WO2021208494A1 - 改性聚氨酯预聚体、双组分聚氨酯胶粘剂及其制备方法 - Google Patents

改性聚氨酯预聚体、双组分聚氨酯胶粘剂及其制备方法 Download PDF

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WO2021208494A1
WO2021208494A1 PCT/CN2020/139812 CN2020139812W WO2021208494A1 WO 2021208494 A1 WO2021208494 A1 WO 2021208494A1 CN 2020139812 W CN2020139812 W CN 2020139812W WO 2021208494 A1 WO2021208494 A1 WO 2021208494A1
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Prior art keywords
polyurethane prepolymer
alkyl
component
ureidopyrimidinone
modified polyurethane
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PCT/CN2020/139812
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English (en)
French (fr)
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宋骏
唐龙
陈建军
黄恒超
缪明松
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广州市白云化工实业有限公司
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Publication of WO2021208494A1 publication Critical patent/WO2021208494A1/zh
Priority to US17/965,748 priority Critical patent/US20230087542A1/en

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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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/042—Graphene or derivatives, e.g. graphene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C08F220/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
    • 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
    • C08G18/08—Processes
    • C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
    • C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
    • C08G18/0861—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers
    • C08G18/0866—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers the dispersing or dispersed phase being an aqueous medium
    • 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
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • 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
    • 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
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • 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
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3215—Polyhydroxy compounds containing aromatic groups or benzoquinone groups
    • 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
    • C08G18/4825—Polyethers containing two hydroxy groups
    • 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
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
    • C08G18/6225—Polymers of esters of acrylic or methacrylic acid
    • C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
    • 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
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6283—Polymers of nitrogen containing compounds having carbon-to-carbon double bonds
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/08—Polyurethanes from polyethers
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium

Definitions

  • the invention relates to the technical field of adhesives, in particular to a modified polyurethane prepolymer, a two-component polyurethane adhesive and a preparation method thereof.
  • Two-component polyurethane adhesives are widely used in automotive, woodworking, food packaging, civil construction and other fields because of their strong adhesion, adjustable curing rate, and strong performance design. It has become the largest variety and largest output of PU adhesives. Adhesive products. However, although aromatic polyurethane adhesives have strong mechanical properties, they have the defect of yellowing and aging, which restricts the high-end development of two-component polyurethane adhesives.
  • the industry can be roughly divided into two methods to solve the above problems.
  • One way is to add anti-aging agents or inorganic fillers that can absorb ultraviolet radiation. This method can only delay the aging to a certain extent, and yellowing and aging will still occur when the natural light exposure time becomes longer. Therefore, this method cannot fundamentally eliminate the yellowing and aging of the polyurethane adhesive, and adding too much anti-yellowing agent or filler will affect the overall mechanical properties of the polyurethane adhesive.
  • Another method is to solve the yellowing problem from the molecular structure design, such as changing the raw material of aromatic isocyanic acid to aliphatic isocyanic acid. This method can effectively avoid yellowing, but this also makes the mechanical strength of the polyurethane colloid obvious. It cannot be used for structural bonding of metal or other materials.
  • the purpose of the present invention is to provide a new type of two-component polyurethane adhesive that has excellent mechanical properties and aging resistance at the same time.
  • the present invention first provides a modified polyurethane prepolymer.
  • the two-component polyurethane adhesive containing the modified polyurethane prepolymer has excellent mechanical properties and aging resistance at the same time.
  • a modified polyurethane prepolymer in parts by weight, prepared from raw materials including the following components: polyurethane prepolymer and graphene oxide;
  • the polyurethane prepolymer is prepared from raw materials including the following components: copolymers containing ureidopyrimidinone groups, and aliphatic isocyanates;
  • the copolymer containing ureidopyrimidinone groups is copolymerized with raw materials including the following components: alkyl acrylate ureido pyrimidinone, alkyl hydroxyethyl acrylate, and the alkyl acrylate ureido pyrimidinone has the formula ( I) Shown structure:
  • the hydroxyethyl alkyl acrylate has a structure represented by formula (II):
  • R 1 is C 1 -C 6 alkyl
  • R 2 is H or C 1 -C 6 alkyl.
  • the copolymer containing ureidopyrimidinone groups has the structure shown in formula (III):
  • the aliphatic isocyanate is hexamethylene diisocyanate (HDI), 4,4'-dicyclohexylmethane diisocyanate (HMDI), isophorone diisocyanate (IPDI), 1, At least one of 4-cyclohexyl diisocyanate and methylcyclohexyl diisocyanate (HTDI).
  • HDI hexamethylene diisocyanate
  • HMDI 4,4'-dicyclohexylmethane diisocyanate
  • IPDI isophorone diisocyanate
  • HTDI methylcyclohexyl diisocyanate
  • the modified polyurethane prepolymer has a structure represented by formula (IV):
  • R 1 is methyl
  • R 2 is H, or methyl.
  • the mass ratio of the alkyl ureidopyrimidinone, hydroxyethyl alkyl acrylate, aliphatic isocyanate and graphene oxide is 100:5-20:60-90:1-30.
  • the mass ratio of the alkyl ureidopyrimidinone, hydroxyethyl alkyl acrylate, aliphatic isocyanate and graphene oxide is 100:8:12:75-85:15-25.
  • the NCO content of the modified polyurethane prepolymer is 11-14%, and the viscosity at 25° C. is 30,000-70,000 mPa ⁇ s.
  • the invention also provides a preparation method of the modified polyurethane prepolymer.
  • a method for preparing the above-mentioned modified polyurethane prepolymer includes the following steps:
  • Step I Dissolve the chain transfer agent, the alkyl ureidopyrimidinone, the alkyl hydroxyethyl acrylate, and the initiator in an organic solvent for copolymerization to obtain the copolymerization reaction containing the ureidopyrimidinone group Thing
  • Step II Add the aliphatic isocyanate to the mixed solution after the reaction in Step I, and react to obtain the polyurethane prepolymer;
  • Step III Add the graphene oxide to the mixed solution after the reaction in Step II, and react to obtain the modified polyurethane prepolymer.
  • the chain transfer agent is cumyl dithiobenzoate, tert-butyl benzocarbodisulfate, bis(benzylthio) methylthione, and 2-phenyl-2- At least one of propylbenzodisulfide.
  • the initiator is azobisisobutyronitrile, and/or benzoyl peroxide.
  • the amount of the chain transfer agent is 0.1-2 wt% of the alkyl acrylate ureidopyrimidinone.
  • the amount of the initiator is 0.1-2 wt% of the alkyl acrylate ureidopyrimidinone.
  • the reaction is carried out under the protection of nitrogen or inert gas.
  • the temperature of the copolymerization reaction in step I is 50-70° C.
  • the time of the copolymerization reaction is 6-18 hours.
  • the reaction temperature in step II is 20-30°C, and the reaction time is 18-28 hours.
  • the temperature of the reaction in step III is 20-30° C., and the reaction time is 1-3 hours.
  • the preparation method of the alkyl acrylate ureidopyrimidinone includes the following steps: adding 2-amino-4-hydroxy-6-methylpyrimidine to an organic solvent, and adding isomethacrylic acid isopropyl after dissolving. Ethyl cyano, reaction, that is.
  • the mass ratio of the 2-amino-4-hydroxy-6-methylpyrimidine and the isocyanoethyl methacrylate is 1:1-2.
  • the reaction temperature is 20-30°C, and the reaction time is 20-60 minutes.
  • the present invention also provides a two-component polyurethane adhesive, which has excellent mechanical properties and aging resistance at the same time.
  • a two-component polyurethane adhesive including component A and component B;
  • the A component is prepared from raw materials including the following components:
  • the B component is the above-mentioned modified polyurethane prepolymer.
  • the A component is prepared from raw materials including the following components:
  • the mass ratio of the A component and the B component is 1 to 3:1.
  • the polyol is one or more of phenyl-modified polyether polyol, polyether polyol, polyester polyol, and short-chain polyol.
  • the viscosity of the polyol at 25° C. is 1000-5000 cps.
  • the polyol has a mass ratio of 5:2-4:1-3 STEPANPOL PS-2002 and
  • the catalyst is an organotin catalyst and/or a tertiary amine catalyst.
  • the organotin catalyst may be, for example, dibutyltin dilaurate, stannous octoate, etc.
  • the tertiary amine catalyst may be, for example, triethylenediamine, triethanolamine, triethylamine, etc.
  • the inorganic filler is at least one of ultrafine calcium carbonate, nano calcium carbonate and aluminum hydroxide.
  • the particle size of the aluminum hydroxide is 1000 mesh to 2000 mesh.
  • the water-removing agent is a liquid water-removing agent and/or a solid water-removing agent.
  • the liquid water scavenger can be monocyclic or bicyclic oxazolidine, and the solid water scavenger can be ultrafine molecular sieve, ultrafine sodium sulfate, ultrafine calcium sulfate, and the like.
  • the invention also provides a preparation method of the above-mentioned two-component polyurethane adhesive.
  • a method for preparing the above-mentioned two-component polyurethane adhesive includes the following steps:
  • component A mixing the polyol and inorganic filler, adding the catalyst, stirring and dispersing, and vacuum defoaming to obtain the component A;
  • Step I Dissolve the chain transfer agent, the alkyl ureidopyrimidinone, the alkyl hydroxyethyl acrylate, and the initiator in an organic solvent for copolymerization to obtain the copolymerization reaction containing the ureidopyrimidinone group Thing
  • Step II Add the aliphatic isocyanate to the mixed solution after the reaction in Step I, and react to obtain the polyurethane prepolymer;
  • Step III Add the graphene oxide to the mixed solution after the reaction in Step II, and react to obtain the modified polyurethane prepolymer.
  • the chain transfer agent is cumyl dithiobenzoate, tert-butyl benzocarbodisulfate, bis(benzylthio) methylthione, and 2-phenyl-2- At least one of propylbenzodisulfide.
  • the initiator is azobisisobutyronitrile and/or benzoyl peroxide.
  • the amount of the chain transfer agent is 0.1-2 wt% of the alkyl acrylate ureidopyrimidinone.
  • the amount of the initiator is 0.1-2 wt% of the alkyl acrylate ureidopyrimidinone.
  • the reaction is carried out under the protection of nitrogen or inert gas.
  • the temperature of the copolymerization reaction in step I is 50-70° C.
  • the time of the copolymerization reaction is 6-18 hours.
  • the reaction temperature in step II is 20-30°C, and the reaction time is 18-28 hours.
  • the temperature of the reaction in step III is 20-30° C., and the reaction time is 1-3 hours.
  • the preparation method of the alkyl acrylate ureidopyrimidinone includes the following steps: adding 2-amino-4-hydroxy-6-methylpyrimidine to an organic solvent, and adding isomethacrylic acid isopropyl after dissolving. Ethyl cyano, reaction, that is.
  • the mass ratio of the 2-amino-4-hydroxy-6-methylpyrimidine and the isocyanoethyl methacrylate is 1:1-2.
  • the reaction temperature is 20-30°C, and the reaction time is 20-60 minutes.
  • the present invention has the following advantages and beneficial effects:
  • ureidopyrimidinone and graphene oxide are introduced into the aliphatic polyurethane chain to obtain a modified polyurethane prepolymer, and further obtain a two-component polyurethane adhesive containing the modified polyurethane prepolymer.
  • Ureapyrimidinone has a quadruple hydrogen bond and is incorporated into the aliphatic polyurethane chain, which can improve the mechanical strength that traditional aliphatic polyurethane adhesives do not have without affecting the aging performance.
  • Ureapyrimidinone further synergistically cooperates with the graphene introduced into the polyurethane main chain, which can greatly improve the mechanical strength and aging resistance of the polyurethane adhesive, and at the same time improve the flame retardant performance, high and low temperature resistance and high humidity resistance of the polyurethane adhesive. Therefore, the two-component polyurethane adhesive of the present invention has excellent bonding performance and outstanding aging resistance.
  • the two-component polyurethane adhesive of the present invention Compared with aromatic polyurethane structural adhesives, the two-component polyurethane adhesive of the present invention not only has better mechanical properties, but also has outstanding advantages in weather resistance, thereby significantly improving the practicality of the two-component polyurethane adhesive of the present invention. It has potential application value in some engineering fields that require harsh sealant conditions.
  • the experimental methods without specific conditions are usually in accordance with conventional conditions or in accordance with the conditions recommended by the manufacturer.
  • Various common chemical reagents used in the examples are all commercially available products.
  • the "plurality” mentioned in the present invention means two or more.
  • “And/or” describes the association relationship of the associated objects, indicating that there can be three types of relationships, for example, A and/or B, which can mean: A alone exists, A and B exist at the same time, and B exists alone.
  • the character “/” generally indicates that the associated objects before and after are in an "or” relationship.
  • the normal temperature or room temperature involved in the following embodiments refers to the indoor temperature when the temperature is 10-30°C.
  • This embodiment provides a new two-component polyurethane adhesive, which is composed of component A and component B with a mass ratio of 1:1; among them:
  • the preparation method of component A is as follows:
  • BASF BASF
  • PS-2002 polyol of STEPANPOL 20 parts by weight
  • BASF 20 parts by weight
  • Polyol and 70 parts by weight of 2000 mesh aluminum hydroxide purchased from Foshan Sanshui Jinge New Material Co., Ltd.
  • stannous octoate was added to the reactor at room temperature.
  • the preparation method of component B is as follows:
  • This embodiment provides a new two-component polyurethane adhesive, which is composed of component A and component B with a mass ratio of 3:1; among them:
  • the preparation method of component A is as follows:
  • BASF BASF
  • PS-2002 polyol of STEPANPOL 20 parts by weight
  • BASF 20 parts by weight
  • Polyol and 70 parts by weight of 2000 mesh aluminum hydroxide purchased from Foshan Sanshui Jinge New Material Co., Ltd.
  • stannous octoate was added to the reactor at room temperature.
  • component B For the preparation of component B, the raw materials and preparation method are roughly the same as those in Example 1, except that 80 parts by weight of hexamethylene diisocyanate (HDI) in step 3 of Example 1 is changed to 80 parts by weight of isophor. Ketone diisocyanate (IPDI).
  • the specific preparation method is as follows:
  • the wavy line part of the B component refers to the repeated chain structure, which can be the intermediate part 2 or the graphene oxide part.
  • IPDI isophorone diisocyanate
  • This comparative example provides a two-component polyurethane adhesive consisting of component A and component B with a mass ratio of 1:1;
  • the preparation method of component A is as follows:
  • BASF BASF
  • PS-2002 polyol of STEPANPOL 20 parts by weight
  • BASF 20 parts by weight
  • Polyol and 70 parts by weight of 2000 mesh aluminum hydroxide purchased from Foshan Sanshui Jinge New Material Co., Ltd.
  • stannous octoate was added to the reactor at room temperature.
  • the preparation method of component B is as follows:
  • This comparative example provides a two-component polyurethane adhesive consisting of component A and component B with a mass ratio of 1:1; among them,
  • the preparation method of component A is as follows:
  • BASF BASF
  • PS-2002 polyol of STEPANPOL 20 parts by weight of BASF.
  • Polyol, 1 part by weight of antioxidant (Tianjin Li'anlong New Material Co., Ltd., model 330), and 5 parts by weight of flame retardant (XS-FR-708) Add 70 parts by weight of 2000 mesh aluminum hydroxide (Foshan Sanshui Jinge New Material Co., Ltd.) into the reactor, stir at room temperature for 20 minutes, then add 1 part by weight of stannous octoate to the reactor, stir and disperse at room temperature. After hours, vacuum degassing to obtain component A with a viscosity of 12000 mPa ⁇ s at 25°C.
  • the preparation method of component B is as follows:
  • the two-component polyurethane adhesives prepared in the foregoing Examples 1-2 and Comparative Examples 1-2 were cured at 60°C for 6 hours and tested for their mechanical properties and flame retardant properties.
  • the specific methods are as follows:
  • Hardness test method GB/T 531.1-2008 vulcanized rubber or thermoplastic rubber indentation hardness test method Part 1: Shore durometer method (Sauer hardness).
  • Adhesion test method GB/T 7124-2008 Determination of the tensile shear strength of adhesives (rigid material versus rigid material).
  • the flame-retardant test method is: GB/24267-2009 flame-retardant sealant for construction.
  • Example 1 Comparing Example 1 and Example 2, using different aliphatic isocyanates as raw materials, the macro-mechanical properties of the polyurethane adhesives prepared are not significantly different.
  • the polyurethane adhesive with ureidopyrimidinone and graphene oxide (Example 1) is better than the one without introducing the above functional groups in hardness, bonding strength, tensile strength and flame retardancy.
  • Polyurethane adhesives (Comparative Example 1) are significantly improved. This is because the ureidopyrimidinone structure in the molecule can form a quadruple hydrogen bond, which strengthens the soft and hard chain forging microscopic phase separation of the polyurethane adhesive, and the macroscopic mechanical properties are stronger, so that the hardness, shear strength and tensile strength are all significant. improve.
  • the introduction of graphene into the polyurethane main chain improves the flame retardant properties of the polyurethane adhesive.
  • Comparing Example 1, Comparative Example 1 and Comparative Example 2 the hardness, shear strength and tensile strength of the polyurethane adhesive of Comparative Example 2 were significantly higher than those of Comparative Example 1, while the hardness, shear strength and tensile strength of the polyurethane adhesive of Example 1 The tensile strength is significantly higher than that of Comparative Example 2. It shows that the rigidity of polyurethane adhesive prepared with aromatic isocyanate as raw material is stronger than that of polyurethane adhesive prepared with aliphatic isocyanate as raw material.
  • the two-component polyurethane adhesives prepared in the above examples 1-2 and comparative examples 1-2 were made into PC/PC shear samples according to the method of GB/T 7124-2008, and the aging resistance was tested after curing at 25°C for 8 days, the specific method as follows:
  • Test Method Constant damp heat is mainly used for accelerated testing of components.
  • Example 1 The two-component polyurethane adhesives prepared in Example 1, Comparative Example 1 and Comparative Example 2 were prepared according to GB/T1040.2-2006 for dumbbell-shaped samples, cured at 25°C for 8 days, and then the samples were placed on the roof of the building. 100 days of natural light exposure, regular sampling for tensile strength test.
  • Comparative Example 1 is an aliphatic polyurethane adhesive. Although the attenuation ratio of shear strength is small in the 100-day light test, the mechanical strength of the colloid itself is not high enough; while in Comparative Example 4, even with the addition of anti-aging agent, as the light time increases, The strength of the colloid is still greatly attenuated.

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Abstract

本发明涉及一种改性聚氨酯预聚体、双组分聚氨酯胶粘剂及其制备方法，该改性聚氨酯预聚体由包括如下组分的原料制备而成：聚氨酯预聚体、氧化石墨烯；所述聚氨酯预聚体由包括如下组分的原料制备而成：含有脲基嘧啶酮基团的共聚物、脂肪族异氰酸酯；所述含有脲基嘧啶酮基团的共聚物由包括如下组分的原料共聚而成：烷基丙烯酸脲基嘧啶酮、烷基丙烯酸羟乙酯；所述烷基丙烯酸脲基嘧啶酮具有式(I)所示结构，所述烷基丙烯酸羟乙酯具有式(II)所示结构。包含该改性聚氨酯预聚体的双组分聚氨酯胶粘剂同时具有优异的力学性能和耐老化性能。

Description

改性聚氨酯预聚体、双组分聚氨酯胶粘剂及其制备方法 技术领域
本发明涉及胶粘剂技术领域，特别是涉及一种改性聚氨酯预聚体、双组分聚氨酯胶粘剂及其制备方法。
背景技术
双组分聚氨酯胶粘剂因其具有粘接力强、固化速率可调、性能设计性强等优点，广泛运用于汽车、木工、食品包装、土木建筑等领域，已成为品种最多且产量最大的PU胶黏剂产品。然而芳香型聚氨酯胶虽然力学性能强，但是存在易黄变老化的缺陷而制约着双组分聚氨酯胶粘剂的高端发展。
业界大致可分为两种方法解决上述问题。一种方式是添加抗老化剂或者能吸收紫外线辐射的无机填料，这种方法只能一定程度上延缓老化，在自然光照射时间变长的情况下仍然会出现黄变老化。因此，此方法不能从根本上消除聚氨酯胶粘剂的黄变老化，同时添加太多抗黄变剂或者填料会影响聚氨酯胶粘剂整体的力学性能。另一种方法则是从分子结构设计上解决黄变问题，比如将芳香型异氰酸原料改为脂肪族异氰酸，此方法可有效避免黄变，但是这也使得聚氨酯胶体的力学强度明显下降，不能用于金属或者其他材料的结构粘接。
因此，开发出力学性能优异且耐黄变老化的聚氨酯胶粘剂对于聚氨酯胶粘剂行业的高端拓展具有重大意义。
发明内容
基于此，本发明的目的在于提供一种新型的双组分聚氨酯胶粘剂，使其同 时具有优异的力学性能和耐老化性能。
为了达到上述目的，本发明首先提供了一种改性聚氨酯预聚体，包含该改性聚氨酯预聚体的双组分聚氨酯胶粘剂同时具有优异的力学性能和耐老化性能。
具体技术方案如下：
一种改性聚氨酯预聚体，以重量份数计，由包括如下组分的原料制备而成：聚氨酯预聚体、氧化石墨烯；
所述聚氨酯预聚体由包括如下组分的原料制备而成：含有脲基嘧啶酮基团的共聚物、脂肪族异氰酸酯；
所述含有脲基嘧啶酮基团的共聚物由包括如下组分的原料共聚而成：烷基丙烯酸脲基嘧啶酮、烷基丙烯酸羟乙酯，所述烷基丙烯酸脲基嘧啶酮具有式(I)所示结构：
Figure PCTCN2020139812-appb-000001
所述烷基丙烯酸羟乙酯具有式(II)所示结构：
Figure PCTCN2020139812-appb-000002
其中，R 1为C 1-C 6烷基；R 2为H、或者C 1-C 6烷基。
在其中一些实施例中，所述含有脲基嘧啶酮基团的共聚物具有式(III)所 示结构：
Figure PCTCN2020139812-appb-000003
其中，n为1-100，m为1-10；R 1为C 1-C 6烷基；R 2为H、或者C 1-C 6烷基。
在其中一些实施例中，所述脂肪族异氰酸酯为六亚甲基二异氰酸酯(HDI)、4,4'-二环己基甲烷二异氰酸酯(HMDI)、异佛尔酮二异氰酸酯(IPDI)、1,4-环己基二异氰酸酯和甲基环己基二异氰酸酯(HTDI)中的至少一种。
在其中一些实施例中，所述改性聚氨酯预聚体具有式(IV)所示结构：
Figure PCTCN2020139812-appb-000004
其中n为1-100，m为1-10；R 1为C 1-C 6烷基；R 2为H、或者C 1-C 6烷基；R为-(CH 2) 6-、
Figure PCTCN2020139812-appb-000005
Figure PCTCN2020139812-appb-000006
在其中一些实施例中，R 1为甲基。
在其中一些实施例中，R 2为H、或者甲基。
在其中一些实施例中，所述烷基丙烯酸脲基嘧啶酮、烷基丙烯酸羟乙酯、脂肪族异氰酸酯和氧化石墨烯的质量比为100:5-20：60-90：1-30。
在其中一些实施例中，所述烷基丙烯酸脲基嘧啶酮、烷基丙烯酸羟乙酯、脂肪族异氰酸酯和氧化石墨烯的质量比为100:8:12：75-85：15-25。
在其中一些实施例中，所述改性聚氨酯预聚体的NCO含量为11-14％，25℃下的粘度为30000-70000mPa.s。
本发明还提供了上述改性聚氨酯预聚体的制备方法。
具体技术方案如下：
一种上述的改性聚氨酯预聚体的制备方法，包括如下步骤：
步骤I：将链转移剂、所述烷基丙烯酸脲基嘧啶酮、所述烷基丙烯酸羟乙酯和引发剂溶解于有机溶剂中进行共聚反应，得所述含有脲基嘧啶酮基团的共聚物；
步骤II：向步骤I反应后的混合溶液中加入所述脂肪族异氰酸酯，反应，得所述聚氨酯预聚体；
步骤III：再向步骤II反应后的混合溶液中加入所述氧化石墨烯，反应，即 得所述改性聚氨酯预聚体。
在其中一些实施例中，所述链转移剂为二硫代苯甲酸枯酯、叔丁基苯并碳二硫酸酯、双(苯甲基硫基)甲硫酮和2-苯基-2-丙基苯并二硫中的至少一种。
在其中一些实施例中，所述引发剂为偶氮二异丁腈、和/或过氧化苯甲酰。
在其中一些实施例中，所述链转移剂的用量为所述烷基丙烯酸脲基嘧啶酮的0.1-2wt％。
在其中一些实施例中，所述引发剂的用量为所述烷基丙烯酸脲基嘧啶酮的0.1-2wt％。
在其中一些实施例中，所述反应在氮气或者惰性气体保护下进行。
在其中一些实施例中，步骤I所述共聚反应的温度为50-70℃，所述共聚反应的时间为6-18小时。
在其中一些实施例中，步骤II所述反应的温度为20-30℃，所述反应的时间为18-28小时。
在其中一些实施例中，步骤III所述反应的温度为20-30℃，所述反应的时间为1-3小时。
在其中一些实施例中，所述烷基丙烯酸脲基嘧啶酮的制备方法包括以下步骤：将2-氨基-4-羟基-6-甲基嘧啶加入到有机溶剂中，溶解后加入甲基丙烯酸异氰基乙酯，反应，即得。
在其中一些实施例中，所述2-氨基-4-羟基-6-甲基嘧啶和所述甲基丙烯酸异氰基乙酯的质量比为1:1-2。
在其中一些实施例中，所述反应的温度为20-30℃，所述反应的时间为20-60分钟。
本发明还提供了一种双组分聚氨酯胶粘剂，该双组分聚氨酯胶粘剂同时具 有优异的力学性能和耐老化性能。
具体技术方案如下：
一种双组分聚氨酯胶粘剂，包括A组分和B组分；
以重量份数计，所述A组分由包括如下组分的原料制备而成：
多元醇                    100份
催化剂                    0.01～5份
无机填料                  50～100份；
所述B组分为上述的改性聚氨酯预聚体。
在其中一些实施例中，所述A组分由包括如下组分的原料制备而成：
多元醇                    100份
催化剂                    0.5～1.5份
无机填料                  65～75份。
在其中一些实施例中，所述A组分和B组分的质量比为1～3:1。
在其中一些实施例中，所述多元醇为苯基改性的聚醚多元醇、聚醚多元醇、聚酯多元醇和短链多元醇中的一种或者多种。
在其中一些实施例中，所述多元醇在25℃的粘度为1000～5000cps。
在其中一些实施例中，所述多元醇为质量比为5:2-4:1-3的
Figure PCTCN2020139812-appb-000007
STEPANPOL PS-2002和
Figure PCTCN2020139812-appb-000008
在其中一些实施例中，所述催化剂为有机锡类催化剂和/或叔胺类催化剂。有机锡类催化剂例如可以是二月桂酸二丁基锡、辛酸亚锡等，叔胺类催化剂例如可以是三亚乙基二胺、三乙醇胺、三乙胺等。
在其中一些实施例中，所述无机填料为超细碳酸钙、纳米碳酸钙和氢氧化铝中的至少一种。
在其中一些实施例中，所述氢氧化铝的粒径为1000目-2000目。
在其中一些实施例中，所述除水剂为液体除水剂和/或固体除水剂。所述液体除水剂可以是单环或双环噁唑烷，所述固体除水剂可以是超细分子筛、超细硫酸钠、超细硫酸钙等。
本发明还提供了上述双组分聚氨酯胶粘剂的制备方法。
具体技术方案如下：
一种上述的双组分聚氨酯胶粘剂的制备方法，包括如下步骤：
A组分的制备：将所述多元醇和无机填料混合，再加入所述催化剂，搅拌分散，真空脱泡，即得所述A组分；
B组分的制备：
步骤I：将链转移剂、所述烷基丙烯酸脲基嘧啶酮、所述烷基丙烯酸羟乙酯和引发剂溶解于有机溶剂中进行共聚反应，得所述含有脲基嘧啶酮基团的共聚物；
步骤II：向步骤I反应后的混合溶液中加入所述脂肪族异氰酸酯，反应，得所述聚氨酯预聚体；
步骤III：再向步骤II反应后的混合溶液中加入所述氧化石墨烯，反应，即得所述改性聚氨酯预聚体。
在其中一些实施例中，所述链转移剂为二硫代苯甲酸枯酯、叔丁基苯并碳二硫酸酯、双(苯甲基硫基)甲硫酮和2-苯基-2-丙基苯并二硫中的至少一种。
在其中一些实施例中，所述引发剂为偶氮二异丁腈和/或过氧化苯甲酰。
在其中一些实施例中，所述链转移剂的用量为所述烷基丙烯酸脲基嘧啶酮的0.1-2wt％。
在其中一些实施例中，所述引发剂的用量为所述烷基丙烯酸脲基嘧啶酮的 0.1-2wt％。
在其中一些实施例中，所述反应在氮气或者惰性气体保护下进行。
在其中一些实施例中，步骤I所述共聚反应的温度为50-70℃，所述共聚反应的时间为6-18小时。
在其中一些实施例中，步骤II所述反应的温度为20-30℃，所述反应的时间为18-28小时。
在其中一些实施例中，步骤III所述反应的温度为20-30℃，所述反应的时间为1-3小时。
在其中一些实施例中，所述烷基丙烯酸脲基嘧啶酮的制备方法包括以下步骤：将2-氨基-4-羟基-6-甲基嘧啶加入到有机溶剂中，溶解后加入甲基丙烯酸异氰基乙酯，反应，即得。
在其中一些实施例中，所述2-氨基-4-羟基-6-甲基嘧啶和所述甲基丙烯酸异氰基乙酯的质量比为1:1-2。
在其中一些实施例中，所述反应的温度为20-30℃，所述反应的时间为20-60分钟。
本发明相对于现有技术，具有如下的优点及有益效果：
本发明将脲基嘧啶酮以及氧化石墨烯引入到脂肪族聚氨酯链中，获得了一种改性聚氨酯预聚体，进一步获得了包含该改性聚氨酯预聚体的双组分聚氨酯胶粘剂。脲基嘧啶酮具有四重氢键，引入到脂肪族聚氨酯链中，可以在不影响老化性能的条件下提高传统脂肪族聚氨酯胶粘剂不具备的力学强度。脲基嘧啶酮进一步协同配合引入到聚氨酯主链上的石墨烯，可以大大提高聚氨酯胶粘剂的力学强度和耐老化性能，同时还提高了聚氨酯胶粘剂的阻燃性能和耐高低温 以及耐高湿的性能，从而使本发明的双组分聚氨酯胶粘剂的粘接性能优异、耐老化性能突出。
本发明的双组分聚氨酯胶粘剂相较于芳香族聚氨酯结构胶，不但力学性能更加优异，在耐候性上也具有突出的优势，从而使得本发明的双组分聚氨酯胶粘剂在实用性上显著提高，在一些对密封胶条件要求苛刻的工程领域具有潜在的应用价值。
具体实施方式
本发明下列实施例中未注明具体条件的实验方法，通常按照常规条件，或按照制造厂商所建议的条件。实施例中所用到的各种常用化学试剂，均为市售产品。
除非另有定义，本发明所使用的所有的技术和科学术语与属于本发明的技术领域的技术人员通常理解的含义相同。本发明的说明书中所使用的术语只是为了描述具体的实施例的目的，不用于限制本发明。
本发明的术语“包括”和“具有”以及它们任何变形，意图在于覆盖不排他的包含。例如包含了一系列步骤的过程、方法、装置、产品或设备没有限定于已列出的步骤或模块，而是可选地还包括没有列出的步骤，或可选地还包括对于这些过程、方法、产品或设备固有的其它步骤。
在本发明中提及的“多个”是指两个或两个以上。“和/或”，描述关联对象的关联关系，表示可以存在三种关系，例如，A和/或B，可以表示：单独存在A，同时存在A和B，单独存在B这三种情况。字符“/”一般表示前后关联对象是一种“或”的关系。
以下结合具体实施例来详细说明本发明。
以下实施例中所涉及的常温或室温指温度为10-30℃时的室内温度。
实施例1
本实施例提供一种新型双组分聚氨酯胶粘剂，由质量比为1:1的A组分和B组分组成；其中：
A组分的制备方法如下：
取50重量份型号为巴斯夫(BASF)
Figure PCTCN2020139812-appb-000009
的多元醇、30重量份型号为斯泰潘公司(STEPANPOL)PS-2002的多元醇、20重量份型号为巴斯夫(BASF)
Figure PCTCN2020139812-appb-000010
的多元醇和70重量份2000目的氢氧化铝(购自佛山市三水金戈新型材料有限公司)加入到反应釜中，常温搅拌20分钟，之后往反应釜中加入1重量份辛酸亚锡，常温下搅拌分散1小时，真空脱泡，得到A组分，25℃下粘度为12000mPa.s。
其中，
Figure PCTCN2020139812-appb-000011
为苯基改性的聚醚多元醇，25℃的粘度为4500-4900mPa.s；PS-2002为聚酯多元醇，25℃的粘度为3000-3200mPa.s；
Figure PCTCN2020139812-appb-000012
为聚醚多元醇25℃的粘度为2000-2300mPa.s。
B组分的制备方法如下：
步骤1：中间体1的制备
Figure PCTCN2020139812-appb-000013
将100份的2-氨基-4-羟基-6-甲基嘧啶加入到200份的无水N,N-二甲基甲酰胺(DMF)中，完全溶解之后迅速加入132份的甲基丙烯酸异氰基乙酯，25℃下反应半小时。反应完毕后旋蒸除去大部分溶剂，剩下的溶液经过洗涤后干燥获得白色产物，即中间体1，产率为95.2％。
中间体1的核磁氢谱(氘代氯仿，ppm)：化学位移在10.2-13.1之间有三个N-H的峰；化学位移在6.21和5.55分别有一个C＝C-H 2的峰；化学位移在5.80附近有一个嘧啶环上的C-H峰；化学位移在4.25-4.28之间有O-CH 2峰；化学位移在3.58附近有个N-CH 2的峰；以及化学位移在1.88-2.25之间有多个甲基的峰。
中间体1的红外谱图：1660cm -1为氨基甲酸酯的羰基峰；1698cm -1为嘧啶芳环上的羰基峰；1725cm -1为酯键羰基峰，3038cm -1为碳碳双键的峰。
步骤2：中间体2的制备
Figure PCTCN2020139812-appb-000014
将1重量份的链转移剂二硫代苯甲酸枯酯、100重量份上述步骤1制备的中间体1、10重量份甲基丙烯酸羟乙酯和1重量份的偶氮二异丁腈溶解于250重量份的无水N,N-二甲基甲酰胺中；反应装置密封好后经过三次冷冻-抽真空-解冻-通氮气的循环操作，以保证反应在无水无氧条件下进行，之后在60℃下反应12小时，得到中间体2，不经纯化，直接用于下一步反应。
中间体2的红外谱图：1660cm -1为氨基甲酸酯的羰基峰；1698cm -1为嘧啶芳环上的羰基峰；1725cm -1为中间体1单体中的酯键羰基峰；1890cm -1为羟乙酯中的羰基峰；3550cm -1为羟基峰。
步骤3：B组分的制备
Figure PCTCN2020139812-appb-000015
往步骤2得到的反应溶液中加入80重量份六亚甲基二异氰酸酯(HDI)，25℃反应24小时后制备得到聚氨酯预聚体，再往所述聚氨酯预聚体溶液中加入20重量份经过冷冻干燥处理的氧化石墨烯粉末(购自常州第六元素材料科技股份有限公司)，25℃下搅拌2小时。最后真空干燥除去溶剂，得到黑褐色粘稠状液体，即得组分B，25℃下粘度为52000mPa.s，NCO含量为13.3％。
实施例2：
本实施例提供一种新型双组分聚氨酯胶粘剂，由质量比为3:1的A组分和B组分组成；其中：
A组分的制备方法如下：
取50重量份型号为巴斯夫(BASF)
Figure PCTCN2020139812-appb-000016
的多元醇、30重量份型号为斯泰潘公司(STEPANPOL)PS-2002的多元醇、20重量份型号为巴斯夫(BASF)
Figure PCTCN2020139812-appb-000017
的多元醇和70重量份2000目的氢氧化铝(购自佛山 市三水金戈新型材料有限公司)加入到反应釜中，常温搅拌20分钟，之后往反应釜中加入1重量份辛酸亚锡，常温下搅拌分散1小时，真空脱泡，得到A组分，25℃下粘度为12000mPa.s。
其中，
Figure PCTCN2020139812-appb-000018
为苯基改性的聚醚多元醇，25℃的粘度为4500-4900mPa.s；PS-2002为聚酯多元醇，25℃的粘度为3000-3200mPa.s；
Figure PCTCN2020139812-appb-000019
为聚醚多元醇25℃的粘度为2000-2300mPa.s。
B组分的制备，其原料和制备方法与实施例1大致相同，唯一不同的是将实施例1步骤3中的80重量份六亚甲基二异氰酸酯(HDI)变为80重量份异佛尔酮二异氰酸酯(IPDI)。具体制备方法如下：
步骤1：中间体1的制备
Figure PCTCN2020139812-appb-000020
将100份的2-氨基-4-羟基-6-甲基嘧啶加入到200份的无水N,N-二甲基甲酰胺(DMF)中，完全溶解之后迅速加入132份的甲基丙烯酸异氰基乙酯，25℃下反应半小时。反应完毕后旋蒸除去大部分溶剂，剩下的溶液经过洗涤后干燥获得白色产物，即中间体1，产率为95.2％。
中间体1的核磁氢谱(氘代氯仿，ppm)：化学位移在10.2-13.1之间有三个N-H的峰；化学位移在6.21和5.55分别有一个C＝C-H 2的峰；化学位移在5.80附近有一个嘧啶环上的C-H峰；化学位移在4.25-4.28之间有O-CH 2峰；化学位移在3.58附近有个N-CH 2的峰；以及化学位移在1.88-2.25之间有多个甲基的峰。
中间体1的红外谱图：1660cm -1为氨基甲酸酯的羰基峰；1698cm -1为嘧啶芳环上的羰基峰；1725cm -1为酯键羰基峰，3038cm -1为碳碳双键的峰。
步骤2：中间体2的制备
Figure PCTCN2020139812-appb-000021
将1重量份的链转移剂二硫代苯甲酸枯酯、100重量份上述步骤1制备的中间体1、10重量份甲基丙烯酸羟乙酯和1重量份的偶氮二异丁腈溶解于250重量份的无水N,N-二甲基甲酰胺中；反应装置密封好后经过三次冷冻-抽真空-解冻-通氮气的循环操作，以保证反应在无水无氧条件下进行，之后在60℃下反应12小时，得到中间体2，不经纯化，直接用于下一步反应。
中间体2的红外谱图：1660cm -1为氨基甲酸酯的羰基峰；1698cm -1为嘧啶芳环上的羰基峰；1725cm -1为中间体1单体中的酯键羰基峰；1890cm -1为羟乙酯中的羰基峰；3550cm -1为羟基峰。
步骤3：B组分的制备
Figure PCTCN2020139812-appb-000022
B组分的波浪线部分指代重复的链结构，可以是中间体2部分，也可以是氧化石墨烯部分。
往步骤2得到的反应溶液中加入80重量份异佛尔酮二异氰酸酯(IPDI)，25℃反应24小时后制备得到聚氨酯预聚体，再往所述聚氨酯预聚体溶液中加入20重量份经过冷冻干燥处理的氧化石墨烯粉末(购自常州第六元素材料科技股份有限公司)，25℃下搅拌2小时。最后真空干燥除去溶剂，得到黑褐色粘稠状液体，即得组分B，25℃下粘度为48000mPa.s，NCO含量为12.1％。
对比例1
本对比例提供一种双组分聚氨酯胶粘剂，由质量比为1:1的A组分和B组分组成；
A组分的制备方法如下：
取50重量份型号为巴斯夫(BASF)
Figure PCTCN2020139812-appb-000023
的多元醇、30重量份型号为斯泰潘公司(STEPANPOL)PS-2002的多元醇、20重量份型号为巴斯夫(BASF)
Figure PCTCN2020139812-appb-000024
的多元醇和70重量份2000目的氢氧化铝(购自佛山市三水金戈新型材料有限公司)加入到反应釜中，常温搅拌20分钟，之后往反应釜中加入1重量份辛酸亚锡，常温下搅拌分散1小时，真空脱泡，得到A组分，25℃下粘度为12000mPa.s。
其中，
Figure PCTCN2020139812-appb-000025
为苯基改性的聚醚多元醇，25℃的粘度为4500-4900mPa.s；PS-2002为聚酯多元醇，25℃的粘度为3000-3200mPa.s；
Figure PCTCN2020139812-appb-000026
为聚醚多元醇25℃的粘度为2000-2300mPa.s。
B组分的制备方法如下：
将100重量份南京博奔聚氨酯有限公司的聚醚多元醇(PPG-2000)和2重量份的1,4-丁二醇投入反应釜中，110℃下真空搅拌3小时。之后往反应釜中加入1重量份的辛酸亚锡和120重量份万华化学的
Figure PCTCN2020139812-appb-000027
在60℃下反应8小时，真空脱泡1小时，获得白色透明粘稠状液体，即组分B，25℃下粘度为40000mPa.s，NCO含量在12.8％。
对比例2：
本对比例提供一种双组分聚氨酯胶粘剂，由质量比为1:1的A组分和B组分组成；其中，
A组分的制备方法如下：
取50重量份型号为巴斯夫(BASF)
Figure PCTCN2020139812-appb-000028
的多元醇、30重量份型号为斯泰潘公司(STEPANPOL)PS-2002的多元醇、20重量份型号为巴斯夫 (BASF)
Figure PCTCN2020139812-appb-000029
的多元醇、1重量份抗氧化剂(天津利安隆新材料股份有限公司，型号为330)、5重量份阻燃剂(旭森非卤消烟阻燃剂有限公司型号为XS-FR-708)和70重量份2000目的氢氧化铝(佛山市三水金戈新型材料有限公司)加入到反应釜中，常温搅拌20分钟，之后往反应釜中加入1重量份辛酸亚锡，常温下搅拌分散1小时，真空脱泡，得到A组分，25℃下粘度为12000mPa.s。
其中，
Figure PCTCN2020139812-appb-000030
为苯基改性的聚醚多元醇，25℃的粘度为4500-4900mPa.s；PS-2002为聚酯多元醇，25℃的粘度为3000-3200mPa.s；
Figure PCTCN2020139812-appb-000031
为聚醚多元醇25℃的粘度为2000-2300mPa.s。
B组分的制备方法如下：
将100重量份南京博奔聚氨酯有限公司的聚醚多元醇(PPG-2000)和2重量份的1,4-丁二醇投入反应釜中，110℃下真空搅拌3小时。之后往反应釜中加入1重量份的辛酸亚锡和120重量份万华化学
Figure PCTCN2020139812-appb-000032
型号的液化MDI，在60℃下反应8小时，真空脱泡1小时，获得白色透明粘稠状液体，即组分B，25℃下粘度为45000mPa.s，NCO含量在12.6％。
将上述实施例1-2以及对比例1-2制备的双组分聚氨酯胶粘剂进行以下性能测试：
1、力学性能及阻燃性能测试
将上述实施例1-2以及对比例1-2制备的双组分聚氨酯胶粘剂在60℃固化6小时后测试其力学性能和阻燃性能，具体方法如下：
硬度测试方法：GB/T 531.1-2008硫化橡胶或热塑性橡胶压入硬度试验方法第1部分：邵氏硬度计法(绍尔硬度)。
粘接力测试方法：GB/T 7124-2008胶粘剂拉伸剪切强度的测定(刚性材料对刚性材料)。
阻燃性测试方法为：GB/24267-2009建筑用阻燃密封胶。
拉伸强度测试方法：GB/T 1040.2-2006塑料拉伸性能的测定第2部分：模塑和挤塑塑料的测定。
测试结果如下表1所示。
表1
Figure PCTCN2020139812-appb-000033
分析表1结果可知：
对比实施例1和实施例2，以不同的脂肪族异氰酸酯为原料，制备得到的聚氨酯胶粘剂的宏观力学性能差别不明显。
对比实施例1和实施例3，引入脲基嘧啶酮和氧化石墨烯的聚氨酯胶粘剂(实施例1)在硬度、粘接强度、拉伸强度和阻燃性能上比不引入上述功能性基团的聚氨酯胶粘剂(对比例1)都明显提高不少。这是由于分子中的脲基嘧啶酮结构可以形成四重氢键，加强了聚氨酯胶粘剂的软硬链锻微观相分离，宏观上力学性能更强，从而硬度、剪切强度和拉伸强度都显著提高。而将石墨烯引入到聚氨酯主链上则提高了聚氨酯胶的阻燃性能。
对比实施例1、对比例1和对比例2，对比例2的聚氨酯胶粘剂的硬度、剪切强度和拉伸强度明显高于对比例1，而实施例1的聚氨酯胶粘剂的硬度、剪切 强度和拉伸强度明显高于对比例2。说明以芳香型异氰酸酯为原料制备的聚氨酯胶粘剂的刚性比以脂肪型异氰酸酯为原料制备的聚氨酯胶粘剂的刚性更强。然而在脂肪型聚氨酯主链中引入脲基嘧啶酮和氧化石墨烯后(实施例1)，其硬度、剪切强度和拉伸强度都比芳香型聚氨酯胶粘剂(对比例2)更高。对比例2的聚氨酯胶粘剂的阻燃等级为V-0是由于加入了阻燃剂，而未加多余阻燃剂的实施例1和实施例2同样能够达到V-0。
2、耐老化性能测试
将上述实施例1-2以及对比例1-2制备的双组分聚氨酯胶粘剂按GB/T 7124-2008方法做成PC/PC剪切样品，25℃固化8天后测试其耐老化性能，具体方法如下：
耐高温高湿(双85,2000小时)测试方法：GB/T 2423.50-2012环境试验第2部分：试验方法试验Cy：恒定湿热主要用于元件的加速试验。
耐高低温循环(-40℃-80℃，1000次)测试方法：GB/T 2423.22-2012环境试验第2部分：试验方法试验N：温度变化。
测试结果如下表2所示。
表2
Figure PCTCN2020139812-appb-000034
分析表2结果可知：在脂肪型聚氨酯主链中引入脲基嘧啶酮和氧化石墨烯 后，聚氨酯胶粘剂的耐高温高湿和耐高低温循环性能都显著提高。
3、耐自然光照测试
将实施例1、对比例1和对比例2制备的双组分聚氨酯胶粘剂按GB/T1040.2-2006制备哑铃型样品，在25℃条件下固化8天，然后将样品放置在房屋楼顶进行自然光照射100天，定期取样进行拉伸强度测试。
测试结果如下表3所示。
表3
Figure PCTCN2020139812-appb-000035
分析表3结果可知：在脂肪型聚氨酯主链中引入脲基嘧啶酮和氧化石墨烯后，聚氨酯胶粘剂在耐自然光照性能显著提高。对比例1是脂肪族聚氨酯胶粘剂，100天的光照测试虽然剪切强度衰减比例较小，但是胶体自身力学强度不够高；而对比例4即使添加了抗老化剂，但随着光照时间的延长，胶体的强度依然大幅度衰减。
综合表1-表3的结果可见：在脂肪型聚氨酯主链中引入脲基嘧啶酮和氧化石墨烯后，可以显著提高聚氨酯胶粘剂的胶体强度，提高其粘结强度和力学性能，同时可以显著提高其耐老化性能。
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技 术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。

Claims (13)

  1. 一种改性聚氨酯预聚体，其特征在于，由包括如下组分的原料制备而成：聚氨酯预聚体、氧化石墨烯；
    所述聚氨酯预聚体由包括如下组分的原料制备而成：含有脲基嘧啶酮基团的共聚物、脂肪族异氰酸酯；
    所述含有脲基嘧啶酮基团的共聚物由包括如下组分的原料共聚而成：烷基丙烯酸脲基嘧啶酮、烷基丙烯酸羟乙酯；
    所述烷基丙烯酸脲基嘧啶酮具有式(I)所示结构：
    Figure PCTCN2020139812-appb-100001
    所述烷基丙烯酸羟乙酯具有式(II)所示结构：
    Figure PCTCN2020139812-appb-100002
    其中，R 1为C 1-C 6烷基；R 2为H、或者C 1-C 6烷基。
  2. 根据权利要求1所述的改性聚氨酯预聚体，其特征在于，所述含有脲基嘧啶酮基团的共聚物具有式(III)所示结构：
    Figure PCTCN2020139812-appb-100003
    其中，n为1-100，m为1-10；R 1为C 1-C 6烷基；R 2为H、或者C 1-C 6烷基。
  3. 根据权利要求1所述的改性聚氨酯预聚体，其特征在于，所述脂肪族异氰酸酯为六亚甲基二异氰酸酯、4,4'-二环己基甲烷二异氰酸酯、异佛尔酮二异氰酸酯、1,4-环己基二异氰酸酯和甲基环己基二异氰酸酯中的至少一种。
  4. 根据权利要求1所述的改性聚氨酯预聚体，其特征在于，所述改性聚氨酯预聚体具有式(IV)所示结构：
    Figure PCTCN2020139812-appb-100004
    其中n为1-100，m为1-10；R 1为C 1-C 6烷基；R 2为H、或者C 1-C 6烷基；
    R为-(CH 2) 6-、
    Figure PCTCN2020139812-appb-100005
    Figure PCTCN2020139812-appb-100006
    或者
    Figure PCTCN2020139812-appb-100007
  5. 根据权利要求1-4任一项所述的改性聚氨酯预聚体，其特征在于，R 1为甲基；及/或，R 2为H、或者甲基。
  6. 根据权利要求1-4任一项所述的改性聚氨酯预聚体，其特征在于，所述烷基丙烯酸脲基嘧啶酮、烷基丙烯酸羟乙酯、脂肪族异氰酸酯和氧化石墨烯的质量比为100:5-20：60-90：1-30；优选地，所述烷基丙烯酸脲基嘧啶酮、烷基丙烯酸羟乙酯、脂肪族异氰酸酯和氧化石墨烯的质量比为100:8:12：75-85：15-25。
  7. 根据权利要1-4任一项所述的改性聚氨酯预聚体，其特征在于，所述改性聚氨酯预聚体的NCO含量为11-14％，25℃下的粘度为30000-70000mPa.s。
  8. 一种权利要求1-7任一项所述的改性聚氨酯预聚体的制备方法，其特征在于，包括如下步骤：
    步骤I：将链转移剂、所述烷基丙烯酸脲基嘧啶酮、所述烷基丙烯酸羟乙酯和引发剂溶解于有机溶剂中进行共聚反应，得所述含有脲基嘧啶酮基团的共聚物；
    步骤II：向步骤I反应后的混合溶液中加入所述脂肪族异氰酸酯，反应，得所述聚氨酯预聚体；
    步骤III：再向步骤II反应后的混合溶液中加入所述氧化石墨烯，反应，即得所述改性聚氨酯预聚体。
  9. 根据权利要求8所述的改性聚氨酯预聚体的制备方法，其特征在于，所述链转移剂为二硫代苯甲酸枯酯、叔丁基苯并碳二硫酸酯、双(苯甲基硫基)甲硫酮和2-苯基-2-丙基苯并二硫中的至少一种；及/或，
    所述引发剂为偶氮二异丁腈和/或过氧化苯甲酰；
    优选地，所述链转移剂的用量为所述烷基丙烯酸脲基嘧啶酮的0.1-2wt％；
    优选地，所述引发剂的用量为所述烷基丙烯酸脲基嘧啶酮的0.1-2wt％。
  10. 根据权利要求8或9所述的改性聚氨酯预聚体的制备方法，其特征在于，步骤I所述共聚反应的温度为50-70℃，所述共聚反应的时间为6-18小时；及/或，
    步骤II所述反应的温度为20-30℃，所述反应的时间为18-28小时；及/或，
    步骤III所述反应的温度为20-30℃，所述反应的时间为1-3小时。
  11. 一种双组分聚氨酯胶粘剂，其特征在于，包括A组分和B组分；
    以重量份数计，所述A组分由包括如下组分的原料制备而成：
    多元醇     100份
    催化剂     0.01～5份
    无机填料   50～100份；
    所述B组分为权利要求1-7任一项所述的改性聚氨酯预聚体。
  12. 根据权利要求11所述的双组分聚氨酯胶粘剂，其特征在于，所述A组分和B组分的质量比为1～3:1；及/或，
    所述多元醇为苯基改性的聚醚多元醇、聚醚多元醇、聚酯多元醇和短链多元醇中的一种或者多种；及/或，
    所述催化剂为有机锡类催化剂和/或叔胺类催化剂；及/或，
    所述无机填料为超细碳酸钙、纳米碳酸钙和氢氧化铝中的至少一种；
    优选地，所述多元醇在25℃的粘度为1000～5000cps；
    优选地，所述有机锡类催化剂为二月桂酸二丁基锡和/或辛酸亚锡，所述叔胺类催化剂例为三亚乙基二胺、三乙醇胺和/或三乙胺；
    优选地，所述氢氧化铝的粒径为1000目-2000目。
  13. 一种权利要求11或12所述的双组分聚氨酯胶粘剂的制备方法，其特征在于，包括如下步骤：
    A组分的制备：将所述多元醇和无机填料混合，再加入所述催化剂，搅拌分散，真空脱泡，即得所述A组分；
    B组分的制备：
    步骤I：将链转移剂、所述烷基丙烯酸脲基嘧啶酮、所述烷基丙烯酸羟乙酯和引发剂溶解于有机溶剂中进行共聚反应，得所述含有脲基嘧啶酮基团的共聚物；
    步骤II：向步骤I反应后的混合溶液中加入所述脂肪族异氰酸酯，反应，得所述聚氨酯预聚体；
    步骤III：再向步骤II反应后的混合溶液中加入所述氧化石墨烯，反应，即得所述改性聚氨酯预聚体。
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