CN107163205B - A kind of unsaturated polyester (UP) performed polymer of ketone group containing and its preparation method and application - Google Patents
A kind of unsaturated polyester (UP) performed polymer of ketone group containing and its preparation method and application Download PDFInfo
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- CN107163205B CN107163205B CN201710331701.7A CN201710331701A CN107163205B CN 107163205 B CN107163205 B CN 107163205B CN 201710331701 A CN201710331701 A CN 201710331701A CN 107163205 B CN107163205 B CN 107163205B
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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 unsaturated polyester (UP) performed polymer of ketone group containing and its preparation method and application.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 reaction occurs under secondary amine/acetic acid catalysis, the unsaturated polyester (UP) performed polymer of ketone group containing is made, which is cured reaction, and the thermosetting property 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 mild, has a good application prospect.
Description
Technical field
The present invention relates to the unsaturated polyester (UP) performed polymer of field of organic compound preparation more particularly to a kind of ketone group containing and its
Preparation method and purposes.
Background technique
Unsaturated polyester (UP) on ordinary meaning refers to by unsaturated dibasic acid or acid anhydrides and dihydric alcohol, monounsaturated dicarboxylic acid or acid
Oligomer made of acid anhydride and dihydric alcohol polycondensation can form thermosetting resin further with vinyl monomer crosslinking copolymerization.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 methacrylate, vinyl ester resin is obtained, also 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, and the various organic reactions such as oxidation, reduction, condensation can occur.If
Ketone group is fixed on macromolecule carrier, can be used for the adsorbing separation of some compounds, or plays group in organic reaction
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 ethylene containing ketone
Base monomer (such as methyl vinyl ketone) or cyclic monomer (such as modified caprolactone) polymerization, but not yet have been reported that and prepare ketone group containing
Unsaturated polyester (UP) method.It has been generally acknowledged that double bond therein is not by shadow if a kind of monomer contains double bond, ketone group and ester group
It rings, and can solidify and be cross-linked into macromolecular polyester, structure is certain to very complicated, and methyl vinyl ketone etc. contains 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 obtains
Macromolecular polyester.In addition aldehyde ketone quasi polymer is not mainstream research direction always, 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 often be protected in organic synthesis, 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 alkalinity or anhydrous condition, and neutral or acid, having can remove under the conditions of water and 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 be completely removed from system, can just obtain pure product, this necessarily increases
The step of having added separating-purifying.
Summary of the invention
The technical problem to be solved by 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 provide a kind of unsaturated polyester (UP) performed polymer of ketone group containing.
The technical solution adopted by the present invention to solve the technical problems is: a kind of unsaturated polyester (UP) performed polymer of ketone group containing,
Its structural formula are as follows:
Wherein, R is the aliphatic carbon chain that carbon atom number is 4-10, either (CH2CH2O)m, m=10-150；Ar is benzene
The carbon phase contraposition of ring, two 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:
It (1) is raw material by dihydric alcohol and ethyl acetoacetate, dihydric alcohol and ethyl acetoacetate the mass ratio of the material are 1:5,
Inorganic acid, organic acid or solid acid are catalyst, and benzene or toluene are reaction dissolvent, are then steamed with removing water within azeotropic 2-3 hours
Solvent out, and the ethyl alcohol generated using high temperature removal reaction, being warming up to 130 DEG C of normal pressures, the reaction was continued 5-6 hours, and biacetyl is made
Acetic acid esters, reaction equation is as follows,
Wherein, R is the aliphatic carbon chain that carbon atom number is 4-10, either (CH2CH2O)m, m=10-150；
Preferably, inorganic acid is the concentrated sulfuric acid in step (1), organic acid is p-methyl benzenesulfonic acid, solid acid is 732 types
Strong-acid ion exchange resin.
Preferably, azeotropic temperature is 90 DEG C when making solvent with benzene in step (1)；When making solvent with toluene, azeotropic temperature
It is 110 DEG C.
(2) the diacetyl acetate ester made from addition reaction dissolvent, binary aromatic aldehyde and step (1) in flask, wherein double second
Ethyl sodio acetoacetic ester and binary aromatic aldehyde the mass ratio of the material are 1:1, and Knoevengel reaction, polycondensation 12- occur under secondary amine/acetic acid catalysis
24 hours, 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 atom number is 4-10, either (CH2CH2O)m, m=10-150；Ar is benzene
The carbon phase contraposition of ring, two sides is set to ortho position, meta or para position；N is 5-10.
Preferably, secondary amine is one or more of piperidines, pyrrolidines, piperazine in step (2).
Preferably, reaction dissolvent is one of tetrahydrofuran, dioxane, ethyl alcohol, methanol or several in step (2)
Kind.
Preferably, polycondensation carries 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
It is used to prepare the thermosetting property unsaturated polyester resin of ketone group containing, the thermosetting property unsaturated polyester resin of the ketone group containing is protected as amino
Reagent is protected, concrete operation step includes:
(1) radical initiator of prepolymer mass 1-5% is dissolved in methylene chloride, then with unsaturated polyester (UP) performed polymer
It is uniformly mixed, solvent volatilization is dry；It is reacted 2 hours under the conditions of 90 DEG C, is warming up to 100 DEG C and reacts 6 hours, made double on strand
Key reacts with each other into cross-linked structure, and the thermosetting property 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 invention has the advantages that the present invention uses the synthetic route for being different from conventional unsaturated polyester resin, it will be easy
It is monomer in the diacetyl acetate ester of the ketocarbonyl-containing of synthesis, is reacted while polycondensation using Knoevengel, on main chain
Double bond is formed, the unsaturated polyester (UP) performed polymer of ketone group containing is made, attached drawing 3 and 4 illustrates that the present invention has synthesized performed polymer,
There is no those skilled in the art to be thought so complicated for structure.Kenovengel reaction is applied in the field of polymers is no more than two
10 years, and field of photovoltaic materials is concentrated on, such as synthesis has the photoelectric material of full conjugate structure, more synthesizes at present
CNPPV (cyano polyphenylene ethylene), and the application in other fields does not draw attention, the present invention reacts Kenovengel
For unsaturated polyester (UP) preparation field, ideal technical effect is achieved.It, can be by adjusting two using unsaturated polyester (UP) as skeleton
The characteristics such as mechanics, thermodynamics and the hydrophilic and hydrophobic of first alcohol type change resin can prepare one kind newly after loading keto functional group
The Reactive polymer material of type, as amido protecting agent, resin can be directly from reaction after deprotection
It is 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
Mildly, it has a good application prospect.
Detailed description of the invention
Present invention will be further explained below with reference to the attached drawings and examples.
Fig. 1 is butanediol diacetyl acetate ester 1 prepared by embodiment 11H NMR spectra.A (2.3ppm) and b
(3.5ppm) respectively corresponds the methyl and methene proton signal of ketone carbonyl two sides, and c (4.2ppm) and d (1.7ppm) are respectively corresponded
Adjacent with oxygen atom and interval methene proton signal in butanediol residue, each signal peak strength integral ratio is 3:2:2:2, with
Structure is coincide.
Fig. 2 is polyethylene glycol diacetyl acetate ester 2 prepared by embodiment 21H NMR spectra.A (2.3ppm) and b
(3.5ppm) respectively corresponds the methyl and methene proton signal of ketone carbonyl two sides, and c (4.3ppm) and d (3.6-3.7ppm) are respectively
Methene proton signals adjacent and other with ester bond in corresponding polyethylene glycol residue, each signal peak strength integral is than being 3:2:2:
9, it coincide with structure.
Fig. 3 is the polymeric reaction product 3 of butanediol diacetyl acetate ester 1 prepared by embodiment 11H NMR spectra.A is (about
1.9-2.4ppm) the methyl proton signal in corresponding acetyl group, the corresponding condensation of b (about 7.9-8.0ppm) generate the proton in double bond
Signal, c (about 3.5-4.2ppm) and d (about 1.2-1.9ppm) respectively correspond adjacent with oxygen atom in butanediol residue and interval
Methene proton signal, the corresponding remaining unreacted aldehyde radical proton signal of e (about 10.0ppm), ph (about 7.2-7.6ppm) are corresponding
Proton signal on phenyl ring.Polycondensation reaction has occurred in b signal peak proof, has obtained 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 spectra.a
Methyl proton signal in (about 2.3ppm) corresponding acetyl group, the corresponding condensation of b (about 7.9-8.0ppm) generate the proton in double bond
Signal, c (about 4.3ppm) and d (3.5-3.8ppm) respectively correspond methylene adjacent and other with ester bond in polyethylene glycol residue
Proton signal, the corresponding remaining unreacted aldehyde radical proton signal of e (about 10.0ppm), ph (about 7.2-7.6ppm) are corresponded on phenyl ring
Proton signal.Polycondensation reaction has occurred in b signal peak proof, has obtained unsaturated polyester (UP) performed polymer.
Specific embodiment
In conjunction with the accompanying drawings, the present invention is further explained in detail.These attached drawings are simplified schematic diagram, only with
Illustration illustrates basic structure of the invention, therefore it only shows the composition relevant to the invention.
Embodiment 1
(1) diacetyl acetate ester is synthesized, is shown below:
In the 250mL flask that stirring rotator, oil water separator, spherical condensation tube, drying tube are housed, butanediol is added
(9.0g, 0.1mol), ethyl acetoacetate (65g, 0.5mol), p-methyl benzenesulfonic acid (0.28g) and 100mL benzene.In 90 DEG C of temperature
Lower azeotropic is spent 2 hours with water removal, is then steamed solvent, and the ethyl alcohol generated using high temperature removal reaction, is warming up to 130 DEG C of normal pressures
Reaction 6 hours.After reaction, ethyl acetate 200mL is added, is washed 3 times, each 100mL with 5% sodium bicarbonate aqueous solution, then
It is washed with deionized water 3 times, anhydrous magnesium sulfate is added in organic phase and is dried overnight.After filtering out anhydrous magnesium sulfate, evaporating solvent under reduced pressure,
Oil pump vacuum distillation, is made 23g colorless oil diacetyl acetate ester, yield 65%.Attached drawing 1 is butanediol diacetyl acetate ester 1
(diacetyl acetate ester)1H NMR spectra.
(2) the unsaturated polyester (UP) performed polymer for synthesizing ketone group containing, is shown below:
In 50mL flask, the diacetyl acetate ester (1.3g, 5mmol) of step (1) preparation, terephthalaldehyde is added
(0.66g, 5mmol) and 10mL tetrahydrofuran, stirring and dissolving.Piperazine (0.023g) and 5 drop acetic acid is added, reaction is stirred at room temperature
24h.40mL n-hexane is slowly added dropwise, stirs simultaneously, stratification removes supernatant liquor, and it is bright to obtain 1.70g by 50 DEG C of dry 12h
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.Attached 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 spectra.
Embodiment 2
(1) diacetyl acetate ester is synthesized, is shown below:
The equal relative molecular mass of the number of polyethylene glycol PEG400 is that the average value of 400, x is about 9.
In the 250mL flask that stirring rotator, oil water separator, spherical condensation tube, drier are housed, PEG400 is added
(10g, 0.025mol), ethyl acetoacetate (16g, 0.125mol), 732 type storng-acid cation exchange resins (3.4g) and
100mL benzene.90 DEG C at a temperature of azeotropic 2 hours with water removal, then steam solvent, and the second generated using high temperature removal reaction
Alcohol, is warming up to 130 DEG C of synthesis under normal pressure 6 hours.After reaction, it filters, and washs ion exchange resin with a small amount of ethyl acetate,
It is incorporated to filtrate.It is evaporated under reduced pressure filtrate and removes solvent and excessive ethyl acetoacetate, obtained 14.8g is colourless or pale yellowish oil is double
Acetoacetic ester, yield 90%.Attached drawing 2 is polyethylene glycol diacetyl acetate ester 2 (diacetyl acetate ester)1H NMR spectra.
(2) the unsaturated polyester (UP) performed polymer (tetrahydrofuran is solvent) for synthesizing ketone group containing, is shown below:
In 50mL flask, the diacetyl acetate ester (1.2g, 2mmol) of step (1) preparation, terephthalaldehyde is added
(0.28g, 2mmol) and 10mL tetrahydrofuran, stirring and dissolving.Piperazine (0.0056g) and 1 drop acetic acid is added, reaction is stirred at room temperature
24h.40mL n-hexane is slowly added dropwise, stirs simultaneously, stratification removes supernatant liquor, and 50 DEG C of dry 12h obtain 1.09g 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.Attached drawing 4 be polyethylene glycol diacetyl acetate ester 2 polymeric reaction product 4 (unsaturated polyester (UP) of ketone group containing is pre-
Aggressiveness)1H NMR spectra.
Embodiment 3
(1) diacetyl acetate ester is synthesized, is shown below:
The equal relative molecular mass of the number of polyethylene glycol PEG400 is that the average value of 400, x is about 9.
In the 250mL flask that stirring rotator, oil water separator, spherical condensation tube, drier are housed, PEG400 is added
(10g, 0.025mol), ethyl acetoacetate (16g, 0.125mol), 732 type storng-acid cation exchange resins (3.4g) and
100mL benzene.90 DEG C at a temperature of azeotropic 2 hours with water removal, then steam solvent, and the second generated using high temperature removal reaction
Alcohol, is warming up to 130 DEG C of synthesis under normal pressure 6 hours.After reaction, it filters, and washs ion exchange resin with a small amount of ethyl acetate,
It is incorporated to filtrate.It is evaporated under reduced pressure filtrate and removes solvent and excessive ethyl acetoacetate, obtained 14.6g is colourless or pale yellowish oil is double
Acetoacetic ester, yield 89%.
(2) the unsaturated polyester (UP) performed polymer (ethyl alcohol is solvent) of ketone group containing is synthesized:
In 50mL flask, the diacetyl acetate ester (1.2g, 2mmol) of step (1) preparation, terephthalaldehyde is added
(0.28g, 2mmol) and 10mL ethyl alcohol, stirring and dissolving.Piperazine (0.0056g) and 1 drop acetic acid is added, reaction is stirred at room temperature for 24 hours.
40mL n-hexane is slowly added dropwise, stirs simultaneously, stratification removes supernatant liquor, and it is orange-yellow to obtain 0.97g by 50 DEG C of dry 12h
The unsaturated polyester (UP) performed polymer of thick ketone group containing, 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 equal relative molecular mass of the number of polyethylene glycol PEG400 is that the average value of 400, x is about 9.
In the 250mL flask that stirring rotator, oil water separator, spherical condensation tube, drier are housed, PEG400 is added
(10g, 0.025mol), ethyl acetoacetate (16g, 0.125mol), 732 type storng-acid cation exchange resins (3.4g) and
100mL benzene.90 DEG C at a temperature of azeotropic 2 hours with water removal, then steam solvent, and the second generated using high temperature removal reaction
Alcohol, is warming up to 130 DEG C of synthesis under normal pressure 6 hours.After reaction, it filters, and washs ion exchange resin with a small amount of ethyl acetate,
It is incorporated to filtrate.It is evaporated under reduced pressure filtrate and removes solvent and excessive ethyl acetoacetate, obtained 14.4g is colourless or pale yellowish oil is double
Acetoacetic ester, yield 87%.
(2) the unsaturated polyester (UP) performed polymer (pyrrolidines is catalyst) of ketone group containing is synthesized:
In 50mL flask, the diacetyl acetate ester (1.2g, 2mmol) of step (1) preparation, terephthalaldehyde is added
(0.28g, 2mmol) and 10mL tetrahydrofuran, stirring and dissolving.Pyrrolidines (0.011g) and 1 drop acetic acid is added, reaction is stirred at room temperature
24h.40mL n-hexane is slowly added dropwise, stirs simultaneously, stratification removes supernatant liquor, and 50 DEG C of dry 12h obtain 1.07g orange
The unsaturated polyester (UP) performed polymer of yellow, viscous ketone group containing, yield 76%, the equal relative molecular mass M of numbern=2800, molecular weight point
Cloth Mw/Mn=2.02.
Embodiment 5
Prepare the thermosetting property unsaturated polyester resin (benzoyl peroxide that 1% resin quality is added) of ketone group containing:
0.005g benzoyl peroxide is dissolved in 3mL methylene chloride, the ketone group containing then prepared with 0.5g embodiment 1 is not
Saturated polyester performed polymer is uniformly mixed, and solvent volatilization is dry.It is reacted 2 hours at 90 DEG C, is warming up to 100 DEG C and reacts 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 property unsaturated polyester resin of base.Cured product methylene chloride extracts 12 hours for 70 DEG C in cable type extractor according, dry
It is afterwards gel fraction with the percentage for extracting preceding resin quality, characterizes curing reaction degree.Gel fraction is 83% under this condition.
Embodiment 6
Prepare the thermosetting property unsaturated polyester resin (benzoyl peroxide that 5% resin quality is added) of ketone group containing:
0.025g benzoyl peroxide is dissolved in 3mL methylene chloride, the ketone group containing then prepared with 0.5g embodiment 1 is not
Saturated polyester performed polymer is uniformly mixed, and solvent volatilization is dry.It is reacted 2 hours at 90 DEG C, is warming up to 100 DEG C and reacts 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 property unsaturated polyester resin of base.Cured product methylene chloride extracts 12 hours for 70 DEG C in cable type extractor according, gel
Score is 90%.
Embodiment 7
Prepare the thermosetting property unsaturated polyester resin (benzoyl peroxide that 1% resin quality is added) of ketone group containing:
0.005g benzoyl peroxide is dissolved in 3mL methylene chloride, the ketone group containing then prepared with 0.5g embodiment 2 is not
Saturated polyester performed polymer is uniformly mixed, and solvent volatilization is dry.It is reacted 2 hours at 90 DEG C, is warming up to 100 DEG C and reacts 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 property unsaturated polyester resin of base.Cured product methylene chloride extracts 12 hours for 70 DEG C in cable type extractor according, gel
Score is 55%.
Embodiment 8
Prepare the thermosetting property unsaturated polyester resin (benzoyl peroxide that 5% resin quality is added) of ketone group containing:
0.005g benzoyl peroxide is dissolved in 3mL methylene chloride, the ketone group containing then prepared with 0.5g embodiment 2 is not
Saturated polyester performed polymer is uniformly mixed, and solvent volatilization is dry.It is reacted 2 hours at 90 DEG C, is warming up to 100 DEG C and reacts 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 property unsaturated polyester resin of base.Cured product methylene chloride extracts 12 hours for 70 DEG C in cable type extractor according, gel
Score is 76%.
Embodiment 9
The thermosetting property unsaturated polyester resin of ketone group containing prepared by embodiment 6 is used to protect the ammonia in para-aminophenol
Base, protection and deprotection process are as follows:
(1) it protects process: the thermosetting property unsaturated polyester resin of 5g ketone group containing is added (hereinafter referred to as in 100mL flask
Resin) and 20mL para-aminophenol mass percent be 5% benzole soln, stirring is heated to 90 DEG C, and flow back 12h.After cooling,
Resin is filtered out, is washed three times with benzene, the resin of load para-aminophenol is made in drying；
(2) be added in 100mL flask the load resin of para-aminophenol of 5g step (1) preparation, 2.5g chloroacetic chloride,
30mL methylene chloride and 14mL triethylamine acid binding agent stir, and react 3h under room temperature, filter out resin, washed and dried with methylene chloride
It is dry, load is made to the resin of amion acetic acid phenol ester；
(3) it is deprotected process: the load of 5g step (2) preparation being added in 100mL flask to amion acetic acid phenol ester
Resin adds 30mL ethyl alcohol and 1mL concentrated hydrochloric acid, is stirred at room temperature for 24 hours, in resin of the resin from load to amion acetic acid phenol ester
It is detached from, is separately separated insoluble in ethyl alcohol and concentrated hydrochloric acid.After resin is filtered out, washing is several times, reusable after dry.It crosses
Solution after filter adds the NaOH of 4mL 1M to be adjusted to alkalinity, reuses the methylene chloride extraction of 50mL to amion acetic acid phenol ester, steams
Dry dichloromethane is made to amion acetic acid phenol ester.
In conclusion ester exchange reaction, which occurs, for dihydric alcohol and ethyl acetoacetate is made diacetyl acetate esters monomer, it is double
Acetoacetic ester monomer can pass through Knoevengel reactive polymeric into the equal relative molecular mass of number 3000 with aromatic dialdehyde
The unsaturated polyester (UP) performed polymer of the ketone group containing of left and right, and double bond on main chain is caused by radical initiator and is crosslinked, form ketone group containing
Thermosetting property unsaturated polyester resin.
Desirable embodiment according to the present invention described above is enlightenment, through the above 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 range is not limited to the contents of the specification, it is necessary to which the technical scope thereof is determined according to the scope of the claim.
Claims (9)
1. a kind of unsaturated polyester (UP) performed polymer of ketone group containing, which is characterized in that the structural formula of the performed polymer are as follows:
Wherein, R is the aliphatic carbon chain that carbon atom number is 4-10, either (CH2CH2O)m-1(CH2CH2), m=10-150；Ar is
Phenyl ring, the carbon relative position of two sides are 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 described in claim 1, which is characterized in that described
The concrete operation step of preparation method includes:
It (1) is raw material by dihydric alcohol and ethyl acetoacetate, dihydric alcohol and ethyl acetoacetate the mass ratio of the material are 1:5, inorganic
Strong acid, organic acid or solid acid are catalyst, and benzene or toluene are reaction dissolvent, to remove water, are then steamed molten within azeotropic 2-3 hours
Agent, and the ethyl alcohol generated using high temperature removal reaction, being warming up to 130 DEG C of normal pressures, the reaction was continued 5-6 hours, and diacetyl acetate is made
Ester, reaction equation is as follows,
Wherein, R is the aliphatic carbon chain that carbon atom number is 4-10, either (CH2CH2O)m-1(CH2CH2), m=10-150；
(2) diacetyl acetate ester made from reaction dissolvent, binary aromatic aldehyde and step (1) is added in flask, wherein biacetyl second
Acid esters and binary aromatic aldehyde the mass ratio of the material are 1:1, and Knoevengel reaction occurs under secondary amine/acetic acid catalysis, and 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 atom number is 4-10, either (CH2CH2O)m-1(CH2CH2), m=10-150；Ar is phenyl ring,
The carbon relative position of two sides 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, which is characterized in that step (1)
Middle inorganic acid is the concentrated sulfuric acid, organic acid is p-methyl benzenesulfonic acid, solid acid is 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, which is characterized 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, which is characterized in that step (2)
Middle secondary amine is one or more of piperidines, pyrrolidines, piperazine.
6. the preparation method of the unsaturated polyester (UP) performed polymer of ketone group containing as claimed in claim 2, which is characterized in that step (2)
Middle reaction dissolvent is one or more of tetrahydrofuran, dioxane, ethyl alcohol, methanol.
7. the preparation method of the unsaturated polyester (UP) performed polymer of ketone group containing as claimed in claim 2, which is characterized in that step (2)
Middle polycondensation carries out at room temperature.
8. a kind of purposes of the unsaturated polyester (UP) performed polymer of ketone group containing as described in claim 1, which is characterized in that the pre-polymerization
Body is used to prepare the thermosetting property unsaturated polyester resin of ketone group containing, and the thermosetting property unsaturated polyester resin of the ketone group containing is used as ammonia
Base protects reagent, and concrete operation step includes:
(1) radical initiator of prepolymer mass 1-5% is dissolved in methylene chloride, is 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
The thermosetting property unsaturated polyester resin of ketone group containing is made at cross-linked structure in this reaction.
9. the purposes of the unsaturated polyester (UP) performed polymer of ketone group containing as claimed in claim 8, which is characterized in that in step (1) certainly
It is benzoyl peroxide, peroxidized t-butyl perbenzoate or azodiisobutyronitrile by base initiator.
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