CN114524921A - Biodegradable high-molecular photoinitiator and preparation and application thereof - Google Patents
Biodegradable high-molecular photoinitiator and preparation and application thereof Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
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- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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Abstract
The invention relates to a biodegradable high-molecular photoinitiator and preparation and application thereof, wherein the photoinitiator has a structure shown as a formula I. The high molecular photoinitiator of the invention keeps the photoinitiation activity of the small molecular photoinitiator, avoids the safety problems of volatile organic gas, mobility and the like generated when the common photoinitiator is used, has biodegradability, can reduce the pollution to the environment through biodegradation, and can be widely applied to the fields of photocuring coating, printing ink, adhesive and photocrosslinking. The preparation method provided by the invention has the advantages of simple process, high efficiency, rapidness, easiness in industrialization and the like.
Description
Technical Field
The invention belongs to the technical field of functional polymers, and particularly relates to a biodegradable polymer photoinitiator, and preparation and application thereof.
Background
The ultraviolet curing technology is a photofabrication process in which a photoinitiator is excited to initiate the rapid crosslinking of a resin matrix through ultraviolet irradiation with a certain wavelength. The photocuring technology has the advantages of high reaction rate, short processing period, high efficiency, energy conservation, environmental protection, cost saving and the like. At present, the ultraviolet curing technology is widely applied to the fields of photocureable coating, printing ink, adhesive and photocrosslinking.
Photoinitiators are a key part of photocuring systems. Photoinitiators are materials that produce reactive intermediates (free radicals or ions) that initiate the polymerization or crosslinking of polyfunctional monomers, oligomers or polymeric substrates upon exposure to radiation of a wavelength. Under the irradiation of ultraviolet light or visible light with certain wavelength, photoinitiator molecules absorb light energy, transition from a ground state to an excited state, and generate active species after the excited state undergoes monomolecular or bimolecular chemical action, so that the reaction of monomer, oligomer or polymer matrix is initiated, and a cross-linked network structure is formed.
The photoinitiator is different in excited wavelength and can be divided into an ultraviolet photoinitiator (the ultraviolet region is 200-400 nm) and a visible photoinitiator (the visible region is 400-700 nm). At present, the light curing technology is mainly ultraviolet light curing, and the used photoinitiator is an ultraviolet light photoinitiator. Visible photoinitiators are limited in production and use due to their sensitivity to sunlight and illumination sources. With the increasing application of photo-curing technology in recent years, more classes of photoinitiators are developed, such as water-soluble photoinitiators, hybrid photoinitiators, macromolecular photoinitiators, and the like.
Conventional photoinitiators are mainly small molecule photoinitiators. The photoinitiators can be mainly divided into two types according to different reaction types, namely free radical photoinitiators and ionic photoinitiators. The radical photoinitiators can be classified into radical photoinitiators of the cleavage type (Norrish type I) and radical photoinitiators of the hydrogen abstraction type (Norrish type II). The cracking type free radical photoinitiator is characterized in that alpha bonds are broken after the initiator absorbs light energy, and two pairs of carbon-carbon double bonds with reactive free radicals are formed through homolysis. Most Norrish type I photoinitiators are aromatic carbonyl compounds with appropriate substituents, such as benzoin and its derivatives, benzil ketals, and acylphosphine oxides. The Norrish II type photoinitiator is characterized in that after the initiator absorbs light energy, bimolecular action is carried out between an excited state and an auxiliary initiator, and active free radicals are formed through hydrogen abstraction reaction or electron/proton transfer. Since the Norrish type II photoinitiator is a bimolecular radical generating process, the reaction rate is slower than that of a unimolecular radical forming Norrish type I photoinitiator. Typical Norrish type II photoinitiators include benzophenones and derivatives thereof, thioxanthones, benzils or quinones, and the like.
On one hand, the small-molecule photoinitiators are easy to generate small-molecule volatile matters in the photocuring process, so that VOC (volatile organic compounds) emission and peculiar smell are generated; on the other hand, the small molecule photoinitiator and fragments thereof are easy to migrate in the material, and the safety of the product or the surface quality of the product is influenced. In view of these circumstances, the nonipol series of macrophotoinitiators were developed by IGM in the netherlands, and specifically, by making the photoinitiators into macromolecules, the initiation activity, the solubility in the matrix resin, and the stability of the photocuring system were improved while the generation and migration of photocuring volatiles were effectively reduced, but the molecular weight thereof was generally 1000 or less, and the problem of the volatilization and migration of initiating residues could not be completely solved because of the fact that the macromolecules were not truly macromolecules. Domestic Beijing university of chemical industry also discloses a series of macromolecular photoinitiators: chinese patents CN201910265332.5 and CN201910265343.3 disclose macromolecular photoinitiators obtained by aldehyde ketone condensation reaction and preparation methods thereof; chinese patents CN201910265507.2 and CN201910265508.7 disclose nitrogen containing macroinitiators derived by free radical copolymerization which themselves provide hydrogen donors; chinese patents CN201210012986.5 and CN201110355051.2 disclose that hydroxybenzophenone and formaldehyde are polymerized to prepare a macromolecular photoinitiator with red shift of ultraviolet absorption.
However, these macroinitiators have problems of uncontrollable chemical structure, uncontrollable molecular weight or low content of initiating groups. Moreover, the initiating groups of these macro-photoinitiators, especially benzophenone photoinitiators, are almost completely in the side chains, and a large proportion of photolytic residues are volatilized and migrated, which does not completely overcome the problems of small molecule photoinitiators. In addition, the existing common small-molecule photoinitiator and large-molecule photoinitiator generally have low thermal stability, and the thermal decomposition temperature of the existing common small-molecule photoinitiator and large-molecule photoinitiator is basically lower than 250 ℃ (for example, the thermal decomposition temperature of the most common photoinitiator benzophenone is 160 ℃), which limits the application of the photoinitiator in the crosslinking modification processing of engineering plastics.
On the other hand, along with the increasing serious problem of environmental pollution, the biological degradability is more and more paid attention by people. At present, most of biodegradable materials are aliphatic polyester, but the application of the aliphatic polyester in various fields is limited due to poor heat resistance and processability of the aliphatic polyester. In recent years, in order to obtain a polymer having both thermal properties and processability which meet the processing requirements, researchers have conducted studies on the synthesis of copolyesters in which aromatic and aliphatic units are combined. Taking the above as a starting point, the preparation of the biodegradable macromolecular photoinitiator with a copolyester structure and controllable molecular weight is a potential solution to the problems of the existing photoinitiators.
Disclosure of Invention
The invention aims to solve the technical problems that the chemical structure of the existing macromolecular initiator is uncontrollable, the molecular weight is uncontrollable, the content of initiating groups is low or a large proportion of photolysis residues are volatilized and migrated, and the small molecular photoinitiator and the macromolecular photoinitiator generally have low thermal stability.
The invention provides a polyester shown in the following structure,
The alkylene group is an alkylene group or an arylene group.
Preferably, said R is1Is alkylene of C2-C10, and R2 is alkylene of C2-C4.
Preferably, the number average molecular weight M of the polyestern1.2k to 100k, and the molecular weight distribution is 1.3 to 3.
More preferably, the polyester has a number average molecular weight of 1.2k to 50k, and more preferably, a number average molecular weight of 1.2k to 20 k.
If the molecular weight is too low, the photoinitiator is not different from a micromolecular photoinitiator, and the problems in the prior art cannot be solved; if the content is too high, the dispersion of the high molecular initiator in the matrix resin is affected, and if the content is too high, the melt flowability is affected, so that the melt processing and molding are adversely affected, and the polymerization cost is also a problem. The reason for determining the range of molecular weight distribution is: too high a molecular weight distribution can affect the initiation efficiency, affect dispersion, and affect the flowability and processability of the matrix resin; too low, it is not possible to ensure low migration and sufficient heat resistance.
The thermal decomposition temperature of the polyester can reach more than or equal to 250 ℃.
The thermal decomposition temperature of the polyester (macromolecular photoinitiator) is more than or equal to 250 ℃. The thermal decomposition temperature in the invention is the temperature of 5 wt% of the weight loss of the high molecular photoinitiator under the nitrogen atmosphere. Since the melt processing temperature of plastics, especially engineering plastics, is usually higher than 250 ℃, the thermal decomposition temperature of polymeric photoinitiators is preferably higher than 250 ℃ when polymeric photoinitiators are used for their modification. On the other hand, the benzophenone fragment is subjected to high molecular weight, so that the thermal stability can be obviously improved, and the thermal decomposition temperature of the polyester (high molecular photoinitiator) obtained by the method can reach more than or equal to 250 ℃ through the molecular design and the polymerization process.
The invention provides a preparation method of polyester, which comprises the following steps:
(1) esterification: mixing benzophenone-4, 4-dicarboxylic acid, aliphatic dibasic acid, aliphatic dihydric alcohol and a catalyst (esterification catalyst) to carry out esterification reaction;
(2) polycondensation: and (2) adding a catalyst (polymerization catalyst) into the product obtained in the step (1), and reacting to obtain the polyester (high-molecular copolyester condensation initiator).
The preferred mode of the above preparation method is as follows:
in the step (1), the aliphatic dibasic acid is one or more of C3-C20 dibasic acids; the aliphatic dihydric alcohol is one or more of C2-C20 dihydric alcohols.
In the step (1), the molar ratio of the benzophenone-4, 4-dicarboxylic acid to the aliphatic dibasic alcohol is 0.1-0.9: 1.0-4.0, and the esterification catalyst accounts for 0.02-2% of the total mass of the dibasic acid.
The reaction in the step (1) is carried out under the condition of protective gas, the reaction temperature is 150-200 ℃, and the reaction time is 2-12 hours.
The protective gas is nitrogen.
The catalyst in the steps (1) and (2) is one or more of an organic tin compound, a titanium compound and antimony oxide.
Further, the catalyst is one or more of stannous octoate, stannous chloride, stannous acetate, tetrabutyl titanate and antimony oxide.
The mass ratio of the polymerization catalyst in the step (2) to the esterification product is 0.02-2%.
The reaction temperature in the step (2) is 220-250 ℃, the pressure is lower than 200Pa, and the time is 0.5-8 h.
The invention provides a photoinitiator which contains the structural polyester.
The invention provides an application of the photoinitiator in the fields of photocuring coating, printing ink, adhesive or photocrosslinking.
The invention adopts esterification reaction, takes benzophenone-4, 4-dicarboxylic acid, aliphatic dibasic acid and aliphatic dihydric alcohol with certain proportion as raw materials, and carries out esterification and polycondensation reaction to obtain the copolyester type photoinitiator with the benzophenone functional group.
The high molecular initiator of the invention is prepared by high molecular weight quantization of the benzophenone photoinitiator, and the prepared photoinitiator has high molecular weight and is a polymer, so that the problem of failure caused by volatilization and thermal decomposition of the benzophenone is not generated when the modified resin is processed and molded at high temperature, namely the thermal stability is good; moreover, the problem that the surface properties of the resin product are affected by the migration of the photoinitiator in the resin product is solved by increasing the molecular weight.
The polymeric photoinitiator of the invention is prepared by polycondensation. Polycondensation is stepwise polymerization, which is different from other chain polymerization in that the polymerization speed is relatively slow, the molecular weight is easy to control, and the molecular weight distribution is narrower; compared with free radical polymerization, the free radical polymerization is easier to generate branching, so that the linear structure of the high-molecular photoinitiator can be better ensured. In addition, the high molecular photoinitiator provided by the invention is a copolymer in molecular structure, and the photoinitiator group benzophenone segments are uniformly distributed on a high molecular chain and controllable in content, so that high initiation efficiency can be ensured, and the structure degradability is endowed.
Advantageous effects
(1) The preparation method of the high-molecular photoinitiator has the advantages of easily available raw materials, low price and simple preparation process, and has wide application prospect in the field of engineering plastic processing.
(2) The structure of the high-molecular photoinitiator contains an aliphatic polyester chain segment and an aromatic polyester chain segment, and the proportion of aliphatic and aromatic components in the biodegradable copolyester photoinitiator can be realized by controlling the feed ratio of benzophenone-4, 4' -dicarboxylic acid to aliphatic dibasic acid.
(3) The high-molecular photoinitiator disclosed by the invention is narrow in molecular weight distribution and excellent in photoinitiation effect, and the problems of volatilization and migration of photoinitiation residues during photolysis of the conventional photoinitiator can be fundamentally solved by the initiation group in the main chain.
(4) The high-molecular photoinitiator has excellent thermal stability and is suitable for cross-linking modification processing of engineering plastics.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum structural characterization of a photoinitiator PDBA obtained in example 1;
FIG. 2 is a photo-polymerization kinetic characterization chart of PDBA, wherein (A) is a real-time infrared spectrum of PDBA; (B) the double bond conversion rate of the polyethylene glycol diacrylate monomer;
FIG. 3 is a graph of the mobility characterization of the photoinitiators, where (A) is the mobility results for photoinitiators BP and PDBA; (B) a close-up view of the mobility of the photoinitiator PDBA is shown.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
(1) Putting benzophenone-4, 4' -dicarboxylic acid, adipic acid and decanediol into a reaction device, adding an esterification catalyst (stannous octoate) into a reaction system, replacing for 2 times by nitrogen, gradually heating to 180 ℃ within 1h under the nitrogen atmosphere, and then carrying out esterification reaction for 8h under normal pressure to obtain an esterification product; wherein, the feeding molar ratio of the benzophenone-4, 4' -dicarboxylic acid, the adipic acid and the decanediol is 0.5:0.5:1.3, and the ratio of the esterification catalyst to the total mass of the dibasic acid is 2 wt%.
(2) Adding a catalyst (stannous octoate) into the esterification product obtained in the step (1), heating the reaction system to 220 ℃, and polymerizing for 8 hours under the condition of 100Pa to obtain a polymerization Product (PDBA); wherein the mass ratio of the catalyst to the esterification product is 2 wt%.
The nuclear magnetism representation result of the prepared high-molecular photoinitiator is shown in the attached figure 1, and the structural formula is as follows:
wherein R1 is a C10 linear alkylene group; r2 is a C4 linear alkylene group; the number average molecular weight of the polymeric photoinitiator was 31k, the molecular weight distribution was 2.2, the functional monomer ratio was 0.52, and the thermal decomposition temperature of the polymeric photoinitiator was 330 ℃.
Example 2
(1) Adding benzophenone-4, 4' -dicarboxylic acid, adipic acid and hexanediol into a reaction device, adding an esterification catalyst (tetrabutyl titanate) into a reaction system, replacing for 2 times by nitrogen, gradually heating to 165 ℃ within 1h under the atmosphere of nitrogen, and then carrying out esterification reaction for 7h under normal pressure to obtain an esterification product; wherein, the feeding molar ratio of the benzophenone-4, 4' -dicarboxylic acid, the adipic acid and the hexanediol is 0.2:0.8:1.2, and the ratio of the esterification catalyst to the total mass of the dibasic acid is 0.04 wt%.
(2) Adding a catalyst (tetrabutyl titanate) into the esterification product obtained in the step (1), heating the reaction system to 230 ℃, and polymerizing for 2.5 hours under the condition of 200Pa to obtain a polymerization product; wherein the mass ratio of the catalyst to the esterification product is 0.04 wt%.
The prepared high-molecular photoinitiator has the structural formula as follows:
wherein R1 is a C6 linear alkylene group; r2 is a C4 linear alkylene group; the number average molecular weight of the polymeric photoinitiator is 10k, the molecular weight distribution is 1.8, the ratio of the functional monomers is 0.23, and the thermal decomposition temperature of the polymeric photoinitiator is 280 ℃.
Example 3
(1) Putting benzophenone-4, 4' -dicarboxylic acid, succinic acid and decanediol into a reaction device, adding an esterification catalyst (stannous octoate) into a reaction system, replacing for 2 times by nitrogen, gradually heating to 175 ℃ within 1h under the nitrogen atmosphere, and then carrying out esterification reaction for 6h under normal pressure to obtain an esterification product; wherein, the feeding molar ratio of the benzophenone-4, 4' -dicarboxylic acid, the succinic acid and the decanediol is 0.4:0.6:1.3, and the ratio of the esterification catalyst to the total mass of the dibasic acid is 0.1 wt%.
(2) Adding a catalyst (stannous octoate) into the esterification product obtained in the step (1), heating the reaction system to 220 ℃, and polymerizing for 4 hours under the condition of 150Pa to obtain a polymerization product; wherein the mass ratio of the catalyst to the esterification product is 0.02 wt%.
The prepared high-molecular photoinitiator has the structural formula as follows:
wherein R1 is a C10 linear alkylene group; r2 is ethyl; the number average molecular weight of the polymeric photoinitiator is 15k, the molecular weight distribution is 3.0, the functional monomer ratio is 0.42, and the thermal decomposition temperature of the polymeric photoinitiator is 321 ℃.
Example 4
(1) Adding benzophenone-4, 4' -dicarboxylic acid, succinic acid and hexanediol into a reaction device, adding an esterification catalyst (tetrabutyl titanate) into a reaction system, performing nitrogen replacement for 2 times, gradually heating to 160 ℃ within 1h under a nitrogen atmosphere, and performing esterification reaction for 4h under normal pressure to obtain an esterification product; wherein, the feeding molar ratio of the benzophenone-4, 4' -dicarboxylic acid, the succinic acid and the hexanediol is 0.6:0.4:1.1, and the ratio of the total mass of the esterification catalyst and the dibasic acid is 0.5 wt%.
(2) Adding a catalyst (tetrabutyl titanate) into the esterification product obtained in the step (1), heating the reaction system to 230 ℃, and polymerizing for 2h under the condition of 200Pa to obtain a polymerization product; wherein the mass ratio of the catalyst to the esterification product is 0.5 wt%.
The prepared high-molecular photoinitiator has the structural formula as follows:
wherein R1 is a C6 linear alkylene group; r2 is ethyl; the number average molecular weight of the polymeric photoinitiator is 6k, the molecular weight distribution is 1.3, the ratio of the functional monomers is 0.65, and the thermal decomposition temperature of the polymeric photoinitiator is 325 ℃.
Example 5
(1) Adding benzophenone-4, 4' -dicarboxylic acid, adipic acid and ethylene glycol into a reaction device, adding an esterification catalyst (antimony oxide) into a reaction system, performing nitrogen displacement for 2 times, gradually heating to 175 ℃ in 1h under the nitrogen atmosphere, and performing esterification reaction for 4h under normal pressure to obtain an esterification product; wherein, the feeding molar ratio of the benzophenone-4, 4' -dicarboxylic acid, the adipic acid and the glycol is 0.2:0.8:1.2, and the ratio of the esterification catalyst to the total mass of the dibasic acid is 0.2 wt%.
(2) Adding a catalyst (antimony oxide) into the esterification product obtained in the step (1), heating the reaction system to 250 ℃, and polymerizing for 1h under the condition of 300Pa to obtain a polymerization product; wherein the mass ratio of the catalyst to the esterification product is 0.2 wt%.
The prepared macromolecular photoinitiator has the structural formula as follows:
wherein R1 is ethyl; r2 is a C4 linear alkylene group; the number average molecular weight of the high molecular photoinitiator is 15k, the molecular weight distribution is 2.2, the ratio of the functional monomer is 0.18, and the thermal decomposition temperature of the high molecular photoinitiator is 250 ℃.
Example 6
(1) Putting benzophenone-4, 4' -dicarboxylic acid, adipic acid and butanediol into a reaction device, adding an esterification catalyst (tetrabutyl titanate) into a reaction system, replacing for 2 times by nitrogen, gradually heating to 170 ℃ within 1h under the atmosphere of nitrogen, and then carrying out esterification reaction for 2h under normal pressure to obtain an esterification product; wherein, the feeding molar ratio of the benzophenone-4, 4' -dicarboxylic acid, the adipic acid and the butanediol is 0.7:0.3:1.5, and the ratio of the esterification catalyst to the total mass of the dibasic acid is 0.05 wt%.
(2) Adding a catalyst (tetrabutyl titanate) into the esterification product obtained in the step (1), heating the reaction system to 240 ℃, and polymerizing for 3h under the condition of 200Pa to obtain a polymerization product; wherein the mass ratio of the catalyst to the esterification product is 0.05 wt%.
The prepared high-molecular photoinitiator has the structural formula as follows:
wherein R1 is a C4 linear alkylene group; r2 is a C4 linear alkylene group; the number average molecular weight of the polymeric photoinitiator was 11k, the molecular weight distribution was 2.8, the functional monomer ratio was 0.77, and the thermal decomposition temperature of the polymeric photoinitiator was 340 ℃.
Example 7
(1) Adding benzophenone-4, 4' -dicarboxylic acid, succinic acid and ethylene glycol into a reaction device, adding an esterification catalyst (antimony oxide) into a reaction system, performing nitrogen replacement for 2 times, gradually heating to 155 ℃ within 1h under the nitrogen atmosphere, and performing esterification reaction for 5h under normal pressure to obtain an esterification product; wherein, the feeding molar ratio of the benzophenone-4, 4' -dicarboxylic acid, the succinic acid and the ethylene glycol is 0.3:0.7:1.5, and the ratio of the esterification catalyst to the total mass of the dibasic acid is 1 wt%.
(2) Adding a catalyst (antimony oxide) into the esterification product obtained in the step (1), heating the reaction system to 235 ℃, and polymerizing for 0.5h under the condition of 200Pa to obtain a polymerization product; wherein the mass ratio of the catalyst to the esterification product is 1 wt%.
The prepared high-molecular photoinitiator has the structural formula as follows:
wherein R1 is ethyl; r2 is ethyl; the number average molecular weight of the polymeric photoinitiator was 1.2k, the molecular weight distribution was 2.3, the functional monomer ratio was 0.33, and the thermal decomposition temperature of the polymeric photoinitiator was 263 ℃.
Example 8
(1) Putting benzophenone-4, 4' -dicarboxylic acid, succinic acid and butanediol into a reaction device, adding an esterification catalyst (tetrabutyl titanate) into a reaction system, replacing for 2 times by nitrogen, gradually heating to 160 ℃ within 1h under the atmosphere of nitrogen, and then carrying out esterification reaction for 4h under normal pressure to obtain an esterification product; wherein, the feeding molar ratio of the benzophenone-4, 4' -dicarboxylic acid, the succinic acid and the butanediol is 0.4:0.6:1.6, and the total mass of the esterification catalyst and the dibasic acid accounts for 0.06 wt%.
(2) Adding a catalyst (tetrabutyl titanate) into the esterification product obtained in the step (1), heating the reaction system to 220 ℃, and polymerizing for 2.5 hours under the condition of 200Pa to obtain a polymerization product; wherein the mass ratio of the catalyst to the esterification product is 0.06 wt%.
The prepared high-molecular photoinitiator has the structural formula as follows:
wherein R1 is a C4 linear alkylene group; r2 is ethyl; the number average molecular weight of the polymeric photoinitiator was 20k, the molecular weight distribution was 2.1, the functional monomer ratio was 0.45, and the thermal decomposition temperature of the polymeric photoinitiator was 282 ℃.
Example 9
(1) The Photoinitiator (PDBA) obtained in example 1 was added in a proportion of 2% by weight to ultra-high molecular weight polyethylene, mixed with a chloroform solution, the solvent was removed by rotary evaporation, and the mixture was pressed into a film at 150 ℃ by a plate vulcanizer, cold-pressed and cut to obtain a polyethylene film of 1 cm. times.3 cm. times.0.5 mm size. Adopting LED @365nm, 980mW/cm2The film is subjected to ultraviolet irradiation under the conditions of 20s, 40s, 60s, 90s, 120s and 150 s. Dissolving the irradiated film with decalin solvent at 180 deg.C for 3h, taking out, oven drying at 185 deg.C for 3h to obtain the final product with irradiation time of 90s when gel content is the highest.
(2) Fixing the irradiation time to 90s, carrying out a crosslinking experiment by using 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt% and 2.5 wt% of the photoinitiator in the mass ratio of the ultra-high molecular weight polyethylene, and carrying out the rest of the method in the same step (1) to obtain the photoinitiator PDBA with the optimal addition content of 1 wt% and the maximum gel content of 94.7%.
Example 10
The Photoinitiator (PDBA) obtained in example 1 was pressed into a film at 70 ℃ using a plate vulcanizer and cold-pressed to prepare a number of 1 cm. times.1 cm. times.50 μm-sized films, and hydrolysis experiments were carried out in a thermostat at 37 ℃ for 4 weeks at pH2.4 and pH7.4, respectively. As a result, the final degradation rates at pH7.4 and pH2.4 were 11.6% and 10.4%, respectively.
Example 11
The Photoinitiator (PDBA) obtained in example 1 was added to polyethylene glycol diacrylate (PEGDA400) having a number average molecular weight of 400 in a molar ratio of 0.1%, and the mixture was thoroughly mixed at 50 ℃ with an LED @365nm, 980mW/cm2Irradiating for 0-60 s, respectively carrying out infrared spectrum test on the cured film products prepared by irradiating for 0s, 0.5s, 1s, 5s, 10s, 30s and 60s, and researching the photoinitiation activity and the double bond conversion rate of the photoinitiator, wherein the result shows that the double bond conversion rate of the macromolecular photoinitiator PDBA to the PEGDA monomer is 52.6%, and the result can be seen in an attached figure 2.
Example 12
The Photoinitiator (PDBA) and Benzophenone (BP) obtained in example 1 were added to polyethylene glycol diacrylate having a number average molecular weight of 400 at a ratio of 0.1 mol%, and mixed well at 50 ℃ using an LED @365nm, 980mW/cm2After 60s of irradiation, the corresponding cured film was obtained. Cleaning the surfaces of the two cured films, respectively soaking the cured films in 0.1g of chloroform solution and 20mL of chloroform solution for 1h, 2h, 3h, 4h and 5h, respectively, carrying out ultraviolet absorption spectrum test on the solution soaked at each time, calculating the mobility through absorbance, and comparing. The final result is that the mobility of the BP-PEGDA system is 1.16% after 5h in chloroform; and the mobility of the PDBA-PEGDA system after 5h in chloroform is 0.0046 percent, as shown in the attached figure 3.
Claims (10)
1. A polyester represented by the following structure (I),
2. The polyester according to claim 1, wherein R is1Is alkylene of C2-C10, R2 is alkylene of C2-C4; the number average molecular weight M of the polyesternIs 1.2k～100k。
3. A method of making a polyester comprising:
(1) mixing benzophenone-4, 4-dicarboxylic acid, aliphatic dibasic acid, aliphatic diol and a catalyst for reaction;
(2) and (2) adding a catalyst into the product obtained in the step (1) for reaction to obtain the polyester.
4. The preparation method according to claim 3, wherein the aliphatic dibasic acid in the step (1) is one or more of dibasic acids of C3-C20; the aliphatic dihydric alcohol is one or more of C2-C20 dihydric alcohols.
5. The method according to claim 3, wherein the molar ratio of the benzophenone-4, 4-dicarboxylic acid, the aliphatic dibasic acid and the aliphatic diol in the step (1) is 0.1 to 0.9:1.0 to 4.0.
6. The preparation method according to claim 3, wherein the reaction in the step (1) is carried out under the condition of protective gas at the temperature of 150-200 ℃ for 2-12 h.
7. The preparation method according to claim 3, wherein the catalyst in steps (1) and (2) is one or more of an organic tin compound, a titanium compound and antimony oxide.
8. The preparation method according to claim 3, wherein the reaction in the step (2) is carried out at a temperature of 220 to 250 ℃ and under a pressure of less than 200Pa for a time of 0.5 to 8 hours.
9. A photoinitiator, wherein the photoinitiator comprises the polyester of claim 1.
10. Use of a photoinitiator according to claim 9 in the field of photocuring coatings, inks, adhesives or photocrosslinking.
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