CN114773610A - Preparation method of polyurethane toughened epoxy resin - Google Patents

Preparation method of polyurethane toughened epoxy resin Download PDF

Info

Publication number
CN114773610A
CN114773610A CN202210571137.7A CN202210571137A CN114773610A CN 114773610 A CN114773610 A CN 114773610A CN 202210571137 A CN202210571137 A CN 202210571137A CN 114773610 A CN114773610 A CN 114773610A
Authority
CN
China
Prior art keywords
epoxy resin
parts
polyurethane
toughened epoxy
stirring
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202210571137.7A
Other languages
Chinese (zh)
Inventor
范晓庆
杨辉辉
杨爽
邹腊年
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Taizhou Huangyan Zhonggui New Material Technology Co ltd
Taizhou Huangyan District Wuhan Institute Of High Performance Composite Technology
Original Assignee
Taizhou Huangyan Zhonggui New Material Technology Co ltd
Taizhou Huangyan District Wuhan Institute Of High Performance Composite Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Taizhou Huangyan Zhonggui New Material Technology Co ltd, Taizhou Huangyan District Wuhan Institute Of High Performance Composite Technology filed Critical Taizhou Huangyan Zhonggui New Material Technology Co ltd
Priority to CN202210571137.7A priority Critical patent/CN114773610A/en
Publication of CN114773610A publication Critical patent/CN114773610A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • 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
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • 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
    • 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
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3897—Low-molecular-weight compounds having heteroatoms other than oxygen containing heteroatoms other than oxygen, halogens, nitrogen, sulfur, phosphorus or silicon
    • 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
    • C08G18/4833—Polyethers containing oxyethylene units
    • 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
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • 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
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/7875—Nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring
    • C08G18/7887—Nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring having two nitrogen atoms in the ring

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention relates to the field of chemical industry, in particular to a preparation method of polyurethane toughened epoxy resin; the method provides a method for synthesizing piperazine modified polyurethane prepolymer by utilizing ferrocene modified polyisocyanate and polypropylene glycol, and then the piperazine modified polyurethane prepolymer and epoxy resin are subjected to graft reaction to prepare toughened epoxy resin; the prepared piperazine modified polyurethane prepolymer can obviously improve the toughness and strength of epoxy resin, the maximum elongation at break of the modified epoxy resin is 84.70%, and the tensile strength of the modified epoxy resin is 27.1MPa which is 30.47 times and 3.04 times of that of the epoxy resin before modification; before modification, the epoxy resin is subjected to brittle fracture, and when the epoxy resin subjected to polyurethane modification is subjected to fracture, the silver lines are obviously increased, so that the epoxy resin is subjected to ductile fracture.

Description

Preparation method of polyurethane toughened epoxy resin
Technical Field
The invention relates to the field of chemical industry, in particular to a preparation method of polyurethane toughened epoxy resin.
Background
Epoxy resin is a typical cross-linked thermosetting polymer material, has various excellent properties such as good mechanical properties, excellent stability, strong bonding capability and low shrinkage rate, is widely used in the related fields of coatings, adhesives, civil engineering materials and the like, and plays an important role in thermosetting resin. However, the epoxy resin is brittle after being cured and has poor impact resistance, so that the wide development of the epoxy resin is limited.
CN 202110118129.2: the invention relates to a preparation method of special epoxy resin with high mechanical strength, which comprises the steps of preparation of an epoxy resin main agent, preparation of a carbon nano tube containing titanium dioxide and nano silicon dioxide, preparation of a reinforcing and toughening solution, preparation of a curing agent and preparation of the epoxy resin. The special epoxy resin with good mechanical property prepared by the method has the advantages of corrosion resistance, higher bending strength, average bending strength equal to or more than 160MPa, bending strength improved by 28 percent and Tg temperature of 160-180 ℃.
CN 202011170041.7: the invention discloses a preparation method of a novel cardanol modified epoxy resin, belonging to the technical field of preparation of epoxy resin, and the preparation method comprises the following steps: putting the mixture of cardanol and azobisisobutyronitrile or azobisisoheptonitrile into a reactor, heating for reaction, then adding a diethyl sulfate-phosphoric acid system (DES-H3PO4) or a diethyl sulfate-sulfuric acid system (DES-H2SO4), heating again for reaction to obtain a cardanol oligomer of an intermediate product, cooling the temperature of the intermediate product to room temperature, adding epichlorohydrin and tetraethylammonium bromide, uniformly mixing, heating for reaction, slowly dropwise adding a 48% NaOH solution, carrying out reduced pressure distillation, and filtering to obtain a final product. The novel epoxy resin prepared by the method has the advantages of good toughness, low viscosity, good chemical resistance and heat resistance, and better performance than common epoxy resin products.
CN 201710506136.3: the invention belongs to the field of high polymer materials, and particularly relates to a preparation method of tetrabromobisphenol A type epoxy resin. The invention provides a preparation method of tetrabromobisphenol A type epoxy resin, which takes tetrabromobisphenol A and epoxy chloropropane as reaction raw materials, and the tetrabromobisphenol A type epoxy resin is prepared by adopting a three-step alkali adding method to react in an isopropanol water solution with a specific proportion. The tetrabromobisphenol A type epoxy resin prepared by the invention has the advantages of low chroma, high transparency, moderate epoxy value, low tetrabromobisphenol A residual quantity, low hydrolysable chlorine content, low inorganic chlorine content and high tetrabromobisphenol A diglycidyl ether content in the tetrabromobisphenol A type epoxy resin. Meanwhile, the tetrabromobisphenol A type epoxy resin prepared by the invention also has the advantages of high dielectric constant and high voltage resistance value, and is an ideal tetrabromobisphenol A type epoxy resin.
The above patents and prior art basically use rubber and thermoplastic modified epoxy resins: the rubber is used as the blend to modify the epoxy resin, so that the epoxy resin can be effectively toughened, and the hardness and the heat resistance of the modified material are obviously reduced; when the epoxy resin is modified by using materials such as thermoplastic resin, the toughening effect and the heat resistance of the epoxy resin are very excellent, and the thermoplastic resin has high molecular weight and high viscosity, so that the processing technology and the bonding capacity of the epoxy resin are greatly influenced after the epoxy resin is added.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method of polyurethane toughened epoxy resin.
A preparation method of polyurethane toughened epoxy resin comprises the following operation steps:
s1: adding 16-22 parts of epoxy resin and 28-34 parts of piperazine modified polyurethane prepolymer into a reaction kettle under the protection of nitrogen according to the parts by weight, heating to 70-90 ℃, stirring, adding 0.05-0.1 part of catalyst, reacting for 1-3h, and vacuum degassing for 0.2-1 h;
s2: and cooling the reacted mixture to 60-90 ℃, and then adding 6-9 parts of curing agent for curing to obtain the toughened epoxy resin.
The epoxy resin is dehydrated in vacuum for 2-4h at the temperature of 100-120 ℃ before use.
The catalyst is dibutyltin dilaurate.
The curing agent is phenolic aldehyde amine epoxy curing agent.
The preparation method of the piperazine modified polyurethane prepolymer comprises the following steps:
adding 10-20 parts of polyether polyol into a reaction kettle according to the mass parts, heating to 40-60 ℃, stirring for 5-10min, then carrying out nitrogen protection, then adding 20-40 parts of piperazine modified polyisocyanate and 0.02-0.06 part of catalyst, heating to 65-80 ℃, carrying out stirring reaction for 120-180min, then cooling to 25-35 ℃, adding 60-100 parts of organic solvent, stirring and mixing uniformly, controlling the temperature to 60-80 ℃, then adding 0.1-3 parts of 3-pyridine neopentyl glycol borate, continuing stirring reaction for 30-60min, pouring the reactant into a mold, tiling to form a film, and thus obtaining the piperazine modified polyurethane prepolymer.
The preparation method of the piperazine modified polyisocyanate comprises the following steps:
s1: adding 10-20 parts of diisocyanate and 20-40 parts of hydroxyethyl acrylate into a closed reaction kettle, heating to 40-60 ℃, reacting for 2-4h, and then performing rotary evaporation at 50-60 ℃ for 1-3h to obtain an intermediate;
s2: adding 40-60 parts of N-butyl ketone into a closed high-pressure reaction kettle, adding 10-20 parts of intermediate, 1.5-3.5 parts of N-aminoethyl piperazine and 3-6 parts of triethylamine, heating and stirring to 50-60 ℃, reacting for 2-4h, and evaporating N-butanone at 80-100 ℃ to obtain the piperazine modified polyisocyanate.
The polyether polyol is polypropylene glycol-400, polypropylene glycol-1000, polypropylene glycol-2000 or polypropylene glycol-4000.
The catalyst is dibutyltin laurate, stannous octoate or stannous oleate.
The organic solvent is N, N-dimethylacetamide or N, N-diethylacetamide.
The stirring speed is 600-900 r/min.
The reaction mechanism is as follows:
diisocyanate and 20-40 parts of hydroxyethyl acrylate to generate acrylic-based isocyanate,
carrying out addition reaction with N-aminoethyl piperazine to obtain piperazine modified polyisocyanate
The technical effects are as follows:
the invention relates to a preparation method of polyurethane toughened epoxy resin, which provides a method that ferrocene modified polyisocyanate and polypropylene glycol are utilized to synthesize piperazine modified polyurethane prepolymer, and then the piperazine modified polyurethane prepolymer and epoxy resin are subjected to grafting reaction to prepare toughened epoxy resin; the prepared piperazine modified polyurethane prepolymer can obviously improve the toughness and strength of epoxy resin, the maximum elongation at break of the modified epoxy resin is 84.70%, and the tensile strength of the modified epoxy resin is 27.1MPa which is 30.47 times and 3.04 times of that of the epoxy resin before modification; before modification, the epoxy resin is subjected to brittle fracture, and when the epoxy resin subjected to polyurethane modification is subjected to fracture, the silver lines are obviously increased, so that the epoxy resin is subjected to ductile fracture.
Drawings
FIG. 1 is an SEM image of a typical impact section of a cured polyurethane toughened epoxy resin prepared in example 2.
As can be seen from FIG. 1, the surface of the impact cross section of the cured polyurethane toughened epoxy resin is rough, obviously toughness fracture occurs, and polymer particles are separated out on the substrate, namely, a 'sea-island' structure occurs.
Detailed Description
The invention is further illustrated by the following specific examples:
measuring the tensile strength and the elongation at break of the adhesive film on a universal mechanical testing machine by adopting a standard plastic tensile property experimental method; measuring three points of the width and the thickness of each sample, and averaging; the samples were held at not less than 5 per group and the results are expressed as arithmetic means.
Example 1
A preparation method of polyurethane toughened epoxy resin comprises the following operation steps:
s1: under the protection of nitrogen, 16g of epoxy resin and 28g of piperazine modified polyurethane prepolymer are added into a reaction kettle, the temperature is raised to 70 ℃, the mixture is stirred, then 0.05-0.1g of catalyst is added, the reaction lasts for 1 hour, and the vacuum degassing lasts for 0.2 hour;
s2: and cooling the reacted mixture to 60 ℃, and then adding 6g of curing agent for curing to obtain the toughened epoxy resin.
The epoxy resin is dewatered in vacuum at 100 ℃ for 2h before use.
The catalyst is dibutyltin dilaurate.
The curing agent is phenolic aldehyde amine epoxy curing agent.
The preparation method of the piperazine modified polyurethane prepolymer comprises the following steps:
adding 10g of polyether polyol into a reaction kettle, heating to 40 ℃, stirring for 5min, then carrying out nitrogen protection, then adding 20g of piperazine modified polyisocyanate and 0.02g of catalyst, heating to 65 ℃, carrying out stirring reaction for 120min, then cooling to 25 ℃, adding 60g of organic solvent, stirring and mixing uniformly, controlling the temperature to 60 ℃, then adding 0.1g of 3-pyridineboronic acid neopentyl glycol, continuing stirring and reacting for 30min, pouring the reactant into a mold, and spreading to form a film, thus obtaining the piperazine modified polyurethane prepolymer.
The preparation method of the piperazine modified polyisocyanate comprises the following steps:
s1: adding 10g of diisocyanate and 20g of hydroxyethyl acrylate into a closed reaction kettle, heating to 40 ℃, reacting for 2 hours, and then carrying out rotary evaporation at 50 ℃ for 1 hour to obtain an intermediate;
s2: adding 40g of N-butyl ketone into a closed high-pressure reaction kettle, adding 10g of intermediate, 1.5g of N-aminoethyl piperazine and 3g of triethylamine, heating and stirring to 50 ℃, reacting for 2h, and evaporating N-butanone at 80 ℃ to obtain the piperazine modified polyisocyanate.
The polyether polyol is polypropylene glycol-400.
The catalyst is dibutyltin laurate.
The organic solvent is N, N-dimethylacetamide.
The stirring speed is 600 r/min.
Example 2
A preparation method of polyurethane toughened epoxy resin comprises the following operation steps:
s1: under the protection of nitrogen, 18g of epoxy resin and 30g of piperazine modified polyurethane prepolymer are added into a reaction kettle, the temperature is raised to 75 ℃, the mixture is stirred, 0.06g of catalyst is added, the reaction lasts for 1.5h, and the vacuum degassing lasts for 0.6 h;
s2: and cooling the reacted mixture to 70 ℃, and then adding 7g of curing agent for curing to obtain the toughened epoxy resin.
The epoxy resin is dewatered in vacuum at 105 ℃ for 2.5h before use.
The catalyst is dibutyltin dilaurate.
The curing agent is phenolic aldehyde amine epoxy curing agent.
The preparation method of the piperazine modified polyurethane prepolymer comprises the following steps:
adding 14g of polyether polyol into a reaction kettle, heating to 45 ℃, stirring for 7min, then carrying out nitrogen protection, then adding 25g of piperazine modified polyisocyanate and 0.03g of catalyst, heating to 70 ℃, carrying out stirring reaction for 140min, then cooling to 28 ℃, adding 70g of organic solvent, stirring and mixing uniformly, controlling the temperature to 65 ℃, then adding 1g of 3-pyridine neopentyl glycol borate, continuing stirring and reacting for 40min, pouring the reactant into a mold, and spreading to form a film, thus obtaining the piperazine modified polyurethane prepolymer.
The preparation method of the piperazine modified polyisocyanate comprises the following steps:
s1: adding 14g of diisocyanate and 25g of hydroxyethyl acrylate into a closed reaction kettle, heating to 45 ℃, reacting for 2.5h, and then carrying out rotary evaporation at 54 ℃ for 1.5h to obtain an intermediate;
s2: adding 45g of N-butanone, 14g of intermediate, 2g of N-aminoethyl piperazine and 4g of triethylamine into a closed high-pressure reaction kettle, heating and stirring to 54 ℃, reacting for 2.5 hours, and evaporating N-butanone at 85 ℃ to obtain the piperazine modified polyisocyanate.
The polyether polyol is polypropylene glycol-1000.
The catalyst is dibutyltin laurate or stannous octoate.
The organic solvent is N, N-dimethylacetamide.
The stirring speed is 700 r/min.
Example 3
A preparation method of polyurethane toughened epoxy resin comprises the following operation steps:
s1: under the protection of nitrogen, 20g of epoxy resin 32g of piperazine modified polyurethane prepolymer is added into a reaction kettle, the temperature is raised to 85 ℃, the mixture is stirred, 0.09g of catalyst is added, the mixture is reacted for 2.5 hours, and vacuum degassing is carried out for 0.8 hour;
s2: and cooling the reacted mixture to 80 ℃, and then adding 8g of curing agent for curing to obtain the toughened epoxy resin.
The epoxy resin was vacuum dewatered at 115 deg.C for 3.5h before use.
The catalyst is dibutyltin dilaurate.
The curing agent is phenolic aldehyde amine epoxy curing agent.
The preparation method of the piperazine modified polyurethane prepolymer comprises the following steps:
adding 18g of polyether polyol into a reaction kettle, heating to 55 ℃, stirring for 8min, then carrying out nitrogen protection, then adding 35g of piperazine modified polyisocyanate and 0.05g of catalyst, heating to 75 ℃, carrying out stirring reaction for 160min, then cooling to 32 ℃, adding 90g of organic solvent, stirring and mixing uniformly, controlling the temperature to 75 ℃, then adding 2g of 3-pyridine neopentyl glycol borate, continuing stirring and reacting for 50min, pouring the reactant into a mold, and spreading to form a film, thus obtaining the piperazine modified polyurethane prepolymer.
The preparation method of the piperazine modified polyisocyanate comprises the following steps:
s1: adding 18g of diisocyanate and 35g of hydroxyethyl acrylate into a closed reaction kettle, heating to 55 ℃, reacting for 3.5h, and then carrying out rotary evaporation at 58 ℃ for 2.5h to obtain an intermediate;
s2: adding 55g of N-butanone, 18g of intermediate, 3g of N-aminoethyl piperazine and 5g of triethylamine into a closed high-pressure reaction kettle, heating and stirring to 58 ℃, reacting for 3.5h, and evaporating N-butanone at 95 ℃ to obtain the piperazine modified polyisocyanate.
The polyether polyol is polypropylene glycol-2000.
The catalyst is stannous octoate or stannous oleate.
The organic solvent is N, N-diethyl acetamide.
The stirring speed is 800 r/min.
Example 4
A preparation method of polyurethane toughened epoxy resin comprises the following operation steps:
s1: under the protection of nitrogen, 22g of epoxy resin and 34g of piperazine modified polyurethane prepolymer are added into a reaction kettle, the temperature is raised to 90 ℃, the mixture is stirred, 0.1g of catalyst is added, the mixture is reacted for 3 hours, and the vacuum degassing is carried out for 1 hour;
s2: and cooling the reacted mixture to 90 ℃, and then adding 9g of curing agent for curing to obtain the toughened epoxy resin.
The epoxy resin is dewatered in vacuum at 120 ℃ for 4h before use.
The catalyst is dibutyltin dilaurate.
The curing agent is phenolic aldehyde amine epoxy curing agent.
The preparation method of the piperazine modified polyurethane prepolymer comprises the following steps:
adding 20g of polyether polyol into a reaction kettle, heating to 60 ℃, stirring for 10min, then carrying out nitrogen protection, then adding 40g of piperazine modified polyisocyanate and 0.06g of catalyst, heating to 80 ℃, carrying out stirring reaction for 180min, then cooling to 35 ℃, adding 100g of organic solvent, stirring and mixing uniformly, controlling the temperature to 80 ℃, then adding 3g of 3-pyridine neopentyl glycol borate, continuing stirring and reacting for 60min, pouring reactants into a mold, and spreading to form a film, thus obtaining the piperazine modified polyurethane prepolymer.
The preparation method of the piperazine modified polyisocyanate comprises the following steps:
s1: adding 20g of diisocyanate and 40g of hydroxyethyl acrylate into a closed reaction kettle, heating to 60 ℃, reacting for 4 hours, and then carrying out rotary evaporation at 60 ℃ for 3 hours to obtain an intermediate;
s2: adding 60g of N-butanone, 20g of intermediate, 3.5g of N-aminoethyl piperazine and 6g of triethylamine into a closed high-pressure reaction kettle, heating and stirring to 60 ℃, reacting for 4 hours, and evaporating N-butanone at 100 ℃ to obtain the piperazine modified polyisocyanate.
The polyether glycol is polypropylene glycol-4000.
The catalyst is stannous octoate or stannous oleate.
The organic solvent is N, N-diethyl acetamide.
The stirring speed is 900 r/min.
Comparative example 1
The same procedure as in example 3 was repeated except that no piperazine-modified polyurethane prepolymer was added;
comparative example 2
The same procedure as in example 3 was repeated except that piperazine-modified polyisocyanate was not added;
comparative example 3
The procedure is as in example 3 except that no polyether polyol is added;
Figure BDA0003659222140000101
Figure BDA0003659222140000111

Claims (10)

1. a preparation method of polyurethane toughened epoxy resin comprises the following operation steps:
s1: adding 16-22 parts of epoxy resin and 28-34 parts of piperazine modified polyurethane prepolymer into a reaction kettle under the protection of nitrogen according to the parts by weight, heating to 70-90 ℃, stirring, adding 0.05-0.1 part of catalyst, reacting for 1-3h, and vacuum degassing for 0.2-1 h;
s2: and cooling the reacted mixture to 60-90 ℃, and then adding 6-9 parts of curing agent for curing to obtain the toughened epoxy resin.
2. The method for preparing the polyurethane toughened epoxy resin according to claim 1, wherein: the epoxy resin is dehydrated for 2-4h under vacuum at the temperature of 100-120 ℃ before use.
3. The method for preparing the polyurethane toughened epoxy resin according to claim 1, wherein: the catalyst is dibutyltin dilaurate.
4. The method for preparing the polyurethane toughened epoxy resin as claimed in claim 1, wherein: the curing agent is phenolic aldehyde amine epoxy curing agent.
5. The method for preparing the polyurethane toughened epoxy resin according to claim 1, wherein: the preparation method of the piperazine modified polyurethane prepolymer comprises the following steps:
adding 10-20 parts of polyether polyol into a reaction kettle according to the mass parts, heating to 40-60 ℃, stirring for 5-10min, then carrying out nitrogen protection, then adding 20-40 parts of piperazine modified polyisocyanate and 0.02-0.06 part of catalyst, heating to 65-80 ℃, carrying out stirring reaction for 120-180min, then cooling to 25-35 ℃, adding 60-100 parts of organic solvent, stirring and mixing uniformly, controlling the temperature to 60-80 ℃, then adding 0.1-3 parts of 3-pyridine neopentyl glycol borate, continuing stirring reaction for 30-60min, pouring the reactant into a mold, tiling to form a film, and thus obtaining the piperazine modified polyurethane prepolymer.
6. The method for preparing the polyurethane toughened epoxy resin according to claim 5, wherein: the preparation method of the piperazine modified polyisocyanate comprises the following steps:
s1: adding 10-20 parts of diisocyanate and 20-40 parts of hydroxyethyl acrylate into a closed reaction kettle, heating to 40-60 ℃, reacting for 2-4h, and then carrying out rotary evaporation for 1-3h at 50-60 ℃ to obtain an intermediate;
s2: adding 40-60 parts of N-butyl ketone into a closed high-pressure reaction kettle, adding 10-20 parts of intermediate, 1.5-3.5 parts of N-aminoethyl piperazine and 3-6 parts of triethylamine, heating and stirring to 50-60 ℃, reacting for 2-4h, and evaporating N-butanone at 80-100 ℃ to obtain the piperazine modified polyisocyanate.
7. The method for preparing the polyurethane toughened epoxy resin according to claim 5, wherein: the polyether polyol is polypropylene glycol-400, polypropylene glycol-1000, polypropylene glycol-2000 or polypropylene glycol-4000.
8. The method for preparing the polyurethane toughened epoxy resin according to claim 5, wherein: the catalyst is dibutyltin laurate, stannous octoate or stannous oleate.
9. The method for preparing the polyurethane toughened epoxy resin according to claim 5, wherein: the organic solvent is N, N-dimethylacetamide or N, N-diethylacetamide.
10. The method for preparing the polyurethane toughened epoxy resin according to claim 5, wherein: the stirring speed is 600-900 r/min.
CN202210571137.7A 2022-05-24 2022-05-24 Preparation method of polyurethane toughened epoxy resin Pending CN114773610A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210571137.7A CN114773610A (en) 2022-05-24 2022-05-24 Preparation method of polyurethane toughened epoxy resin

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210571137.7A CN114773610A (en) 2022-05-24 2022-05-24 Preparation method of polyurethane toughened epoxy resin

Publications (1)

Publication Number Publication Date
CN114773610A true CN114773610A (en) 2022-07-22

Family

ID=82409382

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210571137.7A Pending CN114773610A (en) 2022-05-24 2022-05-24 Preparation method of polyurethane toughened epoxy resin

Country Status (1)

Country Link
CN (1) CN114773610A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116218450A (en) * 2023-03-15 2023-06-06 广东绿树环保涂料科技有限公司 Mildew-proof joint beautifying agent and preparation method thereof
CN116284655A (en) * 2023-01-10 2023-06-23 中威北化科技有限公司 Preparation method of graphene-organosilicon synergistically-reinforced polyurethane grafted modified epoxy resin

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014077074A (en) * 2012-10-11 2014-05-01 Nagoya Electrical Educational Foundation Polyurethane-modified epoxy resin and method for producing the same, and cured product
CN108976425A (en) * 2018-06-14 2018-12-11 湖南大学 A kind of preparation method of polyurethane-epoxy resin block copolymerization water-base resin
CN111072903A (en) * 2019-12-30 2020-04-28 中国科学院山西煤炭化学研究所 Preparation method of cationic waterborne polyurethane emulsion
CN111484627A (en) * 2020-04-26 2020-08-04 赵汉波 Functional boron nitride in-situ modified epoxy resin insulating material and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014077074A (en) * 2012-10-11 2014-05-01 Nagoya Electrical Educational Foundation Polyurethane-modified epoxy resin and method for producing the same, and cured product
CN108976425A (en) * 2018-06-14 2018-12-11 湖南大学 A kind of preparation method of polyurethane-epoxy resin block copolymerization water-base resin
CN111072903A (en) * 2019-12-30 2020-04-28 中国科学院山西煤炭化学研究所 Preparation method of cationic waterborne polyurethane emulsion
CN111484627A (en) * 2020-04-26 2020-08-04 赵汉波 Functional boron nitride in-situ modified epoxy resin insulating material and preparation method thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116284655A (en) * 2023-01-10 2023-06-23 中威北化科技有限公司 Preparation method of graphene-organosilicon synergistically-reinforced polyurethane grafted modified epoxy resin
CN116284655B (en) * 2023-01-10 2024-01-09 中威北化科技有限公司 Preparation method of graphene-organosilicon synergistically-reinforced polyurethane grafted modified epoxy resin
CN116218450A (en) * 2023-03-15 2023-06-06 广东绿树环保涂料科技有限公司 Mildew-proof joint beautifying agent and preparation method thereof

Similar Documents

Publication Publication Date Title
CN114773610A (en) Preparation method of polyurethane toughened epoxy resin
CN110183587B (en) Light-cured self-repairing polyurethane acrylic resin and preparation method thereof
CN110483730B (en) Polyurethane acrylate oligomer and preparation method and application method thereof
WO2008049860A1 (en) Derivatized solid epoxy resin and uses thereof
CN114316885A (en) Modified epoxy resin sealant and preparation method thereof
CN109957031B (en) Cellulose fiber reversible chain extender, preparation thereof and chain extender composition containing same
CN114181605A (en) Single-component water-based polyurethane waterproof coating and preparation method thereof
JPS63305120A (en) Epoxy resin hardening agent from polyamine-polyisocyanate reactant
CN112980376A (en) Waterborne polyurethane adhesive and preparation method thereof
CN115286770B (en) Curing agent based on phenol-carbamate bond, and preparation method and application thereof
CN114276517B (en) Preparation method of epoxy-terminated polybutadiene series liquid rubber
CN114835878A (en) Low-temperature-resistant high-resilience polyurethane elastomer and preparation method thereof
US20220403095A1 (en) Acrylate oligomer and preparation method and application method thereof
CN114133529A (en) Aromatic polyurethane resin and preparation method and application thereof
CN116284681A (en) Preparation method and application of high-temperature-resistant polyurethane resin
CN114106280A (en) Aliphatic polyurethane resin and preparation method and application thereof
CN112409557B (en) Vegetable oil-based polyurethane film and preparation thereof
JPH09278864A (en) Two-package polyurethane resin composition and its production
CN113845640A (en) Polyether polyol for polyurethane foam plastic and preparation method and application thereof
CN113429542A (en) Preparation method of 1, 5-naphthalene diisocyanate polyurethane prepolymer
CN112645905A (en) Epoxy resin with long alkyl side chain and preparation and curing methods thereof
CN110819074A (en) Preparation method of graphene composite material
CN114605646B (en) Thermosetting polyurethane modified polysiloxane material capable of being repeatedly processed and used and preparation method thereof
CN114349912B (en) Modified waterborne polyurethane acrylate composite emulsion and preparation method and application thereof
CN116904102B (en) Single-component polyurethane waterproof paint and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20220722

RJ01 Rejection of invention patent application after publication