CN106832241B - A method of polyethylene terephthalate is prepared using composite catalyst - Google Patents
A method of polyethylene terephthalate is prepared using composite catalyst Download PDFInfo
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- CN106832241B CN106832241B CN201610978237.6A CN201610978237A CN106832241B CN 106832241 B CN106832241 B CN 106832241B CN 201610978237 A CN201610978237 A CN 201610978237A CN 106832241 B CN106832241 B CN 106832241B
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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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- 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
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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
- C08G63/87—Non-metals or inter-compounds thereof
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Abstract
The invention discloses a kind of methods for preparing polyethylene terephthalate using composite catalyst, this method is prepared in the reaction of polyethylene terephthalate using terephthalic acid (TPA) and ethylene glycol as raw material, it is catalyzed using the composite catalyst for including butyl titanate, tetraethyl orthosilicate and phenyl-phosphonic acid, molecular weight height, narrow molecular weight distribution, mechanical property and the good PET of thermal stability can be obtained, and the catalytic activity of the composite catalyst is active 17 times of antimony-based catalyst or more.
Description
Technical field
The present invention relates to synthesis technologies, particularly, are related to a kind of method for synthesizing polyethylene terephthalate.
Background technique
Polyethylene terephthalate (PET) is terephthalic acid (TPA) (PTA) and ethylene glycol (EG) through over-churning and contracting
The product that poly- reaction generates is a kind of synthetic material that yield is maximum, kind is most in the production of China's polyester product, is applied to
The multiple fields such as fiber, film, bottle use.
In recent years, with countries and regions such as America and Europes, the concept of " green fiber " is proposed in succession, and environment-friendly and green fiber is spun
Fabric becomes the trend of Overseas Development.This woven green fiber of raw material being safe from harm to human health and environment is spun
The trend of fabric makes the outlet of China's textile receive threat.This is because the catalyst of common synthesis PET is that antimony system urges
Agent, germanium series catalysts and Titanium series catalyst.
Antimony catalysis catalyst mainly includes antimony oxide, antimony acetate and antimony glycol, although antimony-based catalyst technique
The advantages that comparative maturity has catalytic activity moderate, and side reaction is few, cheap, but Sb catalyst is being widely used
Simultaneously there is also some obvious disadvantages: since antimonial itself has certain toxicity, in nature again with severe toxicity
Arsenic coexists, and therefore, receives certain limitation using the application of Sb catalyst.In addition, due to Sb2O3Or Sb (Ac)3Catalysis is closed
At PET in spinning, remaining Sb can carry PET secretly when melt goes out spinneret orifice and distil together, pollution spinning scene.Environmental protection
Aspect, the EG residue containing Sb have to handle, and Sb can take out the dirt caused to process water by unrestrained in textile dyeing process
Dye, these can all cause the increase antimony ion of processing cost as heavy metal, have chronic toxicity and carcinogenicity to human body, poly-
Content is big in ester, does not meet the requirement of Green Textiles.
Germanium in germanium series catalysts resource scarcity in nature, so that germanium series catalysts are expensive, it is difficult to real
Now it is industrially used.
And Titanium series catalyst, because it does not contain heavy metal, and have many advantages, such as environment-friendly high-efficiency, harmless, becomes
The preferred catalyst that antimony and germanium can be substituted, becomes research hotspot in recent years.
But Titanium series catalyst stability itself is poor, facile hydrolysis, cause with its production PET product thermal stability it is poor,
Yellowish, but also it is low there are catalytic efficiency the problems such as, never obtain large-scale use.
It would therefore be highly desirable to a kind of method for developing environmental-friendly, high catalytic efficiency production PET.
Summary of the invention
To solve the above-mentioned problems, present inventor has performed sharp study, discovery is being with terephthalic acid (TPA) and ethylene glycol
Raw material is prepared in the reaction of polyethylene terephthalate, using including butyl titanate, tetraethyl orthosilicate and phenyl-phosphonic acid
Composite catalyst be catalyzed, it is good that molecular weight height, narrow molecular weight distribution, mechanical property and thermal stability can be obtained
PET, and the catalytic activity of the composite catalyst is active 17 times of antimony-based catalyst or more, thereby completing the present invention.
The present invention provides a kind of method for preparing polyethylene terephthalate, it includes metatitanic acid four that this method, which uses,
The composite catalyst of butyl ester, tetraethyl orthosilicate and phenyl-phosphonic acid is catalyzed, it is preferable that the composite catalyst is anti-in esterification
Reaction system is added before answering.
Detailed description of the invention
Fig. 1 shows the DSC curve figure of each sample in experimental example 2；
Fig. 2 shows the TG curves of each sample in experimental example 3；
Fig. 3 shows the DTG curve of each sample in experimental example 3；
Fig. 4 shows the dynamic curve diagram of sample in experimental example 6；
Fig. 5 shows the inherent viscosity curve graph of sample in experimental example 8；
Fig. 6 shows the DSC curve figure that sample is made in comparative example 2 in experimental example 11；
Fig. 7 shows the DSC curve figure that sample is made in embodiment 3 in experimental example 11；
Fig. 8 shows comparative example 2 and 3 Esterification Stage of embodiment in experimental example 12 and feeds the TG curve graph that sample is made；
Fig. 9 shows comparative example 2 and 3 Esterification Stage of embodiment in experimental example 12 and feeds the DTG curve graph that sample is made；
Figure 10 shows comparative example 2 and 3 polycondensation phase of embodiment in experimental example 12 and feeds the TG curve graph that sample is made；
Figure 11 shows comparative example 2 and 3 polycondensation phase of embodiment in experimental example 12 and feeds the DTG curve graph that sample is made；
Figure 12 shows amount of samples and esterification time relational graph in experimental example 14；
Figure 13 shows amount of samples and polycondensation time chart in experimental example 15；
Figure 14 shows amount of samples and PET form and aspect relational graph in experimental example 17；
Figure 15 shows amount of samples and PET hot property relational graph in experimental example 18；
Figure 16 shows the TG figure that PET is made in different catalysts dosage in experimental example 19；
Figure 17 shows the DTG figure that PET is made in different catalysts dosage in experimental example 19.
Specific embodiment
Present invention will now be described in detail, and the features and advantages of the invention will become with these explanations
It is apparent, clear.
The present invention described below.
According to the present invention, a kind of method for preparing polyethylene terephthalate is provided, wherein this method uses
Composite catalyst is catalyzed.
In the present invention, the raw material for preparing polyethylene terephthalate is terephthalic acid (TPA) and ethylene glycol.
In the present invention, the composite catalyst includes butyl titanate, tetraethyl orthosilicate and phenyl-phosphonic acid.
In the present invention, in the composite catalyst, the mole of butyl titanate, tetraethyl orthosilicate and phenyl-phosphonic acid
The ratio between be butyl titanate mole: the mole of tetraethyl orthosilicate: the mole of phenyl-phosphonic acid=(6~12): 1:(1~
3), preferably (8~10): 1:(1.5~2.5), such as 9:1:2, wherein the mole of butyl titanate is rubbed with wherein titanium elements
That meter；The mole of tetraethyl orthosilicate is with the molar amount of wherein element silicon；The mole of phenyl-phosphonic acid is with wherein P elements
Molar amount.
The inventors discovered that with the dosage of tetraethyl orthosilicate as 1 molar equivalent when, when the mole of butyl titanate
When greater than 12 molar equivalent,
Synthesized PET form and aspect are deteriorated, and yellowish, when less than 6 molar equivalent, catalytic efficiency is lower, and reaction rate becomes
Slowly.
The present inventors have additionally discovered that with the dosage of tetraethyl orthosilicate as 1 molar equivalent when, when the mole of phenyl-phosphonic acid
When greater than 3 molar equivalent,
Phenyl-phosphonic acid easily forms precipitating or gel with metal function in system, the quality of PET is influenced, less than 1 molar equivalent
When, composite catalyst easily hydrolyzes, bad stability.
In a kind of preferred embodiment of the present invention, the composite catalyst further includes dispersing agent, it is preferable that described
Dispersing agent is ethylene glycol.
The inventors discovered that tetraethyl orthosilicate and butyl titanate intersolubility are poor, make tetraethyl orthosilicate, metatitanic acid when simple
When four butyl esters and phenyl-phosphonic acid mix, the immiscible two-phase of the composition self-assembling formation, this not only causes the inconvenience taken,
It is uncertain to also result in the proportion of the composite catalyst when in use, it is unstable so as to cause catalytic efficiency.
It is amazing to be, the inventors discovered that, the ethylene glycol as polymerization reaction raw material is to tetraethyl orthosilicate, metatitanic acid
Four butyl esters and phenyl-phosphonic acid all have good dissolubility, show as using it as composite catalyst made from solvent single
Homogeneous system directly serves as excessive original moreover, the ethylene glycol in system does not need to remove when using the composite catalyst
Material, in this way processing can also promote the positive of reaction to carry out, and improve yield and yield.
In the present invention, based on the total volume of composite catalyst, wherein the molar concentration of titanium elements is (0.1~1)
Mol/L, preferably (0.2~0.8) mol/L, more preferably (0.3~0.6) mol/L, such as 0.457mol/L.
The inventors discovered that working as composite catalyst when the molar concentration of titanium elements in composite catalyst is greater than 1mol/L
When the molar concentration of middle titanium elements is less than 0.1mol/L, catalytic efficiency is reduced, reaction speed decline, therefore, present invention selection
Total volume based on composite catalyst, wherein the molar concentration of titanium elements is (0.1~1) mol/L.
In the present invention, the composite catalyst is made by the following method: by tetraethyl orthosilicate, phenyl-phosphonic acid and
Butyl titanate and dispersant.
In a kind of preferred embodiment of the present invention, the composite catalyst passes through method comprising the following steps system
:
Step 1-1, tetraethyl orthosilicate is added in dispersing agent, optionally stirs, obtains the dispersion of tetraethyl orthosilicate；
Step 1-2, phenyl-phosphonic acid is added in the dispersion of above-mentioned tetraethyl orthosilicate, optionally stirs, is then added
Into butyl titanate.
In the present invention, the composite catalyst is before esterification or reaction system is added in esterification stage.
The inventors discovered that composite catalyst be added opportunity to the form and aspect of PET product, molecular weight, molecular weight distribution,
Hot property and mechanical property have larger impact, are embodied in compared in the polycondensation reaction stage addition catalyst,
Before esterification or esterification stage be added the PET product brightness that the composite catalyst obtains it is high, it is of light color, point
Son amount is big, narrow molecular weight distribution, thermal stability are high, mechanical property is strong.(referring specifically to experimental example 9~13)
Therefore, the composite catalyst is added before esterification or in esterification stage in present invention selection.
The present inventor also found that the additional amount of composite catalyst is to synthesis poly terephthalic acid second two by numerous studies
Reaction time of esterification and polycondensation reaction time produce great influence in alcohol ester, are embodied in the use of composite catalyst
Amount is bigger, and the time of esterification is shorter, and with the increase of composite catalyst usage amount, after polycondensation reaction time first shortens
Increase, is 19 μ g/g (weight of the dosage based on terephthalic acid (TPA), with the weight of wherein titanium elements in the dosage of composite catalyst
Meter) when, the time of polycondensation reaction is most short.(referring specifically to experimental example 14~20)
Therefore, the present invention selects the dosage of composite catalyst for (5~50) μ g/g, preferably (9~40) μ g/g, more excellent
It is selected as (15~30) μ g/g, such as 9.5 μ g/g, 19 μ g/g, 28.5 μ g/g and 38 μ g/g, particularly preferably 19 μ g/g, wherein institute
Weight of the dosage based on terephthalic acid (TPA) is stated, with the poidometer of wherein titanium elements.
In a kind of preferred embodiment of the present invention, it the described method comprises the following steps:
Step 1, esterification: terephthalic acid (TPA), ethylene glycol and composite catalyst are added in polymeric kettle, mixing, preferably
Ground heating, adds ethylene glycol and antioxidant, it is preferable that also add heat stabilizer, continues to mix；
Step 2, polycondensation reaction: first make to enter back into high vacuum shape after a period of time in low vacuum state in reaction kettle
State, then make heating in kettle, being kept stirring to reaction terminates.
In step 1 of the present invention, when initially feeding intake, the weight of terephthalic acid (TPA), ethylene glycol and composite catalyst it
Than the weight for phthalic acid: the weight of ethylene glycol: the weight of composite catalyst=(600~800): (265~365):
(0.10~0.15), preferably (650~750): (280~325): (0.11~0.13), such as 700:315:0.12.
The present invention is not specially limited mixed method, and any liquid phase mixing in the prior art can be used
Mode, such as stirring.
In step 1 of the present invention, it is preferable that be warming up to system and system is warming up to (130~260) DEG C, preferably
(180~255) DEG C, such as 245 DEG C or 255 DEG C.
The inventors discovered that guaranteeing that esterification rate is stable and reaches preset esterification yield under the conditions of above-mentioned temperature.
In step 1 of the present invention, 1~3hr, preferably 1.5~2.5hr, such as 1.5hr are kept under the conditions of above-mentioned temperature.
The inventors discovered that keeping the temperature under the conditions of above-mentioned temperature, heat preservation enables esterification to continue in 1~3 hour, has
Conducive to further increasing esterification yield.
The inventors discovered that adding ethylene glycol after keeping the temperature 30~40min. under the conditions of above-mentioned temperature, making its esterification yield
Reach 99% or more, while antioxidant is added, the oxidative degradation in polycondensation process is inhibited therefore to add into reaction system
Ethylene glycol and antioxidant.
Preferably, heat stabilizer is added into system, the total weight based on terephthalic acid (TPA), with the weight of heat stabilizer
Meter, the amount for the heat stabilizer added are 0.05%~0.2%, preferably 0.08~0.15%, such as 0.1%, in the present invention,
The heat stabilizer is triphenyl phosphite.
In step 1 of the present invention, the total weight based on terephthalic acid (TPA), with the poidometer of ethylene glycol, the ethylene glycol added
Amount be 0.5%~4%, preferably 1%~3%, such as 2%.
In step 1 of the present invention, the total weight based on terephthalic acid (TPA), with the poidometer of antioxidant, the antioxidant added
Amount be 0.03%~0.1%, preferably 0.05~0.08%, such as 0.07%.
In the present invention, antioxidant is preferably antioxidant 1010, antioxidant 1212 etc..
In step 2 of the present invention, it is in reaction system in vacuum environment.
The inventors discovered that system should be made to keep low vacuum state in the polycondensation incipient stage, increasing vacuum in reaction kettle
The process of degree will be carried out slowly, and material viscosity is lower at this time, if vacuum pumping rate is too fast, be easy material being pumped into vacuum
System leads to pipeline blockage.
In step 2 of the present invention, the low vacuum state refers to vacuum degree in -30kPa~-80KPa, preferably -50
~-70kPa, such as -60kPa.
After keeping 30~40min. under low vacuum state in reaction kettle, then make to reach high vacuum state in reaction kettle.
The inventors discovered that low vacuum state is kept for a period of time can prevent vacuum system putty, avoid polymerization can not
It carries out.
In the present invention, the high vacuum state refer in reaction kettle absolute pressure in 50~100Pa, preferably 50~
70Pa, such as 50Pa.
In step 2 of the present invention, under high vacuum state, temperature in the kettle is set to be increased to 200 DEG C~400 DEG C, preferably
250 DEG C~350 DEG C, such as 280 DEG C.
The inventors discovered that can not only guarantee suitable reaction rate, but also can preferably press down under the conditions of above-mentioned temperature
The generation of side reaction processed, and then guarantee the form and aspect of product.
In step 2 of the present invention, the mode of stirring is specially first keep frequency in 50Hz, until power of agitator 50W, then will
Frequency is adjusted to 25Hz；Power to be mixed rises to 35KW, closes stirring, and polycondensation reaction terminates, viscous until reaching suitable polymer
Spend or reach suitable polymer molecular weight.
Optionally, further comprising the steps of:
Step 3, pelletizing: nitrogen extruding and discharging, Cast Strip, then the pellet for PET batten pelletizing will be obtained obtaining are used；
Step 4, drying: the pellet that step 3 is obtained is dried.
Possessed by of the invention the utility model has the advantages that
(1) composite catalyst used in the present invention includes butyl titanate, tetraethyl orthosilicate and phenyl-phosphonic acid, composition
Simply；
(2) the heretofore described reaction for preparing polyethylene terephthalate, it is specific to use terephthalic acid (TPA) and second
Glycol is raw material；
(3) in method provided by the invention, the catalytic activity of composite catalyst used is higher, and specifically, catalysis is lived
Property is about 17 times of antimony oxide；
(4) polyethylene terephthalate (PET) intrinsic viscosity made from this method is high, and molecular weight is high, divides
The advantages of son amount narrowly distributing；
(5) with PET glass transition temperature (Tg) made from this method, melting temperature (Tm) cold crystallization temperature (Tcc) with
Sb2O3It is not much different for catalyst sample, but thermal stability improves；
(6) tensile strength of PET is made with this method and elongation at break improves.
Embodiment
The present invention is further described below by way of specific embodiment.But these embodiments are only exemplary, not
Any restrictions are constituted to protection scope of the present invention.
The preparation of 1 composite catalyst of embodiment
2.23mL tetraethyl orthosilicate is added in ethylene glycol, optionally stirs, obtains the glycol solution of tetraethyl orthosilicate；
1.07mL phenyl-phosphonic acid is added in the glycol solution of above-mentioned tetraethyl orthosilicate, optionally stirs, be then added
In the butyl titanate of 20.47mL, composite catalyst is obtained.
The preparation of 2 composite catalyst of embodiment
2.23mL tetraethyl orthosilicate is added in ethylene glycol, optionally stirs, obtains the glycol solution of tetraethyl orthosilicate；
1.61mL phenyl-phosphonic acid is added in the glycol solution of above-mentioned tetraethyl orthosilicate, optionally stirs, be then added
In the butyl titanate of 27.33mL, composite catalyst is obtained.
The preparation of 3 composite catalyst of embodiment
2.23mL tetraethyl orthosilicate is added in ethylene glycol, optionally stirs, obtains the glycol solution of tetraethyl orthosilicate；
2.14mL phenyl-phosphonic acid is added in the glycol solution of above-mentioned tetraethyl orthosilicate, optionally stirs, be then added
In the butyl titanate of 30.75mL, composite catalyst is obtained.
The preparation of 4 composite catalyst of embodiment
2.23mL tetraethyl orthosilicate is added in ethylene glycol, optionally stirs, obtains the glycol solution of tetraethyl orthosilicate；
2.68mL phenyl-phosphonic acid is added in the glycol solution of above-mentioned tetraethyl orthosilicate, optionally stirs, be then added
In the butyl titanate of 34.17mL, composite catalyst is obtained.
The preparation of 5 composite catalyst of embodiment
2.23mL tetraethyl orthosilicate is added in ethylene glycol, optionally stirs, obtains the glycol solution of tetraethyl orthosilicate；
3.22mL phenyl-phosphonic acid is added in the glycol solution of above-mentioned tetraethyl orthosilicate, optionally stirs, be then added
In the butyl titanate of 41.00mL, composite catalyst is obtained.
The synthesis of 6 polyethylene terephthalate of embodiment
Esterification stage: into polymeric kettle, addition 700g PTA, 314g EG, 0.0112g embodiment 3 are prepared compound
Catalyst (with the poidometer of titanium elements therein) then opens stirring, is heated to 230 DEG C of temperature in kettle from room temperature, controls in kettle
Pressure is in 300-350KPa to water yield 50mL, and standard-sized sheet is discharged needle-valve, adds 13g EG, 0.4g antioxidant under normal pressure
1010 and 0.7g heat stabilizer triphenyl phosphite.It is stirred to react 40min, temperature rise is to 260 DEG C in kettle, esterification stage knot
Beam.
Polycondensation reaction stage: being first in low vacuum stage 30-40min, this process will be carried out slowly, prevent from vacuumizing
It is too fast that material in kettle is caused to be sucked out blocking pipeline, to this stage after, enter back into high vacuum stage of Fig (in reaction kettle absolutely
Pressure is 50Pa), temperature is gradually to 280 DEG C in kettle, and first keep frequency is in 50Hz, until power of agitator 50W, then frequency is adjusted to
25Hz, power to be mixed rise to 35KW.Stirring is closed, polycondensation reaction terminates.
The synthesis of 7 polyethylene terephthalate of embodiment
Esterification stage: what into polymeric kettle prepared by addition 700g PTA, 314g EG and 0.0126g embodiment 3 answers
It closes catalyst (with the poidometer of titanium elements therein), opens stirring, be heated to 230 DEG C of temperature in kettle from room temperature, control kettle internal pressure
Power is in 300-350KPa to water yield 50mL, and standard-sized sheet is discharged needle-valve, adds 13g EG, 0.4g antioxidant under normal pressure
1010 and 0.7g heat stabilizer triphenyl phosphite.It is stirred to react 40min, temperature rise is to 260 DEG C in kettle, esterification stage knot
Beam.
Polycondensation reaction stage: being first in low vacuum stage 30-40min, this process will be carried out slowly, prevent from vacuumizing
It is too fast that material in kettle is caused to be sucked out blocking pipeline, to this stage after, enter back into high vacuum stage of Fig (in reaction kettle absolutely
Pressure is 50Pa), temperature is gradually to 280 DEG C in kettle, and first keep frequency is in 50Hz, until power of agitator 50W, then frequency is adjusted to
25Hz, power to be mixed rise to 35KW.Stirring is closed, polycondensation reaction terminates.
The synthesis of 8 polyethylene terephthalate of embodiment
Esterification stage: into polymeric kettle, addition 700g PTA, 314g EG, 0.0133g embodiment 3 are prepared compound
Catalyst (with the poidometer of titanium elements therein) opens stirring, is heated to 230 DEG C of temperature in kettle from room temperature, controls pressure in kettle
In 300-350KPa to water yield 50mL, standard-sized sheet is discharged needle-valve, adds 13g EG, 0.4g antioxidant 1010 under normal pressure
With 0.7g heat stabilizer triphenyl phosphite.It is stirred to react 40min, to 260 DEG C, esterification stage terminates for temperature rise in kettle.
Polycondensation reaction stage: being first in low vacuum stage 30-40min, this process will be carried out slowly, prevent from vacuumizing
It is too fast that material in kettle is caused to be sucked out blocking pipeline, to this stage after, enter back into high vacuum stage of Fig, temperature gradually arrives in kettle
280 DEG C, first keep frequency is in 50Hz, until power of agitator 50W, then frequency is adjusted to 25Hz, power to be mixed rises to 35KW.It closes
Stirring is closed, polycondensation reaction terminates.
The synthesis of 9 polyethylene terephthalate of embodiment
Esterification stage: into polymeric kettle, addition 700g PTA, 314g EG, 0.014g embodiment 3 are prepared compound
Catalyst (with the poidometer of titanium elements therein) is heated to 230 DEG C of temperature in kettle from room temperature, controls pressure in kettle and is in 300-
350KPa to water yield 50mL, standard-sized sheet are discharged needle-valve, add 13g EG, 0.4g antioxidant 1010 and 0.7g heat under normal pressure
Stabilizer triphenyl phosphite.It is stirred to react 40min, to 260 DEG C, esterification stage terminates for temperature rise in kettle.
Polycondensation reaction stage: being first in low vacuum stage 30-40min, this process will be carried out slowly, prevent from vacuumizing
It is too fast that material in kettle is caused to be sucked out blocking pipeline, to this stage after, enter back into high vacuum stage of Fig (in reaction kettle absolutely
Pressure is 50Pa), temperature is gradually to 280 DEG C in kettle, and first keep frequency is in 50Hz, until power of agitator 50W, then frequency is adjusted to
25Hz, power to be mixed rise to 35KW.Stirring is closed, polycondensation reaction terminates.
The synthesis of 10 polyethylene terephthalate of embodiment
Esterification stage: into polymeric kettle, addition 700g PTA, 314g EG, 0.0154g embodiment 3 are prepared compound
Catalyst (with the poidometer of titanium elements therein) opens stirring, is heated to 230 DEG C of temperature in kettle from room temperature, controls pressure in kettle
In 300-350KPa to water yield 50mL, standard-sized sheet is discharged needle-valve, adds 13g EG, 0.4g antioxidant 1010 under normal pressure
With 0.7g heat stabilizer triphenyl phosphite.It is stirred to react 40min, to 260 DEG C, esterification stage terminates for temperature rise in kettle.
Polycondensation reaction stage: being first in low vacuum stage 30-40min, this process will be carried out slowly, prevent from vacuumizing
It is too fast that material in kettle is caused to be sucked out blocking pipeline, to this stage after, enter back into high vacuum stage of Fig (in reaction kettle absolutely
Pressure is 50Pa), temperature is gradually to 280 DEG C in kettle, and first keep frequency is in 50Hz, until power of agitator 50W, then frequency is adjusted to
25Hz, power to be mixed rise to 35KW.Stirring is closed, polycondensation reaction terminates.
Comparative example
Comparative example 1
The synthesis process of embodiment 3 is repeated, difference is, spent glycol titanium substitutes butyl titanate, and does not add phenyl
Binary composite catalyst is made in phosphonic acids.
Comparative example 2
The synthesis process of embodiment 3 is repeated, difference is, spent glycol titanium substitutes butyl titanate, and composite catalyzing is made
Agent.
Comparative example 3
The synthesis process of embodiment 8 is repeated, difference is, catalyst uses antimony oxide (Sb2O3), and dosage is
334 μ g/g, wherein be based on 1g terephthalic acid (TPA), the dosage of Sb element is 334 μ g.
Comparative example 4
The synthesis process of embodiment 8 is repeated, difference is, catalyst uses titanium ethylene glycolate.
Comparative example 5
The synthesis process of embodiment 8 is repeated, difference is, the binary composite catalyzing that catalyst uses comparative example 1 to prepare
Agent.
Comparative example 6
The synthesis process of embodiment 8 is repeated, difference is, the composite catalyst that catalyst uses comparative example 2 to prepare.
Comparative example 7
The synthesis process of embodiment 8 is repeated, difference is, compound the urging of the preparation of embodiment 3 is added in polycondensation reaction stage
Agent.
Experimental example
The test of 1 coloration of experimental example
Form and aspect are an important indicators of PET product, usually with L value, the expression of b value.When L value is bigger, the brightness of product is got over
Greatly, product will be whiter, otherwise more black；The b value of product is bigger, and the color of product is more yellow, otherwise more blue.
The L value of usual Titanium series catalyst synthesis PET is big, illustrates that PET product brightness is good, and b value is high, shows that product is partially yellow, this
It is that many side reactions are also catalyzed while catalytic esterification, polycondensation main reaction due to catalytic activity height because of Titanium series catalyst,
Exchange reaction of chain aggravation in system simultaneously, causes product form and aspect to turn yellow.
The present invention uses the full-automatic colour difference meter of SC-100 of Beijing Kang Guang optical instrument Co., Ltd production, respectively to reality
It applies the polyethylene terephthalate that example 8 and comparative example 3~6 synthesize to be tested, obtains the coloration b value and L value of sample.Its
In, test temperature is room temperature, and testing time is 5 times, and results are averaged, and test result is as shown in table 1.
The b value and L value for the sample that 1 embodiment 8 of table and comparative example 3~6 synthesize
| Sample | Catalyst amount (μ g/g) | B value | L value |
| Embodiment 8 | 19 | 6.83 | 42.69 |
| Comparative example 3 | 334 | 4.22 | 33.67 |
| Comparative example 4 | 19 | 9.37 | 41.77 |
| Comparative example 5 | 19 | 8.32 | 42.07 |
| Comparative example 6 | 19 | 7.51 | 41.65 |
Note: sample is to have light PET greatly.
As can be seen from Table 1:
(1) in embodiment 8 and 4~comparative example of comparative example 6, the b value for the sample that embodiment 8 obtains is minimum, and L value is maximum,
Illustrate, the PET yellowing obtained using composite catalyst of the present invention is relatively low；
(2) the b value for the sample that embodiment 8 obtains is higher than the b value for the sample that comparative example 3 obtains, that is because titanium system is catalyzed
Caused by agent feature itself, obtained product can slightly turn to be yellow, but for embodiment 8, yellowing has been obtained
It is obviously improved, and can satisfy requirement, therefore, three oxidations two of composite catalyst of the present invention better than toxicity
Antimony.
2 differential scanning calorimetry of experimental example (DSC) test
This experimental example sample used is that embodiment 8 and comparative example 3~6 are made.
Using the Seiko DSC-6200 type differential scanning calorimeter of Japanese Seiko Instruments Inc. to above-mentioned
Sample is tested, wherein nitrogen flow rate is under 50mL/min state, and temperature range is 30 DEG C -300 DEG C, heating rate 10
DEG C/min, sample weight 6-10mg, test results are shown in figure 1, wherein
Curve 1 indicates that the DSC curve of sample is made in comparative example 3；
Curve 2 indicates that the DSC curve of sample is made in comparative example 4；
Curve 3 indicates that the DSC curve of sample is made in comparative example 5；
Curve 4 indicates that the DSC curve of sample is made in comparative example 6；
Curve 5 indicates that the DSC curve of sample is made in embodiment 8；
Data shown in table 2 can be obtained as Fig. 1:
The transition temperature and crystallinity of 2 PET sample of table
| Sample | Tg(℃) | Tcc(℃) | Tm(℃) | Xcc(%) |
| Comparative example 3 | 73.6 | 132.3 | 249.8 | 30.1 |
| Comparative example 4 | 73.9 | 137.2 | 252.3 | 28.7 |
| Comparative example 5 | 73.5 | 141.2 | 252.1 | 26.3 |
| Comparative example 6 | 73.7 | 140.2 | 254.2 | 27.1 |
| Embodiment 8 | 73.0 | 141.0 | 252.9 | 26.6 |
As can be seen from Table 2, the sample that the glass transition temperature and comparative example 3 for the sample that embodiment 8 obtains obtain
Glass transition temperature is very nearly the same, almost unanimously, still, the melting temperature and cold crystallization temperature of the sample that embodiment 8 obtains
Increased.
By table 2 it can also be seen that the usage amount of composite catalyst provided by the invention (dosage of catalyst is with Ti:PTA
Mass ratio meter) less, synthesized PET narrow molecular weight distribution, the PET that PET molecular weight is synthesized with antimony oxide is close, very
It extremely can be higher.
The glass transition temperature (Tg) of the PET sample of composite catalyst synthesis provided by the invention, melting temperature
(Tm), the glass transition temperature (Tg) for the PET sample that cold crystallization temperature (Tcc) and antimony oxide catalyze and synthesize, melting temperature
Degree (Tm), cold crystallization temperature (Tcc) are not much different, and show that the product composition of two kinds of catalyst synthesis, structure are extremely close.
3 thermal weight loss of experimental example (TG) test
This experimental example sample used is embodiment 8, comparative example 3,4 and 6 is made.
Operating method or instrument: it is tested using the WCT-2D microcomputer differential thermal balance of Beijing Optical Instrument Factory's production, in nitrogen
Protection under carry out test sample polyester thermal stability.0-800 DEG C of temperature range, heating rate is 10 DEG C/min, nitrogen stream
Fast 100ml/min, sample weight 6.0-8.0mg.
Test result is as shown in Figures 2 and 3, wherein
Fig. 2 shows the TG test curves of sample；
Fig. 3 shows the DTG curve of sample.
In Fig. 2,
Curve 1 indicates that the TG curve of sample is made in comparative example 3；
Curve 2 indicates that the TG curve of sample is made in comparative example 4；
Curve 3 indicates that the TG curve of sample is made in comparative example 6；
Curve 4 indicates that the TG curve of sample is made in embodiment 8；
In Fig. 3,
The DTG curve of expression 3 sample of comparative example of curve 1；
Curve 2 indicates that the DTG curve of sample is made in comparative example 4；
Curve 3 indicates that the DTG curve of sample is made in comparative example 6；
Curve 4 indicates that the DTG curve of sample is made in embodiment 8.
The weight-loss ratio corresponding temperature of each sample is listed as follows table 3
3 weight-loss ratio corresponding temperature (DEG C) of table
By Fig. 2 and Fig. 3 and table 3 it is found that the PET sample thermal stability ratio that composite catalyst provided by the invention synthesizes
The thermal stability for the PET sample that antimony oxide catalyzes and synthesizes increases.
The anaerobic thermal degradation of polymer is generally divided into two courses, and one is elimination reaction, that is, eliminates some low molecules and wave
Volatile material, such as H2、H2O, HCl etc., and the macromolecular main chain of polymer is basically unchanged；It is another to be broken for macromolecular main chain
Cracking.The thermal degradation of PET is mainly end of the chain thermal degradation and interchain thermal degradation, and wherein interchain thermal degradation is the position β that machine is connected therewith
Hydrogen atom on carbon atom is first broken, and relative molecular weight is caused to decline, and generates carbon-based and vinyl；Two end of the chain thermal degradations are then led
The generation for causing acetaldehyde, causes the decline of sample quality.
By molecular weight analysis it is found that the activity of composite catalyst provided by the invention is high, high-efficient, the PET catalyzed and synthesized
Molecular weight is bigger than the PET molecular weight that antimony oxide catalyzes and synthesizes, so the initial decomposition temperature of PET is increased, compared to
The PET thermal stability that antimony oxide catalyzes and synthesizes slightly improves, and the thermal degradation reaction of the end of the chain of PET has obtained effective suppression
System, so that weightless temperature be made to increase.
4 Mechanics Performance Testing of experimental example
This experimental example sample used is embodiment 8, comparative example 3~5 is made.
Using 5966 universal electrical Material Testing Machine of INSTRON, embodiment 8 and comparative example 3~5 are surveyed respectively
Examination, test result are as shown in table 3, wherein sample marking distance 25mm, rate of extension 10mm/min, testing standard is according to GB/T
1040-92。
4 mechanical experimental results of table
As can be seen from Table 4, high tensile strength and high elongation at break are had both by the sample that embodiment 8 obtains,
In, with comparative example 3 (with Sb2O3For catalyst) it compares, the tensile strength for the sample that embodiment 8 obtains improves 20.4%, fracture
Elongation improves 61.8%.
Wherein, in table 4, the tensile strength that product is made in embodiment 8 increases percentage and elongation at break increases percentage
Than being based on the test value for the sample that comparative example 3 obtains.
5 gel permeation chromatography of experimental example (GPC)
This experimental example sample used is embodiment 8, comparative example 3 and 5 is made.
Using the GPC515-2410 System gel permeation chrommatograph of Water company respectively to embodiment 8 and comparative example 3~5
The polyethylene terephthalate of synthesis is tested, and characterizes the molecular weight and molecular weight distribution of sample, wherein with a first
Phenol is solvent, and sample solution concentration 3-4mg/ml, flow velocity 1.0ml/min, standard sample is polystyrene (PS), and detector temperature is
100℃.Wherein, testing result is as shown in table 5.
The molecular weight and molecular weight distribution for the sample that 5 embodiment 8 of table, comparative example 3 and comparative example 5 synthesize
| Sample | Mw(×104) | Mw/Mn |
| Embodiment 8 | 4.36 | 1.82 |
| Comparative example 3 | 3.85 | 1.94 |
| Comparative example 5 | 3.26 | 1.86 |
As shown in Table 5, the molecular weight of sample made from embodiment 8 is all larger than the sample that comparative example 3 and comparative example 5 obtain
Molecular weight, and the molecular weight distribution of sample made from embodiment 8 is lower, illustrates, can using composite catalyst of the present invention
To obtain the PET product of high molecular weight and distribution of low molecular weight.
The analysis of 6 reaction rate constant of experimental example
The experimental example sample used is that comparative example 3 and embodiment 8 are made.
The sampling of polycondensation kinetics:
Polyester PET polymerization enters polycondensation phase, is initially in low vacuum stage 30-40min, this process is slow
Progress, prevent from vacuumizing it is too fast cause material in kettle to be sucked out blocking pipeline, to this stage after, enter back into high vacuum
In the stage, temperature is gradually to 280 DEG C in kettle, and first keep frequency is in 50Hz, until power of agitator 50W, then frequency is adjusted to 25Hz, wait stir
It mixes power and rises to 35KW.In the process, it at interval of certain time, is sampled with rod iron from feed opening under nitrogen protection effect.
The polycondensation reaction of polyester is the reversible balanced reaction of second level
Polycondensation reaction can be by G.Rafler equation calculation:
Integral arranges:
In formula:
COHFor hydroxyl ethyl ester base concentration；
K is rate constant；
For the average molecular mass of t moment polymer；
For the average molecular mass of initial reactant.
The timing sampling in polycondensation reaction, surveys its intrinsic viscosity [η], can be calculated its averagemolecular wt by formula (3)
Quality.
Wherein K=2.1 × 10-4, α=0.82 is according to the above method, with average molecular mass to polycondensation reaction time
Mapping can obtain the kinetic curve of polycondensation reaction, and the rate constant of each reaction can be obtained by carrying out linear regression processing to data.
As a result as shown in Fig. 4 and table 6,
In Fig. 4,
Curve 1 indicates that the rate constant curve of sample is made in embodiment 8；
Curve 2 indicates that the rate constant curve of sample is made in comparative example 3.
Influence of 6 catalyst of table to slice color and polycondensation reaction rate
As Fig. 4 and table 6 it is found that the rate constant of the reaction of composite catalyst made from embodiment 8 is 91.00 k/ [g.
(mol.min)-1], the rate constant of the reaction of catalyst made from comparative example 3 is 81.51k/ [g. (mol.min)-1], thus
As it can be seen that catalyst of the present invention, in the case where additive amount is only the 1/17 of comparative example, polycondensation reaction rate, which is still higher than, to be compared
Example.
The analysis of 7 catalytic activity of experimental example
This experimental example sample used is embodiment 8, comparative example 3,4 and 6 is made.
With experimental example 6, catalyst activity is calculated by catalyst loading for Examination on experimental operation and instrument, knot
Fruit is as shown in table 7,
Table the time required to the dosage and synthesis of 7 different catalysts of table
In table 7, with the activity of 3 catalyst of comparative example for standard, that is, remember the catalytic activity value of 3 catalyst of comparative example
It is 1 times, the catalytic activity value of other catalyst is compared with the value, obtains the catalytic activity multiple of other catalyst.
As shown in Table 7, because the esterification of terephthalic acid (TPA) PTA and ethylene glycol EG are self-catalyzed reaction, with the present invention
When the composite catalyst of offer synthesizes PET, esterification time shortens, so illustrating composite catalyst provided by the invention to esterification
Reaction have certain catalytic action, the reason is that the titanium element contained in composite catalyst provided by the invention can with to benzene
Dioctyl phthalate PTA and ethylene glycol terephthalate (BHET) carry out ligand complex reaction, and titanium element increases its carbonyl carbon
Electropositive, be conducive to ethylene glycol EG hydroxyl carry out nucleophillic attack, accelerate esterification reaction rate.
Composite catalyst dosage (dosage of catalyst is in terms of Ti:PTA mass ratio) provided by the invention is 19ug.g-1When,
The polycondensation time is 160min, Sb2O3The dosage of catalyst is 334ug.g-1, the polycondensation time is 160min.It can be seen that this hair
The composite catalyst dosage of bright offer is 19ug.g-1Catalytic activity be equivalent to Sb2O3Dosage is 334ug.g-1Catalysis it is living
Property, thereby, it is possible to extrapolate, the catalytic activity of composite catalyst provided by the invention is Sb2O317 times of catalytic activity.
The catalytic activity of titanium ethylene glycolate is higher than 17 times, since titanium ethylene glycolate catalytic activity is excessively high, leads to the b value of PET product
Excessively high, color is excessively yellow.
Influence of the different polymerization times of experimental example 8 to PET product characteristic viscosity
This experimental example sample used is that embodiment 3 and comparative example 3 are made.
Operating method: tetrachloroethanes and phenol 1:1 in mass ratio are uniformly mixed, and relative density is 1.2850g/ml (20
DEG C) mixed solvent.Utilize the inherent viscosity of Ubbelohde viscometer test sample.Wherein, intrinsic viscosity and average relative molecular mass
There are following relationship, capillary diameter 0.8mm, water bath with thermostatic control temperature is 25 ± 0.1 DEG C, calculation formula are as follows:
Wherein:
[η] is inherent viscosity,
t0For the delivery time of pure solvent,
ηr=t/t0For relative viscosity,
ηsp=(ηrIt -1) is specific viscosity,
C is polymer concentration in solution.
As a result as shown in Fig. 5 and table 8,
In Fig. 5,
Curve 1 indicates that the inherent viscosity curve of sample is made in embodiment 8；
Curve 2 indicates that the inherent viscosity curve of sample is made in comparative example 6.
The intrinsic viscosity of product is made in the different polymerization times of table 8
By Fig. 5 and table 8 it is found that in identical polymerization time, reach identical power of agitator, use is provided by the invention
The PET intrinsic viscosity that composite catalyst catalyzes and synthesizes is high, is the catalysis because the activity of composite catalyst provided by the invention is high
It is high-efficient, the PET molecular weight height and narrow molecular weight distribution of synthesis.
Influence of the opportunity to reaction time and PET product form and aspect is added in 9 composite catalyst of experimental example
This experimental example sample used is made by comparative example 2 and embodiment 3, as a result as shown in table 9 below:
Influence of the catalyst compounded addition opportunity of table 9 to synthesis PET reaction time and form and aspect
As shown in Table 9, during synthesizing PET, when polycondensation phase is added catalyst and adds catalyst than Esterification Stage
Esterification and polycondensation rate are obviously slack-off, and polymerization time significantly increases, and the form and aspect of the PET of synthesis are poor.
It is not bound by any theory, inventors believe that, composite catalyst provided by the invention has esterification and polycondensation
Catalytic action, Esterification Stage addition improve esterification rate, shorten esterification time；Simultaneously because Esterification Stage is added, experience
Mixing time is long, than the good dispersion that catalyst is added before polycondensation, and composite catalyst provided by the invention and terephthaldehyde
Sour double hydroxyl ethyl esters form stable complex compound, and composite catalyst stability is high, and hydrolytic inactivation rate is low, therefore polycondensation reaction speed
Rate is also high, and the reaction time shortens.
On the contrary, being added in polycondensation phase, due to the hot environment in reaction kettle, composite catalyst stability is poor, makes this hair
The composite catalyst of bright offer hydrolyzes, and reduces the activity of the composite catalyst, reduces the efficiency of composite catalyst,
And since mixing time is short, composite catalyst dispersibility is poor, and polycondensation reaction time is caused significantly to increase.
In addition, composite catalyst provided by the invention due to catalytic activity height, catalytic esterification, polycondensation main reaction it is same
When be also catalyzed many side reactions, while in system Exchange reaction of chain aggravate, cause product form and aspect turn yellow.
Influence of the opportunity to synthesis PET molecular weight and molecular weight distribution is added in 10 composite catalyst of experimental example
This experimental example sample used is made by comparative example 2 and embodiment 3, poly- with gel permeation chromatography (GPC) test PET
The molecular weight and its molecular weight distribution of object are closed, test result is shown in Table 10.
Influence of the catalyst compounded addition opportunity of table 10 to synthesis PET molecular weight and molecular weight distribution
As shown in Table 10, for catalyst made from comparative example 2, opportunity is added to the molecular weight and molecule of the PET of synthesis
Amount distribution influences little.
And it is larger to the molecular weight effects of the PET of synthesis but right that opportunity is added for composite catalyst made from embodiment 3
Molecular weight distribution influence is unobvious, and the molecular weight of the PET of catalyst synthesis is added before polycondensation obviously than addition catalyst before being esterified
The molecular weight for synthesizing PET is low.
It is not bound by any theory, present inventors believe that be added in polycondensation phase, due to the hot environment in reaction kettle,
Poor catalyst stability hydrolyzes Titanium series catalyst, and butyl titanate is most susceptible to the attack of water.
And titanium ethylene glycolate is relatively small due to hydrolyzing thermodynamics driving potential, and since the viscosity of ethylene glycol solvent is higher,
It reacts slower, so tetrabutyl titanate hydrolysis degree is high, the activity of 2 catalyst of comparative example is reduced, in identical polymerization
Molecular weight achieved is lower in time.
Influence of the opportunity to synthesis PET hot property is added in 11 composite catalyst of experimental example
This experimental example sample used is that comparative example 2 and embodiment 3 are made, and carries out DSC test, as a result such as Fig. 6~Fig. 7 and
Shown in table 11,
In Fig. 6,
Curve 4 indicates that comparative example 2 is made catalyst and is added before esterification；
Curve 4 ' indicates that comparative example 2 is made catalyst and is added before polycondensation；
In Fig. 7,
Curve 5 indicates that embodiment 3 is made catalyst and is added before esterification；
Curve 5 ' indicates that embodiment 3 is made catalyst and is added before polycondensation；
Influence of the catalyst compounded addition opportunity of table 11 to synthesis PET hot property
| Catalyst | Addition opportunity | Tg(℃) | Tcc(℃) | Tm(℃) | Xcc(%) |
| Comparative example 2 | Esterification Stage | 73.7 | 140.2 | 254.2 | 34.0 |
| Comparative example 2 | Polycondensation phase | 72.7 | 135.8 | 251.6 | 30.1 |
| Embodiment 3 | Esterification Stage | 73.0 | 141.0 | 252.9 | 26.6 |
| Embodiment 3 | Polycondensation phase | 72.3 | 136.2 | 252.3 | 29.8 |
It is synthesized it is found that the PET that catalyst synthesizes is added before esterification than catalyst is added before polycondensation by Fig. 6, Fig. 7 and table 11
PET cold crystallization temperature (Tcc) have raising, glass transition temperature (Tg), melting temperature (Tm) are almost the same.It may
The reason of be: polycondensation phase be added catalyst, due to mixing time than Esterification Stage be added the catalyst time it is short, catalyst
Dispersibility is poor, and the locomitivity of macromolecular chain is caused to decline, and is unfavorable for macromolecular chain segment to lattice diffusion, therefore crystal grain
The speed of growth is slower, so cold crystallization temperature (Tcc) has raising.
Influence of the opportunity to synthesis PET thermal stability is added in 12 composite catalyst of experimental example
This experimental example sample used is made by embodiment 3.
Thermal weight loss (TG) tests the thermal stability for reflecting polymer, and test result is shown in Fig. 8~Figure 11, different weight-loss ratios
Corresponding temperature is shown in Table 12,
In fig. 8,
Curve 4 indicates that comparative example 2 is made catalyst and is added before esterification；
Curve 4 ' indicates that comparative example 2 is made catalyst and is added before polycondensation；
In Fig. 9,
Curve 4 indicates that comparative example 2 is made catalyst and is added before esterification；
Curve 4 ' indicates that comparative example 2 is made catalyst and is added before polycondensation；
In Figure 10,
Curve 5 indicates that embodiment 3 is made catalyst and is added before esterification；
Curve 5 ' indicates that embodiment 3 is made catalyst and is added before polycondensation；
In Figure 11,
Curve 5 indicates that embodiment 3 is made catalyst and is added before esterification；
Curve 5 ' indicates that embodiment 3 is made catalyst and is added before polycondensation.
Influence of the catalyst compounded addition opportunity of table 12 to synthesis PET thermal stability
By Fig. 8~Figure 11 and table 12 it is found that the PET ratio that catalyst synthesizes is added before polycondensation for the sample of comparative example 2
The thermal stability that the PET of catalyst synthesis is added before esterification increases.
And catalyst synthesis is added before the sample of embodiment 3 being added before polycondensation the PET ratio esterification of catalyst synthesis
The thermal stability of PET decrease.
It is not bound by any theory, present inventors believe that the sample of comparative example 2 is added catalyst before polycondensation and is closed
At PET molecular weight than be esterified before synthesize molecular weight it is big, narrow molecular weight distribution, so the initial decomposition temperature of polyester has
It is increased, so that weightless temperature be made slightly to improve.
For the sample of embodiment 3, point of the PET molecular weight than synthesis before being esterified of catalyst synthesis is added before polycondensation
Son amount is small, so the initial decomposition temperature of polyester all decreases, so that weightless temperature be made slightly to reduce.
Influence of the catalyst compounded addition opportunity of experimental example 13 to synthesis PET mechanical property
This experimental example sample used is that comparative example 2 and embodiment 3 are made, as a result as shown in table 13:
Influence of the opportunity to synthesis PET mechanical property is added in 13 composite catalyst of table
As shown in Table 13, for the sample of comparative example 2, influence of the opportunity to the mechanical property of the PET of synthesis is added not
Greatly；And for the sample of embodiment 3, opportunity is added to larger, the addition catalyst synthesis PET slice before polycondensation of the PET of synthesis
Tensile strength and elongation at break than catalyst synthesis PET slice is added before being esterified have reduction.
Without being bound by any theory, present inventors believe that being added in polycondensation phase, due to the high temperature ring in reaction kettle
Border, poor catalyst stability hydrolyze Titanium series catalyst, the activity of Titanium series catalyst are reduced, in identical polymerization
Interior molecular weight achieved is lower, and the mechanical property for causing PET to be sliced is deteriorated.
According to above-mentioned analysis it is found that catalyst compounded addition opportunity is preferably added before Esterification Stage.
Influence of the 14 composite catalyst dosage of experimental example to esterification time
This experimental example sample used is made for embodiment 3, respectively with 9.5ug.g-1, 19ug.g-1,28.5ug.g-1,
38ug.g-1Amount synthesize PET, study the influence of the catalyst different amounts to esterification time, as a result as shown in figure 12.
As shown in Figure 12, the esterification of terephthalic acid (TPA) PTA and ethylene glycol EG are self-catalyzed reaction, and embodiment 3 is made
Sample has certain catalytic action to esterification, and as the increase of amount of samples is made in embodiment 3, esterification time is gradual
Shorten, under the esterification yield for reaching requirement, at most shortens esterification time 40min.
Be not bound by any theory, present inventors believe that the titanium element contained during this is catalyst compounded can with to benzene
Dioctyl phthalate PTA and ethylene glycol terephthalate (BHET) carry out ligand complex reaction, and metallic element increases its carbonyl carbon
Electropositive, the hydroxyl for being conducive to ethylene glycol EG carry out nucleophillic attack, accelerate esterification reaction rate；In catalyst amount (catalyst
Dosage in terms of Ti:PTA mass ratio) be 38ug.g-1When catalytic effect it is most obvious.
Influence of the 15 composite catalyst dosage of experimental example to the polycondensation time
This experimental example sample used is made for embodiment 3, respectively with 9.5ug.g-1, 19ug.g-1, 28.5ug.g-1,
38ug.g-1Amount synthesize PET, study the influence of the catalyst different amounts to the polycondensation time, as a result as shown in figure 13.
As shown in Figure 13, start the dosage with 3 sample of embodiment (dosage of catalyst is in terms of Ti:PTA mass ratio)
Increasing, polycondensation reaction rate is accelerated, and polymerization time shortens, thereafter as 3 amount of samples of embodiment increases, polycondensation reaction rate
Slack-off, polymerization time gradually extends, and is not bound by any theory, present inventors believe that main cause is provided by the invention multiple
It is high to close catalyst activity, many side reactions, the dosage mistake of composite catalyst are also catalyzed while catalyzed polycondensation main reaction
Accelerate side reaction speed, while Exchange reaction of chain aggravates in system more, the polycondensation time is caused to extend, while Ti content
Increase the thermal stability and coloration that will affect PET.
Composite catalyst dosage is 19ug.g-1When, the polycondensation time is 170min, and aforementioned Sb2O3The dosage of catalyst is
334ug.g-1When, the polycondensation time is 160min.It can be seen that 3 amount of samples of embodiment is 19ug.g-1Catalytic activity it is suitable
In Sb2O3Dosage is 334ug.g-1Catalytic activity, the catalytic activity of the composite catalyst is about Sb2O3The 17 of catalytic activity
Times.
Influence of the 16 composite catalyst dosage of experimental example to synthesis PET intrinsic viscosity [η]
This experimental example sample used is made for embodiment 3, respectively with 9.5ug.g-1, 19ug.g-1,28.5ug.g-1,
38ug.g-1Amount synthesize PET, the influence of the catalyst different amounts to PET intrinsic viscosity [η] is studied, as a result such as 14 institute of table
Show.
Influence of the 14 different catalysts dosage of table to synthesis PET intrinsic viscosity [η]
As shown in Table 14, start [η] of the PET synthesized with the catalyst dosage (dosage of catalyst is with Ti:
PTA mass ratio meter) increase, become larger, thereafter as the dosage of the catalyst increases, becomes smaller.
It is not bound by any theory, present inventors believe that composite catalyst catalytic activity provided by the invention is high, is urging
Also many side reactions are catalyzed while changing polycondensation main reaction, the dosage of catalyst accelerates side reaction speed, while body
Exchange reaction of chain aggravation in being, with catalysis after causing the increase of [η] of the PET synthesized in the same time first whatever you like to become larger
[η] that the dosage of agent increases synthesis PET becomes smaller.
It can be seen that the optimum amount of 3 sample of embodiment is 19ug.g-1。
Influence of the 17 composite catalyst dosage of experimental example to synthesis PET form and aspect
This experimental example sample used is made for embodiment 3, respectively with 9.5ug.g-1, 19ug.g-1,28.5ug.g-1,
38ug.g-1Amount synthesize PET, study the influence of the catalyst different amounts to PET form and aspect, as a result as shown in Figure 14 and table 15,
In Figure 14, arrow indicates the corresponding ordinate of the curve.
Influence of 15 catalyst amount of table to PET form and aspect
Note: sample is to have light PET greatly.
By Figure 14 and table 15 it is found that PET product b value reaches one most as the increase of 3 amount of samples of embodiment first reduces
Small value, is then further added by, and is not bound by any theory, present inventors believe that this is because the increasing of the dosage with catalyst
Add, the reaction rate of other side reactions also increases, and b value is caused to increase；L value gradually subtracts with the increase of catalyst amount
It is small；Comprehensively consider L value and b value, the optimum amount of 3 sample of embodiment is 19ug.g-1。
Influence of the 18 composite catalyst dosage of experimental example to synthesis PET hot property
This experimental example sample used is made for embodiment 3, respectively with 9.5ug.g-1, 19ug.g-1,28.5ug.g-1,
38ug.g-1Amount synthesize PET, the influence of the catalyst different amounts to PET hot property is studied, as a result such as 16 institute of Figure 15 and table
Show.
Influence of 16 catalyst amount of table to PET hot property
By Figure 15 with table 16 it is found that the PET prepared that sample is made in different amounts embodiment 3 is compared, glass transition
Temperature (Tg), melting temperature (Tm), cold crystallization temperature (Tcc) are almost the same.
Illustrate that embodiment 3 is made the dosage of sample and does not influence substantially on the hot property of the PET prepared.
Influence of the 19 composite catalyst dosage of experimental example to synthesis PET thermal stability
This experimental example sample used is made for embodiment 3, respectively with 9.5ug.g-1, 19ug.g-1,28.5ug.g-1,
38ug.g-1Amount synthesize PET, the influence of the catalyst different amounts to PET thermal stability is studied, as a result such as Figure 16, Tu17He
Shown in table 17, wherein Figure 16 shows the TG curve that PET is made in different catalysts dosage；Figure 17 shows different catalysts dosage system
Obtain the DTG curve of PET.
Influence of 17 catalyst amount of table to PET thermal stability
By Figure 16, Figure 17 and table 17 it is found that sample is made in embodiment 3, within the scope of the catalyst loading studied,
The PET sample synthesized with different amounts is not changed substantially in the corresponding temperature of different weight-loss ratios, illustrates the PET synthesized
The basic indifference of thermal stability.
Influence of the 20 composite catalyst dosage of experimental example to synthesis PET mechanical property
This experimental example sample used is made for embodiment 3, respectively with 9.5ug.g-1, 19ug.g-1,28.5ug.g-1,
38ug.g-1Amount synthesize PET, study the influence of the catalyst different amounts to mechanical property, the PET synthesized be made mute
Bell pattern item carries out Mechanics Performance Testing, studies influence of the catalyst different amounts to synthesis PET mechanical property, mechanical property
Energy test result is shown in Table 18.
18 PET dumbbell shape batten mechanical experimental results of table
As shown in Table 18, with embodiment 3 be made sample synthesis PET tensile strength with catalyst amount increase,
First become larger and becomes smaller afterwards；Elongation at break first becomes larger and becomes smaller afterwards with the increase of catalyst amount.
It is 19ug.g in catalyst amount-1When, the tensile strength of PET batten obtained is best, elongation at break highest,
This shows that the optimum amount of the catalyst is 19ug.g-1。
It is not bound by any theory, present inventors believe that mechanical property and molecular structure, molecular weight and supramolecular structure
Related, composite catalyst catalytic activity provided by the invention is high, and also catalysis is many secondary anti-while catalyzed polycondensation main reaction
It answers, the dosage of composite catalyst accelerates side reaction speed, and Exchange reaction of chain aggravation, causes in simultaneous reactions system
The increase of the molecular weight elder generation whatever you like of the PET synthesized in the same time, which increases after becoming larger with the dosage of composite catalyst, to be synthesized
The molecular weight of PET becomes smaller, so causing the tensile strength of PET sample with the increase of catalyst amount, first becomes larger and becomes smaller afterwards；
Elongation at break first becomes larger and becomes smaller afterwards with the increase of catalyst amount.
It is described the invention in detail above in conjunction with detailed description and exemplary example, but these explanations
It can not be interpreted as limitation of the present invention.It will be appreciated by those skilled in the art that without departing from spirit and scope of the invention the case where
Under, it can be with various equivalent substitutions, modifications or improvements are made to the technical scheme of the invention and its embodiments, these each fall within this
In the range of invention.Scope of protection of the present invention is subject to the appended claims.
Claims (18)
1. a kind of method for preparing polyethylene terephthalate using composite catalyst, which is characterized in that the method makes
With composite catalyst, wherein the composite catalyst includes butyl titanate, tetraethyl orthosilicate and phenyl-phosphonic acid；
In the composite catalyst, the ratio between butyl titanate, mole of tetraethyl orthosilicate and phenyl-phosphonic acid are four fourth of metatitanic acid
The mole of ester: the mole of tetraethyl orthosilicate: the mole of phenyl-phosphonic acid=(6~12): 1:(1~3), wherein metatitanic acid four
The mole of butyl ester is with the molar amount of wherein titanium elements；The mole of tetraethyl orthosilicate is with the molar amount of wherein element silicon；
The mole of phenyl-phosphonic acid is with the molar amount of wherein P elements；The composite catalyst further includes dispersing agent, the dispersing agent
For ethylene glycol；
Total volume based on composite catalyst, wherein the molar concentration of titanium elements is
(0.1~1) mol/L；
The composite catalyst is made by method comprising the following steps:
Step 1-1, tetraethyl orthosilicate is added in dispersing agent, optionally stirs, obtains the dispersion of tetraethyl orthosilicate；
Step 1-2, phenyl-phosphonic acid is added in the dispersion of above-mentioned tetraethyl orthosilicate, optionally stirs, is then added to titanium
In sour four butyl esters；
It is described using composite catalyst prepare polyethylene terephthalate method the following steps are included:
Step 1, esterification: terephthalic acid (TPA), ethylene glycol and composite catalyst are added in polymeric kettle, are mixed, and heating is added
Ethylene glycol and antioxidant 1010 or antioxidant 1212, also add heat stabilizer triphenyl phosphite, continues to mix；
Step 2, polycondensation reaction: first make to enter back into high vacuum state after a period of time, then make in low vacuum state in reaction kettle
Heating in kettle, being kept stirring to reaction terminates.
2. the method according to claim 1, wherein in the composite catalyst, butyl titanate, silicic acid four
The ratio between mole of ethyl ester and phenyl-phosphonic acid is the mole of butyl titanate: the mole of tetraethyl orthosilicate: phenyl-phosphonic acid
Mole is (8~10): 1:(1.5~2.5).
3. according to the method described in claim 2, it is characterized in that, in the composite catalyst, butyl titanate, silicic acid four
The ratio between mole of ethyl ester and phenyl-phosphonic acid is the mole of butyl titanate: the mole of tetraethyl orthosilicate: phenyl-phosphonic acid
Mole is 9:1:2.
4. the method according to claim 1, wherein the molar concentration of titanium elements is (0.2~0.8) mol/L.
5. according to the method described in claim 4, it is characterized in that, the molar concentration of titanium elements is (0.3~0.6) mol/L.
6. according to the method described in claim 5, it is characterized in that, the molar concentration of titanium elements is 0.457mol/L.
7. method described according to claim 1~one of 6, which is characterized in that the composite catalyst before esterification or
Person is added during esterification.
8. method described according to claim 1~one of 6, which is characterized in that the dosage of composite catalyst is (5~50) μ g/
G, wherein weight of the dosage based on terephthalic acid (TPA), with the poidometer of wherein titanium elements.
9. according to the method described in claim 8, it is characterized in that, the dosage of composite catalyst is (9~40) μ g/g.
10. according to the method described in claim 9, it is characterized in that, the dosage of composite catalyst be 9.5 μ g/g, 19 μ g/g,
28.5 μ g/g and 38 μ g/g.
11. according to the method described in claim 10, it is characterized in that, the dosage of composite catalyst is 19 μ g/g.
12. method described according to claim 1~one of 6, further comprising the steps of:
Step 3, pelletizing: nitrogen extruding and discharging, Cast Strip, then the pellet for PET batten pelletizing will be obtained obtaining are used；
Step 4, drying: the pellet that step 3 is obtained is dried.
13. method described according to claim 1~one of 6, which is characterized in that in the esterification reaction,
System is warming up to (130~260) DEG C；
Total weight based on terephthalic acid (TPA), with the poidometer of ethylene glycol, the amount for the ethylene glycol added is 0.5%~4%；
Total weight based on terephthalic acid (TPA), with the poidometer of antioxidant, the amount for the antioxidant added is 0.03%~0.1%；
Total weight based on terephthalic acid (TPA), with the poidometer of heat stabilizer, the amount of the heat stabilizer added is 0.05%~
0.2%；With
The antioxidant is antioxidant 1010.
14. according to the method for claim 13, which is characterized in that in the esterification reaction,
System is warming up to (180~255) DEG C；
The amount for the ethylene glycol added is 1%~3%；
The amount for the antioxidant added is 0.05~0.08%；
The amount for the heat stabilizer added is 0.08~0.15%.
15. according to the method for claim 14, which is characterized in that in the esterification reaction,
System is warming up to 245 DEG C；
The amount for the ethylene glycol added is 2%；
The amount for the antioxidant added is 0.07%；
The amount for the heat stabilizer added is 0.1%.
16. method described according to claim 1~one of 6, which is characterized in that in polycondensation process, make reaction system
Keep high vacuum state；
Under high vacuum state, temperature in the kettle is made to be increased to 200 DEG C~400 DEG C；With
The high vacuum state refers to that absolute pressure is in 50~100Pa in reaction kettle.
17. according to the method for claim 16, which is characterized in that under high vacuum state, temperature in the kettle is made to be increased to 250
DEG C~350 DEG C；With
The high vacuum state refers to that absolute pressure is in 50~70Pa in reaction kettle.
18. according to the method for claim 17, which is characterized in that under high vacuum state, temperature in the kettle is made to be increased to 280
℃；With
The high vacuum state refers to that absolute pressure is in 50Pa in reaction kettle.
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| CN102485770A (en) * | 2010-12-06 | 2012-06-06 | 东丽纤维研究所（中国）有限公司 | Polyester and its production method |
| CN102492121A (en) * | 2011-12-13 | 2012-06-13 | 南昌航空大学 | Preparation method and use of rare earth coated titanium polyesterification catalyst |
| CN103709383A (en) * | 2014-01-06 | 2014-04-09 | 浙江万凯新材料有限公司 | Titanium-based polyester catalyst as well as preparation method and application thereof |
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| CN102485770A (en) * | 2010-12-06 | 2012-06-06 | 东丽纤维研究所（中国）有限公司 | Polyester and its production method |
| CN102492121A (en) * | 2011-12-13 | 2012-06-13 | 南昌航空大学 | Preparation method and use of rare earth coated titanium polyesterification catalyst |
| CN103709383A (en) * | 2014-01-06 | 2014-04-09 | 浙江万凯新材料有限公司 | Titanium-based polyester catalyst as well as preparation method and application thereof |
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