CN108484895A - A kind of phosphorus-titanium complex polyester catalyst and its preparation process - Google Patents
A kind of phosphorus-titanium complex polyester catalyst and its preparation process Download PDFInfo
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- CN108484895A CN108484895A CN201810313004.3A CN201810313004A CN108484895A CN 108484895 A CN108484895 A CN 108484895A CN 201810313004 A CN201810313004 A CN 201810313004A CN 108484895 A CN108484895 A CN 108484895A
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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
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Abstract
The invention discloses a kind of phosphorus titanium complex polyester catalyst, there are one center titanium atom, at least two phosphonate substituted groups and at least two chelate rings for tool in molecular formula；The wherein described chelate ring is bonded by titanyl key with center titanium atom；The structure of each chelate ring is identical or different, and any in five-membered ring~octatomic ring；The structure of each phosphonate substituted group is identical or different, is located on arbitrary chelate ring and passes through C with chelate ring1~C7Any aliphatic alkylidene is connected；It is arbitrary to connect substitution site of the alkylidene of phosphonate groups on ring.Prepared catalyst is other than the dispersibility with good hydrolytic resistance and in ethylene glycol, also there is outstanding catalytic activity and selectivity, the thermal degradation in polycondensation process can be reduced when preparing polyester product using the Titanium series catalyst, and polyester product obtained has the advantages that b values are low, content of carboxyl end group is low, catalytic effect is stablized.
Description
Technical field
The present invention relates to polyester synthetic process field more particularly to a kind of phosphorus-titanium complex polyester catalyst and its prepare work
Skill.
Background technology
Polyethylene terephthalate（Polyethylene terephthalate, abbreviation PET）It is in polyester fiber
The building-up process of most important kind, slice is typically with p-phthalic acid（Pure terephthalic acid, referred to as
PTA）With ethylene glycol（Ethylene glycol, abbreviation EG）For raw material, through direct esterification reaction（direct
esterification）And polycondensation reaction（polycondensation）Two-step method synthesis.Wherein esterification can be by benzene
Dioctyl phthalate itself acidic catalyst, and catalyst need to be added to promote molecular weight to increase in polycondensation reaction.More polycondensation is studied at present
Classified by activated centre with catalyst, mainly there is antimony, germanium and titanium three types.Wherein, Titanium series catalyst due to its is environmentally protective,
Nontoxic, the advantages that catalytic activity is high, the polyester transparent degree of production is good, gray scale declines and be widely studied.But titanium system
The problem that catalyst activity is difficult to control, manufacturing cost is high, side reaction is serious is not solved at all, therefore Titanium series catalyst
Industrial applications are also in the starting stage.
5922828 A of US are disclosed with butyl titanate（Tetrabutyl titanate, abbreviation TBT）It is urged as polycondensation
Agent, collocation antioxidant AT-626 are auxiliary agent so that the synthesized lower technical solution of polymeric acetaldehyde.But the party
There are titanate esters easily to hydrolyze for case, and the defect for causing catalytic activity unstable keeps assay reproducibility poor, and product yellowing.
The Chinese patent of 103709383 A of CN, which is disclosed, is urged using nano silicon dioxide load titanium ethylene glycolate as polycondensation
The application of agent improves dispersion performance and anti-hydrolytic performance compared to TBT, solves the problems, such as that catalytic activity is unstable, and
The catalytic activity of titanium ethylene glycolate is than traditional catalyst Sb2O3Height, catalytic activity are 10 times or so of antimony system catalyst system and catalyzing.But
The problem of catalytic selectivity, is not resolved in the system, and side reaction is more, color value difference problem still has, and product b values are on 8 left sides
The right side, product are partially yellow.
103772673 A of CN then while titanium ethylene glycolate and compound stabilizer, introduce micro blue dyes and red
For dyestuff to improve color value, product b values can reach 1 or so, meet national standard polyester top grade product requirement.But additional dyestuff is not from basic
It is upper to solve the problems, such as side reaction, while improving b values and do not solve acetaldehyde height caused by side reaction, molecular weight distribution unevenness
The problems such as even.
The Chinese patent of CN100341918C reports the reaction production using ethylene glycol, water, magnesium acetate, lactic acid and titanate esters
Object is prepared for liquid catalyst, and the polyester with excellent tone, transparency etc. can be produced with high reaction rate with the catalyst.
But since catalyst is liquid, can settle, therefore the catalyst stability is poor, while the photocatalytic activity of titanium is easy to allow system
Reaction except being expected under light illumination causes the light durability of liquid catalyst poor.
In conclusion in existing titanium series polyester catalyst preparation method, the stabilization of titanium compound structure and catalytic activity
Change be research important directions, wherein the binary alcohol complex of titanium because its stabilization cyclic chelate structures be widely accepted,
Has many advantages, such as good, insensitive to light, the easy storage of hydrolytic resistance.But such catalyst is often due to excessively high activity, cause compared with
More side reactions, makes molecular chain rupture, causes polyester slice viscosity obtained undesirable, xanthochromia caused by thermal degradation is serious.Separately
Outside, the binary alcohol complex of titanium is in solid more, and solubility property is poor, and when configuring slurry, there are certain difficulties.Liquid titanium system
Catalyst can be difficult to avoid dissolving, but the liquid Titanium series catalyst reported requires and is protected from light wet preservation mostly, and guarantees the quality
Phase is shorter than solid catalyst.It is catalyzed with titanium it would therefore be highly desirable to research and develop a kind of activity high, stable in catalytic performance and the polyester that is easy to preserve
Agent.
Invention content
One of the objects of the present invention is to provide a kind of stable in catalytic performance, the polyester product color value catalyzed and synthesized are excellent
Phosphorus-titanium complex polyester catalyst.
Realizing the technical solution of the object of the invention one is：A kind of phosphorus-titanium complex polyester catalyst has one in molecular formula
A center titanium atom, at least two phosphonate substituted groups and at least two chelate rings；The wherein described chelate ring and center titanium
Atom is bonded by titanyl key；The structure of each chelate ring is identical or different, and appoints in five-membered ring~octatomic ring
It is a kind of；The structure of each phosphonate substituted group is identical or different, is located on arbitrary chelate ring and passes through C with chelate ring1
~C7Any aliphatic alkylidene is connected；It is arbitrary to connect substitution site of the alkylidene of phosphonate groups on ring.
Further, there is at least one C on the chelate ring1~C6Alkyl substituent.
To chelating ring carbon in the design of the molecular structure for phosphorus-titanium complex polyester catalyst that an object of the present invention provides
The selection of atomicity will not cause ring unstable due to very little, annulation will not be caused difficult because of too many；Phosphonic acids
Its ring substituents quantity can cause the excessive steric hindrance of substituent group too big too much when ester is connected with chelate ring；Phosphorus and titanium are far apart not
It is easy to be formed effectively coordination.The phosphorus provided-titanium complex polyester catalyst is in addition to good hydrolytic resistance and in ethylene glycol
In dispersibility except, also have outstanding catalytic activity and selectivity, can when preparing polyester product using the Titanium series catalyst
To reduce the thermal degradation in polycondensation process, and polyester product obtained is with b values are low, content of carboxyl end group is low, inherent viscosity is high
Advantage is the Titanium series catalyst of excellent combination property.
The second object of the present invention is to provide a kind of system preparing phosphorus described in goal of the invention one-titanium complex polyester catalyst
Preparation Method.
Realizing the technical solution of the object of the invention two is：A kind of preparation method of phosphorus-titanium complex polyester catalyst comprising
Following steps：
1）By halogenated epoxide and phosphite ester in molar ratio 1:1~1:7 under inert gas protection in 90~180 DEG C
2~8 h of lower reaction obtain remaining product A then by vacuum distillation；
2）Remaining product A is dissolved in water, 3~10 h are reacted at 1~2 atmospheric pressure and 70~120 DEG C, water is removed and obtains product
B；
3）Titanate esters are dissolved in organic solvent 1, product B is then added, 1~6 h is stirred to react at 0~80 DEG C, are evaporated under reduced pressure
Solid product is obtained, as phosphorus-titanium complex polyester catalyst；Titanate esters are 1 with the molar ratio that reacts of product B:1.5~1:
4；
Wherein, the phosphite ester is selected from general formulaCompound, wherein R1Selected from C1~C12Aliphatic alkane
It is any in base or aromatic alkyl or hydrogen；X1And X2It is identical or different, and it is independently selected from C1~C12Aliphatic alkyl or alcoxyl
It is any in base, aromatic alkyl or alkoxy, hydrogen；
The organic solvent 1 is selected from the anhydrous organic solvent that can dissolve titanate esters and product B.
The phosphorus of the object of the invention two-titanium complex polyester catalyst preparation process passes through the modification to organic titanate, adjustment
The coordination of titanium atom and electronegativity in catalyst have achieved the purpose that control catalyst activity and selectivity, and then have been prepared for
A kind of polyester catalyst containing titanium and phosphorus.Phosphorus-titanium complex polyester catalyst entirety building-up process is mitigated with reaction condition, easily
In control, each reactant is free of heavy metal, nontoxic, the relatively low advantage of the requirement to synthesis device and control system, together
When also avoid reaction product thermally decompose risk.It is longer the time required to each synthesis step, in addition to improving reaction conversion ratio as possible
Outside, also make the more blunt interference to outside environmental elements of reaction insensitive, be conducive to the stabilization of each stage product, if the reaction time
Too short reaction to be caused unfinished or conversion ratio deficiency, the reaction time is long, product can be caused to decompose, and wastes heat source；Step
The process of water is removed in rapid 2 to be carried out under the conditions of low-temperature high-vacuum degree, and threat of the product from receiving thermal decomposition can be protected, if
Reaction temperature is less than temperature range lower limit, can cause reaction that cannot carry out or reaction speed is excessively slow, then beyond the temperature range upper limit
Reaction product can be caused to decompose, or cause evaporation of the solvent loss.
Specific implementation mode
It elaborates with reference to embodiments to the present invention.
Embodiment 1
A kind of preparation method of phosphorus-titanium complex polyester catalyst comprising following steps：
1）By β methyl epoxy chloropropane and three n-propyl of phosphorous acid in molar ratio 1:1 under inert gas protection at 180 DEG C
2 h are reacted, remaining product A is then obtained by vacuum distillation1；
2）By remaining product A1It is dissolved in water, 3.5 h are reacted at 1 atmospheric pressure and 98 DEG C, water is removed and obtains product B1；
3）Butyl titanate is dissolved in anhydrous n-hexane, product B is then added1, it is stirred to react 4 h at 30 DEG C, is evaporated under reduced pressure
Solid product is obtained, as phosphorus-titanium complex polyester catalyst I；Titanate esters and product B1Reaction molar ratio be 1:2.
Embodiment 2
1）By epoxychloropropane and diethyl methyl-phosphonite in molar ratio 1:4 react at 115 DEG C under inert gas protection
Then 6.5 h obtain remaining product A by vacuum distillation2；
2）By remaining product A2It is dissolved in water, 3 h are reacted at 2 atmospheric pressure and 120 DEG C, water is removed and obtains product B2；
3）Butyl titanate is dissolved in anhydrous n-hexane, product B is then added2, it is stirred to react 6 h at 0 DEG C, is evaporated under reduced pressure
Solid product is obtained, as phosphorus-titanium complex polyester catalyst II；Titanate esters and product B2Reaction molar ratio be 1:4.
Embodiment 3
1）By β methyl epoxy chloropropane and triethyl phosphite in molar ratio 1:1.5 under inert gas protection at 150 DEG C
4 h are reacted, remaining product A is then obtained by vacuum distillation3；
2）By remaining product A3It is dissolved in water, 7 h are reacted at 1 atmospheric pressure and 80 DEG C, water is removed and obtains product B3；
3）Butyl titanate is dissolved in anhydrous n-hexane, product B is then added3, it is stirred to react 2 h at 60 DEG C, is evaporated under reduced pressure
Solid product is obtained, as phosphorus-titanium complex polyester catalyst III；Titanate esters and product B3Reaction molar ratio be 1:3.
Embodiment 4
1）By β methyl epoxy chloropropane and Trimethyl phosphite in molar ratio 1:7 is anti-at 90 DEG C under inert gas protection
8 h are answered, remaining product A is then obtained by vacuum distillation4；
2）By remaining product A4It is dissolved in water, 10 h are reacted at 1 atmospheric pressure and 70 DEG C, water is removed and obtains product B4；
3）Butyl titanate is dissolved in anhydrous n-hexane, product B is then added4, it is stirred to react 1 h at 80 DEG C, is evaporated under reduced pressure
Solid product is obtained, as phosphorus-titanium complex polyester catalyst IV；Titanate esters and product B4Reaction molar ratio be 1:1.5；
Polyester that embodiment 1-4 is obtained is used separately as to the catalyst of the synthesis technology of PET, obtained PET with Titanium series catalyst
0.64 dL/g of product characteristic viscosity ＞, L values are more than 80, b values and are less than 3, and content of carboxyl end group is less than 20 ppm, product brightness high nothing
Xanthochromia can be used to the processing of textile of chemical fibre, edible bottle without additional dyestuff.
Polyester made from the preparation process of the embodiment of the present invention with phosphorus-titanium complex catalyst all have two or two with
Upper chelating ring structure, and phosphinate substituent group can also be made according to the difference of preparation process there are one each chelate rings
Phosphonate groups are connected to polyester phosphorus-titanium complex catalyst product on a chelate ring simultaneously.
The molar ratio of halogenated epoxide and phosphite ester of the present invention is 1:1~1:7, titanate esters are reacted with product B's
Molar ratio is 1:1.5~1:4, deviateing aforementioned ratio range can cause the reaction of certain raw material endless, waste one of which raw material
And be difficult to remove, and the deviation of product molecule structure can be caused；The reaction temperature of each step can not also be detached from its model
It encloses, if reaction temperature less than temperature range lower limit, can cause, reaction cannot carry out or reaction speed is excessively slow, beyond in temperature range
Limit can then cause side reaction, reaction product decomposition except being expected, or cause evaporation of the solvent loss；It can in reaction time range
Reaction conversion ratio is improved, also makes the more blunt interference to outside environmental elements of reaction insensitive, is conducive to the steady of each stage product
Fixed, if the reaction time can cause less than the range limited, reaction does not complete or conversion ratio is insufficient, and the reaction time is long to cause
Product decomposes, and wastes heat source.The pressure of the vacuum distillation is obtained with realizing that impurity vaporizes subject to remaining product.It is practical
Allow there is production error to the boundary value of each parameter area in production.
The organic solvent 1 is selected from the anhydrous organic solvent that can dissolve titanate esters and product B.
The water used during preparation process is the common water, preferably deionized water such as tap water, distilled water or deionized water
And distilled water.
The preparation process of phosphorus of the present invention-titanium complex polyester catalyst is not limited to described in embodiment, for institute of the present invention
For the those of ordinary skill for belonging to technical field, without departing from the inventive concept of the premise, it can also make and several simply push away
It drills or replaces, all shall be regarded as belonging to protection scope of the present invention.
Claims (3)
1. a kind of phosphorus-titanium complex polyester catalyst, it is characterised in that：There are one center titanium atom, at least two for tool in its molecular formula
A phosphonate substituted group and at least two chelate rings；The wherein described chelate ring passes through titanyl key key with center titanium atom
It closes；The structure of each chelate ring is identical or different, and any in five-membered ring~octatomic ring；Each phosphonate ester takes
It is identical or different for the structure of group, it is located on arbitrary chelate ring and passes through C with chelate ring1~C7Any aliphatic is sub-
Alkyl is connected；It is arbitrary to connect substitution site of the alkylidene of phosphonate groups on ring.
2. phosphorus according to claim 1-titanium complex polyester catalyst, it is characterised in that：Have at least on the chelate ring
One C1~C6Alkyl substituent.
3. a kind of preparation process of polyester Titanium series catalyst described in claim 1, it is characterised in that：It includes following step
Suddenly：
1）By halogenated epoxide and phosphite ester in molar ratio 1:1~1:7 under inert gas protection in 90~180 DEG C
Then 2~8 h of lower reaction obtain remaining product A by vacuum distillation；
2）Remaining product A is dissolved in water, 3~10 h are reacted at 1~2 atmospheric pressure and 70~120 DEG C, water is removed and obtains product
B；
3）Titanate esters are dissolved in organic solvent 1, product B is then added, 1~6 h is stirred to react at 0~80 DEG C, are evaporated under reduced pressure
Obtain solid product, as Titanium series catalyst I；Titanate esters are 1 with the molar ratio that reacts of product B:1.5~1:4；
Wherein, the phosphite ester is selected from general formulaCompound, wherein R1Selected from C1~C12Aliphatic alkane
It is any in base or aromatic alkyl or hydrogen；X1And X2It is identical or different, and it is independently selected from C1~C12Aliphatic alkyl or alcoxyl
It is any in base, aromatic alkyl or alkoxy, hydrogen；
The halogenated epoxide is selected from general formulaCompound, wherein X be selected from halogen atom, R2Selected from master
Carbon chain lengths are C1~C4Any alkylidene, wherein each carbon atom can be independent by any C1~C6Alkyl substitution, R3
Selected from C1~C7Any aliphatic alkylidene；
The titanate esters are selected from general formulaCompound, wherein R4、R5、R6、R7It is identical or different, and be independently selected from
Any C1~C8Aliphatic alkyl；
The organic solvent 1 is selected from the anhydrous organic solvent that can dissolve reactant.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113773480A (en) * | 2020-06-09 | 2021-12-10 | 中国石油化工股份有限公司 | Catalyst composition for preparing polyglycolide and preparation method of polyglycolide |
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| CN108484895B (en) | 2020-06-30 |
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