metal compound is selected from the group consisting of alkaline earth metal carbonates, bicarbonates or C2～C4At least one of the carboxylates, preferably an acetate of an alkaline earth metal; and/or
The alkali metal compound and/or ammonium compound is selected from salts or bases of alkali metals and/or ammonium; preferably, the alkali metal compound is selected from the group consisting of alkali goldHydroxides, carbonates, bicarbonates and C of genus2～C4At least one of carboxylate, wherein the alkali metal is selected from at least one of lithium, sodium, potassium; the ammonium compound is selected from the group consisting of ammonium hydroxide, carbonate, bicarbonate or C2～C4A carboxylate; and/or
The dihydric alcohol is at least one selected from ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, octanediol and decanediol.
10. The method according to claim 8,
the molar ratio of the alkaline earth metal compound to the titanium compound is (0.5-10) to 1, preferably (0.6-8) to 1, wherein the molar amount of the titanium compound is calculated by the molar amount of the titanium element therein, and the molar amount of the alkaline earth metal compound is calculated by the molar amount of the alkaline earth metal element therein; and/or
The molar ratio of the alkali metal compound and/or the ammonium compound to the titanium compound is (0.1-1):1, preferably (0.1-0.8):1, wherein the molar amount of the titanium compound is calculated by the molar amount of the titanium element therein, and the molar amount of the alkali metal compound and/or the ammonium compound is calculated by the molar amount of the alkali metal element and/or the ammonium therein; and/or
The molar use ratio of the dihydric alcohol to the titanium compound is (1-100): 1, and preferably (2-80): 1.
11. The method according to any one of claims 8 to 10, wherein the method comprises the steps of:
step 1, mixing the dihydric alcohol and the titanium compound to obtain a mixed solution I;
step 2, adding the alkaline earth metal compound and the alkali metal compound and/or the ammonium compound into the mixed solution I to obtain a mixed solution II;
and 3, heating and stirring the mixed solution II to obtain the titanium catalyst.
12. The production method according to claim 11,
in the step 1, the titanium compound is dripped into the ethylene glycol, and after the dripping is finished, the mixture is stirred to obtain a white turbid mixed solution I; and/or
In step 3, the temperature is raised to 50-200 ℃, and the mixture is stirred for 0.2-24 h.
13. The titanium-based catalyst obtained by the production method according to any one of claims 8 to 12, which has spherical particles having a particle diameter of 50 to 500 nm.
14. Use of the titanium-based catalyst according to any one of claims 1 to 7 or the titanium-based catalyst according to claim 13 in the preparation of polyesters, in particular polyethylene terephthalate.
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