CN105503674B - A kind of polyfunctional group unsaturated monomer, preparation method and applications based on eugenol - Google Patents
A kind of polyfunctional group unsaturated monomer, preparation method and applications based on eugenol Download PDFInfo
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- CN105503674B CN105503674B CN201510882993.4A CN201510882993A CN105503674B CN 105503674 B CN105503674 B CN 105503674B CN 201510882993 A CN201510882993 A CN 201510882993A CN 105503674 B CN105503674 B CN 105503674B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
- C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
- C07C323/52—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
Abstract
The invention discloses a kind of polyfunctional group unsaturated monomer, preparation method and applications based on eugenol, under uviol lamp and catalyst collective effect, there is click chemistry reaction in eugenol, obtain eugenol mercaptan carboxylic acid's compound with mercaptan carboxylic acid；Eugenol mercaptan carboxylic acid compound and olefin epoxide compound initial ring oxygen ring-opening reaction, obtain the polyfunctional group unsaturated monomer based on eugenol.More active function groups can be introduced in the polyfunctional group unsaturated monomer structure based on eugenol that the present invention is provided, the degree of cross linking of polymer is favorably improved, the glass transition temperature and heat distortion temperature of polymer is improved；The eugenol skeleton contained in monomer structure assigns the good mechanical property of polymer and thermal property, and a large amount of flexible bonds are favorably improved the performances such as intensity, modulus, creep resistant, the pliability of polymer.
Description
Technical field
Invention is related to unsaturated polyester resin polymer monomer, and in particular to a kind of polyfunctional group based on eugenol is not
Saturation monomer, preparation method and applications.
Background technology
In the last hundred years due to petroleum chemical industry flourish so that the application of oil product is increasingly extensive.By oil
The life and production that the various products and its derivative of generation give people bring greatly it is convenient, driven society development and
The progress of human civilization, but the various environmental problems at the same time brought equally can not be ignored.At the same time, petroleum resources are
A kind of unsustainable, non-renewable resource, along with the increasingly depleted of its reserves, will necessarily cause the high score from oil
The continuous improvement of sub- material cost.Recently, under environmental protection, the pressure for reducing production cost and saving petroleum resources, environment
The research and development of bio-based macromolecular material friendly, with sustainable resource as raw material is using increasingly by the weight of people
Depending on.Bio-based macromolecular material with sustainable resource be its main production raw material so that manufacture Polymer Industry reduce to stone
The consumption of oily industrial chemicals, while macromolecular material is decreased in process of production to the pollution of environment, therefore bio-based is high
Molecular material has environmental protection and saves the double effects of petroleum resources, is an important development side of current macromolecular material
To.Eugenol is a kind of natural bio-based source compound nontoxic containing phenyl ring, is had a wide range of applications, based on eugenol
Bio-based polyfunctional group unsaturated monomer be designed to so that cloves phenol-based compounds are obtained in macromolecular material is prepared
Extensive use.
Click chemistry (Click chemistry), is existed by chemist's Barry summer Price (K B Sharpless)
The synthesis concept for introducing for 2001, purport is, by the splicing of junior unit, varied molecule to be completed fast and reliablely
Chemical synthesis.It stresses the combinatorial chemistry new method opened up based on carbon-heteroatom bond (C-X-C) synthesis in particular, can lead to
Click-reaction is crossed simply and efficiently to obtain molecular diversity.
Up to the present, yet there are no in the prior art and fourth is prepared using eugenol by click chemistry and epoxy ring opening reaction
The document and patent report of fragrant phenolic group polyfunctional group unsaturated monomer.
The content of the invention
The invention provides a kind of polyfunctional group unsaturated monomer, preparation method and applications based on eugenol, the life
Product method yield is high, process is simple；Polymer prepared by polyfunctional group unsaturated monomer based on eugenol intensity, modulus,
The aspects such as creep resistant, pliability have excellent mechanical property, while having glass transition temperature and thermal deformation temperature higher
Degree.
A kind of polyfunctional group unsaturated monomer based on eugenol, with structure shown in formula I：
Wherein Y is C1-6Alkyl；Z is olefin alkylation；N is the integer of 1-3.
More active function groups can be introduced in the polyfunctional group unsaturated monomer structure based on eugenol that the present invention is provided,
The degree of cross linking of polymer is favorably improved, the glass transition temperature and heat distortion temperature of polymer is improved；Monomer (refers to the present invention
The polyfunctional group unsaturated monomer based on eugenol) the eugenol skeleton that contains in structure assigns polymer good mechanical property
Energy and thermal property, a large amount of flexible bonds are favorably improved the performances such as intensity, modulus, creep resistant, the pliability of polymer.
In structure shown in formula I compound, olefin alkylation group is female to eugenol by ehter bond or ester bond (unit is polynary) scion grafting
In core, it is connected with the oxygen of eugenol and carboxylic acid containing ethylene linkage in described olefin alkylation group and by saturated carbon.
Preferably, in the structure of formula 1, Z is preferablyN is 1 or 2.
Preferably, in the present invention, the polyfunctional group unsaturated monomer based on eugenol has formula II or the structure of formula III：
Wherein R is C1-6Alkyl.
Preferably, in formula II, the R is C1-6Alkyl or phenyl.
In the structure of formula II, R is C1-6Saturated carbon chains or phenyl.If R is CH2、C2H4、C3H6、C4H8、C5H10、C6H12Or
C6H4.Influences different R different with thermal property generation to the mechanics of polymer.
Present invention also offers a kind of preparation method of the polyfunctional group unsaturated monomer based on eugenol, including following step
Suddenly：
Step a)：Under uviol lamp and catalyst collective effect, there is click chemistry reaction in eugenol, obtain with mercaptan carboxylic acid
To eugenol-mercaptan carboxylic acid's compound；
Step b)：Eugenol-mercaptan carboxylic acid's compound and olefin epoxide compound initial ring oxygen ring-opening reaction, are based on
The polyfunctional group unsaturated monomer of eugenol.
In the presence of uviol lamp and catalyst, the alkene of sulfydryl and eugenol carries out click chemistry reaction, one-step synthesis
Eugenol-mercaptan carboxylic acid's compound.Phenolic hydroxyl group and carboxylic hydroxy group in eugenol-mercaptan carboxylic acid's compound are again and alkene epoxidation
Compound carries out epoxy ring opening reaction (nucleophilic attack), so as to by alkylene access eugenol parent nucleus, obtain based on eugenol
Polyfunctional group unsaturated monomer., without complicated purifying, process is simple, yield be high, suitable for industry for each step of the inventive method
Large-scale production.When monomer is prepared, in can adjusting monomer structure by adjusting the carboxylic acid functional quantity of mercaptan carboxylic acid
Olefin(e) centent, so as to change the performance of polymer, realizes the purpose of artificial adjustment material property.
Eugenol derives from biomass material, and the exploitation of the polyfunctional group unsaturated monomer based on eugenol can promote life
The development of thing sill, so as to promote the sustainable development in the fields such as whole macromolecular material.
Eugenol carries out click chemistry reaction, described mercapto with the compound of mercaptan carboxylic acid under ultraviolet and catalyst action
Yl carboxylic acid is the C of sulfydryl substitution1-6Unitary, binary or tricarboxylic acid.Using unit mercaptan carboxylic acid and polyacid to monomer yield
Influence is little, can be prepared with more multi-functional monomer using polybasic carboxylic acid, can artificially adjust the polymer of preparation
Mechanics and thermal property.
Preferably, described mercaptan carboxylic acid has formula IV or Thiomalic acid；
Wherein, wherein R3It is C1-6Alkyl or phenyl.
The present invention uses mercaptan carboxylic acid, and it can occur click chemistry reaction with eugenol, and reaction condition is simple, instead
Reply water is insensitive to oxygen, monomer yield up to hundred points hundred.This is that other carboxylic acids such as amino carboxylic acid to be compared.
Still more preferably, described mercaptan carboxylic acid is TGA, mercaptopropionic acid, mercaptobutyric acid, mercaptopentanoic acid, sulfydryl
At least one of caproic acid, sulfydryl enanthic acid, mercaptobenzoic acid, Thiomalic acid.
Sulfydryl the position of substitution of above-mentioned preferred mercaptan carboxylic acid and the framework (direct-connected or side chain) of carbochain do not influence the list
The yield of body.
In step a), the mixed solution or methanol solution of the preferred dioxane of reaction dissolvent and ethanol.
Preferably, in step a), uviol lamp wavelength is 220-400nm, reaction temperature is 10-100 DEG C, ultra violet lamp
0.5-72 hours.
In step a), described catalyst is light trigger, and existing free radical photo-initiation can be used in being catalyzed this hair
Bright click chemistry reaction.
Further preferably, described catalyst is dimethoxybenzoin, 2- hydroxy-2-methyl -1- phenylacetones, 1- hydroxyls
Cyclohexyl phenyl ketone, 2- methyl -2- (4- morpholinyls) -1- [4- (methyl mercapto) phenyl] -1- acetone, 2,4,6- trimethylbenzene first
Acyl group-diphenyl phosphine oxide, 2- dimethylamino -2- benzyls -1- [4- (4- morpholinyls) phenyl] -1- butanone, 2- hydroxyl -2- first
One or more of base -1- [4- (2- hydroxyl-oxethyls) phenyl] -1- acetone.
In step a), eugenol is 1 with the mol ratio of mercaptan carboxylic acid:1-20, catalyst is the amount of eugenol material
0.1-20%, reaction temperature is 10-40 DEG C, and the reaction time is 0.5-72h.
The yield and reaction speed of monomer are with the proportional raising of raising of the amount and reaction temperature of catalyst material.
After step a) reactions terminate, decompression rotary evaporation removal reaction dissolvent is washed and obtains eugenol-sulfydryl after drying
Carboxylic acid compound.The yield of eugenol-mercaptan carboxylic acid's compound is 91-98%.
In production process is amplified, the reaction dissolvent of concentration can be molten as reaction to step b using recovery in step a)
Agent.
After the completion of step a) treatment, eugenol-mercaptan carboxylic acid's compound is obtained, its structural formula is formula V:
Sulfydryl monocarboxylic acid after step a) reactions by obtaining the compound of formula VI；
Thiomalic acid reacts by step a), obtains the compound of formula VII：
Wherein R3It is C1-6Alkyl or phenyl.
Described R3It is CH2、C2H4、C3H6、C4H8、C5H10、C6H12Or C6H4。
After the completion of step a) treatment, without further being purified to eugenol-mercaptan carboxylic acid's compound, step is directly carried out
B) reaction.
In step b), the phenolic hydroxyl group and carboxylic hydroxyl in eugenol-mercaptan carboxylic acid's compound are main from steric hindrance small end
Nucleophilic attack olefin epoxide compound, makes epoxy addition, so as to synthesize monomer of the present invention.
The olefin epoxide compound is the epoxide containing alkene, generally alkene acid glycidyl ester.
Existing alkene acid glycidyl ester can participate in epoxy ring opening reaction of the invention, preferably, described
Olefin epoxide compound is GMA or glycidyl acrylate.
In step b), the solvent of the epoxy ring opening reaction is butyl acetate and/or ethanol, and the consumption of solvent is cloves
The 100-2000wt% of phenol-mercaptan carboxylic acid's compound quality.
In step b), the eugenol-mercaptan carboxylic acid's compound is 1 with GMA mol ratio:2-
20。
In step b), the reaction temperature of the epoxy ring opening reaction is 0-200 DEG C, reaction time 0.5-36h.
Preferably, the eugenol-mercaptan carboxylic acid's compound is 1 with GMA mol ratio:2-
10, the reaction temperature of the epoxy ring opening reaction is 85-100 DEG C.
At the temperature and rate of charge, the product yield of epoxy ring opening reaction is higher.
After step b) reactions terminate, vacuum distillation removes mixed solvent, is dried to obtain the polyfunctional group based on eugenol not
Saturation monomer.Obtained monomer need not be further purified, can be directly as the monomer of polymerisation.
Present invention also offers a kind of poly- in unsaturation using the above-mentioned polyfunctional group unsaturated monomer based on eugenol
Application in Lipase absobed.
Such as by the present invention provide monomer and initiator mix with, uviol lamp effect under carry out polymerizing curable, can obtain
To the polymer with premium properties.
The polymerization of monomer of the present invention can all be triggered under UV effects using existing initiator.Due to monomer of the invention tool
There are eugenol and more flexible bond, obtained polymer has good stretch modulus and tensile strength,
Polyfunctional group unsaturated monomer based on eugenol of the invention, directly using the eugenol of biogenetic derivation as original
Prepared by material, it is possible to reduce pollution of the existing petroleum base unsaturated monomer to the dependence of fossil resources and its to environment, is a kind of life
Thing base, green, environment-friendly products, with the double effects for saving petroleum resources and environmental protection.The fourth of biogenetic derivation in the present invention
Fragrant phenol contains and petroleum-based compounds identical benzene ring structure so that polyfunctional group unsaturated monomer of the present invention based on eugenol
The polymer of preparation possesses good mechanical property and thermal property, with the possibility for substituting existing petroleum-based products, makes
With in extensive range.
Polyfunctional group unsaturated monomer based on eugenol of the invention, prepares simply, and easy to operate, controllability is good, easily
In implementation, it is suitable to large-scale industrial production.
Brief description of the drawings
Fig. 1 is the proton nmr spectra of eugenol-mercaptopropionic acid prepared by embodiment 1.
Fig. 2 is the proton nmr spectra of eugenol-mercaptopropionic acid polyfunctional group unsaturated monomer prepared by embodiment 1.
Fig. 3 is the proton nmr spectra of eugenol-Thiomalic acid prepared by embodiment 2.
Fig. 4 is the proton nmr spectra of eugenol-Thiomalic acid polyfunctional group unsaturated monomer prepared by embodiment 3.
Specific embodiment
With reference to embodiment, the present invention is expanded on further.It should be understood that these embodiments be merely to illustrate the present invention without
For limiting the scope of the present invention.
In embodiment, proton nmr spectra1H-NMR uses the type light splitting of 400AVANCE III of Brooker company (Bruker)
Instrument (Spectrometer) is determined, 400MHz, deuterochloroform (CDCL3)。
The yield of eugenol-mercaptan carboxylic acid's compound is calculated by below equation：
The quality of the yield=eugenol-mercaptan carboxylic acid's compound/(molal quantity × eugenol-mercaptan carboxylic acidization of eugenol
The molal weight of compound) * 100%
The yield of the polyfunctional group unsaturated monomer based on eugenol is calculated by below equation：
The quality of yield=polyfunctional group unsaturated monomer based on eugenol/(eugenol-mercaptan carboxylic acid's compound rubs
The molal weight of your number × polyfunctional group unsaturated monomer based on eugenol) * 100%
Embodiment 1
100g eugenols, 65g 3- mercaptopropionic acids, 5g dimethoxybenzoins, the mixing for being dissolved in dioxane and ethanol are molten
In liquid, 365nm ultra violet lamps 72 hours at 10 DEG C, decompression rotary evaporation removal mixed solvent is washed and obtained after drying
Eugenol-mercaptopropionic acid, yield is 96%,1H-NMR is as shown in figure 1, each peak on figure and eugenol-mercaptopropionic acid chemical combination
The hydrogen atom of thing structure is all one-to-one.
The eugenol of the above-mentioned preparations of 100g-mercaptopropionic acid compound is dissolved in the mixed solution of 100g butyl acetates and ethanol
105g GMAs are added afterwards, and 0 DEG C is reacted 36 hours, and vacuum distillation removes mixed solvent, is dried to obtain fourth
Fragrant phenol-mercaptopropionic acid polyfunctional group unsaturated monomer, structural formula such as formula VIII.1H NMR such as Fig. 2, each peak and cloves on figure
The hydrogen atom of phenol-mercaptopropionic acid polyfunctional group unsaturated monomer structure is all one-to-one, and yield is 90%.
By 100 weight portion eugenols-mercaptopropionic acid polyfunctional group unsaturated monomer and 2 weight portion light triggers
(Irgacure184) it is well mixed, UV solidifications is carried out with the box uv cure machine of 500W, obtains many officials based on eugenol
The solidfied material of unsaturated monomer can be rolled into a ball.The stretch modulus of the solidfied material of gained is 530MPa, and elongation at break is 7.0%, stretching
Intensity is 30MPa.
Embodiment 2
100g eugenols, 56g Thiomalic acids, 20g 2- hydroxy-2-methyl -1- phenylacetones, are dissolved in dioxane
In the mixed solution of ethanol, 365nm ultra violet lamps 50 hours at 20 DEG C, decompression rotary evaporation removal mixed solvent, water
Wash and obtain eugenol-Thiomalic acid compound after drying, yield is 98%,1H-NMR is as shown in figure 3, each peak on figure
All it is one-to-one with the hydrogen atom of eugenol-Thiomalic acid structure.
The mixing that the eugenol of the above-mentioned preparations of 100g-Thiomalic acid compound is dissolved in into 300g butyl acetates and ethanol is molten
103g GMAs are added after liquid, 30 DEG C are reacted 24 hours, and vacuum distillation removes mixed solvent, is dried to obtain
Eugenol-Thiomalic acid polyfunctional group unsaturated monomer, structural formula such as formula Ⅸ.1HNMR such as Fig. 4, each peak and fourth on figure
Hydrogen atom above fragrant phenol-Thiomalic acid compound structure is all one-to-one, and yield is 93%.
By 100 weight portion eugenols-Thiomalic acid polyfunctional group unsaturated monomer and 2 weight portion light triggers
(Irgacure184) it is well mixed, UV solidifications is carried out with the box uv cure machine of 500W, obtains many officials based on eugenol
The solidfied material of unsaturated monomer can be rolled into a ball.The stretch modulus of the solidfied material of gained is 826MPa, and elongation at break is 6.8%, stretching
Intensity is 41MPa.
Embodiment 3
100g eugenols, 100g 2- TGAs, 25g 1- hydroxycyclohexyl phenyl ketones, be dissolved in dioxane and
In the mixed solution of ethanol, 365nm ultra violet lamps 36 hours at 30 DEG C, decompression rotary evaporation removal mixed solvent, washing
And eugenol-TGA compound is obtained after drying, yield is 91%.
The eugenol of the above-mentioned preparations of 100g-TGA compound is dissolved in the mixed solution of 400g butyl acetates and ethanol
50g GMAs are added afterwards, and 50 DEG C are reacted 20 hours, and vacuum distillation removes mixed solvent, is dried to obtain fourth
Fragrant phenol-TGA polyfunctional group unsaturated monomer, yield is 97%.
Embodiment 4
100g eugenols, 150g 4- mercaptobutyric acids, 30g 2- methyl -2- (4- morpholinyls) -1- [4- (methyl mercapto) benzene
Base] -1- acetone, it is dissolved in the mixed solution of dioxane and ethanol, 365nm ultra violet lamps 32 hours, subtract at 35 DEG C
Pressure rotary evaporation removal mixed solvent, washes and obtains eugenol-mercaptobutyric acid compound after drying, and yield is 94%.
The eugenol of the above-mentioned preparations of 100g-mercaptobutyric acid compound is dissolved in the mixed solution of 500g butyl acetates and ethanol
50g GMAs are added afterwards, and 60 DEG C are reacted 18 hours, and vacuum distillation removes mixed solvent, is dried to obtain fourth
Fragrant phenol-mercaptobutyric acid polyfunctional group unsaturated monomer, yield is 99%.
Embodiment 5
100g eugenols, 200g 4- mercaptobenzoic acids, 35g 2,4,6- trimethylbenzoy-dipheny phosphine oxides are molten
In the mixed solution of dioxane and ethanol, 365nm ultra violet lamps 30 hours at 40 DEG C, decompression rotary evaporation is removed solution
Mixed solvent, washes and obtains eugenol-mercaptobenzoic acid compound after drying, and yield is 92%.
The mixing that the eugenol of the above-mentioned preparations of 100g-mercaptobenzoic acid compound is dissolved in into 600g butyl acetates and ethanol is molten
104g GMAs are added after liquid, 70 DEG C are reacted 16 hours, and vacuum distillation removes mixed solvent, is dried to obtain
Eugenol-mercaptobenzoic acid polyfunctional group unsaturated monomer, yield is 91%
Embodiment 6
100g eugenols, 250g 5- mercaptopentanoic acids, 40g 2,4,6- trimethylbenzoyl phenyl phosphinic acid ethyl esters, dissolving
In the mixed solution of dioxane and ethanol, 365nm ultra violet lamps 20 hours at 50 DEG C, decompression rotary evaporation removal is mixed
Bonding solvent, washes and obtains eugenol-mercaptopentanoic acid compound after drying, and yield is 94%.
The eugenol of the above-mentioned preparations of 100g-mercaptopentanoic acid compound is dissolved in the mixed solution of 800g butyl acetates and ethanol
200g GMAs are added afterwards, and 90 DEG C are reacted 10 hours, and vacuum distillation removes mixed solvent, is dried to obtain fourth
Fragrant phenol-mercaptopentanoic acid polyfunctional group unsaturated monomer, yield is 96%
Embodiment 7
100g eugenols, 300g 6- mercaptohexanoic acids, 45g 2- dimethylamino -2- benzyls -1- [4- (4- morpholinyls) benzene
Base] -1- butanone, it is dissolved in the mixed solution of dioxane and ethanol, 365nm ultra violet lamps 10 hours, subtract at 80 DEG C
Pressure rotary evaporation removal mixed solvent, washes and obtains eugenol-mercaptohexanoic acid compound after drying, and yield is 97%.
The eugenol of the above-mentioned preparations of 100g-mercaptohexanoic acid compound is dissolved in the mixed solution of 900g butyl acetates and ethanol
200g GMAs are added afterwards, and 150 DEG C are reacted 2 hours, and vacuum distillation removes mixed solvent, is dried to obtain fourth
Fragrant phenol-mercaptohexanoic acid polyfunctional group unsaturated monomer, yield is 95%
Embodiment 8
100g eugenols, 400g 7- sulfydryls enanthic acid, 50g 2- hydroxy-2-methyls -1- [4- (2- hydroxyl-oxethyls) benzene
Base] -1- acetone, it is dissolved in the mixed solution of dioxane and ethanol, 365nm ultra violet lamps 0.5 hour at 100 DEG C,
Decompression rotary evaporation removal mixed solvent, washes and obtains eugenol-sulfydryl enanthic acid compound after drying, and yield is 98%.
The mixing that the eugenol of the above-mentioned preparations of 100g-sulfydryl enanthic acid compound is dissolved in into 1000g butyl acetates and ethanol is molten
220g GMAs are added after liquid, 200 DEG C are reacted 0.5 hour, vacuum distillation removing mixed solvent, dry
To eugenol-sulfydryl enanthic acid polyfunctional group unsaturated monomer, yield is 91%
Above-mentioned is that the present invention is elaborated in conjunction with the embodiments, but embodiments of the present invention do not receive above-mentioned implementation
The limitation of example, other any changes made under patent core guiding theory of the present invention, replacement, combination simplification etc. are included in
Within the protection domain of patent of the present invention.
Claims (9)
1. a kind of polyfunctional group unsaturated monomer based on eugenol, it is characterised in that with formula II or the structure of formula III：
Wherein R is C1-6Alkyl.
2. the preparation method of the polyfunctional group unsaturated monomer of eugenol is based on as claimed in claim 1, it is characterised in that bag
Include following steps：
Step a)：Under uviol lamp and catalyst collective effect, there is click chemistry reaction in eugenol, obtain fourth with mercaptan carboxylic acid
Fragrant phenol-mercaptan carboxylic acid's compound；
Step b)：Eugenol-mercaptan carboxylic acid's compound and olefin epoxide compound initial ring oxygen ring-opening reaction, obtain based on cloves
The polyfunctional group unsaturated monomer of phenol.
3. the preparation method of the polyfunctional group unsaturated monomer based on eugenol according to claim 2, it is characterised in that
Described mercaptan carboxylic acid is the C of sulfydryl substitution1-6Unitary, binary or tricarboxylic acid.
4. the preparation method of the polyfunctional group unsaturated monomer based on eugenol according to claim 3, it is characterised in that
Described mercaptan carboxylic acid is TGA, mercaptopropionic acid, mercaptobutyric acid, mercaptopentanoic acid, mercaptohexanoic acid, sulfydryl enanthic acid, sulfydryl benzene
At least one of formic acid, Thiomalic acid.
5. the preparation method of the polyfunctional group unsaturated monomer based on eugenol according to claim 2, it is characterised in that
In step a), uviol lamp wavelength is 220-400nm, and reaction temperature is 10-100 DEG C, ultra violet lamp 0.5-72 hours.
6. the preparation method of the polyfunctional group unsaturated monomer based on eugenol according to claim 2, it is characterised in that
In step a), eugenol is 1 with the mol ratio of mercaptan carboxylic acid:1-20, catalyst is the 0.1-20% of the amount of eugenol material, instead
Answer temperature for 10-40 DEG C, the reaction time is 0.5-72h.
7. the preparation method of the polyfunctional group unsaturated monomer based on eugenol according to claim 2, it is characterised in that
In step b), the eugenol-mercaptan carboxylic acid's compound is 1 with GMA mol ratio:2-20.
8. the preparation method of the polyfunctional group unsaturated monomer based on eugenol according to claim 2, it is characterised in that
In step b), the reaction temperature of the epoxy ring opening reaction is 0-200 DEG C, reaction time 0.5-36h.
9. the polyfunctional group unsaturated monomer based on eugenol according to claim any one of 1-8 is closed in unsaturated polyester (UP)
Application in.
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| CN106631942B (en) * | 2016-12-08 | 2018-06-05 | 中国科学院宁波材料技术与工程研究所 | A kind of UV optical resin monomers based on eugenol and its preparation method and application |
| CN107417870B (en) * | 2017-04-19 | 2019-06-18 | 中国科学院宁波材料技术与工程研究所 | A kind of organosilicon benzoxazine resin prepolymer and its preparation method and application based on eugenol |
| CN113956438A (en) * | 2021-11-22 | 2022-01-21 | 中国林业科学研究院林产化学工业研究所 | Preparation method of bio-based self-repairing flame-retardant material with high dielectric property |
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| CN101617267A (en) * | 2007-02-20 | 2009-12-30 | 三井化学株式会社 | Sealing liquid crystal is with hardening resin composition and use the manufacture method of the display panels of said composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101617267A (en) * | 2007-02-20 | 2009-12-30 | 三井化学株式会社 | Sealing liquid crystal is with hardening resin composition and use the manufacture method of the display panels of said composition |
Non-Patent Citations (2)
| Title |
|---|
| Polyesters derived from bio-based eugenol and 10-undecenoic acid: synthesis,characterization,and structure-property relationships;Keling Hu 等;《RSC Advances》;20151006;第5卷;第85996-86005页 * |
| synthesis and properties of polyesters derived from renewable eugenol and α, ω-diols via a continuous overheating method;Keling Hu 等;《polymer chemistry》;20150825;第6卷;第7140页Scheme 1，第7139页左栏第2段 * |
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