CN107698745A - A kind of synthetic method of copolyesters - Google Patents
A kind of synthetic method of copolyesters Download PDFInfo
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- CN107698745A CN107698745A CN201711059048.XA CN201711059048A CN107698745A CN 107698745 A CN107698745 A CN 107698745A CN 201711059048 A CN201711059048 A CN 201711059048A CN 107698745 A CN107698745 A CN 107698745A
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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
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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
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Abstract
The invention belongs to be copolymerized Lipase absobed field, and in particular to a kind of synthetic method of copolyesters.The present invention obtains the brand-new degradable copolyester of structure by the copolyreaction of organocatalysis hydroxy acryl acid ester and the class monomer of cyclic monomer two.Wherein hydroxy acryl acid ester monomer includes hydroxy-ethyl acrylate and hydroxyethyl methacrylate and its derivative;Cyclic monomer includes epoxy monomer and lactone monomer.Epoxy monomer such as oxirane, expoxy propane, allyl glycidyl ether etc., lactone monomer include butyrolactone, caprolactone, lactide etc..The polymerization methodses of hydroxy acrylate and unconventional vinyl addition in this method, but carried out by way of proton translocation, so as to obtain the polyester with special construction.This method raw material is easy to get and economic and environment-friendly, and reaction condition is gentle, and reaction rate is fast, difference in functionality group can be incorporated among polyester, expand its application, has good application prospect.
Description
Technical field
The invention belongs to be copolymerized Lipase absobed field, and in particular to a kind of synthetic method of copolyesters.
Background technology
In recent years plastics, rubber and fiber be widely used in life to people bring huge convenient while, also to ring
Border causes huge pressure.Development degradable high polymer material is the important channel for solving these white pollutions.
Aliphatic polyester is a kind of important bio-compatible and environmentally friendly material, is most widely used degradable material
One of material.At present, aliphatic polyester synthetic method is mainly two kinds of polycondensation reaction and ring-opening polymerization.Polycondensation reaction is polymerizeing
During can produce hydrone accessory substance, hardly result in heavy polymer.Though ring-opening polymerization can obtain HMW
Polymer, but monomer available limitednumber, and rarely have the report of copolyreaction.Therefore the method for seeking new polyester synthesis is compeled
The eyebrows and eyelashes.
The present invention is obtained by the copolyreaction of organocatalysis hydroxy acryl acid ester and the class monomer of cyclic monomer two
The degradable copolyester brand-new to structure.Wherein hydroxy acryl acid ester monomer includes hydroxy-ethyl acrylate, hydroxyethyl methacrylate
Ethyl ester, hydroxypropyl acrylate etc. and its derivative;Cyclic monomer includes epoxy monomer and lactone monomer.Epoxy monomer is such as
Oxirane, expoxy propane, propyl glycidyl ether etc., lactone monomer include butyrolactone, caprolactone, lactide etc..We
The polymerization methodses of hydroxy acryl acid ester and unconventional vinyl addition progress in method, but entered by way of proton translocation
OK, resulting polymers are not conventional ethylene based polyalcohol yet, but degradable polyester.This method raw material is easy to get, reaction condition temperature
With, reaction rate is fast, and raw material economics environmental protection, and monomer use range is wide, and difference in functionality group can be incorporated among polyester,
The application of polyester is expanded, there is good application prospect.
The content of the invention
The purpose of the present invention is the deficiency for existing polyester synthesis method, there is provided a kind of method for being copolymerized Lipase absobed.
To achieve the above object, the present invention adopts the following technical scheme that:A kind of method for being copolymerized Lipase absobed, according to following steps
It is rapid to carry out:Using organic molecule as catalyst, hydroxy acryl acid ester and cyclic monomer are monomer, in setting polymeric reaction temperature
Lower progress body or polymerisation in solution, degradable copolyester is obtained after precipitating, filter, drying etc. and post-process.
Wherein described copolymerization mode can occur between different hydroxy acryl acid esters, may also occur at hydroxyl third
Olefin(e) acid ester is between cyclic monomer.
Wherein described hydroxyl vinyl monomer includes hydroxy-ethyl acrylate, hydroxyethyl methacrylate, acrylic acid hydroxypropyl
Ester etc. and its derivative.
Wherein described cyclic monomer includes epoxy monomer and lactone monomer.Epoxy monomer such as oxirane, epoxy
Propane, allyl glycidyl ether etc., lactone monomer include butyrolactone, caprolactone, lactide etc..
Wherein described catalyst is organic micromolecule catalyst, including phosphine nitrile alkali, heterocycle carbine, guanidine etc..
Wherein described polymeric reaction temperature is -20-100 DEG C, and polymerization reaction time is 0.5~12 hour.
Wherein described polymerisation uses polymerisation in bulk or polymerisation in solution;Wherein polymerisation in solution solvent for use be toluene,
Any one in tetrahydrofuran, dichloromethane etc. or two or more mixtures.
The present invention has following advantages compared with prior art:
1) by vinyl monomer and cyclic monomer by way of copolymerization the brand-new degradable copolyester of preparation structure.
2) suitable monomers species is various and has commercial prod, the copolyesters structure-rich of preparation, can introduce a variety of anti-
Answering property group.
3) polymeric reaction condition is gentle:Range of reaction temperature is wide, used catalyst not metal ion, is easily eliminated, no
Influence final polymer property.
4) polymerization rate is fast:Generally when reaction is carried out 30 minutes, monomer conversion is just close to 100%.
Brief description of the drawings
Fig. 1 is the nucleus magnetic hydrogen spectrum figure of the resulting polymers of embodiment 1.Its proportioning is [hydroxy-ethyl acrylate]:[caprolactone]:
[phosphine nitrile alkali P2]=20:80:1.
Fig. 2 is the gel permeation chromatography figure of the resulting polymers of embodiment 1.Its proportioning is [hydroxy-ethyl acrylate]:[in oneself
Ester]:[phosphine nitrile alkali P2]=20:80:1.Institute's number average molecular weight is 8300g/mol, molecular weight distribution 1.73.
Embodiment
With reference to example, the present invention will be further described, but is not limited only to following examples, for not noting especially
Bright technological parameter, it can refer to routine techniques progress.
Embodiment 1
0.2g (1.7mmol) pi-allyl hydroxyl ethyl esters and 0.8g (7.0mmol) caprolactone is taken to insert the 10mL circles with rotor
In the flask of bottom, 1g tetrahydrofurans are then added as solvent, liquid nitrogen frozen, after replacing argon gas three times, add 43.8 μ l
(0.09mmol) phosphine nitrile alkali P2.Reaction is placed in 60 DEG C of oil bath pans, reacts 0.5h.After reaction terminates, dissolved with tetrahydrofuran
Reaction product, terminated with methanol, then precipitation obtains white product in 50mL n-hexanes, 12h is dried in vacuo at 30 DEG C, wherein third
The conversion ratio of olefin(e) acid hydroxyl ethyl ester is up to 97.5%, and the conversion ratio of caprolactone is up to 99.8%.Its number-average molecular weight is 8300g/mol, point
Son amount is distributed as 1.73, sees the nucleus magnetic hydrogen spectrum and gel permeation chromatography figure of Fig. 2 products therefroms, it can be seen that polymer is not carried out
Conventional vinyl polymerize, but by the polymerization methodses of proton translocation come what is carried out, form with pi-allyl hydroxyl ethyl ester and oneself
Ester is the polymer of main chain.
Embodiment 2
0.2g (1.7mmol) pi-allyl hydroxyl ethyl esters and 0.8g (7.0mmol) caprolactone is taken to insert the 10mL circles with rotor
In the flask of bottom, 1g tetrahydrofurans are then added as solvent, liquid nitrogen frozen, after replacing argon gas three times, add 43.8 μ l
(0.09mmol) phosphine nitrile alkali P2.Reaction is placed in 60 DEG C of oil bath pans, reacts 12h.After reaction terminates, dissolved with tetrahydrofuran anti-
Product is answered, is terminated with methanol, then precipitation obtains white product in 50mL n-hexanes, and 12h, wherein propylene are dried in vacuo at 30 DEG C
The conversion ratio of sour hydroxyl ethyl ester is up to 98.5%, and the conversion ratio of caprolactone is up to 99.9%.Its number-average molecular weight is 8500g/mol, molecule
Amount is distributed as 1.79, by the nucleus magnetic hydrogen spectrum and gel permeation chromatography figure of products therefrom, it can be seen that polymer does not carry out tradition
Vinyl polymerization, but by the polymerization methodses of proton translocation come what is carried out, form using pi-allyl hydroxyl ethyl ester and caprolactone as
The polymer of main chain.
Embodiment 3
0.2g (1.7mmol) pi-allyl hydroxyl ethyl esters and 0.8g (7.0mmol) caprolactone is taken to insert the 10mL circles with rotor
In the flask of bottom, 1g tetrahydrofurans are then added as solvent, liquid nitrogen frozen, after replacing argon gas three times, add 43.8 μ l
(0.09mmol) phosphine nitrile alkali P2.Reaction is placed in -20 DEG C of cryogenic thermostat baths, reacts 1h.It is molten with tetrahydrofuran after reaction terminates
Reaction product is solved, is terminated with methanol, then precipitation obtains white product in 50mL n-hexanes, and 12h is dried in vacuo at 30 DEG C, wherein
The conversion ratio of hydroxy-ethyl acrylate is up to 82.3%, and the conversion ratio of caprolactone is up to 88.2%.Its number-average molecular weight is 7100g/mol,
Molecular weight distribution is 1.67, by the nucleus magnetic hydrogen spectrum and gel permeation chromatography figure of products therefrom, it can be seen that polymer is not carried out
Conventional vinyl polymerize, but by the polymerization methodses of proton translocation come what is carried out, form with pi-allyl hydroxyl ethyl ester and oneself
Ester is the polymer of main chain.
Embodiment 4
0.2g (1.7mmol) pi-allyl hydroxyl ethyl esters and 0.8g (7.0mmol) caprolactone is taken to insert the 10mL circles with rotor
In the flask of bottom, 1g tetrahydrofurans are then added as solvent, liquid nitrogen frozen, after replacing argon gas three times, add 43.8 μ l
(0.09mmol) phosphine nitrile alkali P2.Reaction is placed in 100 DEG C of oil bath pans, reacts 1h.After reaction terminates, dissolved with tetrahydrofuran anti-
Product is answered, is terminated with methanol, then precipitation obtains white product in 50mL n-hexanes, and 12h, wherein propylene are dried in vacuo at 30 DEG C
The conversion ratio of sour hydroxyl ethyl ester is up to 99.3%, and the conversion ratio of caprolactone is up to 99.8%.Its number-average molecular weight is 9100g/mol, molecule
Amount is distributed as 1.87, by the nucleus magnetic hydrogen spectrum and gel permeation chromatography figure of products therefrom, it can be seen that polymer does not carry out tradition
Vinyl polymerization, but by the polymerization methodses of proton translocation come what is carried out, form using pi-allyl hydroxyl ethyl ester and caprolactone as
The polymer of main chain.
Embodiment 5
0.2g (1.7mmol) pi-allyl hydroxyl ethyl esters and 0.8g (7.0mmol) caprolactone is taken to insert the 10mL circles with rotor
In the flask of bottom, 1g tetrahydrofurans are then added as solvent, liquid nitrogen frozen, after replacing argon gas three times, add 0.024g
(0.09mmol) ring nitrogen carbone catalyst TPT.Reaction is placed in 100 DEG C of oil bath pans, reacts 1h.After reaction terminates, tetrahydrochysene is used
Furans dissolves reaction product, is terminated with methanol, then precipitation obtains white product in 50mL n-hexanes, is dried in vacuo at 30 DEG C
12h, wherein hydroxy-ethyl acrylate conversion ratio are up to 94.3%, and the conversion ratio of caprolactone is up to 97.5%.Its number-average molecular weight is
8500g/mol, molecular weight distribution 1.67, by the nucleus magnetic hydrogen spectrum and gel permeation chromatography figure of products therefrom, it can be seen that polymerization
Thing does not carry out conventional vinyl polymerization, but is formd by the polymerization methodses of proton translocation come what is carried out with pi-allyl hydroxyl
Ethyl ester and the polymer that caprolactone is main chain.
Embodiment 6
0.2g (1.7mmol) pi-allyl hydroxyl ethyl esters and 0.8g (7.0mmol) caprolactone is taken to insert the 10mL circles with rotor
In the flask of bottom, 1g tetrahydrofurans are then added as solvent, liquid nitrogen frozen, after replacing argon gas three times, add 0.012g
(0.09mmol) bicyclo guanidine TBD.Reaction is placed in 100 DEG C of oil bath pans, reacts 1h.After reaction terminates, dissolved with tetrahydrofuran
Reaction product, terminated with methanol, then precipitation obtains white product in 50mL n-hexanes, 12h is dried in vacuo at 30 DEG C, wherein third
The conversion ratio of olefin(e) acid hydroxyl ethyl ester is up to 97.2%, and the conversion ratio of caprolactone is up to 96.3%.Its number-average molecular weight is 8900g/mol, point
Son amount is distributed as 1.80, by the nucleus magnetic hydrogen spectrum and gel permeation chromatography figure of products therefrom, it can be seen that polymer is not passed
System vinyl polymerization, but formd by the polymerization methodses of proton translocation come what is carried out with pi-allyl hydroxyl ethyl ester and caprolactone
For the polymer of main chain.
Embodiment 7
0.22g (1.7mmol) hydroxyethyl methacrylates and 0.8g (7.0mmol) caprolactone is taken to insert with rotor
In 10mL round-bottomed flasks, 1g tetrahydrofurans are then added as solvent, liquid nitrogen frozen, after replacing argon gas three times, add 43.8 μ l
(0.09mmol) phosphine nitrile alkali P2.Reaction is placed in 60 DEG C of oil bath pans, reacts 1h.After reaction terminates, dissolved with tetrahydrofuran anti-
Product is answered, is terminated with methanol, then precipitation obtains white product in 50mL n-hexanes, and 12h, wherein propylene are dried in vacuo at 30 DEG C
The conversion ratio of sour hydroxyl ethyl ester is up to 97.5%, and the conversion ratio of caprolactone is up to 98.8%.Its number-average molecular weight is 10100g/mol, molecule
Amount is distributed as 1.97, by the nucleus magnetic hydrogen spectrum and gel permeation chromatography figure of products therefrom, it can be seen that polymer does not carry out tradition
Vinyl polymerization, but by the polymerization methodses of proton translocation come what is carried out, form with hydroxyethyl methacrylate and oneself
Ester is the polymer of main chain.
Embodiment 8
0.22g (1.7mmol) hydroxypropyl acrylates and 0.8g (7.0mmol) caprolactone is taken to insert the 10mL circles with rotor
In the flask of bottom, 1g tetrahydrofurans are then added as solvent, liquid nitrogen frozen, after replacing argon gas three times, add 43.8 μ l
(0.09mmol) phosphine nitrile alkali P2.Reaction is placed in 60 DEG C of oil bath pans, reacts 1h.After reaction terminates, dissolved with tetrahydrofuran anti-
Product is answered, is terminated with methanol, then precipitation obtains white product in 50mL n-hexanes, and 12h, wherein propylene are dried in vacuo at 30 DEG C
The conversion ratio of sour hydroxyl ethyl ester is up to 98.9%, and the conversion ratio of caprolactone is up to 99.2%.Its number-average molecular weight is 8800g/mol, molecule
Amount is distributed as 1.83, by the nucleus magnetic hydrogen spectrum and gel permeation chromatography figure of products therefrom, it can be seen that polymer does not carry out tradition
Vinyl polymerization, but by the polymerization methodses of proton translocation come what is carried out, form using pi-allyl hydroxypropyl acrylate and caprolactone as
The polymer of main chain.
Embodiment 9
0.2g (1.7mmol) pi-allyl hydroxyl ethyl esters and 0.6g (7.0mmol) butyrolactone is taken to insert the 10mL circles with rotor
In the flask of bottom, 1g tetrahydrofurans are then added as solvent, liquid nitrogen frozen, after replacing argon gas three times, add 43.8 μ l
(0.09mmol) phosphine nitrile alkali P2.Reaction is placed in 60 DEG C of oil bath pans, reacts 1h.After reaction terminates, dissolved with tetrahydrofuran anti-
Product is answered, is terminated with methanol, then precipitation obtains white product in 50mL n-hexanes, and 12h, wherein propylene are dried in vacuo at 30 DEG C
The conversion ratio of sour hydroxyl ethyl ester is up to 94.3%, and the conversion ratio of butyrolactone is up to 89.5%.Its number-average molecular weight is 6800g/mol, molecule
Amount is distributed as 1.97, by the nucleus magnetic hydrogen spectrum and gel permeation chromatography figure of products therefrom, it can be seen that polymer does not carry out tradition
Vinyl polymerization, but by the polymerization methodses of proton translocation come what is carried out, form using pi-allyl hydroxyl ethyl ester and butyrolactone as
The polymer of main chain.
Embodiment 10
0.2g (1.7mmol) pi-allyl hydroxyl ethyl esters and 1.0g (7.0mmol) lactide is taken to insert the 10mL circles with rotor
In the flask of bottom, 1.2g tetrahydrofurans are then added as solvent, liquid nitrogen frozen, after replacing argon gas three times, add 43.8 μ l
(0.09mmol) phosphine nitrile alkali P2.Reaction is placed in 60 DEG C of oil bath pans, reacts 1h.After reaction terminates, dissolved with tetrahydrofuran anti-
Product is answered, is terminated with methanol, then precipitation obtains white product in 50mL n-hexanes, and 12h, wherein propylene are dried in vacuo at 30 DEG C
The conversion ratio of sour hydroxyl ethyl ester is up to 95.3%, and the conversion ratio of butyrolactone is up to 99.5%.Its number-average molecular weight is 9800g/mol, molecule
Amount is distributed as 2.23, by the nucleus magnetic hydrogen spectrum and gel permeation chromatography figure of products therefrom, it can be seen that polymer does not carry out tradition
Vinyl polymerization, but by the polymerization methodses of proton translocation come what is carried out, form using pi-allyl hydroxyl ethyl ester and butyrolactone as
The polymer of main chain.
Embodiment 11
0.22g (1.7mmol) pi-allyl hydroxypropyl acrylates and 0.2g (3.4mmol) expoxy propane is taken to insert the 10mL with rotor
In round-bottomed flask, 0.6g tetrahydrofurans are then added as solvent, liquid nitrogen frozen, after replacing argon gas three times, add 43.8 μ l
(0.09mmol) phosphine nitrile alkali P2.Reaction is placed in 60 DEG C of oil bath pans, reacts 1h.After reaction terminates, dissolved with tetrahydrofuran anti-
Product is answered, is terminated with methanol, then precipitation obtains white product in 50mL n-hexanes, the conversion ratio of wherein hydroxy-ethyl acrylate reaches
93.5%, the conversion ratio of expoxy propane is up to 79.8%.Its number-average molecular weight is 3480g/mol, molecular weight distribution 1.99, by institute
Obtain the nucleus magnetic hydrogen spectrum and gel permeation chromatography figure of product, it can be seen that polymer does not carry out conventional vinyl polymerization, but logical
The polymerization methodses of proton translocation are crossed come what is carried out, form the polyester ether using pi-allyl hydroxyl ethyl ester and expoxy propane as main chain.
Embodiment 12
0.2g (1.7mmol) pi-allyl hydroxyl ethyl esters and 0.2g (1.7mmol) allyl glycidyl ether is taken to insert to carry and turn
In the 10mL round-bottomed flasks of son, 0.4g tetrahydrofurans are then added as solvent, liquid nitrogen frozen, after replacing argon gas three times, are added
43.8 μ l (0.09mmol) phosphine nitrile alkali P2.Reaction is placed in 60 DEG C of oil bath pans, reacts 1h.After reaction terminates, tetrahydrofuran is used
Reaction product is dissolved, is terminated with methanol, then precipitation obtains light yellow product in 50mL n-hexanes, wherein hydroxy-ethyl acrylate
Conversion ratio is up to 93.5%, and the conversion ratio of allyl glycidyl ether is up to 85.6%.Its number-average molecular weight is 3670g/mol, molecule
Amount is distributed as 2.43, by the nucleus magnetic hydrogen spectrum and gel permeation chromatography figure of products therefrom, it can also be seen that polymer is not carried out
Conventional vinyl polymerize, but by the polymerization methodses of proton translocation come what is carried out, form side chain and contain the poly- of pendency double bond
Ester ether.
Embodiment 13
0.2g (1.7mmol) pi-allyl hydroxyl ethyl esters and 0.8g (7.0mmol) caprolactone is taken to insert the 10mL circles with rotor
In the flask of bottom, not solubilizer, then liquid nitrogen frozen, displacement argon gas three times after, add 43.8 μ l (0.09mmol) phosphine nitrile alkali P2.Will
Reaction is placed in 60 DEG C of oil bath pans, reacts 1h.After reaction terminates, reaction product is dissolved with tetrahydrofuran, is terminated with methanol, then
Precipitation obtains white product in 50mL n-hexanes, 12h is dried in vacuo at 30 DEG C, the conversion ratio of wherein hydroxy-ethyl acrylate reaches
98.3%, the conversion ratio of caprolactone is up to 99.8%.Its number-average molecular weight is 9500g/mol, molecular weight distribution 2.27, by gained
The nucleus magnetic hydrogen spectrum and gel permeation chromatography figure of product, it can be seen that polymer does not carry out conventional vinyl polymerization, but passes through
The polymerization methodses of proton translocation form the polymer using pi-allyl hydroxyl ethyl ester and caprolactone as main chain come what is carried out.
Embodiment 14
0.2g (1.7mmol) pi-allyl hydroxyl ethyl esters and 0.8g (7.0mmol) caprolactone is taken to insert the 10mL circles with rotor
In the flask of bottom, then add 1g toluene be used as solvent, displacement argon gas three times after, addition 43.8 μ l (0.09mmol) phosphine nitrile alkali P2.
Reaction is placed in 60 DEG C of oil bath pans, reacts 1h.After reaction terminates, reaction product is dissolved with tetrahydrofuran, is terminated with methanol, then
Precipitation obtains white product in 50mL n-hexanes, 12h is dried in vacuo at 30 DEG C, the conversion ratio of wherein hydroxy-ethyl acrylate reaches
95.9%, the conversion ratio of caprolactone is up to 97.8%.Its number-average molecular weight is 8800g/mol, molecular weight distribution 2.04, by gained
The nucleus magnetic hydrogen spectrum and gel permeation chromatography figure of product, it can be seen that polymer does not carry out conventional vinyl polymerization, but passes through
The polymerization methodses of proton translocation form the polymer using pi-allyl hydroxyl ethyl ester and caprolactone as main chain come what is carried out.
Embodiment 15
0.2g (1.7mmol) pi-allyl hydroxyl ethyl esters and 0.8g (7.0mmol) caprolactone is taken to insert the 10mL circles with rotor
In the flask of bottom, then add 1g toluene be used as solvent, displacement argon gas three times after, addition 43.8 μ l (0.09mmol) phosphine nitrile alkali P2。
Reaction is placed in 60 DEG C of oil bath pans, reacts 1h.After reaction terminates, reaction product is dissolved with tetrahydrofuran, is terminated with methanol, then
Precipitation obtains white product in 50mL n-hexanes, 12h is dried in vacuo at 30 DEG C, the conversion ratio of wherein hydroxy-ethyl acrylate reaches
97.2%, the conversion ratio of caprolactone is up to 98.4%.Its number-average molecular weight is 8800g/mol, molecular weight distribution 2.11, by gained
The nucleus magnetic hydrogen spectrum and gel permeation chromatography figure of product, it can be seen that polymer does not carry out conventional vinyl polymerization, but passes through
The polymerization methodses of proton translocation form the polymer using pi-allyl hydroxyl ethyl ester and caprolactone as main chain come what is carried out.
Embodiment 16
0.2g (1.7mmol) pi-allyl hydroxyl ethyl esters and 0.8g (7.0mmol) caprolactone is taken to insert the 10mL circles with rotor
In the flask of bottom, then add 1g dichloromethane be used as solvent, displacement argon gas three times after, addition 43.8 μ l (0.09mmol) phosphine nitriles
Alkali P2.Reaction is placed in 60 DEG C of oil bath pans, reacts 1h.After reaction terminates, reaction product is dissolved with tetrahydrofuran, it is whole with methanol
Only, then in 50mL n-hexanes precipitation obtains white product, and 12h, wherein hydroxy-ethyl acrylate conversion are dried in vacuo at 30 DEG C
Rate is up to 98.2%, and the conversion ratio of caprolactone is up to 98.8%.Its number-average molecular weight is 9000g/mol, molecular weight distribution 2.01, by
The nucleus magnetic hydrogen spectrum and gel permeation chromatography figure of products therefrom, it can be seen that polymer does not carry out conventional vinyl polymerization, but
By the polymerization methodses of proton translocation come what is carried out, the polymer using pi-allyl hydroxyl ethyl ester and caprolactone as main chain is formd.
Embodiment 17
0.2g (1.7mmol) pi-allyl hydroxyl ethyl esters and 0.2g (1.7mmol) hydroxyethyl methacrylate is taken to insert to carry and turn
In the 10mL round-bottomed flasks of son, 0.4g tetrahydrofurans are then added as solvent, liquid nitrogen frozen, after replacing argon gas three times, are added
43.8 μ l (0.09mmol) phosphine nitrile alkali P2.Reaction is placed in 60 DEG C of oil bath pans, reacts 1h.After reaction terminates, tetrahydrofuran is used
Reaction product is dissolved, is terminated with methanol, then precipitation obtains white product in 50mL n-hexanes, and 12h is dried in vacuo at 30 DEG C, its
The conversion ratio of middle hydroxy-ethyl acrylate is up to 98.1%, and the conversion ratio of caprolactone is up to 97.8%.Its number-average molecular weight is 5300g/
Mol, molecular weight distribution 1.81, see the nucleus magnetic hydrogen spectrum and gel permeation chromatography figure of Fig. 2 products therefroms, it can be seen that polymer does not have
Have and carry out conventional vinyl polymerization, but formd by the polymerization methodses of proton translocation come what is carried out with pi-allyl hydroxyl ethyl ester
With the polymer that caprolactone is main chain.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (7)
1. a kind of synthetic method of copolyesters, it is characterised in that pass through organocatalysis hydroxy acryl acid ester and ring-type list
The copolyreaction of the class monomer of body two, obtains the brand-new degradable copolyester of structure.
2. copolyesters synthetic method according to claim 1, it is characterised in that copolymerization mode can occur to contain in different
Between hydroxy acrylate, hydroxy acryl acid ester is may also occur between cyclic monomer.
3. copolyesters synthetic method according to claim 1, it is characterised in that hydroxyl vinyl monomer includes acrylic acid
Hydroxyl ethyl ester, hydroxyethyl methacrylate, hydroxypropyl acrylate etc. and its derivative.
4. copolyesters synthetic method according to claim 1, it is characterised in that cyclic monomer includes epoxy monomer and interior
Esters monomer, epoxy monomer such as oxirane, expoxy propane, allyl glycidyl ether etc., lactone monomer are included in fourth
Ester, caprolactone, lactide etc..
5. copolyesters synthetic method according to claim 1, it is characterised in that its catalyst is organic micromolecule catalyst,
Including phosphine nitrile alkali, heterocycle carbine, guanidine etc..
6. copolyesters synthetic method according to claim 1, it is characterised in that the polymeric reaction temperature is -20-100
DEG C, polymerization reaction time is 0.5~12 hour.
7. copolyesters synthetic method according to claim 1, it is characterised in that the polymerisation using polymerisation in bulk or
Person's polymerisation in solution;Wherein polymerisation in solution solvent for use be any one or two kinds in toluene, tetrahydrofuran, dichloromethane etc. with
On mixture.
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CN108467481A (en) * | 2018-03-13 | 2018-08-31 | 常州大学 | A kind of synthetic method of the degradable polymer of the double bond containing pendency |
CN108586762A (en) * | 2018-04-25 | 2018-09-28 | 常州大学 | A kind of click chemistry polymerisation of the hydroxyl and double bond of the base catalysis of phosphine nitrile |
CN109148949A (en) * | 2018-07-31 | 2019-01-04 | 广东工业大学 | A kind of compound all-solid polymer electrolyte with the bipolymer and its preparation of leading lithium ion ability |
CN113603869A (en) * | 2021-07-13 | 2021-11-05 | 华中科技大学 | Polyester brush-shaped polymer, one-pot synthesis method and application thereof |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103421167A (en) * | 2013-07-08 | 2013-12-04 | 常州大学 | One-step synthetic method of degradable branched polyester |
CN103865053A (en) * | 2012-12-10 | 2014-06-18 | 辽宁奥克化学股份有限公司 | Terminal alkenyl unsaturated acid/ester polyoxyalkyl ether, and preparation method and use thereof |
-
2017
- 2017-11-01 CN CN201711059048.XA patent/CN107698745A/en active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103865053A (en) * | 2012-12-10 | 2014-06-18 | 辽宁奥克化学股份有限公司 | Terminal alkenyl unsaturated acid/ester polyoxyalkyl ether, and preparation method and use thereof |
CN103421167A (en) * | 2013-07-08 | 2013-12-04 | 常州大学 | One-step synthetic method of degradable branched polyester |
Non-Patent Citations (2)
Title |
---|
HONGJUN YANG ET AL.: "Hybrid Copolymerization of ε-Caprolactoneand Methyl Methacrylate", 《MACROMOLECULES》 * |
HONGJUN YANG ET AL.: "One-step synthesis of hyperbranched biodegradable polymer", 《RSC ADVANCE》 * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108467481A (en) * | 2018-03-13 | 2018-08-31 | 常州大学 | A kind of synthetic method of the degradable polymer of the double bond containing pendency |
CN108586762A (en) * | 2018-04-25 | 2018-09-28 | 常州大学 | A kind of click chemistry polymerisation of the hydroxyl and double bond of the base catalysis of phosphine nitrile |
CN109148949A (en) * | 2018-07-31 | 2019-01-04 | 广东工业大学 | A kind of compound all-solid polymer electrolyte with the bipolymer and its preparation of leading lithium ion ability |
CN113603869A (en) * | 2021-07-13 | 2021-11-05 | 华中科技大学 | Polyester brush-shaped polymer, one-pot synthesis method and application thereof |
CN113603869B (en) * | 2021-07-13 | 2022-04-26 | 华中科技大学 | Polyester brush-shaped polymer, one-pot synthesis method and application thereof |
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