CN107163205A - A kind of unsaturated polyester (UP) performed polymer of ketone group containing and its production and use - Google Patents
A kind of unsaturated polyester (UP) performed polymer of ketone group containing and its production and use Download PDFInfo
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- CN107163205A CN107163205A CN201710331701.7A CN201710331701A CN107163205A CN 107163205 A CN107163205 A CN 107163205A CN 201710331701 A CN201710331701 A CN 201710331701A CN 107163205 A CN107163205 A CN 107163205A
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- unsaturated polyester
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- ketone group
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- GRZSIUJXKOKKEY-UHFFFAOYSA-N CC(C)(NC)[O]=C Chemical compound CC(C)(NC)[O]=C GRZSIUJXKOKKEY-UHFFFAOYSA-N 0.000 description 1
- SDSGCVCUSADRFA-UHFFFAOYSA-N CCC(c1ccc(C=O)cc1)=O Chemical compound CCC(c1ccc(C=O)cc1)=O SDSGCVCUSADRFA-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G16/00—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00
- C08G16/02—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes
- C08G16/0212—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes with acyclic or carbocyclic organic compounds
- C08G16/0218—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes with acyclic or carbocyclic organic compounds containing atoms other than carbon and hydrogen
- C08G16/0225—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes with acyclic or carbocyclic organic compounds containing atoms other than carbon and hydrogen containing oxygen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
- C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
- C07C69/738—Esters of keto-carboxylic acids or aldehydo-carboxylic acids
Abstract
The present invention relates to field of organic compound preparation, more particularly to a kind of ketone group containing unsaturated polyester (UP) performed polymer and its production and use.By dihydric alcohol and ethyl acetoacetate by ester exchange reaction, diacetyl acetate ester is made；Diacetyl acetate ester and binary aromatic aldehyde are monomer, and Knoevengel reactions occur under secondary amine/acetic acid catalysis, and the unsaturated polyester (UP) performed polymer of ketone group containing is made, and curing reaction occurs for the performed polymer, and the thermosetting unsaturated polyester resin of ketone group containing is made.As amido protecting agent, resin can be filtered directly from reaction solution after deprotection, and last handling process is easy.Raw material selection of the present invention is wide general, and cheap, synthetic route is succinct, and synthesis condition is gentle, has a good application prospect.
Description
Technical field
The present invention relates to field of organic compound preparation, more particularly to a kind of ketone group containing unsaturated polyester (UP) performed polymer and its
Preparation method and purposes.
Background technology
Unsaturated polyester (UP) on ordinary meaning refers to by unsaturated dibasic acid or acid anhydrides and dihydric alcohol, monounsaturated dicarboxylic acid or acid
The oligomer of acid anhydride and dihydric alcohol polycondensation, can further with vinyl monomer crosslinking copolymerization, form thermosetting resin.Typically
Example is that maleic anhydride, phthalic anhydride and 1,2-PD are main Material synthesis unsaturated polyester (UP), with styrene
For cross-linking monomer.In addition, epoxy resin end group can be converted into methacrylic acid ester group, vinyl ester resin is obtained, also be can be considered
A kind of special unsaturated polyester resin.This resinoid is currently widely used for preparing polymer matrix composites, but is seldom used as
Functional material.
Ketone group is a kind of important organic reaction group, can occur the various organic reactions such as oxidation, reduction, condensation.If
Ketone group is fixed on macromolecule carrier, can be used for the adsorbing separation of some compounds, or plays in organic reaction group
The effect of protection.It has been reported that the high molecular method for preparing ketone group containing crossed includes alkene and CO copolymerization, with the ethene containing ketone
Base monomer (such as methyl vinyl ketone) or cyclic monomer (such as modified caprolactone) polymerization, but not yet have been reported that preparation contains ketone
The method of the unsaturated polyester (UP) of base.It has been generally acknowledged that if a kind of monomer contains double bond, ketone group and ester group, double bond therein is not by shadow
Ring, and can solidify and be cross-linked into macromolecular polyester, its structure is certain to very complicated, and methyl vinyl ketone etc. is containing double bond and ketone group
Double bond is although unaffected in small molecule, but such small molecule can only simply polymerize, and no double bond solidification crosslinking is obtained
Macromolecular polyester.It is not mainstream research direction always plus aldoketones polymer, so everybody does not go to study and synthesize to contain
There is the unsaturated polyester (UP) of ketone group.
Amino is a kind of active functional group, need to be often protected by organic synthesis, it is to avoid the generation of side reaction, is commonly used
Blocking group have alkoxy carbonyl group, acyl group, trityl and benzyl etc..Group compounds of aldehydes and ketones can form schiff bases with amino,
It can be stabilized under alkalescence or anhydrous condition, and in neutral or acidity, having can remove under water condition, be also a kind of effective ammonia
Base protective agent.The Carbonyl compounds (such as benzaldehyde, 4-methyl-2 pentanone) of small molecule are adopted extensively in terms of amido protecting
With however, protection reagent is after deprotection, it is necessary to thoroughly removed from system, can just obtain pure product, this necessarily increases
The step of having added separating-purifying.
The content of the invention
The technical problem to be solved in the present invention is：In order to solve to protect during amido protecting reagent after deprotection not
The problem of can be easily separated, the present invention provides a kind of unsaturated polyester (UP) performed polymer of ketone group containing.
The technical solution adopted for the present invention to solve the technical problems is：A kind of unsaturated polyester (UP) performed polymer of ketone group containing,
Its structural formula is：
Wherein, R is the aliphatic carbon chain that carbon number is 4-10, either (CH2CH2O) n, n=10-150；Ar is benzene
Ring, the carbon phase contraposition of both sides is set to ortho position, meta or para position；N is 5-10.
The preparation method of the unsaturated polyester (UP) performed polymer of this ketone group containing is provided, concrete operation step includes：
(1) it is raw material by dihydric alcohol and ethyl acetoacetate, dihydric alcohol and ethyl acetoacetate amount of substance ratio are 1:5, nothing
Machine strong acid, organic acid or solid acid are catalyst, and benzene or toluene are reaction dissolvent, and then azeotropic is steamed for 2-3 hours with removing water
Solvent, and the ethanol generated is reacted using high temperature removal, it is warming up to 130 DEG C of normal pressures and continues to react 5-6 hours, biacetyl second is made
Acid esters, reaction equation is as follows,
Wherein, R is the aliphatic carbon chain that carbon number is 4-10, either (CH2CH2O)n, n=10-150；
Preferably, inorganic acid is that the concentrated sulfuric acid, organic acid are that p-methyl benzenesulfonic acid, solid acid are 732 types in step (1)
Strong-acid ion exchange resin.
Preferably, when making solvent with benzene in step (1), azeotropic temperature is 90 DEG C；When making solvent with toluene, azeotropic temperature
For 110 DEG C.
(2) reaction dissolvent, binary aromatic aldehyde and diacetyl acetate ester made from step (1) are added in flask, wherein double second
Ethyl sodio acetoacetic ester and binary aromatic aldehyde amount of substance ratio are 1:1, Knoevengel reactions, polycondensation 12-24 occur under secondary amine/acetic acid catalysis
Hour, the unsaturated polyester (UP) performed polymer of ketone group containing is made, reaction equation is as follows,
Wherein, R is the aliphatic carbon chain that carbon number is 4-10, either (CH2CH2O) n, n=10-150；Ar is benzene
Ring, the carbon phase contraposition of both sides is set to ortho position, meta or para position；N is 5-10.
Preferably, secondary amine is the one or more in piperidines, pyrrolidines, piperazine in step (2).
Preferably, reaction dissolvent is one kind or several in tetrahydrofuran, dioxane, ethanol, methanol in step (2)
Kind.
Preferably, polycondensation is carried out at room temperature in step (2).
The purposes of the unsaturated polyester (UP) performed polymer of this ketone group containing, the unsaturated polyester (UP) performed polymer of ketone group containing are also provided simultaneously
Thermosetting unsaturated polyester resin for preparing ketone group containing, the thermosetting unsaturated polyester resin of the ketone group containing is protected as amino
Reagent is protected, its concrete operation step includes：
(1) performed polymer quality 1-5% radical initiator is dissolved in dichloromethane, then with unsaturated polyester (UP) performed polymer
Well mixed, solvent volatilization is dry；Reacted 2 hours under the conditions of 90 DEG C, be warming up to 100 DEG C and react 6 hours, made double on strand
Key reacts with each other into cross-linked structure, and the thermosetting unsaturated polyester resin of ketone group containing is made.
Preferably, radical initiator is benzoyl peroxide, peroxidized t-butyl perbenzoate or azo in step (1)
Bis-isobutyronitrile.
The beneficial effects of the invention are as follows the present invention, will be easy using the synthetic route for being different from conventional unsaturated polyester resin
It is monomer in the diacetyl acetate ester of the ketocarbonyl-containing of synthesis, is reacted using Knoevengel while polycondensation, on main chain
Double bond is formed, the unsaturated polyester (UP) performed polymer of ketone group containing is made, the explanation present invention of accompanying drawing 3 and 4 has synthesized performed polymer, its
Structure does not have so complexity that those skilled in the art are thought.Kenovengel reactions are applied in field of polymer technology is no more than two
10 years, and field of photovoltaic materials is concentrated on, such as photoelectric material of the synthesis with full conjugate structure is more synthesized at present
CNPPV (cyano group polyphenylene ethylene), and the application in other fields does not draw attention, the present invention reacts Kenovengel
For unsaturated polyester (UP) preparation field, preferable technique effect is achieved.Using unsaturated polyester (UP) as skeleton, regulation two can be passed through
It is new that a class can be prepared after the characteristics such as mechanics, thermodynamics and the hydrophilic and hydrophobic of first alcohol type change resin, load keto functional group
The Reactive polymer material of type, as amido protecting agent, resin can be directly from reaction after deprotection
Filtered in solution, last handling process is easy.Raw material selection of the present invention is wide general, and cheap, synthetic route is succinct, synthesis condition
Gently, have a good application prospect.
Brief description of the drawings
The present invention is further described with reference to the accompanying drawings and examples.
Fig. 1 is butanediol diacetyl acetate ester 1 prepared by embodiment 11H NMR spectras.A (2.3ppm) and b
(3.5ppm) corresponds to the methyl and methene proton signal of ketone carbonyl both sides respectively, and c (4.2ppm) and d (1.7ppm) are right respectively
Adjacent with oxygen atom in butanediol residue and interval methene proton signal is answered, each signal peak strength integration is than being 3：2：2：2,
It is coincide with structure.
Fig. 2 is polyethylene glycol diacetyl acetate ester 2 prepared by embodiment 21H NMR spectras.A (2.3ppm) and b (3.5
Ppm the methyl and methene proton signal of ketone carbonyl both sides) are corresponded to respectively, and c (4.3ppm) and d (3.6-3.7ppm) are corresponded to respectively
And other methene proton signal adjacent with ester bond in polyethylene glycol residue, each signal peak strength integration is than being 3：2：2：9,
It is coincide with structure.
Fig. 3 is the polymeric reaction product 3 of butanediol diacetyl acetate ester 1 prepared by embodiment 11H NMR spectras.A is (about
1.9-2.4ppm) the methyl proton signal in correspondence acetyl group, b (about 7.9-8.0ppm) correspondence condensations produce the proton in double bond
Signal, c (about 3.5-4.2ppm) and d (about 1.2-1.9ppm) correspond to adjacent with oxygen atom in butanediol residue and interval respectively
Methene proton signal, the remaining unreacted aldehyde radical proton signal of e (about 10.0ppm) correspondences, ph (about 7.2-7.6ppm) correspondences
Proton signal on phenyl ring.B signal peaks proof there occurs polycondensation reaction, obtain unsaturated polyester (UP) performed polymer.
Fig. 4 is the polymeric reaction product 4 of polyethylene glycol diacetyl acetate ester 2 prepared by embodiment 21H NMR spectras.a
Methyl proton signal in (about 2.3ppm) correspondence acetyl group, b (about 7.9-8.0ppm) correspondence condensations produce the proton in double bond
Signal, c (about 4.3ppm) and d (3.5-3.8ppm) correspond to adjacent with ester bond in polyethylene glycol residue and other methylene respectively
On proton signal, the remaining unreacted aldehyde radical proton signal of e (about 10.0ppm) correspondences, ph (about 7.2-7.6ppm) correspondence phenyl ring
Proton signal.B signal peaks proof there occurs polycondensation reaction, obtain unsaturated polyester (UP) performed polymer.
Embodiment
In conjunction with the accompanying drawings, the present invention is further explained in detail.These accompanying drawings are simplified schematic diagram, only with
Illustration illustrates the basic structure of the present invention, therefore it only shows the composition relevant with the present invention.
Embodiment 1
(1) diacetyl acetate ester is synthesized, is shown below：
In equipped with stirring rotator, oil water separator, spherical condensation tube, the 250mL flasks of drying tube, butanediol is added
(9.0 g, 0.1mol), ethyl acetoacetate (65g, 0.5mol), p-methyl benzenesulfonic acid (0.28g) and 100mL benzene.In 90 DEG C of temperature
Then the lower azeotropic of degree steams solvent in 2 hours to remove water, and reacts the ethanol of generation using high temperature removal, is warming up to 130 DEG C of normal pressures
Reaction 6 hours.After reaction terminates, ethyl acetate 200mL is added, is washed with 5% sodium bicarbonate aqueous solution 3 times, each 100mL, then
It is washed with deionized water 3 times, anhydrous magnesium sulfate is added in organic phase and is dried overnight.Filter out after anhydrous magnesium sulfate, remove solvent under reduced pressure,
Oil pump vacuum distillation, is made 23g colorless oil diacetyl acetate esters, yield 65%.Accompanying drawing 1 is butanediol diacetyl acetate ester 1
(diacetyl acetate ester)1H NMR spectras.
(2) the unsaturated polyester (UP) performed polymer of ketone group containing is synthesized, is shown below：
In 50mL flasks, diacetyl acetate ester (1.3g, 5mmol) prepared by step (1), terephthalaldehyde are added
(0.66 g, 5mmol) and 10mL tetrahydrofurans, stirring and dissolving.Piperazine (0.023g) and 5 drop acetic acid are added, reaction is stirred at room temperature
24h.40mL n-hexanes are slowly added dropwise, stir simultaneously, stratification falls supernatant liquor, 50 DEG C of dry 12h obtain 1.70g bright
The unsaturated polyester (UP) performed polymer of yellow, viscous ketone group containing, yield 96%, the equal relative molecular mass M of numbern=2400, molecular weight point
Cloth Mw/Mn=1.53.Accompanying drawing 3 is (the unsaturated polyester (UP) pre-polymerization of ketone group containing of polymeric reaction product 3 of butanediol diacetyl acetate ester 1
Body)1H NMR spectras.
Embodiment 2
(1) diacetyl acetate ester is synthesized, is shown below：
The polyethylene glycol PEG400 equal relative molecular mass of number is about 9 for 400, x average value.
In equipped with stirring rotator, oil water separator, spherical condensation tube, the 250mL flasks of drier, PEG400 is added
(10 g, 0.025mol), ethyl acetoacetate (16g, 0.125mol), 732 type storng-acid cation exchange resins (3.4g) and
100mL benzene.Then azeotropic steams solvent, and the second generated is reacted using high temperature removal in 2 hours to remove water at a temperature of 90 DEG C
Alcohol, is warming up to 130 DEG C of synthesis under normal pressure 6 hours.After reaction terminates, filtering, and ion exchange resin is washed with a small amount of ethyl acetate,
It is incorporated to filtrate.Vacuum distillation filtrate removes solvent and excessive ethyl acetoacetate, and obtained 14.8g is colourless or pale yellowish oil is double
Acetoacetic ester, yield 90%.Accompanying drawing 2 is polyethylene glycol diacetyl acetate ester 2 (diacetyl acetate ester)1H NMR spectrograms.
(2) the unsaturated polyester (UP) performed polymer (tetrahydrofuran is solvent) of ketone group containing is synthesized, is shown below：
In 50mL flasks, diacetyl acetate ester (1.2g, 2mmol) prepared by step (1), terephthalaldehyde are added
(0.28 g, 2mmol) and 10mL tetrahydrofurans, stirring and dissolving.Piperazine (0.0056g) and 1 drop acetic acid are added, reaction is stirred at room temperature
24h.40mL n-hexanes are slowly added dropwise, stir simultaneously, stratification falls supernatant liquor, 50 DEG C of drys 12h, 1.09g are obtained orange
The unsaturated polyester (UP) performed polymer of yellow, viscous ketone group containing, yield 78%, the equal relative molecular mass M of numbern=3100, molecular weight point
Cloth Mw/Mn=1.70.(unsaturated polyester (UP) of ketone group containing is pre- for the polymeric reaction product 4 of polyethylene glycol diacetyl acetate ester 2 for accompanying drawing 4
Aggressiveness)1H NMR spectras.
Embodiment 3
(1) diacetyl acetate ester is synthesized, is shown below：
The polyethylene glycol PEG400 equal relative molecular mass of number is about 9 for 400, x average value.
In equipped with stirring rotator, oil water separator, spherical condensation tube, the 250mL flasks of drier, PEG400 is added
(10 g, 0.025mol), ethyl acetoacetate (16g, 0.125mol), 732 type storng-acid cation exchange resins (3.4g) and
100mL benzene.Then azeotropic steams solvent, and the second generated is reacted using high temperature removal in 2 hours to remove water at a temperature of 90 DEG C
Alcohol, is warming up to 130 DEG C of synthesis under normal pressure 6 hours.After reaction terminates, filtering, and ion exchange resin is washed with a small amount of ethyl acetate,
It is incorporated to filtrate.Vacuum distillation filtrate removes solvent and excessive ethyl acetoacetate, and obtained 14.6g is colourless or pale yellowish oil is double
Acetoacetic ester, yield 89%.
(2) synthesize the unsaturated polyester (UP) performed polymer of ketone group containing (ethanol is solvent)：
In 50mL flasks, diacetyl acetate ester (1.2g, 2mmol) prepared by step (1), terephthalaldehyde are added
(0.28 g, 2mmol) and 10mL ethanol, stirring and dissolving.Piperazine (0.0056g) and 1 drop acetic acid are added, reaction 24 is stirred at room temperature
h.40mL n-hexanes are slowly added dropwise, stir simultaneously, stratification falls supernatant liquor, 50 DEG C of dry 12h obtain 0.97g orange
The unsaturated polyester (UP) performed polymer of the thick ketone group containing of color, yield 66%, the equal relative molecular mass M of numbern=3200, molecular weight distribution
Mw/Mn=2.19.
Embodiment 4
(1) diacetyl acetate ester is synthesized, is shown below：
The polyethylene glycol PEG400 equal relative molecular mass of number is about 9 for 400, x average value.
In equipped with stirring rotator, oil water separator, spherical condensation tube, the 250mL flasks of drier, PEG400 is added
(10g, 0.025mol), ethyl acetoacetate (16g, 0.125mol), 732 type storng-acid cation exchange resins (3.4g) and
100 mL benzene.Then azeotropic steams solvent, and react generation using high temperature removal in 2 hours to remove water at a temperature of 90 DEG C
Ethanol, is warming up to 130 DEG C of synthesis under normal pressure 6 hours.After reaction terminates, filtering, and wash amberlite with a small amount of ethyl acetate
Fat, is incorporated to filtrate.Vacuum distillation filtrate removes solvent and excessive ethyl acetoacetate, is made that 14.4g is colourless or light yellow oil
Shape diacetyl acetate ester, yield 87%.
(2) synthesize the unsaturated polyester (UP) performed polymer of ketone group containing (pyrrolidines is catalyst)：
In 50mL flasks, diacetyl acetate ester (1.2g, 2mmol) prepared by step (1), terephthalaldehyde are added
(0.28 g, 2mmol) and 10mL tetrahydrofurans, stirring and dissolving.Pyrrolidines (0.011g) and 1 drop acetic acid are added, is stirred at room temperature anti-
Answer 24h.40mL n-hexanes are slowly added dropwise, stir simultaneously, stratification falls supernatant liquor, 50℃12h is dried, 1.07g is obtained
The unsaturated polyester (UP) performed polymer of orange-yellow thick ketone group containing, yield 76%, the equal relative molecular mass M of numbern=2800, molecular weight
It is distributed Mw/Mn=2.02.
Embodiment 5
Prepare the thermosetting unsaturated polyester resin (benzoyl peroxide for adding 1% resin quality) of ketone group containing：
0.005g benzoyl peroxides are dissolved in 3mL dichloromethane, the ketone group containing then prepared with 0.5g embodiments 1 is not
Saturated polyester performed polymer is well mixed, and solvent volatilization is dry.Reacted 2 hours at 90 DEG C, be warming up to 100 DEG C and react 6 hours, make molecule
Double bond on chain reacts with each other into cross-linked structure, and resin is solidified into kermesinus transparent solid by thick liquid, is made and contains ketone
The thermosetting unsaturated polyester resin of base.Cured product dichloromethane is extracted 12 hours for 70 DEG C in cable type extractor according, is dried
It is afterwards gel fraction with the percentage of resin quality before extracting, characterizes curing reaction degree.Gel fraction is 83% under the conditions of this.
Embodiment 6
Prepare the thermosetting unsaturated polyester resin (benzoyl peroxide for adding 5% resin quality) of ketone group containing：
0.025g benzoyl peroxides are dissolved in 3mL dichloromethane, the ketone group containing then prepared with 0.5g embodiments 1 is not
Saturated polyester performed polymer is well mixed, and solvent volatilization is dry.Reacted 2 hours at 90 DEG C, be warming up to 100 DEG C and react 6 hours, make molecule
Double bond on chain reacts with each other into cross-linked structure, and resin is solidified into kermesinus transparent solid by thick liquid, is made and contains ketone
The thermosetting unsaturated polyester resin of base.Cured product dichloromethane is extracted 12 hours for 70 DEG C in cable type extractor according, gel
Fraction is 90%.
Embodiment 7
Prepare the thermosetting unsaturated polyester resin (benzoyl peroxide for adding 1% resin quality) of ketone group containing：
0.005g benzoyl peroxides are dissolved in 3mL dichloromethane, the ketone group containing then prepared with 0.5g embodiments 2 is not
Saturated polyester performed polymer is well mixed, and solvent volatilization is dry.Reacted 2 hours at 90 DEG C, be warming up to 100 DEG C and react 6 hours, make molecule
Double bond on chain reacts with each other into cross-linked structure, and resin is solidified into glassy yellow transparent solid by thick liquid, is made and contains ketone
The thermosetting unsaturated polyester resin of base.Cured product dichloromethane is extracted 12 hours for 70 DEG C in cable type extractor according, gel
Fraction is 55%.
Embodiment 8
Prepare the thermosetting unsaturated polyester resin (benzoyl peroxide for adding 5% resin quality) of ketone group containing：
0.005g benzoyl peroxides are dissolved in 3mL dichloromethane, the ketone group containing then prepared with 0.5g embodiments 2 is not
Saturated polyester performed polymer is well mixed, and solvent volatilization is dry.Reacted 2 hours at 90 DEG C, be warming up to 100 DEG C and react 6 hours, make molecule
Double bond on chain reacts with each other into cross-linked structure, and resin is solidified into glassy yellow transparent solid by thick liquid, is made and contains ketone
The thermosetting unsaturated polyester resin of base.Cured product dichloromethane is extracted 12 hours for 70 DEG C in cable type extractor according, gel
Fraction is 76%.
Embodiment 9
The thermosetting unsaturated polyester resin of ketone group containing prepared by embodiment 6 is used to protect the ammonia in para-aminophenol
Base, it protects as follows with deprotection process：
(1) process is protected：The thermosetting unsaturated polyester resin of 5g ketone group containings is added in 100mL flasks (hereinafter referred to as
Resin) and benzole soln that 20mL para-aminophenol mass percent is 5%, stirring is heated to 90 DEG C, and flow back 12h.After cooling,
Resin is filtered out, is washed with benzene three times, is dried, the resin of load para-aminophenol is made；
(2) added in 100mL flasks the load resin of para-aminophenol, 2.5g chloroacetic chlorides prepared by 5g steps (1),
3h is reacted under 30mL dichloromethane and the stirring of 14mL triethylamines acid binding agent, normal temperature, resin is filtered out, is washed and dried with dichloromethane
It is dry, resin of the load to amion acetic acid phenol ester is made；
(3) it is deprotected process：The load of 5g steps (2) preparation is added in 100mL flasks to amion acetic acid phenol ester
Resin, adds 30mL ethanol and 1mL concentrated hydrochloric acids, during 24h, resin of the resin from load to amion acetic acid phenol ester is stirred at room temperature
Depart from, it is separately separated insoluble in ethanol and concentrated hydrochloric acid.After resin is filtered out, washing is several times, reusable after drying.Cross
Solution after filter adds 4mL 1M NaOH to be adjusted to alkalescence, reuses 50mL dichloromethane extraction to amion acetic acid phenol ester, steams
Dry dichloromethane, is made to amion acetic acid phenol ester.
In summary, the obtained diacetyl acetate esters monomer of ester exchange reaction occurs for dihydric alcohol and ethyl acetoacetate, double
Acetoacetic ester monomer can with aromatic dialdehyde by the into several equal relative molecular masses of Knoevengel reactive polymerics 3000
The unsaturated polyester (UP) performed polymer of the ketone group containing of left and right, and trigger double bond on main chain to be crosslinked by radical initiator, form ketone group containing
Thermosetting unsaturated polyester resin.
Desirable embodiment described above according to the present invention is enlightenment, passes through above-mentioned description, relevant staff
Various changes and amendments can be carried out without departing from the scope of the technological thought of the present invention' completely.The skill of this invention
Art scope is not limited to the content on specification, it is necessary to its technical scope is determined according to right.
Claims (9)
1. a kind of unsaturated polyester (UP) performed polymer of ketone group containing, it is characterised in that the structural formula of the performed polymer is：
Wherein, R is the aliphatic carbon chain that carbon number is 4-10, either (CH2CH2O) n, n=10-150；Ar is phenyl ring, two
The carbon relative position of side is ortho position, meta or para position；N is 5-10.
2. a kind of preparation method of the unsaturated polyester (UP) performed polymer of ketone group containing as claimed in claim 1, it is characterised in that described
The concrete operation step of preparation method includes：
(1) it is raw material by dihydric alcohol and ethyl acetoacetate, dihydric alcohol and ethyl acetoacetate amount of substance ratio are 1:5, it is inorganic strong
Acid, organic acid or solid acid are catalyst, and benzene or toluene are reaction dissolvent, and azeotropic steams molten for 2-3 hours to remove water, then
Agent, and the ethanol generated is reacted using high temperature removal, it is warming up to 130 DEG C of normal pressures and continues to react 5-6 hours, diacetyl acetate is made
Ester, reaction equation is as follows,
Wherein, R is the aliphatic carbon chain that carbon number is 4-10, either (CH2CH2O)n, n=10-150；
(2) reaction dissolvent, binary aromatic aldehyde and diacetyl acetate ester, wherein biacetyl second made from step (1) are added in flask
Acid esters and binary aromatic aldehyde amount of substance ratio are 1:1, Knoevengel reactions occur under secondary amine/acetic acid catalysis, polycondensation 12-24 is small
When, the unsaturated polyester (UP) performed polymer of ketone group containing is made, reaction equation is as follows,
R is the aliphatic carbon chain that carbon number is 4-10, either (CH2CH2O) n, n=10-150；Ar is phenyl ring, the carbon of both sides
Relative position is ortho position, meta or para position；N is 5-10.
3. the preparation method of the unsaturated polyester (UP) performed polymer of ketone group containing as claimed in claim 2, it is characterised in that step (1)
Middle inorganic acid is that the concentrated sulfuric acid, organic acid are that p-methyl benzenesulfonic acid, solid acid are 732 type strong-acid ion exchange resins.
4. the preparation method of the unsaturated polyester (UP) performed polymer of ketone group containing as claimed in claim 2, it is characterised in that step (1)
Middle when making solvent with benzene, azeotropic temperature is 90 DEG C；When making solvent with toluene, azeotropic temperature is 110 DEG C.
5. the preparation method of the unsaturated polyester (UP) performed polymer of ketone group containing as claimed in claim 2, it is characterised in that step (2)
Middle secondary amine is the one or more in piperidines, pyrrolidines, piperazine.
6. the preparation method of the unsaturated polyester (UP) performed polymer of ketone group containing as claimed in claim 2, it is characterised in that step (2)
Middle reaction dissolvent is the one or more in tetrahydrofuran, dioxane, ethanol, methanol.
7. the preparation method of the unsaturated polyester (UP) performed polymer of ketone group containing as claimed in claim 2, it is characterised in that step (2)
Middle polycondensation is carried out at room temperature.
8. a kind of purposes of the unsaturated polyester (UP) performed polymer of ketone group containing as claimed in claim 1, it is characterised in that the pre-polymerization
Body is used for the thermosetting unsaturated polyester resin for preparing ketone group containing, and the thermosetting unsaturated polyester resin of the ketone group containing is used as into ammonia
Base protects reagent, and its concrete operation step includes：
(1) performed polymer quality 1-5% radical initiator is dissolved in dichloromethane, then mixed with unsaturated polyester (UP) performed polymer
Uniformly, solvent volatilization is dry；Reacted 2 hours under the conditions of 90 DEG C, be warming up to 100 DEG C and react 6 hours, make double bond on strand that
This reacts into cross-linked structure, and the thermosetting unsaturated polyester resin of ketone group containing is made.
9. the purposes of the unsaturated polyester (UP) performed polymer of ketone group containing as claimed in claim 8, it is characterised in that in step (1) certainly
It is benzoyl peroxide, peroxidized t-butyl perbenzoate or azodiisobutyronitrile by base initiator.
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