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CN-122011327-A - Modified bio-based polyol used for closed type soft high-solid-content polyurethane resin and preparation method thereof

CN122011327ACN 122011327 ACN122011327 ACN 122011327ACN-122011327-A

Abstract

The invention relates to the field of bio-based polyurethane materials, in particular to a modified bio-based polyol used for a closed type soft polyurethane resin with high solid content and a preparation method thereof. The closed type soft high-solid content polyurethane resin comprises 40-60 parts of modified bio-based polyol, 10-30 parts of petroleum-based polyol, 15-25 parts of diisocyanate, 0.1-1 part of end capping agent, 0.01-0.05 part of catalyst, 0.1-1 part of leveling agent and 10-30 parts of organic solvent, wherein the modified bio-based polyol is obtained by decompressing and dehydrating epoxidized soybean oil-based polyol and castor oil-based polyester polyol. The closed soft high-solid polyurethane resin has long operation time, solid content of more than or equal to 70%, biobased content of more than or equal to 50%, viscosity of (1-3) x 10 4 mPa.s, excellent storage stability and film forming flexibility, and is suitable for the fields of clothing, furniture soft packages, synthetic leather and the like.

Inventors

  • YANG RUI
  • XU SHENGHUA
  • JI SHANGCHAO
  • YAN XUESHENG
  • FENG MINCHAO
  • WANG YAN
  • XU JINFANG

Assignees

  • 浙江禾欣科技有限公司
  • 台州禾欣高分子新材料有限公司
  • 浙江惠嘉新材料有限公司

Dates

Publication Date
20260512
Application Date
20260227

Claims (10)

  1. 1. A modified bio-based polyol used for sealing type soft polyurethane resin with high solid content is characterized by comprising 40-60 parts of modified bio-based polyol, 10-30 parts of petroleum-based polyol, 15-25 parts of diisocyanate, 0.1-1 part of end-capping agent, 0.01-0.05 part of catalyst, 0.1-1 part of leveling agent and 10-30 parts of organic solvent, wherein the modified bio-based polyol is obtained by compounding epoxy soybean oil-based polyol and castor oil-based polyester polyol and then decompressing and dehydrating, and the mass of the modified bio-based polyol accounts for 70-80wt% of the total mass of the modified bio-based polyol and the petroleum-based polyol.
  2. 2. The modified bio-based polyol for the closed type soft high-solid polyurethane resin according to claim 1, wherein the modified bio-based polyol is prepared by ring-opening reaction of epoxidized soybean oil and a fluorine-containing alcohol ring-opening agent under the catalysis of boron trifluoride diethyl ether, the molar ratio of hydroxyl groups in the fluorine-containing alcohol ring-opening agent to epoxy groups in the epoxidized soybean oil is (1.2-1.5): 1, the fluorine-containing alcohol ring-opening agent is at least one of trifluoroethanol, pentafluoropropanol and heptafluorobutanol, and the hydroxyl value of the epoxy soybean oil-based polyol is 150-200 mg KOH/g.
  3. 3. The modified bio-based polyol used for the closed type soft high-solid polyurethane resin is characterized in that castor oil-based polyester polyol in the modified bio-based polyol is prepared by conducting transesterification on castor oil and low-crystalline diol under the action of titanate catalysts, the molar ratio of the castor oil to the low-crystalline diol is 1 (2-2.1), the low-crystalline chain extender is at least one of 1, 2-propanediol, 1, 3-propanediol, 3-methyl-1, 3-butanediol and 3-methyl-1, 5-pentanediol, and the hydroxyl value of the castor oil-based polyester polyol is 180-220 mg KOH/g.
  4. 4. The modified bio-based polyol for the closed type soft high-solid polyurethane resin, which is disclosed in claim 3, is characterized in that the modified bio-based polyol is obtained by carrying out decompression dehydration on the modified bio-based polyol after the epoxy soybean oil-based polyol and the castor oil-based polyester polyol are compounded according to the mass ratio of (6-8) (2-4).
  5. 5. The modified bio-based polyol for a closed type soft high-solid content polyurethane resin according to claim 3, wherein the modified bio-based polyol is prepared by the following steps: 1, uniformly mixing epoxidized soybean oil and a fluorine-containing alcohol ring-opening agent according to the molar ratio of (1.2-1.5), adding boron trifluoride diethyl ether, uniformly mixing, heating to 68-75 ℃ for reaction for 3-5 hours, vacuumizing to remove water and redundant alcohol monomers generated by the reaction, sampling and detecting the hydroxyl value of a product after the reaction is finished, stopping the reaction when the hydroxyl value of the product is 150-200 mg KOH/g, filling nitrogen, recovering normal temperature and normal pressure, and discharging to obtain the epoxidized soybean oil based polyol; The castor oil-based polyester polyol is prepared by uniformly mixing castor oil and low-crystalline diol according to a molar ratio of1 (2-2.1), adding titanate catalyst, wherein the mass of the titanate catalyst is equal to 0.08-0.12wt% of the total mass of the castor oil and the low-crystalline diol, uniformly mixing, heating to 210-230 ℃ for reacting for 100-150min, vacuumizing to remove water and redundant alcohol monomers generated by the reaction, sampling and detecting the hydroxyl value of a product after the reaction is finished, stopping the reaction when the hydroxyl value of the product is 180-220 mg KOH/g, filling nitrogen, recovering normal temperature and normal pressure, and discharging to obtain the castor oil-based polyester polyol; S2, uniformly mixing the epoxidized soybean oil-based polyol and the castor oil-based polyester polyol in a mass ratio of (6-8) to (2-4), and heating to 100-120 ℃ for vacuum dehydration treatment for 1-2 hours to obtain the modified bio-based polyol.
  6. 6. The modified bio-based polyol for a closed soft high solid content polyurethane resin of claim 1, wherein the petroleum-based polyol is at least one of poly (1, 2-propylene glycol) PPG, polyethylene glycol PEG, polytetrahydrofuran ether glycol PTMEG) with a number average molecular weight of 1000-2000.
  7. 7. The modified bio-based polyol for the closed type soft high-solid content polyurethane resin according to claim 1, wherein the diisocyanate is at least one of toluene diisocyanate, p-phenylene diisocyanate, naphthalene diisocyanate and diphenylmethane diisocyanate, the catalyst is an organobismuth catalyst, and the organic solvent is at least one of ethyl acetate, acetone, butanone and DMF.
  8. 8. The modified bio-based polyol for a closed type soft high-solid polyurethane resin according to claim 1, wherein the blocking agent is at least one of methyl ethyl ketone oxime, isopropyl alcohol, phenol, 2, 6-dimethylphenol, caprolactam and 3, 5-dimethylpyrazole.
  9. 9. The modified bio-based polyol for the closed type soft high-solid content polyurethane resin according to claim 1, wherein the petroleum-based polyol is polytetrahydrofuran ether glycol PTMEG with a number average molecular weight of 1000, the diisocyanate is toluene diisocyanate, and the blocking agent is butanone oxime.
  10. 10. A process for the preparation of a modified bio-based polyol as claimed in any one of claims 1 to 9 for a closed soft high solids polyurethane resin, comprising the steps of: Step one, adding accurately metered modified bio-based polyol and petroleum-based polyol into a reaction kettle, uniformly mixing, and heating to 100-130 ℃ for vacuum dehydration treatment for 1-3h; step two, adding diisocyanate with accurate measurement after cooling to 60-65 ℃ and uniformly mixing, adjusting the system temperature to 78-85 ℃, and reacting for 3-4 hours under the protection of nitrogen; and thirdly, adding an organic solvent with accurate measurement after the reaction is finished, stirring for 10-15min, then adding an end capping agent, a catalyst and a leveling agent with accurate measurement, uniformly mixing, adjusting the temperature to 78-85 ℃, continuously reacting for 45-120min under the protection of nitrogen, cooling to below 40 ℃ after the reaction is finished, and discharging to obtain the modified bio-based polyol for the closed soft high-solid polyurethane resin.

Description

Modified bio-based polyol used for closed type soft high-solid-content polyurethane resin and preparation method thereof Technical Field The invention relates to the field of bio-based polyurethane materials, in particular to a modified bio-based polyol used for a closed type soft polyurethane resin with high solid content and a preparation method thereof. Background The traditional polyurethane resin depends on petroleum-based polyol, and has the problems of non-regeneration, high VOC emission and the like. In order to get rid of the dependence on petroleum-based polyols, researchers have begun to make polyurethane resins using bio-based polyols. The reported bio-based polyol comprises castor oil derivative polyol, soybean oil polyol, palm oil polyol, vegetable oil polyol and the like, and the prepared bio-based polyurethane resin meets the environmental protection production requirement, but has limitations, and the bio-based polyurethane resin has the defects of high viscosity, low reaction activity and large film forming brittleness when being directly used in a high solid content system, so that the application and development of the bio-based polyurethane resin are limited. For this reason, the inventors have provided a modified bio-based polyol for a closed type soft high solid content polyurethane resin and a method for preparing the same. Disclosure of Invention In order to solve the technical defects of high viscosity, low reactivity and high film forming brittleness of the existing bio-based polyurethane resin of a high-solid-content system, the invention provides a modified bio-based polyol used for a closed soft high-solid-content polyurethane resin and a preparation method thereof. The invention provides a modified bio-based polyol for closed soft polyurethane resin with high solid content, which is realized by the following technical scheme: the modified bio-based polyol is prepared from 40-60 parts of modified bio-based polyol, 10-30 parts of petroleum-based polyol, 15-25 parts of diisocyanate, 0.1-1 part of end-capping agent, 0.01-0.05 part of catalyst, 0.1-1 part of leveling agent and 10-30 parts of organic solvent, wherein the modified bio-based polyol is obtained by compounding epoxy soybean-based polyol and castor oil-based polyester polyol, and then carrying out decompression and dehydration, and the mass of the modified bio-based polyol accounts for 70-80wt% of the total mass of the modified bio-based polyol and the petroleum-based polyol. The epoxy soybean oil-based polyester polyol has high primary hydroxyl content, can improve the reactivity, has excellent flexibility, can improve the film-forming flexibility, has the functions of balancing the crosslinking density and flexibility by compounding the epoxy soybean oil-based polyol and the castor oil-based polyester polyol and controlling the functionality (2.5-3), and endows the closed type soft polyurethane resin with excellent storage stability, film-forming flexibility and reactivity. Preferably, the epoxidized soybean oil-based polyol in the modified bio-based polyol is prepared by ring-opening reaction of epoxidized soybean oil and a fluorine-containing alcohol ring-opening agent under the catalysis of boron trifluoride diethyl ether, wherein the molar ratio of hydroxyl groups in the fluorine-containing alcohol ring-opening agent to epoxy groups in the epoxidized soybean oil is (1.2-1.5): 1, the fluorine-containing alcohol ring-opening agent is at least one of trifluoroethanol, pentafluoropropanol and heptafluorobutanol, and the hydroxyl value of the epoxidized soybean oil-based polyol is 150-200 mg KOH/g. Preferably, the castor oil-based polyester polyol in the modified bio-based polyol is prepared by transesterification of castor oil and low-crystalline diol under the action of titanate catalyst, wherein the molar ratio of the castor oil to the low-crystalline diol is 1 (2-2.1), the low-crystalline chain extender is at least one of 1, 2-propanediol, 1, 3-propanediol, 3-methyl-1, 3-butanediol and 3-methyl-1, 5-pentanediol, and the hydroxyl value of the castor oil-based polyester polyol is 180-220 mg KOH/g. Preferably, the modified bio-based polyol is obtained by carrying out decompression dehydration on the epoxy soybean oil-based polyol and the castor oil-based polyester polyol after the components are compounded according to the mass ratio of (6-8) to (2-4). Preferably, the modified bio-based polyol is prepared as follows: 1, uniformly mixing epoxidized soybean oil and a fluorine-containing alcohol ring-opening agent according to the molar ratio of (1.2-1.5), adding boron trifluoride diethyl ether, uniformly mixing, heating to 68-75 ℃ for reaction for 3-5 hours, vacuumizing to remove water and redundant alcohol monomers generated by the reaction, sampling and detecting the hydroxyl value of a product after the reaction is finished, stopping the reaction when the hydroxyl value of the product is 150-200 mg KOH/g, filling nitr