Search

CN-121975256-A - Polyvinyl alcohol sponge with low formaldehyde content and preparation method and application thereof

CN121975256ACN 121975256 ACN121975256 ACN 121975256ACN-121975256-A

Abstract

The invention relates to a polyvinyl alcohol sponge with low formaldehyde content, a preparation method and application thereof. The formaldehyde molecules can be adsorbed on the surface of the hydroxyapatite by the action force between the grafted amino groups on the surface of the hydroxyapatite and formaldehyde molecules, and primary amine and formaldehyde are converted into relatively stable methylene imine by the amination reaction of formaldehyde under the heating condition. The hydroxyl grafted on the surface of the hydroxyapatite is easier to participate in the crosslinking reaction of the polyvinyl alcohol, so that the nano-hydroxyapatite can be uniformly and stably dispersed in the polyvinyl alcohol sponge, the catalytic performance of the nano-hydroxyapatite is improved, and the loss of the hydroxyapatite in the cleaning process can be effectively avoided. The polyvinyl alcohol sponge has excellent mechanical properties and lower formaldehyde content, and is suitable for preparing medical nasal cavity filling hemostatic materials.

Inventors

  • LI BAOMING
  • Mi Fushan
  • WANG CHANGHUA
  • YANG YINGXIANG

Assignees

  • 福建宸润生物科技有限公司

Dates

Publication Date
20260505
Application Date
20260115

Claims (10)

  1. 1. The raw materials for preparing the polyvinyl alcohol sponge comprise polyvinyl alcohol, and are characterized by further comprising amino and hydroxyl co-grafted hydroxyapatite.
  2. 2. The polyvinyl alcohol sponge according to claim 1, wherein the amino and hydroxyl co-grafted hydroxyapatite is prepared by reacting amino and vinyl co-grafted hydroxyapatite with a mercapto fatty alcohol.
  3. 3. The polyvinyl alcohol sponge according to claim 2, comprising one or more of the following (1) - (6): (1) The surface of the hydroxyapatite is treated by gamma-aminopropyl triethoxy silane and gamma-methacryloxypropyl trimethoxy silane together to prepare the amino and vinyl co-grafted hydroxyapatite; (2) The particle size of the hydroxyapatite is 60-80 nm; (3) The raw materials of the polyvinyl alcohol sponge also comprise a cross-linking agent, an emulsifying agent, a pore-forming agent, a foaming agent and a catalyst; (4) The sulfhydryl fatty alcohol is selected from one or more of 6-sulfhydryl-1-hexanol, sulfhydryl-PEG 4-alcohol, 11-sulfhydryl-1-undecanol and 4- (6-sulfhydryl hexyloxy) benzyl alcohol; (5) The polyvinyl alcohol is one or more selected from the polyvinyl alcohols with the models of 1799, 1788 and 1750; (6) And a photoinitiator is also added in the process of reacting the amino and vinyl co-grafted hydroxyapatite with the mercapto fatty alcohol to generate the amino and hydroxyl co-grafted hydroxyapatite.
  4. 4. A polyvinyl alcohol sponge according to claim 3, comprising one or more of the following (1) - (6): (1) The cross-linking agent is selected from one or more of formaldehyde, glutaraldehyde and glyoxal; (2) The emulsifier is one or more selected from sodium dodecyl sulfate, soap, acacia, sodium alkyl benzene sulfonate, polyoxyethylene lauryl ether, polyoxyethylene stearate, diglycerol polypropylene glycol ether, sodium diisopropylnaphthalene sulfonate, sodium cetyl sulfate and polyoxyethylene fatty acid phosphate; (3) The pore-forming agent is starch; (4) The foaming agent is one or more selected from n-pentane, n-hexane, n-heptane, isobutane, isopentane, tetrahydrofuran, petroleum ether, trichlorofluoromethane, dichlorodifluoromethane and dichlorotetrafluoroethane; (5) The catalyst is selected from one or more of hydrochloric acid, phosphoric acid, nitric acid, sulfuric acid, acetic acid and oxalic acid; (6) The photoinitiator is selected from one or more of 2, 2-dimethoxy-2-phenyl acetophenone, 1-hydroxy cyclohexyl phenyl ketone and diphenyl ketone.
  5. 5. The method for preparing a low formaldehyde content polyvinyl alcohol sponge according to any one of claims 1 to 4, wherein an emulsifier, amino and hydroxyl co-grafted hydroxyapatite are sequentially added into water and uniformly stirred, then polyvinyl alcohol is added to obtain a mixed solution of amino and hydroxyl co-grafted hydroxyapatite and polyvinyl alcohol, and then a pore-forming agent, a cross-linking agent, a foaming agent and a catalyst are sequentially added, after uniform stirring, standing treatment, heating foaming and electron beam irradiation are sequentially carried out to obtain the polyvinyl alcohol sponge.
  6. 6. The method according to claim 5, wherein the polyvinyl alcohol sponge is obtained by further heat treatment after electron beam irradiation.
  7. 7. The method of manufacturing according to claim 6, comprising the steps of: (1) Dispersing hydroxyapatite into an ethanol solution to obtain a hydroxyapatite dispersion liquid, regulating the pH value of the dispersion liquid to 4-6, adding gamma-aminopropyl triethoxysilane and gamma-methacryloxypropyl trimethoxy silicon, uniformly stirring, centrifuging, washing and drying to obtain amino and vinyl co-grafted hydroxyapatite; (2) Adding amino and vinyl co-grafted hydroxyapatite into absolute ethyl alcohol, stirring uniformly to obtain an amino and vinyl co-grafted hydroxyapatite dispersion liquid, sequentially adding mercapto fatty alcohol and a photoinitiator into the dispersion liquid, stirring uniformly under ultraviolet light irradiation, regulating the pH value to 9-11, centrifuging, washing and drying to obtain the amino and hydroxyl co-grafted hydroxyapatite; (3) Sequentially adding an emulsifying agent, amino and hydroxyl co-grafted hydroxyapatite into water, uniformly stirring, adding polyvinyl alcohol, uniformly stirring to obtain amino and hydroxyl co-grafted hydroxyapatite and polyvinyl alcohol mixed solution, sequentially adding a pore-forming agent, a cross-linking agent, a foaming agent and a catalyst, uniformly stirring, sequentially carrying out standing treatment, washing treatment, heating foaming, electron beam irradiation and heating treatment to obtain the polyvinyl alcohol sponge.
  8. 8. The preparation method according to claim 7, characterized by comprising the following specific steps: (1) Adding 10-20 g of hydroxyapatite with the particle size of 60-80 nm into 100-300 mL of 10 wt% ethanol solution, mechanically stirring for 20-40 min, and performing ultrasonic treatment for 30-60 min to obtain hydroxyapatite dispersion, adjusting the pH value of the dispersion to 4-6 by using 1 mol/L glacial acetic acid, adding 0.2-0.6 g of gamma-aminopropyl triethoxysilane and 0.1-0.4 g of gamma-methacryloxypropyl trimethoxysilane, mechanically stirring for 24-36 h, centrifuging, washing by deionized water, vacuum drying at 60 ℃ for 24h, and grinding to obtain amino and vinyl co-grafted hydroxyapatite; (2) Adding 2-6 g of amino and vinyl co-grafted hydroxyapatite into 50-100 g of absolute ethyl alcohol, mechanically stirring for 20-40 min, performing ultrasonic treatment for 30-60 min to obtain an amino and vinyl co-grafted hydroxyapatite dispersion liquid, sequentially adding 0.5-2 g of 6-mercapto-1-hexanol and 0.01-0.05 g of 2, 2-dimethoxy-2-phenylacetophenone into the dispersion liquid, mechanically stirring for 2-4 h under 365 nm ultraviolet irradiation, regulating the pH value of the dispersion liquid to 9-11 by using 1 mol/L ammonia water, performing centrifugal separation, alternately washing for 3 times by using absolute ethyl alcohol and deionized water, performing vacuum drying at 60 ℃ for 24 h, and performing grinding to obtain the amino and hydroxy co-grafted hydroxyapatite; (3) Adding 2-4 g of soluble starch into 4-10 mL of deionized water, mechanically stirring at 50-70 ℃ for 1-2 h to obtain a soluble starch solution, sequentially adding 0.5-2 g of sodium dodecyl sulfate and 1-3 g of amino and hydroxyl co-grafted hydroxyapatite into 150-350 mL of deionized water, mechanically stirring for 20-40 min, ultrasonically treating for 30-60 min, adding 30-50 g of polyvinyl alcohol 1799, continuously mechanically stirring at 100-120 ℃ for 2-4 h to obtain a mixed solution of amino and hydroxyl co-grafted hydroxyapatite and polyvinyl alcohol 1799, adding the soluble starch solution into the mixed solution, mechanically stirring at 30-36 ℃ for 20-40 min, sequentially adding 4-10 mL of formaldehyde, 2-6 mL of n-pentane and 3-9 mL of sulfuric acid, continuously mechanically stirring for 5-10 min, standing at 40-60 ℃ for 12-24 h to obtain a crude product of polyvinyl alcohol sponge, repeatedly rubbing and washing in deionized water until the solution does not contain starch, and carrying out electron radiation treatment at 35 ℃ for 35 ℃ under the conditions of 24 ℃ and 25 ℃ to obtain a 35 ℃ of 35-35 ℃ dried sponge crude product.
  9. 9. Use of a low formaldehyde content polyvinyl alcohol sponge according to any one of claims 1 to 4 or a method of preparation according to any one of claims 5 to 8 for the preparation of a medical material.
  10. 10. The use according to claim 9, wherein the medical material is a nasal packing hemostatic material.

Description

Polyvinyl alcohol sponge with low formaldehyde content and preparation method and application thereof Technical Field The invention relates to the technical field of preparation of medical polymer materials, in particular to a polyvinyl alcohol sponge with low formaldehyde content, a preparation method and application thereof. Background The polyvinyl alcohol sponge is a porous material prepared from polyvinyl alcohol through a cross-linking foaming process, has excellent water absorbability, softness, air permeability and biocompatibility, and is widely applied to the fields of medical treatment, cosmetics and cleaning. The polyvinyl alcohol sponge has the advantages that (1) the porous structure of the polyvinyl alcohol sponge can quickly absorb blood and expand to generate uniform pressure to realize high-efficiency hemostasis when being used as a nasal cavity filling hemostatic material, (2) the polyvinyl alcohol sponge is soft in material and free of fiber falling, so that the irritation and secondary injury risk to nasal mucosa are reduced, (3) the polyvinyl alcohol sponge is good in biocompatibility and suitable for being contacted with human tissues, and (4) the polyvinyl alcohol sponge can be cut according to the shape of the nasal cavity, is high in fitting degree, and clinical applicability is further improved through the design of lubricating before use, soaking physiological saline when taken out and the like. Therefore, the polyvinyl alcohol sponge is particularly suitable for post-operation hemostasis such as nasal endoscopic surgery. The medical polyvinyl alcohol sponge needs to be sterilized in the preparation process. The traditional sterilization treatment method mainly comprises electron beam irradiation sterilization, is a physical technology for realizing sterilization by utilizing high-energy electron beams to penetrate objects and destroying microorganism DNA/RNA through ionizing radiation, and has the advantages of high efficiency, high speed, no chemical residue ‌, strong penetrability ‌, environmental protection, energy conservation and the like. However, in the process of sterilizing the polyvinyl alcohol sponge by electron beam irradiation, a small amount of polyvinyl formal molecular chains are broken, formaldehyde molecules are released, and the formaldehyde content of the polyvinyl alcohol sponge is higher. Formaldehyde stimulates eyes and respiratory tracts in a short period, causes cough and lacrimation, damages immune systems in a long period and increases leukemia risks. Therefore, development of a polyvinyl alcohol sponge with low formaldehyde content for nasal cavity filling hemostatic material is needed. Disclosure of Invention The invention provides a polyvinyl alcohol sponge with low formaldehyde content, which is prepared from raw materials comprising amino and hydroxyl co-grafted hydroxyapatite besides polyvinyl alcohol. The amino and hydroxyl co-grafted hydroxyapatite is prepared by reacting amino and vinyl co-grafted hydroxyapatite with mercapto fatty alcohol. Specifically, the polyvinyl alcohol sponge further comprises one or more of the following (1) - (6): (1) The surface of the hydroxyapatite is treated by gamma-aminopropyl triethoxy silane and gamma-methacryloxypropyl trimethoxy silane together to prepare the amino and vinyl co-grafted hydroxyapatite; (2) The particle size of the hydroxyapatite is 60-80 nm; (3) The raw materials of the polyvinyl alcohol sponge also comprise a cross-linking agent, an emulsifying agent, a pore-forming agent, a foaming agent and a catalyst; (4) The sulfhydryl fatty alcohol is selected from one or more of 6-sulfhydryl-1-hexanol, sulfhydryl-PEG 4-alcohol, 11-sulfhydryl-1-undecanol and 4- (6-sulfhydryl hexyloxy) benzyl alcohol; (5) The polyvinyl alcohol is one or more selected from the polyvinyl alcohols with the models of 1799, 1788 and 1750; (6) And a photoinitiator is also added in the process of reacting the amino and vinyl co-grafted hydroxyapatite with the mercapto fatty alcohol to generate the amino and hydroxyl co-grafted hydroxyapatite. More specifically, the polyvinyl alcohol sponge further comprises one or more of the following (1) - (6): (1) The cross-linking agent is selected from one or more of formaldehyde, glutaraldehyde and glyoxal; (2) The emulsifier is one or more selected from sodium dodecyl sulfate, soap, acacia, sodium alkyl benzene sulfonate, polyoxyethylene lauryl ether, polyoxyethylene stearate, diglycerol polypropylene glycol ether, sodium diisopropylnaphthalene sulfonate, sodium cetyl sulfate and polyoxyethylene fatty acid phosphate; (3) The pore-forming agent is starch; (4) The foaming agent is one or more selected from n-pentane, n-hexane, n-heptane, isobutane, isopentane, tetrahydrofuran, petroleum ether, trichlorofluoromethane, dichlorodifluoromethane and dichlorotetrafluoroethane; (5) The catalyst is selected from one or more of hydrochloric acid, phosphoric acid, nitric acid, sulfuric acid, acetic