CN108641069B - Titanium catalyst for polyester and preparation process thereof - Google Patents
Titanium catalyst for polyester and preparation process thereof Download PDFInfo
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- CN108641069B CN108641069B CN201810312338.9A CN201810312338A CN108641069B CN 108641069 B CN108641069 B CN 108641069B CN 201810312338 A CN201810312338 A CN 201810312338A CN 108641069 B CN108641069 B CN 108641069B
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000003054 catalyst Substances 0.000 title claims abstract description 61
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 53
- 239000010936 titanium Substances 0.000 title claims abstract description 44
- 229920000728 polyester Polymers 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title description 13
- 239000013522 chelant Substances 0.000 claims abstract description 19
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical group OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000006467 substitution reaction Methods 0.000 claims abstract description 10
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 6
- 239000000047 product Substances 0.000 claims description 75
- 239000012043 crude product Substances 0.000 claims description 35
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- 239000003960 organic solvent Substances 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 125000001931 aliphatic group Chemical group 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 235000011054 acetic acid Nutrition 0.000 claims description 7
- 230000000717 retained effect Effects 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 6
- 150000001721 carbon Chemical group 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000012265 solid product Substances 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 4
- 150000008301 phosphite esters Chemical class 0.000 claims description 4
- 239000005711 Benzoic acid Substances 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 235000010233 benzoic acid Nutrition 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 235000011007 phosphoric acid Nutrition 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 7
- 229910052787 antimony Inorganic materials 0.000 abstract description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 abstract description 4
- 231100000956 nontoxicity Toxicity 0.000 abstract description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 3
- 230000009920 chelation Effects 0.000 abstract 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 23
- 238000006243 chemical reaction Methods 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 5
- 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 5
- 239000007788 liquid Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000006068 polycondensation reaction Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 238000007086 side reaction Methods 0.000 description 5
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 4
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 4
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 208000012839 conversion disease Diseases 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 229960004063 propylene glycol Drugs 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 150000003609 titanium compounds Chemical group 0.000 description 2
- ADDWXBZCQABCGO-UHFFFAOYSA-N titanium(iii) phosphide Chemical compound [Ti]#P ADDWXBZCQABCGO-UHFFFAOYSA-N 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- -1 Polyethylene terephthalate Polymers 0.000 description 1
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000001045 blue dye Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical group OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000001044 red dye Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses a titanium catalyst for polyester, which has a central titanium atom, a phosphonate substituent group and one or more chelation groups in the molecular formulaA ring; wherein the chelate ring is bonded to the central titanium atom through a titanyl bond; the structures of the chelate rings are the same or different and are independently selected from any one of four-membered rings to eight-membered rings; the phosphonate substituent group is positioned on any chelate ring and passes through C with the chelate ring1～C4To any alkylene group of (a); the substitution site of the alkylene group to which the phosphonate group is attached on the ring is arbitrary. The catalyst has the advantages of no toxicity, no harm, low dosage and stable catalytic performance, the activity of the catalyst is far higher than that of an antimony catalyst, the dosage of the catalyst is low when the titanium catalyst is used for preparing a polyester product, the residue is less, the influence on the subsequent processing of the polyester is small, and the prepared polyester product has the advantages of low b value, low carboxyl end group content and high intrinsic viscosity, and is a titanium catalyst with excellent comprehensive performance.
Description
Technical Field
The invention relates to the field of polyester synthesis processes, in particular to a titanium catalyst for polyester and a preparation process thereof.
Background
Polyethylene terephthalate (PET) is the most important variety of polyester fiber, and the synthesis process of the slice is usually a two-step synthesis process using Pure Terephthalic Acid (PTA) and Ethylene Glycol (EG) as raw materials and performing direct esterification and polycondensation. Where the esterification reaction can be acid catalyzed by the terephthalic acid itself, and the polycondensation reaction requires the addition of a catalyst to promote molecular weight growth. Currently, most of the catalysts for polycondensation are classified according to the active center, and mainly include three types of antimony, germanium and titanium. Among them, titanium catalysts have been widely studied because of their advantages of environmental protection, no toxicity, no harm, high catalytic activity, good transparency of produced polyesters, low gray level, etc. However, the problems of difficult control of the activity of the titanium catalyst, high preparation cost and serious side reaction are not solved, so the industrial application of the titanium catalyst is still in the beginning stage.
US 5922828A discloses a technical scheme of using Tetrabutyl titanate (TBT for short) as polycondensation catalyst, and an antioxidant AT-626 as an auxiliary agent, so that the acetaldehyde content of the synthesized polymer is low. However, the scheme has the defects that titanate is very easy to hydrolyze, so that the catalytic activity is unstable, the experimental repeatability is poor, and the product is yellow.
CN 103709383A discloses the application of nano-silica supported titanium glycol as polycondensation catalyst, which improves the dispersion property and hydrolysis resistance compared with TBT, solves the problem of unstable catalytic activity, and the catalytic activity of the titanium glycol is more than that of traditional catalyst Sb2O3High catalytic activity about 10 times that of antimony system. However, the problem of catalytic selectivity in the system is not solved, the problems of more side reactions and poor color value still exist, the b value of the product is about 8, and the product is yellow.
CN 103772673A is added with a small amount of blue dye and red dye to improve the color value while compounding titanium glycol and the stabilizer, the b value of the product can reach about 1, and the requirements of national standard polyester superior products are met. However, the problem of side reaction is not solved fundamentally by adding the dye, and the problems of high acetaldehyde content, uneven molecular weight distribution and the like caused by the side reaction are not solved while the b value is improved.
Chinese patent CN100341918C reports that a liquid catalyst is prepared using a reaction product of ethylene glycol, water, magnesium acetate, lactic acid and titanate, and that polyester having excellent color tone, transparency, etc. can be produced at a high reaction rate using the catalyst. However, the catalyst is in a liquid state and can be settled, so that the stability of the catalyst is poor, and meanwhile, the photocatalytic activity of titanium is easy to cause unexpected reactions of a system under illumination, so that the illumination stability of the liquid catalyst is poor.
In summary, in the existing preparation method of titanium-based polyester catalyst, the stabilization of titanium compound structure and catalytic activity is an important direction of research, wherein the diol complex of titanium has been widely accepted due to its stable cyclic chelating structure, and has the advantages of good hydrolysis resistance, insensitivity to light, easy storage, etc. However, such catalysts often cause more side reactions due to too high activity, and break molecular chains, so that the viscosity of the prepared polyester chips is not ideal, and yellowing caused by thermal degradation is severe. In addition, the glycol complex of titanium is mostly solid, and has poor solubility, and it is difficult to prepare a slurry. The liquid titanium catalyst can avoid the difficulty in dissolution, but most of the reported liquid titanium catalysts need to be protected from light and moisture and have shorter shelf life than the solid catalysts. Therefore, it is urgently required to develop a titanium catalyst for polyester, which has high activity, stable catalytic performance and easy storage.
Disclosure of Invention
An object of the present invention is to provide a titanium catalyst for polyester, which has stable catalytic performance and excellent color value.
The technical scheme for realizing the first purpose of the invention is as follows: a titanium catalyst for polyester, which has a central titanium atom, a phosphonate substituent group and one or more chelate rings in the molecular formula; wherein the chelate ring is bonded to the central titanium atom through a titanyl bond; the structures of the chelate rings are the same or different and are independently selected from any one of four-membered rings to eight-membered rings; the phosphonate substituent group is positioned on any chelate ring and passes through C with the chelate ring1～C4To any alkylene group of (a); the substitution site of the alkylene group to which the phosphonate group is attached on the ring is arbitrary.
Further, the chelate ring has one or more C's thereon1～C6Any alkyl substituent of (1).
The titanium catalyst for polyester provided by one purpose of the invention achieves the purpose of regulating and controlling the activity and selectivity of the catalyst by introducing a phosphorus-oxygen bond coordinated with a central titanium atom into a molecule and adjusting the coordination function of the titanium atom and the steric hindrance of a ligand, the charge distribution, the coordination valence state and the front-line track occupation of the central titanium atom, so that the catalyst has the advantages of no toxicity, no harm, low dosage, high activity and stable catalytic performance, the activity of the catalyst is far higher than that of an antimony catalyst, the dosage of the catalyst is low, the residue is little when the titanium catalyst is used for preparing a polyester product, the influence on the subsequent processing of polyester is small, and the prepared polyester product has the advantages of low b value, low terminal carboxyl group content and high intrinsic viscosity, and is a titanium catalyst with excellent comprehensive performance.
The second purpose of the invention is to provide a preparation method of the titanium catalyst for polyester.
The technical scheme for realizing the second aim of the invention is as follows: a preparation method of a titanium catalyst for polyester comprises the following steps:
1) reacting the halogenated ketal and phosphite ester according to a molar ratio of 1: 1-1: 5 at 80-150 ℃ for 4-15 h under the protection of inert gas by stirring to obtain a crude product, cooling the crude product to normal temperature, and distilling to obtain a retained product A;
2) dissolving the remaining product A in a weak acid aqueous solution, hydrolyzing for 3-12 h at 25-60 ℃, and then distilling under reduced pressure to remove the weak acid and water in the mixture to obtain a product B;
3) dissolving organic titanate in an organic solvent 1, adding dihydric alcohol, reacting at 20-80 ℃ for 1-5 h to obtain a crude product, and distilling the crude product to obtain a remaining product C; wherein the molar ratio of the organic titanate to the dihydric alcohol is 1: 0.8-1: 1.5;
4) dissolving the remaining product C in an organic solvent 2, adding the product B, reacting for 2-7 h at 20-70 ℃ to obtain a crude product, distilling the crude product, and collecting the residual solid to obtain an orange powdery solid product, namely the titanium catalyst for polyester; the molar ratio of the remaining product C to the product B is 1: 0.8-1: 1.5;
wherein the phosphite is selected from the group consisting of those having the formula
Wherein R is1、R2、R3Are identical or different and are independently selected from C1～C12Any aliphatic or aromatic alkyl group of (a) or hydrogen;
the halogenated ketal is selected from the general formula
Wherein R is4Selected from a main carbon chain length of C1～C5Wherein each carbon atom may be independently substituted by C1～C6Is substituted with any alkyl group of the general formula
Structure of (1), n1Is taken from 1 to 4, and Y is selected from halogen atoms; z is at R4The substitution site on (A) is arbitrary; r5、R6Are identical or different and are independently selected from C1～C9Any aliphatic alkyl, aromatic alkyl or hydrogen of (a);
the weak acid in the step 2) is a weak acid which is soluble in water and has the pH value of 1-3; preferably, the weak acid is any one of acetic acid, propionic acid, phosphoric acid, oxalic acid or benzoic acid;
the organic titanate is selected from the group consisting of
Wherein R is7、R8、R9、R10Are identical or different and are independently selected from C1～C6Any aliphatic alkyl group of (1), preferably C2～C4Any aliphatic alkyl group of (a);
the dihydric alcohol is selected from the general formula
Wherein R is11Selected from a main carbon chain length of C1～C5Wherein each carbon atom may be independently substituted by C1～C6Any alkyl substitution of (a);
the organic solvent 1 in the step 3) is selected from organic solvents which are not soluble in water;
the organic solvent 2 in step 4) is selected from anhydrous organic solvents which can dissolve the remaining product C and the product B.
The titanium catalyst for polyester of the second purpose of the invention has the advantages of mild reaction conditions, easy control, no heavy metal contained in each reactant, no toxicity, no harm and low requirements on synthesis equipment and a control system, and simultaneously avoids the risk of thermal decomposition of reaction products. The time required by each synthesis step is longer, so that the reaction is slow and insensitive to the interference of external environmental factors except the reaction conversion rate is improved as much as possible, the stability of products in each stage is facilitated, if the reaction time is too short, the reaction is not finished or the conversion rate is insufficient, and if the reaction time is too long, the decomposition of products is caused, and a heat source is wasted; and (3) carrying out the impurity removal process after hydrolysis in the step 2) under the conditions of low temperature and high vacuum degree, so that the product can be protected from being threatened by thermal decomposition, if the reaction temperature is lower than the lower limit of the temperature range, the reaction cannot be carried out or the reaction speed is too slow, and if the reaction temperature exceeds the upper limit of the temperature range, the reaction product can be decomposed, or the solvent can be evaporated and dissipated.
Detailed Description
The present invention will be described in detail with reference to examples.
Example 1
A preparation method of a titanium catalyst for polyester comprises the following steps:
1) the method comprises the steps of stirring and reacting chloroacetophenoketal and triethyl phosphite for 4 hours at 150 ℃ in a molar ratio of 1:1 under the protection of nitrogen to obtain a crude product, cooling the crude product to normal temperature, and distilling to obtain a retained product A1；
2) Leaving product A1Dissolving in 20mL of acetic acid-water mixed solution with the mass ratio of 7:3, stirring and reacting at 40 ℃ for 9h, and then distilling under reduced pressure to remove acetic acid and water in the mixture to obtain a product B1；
3) Dissolving tetrabutyl titanate in 30mL of anhydrous cyclohexane, adding 1, 3-propylene glycol, reacting at 80 ℃ for 1h to obtain a crude product, and distilling to obtain a remaining product C1(ii) a Wherein the mol ratio of the organic titanate to the 1, 3-propylene glycol is 1: 1.25;
4) leaving product C1Dissolved in 40mL of anhydrous cyclohexane and then the product B is added1Reacting at 50 deg.C for 4.5h to obtain crude product, distilling the crude product, and collecting the residual solid to obtain orange powderTitanium catalyst I for polyester as solid product; wherein the product C remains1With product B1Is 1: 0.95.
Example 2
1) The method comprises the steps of stirring and reacting chloroacetophenoketal and triethyl phosphite for 7.5 hours at 105 ℃ under the protection of nitrogen according to the molar ratio of 1:5 to obtain a crude product, cooling the crude product to normal temperature, and distilling to obtain a retained product A2；
2) Leaving product A2Dissolving in 20mL of acetic acid-water mixed solution with the mass ratio of 7:3, stirring and reacting at 60 ℃ for 3h, and then distilling under reduced pressure to remove acetic acid and water in the mixture to obtain a product B2；
3) Dissolving tetrabutyl titanate in 30mL of anhydrous cyclohexane, adding ethylene glycol, reacting at 60 ℃ for 2h to obtain a crude product, and distilling the crude product to obtain a remaining product C2(ii) a Wherein the mol ratio of the organic titanate to the ethylene glycol is 1: 1.5;
4) leaving product C2Dissolved in 40mL of anhydrous cyclohexane and then the product B is added2Reacting at 40 ℃ for 5 hours to obtain a crude product, distilling the crude product, and collecting the residual solid to obtain an orange powdery solid product, namely a titanium catalyst II for polyester; wherein the product C remains2With product B2Is 1: 0.8.
Example 3
A preparation method of a titanium catalyst for polyester comprises the following steps:
1) the method comprises the steps of stirring and reacting chloroacetophenoketal and triethyl phosphite for 15 hours at 80 ℃ under the protection of nitrogen according to the molar ratio of 1:2.5 to obtain a crude product, cooling the crude product to normal temperature, and distilling to obtain a retained product A3；
2) Leaving product A3Dissolving in 20mL of acetic acid-water mixed solution with the mass ratio of 7:3, stirring and reacting at 25 ℃ for 12h, and then distilling under reduced pressure to remove acetic acid and water in the mixture to obtain a product B3；
3) Dissolving tetrabutyl titanate in 30mL of anhydrous cyclohexane, adding 1, 2-propylene glycol, reacting at 45 ℃ for 4h to obtain a crude product, and distilling the crude product to obtain a remaining product C3(ii) a Wherein the mol ratio of the organic titanate to the 1, 2-propylene glycol is 1: 0.8;
4) leaving product C3Dissolved in 40mL of anhydrous cyclohexane and then the product B is added3Reacting at 70 ℃ for 2h to obtain a crude product, distilling the crude product, and collecting the residual solid to obtain an orange powdery solid product, namely a titanium catalyst III for polyester; wherein the product C remains3With product B3In a molar ratio of 1: 1.5.
Example 4
A preparation method of a titanium catalyst for polyester comprises the following steps:
1) the method comprises the steps of stirring and reacting chloroacetophenoketal and triethyl phosphite for 6 hours at 130 ℃ under the protection of nitrogen according to the molar ratio of 1:1.5 to obtain a crude product, cooling the crude product to normal temperature, and distilling to obtain a retained product A4；
2) Leaving product A4Dissolving in 20mL of acetic acid-water mixed solution with the mass ratio of 7:3, stirring and reacting at 50 ℃ for 4h, and then distilling under reduced pressure to remove acetic acid and water in the mixture to obtain a product B4；
3) Dissolving tetrabutyl titanate in 30mL of anhydrous cyclohexane, adding 2, 3-butanediol, reacting at 20 ℃ for 5h to obtain a crude product, and distilling the crude product to obtain a remaining product C4(ii) a Wherein the mol ratio of the organic titanate to the 2, 3-butanediol is 1: 0.95;
4) leaving product C4Dissolved in 40mL of anhydrous cyclohexane and then the product B is added4Reacting at 20 ℃ for 7 hours to obtain a crude product, distilling the crude product, and collecting the residual solid to obtain a titanium catalyst IV for the polyester of a red powdery solid product; wherein the product C remains4With product B4In a molar ratio of 1: 1.25.
The titanium catalysts for polyester obtained in the embodiments 1 to 4 are respectively used as catalysts in the PET synthesis process, the intrinsic viscosity of the obtained PET product is more than 0.64dL/g, the L value is more than 80, the b value is less than 3, the content of terminal carboxyl is less than 20ppm, the product has high brightness and is free from yellowing, and the product can be used for processing chemical fiber textiles and edible bottles without additional dyes.
The phosphorus-titanium composite catalysts for the polyester prepared by the preparation process of the embodiment of the invention have one or more chelate rings, and one phosphonite group is connected to one of the chelate rings. According to different preparation processes, the phosphorus-titanium composite catalyst product for polyester with phosphonate groups simultaneously connected with a chelate ring can be prepared.
The molar ratio of the halogenated ketal to the phosphite ester is 1: 1-1: 5, the molar ratio of the organic titanate to the dihydric alcohol is 1: 0.8-1: 1.5, the molar ratio of the remained product C to the product B is 1: 0.8-1: 1.5, and deviation from the range of the above ratios can cause incomplete reaction of a certain raw material, waste of one raw material and difficulty in removal, and cause deviation of the molecular structure of a product; the reaction temperature of each step can not be deviated from the range, if the reaction temperature is lower than the lower limit of the temperature range, the reaction can not be carried out or the reaction speed is too slow, and if the reaction temperature exceeds the upper limit of the temperature range, the reaction product can be decomposed, or the solvent can be evaporated and dissipated; the reaction conversion rate can be improved within the reaction time range, the reaction is relatively slow and insensitive to the interference of external environmental factors, the stability of products at each stage is facilitated, if the reaction time exceeds the limited range, the reaction is not finished or the conversion rate is insufficient, and if the reaction time is too long, the decomposition of products is caused, and a heat source is wasted; the inert gas can be any gas which can isolate oxygen, is insoluble in the system and does not react with the system, and common inert gases comprise nitrogen, argon and the like. Production errors are allowed to exist for the boundary values of the parameter ranges in actual production. The pressure of the reduced pressure distillation is based on the vaporization of impurities to obtain a retained product. Production errors are allowed to exist for the boundary values of the parameter ranges in actual production.
In the present invention, each raw material of the titanium catalyst for polyester synthesis is a commercially available product, and the selection of the raw material is not limited to the examples, wherein the phosphite ester is selected from the group consisting of the titanium compounds having the general formula
Wherein R is1、R2、R3Are identical or different and are independently selected from C1～C12Any aliphatic or aromatic alkyl group of (2) or hydrogen；
The halogenated ketal is selected from the general formula
Wherein R is4Selected from a main carbon chain length of C1～C5Wherein each carbon atom may be independently substituted by C1～C6Is substituted with any alkyl group of the general formula
Structure of (1), n1Is taken from 1 to 4, and Y is selected from halogen atoms; z is at R4The substitution site on (A) is arbitrary; r5、R6Are identical or different and are independently selected from C1～C9Any aliphatic alkyl, aromatic alkyl or hydrogen of (a);
the weak acid in the step 2) is a weak acid which is soluble in water and has a pH value of 1-3, and preferably, the weak acid is any one of acetic acid, propionic acid, phosphoric acid, oxalic acid or benzoic acid;
the organic titanate is selected from the group consisting of
Wherein R is7、R8、R9、R10Are identical or different and are independently selected from C1～C6Any aliphatic alkyl group of (1), preferably C2～C4Any aliphatic alkyl group of (a);
the dihydric alcohol is selected from the general formula
Wherein R is11Selected from a main carbon chain length of C1～C5Wherein each carbon atom may be independently substituted by C1～C6Any alkyl substitution of (a);
the organic solvent 1 in the step 3) is selected from organic solvents which are not soluble in water;
the organic solvent 2 in step 4) is selected from anhydrous organic solvents which can dissolve the product C and the product B.
The preparation process of the titanium catalyst for polyester according to the present invention is not limited to the examples, and those skilled in the art can make several simple deductions or substitutions without departing from the spirit of the present invention, and all of them should be considered as falling within the protection scope of the present invention.
Claims (5)
1. A titanium catalyst for polyester, which is characterized in that: the compound has a molecular formula of a central titanium atom, a phosphonate substituent group and one or more chelate rings; wherein the chelate ring is bonded to the central titanium atom through a titanyl bond; the structures of the chelate rings are the same or different and are independently selected from any one of four-membered rings to eight-membered rings; the phosphonate substituent group is positioned on any chelate ring and passes through C with the chelate ring1～C4To any alkylene group of (a); the substitution site of the alkylene group to which the phosphonate group is attached on the ring is arbitrary.
2. The titanium-based catalyst for polyester according to claim 1, wherein: the chelate ring having one or more C's thereon1～C6Any alkyl substituent of (1).
3. A process for producing the titanium-based catalyst for polyester according to claim 1 or 2, characterized in that: which comprises the following steps:
1) reacting the halogenated ketal and phosphite ester according to a molar ratio of 1: 1-1: 5 at 80-150 ℃ for 4-15 h under the protection of inert gas by stirring to obtain a crude product, cooling the crude product to normal temperature, and distilling to obtain a retained product A;
2) dissolving the remaining product A in a weak acid aqueous solution, hydrolyzing for 3-12 h at 25-60 ℃, and then distilling under reduced pressure to remove the weak acid and water in the mixture to obtain a product B;
3) dissolving organic titanate in an organic solvent 1, adding dihydric alcohol, reacting at 20-80 ℃ for 1-5 h to obtain a crude product, and distilling the crude product to obtain a remaining product C; wherein the molar ratio of the organic titanate to the dihydric alcohol is 1: 0.8-1: 1.5;
4) dissolving the remaining product C in an organic solvent 2, adding the product B, reacting for 2-7 h at 20-70 ℃ to obtain a crude product, distilling the crude product, and collecting the residual solid to obtain an orange powdery solid product, namely the titanium catalyst for polyester; the molar ratio of the remaining product C to the product B is 1: 0.8-1: 1.5;
wherein the phosphite is selected from the group consisting of those having the formula
Wherein R is1、R2、R3Are identical or different and are independently selected from C1～C12Any aliphatic or aromatic alkyl group of (a) or hydrogen;
the halogenated ketal is selected from the general formula
Wherein R is4Selected from a main carbon chain length of C1～C5Wherein each carbon atom may be independently substituted by C1～C6Is substituted with any alkyl group of the general formula
Structure of (1), n1Is taken from 1 to 4, and Y is selected from halogen atoms; z is at R4The substitution site on (A) is arbitrary; r5、R6Are identical or different and are independently selected from C1～C9Any aliphatic alkyl, aromatic alkyl or hydrogen of (a);
the weak acid in the step 2) is a weak acid which is soluble in water and has the pH value of 1-3;
the organic titanate is selected from the group consisting of
Wherein R is7、R8、R9、R10Are identical or different and are independently selected from C1～C6Any aliphatic alkyl group of (a);
the dihydric alcohol is selected from the general formula
Wherein R is11Selected from a main carbon chain length of C1～C5Wherein each carbon atom may be independently substituted by C1～C6Any alkyl substitution of (a);
the organic solvent 1 in the step 3) is selected from organic solvents which are not soluble in water;
the organic solvent 2 in step 4) is selected from anhydrous organic solvents which can dissolve the remaining product C and the product B.
4. The process according to claim 3, wherein the titanium catalyst is prepared by: the weak acid is any one of acetic acid, propionic acid, phosphoric acid, oxalic acid or benzoic acid.
5. The process according to claim 3, wherein the titanium catalyst is prepared by: r in the organic titanate general formula7、R8、R9、R10Is selected from C2～C4Any aliphatic alkyl group of (a).
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| KR940010346B1 (en) * | 1991-06-12 | 1994-10-22 | 한국과학기술연구원 | Method for producing polybutylene terephthalate polymer |
| KR100854604B1 (en) * | 2001-07-16 | 2008-08-27 | 데이진 가부시키가이샤 | Catalyst for polyester production and polyester production method using the catalyst |
| JP4529485B2 (en) * | 2003-03-07 | 2010-08-25 | 三菱化学株式会社 | Polyester polymerization catalyst, method for producing the same, and method for producing polyester using the same |
| JP2005330476A (en) * | 2004-04-19 | 2005-12-02 | Toray Ind Inc | Polymerization catalyst for polyester |
| CN1951977B (en) * | 2005-10-19 | 2010-09-29 | 东丽纤维研究所（中国）有限公司 | Production method of polyester |
| CN101942078B (en) * | 2009-07-06 | 2012-06-27 | 中国石油化工股份有限公司 | Titanium polyester catalyst for preparing polyester |
| CN102372847A (en) * | 2010-08-18 | 2012-03-14 | 东丽纤维研究所（中国）有限公司 | Polyester and production method thereof |
| US9156941B2 (en) * | 2010-12-20 | 2015-10-13 | Eastman Chemical Company | Color in titanium catalyzed polyesters |
| CN102875786A (en) * | 2011-07-12 | 2013-01-16 | 常州化学研究所 | Synthetic method and application for polydentate ligand chelating titanium catalyst used for polyester preparation |
| CN103665349B (en) * | 2012-09-25 | 2016-01-20 | 中国石油化工股份有限公司 | A kind of method of synthesis polybutylene terephthalate |
| CN103772673A (en) * | 2013-06-13 | 2014-05-07 | 淄博晓光化工材料有限公司 | Method for synthesizing PET polyester chips by using titanium catalyst |
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| CN104774320B (en) * | 2015-03-27 | 2018-12-14 | 中国昆仑工程有限公司 | Composite catalyst and polypropylene terephthalate preparation method |
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| CN105131269B (en) * | 2015-08-17 | 2018-03-23 | 中国石油天然气集团公司 | The preparation method and the PBS production methods using the catalyst of environment-friendly type titanium phosphorus coordination composite catalyst |
| CN107141462B (en) * | 2017-06-06 | 2019-04-23 | 北京化工大学 | A kind of preparation method and application of titanium-based catalyst for polyester |
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