CN114656591A - Water-soluble macromolecular photoinitiator and preparation method and application thereof - Google Patents

Water-soluble macromolecular photoinitiator and preparation method and application thereof Download PDF

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CN114656591A
CN114656591A CN202011538532.2A CN202011538532A CN114656591A CN 114656591 A CN114656591 A CN 114656591A CN 202011538532 A CN202011538532 A CN 202011538532A CN 114656591 A CN114656591 A CN 114656591A
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anhydride
photoinitiator
water
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杨万泰
吴映雪
陈冬
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Beijing University of Chemical Technology
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    • C—CHEMISTRY; METALLURGY
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/04—Anhydrides, e.g. cyclic anhydrides
    • C08F222/06—Maleic anhydride
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    • C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
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    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
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    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/04—Anhydrides, e.g. cyclic anhydrides
    • C08F222/06—Maleic anhydride
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    • C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
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Abstract

The invention relates to a water-soluble macromolecular photoinitiator and a preparation method and application thereof. The acid anhydride monomer is polymerized automatically or the acid anhydride electron-accepting monomer is copolymerized with other electron-donating monomers (such as styrene, vinyl acetate and the like) to prepare an acid anhydride functional polymer, and the polymer is further reacted with a hydroxyl-terminated (or amino-terminated) micromolecule photoinitiator to prepare a water-soluble macromolecule photoinitiator with a photoinitiating group in a side group. The method has the advantages of simple synthetic route and safe and convenient operation, the content of the prepared water-soluble macromolecule photoinitiator photoinitiation group is controllable, the defects that the traditional micromolecule photoinitiator is easy to volatilize, migrate and yellow and the like are overcome, and the water-soluble macromolecule photoinitiator has good water solubility and high initiation activity. Under the irradiation of ultraviolet light, the water-soluble macromolecular photoinitiator can initiate the polymerization of water-soluble monomers (such as acrylamide monomers, acrylic monomers, acrylate monomers and the like) to prepare the water-soluble polymer with a branched structure.

Description

Water-soluble macromolecular photoinitiator and preparation method and application thereof
Technical Field
The invention relates to a photoinitiator, in particular to a water-soluble macromolecule photoinitiator and a preparation method thereof.
Background
The photopolymerization technology, as a polymerization method taking environmental and economic benefits into consideration, has the advantages of mild reaction conditions, high efficiency, small damage to substrates, no environmental pollution and the like, and has been rapidly developed in the fields of coatings, printing inks, adhesives, printing plates and the like since the past. In recent years, with the gradual optimization of each component and condition in a photopolymerization system, the application field of the photopolymerization system has been expanded to dental repair, biological materials, microelectronics and the like.
Photoinitiators have received considerable attention as important components in photopolymerization systems. The conventional photoinitiator is a small-molecule photoinitiator, and during the use process, the photoinitiator is gradually found to have some defects, such as: the micromolecule photoinitiator is easy to migrate in a photocuring resin system, and the mechanical property of a coating film is influenced; most of the materials have hydrophobic property, and are difficult to be compatible with hydrophilic resin; the fragments generated after photolysis can cause problems of toxicity, peculiar smell, yellowing of the coating film and the like. These disadvantages have limited the application and development of photopolymerization technology.
In order to solve the defects of the traditional micromolecular photoinitiator and meet the requirement on environmental protection, researchers pay more attention to developing efficient, low-mobility, non-toxic and harmless photoinitiators, wherein the method for making the photoinitiator large in molecule is a method for effectively improving the defects of the micromolecular photoinitiator, and comprises the following steps: CN103992419A, CN110003365A, CN101735343A and CN 109535124A.
The currently developed macromolecular photoinitiator is mainly used for photocuring crosslinking reaction, in the photopolymerization process, an active center formed after a photoinitiating group of the macromolecular photoinitiator is excited is easy to generate crosslinking reaction to form a crosslinked polymer with a three-dimensional network structure, and a branched polymer with a branched chain structure and controllable quantity and molecular weight of branched chains, especially a high-molecular-weight water-soluble branched polymer, is difficult to prepare. Therefore, the development of the water-soluble macromolecular photoinitiator with excellent initiation performance has important theoretical and practical significance, can integrate the advantages of an aqueous polymerization system and a photopolymerization technology, has the advantages of good solubility, no peculiar smell, no migration, environmental protection and the like, and has important application value in the aspect of industrial application.
Disclosure of Invention
The invention aims to provide a water-soluble macromolecular photoinitiator which has good water solubility, good photoinitiation performance, no migration and good compatibility with polymers and can effectively initiate the polymerization of water-soluble monomers to prepare branched polymers, and a preparation method thereof. In order to make the prepared macromolecule photoinitiator have good water solubility, the molecular structure of the macromolecule photoinitiator must contain hydrophilic groups, and active groups capable of realizing photoinitiation are required. On the basis of analyzing the preparation method of the conventional macromolecular photoinitiator, the invention improves the conventional method: firstly, preparing an anhydride functionalized polymer; secondly, introducing micromolecule photoinitiation groups into the polymer side groups through the reaction of the anhydride functional polymer and the hydroxyl-terminated or amine-terminated micromolecule photoinitiator, and hydrolyzing the residual anhydride to prepare the water-soluble macromolecule initiator with the side groups containing the photoinitiation groups. According to the method, a specific number of hydrophilic groups are introduced into a macromolecular photoinitiator molecular chain, so that the prepared macromolecular photoinitiator has good photoinitiation activity and good solubility in an aqueous system, and is suitable for photopolymerization of a water-soluble monomer. More importantly, the photoinitiating groups in the macromolecular photoinitiator side groups are uniformly distributed, the occurrence of a crosslinking phenomenon can be effectively inhibited (or overcome) when the water-soluble monomer is initiated to polymerize, and the photoinitiator can be used for preparing a water-soluble polymer with a branched structure, in particular an ultrahigh molecular weight water-soluble polymer. In addition, branched polymers have better solubility properties and aqueous branched polymer solutions have better shear resistance properties than linear polymers.
The water-soluble macromolecular photoinitiator prepared by the invention has a structure shown in a general formula (I) or a general formula (II):
Figure BDA0002854238730000031
wherein x is 0-200, y is 5-150, z is 5-50, and n is 0-10; in order to further increase the water solubility of the water-soluble macrophotoinitiator, x is 0 to 100, y is 5 to 100, z is 5 to 40, and n is 0 to 5; further preferred are x-0-50, y-5-50, z-5-40, n-1-5; x1Is H or CH3；Y1Is H or CH3；Y2Is a carboxyl or carboxylate group; z is O or NH;
X2selected from any one of the following groups;
Figure BDA0002854238730000041
PI is a photoinitiating group selected from the group consisting of common cleavage-type photoinitiating groups, preferably any one of the following groups.
Figure BDA0002854238730000042
The preparation method of the water-soluble macromolecular photoinitiator with the structure shown as the general formula (I) or the general formula (II) mainly comprises three steps: (1) the anhydride functional polymer is prepared by self-polymerization of anhydride electron-accepting monomers (electron-acceptor monomers) or copolymerization of anhydride monomers and electron-donating monomers (electron-donor monomers), wherein the anhydride monomers are one or more than two selected from maleic anhydride, citraconic anhydride and itaconic anhydride, and the electron-donating monomers are one or more than two selected from styrene monomers, vinyl acetate, acrylamide monomers, (meth) acrylate monomers and vinyl ether monomers; (2) reacting an anhydride functional polymer with a terminal hydroxyl or amino micromolecule photoinitiator to prepare a water-soluble macromolecule photoinitiator precursor; (3) hydrolyzing the water-soluble macromolecule photoinitiator precursor to prepare the water-soluble macromolecule photoinitiator with the side group containing the photoinitiation group.
In some specific embodiments, the anhydride-functionalized polymer is preferably prepared as a homopolymer of anhydride-based monomers or a copolymer of anhydride-based monomers as follows:
(1) acid anhydride monomer homopolymer:
the preparation method is characterized by adopting a free radical polymerization method, and the preparation raw materials comprise anhydride monomers, a solvent and an initiator;
firstly, dissolving anhydride monomers in a solvent, and mixing to form a uniform polymerization reaction system, wherein the mass percentage concentration of the monomers in the reaction system is 5-60%; then, initiating polymerization by adopting a conventional free radical initiator, wherein the reaction temperature is 60-120 ℃, and the reaction time is 1-10 hours; finally, separating and drying the prepared polymerization product from the reaction system to obtain the anhydride monomer homopolymer;
(2) anhydride functionalized copolymer:
preparing a copolymer of anhydride monomers by free radical copolymerization reaction of anhydride electron-accepting monomers and electron-donating monomers, wherein the preparation raw materials comprise the anhydride electron-accepting monomers, the electron-donating monomers, a solvent and an initiator;
the monomer concentration in the reaction system can influence the molecular weight of the prepared macromolecular photoinitiator, the total mass percent concentration of the monomers is preferably 5-60%, and the more preferably monomer concentration is 10-30%; the molar ratio of the acid anhydride electron accepting monomer to the electron donating monomer in the reaction system is 1:3-3:1, preferably 1:1-1.5:1, and the prepared polymer is an alternating copolymer or a random copolymer.
The initiator used for the polymerization is a conventional free-radical initiator known to the person skilled in the art and may be an azo initiator, a peroxide free-radical initiator or an oxidation-reduction initiation system, the amount of initiator used in the system being from 0.05 to 5.0% by mass, preferably from 0.5 to 2.0% by mass, based on the mass of the monomers. The azo-type initiator includes, but is not limited to: azobisisobutyronitrile, azobisisoheptonitrile, azobisisobutylamidine hydrochloride, azobisisobutylimidazoline hydrochloride, azobiscyanovaleric acid, azobisisopropylimidazoline, and the like; the peroxide initiators include, without limitation: dibenzoyl peroxide, bis (2,4 dichlorobenzoyl) peroxide, ditert-butyl peroxide, lauroyl peroxide, tert-butyl peroxyneoheptanoate, tert-butyl peroxypivalate, tert-butyl peroxyneodecanoate, tert-amyl peroxyneodecanoate, tert-butyl peroxybenzoate, di-sec-butyl peroxydicarbonate, dicetyl peroxydicarbonate, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, dicumyl peroxide, di-tert-butyl peroxide, di-tert-amyl peroxide, and the like.
When the solution polymerization method is employed, the solvent is preferably a highly polar solvent such as acetone, methyl ethyl ketone, methyl propyl ketone, 2-pentanone, 3-methyl-2-butanone, 2-hexanone, 3-hexanone, 2-methyl-3-pentanone, 3-dimethyl-2-butanone, 4-methyl-2-pentanone, 2-heptanone, 3-heptanone, 4-heptanone, ketone solvents such as 2, 4-dimethyl-3-pentanone, 2-octanone, 2, 6-dimethyl-4-heptanone, cyclopentanone, cyclohexanone, cycloheptanone, and methyl isopropyl ketone, tetrahydrofuran, dioxane, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and dimethylsulfoxide, and these solvents may be used alone or in any combination. Dissolving a monomer, initiating polymerization by adopting the free radical initiator at the reaction temperature of 40-120 ℃, preferably 60-90 ℃, reacting for 1-10 hours, precipitating a polymer solution after the reaction is finished, and performing centrifugal separation and drying to obtain an anhydride functionalized polymer;
when the precipitation polymerization is employed, examples of the solvent preferably include: one or more of ester solvents such as ethyl acetate, butyl acetate, benzyl acetate, phenyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, butyl butyrate, and ethyl benzoate, and aromatic hydrocarbon solvents such as toluene, ethylbenzene, and xylene; or a mixed solvent of the above solvent and an aliphatic hydrocarbon solvent such as n-hexane, cyclohexane, n-heptane, petroleum ether, octane, etc.; or one or more of acetone, butanone, methyl acetone, 2-pentanone, 3-methyl-2-butanone, 2-hexanone, 3-hexanone, 2-methyl-3-pentanone, 3-dimethyl-2-butanone, 4-methyl-2-pentanone, 2-heptanone, 3-heptanone, 4-heptanone, 2, 4-dimethyl-3-pentanone, 2-octanone, 2, 6-dimethyl-4-heptanone, cyclopentanone, cyclohexanone, cycloheptanone, methyl isopropyl ketone and other ketone solvents, tetrahydrofuran, dioxane, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and dimethyl sulfoxide, and one or more of aliphatic hydrocarbon solvents such as n-hexane, cyclohexane, n-heptane, petroleum ether, octane, etc. After the monomer is dissolved, the conventional free radical initiator is adopted to initiate polymerization, the reaction temperature is preferably 40-120 ℃, more preferably 60-90 ℃, the reaction is preferably carried out for 1-10 hours, the selected solvent can not dissolve the prepared anhydride functionalized polymer, therefore, the polymer is precipitated from the solvent along with the reaction, and the prepared polymer is directly separated from the reaction system and dried, thus obtaining the anhydride functionalized polymer.
In some specific embodiments, the water-soluble macrophotoinitiator precursor is preferably prepared as follows:
the photo-initiation group is introduced into the side group of the anhydride functional polymer through the reaction of the anhydride group and the hydroxyl or amine group.
In some preferred embodiments, the anhydride functionalized polymer is dispersed and dissolved in a suitable solvent, and a hydroxyl-terminated (or amine-terminated) micromolecular photoinitiator with a structure shown in a general formula (III) is added and mixed to form a uniform reaction system; secondly, adding a catalyst into the reaction system, wherein the reaction temperature is preferably 40-120 ℃, more preferably 40-80 ℃, and the reaction time is preferably 2-20 hours, precipitating, separating and drying a reaction product from the reaction system to obtain the water-soluble macromolecule photoinitiator precursor with the structural formula shown as the general formula (IV) or the general formula (V).
Figure BDA0002854238730000071
Wherein, L is hydroxyl or amido, PI is the photoinitiation group of the micromolecule photoinitiator, and n is 0-10;
Figure BDA0002854238730000081
wherein x is 0-200, y is 5-150, z is 5-50, and n is 0-10; in order to further improve the initiator solubility, x is 0 to 100, y is 5 to 100, z is 5 to 40, and n is 0 to 5; further preferred are x-0-50, y-5-50, z-5-40, n-1-5; x1Is H or CH3；Y1Is H or CH3；Y2Is a carboxyl or carboxylate group; z is O or NH;
X2selected from any one of the following groups:
Figure BDA0002854238730000082
PI is the above-mentioned photoinitiating group selected from any one of the following groups:
Figure BDA0002854238730000091
the hydroxyl-terminated (or amine-terminated) small molecule photoinitiator is preferably represented by a structural formula, wherein n is 0-10, more preferably 1-5, and still more preferably 1-3; solvents used include, without limitation: tetrahydrofuran, dioxane, acetone, butanone, cyclohexanone, methyl isobutyl ketone, methyl isopropyl ketone, ester solvents, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and dimethyl sulfoxide, which can be used singly or in any combination; the catalyst comprises 4-dimethylamino pyridine, triethylamine, p-toluenesulfonic acid, concentrated sulfuric acid, sodium acetate and peroxy acid, and the content of the catalyst in the system is 0.05-2 mass percent, preferably 1-1.5 mass percent of the mass of the anhydride functionalized polymer; the content of the photoinitiator group in the side group of the macromolecular photoinitiator of the reaction product is mainly influenced by the mass ratio of the hydroxyl-terminated or amine-terminated micromolecular photoinitiator and the anhydride functionalized polymer in the system, but the mass ratio is not particularly limited and is usually adjusted according to the content of the photoinitiator group in the prepared macromolecular photoinitiator. The mass ratio of the hydroxyl-terminated or amino-terminated micromolecule photoinitiator to the anhydride functionalized polymer in the reaction system is preferably 1:10-1:2, more preferably 1:5-1:2, and still more preferably 1:5-1: 2.5; the number of photoinitiation groups in each molecular chain of the water-soluble macromolecular photoinitiator (precursor) can be effectively regulated and controlled by further regulating the molecular weight of the anhydride functional polymer.
In some specific embodiments, the water-soluble macrophotoinitiator is preferably prepared as follows:
hydrolyzing residual anhydride in the precursor of the macromolecular photoinitiator to obtain the water-soluble macromolecular photoinitiator shown as the general formula (I) or the general formula (II).
The water-soluble macromolecular photoinitiator prepared by the method can effectively initiate the polymerization of common water-soluble monomers to prepare the water-soluble polymer with a branched structure, compared with the water-soluble polymer with a linear structure, the water-soluble polymer with the branched structure has better water solubility, and the water solution of the water-soluble polymer with the branched structure has lower viscosity and better shear resistance. In the present invention, examples of water-soluble monomers that can be initiated include, without limitation: (meth) acrylamide-based monomers, (meth) acrylic acid, (meth) acrylate salts, N-vinylpyrrolidone, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, 2-acrylamido-2-methylpropanesulfonic acid (salt), allylsulfonate salts, and (meth) acryloyloxyethyltrimethyl ammonium chloride.
In some more specific embodiments, exemplified by the small molecule photoinitiator 2-hydroxy-4' - (2-hydroxyethoxy) -2-methylpropiophenone (hereinafter 2959), the anhydride functionalized polymer styrene-maleic anhydride alternating copolymer (SMA), and the corresponding synthetic water soluble macro-molecule photoinitiator SMA-2959, the synthetic routes for SMA and SMA-2959 are shown in mechanisms 1 and 2, respectively:
Figure BDA0002854238730000101
mechanism 1. synthetic route to polymeric SMA
Figure BDA0002854238730000102
Mechanism 2. synthetic route of macromolecular photoinitiator SMA-2959
The specific operation steps are as follows:
1. 4g of maleic anhydride and 4.24g of styrene are dissolved in 46g of isoamyl acetate, 0.04g of Azodiisobutyronitrile (AIBN) serving as an initiator is added, after uniform mixing, argon is introduced into a reaction system to remove oxygen, the reaction is carried out for 4 hours at 75 ℃, and SMA generated along with the reaction is gradually precipitated from the system. And after the reaction is finished, centrifugally separating the product SMA from the system, washing the product SMA for 1-2 times by using isoamyl acetate to remove unreacted monomers, washing the product SMA for 2-3 times by using petroleum ether, and drying the product SMA to constant weight to obtain the anhydride functionalized polymer SMA, wherein the yield is about 97%, and the number average molecular weight (Mn) of the product SMA is about 20000 as characterized by GPC.
2. 1g of SMA synthesized in the above step 1 and 29590.2 g of a photoinitiator were dissolved in 20mL of anhydrous Tetrahydrofuran (THF), and 10mg of 4-Dimethylaminopyridine (DMAP) as a catalyst was added thereto and reacted under reflux for 5 hours. After the reaction is finished, petroleum ether is used for precipitation, centrifugal separation is carried out, the precipitate is washed by petroleum ether for 2 times, and then vacuum drying is carried out, so as to obtain the water-soluble macromolecular photoinitiator precursor with the side group containing the photoinitiation group.
3. And (3) dissolving the product obtained in the step (2) by using a small amount of THF, and adding a proper amount of sodium bicarbonate to hydrolyze the residual anhydride groups in the water-soluble macromolecular photoinitiator precursor. Reacting for 3 hours at normal temperature, then precipitating with ethanol, centrifugally separating, and drying to constant weight to obtain the macromolecular photoinitiator SMA-2959 with good water solubility.
After the residual anhydride is hydrolyzed, a large amount of carboxyl groups exist on the polymer, so that the polymer has better water solubility. The weight percentage of 2959 in the prepared macromolecular photoinitiator is measured to be 16% through ultraviolet characterization, and by combining the Mn of SMA, the average molecular chain side group of each water-soluble macromolecular photoinitiator contains about 14 2959 photoinitiating groups, namely, the branching degree of the water-soluble polymer prepared by the macromolecular photoinitiator can be deduced to be about 14.
The prepared water-soluble macromolecule photoinitiator can be used as a substitute of a micromolecule photoinitiator, and the polymerization of water-soluble monomers is efficiently initiated. Dissolving the prepared water-soluble macromolecular photoinitiator SMA-29596 mg with the side group containing a photoinitiating group in 20mL of water, adding 30g of water-soluble monomer AM, supplementing 50mL of water, introducing nitrogen into a reaction system after the monomers are dissolved and uniformly mixed, removing oxygen, and placing the mixture under a low-pressure ultraviolet lamp with the wavelength of 254nm for irradiation to initiate the ultraviolet polymerization reaction of the AM, wherein the light intensity of the ultraviolet light is 10mW/cm2Reacting for 3 hours to obtain the water-soluble PAM polymer with a branched structure, wherein the molecular weight is 1.85 multiplied by 10 measured by a Viscosystem AVS370 full-automatic Ubbelohde viscometer7。
According to the molecular structure of the macromolecular photoinitiator, a photoinitiating group exists in a side chain of a polymer, the photoinitiating group is dissociated under the ultraviolet irradiation condition to form an active free radical in the side chain of the polymer, and the active free radical initiates a water-soluble monomer to grow at the chain end of the free radical in an aqueous phase system to form a water-soluble polymer branched chain. Each photoactive initiating group can form a polymer branch chain on the polymer side group, and the number of the water-soluble polymer branch chains formed by the prepared water-soluble macromolecular photoinitiator initiating the polymerization of the water-soluble monomer is correspondingly increased along with the increase of the number of the photoactive groups. By changing the type of the hydroxyl-terminated or amino-terminated micromolecule photoinitiator and the mass ratio of the hydroxyl-terminated or amino-terminated micromolecule photoinitiator to the anhydride functionalized polymer, the type and the number of the photoinitiating groups in the polymer side group can be changed, the macromolecular photoinitiators with different molecular structures and different photoinitiating group contents can be prepared, and the water-soluble polymers with different molecular structures and different branching degrees and branched structures can be further prepared.
Compared with the prior art, the invention has the following characteristics:
(1) the water-soluble macromolecular photoinitiator and the preparation method thereof provided by the invention have the advantages of simple process, high conversion rate and easiness in separation of the obtained product.
(2) The water-soluble macromolecular photoinitiator prepared by the invention is quickly dissolved in aqueous solution and is convenient to use; the composition, structure and photoinitiation capability of the macromolecular photoinitiator have strong designability, and the type, content and distribution of photoinitiation groups in a molecular chain of the macromolecular photoinitiator can be conveniently regulated and controlled.
The water-soluble macromolecule initiator prepared by the invention has the advantages of high photoactivity, no peculiar smell, no migration, good compatibility with polymers and the like, the photoinitiating groups in the side groups are uniformly distributed, the occurrence of a crosslinking phenomenon can be effectively inhibited (or overcome) when the water-soluble monomer is initiated to polymerize, the water-soluble macromolecule initiator can be used as a substitute of a micromolecular initiator to efficiently initiate the photopolymerization of the water-soluble monomer, the molecular weight of the prepared water-soluble polymer product can be conveniently regulated and controlled through the using amount of the initiator, the molecular branching structure and the branching degree are clear, and compared with a linear water-soluble polymer, the water-soluble polymer with the branching structure has better solubility in water and has certain shearing resistance.
Drawings
FIG. 1 is the infrared spectrum (a.SMA; b.SMA-2959) of styrene-maleic anhydride alternating copolymer (SMA) and the prepared water-soluble macromolecule photoinitiator SMA-2959.
FIG. 2 is the ultraviolet-visible absorption spectrum (a.2959; b.SMA-2959) of the small molecule photoinitiator 2959 and the prepared water-soluble macromolecule photoinitiator SMA-2959.
Detailed Description
In order to better illustrate the technology of the present invention, the following examples and comparative examples are given, however, the scope of the present invention is not limited to these examples.
The chemical composition and structure of the product are measured by a Nexus670 infrared spectrometer and a GBC Cintra-20 ultraviolet spectrometerAnd (4) carrying out measurement. The molecular weight of the product macrophotoinitiator was determined by gel permeation chromatography (GPC, Waters515) with polystyrene as the standard and THF as the eluent. Molecular weight of photoinitiated water-soluble polymers
Figure BDA0002854238730000131
AVS370 full-automatic Ubbelohde viscometer measurement. The mass percent concentration of the monomer in the polymerization reaction system is a mass fraction based on the total mass of the polymerization reaction system.
Examples
Preparation of anhydride functionalized polymer
Example 1:
the maleic anhydride-vinyl acetate alternating copolymer (PMV) has the structural formula:
Figure BDA0002854238730000141
monomer maleic anhydride and vinyl acetate, initiator AIBN and solvent butyl acetate are added into a 100mL flask and mixed evenly, the total molar concentration of the monomer is 1mol/L, the molar ratio of the maleic anhydride to the vinyl acetate is 1:1, and the addition amount of the AIBN is 2 percent of the total mass of the monomer. Introducing nitrogen into a reaction system to remove oxygen for 15 minutes, reacting for 4 hours at 75 ℃, after the reaction is finished, centrifugally separating and precipitating, washing a product for 1-2 times by using butyl acetate, washing for three times by using petroleum ether, and then drying in vacuum to obtain the anhydride functionalized alternating copolymer PMV, wherein the yield is about 90%, and the molecular weight is about 5000.
Example 2:
the itaconic anhydride-styrene alternating copolymer (PITA-St) has the formula:
Figure BDA0002854238730000142
monomer itaconic anhydride and styrene, initiator AIBN and solvent isoamyl acetate are added into a 100mL flask and mixed evenly, the total molar concentration of the monomer is 1mol/L, the molar ratio of the itaconic anhydride to the styrene is 1:1, and the dosage of the AIBN is 1 percent of the total mass of the monomer. Introducing nitrogen into a reaction system to remove oxygen for 15 minutes, reacting for 6 hours at 70 ℃, after the reaction is finished, centrifugally separating and precipitating, washing a product for 1-2 times by using isoamyl acetate, washing for three times by using petroleum ether, and then drying in vacuum to obtain an anhydride functionalized polymer itaconic anhydride-styrene alternating copolymer (PITA-St), wherein the yield is about 80%, and the molecular weight is about 10000.
Example 3:
the structural formula of the styrene-maleic anhydride random copolymer (PMA-St) is as follows:
Figure BDA0002854238730000151
monomers, namely maleic anhydride and styrene, an initiator, namely dicumyl peroxide and a solvent, namely isoamyl acetate are added into a 100mL flask and are uniformly mixed, wherein the total molar concentration of the monomers is 1mol/L, the molar ratio of the maleic anhydride to the styrene is 1:1, and the dosage of the initiator is 1 percent of the total mass of the monomers. Introducing nitrogen into a reaction system to remove oxygen for 15 minutes, reacting for 8 hours at 120 ℃, after the reaction is finished, centrifugally separating and precipitating, washing a product for 1-2 times by using isoamyl acetate, washing for three times by using petroleum ether, and drying in vacuum to obtain the anhydride functionalized polymer styrene-maleic anhydride random copolymer (PMA-St), wherein the yield is about 90 percent, and the molecular weight is about 20000.
Preparation of macromolecular photoinitiator
Example 4
SMA, 2959, DMAP, and 20mL of anhydrous THF, as indicated in the formulation in Table 1, were charged to a 50mL flask, with DMAP being 1% of the mass of SMA. After mixing well, the reaction was carried out under reflux for 5 hours. After the reaction, the solution was cooled to room temperature, precipitated with petroleum ether and centrifuged. Dissolving the precipitate with THF, hydrolyzing the rest anhydride groups with appropriate amount of sodium bicarbonate solution, stirring for reaction for 6-8 hr, precipitating with ethanol, centrifuging, and vacuum drying to constant weight to obtain the macromolecular photoinitiator SMA-2959A with good water solubility.
FIG. 1 is an infrared spectrum of SMA and SMA-2959A #, from whichCan know that 1780cm-1Is the stretching vibration peak of C ═ O in the anhydride five-membered ring structure of MAH; 1730cm as can be seen from the infrared spectrum of the hydrolyzed SMA-2959A #-1It is a stretching vibration peak of 2959 which generates an ester group after reacting with an acid anhydride. The reaction of the small molecule photoinitiator 2959 with the anhydride group is illustrated; characteristic peak of anhydride five-membered ring structure 1780cm-1Almost completely disappeared at the same time of 1712cm-1And 1405cm-1New peaks appear at points, corresponding to the stretching vibration peak of C ═ O in the carboxylic acid and the stretching vibration peak of C ═ O in the carboxylic acid salt, respectively, indicating that all the acid anhydride groups have opened. FIG. 2 is an ultraviolet spectrogram of small molecule photoinitiator 2959 and macromolecular photoinitiator SMA-2959A #, with characteristic peaks around 280nm, and through absorption peak intensity and concentrations of small molecule photoinitiator 2959 and macromolecular photoinitiator SMA-2959A #, the content of 2959 photoinitiating groups in the macromolecular photoinitiator can be calculated, and the number of photoinitiating groups in each molecular chain of the water-soluble macromolecular photoinitiator can be further calculated.
Example 5
SMA as shown in the formulation in Table 1, 2959, DMAP, and 20mL of anhydrous THF were charged to a 50mL flask, with DMAP being 1% of the mass of SMA. The ratio of 2959 to SMA was changed, and a macromolecular photoinitiator with different photoinitiating group contents was prepared in the same manner as in example 4, to obtain water-soluble macromolecular photoinitiator SMA-2959B #.
Example 6
SMA as shown in the formulation in Table 1, 2959, DMAP, and 20mL of anhydrous THF were charged to a 50mL flask, with DMAP being 1% of the mass of SMA. The ratio of 2959 to SMA was changed, and a macromolecular photoinitiator with a different content of photoinitiating groups was prepared in the same manner as in example 4, to obtain water-soluble macromolecular photoinitiator SMA-2959C #.
Example 7
PMV, 2959, concentrated sulfuric acid, and 20mL of anhydrous THF, as shown in the formulation of Table 1, were added to a 50mL flask, with concentrated sulfuric acid at 1% by mass of the PMV. Macromolecular photoinitiators with different photoinitiating group contents were prepared in the same manner as in example 4, to obtain water-soluble macromolecular photoinitiator PMV-2959A #.
Example 8
PMV, 2959, concentrated sulfuric acid, and 20mL of anhydrous THF, as shown in the formulation of Table 1, were added to a 50mL flask, with concentrated sulfuric acid at 1% by mass of the PMV. Macromolecular photoinitiators with different photoinitiating group contents were prepared in the same manner as in example 4, to obtain water-soluble macromolecular photoinitiator PMV-2959B #.
Example 9
PITA-St, 2959, DMAP, and 20mL of anhydrous THF as shown in the formulation of Table 1 were charged to a 50mL flask, with the DMAP being 1% by mass of the PITA-St. Macromolecular photoinitiators with different photoinitiating group contents were prepared in the same manner as in example 4, to obtain a water-soluble macromolecular photoinitiator PITA-St-2959.
TABLE 1 Synthesis of Macro photoinitiator formulations
Figure BDA0002854238730000171
Preparation of branched water-soluble polymer
Example 10
Based on the total mass of the polymerization reaction system, the mass fraction of Acrylamide (AM) monomer is 28%, and the dosage of the macromolecular photoinitiator SMA-2959B # is 0.03% of the mass of AM. Adding the monomer, the macromolecular photoinitiator and water into a reaction container for full dissolution, uniformly mixing, introducing nitrogen to remove oxygen for 15 minutes, and irradiating under a low-pressure ultraviolet lamp with the wavelength of 254nm to initiate AM photopolymerization, wherein the light intensity of the ultraviolet light is 10mW/cm2And reacting for 3 hours to obtain Polyacrylamide (PAM) hydrogel. The viscosity average molecular weight of the prepared PAM is measured to be 1.5 multiplied by 107And the prepared PAM has a branched structure, so that the PAM hydrogel is quickly dissolved and has excellent dissolving performance, and the dissolving time of PAM dry powder is less than 1 hour after drying and crushing.
The formulations used in examples 11 to 14 are shown in Table 2, and the procedure was carried out substantially the same as in example 10, by varying the kind and amount of the macrophotoinitiator, branched polyacrylamides of different structures and molecular weights were prepared.
TABLE 2 formula of branched polyacrylamide prepared by photopolymerization of water-soluble monomer initiated by water-soluble macromolecular photoinitiator
Figure BDA0002854238730000181
Comparative example 1:
the mass fraction of the AM monomer was 28%, and 2959 was 0.002% relative to the mass fraction of the AM monomer. Adding the monomer, the photoinitiator and water into a reaction container for full dissolution, uniformly mixing, introducing nitrogen to remove oxygen for 15 minutes, and irradiating under a low-pressure ultraviolet lamp with the wavelength of 254nm to initiate AM ultraviolet polymerization, wherein the light intensity of the ultraviolet light is 10mW/cm2And reacting for 3 hours to obtain the PAM hydrogel. The viscosity average molecular weight of PAM is 7.2 multiplied by 106The molecular weight is smaller; and the prepared PAM is linear polyacrylamide, so that the dissolving time is longer than that of a PAM branched polymer, and the dissolving time of dry powder after drying and crushing is more than 1 hour.

Claims (10)

1. A water-soluble macromolecular photoinitiator, characterized in that the photoinitiator has a structure represented by general formula (I) or general formula (II):
Figure FDA0002854238720000011
wherein x is 0-200, y is 5-150, z is 5-50, and n is 0-10; x1Is H or CH3；Y1Is H or CH3；Y2Is a carboxyl or carboxylate group; z is O or NH;
X2selected from any one of the following groups:
Figure FDA0002854238720000012
PI is a photoinitiating group selected from any one of the following groups:
Figure FDA0002854238720000021
2. a method for preparing the water-soluble macromolecular photoinitiator according to claim 1, comprising the steps of: (1) the acid anhydride functionalized polymer is prepared by the self-polymerization of acid anhydride monomers or the copolymerization of the acid anhydride monomers and electron donor monomers, wherein the acid anhydride monomers are selected from one or more than two of maleic anhydride, citraconic anhydride and itaconic anhydride, and the electron donor monomers are selected from one or more than two of styrene monomers, vinyl acetate, acrylamide monomers, (methyl) acrylate monomers and vinyl ether monomers; (2) reacting an anhydride functional polymer with a hydroxyl-terminated or amino-terminated micromolecule photoinitiator to prepare a water-soluble macromolecule photoinitiator precursor; (3) hydrolyzing the water-soluble macromolecule photoinitiator precursor to prepare the water-soluble macromolecule photoinitiator with the side group containing the photoinitiation group.
3. The method of claim 2, wherein the anhydride functionalized polymer is a homopolymer of an anhydride monomer or a copolymer of an anhydride monomer;
(1) homopolymers of anhydride monomers:
preparing a homopolymer of an anhydride monomer by adopting a free radical polymerization method, wherein the preparation raw materials comprise the anhydride monomer, a solvent and an initiator;
firstly, dissolving an anhydride monomer and an initiator in a solvent, and mixing to form a uniform polymerization reaction system; then, reacting for 1-10 hours at the temperature of 60-120 ℃; finally, precipitating, separating and drying the prepared polymerization product from a reaction system to obtain a homopolymer of the anhydride monomer;
(2) copolymers of anhydride monomers:
preparing a copolymer of anhydride monomers by free radical copolymerization reaction of the anhydride monomers and electron-donating monomers, wherein the preparation raw materials comprise the anhydride monomers, the electron-donating monomers, a solvent and an initiator;
firstly, dissolving an anhydride monomer, an electron donor monomer and an initiator in a solvent, and mixing to form a uniform polymerization reaction system; then, common free radical initiator is adopted to initiate polymerization, the reaction temperature is 40-120 ℃, and the reaction time is 1-10 hours; separating and drying the prepared polymer from a reaction system to obtain the anhydride functionalized polymer.
4. The method of claim 2, wherein the water-soluble macromolecular photoinitiator precursor is prepared by introducing a photoinitiator group into the pendant anhydride-functionalized polymer group by reacting the anhydride-functionalized polymer with a hydroxyl-or amine-terminated small molecule photoinitiator by:
firstly, dissolving an anhydride functional polymer in a solvent, adding a hydroxyl-terminated or amino-terminated micromolecule photoinitiator with a structure shown in a general formula (III), and uniformly mixing;
Figure FDA0002854238720000032
wherein L is hydroxyl or amino, PI is a photoinitiating group, and n is 0-10;
secondly, adding a catalyst into the reaction system, reacting for 2-20 hours at the reaction temperature of 40-120 ℃, and then precipitating, separating and drying a reaction product from the reaction system to obtain a water-soluble macromolecular photoinitiator precursor with a structural formula shown as a general formula (IV) or a general formula (V);
Figure FDA0002854238720000031
Figure FDA0002854238720000041
wherein x is 0-200, y is 5-150, z is 5-50, and n is 0-10; x1Is H or CH3；Y1Is H or CH3；Y2Is a carboxyl or carboxylate group; z is O or NH;
X2selected from any one of the following groups:
Figure FDA0002854238720000042
PI is a photoinitiating group selected from any one of the following groups:
Figure FDA0002854238720000043
and finally, hydrolyzing residual acid anhydride groups in the macromolecular photoinitiator shown in the general formula (IV) or the general formula (V) to obtain the water-soluble macromolecular photoinitiator shown in the general formula (I) or the general formula (II).
5. The method according to claim 2 or 3, wherein in the preparation process of the anhydride monomer homopolymer, the mass percentage concentration of the anhydride monomer in the reaction system is 5-60% based on the total mass of the polymerization reaction system; in the preparation process of the anhydride monomer copolymer, based on the total mass of a polymerization reaction system, the total mass percentage concentration of the anhydride monomer and the electron donor monomer in the reaction system is 5-60%, and the molar ratio of the anhydride monomer to the electron donor monomer is 1:3-3: 1.
6. The method according to claim 2 or 3, wherein the reaction solvent in the preparation of the acid anhydride functionalized polymer comprises ketone solvent, ester solvent, aliphatic hydrocarbon solvent, aromatic hydrocarbon solvent, tetrahydrofuran, dioxane, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and dimethylsulfoxide.
7. The method according to claim 2 or 3, wherein the initiator used in the preparation of the acid anhydride functionalized polymer is a conventional radical initiator, including azo type initiators, peroxide radical initiators or oxidation-reduction initiation systems, and the amount of the initiator used in the system is 0.05 to 5.0 mass% of the total mass of the monomers in the polymerization reaction system.
8. The method according to claim 2 or 4, wherein the solvent used in the reaction system for preparing the water-soluble macromolecule photoinitiator precursor with the side group containing the photoinitiating group through the reaction of the acid anhydride functionalized polymer and the hydroxyl-terminated or amine-terminated micromolecule photoinitiator comprises tetrahydrofuran, dioxane, acetone, butanone, cyclohexanone, methyl isobutyl ketone, methyl isopropyl ketone, ester solvents, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and dimethyl sulfoxide.
9. The method according to claim 2 or 4, wherein in the reaction system for preparing the water-soluble macromolecular photoinitiator precursor with the side group containing the photoinitiating group by introducing the photoinitiating group into the side group of the anhydride functionalized polymer through the reaction of the anhydride functionalized polymer and the hydroxyl-terminated or amine-terminated micromolecular photoinitiator, the mass ratio of the hydroxyl-terminated or amine-terminated micromolecular photoinitiator to the anhydride functionalized polymer is 1:10-1: 2; the catalyst in the reaction system comprises 4-dimethylamino pyridine, triethylamine, p-toluenesulfonic acid, concentrated sulfuric acid, sodium acetate and peroxy acid, and the dosage of the catalyst is 0.05-2% of the mass of the anhydride functionalized polymer.
10. Use of the macrophotoinitiator according to claim 1 for initiating polymerization of water-soluble monomers to prepare water-soluble polymers having a branched structure.
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