CN108727575A - A kind of preparation method of biology base 2,5- furandicarboxylic acids base copolyesters - Google Patents
A kind of preparation method of biology base 2,5- furandicarboxylic acids base copolyesters Download PDFInfo
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- CN108727575A CN108727575A CN201810489016.1A CN201810489016A CN108727575A CN 108727575 A CN108727575 A CN 108727575A CN 201810489016 A CN201810489016 A CN 201810489016A CN 108727575 A CN108727575 A CN 108727575A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/826—Metals not provided for in groups C08G63/83 - C08G63/86
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/87—Non-metals or inter-compounds thereof
Abstract
The present invention relates to a kind of biology bases 2, the preparation method of 5- furandicarboxylic acid base copolyesters, binary acid, aliphatic dihydroxy alcohol I, guiding thing and titanium silicon cobalt composite catalyst are carried out to esterification, prepolymerization reaction and final polycondensation reaction successively after mixing, biology base 2,5-furandicarboxylic acid base copolyesters is made；Guiding thing is that biology base 2,5-furandicarboxylic acid react the carboxylate generated with aliphatic dihydroxy alcohol II, and the molar ratio of the binary acid and aliphatic dihydroxy alcohol I are 1:1.05~1.10, titanium silicon cobalt composite catalyst is that titanium silicon composite catalyst is combined with cobalt series catalyst, and titanium silicon composite catalyst obtains for silicon systems catalyst carrying catalyst in titanium series, and aliphatic dihydroxy alcohol I and aliphatic dihydroxy alcohol II are identical or different.The preparation method of the present invention, side reaction is few, and reaction rate is fast, and product molecular weight distribution obtained is concentrated, viscosity is high and quality is good, great application prospect.
Description
Technical field
The invention belongs to polyester preparation fields, are related to a kind of preparation side of biology base 2,5-furandicarboxylic acid base copolyesters
A kind of method, and in particular to preparation method of biology base 2,5-furandicarboxylic acid base polyacid-aliphatic dihydroxy alcohol copolyesters.
Background technology
Polyester refers to the polymer general name obtained by polyalcohol and polyacid polycondensation.Refer mainly to polyethylene terephthalate
(PET), also include traditionally linear thermoplastics' resins such as polybutylene terephthalate (PBT) and polyarylate.It is a kind of performance
Excellent, widely used polymer.The fields such as fiber, plastics, film have been widely used in it at present.Compared to petroleum base PET,
The monomer 2 of PEF, 5-FDCA are derived from bio-based source, can reduce use and the greenhouse gases (GHG) of non-renewable resources (NREU)
Discharge.Along with the quick consumption of petroleum resources, it is using the polymer that reproducible bio-based monomer is formed in nature
One general orientation of future development.
Biology base 2,5- furandicarboxylic acids (2,5-FDCA) and the structural representation formula of terephthalic acid (TPA) (TPA) are as follows：
Contain aromatic rings in biology base 2,5-furandicarboxylic acid molecular structure, is used for synthesising biological based high molecular material, it can
To substitute terephthalic acid (TPA), M-phthalic acid, adipic acid, succinic acid, bisphenol-A etc. are applied to polyester, polyamide, epoxy resin etc.
The synthesis of bio-based polymers.Therefore, it by U.S. Department of Energy be chosen as 12 kinds of most potential biology base platform chemicals it
One, it is considered " giant being sunk into sleep " by Du Pont and DSM N. V..2,5- furandicarboxylic acids having " rigidity " planar structure as a kind of
Biological based high molecular aromatic ring monomer, can be polymerize with monomers such as glycol, diamines, prepare the new bio haveing excellent performance
Based high molecular synthetic material.Biology base 2,5- furandicarboxylic acids are substituted or the petroleum-based terephthalic acid (TPA) of partial alternative is for slow
Solution petroleum resources have great importance.
In terms of biology base 2,5-furandicarboxylic acid base polyester synthesis, numerous scholars and research institution are deeply ground
Study carefully.Patent CN 201610608996.3 discloses a kind of preparation method of poly- 2,5-furandicarboxylic acid diol ester, in catalyst
Effect is lower successively to obtain poly- 2,5- furandimethyl glycol esters through over-churning, polycondensation.Wherein 2,5- furandicarboxylic acids and aliphatic
Dihydric alcohol molar ratio be up to 1:2；Patent CN 201110246585.1 discloses 2,5- furandicarboxylic acids-terephthaldehyde
Acid-aliphatic dihydroxy alcohol copolyesters and preparation method thereof, under the effect of the catalyst, 2,5-furandicarboxylic acid, terephthalic acid (TPA)
Esterification occurs with aliphatic dihydroxy alcohol, obtains the first intermediate product, then the first intermediate product is subjected to polycondensation reaction, obtains
2,5-furandicarboxylic acid-terephthalic acid (TPA)-aliphatic dihydroxy alcohol copolyesters, the sum of 2,5-furandicarboxylic acid and terephthalic acid (TPA)
It is up to 1 with the molar ratio of aliphatic dihydroxy alcohol:3.
It is had the following problems in the preparation of existing such biology base 2,5- furandicarboxylic acids base polyester：1) existing technology body
Biology base 2,5- furandicarboxylic acids are far above 1 with dihydric alcohol molar ratio of alcohol to acid in system:1, dihydric alcohol is issued in high molar ratio of alcohol to acid
It is born from polycondensation, by-product is generated, large effect is caused to the fibre forming property of polyester, while high molar ratio needs to consume more two
First raw polyol increases cost；2) quality of the Esterification Stage directly concerning final polycondensation product for polyester, biology base 2,5-
Though the structure that furandicarboxylic acid has terephthalic acid (TPA) very much like, thermal stability declines, and the prior art is in high alkyd
It is needed under molar ratio by carrying out sufficient esterification under 3 hours or more esterification times, this is easily caused in esterification process
The generation of side reaction；3) it after completing to be esterified needs that polyester, the spy of precondensation product could be made by precondensation, final polycondensation reaction
Property viscosity generally in 0.25dL/g or more, which results in the final molecular weight distribution that product is made is wider, processing performance is bad,
Phenomena such as lousiness, broken end, waste silk are easily generated in process.
Therefore, the biology base 2 that a kind of side reaction is few, molecular weight distribution is concentrated, viscosity is high, quality is good, 5- furans two are developed
The great realistic meaning of formyl copolyesters preparation method.
Invention content
The purpose of the invention is to overcome above-mentioned problems of the prior art, provide that a kind of side reaction is few, molecule
Amount distribution concentration, the biology base 2,5- furandicarboxylic acid base copolyesters preparation methods that viscosity is high, quality is good.
In order to achieve the above object, the technical solution adopted by the present invention is：
A kind of preparation method of biology base 2,5-furandicarboxylic acid base copolyesters, by binary acid, aliphatic dihydroxy alcohol I, draws
It leads object and titanium silicon cobalt composite catalyst and carries out the obtained life of esterification, prepolymerization reaction and final polycondensation reaction successively after mixing
Object base 2,5- furandicarboxylic acid base copolyesters；
The guiding thing is that biology base 2,5-furandicarboxylic acid reacts the carboxylate generated with aliphatic dihydroxy alcohol II, described
The molar ratio of binary acid and aliphatic dihydroxy alcohol I are 1:1.05~1.10, the titanium silicon cobalt composite catalyst, which is that titanium silicon is compound, urges
Agent is combined with cobalt series catalyst, and the titanium silicon composite catalyst obtains for silicon systems catalyst carrying catalyst in titanium series, institute
It states aliphatic dihydroxy alcohol I and aliphatic dihydroxy alcohol II is identical or different.
As preferred technical solution：
A kind of preparation method of biology base 2,5-furandicarboxylic acid base copolyesters as described above, the biology base 2,5-
Content≤1.0wt% of side reaction product in furandicarboxylic acid base copolyesters.
A kind of preparation method of biology base 2,5-furandicarboxylic acid base copolyesters as described above, is as follows：
(1) esterification；
By binary acid and aliphatic dihydroxy alcohol I with 1:After 1.05~1.10 molar ratio is mixed with beating, it is multiple that titanium silicon cobalt is added
Close catalyst, guiding thing carries out esterification under conditions of 180~240 DEG C and 50~200KPa until water yield reaches theoretical
95% reaction terminating of water yield；The guiding thing is that biology base 2,5- furandicarboxylic acids react generation with aliphatic dihydroxy alcohol II
Carboxylate；The reaction time of esterification of the present invention is 1.5~3.5h, is esterified with the molar ratio of alcohol to acid if do not added guiding thing
Reaction, reaction time of esterification are 3.5~5.0h.The molar ratio of binary acid of the present invention and aliphatic dihydroxy alcohol I esterifications is 1:
1.05~1.10, existing molar ratio of alcohol to acid is higher easily to cause dihydric alcohol to occur to increase side reaction product from polycondensation at high temperature
Ratio, but too low molar ratio of alcohol to acid can cause esterification reaction rate to be remarkably decreased, and substantially prolong the reaction time；The present invention
Esterification temperature is controlled at 180~240 DEG C, this is because esterification process is the endothermic reaction, although excessively high temperature can be into one
Step accelerates esterification reaction rate, but also results in the quickening of rate of side reactions, and too low temperature cannot be satisfied esterification
With course of dissolution to the needs of heat；Esterification slightly positive pressure, control pressure is in 50~200KPa, this is because esterification process
In due to reaction generate small molecule moisture, carry certain direct draught, the promotion of esterification reaction rate can be promoted.Excessively high pressure
Esterification device can be put forward higher requirements, esterification of the present invention carries out on existing apparatus, is not necessarily into one
Step transformation, reduces cost.Also other catalyst in addition to titanium silicon cobalt composite catalyst can be selected, but the increasing of side reaction can be caused
It is subject to and product color is deteriorated, higher catalytic activity may be implemented in compounded catalyst of the present invention, while promoting the color of product
Pool.
(2) prepolymerization reaction；
The agent of heat resistanceheat resistant oxygen and/or antioxidant are added in the product of step (1) in 200~260 DEG C and 100~1000Pa
Under conditions of carry out 15~45min prepolymerization reaction be made inherent viscosity≤0.15dL/g precondensation product；The preshrunk
The stir speed (S.S.) of poly- reaction is 5~20rpm；
Although low viscosity precondensation product, low viscosity can also be obtained by not adding the agent of heat resistanceheat resistant oxygen and/or antioxidant
Precondensation product easily degrade because of thermal oxide in polycondensation process.
The present invention prepolymerization reaction temperature control at 200~260 DEG C, this is because too low reaction temperature cause it is pre-
Polycondensation reaction can not carry out, and excessively high reaction temperature can lead to thermal degradation side reaction enhancing during prepolymerization reaction, formation
Product color is deteriorated.
The prepolymerization reaction pressure control of the present invention is relatively low compared to the poly- vacuum degree of final minification in 100~1000Pa, too low
Pressure (i.e. higher vacuum effectiveness) can cause the performed polymer of low viscosity in prepolymerization reaction to be extracted, and block pipeline, cause to contract
Poly- accident；Excessively high pressure (i.e. worse vacuum effectiveness) can lead to not the removing for realizing polycondensation reaction small molecular, preshrunk
Poly- reaction can not be normally carried out.
The prepolymerization reaction time control of the present invention is in 15~45min, substantially less than reaction time in the prior art, this hair
The performed polymer viscosity that can be resulted in if the bright middle prepolymerization reaction time is too short is too low (being less than 0.10~0.15dL/g),
In high vacuum conditions easily as dihydric alcohol small molecule is extracted together in subsequent final polycondensation reaction, pipeline is blocked；Preshrunk
The molecular weight for the performed polymer that can be resulted in if the poly- reaction time is too long gradually increases, the weight average molecular weight breadth coefficient of product
It broadens, then further broadens after final polycondensation reaction, cannot achieve the weight average molecular weight breadth coefficient collection that patent of the present invention proposes
In purpose.
The prepolymerization reaction stir speed (S.S.) of the present invention is 5~20rpm, and material viscosity is higher than esterification during prepolymerization reaction
Reaction product, is less than final polycondensation reaction product, and too fast stir speed (S.S.) can cause the precondensation product compared with low viscosity in vacuum ring
It is unfavorable to reacting as dihydric alcohol is carried over together under border.The uniform effect of material stirring is not had under too low stir speed (S.S.).
(3) final polycondensation reaction；
Precondensation product made from step (2) carries out 1.5~3.5h under conditions of 220~280 DEG C and 10~100Pa
Final polycondensation reaction biology base 2,5- furandicarboxylic acid base copolyesters is made；The stir speed (S.S.) of the final polycondensation reaction be 5~
10rpm。
The final polycondensation reaction temperature control of the present invention at 220~280 DEG C, too low reaction temperature cause final polycondensation reaction without
Method carries out；Thermal degradation side reaction enhances during excessively high reaction temperature can lead to final polycondensation reaction, and the product color of formation becomes
Difference.
The final polycondensation reaction pressure of the present invention is controlled in 10~100Pa, and too low pressure (i.e. higher vacuum effectiveness) is right
The requirement higher of equipment；Excessively high pressure (i.e. worse vacuum effectiveness) can lead to not realize the de- of polycondensation reaction small molecular
It removes, final polycondensation reaction can not be normally carried out.
The final polycondensation reaction time control of the present invention can lead to shape in 1.5~3.5h if the final polycondensation reaction time is too short
At product spinning rank is not achieved；The thermal degradation of polymer under hot conditions can be caused aobvious if the prepolymerization reaction time is too long
It writes and increases, product declines rapidly after reaching highest weight average molecular weight because of thermal degradation.
The final polycondensation reaction stir speed (S.S.) of the present invention is 5~10rpm, and material viscosity is higher than preshrunk during final polycondensation reaction
Polybutadiene reaction product, product viscosity is higher, and stirring is more difficult to, and too fast stir speed (S.S.) both can not be real for highly viscous polymeric system
The effect now stirred, simultaneously as the too big damage motor of electric current；Material stirring is not had under too low stir speed (S.S.) uniformly to imitate
Fruit.
A kind of preparation method of biology base 2,5-furandicarboxylic acid base copolyesters as described above, the addition of the guiding thing
Amount is 0.5~5.0wt% of binary acid additive amount in step (1)；The additive amount of the titanium silicon cobalt composite catalyst is step (1)
100~200ppm of middle binary acid additive amount；The titanium silicon cobalt composite catalyst is by Titanium series catalyst, silicon systems catalyst and cobalt system
Catalyst is 1 in molar ratio:0.1~10:0.1~10 is combined.
Purpose present invention introduces guiding thing be in order to reduce the ratio of dihydric alcohol in raw material, while accelerate esterification speed
Rate.Guiding thing additive amount is too low, cannot achieve effective dissolving to binary acid in raw material, and esterification reaction rate accelerates unobvious,
Reaction time of esterification can be extended instead；Guiding thing adding too much, though it can play the role of dissolving rapidly to binary acid, at
This can increase, and economy is bad.
The additive amount of titanium silicon cobalt composite catalyst is 100~200ppm of the quality of binary acid, and the present invention is selected with compound
Catalyst, which allows for, should ensure catalytic effect while can play the role of promotion to final product.Too low catalyst adds
Dosage can cause catalytic effect to decline, and the reaction time is elongated, and efficiency reduces；Excessively high catalyst amount can lead to reaction excessively
Soon, it is possible to " implode " danger occur, while also increase cost.
A kind of preparation method of biology base 2,5-furandicarboxylic acid base copolyesters as described above, the Titanium series catalyst are
Butyl titanate or metatitanic acid；The silicon systems catalyst is silica；The cobalt series catalyst is cobalt acetate.Titanium series catalyst
It is carried on silica and forms TiO2-SiO2It compounds with cobalt series catalyst to obtain titanium silicon cobalt composite catalyst after composite catalyst.
The specific preparation method of titanium silicon cobalt composite catalyst is as follows：
Titanium silicon cobalt composite catalyst is by TiO2-SiO2Composite catalyst and cobalt series catalyst mix according to a certain percentage to be added
Enter into polymerization system.Wherein, TiO is obtained using sol-gal process2-SiO2Composite catalyzing agent method is：By suitable positive silicic acid
Ethyl ester, ethyl alcohol, distilled water and nitric acid are added sequentially in three-necked flask, and are uniformly mixed.Three-necked flask is placed on magnetic agitation
It is heated and refluxed on device, sets 65 DEG C, mixing speed 820r/min of heating temperature, flow back 2h.Wait for ethyl orthosilicate complete hydrolysis
Afterwards, 40.0g butyl titanates are added into three-necked flask, stirring 20min makes it mix with reactant to hook.It is titrated using constant pressure
Pipe is slowly added dropwise by given pace steams shop water in right amount.After dripping, then the 2h that flows back at 65 DEG C.It is placed it in after forming gel
It is aged 12h under room temperature.Dry 12h at 110 DEG C, removes the water and alcohol solvent in reaction system in air dry oven,
The solid after drying is ground in mortar.Powder after grinding is put into Muffle furnace, firing temperature is set as 500 DEG C, waits for
Temperature starts timing, roast 3h after reaching set temperature.After the completion of waiting for roast, roast object is taken out, allows its natural cooling, is finally
TiO can be obtained2-SiO2Composite catalyst.
A kind of preparation method of biology base 2,5-furandicarboxylic acid base copolyesters as described above, biology base 2,5- furans two
The esterification yield that formic acid reacts generation guiding thing with aliphatic dihydroxy alcohol II is 90~98%；The binary acid is biology base 2,5- furans
It mutters dioctyl phthalate, terephthalic acid (TPA), M-phthalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, the last of the ten Heavenly stems two
One or more of acid；The aliphatic dihydroxy alcohol I and aliphatic dihydroxy alcohol II is respectively ethylene glycol, propylene glycol, butanediol, penta
One kind in glycol, hexylene glycol, heptandiol, ethohexadiol, nonanediol and decanediol.
A kind of preparation method of biology base 2,5-furandicarboxylic acid base copolyesters as described above, the heat resistanceheat resistant oxygen agent add
Enter 0.005~0.05wt% that amount is binary acid additive amount in step (1)；The addition of the antioxidant is in step (1)
0.001~0.01wt% of binary acid additive amount.
A kind of preparation method of biology base 2,5-furandicarboxylic acid base copolyesters as described above, the heat resistanceheat resistant oxygen agent are phosphorus
One or more of acid, phosphorous acid, trimethyl phosphate, Trimethyl phosphite and triphenyl phosphate；The antioxidant is antioxygen
One or more of agent 1010, antioxidant 168 and antioxidant 616.
A kind of preparation method of biology base 2,5-furandicarboxylic acid base copolyesters as described above, the biology base 2,5-
The weight average molecular weight breadth coefficient of furandicarboxylic acid base copolyesters is 1.2~1.6, and inherent viscosity is 0.60~1.20dL/g, color
Damp degree≤10.
A kind of preparation method of biology base 2,5-furandicarboxylic acid base copolyesters as described above, by the biology base 2,
5- furandicarboxylic acid base copolyesters is made POY, FDY or DTY, processes waste silk rate≤10kg/t, the yarn unevenness of fiber
≤ 1.0%.Biology base 2,5-furandicarboxylic acid base copolyesters is made outside fiber, is alternatively arranged as the raw material of the products such as film, plastics.
It is compared to existing petroleum base terephthalic acid groups polyacid-aliphatic dihydroxy alcohol copolyester fiber, has higher glass
Change transition temperature (glass transition temperature >=70 DEG C), intensity (fiber mechanics intensity >=4.0cN/dtex), modulus (fiber modulus
>=120cN/dtex) and good gas barrier property (under the same conditions, CO2Barrier property promotes 1 times or more, O2Barrier
4 times of performance boost or more).
Invention mechanism：
The preparation process of biology base 2,5- furandicarboxylic acids base copolyesters is generally under the conditions of high molar ratio of alcohol to acid at present
Esterification is carried out, esterification reaction product is after high inherent viscosity precondensation product is made in precondensation, then carries out final polycondensation reaction
Ultimately generate biology base 2,5- furandicarboxylic acid base copolyesters.Wherein there are the following problems：Reaction time of esterification is long, side reaction
It is more, it is of high cost, and also the inherent viscosity of precondensation product is excessively high so that and final biology base 2,5-furandicarboxylic acid base obtained is total
Polyester product molecular weight distribution is wider, and polyester processing performance is bad.
In view of the above problems, the present invention uses relatively low molar ratio of alcohol to acid (1:1.05~1.10) esterification is carried out, significantly
Improve feedstock fat race dihydric alcohol to occur from the problem of polycondensation side reaction.Due to relatively low molar ratio of alcohol to acid, the dissolving of raw material binary acid
Amount is reduced, and esterification reaction rate declines, and to overcome the problems, such as this, present invention addition is by biology base 2,5-furandicarboxylic acid and fat
The carboxylate that race's diol reaction generates is as guiding thing, and raw material binary acid is in biology base 2,5-furandicarboxylic acid and aliphatic two
Solubility in the carboxylate that first alcohol reaction generates is high, and just adding guiding thing in esterification initial period can be by raw material binary
Acid is dissolved in wherein, and dissolving raw material binary acid therein, can to carry out esterification with feedstock fat race dihydric alcohol rapidly further
It generates carboxylate and is redissolved remaining raw material binary acid, accelerate esterification.The present invention in esterification initial period addition by drawing
The method for leading object realizes the enhanced kinetics in esterification process so that esterification enters homogeneous reaction system in advance, compares
Existing technology has been obviously improved entire esterification reaction rate, substantially reduces the time of esterification.
The present invention is also existed the inherent viscosity control of precondensation product by controlling the prepolymerization reaction time (15~45min)
Within 0.15dL/g (the prepolymerization reaction time of the prior art is 1.0~2.0h, and inherent viscosity is in 0.25dL/g or more), most
Afterwards again through final polycondensation reaction, the biology base formed after final polycondensation reaction 2 may be implemented in this way, 5- furandicarboxylic acid bases are total
The molecular weight distribution of polyester is concentrated, its spinning process and quality are obviously improved.
Advantageous effect：
(1) preparation method of a kind of biology base 2,5-furandicarboxylic acid base copolyesters of the invention, using low alkyd mole
Than control binary acid is 1 with aliphatic dihydroxy alcohol molar ratio of material:1.05~1.10, on the one hand reduce aliphatic dihydroxy alcohol
Occurring from polycondensation side reaction so that the content of by-product is low in finally formed biology base 2,5-furandicarboxylic acid base copolyesters,
Product color degree is good, on the other hand, reduces the consumption of alcohol, reduces cost；
(2) preparation method of a kind of biology base 2,5-furandicarboxylic acid base copolyesters of the invention, in low molar ratio of alcohol to acid
Under conditions of, carboxylate is formed with aliphatic dihydroxy alcohol make in esterification initial period addition addition biology base 2,5-furandicarboxylic acid
For guiding thing, the enhanced kinetics in esterification process are realized so that esterification enters homogeneous reaction system in advance, compared to existing
Some technologies are obviously improved entire esterification reaction rate, substantially reduce the time of esterification, further reduce side reaction；
(3) preparation method of a kind of biology base 2,5-furandicarboxylic acid base copolyesters of the invention completes esterification
Afterwards the inherent viscosity for controlling precondensation product can be made to be formed after final polycondensation reaction in this way within 0.15dL/g
The molecular weight distribution of biology base 2,5-furandicarboxylic acid base copolyesters is concentrated, its spinning quality is obviously improved；
(4) preparation method of a kind of biology base 2,5-furandicarboxylic acid base copolyesters of the invention, biology base 2 obtained,
5- furandicarboxylic acid base copolyesters is used for POY, FDY and DTY spinning, processing waste silk rate≤10kg/t, the yarn unevenness of fiber
≤ 1.0%, it can be used for fibre forming manufacture field, can apply in high-grade home textile, the fields such as take.
Specific implementation mode
The invention will be further elucidated with reference to specific embodiments.It should 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 range.
Embodiment 1
A kind of preparation method of biology base 2,5-furandicarboxylic acid base copolyesters, is as follows：
(1) esterification；
By terephthalic acid (TPA) and ethylene glycol with 1:After 1.05 molar ratio is mixed with beating, addition titanium silicon cobalt composite catalyst,
Guiding thing carries out under conditions of 180 DEG C, 100KPa until water yield reaches 95% reaction terminating of theoretical water yield, wherein drawing
It is the carboxylate that biology base 2,5-furandicarboxylic acid reacts that the esterification yield generated is 90% with propylene glycol to lead object, and guiding thing adds
Dosage is the 5.0wt% of terephthalic acid (TPA), and the additive amount of titanium silicon cobalt composite catalyst is the 110ppm of the quality of terephthalic acid (TPA),
Titanium silicon cobalt composite catalyst is 1 in molar ratio by butyl titanate, silica and cobalt acetate:0.8:0.1 is combined；
(2) prepolymerization reaction；
The prepolymerization reaction that phosphoric acid carries out 20min under conditions of 200 DEG C, 1000Pa is added in the product of step (1)
Be made inherent viscosity be 0.10dL/g precondensation product, wherein prepolymerization reaction stir speed (S.S.) be 10rpm stirring under into
Row, the addition of phosphoric acid are the 0.03wt% of addition terephthalic acid (TPA) in step (1)；
(3) final polycondensation reaction；
The final polycondensation reaction that precondensation product made from step (2) carries out 2.0h under conditions of 220 DEG C, 100Pa is made
Biology base 2,5-furandicarboxylic acid base copolyesters, wherein final polycondensation reaction are carried out in the case where stir speed (S.S.) is the stirring of 6rpm.
The weight average molecular weight breadth coefficient of final biology base 2,5-furandicarboxylic acid base copolyesters obtained is 1.2, characteristic
Viscosity is 1.1dL/g, and the content of color 10, side reaction product is 0.9wt%.It is made into biology base 2,5- furans diformazans
Acidic group copolyesters FDY, processing waste silk rate are 9.2kg/t, and the yarn unevenness of fiber is 0.99%.
Embodiment 2
A kind of preparation method of biology base 2,5-furandicarboxylic acid base copolyesters, is as follows：
(1) esterification；
By biology base 2,5- furandicarboxylic acids and propylene glycol with 1:After 1.06 molar ratio is mixed with beating, it is multiple that titanium silicon cobalt is added
Close catalyst, guiding thing carries out under conditions of 220 DEG C, 150KPa until water yield reaches 95% reaction of theoretical water yield eventually
Only, wherein guiding thing be biology base 2,5-furandicarboxylic acid reacted with propylene glycol generate esterification yield be 95% carboxylate, draw
The additive amount for leading object is the 4.5wt% of biology base 2,5-furandicarboxylic acid, and the additive amount of titanium silicon cobalt composite catalyst is biology base
The 100ppm of the quality of 2,5-furandicarboxylic acid, titanium silicon cobalt composite catalyst by metatitanic acid, silica and cobalt acetate by mole
Than being 1:2.5:0.5 is combined；
(2) prepolymerization reaction；
The prepolymerization reaction that phosphorous acid carries out 40min under conditions of 235 DEG C, 200Pa is added in the product of step (1)
Be made inherent viscosity be 0.11dL/g precondensation product, wherein prepolymerization reaction stir speed (S.S.) be 16rpm stirring under into
Row, the addition of phosphorous acid are the 0.01wt% of addition biology base 2,5-furandicarboxylic acid in step (1)；
(3) final polycondensation reaction；
Life is made in the final polycondensation reaction that precondensation product made from step (2) carries out 2.5h under conditions of 250 DEG C, 20Pa
Object base 2,5-furandicarboxylic acid base copolyesters, wherein final polycondensation reaction are carried out in the case where stir speed (S.S.) is the stirring of 6rpm.
The weight average molecular weight breadth coefficient of final biology base 2,5-furandicarboxylic acid base copolyesters obtained is 1.6, characteristic
Viscosity is 1.10dL/g, and the content of color 9, side reaction product is 0.8wt%.It is made into biology base 2,5- furans diformazans
Acidic group copolyesters FDY, processing waste silk rate are 8.9kg/t, and the yarn unevenness of fiber is 0.89%.
Embodiment 3
A kind of preparation method of biology base 2,5-furandicarboxylic acid base copolyesters, is as follows：
(1) esterification；
By suberic acid and butanediol with 1:After 1.07 molar ratio is mixed with beating, titanium silicon cobalt composite catalyst, guiding is added
Object carries out under conditions of 230 DEG C, 50KPa until water yield reaches 95% reaction terminating of theoretical water yield, wherein guiding thing
The carboxylate that the esterification yield generated is 98% is reacted with pentanediol for biology base 2,5-furandicarboxylic acid, the additive amount of guiding thing is
The 4.0wt% of suberic acid, the additive amount of titanium silicon cobalt composite catalyst are the 130ppm of the quality of suberic acid, titanium silicon cobalt composite catalyzing
Agent is 1 in molar ratio by butyl titanate, silica and cobalt acetate:5.0:4.0 being combined；
(2) prepolymerization reaction；
The preshrunk that trimethyl phosphate carries out 25min under conditions of 240 DEG C, 100Pa is added in the product of step (1)
The precondensation product that inherent viscosity is 0.12dL/g is made in poly- reaction, and wherein prepolymerization reaction is in the stirring that stir speed (S.S.) is 8rpm
Lower progress, the addition of trimethyl phosphate are the 0.006wt% of addition suberic acid in step (1)；
(3) final polycondensation reaction；
Life is made in the final polycondensation reaction that precondensation product made from step (2) carries out 1.5h under conditions of 260 DEG C, 10Pa
Object base 2,5-furandicarboxylic acid base copolyesters, wherein final polycondensation reaction are carried out in the case where stir speed (S.S.) is the stirring of 8rpm.
The weight average molecular weight breadth coefficient of final biology base 2,5-furandicarboxylic acid base copolyesters obtained is 1.5, characteristic
Viscosity is 0.85dL/g, and the content of color 8, side reaction product is 0.85wt%.It is made into biology base 2,5- furans two
Formyl copolyesters POY, processing waste silk rate are 9.5kg/t, and the yarn unevenness of fiber is 0.85%.
Embodiment 4
A kind of preparation method of biology base 2,5-furandicarboxylic acid base copolyesters, is as follows：
(1) esterification；
By terephthalic acid (TPA) and propylene glycol with 1:After 1.08 molar ratio is mixed with beating, addition titanium silicon cobalt composite catalyst,
Guiding thing carries out under conditions of 235 DEG C, 80KPa until water yield reaches 95% reaction terminating of theoretical water yield, wherein drawing
It is the carboxylate that biology base 2,5-furandicarboxylic acid reacts that the esterification yield generated is 92% with pentanediol, the addition of guiding thing to lead object
Amount is the 3.5wt% of terephthalic acid (TPA), and the additive amount of titanium silicon cobalt composite catalyst is the 180ppm of the quality of terephthalic acid (TPA), titanium
Silicon cobalt composite catalyst is 1 in molar ratio by metatitanic acid, silica and cobalt acetate:0.1:5.7 being combined；
(2) prepolymerization reaction；
Trimethyl phosphite is added in the product of step (1) and carries out the pre- of 35min under conditions of 245 DEG C, 100Pa
The precondensation product that inherent viscosity is 0.13dL/g is made in polycondensation reaction, and wherein prepolymerization reaction is 17rpm's in stir speed (S.S.)
Stirring is lower to be carried out, and the addition of Trimethyl phosphite is the 0.015wt% of addition terephthalic acid (TPA) in step (1)；
(3) final polycondensation reaction；
Life is made in the final polycondensation reaction that precondensation product made from step (2) carries out 1.5h under conditions of 240 DEG C, 30Pa
Object base 2,5-furandicarboxylic acid base copolyesters, wherein final polycondensation reaction are carried out in the case where stir speed (S.S.) is the stirring of 5rpm.
The weight average molecular weight breadth coefficient of final biology base 2,5-furandicarboxylic acid base copolyesters obtained is 1.2, characteristic
Viscosity is 0.90dL/g, and the content of color 8, side reaction product is 0.9wt%.It is made into biology base 2,5- furans diformazans
Acidic group copolyesters DTY, processing waste silk rate are 9.5kg/t, and the yarn unevenness of fiber is 0.88%.
Embodiment 5
A kind of preparation method of biology base 2,5-furandicarboxylic acid base copolyesters, is as follows：
(1) esterification；
By decanedioic acid and butanediol with 1:After 1.09 molar ratio is mixed with beating, titanium silicon cobalt composite catalyst, guiding is added
Object carries out under conditions of 240 DEG C, 150KPa until water yield reaches 95% reaction terminating of theoretical water yield, wherein guiding thing
The carboxylate that the esterification yield generated is 92% is reacted with hexylene glycol for biology base 2,5-furandicarboxylic acid, the additive amount of guiding thing is
The 3.0wt% of decanedioic acid, the additive amount of titanium silicon cobalt composite catalyst are the 150ppm of the quality of decanedioic acid, titanium silicon cobalt composite catalyzing
Agent is 1 in molar ratio by butyl titanate, silica and cobalt acetate:0.9:3.6 being combined；
(2) prepolymerization reaction；
The preshrunk that triphenyl phosphate carries out 15min under conditions of 250 DEG C, 700Pa is added in the product of step (1)
The precondensation product that inherent viscosity is 0.13dL/g is made in poly- reaction, and wherein prepolymerization reaction is stirring for 20rpm in stir speed (S.S.)
Lower progress is mixed, the addition of triphenyl phosphate is the 0.035wt% of addition decanedioic acid in step (1)；
(3) final polycondensation reaction；
Life is made in the final polycondensation reaction that precondensation product made from step (2) carries out 2.5h under conditions of 220 DEG C, 70Pa
Object base 2,5-furandicarboxylic acid base copolyesters, wherein final polycondensation reaction are carried out in the case where stir speed (S.S.) is the stirring of 9rpm.
The weight average molecular weight breadth coefficient of final biology base 2,5-furandicarboxylic acid base copolyesters obtained is 1.15, characteristic
Viscosity is 0.72dL/g, and the content of color 8, side reaction product is 1wt%.It is made into biology base 2,5- furandicarboxylic acids
Base copolyesters FDY, processing waste silk rate are 9kg/t, and the yarn unevenness of fiber is 0.93%.
Embodiment 6
A kind of preparation method of biology base 2,5-furandicarboxylic acid base copolyesters, is as follows：
(1) esterification；
By azelaic acid and butanediol with 1:After 1.10 molar ratio is mixed with beating, titanium silicon cobalt composite catalyst, guiding is added
Object carries out under conditions of 220 DEG C, 120KPa until water yield reaches 95% reaction terminating of theoretical water yield, wherein guiding thing
The carboxylate that the esterification yield generated is 90% is reacted with heptandiol for biology base 2,5-furandicarboxylic acid, the additive amount of guiding thing is
The 2.0wt% of azelaic acid, the additive amount of titanium silicon cobalt composite catalyst are the 100ppm of the quality of azelaic acid, titanium silicon cobalt composite catalyzing
Agent is 1 in molar ratio by butyl titanate, silica and cobalt acetate:3.8:0.1 is combined；
(2) prepolymerization reaction；
Mixture (the mass ratio 2 of phosphoric acid and phosphorous acid is added in the product of step (1):And antioxidant 1)
The precondensation that inherent viscosity is 0.14dL/g is made in 1010 prepolymerization reactions that 15min is carried out under conditions of 240 DEG C, 500Pa
Product, wherein prepolymerization reaction are carried out in the case where stir speed (S.S.) is the stirring of 11rpm, the addition of the mixture of phosphoric acid and phosphorous acid
Addition for the 0.005wt% of addition azelaic acid in step (1), antioxidant 1010 is addition azelaic acid in step (1)
0.001wt%；
(3) final polycondensation reaction；
Life is made in the final polycondensation reaction that precondensation product made from step (2) carries out 1.5h under conditions of 230 DEG C, 50Pa
Object base 2,5-furandicarboxylic acid base copolyesters, wherein final polycondensation reaction are carried out in the case where stir speed (S.S.) is the stirring of 9rpm.
The weight average molecular weight breadth coefficient of final biology base 2,5-furandicarboxylic acid base copolyesters obtained is 1.55, characteristic
Viscosity is 1.10dL/g, and the content of color 9, side reaction product is 0.8wt%.It is made into biology base 2,5- furans diformazans
Acidic group copolyesters FDY, processing waste silk rate are 9.5kg/t, and the yarn unevenness of fiber is 0.95%.
Embodiment 7
A kind of preparation method of biology base 2,5-furandicarboxylic acid base copolyesters, is as follows：
(1) esterification；
By M-phthalic acid and hexylene glycol with 1:After 1.07 molar ratio is mixed with beating, addition titanium silicon cobalt composite catalyst,
Guiding thing carries out under conditions of 228 DEG C, 150KPa until water yield reaches 95% reaction terminating of theoretical water yield, wherein drawing
It is the carboxylate that biology base 2,5-furandicarboxylic acid reacts that the esterification yield generated is 96% with ethohexadiol to lead object, and guiding thing adds
Dosage is the 0.5wt% of M-phthalic acid, and the additive amount of titanium silicon cobalt composite catalyst is the 160ppm of the quality of M-phthalic acid,
Titanium silicon cobalt composite catalyst is 1 in molar ratio by metatitanic acid, silica and cobalt acetate:8.2:0.8 is combined；
(2) prepolymerization reaction；
The mixture and antioxidant 168 of trimethyl phosphate and Trimethyl phosphite are added in the product of step (1)
The precondensation production that inherent viscosity is 0.15dL/g is made in the prepolymerization reaction that 25min is carried out under conditions of 230 DEG C, 300Pa
Object, wherein prepolymerization reaction are carried out in the case where stir speed (S.S.) is the stirring of 10rpm, the mixing of trimethyl phosphate and Trimethyl phosphite
The addition of object is the 0.04wt% of addition M-phthalic acid in step (1), and the addition of antioxidant 168 is in step (1)
Add the 0.005wt% of M-phthalic acid；
(3) final polycondensation reaction；
Life is made in the final polycondensation reaction that precondensation product made from step (2) carries out 3.5h under conditions of 270 DEG C, 30Pa
Object base 2,5-furandicarboxylic acid base copolyesters, wherein final polycondensation reaction are carried out in the case where stir speed (S.S.) is the stirring of 7rpm.
The weight average molecular weight breadth coefficient of final biology base 2,5-furandicarboxylic acid base copolyesters obtained is 1.31, characteristic
Viscosity is 0.68dL/g, and the content of color 7, side reaction product is 0.95wt%.It is made into biology base 2,5- furans two
Formyl copolyesters FDY, processing waste silk rate are 10kg/t, and the yarn unevenness of fiber is 0.86%.
Embodiment 8
A kind of preparation method of biology base 2,5-furandicarboxylic acid base copolyesters, is as follows：
(1) esterification；
By terephthalic acid (TPA)/azelaic acid (mass ratio 2:1) with pentanediol with 1:After 1.06 molar ratio is mixed with beating, add
Enter titanium silicon cobalt composite catalyst, guiding thing to be carried out under conditions of 234 DEG C, 180KPa until water yield reaches theoretical water yield
95% reaction terminating, wherein guiding thing are that the esterification yield that biology base 2,5-furandicarboxylic acid reacts generation with nonanediol is 98%
Carboxylate, the additive amount of guiding thing are the 0.5wt% of terephthalic acid (TPA)/azelaic acid, and the additive amount of titanium silicon cobalt composite catalyst is
The 200ppm of the quality of terephthalic acid (TPA)/azelaic acid, titanium silicon cobalt composite catalyst is by butyl titanate, silica and cobalt acetate
It is 1 in molar ratio:5.0:5.5 being combined；
(2) prepolymerization reaction；
Mixture (the mass ratio 1 of Trimethyl phosphite and triphenyl phosphate is added in the product of step (1):1) with
And it is 0.10dL/g that antioxidant 616 carries out the prepolymerization reaction obtained inherent viscosity of 20min under conditions of 230 DEG C, 600Pa
Precondensation product, wherein prepolymerization reaction stir speed (S.S.) be 5rpm stirring under carry out, Trimethyl phosphite and tricresyl phosphate
The addition of the mixture of phenyl ester is the 0.05wt% of addition terephthalic acid (TPA)/azelaic acid in step (1), antioxidant 616
Addition is the 0.01wt% of addition terephthalic acid (TPA)/azelaic acid in step (1)；
(3) final polycondensation reaction；
Life is made in the final polycondensation reaction that precondensation product made from step (2) carries out 2.5h under conditions of 250 DEG C, 40Pa
Object base 2,5-furandicarboxylic acid base copolyesters, wherein final polycondensation reaction are carried out in the case where stir speed (S.S.) is the stirring of 8rpm.
The weight average molecular weight breadth coefficient of final biology base 2,5-furandicarboxylic acid base copolyesters obtained is 1.2, characteristic
Viscosity is 0.85dL/g, and the content of color 8, side reaction product is 0.8wt%.It is made into biology base 2,5- furans diformazans
Acidic group copolyesters FDY, processing waste silk rate are 8.1kg/t, and the yarn unevenness of fiber is 0.80%.
Embodiment 9
A kind of preparation method of biology base 2,5-furandicarboxylic acid base copolyesters, is as follows：
(1) esterification；
By decanedioic acid and nonanediol with 1:After 1.10 molar ratio is mixed with beating, titanium silicon cobalt composite catalyst, guiding is added
Object carries out under conditions of 220 DEG C, 70KPa until water yield reaches 95% reaction terminating of theoretical water yield, wherein guiding thing
The carboxylate that the esterification yield generated is 91% is reacted with ethohexadiol for biology base 2,5-furandicarboxylic acid, the additive amount of guiding thing is
The 1.5wt% of decanedioic acid, the additive amount of titanium silicon cobalt composite catalyst are the 200ppm of the quality of decanedioic acid, titanium silicon cobalt composite catalyzing
Agent is 1 in molar ratio by butyl titanate, silica and cobalt acetate:7.5:6.0 being combined；
(2) prepolymerization reaction；
Antioxidant 1010 is added in the product of step (1) and carries out the pre- of 35min under conditions of 250 DEG C, 400Pa
The precondensation product that inherent viscosity is 0.10dL/g is made in polycondensation reaction, and wherein prepolymerization reaction is 15rpm's in stir speed (S.S.)
Stirring is lower to be carried out, and the addition of antioxidant 1010 is the 0.002wt% of addition decanedioic acid in step (1)；
(3) final polycondensation reaction；
Life is made in the final polycondensation reaction that precondensation product made from step (2) carries out 1.5h under conditions of 280 DEG C, 70Pa
Object base 2,5-furandicarboxylic acid base copolyesters, wherein final polycondensation reaction are carried out in the case where stir speed (S.S.) is the stirring of 8rpm.
The weight average molecular weight breadth coefficient of final biology base 2,5-furandicarboxylic acid base copolyesters obtained is 1.46, characteristic
Viscosity is 0.65dL/g, and the content of color 8, side reaction product is 0.85wt%.It is made into biology base 2,5- furans two
Formyl copolyesters FDY, processing waste silk rate are 9kg/t, and the yarn unevenness of fiber is 0.88%.
Embodiment 10
A kind of preparation method of biology base 2,5-furandicarboxylic acid base copolyesters, is as follows：
(1) esterification；
By azelaic acid and ethohexadiol with 1:After 1.05 molar ratio is mixed with beating, titanium silicon cobalt composite catalyst, guiding is added
Object carries out under conditions of 235 DEG C, 200KPa until water yield reaches 95% reaction terminating of theoretical water yield, wherein guiding thing
The carboxylate that the esterification yield generated is 98% is reacted with nonanediol for biology base 2,5-furandicarboxylic acid, the additive amount of guiding thing is
The 2.0wt% of azelaic acid, the additive amount of titanium silicon cobalt composite catalyst are the 180ppm of the quality of azelaic acid, titanium silicon cobalt composite catalyzing
Agent is 1 in molar ratio by metatitanic acid, silica and cobalt acetate:0.3:0.1 is combined；
(2) prepolymerization reaction；
The preshrunk that antioxidant 168 carries out 35min under conditions of 245 DEG C, 100Pa is added in the product of step (1)
The precondensation product that inherent viscosity is 0.12dL/g is made in poly- reaction, and wherein prepolymerization reaction is stirring for 20rpm in stir speed (S.S.)
Lower progress is mixed, the addition of antioxidant 168 is the 0.006wt% of addition azelaic acid in step (1)；
(3) final polycondensation reaction；
Life is made in the final polycondensation reaction that precondensation product made from step (2) carries out 2.0h under conditions of 270 DEG C, 50Pa
Object base 2,5-furandicarboxylic acid base copolyesters, wherein final polycondensation reaction are carried out in the case where stir speed (S.S.) is the stirring of 10rpm.
The weight average molecular weight breadth coefficient of final biology base 2,5-furandicarboxylic acid base copolyesters obtained is 1.56, characteristic
Viscosity is 1.10dL/g, and the content of color 9.5, side reaction product is 0.9wt%.It is made into biology base 2,5- furans two
Formyl copolyesters FDY, processing waste silk rate are 9.7kg/t, and the yarn unevenness of fiber is 0.98%.
Embodiment 11
A kind of preparation method of biology base 2,5-furandicarboxylic acid base copolyesters, is as follows：
(1) esterification；
By suberic acid and nonanediol with 1:After 1.08 molar ratio is mixed with beating, titanium silicon cobalt composite catalyst, guiding is added
Object carries out under conditions of 231 DEG C, 100KPa until water yield reaches 95% reaction terminating of theoretical water yield, wherein guiding thing
The carboxylate that the esterification yield generated is 94% is reacted with heptandiol for biology base 2,5-furandicarboxylic acid, the additive amount of guiding thing is
The 4.0wt% of suberic acid, the additive amount of titanium silicon cobalt composite catalyst are the 150ppm of the quality of suberic acid, titanium silicon cobalt composite catalyzing
Agent is 1 in molar ratio by metatitanic acid, silica and cobalt acetate:0.5:10 are combined；
(2) prepolymerization reaction；
The preshrunk that antioxidant 616 carries out 40min under conditions of 250 DEG C, 800Pa is added in the product of step (1)
The precondensation product that inherent viscosity is 0.10dL/g is made in poly- reaction, and wherein prepolymerization reaction is stirring for 13rpm in stir speed (S.S.)
Lower progress is mixed, the addition of antioxidant 616 is the 0.01wt% of addition suberic acid in step (1)；
(3) final polycondensation reaction；
Life is made in the final polycondensation reaction that precondensation product made from step (2) carries out 3.5h under conditions of 250 DEG C, 50Pa
Object base 2,5-furandicarboxylic acid base copolyesters, wherein final polycondensation reaction are carried out in the case where stir speed (S.S.) is the stirring of 5rpm.
The weight average molecular weight breadth coefficient of final biology base 2,5-furandicarboxylic acid base copolyesters obtained is 1.5, characteristic
Viscosity is 0.63dL/g, and the content of color 7, side reaction product is 0.78wt%.It is made into biology base 2,5- furans two
Formyl copolyesters POY, processing waste silk rate are 8.5kg/t, and the yarn unevenness of fiber is 0.75%.
Embodiment 12
A kind of preparation method of biology base 2,5-furandicarboxylic acid base copolyesters, is as follows：
(1) esterification；
By pimelic acid and heptandiol with 1:After 1.08 molar ratio is mixed with beating, titanium silicon cobalt composite catalyst, guiding is added
Object carries out under conditions of 223 DEG C, 80KPa until water yield reaches 95% reaction terminating of theoretical water yield, wherein guiding thing
The carboxylate that the esterification yield generated is 96% is reacted with pentanediol for biology base 2,5-furandicarboxylic acid, the additive amount of guiding thing is
The 0.5wt% of pimelic acid, the additive amount of titanium silicon cobalt composite catalyst are the 130ppm of the quality of pimelic acid, titanium silicon cobalt composite catalyzing
Agent is 1 in molar ratio by butyl titanate, silica and cobalt acetate:6.0:0.7 is combined；
(2) prepolymerization reaction；
Phosphoric acid is added in the product of step (1) and antioxidant 1010 carries out 45min under conditions of 235 DEG C, 900Pa
Prepolymerization reaction be made inherent viscosity be 0.15dL/g precondensation product, wherein prepolymerization reaction stir speed (S.S.) be 7rpm
Stirring under carry out, the addition of phosphoric acid is the 0.008wt% of addition terephthalic acid (TPA) in step (1), antioxidant 1010
Addition is the 0.009wt% of addition pimelic acid in step (1)；
(3) final polycondensation reaction；
The final polycondensation reaction that precondensation product made from step (2) carries out 3.0h under conditions of 260 DEG C, 100Pa is made
Biology base 2,5-furandicarboxylic acid base copolyesters, wherein final polycondensation reaction are carried out in the case where stir speed (S.S.) is the stirring of 10rpm.
The weight average molecular weight breadth coefficient of final biology base 2,5-furandicarboxylic acid base copolyesters obtained is 1.5, characteristic
Viscosity is 1.12dL/g, and the content of color 9, side reaction product is 0.8wt%.It is made into biology base 2,5- furans diformazans
Acidic group copolyesters DTY, processing waste silk rate are 9.5kg/t, and the yarn unevenness of fiber is 0.98%.
Embodiment 13
A kind of preparation method of biology base 2,5-furandicarboxylic acid base copolyesters, is as follows：
(1) esterification；
By adipic acid and decanediol with 1:After 1.05 molar ratio is mixed with beating, titanium silicon cobalt composite catalyst, guiding is added
Object carries out under conditions of 226 DEG C, 140KPa until water yield reaches 95% reaction terminating of theoretical water yield, wherein guiding thing
The carboxylate that esterification yield for biology base 2,5-furandicarboxylic acid and glycol reaction generation is 90%, the additive amount of guiding thing are
The 3.0wt% of adipic acid, the additive amount of titanium silicon cobalt composite catalyst are the 180ppm of the quality of adipic acid, titanium silicon cobalt composite catalyzing
Agent is 1 in molar ratio by butyl titanate, silica and cobalt acetate:9.2:7.1 being combined；
(2) prepolymerization reaction；
Mixture (the mass ratio 1 of antioxidant 1010 and antioxidant 168 is added in the product of step (1):1) exist
237 DEG C, the prepolymerization reaction for carrying out 15min under conditions of 400Pa the precondensation product that inherent viscosity is 0.14dL/g is made,
Wherein prepolymerization reaction is carried out in the case where stir speed (S.S.) is the stirring of 16rpm, the mixture of antioxidant 1010 and antioxidant 168
Addition be step (1) in addition adipic acid 0.003wt%；
(3) final polycondensation reaction；
Life is made in the final polycondensation reaction that precondensation product made from step (2) carries out 3.0h under conditions of 220 DEG C, 40Pa
Object base 2,5-furandicarboxylic acid base copolyesters, wherein final polycondensation reaction are carried out in the case where stir speed (S.S.) is the stirring of 7rpm.
The weight average molecular weight breadth coefficient of final biology base 2,5-furandicarboxylic acid base copolyesters obtained is 1.5, characteristic
Viscosity is 1.06dL/g, and the content of color 8, side reaction product is 0.9wt%.It is made into biology base 2,5- furans diformazans
Acidic group copolyesters DTY, processing waste silk rate are 9kg/t, and the yarn unevenness of fiber is 0.9%.
Embodiment 14
A kind of preparation method of biology base 2,5-furandicarboxylic acid base copolyesters, is as follows：
(1) esterification；
By glutaric acid and pentanediol with 1:After 1.10 molar ratio is mixed with beating, titanium silicon cobalt composite catalyst, guiding is added
Object carries out under conditions of 230 DEG C, 170KPa until water yield reaches 95% reaction terminating of theoretical water yield, wherein guiding thing
The carboxylate that the esterification yield generated is 97% is reacted with decanediol for biology base 2,5-furandicarboxylic acid, the additive amount of guiding thing is
The 2.5wt% of glutaric acid, the additive amount of titanium silicon cobalt composite catalyst are the 190ppm of the quality of glutaric acid, titanium silicon cobalt composite catalyzing
Agent is 1 in molar ratio by metatitanic acid, silica and cobalt acetate:7.0:0.1 is combined；
(2) prepolymerization reaction；
Mixture (the matter of antioxidant 1010, antioxidant 168 and antioxidant 616 is added in the product of step (1)
Amount is than being 1:1:1) inherent viscosity is made as 0.13dL/g in the prepolymerization reaction that 15min is carried out under conditions of 250 DEG C, 100Pa
Precondensation product, wherein prepolymerization reaction stir speed (S.S.) be 5rpm stirring under carry out, antioxidant 1010, antioxidant
168 and antioxidant 616 mixture addition be step (1) in addition glutaric acid 0.001wt%；
(3) final polycondensation reaction；
Life is made in the final polycondensation reaction that precondensation product made from step (2) carries out 3.5h under conditions of 230 DEG C, 60Pa
Object base 2,5-furandicarboxylic acid base copolyesters, wherein final polycondensation reaction are carried out in the case where stir speed (S.S.) is the stirring of 10rpm.
The weight average molecular weight breadth coefficient of final biology base 2,5-furandicarboxylic acid base copolyesters obtained is 1.2, characteristic
Viscosity is 0.70dL/g, and the content of color 7, side reaction product is 0.75wt%.It is made into biology base 2,5- furans two
Formyl copolyesters FDY, processing waste silk rate are 9.4kg/t, and the yarn unevenness of fiber is 0.95%.
Embodiment 15
A kind of preparation method of biology base 2,5-furandicarboxylic acid base copolyesters, is as follows：
(1) esterification；
By succinic acid and hexylene glycol with 1:After 1.10 molar ratio is mixed with beating, titanium silicon cobalt composite catalyst, guiding is added
Object carries out under conditions of 240 DEG C, 200KPa until water yield reaches 95% reaction terminating of theoretical water yield, wherein guiding thing
The carboxylate that the esterification yield generated is 98% is reacted with decanediol for biology base 2,5-furandicarboxylic acid, the additive amount of guiding thing is
The 5.0wt% of succinic acid, the additive amount of titanium silicon cobalt composite catalyst are the 100ppm of the quality of succinic acid, titanium silicon cobalt composite catalyzing
Agent is 1 in molar ratio by butyl titanate, silica and cobalt acetate:10:0.4 is combined；
(2) prepolymerization reaction；
Mixture (the mass ratio 1 of phosphoric acid and trimethyl phosphate is added in the product of step (1):2) 230 DEG C,
The precondensation product that inherent viscosity is 0.14dL/g, wherein preshrunk is made in the prepolymerization reaction that 20min is carried out under conditions of 300Pa
Poly- reaction is carried out in the case where stir speed (S.S.) is the stirring of 18rpm, and the addition of the mixture of phosphoric acid and trimethyl phosphate is step (1)
The 0.005wt% of middle addition succinic acid；
(3) final polycondensation reaction；
Life is made in the final polycondensation reaction that precondensation product made from step (2) carries out 2.0h under conditions of 230 DEG C, 70Pa
Object base 2,5-furandicarboxylic acid base copolyesters, wherein final polycondensation reaction are carried out in the case where stir speed (S.S.) is the stirring of 9rpm.
The weight average molecular weight breadth coefficient of final biology base 2,5-furandicarboxylic acid base copolyesters obtained is 1.59, characteristic
Viscosity is 1.18dL/g, and the content of color 9, side reaction product is 0.95wt%.It is made into biology base 2,5- furans two
Formyl copolyesters POY, processing waste silk rate are 8.5kg/t, and the yarn unevenness of fiber is 0.85%.
Embodiment 16
A kind of preparation method of biology base 2,5-furandicarboxylic acid base copolyesters, is as follows：
(1) esterification；
By biology base 2,5- furandicarboxylic acids/M-phthalic acid (mass ratio 1:1) with propylene glycol with 1:1.07 mole
After being mixed with beating, titanium silicon cobalt composite catalyst is added, guiding thing carries out under conditions of 233 DEG C, 60KPa until water yield reaches
To 95% reaction terminating of theoretical water yield, wherein guiding thing is that biology base 2,5-furandicarboxylic acid reacts generation with hexylene glycol
The additive amount of the carboxylate that esterification yield is 98%, guiding thing is biology base 2,5-furandicarboxylic acid/M-phthalic acid
The additive amount of 5.0wt%, titanium silicon cobalt composite catalyst are biology base 2, the quality of 5- furandicarboxylic acids/M-phthalic acid
200ppm, titanium silicon cobalt composite catalyst are 1 in molar ratio by metatitanic acid, silica and cobalt acetate:8.8:10 are combined；
(2) prepolymerization reaction；
Mixture (the mass ratio 2 of antioxidant 1010 and antioxidant 168 is added in the product of step (1):1) and
The precondensation that inherent viscosity is 0.12dL/g is made in the prepolymerization reaction that phosphoric acid carries out 30min under conditions of 250 DEG C, 200Pa
Product, wherein prepolymerization reaction are carried out in the case where stir speed (S.S.) is the stirring of 6rpm, and the addition of phosphoric acid is addition life in step (1)
The 0.04wt% of object base 2,5-furandicarboxylic acid/M-phthalic acid, antioxidant 1010 add with the mixture of antioxidant 168
Enter the 0.001wt% that amount is addition biology base 2,5- furandicarboxylic acids/M-phthalic acid in step (1)；
(3) final polycondensation reaction；
Life is made in the final polycondensation reaction that precondensation product made from step (2) carries out 1.5h under conditions of 260 DEG C, 10Pa
Object base 2,5-furandicarboxylic acid base copolyesters, wherein final polycondensation reaction are carried out in the case where stir speed (S.S.) is the stirring of 5rpm.
The weight average molecular weight breadth coefficient of final biology base 2,5-furandicarboxylic acid base copolyesters obtained is 1.4, characteristic
Viscosity is 1.0dL/g, and the content of color 8, side reaction product is 0.80wt%.It is made into biology base 2,5- furans diformazans
Acidic group copolyesters DTY, processing waste silk rate are 9.0kg/t, and the yarn unevenness of fiber is 0.8%.
Embodiment 17
A kind of preparation method of biology base 2,5-furandicarboxylic acid base copolyesters, is as follows：
(1) esterification；
By terephthalic acid (TPA) and propylene glycol with 1:After 1.07 molar ratio is mixed with beating, addition titanium silicon cobalt composite catalyst,
Guiding thing carries out under conditions of 240 DEG C, 50KPa until water yield reaches 95% reaction terminating of theoretical water yield, wherein drawing
It is the carboxylate that biology base 2,5-furandicarboxylic acid reacts that the esterification yield generated is 93% with butanediol, the addition of guiding thing to lead object
Amount is the 3.5wt% of terephthalic acid (TPA), and the additive amount of titanium silicon cobalt composite catalyst is the 150ppm of the quality of terephthalic acid (TPA), titanium
Silicon cobalt composite catalyst is 1 in molar ratio by metatitanic acid, silica and cobalt acetate:10:5.0 being combined；
(2) prepolymerization reaction；
Mixture (the mass ratio 2 of phosphoric acid and phosphorous acid is added in the product of step (1):And antioxidant 1010 1)
With the mixture (mass ratio 3 of antioxidant 168:2) prepolymerization reaction of 45min is carried out under conditions of 260 DEG C, 150Pa
Be made inherent viscosity be 0.13dL/g precondensation product, wherein prepolymerization reaction stir speed (S.S.) be 19rpm stirring under into
The addition of the mixture of row, phosphoric acid and phosphorous acid is the 0.05wt% of addition terephthalic acid (TPA) in step (1), antioxidant
1010 with the 0.01wt% that the addition of the mixture of antioxidant 168 is addition terephthalic acid (TPA) in step (1)；
(3) final polycondensation reaction；
Life is made in the final polycondensation reaction that precondensation product made from step (2) carries out 1.5h under conditions of 250 DEG C, 30Pa
Object base 2,5-furandicarboxylic acid base copolyesters, wherein final polycondensation reaction are carried out in the case where stir speed (S.S.) is the stirring of 10rpm.
The weight average molecular weight breadth coefficient of final biology base 2,5-furandicarboxylic acid base copolyesters obtained is 1.15, characteristic
Viscosity is 0.60dL/g, and the content of color 9, side reaction product is 0.95wt%.It is made into biology base 2,5- furans two
Formyl copolyesters FDY, processing waste silk rate are 9.5kg/t, and the yarn unevenness of fiber is 0.97%.
Claims (10)
1. a kind of preparation method of biology base 2,5-furandicarboxylic acid base copolyesters, it is characterized in that：By binary acid, binary aliphatic
Alcohol I, guiding thing and titanium silicon cobalt composite catalyst carry out esterification, prepolymerization reaction and final polycondensation reaction successively after mixing
Biology base 2,5- furandicarboxylic acid base copolyesters is made；
The guiding thing is that biology base 2,5-furandicarboxylic acid reacts the carboxylate generated, the binary with aliphatic dihydroxy alcohol II
The molar ratio of acid and aliphatic dihydroxy alcohol I are 1:1.05~1.10, the titanium silicon cobalt composite catalyst is titanium silicon composite catalyst
It is combined with cobalt series catalyst, the titanium silicon composite catalyst obtains for silicon systems catalyst carrying catalyst in titanium series, the fat
Fat race dihydric alcohol I and aliphatic dihydroxy alcohol II is identical or different.
2. a kind of preparation method of biology base 2,5-furandicarboxylic acid base copolyesters according to claim 1, feature exist
In content≤1.0wt% of side reaction product in the biology base 2,5-furandicarboxylic acid base copolyesters.
3. a kind of preparation method of biology base 2,5-furandicarboxylic acid base copolyesters according to claim 1, feature exist
In being as follows：
(1) esterification；
After binary acid and aliphatic dihydroxy alcohol I are mixed with beating, titanium silicon cobalt composite catalyst and guiding thing is added 180~240
DEG C and 50~200KPa under conditions of carry out esterification until water yield reaches 95% reaction terminating of theoretical water yield；
(2) prepolymerization reaction；
The agent of heat resistanceheat resistant oxygen and/or antioxidant are added in the product of step (1) in 200~260 DEG C and the condition of 100~1000Pa
The precondensation product of inherent viscosity≤0.15dL/g is made in the lower prepolymerization reaction for carrying out 15~45min；The prepolymerization reaction
Stir speed (S.S.) be 5~20rpm；
(3) final polycondensation reaction；
Precondensation product made from step (2) carries out the final minification of 1.5~3.5h under conditions of 220~280 DEG C and 10~100Pa
Biology base 2,5- furandicarboxylic acid base copolyesters is made in poly- reaction；The stir speed (S.S.) of the final polycondensation reaction is 5~10rpm.
4. a kind of preparation method of biology base 2,5-furandicarboxylic acid base copolyesters according to claim 3, feature exist
In the additive amount of the guiding thing is 0.5~5.0wt% of binary acid additive amount in step (1)；The titanium silicon cobalt composite catalyzing
The additive amount of agent is 100~200ppm of binary acid additive amount in step (1)；Titanium system is catalyzed in the titanium silicon cobalt composite catalyst
The molar ratio of agent, silicon systems catalyst and cobalt series catalyst is 1:0.1~10:0.1~10.
5. a kind of preparation method of biology base 2,5-furandicarboxylic acid base copolyesters according to claim 4, feature exist
In the Titanium series catalyst is butyl titanate or metatitanic acid；The silicon systems catalyst is silica；The cobalt series catalyst
For cobalt acetate.
6. a kind of preparation method of biology base 2,5-furandicarboxylic acid base copolyesters according to claim 1, feature exist
In the esterification yield that biology base 2,5-furandicarboxylic acid reacts generation guiding thing with aliphatic dihydroxy alcohol II is 90~98%；It is described
Binary acid is biology base 2,5- furandicarboxylic acids, terephthalic acid (TPA), M-phthalic acid, succinic acid, glutaric acid, adipic acid, heptan two
One or more of acid, suberic acid, azelaic acid, decanedioic acid；The aliphatic dihydroxy alcohol I and aliphatic dihydroxy alcohol II is respectively second
One kind in glycol, propylene glycol, butanediol, pentanediol, hexylene glycol, heptandiol, ethohexadiol, nonanediol and decanediol.
7. a kind of preparation method of biology base 2,5-furandicarboxylic acid base copolyesters according to claim 3, feature exist
In the addition of the heat resistanceheat resistant oxygen agent is 0.005~0.05wt% of binary acid additive amount in step (1)；The antioxidant
Addition be step (1) in binary acid additive amount 0.001~0.01wt%.
8. a kind of preparation method of biology base 2,5-furandicarboxylic acid base copolyesters according to claim 7, feature exist
In the heat resistanceheat resistant oxygen agent is one or more of phosphoric acid, phosphorous acid, trimethyl phosphate, Trimethyl phosphite and triphenyl phosphate；
The antioxidant is one or more of antioxidant 1010, antioxidant 168 and antioxidant 616.
9. a kind of preparation method of biology base 2,5-furandicarboxylic acid base copolyesters according to claim 1, feature exist
In the weight average molecular weight breadth coefficient of the biology base 2,5-furandicarboxylic acid base copolyesters is 1.2~1.6, and inherent viscosity is
0.60~1.20dL/g, color≤10.
10. a kind of preparation method of biology base 2,5-furandicarboxylic acid base copolyesters according to claim 1, feature exist
In, the biology base 2,5-furandicarboxylic acid base copolyesters is made POY, FDY or DTY, processes waste silk rate≤10kg/t,
Yarn unevenness≤1.0% of fiber.
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