WO2021212358A1 - Hot-melt reaction type polyurethane material, preparation method therefor and use thereof - Google Patents

Hot-melt reaction type polyurethane material, preparation method therefor and use thereof Download PDF

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Publication number
WO2021212358A1
WO2021212358A1 PCT/CN2020/086090 CN2020086090W WO2021212358A1 WO 2021212358 A1 WO2021212358 A1 WO 2021212358A1 CN 2020086090 W CN2020086090 W CN 2020086090W WO 2021212358 A1 WO2021212358 A1 WO 2021212358A1
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WIPO (PCT)
Prior art keywords
hot
polyurethane material
parts
reactive polyurethane
melt
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PCT/CN2020/086090
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French (fr)
Chinese (zh)
Inventor
邹美帅
李晓东
高明
郭晓燕
王硕
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北京理工大学
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Priority to PCT/CN2020/086090 priority Critical patent/WO2021212358A1/en
Publication of WO2021212358A1 publication Critical patent/WO2021212358A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • 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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • 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
    • 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/092—Polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L57/00—Compositions of unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C08L57/02—Copolymers of mineral oil hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/08—Polyurethanes from polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L93/00—Compositions of natural resins; Compositions of derivatives thereof
    • C08L93/04—Rosin

Definitions

  • the invention relates to the technical field of polyurethane materials, in particular to a hot-melt reaction type polyurethane material and a preparation method and application thereof.
  • 3D printing technology is a technology that is based on digital model files and uses bondable materials such as powdered metals or plastics to generate three-dimensional entities by adding materials layer by layer by layered processing and superimposed forming.
  • traditional CNC manufacturing generally uses cutting, grinding, corrosion, melting and other methods on the basis of raw materials to remove excess parts to obtain parts, and then use assembling, welding, etc. The method is combined into the final product; while the 3D printing technology directly decomposes the three-dimensional entity into several two-dimensional planes based on the computer graphics data, and then generates the object of the desired shape by adding the material layer by layer, so it is also called “increase “Material Manufacturing” (AM, Additive Manufacturing) technology.
  • 3D printing technology does not require complex molding processes, original embryos and molds, or a lot of manpower in the manufacturing process, thus simplifying the product manufacturing process, shortening the product development cycle, improving production efficiency and reducing Cost makes product manufacturing more intelligent, precise and efficient.
  • 3D printing technology includes fused deposition modeling technology (FMD), selective laser sintering technology (SLS), light curing technology (SLA), layered solid manufacturing technology (LOM) and digital light processing technology (DLP).
  • FMD fused deposition modeling technology
  • SLS selective laser sintering technology
  • SLA light curing technology
  • LOM layered solid manufacturing technology
  • DLP digital light processing technology
  • FDM has become the most promising process in 3D printing technology due to its advantages in molding materials and cost prices.
  • the raw materials used in FDM are usually thermoplastic polymer materials, including acrylonitrile-butadiene-styrene copolymer (ABS), polylactic acid (PLA), polycarbonate (PC), polyphenylsulfone (PPSF), etc. These materials more or less have problems such as large shrinkage, poor toughness, and poor mechanical properties. Because FDM uses layer-by-layer printing, the problems of FDM printing materials will directly cause the products obtained by the FDM process to have cross-sections and verticals. The technical defect of the direction strength is less.
  • the present invention provides a hot-melt reactive polyurethane material and its preparation method and application.
  • the hot-melt reactive polyurethane material provided by the present invention is used as a 3D printing material, and can solve the technical problem of low cross-section and vertical direction strength in products obtained by the FDM process.
  • the present invention provides a hot-melt reactive polyurethane material, which is prepared by polymerization reaction of raw materials including the following parts by mass:
  • the hot-melt reactive polyurethane material is prepared by polymerization reaction of raw materials including the following parts by mass:
  • the isocyanate includes one or more of diphenylmethane-4,4'-diisocyanate, liquefied MDI and polymethylene polyphenyl polyisocyanate.
  • the polyester polyol preferably includes a crystalline polyester polyol and/or an amorphous polyester polyol.
  • the tackifying resin includes one or more of terpene resin, hydrogenated petroleum resin, rosin resin, and terpene phenol resin.
  • the catalyst preferably includes one or more of stannous octyl ester, dibutyl tin dilaurate, dimorpholine diethyl ether and triethylene diamine.
  • the acid stabilizer includes one or more of phosphoric acid, benzoic acid and citric acid.
  • the viscosity of the hot-melt reactive polyurethane material is 5000-25000 cps, and the NCO content is 0.01-2.0%.
  • the raw material further includes one or more of polyether polyol, chain extender, antioxidant, and ultraviolet absorber.
  • the present invention also provides a preparation method of the hot-melt reactive polyurethane material according to the above technical scheme, which includes the following steps:
  • the temperature of the pre-polymerization reaction is 80-90°C, and the time is 0.5-10h.
  • the temperature of the polymerization reaction is 80-90°C, and the time is 0.5-10h.
  • the step (1) before drying further includes adding a polyether polyol and/or a chain extender.
  • the step (3) also includes adding antioxidants and/or ultraviolet absorbers when mixing.
  • the present invention also provides the application of the hot-melt reactive polyurethane material described in the above technical solution or the hot-melt reactive polyurethane material prepared by the preparation method described in the above technical solution in 3D printing.
  • the hot-melt reactive polyurethane material provided by the present invention is prepared by polymerization reaction of raw materials including the following parts by mass: 10-30 parts of isocyanate, 30-70 parts of polyester polyol, 10-25 parts of acrylic resin, and tackifying resin 10-25 parts, 0.01-1 part of catalyst and 0.01-1 part of acid stabilizer.
  • the isocyanate can polymerize with the polyester polyol to form a polyurethane polymer with NCO active group-terminated, and the symmetrical structure of the isocyanate can promote the crystallization of the polyurethane, increase the crystallinity of the polymer, and then improve the polyurethane material
  • the initial adhesion performance improves the initial adhesion between the cross-section layers of the prepared polyurethane material during the 3D printing process, and shortens the open time.
  • the ester polar group and the tackifying resin contained in the acrylic resin are used to improve the processing performance and bonding strength of the polyurethane material.
  • the addition of an acid stabilizer in the polymerization reaction process of the present invention can not only prevent the formation of gel between the isocyanate and the polyester polyol during the reaction, but also avoid the increase in the viscosity of the polyurethane material due to repeated heating during use.
  • the hot-melt reactive polyurethane material prepared by the invention has the characteristics of NCO active group end-capping, resistance to cracking, low shrinkage, good toughness, excellent mechanical properties and good weather resistance, and can be used as a 3D printing material to enhance 3D printing products
  • the lateral cross-sectional adhesion force solves the technical problem of low cross-section and vertical strength in the products obtained by the FDM process.
  • the preparation method provided by the invention has simple process, easy control of conditions, and easy realization of automatic production.
  • the present invention provides a hot-melt reactive polyurethane material, which is prepared by polymerization reaction of raw materials including the following parts by mass:
  • the raw materials used are all conventional commercial products in the field.
  • the hot-melt reactive polyurethane material provided by the present invention includes 10-30 parts of isocyanate, preferably 10-20 parts, more preferably 15 parts.
  • the isocyanate preferably includes one or more of diphenylmethane-4,4'-diisocyanate, liquefied MDI and polymethylene polyphenyl polyisocyanate.
  • the symmetrical structure of the isocyanate makes the polyurethane molecular structure regular and orderly. After the polymerization reaction with the polyester polyol, it can promote the crystallization of the polymerization reaction product, increase the crystallinity of the polymerization reaction product, and thereby increase the initial adhesion of the polyurethane material.
  • the performance of the polyurethane material in the 3D printing process improves the initial adhesion between the cross-section layers and shortens the open time.
  • the hot-melt reactive polyurethane material provided by the present invention includes 30-70 parts of polyester polyol, preferably 40-60 parts, more preferably 50 parts.
  • the polyester polyol preferably includes crystalline polyester polyol and/or amorphous polyester polyol; the crystalline polyester polyol preferably includes Evonik Degussa dynacoll 7360, dynacoll 7380, dynacoll 7381, dynacoll 7362 One or more of dynacoll 7365, dynacoll 7361, dynacoll 7330 and dynacoll 7320; the amorphous polyester polyol preferably includes Evonik Degussa dynacoll 7130, dynacoll 7140, dynacoll 7150, dynacoll 7131, dynacoll 7190, dynacoll 7210, dynacoll 7230 and one of Or multiple.
  • the crystalline polyester polyol can increase the crystallinity of the polyurethane prepolymer, and its crystallinity determines the initial adhesion performance of the polyurethane material, and the high crystallinity prepolymer exhibits better initial adhesion performance. Improve the initial adhesion between the cross-section layers of the 3D printing material products and shorten the opening time.
  • the liquid amorphous polyester polyol can improve the wettability and bonding performance of the polyurethane material, thereby increasing the initial adhesion between the cross-section layers of the 3D printing material product.
  • the hot-melt reactive polyurethane material provided by the present invention includes 10-25 parts of acrylic resin, preferably 15-20 parts, more preferably 18 parts.
  • the acrylic resin preferably includes Elvacite 4026, Elvacite 2044, Elvacite 2013, Elvacite 2016, Degussa DEGALAN PQ611N, DSM NeoCryl B-725, NeoCryl B-722 and NeoCryl B-804 One or more of.
  • the ester-based polar group contained in the acrylic resin, and the addition of the acrylic resin during the polymerization reaction can significantly improve the initial adhesion, surface gloss, and weather resistance to physical and chemical properties of the polyurethane material. Thermal decomposition temperature improves its thermoplastic properties.
  • the hot-melt reactive polyurethane material provided by the present invention includes 10-25 parts of tackifying resin, preferably 15-20 parts, more preferably 18 parts.
  • the tackifying resin preferably includes one or more of terpene resin, hydrogenated petroleum resin, rosin resin and terpene phenol resin; the terpene resin preferably includes T-80, T-90, One or more of T-100, T-110 and T-120; the hydrogenated petroleum resin preferably includes C5 and/or C9.
  • the tackifying resin can reduce the melt viscosity of the polyurethane material, improve the operation performance, and increase the initial bonding strength and the final bonding strength.
  • the hot melt reactive polyurethane material provided by the present invention includes 0.01 to 1 part of the catalyst, preferably 0.2 to 0.8 part, more preferably 0.4 to 0.6 part.
  • the catalyst preferably includes one or more of stannous octyl ester, dibutyl tin dilaurate, dimorpholine diethyl ether and triethylene diamine.
  • the catalyst can promote the further polymerization reaction of the pre-polymerization reaction product, and can promote the curing of the 3D printed product in the later stage of the prepared hot-melt reactive polyurethane material.
  • the hot melt reactive polyurethane material provided by the present invention includes 0.01 to 1 part of the acid stabilizer, preferably 0.2 to 0.8 part, more preferably 0.4 to 0.6 part.
  • the acid stabilizer preferably includes one or more of phosphoric acid, benzoic acid and citric acid.
  • the acid stabilizer can make the polyurethane material more stable during the preparation and use process, not only can prevent the isocyanate and polyester polyol from generating gel during the reaction, but can also avoid repeated heating during use. Increase the viscosity of hot melt reactive polyurethane materials
  • the hot-melt reactive polyurethane material is a white or light yellow solid.
  • the viscosity of the hot-melt reactive polyurethane material is preferably 5000-25000 cps, more preferably 8000-15000 cps;
  • the NCO content of the hot melt reactive polyurethane material is preferably 0.01 to 2.0%, more preferably 0.1 to 1.5%.
  • the raw material preferably further includes one or more of polyether polyol, chain extender, antioxidant, and ultraviolet absorber.
  • the mass of the polyether polyol preferably accounts for 0-20% of the total mass of the isocyanate, polyester polyol, acrylic resin, tackifying resin, catalyst and acid stabilizer (hereinafter referred to as raw material) , More preferably 5 to 15%, more preferably 8 to 12%.
  • the polyether polyol preferably includes one or more of TMN-400, TMN-700, TMN-1000, TMD1000, TMD3000, TMD-5000, GEP-330N, DL-400 and DL-1000 kind.
  • the addition of polyether polyol can improve the hydrolysis resistance of the hot-melt reactive polyurethane material.
  • the mass of the chain extender preferably accounts for 0 to 5% of the raw material, and more preferably 2 to 4%.
  • the chain extender preferably includes trimethylolpropane, glycerin, dipropylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol One or more of alcohol and 3,3'-dichloro-4,4'-diaminodiphenylmethane.
  • the addition of a chain extender can improve the heat resistance and cohesion of the hot-melt reactive polyurethane material.
  • the weight of the antioxidant preferably accounts for 0 to 2% of the raw material, and more preferably 0.5 to 1.5%.
  • the antioxidant preferably includes 2,6-di-tert-butyl-p-cresol, triethylene glycol bis[ ⁇ -(3-tert-butyl-4-hydroxy-5-methylphenyl ) Propionate), 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) 1,3,5-triazine-2,4,6-( 1H,3H,5H)-trione, 3,9-bis[1,1-dimethyl-2-[(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy] Ethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane, tetra[ ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)]pentaerythritol
  • the mass of the ultraviolet absorber preferably accounts for 0-2% of the raw material, and more preferably 0.5-1.5%.
  • the ultraviolet absorber preferably includes 2-(3,5-di-tert-butyl-2-hydroxyphenyl)benzotriazole, 2-(4,6-bis(2,4-dimethyl Phenyl)-1,3,5-triazin-2-yl)-5-octyloxyphenol, N-(2-ethoxyphenyl)-N'-(4-ethylphenyl)- Among oxamide, 2-(2H-benzotriazol-2-yl)-4,6-di-tert-amylphenol and 2-(2'hydroxy-5'-methylphenyl)benzotriazole One or more.
  • the addition of antioxidants and ultraviolet absorbers can improve the heat resistance and oxidation resistance and yellowing resistance of the hot-melt reactive polyurethane material for 3D printing.
  • the present invention also provides a method for preparing the hot-melt reactive polyurethane material described in the above technical scheme, which includes the following steps:
  • polyester polyol, acrylic resin, tackifying resin and acid stabilizer are mixed and dried to obtain a dry mixture.
  • the mixing sequence of the polyester polyol, acrylic resin, tackifying resin and acid stabilizer is not particularly limited, and any mixing sequence can be adopted.
  • the mixing method is preferably stirring.
  • the mixing is preferably carried out in a reactor.
  • the present invention preferably adds polyether polyol and/or chain extender when the polyester polyol, acrylic resin, tackifying resin and acid stabilizer are mixed.
  • the drying method is preferably vacuum dehydration, the vacuum degree of the vacuum dehydration is preferably ⁇ -0.095MPa; the vacuum dehydration time is preferably 2-10h; the vacuum dehydration temperature is preferably 110- 150°C, more preferably 120 to 140°C.
  • the present invention does not specifically limit the heating rate to the vacuum dehydration temperature, and the heating rate well known to those skilled in the art can be used.
  • the present invention preferably fills the obtained dried product with nitrogen to release the vacuum to obtain the dried mixture.
  • the drying and nitrogen filling to release the vacuum are preferably carried out under constant temperature conditions.
  • the dry mixture and the isocyanate are mixed under a protective atmosphere to perform a pre-polymerization reaction to obtain a pre-polymerization reaction product.
  • the protective atmosphere is preferably nitrogen.
  • the present invention does not specifically limit the cooling rate from the temperature to the prepolymerization reaction temperature, and the cooling rate well known to those skilled in the art can be used.
  • the mixing method is preferably stirring. In the present invention, there is no special limitation on the stirring time and speed, as long as the raw materials can be mixed uniformly.
  • the temperature of the pre-polymerization reaction is preferably 80-90°C, more preferably 83-87°C; the time of the pre-polymerization reaction is preferably 0.5-10h, more preferably 2-8h.
  • the present invention mixes the pre-polymerization reaction product and the catalyst under a protective atmosphere, performs polymerization reaction, and then defoams in a vacuum to obtain the hot-melt reaction type polyurethane material.
  • an antioxidant and/or an ultraviolet absorber when the prepolymerization reaction product and the catalyst are mixed.
  • the protective atmosphere is preferably nitrogen.
  • the mixing method is preferably stirring. In the present invention, there is no special limitation on the stirring time and speed, as long as the raw materials can be mixed uniformly.
  • the temperature of the polymerization reaction is preferably 80-90°C, more preferably 83-87°C; the time of the polymerization reaction is preferably 0.5-10h, more preferably 2-8h.
  • the present invention does not specifically limit the heating rate to the heating temperature, and the heating rate well known to those skilled in the art can be used.
  • the vacuum degassing method is preferably vacuum degassing for 20-60 minutes.
  • the present invention preferably measures the NCO content and viscosity of the obtained polymerization reaction product as qualified, and then vacuum degassing to obtain the hot-melt reaction type polyurethane material.
  • the method for measuring the NCO content is preferably GB/T2793-1995 "Determination of the Nonvolatile Content of Adhesives"; when the NCO content is 0.01% to 2.0%, it is deemed qualified.
  • the method for measuring the viscosity is preferably HG/T3660-1999 "Determination of Melt Viscosity of Hot Melt Adhesives”; when the viscosity is 7000 to 20000 cp (120°C), it is regarded as qualified.
  • the present invention also provides the application of the hot-melt reactive polyurethane material described in the above technical solution or the hot-melt reactive polyurethane material prepared by the preparation method described in the above technical solution in the field of 3D printing.
  • the present invention does not specifically limit the application of the hot-melt reactive polyurethane material, as long as the application is well known to those skilled in the art.
  • Viscosity Measure according to the standard of HG/T3660-1999 "Determination of Melt Viscosity of Hot Melt Adhesives”.
  • Opening time Measure according to the standard of HG/T3716-2003 "Determination of Hot Melt Adhesive Opening Time”.
  • Solid content Measure according to the standard of GB/T2793-1995 "Determination of Adhesive Non-volatile Content”.
  • Curing shrinkage Measure according to the standard of GB/T24148.9-2014 "Plastic Unsaturated Polyester Resin (UP-R) Part 9: Determination of Total Volume Shrinkage”.
  • Bond strength test Conduct bond strength test in accordance with GB/T7124-2008. The initial adhesion strength, the bonding substrate is stainless steel sheet, the sample is tested after being placed in an environment of 23°C ⁇ 2°C, 50%RH ⁇ 5%RH for 1h; the final adhesion strength, the bonding substrate is stainless steel sheet, the sample is tested at 23°C ⁇ 2°C, 50%RH ⁇ 5%RH °C ⁇ 2 °C, 50% RH ⁇ 5% RH environment for 7 days before testing;
  • the hot-melt reactive polyurethane material prepared by the present invention completely meets the strength requirements of fused deposition molding technology (FMD) printed products for cross-section and vertical direction .
  • FMD fused deposition molding technology

Abstract

Disclosed are a hot-melt reaction type polyurethane material, a preparation method therefor and the use thereof. The hot-melt reaction type polyurethane material is prepared by means of a polymerization reaction of the following raw materials in parts by mass: 10-30 parts of an isocyanate, 30-70 parts of a polyester polyol, 10-25 parts of an acrylic resin, 10-25 parts of a tackifying resin, 0.01-1 parts of a catalyst, and 0.01-1 parts of an acidic stabilizer. The hot-melt reaction type polyurethane material has the features of being terminated by a NCO-containing functional group, not being easy to crack, and having a low shrinkage rate, a good toughness, an excellent mechanical performance and a good weather resistance; and when used as a 3D printing material, the material can enhance the adhesion of the transversal section of a 3D printed article, thereby solving the technical problem of the low strength of an article, which is obtained by means of an FDM process, in the cross sectional and vertical directions.

Description

一种热熔反应型聚氨酯材料及其制备方法和应用Hot-melt reaction type polyurethane material and preparation method and application thereof 技术领域Technical field
本发明涉及聚氨酯材料技术领域，尤其是涉及一种热熔反应型聚氨酯材料及其制备方法和应用。The invention relates to the technical field of polyurethane materials, in particular to a hot-melt reaction type polyurethane material and a preparation method and application thereof.
背景技术Background technique
3D打印技术，是一种以数字模型文件为基础，运用粉末状金属或塑料等可粘合材料，采用分层加工、叠加成形的方式逐层增加材料来生成三维实体的技术。与传统的“去除型”制造不同的是：传统的数控制造一般是在原材料的基础上，使用切割、磨削、腐蚀、熔融等方法，去除多余部分，得到零部件，再以拼装、焊接等方法组合成最终产品；而3D打印技术则是直接根据计算机图形数据，将三维实体分解为若干个二维平面，再通过逐层增加材料的方法生成所需形状的物体，因此又称为“增材制造”(AM，Additive Manufacturing)技术。3D打印技术在制造过程中不需要复杂的成型工艺，不需要原胚和模具，亦不需要众多的人力，从而简化了产品的制造程序，缩短了产品的研制周期，提高了生产效率并降低了成本，使得产品制造更加智能化、精准化、高效化。3D printing technology is a technology that is based on digital model files and uses bondable materials such as powdered metals or plastics to generate three-dimensional entities by adding materials layer by layer by layered processing and superimposed forming. Different from the traditional "removal type" manufacturing: traditional CNC manufacturing generally uses cutting, grinding, corrosion, melting and other methods on the basis of raw materials to remove excess parts to obtain parts, and then use assembling, welding, etc. The method is combined into the final product; while the 3D printing technology directly decomposes the three-dimensional entity into several two-dimensional planes based on the computer graphics data, and then generates the object of the desired shape by adding the material layer by layer, so it is also called "increase “Material Manufacturing” (AM, Additive Manufacturing) technology. 3D printing technology does not require complex molding processes, original embryos and molds, or a lot of manpower in the manufacturing process, thus simplifying the product manufacturing process, shortening the product development cycle, improving production efficiency and reducing Cost makes product manufacturing more intelligent, precise and efficient.
3D打印技术包括熔融沉积成型技术(FMD)、选择性激光烧结技术(SLS)、光固化成型技术(SLA)、分层实体制造技术(LOM)和数字光处理技术(DLP)等。其中，FDM因其在成型材料和成本价格等方面的优势，已成为3D打印技术中最有市场前景的一种工艺。3D printing technology includes fused deposition modeling technology (FMD), selective laser sintering technology (SLS), light curing technology (SLA), layered solid manufacturing technology (LOM) and digital light processing technology (DLP). Among them, FDM has become the most promising process in 3D printing technology due to its advantages in molding materials and cost prices.
FDM所使用的原料通常为热塑性高分子材料，包括丙烯腈-丁二烯-苯乙烯共聚物(ABS)、聚乳酸(PLA)、聚碳酸酯(PC)、聚苯砜(PPSF)等，但这些材料或多或少都存在着收缩率较大、韧性差、力学性能差等问题，由于FDM采用逐层打印的方式，FDM打印原料存在的问题会直接导致FDM工艺得到的制品存在截面与垂直的方向强度较小的技术缺陷。The raw materials used in FDM are usually thermoplastic polymer materials, including acrylonitrile-butadiene-styrene copolymer (ABS), polylactic acid (PLA), polycarbonate (PC), polyphenylsulfone (PPSF), etc. These materials more or less have problems such as large shrinkage, poor toughness, and poor mechanical properties. Because FDM uses layer-by-layer printing, the problems of FDM printing materials will directly cause the products obtained by the FDM process to have cross-sections and verticals. The technical defect of the direction strength is less.
发明内容Summary of the invention
鉴于此，本发明提供一种热熔反应型聚氨酯材料及其制备方法和应用。本发明提供的热熔反应型聚氨酯材料用作3D打印材料，能够解决FDM工艺得到的制品中存在的截面与垂直的方向强度小的技术问题。In view of this, the present invention provides a hot-melt reactive polyurethane material and its preparation method and application. The hot-melt reactive polyurethane material provided by the present invention is used as a 3D printing material, and can solve the technical problem of low cross-section and vertical direction strength in products obtained by the FDM process.
为了实现上述发明目的，本发明提供以下技术方案：In order to achieve the above-mentioned purpose of the invention, the present invention provides the following technical solutions:
本发明提供一种热熔反应型聚氨酯材料，由包括以下质量份数的原料经聚合反应制备得到：The present invention provides a hot-melt reactive polyurethane material, which is prepared by polymerization reaction of raw materials including the following parts by mass:
异氰酸酯10～30份、聚酯多元醇30～70份、丙烯酸树脂10～25份、增粘树脂10～25份、催化剂0.01～1份和酸性稳定剂0.01～1份。10-30 parts of isocyanate, 30-70 parts of polyester polyol, 10-25 parts of acrylic resin, 10-25 parts of tackifying resin, 0.01-1 part of catalyst and 0.01-1 part of acid stabilizer.
优选地，所述热熔反应型聚氨酯材料，由包括以下质量份数的原料经聚合反应制备得到：Preferably, the hot-melt reactive polyurethane material is prepared by polymerization reaction of raw materials including the following parts by mass:
异氰酸酯10～20份、聚酯多元醇40～60份、丙烯酸树脂15～20份、增粘树脂15～20、催化剂0.2～0.8份和酸性稳定剂0.2～0.8份。10-20 parts of isocyanate, 40-60 parts of polyester polyol, 15-20 parts of acrylic resin, 15-20 parts of tackifying resin, 0.2-0.8 parts of catalyst and 0.2-0.8 parts of acidic stabilizer.
优选地，所述异氰酸酯包括二苯基甲烷-4,4'-二异氰酸酯、液化MDI和多亚甲基多苯基多异氰酸酯中的一种或多种。Preferably, the isocyanate includes one or more of diphenylmethane-4,4'-diisocyanate, liquefied MDI and polymethylene polyphenyl polyisocyanate.
优选地，所述聚酯多元醇优选包括结晶型聚酯多元醇和/或无定形聚酯多元醇。Preferably, the polyester polyol preferably includes a crystalline polyester polyol and/or an amorphous polyester polyol.
优选地，所述增粘树脂包括萜烯树脂、氢化石油树脂、松香树脂和萜烯酚醛树脂中的一种或多种。Preferably, the tackifying resin includes one or more of terpene resin, hydrogenated petroleum resin, rosin resin, and terpene phenol resin.
优选地，所述催化剂优选包括辛酯亚锡、二月桂酸二丁基锡、二吗啉二乙基醚和三亚乙基二胺中的一种或多种。Preferably, the catalyst preferably includes one or more of stannous octyl ester, dibutyl tin dilaurate, dimorpholine diethyl ether and triethylene diamine.
优选地，所述酸性稳定剂包括磷酸、苯甲酸和柠檬酸中的一种或多种。Preferably, the acid stabilizer includes one or more of phosphoric acid, benzoic acid and citric acid.
优选地，所述热熔反应型聚氨酯材料的粘度为5000～25000cps，NCO含量为0.01～2.0％。Preferably, the viscosity of the hot-melt reactive polyurethane material is 5000-25000 cps, and the NCO content is 0.01-2.0%.
优选地，所述原料还包括聚醚多元醇、扩链剂、抗氧化剂和紫外线吸收剂中的一种或多种。Preferably, the raw material further includes one or more of polyether polyol, chain extender, antioxidant, and ultraviolet absorber.
本发明还提供了上述技术方案所述热熔反应型聚氨酯材料的制备方法，包括以下步骤：The present invention also provides a preparation method of the hot-melt reactive polyurethane material according to the above technical scheme, which includes the following steps:
(1)将聚酯多元醇、丙烯酸树脂、增粘树脂和酸性稳定剂混合干燥，得到干燥混合料；(1) Mix and dry polyester polyol, acrylic resin, tackifying resin and acidic stabilizer to obtain a dry mixture;
(2)在保护气氛下，将所述干燥混合料和异氰酸酯混合进行预聚合反应，得到预聚合反应产物；(2) Under a protective atmosphere, mixing the dry mixture and isocyanate to perform a pre-polymerization reaction to obtain a pre-polymerization reaction product;
(3)在保护气氛下，将所述预聚合反应产物和催化剂混合，进行聚合反应后，真空脱泡，得到所述热熔反应型聚氨酯材料。(3) Under a protective atmosphere, the pre-polymerization reaction product and the catalyst are mixed, and after the polymerization reaction is performed, vacuum defoaming is performed to obtain the hot-melt reaction type polyurethane material.
优选地，所述预聚合反应的温度为80～90℃，时间为0.5～10h。Preferably, the temperature of the pre-polymerization reaction is 80-90°C, and the time is 0.5-10h.
优选地，所述聚合反应的温度为80～90℃，时间为0.5～10h。Preferably, the temperature of the polymerization reaction is 80-90°C, and the time is 0.5-10h.
优选地，所述步骤(1)干燥前还包括加入聚醚多元醇和/或扩链剂。Preferably, the step (1) before drying further includes adding a polyether polyol and/or a chain extender.
优选地，所述步骤(3)混合时还包括加入抗氧化剂和/或紫外线吸收剂。Preferably, the step (3) also includes adding antioxidants and/or ultraviolet absorbers when mixing.
本发明还提供了上述技术方案所述的热熔反应型聚氨酯材料或由上述技术方案所述制备方法制得的热熔反应型聚氨酯材料在3D打印中的应用。The present invention also provides the application of the hot-melt reactive polyurethane material described in the above technical solution or the hot-melt reactive polyurethane material prepared by the preparation method described in the above technical solution in 3D printing.
本发明提供的热熔反应型聚氨酯材料，由包括以下质量份数的原料经聚合反应制备得到：异氰酸酯10～30份、聚酯多元醇30～70份、丙烯酸树脂10～25份、增粘树脂10～25份、催化剂0.01～1份和酸性稳定剂0.01～1份。在本发明中，异氰酸酯能够与聚酯多元醇发生聚合反应，生成含有NCO活性基团封端的聚氨酯聚合物，而异氰酸酯的对称结构能够促进聚氨酯结晶，提高聚合物的结晶度，进而提高聚氨酯材料的初粘性能，使制得的聚氨酯材料在3D打印过程中截面层间初粘力提高，开放时间缩短。在本发明中，利用丙烯酸树脂中含有的酯基极性基团和增粘树脂来提高聚氨酯材料的加工性能和粘结强度。本发明在聚合反应过程中添加酸性稳定剂，不仅可避免异氰酸酯与聚酯多元醇在反应过程中产生凝胶，还可以避免在使用过程中因反复加热而增加聚氨酯材料的粘度。本发明制得的热熔反应型聚氨酯材料具有含NCO活性基团封端、不易开裂、收缩率低、韧性好、力学性能优异和耐候性佳的特点，用作3D打印材料可增强3D打印制品的横向截面粘附力，解决FDM工艺得到的制品中存在的截面与垂直的方向强度小的技术问题。The hot-melt reactive polyurethane material provided by the present invention is prepared by polymerization reaction of raw materials including the following parts by mass: 10-30 parts of isocyanate, 30-70 parts of polyester polyol, 10-25 parts of acrylic resin, and tackifying resin 10-25 parts, 0.01-1 part of catalyst and 0.01-1 part of acid stabilizer. In the present invention, the isocyanate can polymerize with the polyester polyol to form a polyurethane polymer with NCO active group-terminated, and the symmetrical structure of the isocyanate can promote the crystallization of the polyurethane, increase the crystallinity of the polymer, and then improve the polyurethane material The initial adhesion performance improves the initial adhesion between the cross-section layers of the prepared polyurethane material during the 3D printing process, and shortens the open time. In the present invention, the ester polar group and the tackifying resin contained in the acrylic resin are used to improve the processing performance and bonding strength of the polyurethane material. The addition of an acid stabilizer in the polymerization reaction process of the present invention can not only prevent the formation of gel between the isocyanate and the polyester polyol during the reaction, but also avoid the increase in the viscosity of the polyurethane material due to repeated heating during use. The hot-melt reactive polyurethane material prepared by the invention has the characteristics of NCO active group end-capping, resistance to cracking, low shrinkage, good toughness, excellent mechanical properties and good weather resistance, and can be used as a 3D printing material to enhance 3D printing products The lateral cross-sectional adhesion force solves the technical problem of low cross-section and vertical strength in the products obtained by the FDM process.
本发明提供的制备方法工艺简单，条件易控，易于实现自动化生产。The preparation method provided by the invention has simple process, easy control of conditions, and easy realization of automatic production.
具体实施方式Detailed ways
本发明提供一种热熔反应型聚氨酯材料，由包括以下质量份数的原料经聚合反应制备得到：The present invention provides a hot-melt reactive polyurethane material, which is prepared by polymerization reaction of raw materials including the following parts by mass:
异氰酸酯10～30份、聚酯多元醇30～70份、丙烯酸树脂10～25份、增粘树脂10～25份、催化剂0.01～1份和酸性稳定剂0.01～1份。10-30 parts of isocyanate, 30-70 parts of polyester polyol, 10-25 parts of acrylic resin, 10-25 parts of tackifying resin, 0.01-1 part of catalyst and 0.01-1 part of acid stabilizer.
在本发明中，若无特殊说明，所采用的原料均为本领域常规市售产品。In the present invention, unless otherwise specified, the raw materials used are all conventional commercial products in the field.
以质量份数计，本发明提供的热熔反应型聚氨酯材料包括异氰酸酯10～30份，优选为10～20份，更优选为15份。在本发明中，所述异氰酸酯优选包括二苯基甲烷-4,4'-二异氰酸酯、液化MDI和多亚甲基多苯基多异氰酸酯中的一种或多种。在本发明中，异氰酸酯的对称结构使得聚氨酯分子结构规整有序，与聚酯多元醇发生聚合反应后，能够促进聚合反应产物的结晶，提高聚合反应产物的结晶度，进而提高聚氨酯材料的初粘性能，使制得的聚氨酯材料在3D打印过程中截面层间初粘力提高，开放时间缩短。In terms of parts by mass, the hot-melt reactive polyurethane material provided by the present invention includes 10-30 parts of isocyanate, preferably 10-20 parts, more preferably 15 parts. In the present invention, the isocyanate preferably includes one or more of diphenylmethane-4,4'-diisocyanate, liquefied MDI and polymethylene polyphenyl polyisocyanate. In the present invention, the symmetrical structure of the isocyanate makes the polyurethane molecular structure regular and orderly. After the polymerization reaction with the polyester polyol, it can promote the crystallization of the polymerization reaction product, increase the crystallinity of the polymerization reaction product, and thereby increase the initial adhesion of the polyurethane material. The performance of the polyurethane material in the 3D printing process improves the initial adhesion between the cross-section layers and shortens the open time.
以异氰酸酯的质量份数计，本发明提供的热熔反应型聚氨酯材料包括聚酯多元醇30～70份，优选为40～60份，更优选为50份。在本发明中，所述聚酯多元醇优选包括结晶型聚酯多元醇和/或无定形聚酯多元醇；所述结晶型聚酯多元醇优选包括赢创德固赛dynacoll7360、dynacoll7380、dynacoll7381、dynacoll7362、dynacoll7365、dynacoll7361、dynacoll7330和dynacoll7320中的一种或多种；所述无定形聚酯多元醇优选包括赢创德固赛dynacoll7130、dynacoll7140、dynacoll7150、dynacoll7131、dynacoll7190、dynacoll7210、dynacoll7230和dynacoll7250中的一种或多种。在本发明中，结晶型聚酯多元醇可以提高聚氨酯预聚体的结晶度，而其结晶度决定了聚氨酯材料的初粘性能，高结晶度预聚体表现出较好的初粘性能，进而提高3D打印材料制品截面层间初粘力和缩短开放时间。在本发明中，液态无定形聚酯多元醇可提高聚氨酯材料的浸润性和粘结性能，进而提高3D打印材料制品截面层间初粘力。Based on the mass parts of isocyanate, the hot-melt reactive polyurethane material provided by the present invention includes 30-70 parts of polyester polyol, preferably 40-60 parts, more preferably 50 parts. In the present invention, the polyester polyol preferably includes crystalline polyester polyol and/or amorphous polyester polyol; the crystalline polyester polyol preferably includes Evonik Degussa dynacoll 7360, dynacoll 7380, dynacoll 7381, dynacoll 7362 One or more of dynacoll 7365, dynacoll 7361, dynacoll 7330 and dynacoll 7320; the amorphous polyester polyol preferably includes Evonik Degussa dynacoll 7130, dynacoll 7140, dynacoll 7150, dynacoll 7131, dynacoll 7190, dynacoll 7210, dynacoll 7230 and one of Or multiple. In the present invention, the crystalline polyester polyol can increase the crystallinity of the polyurethane prepolymer, and its crystallinity determines the initial adhesion performance of the polyurethane material, and the high crystallinity prepolymer exhibits better initial adhesion performance. Improve the initial adhesion between the cross-section layers of the 3D printing material products and shorten the opening time. In the present invention, the liquid amorphous polyester polyol can improve the wettability and bonding performance of the polyurethane material, thereby increasing the initial adhesion between the cross-section layers of the 3D printing material product.
以异氰酸酯的质量份数计，本发明提供的热熔反应型聚氨酯材料包括丙烯酸树脂10～25份，优选为15～20份，更优选为18份。在本发明中，所述丙烯酸树脂优选包括璐彩特Elvacite 4026、Elvacite 2044、Elvacite 2013、Elvacite 2016、德固赛DEGALAN PQ611N、帝斯曼NeoCryl B-725、NeoCryl B-722和NeoCryl B-804中的一种或多种。在本发明中，丙烯酸树脂中含有的酯基极性基团，在聚合反应过程中添加丙烯酸树脂能够显著提高聚氨酯材料的初粘力、表面光泽度、对物理和化学品的耐候性能，提高其热分解温度，改善其热塑性能。Based on the mass parts of isocyanate, the hot-melt reactive polyurethane material provided by the present invention includes 10-25 parts of acrylic resin, preferably 15-20 parts, more preferably 18 parts. In the present invention, the acrylic resin preferably includes Elvacite 4026, Elvacite 2044, Elvacite 2013, Elvacite 2016, Degussa DEGALAN PQ611N, DSM NeoCryl B-725, NeoCryl B-722 and NeoCryl B-804 One or more of. In the present invention, the ester-based polar group contained in the acrylic resin, and the addition of the acrylic resin during the polymerization reaction can significantly improve the initial adhesion, surface gloss, and weather resistance to physical and chemical properties of the polyurethane material. Thermal decomposition temperature improves its thermoplastic properties.
以异氰酸酯的质量份数计，本发明提供的热熔反应型聚氨酯材料包括增粘树脂10～25份，优选为15～20份，更优选为18份。在本发明中，所述增粘树脂优选包括萜烯树脂、氢化石油树脂、松香树脂和萜烯酚醛树脂中的一种或多种；所述萜烯树脂优选包括T-80、T-90、T-100、T-110和T-120中的一种或多种；所述氢化石油树脂优选包括C5和/或C9。在本发明中，增粘树脂可降低聚氨酯材料的熔融粘度，改善操作性能，提高初粘强度和终粘强度。Based on the mass parts of isocyanate, the hot-melt reactive polyurethane material provided by the present invention includes 10-25 parts of tackifying resin, preferably 15-20 parts, more preferably 18 parts. In the present invention, the tackifying resin preferably includes one or more of terpene resin, hydrogenated petroleum resin, rosin resin and terpene phenol resin; the terpene resin preferably includes T-80, T-90, One or more of T-100, T-110 and T-120; the hydrogenated petroleum resin preferably includes C5 and/or C9. In the present invention, the tackifying resin can reduce the melt viscosity of the polyurethane material, improve the operation performance, and increase the initial bonding strength and the final bonding strength.
以异氰酸酯的质量份数计，本发明提供的热熔反应型聚氨酯材料包括催化剂0.01～1份，优选为0.2～0.8份，更优选为0.4～0.6份。在本发明中，所述催化剂优选包括辛酯亚锡、二月桂酸二丁基锡、二吗啉二乙基醚和三亚乙基二胺中的一种或多种。在本发明中，催化剂能够促进预聚合反应产物进一步发生聚合反应，并且对于制备的热熔反应型聚氨酯材料后期可促进3D打印制品固化。Based on the mass parts of the isocyanate, the hot melt reactive polyurethane material provided by the present invention includes 0.01 to 1 part of the catalyst, preferably 0.2 to 0.8 part, more preferably 0.4 to 0.6 part. In the present invention, the catalyst preferably includes one or more of stannous octyl ester, dibutyl tin dilaurate, dimorpholine diethyl ether and triethylene diamine. In the present invention, the catalyst can promote the further polymerization reaction of the pre-polymerization reaction product, and can promote the curing of the 3D printed product in the later stage of the prepared hot-melt reactive polyurethane material.
以异氰酸酯的质量份数计，本发明提供的热熔反应型聚氨酯材料包括酸性稳定剂0.01～1份，优选为0.2～0.8份，更优选为0.4～0.6份。在本发明中，所述酸性稳定剂优选包括磷酸、苯甲酸和柠檬酸中的一种或多种。在本发明中，酸性稳定剂能够使聚氨酯材料在制备和使用的过程中更加稳定，不仅可避免异氰酸酯与聚酯多元醇在反应过程中产生凝胶，还可以避免在使用过程中因反复加热而增加热熔反应型聚氨酯材料的粘度Based on the mass parts of the isocyanate, the hot melt reactive polyurethane material provided by the present invention includes 0.01 to 1 part of the acid stabilizer, preferably 0.2 to 0.8 part, more preferably 0.4 to 0.6 part. In the present invention, the acid stabilizer preferably includes one or more of phosphoric acid, benzoic acid and citric acid. In the present invention, the acid stabilizer can make the polyurethane material more stable during the preparation and use process, not only can prevent the isocyanate and polyester polyol from generating gel during the reaction, but can also avoid repeated heating during use. Increase the viscosity of hot melt reactive polyurethane materials
在本发明中，所述热熔反应型聚氨酯材料为白色或淡黄色固体，在110～150℃时，所述热熔反应型聚氨酯材料的粘度优选为5000～25000cps，更优选为8000～15000cps；所述热熔反应型聚氨酯材料的NCO含量优选为0.01～2.0％，更优选为0.1～1.5％。In the present invention, the hot-melt reactive polyurethane material is a white or light yellow solid. At 110-150°C, the viscosity of the hot-melt reactive polyurethane material is preferably 5000-25000 cps, more preferably 8000-15000 cps; The NCO content of the hot melt reactive polyurethane material is preferably 0.01 to 2.0%, more preferably 0.1 to 1.5%.
在本发明中，所述原料优选还包括聚醚多元醇、扩链剂、抗氧化剂和 紫外线吸收剂中的一种或多种。In the present invention, the raw material preferably further includes one or more of polyether polyol, chain extender, antioxidant, and ultraviolet absorber.
在本发明中，所述聚醚多元醇的质量优选占所述异氰酸酯、聚酯多元醇、丙烯酸树脂、增粘树脂、催化剂和酸性稳定剂(以下简称原料)的质量之和的0～20％，进一步优选为5～15％，更优选为8～12％。在本发明中，所述聚醚多元醇优选包括TMN-400、TMN-700、TMN-1000、TMD1000、TMD3000、TMD-5000、GEP-330N、DL-400和DL-1000中的一种或多种。在本发明中，聚醚多元醇的加入可提高热熔反应型聚氨酯材料的耐水解性能。In the present invention, the mass of the polyether polyol preferably accounts for 0-20% of the total mass of the isocyanate, polyester polyol, acrylic resin, tackifying resin, catalyst and acid stabilizer (hereinafter referred to as raw material) , More preferably 5 to 15%, more preferably 8 to 12%. In the present invention, the polyether polyol preferably includes one or more of TMN-400, TMN-700, TMN-1000, TMD1000, TMD3000, TMD-5000, GEP-330N, DL-400 and DL-1000 kind. In the present invention, the addition of polyether polyol can improve the hydrolysis resistance of the hot-melt reactive polyurethane material.
在本发明中，所述扩链剂的质量优选占所述原料的0～5％，进一步优选为2～4％。在本发明中，所述扩链剂优选包括三羟甲基丙烷、甘油、一缩二丙二醇、一缩二乙二醇、1,2-丙二醇、1,3-丙二醇、1,4-丁二醇和3,3'-二氯-4,4'-二氨基二苯基甲烷中的一种或多种。在本发明中，扩链剂的加入可提高热熔反应型聚氨酯材料的耐热性和内聚力。In the present invention, the mass of the chain extender preferably accounts for 0 to 5% of the raw material, and more preferably 2 to 4%. In the present invention, the chain extender preferably includes trimethylolpropane, glycerin, dipropylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol One or more of alcohol and 3,3'-dichloro-4,4'-diaminodiphenylmethane. In the present invention, the addition of a chain extender can improve the heat resistance and cohesion of the hot-melt reactive polyurethane material.
在本发明中，所述抗氧化剂的质量优选占所述原料的0～2％，进一步优选为0.5～1.5％。在本发明中，所述抗氧化剂优选包括2,6-二叔丁基对甲酚、二缩三乙二醇双[β-(3-叔丁基-4-羟基-5-甲基苯基)丙酸酯]、1,3,5-三(4-叔丁基-3-羟基-2,6-二甲基苄基)1,3,5-三嗪-2,4,6-(1H,3H,5H)-三酮、3,9-双[1,1-二甲基-2-[(3-叔丁基-4-羟基-5-甲基苯基)丙酰氧基]乙基]-2,4,8,10-四氧杂螺[5,5]十一烷、四[β-(3,5-二叔丁基-4-羟基苯基)]季戊四醇酯和3,5-二叔丁基-4-羟基苯丙酸异辛酯(IRGANOX 1135)中的一种或多种。In the present invention, the weight of the antioxidant preferably accounts for 0 to 2% of the raw material, and more preferably 0.5 to 1.5%. In the present invention, the antioxidant preferably includes 2,6-di-tert-butyl-p-cresol, triethylene glycol bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl ) Propionate), 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) 1,3,5-triazine-2,4,6-( 1H,3H,5H)-trione, 3,9-bis[1,1-dimethyl-2-[(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy] Ethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane, tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)]pentaerythritol ester and 3 , One or more of 5-di-tert-butyl-4-hydroxyphenylpropionic acid isooctyl ester (IRGANOX 1135).
在本发明中，所述紫外吸收剂的质量优选占所述原料的0～2％，进一步优选为0.5～1.5％。在本发明中，所述紫外线吸收剂优选包括2-(3,5-二叔丁基-2-羟基苯基)苯并三唑、2-(4,6-双(2,4-二甲基苯基)-1,3,5-三嗪-2-基)-5-辛氧基酚、N-(2-乙氧基苯基)-N'-(4-乙基苯基)-乙二酰胺、2-(2H-苯并三唑-2-基)-4,6-二叔戊基苯酚和2-(2’羟基-5’-甲基苯基)苯并三唑中的一种或多种。In the present invention, the mass of the ultraviolet absorber preferably accounts for 0-2% of the raw material, and more preferably 0.5-1.5%. In the present invention, the ultraviolet absorber preferably includes 2-(3,5-di-tert-butyl-2-hydroxyphenyl)benzotriazole, 2-(4,6-bis(2,4-dimethyl Phenyl)-1,3,5-triazin-2-yl)-5-octyloxyphenol, N-(2-ethoxyphenyl)-N'-(4-ethylphenyl)- Among oxamide, 2-(2H-benzotriazol-2-yl)-4,6-di-tert-amylphenol and 2-(2'hydroxy-5'-methylphenyl)benzotriazole One or more.
在本发明中，抗氧化剂和紫外吸收剂的加入，可以提高3D打印用热熔反应型聚氨酯材料的耐热抗氧化性能和耐黄变性能。In the present invention, the addition of antioxidants and ultraviolet absorbers can improve the heat resistance and oxidation resistance and yellowing resistance of the hot-melt reactive polyurethane material for 3D printing.
本发明还提供了上述技术方案所述热熔反应型聚氨酯材料的制备方 法，包括以下步骤：The present invention also provides a method for preparing the hot-melt reactive polyurethane material described in the above technical scheme, which includes the following steps:
(1)将聚酯多元醇、丙烯酸树脂、增粘树脂和酸性稳定剂混合干燥，得到干燥混合料；(1) Mix and dry polyester polyol, acrylic resin, tackifying resin and acidic stabilizer to obtain a dry mixture;
(2)在保护气氛下，将所述干燥混合料和异氰酸酯混合进行预聚合反应，得到预聚合反应产物；(2) Under a protective atmosphere, mixing the dry mixture and isocyanate to perform a pre-polymerization reaction to obtain a pre-polymerization reaction product;
(3)在保护气氛下，将所述预聚合反应产物和催化剂混合，进行聚合反应后，真空脱泡，得到所述热熔反应型聚氨酯材料。(3) Under a protective atmosphere, the pre-polymerization reaction product and the catalyst are mixed, and after the polymerization reaction is performed, vacuum defoaming is performed to obtain the hot-melt reaction type polyurethane material.
本发明将聚酯多元醇、丙烯酸树脂、增粘树脂和酸性稳定剂混合干燥，得到干燥混合料。In the present invention, polyester polyol, acrylic resin, tackifying resin and acid stabilizer are mixed and dried to obtain a dry mixture.
本发明对所述聚酯多元醇、丙烯酸树脂、增粘树脂和酸性稳定剂的混合顺序没有特殊的限定，采用任意混合顺序均可。在本发明中，所述混合的方式优选为搅拌。本发明对所述搅拌的时间和速率没有特殊的限定，能够将原料混合均匀即可。在本发明中，所述混合优选在反应釜中进行。In the present invention, the mixing sequence of the polyester polyol, acrylic resin, tackifying resin and acid stabilizer is not particularly limited, and any mixing sequence can be adopted. In the present invention, the mixing method is preferably stirring. In the present invention, there is no special limitation on the stirring time and speed, as long as the raw materials can be mixed uniformly. In the present invention, the mixing is preferably carried out in a reactor.
干燥前，本发明优选在所述聚酯多元醇、丙烯酸树脂、增粘树脂和酸性稳定剂混合时还加入聚醚多元醇和/或扩链剂。Before drying, the present invention preferably adds polyether polyol and/or chain extender when the polyester polyol, acrylic resin, tackifying resin and acid stabilizer are mixed.
在本发明中，所述干燥的方式优选为真空脱水，所述真空脱水的真空度优选＜-0.095MPa；所述真空脱水的时间优选为2～10h；所述真空脱水的温度优选为110～150℃，进一步优选为120～140℃。本发明对升温至所述真空脱水的温度的升温速率没有特殊限定，采用本领域技术人员熟知的升温速率均可。In the present invention, the drying method is preferably vacuum dehydration, the vacuum degree of the vacuum dehydration is preferably <-0.095MPa; the vacuum dehydration time is preferably 2-10h; the vacuum dehydration temperature is preferably 110- 150°C, more preferably 120 to 140°C. The present invention does not specifically limit the heating rate to the vacuum dehydration temperature, and the heating rate well known to those skilled in the art can be used.
干燥后，本发明优选将得到的干燥产物充氮气解除真空后，得到所述干燥混合料。在本发明中，所述干燥和充氮气解除真空均优选在恒定温度条件下进行。After drying, the present invention preferably fills the obtained dried product with nitrogen to release the vacuum to obtain the dried mixture. In the present invention, the drying and nitrogen filling to release the vacuum are preferably carried out under constant temperature conditions.
得到干燥混合料后，本发明在保护气氛下，将所述干燥混合料和异氰酸酯混合进行预聚合反应，得到预聚合反应产物。After the dry mixture is obtained, in the present invention, the dry mixture and the isocyanate are mixed under a protective atmosphere to perform a pre-polymerization reaction to obtain a pre-polymerization reaction product.
在本发明中，所述保护气氛优选为氮气。本发明优选将所述干燥混合料的温度降温至预聚合反应的温度后，再与异氰酸酯混合进行预聚合反应。本发明对所述降温至预聚合反应温度的降温速率没有特殊限定，采用本领域技术人员熟知的降温速率均可。在本发明中，所述混合的方式优选 为搅拌。本发明对所述搅拌的时间和速率没有特殊的限定，能够将原料混合均匀即可。在本发明中，所述预聚合反应的温度优选为80～90℃，进一步优选为83～87℃；所述预聚合反应的时间优选为0.5～10h，进一步优选为2～8h。In the present invention, the protective atmosphere is preferably nitrogen. In the present invention, it is preferable to lower the temperature of the dry mixture to the temperature of the pre-polymerization reaction, and then mix with the isocyanate to perform the pre-polymerization reaction. The present invention does not specifically limit the cooling rate from the temperature to the prepolymerization reaction temperature, and the cooling rate well known to those skilled in the art can be used. In the present invention, the mixing method is preferably stirring. In the present invention, there is no special limitation on the stirring time and speed, as long as the raw materials can be mixed uniformly. In the present invention, the temperature of the pre-polymerization reaction is preferably 80-90°C, more preferably 83-87°C; the time of the pre-polymerization reaction is preferably 0.5-10h, more preferably 2-8h.
得到预聚合反应产物后，本发明在保护气氛下，将所述预聚合反应产物和催化剂混合，进行聚合反应后，真空脱泡，得到所述热熔反应型聚氨酯材料。After the pre-polymerization reaction product is obtained, the present invention mixes the pre-polymerization reaction product and the catalyst under a protective atmosphere, performs polymerization reaction, and then defoams in a vacuum to obtain the hot-melt reaction type polyurethane material.
本发明优选在所述预聚合反应产物和催化剂混合时还加入抗氧化剂和/或紫外线吸收剂。In the present invention, it is preferable to add an antioxidant and/or an ultraviolet absorber when the prepolymerization reaction product and the catalyst are mixed.
在本发明中，所述保护气氛优选为氮气。在本发明中，所述混合的方式优选为搅拌。本发明对所述搅拌的时间和速率没有特殊的限定，能够将原料混合均匀即可。在本发明中，所述聚合反应的温度优选为80～90℃，进一步优选为83～87℃；所述聚合反应的时间优选为0.5～10h，进一步优选为2～8h。本发明对升温至所述加热的温度的升温速率没有特殊限定，采用本领域技术人员熟知的升温速率均可。在本发明中，所述真空脱泡的方式优选为抽真空20～60min脱泡。In the present invention, the protective atmosphere is preferably nitrogen. In the present invention, the mixing method is preferably stirring. In the present invention, there is no special limitation on the stirring time and speed, as long as the raw materials can be mixed uniformly. In the present invention, the temperature of the polymerization reaction is preferably 80-90°C, more preferably 83-87°C; the time of the polymerization reaction is preferably 0.5-10h, more preferably 2-8h. The present invention does not specifically limit the heating rate to the heating temperature, and the heating rate well known to those skilled in the art can be used. In the present invention, the vacuum degassing method is preferably vacuum degassing for 20-60 minutes.
聚合反应后，本发明优选对得到的聚合反应产物的NCO含量和粘度测定合格后，真空脱泡，得到所述热熔反应型聚氨酯材料。After the polymerization reaction, the present invention preferably measures the NCO content and viscosity of the obtained polymerization reaction product as qualified, and then vacuum degassing to obtain the hot-melt reaction type polyurethane material.
在本发明中，所述NCO含量的测定方法优选为GB/T2793—1995《胶粘剂不挥发物含量的测定》；所述NCO含量为0.01％～2.0％时，视为合格。在本发明中，所述粘度的测定方法优选为HG/T3660—1999《热熔胶粘剂熔融粘度的测定》；所述粘度为7000～20000cp(120℃)时，视为合格。In the present invention, the method for measuring the NCO content is preferably GB/T2793-1995 "Determination of the Nonvolatile Content of Adhesives"; when the NCO content is 0.01% to 2.0%, it is deemed qualified. In the present invention, the method for measuring the viscosity is preferably HG/T3660-1999 "Determination of Melt Viscosity of Hot Melt Adhesives"; when the viscosity is 7000 to 20000 cp (120°C), it is regarded as qualified.
本发明还提供了上述技术方案所述的热熔反应型聚氨酯材料或由上述技术方案所述制备方法制得的热熔反应型聚氨酯材料在3D打印领域中的应用。The present invention also provides the application of the hot-melt reactive polyurethane material described in the above technical solution or the hot-melt reactive polyurethane material prepared by the preparation method described in the above technical solution in the field of 3D printing.
本发明对所述热熔反应型聚氨酯材料的应用方式没有特殊的限定，采用本领域技术人员熟知的应用方式即可。The present invention does not specifically limit the application of the hot-melt reactive polyurethane material, as long as the application is well known to those skilled in the art.
下面结合实施例对本发明提供的热熔反应型聚氨酯材料及其制备方 法和应用进行详细的说明，但是不能把它们理解为对本发明保护范围的限定。The hot melt reactive polyurethane material provided by the present invention and its preparation method and application will be described in detail below in conjunction with examples, but they should not be understood as limiting the scope of protection of the present invention.
实施例1Example 1
(1)将称量好的280g dynacoll7360、300g dynacoll7150、140g Elvacite2013、135g T100和0.3g的磷酸加入反应釜中搅拌混合，升温至130℃，在真空度＜-0.095MPa，真空脱水2h，然后充氮气解除真空，加入19.5g的1,4-丁二醇，搅拌均匀，得到干燥混合料；(1) Add the weighed 280g dynacoll7360, 300g dynacoll7150, 140g Elvacite2013, 135g T100 and 0.3g phosphoric acid into the reactor, stir and mix, heat up to 130°C, dehydrate in vacuum for 2h at a vacuum degree of <-0.095MPa, and then charge Release the vacuum with nitrogen, add 19.5 g of 1,4-butanediol, stir evenly to obtain a dry mixture;
(2)将干燥混合料降温至80℃，加入120g二苯基甲烷-4,4'-二异氰酸酯，在氮气气氛下搅拌，温度保持在80℃进行预聚合反应2h，得到预聚合反应产物；(2) Cooling the temperature of the dry mixture to 80°C, adding 120g of diphenylmethane-4,4'-diisocyanate, stirring under a nitrogen atmosphere, and keeping the temperature at 80°C for pre-polymerization for 2 hours to obtain a pre-polymerization product;
(3)向得到的预聚合反应产物中加入5g IRGANOX 1135、0.2g二月桂酸二丁基锡，保持温度80℃，在氮气气氛下搅拌0.5h后，取样测定进一步聚合反应产物的NCO含量和粘度，测量结果为NCO含量为0.73％，粘度为12500cp(120℃)，视为合格产物，抽真空20min脱泡，得到热熔反应型聚氨酯材料。(3) Add 5g of IRGANOX 1135 and 0.2g of dibutyltin dilaurate to the obtained prepolymerization reaction product, keep the temperature at 80°C, stir for 0.5h under a nitrogen atmosphere, and then take a sample to determine the NCO content and viscosity of the further polymerization reaction product. The measurement result is that the NCO content is 0.73%, and the viscosity is 12,500 cp (120° C.), which is regarded as a qualified product, and vacuum is defoamed for 20 minutes to obtain a hot-melt reactive polyurethane material.
对制得的热熔反应型聚氨酯材料的性能进行测试，测试结果参见表1。The performance of the prepared hot-melt reactive polyurethane material was tested, and the test results are shown in Table 1.
性能测试：Performance Testing:
1、外观：目测1. Appearance: visual inspection
2、粘度：按照HG/T3660—1999《热熔胶粘剂熔融粘度的测定》标准进行测定。2. Viscosity: Measure according to the standard of HG/T3660-1999 "Determination of Melt Viscosity of Hot Melt Adhesives".
3、开放时间：按照HG/T3716—2003《热熔胶粘剂开放时间的测定》标准进行测定。3. Opening time: Measure according to the standard of HG/T3716-2003 "Determination of Hot Melt Adhesive Opening Time".
4、固含量：按照GB/T2793—1995《胶粘剂不挥发物含量的测定》标准进行测定。4. Solid content: Measure according to the standard of GB/T2793-1995 "Determination of Adhesive Non-volatile Content".
5、固化收缩率：按照GB/T24148.9—2014《塑料不饱和聚酯树脂(UP-R)第9部分：总体积收缩率测定》标准进行测定。5. Curing shrinkage: Measure according to the standard of GB/T24148.9-2014 "Plastic Unsaturated Polyester Resin (UP-R) Part 9: Determination of Total Volume Shrinkage".
6、粘接强度测试：按照GB/T7124—2008进行粘接强度测试。初粘强度，粘接基材为不锈钢片，样片于23℃±2℃、50％RH±5％RH环境下 放置1h后进行测试；终粘强度，粘接基材为不锈钢片，样片于23℃±2℃、50％RH±5％RH环境下放置7天后进行测试；6. Bond strength test: Conduct bond strength test in accordance with GB/T7124-2008. The initial adhesion strength, the bonding substrate is stainless steel sheet, the sample is tested after being placed in an environment of 23℃±2℃, 50%RH±5%RH for 1h; the final adhesion strength, the bonding substrate is stainless steel sheet, the sample is tested at 23℃±2℃, 50%RH±5%RH ℃ ± 2 ℃, 50% RH ± 5% RH environment for 7 days before testing;
7、力学性能测定：按照GB/T528—2009进行拉伸强度和断裂伸长率的测定，按照GB/T531—2008进行硬度的测定；样块固化条件，23℃±2℃、50％RH±5％RH环境下放置7天。7. Determination of mechanical properties: The tensile strength and elongation at break are measured according to GB/T528-2009, and the hardness is measured according to GB/T531-2008; the curing condition of the sample is 23℃±2℃, 50%RH± Leave it for 7 days in a 5% RH environment.
实施例2Example 2
(1)将称量好的400g dynacoll7360、200g dynacoll7150、140g Elvacite2013、140g T100和0.3g磷酸加入反应釜中搅拌混合，升温至130℃，在真空度＜-0.095MPa，真空脱水2h，然后充氮气解除真空，加入10g的1,4丁二醇，搅拌均匀，得到干燥混合料；(1) Add the weighed 400g dynacoll7360, 200g dynacoll7150, 140g Elvacite2013, 140g T100 and 0.3g phosphoric acid into the reactor, stir and mix, heat up to 130℃, vacuum degree <-0.095MPa, vacuum dehydration for 2h, and then fill with nitrogen Release the vacuum, add 10g of 1,4 butanediol, stir evenly to obtain a dry mixture;
(2)将干燥混合料降温至80℃，加入100g二苯基甲烷-4,4'-二异氰酸酯，在氮气气氛下搅拌，温度保持在80℃进行预聚合反应2h，得到预聚合反应产物；(2) Cooling the temperature of the dry mixture to 80°C, adding 100g of diphenylmethane-4,4'-diisocyanate, stirring under a nitrogen atmosphere, and keeping the temperature at 80°C for pre-polymerization for 2 hours to obtain a pre-polymerization product;
(3)向得到的预聚合反应产物中加入9.5g IRGANOX 1135、0.2g二月桂酸二丁基锡，保持温度80℃，在氮气气氛下搅拌0.5h后，取样测定进一步聚合反应产物的NCO含量和粘度，测量结果为NCO含量为0.95％，粘度为13200cp(120℃)，视为合格产物，抽真空20min脱泡，得到热熔反应型聚氨酯材料。(3) Add 9.5 g of IRGANOX 1135 and 0.2 g of dibutyl tin dilaurate to the obtained pre-polymerization reaction product, keep the temperature at 80°C, stir for 0.5 h under a nitrogen atmosphere, and then take a sample to determine the NCO content and viscosity of the further polymerization reaction product The measurement result is that the NCO content is 0.95% and the viscosity is 13200 cp (120° C.), which is regarded as a qualified product, and vacuum is defoamed for 20 minutes to obtain a hot-melt reactive polyurethane material.
对制得的热熔反应型聚氨酯材料的性能进行测试，测试结果参见表1，测试方法同实施例1。The performance of the prepared hot-melt reactive polyurethane material was tested, the test results are shown in Table 1, and the test method is the same as in Example 1.
实施例3Example 3
(1)将称量好的350g dynacoll7360、300g dynacoll7150、120g Elvacite2013、120g T100和0.3g磷酸加入反应釜中搅拌混合，升温至130℃，在真空度＜-0.095MPa，真空脱水2h，然后充氮气解除真空，得到干燥混合料；(1) Add the weighed 350g dynacoll7360, 300g dynacoll7150, 120g Elvacite2013, 120g T100 and 0.3g phosphoric acid into the reactor, stir and mix, heat up to 130℃, vacuum degree <-0.095MPa, vacuum dehydration for 2h, and then fill with nitrogen Release the vacuum to obtain a dry mixture;
(2)将干燥混合料降温至80℃，加入100g液化MDI，在氮气气氛下搅拌，温度保持在80℃进行预聚合反应2h，得到预聚合反应产物；(2) Cool the dry mixture to 80°C, add 100g of liquefied MDI, stir under a nitrogen atmosphere, and keep the temperature at 80°C for pre-polymerization for 2 hours to obtain a pre-polymerized product;
(3)向得到的预聚合反应产物中加入9.5g IRGANOX 1135、0.2g二月桂酸二丁基锡，保持温度80℃，在氮气气氛下搅拌0.5h后，取样测定进 一步聚合反应产物的NCO含量和粘度，测量结果为NCO含量为1.32％，粘度为11690cp(120℃)，视为合格产物，抽真空20min脱泡，得到热熔反应型聚氨酯材料。(3) Add 9.5 g of IRGANOX 1135 and 0.2 g of dibutyltin dilaurate to the obtained pre-polymerization reaction product, keep the temperature at 80°C, stir for 0.5h under a nitrogen atmosphere, and then take a sample to determine the NCO content and viscosity of the further polymerization reaction product , The measurement result is that the NCO content is 1.32%, the viscosity is 11690cp (120°C), which is regarded as a qualified product, and vacuum is defoamed for 20 minutes to obtain a hot-melt reactive polyurethane material.
对制得的热熔反应型聚氨酯材料的性能进行测试，测试结果参见表1，测试方法同实施例1。The performance of the prepared hot-melt reactive polyurethane material was tested, the test results are shown in Table 1, and the test method is the same as in Example 1.
实施例4Example 4
(1)将称量好的200g dynacoll7360、485g dynacoll7150、100g Elvacite2013、100g T100和0.3g磷酸加入反应釜中搅拌混合，升温至130℃，在真空度＜-0.095MPa，真空脱水2h，然后充氮气解除真空，得到干燥混合料；(1) Add the weighed 200g dynacoll7360, 485g dynacoll7150, 100g Elvacite2013, 100g T100, and 0.3g phosphoric acid into the reactor, stir and mix, heat up to 130℃, under vacuum degree <-0.095MPa, vacuum dehydration for 2h, and then fill with nitrogen Release the vacuum to obtain a dry mixture;
(2)将干燥混合料降温至80℃，加入105g液化MDI，在氮气气氛下搅拌，温度保持在80℃进行预聚合反应2h，得到预聚合反应产物；(2) Cooling the temperature of the dry mixture to 80°C, adding 105g of liquefied MDI, stirring under a nitrogen atmosphere, and keeping the temperature at 80°C for pre-polymerization for 2 hours to obtain a pre-polymerization product;
(3)向得到的预聚合反应产物中加入9.5g IRGANOX 1135、0.2g二月桂酸二丁基锡，保持温度80℃，在氮气气氛下搅拌0.5h后，取样测定进一步聚合反应产物的NCO含量和粘度，测量结果为NCO含量为1.30％，粘度为12800cp(120℃)，视为合格产物，抽真空20min脱泡，得到热熔反应型聚氨酯材料。(3) Add 9.5 g of IRGANOX 1135 and 0.2 g of dibutyltin dilaurate to the obtained pre-polymerization reaction product, keep the temperature at 80°C, stir for 0.5h under a nitrogen atmosphere, and then take a sample to determine the NCO content and viscosity of the further polymerization reaction product , The measurement result is that the NCO content is 1.30%, the viscosity is 12800cp (120°C), which is regarded as a qualified product, and the vacuum is defoamed for 20 minutes to obtain a hot-melt reactive polyurethane material.
对制得的热熔反应型聚氨酯材料的性能进行测试，测试结果参见表1，测试方法同实施例1。The performance of the prepared hot-melt reactive polyurethane material was tested, the test results are shown in Table 1, and the test method is the same as in Example 1.
实施例5Example 5
(1)将称量好的300g dynacoll7360、340g dynacoll7150、150g NeoCryl B-725、100g C5和0.4g苯甲酸加入反应釜中搅拌混合，升温至130℃，在真空度＜-0.095MPa，真空脱水2h，然后充氮气解除真空，得到干燥混合料；(1) Add the weighed 300g dynacoll7360, 340g dynacoll7150, 150g NeoCryl B-725, 100g C5 and 0.4g benzoic acid into the reactor, stir and mix, heat to 130℃, under vacuum degree <-0.095MPa, vacuum dehydration for 2h , And then filled with nitrogen to release the vacuum to obtain a dry mixture;
(2)将干燥混合料降温至80℃，加入100g二苯基甲烷-4,4'-二异氰酸酯，在氮气气氛下搅拌，温度保持在80℃进行预聚合反应2h，得到预聚合反应产物；(2) Cooling the temperature of the dry mixture to 80°C, adding 100g of diphenylmethane-4,4'-diisocyanate, stirring under a nitrogen atmosphere, and keeping the temperature at 80°C for pre-polymerization for 2 hours to obtain a pre-polymerization product;
(3)向得到的预聚合反应产物中加入9.2g 2-(3,5-二叔丁基-2-羟基苯基)苯并三唑、0.4g二吗啉二乙基醚，保持温度80℃，在氮气气氛下搅拌0.5h 后，取样测定进一步聚合反应产物的NCO含量和粘度，测量结果为NCO含量为1.20％，粘度为14000cp(120℃)，视为合格产物，抽真空20min脱泡，得到热熔反应型聚氨酯材料。(3) Add 9.2g of 2-(3,5-di-tert-butyl-2-hydroxyphenyl)benzotriazole and 0.4g of dimorpholine diethyl ether to the obtained prepolymerized reaction product, and keep the temperature at 80 ℃, after stirring for 0.5h in a nitrogen atmosphere, take samples to determine the NCO content and viscosity of the further polymerization reaction product. The measurement result is that the NCO content is 1.20% and the viscosity is 14000cp (120℃), which is regarded as a qualified product. Vacuum for 20min to degas , Get hot-melt reactive polyurethane material.
对制得的热熔反应型聚氨酯材料的性能进行测试，测试结果参见表1，测试方法同实施例1。The performance of the prepared hot-melt reactive polyurethane material was tested, the test results are shown in Table 1, and the test method is the same as in Example 1.
实施例6Example 6
(1)将称量好的400g dynacoll7360、150g TMD3000、150g DEGALAN PQ611N、150g松香树脂和0.5g柠檬酸加入反应釜中搅拌混合，升温至130℃，在真空度＜-0.095MPa，真空脱水2h，然后充氮气解除真空，得到干燥混合料；(1) Add the weighed 400g dynacoll7360, 150g TMD3000, 150g DEGALAN PQ611N, 150g rosin resin and 0.5g citric acid into the reactor, stir and mix, heat up to 130℃, vacuum degree <-0.095MPa, vacuum dehydration for 2h, Then fill with nitrogen to release the vacuum to obtain a dry mixture;
(2)将干燥混合料降温至80℃，加入140g二苯基甲烷-4,4'-二异氰酸酯，在氮气气氛下搅拌，温度保持在80℃进行预聚合反应2h，得到预聚合反应产物；(2) Cooling the dry mixture to 80°C, adding 140g of diphenylmethane-4,4'-diisocyanate, stirring under a nitrogen atmosphere, and maintaining the temperature at 80°C for pre-polymerization for 2 hours to obtain a pre-polymerization product;
(3)向得到的预聚合反应产物中加入9.1g 2-(3,5-二叔丁基-2-羟基苯基)苯并三唑、0.4g三亚乙基二胺，保持温度80℃，在氮气气氛下搅拌0.5h后，取样测定进一步聚合反应产物的NCO含量和粘度，测量结果为NCO含量为0.60％，粘度为8800cp(120℃)，视为合格产物，抽真空20min脱泡，得到热熔反应型聚氨酯材料。(3) Add 9.1g of 2-(3,5-di-tert-butyl-2-hydroxyphenyl)benzotriazole and 0.4g of triethylenediamine to the obtained prepolymerized reaction product, and keep the temperature at 80°C, After stirring for 0.5h in a nitrogen atmosphere, samples were taken to determine the NCO content and viscosity of the further polymerization reaction product. The measurement result was that the NCO content was 0.60% and the viscosity was 8800cp (120°C), which was regarded as a qualified product. Vacuumed for 20min to degas, obtain Hot melt reactive polyurethane material.
对制得的热熔反应型聚氨酯材料的性能进行测试，测试结果参见表1，测试方法同实施例1。The performance of the prepared hot-melt reactive polyurethane material was tested, the test results are shown in Table 1, and the test method is the same as in Example 1.
实施例7Example 7
(1)将称量好的450g dynacoll7360、100g TMD3000、150g Elvacite2013、140g T100和0.3g的磷酸加入反应釜中搅拌混合，升温至130℃，在真空度＜-0.095MPa，真空脱水2h，然后充氮气解除真空，搅拌均匀，得到干燥混合料；(1) Add the weighed 450g dynacoll 7360, 100g TMD3000, 150g Elvacite2013, 140g T100 and 0.3g phosphoric acid into the reactor, stir and mix, heat up to 130°C, dehydrate in vacuum for 2h at a vacuum degree of <-0.095MPa, and then charge Release the vacuum with nitrogen and stir evenly to obtain a dry mixture;
(2)将干燥混合料降温至80℃，加入150g液化MDI，在氮气气氛下搅拌，温度保持在80℃进行预聚合反应2h，得到预聚合反应产物；(2) Cool the dry mixture to 80°C, add 150g of liquefied MDI, stir under a nitrogen atmosphere, and keep the temperature at 80°C for pre-polymerization for 2 hours to obtain a pre-polymerized product;
(3)向得到的预聚合反应产物中加入9.3g IRGANOX 1135、0.4g三亚乙基二胺，保持温度80℃，在氮气气氛下搅拌0.5h后，取样测定进一步 聚合反应产物的NCO含量和粘度，测量结果为NCO含量为0.90％，粘度为10500cp(120℃)，视为合格产物，抽真空20min脱泡，得到热熔反应型聚氨酯材料。(3) Add 9.3g IRGANOX 1135 and 0.4g triethylenediamine to the obtained pre-polymerization reaction product, keep the temperature at 80°C, stir for 0.5h in a nitrogen atmosphere, and then take a sample to determine the NCO content and viscosity of the further polymerization reaction product , The measurement result is that the NCO content is 0.90%, the viscosity is 10500cp (120°C), which is regarded as a qualified product, and the vacuum is defoamed for 20 minutes to obtain a hot-melt reactive polyurethane material.
对制得的热熔反应型聚氨酯材料的性能进行测试，测试结果参见表1。The performance of the prepared hot-melt reactive polyurethane material was tested, and the test results are shown in Table 1.
对比例1Comparative example 1
采用stratasys ABS-M30熔融沉积成型技术(FMD)打印用ABS产品。Adopt Stratasys ABS-M30 Fused Deposition Molding Technology (FMD) to print ABS products.
对制得的ABS产品的性能进行测试，测试方法同实施例1，结果见表1。The performance of the prepared ABS product was tested, and the test method was the same as that in Example 1, and the results are shown in Table 1.
对比例2Comparative example 2
采用万华化学WHT-A880熔融沉积成型技术(FMD)打印用TPU产品。Adopt Wanhua Chemical WHT-A880 Fused Deposition Molding Technology (FMD) to print TPU products.
对制得的TPU产品的性能进行测试，测试方法同实施例1，结果见表1。The performance of the prepared TPU product was tested, and the test method was the same as that in Example 1, and the results are shown in Table 1.
表1实施例1～7制得的聚氨酯材料及对比例1～2的性能测试结果Table 1 Performance test results of polyurethane materials prepared in Examples 1-7 and Comparative Examples 1-2
Figure PCTCN2020086090-appb-000001
Figure PCTCN2020086090-appb-000001
Figure PCTCN2020086090-appb-000002
Figure PCTCN2020086090-appb-000002
从测试结果来看，尤其是初粘强度和终粘强度的数据表明，本发明制得的热熔反应型聚氨酯材料完全满足于熔融沉积成型技术(FMD)打印制品对截面与垂直方向的强度要求。本发明在解决3D打印材料易开裂和层间分离等问题前提下，降低了3D打印FDM工艺材料的使用温度，进而解决3D打印制品表层波浪条纹的问题。Judging from the test results, especially the initial tack strength and final tack strength data show that the hot-melt reactive polyurethane material prepared by the present invention completely meets the strength requirements of fused deposition molding technology (FMD) printed products for cross-section and vertical direction . Under the premise of solving the problems of easy cracking of 3D printing materials and separation between layers, the invention reduces the use temperature of 3D printing FDM process materials, thereby solving the problem of wavy stripes on the surface of 3D printing products.
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。The above are only the preferred embodiments of the present invention. It should be pointed out that for those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and modifications can be made, and these improvements and modifications are also It should be regarded as the protection scope of the present invention.

Claims (15)

  1. 一种热熔反应型聚氨酯材料，其特征在于，由包括以下质量份数的原料经聚合反应制备得到：A hot-melt reactive polyurethane material, characterized in that it is prepared by polymerization reaction of raw materials comprising the following parts by mass:
    异氰酸酯10～30份、聚酯多元醇30～70份、丙烯酸树脂10～25份、增粘树脂10～25份、催化剂0.01～1份和酸性稳定剂0.01～1份。10-30 parts of isocyanate, 30-70 parts of polyester polyol, 10-25 parts of acrylic resin, 10-25 parts of tackifying resin, 0.01-1 part of catalyst and 0.01-1 part of acidic stabilizer.
  2. 根据权利要求1所述的热熔反应型聚氨酯材料，其特征在于，由包括以下质量份数的原料经聚合反应制备得到：The hot-melt reactive polyurethane material according to claim 1, characterized in that it is prepared by polymerization reaction of raw materials including the following parts by mass:
    异氰酸酯10～20份、聚酯多元醇40～60份、丙烯酸树脂15～20份、增粘树脂15～20、催化剂0.2～0.8份和酸性稳定剂0.2～0.8份。10-20 parts of isocyanate, 40-60 parts of polyester polyol, 15-20 parts of acrylic resin, 15-20 parts of tackifying resin, 0.2-0.8 parts of catalyst and 0.2-0.8 parts of acidic stabilizer.
  3. 根据权利要求1或2所述的热熔反应型聚氨酯材料，其特征在于，所述异氰酸酯包括二苯基甲烷-4,4'-二异氰酸酯、液化MDI和多亚甲基多苯基多异氰酸酯中的一种或多种。The hot-melt reactive polyurethane material according to claim 1 or 2, wherein the isocyanate includes diphenylmethane-4,4'-diisocyanate, liquefied MDI and polymethylene polyphenyl polyisocyanate. One or more of.
  4. 根据权利要求1或2所述的热熔反应型聚氨酯材料，其特征在于，所述聚酯多元醇包括结晶型聚酯多元醇和/或无定形聚酯多元醇。The hot-melt reactive polyurethane material according to claim 1 or 2, wherein the polyester polyol comprises a crystalline polyester polyol and/or an amorphous polyester polyol.
  5. 根据权利要求1或2所述的热熔反应型聚氨酯材料，其特征在于，所述增粘树脂包括萜烯树脂、氢化石油树脂、松香树脂和萜烯酚醛树脂中的一种或多种。The hot-melt reactive polyurethane material according to claim 1 or 2, wherein the tackifying resin comprises one or more of terpene resin, hydrogenated petroleum resin, rosin resin, and terpene phenol resin.
  6. 根据权利要求1或2所述的热熔反应型聚氨酯材料，其特征在于，所述催化剂包括辛酯亚锡、二月桂酸二丁基锡、二吗啉二乙基醚和三亚乙基二胺中的一种或多种。The hot-melt reaction type polyurethane material according to claim 1 or 2, wherein the catalyst includes the octyl stannous, dibutyltin dilaurate, dimorpholine diethyl ether and triethylenediamine. One or more.
  7. 根据权利要求1或2所述的热熔反应型聚氨酯材料，其特征在于，所述酸性稳定剂包括磷酸、苯甲酸和柠檬酸中的一种或多种。The hot-melt reactive polyurethane material according to claim 1 or 2, wherein the acid stabilizer comprises one or more of phosphoric acid, benzoic acid and citric acid.
  8. 根据权利要求1或2所述的热熔反应型聚氨酯材料，其特征在于，所述热熔反应型聚氨酯材料的粘度为5000～25000cps，NCO含量为0.01～2.0％。The hot-melt reactive polyurethane material according to claim 1 or 2, wherein the viscosity of the hot-melt reactive polyurethane material is 5000-25000 cps, and the NCO content is 0.01-2.0%.
  9. 根据权利要求1或2所述的热熔反应型聚氨酯材料，其特征在于，所述原料还包括聚醚多元醇、扩链剂、抗氧化剂和紫外线吸收剂中的一种或多种。The hot-melt reactive polyurethane material according to claim 1 or 2, wherein the raw material further comprises one or more of polyether polyol, chain extender, antioxidant, and ultraviolet absorber.
  10. 权利要求1～8任一项所述热熔反应型聚氨酯材料的制备方法，其特征在于，包括以下步骤：The preparation method of the hot-melt reactive polyurethane material according to any one of claims 1 to 8, characterized in that it comprises the following steps:
    (1)将聚酯多元醇、丙烯酸树脂、增粘树脂和酸性稳定剂混合干燥，得到干燥混合料；(1) Mix and dry polyester polyol, acrylic resin, tackifying resin and acidic stabilizer to obtain a dry mixture;
    (2)在保护气氛下，将所述干燥混合料和异氰酸酯混合进行预聚合反应，得到预聚合反应产物；(2) Under a protective atmosphere, mixing the dry mixture and isocyanate to perform a pre-polymerization reaction to obtain a pre-polymerization reaction product;
    (3)在保护气氛下，将所述预聚合反应产物和催化剂混合，进行聚合反应后，真空脱泡，得到所述热熔反应型聚氨酯材料。(3) Under a protective atmosphere, the pre-polymerization reaction product and the catalyst are mixed, and after the polymerization reaction is performed, vacuum defoaming is performed to obtain the hot-melt reaction type polyurethane material.
  11. 根据权利要求10所述的制备方法，其特征在于，所述预聚合反应的温度为80～90℃，时间为0.5～10h。The preparation method according to claim 10, wherein the temperature of the pre-polymerization reaction is 80-90°C, and the time is 0.5-10h.
  12. 根据权利要求10所述的制备方法，其特征在于，所述聚合反应的温度为80～90℃，时间为0.5～10h。The preparation method according to claim 10, wherein the temperature of the polymerization reaction is 80-90°C, and the time is 0.5-10h.
  13. 根据权利要求10所述的制备方法，其特征在于，所述步骤(1)干燥前还包括加入聚醚多元醇和/或扩链剂。The preparation method according to claim 10, wherein the step (1) further comprises adding polyether polyol and/or chain extender before drying.
  14. 根据权利要求10所述的制备方法，其特征在于，所述步骤(3)混合时还包括加入抗氧化剂和/或紫外线吸收剂。The preparation method according to claim 10, wherein the step (3) further comprises adding an antioxidant and/or an ultraviolet absorber when mixing.
  15. 权利要求1～9任一项所述的热熔反应型聚氨酯材料或由权利要求10～14任一项所述制备方法制得的热熔反应型聚氨酯材料在3D打印中的应用。Application of the hot-melt reactive polyurethane material according to any one of claims 1 to 9 or the hot-melt reactive polyurethane material prepared by the preparation method according to any one of claims 10 to 14 in 3D printing.
PCT/CN2020/086090 2020-04-22 2020-04-22 Hot-melt reaction type polyurethane material, preparation method therefor and use thereof WO2021212358A1 (en)

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CN117143511B (en) * 2023-10-30 2024-02-13 福建兴宇树脂有限公司 Polyurethane coating material for high weather-resistant automotive interior leather and preparation method thereof

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