CN113214637A - Polyurethane with uvioresistant performance and preparation method thereof - Google Patents
Polyurethane with uvioresistant performance and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/221—Oxides; Hydroxides of metals of rare earth metal
- C08K2003/2213—Oxides; Hydroxides of metals of rare earth metal of cerium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K2201/011—Nanostructured additives
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The invention relates to the technical field of polyurethane high polymer materials, and particularly discloses polyurethane with uvioresistant performance and a preparation method thereof. The polyurethane obtained by the invention has more lasting, more stable and excellent uvioresistant performance.
Description
Technical Field
The invention belongs to the technical field of polyurethane high polymer materials, and particularly relates to polyurethane with uvioresistant performance and a preparation method thereof.
Background
Polyurethane (PU) is a high polymer material with excellent performance and is widely applied to the fields of automobile manufacturing, transportation, clothing, petrochemical industry, aerospace and the like. However, under the action of light and heat, especially ultraviolet light, ordinary PU materials are easy to age, degrade and turn yellow, which affects the product performance and appearance. To solve this problem, an ultraviolet shielding agent or the like is usually added.
The commonly used UV screening agent is mainly TiO2And ZnO, etc., which are highly preferred because of their excellent properties such as non-toxicity and stability. However, ZnO has a problem of high photocatalytic activity and insufficient absorption capacity on the short wavelength side, and is used for TiO2Although the forbidden band width reaches 3.2eV, the refractive index n is close to 2.7, and the color and the transparency of the product are influenced after the polyurethane resin is blended. And TiO with ultraviolet resistance2And ZnO and other nano-particles are applied to polyurethane resin, and the problems of easy agglomeration, poor stability and the like also exist. However, the conventional surfactants are added to solve the problems, and the surfactants can eliminate the surface charge of the nanoparticles and enhance the lipophilicity of the nanoparticles, so that the nanoparticles can be doped into the polyurethane resin, but the stability and the dispersibility of the combination of the nanoparticles and the polyurethane resin are still not good enough, so that the ultraviolet resistance of the polyurethane resin is greatly reduced; moreover, some nanoparticles with ultraviolet resistance can affect the color of the material after being combined with polyurethane.
Therefore, it is a problem to be solved to find a substance or method which is more suitable for the uv-resistant nanoparticles of polyurethane and combines the uv-resistant nanoparticles of polyurethane with polyurethane resin more stably and uniformly.
Disclosure of Invention
The invention aims to provide polyurethane with ultraviolet resistance, and the polyurethane material has more lasting and stable ultraviolet resistance.
The above object of the present invention is achieved by the following technical solutions: a polyurethane with uvioresistant performance is prepared by taking triisopropyl borate, dihydric alcohol and trihydric alcohol as raw materials, adding a catalyst, controlling reaction parameters to prepare a chelating borate coupling agent containing a dihydroxyl functional group, modifying the surface of a nano rare earth oxide by utilizing the chelating borate coupling agent containing the dihydroxyl functional group to obtain a modified nano rare earth oxide, and carrying out in-situ polymerization by taking the modified nano rare earth oxide, polyisocyanate, a chain extender, polyester polyol or polyether polyol as raw materials to obtain the polyurethane with uvioresistant performance.
Further, the nano rare earth oxide is one or two of nano rare earth cerium oxide and nano rare earth lanthanum oxide.
Further, the catalyst is one or two of sodium methoxide, sodium ethoxide, sodium isopropoxide, sodium tert-butoxide, potassium methoxide, potassium ethoxide, potassium isopropoxide and potassium tert-butoxide.
Further, the molar ratio of the triisopropyl borate to the dihydric alcohol to the trihydric alcohol is 1:1-1.05: 1-1.05.
Further, the dihydric alcohol is one of ethylene glycol, propylene glycol and butanediol.
Further, the triol is one of glycerol and trimethylolpropane.
Further, the mass ratio of the nano rare earth oxide to the chelating borate coupling agent with the dihydroxyl functional group is 100: 0.1-5.
By adopting the technical scheme, 4f electrons of the nano rare earth oxide do not absorb visible light, but show excellent absorption capacity to ultraviolet light, and the nano rare earth oxide is selected to be combined with polyurethane, so that the finally obtained polyurethane material has good ultraviolet resistance, and the original color and luster of the polyurethane material cannot be influenced.
The method comprises the steps of synthesizing a chelating borate coupling agent containing a dihydroxyl functional group by utilizing the mutual reaction among triisopropyl borate, dihydric alcohol and trihydric alcohol, modifying and modifying the surface of a nano rare earth oxide by utilizing the chelating borate coupling agent containing the dihydroxyl functional group, and carrying out in-situ polymerization reaction on the modified nano rare earth oxide serving as a reaction monomer, polyester polyol or polyether polyol, polyisocyanate and a chain extender, so that the nano rare earth oxide is more stably and firmly locked in a polyurethane matrix, and the finally obtained polyurethane has more lasting and excellent ultraviolet resistance.
Another object of the present invention is to provide a method for preparing polyurethane having uv resistance, which has the advantages of convenient and simple operation.
The invention is realized by the following technical scheme that the preparation method of the polyurethane with the uvioresistant performance comprises the following steps:
s1, adding triisopropyl borate and a catalyst into a three-neck flask with a thermometer, a stirrer and a reflux condenser, heating to 80-130 ℃, dropwise adding dihydric alcohol under continuous stirring, heating and refluxing for 60-120 minutes, adding metered trihydric alcohol, continuously performing reflux reaction for 90-150 minutes at 130-180 ℃, and decompressing and steaming out isopropanol to obtain the chelating borate coupling agent containing the dihydroxyl functional group;
s2, drying the nano rare earth oxide at 105 ℃ for 1-4 hours, adding the nano rare earth oxide and the chelating type borate coupling agent containing the dihydroxyl functional group prepared by S1 into a high-speed mixer heated to 115-140 ℃ in proportion for reaction for 15-60 minutes, and cooling to obtain the modified nano rare earth oxide;
s3, heating, melting and uniformly mixing 100 parts by weight of dehydrated polyester polyol or polyether polyol, 0.1-5 parts by weight of modified nano rare earth oxide, 0.1-1 part by weight of antioxidant and 0.1-1 part by weight of lubricant to obtain a first mixture; and accurately adding the first mixture, 50-150 parts of polyisocyanate and 0.5-5 parts of chain extender into a 100 ℃ double-screw extrusion granulator through a metering pump, carrying out melt blending at 190-200 ℃, carrying out in-situ polymerization, then carrying out extrusion and bracing, and carrying out blow-drying and granulation to obtain the polyurethane with the uvioresistant performance.
Further, the polyester polyol is one or more of adipic acid polyester diol, polycarbonate diol, phthalic anhydride polyester diol, polycaprolactone diol, succinic acid polyester diol, glutaric acid polyester diol, azelaic acid polyester diol, dodecanedioic acid polyester diol, 1, 4-cyclohexanedicarboxylic acid polyester diol, dimer acid polyester diol, mixed diacid polyester diol, terephthalic acid polyester diol, polymer polyester diol, isophthalic acid polyester diol and trimellitic acid glycoside polyester polyol.
Further, the polyether polyol is one or more of polytetrahydrofuran diol, polypropylene oxide diol, tetrahydrofuran-propylene oxide copolymer diol, polypropylene oxide-ethylene oxide diol, polyethylene oxide diol, polytrimethylene ether diol, high-activity polyether diol, aniline polyether diol, phenol polyether diol, substituted aniline polyether diol, bisphenol A/ethylene oxide polyether diol, bisphenol A/propylene oxide polyether diol and propylene glycol block polyether.
Further, the polyisocyanate is 4,4' -diphenylmethane diisocyanate (MDI), Toluene Diisocyanate (TDI), Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI), Naphthalene Diisocyanate (NDI), p-phenylene diisocyanate (PPDI), dimethylbiphenyl diisocyanate (TODI), polyphenyl polymethylene polyisocyanate (PAPI), trimethyl-1, 6-hexamethylene diisocyanate (TMHDI), Xylylene Diisocyanate (XDI), tetramethylm-xylylene diisocyanate (TMXDI), 1, 4-cyclohexane diisocyanate (CHDI), methylcyclohexyl diisocyanate (HTDI), cyclohexanedimethylene diisocyanate (HXDI), norbornane diisocyanate (NBDI), dicyclohexylmethane diisocyanate (HMDI), hexamethylene diisocyanate (TMDI), TMD, One or more of Lysine Diisocyanate (LDI).
Further, the chain extender is one or more of ethylene glycol, 1, 4-butanediol, 1, 3-propanediol, ethanolamine and diethyl toluenediamine.
Further, the antioxidant is tris (2, 4-di-tert-butylphenyl) phosphite.
Further, the lubricant is ethylene bis-oleic acid amide.
In conclusion, the invention has the following beneficial effects:
1. the chelating borate coupling agent containing the dihydroxyl functional group modifies the nano rare earth oxide to obtain modified nano rare earth oxide, and then the modified nano rare earth oxide is used as a reaction monomer to carry out in-situ polymerization reaction with polyester polyol or polyether polyol, polyisocyanate and other substances, so that the combination of the nano rare earth oxide and a polyurethane matrix is more uniform, stable and firm, and the ultraviolet resistance of the finally obtained polyurethane material is more durable and excellent;
2. the nano rare earth cerium oxide is selected to be combined with the polyurethane, the nano rare earth cerium oxide not only has the excellent characteristics of no toxicity, stability and the like, but also has good ultraviolet shielding capability, and the original color of the polyurethane cannot be influenced by adding a small amount of the nano rare earth cerium oxide;
3. the chelating borate coupling agent containing the dihydroxyl functional group has good hydrolysis resistance due to the chelating group, can avoid the influence of moisture on a reaction system, and ensures the stability of the polyurethane material with the uvioresistant performance prepared by the method.
Detailed Description
The present invention will be described in further detail with reference to examples.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The first embodiment is as follows: a polyurethane with uvioresistant performance is prepared according to the following steps:
s1, adding 1.0mol of triisopropyl borate and 0.5g of sodium isopropoxide into a three-neck flask with a thermometer, a stirrer and a reflux condenser, heating to 100 ℃, dropwise adding 1.0mol of ethylene glycol under continuous stirring, heating and refluxing for 100 minutes, adding 1.0mol of trimethylolpropane, continuing reflux reaction for 130 minutes at 150 ℃, and distilling isopropanol under reduced pressure to obtain the chelating type borate coupling agent containing the dihydroxyl functional group.
S2, drying the nano rare earth cerium oxide at 105 ℃ for 2 hours, adding the nano rare earth cerium oxide and the chelating type borate coupling agent containing the dihydroxyl functional group prepared by S1 into a high-speed mixer heated to 120 ℃ to react for 30 minutes according to the mass ratio of 100:1, and cooling to obtain the modified nano rare earth cerium oxide.
S3, heating, melting and uniformly mixing 100 parts by weight of dehydrated polytetrahydrofuran diol (Mn is 1200), 0.5 part by weight of modified nano rare earth cerium oxide, 0.2 part by weight of tris (2, 4-di-tert-butylphenyl) phosphite and 0.1 part by weight of ethylene bis-oleamide to obtain a first mixture; and accurately adding the first mixture, 80 parts of isocyanate TDI and 1 part of 1, 4-butanediol into a 100 ℃ double-screw extrusion granulator through a metering pump respectively, carrying out melt blending at 195-200 ℃, carrying out in-situ polymerization, then carrying out extrusion and bracing, and carrying out blow-drying and granulation to obtain the polyurethane with the uvioresistant performance.
Example two: a polyurethane with uvioresistant performance is prepared according to the following steps:
s1, adding 1.0mol of triisopropyl borate and 0.5g of sodium isopropoxide into a three-neck flask with a thermometer, a stirrer and a reflux condenser, heating to 100 ℃, dropwise adding 1.0mol of ethylene glycol under continuous stirring, heating and refluxing for 100 minutes, adding 1.0mol of trimethylolpropane, continuing reflux reaction for 130 minutes at 150 ℃, and distilling isopropanol under reduced pressure to obtain the chelating type borate coupling agent containing the dihydroxyl functional group.
S2, drying the nano rare earth cerium oxide at 105 ℃ for 2 hours, adding the nano rare earth cerium oxide and the chelating type borate coupling agent containing the dihydroxyl functional group prepared by S1 into a high-speed mixer heated to 120 ℃ to react for 30 minutes according to the mass ratio of 100:1, and cooling to obtain the modified nano rare earth cerium oxide.
S3, heating, melting and uniformly mixing 100 parts by weight of dehydrated polytetrahydrofuran diol (Mn is 1200), 1.0 part by weight of modified nano rare earth cerium oxide, 0.2 part by weight of tris (2, 4-di-tert-butylphenyl) phosphite and 0.1 part by weight of ethylene bis-oleamide to obtain a first mixture; and accurately adding the first mixture, 80 parts of isocyanate TDI and 1 part of 1, 4-butanediol into a 100 ℃ double-screw extrusion granulator through a metering pump respectively, carrying out melt blending at 195-200 ℃, carrying out in-situ polymerization, then carrying out extrusion and bracing, and carrying out blow-drying and granulation to obtain the polyurethane with the uvioresistant performance.
Example three: a polyurethane with uvioresistant performance is prepared according to the following steps:
s1, adding 1.0mol of triisopropyl borate and 0.5g of sodium isopropoxide into a three-neck flask with a thermometer, a stirrer and a reflux condenser, heating to 100 ℃, dropwise adding 1.0mol of ethylene glycol under continuous stirring, heating and refluxing for 100 minutes, adding 1.0mol of trimethylolpropane, continuing reflux reaction for 130 minutes at 150 ℃, and distilling isopropanol under reduced pressure to obtain the chelating type borate coupling agent containing the dihydroxyl functional group.
S2, drying the nano rare earth cerium oxide at 105 ℃ for 2 hours, adding the nano rare earth cerium oxide and the chelating type borate coupling agent containing the dihydroxyl functional group prepared by S1 into a high-speed mixer heated to 120 ℃ to react for 30 minutes according to the mass ratio of 100:1, and cooling to obtain the modified nano rare earth cerium oxide.
S3, heating, melting and uniformly mixing 100 parts by weight of dehydrated polytetrahydrofuran diol (Mn is 1200), 2 parts by weight of modified nano rare earth cerium oxide, 0.2 part by weight of tris (2, 4-di-tert-butylphenyl) phosphite and 0.1 part by weight of ethylene bis-oleamide to obtain a first mixture; and accurately adding the first mixture, 80 parts of isocyanate TDI and 1 part of 1, 4-butanediol into a 100 ℃ double-screw extrusion granulator through a metering pump respectively, carrying out melt blending at 195-200 ℃, carrying out in-situ polymerization, then carrying out extrusion and bracing, and carrying out blow-drying and granulation to obtain the polyurethane with the uvioresistant performance.
Example four: a polyurethane with uvioresistant performance is prepared according to the following steps:
s1, adding 1.0mol of triisopropyl borate and 0.5g of sodium isopropoxide into a three-neck flask with a thermometer, a stirrer and a reflux condenser, heating to 100 ℃, dropwise adding 1.0mol of ethylene glycol under continuous stirring, heating and refluxing for 100 minutes, adding 1.0mol of trimethylolpropane, continuing reflux reaction for 130 minutes at 150 ℃, and distilling isopropanol under reduced pressure to obtain the chelating type borate coupling agent containing the dihydroxyl functional group.
S2, drying the nano rare earth cerium oxide at 105 ℃ for 2 hours, adding the nano rare earth cerium oxide and the chelating type borate coupling agent containing the dihydroxyl functional group prepared by S1 into a high-speed mixer heated to 120 ℃ to react for 30 minutes according to the mass ratio of 100:1, and cooling to obtain the modified nano rare earth cerium oxide.
S3, heating, melting and uniformly mixing 100 parts by weight of dehydrated polytetrahydrofuran diol (Mn is 1200), 3 parts by weight of modified nano rare earth cerium oxide, 0.2 part by weight of tris (2, 4-di-tert-butylphenyl) phosphite and 0.1 part by weight of ethylene bis-oleamide to obtain a first mixture; and accurately adding the first mixture, 80 parts of isocyanate TDI and 1 part of 1, 4-butanediol into a 100 ℃ double-screw extrusion granulator through a metering pump respectively, carrying out melt blending at 195-200 ℃, carrying out in-situ polymerization, then carrying out extrusion and bracing, and carrying out blow-drying and granulation to obtain the polyurethane with the uvioresistant performance.
Example five: a polyurethane with uvioresistant performance is prepared according to the following steps:
s1, adding 1.0mol of triisopropyl borate and 0.5g of sodium isopropoxide into a three-neck flask with a thermometer, a stirrer and a reflux condenser, heating to 100 ℃, dropwise adding 1.0mol of ethylene glycol under continuous stirring, heating and refluxing for 100 minutes, adding 1.0mol of trimethylolpropane, continuing reflux reaction for 130 minutes at 150 ℃, and distilling isopropanol under reduced pressure to obtain the chelating type borate coupling agent containing the dihydroxyl functional group.
S2, drying the nano rare earth cerium oxide at 105 ℃ for 2 hours, adding the nano rare earth cerium oxide and the chelating type borate coupling agent containing the dihydroxyl functional group prepared by S1 into a high-speed mixer heated to 120 ℃ to react for 30 minutes according to the mass ratio of 100:1, and cooling to obtain the modified nano rare earth cerium oxide.
S3, heating, melting and uniformly mixing 100 parts by weight of dehydrated polytetrahydrofuran diol (Mn is 1200), 4 parts by weight of modified nano rare earth cerium oxide, 0.2 part by weight of tris (2, 4-di-tert-butylphenyl) phosphite and 0.1 part by weight of ethylene bis-oleamide to obtain a first mixture; and accurately adding the first mixture, 80 parts of isocyanate TDI and 1 part of 1, 4-butanediol into a 100 ℃ double-screw extrusion granulator through a metering pump respectively, carrying out melt blending at 195-200 ℃, carrying out in-situ polymerization, then carrying out extrusion and bracing, and carrying out blow-drying and granulation to obtain the polyurethane with the uvioresistant performance.
Example six: a polyurethane with uvioresistant performance is prepared according to the following steps:
s1, adding 1.0mol of triisopropyl borate and 0.5g of sodium isopropoxide into a three-neck flask with a thermometer, a stirrer and a reflux condenser, heating to 100 ℃, dropwise adding 1.0mol of ethylene glycol under continuous stirring, heating and refluxing for 100 minutes, adding 1.0mol of trimethylolpropane, continuing reflux reaction for 130 minutes at 150 ℃, and distilling isopropanol under reduced pressure to obtain the chelating type borate coupling agent containing the dihydroxyl functional group.
S2, drying the nano rare earth cerium oxide at 105 ℃ for 2 hours, adding the nano rare earth cerium oxide and the chelating type borate coupling agent containing the dihydroxyl functional group prepared by S1 into a high-speed mixer heated to 120 ℃ to react for 30 minutes according to the mass ratio of 100:1, and cooling to obtain the modified nano rare earth cerium oxide.
S3, heating, melting and uniformly mixing 100 parts by weight of dehydrated polytetrahydrofuran diol (Mn is 1200), 5 parts by weight of modified nano rare earth cerium oxide, 0.2 part by weight of tris (2, 4-di-tert-butylphenyl) phosphite and 0.1 part by weight of ethylene bis-oleamide to obtain a first mixture; and accurately adding the first mixture, 80 parts of isocyanate TDI and 1 part of 1, 4-butanediol into a 100 ℃ double-screw extrusion granulator through a metering pump respectively, carrying out melt blending at 195-200 ℃, carrying out in-situ polymerization, then carrying out extrusion and bracing, and carrying out blow-drying and granulation to obtain the polyurethane with the uvioresistant performance.
Comparative example one: heating, melting and uniformly mixing 100 parts by weight of dehydrated polytetrahydrofuran diol (Mn is 1200), 0.2 part of tris (2, 4-di-tert-butylphenyl) phosphite and 0.1 part of ethylene bisoleic amide to obtain a mixture; and accurately adding the mixture, 80 parts of isocyanate TDI and 1 part of 1, 4-butanediol into a 100 ℃ double-screw extrusion granulator through a metering pump respectively, carrying out melt blending at 195-200 ℃, carrying out in-situ polymerization, then carrying out extrusion and bracing, and carrying out blow-drying and granulation to obtain the polyurethane.
Comparative example two: heating, melting and uniformly mixing 100 parts by weight of dehydrated polytetrahydrofuran diol (Mn is 1200), 2 parts by weight of unmodified nano rare earth cerium oxide, 0.2 part by weight of tris (2, 4-di-tert-butylphenyl) phosphite and 0.1 part by weight of ethylene bis-oleamide to obtain a mixture; and accurately adding the mixture, 80 parts of isocyanate TDI and 1 part of 1, 4-butanediol into a 100 ℃ double-screw extrusion granulator through a metering pump respectively, carrying out melt blending at 195-200 ℃, carrying out in-situ polymerization, then carrying out extrusion and bracing, and carrying out blow-drying and granulation to obtain the polyurethane.
Comparative example three: heating, melting and uniformly mixing 100 parts of dehydrated polytetrahydrofuran diol (Mn is 1200), 2 parts of modified nano rare earth cerium oxide modified by AEO-9, 0.2 part of tris (2, 4-di-tert-butylphenyl) phosphite and 0.1 part of ethylene bis-oleic acid amide in parts by weight to obtain a mixture; and accurately adding the mixture, 80 parts of isocyanate TDI and 1 part of 1, 4-butanediol into a 100 ℃ double-screw extrusion granulator through a metering pump respectively, carrying out melt blending at 195-200 ℃, carrying out in-situ polymerization, then carrying out extrusion and bracing, and carrying out blow-drying and granulation to obtain the polyurethane.
Tensile properties of the products obtained in examples one to six, comparative example one, comparative example two and comparative example three were measured before and after 96 hours of uv irradiation, and table 1 was obtained.
TABLE 1 tensile Properties before and after 96h UV irradiation
Comparing the first to sixth embodiments, the second comparative example, and the third comparative example with the first comparative example, it is found that the ultraviolet resistance of the polyurethane can be effectively improved by adding the nano rare earth cerium oxide.
Comparing the third example with the second comparative example, it is found that the polyurethane material obtained by modifying the nano rare earth cerium oxide with the self-made chelating borate coupling agent containing the dihydroxy functional group and performing in-situ polymerization with other reaction monomers for preparing polyurethane as the reaction monomer has better ultraviolet resistance compared with the polyurethane material obtained by directly blending the unmodified nano rare earth cerium oxide with other reaction monomers for preparing polyurethane.
Comparing the third example with the third comparative example, it is found that the ultraviolet resistance effect of the polyurethane material obtained by modifying the nano rare earth cerium oxide with the self-made chelating borate coupling agent containing the dihydroxyl functional group and performing in-situ polymerization with other reaction monomers for preparing polyurethane by using the nano rare earth cerium oxide as the reaction monomer is better than that of the polyurethane material prepared by modifying the nano rare earth cerium oxide with the common surfactant.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (11)
1. The polyurethane with the uvioresistant performance is characterized in that triisopropyl borate, dihydric alcohol and trihydric alcohol are used as raw materials, a catalyst is added, reaction parameters are controlled to prepare a chelating borate coupling agent containing a dihydroxy functional group, then the chelating borate coupling agent containing the dihydroxy functional group is used for modifying the surface of a nano rare earth oxide to obtain a modified nano rare earth oxide, and the modified nano rare earth oxide, polyisocyanate, a chain extender, polyester polyol or polyether polyol are used as raw materials to carry out in-situ polymerization to obtain the polyurethane with the uvioresistant performance.
2. The polyurethane with ultraviolet resistance of claim 1, wherein the nano rare earth oxide is one or both of nano rare earth cerium oxide and nano rare earth lanthanum oxide.
3. The polyurethane with ultraviolet resistance of claim 1, wherein the catalyst is one or two of sodium methoxide, sodium ethoxide, sodium isopropoxide, sodium tert-butoxide, potassium methoxide, potassium ethoxide, potassium isopropoxide and potassium tert-butoxide.
4. The polyurethane with ultraviolet resistance of claim 1, wherein the molar ratio of the triisopropyl borate to the dihydric alcohol to the trihydric alcohol is 1:1-1.05: 1-1.05.
5. The polyurethane of claim 1, wherein the diol is one of ethylene glycol, propylene glycol, and butylene glycol.
6. The polyurethane of claim 1, wherein the triol is one of glycerol and trimethylolpropane.
7. The polyurethane with the uvioresistant performance according to claim 1, wherein the mass ratio of the nano rare earth oxide to the chelating borate coupling agent with the dihydroxyl functional group is 100: 0.1-5.
8. A method for preparing polyurethane with ultraviolet resistance according to claim 1, which is characterized by comprising the following steps:
s1, adding triisopropyl borate and a catalyst into a three-neck flask with a thermometer, a stirrer and a reflux condenser, heating to 80-130 ℃, dropwise adding dihydric alcohol under continuous stirring, heating and refluxing for 60-120 minutes, adding metered trihydric alcohol, continuously performing reflux reaction for 90-150 minutes at 130-180 ℃, and decompressing and steaming out isopropanol to obtain the chelating borate coupling agent containing the dihydroxyl functional group;
s2, drying the nano rare earth oxide at 105 ℃ for 1-4 hours, adding the nano rare earth oxide and the chelating type borate coupling agent containing the dihydroxyl functional group prepared by S1 into a high-speed mixer heated to 115-140 ℃ in proportion for reaction for 15-60 minutes, and cooling to obtain the modified nano rare earth oxide;
s3, heating, melting and uniformly mixing 100 parts by weight of dehydrated polyester polyol or polyether polyol, 0.1-5 parts by weight of modified nano rare earth oxide, 0.1-1 part by weight of antioxidant and 0.1-1 part by weight of lubricant to obtain a first mixture; and accurately adding the first mixture, 50-150 parts of polyisocyanate and 0.5-5 parts of chain extender into a 100 ℃ double-screw extrusion granulator through a metering pump, carrying out melt blending at 190-200 ℃, carrying out in-situ polymerization, then carrying out extrusion and bracing, and carrying out blow-drying and granulation to obtain the polyurethane with the uvioresistant performance.
9. The method for preparing polyurethane with ultraviolet resistance according to claim 8, wherein the polyester polyol is one or more of adipic acid polyester diol, polycarbonate diol, phthalic anhydride polyester diol, polycaprolactone diol, succinic acid polyester diol, glutaric acid polyester diol, azelaic acid polyester diol, dodecanedioic acid polyester diol, 1, 4-cyclohexanedicarboxylic acid polyester diol, dimer acid polyester diol, mixed diacid polyester diol, terephthalic acid polyester diol, polymer polyester diol, isophthalic acid polyester diol, trimellitic acid glycoside polyester polyol.
10. The method for preparing polyurethane with ultraviolet resistance according to claim 8, wherein the polyether polyol is one or more of polytetrahydrofuran diol, polypropylene oxide diol, tetrahydrofuran-propylene oxide copolymer diol, polypropylene oxide-ethylene oxide diol, polyethylene oxide diol, polytrimethylene ether diol, high activity polyether diol, aniline polyether diol, phenol polyether diol, substituted aniline polyether diol, bisphenol A/ethylene oxide polyether diol, bisphenol A/propylene oxide polyether diol, and propylene glycol block polyether.
11. The method of claim 8, wherein the polyisocyanate is 4,4' -diphenylmethane diisocyanate (MDI), Toluene Diisocyanate (TDI), Hexamethylene Diisocyanate (HDI), isophorone diisocyanate, Naphthalene Diisocyanate (NDI), p-phenylene diisocyanate (PPDI), dimethylbiphenyl diisocyanate (TODI), polyphenyl polymethylene polyisocyanate (PAPI), trimethyl-1, 6-hexamethylene diisocyanate (TMHDI), Xylylene Diisocyanate (XDI), tetramethylm-xylylene diisocyanate (TMXDI), 1, 4-cyclohexane diisocyanate (CHDI), methylcyclohexyl diisocyanate (HTDI), cyclohexanedimethylene diisocyanate (HXDI), norbornane diisocyanate (NBDI), or mixtures thereof, One or more of dicyclohexyl methane diisocyanate (HMDI), hexamethylene diisocyanate (TMDI) and Lysine Diisocyanate (LDI).
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| PCT/CN2021/139968 WO2022242167A1 (en) | 2021-05-17 | 2021-12-21 | Polyurethane having anti-ultraviolet performance and preparation method therefor |
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| WO2022242167A1 (en) * | 2021-05-17 | 2022-11-24 | 福建师范大学泉港石化研究院 | Polyurethane having anti-ultraviolet performance and preparation method therefor |
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