CN108148189A - A kind of synthetic method of biology base degradable copolyester - Google Patents
A kind of synthetic method of biology base degradable copolyester Download PDFInfo
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- CN108148189A CN108148189A CN201810075663.8A CN201810075663A CN108148189A CN 108148189 A CN108148189 A CN 108148189A CN 201810075663 A CN201810075663 A CN 201810075663A CN 108148189 A CN108148189 A CN 108148189A
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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
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
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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
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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
- C08G63/78—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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
- C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
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- Polyesters Or Polycarbonates (AREA)
Abstract
A kind of synthetic method of biology base degradable copolyester of the present invention belongs to synthesis of polymer material technical field, by two kinds of diol mixtures, terephthalic acid (TPA), catalyst and additive under inert atmosphere 150kPa pressure conditions, disperses 10~15 minutes；240~260 DEG C are warming up to, by boost in pressure to 300kPa, carries out esterification, after esterification, temperature is adjusted to 250~280 DEG C, pressure is adjusted to 20~100Pa, and polycondensation 1~4 hour obtains biology base degradable copolyester product.Catalyst usage amount of the present invention is small, and polymerization temperature is low, and the biology base degradable copolyester of preparation has very high glass transition temperature and excellent mechanical performance.
Description
Technical field
The invention belongs to synthesis of polymer material technical field, more particularly to a kind of synthetic method of biology base copolyesters.
Background technology
At present, application percentage of the high molecular material in daily necessities is higher and higher, and performer is more next in life
More important role gradually instead of other inorganic metals and nonmetallic materials, occupies absolute predominance.But due to it
It is difficult to degrade, therefore bring serious environmental problem；Its raw material is substantially from traditional non-renewable fossil resources simultaneously,
Therefore research and development can be applied to the reproducible high molecular material of biology base, and biology base high molecular material has very high market prospects
With application value.
Polyethylene terephthalate (PET) and polypropylene terephthalate (PTT) are well-known application
Two major class of polyester, because they have good performance in terms of intensity, flexibility and mechanical property.For example, PET has succeeded
Applied to the various types of water bottles of manufacture and fiber derivative；PTT also be used to manufacture clothes and carpet etc..Due to this two kinds of days
The polyester material often used has excellent physical property, application in the world, therefore applies biology base dihydric alcohol
Modified PET is of great significance with PTT.The glass transition temperature of PET and PTT is relatively low, limits it under the high temperature conditions
It uses, meanwhile, the intractability difficult to degrade for also increasing corresponding waste.By the method for copolymerization, in poly terephthalic acid second
In diol ester and the polyester chain of propylene glycol ester terephthalate, a kind of glycol of the renewable macromolecule of biology base is introduced, it can
To increase the high temperature resistance of corresponding polyester material, while biodegradable chain link has also been introduced.Patent CN 1298343A by
E.I.Du Pont Company discloses polyester and preparation process containing isobide first, and patent description aromatic diacid is esterified with glycol
Polycondensation forms polyester, but the logarithmic viscosity number of its product is relatively low, is not suitable for carrying out industry life as application high molecular material
Production.Patent US 5959066 is prepared for the PEIT with certain mechanical property using direct melt esterification and process for solid state polycondensation.But because
The content of isobide is relatively low in structural unit, and the heat resistance of material is only capable of obtaining small raising.In patent CN 1675282A
A kind of melt polymerization process for preparing PEIT is provided, and by selecting suitable catalyst and controlling in the preparation method
The important technical parameter of each step, inhibits or reduces to the greatest extent the formation of diethylene glycol (DEG), so as to reach the mesh for preparing light color pool PEIT
, but its reaction temperature is higher, and catalyst usage amount is high, and the reaction time is long, and log viscosities are relatively low.Patent CN 1711302A are public
The synthesis of the polyester material containing isobide is opened, the method used is to carry out pre-polymerization under aqueous solution, and shortcoming is to react
Complex steps increase enforcement difficulty during many industrial productions.
Invention content
Present invention aims at a kind of relative low temperature is provided, the reaction time is short, and be suitble to commercial Application passes through direct esterification
The method of method synthesising biological base degradable copolyester.
To realize the purpose, the present invention is using alcohol antimony -ol titanium complex catalyst, using terephthalic acid (TPA), isobide, second
Glycol, 1,3-PD are copolymeric material, and the degradable copolyesters of synthesising biological base, specific technical solution is as follows：
A kind of synthetic method of biology base degradable copolyester, two kinds of diol mixtures are put into 100 DEG C of low pressure
In polymerization reaction kettle, terephthalic acid (TPA) is added, add in catalyst and additive, under inert atmosphere 150kPa pressure conditions, point
It dissipates 10~15 minutes；240~260 DEG C are to slowly warm up to, while is filled with inert gas, after boost in pressure to 300kPa, is kept
The constant carry out esterification of pressure and temperature, monitoring reaction esterification water volume, when water to be esterified reaches more than 96% theoretical value,
Esterification terminates, and temperature is adjusted to 250~280 DEG C, pressure is adjusted to 20~100Pa, and polycondensation 1~4 is small on this condition
When, obtain biology base degradable copolyester product；
Two kinds of diol mixtures refer to the mixture of isobide and ethylene glycol or isobide and 1,3- third
The mixture of glycol, wherein isobide are 1 with the molar ratio of ethylene glycol or 1,3-PD：3~19；
The catalyst is alcohol antimony catalyst or alcohol antimony -ol titanium complex catalyst, the alcohol antimony are antimony glycol, fourth
One kind in glycol antimony, 1,3-PD antimony, hexylene glycol antimony, the alcohol titanium are purity titanium tetraethoxide, butyl titanate, metatitanic acid four
One kind in isopropyl ester, titanium ethylene glycolate, 1,3- propylene glycol titaniums；When two kinds of diol mixtures are isobide and second two
During the mixture of alcohol, the catalyst used is alcohol antimony catalyst, and dosage is 0.1 ‰~the 0.25 ‰ of terephthalic acid (TPA) molal quantity；
When two kinds of dihydric alcohols are the mixtures of isobide and 1,3-PD, the catalyst used is that alcohol antimony -ol titanium is answered
The dosage of conjunction catalyst, alcohol antimony and alcohol titanium is 0.1 ‰~the 0.25 ‰ of terephthalic acid (TPA) molal quantity；
The additive is stabilizer or the additive package of stabilizer and antioxidant；When two kinds of dihydric alcohols mix
When closing object as the mixture of isobide and ethylene glycol, the additive used is stabilizer, and dosage is terephthalic acid (TPA) mole
Several 0.1 ‰~0.25 ‰；When two kinds of diol mixtures is the mixtures of isobide and 1,3-PD, make
Additive is the additive package of stabilizer and antioxidant, and the dosage of stabilizer and antioxidant is terephthalic acid (TPA) mole
Several 0.1 ‰~0.25 ‰；
Preferably, two kinds of diol mixtures and the molar ratio of terephthalic acid (TPA) are 1.0~1.6：1.
The alcohol antimony catalyst can specifically be prepared as follows：It is 1.46 by mass ratio：19.03 Sb2O3And 1,3-
Propylene glycol and toluene are sequentially added in round-bottomed flask, and round-bottomed flask with oil water separator is connected, one is terminated on water knockout drum
A spherical condensation tube, under the conditions of magnetic agitation, back flow reaction steams the first in system after 4 hours under the conditions of 190 DEG C of oil bath temperature
System temperature is down to 140 DEG C and kept, is evaporated under reduced pressure with vacuum pump, to be steamed until there is no 1,3-PDs by benzene, will
To solid continue to be dried under reduced pressure 2 hours, obtain 1,3-PD antimony solid powder.
The alcohol titanium catalyst can specifically be prepared as follows：1,3-PD is added in round-bottomed flask, and is added
Enter absolute ethyl alcohol dilution, stirring, be warming up to 75 DEG C, butyl titanate, 1,3- in mass ratio the third two is added dropwise with constant pressure funnel
Alcohol：Butyl titanate=3.04：6.81, reaction stops reaction after 3 hours, is evaporated under reduced pressure under the conditions of 80 DEG C, works as liquor capacity
When being reduced to original half, stop heating, stand overnight, incline supernatant liquor, is washed with absolute ethyl alcohol, is dried in 80 DEG C of air blast
It is 12 hours dry in case, obtain 1,3-PD titanium white powder.
The present invention is raw material using terephthalic acid (TPA) and isobide, adds in ethylene glycol or 1,3-PD is used as and is copolymerized into
Point, with alcohol antimony -ol titanium complex catalyst, synthesis obtains biology base degradable copolyester, and reaction temperature is relatively low, and the reaction time is short,
Synthesis step is few.When using ethylene glycol as copolymer composition, obtained product is PEIT, glass transition temperature up to 80~
95 DEG C, heat decomposition temperature is significantly raised；When using 1,3-PD as copolymer composition, obtained product is PTIT, glass
Change transition temperature and rise to 45~55 DEG C.The PET and PTT that its mechanical performance compares abiotic base simultaneously have better tensile property,
Higher elasticity modulus by modification by copolymerization, increases the trying out property of high temperature of PET and the mechanical performance of PTT, is suitble to industry raw
Production.
To sum up, compared with prior art, the present invention haing the following advantages：
1st, catalyst usage amount is small, and composite catalyst all works in Esterification Stage and polycondensation phase.The composite catalyst
Usage amount invented far below equivalent technology, generally 0.1 ‰~0.25 ‰, required stabilizer and antioxidant ratio are also much low
It is invented in same technique.
2nd, polymerization temperature is low, and Esterification Stage temperature is 240~260 DEG C, pressure 300kPa, is conducive to the small of esterification generation
Molecule discharges system, and generally at 250-280 DEG C, pressure is conducive under composite catalyst effect in 20~100Pa condensation temperature
Oligomer polycondensation is molecular weight raising, while is conducive to low boiling point polymer and isolates system with excessive dihydric alcohol.Its characteristic
Viscosity can reach 0.70~0.95.
3rd, the biology base degradable copolyester prepared by the present invention has higher glass transition temperature and better machine
Tool performance.
Description of the drawings
Fig. 1 is the PEIT polyester nuclear magnetic resonance spectroscopies of different isobide doping in Examples 1 to 5.
Fig. 2 is the PTIT polyester nuclear magnetic resonance spectroscopies of different isobide doping in embodiment 6~10.
Fig. 3 is the nuclear magnetic resonance spectroscopy of 1,3- propylene glycol antimony prepared by embodiment 11.
Specific embodiment
With reference to example, the present invention is described further, but use condition of the present invention is not only applicable to following reality
Example.
Embodiment 1
By the terephthalic acid (TPA) of the ethylene glycol of 3.43mol, the isobide of 0.18mol and 3.61mol put into 100 DEG C it is lazy
Property gas shield reaction kettle in, add in 0.85mmol glycol antimony catalysts and 0.85mmol stabilizer triphenyl phosphates, use
Inert gas replacement reaction gas reactor three times, prevents oxidic raw materials.Open stirring, the speed of 15r/min under 150kPa pressure
Degree stirring 10 minutes, each substance in catalyst and reaction kettle is uniformly dispersed, then in 30 minutes, temperature is risen to 240 DEG C,
Pressure rises to 300kPa, and maintenance reaction pressure is 300kPa, react to the amount of esterification water reach the 96% of theoretical value when at 35 points
Restore in clock to normal pressure, restore to be warming up to slow inert gas flow purging three to five times after normal pressure 260 DEG C, while by body
It is that pressure is down to 100Pa, this decompression heating need to be used 40 minutes.Vacuum degree to be then down to 20Pa, is reacted 3 hours, reaction terminates,
Vacuum is closed, is passed through inert gas, stands 5 minutes, opens reaction kettle discharging, water-bath cooling batten, pelletizing.Pass through skill of the present invention
Less than 6 hours the time required to polyester material prepared by art, the reaction time is significantly reduced relative to the prior art.The polyester material
The inherent viscosity of material is 0.73, content of carboxyl end group 10.35mol/t, and the polyester material prepared by the present invention compares equivalent technology
Invention obtains higher inherent viscosity, while endgroup content is also relatively small, illustrates that the polymer chain length obtained is larger, glass
It is 81.8 DEG C to change inversion temperature, relative to without isosorbide modified polyethylene terephthalate (PET) glass transition
Temperature improves 20 DEG C, and heat decomposition temperature is 398.7 DEG C, and fusing point is 226.2 DEG C, tensile strength 44.6MPa, and elasticity modulus is
1531MPa.The nuclear magnetic resonance spectroscopy of gained polyester material in its chemical composition as shown in Figure 1, contain second as can be seen from Figure 1
Diol segment and isobide segment, thus can determine the chemical composition and ratio of polymer.
Embodiment 2
By the terephthalic acid (TPA) of the ethylene glycol of 3.54mol, the isobide of 0.39mol and 3.61mol put into 100 DEG C it is lazy
Property gas shield reaction kettle in, add in 0.65mmol hexylene glycols antimony catalyst and 0.65mmol stabilizer triphenyl phosphates, use
Inert gas replacement reaction gas reactor three times, prevents oxidic raw materials.Open stirring, the speed of 15r/min under 150kPa pressure
Degree stirring 10 minutes, each substance in catalyst and reaction kettle is uniformly dispersed, then in 30 minutes, temperature is risen to 240 DEG C,
Pressure rises to 300kPa, and maintenance reaction pressure is 300kPa, react to the amount of esterification water reach the 96% of theoretical value when at 35 points
Restore in clock to normal pressure, restore to be warming up to slow inert gas flow purging three to five times after normal pressure 260 DEG C, while by body
It is that pressure is down to 100Pa, this decompression heating need to be used 40 minutes.Vacuum degree is then down to 20Pa, is reacted 3.2 hours, reaction knot
Beam closes vacuum, is passed through inert gas, stands 5 minutes, opens reaction kettle discharging, water-bath cooling batten, pelletizing.By this hair
Less than 6 hours the time required to polyester material prepared by bright technology, product property viscosity is 0.66, and content of carboxyl end group is
28.49mol/t, glass transition temperature are 84.5 DEG C, and heat decomposition temperature is 431.6 DEG C, and fusing point is 205.7 DEG C, tensile strength
For 53.8MPa, elasticity modulus 1408MPa.The nuclear magnetic resonance spectroscopy of gained polyester material is as shown in Figure 1, can from figure
Go out in its chemical composition to contain ethylene glycol segment and isobide segment, while isobide ingredient is higher than example 1.
Embodiment 3
By the terephthalic acid (TPA) of the ethylene glycol of 3.69mol, the isobide of 0.65mol and 3.61mol put into 100 DEG C it is lazy
Property gas shield reaction kettle in, add in 0.75mmol 1,3-PDs antimony catalyst and 0.75mmol stabilizer phosphoric acid triphens
Ester with inert gas replacement reaction gas reactor three times, prevents oxidic raw materials.Open stirring, the 15r/min under 150kPa pressure
Speed stir 10 minutes, each substance in catalyst and reaction kettle is uniformly dispersed, then in 30 minutes, temperature is risen to
240 DEG C, pressure rises to 300kPa, and maintenance reaction pressure is 300kPa, react to the amount of esterification water reach the 96% of theoretical value when
Restored in 35 minutes to normal pressure, purged three to five times with slow inert gas flow after restoring normal pressure, be warming up to 260 DEG C, together
When system pressure is down to 100Pa, this decompression heating need to be used 40 minutes.Vacuum degree is then down to 20Pa, is reacted 3.5 hours,
Reaction terminates, and closes vacuum, is passed through inert gas, stands 5 minutes, opens reaction kettle discharging, water-bath cooling batten, pelletizing.Production
Object inherent viscosity is 0.60, and content of carboxyl end group 29.12mol/t, glass transition temperature is 85.8 DEG C, and heat decomposition temperature is
427.8 DEG C, tensile strength 49.0MPa, elasticity modulus 1418MPa.The nuclear magnetic resonance spectroscopy of gained polyester material such as Fig. 1 institutes
Show, ethylene glycol segment and isobide segment, while isobide ingredient are as can be seen from the figure contained in its chemical composition
Higher than example 1,2.
Embodiment 4
By the terephthalic acid (TPA) of the ethylene glycol of 3.76mol, the isobide of 0.94mol and 3.61mol put into 100 DEG C it is lazy
Property gas shield reaction kettle in, add in 0.80mmol 1,4-butanediol antimony catalyst and 0.80mmol stabilizer phosphoric acid triphens
Ester with inert gas replacement reaction gas reactor three times, prevents oxidic raw materials.Open stirring, the 15r/min under 150kPa pressure
Speed stir 10 minutes, each substance in catalyst and reaction kettle is uniformly dispersed, then in 30 minutes, temperature is risen to
240 DEG C, pressure rises to 300kPa, and maintenance reaction pressure is 300kPa, react to the amount of esterification water reach the 96% of theoretical value when
Restored in 35 minutes to normal pressure, purged three to five times with slow inert gas flow after restoring normal pressure, be warming up to 260 DEG C, together
When system pressure is down to 100Pa, this decompression heating need to be used 40 minutes.Vacuum degree is then down to 20Pa, is reacted 3.6 hours,
Reaction terminates, and closes vacuum, is passed through inert gas, stands 5 minutes, opens reaction kettle discharging, water-bath cooling batten, pelletizing.Production
Object inherent viscosity is 0.70, and content of carboxyl end group 22.05mol/t, glass transition temperature is 89.63 DEG C, and heat decomposition temperature is
428.0 DEG C, tensile strength 48.8MPa, elasticity modulus 1110MPa.The nuclear magnetic resonance spectroscopy of gained polyester material such as Fig. 1 institutes
Show, ethylene glycol segment and isobide segment, while isobide ingredient are as can be seen from the figure contained in its chemical composition
Further raising.
Embodiment 5
By the terephthalic acid (TPA) of the ethylene glycol of 4.33mol, the isobide of 1.44mol and 3.61mol put into 100 DEG C it is lazy
Property gas shield reaction kettle in, add in 0.50mmol 1,3-PDs antimony catalyst and 0.50mmol stabilizer phosphoric acid triphens
Ester with inert gas replacement reaction gas reactor three times, prevents oxidic raw materials.Open stirring, the 15r/min under 150kPa pressure
Speed stir 10 minutes, each substance in catalyst and reaction kettle is uniformly dispersed, then in 30 minutes, temperature is risen to
240 DEG C, pressure rises to 300kPa, and maintenance reaction pressure is 300kPa, react to the amount of esterification water reach the 96% of theoretical value when
Restored in 35 minutes to normal pressure, purged three to five times with slow inert gas flow after restoring normal pressure, be warming up to 260 DEG C, together
When system pressure is down to 100Pa, this decompression heating need to be used 40 minutes.Vacuum degree is then down to 20Pa, is reacted 3.8 hours,
Reaction terminates, and closes vacuum, is passed through inert gas, stands 5 minutes, opens reaction kettle discharging, water-bath cooling batten, pelletizing.Production
Object inherent viscosity is 0.68, and content of carboxyl end group 22.48mol/t, glass transition temperature is 94.6 DEG C, and heat decomposition temperature is
427.8 DEG C, tensile strength 55.8MPa, elasticity modulus 1580MPa.The nuclear magnetic resonance spectroscopy of gained polyester material such as Fig. 1 institutes
Show, ethylene glycol segment and isobide segment, while isobide ingredient are as can be seen from the figure contained in its chemical composition
Further raising.
Embodiment 6
The 1,3- propylene glycol of 3.43mol, the isobide of 0.18mol and the terephthalic acid (TPA) of 3.61mol are put into 100
In the reaction kettle of DEG C inert gas shielding, the 1,3-PD titanium for adding in 0.55mmol 1,3-PDs antimony and 0.55mmol is made
For catalyst and 0.55mmol stabilizers triphenyl phosphate and 0.55mmol antioxidant 1010s (four [β-(3,5- di-t-butyl -4-
Hydroxy phenyl) propionic acid] pentaerythritol ester), with inert gas replacement reaction gas reactor three times, prevent oxidic raw materials.Unlatching is stirred
It mixes, the speed of 15r/min stirs 10 minutes under 150kPa pressure, each substance in catalyst and reaction kettle is uniformly dispersed, so
Afterwards in 30 minutes, temperature is risen to 240 DEG C, pressure rises to 300kPa, and maintenance reaction pressure is 300kPa, is reacted to esterification water
Amount restored in 35 minutes to normal pressure when reaching the 96% of theoretical value, restore after normal pressure with slow inert gas flow purging three
To five times, 250 DEG C are to slowly warm up to, while system pressure is down to 100Pa, this decompression heating needs 40 minutes.Then by vacuum
Degree is down to 20Pa, reacts 3.5 hours, and reaction terminates, and closes vacuum, is passed through inert gas, stands 5 minutes, opens reaction kettle and goes out
Material, water-bath cooling batten, pelletizing.Product property viscosity is 0.85, content of carboxyl end group 33.01mol/t, glass transition temperature
It it is 45.0 DEG C, heat decomposition temperature is 397.1 DEG C, and fusing point is 214.3 DEG C, tensile strength 39.88MPa, and elasticity modulus is
1194MPa.The nuclear magnetic resonance spectroscopy of gained polyester material in its chemical composition as shown in Fig. 2, as can be seen from the figure contain
Isobide segment.
Embodiment 7
The 1,3- propylene glycol of 4.70mol, the isobide of 0.52mol and the terephthalic acid (TPA) of 3.61mol are put into 100
In the reaction kettle of DEG C inert gas shielding, add in the titanium ethylene glycolate of 0.60mmol antimony glycols and 0.60mmol as catalyst and
0.60mmol stabilizers triphenyl phosphate and 0.60mmol antioxidant 1010s, with inert gas replacement reaction gas reactor three times,
Prevent oxidic raw materials.Stirring is opened, the speed of 15r/min stirs 10 minutes under 150kPa pressure, by catalyst and reaction kettle
Interior each substance is uniformly dispersed, and then in 30 minutes, temperature is risen to 240 DEG C, pressure rises to 300kPa, and maintenance reaction pressure is
300kPa is reacted and was restored when reaching the 96% of theoretical value to the amount of esterification water to normal pressure in 35 minutes, is restored after normal pressure with slow
Slow inert gas flow purges three to five times, is to slowly warm up to 250 DEG C, while system pressure is down to 100Pa, this decompression heating
It needs 40 minutes.Vacuum degree is then down to 20Pa, is reacted 3.8 hours, reaction terminates, and closes vacuum, is passed through inert gas, stands
5 minutes, open reaction kettle discharging, water-bath cooling batten, pelletizing.Product property viscosity is 0.86, and content of carboxyl end group is
21.00mol/t, glass transition temperature are 48.0 DEG C, and heat decomposition temperature is 396.5 DEG C, 212.8 DEG C of fusing point, and tensile strength is
47.56MPa, elasticity modulus 1140MPa.The nuclear magnetic resonance spectroscopy of gained polyester material is as shown in Fig. 2, as can be seen from the figure
Isobide segment is contained in its chemical composition, while isobide ingredient is higher than example 6.
Embodiment 8
The 1,3- propylene glycol of 4.60mol, the isobide of 0.81mol and the terephthalic acid (TPA) of 3.61mol are put into 100
In the reaction kettle of DEG C inert gas shielding, add in the butanediol titanium of 0.65mmol hexylene glycols antimony and 0.65mmol as catalyst and
0.65mmol stabilizers triphenyl phosphate and 0.65mmol antioxidant 1010s, with inert gas replacement reaction gas reactor three times,
Prevent oxidic raw materials.Stirring is opened, the speed of 15r/min stirs 10 minutes under 150kPa pressure, by catalyst and reaction kettle
Interior each substance is uniformly dispersed, and then in 30 minutes, temperature is risen to 240 DEG C, pressure rises to 300kPa, and maintenance reaction pressure is
300kPa is reacted and was restored when reaching the 96% of theoretical value to the amount of esterification water to normal pressure in 35 minutes, is restored after normal pressure with slow
Slow inert gas flow purges three to five times, is to slowly warm up to 250 DEG C, while system pressure is down to 100Pa, this decompression heating
It needs 40 minutes.Vacuum degree is then down to 20Pa, is reacted 3.8 hours, reaction terminates, and closes vacuum, is passed through inert gas, stands
5 minutes, open reaction kettle discharging, water-bath cooling batten, pelletizing.Product property viscosity is 0.82, and content of carboxyl end group is
10.50mol/t, glass transition temperature are 54.5 DEG C, and heat decomposition temperature is 387.0 DEG C, and fusing point is 210.8 DEG C, tensile strength
For 46.80MPa, elasticity modulus 1117MPa.The nuclear magnetic resonance spectroscopy of gained polyester material is as shown in Fig. 2, can from figure
Go out in its chemical composition to contain isobide segment, while isobide ingredient is apparently higher than example 6,7.
Embodiment 9
The 1,3- propylene glycol of 4.33mol, the isobide of 1.08mol and the terephthalic acid (TPA) of 3.61mol are put into 100
In the reaction kettle of DEG C inert gas shielding, the butyl titanate of 0.70mmol butanediols antimony and 0.70mmol are added in as catalyst
With 0.70mmol stabilizers triphenyl phosphate and 0.70mmol antioxidant 1010s, gas reactor three is reacted with inert gas replacement
It is secondary, prevent oxidic raw materials.Stirring is opened, the speed of 15r/min stirs 10 minutes under 150kPa pressure, by catalyst and reaction
Each substance is uniformly dispersed in kettle, then in 30 minutes, temperature is risen to 240 DEG C, pressure rises to 300kPa, maintains reaction pressure
For 300kPa, react and restored when reaching the 96% of theoretical value to the amount of esterification water to normal pressure in 35 minutes, used after restoring normal pressure
Slow inert gas flow purges three to five times, is to slowly warm up to 250 DEG C, while system pressure is down to 100Pa, this decompression rises
Temperature needs 40 minutes.Vacuum degree is then down to 20Pa, is reacted 3.8 hours, reaction terminates, and closes vacuum, is passed through inert gas, quiet
It puts 5 minutes, opens reaction kettle discharging, water-bath cooling batten, pelletizing.Product property viscosity is 0.72, and content of carboxyl end group is
37.47mol/t, glass transition temperature are 48.4 DEG C, and heat decomposition temperature is 398.1 DEG C, and fusing point is 207.8 DEG C, tensile strength
For 46.0MPa, elasticity modulus 1177MPa.The nuclear magnetic resonance spectroscopy of gained polyester material is as shown in Fig. 2, can from figure
Go out in its chemical composition to contain isobide segment, while isobide ingredient is higher than example 6~8.
Embodiment 10
The 1,3- propylene glycol of 4.33mol, the isobide of 1.44mol and the terephthalic acid (TPA) of 3.61mol are put into 100
In the reaction kettle of DEG C inert gas shielding, the 1,3-PD titanium of 0.90mmol antimony glycols and 0.90mmol is added in as being catalyzed
Agent and 0.90mmol stabilizers triphenyl phosphate and 0.90mmol antioxidant 1010s react gas reactor three with inert gas replacement
It is secondary, prevent oxidic raw materials.Stirring is opened, the speed of 15r/min stirs 10 minutes under 150kPa pressure, by catalyst and reaction
Each substance is uniformly dispersed in kettle, then in 30 minutes, temperature is risen to 240 DEG C, pressure rises to 300kPa, maintains reaction pressure
For 300kPa, react and restored when reaching the 96% of theoretical value to the amount of esterification water to normal pressure in 35 minutes, used after restoring normal pressure
Slow inert gas flow purges three to five times, is to slowly warm up to 250 DEG C, while system pressure is down to 100Pa, this decompression rises
Temperature needs 40 minutes.Vacuum degree is then down to 20Pa, is reacted 4 hours, reaction terminates, and closes vacuum, is passed through inert gas, stands
5 minutes, open reaction kettle discharging, water-bath cooling batten, pelletizing.Product property viscosity is 0.73, and content of carboxyl end group is
23.28mol/t, glass transition temperature are 50.91 DEG C, and heat decomposition temperature is 391.2 DEG C, and fusing point is 201.3 DEG C, tensile strength
For 43.91MPa, elasticity modulus 1299MPa.The nuclear magnetic resonance spectroscopy of gained polyester material is as shown in Fig. 2, can from figure
Go out in its chemical composition to contain isobide segment, while isobide ingredient is apparently higher than example 6~9.
Embodiment 11
By 1.46g Sb2O3, 19.03g 1,3-PDO and 15ml toluene is sequentially added in 100ml round-bottomed flasks, by round bottom
Flask is connected with oil water separator, one spherical condensation tube of termination on water knockout drum, under the conditions of magnetic agitation, oil bath temperature 190
Back flow reaction under the conditions of DEG C, after reacting about 4h, a small amount of water of deposition in water knockout drum column, system becomes the liquid of clear in flask
Body.The toluene in system is steamed, treats that system temperature is down to 140 DEG C, is evaporated under reduced pressure with vacuum pump, makes temperature stabilization 140
DEG C, it to be steamed until there is no 1,3-PDs, white or light yellow solid is obtained in bottle, maintains this temperature-resistant, it is dry to continue decompression
Dry 2h obtains 1,3-PD antimony solid powder 1.64g, yield 70.4%.The nuclear magnetic resonance spectroscopy of product as shown in figure 3,
The ligand composition of alcohol antimony catalyst is determined.
Embodiment 12
3.04g 1,3-PDO are added in 100ml round-bottomed flasks, the dilution of 20mL absolute ethyl alcohols, stirring is added in, is warming up to 75
DEG C, 6.81g butyl titanates are added dropwise with constant pressure funnel, time for adding 25min stops reaction after reacting 3h, subtracts instead
Distilling apparatus is pressed, is evaporated under reduced pressure under the conditions of 80 DEG C, when liquor capacity is reduced to original half, begins with a large amount of white solids
It is precipitated, stops heating, stand overnight, incline supernatant liquor, is washed with a small amount of absolute ethyl alcohol, dry in 80 DEG C of air blast drying boxes
12h, product is placed in spare in drier, obtains 1,3-PD titanium white powder 2.87g, yield 73.2%.Wherein 1,3-
The elemental analysis of propylene glycol titanium is as shown in table 1, and alcohol titanium catalyst ingredient is analyzed as can be seen from Table 1, it is determined that alcohol titanium is urged
The composition of agent.
The elemental analysis of 1 1,3- propylene glycol titanium catalysts of table
。
Claims (4)
1. a kind of synthetic method of biology base degradable copolyester, two kinds of diol mixtures are put into 100 DEG C of low pressure and are gathered
It closes in reaction kettle, adds terephthalic acid (TPA), add in catalyst and additive, under inert atmosphere 150kPa pressure conditions, dispersion
10~15 minutes；240~260 DEG C are to slowly warm up to, while is filled with inert gas, after boost in pressure to 300kPa, keeps pressure
Power and temperature-resistant carry out esterification, monitoring reaction esterification water volume, when water to be esterified reaches more than 96% theoretical value, ester
To change reaction to terminate, temperature is adjusted to 250~280 DEG C, pressure is adjusted to 20~100Pa, on this condition polycondensation 1~4 hour,
Obtain biology base degradable copolyester product；
Two kinds of diol mixtures refer to the mixture of isobide and ethylene glycol or isobide and 1,3- propylene glycol
Mixture, the wherein molar ratio of isobide and ethylene glycol or 1,3-PD is 1:3~19；
The catalyst is alcohol antimony catalyst or alcohol antimony -ol titanium complex catalyst, the alcohol antimony are antimony glycol, butanediol
One kind in antimony, 1,3-PD antimony, hexylene glycol antimony, the alcohol titanium are purity titanium tetraethoxide, butyl titanate, four isopropyl of metatitanic acid
One kind in ester, titanium ethylene glycolate, 1,3- propylene glycol titaniums；When two kinds of diol mixtures are isobide and ethylene glycol
During mixture, the catalyst used is alcohol antimony catalyst, and dosage is 0.1 ‰~the 0.25 ‰ of terephthalic acid (TPA) molal quantity；Work as institute
When the two kinds of dihydric alcohols stated are the mixtures of isobide and 1,3-PD, the catalyst that uses, which is that alcohol antimony -ol titanium is compound, urges
The dosage of agent, alcohol antimony and alcohol titanium is 0.1 ‰~the 0.25 ‰ of terephthalic acid (TPA) molal quantity；
The additive is stabilizer or the additive package of stabilizer and antioxidant；When two kinds of diol mixtures
During for the mixture of isobide and ethylene glycol, the additive used is stabilizer, and dosage is terephthalic acid (TPA) molal quantity
0.1 ‰~0.25 ‰；When two kinds of diol mixtures is the mixtures of isobide and 1,3-PD, use
The dosage of additive package of the additive for stabilizer and antioxidant, stabilizer and antioxidant is terephthalic acid (TPA) molal quantity
0.1 ‰~0.25 ‰.
A kind of 2. synthetic method of biology base degradable copolyester according to claim 1, which is characterized in that described two
Kind diol mixture and the molar ratio of terephthalic acid (TPA) are 1.0~1.6:1.
3. the synthetic method of a kind of biology base degradable copolyester according to claim 1 or 2, which is characterized in that described
Alcohol antimony catalyst prepare as follows：It is 1.46 by mass ratio:19.03 Sb2O3With 1,3- propylene glycol and toluene
It sequentially adds in round-bottomed flask, round-bottomed flask is connected with oil water separator, a spherical condensation tube, magnetic are terminated on water knockout drum
Under power stirring condition, back flow reaction steams the toluene in system, system temperature is dropped after 4 hours under the conditions of 190 DEG C of oil bath temperature
It to 140 DEG C and keeps, is evaporated under reduced pressure with vacuum pump, to be steamed until there is no 1,3-PDs, obtained solid is continued to subtract
It press dry dry 2 hours, obtains 1,3-PD antimony solid powder.
4. the synthetic method of a kind of biology base degradable copolyester according to claim 1 or 2, which is characterized in that described
Alcohol titanium catalyst can specifically prepare as follows：1,3-PD is added in round-bottomed flask, and it is dilute to add in absolute ethyl alcohol
It releases, stir, be warming up to 75 DEG C, butyl titanate, in mass ratio 1,3-PD is added dropwise with constant pressure funnel：Butyl titanate
=3.04:6.81, reaction stops reaction after 3 hours, is evaporated under reduced pressure under the conditions of 80 DEG C, when liquor capacity is reduced to original half
When, stop heating, stand overnight, incline supernatant liquor, is washed with absolute ethyl alcohol, and dry 12 is small in 80 DEG C of air blast drying boxes
When, obtain 1,3-PD titanium white powder.
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| CN109897171A (en) * | 2019-03-29 | 2019-06-18 | 新凤鸣集团股份有限公司 | A kind of method that ecological efficient compounding polycondensation catalyst prepares polyester |
| CN111560115A (en) * | 2020-04-22 | 2020-08-21 | 浙江恒澜科技有限公司 | Preparation method of moisture-absorbing flame-retardant modified PTT polyester |
| CN111607074A (en) * | 2020-06-19 | 2020-09-01 | 海宁澜钛新材料有限公司 | Method for preparing terephthalic acid-ethylene glycol-isosorbide copolyester by antimony-titanium bimetallic catalysis |
| CN112341611A (en) * | 2020-11-20 | 2021-02-09 | 吉林大学 | Degradable modified polyester with high heat resistance and good mechanical property and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109897171A (en) * | 2019-03-29 | 2019-06-18 | 新凤鸣集团股份有限公司 | A kind of method that ecological efficient compounding polycondensation catalyst prepares polyester |
| CN111560115A (en) * | 2020-04-22 | 2020-08-21 | 浙江恒澜科技有限公司 | Preparation method of moisture-absorbing flame-retardant modified PTT polyester |
| CN111560115B (en) * | 2020-04-22 | 2022-07-26 | 浙江恒逸石化研究院有限公司 | Preparation method of moisture-absorbing flame-retardant modified PTT polyester |
| CN111607074A (en) * | 2020-06-19 | 2020-09-01 | 海宁澜钛新材料有限公司 | Method for preparing terephthalic acid-ethylene glycol-isosorbide copolyester by antimony-titanium bimetallic catalysis |
| CN111607074B (en) * | 2020-06-19 | 2022-08-12 | 海宁澜钛新材料有限公司 | Method for preparing terephthalic acid-ethylene glycol-isosorbide copolyester by antimony-titanium bimetallic catalysis |
| CN112341611A (en) * | 2020-11-20 | 2021-02-09 | 吉林大学 | Degradable modified polyester with high heat resistance and good mechanical property and preparation method thereof |
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