POSS polymer prepared by photo-initiation technology and method

Abstract

The invention discloses a method for preparing a POSS (Polyhedral Oligomeric Silsesquioxane) polymer by a photo-initiation technology. The method comprises the following steps: step 1, preparing POSS-Vi dispersion liquid; step 2, preparation of a monomer emulsion; and 3, carrying out photo-initiation polymerization to obtain a target polymer. According to the method, the limitation that traditional thermal initiation is prone to implosion and long in reaction time is overcome by precisely regulating and controlling the light initiation reaction condition, and the POSS polymer with a cage-shaped multi-branch chain structure and rich in active functional groups on the side chain is prepared. The invention also provides the POSS polymer prepared by the method.

Description

Technical Field

[0001] This invention belongs to the field of polymer technology, specifically relating to POSS polymers prepared by photoinitiation technology, and also to a method for preparing POSS polymers by photoinitiation technology. Background Technology

[0002] Cage-like silsesquioxanes (POSS), as a typical organic-inorganic nanohybrid molecule, possess a cage-like framework core with highly designable organic functional groups (R groups) at the vertices, exhibiting controllable molecular size and a high degree of functionalization. This unique molecular hybrid structure makes it a functional bridge connecting organic polymers and inorganic materials. Through the active groups at its vertices, it achieves covalent bonding or physical entanglement with other polymers, enabling its cage-like framework to provide support at the molecular scale. This improves the mechanical and thermal properties, aging resistance, and biocompatibility of the materials, resulting in excellent application performance in many cutting-edge technology fields. For example, POSS can enhance the mechanical properties of high-performance composite materials, reduce the dielectric constant of materials in precision electronic packaging, construct dense layers to resist atomic oxygen erosion and space radiation in aerospace special protection, and serve as a core component in high-performance tissue engineering scaffolds and controlled drug release systems in biomedical materials.

[0003] Researchers typically use vinyl-containing POSS and vinyl monomers to prepare POSS polymers via thermally initiated free radical polymerization. This requires high ambient temperatures and long reaction times to drive the pyrolysis of the initiator. When the polymerization reaction releases heat, the ambient temperature limits the rate of heat dissipation, causing heat accumulation in the reaction system. This heat accelerates the decomposition of the initiator, generating more free radicals and further releasing heat. Once this chain reaction begins, it is difficult to interrupt instantly by external means, posing a significant risk of localized explosive polymerization. Summary of the Invention

[0004] The first objective of this invention is to provide a method for preparing POSS polymers using photoinitiation technology. By controlling the photoinitiation reaction conditions, the limitations of traditional thermal initiation, such as easy rapid polymerization and long reaction time, are overcome, and POSS polymers with cage-like multi-branched structures and side chains rich in active functional groups are prepared.

[0005] The second objective of this invention is to provide a POSS polymer prepared by photoinitiation technology.

[0006] The first technical solution adopted in this invention is: A method for preparing POSS polymers using photoinitiation technology includes the following steps: Step 1: Preparation of POSS-Vi (vinyl cage silsesquioxane) dispersion; Step 2: Preparation of monomer emulsion; Step 3: Photoinitiated polymerization yields the target polymer.

[0007] The invention is further characterized in that: Step 1 is as follows: Weigh 2 parts by weight of POSS-Vi and 10 parts by weight of tetrahydrofuran. Add POSS-Vi to tetrahydrofuran and disperse for 5 min to 20 min at a temperature of 20℃-30℃ and a stirring speed of 100 r / min-300 r / min to obtain a uniform POSS-Vi dispersion. Step 2 is as follows: Weigh out 94-98 parts by weight of water-soluble allyl monomer, 94-98 parts by weight of oil-soluble allyl monomer, 2-6 parts by weight of photoinitiator, 50 parts by weight of water, 20 parts by weight of tetrahydrofuran, and 1 part by weight of surfactant in sequence. Mix the weighed water-soluble allyl monomer, oil-soluble allyl monomer, photoinitiator, water, tetrahydrofuran, and surfactant in proportion, and emulsify at high speed for 1-5 minutes to obtain a stable monomer emulsion.

[0008] In step 2, the water-soluble allyl monomer is acrylamide.

[0009] In step 2, the oil-soluble allyl monomer is butyl acrylate.

[0010] In step 2, the photoinitiator is 2-hydroxy-4′-(2-hydroxyethoxy)-2-methylphenylacetone or benzoin dimethyl ether or a mixture of 2-hydroxy-4′-(2-hydroxyethoxy)-2-methylphenylacetone and benzoin dimethyl ether in a mass ratio of 1:1.

[0011] In step 2, the surfactant is sodium dodecylbenzenesulfonate.

[0012] Step 3 specifically involves: Under conditions of 20℃-30℃ and stirring speed of 100r / min-300r / min, the monomer emulsion obtained in step 2 was irradiated with an ultraviolet light source to initiate the polymerization reaction. Subsequently, the obtained monomer emulsion was added dropwise to the POSS-Vi dispersion obtained in step 1 for 20min-30min, and ultraviolet light irradiation was continuously carried out during the dropwise addition. After the dropwise addition was completed, the reaction was continued under ultraviolet light irradiation for 15min-30min. After the irradiation was stopped, stirring was continued for 2h-3h to obtain the target polymer emulsion.

[0013] The second technical solution adopted in this invention is: The POSS polymer prepared by photoinitiation technology was obtained using the method described above.

[0014] The beneficial effects of this invention are: (1) Compared with traditional thermally initiated polymerization, the photoinitiation technology used in this invention has the characteristics of strong controllability, fast response, and high efficiency. By controlling the switch of the light source, the polymerization process can be controlled, thereby avoiding the risk of explosive polymerization caused by the accumulation of reaction heat and improving the stability of the polymerization process. In addition, the photoinitiation system can also reduce thermally induced side reactions. Therefore, using photoinitiation technology to prepare POSS polymers with specific functional side chains provides a simple and efficient technical route for the preparation of high-performance POSS polymers.

[0015] (2) The method of the present invention uses a photoinitiation system to prepare POSS polymers. By utilizing the high efficiency and immediate responsiveness of the photoinitiation reaction, the free radical polymerization process can be controlled, avoiding the accumulation of heat in the reaction system during the polymerization process, thereby avoiding the risk of explosive polymerization in traditional thermally initiated polymerization.

[0016] (3) The POSS-Vi used in the method of this invention has a regular organic-inorganic hybrid structure, exhibiting a cage-like framework with multiple vinyl functional groups at the vertices. This invention utilizes a photoinitiator irradiated with ultraviolet light to generate free radicals, initiating free radical polymerization of acrylamide, butyl acrylate, and the vinyl groups of POSS-Vi. During the free radical polymerization process, with the cage-like framework of POSS-Vi as the center, the acrylamide and butyl acrylate monomers grow outward through free radical polymerization, forming a multi-branched structure with inorganic nanoparticles as the core and radiating outwards. The conversion rate was measured, and the results showed that the monomer conversion rate was as high as 90% or more, and the POSS polymer was successfully synthesized. The high-density amide groups introduced into the side chains provide abundant active sites for subsequent functionalization modifications, and the ester groups improve the water resistance and flexibility of the POSS polymer. This POSS polymer has the characteristics of high conversion rate and low viscosity, with a monomer conversion rate of up to 90% or more and a rotational viscosity of less than 150 mPa·s, which is convenient for later use. The method of this invention has mild process conditions and is easy to operate, providing a simple and efficient technical route for the preparation of high-performance POSS polymers. Detailed Implementation

[0017] The present invention will now be described in detail with reference to specific embodiments.

[0018] This invention provides a method for preparing POSS polymers using photoinitiation technology, specifically comprising the following steps: Step 1: Preparation of POSS-Vi (vinyl cage silsesquioxane) dispersion: Weigh 2 parts by weight of POSS-Vi and 10 parts by weight of tetrahydrofuran. Add POSS-Vi to tetrahydrofuran and disperse for 5 min to 20 min at a temperature of 20℃-30℃ and a stirring speed of 100 r / min-300 r / min to obtain a uniform POSS-Vi dispersion. Step 2: Preparation of monomer emulsion: Weigh out 94-98 parts by weight of water-soluble allyl monomer, 94-98 parts by weight of oil-soluble allyl monomer, 2-6 parts by weight of photoinitiator, 50 parts by weight of water, 20 parts by weight of tetrahydrofuran, and 1 part by weight of surfactant in sequence; mix the weighed water-soluble allyl monomer, oil-soluble allyl monomer, photoinitiator, water, tetrahydrofuran, and surfactant in proportion, and emulsify by high-speed shearing for 1-5 minutes to obtain a stable monomer emulsion; Among them, the water-soluble allyl monomer is acrylamide; The oil-soluble allyl monomer is butyl acrylate; The photoinitiator is 2-hydroxy-4′-(2-hydroxyethoxy)-2-methylphenylacetone or benzoin dimethyl ether or a mixture of 2-hydroxy-4′-(2-hydroxyethoxy)-2-methylphenylacetone and benzoin dimethyl ether in a mass ratio of 1:1; The surfactant is sodium dodecylbenzenesulfonate; Step 3: Photoinitiated polymerization: Under conditions of 20℃-30℃ and stirring speed of 100r / min-300r / min, the monomer emulsion obtained in step 2 was irradiated with an ultraviolet light source to initiate the polymerization reaction. Subsequently, the obtained monomer emulsion was added dropwise to the POSS-Vi dispersion obtained in step 1 for 20min-30min, and ultraviolet light irradiation was continuously carried out during the dropwise addition. After the dropwise addition was completed, the reaction was continued under ultraviolet light irradiation for 15min-30min. After the irradiation was stopped, stirring was continued for 2h-3h to obtain the target polymer emulsion.

[0019] The pharmaceuticals used in the examples are: analytical grade dimethyl benzoate, analytical grade 2-hydroxy-4′-(2-hydroxyethoxy)-2-methylphenylacetone, and analytical grade vinyl cage silsesquioxane produced by Shanghai Maclean Biochemical Technology Co., Ltd.; analytical grade acrylamide produced by Tianjin Kemeio Chemical Reagent Co., Ltd.; analytical grade butyl acrylate produced by Tianjin Fuchen Chemical Reagent Co., Ltd.; analytical grade sodium dodecylbenzenesulfonate produced by Tianjin Damao Chemical Reagent Co., Ltd.; and tetrahydrofuran produced by Fuyu Chemical Co., Ltd.

[0020] Example 1: Step 1: Preparation of POSS-Vi dispersion: Weigh 2 parts by weight of POSS-Vi and add it to 10 parts by weight of tetrahydrofuran. Place the mixture in a three-necked flask equipped with a stirrer and a condenser. Disperse the mixture for 15 minutes at 20°C and a stirring speed of 100 r / min to obtain a clear, transparent and homogeneous POSS-Vi dispersion.

[0021] Step 2: Preparation of monomer emulsion: 98 parts by weight of acrylamide, 98 parts by weight of butyl acrylate, 5 parts by weight of benzoin dimethyl ether and 2-hydroxy-4′-(2-hydroxyethoxy)-2-methylphenylacetone (mass ratio 1:1), 50 parts by weight of deionized water, 20 parts by weight of tetrahydrofuran, and 1 part by weight of sodium dodecylbenzenesulfonate surfactant were weighed sequentially. The above raw materials were mixed and sheared and emulsified using a high-speed shear emulsifier for 1 min to prepare a milky white, stable monomer emulsion.

[0022] Step 3: Photoinitiated polymerization: Under conditions of controlled temperature of 20℃ and stirring speed of 100 r / min, the monomer emulsion obtained in step 2 was irradiated with a UV light source to initiate polymerization. Subsequently, the monomer emulsion obtained in step 2 was slowly added dropwise to the dispersion obtained in step 1, with the addition time controlled at 30 min. Throughout the addition process, the system was continuously irradiated with UV light. After the addition was completed, the reaction was continued for another 30 min under UV irradiation conditions. After irradiation was stopped, stirring was continued for 2 h to obtain the target polymer emulsion. Its monomer conversion rate was measured to be 90.02%, and its rotational viscosity was 149 mPa·s.

[0023] Example 2: Step 1: Preparation of vinyl cage-like silsesquioxane (POSS-Vi) dispersion: Weigh 2 parts by weight of POSS-Vi and add it to 10 parts by weight of tetrahydrofuran. Place the mixture in a three-necked flask equipped with a stirrer and a condenser. Disperse the mixture for 15 minutes at 25°C and a stirring speed of 150 r / min to obtain a clear, transparent and homogeneous POSS-Vi dispersion.

[0024] Step 2: Preparation of monomer emulsion: 97 parts by weight of acrylamide, 97 parts by weight of butyl acrylate, 6 parts by weight of 2-hydroxy-4′-(2-hydroxyethoxy)-2-methylphenylacetone, 50 parts by weight of deionized water, 20 parts by weight of tetrahydrofuran, and 1 part by weight of sodium dodecylbenzenesulfonate surfactant were weighed sequentially. The above raw materials were mixed and sheared and emulsified using a high-speed shear emulsifier for 3 minutes to prepare a milky white, stable monomer emulsion.

[0025] Step 3: Photoinitiated polymerization: Under conditions of controlled temperature of 25℃ and stirring speed of 200 r / min, the monomer emulsion obtained in step 2 was irradiated with an ultraviolet light source to initiate polymerization. Subsequently, the monomer emulsion obtained in step 2 was slowly added dropwise to the dispersion obtained in step 1, with the addition time controlled at 25 min. Throughout the addition process, the system was continuously irradiated with ultraviolet light. After the addition was completed, the reaction was continued under ultraviolet light irradiation conditions for 30 min, and then stirred for 2.5 h after irradiation was stopped to obtain the target polymer emulsion. Its monomer conversion rate was measured to be 92.20%, and its rotational viscosity was 121 mPa·s.

[0026] Example 3: Step 1: Preparation of vinyl cage-like silsesquioxane (POSS-Vi) dispersion: Weigh 2 parts by weight of POSS-Vi and add it to 10 parts by weight of tetrahydrofuran. Place the mixture in a three-necked flask equipped with a stirrer and a condenser. Disperse the mixture for 15 minutes at 25°C and a stirring speed of 300 r / min to obtain a clear, transparent and homogeneous POSS-Vi dispersion.

[0027] Step 2: Preparation of monomer emulsion: 94 parts by weight of acrylamide, 94 parts by weight of butyl acrylate, 6 parts by weight of benzoin dimethyl ether, and 2-hydroxy-4′-(2-hydroxyethoxy)-2-methylphenylacetone (mass ratio 1:1), 50 parts by weight of deionized water, 20 parts by weight of tetrahydrofuran, and 1 part by weight of sodium dodecylbenzenesulfonate surfactant were weighed sequentially. The above raw materials were mixed and sheared and emulsified using a high-speed shear emulsifier for 5 minutes to prepare a milky white, stable monomer emulsion.

[0028] Step 3: Photoinitiated polymerization: Under conditions of controlled temperature of 25℃ and stirring speed of 300 r / min, the monomer emulsion obtained in step 2 was irradiated with a UV light source to initiate polymerization. Subsequently, the monomer emulsion obtained in step 2 was slowly added dropwise to the dispersion obtained in step 1, with the addition time controlled at approximately 20 min. Throughout the addition process, the system was continuously irradiated with UV light. After the addition was complete, the reaction was continued under UV irradiation conditions for another 30 min, and then stirred for another 3 h after irradiation was stopped to obtain the target polymer emulsion. Its monomer conversion rate was measured to be 94.2%, and its rotational viscosity was 92 mPa·s. After drying into a film, its tensile strength was measured to be 9.62 MPa.

[0029] Example 4 Step 1: Preparation of POSS-Vi dispersion: Weigh 2 parts by weight of POSS-Vi and add it to 10 parts by weight of tetrahydrofuran. Place the mixture in a three-necked flask equipped with a stirrer and a condenser. Disperse the mixture for 15 minutes at 30°C and a stirring speed of 100 r / min to obtain a clear, transparent and homogeneous POSS-Vi dispersion.

[0030] Step 2: Preparation of monomer emulsion: 98 parts by weight of acrylamide, 98 parts by weight of butyl acrylate, 2 parts by weight of benzoin dimethyl ether, 50 parts by weight of deionized water, 20 parts by weight of tetrahydrofuran, and 1 part by weight of sodium dodecylbenzenesulfonate surfactant were weighed sequentially. The above raw materials were mixed and sheared and emulsified using a high-speed shear emulsifier for 1 minute to prepare a milky white, stable monomer emulsion.

[0031] Step 3: Photoinitiated polymerization: Under conditions of controlled temperature of 20℃ and stirring speed of 100 r / min, the monomer emulsion obtained in step 2 was irradiated with an ultraviolet light source to initiate polymerization. Subsequently, the monomer emulsion obtained in step 2 was slowly added dropwise to the dispersion obtained in step 1, with the addition time controlled at 30 min. Throughout the addition process, the system was continuously irradiated with ultraviolet light. After the addition was completed, the reaction was continued for another 30 min under ultraviolet light irradiation conditions. After irradiation was stopped, stirring was continued for 2 h to obtain the target polymer emulsion.

[0032] Example 5 Step 1: Preparation of POSS-Vi dispersion: Weigh 2 parts by weight of POSS-Vi and add it to 10 parts by weight of tetrahydrofuran. Place the mixture in a three-necked flask equipped with a stirrer and a condenser. Disperse the mixture for 15 minutes at 20°C and a stirring speed of 100 r / min to obtain a clear, transparent and homogeneous POSS-Vi dispersion.

[0033] Step 2: Preparation of monomer emulsion: 94 parts by weight of acrylamide, 94 parts by weight of butyl acrylate, 6 parts by weight of benzoin dimethyl ether, 50 parts by weight of deionized water, 20 parts by weight of tetrahydrofuran, and 1 part by weight of sodium dodecylbenzenesulfonate surfactant were weighed sequentially. The above raw materials were mixed and sheared and emulsified for 1 minute using a high-speed shear emulsifier to prepare a milky white, stable monomer emulsion.

[0034] Step 3: Photoinitiated polymerization: Under conditions of controlled temperature of 20℃ and stirring speed of 100 r / min, the monomer emulsion obtained in step 2 was irradiated with an ultraviolet light source to initiate polymerization. Subsequently, the monomer emulsion obtained in step 2 was slowly added dropwise to the dispersion obtained in step 1, with the addition time controlled at 30 min. Throughout the addition process, the system was continuously irradiated with ultraviolet light. After the addition was completed, the reaction was continued for another 30 min under ultraviolet light irradiation conditions. After irradiation was stopped, stirring was continued for 2 h to obtain the target polymer emulsion.

[0035] Example 6 Step 1: Preparation of POSS-Vi dispersion: Weigh 2 parts by weight of POSS-Vi and add it to 10 parts by weight of tetrahydrofuran. Place the mixture in a three-necked flask equipped with a stirrer and a condenser. Disperse the mixture for 15 minutes at 20°C and a stirring speed of 100 r / min to obtain a clear, transparent and homogeneous POSS-Vi dispersion.

[0036] Step 2: Preparation of monomer emulsion: 98 parts by weight of acrylamide, 98 parts by weight of butyl acrylate, 2 parts by weight of benzoin dimethyl ether, 50 parts by weight of deionized water, 20 parts by weight of tetrahydrofuran, and 1 part by weight of sodium dodecylbenzenesulfonate surfactant were weighed sequentially. The above raw materials were mixed and sheared and emulsified using a high-speed shear emulsifier for 1 minute to prepare a milky white, stable monomer emulsion.

[0037] Step 3: Photoinitiated polymerization: Under conditions of controlled temperature of 20℃ and stirring speed of 100 r / min, the monomer emulsion obtained in step 2 was irradiated with an ultraviolet light source to initiate polymerization. Subsequently, the monomer emulsion obtained in step 2 was slowly added dropwise to the dispersion obtained in step 1, with the addition time controlled at 30 min. Throughout the addition process, the system was continuously irradiated with ultraviolet light. After the addition was completed, the reaction was continued for another 30 min under ultraviolet light irradiation conditions. After irradiation was stopped, stirring was continued for 2 h to obtain the target polymer emulsion.

Claims

1. A method for preparing POSS polymers using photoinitiation technology, characterized in that, Includes the following steps: Step 1: Preparation of POSS-Vi dispersion; Step 2: Preparation of monomer emulsion; Step 3: Photoinitiated polymerization yields the target polymer.

2. The method for preparing POSS polymers using photoinitiation technology according to claim 1, characterized in that, Step 1 is as follows: Weigh 2 parts by weight of POSS-Vi and 10 parts by weight of tetrahydrofuran. Add POSS-Vi to the tetrahydrofuran and disperse for 5 min to 20 min at a temperature of 20℃-30℃ and a stirring speed of 100 r / min-300 r / min to obtain a uniform POSS-Vi dispersion.

3. The method for preparing POSS polymers using photoinitiation technology according to claim 1, characterized in that, Step 2 is as follows: Weigh out 94-98 parts by weight of water-soluble allyl monomer, 94-98 parts by weight of oil-soluble allyl monomer, 2-6 parts by weight of photoinitiator, 50 parts by weight of water, 20 parts by weight of tetrahydrofuran, and 1 part by weight of surfactant in sequence. Mix the weighed water-soluble allyl monomer, oil-soluble allyl monomer, photoinitiator, water, tetrahydrofuran, and surfactant in proportion, and emulsify at high speed for 1-5 minutes to obtain a stable monomer emulsion.

4. The method for preparing POSS polymers using photoinitiation technology according to claim 3, characterized in that, In step 2, the water-soluble allyl monomer is acrylamide.

5. The method for preparing POSS polymers using photoinitiation technology according to claim 3, characterized in that, In step 2, the oil-soluble allyl monomer is butyl acrylate.

6. The method for preparing POSS polymers using photoinitiation technology according to claim 3, characterized in that, In step 2, the photoinitiator is 2-hydroxy-4′-(2-hydroxyethoxy)-2-methylphenylacetone or benzoin dimethyl ether or a mixture of 2-hydroxy-4′-(2-hydroxyethoxy)-2-methylphenylacetone and benzoin dimethyl ether in a mass ratio of 1:

1.

7. The method for preparing POSS polymers using photoinitiation technology according to claim 3, characterized in that, In step 2, the surfactant is sodium dodecylbenzenesulfonate.

8. The method for preparing POSS polymers using photoinitiation technology according to claim 1, characterized in that, Step 3 specifically involves: Under conditions of 20℃-30℃ and stirring speed of 100r / min-300r / min, the monomer emulsion obtained in step 2 was irradiated with an ultraviolet light source to initiate the polymerization reaction. Subsequently, the obtained monomer emulsion was added dropwise to the POSS-Vi dispersion obtained in step 1 for 20min-30min, and ultraviolet light irradiation was continuously carried out during the dropwise addition. After the dropwise addition was completed, the reaction was continued under ultraviolet light irradiation for 15min-30min. After the irradiation was stopped, stirring was continued for 2h-3h to obtain the target polymer emulsion.

9. A POSS polymer prepared by photoinitiation technology, characterized in that, It is prepared by the method described in any one of claims 1-8.