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CN-121991314-A - Polyurethane resin composition and preparation method thereof

CN121991314ACN 121991314 ACN121991314 ACN 121991314ACN-121991314-A

Abstract

The invention discloses a polyurethane resin composition and a preparation method thereof, wherein the polyurethane resin composition comprises, by weight, 1:30-50 parts of polyether polyol, 2:10-30 parts of polyether polyol, 3:5-15 parts of polyether polyol, 10-30 parts of fluorine-containing phthalic anhydride polyester polyol, 5-10 parts of chain extender, 1-10 parts of cross-linking agent, 0.5-2 parts of foam stabilizer, 0.5-1.5 parts of composite catalyst, 0.1-2 parts of water, 0.5-3 parts of ultraviolet-resistant aging agent, 5-10 parts of flame retardant, 0-5 parts of color paste and 0.5 parts of B component comprising polymethylene polyphenyl polyisocyanate. The polyurethane resin composition has the advantages of high reaction activity and short demolding time, and the polyurethane material prepared from the polyurethane resin composition has the advantages of high surface quality, high mechanical property, high flame retardance and high temperature resistance, and solves the technical problems that the existing polyurethane product cannot be simultaneously demolded quickly and the high performance cannot be met.

Inventors

  • WEN RONGZHENG
  • DU JUNCHAO
  • SUN HAIOU
  • YAO ZHE
  • HE YANNAN
  • LUO LU
  • SHEN SHAOWEI

Assignees

  • 黎明化工研究设计院有限责任公司

Dates

Publication Date
20260508
Application Date
20251118

Claims (10)

  1. 1.A polyurethane resin composition is composed of a component A and a component B: The component A comprises the following components in parts by weight: 1 to 50 parts of polyether polyol, 2 to 10 to 30 parts of polyether polyol, 3 to 5 to 15 parts of polyether polyol, 10 to 30 parts of fluorine-containing phthalic anhydride polyester polyol, 5 to 10 parts of chain extender, 1 to 10 parts of cross-linking agent, 0.5 to 2 parts of foam stabilizer, 0.5 to 1.5 parts of composite catalyst, 0.1 to 2 parts of water, 0.5 to 3 parts of ultraviolet-resistant aging agent, 5 to 10 parts of flame retardant and 0 to 5 parts of color paste; The polyether polyol 1 is a functional degree 5, sucrose and glycerol are used as co-initiators, a polymerization unit is propylene oxide, and the hydroxyl value is 400-500 mg KOH/g; The polyether polyol 2 is a trimethylolpropane initiator with a functionality of 3, a polymerization unit is ethylene oxide, and a hydroxyl value is 200-400 mg KOH/g; the polyether polyol 3 is a functionality 3, glycerol is used as an initiator, a polymerization unit is ethylene oxide-propylene oxide, the content of primary hydroxyl is more than or equal to 85%, and the hydroxyl value is 20-50 mg KOH/g; The fluorine-containing phthalic anhydride polyester polyol is prepared by reacting fluorine-containing phthalic anhydride with micromolecular polyol, and the hydroxyl value is 200-450 mg KOH/g; the component B comprises polymethylene polyphenyl polyisocyanates.
  2. 2. The polyurethane resin composition according to claim 1, wherein the fluorine-containing phthalic anhydride is one or more of 4-fluorophthalic anhydride, tetrafluorophthalic anhydride, 3, 6-difluorophthalic anhydride, and hexafluorodianhydride.
  3. 3. The polyurethane resin composition according to claim 1, wherein the small molecule polyol is one or more of ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, hexylene glycol, methylpropylene glycol, methylpentanediol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, cyclohexanedimethanol, glycerol, pentaerythritol.
  4. 4. The polyurethane resin composition according to claim 1, wherein the chain extender is an alcohol chain extender and/or an amine chain extender, the alcohol chain extender is preferably one or more of ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, neopentyl glycol, 1, 4-cyclohexane-dimethanol, 1, 4-butanediol, methyl propylene glycol, and the amine chain extender is selected from one or more of 4,4' -bis-sec-butylaminodiphenyl methane, diethyl toluene diamine, m-phenylene diamine, diethanolamine.
  5. 5. The polyurethane resin composition according to claim 1, wherein the crosslinking agent is one or more of glycerin, triethanolamine, pentaerythritol, trimethylolethane, trimethylolpropane, and triethylol isocyanurate.
  6. 6. The polyurethane resin composition according to claim 1, wherein the composite catalyst is a mixture of a foaming catalyst and a gel catalyst.
  7. 7. The polyurethane resin composition according to claim 6, wherein the foaming catalyst is an amine catalyst, preferably one or more of triethylamine, triethylenediamine, tributylamine, N-methylmorpholine, N-ethylmorpholine, N, N, N ', N ' -tetramethylethylenediamine, pentamethyldiethylenetriamine, pentamethyldipropylenetriamine, bis- (dimethylaminoalkyl) piperazine, N, N ' -dimethylbenzylamine, N, N-dimethylcyclohexylamine, N, N-diethylbenzylamine, N, N, N ', N ' -tetramethyl-1, 3-butanediamine, N, N-dimethyl-B-phenyl-ethylamine, bis- (dimethylaminopropyl) urea, bis- (dimethylaminopropyl) amine, 1, 2-dimethylimidazole, 2-methylimidazole, and the gel catalyst is an organometallic catalyst, preferably an organometallic compound of tin, titanium, bismuth.
  8. 8. The polyurethane resin composition according to claim 1, wherein the polymethylene polyphenyl polyisocyanate is selected from one or a mixture of 44V20L from bayer company, M20A from basf, MR200 of japan polyurethane, and 5005 from hensi michaux company.
  9. 9. The polyurethane resin composition according to claim 1, wherein the weight ratio of the component a to the component B is 1:1.1 to 1.4, preferably 1:1.1 to 1.3.
  10. 10. A method for preparing the polyurethane resin composition according to any one of claims 1 to 9, which is used for preparing polyurethane materials by a Reaction Injection Molding (RIM) process.

Description

Polyurethane resin composition and preparation method thereof Technical Field The invention relates to the field of polyurethane, in particular to a polyurethane resin composition for a reaction injection molding process. Background Polyurethane reaction injection molding (Polyurethane-Reaction Injection Molding) is called PU-RIM for short, and is a new technology applied to the production of rapid molded products. The double-component polyurethane material with low viscosity and high reactivity is mixed through high-speed collision and then injected into a mold cavity to quickly perform polymerization reaction, so that a product with the shape of the mold cavity is prepared. The process has the characteristics of high material mixing efficiency, good fluidity, adjustable material performance, short production period and low cost. With the continuous updating and upgrading of products and the continuous improvement of the requirements of host factories on high performance of materials, for some products such as thin-wall products, shells, wood-like materials and the like, the performance of the conventional polyurethane reaction injection molding products cannot meet the use requirements because the strength and toughness of the products are not high. In order to improve the strength of the material, reinforcing fillers such as glass fibers, carbon fibers, calcium carbonate and the like are generally added, but the reinforcing fillers can reduce the in-mold flow of polyurethane stock solution and easily cause defects of the product. Therefore, it is a problem to be solved at present to provide a polyurethane rigid foam having high mechanical strength and high surface quality. Chinese patent CN 109294215A discloses a polyurethane resin composition and use and a high strength high modulus polyurethane material. The epoxy functionalized polyphenyl ether microsphere comprises an oligomer polyol, a small molecular chain extender and a compatilizer as the component A, an isocyanate component as the component B and an epoxy functionalized polyphenyl ether microsphere particle as the component C. And (3) stirring and mixing A, B and the C component, and then performing heat curing to prepare the polyurethane material with high strength and high modulus. The method needs to prepare the polyphenyl ether microsphere particles with the surface epoxy functionalization, has complex process, environment-friendly solvent used in the process, uneven dispersion in the polyurethane material doped in the later period, high molding temperature, long demolding time, high energy consumption and cost, no flame retardant added, and poor flame retardance of the material. Chinese patent CN 102504182a discloses a process for preparing rigid polyurethane. The patent adopts polymer polyol with the functionality of 3, prepares prepolymer by reacting with diisocyanate at a specific temperature and under a specific condition, and adds an amine chain extender for vulcanization treatment to form a macromolecular structure with high-temperature stability, so that the high-temperature resistance of the material is improved, but specific requirements on the strength, the modulus and other properties of the material are not provided. The method needs to prepare the polyurethane prepolymer, has high energy consumption and cost, high raw material viscosity and inconvenient use, and the preparation method of the later-stage material is complex, long in demolding time and low in production efficiency. Chinese patent CN 118702906A discloses a polyether polyol for polyurethane wood-like material and its preparation method. The fluorine-containing polyether polyol is adopted to improve the surface state of the wood-like material, reduce defects such as needle eye bubbles and the like, and improve the strength and the mold release of the material to a certain extent. The material prepared by the method has the advantages of general strength, unobvious performance improvement, long curing time of the material and influence on production efficiency because no chain extension cross-linking agent is added. Chinese patent CN 111499828a discloses a resin composition for low-density high-flame-retardant polyurethane material and its application. The flame-retardant polyether ester polyol with a melamine structure is autonomously synthesized to be synergistic with a flame retardant to prepare a low-density high-flame-retardance polyurethane product. The method adopts a long glass fiber reinforced polyurethane process, the used glass fiber can obstruct the flow of materials and the overflow of foaming gas in a die, bubbles are easily formed on the surface of a product or the material is lacked on the inner surface of the product, and the mechanical property and the temperature resistance of the material are general and can not meet the use requirement of a high-strength scene of the material. Disclosure of Invention Aiming at the new requirements of the PU-RIM a