CN114656591B - 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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CN114656591B
CN114656591B CN202011538532.2A CN202011538532A CN114656591B CN 114656591 B CN114656591 B CN 114656591B CN 202011538532 A CN202011538532 A CN 202011538532A CN 114656591 B CN114656591 B CN 114656591B
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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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Abstract

The invention relates to a water-soluble macromolecular photoinitiator, a preparation method and application thereof. The anhydride functional polymer is prepared by the self-polymerization of anhydride monomers or the copolymerization of anhydride electron-accepting monomers and other electron-donating monomers (such as styrene, vinyl acetate and the like), and the polymer is further reacted with a small molecular photoinitiator with terminal hydroxyl groups (or amino groups) to prepare the water-soluble macromolecular photoinitiator with the lateral group containing photoinitiating groups. The method disclosed by the invention is simple in synthetic route and safe and convenient to operate, the content of the photoinitiating groups of the prepared water-soluble macromolecular photoinitiator is controllable, the defects of easiness in volatilization, migration, yellowing and the like of the traditional small-molecular photoinitiator are overcome, and the water-soluble macromolecular photoinitiator has good water solubility and high initiation activity. Under ultraviolet light irradiation, the water-soluble macromolecular photoinitiator can initiate polymerization of water-soluble monomers (such as acrylamide, acrylic acid salts 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 macromolecular photoinitiator and a preparation method thereof, and the prepared water-soluble macromolecular photoinitiator can be used for photopolymerization of various water-soluble monomers such as acrylamide monomers, (methyl) acrylic acid salts and the like.
Background
As a polymerization method which gives consideration to both environmental and economic benefits, the photopolymerization technology has the advantages of mild reaction conditions, high efficiency, small damage to the base material, no environmental pollution and the like, and has been rapidly developed in the fields of paint, ink, adhesive, printing plates and the like since the advent of the technology. In recent years, with the gradual optimization of each component and condition in a photopolymerization system, the application fields of the photopolymerization system are expanded to dental restoration, biological materials, microelectronics and the like.
Photoinitiators have been of great interest as an important component in photopolymerization systems. Traditional photoinitiators are small molecule photoinitiators, which have been found to suffer from several drawbacks during use, such as: the small molecular photoinitiator is easy to migrate in a photo-curing resin system, and the mechanical property of a coating film is affected; most of the hydrophilic resins have hydrophobic properties, and are difficult to be compatible with hydrophilic resins; fragments generated after photolysis can cause problems such as toxicity, peculiar smell, yellowing of coating films and the like. These drawbacks limit the application and development of photopolymerization technology.
In order to solve the disadvantages of the traditional small molecular photoinitiators and meet the requirements on environmental protection, researchers pay more attention to develop efficient, low-mobility, nontoxic and harmless photoinitiators, wherein the large-molecular photoinitiator is a method for effectively improving the shortages of the small molecular photoinitiators, such as: CN103992419A, CN110003365A, CN101735343A, CN109535124a.
The macromolecule photoinitiator developed at present is mainly used for photocuring crosslinking reaction, in the photopolymerization process, the active center formed by the photoinitiation group of the macromolecule photoinitiator after being excited is easy to generate crosslinking reaction, so that a crosslinked polymer with a three-dimensional network structure is formed, and a branched polymer with a branched chain structure and controllable quantity and molecular weight of branched chains, particularly 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 a water-based 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 polymerization of water-soluble monomers to prepare branched polymers, and a preparation method thereof. In order to make the prepared macromolecular photoinitiator have good water solubility, the molecular structure of the macromolecular photoinitiator must contain hydrophilic groups, and at the same time, active groups capable of realizing photoinitiation are required. The invention improves the prior method on the basis of analyzing the prior known preparation method of the macromolecular photoinitiator: firstly, preparing an anhydride functionalized polymer; secondly, introducing a small molecular photoinitiation group into a polymer side group through the reaction of an anhydride functionalized polymer and a hydroxyl-terminated or amine-terminated small molecular photoinitiator, and hydrolyzing the residual anhydride to prepare the water-soluble macromolecular photoinitiator with the side group containing the photoinitiation group. According to the method, a specific number of hydrophilic groups are introduced into a molecular chain of the macromolecular photoinitiator, so that the prepared macromolecular photoinitiator has good photoinitiation activity and good solubility in an aqueous system, and is suitable for photopolymerization of water-soluble monomers. More importantly, photoinitiation groups in the macromolecular photoinitiator side groups are uniformly distributed, so that the crosslinking phenomenon can be effectively inhibited (or overcome) when the polymerization of the water-soluble monomer is initiated, and the preparation method can be used for preparing the water-soluble polymer with a branched structure, in particular to the ultra-high 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=0-200, y=5-150, z=5-50, n=0-10; to further enhance the water solubility of the water-soluble macromolecular photoinitiator, it is preferable that x=0 to 100, y=5 to 100, z=5 to 40, n=0 to 5; further preferred are x=0-50, y=5-50, z=5-40, n=1-5; x is X 1 Is H or CH 3 ；Y 1 Is H or CH 3 ；Y 2 Is a carboxyl or carboxylate group; z is O or NH;
X 2 any one selected from the following groups;
Figure BDA0002854238730000041
PI is a photoinitiating group selected from the group consisting of commonly cleaved photoinitiating groups, preferably any one of the following groups.
Figure BDA0002854238730000042
The preparation method of the water-soluble macromolecular photoinitiator with the structure shown in the general formula (I) or the general formula (II) mainly comprises the following three steps: (1) Preparing an anhydride functionalized polymer by self-polymerizing an anhydride electron-accepting monomer (electron acceptor monomer) or copolymerizing an anhydride monomer and an electron-donating monomer (electron donor monomer), wherein the anhydride monomer is one or more than two selected from maleic anhydride, citraconic anhydride and itaconic anhydride, and the electron-donating monomer is one or more than two selected from styrene monomer, vinyl acetate, acrylamide monomer, (methyl) acrylic ester monomer and vinyl ether monomer; (2) The anhydride functionalized polymer reacts with a hydroxyl-terminated or amino-terminated micromolecular photoinitiator to prepare a water-soluble macromolecule photoinitiator precursor; (3) The water-soluble macromolecular photoinitiator precursor is hydrolyzed to prepare the water-soluble macromolecular photoinitiator with the side group containing photoinitiating groups.
In some specific embodiments, the preparation of the anhydride-functionalized polymer is preferably a homopolymer of an anhydride-based monomer or a copolymer of an anhydride-based monomer as follows:
(1) Anhydride monomer homopolymer:
the preparation method adopts 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 is carried out for 1-10 hours; finally, separating and drying the prepared polymerization product from the reaction system to obtain an anhydride monomer homopolymer;
(2) Anhydride functionalized copolymer:
preparing a copolymer of an anhydride monomer through a free radical copolymerization reaction of the anhydride electron-accepting monomer and an electron-donating monomer, wherein the preparation raw materials comprise the anhydride electron-accepting monomer, the electron-donating monomer, a solvent and an initiator;
the concentration of the monomer in the reaction system can influence the molecular weight of the prepared macromolecular photoinitiator, and the total mass percent concentration of the monomer is preferably 5-60%, more preferably 10-30%; the molar ratio of the 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 radical initiator well known to those skilled in the art and may be an azo-type initiator, a peroxide radical initiator or a redox initiation system in which the initiator is used in an amount of 0.05 to 5.0 mass%, preferably 0.5 to 2.0 mass% based on the mass of the monomer. The azo initiator includes but is not limited to: azobisisobutyronitrile, azobisisoheptonitrile, azobisisobutylamidine hydrochloride, azobisiso Ding Mi hydrochloride, azobiscyano valeric acid, azobisisopropyl imidazoline, and the like; the peroxide initiator includes, but is not limited to: dibenzoyl peroxide, bis (2, 4 dichlorobenzoyl) peroxide, ditert-butyl peroxide, lauroyl peroxide, t-butyl peroxyneoheptanoate, t-butyl peroxypivalate, t-butyl peroxyneodecanoate, t-amyl peroxyneodecanoate, t-butyl peroxybenzoate, di-sec-butyl peroxydicarbonate, di (hexadecyl) dicarbonate, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, dicumyl peroxide, di-t-butyl peroxide, di-t-amyl peroxide, and the like.
When the solution polymerization method is employed, the solvent is preferably selected from solvents having a large polarity, such as 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 the like, tetrahydrofuran, dioxane, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, and the like, and these solvents may be used alone or in any combination. Dissolving monomers, initiating polymerization by adopting the free radical initiator, reacting for 1-10 hours at the temperature of 40-120 ℃, preferably 60-90 ℃, precipitating a polymer solution after the reaction is finished, centrifugally separating and drying to obtain an anhydride functionalized polymer;
when a precipitation polymerization mode 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 a mixed solvent comprising 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, tetrahydrofuran, dioxane, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and dimethylsulfoxide, and one or more of an aliphatic hydrocarbon solvent such as N-hexane, cyclohexane, N-heptane, petroleum ether, octane, and the like. After dissolution of the monomers, polymerization is initiated by the conventional radical initiator, the reaction temperature is preferably 40-120 ℃, more preferably 60-90 ℃, the reaction is preferably carried out for 1-10 hours, the selected solvent cannot dissolve the prepared anhydride functionalized polymer, so that 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 macromolecular photoinitiator precursor is preferably prepared as follows:
photo-initiation groups are introduced into the pendant groups of the anhydride functionalized polymer by reaction of the anhydride groups with hydroxyl or amine groups.
In some preferred embodiments, the anhydride functionalized polymer is dispersed and dissolved in a proper solvent, and a hydroxyl-terminated (or amino-terminated) small molecular photoinitiator with a structure shown in a general formula (III) is added and mixed to form a uniform reaction system; and 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, and precipitating, separating and drying the reaction product from the reaction system to obtain the water-soluble macromolecular photoinitiator precursor with the structural formula shown in the general formula (IV) or the general formula (V).
Figure BDA0002854238730000071
Wherein L is hydroxyl or amino, PI is the photoinitiation group of the small molecule photoinitiator, and n=0-10;
Figure BDA0002854238730000081
wherein x=0-200, y=5-150, z=5-50, n=0-10; to further increase initiator solubility, it is preferred that x=0-100, y=5-100, z=5-40, n=0-5; further preferred are x=0-50, y=5-50, z=5-40, n=1-5; x is X 1 Is HOr CH 3 ；Y 1 Is H or CH 3 ；Y 2 Is a carboxyl or carboxylate group; z is O or NH;
X 2 selected from any one of the following groups:
Figure BDA0002854238730000082
PI is the photoinitiating group described above, selected from any one of the following groups:
Figure BDA0002854238730000091
the hydroxyl (or amine) terminated small molecule photoinitiator used is preferably of the formula n=0-10, more preferably 1-5, still more preferably 1-3; solvents used include, but are not limited to: tetrahydrofuran, dioxane, acetone, butanone, cyclohexanone, methyl isobutyl ketone, methyl isopropyl ketone, ester solvents, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, alone or in any combination; the catalyst comprises 4-dimethylaminopyridine, pyridine, triethylamine, p-toluenesulfonic acid, concentrated sulfuric acid, sodium acetate and peroxyacid, 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 photoinitiating group content in the macromolecule photoinitiator side group of the reaction product is mainly influenced by the mass ratio of the hydroxyl-terminated or amine-terminated small molecule photoinitiator and the anhydride functionalized polymer in the system, but the mass ratio is not particularly limited, and is usually regulated according to the photoinitiating group content in the designed macromolecule photoinitiator. The mass ratio of the hydroxyl-terminated or amine-terminated small molecule 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 photoinitiating 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 functionalized polymer.
In some specific embodiments, the water-soluble macromolecular photoinitiator is preferably prepared as follows:
and hydrolyzing residual anhydride in the macromolecular photoinitiator precursor to obtain the water-soluble macromolecular photoinitiator shown in the general formula (I) or the general formula (II).
The water-soluble macromolecular photoinitiator prepared by the method can effectively initiate common water-soluble monomer polymerization to prepare the water-soluble polymer with a branched structure, and compared with the water-soluble polymer with a linear structure, the water-soluble polymer with a branched structure has better water solubility, and the water solution of the water-soluble polymer with a branched structure has lower viscosity and better shearing resistance. In the present invention, examples of the water-soluble monomer that can be initiated include, but are not limited to: (meth) acrylamide monomers, (meth) acrylic acid salts, N-vinylpyrrolidone, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, 2-acrylamide-2-methylpropanesulfonic acid (salt), allylsulfonate, and (meth) acryloyloxyethyl trimethyl ammonium chloride.
In some more specific embodiments, taking the small molecule photoinitiator 2-hydroxy-4' - (2-hydroxyethoxy) -2-methylpropionophenone (hereinafter 2959), the anhydride functionalized polymer styrene-maleic anhydride alternating copolymer (SMA), and the corresponding synthetic water soluble macromolecular photoinitiator SMA-2959 as examples, the synthetic routes for SMA and SMA-2959 are shown in mechanisms 1 and 2, respectively:
Figure BDA0002854238730000101
mechanism 1. Synthetic route to Polymer SMA
Figure BDA0002854238730000102
Mechanism 2. Synthetic route to 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 azo-bis-isobutyronitrile (AIBN) serving as an initiator is added, the mixture is uniformly mixed, 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. After the reaction, the product SMA is centrifugally separated from the system, washed with isoamyl acetate for 1-2 times, unreacted monomers are removed, washed with petroleum ether for 2-3 times, and then dried to constant weight, so that the anhydride functionalized polymer SMA is obtained, the yield is about 97%, and the number average molecular weight (Mn) of the product SMA is about 20000 by GPC.
2. 1g of SMA synthesized in the step 1 and 2959.2 g of photoinitiator were dissolved in 20mL of anhydrous Tetrahydrofuran (THF), 10mg of 4-Dimethylaminopyridine (DMAP) catalyst was added thereto, and the mixture was reacted under reflux for 5 hours. And (3) after the reaction is finished, petroleum ether is used for precipitation, centrifugal separation is carried out, the precipitation is washed for 2 times by petroleum ether, and then vacuum drying is carried out, so that the water-soluble macromolecular photoinitiator precursor with the side group containing the photoinitiating group is obtained.
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, precipitating with ethanol, centrifuging, and drying to constant weight to obtain the macromolecular photoinitiator SMA-2959 with good water solubility.
After the residual anhydride is hydrolyzed, a large number of carboxyl groups exist on the polymer, so the polymer has better water solubility. The mass fraction of 2959 in the prepared macromolecular photoinitiator is 16% by ultraviolet characterization, and the average number of 2959 photoinitiating groups in each water-soluble macromolecular photoinitiator molecular chain side group can be calculated by combining Mn of SMA, so that the branching degree of the water-soluble polymer prepared by initiating the macromolecular photoinitiator can be deduced to be about 14.
The prepared water-soluble macromolecular photoinitiator can be used as a substitute of a small molecular initiator to efficiently initiate the polymerization of water-soluble monomers. Dissolving the prepared water-soluble macromolecular photoinitiator SMA-2959 mg with the lateral group containing photoinitiating groups in 20mL of water, adding 30g of water-soluble monomer AM, adding 50mL of water, and introducing nitrogen into the reaction system after the monomers are dissolved and uniformly mixedAfter deoxidizing, the ultraviolet polymerization of AM is initiated by irradiation under a low-pressure ultraviolet lamp with the wavelength of 254nm, and the ultraviolet light intensity is 10mW/cm 2 The water-soluble PAM polymer with a branched structure is obtained after 3 hours of reaction, and the molecular weight is 1.85 multiplied by 10 measured by a viscosimeter of Viscosystem AVS370 7 。
From the molecular structure of the macromolecular photoinitiator, the photoinitiating group exists in the side chain of the polymer, the photoinitiating group is dissociated under the ultraviolet irradiation condition, active free radicals are formed in the side chain of the polymer, and the active free radicals trigger the water-soluble monomer to grow at the chain end of the free radicals in the aqueous phase system, so that the water-soluble polymer branched chain is formed. Each photoactive initiating group can form a polymer branched chain on a polymer side group, and the number of water-soluble polymer branched chains formed by initiating the polymerization of a water-soluble monomer by the prepared water-soluble macromolecular photoinitiator correspondingly increases along with the increase of the number of photoactive groups. By changing the types of the hydroxyl-terminated or amine-terminated small molecular photoinitiators and the mass ratio of the hydroxyl-terminated or amine-terminated small molecular photoinitiators to the anhydride functionalized polymer, the types and the number of photoinitiating groups in the polymer side groups can be changed, and macromolecular photoinitiators with different molecular structures and different photoinitiating group contents can be prepared, so that branched structure water-soluble polymers with different molecular structures and different branching degrees can be 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 easy separation of the obtained product.
(2) The water-soluble macromolecular photoinitiator prepared by the invention is rapidly dissolved in aqueous solution and is convenient to use; the composition, structure and photoinitiation capability of the macromolecular photoinitiator are very strong in designability, and the types, contents and distribution of photoinitiation groups in the molecular chain of the macromolecular photoinitiator can be conveniently regulated and controlled.
The water-soluble macromolecular initiator prepared by the invention has the advantages of high photoactivity, no peculiar smell, no migration, good compatibility with polymers and the like, photoinitiation groups in side groups are uniformly distributed, the occurrence of crosslinking phenomenon can be effectively inhibited (or overcome) when the polymerization of water-soluble monomers is initiated, the water-soluble macromolecular initiator can be used as a substitute for the small-molecular initiator to efficiently initiate the photopolymerization of the water-soluble monomers, the molecular weight of the prepared water-soluble polymerization product can be conveniently regulated and controlled by the use amount of the initiator, and the molecular branching structure and branching degree are definite.
Drawings
FIG. 1 is an infrared spectrum of styrene-maleic anhydride alternating copolymer (SMA) and of the water-soluble macromolecular photoinitiator SMA-2959 prepared (a. SMA; b. SMA-2959).
FIG. 2 is an ultraviolet-visible absorption spectrum of a small molecular photoinitiator 2959 and a water-soluble macromolecular photoinitiator SMA-2959 prepared (a.2959; b.SMA-2959).
Detailed Description
In order to better illustrate the technology of the present invention, examples and comparative examples are described below, however, the scope of the present invention is not limited to these examples.
The chemical composition and structure of the product are measured by using a Nexus670 infrared spectrometer and a GBC Cintra-20 ultraviolet spectrometer. The molecular weight of the product macromolecular photoinitiator was determined by gel permeation chromatography (GPC, waters 515) with polystyrene as a calibration and THF as a eluent. Molecular weight of the photoinitiated water-soluble polymer is determined by
Figure BDA0002854238730000131
AVS370 fully automated Ubbelohde viscometer measurement. The mass percent concentration of the monomer in the polymerization reaction system is the mass fraction based on the total mass of the polymerization reaction system.
Examples
Preparation of anhydride functionalized polymers
Example 1:
the structural formula of the maleic anhydride-vinyl acetate alternating copolymer (PMV) is as follows:
Figure BDA0002854238730000141
the monomer maleic anhydride and vinyl acetate, initiator AIBN and solvent butyl acetate are added into a 100mL flask, the mixture is uniformly mixed, 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 AIBN is 2% of the total mass of the monomer. Introducing nitrogen into the reaction system to deoxidize for 15 minutes, reacting for 4 hours at 75 ℃, centrifuging to separate precipitate after the reaction is finished, washing the product with butyl acetate for 1-2 times, washing with petroleum ether for three times, and then vacuum drying to obtain the anhydride functionalized alternating copolymer PMV, wherein the yield is about 90%, and the molecular weight is about 5000.
Example 2:
the structural formula of the itaconic anhydride-styrene alternating copolymer (PITA-St) is as follows:
Figure BDA0002854238730000142
the monomer itaconic anhydride and styrene, initiator AIBN and solvent isoamyl acetate are added into a 100mL flask, and are uniformly mixed, 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 AIBN is 1% of the total mass of the monomer. Introducing nitrogen into the reaction system to deoxidize for 15 minutes, reacting for 6 hours at 70 ℃, centrifuging to separate precipitate after the reaction is finished, washing the product with isoamyl acetate for 1-2 times, washing with petroleum ether for three times, and vacuum drying to obtain the 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
adding monomer maleic anhydride and styrene, initiator dicumyl peroxide and solvent isoamyl acetate into a 100mL flask, uniformly mixing, 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 use amount of the initiator is 1% of the total mass of the monomers. Introducing nitrogen into the reaction system to deoxidize for 15 minutes, reacting for 8 hours at 120 ℃, centrifuging to separate precipitate after the reaction is finished, washing the product with isoamyl acetate for 1-2 times, washing with petroleum ether for three times, and then vacuum drying to obtain the anhydride functionalized polymer styrene-maleic anhydride random copolymer (PMA-St), wherein the yield is about 90%, and the molecular weight is about 20000.
Preparation of macromolecular photoinitiators
Example 4
SMA, 2959, DMAP, and 20mL of anhydrous THF, as shown in the formulation of Table 1, were added to a 50mL flask, with DMAP being 1% of the SMA mass. After mixing well, the mixture was reacted under reflux for 5 hours. After the reaction was completed, the solution was cooled to room temperature, precipitated with petroleum ether, and centrifuged. Dissolving the precipitate with THF, hydrolyzing the residual anhydride group with proper amount of sodium bicarbonate solution, stirring for reaction for 6-8 hours, precipitating with ethanol, centrifuging, and vacuum drying to constant weight to obtain the macromolecular photoinitiator SMA-2959A#.
As shown in FIG. 1, which shows the infrared spectra of SMA and SMA-2959A#, 1780cm was found from the infrared spectra of SMA -1 A stretching vibration peak of C=O in an anhydride five-membered ring structure of MAH; as can be seen from the infrared spectrum of SMA-2959A# after hydrolysis, 1730cm -1 Is a stretching vibration peak of 2959 generated ester group after reaction with anhydride. Indicating that the small molecule photoinitiator 2959 reacted with an anhydride group; anhydride five-membered ring structural characteristic peak 1780cm -1 Almost completely disappear at 1712cm -1 And 1405cm -1 New peaks appear, corresponding to the stretching vibration peak of c=o in the carboxylic acid and the stretching vibration peak of c=o in the carboxylate, respectively, indicating that all anhydride groups have been ring opened. FIG. 2 is an ultraviolet spectrum of a small molecular photoinitiator 2959 and a large molecular photoinitiator SMA-2959A#, with characteristic peaks at about 280nm, and the content of 2959 photoinitiating groups in the large molecular photoinitiator can be calculated by the absorption peak intensity and the concentrations of the small molecular photoinitiator 2959 and the large molecular photoinitiator SMA-2959A#, and further calculatedAnd calculating the number of photoinitiating groups in each molecular chain of the water-soluble macromolecular photoinitiator.
Example 5
SMA, 2959, DMAP, and 20mL of anhydrous THF, as shown in the formulation of Table 1, were added to a 50mL flask, with DMAP being 1% of the SMA mass. Changing the ratio of 2959 to SMA, preparing macromolecular photoinitiator with different photoinitiating group content in the same way as in example 4 to obtain water-soluble macromolecular photoinitiator SMA-2959B#.
Example 6
SMA, 2959, DMAP, and 20mL of anhydrous THF, as shown in the formulation of Table 1, were added to a 50mL flask, with DMAP being 1% of the SMA mass. The ratio of 2959 to SMA was varied to prepare a macromolecular photoinitiator having different photoinitiating group content in the same manner as in example 4 to obtain a water-soluble macromolecular photoinitiator SMA-2959C#.
Example 7
PMV, 2959 as shown in the formulation of Table 1, concentrated sulfuric acid, which is 1% of the mass of PMV, and 20mL of anhydrous THF were added to a 50mL flask. Macromolecular photoinitiator with different photoinitiating group content was prepared in the same manner as in example 4 to obtain a water-soluble macromolecular photoinitiator PMV-2959A#.
Example 8
PMV, 2959 as shown in the formulation of Table 1, concentrated sulfuric acid, which is 1% of the mass of PMV, and 20mL of anhydrous THF were added to a 50mL flask. Macromolecular photoinitiator with different photoinitiating group content is prepared in the same manner as in example 4, and the water-soluble macromolecular photoinitiator PMV-2959B#.
Example 9
PITA-St, 2959, DMAP, which was 1% by mass of PITA-St, and 20mL of anhydrous THF, as shown in the formulation of Table 1, were charged into a 50mL flask. Macromolecular photoinitiator with different photoinitiating group content was prepared in the same manner as in example 4 to obtain a water-soluble macromolecular photoinitiator PITA-St-2959.
Table 1 formulation for synthesizing macrophotoinitiators
Figure BDA0002854238730000171
Preparation of branched structure water-soluble polymers
Example 10
Based on the total mass of the polymerization reaction system, the mass fraction of the Acrylamide (AM) monomer is 28%, and the using amount of the macromolecular photoinitiator SMA-2959B# is 0.03% of the mass of the AM. Adding monomer, macromolecular photoinitiator and water into a reaction vessel, fully dissolving, uniformly mixing, introducing nitrogen to remove oxygen for 15 minutes, and then placing under a low-pressure ultraviolet lamp with the wavelength of 254nm to initiate AM photopolymerization, wherein the ultraviolet light intensity is 10mW/cm 2 The reaction time was 3 hours, and a Polyacrylamide (PAM) hydrogel was obtained. The PAM prepared by measurement has a viscosity average molecular weight of 1.5X10 7 And the PAM has a branched structure, so that the PAM hydrogel is rapidly dissolved, the dissolution performance is excellent, and the dissolution time of the PAM dry powder after drying and crushing is less than 1 hour.
The formulations used in examples 11-14 are shown in Table 2, and the procedure is essentially the same as in example 10, except that the branched polyacrylamides of different structures and molecular weights are prepared by varying the type and amount of macroinitiator.
TABLE 2 formulation for preparing branched polyacrylamide by photopolymerization of water-soluble monomer initiated by water-soluble macromolecular photoinitiator
Figure BDA0002854238730000181
Comparative example 1:
the mass fraction of AM monomer was 28%, and 2959 was 0.002% relative to the mass fraction of AM monomer. Adding monomer, photoinitiator and water into a reaction vessel, fully dissolving, uniformly mixing, introducing nitrogen to remove oxygen for 15 minutes, and irradiating under a low-pressure ultraviolet lamp with a wavelength of 254nm to initiate ultraviolet polymerization of AM, wherein the ultraviolet light intensity is 10mW/cm 2 The reaction was carried out for 3 hours to obtain PAM hydrogel. PAM viscosity average molecular weight of 7.2X10 6 The molecular weight is smaller; and because the PAM is linear polyacrylamide, longer dissolution time is required compared with PAM branched polymerThe dissolution time of the dry powder after drying and crushing is more than 1 hour.

Claims (9)

1. Use of a water-soluble macromolecular photoinitiator for initiating polymerization of water-soluble monomers for preparing water-soluble polymers having a branched structure, characterized in that the initiator has a structure according to general formula (i) or general formula (ii):
Figure FDA0004214480080000011
wherein x=0-200, y=50-150, z=5-40, n=0-10; x is X 1 Is H or CH 3 ；Y 1 Is H or CH 3 ；Y 2 Is a carboxyl or carboxylate group; z is O or NH;
X 2 selected from any one of the following groups:
Figure FDA0004214480080000012
PI is a photoinitiating group selected from any one of the following groups:
Figure FDA0004214480080000021
2. use according to claim 1, characterized in that it comprises the following steps: (1) The anhydride monomer is self-polymerized or is copolymerized with an electron donor monomer to prepare an anhydride functionalized polymer, wherein the anhydride monomer is one or more than two selected from maleic anhydride, citraconic anhydride and itaconic anhydride, and the electron donor monomer is one or more than two selected from styrene monomer, vinyl acetate, acrylamide monomer, (methyl) acrylic ester monomer and vinyl ether monomer; (2) The anhydride functionalized polymer reacts with a hydroxyl-terminated or amine-terminated small molecule photoinitiator to prepare a water-soluble macromolecular photoinitiator precursor; (3) The water-soluble macromolecular photoinitiator precursor is hydrolyzed to prepare the water-soluble macromolecular photoinitiator with the side group containing photoinitiating groups.
3. Use according to claim 2, characterized in that the anhydride functionalized polymer is a homopolymer of an anhydride-based monomer or a copolymer of an anhydride-based 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 anhydride monomers and an initiator in a solvent, and mixing to form a uniform polymerization reaction system; then, reacting for 1-10 hours at 60-120 ℃; finally, precipitating, separating and drying the prepared polymerization product from the reaction system to obtain a homopolymer of the anhydride monomer;
(2) Copolymers of anhydride-based monomers:
preparing a copolymer of an anhydride monomer through a free radical copolymerization reaction of the anhydride monomer and an electron donor monomer, wherein the preparation raw materials comprise the anhydride monomer, the electron donor monomer, a solvent and an initiator;
firstly, dissolving anhydride monomers, electron donor monomers and an initiator in a solvent, and mixing to form a uniform polymerization reaction system; then, initiating polymerization by adopting a common free radical initiator, wherein the reaction temperature is 40-120 ℃ and the reaction time is 1-10 hours; and separating and drying the prepared polymer from the reaction system to obtain the anhydride functionalized polymer.
4. Use according to claim 2, characterized in that the water-soluble macromolecular photoinitiator precursor is prepared by introducing photoinitiating groups into the side groups of the anhydride functionalized polymer by reaction of the anhydride functionalized polymer with hydroxyl-terminated or amine-terminated small molecule photoinitiators, as follows:
firstly, dissolving an anhydride functionalized polymer in a solvent, adding a hydroxyl-terminated or amine-terminated small molecule photoinitiator with a structure shown in a general formula (III), and uniformly mixing;
Figure FDA0004214480080000032
wherein L is hydroxyl or amine, PI is a photoinitiating group, n=0-10;
secondly, adding a catalyst into a reaction system, reacting for 2-20 hours at the 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 FDA0004214480080000031
Figure FDA0004214480080000041
wherein x=0-200, y=50-150, z=5-40, n=0-10; x is X 1 Is H or CH 3 ；Y 1 Is H or CH 3 ；Y 2 Is a carboxyl or carboxylate group; z is O or NH;
X 2 selected from any one of the following groups:
Figure FDA0004214480080000042
PI is a photoinitiating group selected from any one of the following groups:
Figure FDA0004214480080000043
finally, hydrolyzing the residual 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 use according to claim 2 or 3, wherein in the preparation of the homopolymer of the acid anhydride type monomer, the concentration of the acid anhydride type monomer in the reaction system is 5 to 60% by mass based on the total mass of the polymerization reaction system; in the preparation process of the anhydride monomer copolymer, the total mass percentage concentration of the anhydride monomer and the electron donor monomer in the reaction system is 5-60% based on the total mass of the polymerization reaction system, and the molar ratio of the anhydride monomer to the electron donor monomer is 1:3-3:1.
6. Use according to claim 2 or 3, characterized in that the reaction solvent in the preparation of the anhydride functionalized polymer comprises ketone solvents, ester solvents, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, tetrahydrofuran, dioxane, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide.
7. Use according to claim 2 or 3, characterized in that the initiator used in the preparation of the anhydride functionalized polymer is a conventional radical initiator, including azo-type initiators, peroxide radical initiators or redox-initiated systems, the amount of initiator in the system being 0.05-5.0 mass% of the total mass of monomers in the polymerization system.
8. The use according to claim 2 or 4, wherein in the reaction system for preparing the water-soluble macromolecular photoinitiator precursor containing photoinitiating groups on the side groups by reacting the anhydride functionalized polymer with the hydroxyl-terminated or amine-terminated small molecular photoinitiator, the solvent used comprises tetrahydrofuran, dioxane, acetone, butanone, cyclohexanone, methyl isobutyl ketone, methyl isopropyl ketone, ester solvents, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide.
9. The use according to claim 2 or 4, wherein the photoinitiating group is introduced into the side group of the anhydride functionalized polymer through the reaction of the anhydride functionalized polymer and the hydroxyl-terminated or amine-terminated small molecule photoinitiator, and the mass ratio of the hydroxyl-terminated or amine-terminated small molecule photoinitiator to the anhydride functionalized polymer is 1:10-1:2 in the reaction system for preparing the water-soluble macromolecular photoinitiator precursor with the photoinitiating group on the side group; the catalyst in the reaction system comprises 4-dimethylaminopyridine, pyridine, triethylamine, p-toluenesulfonic acid, concentrated sulfuric acid, sodium acetate and peroxy acid, and the dosage of the catalyst is 0.05-2 mass percent of the mass of the anhydride functionalized polymer.
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