CN107955142A - Preparation method containing isobide polyester - Google Patents
Preparation method containing isobide polyester Download PDFInfo
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- CN107955142A CN107955142A CN201610902237.8A CN201610902237A CN107955142A CN 107955142 A CN107955142 A CN 107955142A CN 201610902237 A CN201610902237 A CN 201610902237A CN 107955142 A CN107955142 A CN 107955142A
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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
- C08G63/40—Polyesters derived from ester-forming derivatives of polycarboxylic acids or of polyhydroxy compounds, other than from esters thereof
- C08G63/42—Cyclic ethers; Cyclic carbonates; Cyclic sulfites; Cyclic orthoesters
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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
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The present invention relates to a kind of preparation method containing ethylene glycol, isobide and terephthalic acid (TPA) composition polyester, mainly solve isobide exists in the prior art and easily decompose in the course of the polymerization process, the problem of proportion of goods damageds are high.By using the preparation method containing isobide polyester, comprise the following steps：A) using terephthalic acid (TPA), glycol as raw material, wherein the molar ratio of glycol and terephthalic acid (TPA) is 1.05:1~1.3:1, catalyst is added, is 220~250 DEG C in esterification reaction temperature, esterification reaction pressure carries out esterification under the conditions of being 10.4KPa~0.5MPa, obtains prepolymer；B) it is 250~265 DEG C in melt polycondensation reaction temperature by obtained prepolymer, melt polycondensation reaction pressure obtains the technical solution of polymerizate to carry out melt polycondensation reaction under the vacuum condition less than 150Pa, the problem is preferably resolved, in the industrialized production available for polyester containing isosorbide product.
Description
Technical field
The present invention relates to a kind of method that catalyst preparation using improvement contains isobide polyester, by varying catalysis
The formula of agent, has reached reduction reaction temperature, reduces monomer and decomposes, and lifts the more difficult isosorbide monomer for participating in reaction final
The effect of ratio is retained in polymer.
Background technology
1:4；3:6- bis- is dehydrated-and D-glucitol also known as isobide be that one kind can be passed through by renewable resources such as sugar, starch
The polyester raw material obtained after hydrogenation and acid-catalyzed dehydration, it can polymerize to obtain poly terephthalic acid with ethylene glycol, terephthalic acid (TPA)
Ethylene glycol is total to Coronex (PEIT).The polyester possesses the glass transition temperature (Tg) than conventional PET highers, this makes it can
Apply in the products such as bottle, hot-fill container, film, heavy-gauge sheeting, fiber, wire rod and optical goods.To appearance in these fields
There is higher requirement, isosorbide monomer easily forms the accessory substance with deterioration color and luster in pyroreaction, therefore reduces and close
Temperature into PEIT helps to improve its properties of product.Meanwhile isosorbide monomer is quite high relative to other polyester raw materials
It is expensive, due to the behavior by thermosetting color-forming by-products in its building-up process, the excess loss of isosorbide monomer can be caused,
Cause the isobide segment ratio that is retained in final polymer much smaller than the isobide ratio of input, add it is extra into
This, influences the economy of such production of polyester.
Report use preparation process of polyester of the isobide as comonomer in CN99805312, used in report antimony,
Titanium or germanium class catalyst are used for the synthesis of high reduced viscosity PEIT, can obtain logarithmic specific concentration viscosity by direct synthetic method
Reach the PEIT polymer of 0.65dl/g.The polycondensation reaction temperature polymerizeing in report is up to 275~285 DEG C, isoscrbierite unit
Retention rate be less than 60%.
A kind of manufacturer of terephthalic acid (TPA)-ethylene glycol-isobide copolyester polymer is reported in CN03819324
Method, its feature are to be made a kind of PEIT polymer in light color pool, it uses germanium dioxide catalyst, and add cobalt acetate,
Product hunter b value is obtained after the toning such as Clariant@RSB violet less than 2.Do not referred in patent anti-using catalyst degradation
Answer required temperature, the retention rate of isoscrbierite unit is 70% or so in the polymer of synthesis.
The method that PEIT is prepared using titanium catalyst is reported in CN201110257448, its feature is anti-using halo
The interior hydroxyl and outer hydroxyl of isobide should be modified respectively with p-methyl benzenesulfonic acid acyl chlorides, the isobide after modification can be with
Fully reacted with terephthalic acid (TPA), the ratio of bioresource carbon in the polyester can reach 33%-100%.The conjunction of polyester in patent
It is larger into method and normal polyester difference, although not referred in text, it is used for different sorb due to the use of multistep organic reaction
The chemical modification of alcohol, the yield and manufacture cost of the isobide that certainly will be influenced.Need to reach using solid phase in the patented method
To target intrinsic viscosity.
Isobide and terephthalic acid (TPA) and terephthalic acid (TPA) are formed with dihydric alcohol without report in reported above
The reactions of esterification products have the catalyst of facilitation, obtain at a lower reaction temperature needed for molecular weight preparation method.
Invention describes a kind of suitable for preparing the effective catalyst of polyester containing isosorbide at a lower temperature and being prepared with it
The method of isobide polyester.By the technical optimization of the present invention, isobide retention rate ＞ 50%, inherent viscosity can be prepared
Polyethylene terephthalate more than 0.40dl/g is total to Coronex.
The content of the invention
The technical problems to be solved by the invention are that isobide easily decomposes in the course of the polymerization process in the prior art, the proportion of goods damageds
The problem of high, there is provided a kind of preparation method containing isobide polyester, this method have under relatively low reaction temperature such as 250
DEG C when effectively facilitate the advantages of isobide participates in polyesterification reaction, reduces isobide loss at high temperature, and obtain
Polyester has the advantages that good isobide retention rate.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is as follows：It is a kind of containing isobide polyester
Preparation method, comprises the following steps：
A) using terephthalic acid (TPA), glycol as raw material, wherein the molar ratio of glycol and terephthalic acid (TPA) is 1.05:1~1.3:
1, add catalyst, esterification reaction temperature be 220~250 DEG C, esterification reaction pressure be 10.4KPa~0.5MPa under the conditions of into
Row esterification, obtains prepolymer；
B) by obtained prepolymer melt polycondensation reaction temperature be 250~265 DEG C, melt polycondensation reaction pressure be less than
Melt polycondensation reaction is carried out under the vacuum condition of 150Pa and obtains polymerizate；
Wherein, the glycol includes ethylene glycol and isobide.
In above-mentioned technical proposal, the polymerizate presses 60 in phenol tetrachloroethane：40 ratios, which mix, makees solvent, 25 DEG C
At a temperature of with the inherent viscosity of determination of ubbelohde viscometer be not less than 0.50dl/g.
In such scheme, used catalyst preferably comprises the reaction product of following components：
A) organic titanic compound,
B) hydroxy compounds,
C) metal organic salt, wherein metallic element be selected from IA races metallic element, Group IIA metal element, aluminium, tin, zinc, zirconium,
At least one metallic element of lanthanum or hafnium,
D) phosphorus compound；It is preferred that its preparation method is as follows：
By the organic titanic compound and hydroxy compounds when 0~200 DEG C of reaction 0.1~24 is small, then add into product
Enter the metal organic salt and phosphorus compound, it is then low present in removal system when 0~200 DEG C of reaction 0.1~24 is small
The catalyst of polyester preparation is obtained after carbon alcohol and/or water.
In such scheme, the organic titanic compound has the structure of general formula (I):
Wherein R1~R4It is independently chosen from the fat-based of 1~10 carbon atom, R1~R4In any can be between any two
Cyclization.
In such scheme, the hydroxy compounds is to be one or more selected from ethanol, isopropanol, the monohydric alcohol of butanol；
Or selected from ethylene glycol, 1,2 propane diols, 1,3 propane diols, 1,4 butanediols dihydric alcohol；Or selected from glycerine, pentaerythrite, sorbose
The polyhydroxy-alcohol of alcohol, mannitol；Or the hydroxycarboxylic acid selected from lactic acid, citric acid, malic acid or tartaric acid.
In such scheme, the phosphorus compound has the structure of general formula (II)：
Wherein R5、R6And R7H, C are independently selected from addition to it cannot be at the same time H2~C6Alkyl.
In such scheme, the metal organic salt is sour with organic acid of the dissociation constant more than 4.0pKa in metal ion
The salt that root is formed.
In such scheme, the amount of the hydroxy compounds of the addition using contained total hydroxyl moles and titanium elements molar ratio as
(0.1~10):1；For the amount of metal organic salt in terms of contained metal molar number, the molar ratio with titanium elements in titanium compound is (0.1
~10):1；In terms of institute's phosphorus element-containing molal quantity, the molar ratio with titanium elements in titanium compound is the amount of phosphorus compound
(0.0001~10):1.
In such scheme, the quality that the catalyst of the polyester preparation adds is calculated as 0.1-120mg/ with titanium elements quality
Kg terephthalic acid (TPA)s.
In such scheme, the molar ratio of the ethylene glycol and isobide is preferably 1:1~18:1, isobide is most
The molar ratio relative to terephthalic acid (TPA) segment retained in final polymerization thing is relatively right higher than reaction starting stage isobide
More than the 50% of the molar ratio of phthalic acid segment；The molar ratio of the further preferred ethylene glycol and isobide is 6:
1~15:1, the molar ratio relative to terephthalic acid (TPA) segment that isobide retains in final polymer at this time is higher than anti-
Starting stage isobide is answered relative to more than the 80% of the molar ratio of terephthalic acid (TPA) segment.
The conventional additives of polyesterification reaction, for example, Color modifiers (cobalt compound, pigment or dyestuff), stabilizer (by
Hinder phenols, phosphorous acid esters and thioether class), filler etc. also is added in pet reaction mixture.These additives can be with
Add in any stage of polymerisation, preferably added before polycondensation phase starts.
In the present invention, the inherent viscosity of polyester and form and aspect are tested by method described in GB/T 14189-2008：Characteristic
Viscosity test presses 60 using phenol tetrachloroethane：40 ratios, which mix, makees solvent, and determination of ubbelohde viscometer is used at a temperature of 25 DEG C.
The retention rate of isobide in the polyester is calculated according to the result of H-NMR.
Method using the present invention, since described is used for catalyst and relatively low melt polycondensation reaction temperature prepared by polyester
Degree has mutual synergistic function between the two, and 260 DEG C can be such as less than at a temperature of relatively low melt polycondensation reaction by having,
For another example 250 DEG C when the advantages of causing isobide retention rate high, especially suitable for needing to reduce isobide loss and to poly-
Compound appearance has certain requirements the production of polyester containing isosorbide product, and inherent viscosity index is more than 0.50dl/g, different sorb
Alcohol retention rate achieves preferable technique effect up to more than 88%.
Below by embodiment, the present invention is further elaborated.
Embodiment
【Embodiment 1】
142g tetraisopropyl titanates are mixed with 46g ethanol, 90g lactic acid, in stirred reactor, 100 DEG C of temperature
Under the conditions of reaction 4 it is small when, into reactant add magnesium acetate 36g, triethyl phosphate 91g, in the reactor with stirring,
When reaction 4 is small under 120 DEG C of temperature conditionss.Reaction product is placed in the reactor for possessing fractionating device, distillates ethanol and isopropyl
Alcohol, is made catalyst.Catalyst is mixed with ethylene glycol, wherein the mass fraction of titanium atom is 4%.
600g terephthalic acid (TPA)s and 224g ethylene glycol, 53g isobides and catalyst 1.8g, mixing are made into slurry, add
Into polymeric kettle, esterification is carried out, esterification start temperature is 220 DEG C, pressure 0.25MPa, is discharged by rectifier unit anti-
The water that should be generated, reaction 1 it is small when after reaction temperature is gradually risen to 230~250 DEG C, according to the temperature adjustment on rectifier unit top
Reaction pressure, keeps top temperature under pressure at that time on 10~20 DEG C of the boiling point of water, and if top, temperature reduces pressure if being less than the temperature
Power, it is on the contrary then keep pressure it is constant.Normal pressure is down to after esterification, initially enters polycondensation phase, vacuumizes holding reaction pressure
0.5KPa, fluid temperature 250 DEG C one hour, vacuumizes and is decompressed to system pressure and is less than 130Pa, 250 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.
PEIT inherent viscosity 0.625dl/g are obtained, isobide is 8.4% with respect to the molar ratio of terephthalic acid (TPA) segment,
Retention rate is 84%.
【Embodiment 2】
142g tetraisopropyl titanates are mixed with 46g ethanol, 192g citric acids, in stirred reactor, 100 DEG C of temperature
When reaction 4 is small under the conditions of degree, magnesium acetate 36g, triethyl phosphate 91g are added into reactant, in the reactor with stirring,
When reaction 4 is small under 120 DEG C of temperature conditionss.Reaction product is placed in the reactor for possessing fractionating device, distillates ethanol and isopropyl
Alcohol, is made catalyst.Catalyst is mixed with ethylene glycol, wherein the mass fraction of titanium atom is 4%.
600g terephthalic acid (TPA)s and 224g ethylene glycol, 53g isobides and catalyst 1.8g, mixing are made into slurry, add
Into polymeric kettle, esterification is carried out, esterification start temperature is 220 DEG C, pressure 0.25MPa, is discharged by rectifier unit anti-
The water that should be generated, reaction 1 it is small when after reaction temperature is gradually risen to 230~250 DEG C, according to the temperature adjustment on rectifier unit top
Reaction pressure, keeps top temperature under pressure at that time on 10~20 DEG C of the boiling point of water, and if top, temperature reduces pressure if being less than the temperature
Power, it is on the contrary then keep pressure it is constant.Normal pressure is down to after esterification, initially enters polycondensation phase, vacuumizes holding reaction pressure
0.5KPa, fluid temperature 250 DEG C one hour, vacuumizes and is decompressed to system pressure and is less than 130Pa, 250 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.
PEIT inherent viscosity 0.651dl/g are obtained, isobide is 8.8% with respect to the molar ratio of terephthalic acid (TPA) segment,
Retention rate is 88%.
【Embodiment 3】
142g tetraisopropyl titanates are mixed with 46g ethanol, 192g citric acids, in stirred reactor, 100 DEG C of temperature
When reaction 4 is small under the conditions of degree, zinc lactate 61g, triethyl phosphate 91g are added into reactant, in the reactor with stirring,
When reaction 4 is small under 120 DEG C of temperature conditionss.Reaction product is placed in the reactor for possessing fractionating device, distillates ethanol and isopropyl
Alcohol, is made catalyst.Catalyst is mixed with ethylene glycol, wherein the mass fraction of titanium atom is 4%.
600g terephthalic acid (TPA)s and 224g ethylene glycol, 53g isobides and catalyst 1.8g, mixing are made into slurry, add
Into polymeric kettle, esterification is carried out, esterification start temperature is 220 DEG C, pressure 0.25MPa, is discharged by rectifier unit anti-
The water that should be generated, reaction 1 it is small when after reaction temperature is gradually risen to 230~250 DEG C, according to the temperature adjustment on rectifier unit top
Reaction pressure, keeps top temperature under pressure at that time on 10~20 DEG C of the boiling point of water, and if top, temperature reduces pressure if being less than the temperature
Power, it is on the contrary then keep pressure it is constant.Normal pressure is down to after esterification, initially enters polycondensation phase, vacuumizes holding reaction pressure
0.5KPa, fluid temperature 250 DEG C one hour, vacuumizes and is decompressed to system pressure and is less than 130Pa, 250 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.
PEIT inherent viscosity 0.674dl/g are obtained, isobide is 8.2% with respect to the molar ratio of terephthalic acid (TPA) segment,
Retention rate is 82%.
【Embodiment 4】
By 84g titanium ethylene glycolates (Ti (OCH2CH2O)2) and 46g ethanol, 192g citric acids mixing, with stirred reactor
In, when reaction 4 is small under 100 DEG C of temperature conditionss, magnesium acetate 36g, triethyl phosphate 91g, with stirring are added into reactant
Reactor in, under 120 DEG C of temperature conditionss react 4 it is small when.Reaction product is placed in the reactor for possessing fractionating device, is distillated
Ethanol, is made catalyst.Catalyst is mixed with ethylene glycol, wherein the mass fraction of titanium atom is 4%.
600g terephthalic acid (TPA)s and 224g ethylene glycol, 53g isobides and catalyst 1.8g, mixing are made into slurry, add
Into polymeric kettle, esterification is carried out, esterification start temperature is 220 DEG C, pressure 0.25MPa, is discharged by rectifier unit anti-
The water that should be generated, reaction 1 it is small when after reaction temperature is gradually risen to 230~250 DEG C, according to the temperature adjustment on rectifier unit top
Reaction pressure, keeps top temperature under pressure at that time on 10~20 DEG C of the boiling point of water, and if top, temperature reduces pressure if being less than the temperature
Power, it is on the contrary then keep pressure it is constant.Normal pressure is down to after esterification, initially enters polycondensation phase, vacuumizes holding reaction pressure
0.5KPa, fluid temperature 250 DEG C one hour, vacuumizes and is decompressed to system pressure and is less than 130Pa, 250 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.
PEIT inherent viscosity 0.587dl/g are obtained, isobide is 8.2% with respect to the molar ratio of terephthalic acid (TPA) segment,
Retention rate is 82%.
【Embodiment 5】
By 84g titanium ethylene glycolates (Ti (OCH2CH2O)2) mixed with 90g lactic acid, in stirred reactor, 100 DEG C of temperature
Under the conditions of reaction 4 it is small when, into reactant add magnesium acetate 36g, triethyl phosphate 91g, in the reactor with stirring,
When reaction 4 is small under 120 DEG C of temperature conditionss.Reaction product is placed in the reactor for possessing fractionating device, distillates ethanol, is made and urges
Agent.Catalyst is mixed with ethylene glycol, wherein the mass fraction of titanium atom is 4%.
600g terephthalic acid (TPA)s and 224g ethylene glycol, 53g isobides and catalyst 1.8g, mixing are made into slurry, add
Into polymeric kettle, esterification is carried out, esterification start temperature is 220 DEG C, pressure 0.25MPa, is discharged by rectifier unit anti-
The water that should be generated, reaction 1 it is small when after reaction temperature is gradually risen to 230~250 DEG C, according to the temperature adjustment on rectifier unit top
Reaction pressure, keeps top temperature under pressure at that time on 10~20 DEG C of the boiling point of water, and if top, temperature reduces pressure if being less than the temperature
Power, it is on the contrary then keep pressure it is constant.Normal pressure is down to after esterification, initially enters polycondensation phase, vacuumizes holding reaction pressure
0.5KPa, fluid temperature 250 DEG C one hour, vacuumizes and is decompressed to system pressure and is less than 130Pa, 250 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.
PEIT inherent viscosity 0.613dl/g are obtained, isobide is 8.4% with respect to the molar ratio of terephthalic acid (TPA) segment,
Retention rate is 84%.
【Embodiment 6】
142g tetraisopropyl titanates are mixed with 46g ethanol, 90g lactic acid, in stirred reactor, 100 DEG C of temperature
Under the conditions of reaction 4 it is small when, into reactant add zirconium acetate 82g, triethyl phosphate 91g, in the reactor with stirring,
When reaction 4 is small under 120 DEG C of temperature conditionss.Reaction product is placed in the reactor for possessing fractionating device, distillates ethanol and isopropyl
Alcohol, is made catalyst.Catalyst is mixed with ethylene glycol, wherein the mass fraction of titanium atom is 4%.
600g terephthalic acid (TPA)s and 224g ethylene glycol, 53g isobides and catalyst 1.8g, mixing are made into slurry, add
Into polymeric kettle, esterification is carried out, esterification start temperature is 220 DEG C, pressure 0.25MPa, is discharged by rectifier unit anti-
The water that should be generated, reaction 1 it is small when after reaction temperature is gradually risen to 230~250 DEG C, according to the temperature adjustment on rectifier unit top
Reaction pressure, keeps top temperature under pressure at that time on 10~20 DEG C of the boiling point of water, and if top, temperature reduces pressure if being less than the temperature
Power, it is on the contrary then keep pressure it is constant.Normal pressure is down to after esterification, initially enters polycondensation phase, vacuumizes holding reaction pressure
0.5KPa, fluid temperature 250 DEG C one hour, vacuumizes and is decompressed to system pressure and is less than 130Pa, 250 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.
PEIT inherent viscosity 0.581dl/g are obtained, isobide is 9.0% with respect to the molar ratio of terephthalic acid (TPA) segment,
Retention rate is 90%.
【Embodiment 7】
142g tetraisopropyl titanates are mixed with 46g ethanol, 182g D-sorbites, in stirred reactor, 100 DEG C
When reaction 4 is small under temperature conditionss, magnesium acetate 36g, triethyl phosphate 91g are added into reactant, in the reactor with stirring
In, when reaction 4 is small under 120 DEG C of temperature conditionss.Reaction product is placed in the reactor for possessing fractionating device, distillates ethanol and different
Propyl alcohol, is made catalyst.Catalyst is mixed with ethylene glycol, wherein the mass fraction of titanium atom is 4%.
600g terephthalic acid (TPA)s and 224g ethylene glycol, 53g isobides and catalyst 1.8g, mixing are made into slurry, add
Into polymeric kettle, esterification is carried out, esterification start temperature is 220 DEG C, pressure 0.25MPa, is discharged by rectifier unit anti-
The water that should be generated, reaction 1 it is small when after reaction temperature is gradually risen to 230~250 DEG C, according to the temperature adjustment on rectifier unit top
Reaction pressure, keeps top temperature under pressure at that time on 10~20 DEG C of the boiling point of water, and if top, temperature reduces pressure if being less than the temperature
Power, it is on the contrary then keep pressure it is constant.Normal pressure is down to after esterification, initially enters polycondensation phase, vacuumizes holding reaction pressure
0.5KPa, fluid temperature 250 DEG C one hour, vacuumizes and is decompressed to system pressure and is less than 130Pa, 250 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.
PEIT inherent viscosity 0.610dl/g are obtained, isobide is 8.4% with respect to the molar ratio of terephthalic acid (TPA) segment,
Retention rate is 84%.
【Embodiment 8】
142g tetraisopropyl titanates are mixed with 46g ethanol, 192g citric acids, in stirred reactor, 100 DEG C of temperature
When reaction 4 is small under the conditions of degree, zinc lactate 61g, triethyl phosphate 91g are added into reactant, in the reactor with stirring,
When reaction 4 is small under 120 DEG C of temperature conditionss.Reaction product is placed in the reactor for possessing fractionating device, distillates ethanol and isopropyl
Alcohol, is made catalyst.Catalyst is mixed with ethylene glycol, wherein the mass fraction of titanium atom is 4%.
600g terephthalic acid (TPA)s and 224g ethylene glycol, 53g isobides and catalyst 1.8g, mixing are made into slurry, add
Into polymeric kettle, esterification is carried out, esterification start temperature is 220 DEG C, pressure 0.25MPa, is discharged by rectifier unit anti-
The water that should be generated, reaction 1 it is small when after reaction temperature is gradually risen to 230~250 DEG C, according to the temperature adjustment on rectifier unit top
Reaction pressure, keeps top temperature under pressure at that time on 10~20 DEG C of the boiling point of water, and if top, temperature reduces pressure if being less than the temperature
Power, it is on the contrary then keep pressure it is constant.Normal pressure is down to after esterification, initially enters polycondensation phase, vacuumizes holding reaction pressure
0.5KPa, fluid temperature 260 DEG C one hour, vacuumizes and is decompressed to system pressure and is less than 130Pa, 260 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.
PEIT inherent viscosity 0.713dl/g are obtained, isobide is 8.0% with respect to the molar ratio of terephthalic acid (TPA) segment,
Retention rate is 80%.
【Embodiment 9】
142g tetraisopropyl titanates are mixed with 46g ethanol, 192g citric acids, in stirred reactor, 100 DEG C of temperature
When reaction 4 is small under the conditions of degree, zinc lactate 61g, triethyl phosphate 91g are added into reactant, in the reactor with stirring,
When reaction 4 is small under 120 DEG C of temperature conditionss.Reaction product is placed in the reactor for possessing fractionating device, distillates ethanol and isopropyl
Alcohol, is made catalyst.Catalyst is mixed with ethylene glycol, wherein the mass fraction of titanium atom is 4%.
600g terephthalic acid (TPA)s and 202g ethylene glycol, 106g isobides and catalyst 1.8g, mixing are made into slurry, add
Into polymeric kettle, esterification is carried out, esterification start temperature is 220 DEG C, pressure 0.25MPa, is discharged by rectifier unit anti-
The water that should be generated, reaction 1 it is small when after reaction temperature is gradually risen to 230~250 DEG C, according to the temperature adjustment on rectifier unit top
Reaction pressure, keeps top temperature under pressure at that time on 10~20 DEG C of the boiling point of water, and if top, temperature reduces pressure if being less than the temperature
Power, it is on the contrary then keep pressure it is constant.Normal pressure is down to after esterification, initially enters polycondensation phase, vacuumizes holding reaction pressure
0.5KPa, fluid temperature 250 DEG C one hour, vacuumizes and is decompressed to system pressure and is less than 130Pa, 250 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.
PEIT inherent viscosity 0.615dl/g are obtained, isobide is 15.6% with respect to the molar ratio of terephthalic acid (TPA) segment,
Retention rate is 78%.
【Comparative example 1】
600g terephthalic acid (TPA)s and 224g ethylene glycol, 53g isobides and tetraisopropyl titanate 0.35g, mixing are made into slurry
Material, is added in polymeric kettle, carries out esterification, esterification start temperature is 220 DEG C, and pressure 0.25MPa, passes through rectifier unit
Discharge reaction generation water, reaction 1 it is small when after reaction temperature is gradually risen to 230~250 DEG C, according to the temperature on rectifier unit top
Degree adjusts reaction pressure, keeps top temperature under pressure at that time on 10~20 DEG C of the boiling point of water, if temperature is less than the temperature if top
Reduce pressure, it is on the contrary then holding pressure it is constant.Normal pressure is down to after esterification, initially enters polycondensation phase, it is anti-to vacuumize holding
Answer pressure 0.5KPa, fluid temperature 250 DEG C one hour, vacuumizes and is decompressed to system pressure and is less than 130Pa, 250 DEG C of reaction temperature,
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.
PEIT inherent viscosity 0.363dl/g are obtained, isobide is 6.4% with respect to the molar ratio of terephthalic acid (TPA) segment,
Retention rate is 64%.
【Comparative example 2】
600g terephthalic acid (TPA)s and 224g ethylene glycol, 53g isobides and antimony oxide 0.21g, which are mixed, is made into slurry,
It is added in polymeric kettle, carries out esterification, esterification start temperature is 220 DEG C, and pressure 0.25MPa, is arranged by rectifier unit
Go out reaction generation water, reaction 1 it is small when after reaction temperature is gradually risen to 230~250 DEG C, according to the temperature on rectifier unit top
Reaction pressure is adjusted, keeps top temperature under pressure at that time on 10~20 DEG C of the boiling point of water, temperature drops if being less than the temperature if top
Low-pressure, it is on the contrary then keep pressure it is constant.Normal pressure is down to after esterification, initially enters polycondensation phase, vacuumizes holding reaction
Pressure 0.5KPa, fluid temperature 250 DEG C one hour, vacuumizes and is decompressed to system pressure and is less than 130Pa, 250 DEG C of reaction temperature, 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, cools down, cut
Grain.
PEIT inherent viscosity 0.543dl/g are obtained, isobide is 6.2% with respect to the molar ratio of terephthalic acid (TPA) segment,
Retention rate is 62%.
【Comparative example 3】
600g terephthalic acid (TPA)s and 224g ethylene glycol, 53g isobides and germanium dioxide 0.16g, which are mixed, is made into slurry, adds
Enter into polymeric kettle, carry out esterification, esterification start temperature is 220 DEG C, and pressure 0.25MPa, is discharged by rectifier unit
React generation water, reaction 1 it is small when after reaction temperature is gradually risen to 230~250 DEG C, according to the temperature tune on rectifier unit top
Reaction pressure is saved, keeps top temperature under pressure at that time on 10~20 DEG C of the boiling point of water, temperature reduces if being less than the temperature if top
Pressure, it is on the contrary then keep pressure it is constant.Normal pressure is down to after esterification, initially enters polycondensation phase, vacuumizes holding reaction pressure
Power 0.5KPa, fluid temperature 260 DEG C one hour, vacuumizes and is decompressed to system pressure and is less than 130Pa, 250 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.
PEIT inherent viscosity 0.492dl/g are obtained, isobide is 6.8% with respect to the molar ratio of terephthalic acid (TPA) segment,
Retention rate is 68%.
【Comparative example 4】
142g tetraisopropyl titanates are mixed with 46g ethanol, 192g citric acids, in stirred reactor, 100 DEG C of temperature
When reaction 4 is small under the conditions of degree, zinc lactate 61g, triethyl phosphate 91g are added into reactant, in the reactor with stirring,
When reaction 4 is small under 120 DEG C of temperature conditionss.Reaction product is placed in the reactor for possessing fractionating device, distillates ethanol and isopropyl
Alcohol, is made catalyst.Catalyst is mixed with ethylene glycol, wherein the mass fraction of titanium atom is 4%.
600g terephthalic acid (TPA)s and 224g ethylene glycol, 53g isobides and catalyst 1.8g, mixing are made into slurry, add
Into polymeric kettle, esterification is carried out, esterification start temperature is 220 DEG C, pressure 0.25MPa, is discharged by rectifier unit anti-
The water that should be generated, reaction 1 it is small when after reaction temperature is gradually risen to 230~250 DEG C, according to the temperature adjustment on rectifier unit top
Reaction pressure, keeps top temperature under pressure at that time on 10~20 DEG C of the boiling point of water, and if top, temperature reduces pressure if being less than the temperature
Power, it is on the contrary then keep pressure it is constant.Normal pressure is down to after esterification, initially enters polycondensation phase, vacuumizes holding reaction pressure
0.5KPa, fluid temperature 280 DEG C one hour, vacuumizes and is decompressed to system pressure and is less than 130Pa, 280 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.
PEIT inherent viscosity 0.719dl/g are obtained, isobide is 4.8% with respect to the molar ratio of terephthalic acid (TPA) segment,
Retention rate is 48%.
Table 1
Claims (10)
1. the preparation method containing isobide polyester, comprises the following steps：
A) using terephthalic acid (TPA), glycol as raw material, wherein the molar ratio of glycol and terephthalic acid (TPA) is 1.05:1~1.3:1, add
Enter catalyst, be 220~250 DEG C in esterification reaction temperature, esterification reaction pressure carries out ester under the conditions of being 10.4KPa~0.5MPa
Change reaction, obtain prepolymer；
B) by obtained prepolymer melt polycondensation reaction temperature be 250~265 DEG C, melt polycondensation reaction pressure be less than
Melt polycondensation reaction is carried out under the vacuum condition of 150Pa and obtains polymerizate；
Wherein, the glycol includes ethylene glycol and isobide.
2. the preparation method according to claim 1 containing isobide polyester, it is characterised in that used catalyst is
Include the reaction product of following components：
A) organic titanic compound,
B) hydroxy compounds,
C) metal organic salt, wherein metallic element be selected from IA races metallic element, Group IIA metal element, aluminium, tin, zinc, zirconium, lanthanum or
At least one metallic element of hafnium,
D) phosphorus compound.
3. the preparation method according to claim 2 containing isobide polyester, it is characterised in that the preparation of the catalyst
Method is as follows：
By the organic titanic compound and hydroxy compounds when 0~200 DEG C of reaction 0.1~24 is small, then institute is added into product
The metal organic salt and phosphorus compound stated, when 0~200 DEG C of reaction 0.1~24 is small, then low-carbon alcohols present in removal system
And/or the catalyst of polyester preparation is obtained after water.
4. the preparation method according to claim 2 containing isobide polyester, it is characterised in that the organic titanium chemical combination
Thing has the structure of general formula (I):
Wherein R1~R4It is independently chosen from the fat-based of 1~10 carbon atom, R1~R4In it is any can be between any two into
Ring.
5. the preparation method according to claim 2 containing isobide polyester, it is characterised in that the hydroxy compounds
For one or more monohydric alcohols for being selected from ethanol, isopropanol, butanol；Or selected from ethylene glycol, 1,2 propane diols, 1,3 propane diols, 1,4
The dihydric alcohol of butanediol；Or selected from glycerine, pentaerythrite, D-sorbite, mannitol polyhydroxy-alcohol；Or selected from lactic acid, lemon
The hydroxycarboxylic acid of acid, malic acid or tartaric acid.
6. the preparation method according to claim 2 containing isobide polyester, it is characterised in that the phosphorus compound tool
There is the structure of general formula (II)：
Wherein R5、R6And R7H, C are independently selected from addition to it cannot be at the same time H2~C6Alkyl.
7. the preparation method according to claim 2 containing isobide polyester, it is characterised in that the metal organic salt
For the salt formed in metal ion with organic acid acid group of the dissociation constant more than 4.0pKa.
8. the preparation method according to claim 2 containing isobide polyester, it is characterised in that the hydroxylating of the addition
The amount of compound is using contained total hydroxyl moles and titanium elements molar ratio as (0.1~10):1；The amount of metal organic salt is with contained gold
Belong to molal quantity meter, the molar ratio with titanium elements in titanium compound is (0.1~10):1；The amount of phosphorus compound is rubbed with institute's phosphorus element-containing
That number meter, the molar ratio with titanium elements in titanium compound is (0.0001~10):1.
9. the preparation method according to claim 1 containing isobide polyester, it is characterised in that prepared by the polyester uses
Catalyst add quality 0.1-120mg/kg terephthalic acid (TPA)s are calculated as with titanium elements quality.
10. the preparation method according to claim 1 containing isobide polyester, it is characterised in that the ethylene glycol and different
The molar ratio of sorbierite is 1:1~18:1, isobide retained in final polymer relative to terephthalic acid (TPA) segment
Molar ratio higher than reaction 50% of starting stage isobide with respect to terephthalic acid (TPA) molar ratio；Further preferably：Institute
The molar ratio for stating ethylene glycol and isobide is 6:1~15:1, isobide retained in final polymer relatively to benzene
The molar ratio of dioctyl phthalate segment is higher than 80% of starting stage isobide with respect to terephthalic acid (TPA) molar ratio of reaction.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111234195A (en) * | 2018-11-29 | 2020-06-05 | 中国科学院大连化学物理研究所 | Quaternary ammonium salt catalyst, application thereof and isosorbide modified polyester |
| CN112851919A (en) * | 2019-11-12 | 2021-05-28 | 中国科学院化学研究所 | 1,4, 3, 6-diglycidyl hexaol modified PET polyester and semi-continuous preparation method thereof |
| CN113185682A (en) * | 2021-04-27 | 2021-07-30 | 中国石油化工股份有限公司 | Modified copolyester and preparation method thereof |
| CN114276363A (en) * | 2021-12-30 | 2022-04-05 | 国科温州研究院(温州生物材料与工程研究所) | Method for purifying isosorbide by adopting recrystallization of dihydric alcohol |
| WO2024045640A1 (en) * | 2022-08-31 | 2024-03-07 | 科泽新材料股份有限公司 | Method for preparing peit copolyester |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102264794A (en) * | 2008-12-31 | 2011-11-30 | Sk化学株式会社 | Method for preparing a polyester resin in which isosorbide is copolymerized |
| CN102477151A (en) * | 2010-11-25 | 2012-05-30 | 东丽纤维研究所（中国）有限公司 | Catalyst for preparation of polyester, its preparation method, and production method of polyester |
| 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 CN201610902237.8A patent/CN107955142B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102264794A (en) * | 2008-12-31 | 2011-11-30 | Sk化学株式会社 | Method for preparing a polyester resin in which isosorbide is copolymerized |
| CN102477151A (en) * | 2010-11-25 | 2012-05-30 | 东丽纤维研究所（中国）有限公司 | Catalyst for preparation of polyester, its preparation method, and production method of polyester |
| 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 |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111234195A (en) * | 2018-11-29 | 2020-06-05 | 中国科学院大连化学物理研究所 | Quaternary ammonium salt catalyst, application thereof and isosorbide modified polyester |
| CN111234195B (en) * | 2018-11-29 | 2021-05-28 | 中国科学院大连化学物理研究所 | Quaternary ammonium salt catalyst, application thereof and isosorbide modified polyester |
| CN112851919A (en) * | 2019-11-12 | 2021-05-28 | 中国科学院化学研究所 | 1,4, 3, 6-diglycidyl hexaol modified PET polyester and semi-continuous preparation method thereof |
| CN112851919B (en) * | 2019-11-12 | 2022-08-26 | 中国科学院化学研究所 | 1,4, 3, 6-diglycidyl hexaol modified PET polyester and semi-continuous preparation method thereof |
| CN113185682A (en) * | 2021-04-27 | 2021-07-30 | 中国石油化工股份有限公司 | Modified copolyester and preparation method thereof |
| CN114276363A (en) * | 2021-12-30 | 2022-04-05 | 国科温州研究院(温州生物材料与工程研究所) | Method for purifying isosorbide by adopting recrystallization of dihydric alcohol |
| CN114276363B (en) * | 2021-12-30 | 2023-12-29 | 国科温州研究院(温州生物材料与工程研究所) | Method for purifying isosorbide by adopting dihydric alcohol recrystallization |
| WO2024045640A1 (en) * | 2022-08-31 | 2024-03-07 | 科泽新材料股份有限公司 | Method for preparing peit copolyester |
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