CN109776736B - Organic salt microsphere and preparation method thereof - Google Patents
Organic salt microsphere and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of powder materials, in particular to an organic salt microsphere and a preparation method thereof. Melting and condensation polymerizing the component A, the component B and the component C to form an aliphatic unsaturated polymer with a molecular main chain containing ester bonds and ether bonds, self-emulsifying and radiation crosslinking the aliphatic unsaturated polymer to obtain a radiation crosslinking aliphatic polymer emulsion, and salinizing and drying the radiation crosslinking aliphatic polymer emulsion to obtain micro-nano organic salt microspheres; the component A is a mixture of aliphatic saturated dibasic acid and/or anhydride and aliphatic unsaturated dibasic acid and/or anhydride, the component B is aliphatic dihydric alcohol, and the component C is polyether dihydric alcohol. In the process of preparing the aliphatic unsaturated polymer emulsion, the aliphatic unsaturated polymer emulsion with carboxyl functional groups enriched on the surfaces of latex particles can be prepared without adding an emulsifier; when the organic salt microspheres are used for modifying the polymer, the crystallinity and the crystallization rate of the polymer can be improved, and the performance of the polymer can be improved.
Description
Technical Field
The invention relates to the technical field of powder materials, in particular to a micro-nano organic salt microsphere with biodegradability, organic polymer material characteristics and inorganic salt characteristics and a preparation method thereof.
Background
The powder particles can improve the heat resistance, tear resistance and sound insulation performance of products in the manufacturing of products such as paper making, rubber, paint, coating, building materials and the like, and improve the strength, smoothness and the like of the products, and are common fillers. The development of the micronization of powder particles and the functionalization and compounding of the particles opens up a new place for the application of powder technology in the fields of material science and engineering.
The common powder particle fillers comprise calcium carbonate, montmorillonite, talcum powder and the like, the powder materials belong to inorganic materials, have certain strength and modulus, and are excellent in the aspects of improving the strength of plastics and rubber, but the inorganic powder materials mostly belong to small molecular substances, do not have the characteristics of high molecular materials, are poor in compatibility with polymer matrixes, and are greatly limited in application.
How to prepare a powder material with both the characteristics of an organic polymer material and inorganic salt so as to exert the dual advantages of inorganic matters and organic matters has important research and application values for developing novel powder materials.
Patent CN102311669A describes a modified talc powder and its preparation method: putting the dried talcum powder material into a temperature-controllable high-speed mixer; weighing a modifier according to the mass ratio of talcum powder: modifier 100: (0.5 to 2.5); and (3) mixing the materials, uniformly adding the weighed modifier into a high-speed mixer filled with talcum powder, stirring at the temperature of 80-120 ℃ for 12-25 min, and taking out to obtain the modified talcum powder. The modifier is a mixture of polyol laurate and an organosilicon/polyether copolymer, the organosilicon/polyether copolymer is alpha, omega-bis (trimethylsiloxy) polydimethyl polymethyl (R-polyoxyethylene polyoxypropylene ether group) siloxane, and R is H, alkyl or alkyl containing hydroxyl. The method has complex working procedures and high production cost in the process of preparing the modifier.
Patent CN105733316A describes a preparation method of organic acid salt intercalation modified montmorillonite, firstly adding inorganic salt with the proportion of 0.1-3.0 CEC (CEC is cation exchange capacity of montmorillonite) into montmorillonite suspension to generate ion exchange reaction; removing the solvent in the obtained product by centrifugation, filtration or rotary evaporation, washing the obtained product with deionized water and ethanol for multiple times, drying, grinding and sieving to obtain the primary modified montmorillonite. Adding 0.1-4.0 CEC proportion of organic acid salt of the anionic modifier into the suspension of the primary modified montmorillonite; and removing the solvent in the obtained product by centrifugation, filtration or rotary evaporation, washing the obtained product with deionized water and ethanol for multiple times, drying, grinding and sieving to obtain the secondary modified montmorillonite. The method has complex preparation process, excessive solvent and troublesome subsequent treatment.
The inorganic powder particles described in the above patents do not have the properties of biodegradability and organic polymer material, and thus limit their applications in some fields.
Disclosure of Invention
The invention aims to provide a micro-nano organic salt microsphere with biodegradability, organic polymer material characteristics and inorganic salt characteristics and a preparation method thereof.
The technical scheme of the invention is as follows:
an organic salt microsphere is prepared by melt polycondensation of a component A, a component B and a component C to form an aliphatic unsaturated polymer with an ester bond and an ether bond in a molecular main chain, self-emulsification and irradiation crosslinking of the aliphatic unsaturated polymer to obtain a radiation crosslinking aliphatic polymer emulsion, salinization and drying of the radiation crosslinking aliphatic polymer emulsion to obtain a micro-nano organic salt microsphere; the component A is a mixture of aliphatic saturated dibasic acid and/or anhydride and aliphatic unsaturated dibasic acid and/or anhydride, the component B is aliphatic dihydric alcohol, the component C is polyether dihydric alcohol, the molar ratio of the sum of the component B and the component C to the component A is 1.0: 1.02-1.3, and the molar ratio of the component B to the component C is 0.95-0.7: 0.05-0.3.
Further, the aliphatic unsaturated dibasic acid and/or anhydride accounts for 5-60% of the total molar weight of the mixture of the aliphatic saturated dibasic acid and/or anhydride and the aliphatic unsaturated dibasic acid and/or anhydride; the aliphatic saturated dibasic acid and/or anhydride is any one of succinic acid, sebacic acid, adipic acid, succinic anhydride and adipic anhydride or a mixture of any proportion thereof, and the aliphatic unsaturated dibasic acid and/or anhydride is any one of itaconic acid, fumaric acid, itaconic anhydride and maleic anhydride or a mixture of any proportion thereof.
Further, the aliphatic diol is any one of 1, 3-propylene glycol, 1, 4-butanediol, 2, 3-butanediol and 1, 10-decanediol or a mixture of the 1, 3-propanediol and the 1, 4-butanediol in any proportion.
Further, the polyether glycol is any one of diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, PEG-200, PEG-400, PEG-600, PPG-200, PPG-400 and PPG-600 or a mixture of any proportion thereof.
A preparation method of the organic salt microspheres comprises the following steps:
(1) synthesis of carboxyl terminated aliphatic unsaturated polymers
Mixing the component A, the component B and the component C according to a certain molar ratio, adding 0.01-0.5% of antioxidant and 0.01-0.5% of polymerization inhibitor of the total mass of the component A, the component B and the component C into the mixture, stirring and heating to 140-180 ℃ under an inert gas state, reacting for 0.5-3 hours, adding 0.01-1% of antioxidant and 0.01-0.5% of catalyst of the total mass of the component A, the component B and the component C, stirring and heating to 180-220 ℃ under the pressure ranging from 1 atmosphere and normal pressure to 20Pa, reacting for 2-6 hours, preparing the aliphatic unsaturated polymer with the number average molecular weight of 1000-25000, ester bond and ether bond in the molecular main chain and carboxyl end capping, and measuring the acid value;
(2) preparation of radiation-crosslinked aliphatic Polymer emulsions
Putting the aliphatic unsaturated polymer prepared in the step (1) into a container, adding a proper amount of deionized water, stirring for 0.5-2 hours, and performing self-emulsification to obtain an aliphatic unsaturated polymer emulsion with a solid content of 20-50%; adding a radiation sensitizer which accounts for 0.5-8% of the mass of the aliphatic unsaturated polymer into the emulsion, uniformly mixing, and under the protection of inert gas, irradiating by using high-energy electron beams or gamma rays, wherein the radiation dose range is 5-100 kGy, so as to prepare the radiation crosslinking aliphatic polymer emulsion;
(3) preparation of organic salt microspheres
Placing the radiation crosslinking aliphatic polymer emulsion prepared in the step (2) into a container, stirring, calculating the mass of a required alkaline substance according to the acid value of an aliphatic unsaturated polymer, preparing the alkaline substance into a solution, slowly pouring the solution into the radiation crosslinking aliphatic polymer emulsion until the emulsion is neutral, preparing an organic salt emulsion, and reacting the surface carboxyl of emulsion colloidal particles with the alkaline substance to form a carboxylate structure; and drying the organic salt emulsion to obtain the micro-nano organic salt microspheres.
The stirring and dispersing mode is mechanical stirring, magnetic stirring or ultrasonic oscillation and the like.
Further, the antioxidant is any one of antioxidant 246, antioxidant 300, bht, antioxidant 9701, antioxidant 1010, antioxidant 168 and antioxidant 1076 or a mixture of any proportion thereof.
Further, the polymerization inhibitor is any one of hydroquinone, 4-methoxyphenol, o-methyl hydroquinone, p-benzoquinone and aluminum salt of N-nitrosophenylhydroxylamine or a mixture of hydroquinone, 4-methoxyphenol and o-methyl hydroquinone in any proportion.
Further, the catalyst is any one of tetrabutyl titanate, tetraisopropyl titanate, tetraethyl titanate, p-toluenesulfonic acid, lithium isooctanoate, butyl stannic acid, stannous oxalate, stannous chloride and stannous octoate or a mixture of the stannous octoate in any proportion.
Further, the radiation sensitizer is any one of triallyl isocyanurate, triallyl cyanurate, 1, 4-butanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate or pentaerythritol tetra (meth) acrylate, 1, 6-hexanediol diacrylate or a mixture thereof in any proportion.
Further, the alkaline substance is any one of sodium bicarbonate, calcium bicarbonate, sodium hydroxide, magnesium hydroxide, potassium hydroxide and calcium hydroxide or a mixture of the sodium bicarbonate, the calcium bicarbonate, the sodium hydroxide, the magnesium hydroxide, the potassium hydroxide and the calcium hydroxide in any proportion.
Further, the drying mode is any one of spray drying, vacuum drying or freeze drying, the inlet temperature of a spray dryer is 100-200 ℃, the outlet temperature is 30-110 ℃, and the spray pressure is 0.1-0.5 MPa; vacuum drying, wherein the temperature of a vacuum drying oven is set to be 50-70 ℃, and the vacuum degree is 2000 Pa; freeze drying, wherein the freezing temperature of a freeze dryer is set to be-40 to-60 ℃, and the vacuum degree is set to be 30 to 50 Pa.
Furthermore, the average particle size of the prepared organic salt microspheres is 50 nm-5 μm, the gel content is 70-90%, and the glass transition temperature is-65 ℃ to-50 ℃.
The invention has the following beneficial effects:
(1) in the process of preparing the aliphatic unsaturated polymer emulsion, emulsifier is not required to be added, and the aliphatic unsaturated polymer emulsion with carboxyl functional groups enriched on the surfaces of latex particles can be prepared by self-emulsification through stirring;
(2) the molecular main chain of the organic salt microsphere contains a large number of ether bonds and ester bonds, and the glass transition temperature (T)g) Low, good low temperature resistance; meanwhile, carboxyl on the surface of the microsphere reacts with alkaline substances to form a carboxylate structure, so that the microsphere has excellent high-temperature resistance;
(3) the organic salt microspheres can be well dispersed in the polymer, the crystallization nucleation capability of the polymer can be improved, the crystallinity and the crystallization rate of the polymer are improved, and the mechanical property of the polymer is obviously improved.
(4) The organic salt microspheres have excellent biodegradability and belong to environment-friendly materials.
Detailed Description
The present invention will be described in further detail below with reference to examples.
Example 1:
1. 18.27g (0.240mol) of 1, 3-propanediol, 21.18g (0.235mol) of 1, 4-butanediol, 3.00g (0.015mol) of PEG-200, 4.00g (0.010mol) of PPG-400 and 28.60g (0.2422mol) of succinic acid, 49.01g (0.2423mol) of sebacic acid and 1.65g (0.0127mol) of itaconic acid, 1.44g (0.0128mol) of itaconic anhydride are added into a four-neck flask provided with a mechanical stirrer, a nitrogen inlet and outlet, a heating device and a thermometer, 63.6mg of antioxidant 1010 and 63.6mg of antioxidant 168 and 127.1mg of hydroquinone are added, nitrogen is introduced while stirring, the temperature is gradually increased to 170 ℃, the reaction is carried out for 3 hours, then 127.1mg of antioxidant 1010 and 127.1mg of antioxidant 168 and 381.4mg of stannous oxalate are added, the pressure in the reaction device is gradually reduced to 100Pa from atmospheric pressure, the atmospheric pressure is increased while stirring to 200 ℃ to obtain the weight average molecular weight of 50597 hours, the molecular weight of the reaction is carried out for 5 hours, and the molecular weight of 50597 hours, the molecular weight of the mixture is 97, The aliphatic unsaturated polymer having a polydispersity of 2.03 and a molecular main chain containing ester bonds and ether bonds and having a carboxyl group end capping had an acid value of 21.
2. Weighing 30.00g of the aliphatic unsaturated polymer, placing the aliphatic unsaturated polymer in a beaker, adding 70.00g of deionized water, mechanically stirring for 1 hour to prepare an emulsion with the solid content of 30 percent, adding 1.80g of trimethylolpropane tri (methyl) acrylate into the emulsion, uniformly mixing, and adding N2Under protection, the emulsion is irradiated by high-energy electron beams with the radiation dose of 40kGy to prepare the radiation crosslinking aliphatic polymer emulsion, and the pH of the emulsion is measured to be 4.73.
3. Placing the radiation crosslinking aliphatic polymer emulsion prepared in the step into a container, stirring, then weighing 0.57g of sodium bicarbonate according to the acid value calculation of the aliphatic unsaturated polymer, placing the sodium bicarbonate into a beaker, adding 100.00g of deionized water to prepare a solution, slowly pouring the sodium bicarbonate solution into the radiation crosslinking aliphatic polymer emulsion until the emulsion is neutral, and preparing the organic salt emulsion, wherein the particle size of emulsion particles is 4.911 mu m, and the pH value of the emulsion is 7.00.
4. And (3) carrying out spray drying on the organic salt emulsion prepared in the step to prepare the organic salt microspheres with the gel content of 70%, the glass transition temperature of-53 ℃ and the particle size of 4.911 mu m. The degradation rate of the organic salt microspheres in the lipase buffer solution at 37 ℃ after 15 days is 33.9%. The inlet temperature of the spray dryer is 150 ℃, and the outlet temperature is 90 ℃; the spraying pressure was 0.3 MPa.
Example 2:
1. 16.37g (0.215mol) of 1, 3-propanediol, 18.93g (0.210mol) of 1, 4-butanediol, 7.00g (0.035mol) of PEG-200, 5.37g (0.040mol) of dipropylene glycol, 20.67g (0.175mol) of succinic acid, 25.79g (0.1275mol) of sebacic acid, 16.11g (0.1238mol) of itaconic acid, 14.36g (0.1237mol) of fumaric acid are added into a four-neck flask provided with a mechanical stirrer, a nitrogen inlet and outlet, a heating device and a thermometer, 62.3mg of antioxidant 1010 and 62.3mg of antioxidant 168 and 124.6mg of hydroquinone are added, nitrogen is introduced while stirring, the temperature is gradually increased to 170 ℃, the reaction is carried out for 2 hours, then 124.6mg of antioxidant 1010 and 124.6mg of oxalic acid antioxidant 168 and 373.8mg of stannous are added, the pressure in the reaction device is gradually reduced to 500Pa, the atmospheric pressure is increased while stirring is carried out, the temperature is increased to 200 ℃, the weight average molecular weight is 20000 hours, and the molecular weight is 50, The carboxyl group-terminated aliphatic unsaturated polymer having a polydispersity of 2.00 and an ester bond and an ether bond in the molecular main chain was found to have an acid value of 26.
2. Weighing 30.00g of the aliphatic unsaturated polymer, placing the aliphatic unsaturated polymer in a beaker, adding 70.00g of deionized water, mechanically stirring for 1 hour to prepare an emulsion with the solid content of 30 percent, adding 1.20g of trimethylolpropane tri (methyl) acrylate into the emulsion, uniformly mixing, and adding N2Under protection, the emulsion is irradiated by high-energy electron beams with the radiation dose of 30kGy to prepare the radiation crosslinking aliphatic polymer emulsion, and the pH of the emulsion is measured to be 4.43.
3. Placing the radiation crosslinking aliphatic polymer emulsion prepared in the step into a container, stirring, then weighing 0.70g of sodium bicarbonate according to the acid value calculation of the aliphatic unsaturated polymer, placing the sodium bicarbonate into a beaker, adding 100.00g of deionized water to prepare a solution, slowly pouring the sodium bicarbonate solution into the radiation crosslinking aliphatic polymer emulsion until the emulsion is neutral, and preparing the organic salt emulsion, wherein the particle size of emulsion particles is 3.531 mu m, and the pH value of the emulsion is 7.01.
4. And (3) carrying out spray drying on the organic salt emulsion prepared in the step to prepare the organic salt microspheres with the gel content of 86%, the glass transition temperature of-53 ℃ and the particle size of 3.531 mu m. The degradation rate of the organic salt microspheres in the lipase buffer solution at 37 ℃ after 15 days is 34.5%. The inlet temperature of the spray dryer is 150 ℃, and the outlet temperature is 90 ℃; the spraying pressure was 0.3 MPa.
Example 3:
1. adding 16.37g (0.215mol) of 1, 3-propanediol, 18.93g (0.210mol) of 1, 4-butanediol, 7.00g (0.035mol) of PEG-200, 5.37g (0.040mol) of dipropylene glycol, 19.49g (0.165mol) of succinic acid, 33.38g (0.165mol) of sebacic acid, 17.57g (0.135mol) of itaconic acid, 15.67g (0.135mol) of fumaric acid into a four-neck flask provided with a mechanical stirrer, a nitrogen inlet and outlet, a heating device and a thermometer, adding 66.9mg of antioxidant 1010, 66.9mg of antioxidant 168 and 133.8mg of hydroquinone, introducing nitrogen while stirring, gradually heating to 170 ℃, reacting for 2 hours, adding 133.8mg of antioxidant 1010, 133.8mg of antioxidant 168 and 401.4mg of oxalic acid, gradually reducing the pressure in the reaction device from one Pa to 500Pa to atmospheric pressure, stirring while heating to 200 ℃ to obtain a weight-average molecular weight of 3500 and 84 hours, and a weight average molecular weight of 3500 and 84 hours, The aliphatic unsaturated polymer having a polydispersity of 2.03 and a molecular main chain containing ester bonds and ether bonds and having a carboxyl group end capping had an acid value of 31.
2. Weighing 30.00g of the aliphatic unsaturated polymer, placing the aliphatic unsaturated polymer in a beaker, adding 70.00g of deionized water, mechanically stirring for 1 hour to prepare an emulsion with the solid content of 30 percent, adding 1.20g of trimethylolpropane tri (methyl) acrylate into the emulsion, uniformly mixing, and adding N2Under protection, the emulsion is irradiated by high-energy electron beams with the radiation dose of 30kGy to prepare the radiation crosslinking aliphatic polymer emulsion, and the pH of the emulsion is measured to be 4.12.
3. Placing the radiation crosslinking aliphatic polymer emulsion prepared in the step into a container, stirring, then weighing 0.84g of sodium bicarbonate according to the acid value calculation of the aliphatic unsaturated polymer, placing the sodium bicarbonate into a beaker, adding 100.00g of deionized water to prepare a solution, slowly pouring the sodium bicarbonate solution into the radiation crosslinking aliphatic polymer emulsion until the emulsion is neutral, and preparing the organic salt emulsion, wherein the particle size of emulsion particles is 3.220 mu m, and the pH value of the emulsion is 7.01.
4. And (3) carrying out spray drying on the organic salt emulsion prepared in the step to prepare the organic salt microspheres with the gel content of 86%, the glass transition temperature of-55 ℃ and the particle size of 3.220 microns. The degradation rate of the organic salt microspheres in the lipase buffer solution at 37 ℃ after 15 days is 35.0%. The inlet temperature of the spray dryer is 150 ℃, and the outlet temperature is 90 ℃; the spraying pressure was 0.3 MPa.
Example 4:
1. 13.32g (0.175mol) of 1, 3-propanediol, 15.78g (0.175mol) of 1, 4-butanediol, 5.31g (0.050mol) of diethylene glycol, 9.61g (0.050mol) of tripropylene glycol, 20.00g (0.050mol) of PPG-400 and 20.67g (0.175mol) of succinic acid, 76.35g (0.3775mol) of sebacic acid, 4.66g (0.0475mol) of maleic anhydride and 5.81g (0.050mol) of fumaric acid are added into a four-neck flask provided with a mechanical stirrer, a nitrogen inlet and outlet, a heating device and a thermometer, 85.7mg of antioxidant 1010 and 85.7mg of antioxidant 168 and 85.7mg of p-benzoquinone are added, nitrogen is introduced while stirring, the temperature is gradually increased to 170 ℃, the reaction is carried out for 1 hour, 85.7mg of antioxidant 1010 and 85.7mg of antioxidant 168 and 85.7mg of stannous oxalate are added to prepare the weight average molecular weight, the weight and molecular weight of the mixture are increased to 200 hours while stirring, the reaction is carried out for 1 hour, the reaction, the weight is increased to 1006 and the reaction is carried out for 1 hour, the reaction time, The carboxyl group-terminated aliphatic unsaturated polymer having a polydispersity of 2.00 and an ester bond and ether bond in the molecular main chain was found to have an acid value of 37.
2. Weighing 40.00g of the aliphatic unsaturated polymer, placing the aliphatic unsaturated polymer in a beaker, adding 60.00g of deionized water, magnetically stirring for 1 hour to prepare emulsion with the solid content of 40 percent, adding 1.20g of trimethylolpropane tri (methyl) acrylate into the emulsion, uniformly mixing, and adding N2Under protection, the emulsion is irradiated by high-energy electron beams with the radiation dose of 50kGy to prepare the radiation crosslinking aliphatic polymer emulsion, and the pH of the emulsion is 3.81.
3. Placing the radiation crosslinking aliphatic polymer emulsion prepared in the step into a container, stirring, then weighing 0.89g of potassium hydroxide according to the acid value calculation of the aliphatic unsaturated polymer, placing the potassium hydroxide into a beaker, adding 100.00g of deionized water to prepare a solution, slowly pouring the potassium hydroxide solution into the radiation crosslinking aliphatic polymer emulsion until the emulsion is neutral, and preparing the organic salt emulsion, wherein the particle size of emulsion particles is 52nm, and the pH value of the emulsion is 7.02.
4. And (3) drying the organic salt emulsion prepared in the step in vacuum to prepare the organic salt microspheres with the gel content of 74%, the glass transition temperature of-65 ℃ and the particle size of 52 nm. The degradation rate of the organic salt microspheres in the lipase buffer solution at 37 ℃ after 15 days is 42.8%. The temperature of the vacuum drying oven is 50 ℃ and the vacuum degree is 2000 Pa.
Example 5:
1. 13.32g (0.175mol) of 1, 3-propanediol, 15.78g (0.175mol) of 1, 4-butanediol, 5.31g (0.050mol) of diethylene glycol, 9.61g (0.050mol) of tripropylene glycol, 20.00g (0.050mol) of PPG-400 and 24.80g (0.210mol) of succinic acid, 42.48g (0.210mol) of sebacic acid and 11.71g (0.090mol) of itaconic acid, 10.45g (0.090mol) of fumaric acid are added into a four-neck flask equipped with a mechanical stirrer, a nitrogen inlet and outlet, a heating device and a thermometer, 76.7mg of antioxidant 1010 and 76.7mg of antioxidant 168 and 153.4mg of hydroquinone are added, nitrogen gas is introduced while stirring, the temperature is gradually increased to 170 ℃, the reaction is carried out for 2 hours, 153.4mg of antioxidant 1010 and antioxidant 168 and 306.9mg of tetrabutyl titanate are added into the four-neck flask, the four-neck flask is gradually heated to react under normal pressure and atmospheric pressure, the molecular weight is gradually increased to 1000 hours and the temperature is increased to 58 ℃ while stirring and the molecular weight is increased to 200 ℃ and the molecular weight is increased to 58 Pa, The weight average molecular weight was 18607, the polydispersity was 1.85, the molecular main chain contained ester bond and ether bond, and the acid value of the carboxyl group-terminated aliphatic unsaturated polymer was 30.
2. Weighing 40.00g of the aliphatic unsaturated polymer, placing the aliphatic unsaturated polymer in a beaker, adding 60.00g of deionized water, mechanically stirring for 1 hour to prepare emulsion with the solid content of 40 percent, adding 3.20g of trimethylolpropane tri (methyl) acrylate into the emulsion, uniformly mixing, and adding N2Under protection, the emulsion is irradiated by high-energy electron beams with the radiation dose of 20kGy to prepare the radiation crosslinking aliphatic polymer emulsion, and the pH value of the emulsion is measured to be 4.04.
3. Placing the radiation crosslinking aliphatic polymer emulsion prepared in the step into a container, stirring, then weighing 1.08g of sodium bicarbonate according to the acid value calculation of the aliphatic unsaturated polymer, placing the sodium bicarbonate into a beaker, adding 100.00g of deionized water to prepare a solution, slowly pouring the sodium bicarbonate solution into the radiation crosslinking aliphatic polymer emulsion until the emulsion is neutral, and preparing the organic salt emulsion, wherein the particle size of emulsion particles is 1.141 mu m, and the pH of the emulsion is 7.03.
4. And (3) carrying out spray drying on the organic salt emulsion prepared in the step to prepare the organic salt microspheres with the gel content of 85%, the glass transition temperature of-61 ℃ and the particle size of 1.141 mu m. The degradation rate of the organic salt microspheres in the lipase buffer solution at 37 ℃ after 15 days is 36.7%. The inlet temperature of the spray dryer is 150 ℃, and the outlet temperature is 90 ℃; the spraying pressure was 0.3 MPa.
Example 6:
1. 13.32g (0.175mol) of 1, 3-propanediol, 15.77g (0.175mol) of 1, 4-butanediol, 5.31g (0.050mol) of diethylene glycol, 9.61g (0.050mol) of tripropylene glycol, 20.00g (0.050mol) of PPG-400 and 12.99g (0.110mol) of succinic acid, 22.25g (0.110mol) of sebacic acid and 21.47g (0.165mol) of itaconic acid, 19.15g (0.165mol) of fumaric acid are added into a four-neck flask provided with a mechanical stirrer, a nitrogen inlet and outlet, a heating device and a thermometer, 69.9mg of antioxidant 1010 and 69.9mg of antioxidant 168, 139.9mg of p-benzoquinone are added, nitrogen is introduced while stirring, the temperature is gradually increased to 170 ℃, the reaction is carried out for 2 hours, 139.9mg of antioxidant 1010 and 139.9mg of antioxidant 168 and 139.8 mg of stannous oxalate are added into the reaction device, the reaction is carried out under the conditions of atmospheric pressure, the atmospheric pressure is reduced to 800 hours, the pressure is gradually increased, the reaction is carried out, the temperature is gradually increased to 200 hours, and the molecular weight is increased to 200 ℃ and the temperature is gradually increased to 200 ℃ and the pressure is increased to 2 hours, the equivalent, The weight average molecular weight was 28061, the polydispersity was 1.87, the molecular main chain contained ester bond and ether bond, and the acid value of the carboxyl group-terminated aliphatic unsaturated polymer was found to be 27.
2. Weighing 40.00g of the aliphatic unsaturated polymer, placing the aliphatic unsaturated polymer in a beaker, adding 60.00g of deionized water, mechanically stirring for 1 hour to prepare emulsion with the solid content of 40 percent, adding 1.60g of trimethylolpropane tri (methyl) acrylate into the emulsion, uniformly mixing, and adding N2Under protection, the emulsion is irradiated by high-energy electron beams with the radiation dose of 20kGy to prepare the radiation crosslinking aliphatic polymer emulsion, and the pH of the emulsion is measured to be 4.37.
3. Placing the radiation crosslinking aliphatic polymer emulsion prepared in the step into a container, stirring, then weighing 0.97g of sodium bicarbonate according to the acid value calculation of the aliphatic unsaturated polymer, placing the sodium bicarbonate into a beaker, adding 100.00g of deionized water to prepare a solution, slowly pouring the sodium bicarbonate solution into the radiation crosslinking aliphatic polymer emulsion until the emulsion is neutral, and preparing the organic salt emulsion, wherein the particle size of emulsion particles is 1.511 mu m, and the pH value of the emulsion is 7.02.
4. And (3) drying the organic salt emulsion prepared in the step in vacuum to prepare the organic salt microspheres with the gel content of 90%, the glass transition temperature of-58 ℃ and the particle size of 1.511 mu m. The degradation rate of the organic salt microspheres in the lipase buffer solution at 37 ℃ after 15 days is 35.6%. The temperature of the vacuum drying oven was 55 ℃ and the vacuum degree was 2000 Pa.
Example 7:
1. adding 15.22g (0.200mol) of 1, 3-propanediol, 18.02g (0.200mol) of 1, 4-butanediol, 10.00g (0.050mol) of PEG-200, 20.00g (0.050mol) of PPG-400 and 28.60g (0.2422mol) of succinic acid, 49.01g (0.2423mol) of sebacic acid and 1.65g (0.0127mol) of itaconic acid, 1.44g (0.0128mol) of itaconic anhydride into a four-neck flask provided with a mechanical stirrer, a nitrogen inlet and a nitrogen outlet, a heating device and a thermometer, adding 72.0mg of antioxidant 1010, 72.0mg of antioxidant 168, 143.9mg of hydroquinone, stirring while introducing nitrogen, gradually heating to 170 ℃, reacting for 3 hours, then adding 143.9mg of antioxidant 1010, 143.9mg of antioxidant 168, 431.8mg of oxalic acid, gradually reducing the pressure in the reaction device from normal pressure to 100Pa, stirring while heating to 200 ℃, reacting for 5 hours to obtain 2435-hour of antioxidant with the weight-average molecular weight of 52061 and 52061 molecular weight of 52061, The carboxyl group-terminated aliphatic unsaturated polymer having a polydispersity of 2.09 and an ester bond and an ether bond in the molecular main chain was found to have an acid value of 21.
2. Weighing 30.00g of the aliphatic unsaturated polymer, placing the aliphatic unsaturated polymer in a beaker, adding 70.00g of deionized water, mechanically stirring for 1 hour to prepare an emulsion with the solid content of 30 percent, adding 1.80g of trimethylolpropane tri (methyl) acrylate into the emulsion, uniformly mixing, and adding N2Under protection, the emulsion is irradiated by high-energy electron beams with the radiation dose of 40kGy to prepare the radiation crosslinking aliphatic polymer emulsion, and the pH of the emulsion is measured to be 4.72.
3. Placing the radiation crosslinking aliphatic polymer emulsion prepared in the step into a container, stirring, then weighing 0.57g of sodium bicarbonate according to the acid value calculation of the aliphatic unsaturated polymer, placing the sodium bicarbonate into a beaker, adding 100.00g of deionized water to prepare a solution, slowly pouring the sodium bicarbonate solution into the radiation crosslinking aliphatic polymer emulsion until the emulsion is neutral, and preparing the organic salt emulsion, wherein the particle size of emulsion particles is 4.001 mu m, and the pH of the emulsion is 7.01.
4. And (3) carrying out spray drying on the organic salt emulsion prepared in the step to prepare the organic salt microspheres with the gel content of 70%, the glass transition temperature of-57 ℃ and the particle size of 4.001 mu m. The degradation rate of the organic salt microspheres in the lipase buffer solution at 37 ℃ after 15 days is 34.5%. The inlet temperature of the spray dryer is 150 ℃, the outlet temperature is 90 ℃, and the spray pressure is 0.3 MPa.
Example 8
1. 16.37g (0.215mol) of 1, 3-propanediol, 18.93g (0.210mol) of 1, 4-butanediol, 7.00g (0.035mol) of PEG-200, 5.37g (0.040mol) of dipropylene glycol, 24.80g (0.210mol) of succinic acid, 42.48g (0.210mol) of sebacic acid, 11.71g (0.090mol) of itaconic acid, 10.45g (0.090mol) of fumaric acid, 68.5mg of antioxidant 1010, 68.5mg of antioxidant 168 and 137.1mg of hydroquinone, introducing nitrogen while stirring, gradually heating to 170 ℃, reacting for 1 hour, then adding 137.1mg of antioxidant 1010, 137.1mg of antioxidant 168 and 274.2mg of tetrabutyl titanate, gradually reducing the pressure to the atmospheric pressure in the reaction device to 1500, stirring while heating to 200 hours, reacting for 3 hours, and obtaining the weight average molecular weight of the prepolymer with the molecular weight of 7042 and the molecular weight of the prepolymer after reaction, and the molecular weight of the prepolymer are respectively being 42 and 70090, and the weight of the tetrabutyl, The aliphatic unsaturated polymer having a polydispersity of 1.85, an ester bond and an ether bond in the main molecular chain, and a carboxyl group-terminated end, was found to have an acid value of 30.
2. 50.00g of the above aliphatic unsaturated polymer was weighed and placed in a beaker, 50.00g of deionized water was added, mechanical stirring was carried out for 1 hour to prepare an emulsion having a solid content of 50%, 3.50g of trimethylolpropane tri (meth) acrylate was added to the emulsion, and the mixture was uniformly mixed under N2Under protection, the emulsion is irradiated by high-energy electron beams with the radiation dose of 20kGy to prepare the radiation crosslinking aliphatic polymer emulsion, and the pH of the emulsion is measured to be 4.03.
3. Placing the radiation crosslinking aliphatic polymer emulsion prepared in the step into a container, stirring, then weighing 1.35g of sodium bicarbonate according to the acid value calculation of the aliphatic unsaturated polymer, placing the sodium bicarbonate into a beaker, adding 100.00g of deionized water to prepare a solution, slowly pouring the sodium bicarbonate solution into the radiation crosslinking aliphatic polymer emulsion until the emulsion is neutral, and preparing the organic salt emulsion, wherein the particle size of emulsion particles is measured to be 2.012 mu m, and the pH of the emulsion is 7.03.
4. And (3) spray drying the organic salt emulsion prepared in the step to prepare the organic salt microspheres with the gel content of 85%, the glass transition temperature of-55 ℃ and the particle size of 2.012 microns. The degradation rate of the organic salt microspheres in the lipase buffer solution at 37 ℃ after 15 days is 38.3%. The inlet temperature of the spray dryer is 150 ℃, and the outlet temperature is 90 ℃; the spraying pressure was 0.3 MPa.
Example 9
1. 13.32g (0.175mol) of 1, 3-propanediol, 15.77g (0.175mol) of 1, 4-butanediol, 5.31g (0.050mol) of diethylene glycol, 9.61g (0.050mol) of tripropylene glycol, 20.00g (0.050mol) of PPG-400 and 22.67g (0.192mol) of succinic acid, 39.03g (0.193mol) of sebacic acid and 10.80g (0.0.083mol) of itaconic acid, 9.52g (0.082mol) of fumaric acid are added into a four-neck flask equipped with a mechanical stirrer, a nitrogen inlet and outlet, a heating device and a thermometer, 73.0mg of antioxidant 1010 and 73.0mg of antioxidant 168, 146.0mg of p-benzoquinone are added, nitrogen gas is introduced while stirring, the temperature is gradually increased to 170 ℃, the reaction is carried out for 2 hours, 146.0mg of antioxidant 1010 and 146.0mg of antioxidant 168, 292.1mg of stannous oxalate are added into the reaction device, the reaction is carried out under the conditions of atmospheric pressure, the pressure is gradually reduced to 800 hours, the reaction is carried out while stirring, the temperature is gradually increased to 200 hours, and the molecular weight is increased to 15008 ℃ and the reaction is increased to 200 hours, the reaction is carried out, the reaction is, The weight average molecular weight was 28215, the polydispersity was 1.88, the molecular main chain contained ester bond and ether bond, and the acid value of the carboxyl group-terminated aliphatic unsaturated polymer was found to be 27.
2. Weighing 40.00g of the aliphatic unsaturated polymer, placing the aliphatic unsaturated polymer in a beaker, adding 60.00g of deionized water, mechanically stirring for 1 hour to prepare emulsion with the solid content of 40 percent, adding 1.60g of trimethylolpropane tri (methyl) acrylate into the emulsion, uniformly mixing, and adding N2Under protection, the emulsion is irradiated by high-energy electron beams with the radiation dose of 20kGy to prepare the radiation crosslinking aliphatic polymer emulsion, and the pH of the emulsion is measured to be 4.31.
3. Placing the radiation crosslinking aliphatic polymer emulsion prepared in the step into a container, stirring, then weighing 0.97g of sodium bicarbonate according to the acid value calculation of the aliphatic unsaturated polymer, placing the sodium bicarbonate into a beaker, adding 100.00g of deionized water to prepare a solution, slowly pouring the sodium bicarbonate solution into the radiation crosslinking aliphatic polymer emulsion until the emulsion is neutral, and preparing the organic salt emulsion, wherein the particle size of emulsion particles is 1.508 mu m, and the pH of the emulsion is 7.01.
4. And (3) drying the organic salt emulsion prepared in the step in vacuum to prepare the organic salt microspheres with the gel content of 75%, the glass transition temperature of-63 ℃ and the particle size of 1.508 mu m. The degradation rate of the organic salt microspheres in the lipase buffer solution at 37 ℃ after 15 days is 37.1%. The temperature of the vacuum drying oven was 55 ℃ and the vacuum degree was 2000 Pa.
Example 10
1. Adding 14.46g (0.190mol) of 1, 3-propanediol, 16.67g (0.185mol) of 1, 4-butanediol, 13.00g (0.065mol) of PPG-200, 9.01g (0.060mol) of triethylene glycol, 14.17g (0.12mol) of succinic acid, 24.27g (0.12mol) of sebacic acid, 23.42g (0.180mol) of itaconic acid, 17.65g (0.180mol) of maleic anhydride into a four-neck flask provided with a mechanical stirrer, a nitrogen inlet and outlet, a heating device and a thermometer, adding 66.3mg of antioxidant 1010, 66.3mg of antioxidant 168 and 132.6mg of hydroquinone, introducing nitrogen while stirring, gradually raising the temperature to 170 ℃, reacting for 1 hour, adding 66.3mg of antioxidant 1010, 66.3mg of antioxidant 168 and 132.6mg of oxalic acid antioxidant 168, and 132.6mg of stannous, gradually reducing the pressure in the reaction device from normal pressure to 2000 atmospheric pressure, raising the temperature to 200 ℃ while stirring, the weight average molecular weight and molecular weight average molecular weight of 50 and 44 Pa of 50 hours while stirring, The carboxyl group-terminated aliphatic unsaturated polymer having a polydispersity of 1.97 and an ester bond and an ether bond in the molecular main chain was found to have an acid value of 31.
2. 50.00g of the above aliphatic unsaturated polymer was weighed and placed in a beaker, 50.00g of deionized water was added, magnetic stirring was carried out for 1 hour to prepare an emulsion having a solid content of 50%, 2.00g of trimethylolpropane tri (meth) acrylate was added to the emulsion, and the mixture was uniformly mixed and stirred under N2Under protection, the radiation crosslinking aliphatic polymer emulsion is prepared by high-energy electron beam irradiation with the radiation dose of 5kGy, and the pH value is 4.03.
3. Placing the radiation crosslinking aliphatic polymer emulsion prepared in the step into a container, stirring, weighing 1.39g of sodium bicarbonate according to the acid value calculation of the aliphatic unsaturated polymer, placing the sodium bicarbonate into a beaker, adding 100.00g of deionized water to prepare a solution, slowly pouring the sodium bicarbonate solution into the radiation crosslinking aliphatic polymer emulsion until the emulsion is neutral, and preparing the organic salt emulsion, wherein the particle size of emulsion particles is 1.121 mu m, and the pH value is measured to be 7.02.
4. And (3) drying the organic salt emulsion prepared in the step in vacuum to prepare the organic salt microspheres with the gel content of 75%, the glass transition temperature of-64 ℃ and the particle size of 1.121 mu m. The degradation rate of the organic salt microspheres in the lipase buffer solution at 37 ℃ after 15 days is 40.4%. The temperature of the vacuum drying oven was 55 ℃ and the vacuum degree was 2000 Pa.
Example 11:
1. 13.32g (0.175mol) of 1, 3-propanediol, 15.77g (0.175mol) of 1, 4-butanediol, 5.31g (0.050mol) of diethylene glycol, 9.61g (0.050mol) of tripropylene glycol, 20.00g (0.050mol) of PPG-400 and 19.48g (0.165mol) of succinic acid, 33.37g (0.165mol) of sebacic acid and 17.56g (0.135mol) of itaconic acid, 13.24g (0.135mol) of maleic anhydride are added into a four-neck flask provided with a mechanical stirrer, a nitrogen inlet and outlet, a heating device and a thermometer, 73.83mg of antioxidant 1010 and 73.83mg of antioxidant 168 and 147.7mg of hydroquinone are added, nitrogen is introduced while stirring, the temperature is gradually increased to 170 ℃, the reaction is carried out for 1 hour, then 73.8mg of antioxidant 1010 and 73.8mg of antioxidant 168 and 147.7mg of stannous oxalate are added into the reaction device to prepare the reaction product, the reaction is carried out under the atmospheric pressure, the reaction is carried out while stirring, the reaction is carried out for 3 hours, the reaction is carried out for 2 hours, the reaction is carried out, the molecular weight is carried out, and the reaction is carried out for 2 hours, the reaction is carried out, the pressure is carried out, the, The weight average molecular weight was 8064, the polydispersity was 2.01, the molecular main chain contained an ester bond and an ether bond, and the acid value of the carboxyl group-terminated aliphatic unsaturated polymer was measured to be 31.
2. Weighing 40.00g of the aliphatic unsaturated polymer, placing the aliphatic unsaturated polymer in a beaker, adding 60.00g of deionized water, mechanically stirring for 1 hour to prepare emulsion with the solid content of 40 percent, adding 1.60g of trimethylolpropane tri (methyl) acrylate into the emulsion, uniformly mixing, and adding N2Under the protection, the radiation cross-linking aliphatic polymer emulsion is prepared by the irradiation of high-energy electron beams with the radiation dose of 30kGy, and the testThe pH of the emulsion was 3.96.
3. Placing the radiation crosslinking aliphatic polymer emulsion prepared in the step into a container, stirring, then weighing 1.12g of sodium bicarbonate according to the acid value calculation of the aliphatic unsaturated polymer, placing the sodium bicarbonate into a beaker, adding 100.00g of deionized water to prepare a solution, slowly pouring the sodium bicarbonate solution into the radiation crosslinking aliphatic polymer emulsion until the emulsion is neutral, and preparing the organic salt emulsion, wherein the particle size of emulsion particles is 398nm and the pH of the emulsion is 7.01.
4. And (3) freeze-drying the organic salt emulsion prepared in the step to prepare the organic salt microspheres with the gel content of 86%, the glass transition temperature of-63 ℃ and the particle size of 398 nm. The degradation rate of the organic salt microspheres in the lipase buffer solution at 37 ℃ after 15 days is 40.9%. The temperature of the freeze dryer is-50 ℃ and the vacuum degree is 50 Pa.
Example 12
1. 15.22g (0.200mol) of 1, 3-propanediol, 18.02g (0.200mol) of 1, 4-butanediol, 10.00g (0.050mol) of PEG-200, 20.00g (0.050mol) of PPG-400 and 20.67g (0.175mol) of succinic acid, 25.79g (0.1275mol) of sebacic acid and 16.11g (0.1238mol) of itaconic acid, 14.36g (0.1237mol) of fumaric acid are added into a four-neck flask provided with a mechanical stirrer, a nitrogen inlet and outlet, a heating device and a thermometer, 70.1mg of antioxidant 1010, 70.1mg of antioxidant 168 and 140.2mg of hydroquinone are added, nitrogen is introduced while stirring, the temperature is gradually increased to 170 ℃ for 2 hours, then 140.2mg of antioxidant 1010, 140.2mg of antioxidant 168 and 280.3mg of stannous oxalate are added, the pressure in the reaction device is gradually reduced to 800Pa under atmospheric pressure, the atmospheric pressure is increased while stirring to 200 ℃ to obtain the reaction temperature, the weight average molecular weight of 10 hours, and the molecular weight of the reaction is 10 hours and the weight of the stannous The carboxyl group-terminated aliphatic unsaturated polymer having a polydispersity of 2.00 and an ester bond and an ether bond in the molecular main chain was found to have an acid value of 26.
2. Weighing 30.00g of the aliphatic unsaturated polymer, placing the aliphatic unsaturated polymer in a beaker, adding 70.00g of deionized water, magnetically stirring for 1 hour to prepare an emulsion with the solid content of 30 percent, adding 1.20g of pentaerythritol tetra (methyl) acrylate into the emulsion, uniformly mixing, and adding N2Under protection, high-energy electrons with the radiation dose of 30kGyThe emulsion was irradiated with a beam to prepare a radiation-crosslinked aliphatic polymer emulsion, and the pH of the emulsion was found to be 4.33.
3. Placing the radiation crosslinking aliphatic polymer emulsion prepared in the step into a container, stirring, then weighing 0.70g of sodium bicarbonate according to the acid value calculation of the aliphatic unsaturated polymer, placing the sodium bicarbonate into a beaker, adding 100.00g of deionized water to prepare a solution, slowly pouring the sodium bicarbonate solution into the radiation crosslinking aliphatic polymer emulsion until the emulsion is neutral, and preparing the organic salt emulsion, wherein the particle size of emulsion particles is 2.511 mu m, and the pH value of the emulsion is 7.01.
4. And (3) carrying out spray drying on the organic salt emulsion prepared in the step to prepare the organic salt microspheres with the gel content of 86%, the glass transition temperature of-60 ℃ and the particle size of 2.511 mu m. The degradation rate of the organic salt microspheres in the lipase buffer solution at 37 ℃ after 15 days is 35.8%. The inlet temperature of the spray dryer is 150 ℃, and the outlet temperature is 90 ℃; the spraying pressure was 0.3 MPa.
Example 13
1. 18.27g (0.240mol) of 1, 3-propanediol, 21.18g (0.235mol) of 1, 4-butanediol, 3.00g (0.015mol) of PEG-200, 4.00g (0.010mol) of PPG-400 and 12.05g (0.102mol) of succinic acid, 20.63g (0.102mol) of sebacic acid, 19.91g (0.153mol) of itaconic acid, 17.76g (0.153mol) of fumaric acid are added into a four-neck flask provided with a mechanical stirrer, a nitrogen inlet and outlet, a heating device and a thermometer, 58.4mg of antioxidant 1010 and 58.4mg of antioxidant 168 and 116.8mg of p-benzoquinone are added, nitrogen is introduced while stirring, the temperature is gradually increased to 170 ℃ for 3 hours, then 116.8mg of antioxidant 1010 and 116.8mg of antioxidant 168 and 350.4mg of stannous are added, the pressure in the reaction device is gradually reduced to 100Pa, the atmospheric pressure is increased while stirring to 200 ℃ to obtain the reaction temperature, the weight average molecular weight of 24879 hours, the weight of the stannous chloride is 8704 hour, The aliphatic unsaturated polymer having a polydispersity of 2.03 and a molecular main chain containing ester bonds and ether bonds and having a carboxyl group end capping had an acid value of 21.
2. 30.00g of the above aliphatic unsaturated polymer was weighed in a beaker, 70.00g of deionized water was added, magnetic stirring was carried out for 1 hour to prepare an emulsion having a solid content of 30%, and 1.20g of trimethylolpropane tris (t) (b) (c) (d) (e) was added to the emulsionMethyl) acrylate, mixed homogeneously in N2Under protection, the emulsion is irradiated by high-energy electron beams with the radiation dose of 20kGy to prepare the radiation crosslinking aliphatic polymer emulsion, and the pH of the emulsion is measured to be 4.72.
3. Placing the radiation crosslinking aliphatic polymer emulsion prepared in the step into a container, stirring, then weighing 0.57g of sodium bicarbonate according to the acid value calculation of the aliphatic unsaturated polymer, placing the sodium bicarbonate into a beaker, adding 100.00g of deionized water to prepare a solution, slowly pouring the sodium bicarbonate solution into the radiation crosslinking aliphatic polymer emulsion until the emulsion is neutral, and preparing the organic salt emulsion, wherein the particle size of emulsion particles is 4.910 mu m, and the pH value of the emulsion is 7.00.
4. And (3) drying the organic salt emulsion prepared in the step in vacuum to prepare the organic salt microspheres with the gel content of 90%, the glass transition temperature of-50 ℃ and the particle size of 4.910 mu m. The degradation rate of the organic salt microspheres in the lipase buffer solution at 37 ℃ after 15 days is 32.8%. The temperature of the vacuum drying oven was 55 ℃ and the vacuum degree was 2000 Pa.
Comparative example 1
1. 18.26g (0.240mol) of 1, 3-propanediol, 21.63g (0.240mol) of 1, 4-butanediol, 2.00g (0.010mol) of PEG-200, 1.34g (0.010mol) of dipropylene glycol, 24.80g (0.210mol) of succinic acid, 42.48g (0.210mol) of sebacic acid, 11.71g (0.090mol) of itaconic acid, 10.45g (0.090mol) of fumaric acid, 66.3mg of antioxidant 1010, 66.3mg of antioxidant 168, 132.7mg of hydroquinone, introducing nitrogen while stirring, gradually raising the temperature to 170 ℃, reacting for 1 hour, then adding 132.7mg of antioxidant 1010, 132.7mg of antioxidant 168, 265.3mg of tetrabutyl titanate, gradually reducing the pressure to the atmospheric pressure in the reaction device to 1500, raising the temperature to 200 Pa while stirring, reacting for 1 hour, and obtaining the weight average molecular weight of the prepolymer after reaction, 7013025 hours, wherein the weight average molecular weight of the prepolymer is 25 hours, the molecular weight of the prepolymer is kept at the molecular weight of the prepolymer, The aliphatic unsaturated polymer having a polydispersity of 1.85, an ester bond and an ether bond in the main molecular chain, and a carboxyl group-terminated end, was found to have an acid value of 30.
2. 50.00g of the above-mentioned aliphatic unsaturated polymer was weighed into a beaker, 50.00g of deionized water was added, and 2.50g of APG08 was added10 and 2.51g SDBS, mechanically stirring for 1 hr to obtain emulsion with solid content of 50%, adding 3.50g trimethylolpropane tri (meth) acrylate into the emulsion, mixing, and adding N2Under protection, the emulsion is irradiated by high-energy electron beams with the radiation dose of 20kGy to prepare the radiation crosslinking aliphatic polymer emulsion, and the pH of the emulsion is measured to be 4.03.
3. Placing the radiation crosslinking aliphatic polymer emulsion prepared in the step into a container, stirring, then weighing 1.08g of sodium bicarbonate according to the acid value calculation of the aliphatic unsaturated polymer, placing the sodium bicarbonate into a beaker, adding 100.00g of deionized water to prepare a solution, slowly pouring the sodium bicarbonate solution into the radiation crosslinking aliphatic polymer emulsion until the emulsion is neutral, and preparing the organic salt emulsion, wherein the particle size of emulsion particles is 262nm, and the pH value of the emulsion is 7.04.
4. And (3) carrying out spray drying on the organic salt emulsion prepared in the step to prepare the organic salt microspheres with the gel content of 85%, the glass transition temperature of-51 ℃ and the particle size of 262 nm. The degradation rate of the organic salt microspheres in the lipase buffer solution at 37 ℃ after 15 days is 38.1%. The inlet temperature of the spray dryer is 150 ℃, and the outlet temperature is 90 ℃; the spraying pressure was 0.3 MPa.
Comparative example 2:
1. 16.37g (0.215mol) of 1, 3-propanediol, 18.93g (0.210mol) of 1, 4-butanediol, 7.00g (0.035mol) of PEG-200, 5.37g (0.040mol) of dipropylene glycol, 24.80g (0.210mol) of succinic acid, 42.48g (0.210mol) of sebacic acid, 11.71g (0.090mol) of itaconic acid, 10.45g (0.090mol) of fumaric acid are added into a four-neck flask provided with a mechanical stirrer, a nitrogen inlet and outlet, a heating device and a thermometer, 73.9mg of antioxidant 1010, 73.9mg of antioxidant 168 and 147.8mg of hydroquinone are added, nitrogen is introduced while stirring, the temperature is gradually increased to 170 ℃, the reaction is carried out for 1 hour, then the antioxidant 1010, 147.8mg of antioxidant 168 and 147.6 mg of tetrabutyl titanate are added, the pressure in the reaction device is gradually reduced to the atmospheric pressure, the atmospheric pressure is reduced to 1500, the atmospheric pressure while the stirring is carried out, the temperature is increased while the stirring is carried out, the reaction is carried out for 1 hour, the weight average molecular weight is 3 hours, the molecular weight average molecular weight is 42 hours, and the molecular weight average molecular weight is 42 hours, 42 hours are increased to the weight average molecular weight of 70295, and the weight of 42 hours are increased to 50 hours, and 42 hours are obtained, The aliphatic unsaturated polymer having a polydispersity of 1.85, an ester bond and an ether bond in the main molecular chain, and a carboxyl group-terminated end, was found to have an acid value of 30.
2. 50.00g of the above aliphatic unsaturated polymer was weighed into a beaker, 50.00g of deionized water was added, and the mixture was mechanically stirred for 1 hour, so that the emulsion could not be formed by self-emulsification.
Comparative example 3
1. 16.37g (0.215mol) of 1, 3-propanediol, 18.93g (0.210mol) of 1, 4-butanediol, 7.00g (0.035mol) of PEG-200, 5.37g (0.040mol) of dipropylene glycol, 24.80g (0.210mol) of succinic acid, 42.48g (0.210mol) of sebacic acid, 11.71g (0.090mol) of itaconic acid, 10.45g (0.090mol) of fumaric acid, 68.5mg of antioxidant 1010, 68.5mg of antioxidant 168 and 137.1mg of hydroquinone, introducing nitrogen while stirring, gradually heating to 170 ℃, reacting for 1 hour, then adding 137.1mg of antioxidant 1010, 137.1mg of antioxidant 168 and 274.2mg of tetrabutyl titanate, gradually reducing the pressure to the atmospheric pressure in the reaction device to 1500, stirring while heating to 200 hours, reacting for 3 hours, and obtaining the weight average molecular weight of the prepolymer with the molecular weight of 7042 and the molecular weight of the prepolymer after reaction, and the molecular weight of the prepolymer are respectively being 42 and 70090, and the weight of the tetrabutyl, The aliphatic unsaturated polymer having a polydispersity of 1.85, an ester bond and an ether bond in the main molecular chain, and a carboxyl group-terminated end, was found to have an acid value of 30.
2. 50.00g of the above aliphatic unsaturated polymer was weighed and placed in a beaker, 50.00g of deionized water was added, mechanical stirring was carried out for 1 hour to prepare an emulsion having a solid content of 50%, 3.50g of trimethylolpropane tri (meth) acrylate was added to the emulsion, and the mixture was uniformly mixed under N2Under protection, the radiation crosslinking aliphatic polymer emulsion is prepared by irradiation of high-energy electron beams with the radiation dose of 20 kGy.
3. And (3) spray drying the radiation crosslinking aliphatic polymer emulsion prepared in the step to prepare the radiation crosslinking aliphatic polymer microsphere with the gel content of 85%, the glass transition temperature of-55 ℃ and the particle size of 2.012 mu m. The degradation rate of the radiation cross-linked aliphatic polymer microspheres in a lipase buffer solution at 37 ℃ after 15 days is 27.1%. The inlet temperature of the spray dryer is 150 ℃, and the outlet temperature is 90 ℃; the spraying pressure was 0.3 MPa.
COMPARATIVE EXAMPLE 4(CN 103012818A, EXAMPLE 5)
1. Into a reaction apparatus equipped with magnetic stirring, nitrogen inlet/outlet, heating apparatus, and thermometer, 12.16g (0.18mol) of 1, 3-propanediol, 18.23g (0.18mol) of 1, 4-butanediol, 12.4g (0.105mol) of succinic acid, 21.24g (0.105mol) of sebacic acid, and 10.09g (0.09mol) of itaconic anhydride were charged, and the temperature was raised to 180 ℃ under nitrogen protection and stirring, followed by esterification reaction for 1 hour to obtain a polyester prepolymer. 369.5mg of p-toluenesulfonic acid, 369.5mg of tetrabutyl titanate and 295.6mg of o-methyl hydroquinone are added into the prepared polyester prepolymer, the temperature is increased to 220 ℃, the pressure in a reaction device is 1 atmosphere, the pressure is gradually reduced to 1000Pa under normal pressure, and the reaction is carried out for 3 hours to prepare the bio-based aliphatic unsaturated polyester with the number average molecular weight of 13721, the weight average molecular weight of 15367 and the polydispersity of 1.12. After the temperature is reduced to 150 ℃, 4.4334g of trimethylolpropane tri (methyl) acrylate and 7.3890g of sorbitan monostearate are added, the mixture is uniformly stirred and cooled, and the pasty biobased aliphatic unsaturated polyester mixture is prepared.
2. Weighing 11.6g of the pasty biobased aliphatic unsaturated polyester mixture (containing 10g of biobased aliphatic unsaturated polyester, 0.6g of trimethylolpropane tri (meth) acrylate and 1g of sorbitan monostearate), placing the mixture into a water bath container at 30 ℃, adding 0.15g of sodium dodecyl sulfate, 1.82g of sodium dodecyl benzene sulfonate and 36.43g of deionized water, and mechanically stirring for 1 hour to prepare an emulsion with the mass fraction of the biobased aliphatic unsaturated polyester being 20%, wherein the micelle particle size of the emulsion is 197 nm.
3. And (3) irradiating and vulcanizing the bio-based aliphatic unsaturated polyester emulsion prepared in the step by using a high-energy electron beam, wherein the radiation dose is 20kGy, and preparing the bio-based vulcanized polyester rubber emulsion with the crosslinked polyester molecular chain.
4. And (3) carrying out spray drying on the bio-based vulcanized polyester rubber emulsion to obtain bio-based vulcanized polyester rubber particles with the gel content of 85%, the glass transition temperature of-40 ℃ and the particle size of 197 nm. The degradation rate of the bio-based vulcanized polyester rubber particles in the lipase buffer solution at 37 ℃ after 15 days is 19.1 percent. The technological parameters of spray drying are as follows: the inlet temperature of the spray dryer is 180 ℃, and the outlet temperature is 60 ℃; the spraying pressure was 0.25 MPa.
And (3) performance testing:
glass transition temperature (T)g) The determination of (1): the glass transition temperature of the organic salt microspheres was measured using a differential scanning calorimeter. The sample was measured at about 8 mg. The test conditions were: under the protection of nitrogen, raising the temperature from room temperature to 150 ℃, keeping the temperature for 3min to eliminate the thermal history, then lowering the temperature to-100 ℃, keeping the temperature for 5min, finally raising the temperature to 150 ℃, wherein the temperature raising and lowering rate is 10 ℃/min, and the glass transition temperature of the organic salt microspheres is measured through a DSC curve.
Determination of gel content: and (3) measuring the gel content of the organic salt microspheres by a Soxhlet extraction method. Drying the organic salt microspheres (with the mass of W)0) Lens paper and 200-mesh copper mesh (the total mass of the two is W)1) Tightly wrapping, and placing into an extraction tube of a Soxhlet extractor. The flask was charged with an appropriate amount of toluene and zeolite (anti-bumping). Closely connecting all parts of the Soxhlet extractor, heating and refluxing in an oil bath pan at 135 deg.C for 24 hr, and finishing the extraction experiment when the extractive solution in the extraction tube has no residual oil on the lens paper. Taking out the sample coated with the copper mesh, washing the residual solvent on the surface with distilled water, drying in a vacuum drying oven at 50 ℃ to constant weight, and recording the total mass as W2The gel content of the sample was found according to equation 1:
determination of molecular weight: the molecular weight and the distribution of the synthesized aliphatic unsaturated polymer were measured by Gel Permeation Chromatography (GPC), and the mobile phase was tetrahydrofuran and the flow rate was 0.35 mL/min.
Testing the particle size distribution: and (3) measuring the particle size of the radiation crosslinking aliphatic polymer emulsion by using a laser particle size analyzer. The radiation crosslinked aliphatic polymer emulsion was diluted with distilled water to a solid content of about 0.1%, and 1.5mL of the emulsion was placed in a transparent cuvette for measurement. The test temperature is 20 ℃, the temperature is kept constant for 2min, and the test time is 120 s.
Thermal decomposition temperature test: the sample thermal decomposition temperature was measured using a thermogravimetric analyzer. Placing a sample with the mass of about 5mg in a platinum disk, and heating from room temperature to 600 ℃ under the protection of nitrogen at the heating rate of 10 ℃/min and the nitrogen flow of 50 ml/min.
The biodegradability test was carried out as follows: the mass loss rate (degradation rate,%) of the sample was calculated after degrading the sample in a lipase solution at 37 ℃ for 15 days. Preparing the lipase solution: a certain mass of lipase is dissolved in 250ml of mixed phosphate solution (0.025M) with the pH value of 6.86 to prepare lipase solution with the concentration of 5 mg/ml.
TABLE 1 organic salt microsphere parameters and Properties
The test results of example 1 and example 7 show that by changing the ratio of the component B to the component C, the particle size of the organic salt microspheres and the T of the organic salt microspheres can be controlledg. The organic salt microspheres in example 7 have smaller particle sizes because the component C has higher content, the molecular chains contain more ether bonds, the self-emulsifying capacity is stronger, and meanwhile, T is highergIs also relatively low; the test results of the embodiment 2 and the embodiment 3 show that the molecular weight of the aliphatic unsaturated polymer can be regulated and controlled by changing the molar ratio of the component A to the sum of the component B and the component C, the aliphatic unsaturated polymer prepared in the embodiment 2 has larger molecular weight, longer molecular chain and larger particle size of the organic salt microspheres; the test results of the embodiment 6 and the embodiment 9 show that the gel content can be adjusted and controlled by adjusting the proportion of the unsaturated acid or the anhydride in the aliphatic unsaturated polymer, and the organic salt microspheres in the embodiment 6 have relatively large proportion of the unsaturated acid and the anhydride and relatively high gel content; the test results of example 8 and comparative example 3 can be used to obtainIn the organic salt microspheres prepared in example 8, the carboxyl groups on the surface of the emulsion colloidal particles react with the alkaline substance to form a carboxylate structure, and the organic salt microspheres have excellent high temperature resistance. As can be seen from comparative example 1, when the content of component C in the aliphatic unsaturated polymer is less than 5% of the total molar amount of component B and component C, emulsification can be completed only by adding a proper amount of emulsifier, otherwise self-emulsification cannot be performed to form an emulsion; as can be seen from comparative example 2, when the content of component C is more than 30% of the total molar amount of component B and component C, since the hydrophilic ability of the molecular chain is too strong, self-emulsification to form an emulsion is not possible.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, but rather the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention as defined by the appended claims.
Claims (8)
1. An organic salt microsphere is characterized in that a component A, a component B and a component C are subjected to melt polycondensation to form an aliphatic unsaturated polymer with an ester bond and an ether bond in a molecular main chain, the aliphatic unsaturated polymer is subjected to self-emulsification and irradiation crosslinking to obtain a radiation crosslinking aliphatic polymer emulsion, and the radiation crosslinking aliphatic polymer emulsion is salted and dried to obtain the micro-nano organic salt microsphere; the component A is a mixture of aliphatic saturated dibasic acid and/or anhydride and aliphatic unsaturated dibasic acid and/or anhydride, the component B is aliphatic dihydric alcohol, the component C is polyether dihydric alcohol, the molar ratio of the sum of the component B and the component C to the component A is 1.0: 1.02-1.3, and the molar ratio of the component B to the component C is 0.95-0.7: 0.05-0.3;
the preparation method of the organic salt microspheres is characterized by comprising the following steps:
(1) synthesis of carboxyl terminated aliphatic unsaturated polymers
Mixing a component A, a component B and a component C according to a certain molar ratio, adding 0.01-0.5% of antioxidant and 0.01-0.5% of polymerization inhibitor of the total mass of the component A, the component B and the component C into the mixture, stirring and heating to 140-180 ℃ under an inert gas state, reacting for a period of time, adding 0.01-1% of antioxidant and 0.01-0.5% of catalyst of the total mass of the component A, the component B and the component C, stirring and heating to 180-220 ℃ under a normal pressure or negative pressure state, reacting for a period of time to prepare an aliphatic unsaturated polymer with a number average molecular weight of 1000-25000, an ester bond and a carboxyl end capping in a molecular main chain, and measuring the acid value of the aliphatic unsaturated polymer;
(2) preparation of radiation-crosslinked aliphatic Polymer emulsions
Putting the aliphatic unsaturated polymer prepared in the step (1) into a container, adding a proper amount of deionized water, stirring for a period of time, and performing self-emulsification to prepare aliphatic unsaturated polymer emulsion; adding a proper amount of radiation sensitizer into the emulsion, uniformly mixing, and preparing into radiation crosslinking aliphatic polymer emulsion by high-energy electron beam or gamma ray radiation under the protection of inert gas;
(3) preparation of organic salt microspheres
Placing the radiation crosslinking aliphatic polymer emulsion prepared in the step (2) into a container, stirring, calculating the mass of a required alkaline substance according to the acid value of an aliphatic unsaturated polymer, preparing the alkaline substance into a solution, slowly pouring the solution into the radiation crosslinking aliphatic polymer emulsion until the emulsion is neutral, preparing an organic salt emulsion, and reacting the surface carboxyl of emulsion colloidal particles with the alkaline substance to form a carboxylate structure; drying the organic salt emulsion to obtain micro-nano organic salt microspheres;
the alkaline substance is any one of sodium bicarbonate, calcium bicarbonate, sodium hydroxide, magnesium hydroxide, potassium hydroxide and calcium hydroxide or a mixture of any proportion of the sodium bicarbonate, the calcium bicarbonate, the sodium hydroxide, the magnesium hydroxide, the potassium hydroxide and the calcium hydroxide; the drying mode is any one of spray drying, vacuum drying or freeze drying.
2. The organic salt microspheres of claim 1, wherein the aliphatic unsaturated dibasic acid and/or anhydride accounts for 5-60% of the total molar amount of the mixture of the aliphatic saturated dibasic acid and/or anhydride and the aliphatic unsaturated dibasic acid and/or anhydride; the aliphatic saturated dibasic acid and/or anhydride is any one of succinic acid, sebacic acid, adipic acid, succinic anhydride and adipic anhydride or a mixture of any proportion thereof, and the aliphatic unsaturated dibasic acid and/or anhydride is any one of itaconic acid, fumaric acid, itaconic anhydride and maleic anhydride or a mixture of any proportion thereof.
3. The organic salt microspheres of claim 1, wherein the aliphatic diol is any one of 1, 3-propanediol, 1, 4-butanediol, 2, 3-butanediol, 1, 10-decanediol, or a mixture thereof in any proportion.
4. The organic salt microspheres of claim 1, wherein the polyether glycol is any one of diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, PEG-200, PEG-400, PEG-600, PPG-200, PPG-400, PPG-600, or a mixture thereof in any ratio.
5. The organic salt microspheres according to claim 1, wherein the organic salt microspheres have an average particle size of 50nm to 5 μm, a gel content of 70 to 90%, and a glass transition temperature of-65 to-50 ℃.
6. The organic salt microspheres of claim 1, wherein the antioxidant is any one of antioxidant 246, antioxidant 300, bht, antioxidant 9701, antioxidant 1010, antioxidant 168, antioxidant 1076, or a mixture thereof in any proportion; the polymerization inhibitor is any one of hydroquinone, 4-methoxyphenol, o-methyl hydroquinone, p-benzoquinone and N-nitrosophenylhydroxylamine aluminum salt or a mixture of hydroquinone, 4-methoxyphenol, o-methyl hydroquinone, p-benzoquinone and N-nitrosophenylhydroxylamine aluminum salt in any proportion.
7. The organic salt microspheres of claim 1, wherein the catalyst is one of tetrabutyl titanate, tetraisopropyl titanate, tetraethyl titanate, p-toluenesulfonic acid, lithium isooctanoate, butylstannic acid, stannous oxalate, stannous chloride, stannous octoate, or a mixture thereof in any proportion.
8. The organic salt microspheres of claim 1, wherein the radiation sensitizer is any one of triallyl isocyanurate, triallyl cyanurate, 1, 4-butanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1, 6-hexanediol diacrylate, or a mixture thereof in any ratio.
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