CN103483571B - A kind of containing full bio-based polyester of double bond and its preparation method and application - Google Patents
A kind of containing full bio-based polyester of double bond and its preparation method and application Download PDFInfo
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- CN103483571B CN103483571B CN201310379207.XA CN201310379207A CN103483571B CN 103483571 B CN103483571 B CN 103483571B CN 201310379207 A CN201310379207 A CN 201310379207A CN 103483571 B CN103483571 B CN 103483571B
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Abstract
The invention discloses a kind of double bond containing full bio-based polyester, for the compound of formula I structure, wherein, R1, R2 are alkyl or aryl, m and n is mean polymerisation degree, 1≤n≤1000,0≤m≤1000, containing double bond active group, can carry out follow-up crosslinked or modification, expand the range of application that it is possible, for the preparation of urethane.Present invention also offers a kind of preparation method of double bond containing full bio-based polyester, adopt esterification-polycondensation two-stage process route and adopt ester exchange process route, preparation is simple, easy to implement, workable, be conducive to industrialization scale operation, possess wide application prospect.
Description
Technical field
The invention belongs to the technical field preparing polyester, be specifically related to a kind of containing full bio-based polyester of double bond and its preparation method and application.
Background technology
Polyester is heterogeneous chain polymer main chain having-COO-ester group group.Polyester kind is a lot, comprises aliphatics and aromatic polyester, saturated and unsaturated polyester, linear and build polyester.The application of polyester is also extremely extensive, and linear aliphatic polyesters can be used as the prepolymer of urethane; Linear aromatic polyester, as dacron polyester, can be used as synthon and engineering plastics; Unsaturated polyester, leaves double bond in main chain, can be used for reinforced plastics with other double bond containing reactive monomer copolymerization; Synolac, belongs to linear or the random prepolymer of side chain, and residual groups can crosslinking curing further, therefore, can be used as coating.
But, most production in the world at present, life needed for chemical industry raw material and various macromolecule engineering material, industrial coating etc. all come from petrochemicals.Except a few polyester kind (polylactide, carbon dioxide copolymerization ester, PHA), the alcohol that most production of polyester is used and acid also come from petroleum chemical industry.
Along with world petroleum resource is day by day exhausted and problem of environmental pollution is on the rise, be that the conventional polymer industry of raw material is faced with unprecedented challenge with petrochemicals.Obtain the extensive concern of industry member and academia as the raw material of chemical industry using renewable biomass resource replacement fossil resources such as starch, Mierocrystalline cellulose, xylogen, polysaccharide.Many Chemical products commercializations deriving from biomass resource, as Dupont (DUEPONT) company biological fermentation process produces 1,3-PD; The co-partnership company CDP of U.S. Jia Ji (CARGILL) and DOW Chemical (DOWCHEMICAL) adopts biological fermentation process production poly(lactic acid); Sweden pula gram (PURAC) company utilizes fermentation technique to produce high-pure lactic acid etc.Other business-like bio-based monomer also have methylene-succinic acid, ethylene glycol, hexanodioic acid, 1, 4-succinic acid, sebacic acid, decanediol etc.Take biomass resource as raw material production chemical and will be following developing direction with gained bio-based chemicals production macromolecular material.
Chinese invention patent application as application number 201210258520.3 discloses a kind of biological poly aromatic ester and preparation method thereof, carries out esterification obtain esterification products with FDCA and diphenolic acid or bis-phenol acid esters under the effect of Esterified Enzyme; Application number be 201210258344.3 Chinese invention patent application disclose a kind of bio-based polyester and preparation method thereof, carry out esterification-polycondensation with FDCA and Isosorbide-5-Nitrae-pentanediol and obtain polyester; Application number be 201110138492.7 Chinese invention patent application disclose a kind of bio-based high-branched polyester and preparation method thereof, be raw material with vegetables oil, cause mass polymerization by free radical, purify obtain high-branched polyester.
Above-mentioned polyester is bio-based polyester that is saturated or branching, is found by patent searching and document, not yet has with the report of the methylene-succinic acid of bio-based source and the bio-based dibasic alcohol unsaturated full bio-based polyester that is Material synthesis.
Summary of the invention
The invention provides a kind of double bond containing full bio-based polyester, containing double bond active group, follow-up crosslinked or modification can be carried out, expand the range of application that it is possible.
A kind of double bond containing full bio-based polyester is the compound of formula I structure;
Wherein, R
1, R
2for alkyl or aryl, m and n is mean polymerisation degree, 1≤n≤1000,0≤m≤1000.
By regulating n, m value, the content of carbon-carbon double bond in double bond containing full bio-based polyester in double bond containing full bio-based polyester can be regulated, thus regulate the performance of double bond containing full bio-based polyester.
As preferably, R
1for
or
r
2for
or
As preferably, n=28 ~ 300, m=0 ~ 108, further preferably, n=28, m=29.
Present invention also offers a kind of preparation method of double bond containing full bio-based polyester, adopt esterification-polycondensation two-stage process route, preparation is simple, easy to implement, workable.
A preparation method for double bond containing full bio-based polyester, comprises the following steps:
Under the protection of protective gas, bio-based diacid, bio-based glycol, catalyzer, thermo-stabilizer and oxidation inhibitor are joined in reactor, first 150 DEG C ~ 180 DEG C, carry out esterification 1h ~ 3h under 20KPa ~ 100KPa, then at 200 DEG C ~ 240 DEG C, 1KPa ~ 50KPa polycondensation 0.5h ~ 1h, finally be evacuated to below 100Pa, continue reaction 1h ~ 3h, obtain the double bond containing full bio-based polyester of formula I structure;
Described bio-based diacid at least comprises methylene-succinic acid, and described bio-based glycol is HO-R
2-OH.Wherein, HO-R
2r in-OH
2with the R in formula I
2there is identical meanings.
In the present invention, by regulating methylene-succinic acid and HOOC-R
1ratio between-COOH, thus regulate the ratio of carbon-carbon double bond in double bond containing full bio-based polyester.
As preferably, described bio-based diacid also comprises HOOC-R
1-COOH, described HOOC-R
1-COOH is one or more in succinic acid, hexanodioic acid, sebacic acid, undecane diacid, dodecanedioic acid, tetradecane diacid, FDCA, rosinyl diprotic acid.HOOC-R
1r in-COOH
1with the R in formula I
1there is identical meanings.
When described bio-based diacid is only containing methylene-succinic acid, in the double bond containing full bio-based polyester obtained, m=0.
As preferably, described bio-based glycol is ethylene glycol, 1,4-butyleneglycol, 1, ammediol, 1,9-the ninth of the ten Heavenly Stems-glycol, decanediol, undecane, dodecanediol, tetradecane diols, rosinyl glycol, Isosorbide, one or more (comprising two kinds) in 2,5-furyl glycol.Further preferably, described bio-based glycol is ethylene glycol, 1,3-PD, BDO or decanediol.
As preferably, described bio-based diacid and the mol ratio of bio-based glycol are 1:0.5 ~ 2, wherein, in described bio-based diacid, the molecular fraction of methylene-succinic acid is 30% ~ 100%, can ensure the content of the relative ideal of carbon-carbon double bond in double bond containing full bio-based polyester.Further preferably, described bio-based diacid and the mol ratio of bio-based glycol are 1:1 ~ 1.8.
Used catalyst can be inorganic acids catalyzer as the one in sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, tosic acid etc. or two or more, also can be solid acid catalyst or is the one of aluminum compound, tin compound, antimony compounds, titanium compound and zn cpds kind or two or more.As preferably, described catalyzer is one or more in sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, tosic acid, stannous octoate, tetrabutyl titanate, antimonous oxide, dibutyl tin laurate.
It is a small amount of that catalyst levels can adopt those skilled in the art to know, and as preferably, the mol ratio of described catalyzer and bio-based diacid is 0.01 ~ 1:100, further preferably, is 0.01 ~ 0.5:100, further preferably, is 0.01 ~ 0.1:100.
Thermo-stabilizer used is phosphoric acid or phosphorons acid compound, as preferably, described thermo-stabilizer is one or more in phosphoric acid, phosphorous acid, tetra-sodium, ammonium phosphate, trimethyl phosphite 99, triethyl phosphate, dimethyl phosphate, triphenylphosphate, diphenyl phosphate, triphenyl phosphite, diphenyl phosphite, ammonium phosphite.The addition of thermo-stabilizer be those skilled in the art know a small amount of.
Oxidation inhibitor used is one or both in aromatic amine oxidation inhibitor, phenolic antioxidant, and as preferably, described oxidation inhibitor is one or more in pentanoic, Ursol D, antioxidant 1010, antioxidant 264, Resorcinol, benzoquinones etc.Oxidation inhibitor can adopt commercially available prod.The addition of oxidation inhibitor be those skilled in the art know a small amount of.
Present invention also offers a kind of preparation method of double bond containing full bio-based polyester, adopt ester exchange process route, preparation is simple, easy to implement, workable.
A preparation method for double bond containing full bio-based polyester, comprises the following steps:
Under the protection of protective gas; biomass acid dimethyl and bio-based dibasic alcohol are joined in reactor; first at 150 DEG C ~ 180 DEG C reaction 0.5h ~ 1h; then at 180 DEG C ~ 240 DEG C reaction 1h ~ 3h; again 150 DEG C ~ 160 DEG C, 1KPa ~ 50KPa reacts 0.5h ~ 2h, finally add catalyzer, thermo-stabilizer and oxidation inhibitor, be evacuated to below 100Pa; be warming up to 180 DEG C ~ 240 DEG C reaction 1h ~ 3h, obtain the double bond containing full bio-based polyester of formula I structure.
Described biomass acid dimethyl at least comprises dimethyl itaconate, and described bio-based glycol is HO-R
2-OH, wherein, HO-R
2r in-OH
2with the R in formula I
2there is identical meanings.
As preferably, described biomass acid dimethyl also comprises
wherein, R
1with the R in formula I
1there is identical meanings.
When described biomass acid dimethyl is only containing dimethyl itaconate, in the double bond containing full bio-based polyester obtained, m=0.
As preferably, described bio-based glycol is ethylene glycol, 1,4-butyleneglycol, 1, ammediol, 1, one or more (comprising two kinds) in 9-nonanediol, decanediol, undecane, dodecanediol, tetradecane diols, rosinyl glycol, Isosorbide, 2,5-furyl glycol.Further preferably, described bio-based glycol is ethylene glycol, 1,3-PD, BDO or decanediol.
As preferably, described biomass acid dimethyl and the mol ratio of bio-based glycol are 1:0.5 ~ 2, wherein, in described biomass acid dimethyl, the molecular fraction of dimethyl itaconate is 30% ~ 100%, can ensure the content of the relative ideal of carbon-carbon double bond in double bond containing full bio-based polyester.Described biomass acid dimethyl and the mol ratio of bio-based glycol are 1:1.
Used catalyst can be inorganic acids catalyzer as the one in sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, tosic acid etc. or two or more, also can be solid acid catalyst or is the one of aluminum compound, tin compound, antimony compounds, titanium compound and zn cpds kind or two or more.As preferably, described catalyzer is one or more in sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, tosic acid, stannous octoate, tetrabutyl titanate, antimonous oxide, dibutyl tin laurate.
It is a small amount of that catalyst levels can adopt those skilled in the art to know, and as preferably, the mol ratio of described catalyzer and biomass acid dimethyl is 0.01 ~ 1:100, further preferably, being 0.01 ~ 0.5:100, further preferably, is 0.01 ~ 0.1:100.
Thermo-stabilizer used is phosphoric acid or phosphorons acid compound, as preferably, described thermo-stabilizer is one or more in phosphoric acid, phosphorous acid, tetra-sodium, ammonium phosphate, trimethyl phosphite 99, triethyl phosphate, dimethyl phosphate, triphenylphosphate, diphenyl phosphate, triphenyl phosphite, diphenyl phosphite, ammonium phosphite.The addition of thermo-stabilizer be those skilled in the art know a small amount of.
Oxidation inhibitor used is one or both in aromatic amine oxidation inhibitor, phenolic antioxidant, and as preferably, described oxidation inhibitor is one or more in pentanoic, Ursol D, antioxidant 1010, antioxidant 264, Resorcinol, benzoquinones etc.Oxidation inhibitor can adopt commercially available prod.The addition of oxidation inhibitor be those skilled in the art know a small amount of.
Double bond containing full bio-based polyester prepared by the present invention is as soft section in urethane synthesis, and synthesis of polyurethane, namely for the preparation of urethane, specifically as contained double bond bio-based polyurethane, radical crosslinking type bio-based polyurethane and ultraviolet light solidfication water polyurethane.
Containing a preparation method for double bond bio-based polyurethane, comprise the following steps:
To mix containing double bond bio-based polyester, isophorone diisocyanate, catalyst dibutyltin dilaurylate and solvent 2-butanone, within 2 ~ 4 hours, obtain prepolymer system 60 DEG C ~ 80 DEG C reactions;
Chainextender BDO is dissolved in solvent 2-butanone, is added drop-wise in prepolymer system, at 70 ~ 90 DEG C of reaction 3 ~ 5h, except desolventizing can obtain containing double bond bio-based polyurethane.
A preparation method for radical crosslinking type bio-based polyurethane, comprises the following steps:
To be dissolved in trichloromethane containing double bond bio-based polyurethane, and add radical initiator dicumyl peroxide, mix, treat that solvent evaporates is complete, in 140 DEG C ~ 160 DEG C reactions 10 ~ 20 minutes, obtain radical crosslinking type bio-based polyurethane.
A preparation method for ultraviolet light solidfication water polyurethane, comprises the following steps:
By double bond containing full bio-based polyester, isophorone diisocyanate, 2, 2-dimethylol propionic acid, 1, 4-butyleneglycol and dibutyl tin laurate join in reactor as catalyzer, under nitrogen protection in 70 DEG C ~ 80 DEG C reactions, butanone adjusting viscosity is added in reaction process, 30 DEG C ~ 50 DEG C are cooled to after 3 ~ 5h hour, add in triethylamine and carboxyl salify, continue stirring reaction 30min again, then ultraviolet initiator benzophenone 0.2g is added, stir, then adding water stirring and emulsifying is emulsion, take off solvent, solidify under ultraviolet lamp, ultraviolet light solidfication water polyurethane can be obtained.
Compared with prior art, tool of the present invention has the following advantages:
One, the raw material that the present invention adopts is bio-based source, and do not rely on petroleum resources, the double bond containing full bio-based polyester of gained has the feature of environmental protection and recyclability.
Two, the present invention is containing in double bond bio-based polyester, and double bond content controllable, double bond containing full bio-based molecular weight of polyesters can regulate and control accordingly according to different demand.
Three, the double bond containing full bio-based polyester of the present invention, not only can be applied in the Application Areas of conventional polyester material and unsaturated polyester resin, and, double bond in this double bond containing full bio-based polyester can proceed follow-up modification and reaction as active group, thus can be applied in urethane synthesis, epoxy resin, coating, lubricant, elastomerics, modifying plastics other etc. aspect.This type of bio-based polyester not only has the extraordinary feature of environmental protection and recyclability, and this bio-based polyester contains double bond active group, can carry out follow-up crosslinked or modification, expand the range of application that it is possible, have extraordinary using value and application potential.
Four, the preparation method of the double bond containing full bio-based polyester of the present invention, simple possible, easy to implement, be conducive to industrialization scale operation, possess wide application prospect.
Accompanying drawing explanation
Fig. 1 is the proton nmr spectra of double bond containing full bio-based polyester prepared by embodiment 1;
Fig. 2 is the Infrared Characterization spectrogram of double bond containing full bio-based polyester prepared by embodiment 1.
Embodiment
Below will be specifically described the present invention by embodiment, for embodiment be in order to content of the present invention is described better, but be not that content of the present invention is only limitted to illustrated embodiment.Those of ordinary skill in the art know when not departing from spirit of the present invention or essential characteristic, suitable amendment can be carried out to the proportioning of raw material, material choice, operational condition, synthesis technique, material structure etc., therefore, embodiment disclosed in embodiment is illustrative in all respects, instead of restrictive.
Embodiment 1
(1) under nitrogen protection by methylene-succinic acid 0.5mol, hexanodioic acid (HOOC-R
1-COOH, R
1with R in formula I
1there is identical meanings) 0.5mol, decanediol (HO-R
2-OH, R
2with R in formula I
2there is identical meanings) 1.3mol and tosic acid 0.001mol, triphenylphosphate 1.86g, Resorcinol 2.33g, join in reactor, reaction system is warming up to 150 DEG C, esterification is carried out under pressure 100KPa, fully stir in reaction process, remove the water that reaction produces, the reaction times is 1h.
(2) after esterification terminates, reaction system is warming up to 200 DEG C, and decompression step by step is to 50KPa, reaction 0.5h, then continues to be evacuated to about 96Pa, and continue reaction 3h and terminate, reaction terminates rear discharging, obtains product (double bond containing full bio-based polyester).
The proton nmr spectra of double bond containing full bio-based polyester prepared by embodiment 1 as shown in Figure 1, as we know from the figure, 5.7ppm, 6.3ppm place is the chemical shift of two hydrogen of double bond end on methylene-succinic acid, and the peak at 2.3ppm place is the chemical shift of totally four hydrogen atoms on two carbon atoms adjacent with carboxyl in hexanodioic acid.The peak at 1.3ppm place is the chemical shift of 12 hydrogen atoms on six carbon atom in the middle of decanediol.The mol ratio that can be obtained methylene-succinic acid and hexanodioic acid by the calculating of nuclear-magnetism integral area is 0.98, conforms to theoretical molar ratio 1.The ratio that nuclear-magnetism calculates diprotic acid and dibasic alcohol is 1:1.2.
The Infrared Characterization spectrogram of double bond containing full bio-based polyester prepared by embodiment 1 as shown in Figure 2.As can be known from Fig. 2,1730cm
-1the absorption peak at place is the absorption peak of ester functional groups in said structure, 1640cm
-1the strong absorption peak at place and 3030cm
-1the weak absorbing peak at place is the infrared absorption peak of double bond in said structure, 3450cm
-1and 3550cm
-1two weak absorbing peaks at place are the absorption peak of molecule chain end hydroxyl.
Testing its number-average molecular weight with gel permeation chromatography is 3.5 × 10
4.
By proton nmr spectra and Infrared Characterization spectrogram, and in conjunction with its number-average molecular weight, showing double bond containing full bio-based polyester, is the compound of formula I structure;
Wherein, R
1for
r
2for
n=34, m=35.
Embodiment 2
(1) under nitrogen protection by methylene-succinic acid 0.5mol, hexanodioic acid (HOOC-R
1-COOH, R
1with R in formula I
1there is identical meanings) 0.5mol, decanediol (HO-R
2-OH, R
2with R in formula I
2there is identical meanings) 1.8mol and tosic acid 0.01mol, triphenylphosphate 0.466g, Resorcinol 0.05g, join in reactor, reaction system is warming up to 180 DEG C, esterification is carried out under pressure 20KPa, fully stir in reaction process, remove the water that reaction produces, the reaction times is 2.5h.
(2) after esterification terminates, reaction system is warming up to 220 DEG C, and decompression step by step is to 20KPa, reaction 1h, then continues to be evacuated to about 96Pa, and continue reaction 2h and terminate, reaction terminates rear discharging, obtains product (double bond containing full bio-based polyester).
According to the proton nmr spectra of double bond containing full bio-based polyester prepared by embodiment 2,5.7ppm, 6.3ppm place is the chemical shift of two hydrogen of double bond end on methylene-succinic acid, and the peak at 2.3ppm place is the chemical shift of totally four hydrogen atoms on two carbon atoms adjacent with carboxyl in hexanodioic acid.The peak at 1.3ppm place is the chemical shift of 12 hydrogen atoms on six carbon atom in the middle of decanediol.Calculated by integral area, the mol ratio of methylene-succinic acid and hexanodioic acid is 0.975, and the mol ratio of diprotic acid and dibasic alcohol is 1:1.7.
According to the Infrared Characterization spectrogram of double bond containing full bio-based polyester prepared by embodiment 2,1730cm
-1the absorption peak at place is the absorption peak of ester functional groups in said structure; 1640cm
-1the strong absorption peak at place and 3030cm
-1the weak absorbing peak at place is the infrared absorption peak of double bond in said structure, 3450cm
-1and 3550cm
-1two weak absorbing peaks at place are the absorption peak of molecule chain end hydroxyl.
Testing its number-average molecular weight with gel permeation chromatography is 2.9 × 10
4.
By proton nmr spectra and Infrared Characterization spectrogram, and in conjunction with its number-average molecular weight, showing double bond containing full bio-based polyester, is the compound of formula I structure;
Wherein, R
1for
r
2for
n=28, m=29.
Embodiment 3
(1) by dimethyl itaconate 1mol, BDO (HO-R
2-OH) 0.5mol, dodecanediol (HO-R
2-OH) 0.5mol joins in the reactor of protection of inert gas, then temperature reaction system to 150 DEG C, reaction 0.5h; be warming up to 180 DEG C again; react 1h under keeping this temperature, carry out normal pressure transesterification reaction, until flow of methanol output reaches about the 95wt% of theoretical value.
Wherein, R in BDO
2for
r in dodecanediol
2for
(2) reaction system is cooled to 150 DEG C, connects vacuum system, be evacuated to 50KPa, reaction 1h, removes monomer and the small molecule by-product of not participating in reaction in reaction system.Stop vacuumizing and passing into nitrogen, add tetrabutyl titanate 0.005mol, triphenylphosphate 0.3g, antioxidant 1010 0.5g make it disperse completely, stop logical nitrogen, continue to be evacuated to below 100Pa, and be warming up to 220 DEG C, stir, isothermal reaction 3h terminates simultaneously, namely obtains product (double bond containing full bio-based polyester).
According to the proton nmr spectra of double bond containing full bio-based polyester prepared by embodiment 3,5.7ppm, 6.3ppm place is the chemical shift of two hydrogen of double bond end on methylene-succinic acid, the peak at 1.3ppm place is the chemical shift of 16 hydrogen atoms on eight carbon atoms in the middle of dodecane dibasic alcohol, the peak at 4.1ppm place is be connected with ester group 1, the hydrogen of carbon atom on 4-butyleneglycol and dodecane dibasic alcohol, both respectively account for 50%.Calculated by integral area, the mol ratio of BDO and dodecane dibasic alcohol is 0.99, and the mol ratio of diprotic acid and dibasic alcohol is 1:1.05.
According to the Infrared Characterization spectrogram of double bond containing full bio-based polyester prepared by embodiment 3,1730cm
-1the absorption peak at place is the absorption peak of ester functional groups in said structure; 1640cm
-1the strong absorption peak at place and 3030cm
-1the weak absorbing peak at place is the infrared absorption peak of double bond in said structure, 3450cm
-1and 3500cm
-1two weak absorbing peaks at place are respectively the absorption peak of molecule chain end hydroxyl and carboxyl.
Testing its number-average molecular weight with gel permeation chromatography is 4.5 × 10
4.
By proton nmr spectra and Infrared Characterization spectrogram, and in conjunction with its number-average molecular weight, showing double bond containing full bio-based polyester, is the compound of formula I structure;
Wherein, R in each molecule
2select
in one, n=94, m=0.
Namely the double bond containing full bio-based polyester of gained is the mixture of two kinds of molecular structures, comprises following two kinds of molecular structures:
(1) formula I structure, wherein R
2for
(2) formula I structure, wherein R
2for
Embodiment 4
(1) under nitrogen protection by methylene-succinic acid 1mol, ethylene glycol (HO-R
2-OH) 0.8mol, decanediol (HO-R
2-OH) 0.5mol and stannous octoate 0.0015mol, trimethyl phosphite 1g, Ursol D 0.8g join in reactor.Reaction system is warming up to 180 DEG C, carries out esterification, fully stir in reaction process under 50KPa, remove the water of generation, the reaction times is 3h.
Wherein, R in ethylene glycol
2for
r in decanediol
2for
(2) after esterification terminates, reaction system is warming up to 240 DEG C, and decompression step by step is to 1KPa, reaction 0.5h, then continues to be evacuated to below 100Pa, and continue reaction 1h and terminate, namely discharging obtains product (double bond containing full bio-based polyester).
According to the proton nmr spectra of double bond containing full bio-based polyester prepared by embodiment 4,5.7ppm, 6.3ppm place is the chemical shift of two hydrogen of double bond end on methylene-succinic acid, the peak at 4.4ppm place is the chemical shift of 4 hydrogen atoms on two carbon atoms on ethylene glycol, and the peak at 4.1ppm place is the chemical shift of carbon atom hydrogen on the decanediol that is connected with ester group.Calculated by integral area, the mol ratio of decanediol and ethylene glycol is 1:1.5, and the mol ratio of diprotic acid and dibasic alcohol is 1:1.18.
According to the Infrared Characterization spectrogram of double bond containing full bio-based polyester prepared by embodiment 4,1730cm
-1the absorption peak at place is the absorption peak of ester functional groups in said structure; 1640cm
-1the strong absorption peak at place and 3030cm
-1the weak absorbing peak at place is the infrared absorption peak of double bond in said structure, 3450cm
-1and 3550cm
-1two weak absorbing peaks at place are the absorption peak of molecule chain end hydroxyl.
Testing its number-average molecular weight with gel permeation chromatography is 4.0 × 10
4.
By proton nmr spectra and Infrared Characterization spectrogram, and in conjunction with its number-average molecular weight, showing double bond containing full bio-based polyester, is the compound of formula I structure;
Wherein, R in each molecule
2select
in one, n=200, m=0.Namely the double bond containing full bio-based polyester of gained is the mixture of four kinds of molecular structures, comprises following two kinds of molecular structures:
(1) formula I structure, wherein R
2for
(2) formula I structure, wherein R
2for
Embodiment 5
(1) by dimethyl itaconate 0.3mol, dimethyl adipate 0.7mol, dodecanediol (HO-R
2-OH) 1.0mol joins in the reactor of protection of inert gas, then temperature reaction system to 150 DEG C, reaction 0.5h; be warming up to 180 DEG C again; react 1h under keeping this temperature, carry out normal pressure transesterification reaction, until flow of methanol output reaches about the 95wt% of theoretical value.
R in dimethyl adipate
1for
r in dodecanediol
2for
(2) system is cooled to 150 DEG C, connects vacuum system, be evacuated to 50KPa, reaction 1h, removes monomer and the small molecule by-product of not participating in reaction in reaction system.Stop vacuumizing and passing into nitrogen, add antimonous oxide 0.005mol, triphenylphosphate 0.3g, antioxidant 1010 0.5g make it disperse completely, stop logical nitrogen, continue to be evacuated to below 100Pa, and be warming up to 220 DEG C, rapid stirring simultaneously, isothermal reaction 3h terminates, and namely obtains product (double bond containing full bio-based polyester).
According to the proton nmr spectra of double bond containing full bio-based polyester prepared by embodiment 5,5.7ppm, 6.3ppm place is the chemical shift of two hydrogen of double bond end on methylene-succinic acid, the peak at 2.3ppm place is the chemical shift of 4 hydrogen atoms on two carbon atoms adjacent with ester group in hexanodioic acid, and the peak at 1.3ppm place is the chemical shift of 16 hydrogen atoms on eight carbon atoms in the middle of dodecane dibasic alcohol.Calculated by integral area, the mol ratio of methylene-succinic acid and hexanodioic acid is 1:2.24, and the mol ratio of diprotic acid and dibasic alcohol is 1:1.03.
According to the Infrared Characterization spectrogram of double bond containing full bio-based polyester prepared by embodiment 5,1730cm
-1the absorption peak at place is the absorption peak of ester functional groups in said structure; 1640cm
-1the strong absorption peak at place and 3030cm
-1the weak absorbing peak at place is the infrared absorption peak of double bond in said structure, 3450cm
-1and 3550cm
-1two weak absorbing peaks at place are the absorption peak of molecule chain end hydroxyl and carboxyl.
Testing its number-average molecular weight with gel permeation chromatography is 4.8 × 10
4.
By proton nmr spectra and Infrared Characterization spectrogram, and in conjunction with its number-average molecular weight, showing double bond containing full bio-based polyester, is the compound of formula I structure;
Wherein, R
1for
r
2for
n=47, m=109.
Embodiment 6
(1) under nitrogen protection by methylene-succinic acid 0.3mol, sebacic acid (HOOC-R
1-COOH, R
1with R in formula I
1there is identical meanings) 0.7mol, BDO (HO-R
2-OH, R
2with R in formula I
2there is identical meanings) 1.5mol and tosic acid 0.01mol, triphenylphosphate 0.466g, Resorcinol 0.05g, join in reactor, reaction system is warming up to 180 DEG C, esterification is carried out under pressure 20KPa, fully stir in reaction process, remove the water that reaction produces, the reaction times is 2.5h.
(2) after esterification terminates, reaction system is warming up to 220 DEG C, and decompression step by step is to 20KPa, reaction 1h, then continues to be evacuated to about 96Pa, and continue reaction 2h and terminate, reaction terminates rear discharging, obtains product (double bond containing full bio-based polyester).
According to the proton nmr spectra of double bond containing full bio-based polyester prepared by embodiment 6,5.7ppm, 6.3ppm place is the chemical shift of two hydrogen of double bond end on methylene-succinic acid, the peak at 4.1ppm place is 1, with the chemical shift of hydrogen on ester group adjacent carbons in 4-butyleneglycol, the peak at 1.3ppm place is the chemical shift of 8 hydrogen atoms on 4 methylene radical in the middle of sebacic acid.Calculated by integral area, the mol ratio of methylene-succinic acid and sebacic acid is 1:2.18, and the mol ratio of diprotic acid and dibasic alcohol is 1:1.38.
According to the Infrared Characterization spectrogram of double bond containing full bio-based polyester prepared by embodiment 6,1730cm
-1the absorption peak at place is the absorption peak of ester functional groups in said structure; 1640cm
-1the strong absorption peak at place and 3030cm
-1the weak absorbing peak at place is the infrared absorption peak of double bond in said structure, 3450cm
-1and 3550cm
-1two weak absorbing peaks at place are the absorption peak of molecule chain end hydroxyl.
Testing its number-average molecular weight with gel permeation chromatography is 3.6 × 10
4.
By proton nmr spectra and Infrared Characterization spectrogram, and in conjunction with its number-average molecular weight, showing double bond containing full bio-based polyester, is the compound of formula I structure;
Wherein, R
1for
r
2for
n=46, m=108.
Embodiment 7
(1) by dimethyl itaconate 0.3mol, FDCA dimethyl ester 0.7mol, BDO (HO-R
2-OH) 1mol joins in the reactor of protection of inert gas, then temperature reaction system to 150 DEG C, reaction 0.5h; be warming up to 180 DEG C again; react 1h under keeping this temperature, carry out normal pressure transesterification reaction, until flow of methanol output reaches about the 95wt% of theoretical value.
R in FDCA dimethyl ester
1for
r in BDO
2for
(2) system is cooled to 150 DEG C, connects vacuum system, be evacuated to 50KPa, reaction 1h, removes monomer and the small molecule by-product of not participating in reaction in reaction system.Stop vacuumizing and passing into nitrogen, add antimonous oxide 0.005mol, triphenylphosphate 0.3g, antioxidant 1010 0.5g make it disperse completely, stop logical nitrogen, continue to be evacuated to below 100Pa, and be warming up to 220 DEG C, rapid stirring simultaneously, isothermal reaction 3h terminates, and namely obtains product (double bond containing full bio-based polyester).
According to the proton nmr spectra of double bond containing full bio-based polyester prepared by embodiment 7,5.7ppm, 6.3ppm place is the chemical shift of two hydrogen of double bond end on methylene-succinic acid, and the peak at 7.5ppm place is the chemical shift of hydrogen atom in furan nucleus double bond.The multiplet at 4.1 ~ 4.3ppm place is the chemical shift with hydrogen on ester group adjacent carbons in BDO.Calculated by integral area, the mol ratio of methylene-succinic acid and furandicarboxylic acid is 1:2.3, and the mol ratio of diprotic acid and dibasic alcohol is 1:1.04.
According to the Infrared Characterization spectrogram of double bond containing full bio-based polyester prepared by embodiment 7,1730cm
-1the absorption peak at place is the absorption peak of ester functional groups in said structure; 1640cm
-1the strong absorption peak at place and 3030cm
-1the weak absorbing peak at place is the infrared absorption peak of double bond in said structure, 3450cm
-1and 3500cm
-1two weak absorbing peaks at place are the absorption peak of molecule chain end hydroxyl and carboxyl.
Testing its number-average molecular weight with gel permeation chromatography is 2.0 × 10
4.
By proton nmr spectra and Infrared Characterization spectrogram, and in conjunction with its number-average molecular weight, showing double bond containing full bio-based polyester, is the compound of formula I structure;
Wherein, R
1for
r
2for
n=30, m=69.
Embodiment 8
(1) by dimethyl itaconate 0.3mol, 2; 5-furandicarboxylic acid dimethyl ester 0.7mol, 1; ammediol 1.0mol joins in the reactor of protection of inert gas; then temperature reaction system is to 150 DEG C; reaction 0.5h, then be warming up to 170 DEG C, react 1h under keeping this temperature; carry out normal pressure transesterification reaction, until flow of methanol output reaches about the 95wt% of theoretical value.
R in FDCA dimethyl ester
1for
r in 1,3-PD
2for
(2) system is cooled to 150 DEG C, connects vacuum system, be evacuated to 50KPa, reaction 1h, removes monomer and the small molecule by-product of not participating in reaction in reaction system.Stop vacuumizing and passing into nitrogen, add dibutyl tin laurate 0.005mol, triphenyl phosphite 0.3g, antioxidant 1010 0.5g make it disperse completely, stop logical nitrogen, continue to be evacuated to below 100Pa, and be warming up to 220 DEG C, rapid stirring simultaneously, isothermal reaction 3h terminates, and namely obtains product (double bond containing full bio-based polyester).
According to the proton nmr spectra of double bond containing full bio-based polyester prepared by embodiment 8,5.7ppm, 6.3ppm place is the chemical shift of two hydrogen of double bond end on methylene-succinic acid, and the peak at 7.5ppm place is the chemical shift of hydrogen atom in furan nucleus double bond.The multiplet at 4.1 ~ 4.3ppm place is the chemical shift with hydrogen on ester group adjacent carbons in 1,3-PD.Calculated by integral area, the mol ratio of methylene-succinic acid and furandicarboxylic acid is 1:2.2, and the mol ratio of diprotic acid and dibasic alcohol is 1:1.06.
According to the Infrared Characterization spectrogram of double bond containing full bio-based polyester prepared by embodiment 8,1730cm
-1the absorption peak at place is the absorption peak of ester functional groups in said structure; 1640cm
-1the strong absorption peak at place and 3030cm
-1the weak absorbing peak at place is the infrared absorption peak of double bond in said structure, 3450cm
-1and 3500cm
-1two weak absorbing peaks at place are the absorption peak of molecule chain end hydroxyl and carboxyl.
Testing its number-average molecular weight with gel permeation chromatography is 1.8 × 10
4.
By proton nmr spectra and Infrared Characterization spectrogram, and in conjunction with its number-average molecular weight, showing double bond containing full bio-based polyester, is the compound of formula I structure;
Wherein, R
1for
r
2for
n=29, m=67.
Application examples 1
Adopt double bond containing full bio-based polyester prepared by embodiment 2, the hydroxyl value containing double bond bio-based polyester according to HG/T2709-1995 standard test gained is 84mgKOH/g.
One, containing the synthesis of double bond bio-based polyurethane
Will containing double bond bio-based polyester 13g (10mmol), isophorone diisocyanate (IPDI) 4.4456g (20mmol), catalyst dibutyltin dilaurylate (DBTDL) 3 and solvent 2-butanone 30g, join with in churned mechanically there-necked flask, within 3 hours, obtain prepolymer in 65 DEG C of reactions.Chainextender BDO 0.9012g (10mmol) is dissolved in 15g solvent 2-butanone, is added drop-wise in reaction system with constant pressure funnel, is warming up to 80 DEG C simultaneously, and reaction 4h, until 2266cm on infrared spectrum
-1the infrared absorption peak of place's isocyanic ester disappears, and stopped reaction obtains containing double bond bio-based polyurethane solution.
Be poured on film forming in the mould of tetrafluoroethylene by containing double bond bio-based polyurethane solution, treat that solvent evaporates is complete, the material of film forming is containing double bond bio-based polyurethane, then cuts out sample according to GB GB/T582-1998, test mechanical property.Gained is 3.1 × 10 containing the number-average molecular weight of double bond bio-based polyurethane
4, weight-average molecular weight is 7.3 × 10
4.Gained contains the tensile strength of double bond bio-based polyurethane at 13MPa, and elongation at break is 1100%.
Two, radical crosslinking type bio-based polyurethane
The double bond bio-based polyurethane 10g that contains of film forming is dissolved in trichloromethane, add the radical initiator dicumyl peroxide of 0.05g, stir, then solution is poured in Teflon mould film forming, treat that solvent evaporates is complete, in 150 DEG C of vacuum drying ovens, be incubated 15 minutes, at this temperature, radical initiator decomposes and causes containing the double bond generation crosslinking reaction on double bond bio-based polyurethane.Bio-based polyurethane film (i.e. radical crosslinking type bio-based polyurethane) after crosslinked is cut out sample according to GB GB/T582-1998, test mechanical property.Crosslinked back draft intensity brings up to the 20MPa after being cross-linked from uncrosslinked 13MPa, and elongation at break is 450%.
Application examples 2
Double bond containing full bio-based polyester 13g (10mmol) prepared by embodiment 2, isophorone diisocyanate (IPDI) 4.446g, 2; 2-dimethylol propionic acid (DMPA) 0.651g, 1; 4-butyleneglycol 1.351g and 2 dibutyl tin laurate joins as catalyzer and is equipped with in churned mechanically 250ml there-necked flask; under nitrogen protection in 75 DEG C of reactions, in reaction process, add appropriate butanone adjusting viscosity.Be cooled to 40 DEG C after 4 hours, add in 0.61g triethylamine and carboxyl salify on DMPA, high-speed stirring reaction 30min.Add ultraviolet initiator benzophenone 0.2g, stir, then adding the emulsification of 80g deionized water high-speed stirring is emulsion, and at 50 DEG C, vacuum is taken off solvent and can be obtained the finished product (ultraviolet light solidfication water polyurethane).
Emulsion is poured into film forming in Teflon mould, after abundant drying, under being placed in 500W ultraviolet lamp, solidify 2min, then cut out sample according to GB GB/T582-1998, test mechanical property.The mechanical strength of the ultraviolet light solidfication water polyurethane of gained film forming is at 3.5MPa, and elongation at break is 550%.
Claims (5)
1. a double bond containing full bio-based polyester, is characterized in that, is the compound of formula I structure;
Wherein, m and n is mean polymerisation degree, n=28 ~ 300, m=0 ~ 108;
R
1for
r
2for
2. the preparation method of double bond containing full bio-based polyester according to claim 1, is characterized in that, comprise the following steps:
Under the protection of protective gas, bio-based diacid, bio-based glycol, catalyzer, thermo-stabilizer and oxidation inhibitor are joined in reactor, first 150 DEG C ~ 180 DEG C, carry out esterification 1h ~ 3h under 20KPa ~ 100KPa, then at 200 DEG C ~ 240 DEG C, 1KPa ~ 50KPa polycondensation 0.5h ~ 1h, finally be evacuated to below 100Pa, continue reaction 1h ~ 3h, obtain the double bond containing full bio-based polyester of formula I structure;
Described bio-based diacid at least comprises methylene-succinic acid, and described bio-based glycol is HO-R
2-OH, wherein, HO-R
2r in-OH
2with the R in formula I
2there is identical meanings.
3. the preparation method of double bond containing full bio-based polyester according to claim 1, is characterized in that, comprise the following steps:
Under the protection of protective gas, biomass acid dimethyl and bio-based dibasic alcohol are joined in reactor, first at 150 DEG C ~ 180 DEG C reaction 0.5h ~ 1h, then at 180 DEG C ~ 240 DEG C reaction 1h ~ 3h, again 150 DEG C ~ 160 DEG C, 1KPa ~ 50KPa reacts 0.5h ~ 2h, finally add catalyzer, thermo-stabilizer and oxidation inhibitor, be evacuated to below 100Pa, be warming up to 180 DEG C ~ 240 DEG C reaction 1h ~ 3h, obtain the double bond containing full bio-based polyester of formula I structure;
Described biomass acid dimethyl at least comprises dimethyl itaconate, and described bio-based glycol is HO-R
2-OH.
4. the preparation method of double bond containing full bio-based polyester according to claim 3, it is characterized in that, described biomass acid dimethyl also comprises:
5. the application in urethane prepared by double bond containing full bio-based polyester according to claim 1.
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| GB201402580D0 (en) * | 2014-02-14 | 2014-04-02 | Croda Int Plc | Polyurethane elastomers |
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| JP2018500402A (en) | 2014-11-03 | 2018-01-11 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | New polyurethane dispersions based on renewable raw materials |
| US10344307B2 (en) | 2015-06-15 | 2019-07-09 | Biome Bioplastics Limited | Processes for the formation of furandicarboxylic acid (FDCA) via a multistep biocatalytic oxidation reaction of 5-hydroxymethylfurfural (HMF) |
| CN106432701A (en) * | 2016-09-14 | 2017-02-22 | 中国科学院宁波材料技术与工程研究所 | Bio-based unsaturated polyester as well as preparation method and application thereof |
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| CN111138679B (en) * | 2019-12-31 | 2021-10-19 | 青岛科凯达新能源科技有限公司 | Bio-based liquid warm mixing agent and preparation method and application thereof |
| WO2022060043A1 (en) | 2020-09-16 | 2022-03-24 | 코오롱인더스트리 주식회사 | Novel catalyst material for producing polyester, method for producing polyester using same, and polyester produced thereby |
| KR20220036869A (en) | 2020-09-16 | 2022-03-23 | 코오롱인더스트리 주식회사 | Novel catalyst for preparing polyester, method for preparing polyester by using the same, and polyester prepared by using the same |
| JP2023540343A (en) | 2020-09-17 | 2023-09-22 | コーロン インダストリーズ インク | polyester polymer |
| CN113801305A (en) * | 2021-08-13 | 2021-12-17 | 中国科学院宁波材料技术与工程研究所 | Degradable bio-based polyester and preparation method, degradation method and application thereof |
| CN114621424B (en) * | 2022-01-07 | 2023-06-13 | 浙江恒逸石化研究院有限公司 | Preparation method of aliphatic-aromatic linear copolyester containing itaconic acid |
| CN114456335A (en) * | 2022-03-11 | 2022-05-10 | 中国医学科学院生物医学工程研究所 | Biodegradable elastomer material and preparation method thereof |
| CN116199871A (en) * | 2023-02-24 | 2023-06-02 | 四川轻化工大学 | All-bio-based polyester and preparation method thereof |
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