CN107955149A - The production method of the polypropylene terephthalate of low cyclic dimer content - Google Patents
The production method of the polypropylene terephthalate of low cyclic dimer content Download PDFInfo
- Publication number
- CN107955149A CN107955149A CN201610906682.1A CN201610906682A CN107955149A CN 107955149 A CN107955149 A CN 107955149A CN 201610906682 A CN201610906682 A CN 201610906682A CN 107955149 A CN107955149 A CN 107955149A
- Authority
- CN
- China
- Prior art keywords
- polypropylene terephthalate
- cyclic dimer
- production method
- catalyst
- dimer content
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 0 CC*(*COC(C(C)*)=N)C(O*)=O Chemical compound CC*(*COC(C(C)*)=N)C(O*)=O 0.000 description 1
Classifications
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The present invention relates to a kind of production method of the polypropylene terephthalate of low cyclic dimer content, phenomena such as mainly solving in polypropylene terephthalate existing in the prior art that cyclic dimer is on the high side, causing " hazing " in production process, " bloom ".By using comprising the following steps：A) with terephthalic acid (TPA), other aromatic diacids, 1,3 propane diols are raw material, add the catalyst with least one of general formula (I), (II), (III) or logical formula (IV) structure, it it is 220~300 DEG C in esterification reaction temperature, esterification reaction pressure carries out esterification under the conditions of being 0.1~0.5MPa, obtains prepolymer；B) obtained prepolymer is subjected to precondensation；Then carry out melt polycondensation reaction and obtain the technical solution of polymerizate, preferably solve the problems, such as this, in the industrialized production available for the polypropylene terephthalate of low cyclic dimer content.
Description
Technical field
The present invention relates to a kind of production method of polypropylene terephthalate, contains available for low cyclic dimer is manufactured
The polypropylene terephthalate of amount, reaches and reduces " hazing ", the target of " bloom " phenomenon in spinning, film manufacturing process.
The generation of low cyclic dimer in the course of the polymerization process can effectively be suppressed using the present invention, final cyclic dimer content is less than polymerization
The 2% of thing gross weight.
Background technology
The progressively polymerization technique used in the production process of polyester can be with the structure of generating portion low polymerization degree, ring-type two
Dimeric structure itself occlusion cyclization, has higher heat endurance, while do not possess molecular weight and continue to increase required active group
Group, thus can be blended in polypropylene terephthalate polymer and be difficult to remove.Polyethylene terephthalate (PET)
The influence of oligomer and cyclic dimer is generally received in the production and processing of fiber and film product, has also obtained relevant grind
Study carefully.And in the production process of polypropylene terephthalate, cyclic dimer also can be with generation, and seriously affects poly- pair
The processing performance of benzene dicarboxylic acid trimethylene glycol ester.However, to cyclic dimer research quantity in polypropylene terephthalate very
It is few.The cyclic dimer of high-content can form bloom in spinning process in spinneret hole, cause spinneret to block, and fly silk, break
Phenomena such as silk.The cyclic dimer content of the polypropylene terephthalate of usual processing route production is higher than total polymer
The 3% of amount.Reducing the content of cyclic dimer helps to lift the appearance and performance of product, and can reduce in spinning, note
Frosting, phenomena such as steeping of turning white, reduce stop cleaning number, improve product yield during modeling.
Report to reduce using the method for dichloromethane, methanol, ethanol equal solvent soxhlet extraction in CN102421820A and gather
The method of cyclic dimer content in propylene glycol ester terephthalate.This method can effectively reduce the content of cyclic dimer, suppression
Frosting phenomenon processed, but substantial amounts of toxic solvent has been used in this method, as large-scale application can cause environment serious danger
Evil, and since a large amount of of solvent use, being significantly increased for production cost can be caused.
The balance in polypropylene terephthalate polymerization process can be changed by catalyst structure design, so as to subtract
The method of few cyclic dimer content.Invention describes a kind of production method of polypropylene terephthalate, spy is used
The polypropylene terephthalate of the Catalyst Production low content cyclic dimer of different structure.The production method can utilize existing
Polyester production device is produced, without extra economic input and increase environmental pressure.
The content of the invention
The technical problems to be solved by the invention are lack low content cyclic dimer poly- pairs existing in the prior art
The production method of benzene dicarboxylic acid trimethylene glycol ester, there is provided one kind production cyclic dimer content reduces 50%, less than 2% polymer
The production method of percentage by weight.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is as follows：A kind of low cyclic dimer content
The production method of polypropylene terephthalate, comprises the following steps：
A) using the aromatic diacid including terephthalic acid (TPA), 1,3-PD as raw material, add with general formula (I), (II),
(III) or at least one of logical formula (IV) structure catalyst, be 220~300 DEG C in esterification reaction temperature, esterification reaction pressure
To carry out esterification under the conditions of 0.1~0.5MPa, prepolymer is obtained；
B) be 245~265 DEG C in prepolymerization reaction temperature by obtained prepolymer, prepolymerization reaction pressure for 300~
Precondensation is carried out under the vacuum condition of 1000Pa；Then it is 245~265 DEG C in melt polycondensation reaction temperature, melt polycondensation reaction
Pressure obtains polymerizate to carry out melt polycondensation reaction under the vacuum condition less than 150Pa；
Wherein, R5、R6For the straight chained alkyl that carbon number is 2~12, R7Carbon number for 2~8 and containing 1 to 2
A carboxyl, titanium atom and R7Molar ratio meet 0.1<Ti/R7<0.5, M is at least one of magnesium, aluminium, zinc, zirconium.
Wherein, R5、R6For the straight chained alkyl that carbon number is 2~12, R7Carbon number for 2~8 and containing 1 to 2
A carboxyl, titanium atom and R7Molar ratio meet 0.5<Ti/R7<1.5, M be at least one of magnesium, aluminium, zinc, zirconium.
Wherein, R7Carbon number for 2~8 and contain 1 to 2 carboxyls, titanium atom and R7Molar ratio meet 1.5<
Ti/R7<2, M be at least one of magnesium, aluminium, zinc, zirconium.
Wherein, R7Carbon number for 2~8 and contain 1 to 2 carboxyls, titanium atom and R7Molar ratio meet 2<Ti/
R7<3, M be at least one of magnesium, aluminium, zinc, zirconium.
In above-mentioned technical proposal, the catalyst is made by the material including following structures：
A) titanium compound that formula (V) represents is led to,
Wherein R1~R4It is independently chosen from the alkyl of 1~10 carbon atom.
B) saturated straight chain R5Or/and R6Carbon number is the saturated straight chain dihydric alcohol of 2~12,
C) there is the hydroxycarboxylic acid HOR of at least two carboxyls7COOH, wherein R7Carbon number 2~8 and to be arrived containing 1
2 carboxyls,
D) metal organic salt, wherein metallic element M are selected from magnesium, aluminium, zinc, at least one metallic element of zirconium；
Its preparation method is as follows：
The organic titanic compound is small in 10~150 DEG C of reactions 0.1~24 with saturated straight chain dihydric alcohol and hydroxycarboxylic acid
When, then the metal organic salt is added into product, when 10~150 DEG C of reactions 0.1~24 are small, then deposited in removal system
Low-carbon alcohols and/or water after obtain the catalyst of polypropylene terephthalate preparation.
In above-mentioned technical proposal, the straight dihydric alcohol is selected from ethylene glycol, 1,2 propane diols, 1,3 propane diols, Isosorbide-5-Nitrae fourth two
At least one of alcohol is a variety of.
In above-mentioned technical proposal, the hydroxycarboxylic acid with least two carboxyls is preferably malic acid, tartaric acid, lemon
At least one of lemon acid.
In above-mentioned technical proposal, the metal organic salt is preferably that magnesium, aluminium, zinc, zirconium and dissociation constant are more than 4.0pKa
Organic acid acid group formed salt.
In above-mentioned technical proposal, the amount of the straight dihydric alcohol of preferably described addition is with contained straight dihydric alcohol molal quantity and titanium
Elemental mole ratios are (0.1~10):1；The amount of the hydroxycarboxylic acid of the addition is rubbed with contained hydroxycarboxylic acid molal quantity with titanium elements
Your ratio is (0.1~3):1；The amount of metal organic salt is in terms of contained metal molar number, the molar ratio with titanium elements in titanium compound
For (0.1~10):1.
In above-mentioned technical proposal, arbitrary proportion may be present in the catalyst of the production polypropylene terephthalate
Water, catalyst are in uniform solution.
In above-mentioned technical proposal, the catalyst is made by aforementioned four component can solve present invention problem, but
It is common auxiliary agent in can also being produced with polypropylene terephthalate such as phosphorus stabilizer agent, antioxidant, carbon black, color dyes
Common addition is without influencing using effect.The catalyst can be added in any stage of polymerisation.The catalyst adds
The quality entered is calculated as 10-150mg/kg polyacids or polybasic ester with titanium elements quality.
In the present invention, the inherent viscosity of polypropylene terephthalate and form and aspect pass through in GB/T 14189-2008
The method is tested：Inherent viscosity test presses 60 using phenol tetrachloroethane：40 ratios, which mix, makees solvent, at a temperature of 25 DEG C
Use determination of ubbelohde viscometer.
In the present invention, the cyclic dimer content of polypropylene terephthalate can pass through liquid phase after soxhlet extraction
Chromatography tests to obtain.Use CH2Cl2Polypropylene terephthalate is extracted as solvent, passes through liquid-phase chromatographic analysis
Cyclic dimer content in extract simultaneously calculates its content in the polymer.
For producing polypropylene terephthalate under economic speed, method of the invention is effective.
By the present invention in that with the catalyst of special designing, reduce cyclic dimer in polypropylene terephthalate polymerization process
Production, the content of cyclic dimer in the polymer reduces 50% compared to routine techniques.Use poly- pair produced by the invention
Without " frosting ", " white haze " phenomenon in the process that benzene dicarboxylic acid trimethylene glycol ester application conventional spinning processes carry out, spray is extended
The service life of filament plate, reduces shut-down cleaning, improves the yield and product matter of polypropylene terephthalate
Amount.
Technical solution using the present invention, for producing polypropylene terephthalate, obtained poly terephthalic acid
Propylene glycol ester inherent viscosity can be less than 0.9%, achieve preferable technique effect up to 0.921dL/g, cyclic dimer content.
Brief description of the drawings
Fig. 1 is the embodiment of the present invention 2, the infrared spectrum of 4 product of comparative example.
As seen from Figure 1, product of the present invention only retains R7Carboxyl characteristic peak, CO stretch peak disappearance, illustrate the present invention
Catalyst contain the material of formula (I)~structure shown in (IV)；And product is only mixture feature in comparative example 4.
Below by embodiment, the present invention is further elaborated.
Embodiment
【Embodiment 1】
142g tetraisopropyl titanates are mixed with 124g ethylene glycol, 22.5g tartaric acid, in stirred reactor, 100
When reaction 4 is small under DEG C temperature conditionss, zinc lactate 37g, in the reactor with stirring, 120 DEG C of temperature are added into reactant
Under the conditions of reaction 4 it is small when.Reaction product is placed in the reactor for possessing fractionating device, distillates isopropyl alcohol and water, catalysis is made
Agent.Catalyst is mixed with 1,3-PD, wherein the mass fraction of titanium atom is 4%.
600 grams of terephthalic acid (TPA)s, 440 gram 1,3 propane diols, catalyst 1.49g and stabilizer, which mix, is made into slurry, is added to
In polymeric kettle, esterification is carried out, esterification temperature is 230 DEG C, pressure 0.25MPa, and reaction generation is discharged by rectifier unit
Water, reaction 2 it is small when.Normal pressure is down to after esterification, initially enters precondensation stage, vacuumizes holding reaction pressure
0.5KPa, fluid temperature 245 DEG C one hour, vacuumizes and is decompressed to system pressure and is less than 130Pa, 245 DEG C of reaction temperature, works as system
Reaction reach 3 it is small when after stop reaction, reaction product is continuously extruded from polymeric kettle bottom with bar shaped afterwards, cooling, pelletizing.
Obtain polypropylene terephthalate inherent viscosity 0.912dl/g, cyclic dimer content 1.5%.
【Embodiment 2-4】
Using method for preparing catalyst same as Example 1, the additive amount difference lies in tartaric acid be respectively 75g,
120g and 190g.
【Embodiment 5-6】
Using method for preparing catalyst same as Example 1, difference lies in straight dihydric alcohol to use 1,3 propane diols respectively
172g and 1,4 butanediol 180g.
【Embodiment 7-8】
Using method for preparing catalyst same as Example 1, difference lies in hydroxycarboxylic acid respectively using malic acid 20g and
Citric acid 29g.
【Embodiment 9-10】
Using method for preparing catalyst same as Example 1, difference lies in metal organic salt to use magnesium carbonate respectively
13g and hypochlorous acid zirconium 30g.
【Embodiment 11】
Using method for preparing catalyst same as Example 1, difference lies in catalyst, stabilizer to add after esterification
Enter.
【Comparative example 1】
With 1,3- the third two after 142g tetraisopropyl titanates are mixed with 124g ethylene glycol, 22.5g tartaric acid, zinc lactate 37g
The catalyst that the mass fraction that alcohol is made into titanium atom is 4%.
600 grams of terephthalic acid (TPA)s, 440 gram 1,3 propane diols, catalyst 1.49g and stabilizer, which mix, is made into slurry, is added to
In polymeric kettle, esterification is carried out, esterification temperature is 230 DEG C, pressure 0.25MPa, and reaction generation is discharged by rectifier unit
Water, reaction 2 it is small when.Normal pressure is down to after esterification, initially enters precondensation stage, vacuumizes holding reaction pressure
0.5KPa, fluid temperature 245 DEG C one hour, vacuumizes and is decompressed to system pressure and is less than 130Pa, 245 DEG C of reaction temperature, works as system
Reaction reach 3 it is small when after stop reaction, reaction product is continuously extruded from polymeric kettle bottom with bar shaped afterwards, cooling, pelletizing.
【Comparative example 2】
In the reactor equipped with blender, condenser and thermometer, tetraisopropyl titanate 142g is added, into reactor
Ethylene glycol 124g is slowly dropped into, separates out white depositions, when reaction 2 is small at 70 DEG C, tartaric acid 120g is added into reactor
Zinc lactate 37g, 1,3-PD 100g reacted at 90 DEG C 3 it is small when, obtain light yellow transparent liquid, by product and 1,3- the third two
Alcohol mixes, and wherein the mass fraction of titanium atom is 4%.
600 grams of terephthalic acid (TPA)s, 440 gram 1,3 propane diols, catalyst 1.49g and stabilizer, which mix, is made into slurry, is added to
In polymeric kettle, esterification is carried out, esterification temperature is 230 DEG C, pressure 0.25MPa, and reaction generation is discharged by rectifier unit
Water, reaction 2 it is small when.Normal pressure is down to after esterification, initially enters precondensation stage, vacuumizes holding reaction pressure
0.5KPa, fluid temperature 245 DEG C one hour, vacuumizes and is decompressed to system pressure and is less than 130Pa, 245 DEG C of reaction temperature, works as system
Reaction reach 3 it is small when after stop reaction, reaction product is continuously extruded from polymeric kettle bottom with bar shaped afterwards, cooling, pelletizing.
【Comparative example 3】
600 grams of terephthalic acid (TPA)s, 440 gram 1,3 propane diols, antimony glycol (Sb2(OCH2CH2O)3) 0.26g and stabilizer mix
Be made into slurry, be added in polymeric kettle, carry out esterification, esterification temperature be 230 DEG C, pressure 0.25MPa, passes through rectifying
The water of device discharge reaction generation, when reaction 2 is small.Normal pressure is down to after esterification, initially enters precondensation stage, vacuumizes guarantor
Hold reaction pressure 0.5KPa, fluid temperature 245 DEG C one hour, vacuumizes and be decompressed to system pressure and be less than 130Pa, reaction temperature
245 DEG C, when system reaction reach 3 it is small when after stop reaction, reaction product is continuously extruded from polymeric kettle bottom with bar shaped afterwards,
Cooling, pelletizing.
【Comparative example 4】
600 grams of terephthalic acid (TPA)s, 440 gram 1,3 propane diols, tetraisopropyl titanate 0.352g and stabilizer, which mix, is made into slurry
Material, is added in polymeric kettle, carries out esterification, and esterification temperature is 230 DEG C, and pressure 0.25MPa, is discharged by rectifier unit
The water of generation is reacted, when reaction 2 is small.Normal pressure is down to after esterification, initially enters precondensation stage, vacuumizes holding reaction pressure
Power 0.5KPa, fluid temperature 245 DEG C one hour, vacuumizes and is decompressed to system pressure and is less than 130Pa, 245 DEG C of reaction temperature, works as body
Be reaction reach 3 it is small when after stop reaction, reaction product is continuously extruded from polymeric kettle bottom with bar shaped afterwards, cooling, pelletizing.
【Comparative example 5】
600 grams of terephthalic acid (TPA)s, 440 gram 1,3 propane diols mix and are made into slurry, are added in polymeric kettle, be esterified anti-
Should, esterification temperature is 230 DEG C, pressure 0.25MPa, the water of reaction generation is discharged by rectifier unit, when reaction 2 is small.Esterification
After be down to normal pressure and add tetraisopropyl titanate 0.352g and stabilizer, initially enter precondensation stage, vacuumize holding
Reaction pressure 0.5KPa, fluid temperature 245 DEG C one hour, vacuumizes and is decompressed to system pressure and is less than 130Pa, reaction temperature 245
DEG C, when system reaction reach 3 it is small when after stop reaction, reaction product is continuously extruded from polymeric kettle bottom with bar shaped afterwards, it is cold
But, pelletizing.
【Comparative example 6】
142g tetraisopropyl titanates are mixed with 92g ethanol, 22.5g tartaric acid, in stirred reactor, 100 DEG C
When reaction 4 is small under temperature conditionss, zinc lactate 37g, in the reactor with stirring, 120 DEG C of temperature strips are added into reactant
When reaction 4 is small under part.Reaction product is placed in the reactor for possessing fractionating device, isopropyl alcohol and water is distillated, catalyst is made.
Catalyst is mixed with 1,3-PD, wherein the mass fraction of titanium atom is 4%.
600 grams of terephthalic acid (TPA)s, 440 gram 1, (50ppm is relatively to benzene for 3 propane diols, catalyst 1.49g and stabilizer phosphoric acid
Dioctyl phthalate) mix and be made into slurry, it is added in polymeric kettle, carries out esterification, esterification temperature is 230 DEG C, and pressure is
0.25MPa, the water of reaction generation is discharged by rectifier unit, when reaction 2 is small.Normal pressure is down to after esterification, is initially entered pre-
Polycondensation phase, vacuumizes and keeps reaction pressure 0.5KPa, fluid temperature 245 DEG C one hour, vacuumizes that to be decompressed to system pressure low
In 130Pa, 245 DEG C of reaction temperature, when system reaction reach 3 it is small when after stop reaction, afterwards by reaction product from bottom of polymerizing pot
Portion is continuously extruded with bar shaped, cooling, pelletizing.
Obtain polypropylene terephthalate inherent viscosity 0.879dl/g, cyclic dimer content 4.3%.
Table 1
Claims (10)
1. a kind of production method of the polypropylene terephthalate of low cyclic dimer content, comprises the following steps：
A) using the aromatic diacid including terephthalic acid (TPA), 1,3-PD as raw material, add with general formula (I), (II), (III)
Or the catalyst of at least one of logical formula (IV) structure, it is 220~300 DEG C in esterification reaction temperature, esterification reaction pressure 0.1
Esterification is carried out under the conditions of~0.5MPa, obtains prepolymer；
B) it is 245~265 DEG C in prepolymerization reaction temperature by obtained prepolymer, prepolymerization reaction pressure is 300~1000Pa
Vacuum condition under carry out precondensation；Then it is 245~265 DEG C in melt polycondensation reaction temperature, melt polycondensation reaction pressure is
Melt polycondensation reaction is carried out under vacuum condition less than 150Pa and obtains polymerizate；
Wherein, R5、R6For the straight chained alkyl that carbon number is 2~12, R7Carbon number for 2~8 and contain 1 to 2 carboxylics
Base, titanium atom and R7Molar ratio meet 0.1<Ti/R7<0.5, M is at least one of magnesium, aluminium, zinc, zirconium；
Wherein, R5、R6For the straight chained alkyl that carbon number is 2~12, R7Carbon number for 2~8 and contain 1 to 2 carboxylics
Base, titanium atom and R7Molar ratio meet 0.5<Ti/R7<1.5, M be at least one of magnesium, aluminium, zinc, zirconium；
Wherein, R7Carbon number for 2~8 and contain 1 to 2 carboxyls, titanium atom and R7Molar ratio meet 1.5<Ti/R7<
2, M be at least one of magnesium, aluminium, zinc, zirconium；
Wherein, R7Carbon number for 2~8 and contain 1 to 2 carboxyls, titanium atom and R7Molar ratio meet 2<Ti/R7<3,
M is at least one of magnesium, aluminium, zinc, zirconium.
2. the production method of the polypropylene terephthalate of low cyclic dimer content according to claim 1, it is special
Sign is the catalyst being made by the material including following structures：
A) titanium compound that formula (V) represents is led to,
Wherein R1~R4It is independently chosen from the alkyl of 1~10 carbon atom.
B) saturated straight chain R5Or/and R6Carbon number is the saturated straight chain dihydric alcohol of 2~12,
C) there is the hydroxycarboxylic acid HOR of at least two carboxyls7COOH, wherein R7Carbon number for 2~8 and containing 1 to 2
Carboxyl,
D) metal organic salt, wherein metallic element M are selected from magnesium, aluminium, zinc, at least one metallic element of zirconium；
Its preparation method is as follows：
By the organic titanic compound and saturated straight chain dihydric alcohol and hydroxycarboxylic acid when 10~150 DEG C of reactions 0.1~24 are small, then
The metal organic salt is added into product, when 10~150 DEG C of reactions 0.1~24 are small, then present in removal system
The catalyst of polypropylene terephthalate preparation is obtained after low-carbon alcohols and/or water.
3. the production method of the polypropylene terephthalate of low cyclic dimer content according to claim 2, it is special
Sign be the straight dihydric alcohol be selected from least one of ethylene glycol, 1,2 propane diols, 1,3 propane diols, 1,4 butanediols or
It is a variety of.
4. the production method of the polypropylene terephthalate of low cyclic dimer content according to claim 2, it is special
Sign is the hydroxycarboxylic acid with least two carboxyls at least one of malic acid, tartaric acid, citric acid.
5. the production method of the polypropylene terephthalate of low cyclic dimer content according to claim 2, it is special
Sign is the salt that the metal organic salt is formed for the organic acid acid group of magnesium, aluminium, zinc, zirconium and dissociation constant more than 4.0pKa.
6. the production method of the polypropylene terephthalate of low cyclic dimer content according to claim 2, it is special
Sign be the amount of the straight dihydric alcohol of the addition using contained straight dihydric alcohol molal quantity and titanium elements molar ratio as (0.1~
10):1；The amount of the hydroxycarboxylic acid of the addition is using contained hydroxycarboxylic acid molal quantity and titanium elements molar ratio as (0.1~3):1；Gold
Belong to the amount of organic salt in terms of contained metal molar number, the molar ratio with titanium elements in titanium compound is (0.1~10):1.
7. the production method of the polypropylene terephthalate of low cyclic dimer content according to claims 1 to 6, its
It is characterized in that may be present the water of arbitrary proportion in the catalyst, catalyst is in uniform solution.
8. the production method of the polypropylene terephthalate of low cyclic dimer content according to claims 1 to 6, its
It is characterized in that the catalyst further includes at least one of phosphorus stabilizer agent, antioxidant, carbon black, color dye.
9. the production method of the polypropylene terephthalate of low cyclic dimer content according to claims 1 to 6, its
It is characterized in that, the catalyst can be added in any stage of polymerisation.
10. the production method of the polypropylene terephthalate of low cyclic dimer content according to claims 1 to 6,
It is characterized in that, the quality that the catalyst of the polypropylene terephthalate preparation adds is calculated as with titanium elements quality
10-150mg/kg polyacids or polybasic ester.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610906682.1A CN107955149B (en) | 2016-10-18 | 2016-10-18 | Process for producing polytrimethylene terephthalate with low cyclic dimer content |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610906682.1A CN107955149B (en) | 2016-10-18 | 2016-10-18 | Process for producing polytrimethylene terephthalate with low cyclic dimer content |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107955149A true CN107955149A (en) | 2018-04-24 |
| CN107955149B CN107955149B (en) | 2020-04-17 |
Family
ID=61953532
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610906682.1A Active CN107955149B (en) | 2016-10-18 | 2016-10-18 | Process for producing polytrimethylene terephthalate with low cyclic dimer content |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107955149B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102421820A (en) * | 2009-03-03 | 2012-04-18 | 纳幕尔杜邦公司 | Poly(trimethylene terephthalate) pellets with reduced oligomers and method to measure oligomer reduction |
| CN105273176A (en) * | 2014-07-03 | 2016-01-27 | 中国石油化工股份有限公司 | Catalyst used for preparation of polyester, preparation method and application thereof |
-
2016
- 2016-10-18 CN CN201610906682.1A patent/CN107955149B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102421820A (en) * | 2009-03-03 | 2012-04-18 | 纳幕尔杜邦公司 | Poly(trimethylene terephthalate) pellets with reduced oligomers and method to measure oligomer reduction |
| CN105273176A (en) * | 2014-07-03 | 2016-01-27 | 中国石油化工股份有限公司 | Catalyst used for preparation of polyester, preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107955149B (en) | 2020-04-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107964092A (en) | Produce catalyst of polypropylene terephthalate and its preparation method and application | |
| CN105237750B (en) | A kind of synthetic method of HMW polyadipate mutual-phenenyl two acid bromide two alcohol ester | |
| CN107955142B (en) | Process for preparing isosorbide-containing polyesters | |
| LV13428B (en) | Polymerization catalyst for preparing polyesters, preparation of polyethylene terephthalate and use of polymerization catalyst | |
| CN101121777B (en) | Titanium series polyester catalyst | |
| US20210147620A1 (en) | Process for preparing poly(trimethylene furan dicarboxylate) | |
| CN101323661B (en) | Process for producing polyester | |
| CN103304795A (en) | Organosilicone copolyester | |
| CN104163913A (en) | Preparation method of polybutylece aliphatic diacid terephthalate type copolyester | |
| US7049390B2 (en) | Poly(1,3-propylene-co-1,4:3,6-dianhydro-D-sorbitol terephthalate) and manufacturing process | |
| KR20140076356A (en) | Method for continuous production of biodegradable aliphatic/aromatic polyester copolymer | |
| CN107955148A (en) | Produce the catalyst and preparation method and application of polypropylene terephthalate | |
| CN101173038B (en) | Method for producing polyester | |
| CN103772672B (en) | The production method of full-dull titanium polyester | |
| JP2023036861A (en) | Process for preparing poly(trimethylene furandicarboxylate) using zinc catalyst | |
| CN107955149A (en) | The production method of the polypropylene terephthalate of low cyclic dimer content | |
| CN109666131B (en) | Preparation method of polybutylene terephthalate resin | |
| CN104558554B (en) | The preparation method of polyester resin | |
| CN107955141A (en) | The preparation method of polypropylene terephthalate composition | |
| CN111269404B (en) | Composite catalyst suitable for synthesizing polytrimethylene terephthalate and preparation method of polytrimethylene terephthalate | |
| CN103739834A (en) | Production method of solid-phase-polymerized titanium-containing polyester | |
| JP6445610B2 (en) | Catalyst, method for producing the same, composition for producing polyester containing the same, and method for producing polyester using the same | |
| CN101148500B (en) | Method for preparing titanium series polyester catalyst | |
| CN104558553A (en) | Method for preparing poly(propanediol terephthalate) by solid phase polycondensation | |
| CN113881023B (en) | Method for preparing polyester by solid phase polycondensation and obtained polyester |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |