CN108484895B - Phosphorus-titanium composite polyester catalyst and preparation process thereof - Google Patents
Phosphorus-titanium composite polyester catalyst and preparation process thereof Download PDFInfo
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- CN108484895B CN108484895B CN201810313004.3A CN201810313004A CN108484895B CN 108484895 B CN108484895 B CN 108484895B CN 201810313004 A CN201810313004 A CN 201810313004A CN 108484895 B CN108484895 B CN 108484895B
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- 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
Abstract
The invention discloses a phosphorus-titanium composite polyester catalyst, which has a central titanium atom, at least two phosphonate substituent groups and at least two chelate rings in the molecular formula; wherein the chelate ring and the central titanium atom are both bonded by a titanyl bond; the structures of the chelate rings are the same or different and are independently selected from any one of five-membered rings to eight-membered rings; the structures of the phosphonate substituent groups are the same or different, and the phosphonate substituent groups are positioned on any chelate ring and pass through C with the chelate ring1～C7Any one of the aliphatic alkylene groups is linked; the substitution site of the alkylene group to which the phosphonate group is attached on the ring is arbitrary. The prepared catalyst has good hydrolysis resistance and dispersibility in ethylene glycol, and also has excellent catalytic activity and selectivity, thermal degradation in the polycondensation process can be reduced when the titanium catalyst is used for preparing polyester products, and the prepared polyester products have the advantages of low b value, low carboxyl end group content and stable catalytic effect.
Description
Technical Field
The invention relates to the field of polyester synthesis processes, in particular to a phosphorus-titanium composite polyester catalyst 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
The invention aims to provide a phosphorus-titanium composite polyester catalyst which has stable catalytic performance and excellent color value of a polyester product obtained by catalytic synthesis.
The technical scheme for realizing the first purpose of the invention is as follows: a phosphorus-titanium composite polyester catalyst has a central titanium atom, at least two phosphonate substituent groups and at least two chelate rings in the molecular formula; wherein the chelate ring and the central titanium atom are both bonded by a titanyl bond; the structures of the chelate rings are the same or different and are independently selected from any one of five-membered rings to eight-membered rings; the structures of the phosphonate substituent groups are the same or different, and the phosphonate substituent groups are positioned on any chelate ring and pass through C with the chelate ring1～C7Any one of the aliphatic alkylene groups is linked; the substitution site of the alkylene group to which the phosphonate group is attached on the ring is arbitrary.
Further, the chelate ring has at least one C1～C6An alkyl substituent of (a).
The selection of the number of the carbon atoms of the chelating ring in the design of the molecular structure of the phosphorus-titanium composite polyester catalyst provided by one of the purposes of the invention does not cause instability of the ring due to too few carbon atoms, and does not cause difficulty in ring formation reaction due to too many carbon atoms; too many ring substituents on the phosphonate ester when attached to the chelating ring cause too great a steric hindrance of the substituents; phosphorus is too far from titanium to form an effective coordination. The phosphorus-titanium composite polyester catalyst has good hydrolysis resistance and dispersibility in ethylene glycol, and also has excellent catalytic activity and selectivity, thermal degradation in the polycondensation process can be reduced when the titanium catalyst is used for preparing polyester products, and the prepared polyester products have the advantages of low b value, low content of terminal carboxyl groups and high intrinsic viscosity, and are the titanium catalyst with excellent comprehensive performance.
The second purpose of the invention is to provide a preparation method of the phosphorus-titanium composite polyester catalyst.
The technical scheme for realizing the second aim of the invention is as follows: a preparation method of a phosphorus-titanium composite polyester catalyst comprises the following steps:
1) reacting a halogenated epoxy compound with phosphite ester according to a molar ratio of 1: 1-1: 7 for 2-8 hours at 90-180 ℃ under the protection of inert gas, and then carrying out reduced pressure distillation to obtain a retained product A;
2) dissolving the remaining product A in water, reacting for 3-10 h at 70-120 ℃ under 1-2 atmospheric pressure, and removing water to obtain a product B;
3) dissolving titanate in an organic solvent 1, adding a product B, stirring and reacting for 1-6 h at 0-80 ℃, and carrying out reduced pressure distillation to obtain a solid product, namely the phosphorus-titanium composite polyester catalyst; the reaction feeding molar ratio of titanate to the product B is 1: 1.5-1: 4;
wherein the phosphite is selected from the group consisting of
Wherein R is1Is selected from C1～C12Any of aliphatic alkyl groups or aromatic alkyl groups of (1) or hydrogen; x1And X2Are identical or different and are independently selected from C1～C12Any of aliphatic alkyl or alkoxy, aromatic alkyl or alkoxy, and hydrogen;
the halogenated epoxy compound is selected from the general formula
Wherein X is selected from halogen atoms, R2Selected from a main carbon chain length of C1～C4Wherein each carbon atom may be independently substituted by any C1～C6Alkyl substitution of R3Is selected from C1～C7Any aliphatic alkylene group of (a);
the titanate is selected from the group consisting of
Wherein R is4、R5、R6、R7Are the same or different and are independently selected from any C1～C8An aliphatic alkyl group of (a);
the organic solvent 1 is selected from anhydrous organic solvents capable of dissolving the titanate and the product B.
The phosphorus-titanium composite polyester catalyst preparation process of the second purpose of the invention adjusts the coordination and electronegativity of titanium atoms in the catalyst by modifying organic titanate, achieves the purpose of controlling the activity and selectivity of the catalyst, and further prepares a polyester catalyst containing titanium and phosphorus. The integral synthesis process of the phosphorus-titanium composite polyester catalyst 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; the process of removing water in the step 2 needs to be carried out 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 phosphorus-titanium composite polyester catalyst comprises the following steps:
1) β -methyl epichlorohydrin and tri-n-propyl phosphite are reacted for 2 hours at 180 ℃ under the protection of inert gas according to the mol ratio of 1:1, and then the residual product A is obtained by reduced pressure distillation1；
2) Leaving product A1Dissolving in water, reacting at 98 deg.C under 1 atmosphere for 3.5 h, and removing water to obtain product B1；
3) Dissolving tetrabutyl titanate in anhydrous n-hexane, and adding the product B1Stirring and reacting for 4 hours at the temperature of 30 ℃, and distilling under reduced pressure to obtain a solid product, namely the phosphorus-titanium composite polyester catalyst I; titanate and product B1The molar ratio of the reaction feed of (1: 2).
Example 2
1) Reacting epoxy chloropropane and diethyl methylphosphonite according to the molar ratio of 1:4 for 6.5 h at 115 ℃ under the protection of inert gas, and then distilling under reduced pressure to obtain a remaining product A2；
2) Leaving product A2Dissolving in water, reacting at 120 deg.C under 2 atm for 3 hr, and removing water to obtain product B2；
3) Dissolving tetrabutyl titanate in anhydrous n-hexane, and adding the product B2Stirring and reacting for 6h at 0 ℃, and carrying out reduced pressure distillation to obtain a solid product, namely the phosphorus-titanium composite polyester catalyst II; titanate and product B2The molar ratio of the reaction feed of (1: 4).
Example 3
1) β -methyl epichlorohydrin and triethyl phosphite are reacted for 4 hours at 150 ℃ under the protection of inert gas according to the mol ratio of 1:1.5, and then reduced pressure distillation is carried out to obtain the productTo the remaining product A3；
2) Leaving product A3Dissolving in water, reacting at 1 atm and 80 deg.C for 7 h, removing water to obtain product B3；
3) Dissolving tetrabutyl titanate in anhydrous n-hexane, and adding the product B3Stirring and reacting for 2 h at 60 ℃, and carrying out reduced pressure distillation to obtain a solid product, namely the phosphorus-titanium composite polyester catalyst III; titanate and product B3The molar ratio of the reaction feed of (1: 3).
Example 4
1) β -methyl epichlorohydrin and trimethyl phosphite are reacted for 8 hours at 90 ℃ under the protection of inert gas according to the mol ratio of 1:7, and then the product A is obtained by reduced pressure distillation4；
2) Leaving product A4Dissolving in water, reacting at 70 deg.C and 1 atm for 10 hr, removing water to obtain product B4；
3) Dissolving tetrabutyl titanate in anhydrous n-hexane, and adding the product B4Stirring and reacting for 1 h at the temperature of 80 ℃, and carrying out reduced pressure distillation to obtain a solid product, namely a phosphorus-titanium composite polyester catalyst IV; titanate and product B4The molar ratio of the reaction feeding of (1) to (1.5);
the titanium catalysts for the polyester obtained in the embodiments 1 to 4 are respectively used as catalysts for a PET synthesis process, the intrinsic viscosity of the obtained PET product is more than 0.64 dL/g, the L value is more than 80, the b value is lower than 3, the content of terminal carboxyl is less than 20 ppm, 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 disclosed by the embodiment of the invention have two or more chelate ring structures, and each chelate ring has a phosphonite substituent group, so that the phosphorus-titanium composite catalyst product for the polyester with a phosphonate group simultaneously connected with one chelate ring can be prepared according to different preparation processes.
The molar ratio of the halogenated epoxy compound to the phosphite ester is 1: 1-1: 7, the molar ratio of the titanate to the reaction charge of the product B is 1: 1.5-1: 4, and deviation from the range of the above ratio can cause incomplete reaction of a certain raw material, waste of one raw material and difficulty in removal, and can cause deviation of the molecular structure of the product; the reaction temperature of each step can not deviate 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, unexpected side reactions, decomposition of reaction products or evaporation and dissipation of a solvent can be caused; 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 is lower than 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 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 represented by the general formula
Wherein R is1Is selected from C1～C12Any of aliphatic alkyl groups or aromatic alkyl groups of (1) or hydrogen; x1And X2Are identical or different and are independently selected from C1～C12Any of aliphatic alkyl or alkoxy, aromatic alkyl or alkoxy, and hydrogen;
the halogenated epoxy compound is selected from the general formula
Wherein X is selected from halogen atoms, R2Selected from a main carbon chain length of C1～C4Wherein each carbon atom may be independently substituted by any C1～C6Alkyl substitution of R3Is selected from C1～C7Any aliphatic alkylene group of (a);
the titanate is selected from the group consisting of
Wherein R is4、R5、R6、R7Are the same or different and are independently selected from any C1～C8An aliphatic alkyl group of (a);
the organic solvent 1 is selected from anhydrous organic solvents capable of dissolving the titanate and the product B.
The water used in the preparation process is common water such as tap water, distilled water or deionized water, preferably deionized water and distilled water.
The preparation process of the phosphorus-titanium composite polyester catalyst of 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 (3)
1. A phosphorus-titanium composite polyester catalyst is characterized in that: the compound has a molecular formula of a central titanium atom, at least two phosphonate substituent groups and at least two chelate rings; wherein the chelate ring and the central titanium atom are both bonded by a titanyl bond; the structures of the chelate rings are the same or different and are independently selected from any one of five-membered rings to eight-membered rings; the structures of the phosphonate substituent groups are the same or different, and the phosphonate substituent groups are positioned on any chelate ring and pass through C with the chelate ring1～C7Any one of the aliphatic alkylene groups is linked; the substitution site of the alkylene group to which the phosphonate group is attached on the ring is arbitrary.
2. The phosphorus-titanium composite polyester catalyst according to claim 1, wherein: said chelate ring having at least one C1～C6An alkyl substituent of (a).
3. A process for preparing the phosphorus-titanium composite polyester catalyst according to claim 1, characterized in that: which comprises the following steps:
1) reacting a halogenated epoxy compound with phosphite ester according to a molar ratio of 1: 1-1: 7 for 2-8 hours at 90-180 ℃ under the protection of inert gas, and then carrying out reduced pressure distillation to obtain a retained product A;
2) dissolving the remaining product A in water, reacting for 3-10 h at 70-120 ℃ under 1-2 atmospheric pressure, and removing water to obtain a product B;
3) dissolving titanate in an organic solvent 1, adding a product B, stirring and reacting for 1-6 h at 0-80 ℃, and carrying out reduced pressure distillation to obtain a solid product, namely the phosphorus-titanium composite polyester catalyst; the reaction feeding molar ratio of titanate to the product B is 1: 1.5-1: 4; wherein the phosphite is selected from the group consisting of
Wherein R is1Is selected from C1～C12Any of aliphatic alkyl groups or aromatic alkyl groups of (1) or hydrogen; x1And X2Are identical or different and are independently selected from C1～C12Any of aliphatic alkyl or alkoxy, aromatic alkyl or alkoxy, and hydrogen;
the halogenated epoxy compound is selected from the general formula
Wherein X is selected from halogen atoms, R2Selected from a main carbon chain length of C1～C4Wherein each carbon atom may be independently substituted by any C1～C6Alkyl substitution of R3Is selected from C1～C7Any aliphatic alkylene group of (a);
the titanate is selected from the group consisting of
Wherein R is4、R5、R6、R7Are the same or different and are independently selected from any C1～C8An aliphatic alkyl group of (a);
the organic solvent 1 is selected from anhydrous organic solvents capable of dissolving reactants.
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