CN107987260A - Modified poly ester and preparation method thereof - Google Patents
Modified poly ester and preparation method thereof Download PDFInfo
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- CN107987260A CN107987260A CN201711341927.1A CN201711341927A CN107987260A CN 107987260 A CN107987260 A CN 107987260A CN 201711341927 A CN201711341927 A CN 201711341927A CN 107987260 A CN107987260 A CN 107987260A
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- poly ester
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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
- C08G63/85—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 modified poly ester and preparation method thereof, and terephthalic acid (TPA), ethylene glycol and branched dihydric alcohol successively are carried out esterification after mixing and polycondensation reaction obtains modified poly ester, wherein the structural formula of branched dihydric alcohol is as follows：In formula, R1And R2It is each independently selected from the straight-chain alkyl-sub that carbon number is 1~3, R3Selected from the alkyl that carbon number is 1~5, R4Selected from the alkyl that carbon number is 2~5.The strand of final obtained modified poly ester includes terephthalic acid (TPA) segment, ethylene glycol segment and branched dihydric alcohol segment, content≤0.6wt% of cyclic oligomer in modified poly ester.The method of the present invention can significantly reduce the content of cyclic oligomer in polyester and the performance of polyester in itself will not be had an impact, and obtained modified poly ester molecular weight height and narrowly distributing, have fabulous promotional value.
Description
Technical field
The invention belongs to polymer modification field, is related to a kind of modified poly ester and preparation method thereof.
Background technology
Polyethylene terephthalate (PET) is a kind of polymer of function admirable, and PET is high, strong with modulus because of it
The advantages that degree is high, conformality is good and barrier property is good, is widely used in the fields such as fiber, bottle packaging, film and sheet material, yield
Cumulative year after year, position in industry are obviously improved.
But during the polycondensation reaction of synthesis ethylene terephthalate, particularly when generating linear polymer,
Since high-temperature oxydation is degraded, also association is linear and cyclic oligomer, cyclic oligomer are due to the macromolecular end of the chain in polycondensation phase
Return what is stung cyclisation and formed, about 70% above is cyclic trimer, cyclic trimer have easily aggregation, Yi Jie in cyclic oligomer
The characteristic such as brilliant, chemistry and heat-resistant stability height, generation cyclic trimer can there are following influence on polyester processing：(1) can cause
The blocking of filament spinning component, influences the service life of fondant filter and component；(2) it can separate out, deposit in fiber heat-setting process
On heating roller, frictional force is caused to increase and heat irregular；(3) dyeing course can make dyestuff centered on cyclic trimer
Assemble and be adhered to fiber surface, phenomena such as dyestuff color dot, spot and dyeing defect occurs in fiber surface, influences what is formed by its weaving
The feel and coloured light of fabric, the normal flow stream velocity of melt can be limited by being simultaneously filled with the cyclic oligomer of pipeline and valve, be caused
Stock-dye is irregular, poor reproducibility；(4) fiber surface is adhered to, causes, around yarn difficulty, broken yarn occur and thickness is unequal existing
As influencing the mechanical properties such as fracture strength and the elongation at break of fiber, seriously affecting product quality.
It is growing with polyester fiber yield, polyester quality requirement is also increasingly improved, therefore by cyclic oligomer
The problem of caused polyester post-processing, gradually causes people to pay close attention to, in particular with the fast development of microdenier polyester fibers, market
Dyeing to polyester fiber proposes the requirement of higher.In order to reduce the production of the cyclic oligomer during polyester polycondensation reaction
Raw, domestic and international researcher has carried out substantial amounts of research.The main method for reducing the cyclic oligomer in polyester at this stage has：(1)
Pentavalent phosphorous compound or ether compound are added, it is combined with the metallic catalyst in process of polyester synthesizing, or increase heat
The amount of stabilizer, so as to produce stabilization to polyester, thus can suppress the generation of cyclic trimer under high-temperature fusion；
(2) residence time of polyester fondant at high temperature is reduced.But molecular weight of polyesters can be caused to reduce for the above method and distribution is widened, shadow
Ring the quality of final obtained fiber, while the reduction effect to cyclic trimer oligomer and unobvious.
Therefore, studying a kind of can significantly reduce the content of cyclic oligomer in polyester and will not be to the performance of polyester in itself
The method tool having an impact is of great significance.
The content of the invention
The purpose of the invention is to overcome the above-mentioned prior art to significantly reduce the content of cyclic oligomer in polyester
And the problem of harmful effect being produced to the performance of polyester in itself, there is provided a kind of to significantly reduce cyclic oligomer in polyester
Content and the method that will not be had an impact to the performance of polyester in itself, mainly have specific knot by increasing in polyester raw material
What the branched dihydric alcohol of structure was realized.
In order to achieve the above object, the technical solution adopted by the present invention is：
Modified poly ester, the strand of modified poly ester include terephthalic acid (TPA) segment, ethylene glycol segment and branched binary
Alcohol segment, the structural formula of branched dihydric alcohol are as follows：
In formula, R1And R2It is each independently selected from the straight-chain alkyl-sub that carbon number is 1~3, R3It is 1 selected from carbon number
~5 alkyl, R4Selected from the alkyl that carbon number is 2~5, the purpose that carbon atom number limits：Due to introducing branch in dihydric alcohol
Chain structure and backbone, can weaken the electronegativity of alkoxy portion, and the carbon atom number of branched structure is too small, to alkoxy
Partial electronegativity influence is small, has little significance to the generation for reducing cyclic oligomer；The carbon atom number of branched structure is excessive, meeting
Intermolecular entanglement is produced, the distribution to molecular weight has an impact.
As preferable technical solution：
Modified poly ester as described above, content≤0.6wt% of cyclic oligomer, prior art system in the modified poly ester
The amount of cyclic oligomer is 1.5~2.1wt% in the polyester obtained, and the present invention significantly reduces cyclic oligomer relative to the prior art
The growing amount of thing.
Modified poly ester as described above, the number-average molecular weight 20000~27000 of the modified poly ester, molecular weight distribution refers to
Number is 1.8~2.2, and the molecular weight of modified poly ester produced by the present invention is higher, and molecular weight distribution is relatively narrow, disclosure satisfy that spinning adds
The demand of work, and be conducive to the excellent fiber of processability.
Modified poly ester as described above, the molar content of branched dihydric alcohol segment is to benzene two in the modified poly ester
The 3~5% of formic acid segment molar content, the molar content of branched dihydric alcohol segment is relatively low in modified poly ester of the invention,
Be conducive to keep the excellent performance of polyester itself.
Modified poly ester as described above, the branched dihydric alcohol are 2- Ethyl-2-Methyls -1,3-PD, 2,2-
Diethyl -1,3- propane diols, 2-butyl-2-ethyl-1,3-propanediol, 3,3- diethyl -1,5- pentanediols, 4,4- diethyl -
1,7- heptandiols, 4,4- bis- (1,-Methylethyl) -1,7- heptandiols, 3,3- dipropyl -1,5- pentanediols, 4,4- dipropyl -1,
7- heptandiols, 4- methyl -4- (1,1- dimethyl ethyls) -1,7- heptandiols, 3- methyl -3- amyl groups -1,6-HD or 3,3-
Diamyl -1,5- pentanediols.
The present invention also provides a kind of method for preparing modified poly ester as described above, by terephthalic acid (TPA), ethylene glycol and institute
Stating branched dihydric alcohol, successively progress esterification and polycondensation reaction obtain modified poly ester after mixing.
As preferable technical solution：
Method as described above, comprises the following steps that：
(1) esterification；
Terephthalic acid (TPA), ethylene glycol and the branched dihydric alcohol are made into slurry, add catalyst, delustering agent and steady
Determine agent after mixing, the pressurization progress esterification in nitrogen atmosphere, moulding pressure is normal pressure~0.3MPa, esterification
Temperature is 250~260 DEG C, is esterification terminal when the water quantity of distillate in esterification reaches more than the 90% of theoretical value；
(2) polycondensation reaction；
After esterification, start the polycondensation reaction in low vacuum stage under condition of negative pressure, the staged pressure 30~
Steadily is evacuated to by normal pressure below absolute pressure 500Pa in 50min, reaction temperature is 260~270 DEG C, the reaction time for 30~
50min, then proceedes to vacuumize, and carries out the polycondensation reaction of high vacuum stage of Fig, reaction pressure is further reduced to absolute pressure
Below 100Pa, reaction temperature are 275~285 DEG C, and the reaction time is 50~90min, and modified poly ester is made.
Method as described above, in step (1), mole of terephthalic acid (TPA), ethylene glycol and the branched dihydric alcohol
Than for 1:1.2~2.0:0.03~0.06, the addition of the catalyst is the 0.01~0.05% of terephthalic acid (TPA) weight, institute
The addition for stating delustering agent is the 0.20~0.25% of terephthalic acid (TPA) weight, and the addition of the stabilizer is terephthalic acid (TPA)
The 0.01~0.05% of weight.
Method as described above, the catalyst are antimony oxide, antimony glycol or antimony acetate, and the delustering agent is two
Titanium oxide, the stabilizer are triphenyl phosphate, trimethyl phosphate or Trimethyl phosphite.
Invention mechanism：
In organic compound, the angle between two chemical bonds that the same atom of intramolecular is formed is known as bond angle, and bond angle leads to
Commonly use the number of degrees to represent, the electronegativity of central atom and coordination atom in organic compound molecule, the bond angle of molecule can be influenced.When with
Central atom bonding coordination atom electronegativity increase when, coordination atom electron-withdrawing power enhancing, bond electron pair will to
The movement of position body direction, from central atom farther out, make it is close to each other because repulsion reduces between key pair so that bond angle also reduces therewith,
On the contrary, when the electronegativity for the coordination atom being bonded with central atom reduces, the enhancing of coordination atom electron donation, bonding electrons
To will be moved to central atom direction, from central atom closer to making to be located remotely from each other because repulsion increases between key pair, so that bond angle
Increase therewith.
According to Pauling Electronegativities, the electronegativity of C, H and O atom is respectively 2.55,2.20 and 3.44, and according to
Valence electron balancing energy is theoretical, and the calculation formula of Group Electronegativity is shown below：
In formula, χiFor the electronegativity of i atoms neutral atom before bonding,For valence electron number in i atoms, niFor i
The number of atom in the molecule.Calculation procedure for more complicated Group Electronegativity is mainly：Simple group is calculated first
Electronegativity, then regard simple group as electronegativity that quasiatom calculates more complicated group again, such successive iteration, finally
Obtain the electronegativity of Targeting groups.It should be noted that when calculating the electronegativity of quasiatom, base (for example, group-
Base of OH is O atom) in the valence electron of non-bonding regard the valence electron of quasiatom as.
C atoms can be with the O atom knot of hydroxyl in dihydric alcohol after the C-O keys fracture of carboxyl in terephthalic acid (TPA) in the present invention
Close and form new C-O keys in ester group, the key C-C that the C atoms in ester group are formed with C atoms on phenyl ring and the chemical bond newly formed
Bond angle between C-O is denoted as α, and the change of bond angle α can influence annulation, and when α is less than 109 °, molecule is easy to cyclic, and with
The increase of α, the probability of molecule cyclization can decline.Present invention introduces branched dihydric alcohol, structural formula is shown below：
In formula, R1And R2It is each independently selected from the straight-chain alkyl-sub that carbon number is 1~3, R3It is 1 selected from carbon number
~5 alkyl, R4Selected from the alkyl that carbon number is 2~5.The diol structure due to introducing branched structure and backbone,
It can weaken the electronegativity of its alkoxy portion, can also be drawn in the diol structure with two by the calculation formula of Group Electronegativity
The electronegativity for the group that carbonyl is connected is between 2.59~2.79 in acid, and the group being connected in ethylene glycol with carbonyl in diacid-
OCH2CH2- electronegativity be 3.04, thus its alkoxy is than-the OCH in ethylene glycol2CH2- there is stronger electron, because
Bond electron pair on this chemical bond C-O key for newly to be formed will be moved to center C atomic orientations, from central atom closer to,
Make to be located remotely from each other because repulsion increases between key pair, so that bond angle α is more than 109 °, generate the probability increase of linear polymer,
So as to reduce the generation of cyclic oligomer.
Beneficial effect：
(1) a kind of modified poly ester of the invention, molecular weight height and narrowly distributing, have excellent dyeability available for preparing
With the fiber of mechanical property.
(2) preparation method of a kind of modified poly ester of the invention, by introducing branched dihydric alcohol, changes polyester point
The bond angle of son, so as to significantly reduce the generation of cyclic oligomer in process of polyester synthesizing.
(3) preparation method of a kind of modified poly ester of the invention, preparation process advantages of simple and will not be to polyester in itself
Performance produces harmful effect, there is fabulous promotional value.
Embodiment
The invention will be further elucidated with reference to specific embodiments.It is to be understood that these embodiments are merely to illustrate this hair
It is bright rather than limit the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, art technology
Personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Fixed scope.
Embodiment 1
The preparation method of modified poly ester, comprises the following steps that：
(1) esterification；
It is 1 by molar ratio:1.2:0.03 terephthalic acid (TPA), ethylene glycol and 2- Ethyl-2-Methyl -1,3- propane diols is made into
Slurry, adds antimony oxide, titanium dioxide and triphenyl phosphate after mixing, and pressurizeing in nitrogen atmosphere, it is anti-be esterified
Should, moulding pressure is normal pressure, and the temperature of esterification is 250 DEG C, when the water quantity of distillate in esterification reaches theoretical value
It is esterification terminal when 90%, wherein the addition of antimony oxide is the 0.01% of terephthalic acid (TPA) weight, titanium dioxide
Addition be the 0.20% of terephthalic acid (TPA) weight, the addition of triphenyl phosphate is the 0.05% of terephthalic acid (TPA) weight,
The structural formula of wherein 2- Ethyl-2-Methyls -1,3- propane diols is as follows：
(2) polycondensation reaction；
After esterification, under condition of negative pressure start the low vacuum stage polycondensation reaction, in 30min by pressure by
It is 500Pa that normal pressure, which is steadily evacuated to absolute pressure, and reaction temperature is 260 DEG C, and reaction time 40min, then proceedes to vacuumize, into
The polycondensation reaction of row high vacuum stage of Fig, it is 100Pa reaction pressure is further reduced to absolute pressure, and reaction temperature is 275 DEG C, instead
It is 70min between seasonable, modified poly ester is made.
The strand of final obtained modified poly ester includes terephthalic acid (TPA) segment, ethylene glycol segment and 2- ethyl -2- first
Base -1,3-PD segment, the content of cyclic oligomer is 0.6wt% in modified poly ester, number-average molecular weight 20000, molecular weight
Profile exponent is 2.0, and the molar content of 2- Ethyl-2-Methyls -1,3-PD segment is terephthalic acid (TPA) chain in modified poly ester
The 3% of section molar content.
Comparative example 1
A kind of preparation method of polyester, basically identical with embodiment 1, step is：
(1) esterification；
It is 1 by molar ratio:1.2 terephthalic acid (TPA) and ethylene glycol is made into slurry, add antimony oxide, titanium dioxide and
Triphenyl phosphate after mixing, in nitrogen atmosphere pressurization carry out esterification, moulding pressure is normal pressure, the temperature of esterification
Spend for 250 DEG C, be esterification terminal when the water quantity of distillate in esterification reaches the 90% of theoretical value, wherein three oxidations two
The addition of antimony is the 0.01% of terephthalic acid (TPA) weight, and the addition of titanium dioxide is the 0.20% of terephthalic acid (TPA) weight,
The addition of triphenyl phosphate is the 0.05% of terephthalic acid (TPA) weight；
(2) polycondensation reaction；
After esterification, under condition of negative pressure start the low vacuum stage polycondensation reaction, in 30min by pressure by
It is 500Pa that normal pressure, which is steadily evacuated to absolute pressure, and reaction temperature is 260 DEG C, and reaction time 40min, then proceedes to vacuumize, into
The polycondensation reaction of row high vacuum stage of Fig, it is 100Pa reaction pressure is further reduced to absolute pressure, and reaction temperature is 275 DEG C, instead
It is 70min between seasonable.
The content of cyclic oligomer is 2.1wt% in obtained polyester, number-average molecular weight 25000, molecular weight distribution
Index is 1.92.Understood with the contrast of embodiment 1, the present invention is that the branched dihydric alcohol of specific structure is introduced in polyester molecule
Modified poly ester is made, prepared modified poly ester significantly reduces the growing amount of cyclic oligomer.
Comparative example 2
A kind of preparation method of modified poly ester, basically identical with embodiment 1, step is：
(1) esterification；
It is 1 by molar ratio:1.2:0.03 terephthalic acid (TPA), ethylene glycol and 2- amyl group -1,3 propane diols is made into slurry, adds
Enter antimony oxide, titanium dioxide and triphenyl phosphate after mixing, pressurization progress esterification, pressurization in nitrogen atmosphere
Pressure is normal pressure, and the temperature of esterification is 250 DEG C, is ester when the water quantity of distillate in esterification reaches the 90% of theoretical value
Change reaction end, the wherein addition of antimony oxide is the 0.01% of terephthalic acid (TPA) weight, and the addition of titanium dioxide is
The 0.20% of terephthalic acid (TPA) weight, the addition of triphenyl phosphate are the 0.05% of terephthalic acid (TPA) weight；
(2) polycondensation reaction；
After esterification, under condition of negative pressure start the low vacuum stage polycondensation reaction, in 30min by pressure by
It is 500Pa that normal pressure, which is steadily evacuated to absolute pressure, and reaction temperature is 260 DEG C, and reaction time 40min, then proceedes to vacuumize, into
The polycondensation reaction of row high vacuum stage of Fig, it is 100Pa reaction pressure is further reduced to absolute pressure, and reaction temperature is 275 DEG C, instead
It is 70min between seasonable, modified poly ester is made.
The more a height of 1.5wt% of the content of cyclic oligomer in prepared modified poly ester, number-average molecular weight 15000,
Molecular weight distributing index is 1.95, understands that the distinguishing characteristics of two kinds of preparation methods is the band introduced in slurry with the contrast of embodiment 1
The dihydric alcohol species of side chain is different, and the growing amount of cyclic oligomer is also different in the molecular structure for the modified poly ester prepared, because
The preparation method of this modified poly ester of the present invention can more significantly reduce the growing amount of cyclic oligomer in molecular structure, application prospect
It is very considerable.
Embodiment 2
The preparation method of modified poly ester, comprises the following steps that：
(1) esterification；
It is 1 by molar ratio:1.3:0.04 terephthalic acid (TPA), ethylene glycol and 2,2- diethyl -1,3- propane diols is made into slurry
Material, adds antimony glycol, titanium dioxide and trimethyl phosphate after mixing, the pressurization progress esterification in nitrogen atmosphere,
Moulding pressure is normal pressure, and the temperature of esterification is 260 DEG C, when the water quantity of distillate in esterification reaches the 91% of theoretical value
For esterification terminal, the wherein addition of antimony glycol is the 0.02% of terephthalic acid (TPA) weight, the addition of titanium dioxide
For the 0.21% of terephthalic acid (TPA) weight, the addition of trimethyl phosphate is the 0.03% of terephthalic acid (TPA) weight, wherein 2,2-
The structural formula of diethyl -1,3- propane diols is as follows：
(2) polycondensation reaction；
After esterification, under condition of negative pressure start the low vacuum stage polycondensation reaction, in 35min by pressure by
It is 490Pa that normal pressure, which is steadily evacuated to absolute pressure, and reaction temperature is 261 DEG C, and reaction time 30min, then proceedes to vacuumize, into
The polycondensation reaction of row high vacuum stage of Fig, it is 100Pa reaction pressure is further reduced to absolute pressure, and reaction temperature is 277 DEG C, instead
It is 85min between seasonable, modified poly ester is made.
The strand of final obtained modified poly ester include terephthalic acid (TPA) segment, ethylene glycol segment and 2,2- diethyl-
1,3-PD segment, the content of cyclic oligomer is 0.6wt% in modified poly ester, number-average molecular weight 27000, molecular weight distribution
Index is 1.8, and the molar content of 2,2- diethyl -1,3-PD segment contains for terephthalic acid (TPA) segment mole in modified poly ester
The 5% of amount.
Comparative example 3
A kind of preparation method of modified poly ester, basically identical with embodiment 2, step is：
(1) esterification；
It is 1 by molar ratio:1.3:0.04 terephthalic acid (TPA), ethylene glycol and 2- hexyl -1,3 propane diols is made into slurry, adds
Enter antimony glycol, titanium dioxide and trimethyl phosphate after mixing, the pressurization progress esterification in nitrogen atmosphere, pressurization pressure
Power is normal pressure, and the temperature of esterification is 260 DEG C, is esterification when the water quantity of distillate in esterification reaches the 91% of theoretical value
The addition of reaction end, wherein antimony glycol is the 0.02% of terephthalic acid (TPA) weight, and the addition of titanium dioxide is to benzene
The 0.21% of dioctyl phthalate weight, the addition of trimethyl phosphate are the 0.03% of terephthalic acid (TPA) weight；
(2) polycondensation reaction；
After esterification, under condition of negative pressure start the low vacuum stage polycondensation reaction, in 35min by pressure by
It is 490Pa that normal pressure, which is steadily evacuated to absolute pressure, and reaction temperature is 261 DEG C, and reaction time 30min, then proceedes to vacuumize, into
The polycondensation reaction of row high vacuum stage of Fig, it is 100Pa reaction pressure is further reduced to absolute pressure, and reaction temperature is 277 DEG C, instead
It is 85min between seasonable, modified poly ester is made.
The more a height of 1.8wt% of the content of cyclic oligomer in prepared modified poly ester, number-average molecular weight 16000,
Molecular weight distributing index is 2.03, understands that the distinguishing characteristics of two kinds of preparation methods is the band introduced in slurry with the contrast of embodiment 2
The dihydric alcohol species of side chain is different, and the growing amount of cyclic oligomer is also different in the molecular structure for the modified poly ester prepared, because
The preparation method of this modified poly ester of the present invention can more significantly reduce the growing amount of cyclic oligomer in molecular structure, application prospect
It is very considerable.
Embodiment 3
The preparation method of modified poly ester, comprises the following steps that：
(1) esterification；
It is 1 by molar ratio:1.4:0.05 terephthalic acid (TPA), ethylene glycol and 2-butyl-2-ethyl-1,3-propanediol is made into
Slurry, adds antimony acetate, titanium dioxide and Trimethyl phosphite after mixing, and pressurizeing in nitrogen atmosphere, it is anti-be esterified
Should, moulding pressure 0.1MPa, the temperature of esterification is 252 DEG C, when the water quantity of distillate in esterification reaches theoretical value
It is esterification terminal when 92%, wherein the addition of antimony acetate is the 0.03% of terephthalic acid (TPA) weight, and titanium dioxide adds
Entering 0.23% that amount is terephthalic acid (TPA) weight, the addition of Trimethyl phosphite is the 0.01% of terephthalic acid (TPA) weight, its
The structural formula of middle 2-butyl-2-ethyl-1,3-propanediol is as follows：
(2) polycondensation reaction；
After esterification, under condition of negative pressure start the low vacuum stage polycondensation reaction, in 40min by pressure by
It is 495Pa that normal pressure, which is steadily evacuated to absolute pressure, and reaction temperature is 263 DEG C, and reaction time 45min, then proceedes to vacuumize, into
The polycondensation reaction of row high vacuum stage of Fig, it is 95Pa reaction pressure is further reduced to absolute pressure, and reaction temperature is 278 DEG C, instead
It is 60min between seasonable, modified poly ester is made.
The strand of final obtained modified poly ester includes terephthalic acid (TPA) segment, ethylene glycol segment and 2- butyl -2- second
Base -1,3-PD segment, the content of cyclic oligomer is 0.5wt% in modified poly ester, number-average molecular weight 21000, molecular weight
Profile exponent is 2.2, and the molar content of 2- butyl -2- ethyls -1,3-PD segment is terephthalic acid (TPA) chain in modified poly ester
The 4% of section molar content.
Comparative example 4
A kind of preparation method of modified poly ester, basically identical with embodiment 3, step is：
(1) esterification；
It is 1 by molar ratio:1.4:0.05 terephthalic acid (TPA), ethylene glycol and 2- heptyl -1,3 propane diols is made into slurry, adds
Enter antimony acetate, titanium dioxide and Trimethyl phosphite after mixing, the pressurization progress esterification in nitrogen atmosphere, pressurization pressure
Power is 0.1MPa, and the temperature of esterification is 252 DEG C, is ester when the water quantity of distillate in esterification reaches the 92% of theoretical value
Change reaction end, the wherein addition of antimony acetate is the 0.03% of terephthalic acid (TPA) weight, and the addition of titanium dioxide is to benzene
The 0.23% of dioctyl phthalate weight, the addition of Trimethyl phosphite are the 0.01% of terephthalic acid (TPA) weight；
(2) polycondensation reaction；
After esterification, under condition of negative pressure start the low vacuum stage polycondensation reaction, in 40min by pressure by
It is 495Pa that normal pressure, which is steadily evacuated to absolute pressure, and reaction temperature is 263 DEG C, and reaction time 45min, then proceedes to vacuumize, into
The polycondensation reaction of row high vacuum stage of Fig, it is 95Pa reaction pressure is further reduced to absolute pressure, and reaction temperature is 278 DEG C, instead
It is 60min between seasonable, modified poly ester is made.
The more a height of 2.1wt% of the content of cyclic oligomer in prepared modified poly ester, number-average molecular weight 15900,
Molecular weight distributing index is 1.98, is understood with the contrast of embodiment 3, due to the branched dihydric alcohol introduced in two kinds of preparation methods
Species is different, and the growing amount of cyclic oligomer is also different in the molecular structure for the modified poly ester prepared, therefore the present invention is modified
The preparation method of polyester can significantly reduce the growing amount of cyclic oligomer in molecular structure.
Embodiment 4
The preparation method of modified poly ester, comprises the following steps that：
(1) 3,3- diethyl -1,5- pentanediols are prepared；
, then will concentration by 3,3- diethyl-propionic aldehyde, acetaldehyde and triethylamine react 20min under 90-95 DEG C, blanket of nitrogen
Liquid, which adds, to be had in the hydrogenation reactor of thunder girl's Raney nickel, is reacted at 2.914MPa hydrogen pressure and 100 DEG C, and reaction is finished, and cooling, makes
Catalyst separates out, and after the processing of solution spent ion exchange resin, water is steamed in decompression, separates, and purification, obtains 3,3- diethyl -1,5- penta
Glycol, wherein the structural formula of 3,3- diethyl -1,5-PD is as follows：
(2) esterification；
It is 1 by molar ratio:1.5:0.06 terephthalic acid (TPA), ethylene glycol and 3,3- diethyl -1,5- pentanediols is made into slurry
Material, adds antimony oxide, titanium dioxide and triphenyl phosphate after mixing, and pressurizeing in nitrogen atmosphere, it is anti-be esterified
Should, moulding pressure 0.3MPa, the temperature of esterification is 255 DEG C, when the water quantity of distillate in esterification reaches theoretical value
It is esterification terminal when 95%, wherein the addition of antimony oxide is the 0.04% of terephthalic acid (TPA) weight, titanium dioxide
Addition be the 0.25% of terephthalic acid (TPA) weight, the addition of triphenyl phosphate is the 0.01% of terephthalic acid (TPA) weight；
(3) polycondensation reaction；
After esterification, under condition of negative pressure start the low vacuum stage polycondensation reaction, in 50min by pressure by
It is 400Pa that normal pressure, which is steadily evacuated to absolute pressure, and reaction temperature is 265 DEG C, and reaction time 33min, then proceedes to vacuumize, into
The polycondensation reaction of row high vacuum stage of Fig, it is 90Pa reaction pressure is further reduced to absolute pressure, and reaction temperature is 280 DEG C, instead
It is 50min between seasonable, modified poly ester is made.
The strand of final obtained modified poly ester include terephthalic acid (TPA) segment, ethylene glycol segment and 3,3- diethyl-
1,5-PD segment, the content of cyclic oligomer is 0.2wt% in modified poly ester, number-average molecular weight 23000, molecular weight distribution
Index is 1.9, and the molar content of 3,3- diethyl -1,5-PD segment contains for terephthalic acid (TPA) segment mole in modified poly ester
The 3.5% of amount.
Embodiment 5
The preparation method of modified poly ester, comprises the following steps that：
(1) 4,4- diethyl -1,7- heptandiols are prepared；
, then will concentration by 4,4- diethyl-butyraldehyde, propionic aldehyde and triethylamine react 20min under 90-95 DEG C, blanket of nitrogen
Liquid, which adds, to be had in the hydrogenation reactor of thunder girl's Raney nickel, is reacted at 2.914MPa hydrogen pressure and 100 DEG C, and reaction is finished, and cooling, makes
Catalyst separates out, and after the processing of solution spent ion exchange resin, water is steamed in decompression, separates, purification, obtains 4,4- diethyl -1,7- heptan
Glycol, wherein the structural formula of 4,4- diethyl -1,7- heptandiols is as follows：
(2) esterification；
It is 1 by molar ratio:1.6:0.03 terephthalic acid (TPA), ethylene glycol and 4,4- diethyl -1,7- heptandiols is made into slurry
Material, adds antimony glycol, titanium dioxide and trimethyl phosphate after mixing, the pressurization progress esterification in nitrogen atmosphere,
Moulding pressure is normal pressure, and the temperature of esterification is 257 DEG C, when the water quantity of distillate in esterification reaches the 92% of theoretical value
For esterification terminal, the wherein addition of antimony glycol is the 0.05% of terephthalic acid (TPA) weight, the addition of titanium dioxide
For the 0.20% of terephthalic acid (TPA) weight, the addition of trimethyl phosphate is the 0.04% of terephthalic acid (TPA) weight；
(3) polycondensation reaction；
After esterification, under condition of negative pressure start the low vacuum stage polycondensation reaction, in 33min by pressure by
It is 450Pa that normal pressure, which is steadily evacuated to absolute pressure, and reaction temperature is 270 DEG C, and reaction time 30min, then proceedes to vacuumize, into
The polycondensation reaction of row high vacuum stage of Fig, it is 95Pa reaction pressure is further reduced to absolute pressure, and reaction temperature is 275 DEG C, instead
It is 60min between seasonable, modified poly ester is made.
The strand of final obtained modified poly ester include terephthalic acid (TPA) segment, ethylene glycol segment and 4,4- diethyl-
1,7- heptandiol segment, the content of cyclic oligomer is 0.5wt% in modified poly ester, number-average molecular weight 25000, molecular weight distribution
Index is 2.1, and the molar content of 4,4- diethyl -1,7- heptandiol segment contains for terephthalic acid (TPA) segment mole in modified poly ester
The 5% of amount.
Embodiment 6
The preparation method of modified poly ester, comprises the following steps that：
(1) 4,4- bis- (1,-Methylethyl) -1,7- heptandiols are prepared；
Under 90-95 DEG C, blanket of nitrogen, by 4,4- bis- (1- Methylethyls)-butyraldehyde, propionic aldehyde and triethylamine react 20min, so
Concentrate, which is added, afterwards has in the hydrogenation reactor of thunder girl's Raney nickel, reacts, reacts at 2.914MPa hydrogen pressure and 100 DEG C
Finish, cooling, separates out catalyst.After the processing of solution spent ion exchange resin, water is steamed in decompression, separates, and purification, obtains 4,4- bis-
(1,-Methylethyl) -1,7- heptandiols, wherein the structural formula of 4,4- bis- (1,-Methylethyl) -1,7- heptandiols is as follows：
(2) esterification；
It is 1 by molar ratio:1.7:0.05 terephthalic acid (TPA), ethylene glycol and 4,4- bis- (1,-Methylethyl) -1,7- heptan two
Alcohol is made into slurry, adds antimony acetate, titanium dioxide and Trimethyl phosphite after mixing, the pressurization progress ester in nitrogen atmosphere
Change reaction, moulding pressure 0.2MPa, the temperature of esterification is 253 DEG C, when the water quantity of distillate in esterification reaches theoretical
Value 96% when be esterification terminal, wherein the addition of antimony acetate be terephthalic acid (TPA) weight 0.01%, titanium dioxide
Addition be the 0.20% of terephthalic acid (TPA) weight, the addition of Trimethyl phosphite is terephthalic acid (TPA) weight
0.05%；
(3) polycondensation reaction；
After esterification, under condition of negative pressure start the low vacuum stage polycondensation reaction, in 38min by pressure by
It is 480Pa that normal pressure, which is steadily evacuated to absolute pressure, and reaction temperature is 262 DEG C, and reaction time 38min, then proceedes to vacuumize, into
The polycondensation reaction of row high vacuum stage of Fig, it is 98Pa reaction pressure is further reduced to absolute pressure, and reaction temperature is 279 DEG C, instead
It is 80min between seasonable, modified poly ester is made.
The strand of final obtained modified poly ester include terephthalic acid (TPA) segment, ethylene glycol segment and 4,4- bis- (1 ,-first
Base ethyl) -1,7- heptandiol segments, the content of cyclic oligomer is 0.55wt% in modified poly ester, number-average molecular weight 27000,
Molecular weight distributing index is 2.2, and the molar content of 4,4- bis- (1,-Methylethyl) -1,7- heptandiol segments is in modified poly ester
The 4% of terephthalic acid (TPA) segment molar content.
Embodiment 7
The preparation method of modified poly ester, comprises the following steps that：
(1) 3,3- dipropyl -1,5- pentanediols are prepared；
, then will concentration by 3,3- dipropyl-propionic aldehyde, acetaldehyde and triethylamine react 20min under 90-95 DEG C, blanket of nitrogen
Liquid, which adds, to be had in the hydrogenation reactor of thunder girl's Raney nickel, is reacted at 2.914MPa hydrogen pressure and 100 DEG C, and reaction is finished, and cooling, makes
Catalyst separates out.After the processing of solution spent ion exchange resin, water is steamed in decompression, separates, and purification, obtains 3,3- dipropyl -1,5- penta
Glycol, wherein the structural formula of 3,3- dipropyl -1,5-PD is as follows：
(2) esterification；
It is 1 by molar ratio:1.8:0.03 terephthalic acid (TPA), ethylene glycol and 3,3- dipropyl -1,5- pentanediols is made into slurry
Material, adds antimony oxide, titanium dioxide and triphenyl phosphate after mixing, and pressurizeing in nitrogen atmosphere, it is anti-be esterified
Should, moulding pressure 0.3MPa, the temperature of esterification is 250 DEG C, when the water quantity of distillate in esterification reaches theoretical value
It is esterification terminal when 90%, wherein the addition of antimony oxide is the 0.03% of terephthalic acid (TPA) weight, titanium dioxide
Addition be the 0.24% of terephthalic acid (TPA) weight, the addition of triphenyl phosphate is the 0.02% of terephthalic acid (TPA) weight；
(3) polycondensation reaction；
After esterification, under condition of negative pressure start the low vacuum stage polycondensation reaction, in 42min by pressure by
It is 455Pa that normal pressure, which is steadily evacuated to absolute pressure, and reaction temperature is 264 DEG C, and reaction time 45min, then proceedes to vacuumize, into
The polycondensation reaction of row high vacuum stage of Fig, it is 85Pa reaction pressure is further reduced to absolute pressure, and reaction temperature is 285 DEG C, instead
It is 75min between seasonable, modified poly ester is made.
The strand of final obtained modified poly ester include terephthalic acid (TPA) segment, ethylene glycol segment and 3,3- dipropyl-
1,5-PD segment, the content of cyclic oligomer is 0.45wt% in modified poly ester, number-average molecular weight 26500, molecular weight point
Cloth index is 2.2, and the molar content of 3,3- dipropyl -1,5-PD segment is terephthalic acid (TPA) segment mole in modified poly ester
The 4.5% of content.
Embodiment 8
The preparation method of modified poly ester, comprises the following steps that：
(1) 4,4- dipropyl -1,7- heptandiols are prepared；
, then will concentration by 4,4- dipropyl-butyraldehyde, acetaldehyde and triethylamine react 20min under 90-95 DEG C, blanket of nitrogen
Liquid, which adds, to be had in the hydrogenation reactor of thunder girl's Raney nickel, is reacted at 2.914MPa hydrogen pressure and 100 DEG C, and reaction is finished, and cooling, makes
Catalyst separates out.After the processing of solution spent ion exchange resin, water is steamed in decompression, separates, purification, obtains 4,4- dipropyl -1,7- heptan
Glycol, wherein the structural formula of 4,4- dipropyl -1,7- heptandiols is as follows：
(2) esterification；
It is 1 by molar ratio:1.9:0.04 terephthalic acid (TPA), ethylene glycol and 4,4- dipropyl -1,7- heptandiols is made into slurry
Material, adds antimony glycol, titanium dioxide and trimethyl phosphate after mixing, the pressurization progress esterification in nitrogen atmosphere,
Moulding pressure is 0.3MPa, and the temperature of esterification is 260 DEG C, when the water quantity of distillate in esterification reaches the 93% of theoretical value
When be esterification terminal, wherein the addition of antimony glycol be terephthalic acid (TPA) weight 0.04%, the addition of titanium dioxide
Measure as the 0.21% of terephthalic acid (TPA) weight, the addition of trimethyl phosphate is the 0.03% of terephthalic acid (TPA) weight；
(3) polycondensation reaction；
After esterification, under condition of negative pressure start the low vacuum stage polycondensation reaction, in 45min by pressure by
It is 475Pa that normal pressure, which is steadily evacuated to absolute pressure, and reaction temperature is 265 DEG C, and reaction time 48min, then proceedes to vacuumize, into
The polycondensation reaction of row high vacuum stage of Fig, it is 88Pa reaction pressure is further reduced to absolute pressure, and reaction temperature is 283 DEG C, instead
It is 80min between seasonable, modified poly ester is made.
The strand of final obtained modified poly ester include terephthalic acid (TPA) segment, ethylene glycol segment and 4,4- dipropyl-
1,7- heptandiol segment, the content of cyclic oligomer is 0.6wt% in modified poly ester, number-average molecular weight 23000, molecular weight distribution
Index is 2.0, and the molar content of 4,4- dipropyl -1,7- heptandiol segment contains for terephthalic acid (TPA) segment mole in modified poly ester
The 3% of amount.
Embodiment 9
The preparation method of modified poly ester, comprises the following steps that：
(1) 4- methyl -4- (1,1- dimethyl ethyls) -1,7- heptandiols are prepared；
Under 90-95 DEG C, blanket of nitrogen, by 4- methyl -4- (1,1- dimethyl ethyl)-butyraldehyde, propionic aldehyde and triethylamine react
20min, then adding concentrate has in the hydrogenation reactor of thunder girl's Raney nickel, anti-at 2.914MPa hydrogen pressure and 100 DEG C
Should, reaction is finished, and cooling, separates out catalyst, and after the processing of solution spent ion exchange resin, water is steamed in decompression, separates, and purification, obtains
4- methyl -4- (1,1- dimethyl ethyl) -1,7- heptandiols, wherein 4- methyl -4- (1,1- dimethyl ethyl) -1,7- heptandiols
Structural formula it is as follows：
(2) esterification；
It is 1 by molar ratio:2.0:0.05 terephthalic acid (TPA), ethylene glycol and 4- methyl -4- (1,1- dimethyl ethyls) -1,
7- heptandiols are made into slurry, add antimony acetate, titanium dioxide and trimethyl phosphate after mixing, pressurize in nitrogen atmosphere into
Row esterification, moulding pressure are normal pressure MPa, and the temperature of esterification is 251 DEG C, when the water quantity of distillate in esterification reaches
Theoretical value 96% when be esterification terminal, wherein the addition of antimony acetate be terephthalic acid (TPA) weight 0.05%, dioxy
The addition for changing titanium is the 0.22% of terephthalic acid (TPA) weight, and the addition of trimethyl phosphate is terephthalic acid (TPA) weight
0.04%；
(3) polycondensation reaction；
After esterification, under condition of negative pressure start the low vacuum stage polycondensation reaction, in 30min by pressure by
It is 420Pa that normal pressure, which is steadily evacuated to absolute pressure, and reaction temperature is 267 DEG C, and reaction time 50min, then proceedes to vacuumize, into
The polycondensation reaction of row high vacuum stage of Fig, it is 80Pa reaction pressure is further reduced to absolute pressure, and reaction temperature is 280 DEG C, instead
It is 90min between seasonable, modified poly ester is made.
The strand of final obtained modified poly ester include terephthalic acid (TPA) segment, ethylene glycol segment and 4- methyl -4- (1,
1- dimethyl ethyls) -1,7- heptandiol segments, the content of cyclic oligomer is 0.25wt% in modified poly ester, number-average molecular weight
24000, molecular weight distributing index 2.2,4- methyl -4- (1,1- dimethyl ethyl) -1,7- heptandiol segments in modified poly ester
Molar content be terephthalic acid (TPA) segment molar content 4%.
Embodiment 10
The preparation method of modified poly ester, comprises the following steps that：
(1) 3- methyl -3- amyl groups -1,6-HD is prepared；
Under 90-95 DEG C, blanket of nitrogen, then 3- methyl -3- amyl groups-propionic aldehyde, propionic aldehyde and triethylamine react 20min will
Concentrate, which adds, to be had in the hydrogenation reactor of thunder girl's Raney nickel, is reacted at 2.914MPa hydrogen pressure and 100 DEG C, reaction is finished, cold
But, separate out catalyst.After the processing of solution spent ion exchange resin, water is steamed in decompression, separates, and purification, obtains 3- methyl -3- penta
Base -1,6- hexylene glycol, the structural formula of wherein 3- methyl -3- amyl group -1,6- hexylene glycols are as follows：
(2) esterification；
It is 1 by molar ratio:1.2:0.06 terephthalic acid (TPA), ethylene glycol and 3- methyl -3- amyl groups -1,6-HD is made into
Slurry, adds antimony glycol, titanium dioxide and Trimethyl phosphite after mixing, and pressurizeing in nitrogen atmosphere, it is anti-be esterified
Should, moulding pressure 0.1MPa, the temperature of esterification is 255 DEG C, when the water quantity of distillate in esterification reaches theoretical value
It is esterification terminal when 92%, wherein the addition of antimony glycol is the 0.01% of terephthalic acid (TPA) weight, titanium dioxide
Addition is the 0.20% of terephthalic acid (TPA) weight, and the addition of Trimethyl phosphite is the 0.01% of terephthalic acid (TPA) weight；
(3) polycondensation reaction；
After esterification, under condition of negative pressure start the low vacuum stage polycondensation reaction, in 50min by pressure by
It is 490Pa that normal pressure, which is steadily evacuated to absolute pressure, and reaction temperature is 269 DEG C, and reaction time 30min, then proceedes to vacuumize, into
The polycondensation reaction of row high vacuum stage of Fig, it is 100Pa reaction pressure is further reduced to absolute pressure, and reaction temperature is 281 DEG C, instead
It is 55min between seasonable, modified poly ester is made.
The strand of final obtained modified poly ester includes terephthalic acid (TPA) segment, ethylene glycol segment and 3- methyl -3- penta
Base -1,6- hexylene glycol segment, the content of cyclic oligomer is 0.1wt% in modified poly ester, number-average molecular weight 20000, molecular weight
Profile exponent is 1.9, and the molar content of 3- methyl -3- amyl group -1,6- hexylene glycol segments is terephthalic acid (TPA) chain in modified poly ester
The 3.5% of section molar content.
Embodiment 11
The preparation method of modified poly ester, comprises the following steps that：
(1) 3,3- diamyl -1,5- pentanediols are prepared；
, then will concentration by 3,3- diamyl-propionic aldehyde, acetaldehyde and triethylamine react 20min under 90-95 DEG C, blanket of nitrogen
Liquid, which adds, to be had in the hydrogenation reactor of thunder girl's Raney nickel, is reacted at 2.914MPa hydrogen pressure and 100 DEG C, and reaction is finished, and cooling, makes
Catalyst separates out.After the processing of solution spent ion exchange resin, water is steamed in decompression, separates, and purification, obtains 3,3- diamyl -1,5- penta
Glycol, wherein the structural formula of 3,3- diamyl -1,5-PD is as follows：
(2) esterification；
It is 1 by molar ratio:2.0:0.03 terephthalic acid (TPA), ethylene glycol and 3,3- diamyl -1,5- pentanediols is made into slurry
Material, adds antimony acetate, titanium dioxide and Trimethyl phosphite after mixing, the pressurization progress esterification in nitrogen atmosphere,
Moulding pressure is 0.2MPa, and the temperature of esterification is 250 DEG C, when the water quantity of distillate in esterification reaches the 97% of theoretical value
When be esterification terminal, wherein the addition of antimony acetate be terephthalic acid (TPA) weight 0.01%, the addition of titanium dioxide
For the 0.23% of terephthalic acid (TPA) weight, the addition of Trimethyl phosphite is the 0.05% of terephthalic acid (TPA) weight；
(3) polycondensation reaction；
After esterification, under condition of negative pressure start the low vacuum stage polycondensation reaction, in 45min by pressure by
It is 500Pa that normal pressure, which is steadily evacuated to absolute pressure, and reaction temperature is 260 DEG C, and reaction time 40min, then proceedes to vacuumize, into
The polycondensation reaction of row high vacuum stage of Fig, it is 92Pa reaction pressure is further reduced to absolute pressure, and reaction temperature is 277 DEG C, instead
It is 80min between seasonable, modified poly ester is made.
The strand of final obtained modified poly ester include terephthalic acid (TPA) segment, ethylene glycol segment and 3,3- diamyl-
1,5-PD segment, the content of cyclic oligomer is 0.35wt% in modified poly ester, number-average molecular weight 25500, molecular weight point
Cloth index is 1.8, and the molar content of 3,3- diamyl -1,5-PD segment is terephthalic acid (TPA) segment mole in modified poly ester
The 5% of content.
Claims (9)
1. modified poly ester, it is characterized in that：The strand of modified poly ester includes terephthalic acid (TPA) segment, ethylene glycol segment and with side chain
Dihydric alcohol segment, the structural formula of branched dihydric alcohol is as follows：
In formula, R1And R2It is each independently selected from the straight-chain alkyl-sub that carbon number is 1~3, R3It is 1~5 selected from carbon number
Alkyl, R4Selected from the alkyl that carbon number is 2~5.
2. modified poly ester according to claim 1, it is characterised in that the content of cyclic oligomer in the modified poly ester≤
0.6wt%.
3. modified poly ester according to claim 1, it is characterised in that the number-average molecular weight 20000 of the modified poly ester~
27000, molecular weight distributing index is 1.8~2.2.
4. modified poly ester according to claim 1, it is characterised in that branched dihydric alcohol segment in the modified poly ester
Molar content be terephthalic acid (TPA) segment molar content 3~5%.
5. modified poly ester according to claim 4, it is characterised in that the branched dihydric alcohol is 2- ethyl -2- first
Base -1,3- propane diols, 2,2- diethyl -1,3- propane diols, 2-butyl-2-ethyl-1,3-propanediol, 3,3- diethyl -1,5-
Pentanediol, 4,4- diethyl -1,7- heptandiols, 4,4- bis- (1,-Methylethyl) -1,7- heptandiols, 3,3- dipropyl -1,5- penta
Glycol, 4,4- dipropyl -1,7- heptandiols, 4- methyl -4- (1,1- dimethyl ethyls) -1,7- heptandiols, 3- methyl -3- penta
Base -1,6-HD or 3,3- diamyl -1,5- pentanediols.
6. the method such as Claims 1 to 5 any one of them modified poly ester is prepared, it is characterized in that：By terephthalic acid (TPA), second two
Successively progress esterification and polycondensation reaction obtain modified poly ester after mixing for alcohol and the branched dihydric alcohol.
7. according to the method described in claim 6, it is characterized in that, comprise the following steps that：
(1) esterification；
Terephthalic acid (TPA), ethylene glycol and the branched dihydric alcohol are made into slurry, add catalyst, delustering agent and stabilizer
After mixing, pressurization carries out esterification in nitrogen atmosphere, and moulding pressure is normal pressure~0.3MPa, the temperature of esterification
It is esterification terminal when the water quantity of distillate in esterification reaches more than the 90% of theoretical value for 250~260 DEG C；
(2) polycondensation reaction；
After esterification, start the polycondensation reaction in low vacuum stage under condition of negative pressure, the staged pressure is in 30~50min
Interior to be steadily evacuated to by normal pressure below absolute pressure 500Pa, reaction temperature is 260~270 DEG C, and the reaction time is 30~50min, so
After continue to vacuumize, carry out the polycondensation reaction of high vacuum stage of Fig, reaction pressure is further reduced to below absolute pressure 100Pa,
Reaction temperature is 275~285 DEG C, and the reaction time is 50~90min, and modified poly ester is made.
8. the method according to the description of claim 7 is characterized in that in step (1), terephthalic acid (TPA), ethylene glycol and the band
The molar ratio of the dihydric alcohol of side chain is 1:1.2~2.0:0.03~0.06, the addition of the catalyst is terephthalic acid (TPA) weight
The 0.01~0.05% of amount, the addition of the delustering agent are the 0.20~0.25% of terephthalic acid (TPA) weight, the stabilizer
Addition be terephthalic acid (TPA) weight 0.01~0.05%.
9. according to the method described in claim 8, it is characterized in that, the catalyst is antimony oxide, antimony glycol or vinegar
Sour antimony, the delustering agent are titanium dioxide, and the stabilizer is triphenyl phosphate, trimethyl phosphate or Trimethyl phosphite.
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| CN109680357A (en) * | 2018-12-27 | 2019-04-26 | 江苏恒力化纤股份有限公司 | There is light black terylene long filament and preparation method thereof |
| CN109735929A (en) * | 2018-12-27 | 2019-05-10 | 江苏恒力化纤股份有限公司 | Binary acid modified polyester fibre and preparation method thereof with tert-butyl side group |
| CN112708117A (en) * | 2020-12-29 | 2021-04-27 | 江苏恒力化纤股份有限公司 | High-barrier bottle-grade polyester and preparation method thereof |
| CN112759750A (en) * | 2020-12-29 | 2021-05-07 | 江苏恒力化纤股份有限公司 | Anti-aging polyester film and preparation method thereof |
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| CN109680357A (en) * | 2018-12-27 | 2019-04-26 | 江苏恒力化纤股份有限公司 | There is light black terylene long filament and preparation method thereof |
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| CN109680357B (en) * | 2018-12-27 | 2020-10-16 | 江苏恒力化纤股份有限公司 | Lustrous black polyester filament yarn and preparation method thereof |
| CN112708117A (en) * | 2020-12-29 | 2021-04-27 | 江苏恒力化纤股份有限公司 | High-barrier bottle-grade polyester and preparation method thereof |
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| CN112759750B (en) * | 2020-12-29 | 2022-05-10 | 江苏恒力化纤股份有限公司 | Anti-aging polyester film and preparation method thereof |
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