CN108341937A - A kind of polyester and its preparation method and application of biology base carbonate-containing structure - Google Patents
A kind of polyester and its preparation method and application of biology base carbonate-containing structure Download PDFInfo
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- CN108341937A CN108341937A CN201810135031.6A CN201810135031A CN108341937A CN 108341937 A CN108341937 A CN 108341937A CN 201810135031 A CN201810135031 A CN 201810135031A CN 108341937 A CN108341937 A CN 108341937A
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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
- C08G63/64—Polyesters containing both carboxylic ester groups and carbonate groups
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The present invention provides a kind of polyester and its preparation method and application of biology base carbonate-containing structure, which is.Preparation method is first to be reacted under the action of catalyst as raw material with triphosgene using a kind of bio-based monomer in vanillic aldehyde, syringaldehyde or parahydroxyben-zaldehyde, and the dialdehyde monomer of biology base carbonate-containing structure is obtained after reaction product is recrystallized；It is that raw material is reacted with sodium borohydride by dialdehyde monomer, reaction product is recrystallized or crossed the glycol polymerisable monomer that can be obtained biology base carbonate-containing structure after post separation；Glycol polymerisable monomer is reacted under the action of catalyst with acyl chlorides, then instills in anti-solvent and regenerates, washing after purification, obtains the polyester of biology base carbonate-containing structure.The polyester of the present invention is biology base carbonate-containing structure, environmentally friendly；Preparation method is simple, and unharmful substance generates in production, and pollution is small, at low cost.
Description
Technical field
The invention belongs to polymeric material fields, more particularly to a kind of polyester and its system of biology base carbonate-containing structure
Preparation Method and application.
Background technology
Serious energy crisis and environmental problem are resulted in the transition exploitation of fossil resource, ring is synthesized from bio-based monomer
It protects and reproducible bio-based materials increasingly attracts attention as the substitute of petroleum-based products.Bio-based materials are kept away
Dependence of the mankind to fossil resource has been opened, the advantage with low-carbon environment-friendly, however the usage amount of current bio-based materials is also not
The 1% of sufficient high molecular material.Therefore bio-based materials will be one of the important directions of the field of polymers future development.There is research
The petroleum based material the result shows that bio-based materials can match in excellence or beauty completely in performance and in price, some bio-based materials are
Generate economic and social benefit.
Makrolon belongs to polyester, is the high molecular polymer containing carbonate group in strand, according to the structure of ester group
Aliphatic, aromatic series, aliphatic-aromatic three types can be divided into.Wherein due to aliphatic and the poly- carbonic acid of aliphatic-aromatic
The mechanical performance of ester is relatively low, and to limit its application in terms of engineering plastics, and aromatic makrolon is because it is molten
Point is high, and thermal stability is good, and mechanical performance is strong, is widely used in numerous fields.It is industrial at present widely applied
Makrolon is mainly made by phosgenation, cyclic carbonate ring-opening polymerisation method and ester-interchange method.Document
（Macromolecules, 1998, 31(22):7865-7870.）It has been reported that and prepares cyclic annular poly- carbonic acid using phosgene and bisphenol-A
Ester material, but due to the use of phosgene severe toxicity, and a large amount of hydrogen chloride of by-product cause heavy corrosion, working condition to dislike equipment
Bad, pollution is larger, while the polycarbonate molecular weight of its synthesis is smaller, and phosgenation is eliminated substantially.And synthesis of cyclic carbonic acid
The cost of ester is higher, without great industrial application value.Document（Macromolecules, 2013, 46(9):3301- 3308.）It has been reported that and makrolon is prepared by dimethyl carbonate and dihydric alcohol, but this method generates a large amount of methanol and carbonic acid
The azeotropic mixture of dimethyl ester needs to recycle methanol and dimethyl carbonate by complicated processing, causes entirely to prepare poly- carbon
The technique of acid esters glycol is extremely complex, and the organic volatiles such as methanol generated easily pollute environment.
Invention content
The purpose of the present invention is to provide a kind of polyester and its preparation method and application of biology base carbonate-containing structure.This
The polyester of invention is biology base carbonate-containing structure, environmentally friendly；Preparation method is simple, and unharmful substance produces in production
Raw, pollution is small, at low cost.
The technical scheme is that：
A kind of polyester of biology base carbonate-containing structure, structural formula are as follows：
Wherein R, R1For hydrogen or methoxyl group, 1≤n≤1000, R2For one kind in having structure：
1）Alkane：, wherein R3、R4For the halides of proton or any one the position of substitution, alkene, methyl, ethyl, third
Base, isopropyl, methoxyl group, ethyoxyl, nitro, cyano, sulfydryl, hydroxyl or ketone group, 1≤m≤20；
2）Heterochain alkane：, wherein 1≤p≤20；
3）Alkene：, wherein R5、R6For the halides of proton or any one the position of substitution, alkene, methyl, ethyl, third
Base, isopropyl, methoxyl group, ethyoxyl, nitro, cyano, sulfydryl, hydroxyl or ketone group；
4）Cycloalkane-CxH2x-2, 1≤x≤20；
5）Alkynes：- CyH2y-4, wherein 1≤y≤20;
6）Aromatic series：、、、、、、、、、、、Or；
7）Heterocycle：Or。
A kind of preparation method of the polyester of biology base carbonate-containing structure above-mentioned, includes the following steps：
1）Make in catalyst by raw material and triphosgene of a kind of bio-based monomer in vanillic aldehyde, syringaldehyde or parahydroxyben-zaldehyde
With lower reaction, the dialdehyde monomer of biology base carbonate-containing structure is obtained after reaction product is recrystallized；
2）With step 1）The dialdehyde monomer of gained is that raw material is reacted with sodium borohydride, after reaction product is recrystallized or crosses post separation
It can be obtained the glycol polymerisable monomer of biology base carbonate-containing structure；
3）By step 2）The glycol polymerisable monomer of gained reacts under the action of catalyst with acyl chlorides, then instills in anti-solvent again
Raw, washing after purification, obtains the polyester of biology base carbonate-containing structure.
The preparation method of the polyester of biology base carbonate-containing structure above-mentioned, it is specific as follows：
1）It is dissolution of raw material in dichloromethane solution using a kind of bio-based monomer in vanillic aldehyde, syringaldehyde or parahydroxyben-zaldehyde
In, with catalyst：The molar ratio of bio-based monomer is 1.5-1:Organic alkali catalyst is added in 1 ratio, with bio-based monomer：Three
The molar ratio of phosgene is 6：Triphosgene is added in the ratio of 1-2, is reacted 1-10 hours at 0 DEG C -60 DEG C, reaction product is recrystallized
The dialdehyde monomer of biology base carbonate-containing structure is obtained afterwards；
2）By step 1）The dialdehyde monomer of gained and sodium borohydride in molar ratio 1：It is dissolved in tetrahydrofuran solution after 2-4 mixing,
It is reacted 1-24 hours at 0 DEG C -60 DEG C, reaction product is recrystallized or can be obtained biology base carbonate-containing structure after crossing post separation
Glycol polymerisable monomer；
3）By step 2）Glycol polymerisable monomer, acyl chlorides and the organic alkali catalyst of gained in molar ratio 1：1：The ratio of 2-2.5
It is dissolved in tetrahydrofuran solution after mixing, is reacted at 0 DEG C -60 DEG C 1-24 hours, then instill in anti-solvent and regenerate, washing is pure
After change, the polyester of biology base carbonate-containing structure is obtained.
The preparation method of the polyester of biology base carbonate-containing structure above-mentioned, the organic alkali catalyst be Trimethylamine,
Triethylamine, tripropylamine, tri-butylamine, pyridine, N, N- lutidines, 1,8- diazabicylos-bicyclic (5,4,0) -7-
Hendecene, 1,5 1 diazabicylos (4,3,0) -5- nonenes, tri- azabicyclos of 1,5,7- [4.4.0] decyl-, 5 alkene, 1,4- diazas
One or more of two rings [2.2.2] octane, pyrrolidines.
The preparation method of the polyester of biology base carbonate-containing structure above-mentioned, the step 1）In be to use bio-based monomer
Dichloromethane dissolves, and after catalyst is added, the dichloromethane solution of triphosgene is added dropwise under ice bath and intense agitation；Step
2）In be to dissolve dialdehyde monomer with tetrahydrofuran, sodium borohydride is added under ice bath and intense agitation；Step 3）In be
Glycol polymerisable monomer is dissolved in tetrahydrofuran solution, acyl chlorides and catalysis are then added under ice bath and intense agitation
Agent is reacted under nitrogen protection.
The preparation method of the polyester of biology base carbonate-containing structure above-mentioned, the step 1）Recrystallization method be dichloro
Methane/petroleum ether recrystallization；Step 2）Recrystallization or cross post separation method be after being quenched by saturated aqueous ammonium chloride, through second
Acetoacetic ester/petroleum ether recrystallization or with petroleum ether and ethyl acetate by volume 4:Separately add the triethylamine of 1% volume after 1 mixing
Mixed solvent is that eluant, eluent carries out post separation.
The preparation method of the polyester of biology base carbonate-containing structure above-mentioned, the anti-solvent can be selected as ether, first
One or more of alcohol, ethyl alcohol, water.
The preparation method of the polyester of biology base carbonate-containing structure above-mentioned, the step 1）Middle catalyst：Biology base list
The molar ratio of body is 1.25:1；Step 2）The molar ratio of middle dialdehyde monomer and sodium borohydride is 1：3；Step 3）Middle glycol is polymerizable
The molar ratio of monomer, acyl chlorides and organic alkali catalyst is 1：1：2.25.
The preparation method of the polyester of biology base carbonate-containing structure above-mentioned, the step 3）In, acyl chlorides is following substance
One or more of：
1）Aliphatic diacid chloride：, wherein 0≤n≤10,Wherein R, R1It is independent hydrogen or first
Base, 0≤n≤10,Wherein 1≤n≤20；
2）Aromatic diacid chlorides：、、。
A kind of polyester of biology base carbonate-containing structure above-mentioned electronic apparatus, building materials, automobile making, aerospace,
Application in terms of dietetic food packaging and optical material.
Beneficial effects of the present invention：
1, for the present invention using bio-based monomer vanillic aldehyde, syringaldehyde or parahydroxyben-zaldehyde as raw material, abundance is at low cost
Honest and clean, the aromatic group in structure can provide hot property and mechanical performance for material.By being gathered around on the main polymer chain synthesized by it
Have symmetrical rigid structure and structural carbonate, compared with general dihydric alcohol have more excellent hydrolytic resistance, light resistance,
Heat resistance.And it is as a kind of dihydric alcohol of novel biology base carbonate-containing structure, can by being chemically converted to polyester,
Preparation process is simple, at low cost, and pollution is small.
2, the present invention is contained using the glycol polymerisable monomer of the biology base carbonate-containing structure biology base novel as material construction
The polyester material of structural carbonate has better biocompatibility and hypotoxicity than traditional bisphenol-a polycarbonate；
3, the present invention contains carbonic acid using the glycol polymerisable monomer of the biology base carbonate-containing structure biology base novel as material construction
The polyester material of ester structure will be such that the preparation of its derivatization product has latent due to having the groups such as methoxyl group, alkyl on phenyl ring
Application value, bio-based polymers have excellent mechanical performance and hot property, and show various excellent specific properties, such as shape
Shape memory, self-repair function are expected to replace traditional oil based polyalcohol.
By comparing a variety of polyalcohols and methyl diphenylene diisocyanate（MDI）The fundamental characteristics of the polyester material of synthesis
And mechanical performance, details see the table below.
Note：PCDL is the dihydric alcohol of carbonate-containing structure, and PTMG is PolyTHF, and PHA is polyadipate 1,6- oneself two
Acid esters, PCL are polycaprolactone.
The result shows that the polymer of carbonate-containing structure has more than general polyether type polymer, polyester polymer material
Excellent heat resistance, weatherability, hydrolytic resistance and chemical-resistant assigns the better mechanical property of material.
Description of the drawings
Fig. 1 is the infrared spectrum of the polyester for the biology base carbonate-containing structure that glycol is synthesized with succinyl chloride；
Fig. 2 is the infrared spectrum of the glycol of the biology base carbonate-containing structure synthesized by vanillic aldehyde；
Fig. 3 is the hydrogen spectrogram of the glycol of the biology base carbonate-containing structure synthesized by vanillic aldehyde；
Fig. 4 is the carbon spectrogram of the glycol of the biology base carbonate-containing structure synthesized by vanillic aldehyde；
Fig. 5 is the hydrogen spectrogram of the polyester for the biology base carbonate-containing structure that glycol is synthesized with succinyl chloride；
Fig. 6 is the carbon spectrogram of the polyester for the biology base carbonate-containing structure that glycol is synthesized with succinyl chloride；
Fig. 7 is the thermal multigraph of the polyester for the biology base carbonate-containing structure that glycol is synthesized with succinyl chloride；
Fig. 8 is the DSC figures of the polyester for the biology base carbonate-containing structure that glycol is synthesized with succinyl chloride.
Specific implementation mode
Below by specific embodiment, technical scheme of the present invention will be further explained in detail.
In the present invention, if not refering in particular to, used raw material and equipment etc. are commercially available or commonly used in the art,
Wherein dichloromethane, tetrahydrofuran and acyl chlorides, which pass through, removes water process.Method in following embodiments is unless otherwise instructed
The conventional method of this field.
Total embodiment：
Embodiment 1：A kind of preparation method of the polyester of biology base carbonate-containing structure, includes the following steps：
（1）It weighs vanillic aldehyde and triethylamine is dissolved in dichloromethane, the dichloromethane of triphosgene is slowly added dropwise under condition of ice bath
Alkane solution, vanillic aldehyde are 6 with triphosgene and the molar ratio of triethylamine:1:7.5, after being added dropwise to complete, it is gradually increased to react at room temperature
5h, with the dilute hydrochloric acid and water washing of 1mol/L, inorganic phase is extracted with dichloromethane, is spin-dried for solvent, with dichloromethane/n-hexane weight
Crystallize biology base carbonate-containing structure dialdehyde monomer；
（2）Sodium borohydride is added to step by several times under condition of ice bath（1）In obtained biology base carbonate-containing structure
In the tetrahydrofuran solution of dialdehyde monomer, the molar ratio for controlling dialdehyde monomer and sodium borohydride is 1：3, it is gradually risen after being added dropwise to complete
It to room temperature reaction 12h, is quenched with saturated ammonium chloride, is filtered to remove the borate of generation, extracted with ethyl acetate and saturated salt solution
It takes, is spin-dried for solvent, with ethyl acetate/n-hexane recrystallization or petroleum ether and ethyl acetate（Volume ratio is 4:1, separately add 1% volume
Triethylamine）Mixed solvent be eluant, eluent carry out post separation, obtain the glycol polymerisable monomer of biology base carbonate-containing structure；
（3）To step under condition of ice bath（2）In obtained biology base carbonate-containing structure glycol polymerisable monomer and acyl chlorides
Tetrahydrofuran solution in be added dropwise pyridine, the molar ratio of glycol, acyl chlorides and pyridine is 1：1：2.2, it reacts for 24 hours under room temperature in vacuo,
It instills in ether and is collected by centrifugation to obtain polyester.
Embodiment 2：A kind of preparation method of biology base carbonate-containing structure glycol polymerisable monomer, includes the following steps：
（1）Claim syringaldehyde and Trimethylamine to be dissolved in dichloromethane, the dichloromethane of triphosgene is slowly added dropwise under condition of ice bath
Solution, syringaldehyde are 6 with triphosgene and the molar ratio of Trimethylamine:1:6, after being added dropwise to complete, it is gradually increased to room temperature reaction 1h, is used
The dilute hydrochloric acid and water washing of 1mol/L, inorganic phase are extracted with dichloromethane, are spin-dried for solvent, are recrystallized with dichloromethane/n-hexane
Obtain the dialdehyde monomer of biology base carbonate-containing structure；
（2）Sodium borohydride is added to step by several times under condition of ice bath（1）In obtained biology base carbonate-containing structure
In the tetrahydrofuran solution of dialdehyde monomer, the molar ratio for controlling dialdehyde monomer and sodium borohydride is 1：2, it is gradually risen after being added dropwise to complete
It to room temperature reaction 1h, is quenched with saturated ammonium chloride, is filtered to remove the borate of generation, extracted with ethyl acetate and saturated salt solution
It takes, is spin-dried for solvent, with ethyl acetate/n-hexane recrystallization or petroleum ether and ethyl acetate（Volume ratio is 4:1, separately add 1% volume
Triethylamine）Mixed solvent be eluant, eluent carry out post separation, obtain the glycol polymerisable monomer of biology base carbonate-containing structure；
（3）To step under condition of ice bath（2）In obtained biology base carbonate-containing structure glycol polymerisable monomer and acyl chlorides
Tetrahydrofuran solution in be added dropwise pyridine, the molar ratio of glycol, acyl chlorides and pyridine is 1：1：12h is reacted under 2,0 DEG C of vacuum, is instilled
It is collected by centrifugation to obtain polyester in ethyl alcohol.
Embodiment 3：A kind of preparation method of biology base carbonate-containing structure glycol polymerisable monomer, includes the following steps：
（1）It weighs vanillic aldehyde and triethylamine is dissolved in dichloromethane, the dichloromethane of triphosgene is slowly added dropwise under condition of ice bath
Alkane solution, vanillic aldehyde are 6 with triphosgene and the molar ratio of triethylamine:1:9, after being added dropwise to complete, it is gradually increased to react at room temperature
10h, with the dilute hydrochloric acid and water washing of 1mol/L, inorganic phase is extracted with dichloromethane, is spin-dried for solvent, with dichloromethane/n-hexane
Recrystallize biology base carbonate-containing structure dialdehyde monomer；
（2）Sodium borohydride is added to step by several times under condition of ice bath（1）In obtained biology base carbonate-containing structure
In the tetrahydrofuran solution of dialdehyde monomer, the molar ratio for controlling dialdehyde monomer and sodium borohydride is 1：4, it is gradually risen after being added dropwise to complete
For 24 hours to room temperature reaction, it is quenched with saturated ammonium chloride, is filtered to remove the borate of generation, extracted with ethyl acetate and saturated salt solution
It takes, is spin-dried for solvent, with ethyl acetate/n-hexane recrystallization or petroleum ether and ethyl acetate（Volume ratio is 4:1, separately add 1% volume
Triethylamine）Mixed solvent be eluant, eluent carry out post separation, obtain the glycol polymerisable monomer of biology base carbonate-containing structure；
（3）To step under condition of ice bath（2）In obtained biology base carbonate-containing structure glycol polymerisable monomer and acyl chlorides
Tetrahydrofuran solution in be added dropwise pyridine, the molar ratio of glycol, acyl chlorides and pyridine is 1：1：1h is reacted under 2.5,60 DEG C of vacuum, is dripped
Enter and is collected by centrifugation to obtain polyester in water.
Following instance helps to understand this patent.
Embodiment 4：
Weigh vanillic aldehyde 9.13g（0.06 mole）, triethylamine 10.5ml（0.075 mole）In single-necked flask, 100ml bis- is added
Chloromethanes dissolves, and triphosgene 2.97g is slowly added dropwise under condition of ice bath（0.01 mole）Dichloromethane solution, be added dropwise to complete
Afterwards, it is gradually increased to room temperature reaction 2h, with the dilute hydrochloric acid and water washing of 1mol/L.Inorganic phase is extracted with dichloromethane, is spin-dried for solvent,
White solid carbonic acid two (2- methoxyl group -4- aldehyde radicals phenyl) ester is obtained with n-hexane-recrystallize with dichloromethane, vacuum drying for 24 hours, is produced
Rate 93%；
Weigh carbonic acid two (2- methoxyl group -4- aldehyde radicals phenyl) ester 6.606g（0.02 mole）In twoport flask, it is dissolved in
In 100ml tetrahydrofuran solutions, sodium borohydride 2.27g is added in batches under condition of ice bath（0.06 mole）, it is gradually increased to room
Temperature reaction 8h, is quenched with saturated ammonium chloride, is filtered to remove the borate of generation, extracted with ethyl acetate and saturated salt solution, rotation
Dry solvent, with recrystallization from ethyl acetate/petroleum ether or petroleum ether and ethyl acetate（Volume ratio is 4:1, another plus 1% volume three second
Amine）Mixed solvent be eluant, eluent carry out post separation.Vacuum drying for 24 hours, obtains the glycol of biology base carbonate-containing structure, yield
86%.Its infrared, nuclear-magnetism is shown in attached drawing 2,3,4；
To the glycol 0.669g of stirring under condition of ice bath（2.0mmol）With succinyl chloride 224ul（2.0mmol）THF solution in
Pyridine 354ul is added dropwise（4.4mmol）THF solution, reaction for 24 hours, instill cold ether in precipitation be collected by centrifugation to obtain polyester, use first
Alcohol washs three times, is dried in vacuo for 24 hours, yield 78%.Product is that solvent carries out GPC tests by n,N-Dimethylformamide, is obtained
Number-average molecular weight is 7925.Its infrared, nuclear-magnetism, thermogravimetric, DSC are shown in attached drawing 1,5,6,7,8.
Above-mentioned embodiment is only a preferred solution of the present invention, not the present invention is made in any form
Limitation, on the premise of not exceeding the technical scheme recorded in the claims also other variations and modifications.
Claims (10)
1. a kind of polyester of biology base carbonate-containing structure, which is characterized in that its structural formula is as follows：
Wherein R, R1For hydrogen or methoxyl group, 1≤n≤1000, R2For one kind in having structure：
1）Alkane：, wherein R3、R4For the halides of proton or any one the position of substitution, alkene, methyl, ethyl, propyl,
Isopropyl, methoxyl group, ethyoxyl, nitro, cyano, sulfydryl, hydroxyl or ketone group, 1≤m≤20；
2）Heterochain alkane：, wherein 1≤p≤20；
3）Alkene：, wherein R5、R6For the halides of proton or any one the position of substitution, alkene, methyl, ethyl, third
Base, isopropyl, methoxyl group, ethyoxyl, nitro, cyano, sulfydryl, hydroxyl or ketone group；
4）Cycloalkane-CxH2x-2, 1≤x≤20；
5）Alkynes：- CyH2y-4, wherein 1≤y≤20;
6）Aromatic series：、、、、、、、、、、、Or；
7）Heterocycle：Or。
2. a kind of preparation method of the polyester of biology base carbonate-containing structure according to claim 1, which is characterized in that packet
Include following steps：
1）Make in catalyst by raw material and triphosgene of a kind of bio-based monomer in vanillic aldehyde, syringaldehyde or parahydroxyben-zaldehyde
With lower reaction, the dialdehyde monomer of biology base carbonate-containing structure is obtained after reaction product is recrystallized；
2）With step 1）The dialdehyde monomer of gained is that raw material is reacted with sodium borohydride, after reaction product is recrystallized or crosses post separation
It can be obtained the glycol polymerisable monomer of biology base carbonate-containing structure；
3）By step 2）The glycol polymerisable monomer of gained reacts under the action of catalyst with acyl chlorides, then instills in anti-solvent again
Raw, washing after purification, obtains the polyester of biology base carbonate-containing structure.
3. the preparation method of the polyester of biology base carbonate-containing structure according to claim 2, which is characterized in that specifically such as
Under：
1）It is dissolution of raw material in dichloromethane solution using a kind of bio-based monomer in vanillic aldehyde, syringaldehyde or parahydroxyben-zaldehyde
In, with catalyst：The molar ratio of bio-based monomer is 1.5-1:Organic alkali catalyst is added in 1 ratio, with bio-based monomer：Three
The molar ratio of phosgene is 6：Triphosgene is added in the ratio of 1-2, is reacted 1-10 hours at 0 DEG C -60 DEG C, reaction product is recrystallized
The dialdehyde monomer of biology base carbonate-containing structure is obtained afterwards；
2）By step 1）The dialdehyde monomer of gained and sodium borohydride in molar ratio 1：It is dissolved in tetrahydrofuran solution after 2-4 mixing,
It is reacted 1-24 hours at 0 DEG C -60 DEG C, reaction product is recrystallized or can be obtained biology base carbonate-containing structure after crossing post separation
Glycol polymerisable monomer；
3）By step 2）Glycol polymerisable monomer, acyl chlorides and the organic alkali catalyst of gained in molar ratio 1：1：The ratio of 2-2.5
It is dissolved in tetrahydrofuran solution after mixing, is reacted at 0 DEG C -60 DEG C 1-24 hours, then instill in anti-solvent and regenerate, washing is pure
After change, the polyester of biology base carbonate-containing structure is obtained.
4. the preparation method of the polyester of biology base carbonate-containing structure according to claim 2 or 3, it is characterised in that：Institute
It is Trimethylamine, triethylamine, tripropylamine, tri-butylamine, pyridine, N, N- lutidines, 1,8- to state organic alkali catalyst
Bicyclic (5,4, the 0) -7- hendecenes of diazabicylo -, 1,5 one diazabicylo (4,3,0) -5- nonenes, 1,5,7- tri- azepines are double
One or more of 5 alkene of ring [4.4.0] decyl-, 1,4- diazabicylos [2.2.2] octane, pyrrolidines.
5. the preparation method of the polyester of biology base carbonate-containing structure according to claim 2 or 3, it is characterised in that：Institute
State step 1）In be to dissolve bio-based monomer with dichloromethane, be added catalyst after, dripped under ice bath and intense agitation
Add the dichloromethane solution of triphosgene；Step 2）In be to dissolve dialdehyde monomer with tetrahydrofuran, ice bath and be vigorously stirred item
Sodium borohydride is added under part；Step 3）In be that glycol polymerisable monomer is dissolved in tetrahydrofuran solution, then in ice bath and
Acyl chlorides and catalyst are added under intense agitation, is reacted under nitrogen protection.
6. the preparation method of the polyester of biology base carbonate-containing structure according to claim 2 or 3, it is characterised in that：Institute
State step 1）Recrystallization method be dichloromethane/petroleum ether recrystallization；Step 2）Recrystallization or cross post separation method be by
After saturated aqueous ammonium chloride quenching, through recrystallization from ethyl acetate/petroleum ether or with petroleum ether and ethyl acetate by volume 4:1
It is that eluant, eluent carries out post separation separately to add the mixed solvent of the triethylamine of 1% volume after mixing.
7. the preparation method of the polyester of biology base carbonate-containing structure according to claim 2 or 3, it is characterised in that：Institute
One or more of ether, methanol, ethyl alcohol, water can be selected as by stating anti-solvent.
8. the preparation method of the polyester of biology base carbonate-containing structure according to claim 2 or 3, it is characterised in that：Institute
State step 1）Middle catalyst：The molar ratio of bio-based monomer is 1.25:1；Step 2）Mole of middle dialdehyde monomer and sodium borohydride
Than being 1：3；Step 3）The molar ratio of middle glycol polymerisable monomer, acyl chlorides and organic alkali catalyst is 1：1：2.25.
9. the preparation method of the polyester of biology base carbonate-containing structure according to claim 2 or 3, it is characterised in that：Institute
State step 3）In, acyl chlorides is one or more of following substance：
1）Aliphatic diacid chloride：, wherein 0≤n≤10,Wherein R, R1It is independent hydrogen or first
Base, 0≤n≤10,Wherein 1≤n≤20；
2）Aromatic diacid chlorides：、、。
10. a kind of polyester according to claim 1-9 any one of them biology base carbonate-containing structures in electronic apparatus, build
Application in terms of material, automobile making, aerospace, dietetic food packaging and optical material.
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| CN201810135031.6A CN108341937B (en) | 2018-02-09 | 2018-02-09 | Bio-based polyester containing carbonate structure and preparation method and application thereof |
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| CN201810135031.6A CN108341937B (en) | 2018-02-09 | 2018-02-09 | Bio-based polyester containing carbonate structure and preparation method and application thereof |
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| CN108341937A true CN108341937A (en) | 2018-07-31 |
| CN108341937B CN108341937B (en) | 2020-08-07 |
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| CN109438687A (en) * | 2018-10-31 | 2019-03-08 | 武汉科技大学 | A kind of bridge chain structure biology base polyester, preparation method and applications |
| CN110183328A (en) * | 2019-05-30 | 2019-08-30 | 贵州大学 | One kind diene monomers containing carboxylate structure and its polyester and sulfur-bearing polyester |
| CN110540529A (en) * | 2019-03-26 | 2019-12-06 | 贵州大学 | Dihydric alcohol-based carbonate polymerizable monomer and polymer thereof |
| CN113817153A (en) * | 2021-09-30 | 2021-12-21 | 大连理工大学 | Cyano-functionalized carbonate monomer, cyano-functionalized polycarbonate and preparation method |
| CN115772258A (en) * | 2022-11-24 | 2023-03-10 | 江南大学 | Preparation method of intrinsic degradable bioactive polyester |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109438687A (en) * | 2018-10-31 | 2019-03-08 | 武汉科技大学 | A kind of bridge chain structure biology base polyester, preparation method and applications |
| CN110540529A (en) * | 2019-03-26 | 2019-12-06 | 贵州大学 | Dihydric alcohol-based carbonate polymerizable monomer and polymer thereof |
| CN110540529B (en) * | 2019-03-26 | 2023-01-24 | 贵州大学 | Dihydric alcohol-based carbonate polymerizable monomer and polymer thereof |
| CN110183328A (en) * | 2019-05-30 | 2019-08-30 | 贵州大学 | One kind diene monomers containing carboxylate structure and its polyester and sulfur-bearing polyester |
| CN113817153A (en) * | 2021-09-30 | 2021-12-21 | 大连理工大学 | Cyano-functionalized carbonate monomer, cyano-functionalized polycarbonate and preparation method |
| CN115772258A (en) * | 2022-11-24 | 2023-03-10 | 江南大学 | Preparation method of intrinsic degradable bioactive polyester |
| CN115772258B (en) * | 2022-11-24 | 2024-04-30 | 江南大学 | Preparation method of intrinsic type degradable bioactive polyester |
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