CN115304484B - Triitaconic acid derived penta-functionality hybrid monomer and preparation method and application thereof - Google Patents

Triitaconic acid derived penta-functionality hybrid monomer and preparation method and application thereof Download PDF

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CN115304484B
CN115304484B CN202210960906.2A CN202210960906A CN115304484B CN 115304484 B CN115304484 B CN 115304484B CN 202210960906 A CN202210960906 A CN 202210960906A CN 115304484 B CN115304484 B CN 115304484B
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itaconic acid
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toluene
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金明
肖月彬
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Tongji University
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Abstract

The invention provides a tri-itaconic acid derived penta-functionality hybrid monomer, a preparation method and application thereof, wherein three itaconic acid structures of the monomer are connected with glycol to form a free radical polymerizable part through ester formation, and itaconic acid carboxyl groups at two ends are further formed into an ester with R containing a cationic polymerizable group. The molecule realizes the functions of five-functionality free radical and cation hybridization monomer through double bonds in itaconic acid and cation polymerizable groups introduced in R groups, balances the free radical and cation hybridization polymerization, ensures the rapid photocuring performance of the monomer through high functionality, ensures the characteristics of high hardness, high wear resistance and the like of the product, and is far superior to the difunctional hybridization monomer consisting of one free radical and one cation group; the five-element degree of functionality of the product plays a role of a cross-linking agent in a photocuring system, and has high curing speed and excellent performance.

Description

Triitaconic acid derived penta-functionality hybrid monomer and preparation method and application thereof
Technical Field
The invention belongs to the technical field of novel photocuring material organic chemicals, and particularly relates to a free radical and hybrid photocuring monomer derived from three itaconic acids, wherein five photopolymerizable groups are shared in the structure, and a preparation method and application thereof, in particular to application in the field of UV-LED photocuring materials.
Background
The photo-curing technology is a process of polymerizing liquid photosensitive resin into solid under the induction of light, has the characteristics of high efficiency, high speed, economy, energy conservation, environment friendliness and the like, and is widely applied to the fields of adhesives, photo-curing coatings, printing ink, photoresist, 3D micro-construction, biological medicine and the like. The photo-curable monomer is a key factor controlling the properties of the whole cured product, and its reactivity, dilutability, etc. directly affect the photo-curing rate, curing degree, and end product properties. In particular, in the application of radical curing to coating materials and the like, the photo-curing is usually performed under an air atmosphere. Therefore, oxygen in the air diffuses into the polymerization system and reacts with radicals generated under the irradiation of the photoinitiator, thereby inhibiting the progress of photopolymerization, which is one of the most difficult oxygen inhibition in the field of photocuring. Can lead to problems such as poor surface properties and even tackiness of the cured coating. One solution is to increase the functionality of the monomer, since the polyfunctional monomer cures at a lower conversion; another method is free radical cationic hybrid polymerization, which is a polymerization mode that free radicals and cations simultaneously occur and become interpenetrating networks, wherein the free radical polymerization can provide the system temperature required by the cationic polymerization, and the cationic polymerization can improve the oxidation resistance of the free radical polymerization and often shows higher functional group conversion rate than the free radical polymerization and the cationic polymerization alone. Currently, the hybrid monomers commercially available are mainly oxetane esters or epoxycyclohexane esters of (meth) acrylic acid. The polymerization properties, such as curing speed and surface hardness, are often inferior to those of the polyfunctional monomer because of the presence of one double bond and one epoxy group in the molecule. The reason for this is that the polyfunctional monomer forms a highly crosslinked photocurable system even at a low conversion of functional groups, and therefore exhibits advantages such as a high photocuring speed and a high hardness. Currently, there is an urgent need in the art of photocuring for high performance, low cost multifunctional hybrid monomers.
In addition, as petroleum resources become increasingly depleted, the search for sustainable, high quality, inexpensive petroleum substitutes is critical to the existence and development of the polymer industry. The bio-based polymer material takes renewable resources as main raw materials, reduces the consumption of petrochemical products in the plastic industry, reduces the pollution to the environment in the production process of petroleum-based raw materials, is an important development direction of the current polymer material, and has important practical value and wide development space. Biomass-based photocurable materials have received increasing attention since the 21 st century. Itaconic acid is a small molecule compound with an unsaturated double bond and a terminal carboxyl group, and due to its scalability, sustainability and non-toxicity, the renewable energy laboratory in the united states energy country has promulgated itaconic acid as one of the first twelve renewable chemicals available as biomass energy. Itaconic acid is named as methylene succinic acid and methylene succinic acid, is the fifth largest organic acid in the world (citric acid, gluconic acid, lactic acid and malic acid in sequence in the first four positions), and is an unsaturated binary organic acid. The itaconic acid is considered as a biomass renewable raw material, and is prepared by taking agricultural and sideline products such as starch, sucrose, molasses, wood dust, straw and the like as raw materials, taking aspergillus terreus as a strain for fermentation for two days, and then filtering, concentrating, decolorizing, crystallizing and drying. Patent publication No. CN114369027A, "itaconic acid diester-type photo-curing monomer, composition, preparation method and application", describes a photo-curing monomer containing three unsaturated double bonds, in which two itaconic acids are olefinated with dialkyl to synthesize a diester structure.
Disclosure of Invention
In view of the deficiencies in photopolymerization performance of hybrid monomers, a primary object of the present invention is to provide a monomer derived from bio-based itaconic acid with free radical and hybrid five functionalities. The molecular main body is formed by connecting three itaconic acids through glycol diester, and forming ester with carboxyl groups at two end groups and a cationic polymerizable group.
The second object of the invention is to provide a preparation method of the tri-itaconic acid derived free radical and hybrid five-functionality hybrid monomer.
A third object of the present invention is to provide the use of the above tri-itaconic acid derived radical and hybrid five-functionality hybrid monomer in the field of photocuring.
The preparation method takes the biomass material itaconic acid as a main body to prepare the photo-polymerization monomer containing three itaconic acid derivatives, and the monomer continuously introduces two cationic polymerizable groups at the end group, so that the five-functionality free radical and the hybrid photo-polymerization monomer are realized, and the photo-curing composition participated by the monomer has good photo-polymerization performance.
To achieve the above object, the solution of the present invention is:
three itaconic acid are derived from free radicals and hybridized five-functionality hybridized monomers, wherein three itaconic acid structures contain double bonds and groups capable of participating in free radical polymerization, and cationic polymerizable groups contained in R at two ends form three hybridized monomers capable of free radical polymerization and two cationic polymerizable five-functionality.
The specific molecular structure is shown as a general formula (I), wherein three itaconic acid structures are connected with glycol to form ester, and itaconic acid carboxyl groups at two ends are further esterified with R groups to prepare the compound. The molecule contains three double bonds, and R contains vinyl ether structure, glycidyl ether structure, oxetane structure or epoxy cyclohexane structure and other groups capable of cationic polymerization to form five-functionality hybrid monomer.
Figure BDA0003792830600000021
Wherein the R structure contains a group capable of being polymerized by cationic initiation, specifically, a vinyl ether structure, a glycidyl ether structure, an oxetane structure or an epoxycyclohexane structure, and more specifically, one of the following structural formulas (A), (B), (C) or (D) can be selected:
Figure BDA0003792830600000031
wherein R is 1 、R 2 、R 3 Selected from a hydrogen atom or a methyl group;
x is expressed as empty; or X is C1-12 alkanyl, optionally one or more of them-CH 2 Can be each independently replaced by-O-, CO- & gtCOO-, -OCO-, or a benzene ring.
Further, the molecule contains three free radical polymerizable double bonds in itaconic acid structure, and a highly crosslinked free radical polymer can be formed after photoinitiation.
Further, the cation polymerizable group of the molecular end group can be introduced into a vinyl ether structure, a glycidyl ether structure, an oxetane structure, an epoxycyclohexane structure or the like, thereby realizing the function of the free radical-cation hybridization type polyfunctional monomer.
The invention also provides a preparation method of the tri-itaconic acid derived penta-functionality hybrid monomer, which comprises the following preparation processes:
Figure BDA0003792830600000032
in the above preparation method, the raw materials used are known compounds in the prior art, and can be prepared simply by commercially available or known synthetic methods. The preparation method comprises the following steps:
(a) Itaconic acid (1 equivalent) and 2-bromoethanol (2.2 equivalent) and toluene (20 mL of itaconic acid is contained in each 100g of toluene) are added into a flask provided with a water separator, then 0.05 equivalent of catalyst and 0.05 equivalent of polymerization inhibitor are added, heating reflux is carried out for 24-48h, after toluene is distilled off in a rotating way, and then the target product itaconic acid di- (2-bromoethyl) can be prepared through vacuum reduced pressure distillation.
(b) Itaconic acid (1.0 eq.) and acetic anhydride (1.0 eq.) were placed in a round bottom flask together with toluene (20 mL of itaconic acid per 100g of toluene). Sulfuric acid (0.08 wt%) was added with stirring, mixed and heated, and then the generated acetic acid was removed under reduced pressure. The itaconic anhydride is dried under vacuum and reacted directly after drying to avoid hydrolysis.
(c) The reaction was carried out by adding an alcohol containing an R group (1.0 equivalent) to the itaconic anhydride of step (b) above together with toluene (20 mL of itaconic acid per 100g of toluene), depending on the structure of the R group in the alcohol. The disappearance of the anhydride signal was monitored by FT-IR (1850 cm -1 And 1770cm -1 ) At the time, it indicates a reaction junctionA bundle. Toluene was removed under reduced pressure and the product was dried under vacuum without further filtration or purification to obtain itaconic acid- β -mono R ester.
(d) Itaconic acid-beta-mono R ester (2 equivalent), itaconic acid di- (2-bromoethyl ester) (1 equivalent), acid-binding agent (2 equivalent), polymerization inhibitor (0.05 equivalent) and proper amount of solvent are taken and added into a reactor for reaction until the reaction is finished by GC monitoring. The catalyst was washed with deionized water, dried over anhydrous sodium sulfate, and the solvent was distilled off. Purification can be achieved by silica gel column chromatography or vacuum distillation.
Further, in the step (a), the catalyst is p-toluenesulfonic acid.
Further, in the step (a), the polymerization inhibitor is hydroquinone.
Further, in the step (b), the temperature of the mixed heating is 50 ℃ and the time is 3 hours.
Further, in step (c), the alcohol containing an R group is selected from one of the following structural formulas:
Figure BDA0003792830600000041
wherein R is 1 、R 2 、R 3 Selected from a hydrogen atom or a methyl group;
x is expressed as empty; or X is an alkanyl radical having 1 to 12 carbon atoms, one or more of which-CH 2 Can be each independently replaced by-O-, -CO-, -COO-, -OCO-, or a benzene ring.
Further, in the step (c), the reaction temperature is 50-80 ℃ and the reaction time is 16-40h.
Further, in the step (d), the reaction temperature is 50-80 ℃ and the reaction time is 12-40h.
Further, in the step (d), the acid-binding agent is selected from more than one of potassium carbonate or tetramethylguanidine.
Further, in the step (d), the polymerization inhibitor is selected from at least one of hydroquinone or phenothiazine.
Further, in the step (d), the solvent is selected from more than one of DMF or DMSO.
The invention also provides application of the tri-itaconic acid derived penta-functionality hybrid monomer as a radiation curing monomer. Specifically, the composition is used as a monomer in a photo-curing composition, and the photo-curing composition comprises one or more of the monomers, commercial photoinitiator and other photo-polymerizable monomers, oligomers and resins, and can also comprise auxiliary components such as inorganic filler, organic filler, colorant, other additives and solvents, and the like, which are added according to actual needs.
Further, the photoinitiator may be a radical and/or cationic photoinitiator such as alpha-hydroxy ketone, alpha-amino ketone, acylphosphine oxide, thioxanthone, oxime ester, sulfonium salt, iodonium salt, and the like, and mixtures thereof. To promote the use efficiency of the light sources with different wavelengths, different sensitizers can be added, including but not limited to anthracene sensitizers, pyrazoline sensitizers and coumarin sensitizers; the addition amount of the sensitizer and the initiator is 1-5% of the total mass of the formula, and the proportion of the sensitizer and the initiator is adjusted according to the requirement.
Further, the monomer and the composition can be used for various photo-initiated polymerization systems such as various photo-cured coatings, printing inks, adhesives, 3D printing, electronic packaging and the like, and particularly for the photo-initiated polymerization systems which are required to be cured rapidly, have high hardness and high wear resistance.
Further, the light source for excitation of the radiation curing photoinitiator is selected from one or more of ultraviolet light and visible light.
Further, the light source of the radiation curing photoinitiator is selected from more than one of a mercury lamp capable of emitting ultraviolet light, visible light, an LED light source and an LDI light source.
Further, the radiation-curable photoinitiator comprises 0.01 to 30 parts by weight of a commercial photoinitiator (3, 4-epoxycyclohexylcarboxylic acid-3 ',4' -epoxycyclohexylmethyl ester) and 100 parts by weight of one or more and/or free radicals (tripropylene glycol diacrylate) and cationically curable monomers (3, 4-epoxycyclohexylcarboxylic acid-3 ',4' -epoxycyclohexylmethyl ester), oligomers or resins or mixtures or copolymers of the three, wherein the compounds comprise a tri-itaconic acid derived pentafunctional hybrid monomer and a commercial monomer.
Further, the radiation-curable photoinitiator comprises 0.5 to 10 parts by weight of a commercial photoinitiator and 100 parts by weight of one or more and/or free radical and cationic curable monomers, oligomers or resins or mixtures or copolymers of the three compounds.
Further, according to actual needs, an inorganic filler, an organic filler, a colorant, other additives, a solvent and other auxiliary components are added, and the colorant is selected from pigments or dyes. Other additives include ultraviolet absorbers, light stabilizers, flame retardants, leveling agents (BYK 307) or defoamers (BYK 055).
The method comprises the following specific steps: (1) according to monomers and resin: and (3) a photoinitiator: the mass ratio of the auxiliary agent is 100: (0.5-1): (0-4.5) proportioning raw materials; (2) stirring to fully dissolve the components; (3) Illuminating the polymerization system with light sources of different wavelengths or different light intensities; (4) The polymerization conversion can be studied by the change of its characteristic peak by the infrared method.
Wherein: the light source in step (3) may be mercury lamps (high, medium and low pressure), as well as LEDs light sources emitting wavelengths of 365-425nm, LDI light sources.
Further, a radically polymerizable monomer, oligomer or resin or a mixture or copolymer of the three refers to a compound or mixture in which olefinic bonds are crosslinked by radical polymerization, mainly various olefins or acrylates.
Commercially available free radically polymerized ethylenically polymerizable polymers include, but are not limited to, (meth) acrylates, acrolein, olefins, conjugated dienes, styrene, maleic anhydride, fumaric anhydride, vinyl acetate, vinyl pyrrolidone, vinyl imidazole, (meth) acrylic acid derivatives such as (meth) acrylamides, vinyl halides, vinylidene halides, and the like.
Suitable ethylenically oligomers and resins include, but are not limited to, (meth) acrylic copolymers of (meth) acryl functional groups, urethane (meth) acrylates, polyester (meth) acrylates, unsaturated polyesters, polyether (meth) acrylates, silicone (meth) acrylates, epoxy (meth) acrylates, and the like, as well as water soluble or water dispersible analogs of the foregoing.
Further, monomers, oligomers or prepolymers containing cationically polymerizable groups, or mixtures or copolymers of the three, are various compounds which can be crosslinked by cationic photoinitiators, such as compounds having epoxy, oxetane or vinyl ethers.
Examples of the compound having an epoxy, oxetane or vinyl ether include monofunctional glycidyl ethers, polyfunctional aliphatic glycidyl ethers, polyfunctional aromatic glycidyl ethers, glycidyl esters and aliphatic epoxy compounds.
Examples of the monofunctional glycidyl ether include allyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, 2-ethylhexyl glycidyl ether, sec-butylphenyl glycidyl ether, tert-butylphenyl glycidyl ether, and 2-methyloctylglycidyl ether.
Examples of the polyfunctional aliphatic glycidyl ether include 1, 6-hexanediol glycidyl ether, trimethylolpropane triglycidyl ether, neopentyl glycol diglycidyl ether, glycerol triglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether.
Examples of the polyfunctional aromatic glycidyl ether include bisphenol a glycidyl ether, bisphenol F glycidyl ether, brominated bisphenol a glycidyl ether, bisphenol glycidyl ether, tetramethyl biphenol glycidyl ether, resorcinol glycidyl ether, and the like.
Examples of the glycidyl esters include glycidyl acrylate, glycidyl methacrylate, diglycidyl phthalate, and diglycidyl hexahydrophthalate.
Examples of the aliphatic epoxy compound include 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexylformate, 3, 4-epoxycyclohexylethyl-3, 4-epoxycyclohexylformate, vinylcyclohexenyl dioxide, propenyl cyclohexenyl dioxide, and 3, 4-epoxy-4-methylcyclohexyl-2-propenyl oxide.
In the photocurable composition of the present invention, the polymerizable component may be in the form of a polymer such as an oligomer or a prepolymer, or a copolymer formed from at least one of a monomer, an oligomer, and a prepolymer. In addition, it may be in the form of an aqueous dispersion.
Examples of the epoxy-, oxetane-or vinyl ether-group-containing polymer include epoxy-containing polymers and resins such as bisphenol a epoxy resin, dicyclopentadiene epoxy resin, diaminodiphenylmethane epoxy resin, aminophenol epoxy resin, naphthalene epoxy resin, novolak epoxy resin, biphenyl epoxy resin, hydrogenated biphenyl epoxy resin, and aliphatic epoxy resin.
The above-mentioned radical polymerizable vinyl-containing commercial monomers, or cationic polymerizable epoxy-containing commercial monomers, and various oligomers, prepolymers, or copolymers are well known to those skilled in the art, and are not particularly limited.
Exemplary compounds conforming to the structure of formula (I) are listed below:
Figure BDA0003792830600000071
by adopting the scheme, the invention has the beneficial effects that:
1. according to the invention, three itaconic acids are connected through glycol ester, and then a vinyl ether structure, a glycidyl ether structure, an oxetane structure or an epoxycyclohexane structure is introduced at the chain end position to form three hybrid monomers capable of free radical polymerization and two cationic polymerization five-functionality degrees, and the characteristics of biomass source, no toxicity and no pollution of the itaconic acid are fully utilized, and the preparation process is simple, the raw materials are easy to obtain, and industrial production is easy to realize.
2. The hybrid monomer prepared by the invention contains free radical polymerizable double bonds in three itaconic acid and two cationic polymerizable groups at the end groups, has the characteristics of a five-functionality hybrid photocuring monomer, balances free radical and cationic hybrid polymerization, has the characteristics of high-functionality endowed monomers with rapid photocuring performance, and endows products with high hardness, high wear resistance and the like, and is far superior to a difunctional hybrid monomer consisting of one free radical and one cationic group; the five-element degree of functionality of the product plays a role of a cross-linking agent in a photocuring system, and has high curing speed and excellent performance.
3. The three itaconic acid derived free radicals and the hybrid monomer in the invention have low volatility, low odor after curing and high requirements on the photo-curing composition, and have good application prospects in the fields of food and medicine packaging coatings, contact biomedical materials and the like.
In summary, the present invention accomplishes the functions of five-functional free radical and cationic hybrid monomers through the double bond in itaconic acid and the cationic polymerizable group introduced in the R group. The preparation process is simple, is easy to implement and control, takes the bio-based itaconic acid as a raw material, reduces or avoids the use of petrochemical products from a synthesis source, and has the double effects of saving resources and protecting the environment. The hybrid monomer structure has the advantages of high curing speed, high hardness of cured products and the like, and has wide application prospect in free radical-cation hybrid polymerization.
Drawings
FIG. 1 is a structural general diagram of a tri-itaconic acid derived pentafunctional hybrid monomer of the present invention.
Detailed Description
The technical scheme of the invention is further described in detail below with reference to a plurality of examples, the examples are implemented on the premise of the technical scheme of the invention, and detailed implementation modes and specific operation processes are given, but the protection scope of the invention is not limited to the examples below.
The experimental materials used in the examples below, unless otherwise specified, were all commercially available from conventional biochemistry reagents.
Example 1:
preparation of (I) -1
(1) Itaconic acid (1 equivalent) and 2-bromoethanol (2.2 equivalents) and toluene (20 mL of itaconic acid is contained in each 100g of toluene) are added into a flask provided with a water separator, then 0.05 equivalent of p-toluenesulfonic acid and 0.05 equivalent of hydroquinone are added, heating reflux is carried out for 24 hours, after toluene is distilled off, and then the target product itaconic acid di- (2-bromoethyl) can be prepared by vacuum reduced pressure distillation.
(2) Itaconic acid (1.0 eq.) and acetic anhydride (1.0 eq.) were placed in a round bottom flask together with toluene (20 mL of itaconic acid per 100g of toluene). Sulfuric acid (0.08 wt%) was added with stirring, heated with mixing at 50℃for 3 hours, and then the generated acetic acid was removed under reduced pressure. The itaconic anhydride is dried under vacuum and reacted directly after drying to avoid hydrolysis.
(3) Preparation of itaconic acid- β -monoester (I) -1a: 2-ethyleneoxyethanol (1.0 eq.) was added to itaconic anhydride (1.0 eq.) of step (2) along with toluene (20 mL itaconic acid per 100g toluene) and reacted at 50℃for 16h. The disappearance of the anhydride signal was monitored by FT-IR (1850 cm -1 And 1770cm -1 ). Toluene was removed under reduced pressure and the product was dried under vacuum without further filtration or purification to obtain itaconic acid- β -monoester. The purity was monitored by HPLC to be 98% or higher.
(I)-1a：MS(C 9 H 12 O 5 ): m/e 200.07; experimental results: 201.07 (M+H) + )。
(4) Preparing a target product (I) -1: into a 500mL three-necked flask, 0.2mol of itaconic acid-beta-monoester, 55.2g (0.4 mol) of potassium carbonate and 250mL of DMF were added, and then 0.01mol of hydroquinone was added as a polymerization inhibitor, heated to 70℃and stirred for 30min, 34.2g (0.4 mol) of di- (2-bromoethyl) itaconic acid was taken and added dropwise to the reaction system, stirring was continued for 12h, and TLC monitoring was carried out to end the reaction. The inorganic salts were filtered off and most of the organic solvent DMF was distilled off. Dichloromethane, deionized water extraction, drying, evaporating to dryness, and performing silica gel column chromatography (mobile phase is n-hexane to ethyl acetate 9 to 1), wherein the GC monitoring purity is more than 98%.
(I) -1: yield 78%; MS (C) 27 H 34 O 14 ): m/e 582.19; experimental results: 583.19 (M+H) + )。
Part of the reaction process is as follows:
Figure BDA0003792830600000081
example 2:
preparation of (I) -2
(1) Itaconic acid (1 equivalent) and 2-bromoethanol (2.2 equivalents) and toluene (20 mL of itaconic acid is contained in each 100g of toluene) are added into a flask provided with a water separator, then 0.05 equivalent of p-toluenesulfonic acid and 0.05 equivalent of hydroquinone are added, heating reflux is carried out for 24 hours, after toluene is distilled off, and then the target product itaconic acid di- (2-bromoethyl) can be prepared by vacuum reduced pressure distillation.
(2) Itaconic acid (1.0 eq.) and acetic anhydride (1.0 eq.) were placed in a round bottom flask together with toluene (20 mL of itaconic acid per 100g of toluene). Sulfuric acid (0.08 wt%) was added with stirring, heated with mixing at 50℃for 3 hours, and then the generated acetic acid was removed under reduced pressure. The itaconic anhydride is dried under vacuum and reacted directly after drying to avoid hydrolysis.
(3) Preparation of itaconic acid- β -monoester (I) -2a: 4-ethyleneoxybutanol (1.0 eq.) was added to itaconic anhydride (1.0 eq.) of step (2) together with toluene (20 mL of itaconic acid per 100g of toluene) and reacted at 60℃for 40h. The disappearance of the anhydride signal was monitored by FT-IR (1850 cm -1 And 1770cm -1 ). Toluene was removed under reduced pressure and the product was dried under vacuum without further filtration or purification to obtain itaconic acid- β -monoester. The purity was monitored by HPLC to be 98% or higher.
(I)-2a：MS(C 11 H 16 O 5 ): m/e 228.10; experimental results: 229.10 (M+H) + )。
(4) Preparing a target product (I) -2: into a 500mL three-necked flask, 0.2mol of itaconic acid-beta-monoester, 55.2g (0.4 mol) of potassium carbonate and 250mL of DMF were added, 0.01mol of hydroquinone was added as a polymerization inhibitor, the mixture was heated to 70℃and stirred for 30min, 34.2g (0.4 mol) of di- (2-bromoethyl) itaconic acid was taken and added dropwise to the reaction system, stirring was continued for 40h, and TLC monitoring was performed to complete the reaction. The inorganic salts were filtered off and most of the organic solvent DMF was distilled off. Dichloromethane, deionized water extraction, drying, evaporating to dryness, and performing silica gel column chromatography (mobile phase is n-hexane to ethyl acetate 9 to 1), wherein the GC monitoring purity is more than 98%.
(I) -2: yield 74%; MS (C) 31 H 42 O 14 ): m/e 638.26; experimental results: 639.26 (M+H) + )。
Part of the reaction process is as follows:
Figure BDA0003792830600000091
example 3:
preparation of (I) -3
(1) Itaconic acid (1 equivalent) and 2-bromoethanol (2.2 equivalents) and toluene (20 mL of itaconic acid is contained in each 100g of toluene) are added into a flask provided with a water separator, then 0.05 equivalent of p-toluenesulfonic acid and 0.05 equivalent of hydroquinone are added, heating reflux is carried out for 24 hours, after toluene is distilled off, and then the target product itaconic acid di- (2-bromoethyl) can be prepared by vacuum reduced pressure distillation.
(2) Itaconic acid (1.0 eq.) and acetic anhydride (1.0 eq.) were placed in a round bottom flask together with toluene (20 mL of itaconic acid per 100g of toluene). Sulfuric acid (0.08 wt%) was added with stirring, heated with mixing at 50℃for 3 hours, and then the generated acetic acid was removed under reduced pressure. The itaconic anhydride is dried under vacuum and reacted directly after drying to avoid hydrolysis.
(3) Preparation of itaconic acid- β -monoester (I) -3a: glycidyl ether (1.0 eq.) was added to itaconic anhydride (1.0 eq.) of step (2) along with toluene (20 mL of itaconic acid per 100g of toluene) and reacted at 70 ℃ for 20h. The disappearance of the anhydride signal was monitored by FT-IR (1850 cm -1 And 1770cm -1 ). Toluene was removed under reduced pressure and the product was dried under vacuum without further filtration or purification to obtain itaconic acid- β -monoester. The purity was monitored by HPLC to be 98% or higher.
(I)-3a：MS(C 8 H 10 O 5 ): m/e 186.05; experimental results: 187.05 (M+H) + )。
(4) Preparing a target product (I) -3: to a 500mL three-necked flask, 0.2mol of itaconic acid-beta-monoester, 55.2g (0.4 mol) of potassium carbonate and 250mL of DMSO were added, and then 0.01mol of hydroquinone was added as a polymerization inhibitor, and the mixture was heated to 70℃and stirred for 30 minutes, 34.2g (0.4 mol) of di- (2-bromoethyl) itaconic acid was added dropwise to the reaction system, and stirring was continued for 24 hours, and TLC monitoring was performed to complete the reaction. The inorganic salts were filtered off and most of the organic solvent DMSO was distilled off. Dichloromethane, deionized water extraction, drying, evaporating to dryness, and performing silica gel column chromatography (mobile phase is n-hexane to ethyl acetate 9 to 1), wherein the GC monitoring purity is more than 98%.
(I) -3: yield 79%; MS (C) 25 H 30 O 14 ): m/e 554.16; experimental results: 555.16 (M+H) + )。
Part of the reaction process is as follows:
Figure BDA0003792830600000101
example 4:
preparation of (I) -4
(1) Itaconic acid (1 equivalent) and 2-bromoethanol (2.2 equivalents) and toluene (20 mL of itaconic acid is contained in each 100g of toluene) are added into a flask provided with a water separator, then 0.05 equivalent of p-toluenesulfonic acid and 0.05 equivalent of hydroquinone are added, heating reflux is carried out for 24 hours, after toluene is distilled off, and then the target product itaconic acid di- (2-bromoethyl) can be prepared by vacuum reduced pressure distillation.
(2) Itaconic acid (1.0 eq.) and acetic anhydride (1.0 eq.) were placed in a round bottom flask together with toluene (20 mL of itaconic acid per 100g of toluene). Sulfuric acid (0.08 wt%) was added with stirring, heated with mixing at 50℃for 3 hours, and then the generated acetic acid was removed under reduced pressure. The itaconic anhydride is dried under vacuum and reacted directly after drying to avoid hydrolysis.
(3) Preparation of itaconic acid- β -monoester (I) -4a: 3-ethyl-3-hydroxymethyl oxetane (1.0 equivalent) was added to itaconic anhydride (1.0 equivalent) of step (2) together with toluene (20 mL of itaconic acid per 100g of toluene) and reacted at 70℃for 36 hours. The disappearance of the anhydride signal was monitored by FT-IR (1850 cm -1 And 1770cm -1 ). Toluene was removed under reduced pressure and the product was dried under vacuum without further additionFiltering or purifying in one step to obtain itaconic acid-beta-monoester. The purity was monitored by HPLC to be 98% or higher.
(I)-4a：MS(C 11 H 16 O 5 ): m/e 228.10; experimental results: 229.10 (M+H) + )。
(4) Preparing a target product (I) -4: 0.2mol of itaconic acid-beta-monoester, tetramethyl guanidine (0.4 mol) and 250mL of DMSO are added into a 500mL three-necked flask, 0.01mol of hydroquinone is added as a polymerization inhibitor, the mixture is heated to 50 ℃, the mixture is stirred for 30min, 34.2g (0.4 mol) of itaconic acid di- (2-bromoethyl) is taken and dropwise added into a reaction system, stirring is continued for 36h, and TLC monitoring reaction is finished. The salt was filtered off and most of the organic solvent DMSO was evaporated off. Dichloromethane, deionized water extraction, drying, evaporating to dryness, and performing silica gel column chromatography (mobile phase is n-hexane to ethyl acetate 9 to 1), wherein the GC monitoring purity is more than 98%.
(I) -4: yield 75%; MS (C) 31 H 42 O 14 ): m/e 638.26; experimental results: 639.26 (M+H) + )。
Part of the reaction process is as follows:
Figure BDA0003792830600000111
example 5:
preparation of (I) -5
(1) Itaconic acid (1 equivalent) and 2-bromoethanol (2.2 equivalents) and toluene (20 mL of itaconic acid is contained in each 100g of toluene) are added into a flask provided with a water separator, then 0.05 equivalent of p-toluenesulfonic acid and 0.05 equivalent of polymerization inhibitor are added, heating reflux is carried out for 48 hours, after toluene is distilled off, vacuum reduced pressure distillation is carried out, and the target product itaconic acid di- (2-bromoethyl) can be prepared.
(2) Itaconic acid (1.0 eq.) and acetic anhydride (1.0 eq.) were placed in a round bottom flask together with toluene (20 mL of itaconic acid per 100g of toluene). Sulfuric acid (0.08 wt%) was added with stirring, heated with mixing at 50℃for 3 hours, and then the generated acetic acid was removed under reduced pressure. The itaconic anhydride is dried under vacuum and reacted directly after drying to avoid hydrolysis.
(3) Preparation of itaconic acid- β -monoester (I) -5a:7-oxo-bicyclo [4.1.0]Hexane-3-yl-methanol (1.0 eq.) was added to itaconic anhydride (1.0 eq.) of step (2) together with toluene (20 mL of itaconic acid per 100g of toluene) and reacted at 70℃for 30h. The disappearance of the anhydride signal was monitored by FT-IR (1850 cm -1 And 1770cm -1 ). Toluene was removed under reduced pressure and the product was dried under vacuum without further filtration or purification to obtain itaconic acid- β -monoester. The purity was monitored by HPLC to be 98% or higher.
(I)-5a：MS(C 12 H 16 O 5 ): m/e 240.10; experimental results: 241.10 (M+H) + )。
(4) Preparing a target product (I) -5: into a 500mL three-necked flask, 0.2mol of itaconic acid-beta-monoester, 55.2g (0.4 mol) of potassium carbonate and 250mL of DMF were added, 0.01mol of hydroquinone was added as a polymerization inhibitor, the mixture was heated to 70℃and stirred for 30min, 34.2g (0.4 mol) of di- (2-bromoethyl) itaconic acid was taken and added dropwise to the reaction system, stirring was continued for 20h, and TLC was monitored to finish the reaction. The inorganic salts were filtered off and most of the organic solvent DMF was distilled off. Dichloromethane, deionized water extraction, drying, evaporating to dryness, and performing silica gel column chromatography (mobile phase is n-hexane to ethyl acetate 9 to 1), wherein the GC monitoring purity is more than 98%.
(I) -5: yield 76%; MS (C) 33 H 42 O 14 ): m/e 662.26; experimental results: 662.26 (M+H) + )。
Part of the reaction process is as follows:
Figure BDA0003792830600000112
< experiment >
The following experiments were performed with the products of the above examples, respectively.
< experiment 1>
Photo-curing experiments of various five-functionality hybrid monomers prepared in examples under light excitation of weak light intensity and coating property test:
monomers (I) -1, (I) -2, (I) -3, (I) -4, (I) -5:10 parts by mass
Difunctional monomer (tripropylene glycol diacrylate, TPGDA, sartomer): 43 parts by mass
Difunctional cationically polymerizable monomer (3, 4-epoxycyclohexylcarboxylic acid-3 ',4' -epoxycyclohexylmethyl ester, EPOX, tetter): 44 parts by mass
Photoinitiator (4-phenylsulfanyl phenyl-diphenylsulfonium hexafluoroantimonate, PAG-002, new sailing material): 2 parts by mass
Leveling agent (BYK 307, pick chemistry): 0.5 part by mass
Defoamer (BYK 055, pick chemistry): 0.5 part by mass
The five photo-curing solutions prepared above are coated on a glass slide to form a coating layer with the thickness of about 100 mu m, and the coating area is 2cm wide and 5cm long and is 10cm 2 Is produced in Guangzhou and Guangdong, and has a unit power of 20mW/cm 2 An LED light source with the emission wavelength of 365nm is used as an excitation light source and is placed on a conveyor belt to irradiate through the light belt at the speed of 3 m/s. The total weight was weighed with an analytical balance, the surface of the cured product was wiped with an acetone cotton ball, weighed again, and the thickness lost was calculated by dividing the mass lost by the area coated, i.e. the thickness of the formulation which did not cure due to oxygen inhibition. The lower the thickness, the better the effect of the tack-free of the photocurable composition. Can be used to characterize the curing effect under an air atmosphere. The uncured thicknesses of the different formulations are shown in table 1.
< experiment 2>
Photo-curing experiments under weak light intensity without adding the hybrid polymerization of examples and coating property test:
difunctional radical polymerizable monomer (tripropylene glycol diacrylate, TPGDA, sartomer): 48 parts by mass
Difunctional cationically polymerizable monomer (3, 4-epoxycyclohexylcarboxylic acid-3 ',4' -epoxycyclohexylmethyl ester, EPOX, tetter): 49 parts by mass
Photoinitiator (3, 4-epoxycyclohexylmethyl 3',4' -epoxycyclohexylmethyl ester, PAG-002, new sailing material): 2 parts by mass
Leveling agent (BYK 307, pick chemistry): 0.5 part by mass
Defoamer (BYK 055, pick chemistry): 0.5 part by mass
In the comparative experiment, the test of adding 5 parts by mass of difunctional radical and cationic polymerization monomers TPGDA and EPOX, respectively, instead of the hybrid monomers in the examples, the remaining various formulation components and the photo-curing conditions and the thickness of the uncured layer were all completely identical. The specific results are shown in Table 1.
TABLE 1 uncured layer thickness after exposure to light for each photocurable composition
Figure BDA0003792830600000121
Figure BDA0003792830600000131
< experiment 3>
Photo-curing experiments and coating Property tests of the various monomers prepared in examples under intense light:
example formulations and comparative experiments formulations<Experiment 1>And<experiment 2>Identical, the light curing process was carried out except that the light intensity of the light source of the photo-curing machine was adjusted to 1000mW/cm 2 In addition, other parameters were unchanged, and the surface hardness was measured with a pencil hardness tester after curing.
Pencil hardness test according to national standard GB/T6739-2006, a pencil with the hardness of 9H-9B is used for scratching a cured film by using a pencil scratch instrument, and soft cloth or rubber is used for lightly wiping, wherein the hardness of the pencil without scratch is the hardness of the film. The specific results are shown in Table 2.
TABLE 2 surface hardness of each photocurable composition after intense light irradiation
Photocurable composition Hardness of pencil
Formula containing monomer (I) -1 4H
Formula containing monomer (I) -2 4H
Formula containing monomer (I) -3 5H
Formulations containing monomers (I) -4 6H
Formula containing monomer (I) -5 6H
Formula of comparative experiment 3H
The hardness after photo-curing of the formulation to which the examples were added was significantly better. The five-functional hybrid monomer is shown to significantly improve the degree of crosslinking of the cured surface.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent that the described embodiments are some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.

Claims (1)

1. A trifunctional hybrid monomer derived from tri-itaconic acid, characterized by: the molecular structure is as follows:
Figure FDA0004219521230000011
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