CN105482084B - A kind of polyester containing unsaturated double-bond and preparation method thereof - Google Patents
A kind of polyester containing unsaturated double-bond and preparation method thereof Download PDFInfo
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- CN105482084B CN105482084B CN201511016167.8A CN201511016167A CN105482084B CN 105482084 B CN105482084 B CN 105482084B CN 201511016167 A CN201511016167 A CN 201511016167A CN 105482084 B CN105482084 B CN 105482084B
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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
- C08G63/83—Alkali metals, alkaline earth metals, beryllium, magnesium, copper, silver, gold, zinc, cadmium, mercury, manganese, 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
- C08G63/78—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
- C08G63/86—Germanium, antimony, or compounds thereof
- C08G63/866—Antimony or compounds thereof
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Abstract
The present invention relates to a kind of polyester containing unsaturated double-bond and preparation method thereof, for terephthalic acid (TPA), unsaturated dibasic acid and ethylene glycol, through esterification and under the effect of the mixture through catalytic of ethylene glycol magnesium and antimony glycol, polyester is made in polycondensation, again polyester slice is obtained through pelletizing, in the polyester slice, content of carboxyl end group is less than 20mol/t, oligomer mass percentage content is less than 1.0%, and the mass percentage content of diethylene glycol (DEG) is less than 1.0%.Ethylene glycol magnesium in the present invention is gentleer, while is also thermal degradation catalyst, and its thermal degradation coefficient very little, the side reaction triggered during the course of the reaction is less, reduces the generation of end carboxyl in process and oligomer；Oligomer is reduced in polymerization process of the present invention, the reduction of thermal degradation in process, greatly reduce the impurity in polyester, the amount of nucleator in polyester is also reduced simultaneously, the probability of homogeneous nucleation is added on the basis of heterogeneous nucleation is reduced, is advantageous to growing up and crystallizing integrity optimization for crystallite dimension in polyester industrial silk fiber.
Description
Technical field
The invention belongs to polyester preparing technical field, is related to a kind of polyester containing unsaturated double-bond and preparation method thereof, particularly
A kind of polyester and its preparation side containing unsaturated double-bond and polycondensation catalyst using ethylene glycol magnesium and the mixture of antimony glycol
Method.
Background technology
Polyethylene terephthalate (PET) is a kind of polymer of function admirable, PET with its modulus is high, intensity is high,
It is well-pressed, conformality is good, pure health, barrier property are good etc., be widely used in fiber, the field such as bottle is packed, film and sheet material,
Yield cumulative year after year, position in industry are obviously improved.
Polyester containing unsaturated double-bond is unsaturated polyester (UP), and it refers to by saturation/unsaturated dihydric alcohol and saturation/no
Monounsaturated dicarboxylic acid polycondensation and the chain macromolecule compound formed, contain ester bond and unsaturated double-bond simultaneously in molecular backbone, because
This has the characteristic of ester bond and unsaturated double-bond.Because it is linear macromolecule structure, therefore also referred to as linear unsaturated polyester.Insatiable hunger
With polyester because it has the good system of mouldability and manufacturability, preferable mechanical property, corrosion resistance and electric insulating quality etc. one
The advantages of row, in the various aspects of production and living, have a wide range of applications.Unsaturated polyester (UP) is more to be applied to resin side
Face, main ships and light boats, vehicle part, sports equipment and polyester coating, technology for producing artificial jadeware product, artificial marble etc..In polyester
Fiber introduces unsaturated double-bond, and effectively and safely controls its crosslinking, by the mechanical property of polyester fiber, heat resistance, resistance to
Chemical property, fire resistance have a raising compared with amplitude, how with good unsaturated double-bond be in polyester fiber production technology very
Important problem.
End carboxyl, oligomer, diethylene glycol (DEG) (DEG) content are the important quality index of polyester slice, wherein oligomer, two sweet
Alcohol is all oligomer, and they not only reflect the quality of production status, also affects the product quality of spinning processing.Therefore,
Reducing the end carboxyl in polyester slice, oligomer, diethylene glycol content just turns into the critically important link of raising polyester product quality.Control
Content of the three processed in polyester slice is extremely important to the quality for lifting polyester fiber.Heat endurance of the end carboxyl to polymer
Influence very big.Only control polyester content of carboxyl end group is stable in production, its relative molecular mass distribution of the control that could stablize
Homogeneity.Content of the diethylene glycol (DEG) in polyester slice is a critically important quality index in production of polyester.Because it is direct
The fusing point of polyester slice is had influence on, the fusing point of polyester slice can drastically decline with the increase of wherein DEG content, so it is not only
The quality of production status is reflected, directly influences the quality of post-processing-spinning technique and silk.Oligomer in polyester refers to
Oligomer of the degree of polymerization less than 10 is divided into linear oligomerization thing and cyclic oligomer, wherein with ring-type aggressiveness particularly cyclic trimer
In the majority, oligomer is mainly concerned with heterogeneous nucleation, spinning processing etc., and performance to polyester and the processing of rear road cause certain bad
Influence.
The content of the invention
It is an object of the invention to provide a kind of polyester containing unsaturated double-bond and preparation method thereof, is that one kind contains unsaturated double-bond
And polycondensation catalyst is using polyester of mixture of ethylene glycol magnesium and antimony glycol and preparation method thereof.The present invention uses second two
The mixture of magnesium alkoxide and antimony glycol is polycondensation catalyst, important is thermal degradation coefficient very little, thermal degradation is reduced to it is minimum,
The influence that end carboxyl, oligomer, diethylene glycol content are processed to Direct-spinning of PET Fiber is reduced, while also ensure that in polyester production process not
The stability of saturation double bond.
One kind polyester containing unsaturated double-bond of the present invention is terephthalic acid (TPA), unsaturated dibasic acid and ethylene glycol through esterification
With under the effect of the mixture through catalytic of ethylene glycol magnesium and antimony glycol polycondensation be made, then obtain polyester slice through pelletizing；
In the polyester slice containing unsaturated double-bond, content of carboxyl end group is less than 20mol/t, oligomer mass percentage content
Less than 1.0%, the mass percentage content of diethylene glycol (DEG) is less than 1.0%；In one macromolecular chain of the polyester containing unsaturated double-bond
It is average that 1~6 unsaturated double-bond provided by unsaturated dibasic acid molecule is provided.
The molecular formula of the ethylene glycol magnesium is Mg (OCH2CH2OH)2。
Unsaturated polyester (UP) is the unsaturated bond containing non-aromatic in its molecular structure for saturated polyester,
Unsaturated polyester (UP) molecule is generally long chain type molecular structure.Reaction can be crosslinked between the long-chain molecule of unsaturated polyester (UP) to be formed
Baroque huge network molecule.The structure of network molecule is probably divided into three classes：Uniform continuous net-shaped structure；It is uneven
Continuous net-shaped structure, i.e., the larger network structure of density is interconnected by density less chain molecule；Discontinuously
Network structure, highdensity continuous net-shaped structure disperses are among the component not being bonded.Common unsaturated polyester (UP) is handed over
After connection reaction, to generate based on uneven continuous net-shaped structure.Its mechanical property after unsaturated polyester cross-linking, heat resistance,
Chemical-resistance, fire resistance will have raising compared with amplitude.Selective cross-linking is after the completion of fiber preparation, by ultraviolet light-initiated
Mode carry out, ensure that stabilization of the double bond in process of polyester.
The generation of end carboxyl is mainly in esterification and polycondensation phase, the main side reaction in polycondensation process in polyester
Thermal degradation, increase with response intensity, thermal degradation accelerates, and degraded causes PET conglutination to decline, carboxyl end group value rise.Content of carboxyl end group
Height, the heat endurance of polyester resin is poor, and end carboxyl can carry out acidolysis reaction to ester group, can accelerate the hydrolysis of ester group, simultaneously
The reduction of the electrical insulation capabilities such as the volume resistance of polyester can be made.The carboxylic acid of polyester and the polyester macromolecule chain of carboxylic acid reactant salt generation
Salt, nucleus is consisted of, polyester is accelerated heterogeneous nucleation.Diethylene glycol (DEG) (DEG) directly influences the fusing point of polyester slice, and polyester is cut
The fusing point of piece can drastically decline with the increase of wherein DEG content, so it not only reflects the quality of production status, also directly
Have influence on the quality of post-processing-spinning technique and silk.Diethylene glycol (DEG) is the ehter bond for being very easy to oxidation, and drop is easily produced when heated
Solution.In the synthesis and process of polyester, the generation of oligomer is mainly closely bound up with PET thermal degradations and thermal oxidative degradation,
Oligomer is mainly concerned with heterogeneous nucleation, spinning processing etc., and the performance and the processing of rear road to polyester cause certain harmful effect.
One kind polyester containing unsaturated double-bond as described above, the number-average molecular weight of the polyester containing unsaturated double-bond are
15000~22000.
One kind polyester containing unsaturated double-bond as described above, in the mixture of the ethylene glycol magnesium and antimony glycol, second two
Magnesium alkoxide is 2~3 with antimony glycol mass ratio:1.
Present invention also offers a kind of preparation method of polyester containing unsaturated double-bond, is terephthalic acid (TPA), unsaturated binary
Polyester is made in polycondensation through esterification and under the effect of the mixture through catalytic of ethylene glycol magnesium and antimony glycol for acid and ethylene glycol, then through pelletizing
Obtain polyester slice.
A kind of preparation method of polyester containing unsaturated double-bond as described above, specifically includes following steps：
(1) preparation of catalyst glycol magnesium：
Add ethylene glycol in single-cell for electrolyzation, supporting electrolyte is magnesium chloride, and metal MAG block is anode, and negative electrode is graphite；
Logical direct current, 6~10V of starting voltage, cathode-current density be 150~200mA, are electrolysed 10~12 hours at 50~60 DEG C, electric
Solution takes out electrode after terminating, and obtains white suspension；It is filtered under diminished pressure, white solid is washed with absolute ethyl alcohol, and second two is obtained after drying
Magnesium alkoxide；
(2) preparation of polyester, including esterification and polycondensation reaction：
The esterification：
Using terephthalic acid (TPA), unsaturated dibasic acid and ethylene glycol as raw material, after being made into uniform sizing material be esterified instead
Should, obtain esterification products；Esterification is pressurizeed in nitrogen atmosphere, Stress control in normal pressure~0.3MPa, temperature 250~
260 DEG C, what esterification water quantity of distillate reached theoretical value more than 90% is esterification terminal；
The polycondensation reaction：
Including polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig：
The polycondensation reaction low vacuum stage, catalyst, stabilizer and ultraviolet initiator are added in esterification products,
Start polycondensation reaction under conditions of negative pressure, the staged pressure is steadily evacuated to below absolute pressure 500Pa by normal pressure, and temperature control exists
260~270 DEG C, the reaction time is 30~50 minutes；The catalyst is the mixture of ethylene glycol magnesium and antimony glycol；
The polycondensation reaction high vacuum stage of Fig, after the polycondensation reaction low vacuum stage, continue to vacuumize, make reaction pressure
Power is down to absolute pressure and is less than 100Pa, and reaction temperature control is at 275~280 DEG C, 50~90 minutes reaction time；
Polyester is made, polyester slice is obtained through pelletizing；
A kind of preparation method of polyester containing unsaturated double-bond as described above, the ethylene glycol and the terephthalic acid (TPA)
Mol ratio is 1.2~2.0:1.
A kind of preparation method of polyester containing unsaturated double-bond as described above, the mixing of the ethylene glycol magnesium and antimony glycol
In thing, ethylene glycol magnesium is 2~3 with antimony glycol mass ratio:1；The catalyst amount is the terephthalic acid (TPA) quality
0.01%~0.05%.Comparison temperature is belonged to as polycondensation catalyst, ethylene glycol magnesium using ethylene glycol magnesium and antimony glycol mixture
One kind of sum, its thermal degradation coefficient very little, the side reaction triggered during the course of the reaction is less, reduces and holds carboxylic in process
The generation of base and oligomer, while also ensure that the stability of unsaturated double-bond in polyester production process.
A kind of preparation method of polyester containing unsaturated double-bond as described above, the stabilizer are selected from triphenyl phosphate, phosphorus
One kind in sour trimethyl and Trimethyl phosphite, stabilizing agent dosage for the terephthalic acid (TPA) weight 0.01%~
0.05%.For stabilizer mainly based on phosphate, main function is free radical caused by catching reaction in the course of the polymerization process, is reduced
Side reaction, while also protect unsaturated double-bond.
A kind of preparation method of polyester containing unsaturated double-bond as described above, described unsaturated dibasic acid and terephthaldehyde
Sour mol ratio is 1~5:100.
A kind of preparation method of heat-resistance polyester containing unsaturated double-bond as described above, the unsaturated dibasic acid are along fourth
One kind in enedioic acid, fumaric acid, muconic acid.
A kind of preparation method of heat-resistance polyester containing unsaturated double-bond as described above, the ultraviolet initiator is cycloalkanes
One kind in sour cobalt, cobalt acetate, zinc naphthenate, zinc stearate, zinc acetate, addition for terephthalic acid (TPA) weight 0.03%~
0.05%.
Light trigger is the key component of cross-linking system, and initiator molecule (250~420nm) between ultraviolet region has necessarily
Absorbing ability, initiator molecule can also continue to transit to and excite three lines from ground state transition to active excitation state after absorbing luminous energy
State；In its excited singlet, it is also possible to which after excited triplet state undergoes unimolecule or bimolecular chemical action, generation can draw
The biologically active fragment of bill body polymerization, these biologically active fragments can be free radical, trigger cross-linking reaction.
Selection metal salt is primarily due to it as initiator has higher heat endurance, i.e., in polymerization, spinning process
It is middle to keep stable, while cobalt salt does not produce negative impact with zinc salt to polyester reaction, cobalt salt also can be as the tune of polyester
Toner.
Due to unsaturated double-bond be present in unsaturated polyester (UP) molecular structure, under the conditions of existing for initiator, unsaturation is poly-
Reaction can be crosslinked between the long-chain molecule of ester and forms baroque huge network molecule.Crosslinking is that raising is polymer
Can one of most direct most efficient method, by crosslinking the degree of cross linking of system can be made raise, relative molecular mass increases, and
So that the physical and chemical performance of polymer significantly improves.
Polyester fondant degraded influences have two aspects to product quality, i.e., viscosity reduces and relative molecular mass distribution broadens,
Degradation reaction is small on PET conglutination drop influence, but its influence to relative molecular mass distribution is bigger, makes molecular mass point
Cloth broadens.The principal element for causing thermal degradation is high temperature and catalyst, and high temperature is that response intensity is too high, causes degraded to accelerate, production
End carboxyl has been given birth to, while has also increased cyclic oligomer；Catalyst is then related to the degradation reaction constant of catalyst, in polycondensation
Cheng Zhong, the effect of catalyst, which is not only in that, can be catalyzed generation main reaction, so as to influence the speed and yield of reaction, while can also urge
Thermal degradation and ehter bond generation, increase the content of diethylene glycol (DEG), so as to increase the content of end carboxyl.
It is an object of the invention to provide a kind of polyester, using relatively mild a kind of polycondensation catalyst ethylene glycol magnesium, is reacting
During the less side reaction that triggers it is less, efficiently controlled the less heat drop in the content and process of end carboxyl
Solution, reduces the generation of oligomer in process, while also ensure that the stabilization of unsaturated double-bond in polyester production process
Property.Unsaturated double-bond is introduced in polyester fiber, and effectively and safely controls its crosslinking, by the mechanical property of polyester fiber,
Heat resistance, chemical-resistance, fire resistance have the raising compared with amplitude.
Beneficial effect：
● belong to comparatively gentle one as polycondensation catalyst, ethylene glycol magnesium using ethylene glycol magnesium and antimony glycol mixture
Class, its thermal degradation coefficient very little, the side reaction triggered during the course of the reaction is less, reduces end carboxyl in process and low
The generation of polymers, while also ensure that the stability of unsaturated double-bond in polyester production process.
● the content of carboxyl end group of polyester slice is less than 20mol/t, and oligomer mass percentage content is less than 1.0%, and two is sweet
The mass percentage content of alcohol is less than 1.0%, is advantageous to further improve the quality of fiber.In described one macromolecular chain of polyester
It is average that 1~6 unsaturated double-bond provided by unsaturated dibasic acid molecule is provided.
● unsaturated double-bond is introduced in polyester, and its crosslinking is effectively and safely controlled after the completion of polyester fiber preparation, will
There is the raising compared with amplitude to the mechanical property of polyester fiber, heat resistance, chemical-resistance, fire resistance.
Embodiment
The invention will be further elucidated with reference to specific embodiments.It should be understood that these embodiments are merely to illustrate this hair
Bright rather than limitation the scope of the present invention.In addition, it is to be understood that after the content of the invention lectured has been read, art technology
Personnel can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited
Fixed scope.
One kind polyester containing unsaturated double-bond of the present invention, polyester containing unsaturated double-bond are terephthalic acid (TPA), unsaturated binary
Polycondensation is made through esterification and under the effect of the mixture through catalytic of ethylene glycol magnesium and antimony glycol for acid and ethylene glycol, then is obtained through pelletizing
Polyester slice；In polyester slice, content of carboxyl end group is less than 20mol/t, and oligomer mass percentage content is less than 1.0%, and two is sweet
The mass percentage content of alcohol is less than 1.0%；In one macromolecular chain of the polyester containing unsaturated double-bond averagely containing 1~6 by
The unsaturated double-bond that unsaturated dibasic acid molecule is provided；The molecular formula of ethylene glycol magnesium is Mg (OCH2CH2OH)2。
Wherein, the number-average molecular weight of the polyester containing unsaturated double-bond is 15000~22000.
Wherein, in the mixture of ethylene glycol magnesium and antimony glycol, ethylene glycol magnesium is 2~3 with antimony glycol mass ratio:1.
Embodiment 1
A kind of preparation method of polyester containing unsaturated double-bond, specifically includes following steps：
(1) preparation of catalyst glycol magnesium：
Ethylene glycol is added in single-cell for electrolyzation, supporting electrolyte is magnesium chloride, and metal MAG block is anode, and negative electrode is stone
Ink；Logical direct current, starting voltage 6V, cathode-current density 150mA, it is electrolysed 10 hours at 50 DEG C, electrolysis takes out electricity after terminating
Pole, obtain white suspension；It is filtered under diminished pressure, white solid is washed with absolute ethyl alcohol, and ethylene glycol magnesium is obtained after drying；
(2) preparation of polyester, including esterification and polycondensation reaction：
Esterification：
Using terephthalic acid (TPA), unsaturated dibasic acid maleic acid and ethylene glycol as raw material, ethylene glycol and to benzene two
The mol ratio of formic acid is 1.2:1, unsaturated dibasic acid is 1 with terephthalic acid (TPA) mol ratio:100, carried out after being made into uniform sizing material
Esterification, obtain esterification products；Esterification is pressurizeed in nitrogen atmosphere, and Stress control is in normal pressure, and temperature is at 250 DEG C, ester
It is esterification terminal to change water quantity of distillate to reach the 91% of theoretical value,；
Polycondensation reaction：
Including polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig：
In the polycondensation reaction low vacuum stage, addition catalyst, stabilizer triphenyl phosphate and ultraviolet light draw in esterification products
Agent cobalt naphthenate is sent out, triphenyl phosphate dosage is the 0.01% of terephthalic acid (TPA) weight, and cobalt naphthenate addition is terephthaldehyde
The 0.03% of sour weight, starts polycondensation reaction under conditions of negative pressure, and the staged pressure is steadily evacuated to absolute pressure by normal pressure
498Pa, for temperature control at 260 DEG C, the reaction time is 30 minutes；Catalyst is the mixture of ethylene glycol magnesium and antimony glycol, second
Two magnesium alkoxides are 2 with antimony glycol mass ratio:1；Polycondensation reaction high vacuum stage of Fig, after the polycondensation reaction low vacuum stage, continue to take out
Vacuum, reaction pressure is set to be down to absolute pressure 98Pa, reaction temperature control is at 275 DEG C, 50 minutes reaction time；Obtained number is divided equally
Son amount is 15000 polyester, and polyester slice is obtained through pelletizing.
Embodiment 2
A kind of preparation method of polyester containing unsaturated double-bond, specifically includes following steps：
(1) preparation of catalyst glycol magnesium：
Ethylene glycol is added in single-cell for electrolyzation, supporting electrolyte is magnesium chloride, and metal MAG block is anode, and negative electrode is stone
Ink；Logical direct current, starting voltage 10V, cathode-current density 200mA, it is electrolysed 12 hours at 60 DEG C, electrolysis takes out electricity after terminating
Pole, obtain white suspension；It is filtered under diminished pressure, white solid is washed with absolute ethyl alcohol, and ethylene glycol magnesium is obtained after drying；
(2) preparation of polyester, including esterification and polycondensation reaction：
Esterification：
Using terephthalic acid (TPA), unsaturated dibasic acid fumaric acid and ethylene glycol as raw material, ethylene glycol and to benzene two
The mol ratio of formic acid is 2.0:1, unsaturated dibasic acid is 5 with terephthalic acid (TPA) mol ratio:100, carried out after being made into uniform sizing material
Esterification, obtain esterification products；Esterification is pressurizeed in nitrogen atmosphere, Stress control in 0.3MPa, temperature at 260 DEG C,
What esterification water quantity of distillate reached theoretical value 95% is esterification terminal,；
Polycondensation reaction：
Including polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig：
In the polycondensation reaction low vacuum stage, addition catalyst, stabilizer trimethyl phosphate and ultraviolet light draw in esterification products
Agent cobalt acetate is sent out, trimethyl phosphate dosage is the 0.05% of terephthalic acid (TPA) weight, and cobalt acetate addition is terephthalic acid (TPA) weight
The 0.05% of amount, starts polycondensation reaction under conditions of negative pressure, and the staged pressure is steadily evacuated to absolute pressure 495Pa by normal pressure,
For temperature control at 270 DEG C, the reaction time is 50 minutes；Catalyst is the mixture of ethylene glycol magnesium and antimony glycol, ethylene glycol magnesium
It is 3 with antimony glycol mass ratio:1；Polycondensation reaction high vacuum stage of Fig, after the polycondensation reaction low vacuum stage, continue to vacuumize, make
Reaction pressure is down to absolute pressure 95Pa, and reaction temperature control is at 280 DEG C, 90 minutes reaction time；Obtained number-average molecular weight is
22000 polyester, polyester slice is obtained through pelletizing.
Embodiment 3
A kind of preparation method of polyester containing unsaturated double-bond, specifically includes following steps：
(1) preparation of catalyst glycol magnesium：
Ethylene glycol is added in single-cell for electrolyzation, supporting electrolyte is magnesium chloride, and metal MAG block is anode, and negative electrode is stone
Ink；Logical direct current, starting voltage 7V, cathode-current density 160mA, it is electrolysed 11 hours at 55 DEG C, electrolysis takes out electricity after terminating
Pole, obtain white suspension；It is filtered under diminished pressure, white solid is washed with absolute ethyl alcohol, and ethylene glycol magnesium is obtained after drying；
(2) preparation of polyester, including esterification and polycondensation reaction：
Esterification：
Using terephthalic acid (TPA), unsaturated dibasic acid muconic acid and ethylene glycol as raw material, ethylene glycol and to benzene two
The mol ratio of formic acid is 1.5:1, unsaturated dibasic acid is 2 with terephthalic acid (TPA) mol ratio:100, carried out after being made into uniform sizing material
Esterification, obtain esterification products；Esterification is pressurizeed in nitrogen atmosphere, Stress control in 0.2MPa, temperature at 255 DEG C,
What esterification water quantity of distillate reached theoretical value 92% is esterification terminal,；
Polycondensation reaction：
Including polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig：
In the polycondensation reaction low vacuum stage, catalyst, stabilizer Trimethyl phosphite and ultraviolet light are added in esterification products
Initiator zinc naphthenate, Trimethyl phosphite dosage are the 0.02% of terephthalic acid (TPA) weight, and zinc naphthenate addition is to benzene
The 0.04% of dioctyl phthalate weight, starts polycondensation reaction under conditions of negative pressure, and the staged pressure is steadily evacuated to absolute pressure by normal pressure
Power 498Pa, for temperature control at 265 DEG C, the reaction time is 35 minutes；Catalyst is the mixture of ethylene glycol magnesium and antimony glycol,
Ethylene glycol magnesium is 2 with antimony glycol mass ratio:1；Polycondensation reaction high vacuum stage of Fig, after the polycondensation reaction low vacuum stage, continue
Vacuumize, reaction pressure is down to absolute pressure 96Pa, reaction temperature control is at 278 DEG C, 55 minutes reaction time；It is equal that number is made
Molecular weight is 16000 polyester, and polyester slice is obtained through pelletizing.
Embodiment 4
A kind of preparation method of polyester containing unsaturated double-bond, specifically includes following steps：
(1) preparation of catalyst glycol magnesium：
Ethylene glycol is added in single-cell for electrolyzation, supporting electrolyte is magnesium chloride, and metal MAG block is anode, and negative electrode is stone
Ink；Logical direct current, starting voltage 8V, cathode-current density 160mA, it is electrolysed 11 hours at 55 DEG C, electrolysis takes out electricity after terminating
Pole, obtain white suspension；It is filtered under diminished pressure, white solid is washed with absolute ethyl alcohol, and ethylene glycol magnesium is obtained after drying；
(2) preparation of polyester, including esterification and polycondensation reaction：
Esterification：
Using terephthalic acid (TPA), unsaturated dibasic acid maleic acid and ethylene glycol as raw material, ethylene glycol and to benzene two
The mol ratio of formic acid is 1.5:1, unsaturated dibasic acid is 2 with terephthalic acid (TPA) mol ratio:100, carried out after being made into uniform sizing material
Esterification, obtain esterification products；Esterification is pressurizeed in nitrogen atmosphere, Stress control in 0.2MPa, temperature at 255 DEG C,
What esterification water quantity of distillate reached theoretical value 95% is esterification terminal,；
Polycondensation reaction：
Including polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig：
In the polycondensation reaction low vacuum stage, addition catalyst, stabilizer trimethyl phosphate and ultraviolet light draw in esterification products
Agent zinc stearate is sent out, trimethyl phosphate dosage is the 0.03% of terephthalic acid (TPA) weight, and ultraviolet initiator addition is to benzene
The 0.04% of dioctyl phthalate weight, starts polycondensation reaction under conditions of negative pressure, and the staged pressure is steadily evacuated to absolute pressure by normal pressure
Power 490Pa, for temperature control at 268 DEG C, the reaction time is 40 minutes；Catalyst is the mixture of ethylene glycol magnesium and antimony glycol,
Ethylene glycol magnesium is 3 with antimony glycol mass ratio:1；Polycondensation reaction high vacuum stage of Fig, after the polycondensation reaction low vacuum stage, continue
Vacuumize, reaction pressure is down to absolute pressure 96Pa, reaction temperature control is at 278 DEG C, 60 minutes reaction time；It is equal that number is made
Molecular weight is 18000 polyester, and polyester slice is obtained through pelletizing.
Embodiment 5
A kind of preparation method of polyester containing unsaturated double-bond, specifically includes following steps：
(1) preparation of catalyst glycol magnesium：
Ethylene glycol is added in single-cell for electrolyzation, supporting electrolyte is magnesium chloride, and metal MAG block is anode, and negative electrode is stone
Ink；Logical direct current, starting voltage 8V, cathode-current density 180mA, it is electrolysed 11 hours at 55 DEG C, electrolysis takes out electricity after terminating
Pole, obtain white suspension；It is filtered under diminished pressure, white solid is washed with absolute ethyl alcohol, and ethylene glycol magnesium is obtained after drying；
(2) preparation of polyester, including esterification and polycondensation reaction：
Esterification：
Using terephthalic acid (TPA), unsaturated dibasic acid fumaric acid and ethylene glycol as raw material, ethylene glycol and to benzene two
The mol ratio of formic acid is 1.6:1, unsaturated dibasic acid is 4 with terephthalic acid (TPA) mol ratio:100, carried out after being made into uniform sizing material
Esterification, obtain esterification products；Esterification is pressurizeed in nitrogen atmosphere, Stress control in 0.1MPa, temperature at 255 DEG C,
What esterification water quantity of distillate reached theoretical value more than 90% is esterification terminal,；
Polycondensation reaction：
Including polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig：
In the polycondensation reaction low vacuum stage, addition catalyst, stabilizer trimethyl phosphate and ultraviolet light draw in esterification products
Agent zinc acetate is sent out, trimethyl phosphate dosage is the 0.03% of terephthalic acid (TPA) weight, and zinc acetate addition is terephthalic acid (TPA) weight
The 0.03% of amount, starts polycondensation reaction under conditions of negative pressure, and the staged pressure is steadily evacuated to absolute pressure 492Pa by normal pressure,
For temperature control at 264 DEG C, the reaction time is 40 minutes；Catalyst is the mixture of ethylene glycol magnesium and antimony glycol, ethylene glycol magnesium
It is 3 with antimony glycol mass ratio:1；Polycondensation reaction high vacuum stage of Fig, after the polycondensation reaction low vacuum stage, continue to vacuumize, make
Reaction pressure is down to absolute pressure 96Pa, and reaction temperature control is at 276 DEG C, 70 minutes reaction time；Obtained number-average molecular weight is
21000 polyester, polyester slice is obtained through pelletizing.
Claims (9)
1. a kind of preparation method of polyester containing unsaturated double-bond, it is characterized in that：Terephthalic acid (TPA), unsaturated dibasic acid and ethylene glycol
Through esterification and the obtained polyester of polycondensation under the effect of the mixture through catalytic of ethylene glycol magnesium and antimony glycol, then obtain polyester through pelletizing and cut
Piece；
In the polyester slice, content of carboxyl end group is less than 20mol/t, and oligomer mass percentage content is less than 1.0%, diethylene glycol (DEG)
Mass percentage content be less than 1.0%；Averagely contain 1~6 in one macromolecular chain of the polyester containing unsaturated double-bond
The unsaturated double-bond provided by unsaturated dibasic acid molecule；
The molecular formula of the ethylene glycol magnesium is Mg (OCH2CH2OH)2；
In the mixture of the ethylene glycol magnesium and antimony glycol, ethylene glycol magnesium is 2~3 with antimony glycol mass ratio:1.
A kind of 2. preparation method of polyester containing unsaturated double-bond according to claim 1, it is characterised in that specifically include with
Lower step：
(1) preparation of catalyst glycol magnesium：
Ethylene glycol is added in single-cell for electrolyzation, supporting electrolyte is magnesium chloride, and metal MAG block is anode, and negative electrode is graphite；It is logical
Direct current, 6~10V of starting voltage, cathode-current density are 150~200mA, are electrolysed 10~12 hours at 50~60 DEG C, electrolysis
Electrode is taken out after end, obtains white suspension；It is filtered under diminished pressure, white solid is washed with absolute ethyl alcohol, and ethylene glycol is obtained after drying
Magnesium；
(2) preparation of polyester, including esterification and polycondensation reaction：
The esterification：
Using terephthalic acid (TPA), unsaturated dibasic acid and ethylene glycol as raw material, esterification is carried out after being made into uniform sizing material, is obtained
To esterification products；Esterification is pressurizeed in nitrogen atmosphere, Stress control in normal pressure~0.3MPa, temperature at 250~260 DEG C,
What esterification water quantity of distillate reached theoretical value more than 90% is esterification terminal；
The polycondensation reaction：
Including polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig：
The polycondensation reaction low vacuum stage, catalyst, stabilizer and ultraviolet initiator are added in esterification products, in negative pressure
Under conditions of start polycondensation reaction, the staged pressure is steadily evacuated to below absolute pressure 500Pa by normal pressure, and temperature control is 260
~270 DEG C, the reaction time is 30~50 minutes；The catalyst is the mixture of ethylene glycol magnesium and antimony glycol；
The polycondensation reaction high vacuum stage of Fig, after the polycondensation reaction low vacuum stage, continue to vacuumize, drop reaction pressure
It is less than 100Pa to absolute pressure, reaction temperature control is at 275~280 DEG C, 50~90 minutes reaction time；
Polyester is made, polyester slice is obtained through pelletizing.
A kind of 3. preparation method of polyester containing unsaturated double-bond according to claim 1 or 2, it is characterised in that the second
The mol ratio of glycol and the terephthalic acid (TPA) is 1.2~2.0:1.
A kind of 4. preparation method of polyester containing unsaturated double-bond according to claim 2, it is characterised in that the ethylene glycol
In the mixture of magnesium and antimony glycol, ethylene glycol magnesium is 2~3 with antimony glycol mass ratio:1；The catalyst amount is described
The 0.01%~0.05% of terephthalic acid (TPA) quality.
A kind of 5. preparation method of polyester containing unsaturated double-bond according to claim 2, it is characterised in that the stabilizer
One kind in triphenyl phosphate, trimethyl phosphate and Trimethyl phosphite, stabilizing agent dosage are terephthalic acid (TPA) weight
0.01%~0.05%.
A kind of 6. preparation method of polyester containing unsaturated double-bond according to claim 2, it is characterised in that described insatiable hunger
It is 1~5 with binary acid and terephthalic acid (TPA) mol ratio:100；The unsaturated dibasic acid be maleic acid, fumaric acid,
One kind in muconic acid.
A kind of 7. preparation method of polyester containing unsaturated double-bond according to claim 2, it is characterised in that the ultraviolet light
Initiator is one kind in cobalt naphthenate, cobalt acetate, zinc naphthenate, zinc stearate, zinc acetate, and addition is terephthalic acid (TPA) weight
The 0.03%~0.05% of amount.
8. using a kind of polyester containing unsaturated double-bond, its feature made from the preparation method described in any one of claim 1~7
It is：The polyester containing unsaturated double-bond be terephthalic acid (TPA), unsaturated dibasic acid and ethylene glycol through esterification and in ethylene glycol magnesium and
The lower polycondensation of mixture through catalytic effect of antimony glycol is made, then obtains polyester slice through pelletizing.
9. one kind polyester containing unsaturated double-bond according to claim 8, it is characterised in that the polyester containing unsaturated double-bond
Number-average molecular weight be 15000~22000.
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| CN109537080B (en) * | 2018-11-29 | 2021-05-11 | 上海炼升化工股份有限公司 | Liquid flame retardant based on phenyl phosphoryl propionic acid diethylene glycol ester and preparation method thereof |
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