CN103483571A - Double-bond-containing all-bio-based polyesters, and preparation method and application thereof - Google Patents
Double-bond-containing all-bio-based polyesters, and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses double-bond-containing all-bio-based polyesters disclosed as Formula I, wherein R1 and R2 are respectively an alkyl or aryl group, m and n are average polymerization degree, 1<=n<=1000, and 0<=m<=1000. The double-bond-containing all-bio-based polyesters contain double-bond active groups, can be subjected to subsequent crosslinking or modification, widen the possible application range, and are used for preparing polyurethane. The invention also discloses a preparation method of the double-bond-containing all-bio-based polyesters, which adopts an esterification-polycondensation two-stage process route and an ester exchange process route. The preparation method is simple and easy to implement and beneficial to industrialized large-scale production, and has high operability and wide application prospects.
Description
Technical field
The invention belongs to the technical field for preparing polyester, be specifically related to a kind of containing two full bio-based polyester of key and its preparation method and application.
Background technology
Polyester is the heterogeneous chain polymer of have on main chain-COO-ester group group.The 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 polyester can be used as the prepolymer of urethane; Linear aromatic polyester, as dacron polyester, can be used as synthon and engineering plastics; Unsaturated polyester, leave two keys in main chain, can be with other double bond containing reactive monomer copolymerization for reinforced plastics; Synolac, belong to the linear or random prepolymer of side chain, and residual groups is crosslinking curing further, therefore, can be used as coating.
Yet most production in the world at present, the chemical industry raw material of living required 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 are 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, traditional Polymeric Industry that the petrochemicals of take are raw material is faced with unprecedented challenge.The renewable biomass resources such as starch, Mierocrystalline cellulose, xylogen, polysaccharide of usining replace the petrochemical industry resource to obtain the extensive concern of industry member and academia as the raw material of chemical industry.Many commercializations of Chemical products that derive from biomass resource, as Dupont (DUEPONT), company produces 1,3-PD with biological fermentation process; The CDP of co-partnership company of U.S. Jia Ji (CARGILL) and DOW Chemical (DOW CHEMICAL) 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 monomers also have methylene-succinic acid, ethylene glycol, hexanodioic acid, 1, 4-succinic acid, sebacic acid, decanediol etc.Take biomass resource as the raw material production chemical and will be following developing direction with gained bio-based chemicals production macromolecular material.
As the Chinese invention patent application of application number 201210258520.3 discloses a kind of biological poly aromatic ester and preparation method thereof, carry out esterification with FDCA and diphenolic acid or bis-phenol acid esters under the effect of Esterified Enzyme and make esterification products; The Chinese invention patent application that application number is 201210258344.3 discloses a kind of bio-based polyester and preparation method thereof, carries out esterification-polycondensation with FDCA and Isosorbide-5-Nitrae-pentanediol and obtains polyester; The Chinese invention patent application that application number is 201110138492.7 discloses a kind of bio-based high-branched polyester and preparation method thereof, take vegetables oil as raw material, by free radical, causes mass polymerization, purifies and obtains high-branched polyester.
Above-mentioned polyester is bio-based polyester saturated or branching, by patent searching and document, finds, not yet has to take the methylene-succinic acid in bio-based source and the report that the bio-based dibasic alcohol is the synthetic unsaturated full bio-based polyester of raw material.
Summary of the invention
The invention provides a kind of double bond containing full bio-based polyester, contain two key active groups, can carry out follow-up crosslinked or modification, enlarge its possible range of application.
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 are mean polymerisation degree, 1≤n≤1000,0≤m≤1000.
By regulating n, m value, can regulate the content of carbon-carbon double bond in double bond containing full bio-based polyester in double bond containing full bio-based polyester, thus the performance of regulating 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.
The present invention also provides a kind of preparation method of double bond containing full bio-based polyester, adopts esterification-polycondensation two-stage process route, and preparation is simple, easy to implement, workable.
A kind of preparation method of 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 under 150 ℃～180 ℃, 20KPa～100KPa, carry out esterification 1h～3h, then at 200 ℃～240 ℃, 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 the ratio of carbon-carbon double bond in double bond containing full bio-based polyester regulated.
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, dodecane diprotic 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 only contains methylene-succinic acid, in resulting double bond containing full bio-based polyester, m=0.
As preferably, described bio-based glycol is ethylene glycol, 1,4-butyleneglycol, 1, ammediol, 1, the 9-ninth of the ten Heavenly Stems-glycol, decanediol, undecane glycol, dodecanediol, tetradecane glycol, rosinyl glycol, Isosorbide, 2, one or more in 5-furyl glycol (comprising two kinds).Further preferably, described bio-based glycol is ethylene glycol, 1,3-PD, BDO or decanediol.
As preferably, the mol ratio of described bio-based diacid and bio-based glycol is 1:0.5～2, wherein, in described bio-based diacid, the molecular fraction of methylene-succinic acid is 30%～100%, can guarantee the content of the relative ideal of carbon-carbon double bond in double bond containing full bio-based polyester.Further preferably, the mol ratio of described bio-based diacid and bio-based glycol is 1:1～1.8.
What used catalyst can be the inorganic acids catalyzer as in sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, tosic acid etc. is a kind of or two or more, can be also solid acid catalyst or a kind of or two or more for aluminum compound, tin compound, antimony compounds, titanium compound and zn cpds kind.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 preferred, is 0.01～0.5:100, further preferred, 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 for 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 for those skilled in the art know a small amount of.
The present invention also provides a kind of preparation method of double bond containing full bio-based polyester, adopts the ester exchange process route, and preparation is simple, easy to implement, workable.
A kind of preparation method of double bond containing full bio-based polyester comprises the following steps:
Under the protection of protective gas; biomass two dimethyl phthalates and bio-based dibasic alcohol are joined in reactor; first at 150 ℃～180 ℃ reaction 0.5h～1h; then at 180 ℃～240 ℃ reaction 1h～3h; react 0.5h～2h at 150 ℃～160 ℃, 1KPa～50KPa again, finally add catalyzer, thermo-stabilizer and oxidation inhibitor, be evacuated to below 100Pa; be warming up to 180 ℃～240 ℃ reaction 1h～3h, obtain the double bond containing full bio-based polyester of formula I structure.
Described biomass two dimethyl phthalates at least comprise 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 two dimethyl phthalates also comprise
wherein, R
1with the R in formula I
1there is identical meanings.
When described biomass two dimethyl phthalates only contain dimethyl itaconate, in resulting double bond containing full bio-based polyester, m=0.
As preferably, described bio-based glycol is ethylene glycol, 1,4-butyleneglycol, 1, ammediol, 1,9-nonanediol, decanediol, undecane glycol, dodecanediol, tetradecane glycol, rosinyl glycol, Isosorbide, 2, one or more in 5-furyl glycol (comprising two kinds).Further preferably, described bio-based glycol is ethylene glycol, 1,3-PD, BDO or decanediol.
As preferably, the mol ratio of described biomass two dimethyl phthalates and bio-based glycol is 1:0.5～2, wherein, the molecular fraction of described biomass two dimethyl phthalate underpants health dimethyl phthalates is 30%～100%, can guarantee the content of the relative ideal of carbon-carbon double bond in double bond containing full bio-based polyester.The mol ratio of described biomass two dimethyl phthalates and bio-based glycol is 1:1.
What used catalyst can be the inorganic acids catalyzer as in sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, tosic acid etc. is a kind of or two or more, can be also solid acid catalyst or a kind of or two or more for aluminum compound, tin compound, antimony compounds, titanium compound and zn cpds kind.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 two dimethyl phthalates is 0.01～1:100, further preferably, be 0.01～0.5:100, further preferred, be 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 for 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 for those skilled in the art know a small amount of.
During double bond containing full bio-based polyester prepared by the present invention is synthetic as urethane soft section, synthesis of polyurethane, for the preparation of urethane, concrete as containing two key bio-based polyurethanes, radical crosslinking type bio-based polyurethane and ultraviolet light solidfication water polyurethane.
A kind of preparation method containing two key bio-based polyurethanes comprises the following steps:
To mix containing two key bio-based polyester, isophorone diisocyanate, catalyzer dibutyl tin laurate and solvent 2-butanone, 60 ℃～80 ℃ reactions, within 2～4 hours, obtain prepolymer system;
The chainextender BDO is dissolved in the solvent 2-butanone, is added drop-wise in prepolymer system, at 70～90 ℃ of reaction 3～5h, except desolventizing can obtain containing two key bio-based polyurethanes.
A kind of preparation method of radical crosslinking type bio-based polyurethane comprises the following steps:
To be dissolved in trichloromethane containing two key bio-based polyurethanes, add the radical initiator dicumyl peroxide, mix, treat that solvent evaporates is complete, in 140 ℃～160 ℃ reactions 10～20 minutes, obtain radical crosslinking type bio-based polyurethane.
A kind of preparation method of ultraviolet light solidfication water polyurethane comprises the following steps:
By double bond containing full bio-based polyester, isophorone diisocyanate, 2, the 2-dimethylol propionic acid, 1, 4-butyleneglycol and dibutyl tin laurate join in reactor as catalyzer, under nitrogen protection in 70 ℃～80 ℃ reactions, add the butanone adjusting viscosity in reaction process, be cooled to 30 ℃～50 ℃ after 3～5h hour, add in triethylamine and the carboxyl salify, continue again stirring reaction 30min, then add ultraviolet initiator benzophenone 0.2g, stir, then adding the water stirring and emulsifying is emulsion, take off solvent, under ultraviolet lamp, solidify, can obtain ultraviolet light solidfication water polyurethane.
Compared with prior art, the present invention has following advantage:
One, the raw material that the present invention adopts is the bio-based source, does not rely on petroleum resources, and 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 two key bio-based polyester, and double bond content can regulate and control, and double bond containing full bio-based molecular weight of polyesters can regulate and control accordingly according to different demands.
Three, the double bond containing full bio-based polyester of the present invention, not only can be applied in the Application Areas of traditional polyester material and unsaturated polyester resin, and, two keys in this double bond containing full bio-based polyester can be used as active group and can proceed follow-up modification and reaction, thus can be applied in that urethane is synthetic, 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 two key active groups, can carry out follow-up crosslinked or modification, enlarges its possible range of application, has 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 large-scale industrialization production, possess wide application prospect.
The accompanying drawing explanation
The proton nmr spectra of the double bond containing full bio-based polyester that Fig. 1 is embodiment 1 preparation;
The Infrared Characterization spectrogram of the double bond containing full bio-based polyester that Fig. 2 is embodiment 1 preparation.
Embodiment
Below will to the present invention, be specifically described by embodiment, for embodiment be for content of the present invention is described better, but be not that content of the present invention only limits to illustrated embodiment.Those of ordinary skill in the art know in the situation that do not depart from spirit of the present invention or essential characteristic, can carry out suitable modification to the proportioning of raw material, material choice, operational condition, synthesis technique, material structure etc., therefore, the disclosed embodiment of embodiment is illustrative in all respects, rather than restrictive.
(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 ℃, carry out esterification under pressure 100KPa, in reaction process, fully stir, remove the water that reaction produces, the reaction times is 1h.
(2) after esterification finishes, reaction system is warming up to 200 ℃, and decompression step by step is to 50KPa, reaction 0.5h, then continue to be evacuated to the 96Pa left and right, continues reaction 3h and finish, and discharging after reaction finishes, obtain product (double bond containing full bio-based polyester).
The proton nmr spectra of the double bond containing full bio-based polyester of embodiment 1 preparation as shown in Figure 1, as we know from the figure, 5.7ppm, 6.3ppm locate the chemical shift into two hydrogen of two key ends on methylene-succinic acid, 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.1.3ppm the peak of locating is the chemical shift of 12 hydrogen atoms on six carbon atom in the middle of decanediol.The mol ratio that calculating by the nuclear-magnetism integral area can obtain methylene-succinic acid and hexanodioic acid is 0.98, with theoretical molar ratio 1, conforms to.The ratio that nuclear-magnetism calculates diprotic acid and dibasic alcohol is 1:1.2.
The Infrared Characterization spectrogram of the double bond containing full bio-based polyester of embodiment 1 preparation as shown in Figure 2.As can be known from Fig. 2,1730cm
-1the absorption peak at place is the absorption peak of ester group functional group in said structure, 1640cm
-1strong absorption peak and the 3030cm at place
-1the weak absorption peak at place is the infrared absorption peak of two keys in said structure, 3450cm
-1and 3550cm
-1two absorption peaks that weak absorption peak is the molecule chain end hydroxyl at place.
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 ℃, carry out esterification under pressure 20KPa, in reaction process, fully stir, remove the water that reaction produces, the reaction times is 2.5h.
(2) after esterification finishes, reaction system is warming up to 220 ℃, and decompression step by step is to 20KPa, reaction 1h, then continue to be evacuated to the 96Pa left and right, continues reaction 2h and finish, and discharging after reaction finishes, obtain product (double bond containing full bio-based polyester).
The proton nmr spectra of the double bond containing full bio-based polyester prepared according to embodiment 2 is known, 5.7ppm, 6.3ppm locate the chemical shift into two hydrogen of two key ends on methylene-succinic acid, 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.1.3ppm the peak of locating is the chemical shift of 12 hydrogen atoms on six carbon atom in the middle of decanediol.By integral area, calculate, 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.
The Infrared Characterization spectrogram of the double bond containing full bio-based polyester prepared according to embodiment 2 is known, 1730cm
-1the absorption peak at place is the absorption peak of ester group functional group in said structure; 1640cm
-1strong absorption peak and the 3030cm at place
-1the weak absorption peak at place is the infrared absorption peak of two keys in said structure, 3450cm
-1and 3550cm
-1two absorption peaks that weak absorption peak is the molecule chain end hydroxyl at place.
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, and then temperature reaction system to 150 ℃, react 0.5h; be warming up to again 180 ℃; keep reacting 1h at this temperature, carry out the normal pressure transesterification reaction, until the methyl alcohol discharge reaches the 95wt% left and right of theoretical value.
Wherein, R in BDO
2for
r in dodecanediol
2for
(2) reaction system is cooled to 150 ℃, connects vacuum system, be evacuated to 50KPa, reaction 1h, remove 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 and it is disperseed fully, stop logical nitrogen, continue to be evacuated to below 100Pa, and be warming up to 220 ℃, stir, isothermal reaction 3h finishes, and obtains product (double bond containing full bio-based polyester) simultaneously.
The proton nmr spectra of the double bond containing full bio-based polyester prepared according to embodiment 3 is known, 5.7ppm, 6.3ppm locate the chemical shift into two hydrogen of two key ends on methylene-succinic acid, 1.3ppm the chemical shift that the peak of locating is 16 hydrogen atoms on the carbon atoms of eight of centres of dodecane dibasic alcohol, 4.1ppm the peak of locating for ester group, be connected 1, the hydrogen of carbon atom on 4-butyleneglycol and dodecane dibasic alcohol, both respectively account for 50%.By integral area, calculate, 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.
The Infrared Characterization spectrogram of the double bond containing full bio-based polyester prepared according to embodiment 3 is known, 1730cm
-1the absorption peak at place is the absorption peak of ester group functional group in said structure; 1640cm
-1strong absorption peak and the 3030cm at place
-1the weak absorption peak at place is the infrared absorption peak of two keys in said structure, 3450cm
-1and 3500cm
-1two weak absorption 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 a kind of, n=94, m=0.
The mixture that the double bond containing full bio-based polyester that is gained is 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 ℃, carries out esterification under 50KPa, fully stir in reaction process, remove the water of generation, the reaction times is 3h.
Wherein, R in ethylene glycol
2for
r in decanediol
2for
(2) after esterification finishes, reaction system is warming up to 240 ℃, and decompression step by step is to 1KPa, reaction 0.5h, then continue to be evacuated to below 100Pa, continues reaction 1h and finish, and discharging obtains product (double bond containing full bio-based polyester).
The proton nmr spectra of the double bond containing full bio-based polyester prepared according to embodiment 4 is known, 5.7ppm, 6.3ppm locate the chemical shift into two hydrogen of two key ends on methylene-succinic acid, 4.4ppm the peak of locating is the chemical shift of 4 hydrogen atoms on two carbon atoms on ethylene glycol, the chemical shift that the peak at 4.1ppm place is carbon atom hydrogen on the decanediol be connected with ester group.By integral area, calculate, 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.
The Infrared Characterization spectrogram of the double bond containing full bio-based polyester prepared according to embodiment 4 is known, 1730cm
-1the absorption peak at place is the absorption peak of ester group functional group in said structure; 1640cm
-1strong absorption peak and the 3030cm at place
-1the weak absorption peak at place is the infrared absorption peak of two keys in said structure, 3450cm
-1and 3550cm
-1two absorption peaks that weak absorption peak is the molecule chain end hydroxyl at place.
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 a kind of, n=200, m=0.The mixture that the double bond containing full bio-based polyester that is gained is 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, and then temperature reaction system to 150 ℃, react 0.5h; be warming up to again 180 ℃; keep reacting 1h at this temperature, carry out the normal pressure transesterification reaction, until the methyl alcohol discharge reaches the 95wt% left and right of theoretical value.
R in dimethyl adipate
1for
r in dodecanediol
2for
(2) system is cooled to 150 ℃, connects vacuum system, be evacuated to 50KPa, reaction 1h, remove 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 and it is disperseed fully, stop logical nitrogen, continue to be evacuated to below 100Pa, and be warming up to 220 ℃, the while rapid stirring, isothermal reaction 3h finishes, and obtains product (double bond containing full bio-based polyester).
The proton nmr spectra of the double bond containing full bio-based polyester prepared according to embodiment 5 is known, 5.7ppm, 6.3ppm locate the chemical shift into two hydrogen of two key ends on methylene-succinic acid, 2.3ppm the chemical shift that the peak of locating is 4 hydrogen atoms on two carbon atoms adjacent with ester group in hexanodioic acid, the peak at 1.3ppm place is the chemical shift of 16 hydrogen atoms on eight carbon atoms in the middle of the dodecane dibasic alcohol.By integral area, calculate, 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.
The Infrared Characterization spectrogram of the double bond containing full bio-based polyester prepared according to embodiment 5 is known, 1730cm
-1the absorption peak at place is the absorption peak of ester group functional group in said structure; 1640cm
-1strong absorption peak and the 3030cm at place
-1the weak absorption peak at place is the infrared absorption peak of two keys in said structure, 3450cm
-1and 3550cm
-1two absorption peaks that weak absorption peak is molecule chain end hydroxyl and carboxyl at place.
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 ℃, carry out esterification under pressure 20KPa, in reaction process, fully stir, remove the water that reaction produces, the reaction times is 2.5h.
(2) after esterification finishes, reaction system is warming up to 220 ℃, and decompression step by step is to 20KPa, reaction 1h, then continue to be evacuated to the 96Pa left and right, continues reaction 2h and finish, and discharging after reaction finishes, obtain product (double bond containing full bio-based polyester).
The proton nmr spectra of the double bond containing full bio-based polyester prepared according to embodiment 6 is known, 5.7ppm, 6.3ppm locate the chemical shift into two hydrogen of two key ends on methylene-succinic acid, 4.1ppm the peak of locating is 1, in the 4-butyleneglycol with the ester group adjacent carbons on the chemical shift of hydrogen, the peak at 1.3ppm place is the chemical shift of 8 hydrogen atoms on 4 methylene radical in the middle of sebacic acid.By integral area, calculate, 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.
The Infrared Characterization spectrogram of the double bond containing full bio-based polyester prepared according to embodiment 6 is known, 1730cm
-1the absorption peak at place is the absorption peak of ester group functional group in said structure; 1640cm
-1strong absorption peak and the 3030cm at place
-1the weak absorption peak at place is the infrared absorption peak of two keys in said structure, 3450cm
-1and 3550cm
-1two absorption peaks that weak absorption peak is the molecule chain end hydroxyl at place.
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, and then temperature reaction system to 150 ℃, react 0.5h; be warming up to again 180 ℃; keep reacting 1h at this temperature, carry out the normal pressure transesterification reaction, until the methyl alcohol discharge reaches the 95wt% left and right of theoretical value.
R in the FDCA dimethyl ester
1for
r in BDO
2for
(2) system is cooled to 150 ℃, connects vacuum system, be evacuated to 50KPa, reaction 1h, remove 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 and it is disperseed fully, stop logical nitrogen, continue to be evacuated to below 100Pa, and be warming up to 220 ℃, the while rapid stirring, isothermal reaction 3h finishes, and obtains product (double bond containing full bio-based polyester).
The proton nmr spectra of the double bond containing full bio-based polyester prepared according to embodiment 7 is known, 5.7ppm, the chemical shift that the 6.3ppm place is two hydrogen of two key ends on methylene-succinic acid, the chemical shift that the peak at 7.5ppm place is hydrogen atom on the two keys of furan nucleus.4.1 the multiplet at～4.3ppm place be in BDO with the ester group adjacent carbons on the chemical shift of hydrogen.By integral area, calculate, 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.
The Infrared Characterization spectrogram of the double bond containing full bio-based polyester prepared according to embodiment 7 is known, 1730cm
-1the absorption peak at place is the absorption peak of ester group functional group in said structure; 1640cm
-1strong absorption peak and the 3030cm at place
-1the weak absorption peak at place is the infrared absorption peak of two keys in said structure, 3450cm
-1and 3500cm
-1two absorption peaks that weak absorption peak is molecule chain end hydroxyl and carboxyl at place.
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 to 150 ℃; reaction 0.5h, then be warming up to 170 ℃, keep reacting 1h at this temperature; carry out the normal pressure transesterification reaction, until the methyl alcohol discharge reaches the 95wt% left and right of theoretical value.
R in the FDCA dimethyl ester
1for
r in 1,3-PD
2for
(2) system is cooled to 150 ℃, connects vacuum system, be evacuated to 50KPa, reaction 1h, remove 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 and it is disperseed fully, stop logical nitrogen, continue to be evacuated to below 100Pa, and be warming up to 220 ℃, the while rapid stirring, isothermal reaction 3h finishes, and obtains product (double bond containing full bio-based polyester).
The proton nmr spectra of the double bond containing full bio-based polyester prepared according to embodiment 8 is known, 5.7ppm, the chemical shift that the 6.3ppm place is two hydrogen of two key ends on methylene-succinic acid, the chemical shift that the peak at 7.5ppm place is hydrogen atom on the two keys of furan nucleus.4.1 the multiplet at～4.3ppm place be in 1,3-PD with the ester group adjacent carbons on the chemical shift of hydrogen.By integral area, calculate, 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.
The Infrared Characterization spectrogram of the double bond containing full bio-based polyester prepared according to embodiment 8 is known, 1730cm
-1the absorption peak at place is the absorption peak of ester group functional group in said structure; 1640cm
-1strong absorption peak and the 3030cm at place
-1the weak absorption peak at place is the infrared absorption peak of two keys in said structure, 3450cm
-1and 3500cm
-1two absorption peaks that weak absorption peak is molecule chain end hydroxyl and carboxyl at place.
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 the double bond containing full bio-based polyester of embodiment 2 preparations, the hydroxyl value that contains two key bio-based polyester according to HG/T 2709-1995 standard test gained is 84mg KOH/g.
One, synthesizing containing two key bio-based polyurethanes
Will be containing two key bio-based polyester 13g (10mmol), isophorone diisocyanate (IPDI) 4.4456g (20mmol), 3 of catalyzer dibutyl tin laurates (DBTDL) and solvent 2-butanone 30g, join with in churned mechanically there-necked flask, in 65 ℃ of reactions, within 3 hours, obtain prepolymer.Chainextender BDO 0.9012g (10mmol) is dissolved in 15g solvent 2-butanone, with constant pressure funnel, is added drop-wise in reaction system, is warming up to 80 ℃ simultaneously, and reaction 4h, until 2266cm on infrared spectrum
-1the infrared absorption peak of place's isocyanic ester disappears, and stopped reaction obtains containing two key bio-based polyurethane solution.
To be poured on film forming in the mould of tetrafluoroethylene containing two key bio-based polyurethane solution, and treat that solvent evaporates will be complete, the material of film forming is containing two key bio-based polyurethanes, then according to GB GB/T582-1998, cuts out sample, the test mechanical property.Gained is 3.1 * 10 containing the number-average molecular weight of two key bio-based polyurethanes
4, weight-average molecular weight is 7.3 * 10
4.Gained contains the tensile strength of two key bio-based polyurethanes at 13MPa, and elongation at break is 1100%.
Two, radical crosslinking type bio-based polyurethane
By being dissolved in trichloromethane containing two key bio-based polyurethane 10g of film forming, the radical initiator dicumyl peroxide that adds 0.05g, stir, then solution is poured into to film forming in the tetrafluoroethylene mould, treat that solvent evaporates is complete, in 150 ℃ of vacuum drying ovens, insulation is 15 minutes, and at this temperature, radical initiator decomposes and causes containing the two key generation crosslinking reactions on two key bio-based polyurethanes.Bio-based polyurethane film after crosslinked (being radical crosslinking type bio-based polyurethane) is cut out to sample according to GB GB/T582-1998, the test mechanical property.Crosslinked back draft intensity is brought up to the 20MPa crosslinked from uncrosslinked 13MPa, and elongation at break is 450%.
Application examples 2
Double bond containing full bio-based polyester 13g (10mmol), isophorone diisocyanate (IPDI) 4.446g, 2 by embodiment 2 preparations; 2-dimethylol propionic acid (DMPA) 0.651g, 1; 4-butyleneglycol 1.351g and 2 dibutyl tin laurates join and are equipped with in churned mechanically 250ml there-necked flask as catalyzer; in 75 ℃ of reactions, add appropriate butanone adjusting viscosity in reaction process under nitrogen protection.Be cooled to 40 ℃ after 4 hours, add in the 0.61g triethylamine and DMPA on the carboxyl salify, 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 50 ℃ of lower vacuum are taken off solvent and can be obtained the finished product (ultraviolet light solidfication water polyurethane).
Pour emulsion in tetrafluoroethylene mould film forming, after abundant drying, be placed under the 500W ultraviolet lamp and solidify 2min, then according to GB GB/T582-1998, cut out sample, the 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 (10)
1. a double bond containing full bio-based polyester, is characterized in that, is the compound of formula I structure;
Wherein, R
1, R
2for alkyl or aryl, m and n are mean polymerisation degree, 1≤n≤1000,0≤m≤1000.
2. double bond containing full bio-based polyester according to claim 1, is characterized in that R
1for
or
r
2for
or
3. double bond containing full bio-based polyester according to claim 1, is characterized in that n=28～300, m=0～108.
4. according to the preparation method of the described double bond containing full bio-based polyester of claim 1～3 any one, it 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 under 150 ℃～180 ℃, 20KPa～100KPa, carry out esterification 1h～3h, then at 200 ℃～240 ℃, 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.
5. the preparation method of double bond containing full bio-based polyester according to claim 4, is characterized in that, 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, dodecane diprotic acid, tetradecane diacid, FDCA, rosinyl diprotic acid;
Wherein, HOOC-R
1r in-COOH
1with the R in formula I
1there is identical meanings.
6. the preparation method of double bond containing full bio-based polyester according to claim 4, it is characterized in that, described bio-based glycol is ethylene glycol, 1,4-butyleneglycol, 1, ammediol, 1,9-nonanediol, decanediol, undecane glycol, dodecanediol, tetradecane glycol, rosinyl glycol, Isosorbide, 2, one or more in 5-furyl glycol.
7. according to the preparation method of the described double bond containing full bio-based polyester of claim 1～3 any one, it is characterized in that, comprise the following steps:
Under the protection of protective gas, biomass two dimethyl phthalates and bio-based dibasic alcohol are joined in reactor, first at 150 ℃～180 ℃ reaction 0.5h～1h, then at 180 ℃～240 ℃ reaction 1h～3h, react 0.5h～2h at 150 ℃～160 ℃, 1KPa～50KPa again, finally add catalyzer, thermo-stabilizer and oxidation inhibitor, be evacuated to below 100Pa, be warming up to 180 ℃～240 ℃ reaction 1h～3h, obtain the double bond containing full bio-based polyester of formula I structure;
Described biomass two dimethyl phthalates at least comprise 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.
8. the preparation method of double bond containing full bio-based polyester according to claim 7, is characterized in that, described biomass two dimethyl phthalates also comprise:
Wherein, R
1with the R in formula I
1there is identical meanings.
9. the preparation method of double bond containing full bio-based polyester according to claim 7, it is characterized in that, described bio-based glycol is ethylene glycol, 1,4-butyleneglycol, 1, ammediol, 1,9-nonanediol, decanediol, undecane glycol, dodecanediol, tetradecane glycol, rosinyl glycol, Isosorbide, 2, one or more in 5-furyl glycol.
10. according to the application of the described double bond containing full bio-based polyester of claim 1～3 any one in preparing urethane.
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