WO2018036506A1 - Epoxy resin composition with rapid curing and low linear shrinkage - Google Patents

Epoxy resin composition with rapid curing and low linear shrinkage Download PDF

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Publication number
WO2018036506A1
WO2018036506A1 PCT/CN2017/098601 CN2017098601W WO2018036506A1 WO 2018036506 A1 WO2018036506 A1 WO 2018036506A1 CN 2017098601 W CN2017098601 W CN 2017098601W WO 2018036506 A1 WO2018036506 A1 WO 2018036506A1
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Prior art keywords
epoxy resin
fiber
resin composition
curing agent
linear shrinkage
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PCT/CN2017/098601
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French (fr)
Chinese (zh)
Inventor
川本俊彥
譚水平
楊裕境
顧耿豪
林縈薰
Original Assignee
惠柏新材料科技（上海）股份有限公司
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Publication of WO2018036506A1 publication Critical patent/WO2018036506A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28—Shaping operations therefor
    • B29C70/40—Shaping or impregnating by compression not applied
    • B29C70/42—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles
    • B29C70/46—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles using matched moulds, e.g. for deforming sheet moulding compounds [SMC] or prepregs
    • B29C70/48—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles using matched moulds, e.g. for deforming sheet moulding compounds [SMC] or prepregs and impregnating the reinforcements in the closed mould, e.g. resin transfer moulding [RTM], e.g. by vacuum
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/5006—Amines 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/5026—Amines cycloaliphatic
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/5033—Amines aromatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C08L63/04—Epoxynovolacs
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Definitions

  • the invention relates to the technical field of epoxy resins and curing agents, in particular to an epoxy resin composition which rapidly cures low linear shrinkage.
  • Epoxy resins have excellent reactivity, adhesion, chemical resistance, heat resistance, mechanical properties, electrical properties, and good mold handling properties. Therefore, it is widely used in coatings, electrical and electronic materials, composite materials, building materials, aerospace materials, etc., especially for aerospace materials and structural components and their components for high-speed railways and subways. Resin and glass fiber or carbon fiber, as well as fiberglass or carbon fiber braid composites, but the production of these materials requires a long curing time or a higher molding temperature.
  • thermosetting resin is liable to form a stress residue in the cured product under rapid curing conditions, and the faster the curing speed, the larger the residual stress and the higher the curing shrinkage rate. Therefore, the dimensional stability of the cured product is poor, and the mechanical properties are also lowered.
  • the types of the epoxy resin and the curing agent also affect the curing shrinkage rate.
  • the aromatic epoxy resin and the aromatic curing agent have a small shrinkage ratio after curing. On the contrary, the aliphatic epoxy resin and the curing agent have a large curing shrinkage rate.
  • aromatic epoxy resins and aromatic curing agents are mostly solid or high viscosity viscous liquids at normal temperature, and a large amount of aliphatic diluents must be used to lower the viscosity to improve the convenience of operation. Therefore, it is easy to cause an increase in the curing time, and the curing shrinkage rate of the cured product becomes large, so that the rapid curing of the low shrinkage resin composition is extremely difficult to prepare.
  • the present invention provides a fast curing low linear shrinkage epoxy resin composition.
  • the invention discloses a fast curing low linear shrinkage epoxy resin composition, which is composed of an epoxy resin, an amine curing agent and an additive, the epoxy equivalent of the epoxy resin and the active hydrogen equivalent of the amine curing agent.
  • the ratio is 1.0/0.8 ⁇ 1.0/1.2; among them:
  • the epoxy resin comprises an aromatic epoxy resin in an amount of 85 to 100% by weight based on the total weight of the epoxy resin, and an aliphatic epoxy resin and/or an alicyclic epoxy resin in an amount of 0 to 15% by weight based on the total weight of the epoxy resin;
  • the aliphatic amine curing agent and/or the alicyclic amine curing agent in the amine curing agent accounts for 60 to 100% of the total weight of the amine curing agent;
  • the additive is added in an amount of 0 to 50% by weight based on the total weight of the epoxy resin and the amine curing agent, and the additive includes a flame retardant, a releasing agent, a coupling agent, a dispersing agent, an antifoaming agent, and a stabilizer.
  • the epoxy resin compositions have a gel time of at least 170 seconds at 120 ° C, and a linear shrinkage of the cured product after curing is 1.0% or less.
  • the releasing agent is added in an amount of 0 to 5% by weight based on the total weight of the epoxy resin and the amine curing agent; and the defoaming agent is added in an amount of the epoxy resin and the amine curing agent. 0 to 3% by weight.
  • the coupling agent is added in an amount of from 0 to 5% by weight based on the total of the epoxy resin and the amine curing agent.
  • the flame retardant is added in an amount of from 0 to 40% by weight based on the total weight of the epoxy resin and the amine curing agent.
  • the epoxy resin composition is suitable for high pressure resin transfer molding, medium and low pressure resin transfer molding, ordinary resin transfer molding process, casting process, vacuum flow guiding process, and hand layup process curing molding. Process.
  • the invention also discloses a method for preparing a cured product using a fast curing low linear shrinkage epoxy resin composition, comprising:
  • Step 1 After pre-forming the laminated fiber and/or fiber woven fabric, putting it into a preheated mold, or directly laying the fiber and/or fiber woven fabric into the preheated mold;
  • Step 2 clamping the mold and vacuuming
  • Step 3 injecting the epoxy resin composition into a mold
  • Step 4 After the epoxy resin composition is cured and molded with the fiber and/or the fiber braid, the cured product is taken out by mold opening.
  • the fiber comprises glass fiber, carbon fiber, polyamide fiber Dimensions, polyimide, graphite, phenolic, polyphenylene sulfide, nylon, aramid, polyester, polyurethane, polyethylene, polypropylene, polystyrene and polypropylene One or more of nitrile fibers;
  • the fiber woven fabric is a woven fabric of the above single fibers, or a mixed woven fabric of a plurality of fibers.
  • the preforming is a process of pressing the laminated fibers and/or fiber woven fabric into a desired shape to prepare a cured product by pressurization.
  • the mold has a preheating temperature of 90 to 180 ° C and the curing molding time is not higher than 20 minutes.
  • the cured product is suitable for automobile body components, rail vehicle components, building materials, aerospace tool components, electronic and electrical materials, sports equipment and medical appliances.
  • the invention discloses a rapid curing low linear shrinkage epoxy resin composition, the gel time of the composition at 120 ° C is less than 170 seconds, and the linear shrinkage of the cured product after curing is 1.0% or less, achieving rapid curing low.
  • the effect of linear shrinkage it can be applied to the components of new energy vehicles, rail transit, and aerospace tools, which can increase the productivity and yield of finished products, and achieve the effects of energy saving, carbon reduction and environmental protection.
  • Example 1 The present invention provides a fast curing low linear shrinkage epoxy resin composition composed of an epoxy resin, an amine curing agent and an additive, an epoxy equivalent of an epoxy resin and an active hydrogen equivalent of an amine curing agent.
  • the ratio of the composition is 1.0/0.8 to 1.0/1.2; the hot plate gel time of the composition at 120 ° C is less than 170 seconds, and the linear shrinkage of the cured product is 1.0% or less. among them:
  • the epoxy resin includes an aromatic epoxy resin in an amount of 85 to 100% by weight based on the total weight of the epoxy resin, and an aliphatic epoxy resin and/or an alicyclic epoxy resin in an amount of 0 to 15% by weight based on the total weight of the epoxy resin.
  • the invention makes Epoxy resin used, specifically phenyl glycidyl ether, o-methylphenyl glycidyl ether, C12-C14 polyalkyl glycidyl ether, n-butyl glycidyl ether, decyl glycidyl ether, new sunflower shrinkage
  • Monofunctional epoxy resin such as glyceride, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol AD epoxy resin, bisphenol epoxy resin, 2,6 dimethyl double Phenol epoxy resin, tetrabromobisphenol A epoxy resin, brominated phenolic epoxy resin, tetrachlorobisphenol A epoxy resin, naphthalene diphenol epoxy resin, benzenediol epoxy resin, diphenol hexafluoropropane
  • a bifunctional aromatic epoxy resin such as an epoxy resin or a phthalic acid di epoxy resin.
  • Hydrogenated bisphenol A epoxy resin such as cyclohexanecarboxylic acid-3',4'-epoxycyclohexanemethyl ester, p-hydroxyaniline triepoxy resin, 1,2-epoxycyclohexane, 4,5 - Dicarboxylic acid epoxy resin, pyrogallol tri epoxy resin, trisphenol methane tri epoxy resin, glycerol g
  • the aliphatic amine curing agent and/or the alicyclic amine curing agent in the amine curing agent accounts for 60 to 100% of the total weight of the amine curing agent; wherein: the curing agent used in the present invention specifically has diethylenetriamine, Triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, ethylenediamine, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspirodecane adduct , polyamide, polyamide polyamine, polymeric ammonia, polyether ammonia and other fatty amines, montanane diamine, isophorone diamine, N-aminoethylpyridazine, bis(4-aminocyclohexyl)methane , bis(4-amino-3-methylcyclohexyl)methane, alicyclic amines such as hydrogenated m-xylylenediamine
  • the present invention may also use imidazoles as curing agents or accelerators, specifically 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, C11 imidazole , C17 imidazole, etc., not limited to the above listed, all imidazoles which can cure epoxy resins can be used, either alone or in combination.
  • tertiary ammonia such as triethylamine, N-methylmorpholine, and tetramethylammonium chloride, tetramethylammonium bromide, tetraethylammonium chloride, tetraethylammonium bromide, trimethyl
  • a quaternary ammonium salt such as decyl ammonium chloride, trimethyl decyl ammonium bromide or triethyl decyl ammonium bromide, or a basal ammonium salt such as a quaternary phosphonium salt can also be used as a promoter, and the amount used is 50 ppm to 50000 ppm may be used in combination with an alkaline substance such as sodium hydroxide or potassium hydroxide.
  • Lewis acid catalysts such as p-toluenesulfonic acid, salicylic acid, boron fluoride, oxalic acid, and tin chloride may also be used depending on
  • the epoxy resin composition of the present invention may be added with an additive as needed, and the additive is added in an amount of 0 to 50% by weight based on the total weight of the epoxy resin and the amine curing agent, and the additive includes a flame retardant, a mold release agent, a coupling agent, and a dispersion.
  • the additive includes a flame retardant, a mold release agent, a coupling agent, and a dispersion.
  • a dose an antifoaming agent, a stabilizer, and the like.
  • metal stone base, organic wax, Brazilian wax and other mold release agent the added amount is 0 ⁇ 5% of the total weight of epoxy resin and amine curing agent; polyurethane, silane, long-chain fat, interface activity
  • An antifoaming agent such as a dose is added in an amount of from 0 to 3% based on the total weight of the epoxy resin and the amine curing agent.
  • the coupling agent is added in an amount of from 0 to 5% by weight based on the total weight of the epoxy resin and the amine curing agent, which enhances the binding force of the resin composition to the fiber or the fiber woven fabric, and the function of curing the finished product.
  • the epoxy resin composition of the invention can be applied to high pressure resin transfer molding HP-RTM, medium and low pressure resin transfer molding and common resin transfer molding process (RTM), vacuum flow guiding process, casting process, hand lay process, etc. Curing molding process.
  • Example 2 The present invention also discloses a method for preparing a cured product using a fast curing low linear shrinkage epoxy resin composition, comprising:
  • Step 1 After pre-forming the laminated fiber and/or fiber woven fabric, put it into a preheated mold, or directly place the fiber and/or fiber woven fabric into the preheated mold; wherein:
  • Fibers include glass fiber, carbon fiber, polyamide fiber, polyimide fiber, graphite fiber, phenolic resin fiber, polyphenylene sulfide fiber, nylon fiber, aramid fiber, polyester fiber, polyurethane fiber, polyethylene fiber, poly One or more of propylene fiber, polystyrene fiber, polyacrylonitrile fiber, etc.; the fiber woven fabric is a woven fabric of the above single fiber, or a mixed woven fabric of a plurality of fibers;
  • Preforming is a process of pressing a laminated fiber and/or a fiber woven fabric into a desired preparation of a cured product by pressurization. shape.
  • Step 2 clamping the mold and vacuuming
  • Step 3 injecting the epoxy resin composition into the mold
  • Step 4 After the epoxy resin composition is cured and molded with the fiber and/or the fiber braid, the cured product is taken out by mold opening.
  • the preheating temperature of the mold is 90 to 180 ° C, and the curing molding time is not higher than 20 minutes.
  • the cured product is suitable for automobile body components, rail vehicle components, building materials, aerospace tool components, electronic and electrical materials, sports equipment and medical instruments.
  • Example 3 The present invention provides a fast curing low linear shrinkage epoxy resin composition comprising an epoxy resin (A) and an amine curing agent (B), and an additive (C).
  • the epoxy resin (A) of the composition is an aliphatic epoxy resin having not less than 85% by weight based on the total weight of the epoxy resin (A), and 15% by weight or less of the total weight of the epoxy resin (A). Or alicyclic epoxy resin.
  • the amine curing agent (B) is composed of a total of aliphatic amine and alicyclic amine not less than 60% by weight of the amine curing agent (B); the additive (C) is a flame retardant, a releasing agent, a coupling agent Additives such as a dispersing agent, an antifoaming agent, and a stabilizer may be added singly or in combination.
  • the gel time of this composition at 120 ° C was 170 seconds or less, and the linear shrinkage of the object after curing was 1.0% or less.
  • the composition of the present invention is composed of an epoxy resin (A) and a curing agent (B) additive (C), and the composition can be solidified in a range of 90 to 180 ° C in 20 minutes, and the molding temperature is lower than 90 ° C.
  • the curing time is long, the curing is not complete, the mechanical properties of the finished product are lowered, and the process cycle time is long, which is not conducive to the production capacity.
  • the molding temperature is higher than 180 °C, although the process time can be shortened to facilitate the production capacity, the energy consumption is large, and the finished product is easily deformed during demolding, and the curing temperature is preferably 100 to 160 ° C, more preferably 100 to 140 ° C.
  • the curing molding temperature and time can be appropriately adjusted.
  • the curing time is less than 20 minutes, preferably less than 15 minutes, more preferably less than 10 minutes, and most preferably less than 5 minutes.
  • the curing time is longer than the production capacity, and the curing time is short, the curing is incomplete, and the curing time is not limited.
  • the temperature is adjusted, the most important thing is to adjust the curing agent or the type of resin to match.
  • the linear shrinkage ratio of the cured product is 1.0% or less and the linear shrinkage ratio is more than 1.0%, the dimensional stability of the molded article is poor, and the number of defective products is large, and the cost is increased.
  • the amine curing agent (B) in the epoxy resin composition the sum of the aliphatic amines and the alicyclic amines is at least not less than 60% of the total amount of the curing agent, and the epoxy equivalent of the epoxy resin (A) / curing agent ( B) lively
  • the hydrogen equivalent ratio is 1.0/0.8 to 1.0/1.2, the hot plate gel time at 120 ° C is 170 seconds or less.
  • the process of solidification molding is to pre-form the laminated fiber or fiber woven fabric into a mold, and after the mold is closed, it can be vacuumed in order to eliminate the air in the mold, and then the resin and the curing agent are mixed and defoamed. After being injected into the mold, the finished product is opened by the mold at the set time.
  • Bisphenol A epoxy resin epoxy equivalent 170-200 g/eq, bisphenol A epoxy resin, either alone or in combination.
  • Phenolic epoxy resin epoxy equivalent 160 to 190 g/eq, phenolic epoxy resin, either alone or in combination.
  • Aliphatic epoxy resin epoxy equivalent 125-155 g/eq, aliphatic epoxy resin, either alone or in combination.
  • the epoxy equivalent is determined according to the epoxy equivalent of the plastic epoxy compound of GB/T 4612-2008.
  • Aliphatic amines diethyltriamine, triethyltetramine, tetraethylpentamine, N-aminoethylpyridazine, diethylaminopropylamine, polyetheramine, dicyandiamide, etc., may be used alone or in combination. use.
  • Alicyclic amine montan diamine, isophorone diamine, bis(4-amino-3-methylcyclohexyl)methane, bis(4-aminocyclohexyl)methane, hydrogenated m-xylylenediamine Etc., they can be used alone or in combination.
  • aromatic amine m-xylylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, etc. may be used singly or in combination.
  • Active hydrogen equivalent The number of hydrogen atoms bonded to a nitrogen atom in the ammonia-based curing agent, and the equivalent thereof is a value obtained by dividing the molecular weight of the ammonia by the number of hydrogen atoms bonded to the nitrogen atom.
  • the epoxy resin composition of the present invention has a gel time of at least 170 seconds at 120 ° C, and a linear shrinkage ratio of 1.0% or less after curing, which achieves the effect of rapid curing and low linear shrinkage.
  • the fast-curing low-shrinkage epoxy resin composition and the fiber, and/or the fiber braid are mixed and impregnated, and the cured product after pressure-heat molding is used for automobile body parts, components, rail vehicle components, and building materials.
  • aerospace tool components, electronic and electrical materials, sports equipment, medical equipment, etc. can be used to replace bulky steel, especially new energy vehicles that will be popularized in the near future and in the near future, for the protection of the global environment and energy conservation. The expected results will be achieved. It can be applied to the components of new energy vehicles, rail transit and aerospace tools, which can increase the productivity and yield of finished products, and achieve the effects of energy saving, carbon reduction and environmental protection.

Abstract

An epoxy resin composition with rapid curing and low linear shrinkage, composed of an epoxy resin, an amine curing agent, and an additive. The ratio of the epoxy equivalent of the epoxy resin to the active hydrogen equivalent of the amine curing agent is 1.0/0.8 to 1.0/1.2. The epoxy resin comprises an aromatic epoxy resin constituting 85-100% of the total weight of the epoxy resin and an aliphatic epoxy resin and/or an alicyclic epoxy resin constituting 0-15% of the total weight of the epoxy resin. An aliphatic amine curing agent and/or an alicyclic amine curing agent in the amine curing agent constitute/constitutes 60-100% of the total weight of the amine curing agent. The added amount of the additive is 0-50% of the total weight of the epoxy resin and the amine curing agent. The epoxy resin composition has a gelation time less than 170 seconds at 120°C and a linear shrinkage percentage of 1.0% or less after curing, achieving the effect of rapid curing and low linear shrinkage. The epoxy resin composition is applicable to parts and components of a new energy vehicle, rail transit, and aerospace vehicle, and can improve productivity and product yield, achieving the effects of energy saving, reducing carbon emission, and environmental protection.

Description

一种快速固化低线性收缩的环氧树脂组成物Epoxy resin composition for rapid curing and low linear shrinkage 技术领域Technical field
本发明涉及环氧树脂及固化剂技术领域，具体涉及一种快速固化低线性收缩的环氧树脂组成物。The invention relates to the technical field of epoxy resins and curing agents, in particular to an epoxy resin composition which rapidly cures low linear shrinkage.
背景技术Background technique
近年来为了保护地球环境，世界各国竞相开发清洁能源，例如风力发电，太阳能发电等等，也随着清洁能源的发展，汽车工业也随之进化，新能源汽车逐步上市，为了配合新能源汽车的发展，车身必须轻量化才能提升车速和提高行车距离，方能使得新能源的效率发挥极大化。In recent years, in order to protect the global environment, countries around the world are competing to develop clean energy, such as wind power, solar power, etc., and with the development of clean energy, the automobile industry has also evolved, and new energy vehicles are gradually listed, in order to cooperate with new energy vehicles. Development, the body must be lightweight to increase the speed and increase the distance of travel, in order to maximize the efficiency of new energy.
环氧树脂具有优异的反应性，接着性，耐化学药品性，耐热性，机械特性，电气特性以及良好的成型操作性。因此在涂料，电子电气材料，复合材料，建筑材料，宇宙航空材料等领域被广泛的使用，特别是宇宙航天航空材料以及高速铁路和地铁等电车车辆结构件及其零组件，已经大量采用环氧树脂与玻璃纤维或炭纤维，以及玻纤或炭纤的编织物复合材料，但是这些材料的生产制造大都须要较长的固化时间或较高的成型温度。Epoxy resins have excellent reactivity, adhesion, chemical resistance, heat resistance, mechanical properties, electrical properties, and good mold handling properties. Therefore, it is widely used in coatings, electrical and electronic materials, composite materials, building materials, aerospace materials, etc., especially for aerospace materials and structural components and their components for high-speed railways and subways. Resin and glass fiber or carbon fiber, as well as fiberglass or carbon fiber braid composites, but the production of these materials requires a long curing time or a higher molding temperature.
一般而言热固性树脂在快速固化条件下，固化物中容易形成应力的残留，固化速度越快残留应力越大，固化收缩率也越大。因此固化物的尺寸安定性不良，机械性能也随之降低。还有，环氧树脂以及固化剂的种类也会影响固化收缩率，一般而言芳香族类的环氧树脂以及芳香族类的固化剂固化后的收缩率较小。反之脂肪族类的环氧树脂以及固化剂固化收缩率较大。但是芳香族类的环氧树脂以及芳香族类的固化剂在常温之下大都为固态或者是高粘度的粘稠液态，必须使用大量的脂肪族类稀释剂降低粘度以提高操作的便利性，也因此容易造成固化时间的加长，以及固化物的固化收缩率变大，因此快速固化低收缩率树脂组成物的调配极为困难。In general, the thermosetting resin is liable to form a stress residue in the cured product under rapid curing conditions, and the faster the curing speed, the larger the residual stress and the higher the curing shrinkage rate. Therefore, the dimensional stability of the cured product is poor, and the mechanical properties are also lowered. Further, the types of the epoxy resin and the curing agent also affect the curing shrinkage rate. Generally, the aromatic epoxy resin and the aromatic curing agent have a small shrinkage ratio after curing. On the contrary, the aliphatic epoxy resin and the curing agent have a large curing shrinkage rate. However, aromatic epoxy resins and aromatic curing agents are mostly solid or high viscosity viscous liquids at normal temperature, and a large amount of aliphatic diluents must be used to lower the viscosity to improve the convenience of operation. Therefore, it is easy to cause an increase in the curing time, and the curing shrinkage rate of the cured product becomes large, so that the rapid curing of the low shrinkage resin composition is extremely difficult to prepare.
发明内容Summary of the invention
针对上述问题中存在的不足之处，本发明提供一种快速固化低线性收缩的环氧树脂组成物。 In view of the deficiencies in the above problems, the present invention provides a fast curing low linear shrinkage epoxy resin composition.
本发明公开了一种快速固化低线性收缩的环氧树脂组成物，由环氧树脂、胺类固化剂和添加剂组成，所述环氧树脂的环氧当量与胺类固化剂的活泼氢当量的比例为1.0/0.8～1.0/1.2；其中：The invention discloses a fast curing low linear shrinkage epoxy resin composition, which is composed of an epoxy resin, an amine curing agent and an additive, the epoxy equivalent of the epoxy resin and the active hydrogen equivalent of the amine curing agent. The ratio is 1.0/0.8~1.0/1.2; among them:
所述环氧树脂包括占环氧树脂总重量85～100％的芳香族环氧树脂及占环氧树脂总重量0～15％的脂肪族环氧树脂和/或脂环族环氧树脂；The epoxy resin comprises an aromatic epoxy resin in an amount of 85 to 100% by weight based on the total weight of the epoxy resin, and an aliphatic epoxy resin and/or an alicyclic epoxy resin in an amount of 0 to 15% by weight based on the total weight of the epoxy resin;
所述胺类固化剂中脂肪胺类固化剂和/或脂环胺类固化剂占胺类固化剂总重量的60～100％；The aliphatic amine curing agent and/or the alicyclic amine curing agent in the amine curing agent accounts for 60 to 100% of the total weight of the amine curing agent;
所述添加剂的加入量为环氧树脂和胺类固化剂总重量的0～50％，所述添加剂包括阻燃剂、脱模剂、偶联剂、分散剂、消泡剂和安定剂中的一种或多种；该环氧树脂组成物在120℃的凝胶时间为170秒以下，固化后固化物的线性收缩率为1.0％以下。The additive is added in an amount of 0 to 50% by weight based on the total weight of the epoxy resin and the amine curing agent, and the additive includes a flame retardant, a releasing agent, a coupling agent, a dispersing agent, an antifoaming agent, and a stabilizer. One or more of the epoxy resin compositions have a gel time of at least 170 seconds at 120 ° C, and a linear shrinkage of the cured product after curing is 1.0% or less.
作为本发明的进一步改进，所述脱模剂的加入量为环氧树脂和胺类固化剂总重量的0～5％；所述消泡剂的加入量为环氧树脂和胺类固化剂总重量的0～3％。As a further improvement of the present invention, the releasing agent is added in an amount of 0 to 5% by weight based on the total weight of the epoxy resin and the amine curing agent; and the defoaming agent is added in an amount of the epoxy resin and the amine curing agent. 0 to 3% by weight.
作为本发明的进一步改进，所述偶联剂的加入量为环氧树脂和胺类固化剂总重量的0～5％。As a further improvement of the present invention, the coupling agent is added in an amount of from 0 to 5% by weight based on the total of the epoxy resin and the amine curing agent.
作为本发明的进一步改进，所述阻燃剂的加入量为环氧树脂和胺类固化剂总重量的0～40％。As a further improvement of the present invention, the flame retardant is added in an amount of from 0 to 40% by weight based on the total weight of the epoxy resin and the amine curing agent.
作为本发明的进一步改进，所述环氧树脂组成物适用于高压树脂传递模塑、中低压树脂传递模塑、普通树脂传递模塑工艺、浇铸工艺、真空导流工艺，手糊工艺的固化成型制程。As a further improvement of the present invention, the epoxy resin composition is suitable for high pressure resin transfer molding, medium and low pressure resin transfer molding, ordinary resin transfer molding process, casting process, vacuum flow guiding process, and hand layup process curing molding. Process.
本发明还公开了一种使用快速固化低线性收缩的环氧树脂组成物制备固化物的方法，包括：The invention also discloses a method for preparing a cured product using a fast curing low linear shrinkage epoxy resin composition, comprising:
步骤1、将迭合的纤维和/或纤维编织物进行预成型后，放入到预热的模具内，或将纤维和/或纤维编织物直接铺放到预热的模具内；Step 1. After pre-forming the laminated fiber and/or fiber woven fabric, putting it into a preheated mold, or directly laying the fiber and/or fiber woven fabric into the preheated mold;
步骤2、将模具合模，抽真空；Step 2: clamping the mold and vacuuming;
步骤3、将所述环氧树脂组成物注入模具中；Step 3, injecting the epoxy resin composition into a mold;
步骤4、环氧树脂组成物与纤维和/或纤维编织物固化成型后，开模取出固化物。Step 4. After the epoxy resin composition is cured and molded with the fiber and/or the fiber braid, the cured product is taken out by mold opening.
作为本发明的进一步改进，所述纤维包括玻璃纤维，炭纤维，聚酰胺纤 维，聚酰亚胺纤维，石墨纤维，酚醛树脂纤维，聚苯硫醚纤维，尼龙纤维，芳纶纤维，聚酯纤维，聚氨酯纤维，聚乙烯纤维，聚丙烯纤维，聚苯乙烯纤维和聚丙烯腈纤维中的一种或多种；As a further improvement of the present invention, the fiber comprises glass fiber, carbon fiber, polyamide fiber Dimensions, polyimide, graphite, phenolic, polyphenylene sulfide, nylon, aramid, polyester, polyurethane, polyethylene, polypropylene, polystyrene and polypropylene One or more of nitrile fibers;
所述纤维编织物为上述单一纤维的编织物，或多种纤维的混合编织物。The fiber woven fabric is a woven fabric of the above single fibers, or a mixed woven fabric of a plurality of fibers.
作为本发明的进一步改进，所述预成型是通过加压将迭合的纤维和/或纤维编织物压制成所需制备固化物的形状。As a further improvement of the present invention, the preforming is a process of pressing the laminated fibers and/or fiber woven fabric into a desired shape to prepare a cured product by pressurization.
作为本发明的进一步改进，所述模具的预热温度为90～180℃，所述固化成型的时间不高于20分钟。As a further improvement of the present invention, the mold has a preheating temperature of 90 to 180 ° C and the curing molding time is not higher than 20 minutes.
作为本发明的进一步改进，所述固化物适用于汽车车体零组件，轨道交通工具零组件，建筑材料，宇宙航空工具零组件，电子电器材料，运动器材和医疗器具。As a further improvement of the present invention, the cured product is suitable for automobile body components, rail vehicle components, building materials, aerospace tool components, electronic and electrical materials, sports equipment and medical appliances.
与现有技术相比，本发明的有益效果为：Compared with the prior art, the beneficial effects of the present invention are:
本发明公开了一种快速固化低线性收缩的环氧树脂组成物，该组成物在120℃的凝胶时间为170秒以下，固化后固化物的线性收缩率为1.0％以下，达到快速固化低线性收缩的效果；可应用于新能源汽车、轨道交通、航空航天工具的零组件，可以提高产能和成品收率，达到节能减碳、保护环境的效果。The invention discloses a rapid curing low linear shrinkage epoxy resin composition, the gel time of the composition at 120 ° C is less than 170 seconds, and the linear shrinkage of the cured product after curing is 1.0% or less, achieving rapid curing low. The effect of linear shrinkage; it can be applied to the components of new energy vehicles, rail transit, and aerospace tools, which can increase the productivity and yield of finished products, and achieve the effects of energy saving, carbon reduction and environmental protection.
具体实施方式detailed description
为使本发明实施例的目的、技术方案和优点更加清楚，下面对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例是本发明的一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动的前提下所获得的所有其他实施例，都属于本发明保护的范围。The embodiments of the present invention will be described clearly and completely in the following description of the embodiments of the present invention. It is obvious that the described embodiments are a part of the embodiments of the present invention, and not all of them. An embodiment. All other embodiments obtained by a person of ordinary skill in the art based on the embodiments of the present invention without creative efforts are within the scope of the present invention.
下面对本发明做进一步的详细描述：The present invention is further described in detail below:
实施例1：本发明提供一种快速固化低线性收缩的环氧树脂组成物，由环氧树脂、胺类固化剂和添加剂组成，环氧树脂的环氧当量与胺类固化剂的活泼氢当量的比例为1.0/0.8～1.0/1.2；该组成物在120℃下的热板凝胶时间为小于170秒，固化后物的线性收缩率为1.0％以下。其中：Example 1: The present invention provides a fast curing low linear shrinkage epoxy resin composition composed of an epoxy resin, an amine curing agent and an additive, an epoxy equivalent of an epoxy resin and an active hydrogen equivalent of an amine curing agent. The ratio of the composition is 1.0/0.8 to 1.0/1.2; the hot plate gel time of the composition at 120 ° C is less than 170 seconds, and the linear shrinkage of the cured product is 1.0% or less. among them:
环氧树脂包括占环氧树脂总重量85～100％的芳香族环氧树脂及占环氧树脂总重量0～15％的脂肪族环氧树脂和/或脂环族环氧树脂。其中：本发明所使 用的环氧树脂，具体有苯基缩水甘油醚，邻甲基苯基缩水甘油醚，C12～C14多烷基缩水甘油醚，正丁基缩水甘油醚，卞基缩水甘油醚，新葵酸缩水甘油酯等单官能环氧树脂，双酚A环氧树脂，双酚F环氧树脂，双酚S环氧树脂，双酚AD环氧树脂，双酚环氧树脂，2,6二甲基双酚环氧树脂，四溴双酚A环氧树脂，溴化酚醛环氧树脂，四氯双酚A环氧树脂，萘二酚环氧树脂，苯二酚环氧树脂，二酚基六氟丙烷环氧树脂，邻苯二甲酸二环氧树脂等双官能芳香族环氧树脂。氢化双酚A环氧树脂，四氢邻苯二甲酸二环氧树脂，六氢邻苯二甲酸二环氧树脂，乙二醇二缩水甘油醚，聚乙二醇二缩水甘油醚，1,2丙二醇二缩水甘油醚，聚丙二醇二缩水甘油醚，1,4丁二醇二缩水甘油醚，1,6己二醇二缩水甘油醚，新戊二醇二缩水甘油醚，3,4-环氧基环己烷甲酸-3',4'-环氧基环己烷甲酯等脂肪族双官能环氧树脂，对羟基苯胺三环氧树脂，1,2-环氧环己烷,4,5-二甲酸环氧树脂，均苯三酚三环氧树脂，三酚基甲烷三环氧树脂，丙三醇缩水甘油醚，三羟甲基丙烷缩水甘油醚，均苯三酸三环氧树脂，三聚氰酸三缩水甘油醚，异三聚氰酸三缩水甘油胺等三官能芳香族环氧树脂，4,4'-二氨基二苯甲烷环氧树脂，4,4'-二氨基二苯砜环氧树脂，4,4'-二氨基二苯醚环氧树脂，四酚基乙烷四环氧树脂，间苯二酚甲醛四缩水甘油醚等四官能芳香族环氧树脂，以及酚醛环氧树脂，邻甲基酚醛环氧树脂，双酚A酚醛环氧树脂等多官能环氧树脂，以及上述各种树脂的改性诱导体，高纯化的单体，不限于上述所记载的环氧树脂，凡是具有环氧基团的化合物都可用于本发明，可以单独使用，也可以混合使用。The epoxy resin includes an aromatic epoxy resin in an amount of 85 to 100% by weight based on the total weight of the epoxy resin, and an aliphatic epoxy resin and/or an alicyclic epoxy resin in an amount of 0 to 15% by weight based on the total weight of the epoxy resin. Wherein: the invention makes Epoxy resin used, specifically phenyl glycidyl ether, o-methylphenyl glycidyl ether, C12-C14 polyalkyl glycidyl ether, n-butyl glycidyl ether, decyl glycidyl ether, new sunflower shrinkage Monofunctional epoxy resin such as glyceride, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol AD epoxy resin, bisphenol epoxy resin, 2,6 dimethyl double Phenol epoxy resin, tetrabromobisphenol A epoxy resin, brominated phenolic epoxy resin, tetrachlorobisphenol A epoxy resin, naphthalene diphenol epoxy resin, benzenediol epoxy resin, diphenol hexafluoropropane A bifunctional aromatic epoxy resin such as an epoxy resin or a phthalic acid di epoxy resin. Hydrogenated bisphenol A epoxy resin, tetrahydrophthalic acid diepoxy resin, hexahydrophthalic acid diepoxy resin, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, 1, 2 Propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,4 butanediol diglycidyl ether, 1,6 hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 3,4-epoxy An aliphatic difunctional epoxy resin such as cyclohexanecarboxylic acid-3',4'-epoxycyclohexanemethyl ester, p-hydroxyaniline triepoxy resin, 1,2-epoxycyclohexane, 4,5 - Dicarboxylic acid epoxy resin, pyrogallol tri epoxy resin, trisphenol methane tri epoxy resin, glycerol glycidyl ether, trimethylolpropane glycidyl ether, trimesic acid tri epoxy resin, Trifunctional aromatic epoxy resin such as triglycidyl ether cyanurate, triglycidyl isocyanurate, 4,4'-diaminodiphenylmethane epoxy resin, 4,4'-diaminodiphenyl Sulfone epoxy resin, 4,4'-diaminodiphenyl ether epoxy resin, tetraphenol ethane tetra epoxy resin, resorcinol formaldehyde tetraglycidyl ether and other tetrafunctional aromatic epoxy resins, and phenol A polyfunctional epoxy resin such as an epoxy resin, an o-methyl novolac epoxy resin, a bisphenol A phenolic epoxy resin, or a modified inducer of the above various resins, and a highly purified monomer is not limited to the above-described ring The oxygen resin, any compound having an epoxy group can be used in the present invention, and it may be used singly or in combination.
胺类固化剂中脂肪胺类固化剂和/或脂环胺类固化剂占胺类固化剂总重量的60～100％；其中：本发明所使用的固化剂具体而言有二乙烯三胺，三乙烯四胺，四乙烯五胺，二乙氨基丙胺，乙二胺，3,9-双(3-胺丙基)-2,4,8,10-四氧杂螺十一烷加合物，聚酰胺，聚酰胺多氨，聚合氨，聚醚氨等脂肪胺类，孟烷二胺，异佛尔酮二胺，N-氨乙基呱嗪，双(4-胺基环己基)甲烷，双(4-胺基-3-甲基环己基)甲烷，氢化间苯二甲胺等脂环胺类；间苯二胺，间苯二甲胺，二胺基二苯基甲烷，二胺基二苯砜，二胺基二苯醚，二胺基二苯酮，二胺基二苯硫等芳香胺类，以及其他双氰胺，己二酸二酰肼，聚硫醇，氨类加成物等，并无特殊限制于上述所列，凡是可以和环氧树脂反应的氨类都可使用。可以单独使用，也可以混合使用。 The aliphatic amine curing agent and/or the alicyclic amine curing agent in the amine curing agent accounts for 60 to 100% of the total weight of the amine curing agent; wherein: the curing agent used in the present invention specifically has diethylenetriamine, Triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, ethylenediamine, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspirodecane adduct , polyamide, polyamide polyamine, polymeric ammonia, polyether ammonia and other fatty amines, montanane diamine, isophorone diamine, N-aminoethylpyridazine, bis(4-aminocyclohexyl)methane , bis(4-amino-3-methylcyclohexyl)methane, alicyclic amines such as hydrogenated m-xylylenediamine; m-phenylenediamine, m-xylylenediamine, diaminodiphenylmethane, diamine Aromatic amines such as diphenyl sulfone, diaminodiphenyl ether, diamino benzophenone, diaminodiphenyl sulphide, and other dicyandiamide, adipic acid dihydrazide, polythiol, ammonia The contents are not particularly limited to those listed above, and any ammonia which can react with the epoxy resin can be used. They can be used alone or in combination.
除了上述胺类固化剂以外，本发明也可以使用咪唑类当固化剂或促进剂，具体而言有2-甲基咪唑，2-苯基咪唑，2-乙基4-甲基咪唑，C11咪唑，C17咪唑等，不限上述所列，凡是可以固化环氧树脂的咪唑类均可使用，可单独使用也可混合使用。其他如三乙基氨，N-甲基吗啉等三级氨，以及四甲基氯化铵、四甲基溴化铵、四乙基氯化铵、四乙基溴化铵、三甲基卞基氯化铵、三甲基卞基溴化铵、三乙基卞基溴化铵等四级铵盐，以及四级磷鎓盐等盐基性物质也可使用作为促进剂，使用量为50ppm～50000ppm，也可和氢氧化钠、氢氧化钾等碱性物质并用。也可使用诸如对甲基苯磺酸，水杨酸，氟化硼，草酸，氯化锡等路易斯酸触媒，视固化条件的需求使用。In addition to the above amine curing agents, the present invention may also use imidazoles as curing agents or accelerators, specifically 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, C11 imidazole , C17 imidazole, etc., not limited to the above listed, all imidazoles which can cure epoxy resins can be used, either alone or in combination. Other tertiary ammonia such as triethylamine, N-methylmorpholine, and tetramethylammonium chloride, tetramethylammonium bromide, tetraethylammonium chloride, tetraethylammonium bromide, trimethyl A quaternary ammonium salt such as decyl ammonium chloride, trimethyl decyl ammonium bromide or triethyl decyl ammonium bromide, or a basal ammonium salt such as a quaternary phosphonium salt can also be used as a promoter, and the amount used is 50 ppm to 50000 ppm may be used in combination with an alkaline substance such as sodium hydroxide or potassium hydroxide. Lewis acid catalysts such as p-toluenesulfonic acid, salicylic acid, boron fluoride, oxalic acid, and tin chloride may also be used depending on the requirements of the curing conditions.
本发明的环氧树脂组成物视需要可加入添加剂，添加剂的加入量为环氧树脂和胺类固化剂总重量的0～50％，添加剂包括阻燃剂、脱模剂、偶联剂、分散剂、消泡剂和安定剂等中的一种或多种。例如：金属石碱，有机蜡，巴西蜡等脱模剂，其添加量为环氧树脂和胺类固化剂总重量的0～5％；聚氨酯类，硅烷类，长链型脂肪类，界面活性剂类等消泡剂，其添加量为环氧树脂和胺类固化剂总重量的0～3％。偶联剂添加量为环氧树脂和胺类固化剂总重量的0～5％，提高树脂组成物与纤维或纤维编织物的结合力，以及固化产成品的功能。含磷阻燃剂，含磷氮阻燃剂，含溴阻燃剂，氢氧化铝，氢氧化镁等有机、无机阻燃剂，其添加量为环氧树脂和胺类固化剂总重量的0～40％。本发明的环氧树脂组成物可适用于高压树脂传递模塑HP-RTM，中、低压树脂传递模塑以及普通树脂传递模塑工艺(RTM)，真空导流工艺，浇铸工艺，手糊工艺等固化成型制程。The epoxy resin composition of the present invention may be added with an additive as needed, and the additive is added in an amount of 0 to 50% by weight based on the total weight of the epoxy resin and the amine curing agent, and the additive includes a flame retardant, a mold release agent, a coupling agent, and a dispersion. One or more of a dose, an antifoaming agent, a stabilizer, and the like. For example: metal stone base, organic wax, Brazilian wax and other mold release agent, the added amount is 0 ~ 5% of the total weight of epoxy resin and amine curing agent; polyurethane, silane, long-chain fat, interface activity An antifoaming agent such as a dose is added in an amount of from 0 to 3% based on the total weight of the epoxy resin and the amine curing agent. The coupling agent is added in an amount of from 0 to 5% by weight based on the total weight of the epoxy resin and the amine curing agent, which enhances the binding force of the resin composition to the fiber or the fiber woven fabric, and the function of curing the finished product. Phosphorus-containing flame retardant, phosphorus-nitrogen-containing flame retardant, bromine-containing flame retardant, aluminum hydroxide, magnesium hydroxide and other organic and inorganic flame retardants, the added amount of which is 0% of the total weight of epoxy resin and amine curing agent ~40%. The epoxy resin composition of the invention can be applied to high pressure resin transfer molding HP-RTM, medium and low pressure resin transfer molding and common resin transfer molding process (RTM), vacuum flow guiding process, casting process, hand lay process, etc. Curing molding process.
实施例2：本发明还公开了一种使用快速固化低线性收缩的环氧树脂组成物制备固化物的方法，包括：Example 2: The present invention also discloses a method for preparing a cured product using a fast curing low linear shrinkage epoxy resin composition, comprising:
步骤1、将迭合的纤维和/或纤维编织物进行预成型后，放入到预热的模具内，或将纤维和/或纤维编织物直接铺放到预热的模具内；其中：Step 1. After pre-forming the laminated fiber and/or fiber woven fabric, put it into a preheated mold, or directly place the fiber and/or fiber woven fabric into the preheated mold; wherein:
纤维包括玻璃纤维，炭纤维，聚酰胺纤维，聚酰亚胺纤维，石墨纤维，酚醛树脂纤维，聚苯硫醚纤维，尼龙纤维，芳纶纤维，聚酯纤维，聚氨酯纤维，聚乙烯纤维，聚丙烯纤维，聚苯乙烯纤维，聚丙烯腈纤维等中的一种或多种；纤维编织物为上述单一纤维的编织物，或多种纤维的混合编织物；Fibers include glass fiber, carbon fiber, polyamide fiber, polyimide fiber, graphite fiber, phenolic resin fiber, polyphenylene sulfide fiber, nylon fiber, aramid fiber, polyester fiber, polyurethane fiber, polyethylene fiber, poly One or more of propylene fiber, polystyrene fiber, polyacrylonitrile fiber, etc.; the fiber woven fabric is a woven fabric of the above single fiber, or a mixed woven fabric of a plurality of fibers;
预成型是通过加压将迭合的纤维和/或纤维编织物压制成所需制备固化物 的形状。Preforming is a process of pressing a laminated fiber and/or a fiber woven fabric into a desired preparation of a cured product by pressurization. shape.
步骤2、将模具合模，抽真空；Step 2: clamping the mold and vacuuming;
步骤3、将环氧树脂组成物注入模具中；Step 3, injecting the epoxy resin composition into the mold;
步骤4、环氧树脂组成物与纤维和/或纤维编织物固化成型后，开模取出固化物。Step 4. After the epoxy resin composition is cured and molded with the fiber and/or the fiber braid, the cured product is taken out by mold opening.
进一步，模具的预热温度为90～180℃，固化成型的时间不高于20分钟。Further, the preheating temperature of the mold is 90 to 180 ° C, and the curing molding time is not higher than 20 minutes.
进一步，固化物适用于汽车车体零组件，轨道交通工具零组件，建筑材料，宇宙航空工具零组件，电子电器材料，运动器材和医疗器具等。Further, the cured product is suitable for automobile body components, rail vehicle components, building materials, aerospace tool components, electronic and electrical materials, sports equipment and medical instruments.
实施例3：本发明提供一种快速固化低线性收缩的环氧树脂组成物，该组成物由环氧树脂(A)和胺类固化剂(B)，以及添加剂(C)所构成。该组成物的环氧树脂(A)是由不少于环氧树脂(A)总重量85％的芳香族环氧树脂，以及不大于环氧树脂(A)总重量15％的脂肪族和/或脂环族环氧树脂所构成。胺类固化剂(B)是由脂肪胺和脂环胺类的总和不小于胺类固化剂(B)总重量60％所构成；添加剂(C)为阻燃剂、脱模剂、偶联剂、分散剂、消泡剂、安定剂等助剂，可以单独添加也可混合添加。此组成物在120℃的凝胶时间为170秒以下，固化后物的线性收缩率为1.0％以下。Example 3: The present invention provides a fast curing low linear shrinkage epoxy resin composition comprising an epoxy resin (A) and an amine curing agent (B), and an additive (C). The epoxy resin (A) of the composition is an aliphatic epoxy resin having not less than 85% by weight based on the total weight of the epoxy resin (A), and 15% by weight or less of the total weight of the epoxy resin (A). Or alicyclic epoxy resin. The amine curing agent (B) is composed of a total of aliphatic amine and alicyclic amine not less than 60% by weight of the amine curing agent (B); the additive (C) is a flame retardant, a releasing agent, a coupling agent Additives such as a dispersing agent, an antifoaming agent, and a stabilizer may be added singly or in combination. The gel time of this composition at 120 ° C was 170 seconds or less, and the linear shrinkage of the object after curing was 1.0% or less.
本发明组成物由环氧树脂(A)和固化剂(B)添加剂(C)所构成，该组成物可以在90～180℃的范围内于20分钟内固化成型，成型温度低于90℃，则固化时间长，容易发生固化不完全，成品的机械性能降低，而且制程循环时间长，不利于产能。成型温度高于180℃时，虽然可以缩短制程时间有利于产能，但是耗费能源大，成品脱模时容易变形，固化成型温度较好是100～160℃，更好的是100～140℃，最好的是100～120℃，无特别限制在某温度，只要能得到优良的机械性能及最小线性收缩率的成品，同时又有较短的制程循环时间，固化成型温度和时间可以适当调整。固化成型时间20分钟以下，较好是15分钟以下，更好的是10分钟以下，最好是5分钟以下，固化时间长较不利于产能，固化时间短容易发生固化不完全，固化时间除了可以随着温度的高低调整，最主要是调整固化剂或者是树脂的种类来搭配。固化物的线性收缩率为1.0％以下，线性收缩率大于1.0％时，成形品的尺寸安定性不良，不合格品多，提高成本。环氧树脂组成物中的胺类固化剂(B)，脂肪胺类与脂环胺类的总和至少不小于固化剂总量的60％，环氧树脂(A)的环氧当量/固化剂(B)的活泼 氢当量＝1.0/0.8～1.0/1.2的配比时，才能达到120℃的热板凝胶时间为170秒以下。固化成型的流程是先将迭合的纤维或纤维编织物预成型后，放入模具中，合模后为了把模具内的空气消除可以抽真空的方式实施，然后把树脂与固化剂混合脱泡后注入模具中，达到所定的时间即将开模取出成品。The composition of the present invention is composed of an epoxy resin (A) and a curing agent (B) additive (C), and the composition can be solidified in a range of 90 to 180 ° C in 20 minutes, and the molding temperature is lower than 90 ° C. The curing time is long, the curing is not complete, the mechanical properties of the finished product are lowered, and the process cycle time is long, which is not conducive to the production capacity. When the molding temperature is higher than 180 °C, although the process time can be shortened to facilitate the production capacity, the energy consumption is large, and the finished product is easily deformed during demolding, and the curing temperature is preferably 100 to 160 ° C, more preferably 100 to 140 ° C. It is preferably 100 to 120 ° C, and is not particularly limited to a certain temperature. As long as a product having excellent mechanical properties and a minimum linear shrinkage ratio can be obtained, and a short process cycle time is obtained, the curing molding temperature and time can be appropriately adjusted. The curing time is less than 20 minutes, preferably less than 15 minutes, more preferably less than 10 minutes, and most preferably less than 5 minutes. The curing time is longer than the production capacity, and the curing time is short, the curing is incomplete, and the curing time is not limited. As the temperature is adjusted, the most important thing is to adjust the curing agent or the type of resin to match. When the linear shrinkage ratio of the cured product is 1.0% or less and the linear shrinkage ratio is more than 1.0%, the dimensional stability of the molded article is poor, and the number of defective products is large, and the cost is increased. The amine curing agent (B) in the epoxy resin composition, the sum of the aliphatic amines and the alicyclic amines is at least not less than 60% of the total amount of the curing agent, and the epoxy equivalent of the epoxy resin (A) / curing agent ( B) lively When the hydrogen equivalent ratio is 1.0/0.8 to 1.0/1.2, the hot plate gel time at 120 ° C is 170 seconds or less. The process of solidification molding is to pre-form the laminated fiber or fiber woven fabric into a mold, and after the mold is closed, it can be vacuumed in order to eliminate the air in the mold, and then the resin and the curing agent are mixed and defoamed. After being injected into the mold, the finished product is opened by the mold at the set time.
以下具体列举实施例和比较例以对本发明具体实施方式的说明，但是本发明并非仅限于此些实施例中所列举的环氧树脂，胺类固化剂以及添加剂。The following examples and comparative examples are specifically given to illustrate the specific embodiments of the present invention, but the present invention is not limited to the epoxy resins, amine curing agents and additives listed in the examples.
表1中记载：Table 1 records:
双酚A环氧树脂：环氧当量170～200g/eq，双酚A环氧树脂，可以单独使用也可以混合使用。Bisphenol A epoxy resin: epoxy equivalent 170-200 g/eq, bisphenol A epoxy resin, either alone or in combination.
酚醛环氧树脂：环氧当量160～190g/eq，酚醛环氧树脂，可以单独使用也可以混合使用。Phenolic epoxy resin: epoxy equivalent 160 to 190 g/eq, phenolic epoxy resin, either alone or in combination.
脂肪族环氧树脂：环氧当量125～155g/eq，脂肪族环氧树脂，可以单独使用也可以混合使用。Aliphatic epoxy resin: epoxy equivalent 125-155 g/eq, aliphatic epoxy resin, either alone or in combination.
环氧当量按照GB/T 4612-2008塑料环氧化合物的环氧当量测定。The epoxy equivalent is determined according to the epoxy equivalent of the plastic epoxy compound of GB/T 4612-2008.
脂肪族胺：二乙基三胺，三乙基四胺，四乙基五胺，N-氨乙基呱嗪，二乙氨基丙胺，聚醚胺，双氰胺等，可以单独使用也可以混合使用。Aliphatic amines: diethyltriamine, triethyltetramine, tetraethylpentamine, N-aminoethylpyridazine, diethylaminopropylamine, polyetheramine, dicyandiamide, etc., may be used alone or in combination. use.
脂环族胺：孟烷二胺，异佛尔酮二胺，双(4-胺基-3-甲基环己基)甲烷，双(4-胺基环己基)甲烷，氢化间苯二甲胺等，可以单独使用也可以混合使用。Alicyclic amine: montan diamine, isophorone diamine, bis(4-amino-3-methylcyclohexyl)methane, bis(4-aminocyclohexyl)methane, hydrogenated m-xylylenediamine Etc., they can be used alone or in combination.
芳香族胺：间苯二甲胺，二胺基二苯基甲烷，二胺基二苯基砜等，可以单独使用也可以混合使用。The aromatic amine: m-xylylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, etc. may be used singly or in combination.
活泼氢当量：氨类固化剂中与氮原子结合的氢原子数目，其当量为氨类分子量除以与氮原子结合的氢原子数所得的值。Active hydrogen equivalent: The number of hydrogen atoms bonded to a nitrogen atom in the ammonia-based curing agent, and the equivalent thereof is a value obtained by dividing the molecular weight of the ammonia by the number of hydrogen atoms bonded to the nitrogen atom.
凝胶时间：将环氧树脂和固化剂按所定的比例混合后，以MD GT-2型的胶固化测试仪在120℃测试。Gel time: The epoxy resin and the curing agent were mixed at a predetermined ratio, and then tested at 120 ° C with a MD GT-2 type gel curing tester.
线性收缩率：依据GB/T15223-2008测试树脂、固化剂的混合密度，将测得的树脂与固化剂混合固化后的固化块密度。依据ISO3521:2000计算体积收缩率，体积收缩率＝((固化块密度-混合密度)/固化块密度)x 100％，线性收缩率＝(1+体积收缩率)1/3-1。 Linear shrinkage: According to GB/T15223-2008 test resin, curing agent mixing density, the measured resin and curing agent mixed curing solidified block density. Volume shrinkage was calculated according to ISO 3521:2000, volume shrinkage = ((cured block density - mixed density) / solidified block density) x 100%, linear shrinkage = (1 + volume shrinkage) 1/3 -1.
表1Table 1
Figure PCTCN2017098601-appb-000001
Figure PCTCN2017098601-appb-000001
如表1，本发明的环氧树脂组成物在120℃的凝胶时间为170秒以下，固化后物的线性收缩率为1.0％以下，达到快速固化低线性收缩的效果。本快速固化低收缩环氧树脂组成物与纤维、和/或纤维编织物经过混合含浸，加压加热模压固化成型后的固化物可用于汽车车体，零组件，轨道交通工具零组件，建筑材料，宇宙航空工具零组件，电子电器材料，运动器材，医疗器具等，可用以取代笨重的钢材，特别是近期以及不久的将来即将普及化的新能源交通工具，对于地球环境的保护以及能源的节约将可得到预期的成效。可应用于新能源汽车、轨道交通、航空航天工具的零组件，可以提高产能和成品收率，达到节能减碳、保护环境的效果。As shown in Table 1, the epoxy resin composition of the present invention has a gel time of at least 170 seconds at 120 ° C, and a linear shrinkage ratio of 1.0% or less after curing, which achieves the effect of rapid curing and low linear shrinkage. The fast-curing low-shrinkage epoxy resin composition and the fiber, and/or the fiber braid are mixed and impregnated, and the cured product after pressure-heat molding is used for automobile body parts, components, rail vehicle components, and building materials. , aerospace tool components, electronic and electrical materials, sports equipment, medical equipment, etc., can be used to replace bulky steel, especially new energy vehicles that will be popularized in the near future and in the near future, for the protection of the global environment and energy conservation. The expected results will be achieved. It can be applied to the components of new energy vehicles, rail transit and aerospace tools, which can increase the productivity and yield of finished products, and achieve the effects of energy saving, carbon reduction and environmental protection.
以上仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。 The above are only the preferred embodiments of the present invention, and are not intended to limit the present invention, and various modifications and changes can be made to the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and scope of the present invention are intended to be included within the scope of the present invention.

Claims (10)

  1. 一种快速固化低线性收缩的环氧树脂组成物，其特征在于，由环氧树脂、胺类固化剂和添加剂组成，所述环氧树脂的环氧当量与胺类固化剂的活泼氢当量的比例为1.0/0.8～1.0/1.2；其中：A fast curing low linear shrinkage epoxy resin composition characterized by comprising an epoxy resin, an amine curing agent and an additive, the epoxy equivalent of the epoxy resin and the active hydrogen equivalent of the amine curing agent The ratio is 1.0/0.8~1.0/1.2; among them:
    所述环氧树脂包括占环氧树脂总重量85～100％的芳香族环氧树脂及占环氧树脂总重量0～15％的脂肪族环氧树脂和/或脂环族环氧树脂；The epoxy resin comprises an aromatic epoxy resin in an amount of 85 to 100% by weight based on the total weight of the epoxy resin, and an aliphatic epoxy resin and/or an alicyclic epoxy resin in an amount of 0 to 15% by weight based on the total weight of the epoxy resin;
    所述胺类固化剂中脂肪胺类固化剂和/或脂环胺类固化剂占胺类固化剂总重量的60～100％；The aliphatic amine curing agent and/or the alicyclic amine curing agent in the amine curing agent accounts for 60 to 100% of the total weight of the amine curing agent;
    所述添加剂的加入量为环氧树脂和胺类固化剂总重量的0～50％，所述添加剂包括阻燃剂、脱模剂、偶联剂、分散剂、消泡剂和安定剂中的一种或多种；The additive is added in an amount of 0 to 50% by weight based on the total weight of the epoxy resin and the amine curing agent, and the additive includes a flame retardant, a releasing agent, a coupling agent, a dispersing agent, an antifoaming agent, and a stabilizer. One or more;
    该环氧树脂组成物在120℃的凝胶时间为170秒以下，固化后固化物的线性收缩率为1.0％以下。The epoxy resin composition had a gel time of 120 seconds or less at 120 ° C, and the linear shrinkage ratio of the cured product after curing was 1.0% or less.
  2. 如权利要求1所述的快速固化低线性收缩的环氧树脂组成物，其特征在于，所述脱模剂的加入量为环氧树脂和胺类固化剂总重量的0～5％；所述消泡剂的加入量为环氧树脂和胺类固化剂总重量的0～3％。The fast curing low linear shrinkage epoxy resin composition according to claim 1, wherein the releasing agent is added in an amount of from 0 to 5% by weight based on the total weight of the epoxy resin and the amine curing agent; The defoaming agent is added in an amount of from 0 to 3% based on the total weight of the epoxy resin and the amine curing agent.
  3. 如权利要求1所述的快速固化低线性收缩的环氧树脂组成物，其特征在于，所述偶联剂的加入量为环氧树脂和胺类固化剂总重量的0～5％。The fast curing low linear shrinkage epoxy resin composition according to claim 1, wherein the coupling agent is added in an amount of from 0 to 5% by weight based on the total of the epoxy resin and the amine curing agent.
  4. 如权利要求1所述的快速固化低线性收缩的环氧树脂组成物，其特征在于，所述阻燃剂的加入量为环氧树脂和胺类固化剂总重量的0～40％。The fast curing low linear shrinkage epoxy resin composition according to claim 1, wherein the flame retardant is added in an amount of from 0 to 40% by weight based on the total of the epoxy resin and the amine curing agent.
  5. 如权利要求1所述的快速固化低线性收缩的环氧树脂组成物，其特征在于，所述环氧树脂组成物适用于高压树脂传递模塑、中低压树脂传递模塑、普通树脂传递模塑工艺，浇铸工艺，真空导流工艺和手糊工艺的固化成型制程。The fast curing low linear shrinkage epoxy resin composition according to claim 1, wherein the epoxy resin composition is suitable for high pressure resin transfer molding, medium and low pressure resin transfer molding, and general resin transfer molding. Curing process for process, casting process, vacuum flow process and hand lay-up process.
  6. 一种使用如权利要求1所述的快速固化低线性收缩的环氧树脂组成物制备固化物的方法，其特征在于，包括：A method of preparing a cured product using the fast curing low linear shrinkage epoxy resin composition of claim 1 , comprising:
    步骤1、将迭合的纤维和/或纤维编织物进行预成型后，放入到预热的模具内，或将纤维和/或纤维编织物直接铺放到预热的模具内；Step 1. After pre-forming the laminated fiber and/or fiber woven fabric, putting it into a preheated mold, or directly laying the fiber and/or fiber woven fabric into the preheated mold;
    步骤2、将模具合模，抽真空；Step 2: clamping the mold and vacuuming;
    步骤3、将所述环氧树脂组成物注入模具中；Step 3, injecting the epoxy resin composition into a mold;
    步骤4、环氧树脂组成物与纤维和/或纤维编织物固化成型后，开模取出 固化物。Step 4. After the epoxy resin composition and the fiber and/or the fiber braid are solidified and molded, the mold is taken out. Cured product.
  7. 如权利要求6所述的使用快速固化低线性收缩的环氧树脂组成物制备固化物的方法，其特征在于，所述纤维包括玻璃纤维，炭纤维，聚酰胺纤维，聚酰亚胺纤维，石墨纤维，酚醛树脂纤维，聚苯硫醚纤维，尼龙纤维，芳纶纤维，聚酯纤维，聚氨酯纤维，聚乙烯纤维，聚丙烯纤维，聚苯乙烯纤维和聚丙烯腈纤维中的一种或多种；A method of preparing a cured product using a fast curing low linear shrinkage epoxy resin composition according to claim 6, wherein the fiber comprises glass fiber, carbon fiber, polyamide fiber, polyimide fiber, graphite One or more of fiber, phenolic resin fiber, polyphenylene sulfide fiber, nylon fiber, aramid fiber, polyester fiber, polyurethane fiber, polyethylene fiber, polypropylene fiber, polystyrene fiber and polyacrylonitrile fiber ;
    所述纤维编织物为上述单一纤维的编织物，或多种纤维的混合编织物。The fiber woven fabric is a woven fabric of the above single fibers, or a mixed woven fabric of a plurality of fibers.
  8. 如权利要求6所述的使用快速固化低线性收缩的环氧树脂组成物制备固化物的方法，其特征在于，所述预成型是通过加压将迭合的纤维和/或纤维编织物压制成所需制备固化物的形状。A method of preparing a cured product using a fast curing low linear shrinkage epoxy resin composition according to claim 6, wherein the preforming is by pressing the laminated fiber and/or fiber woven fabric by pressurization. The shape of the cured product is required to be prepared.
  9. 如权利要求6所述的使用快速固化低线性收缩的环氧树脂组成物制备固化物的方法，其特征在于，所述模具的预热温度为90～180℃，所述固化成型的时间不高于20分钟。A method for preparing a cured product using a fast curing low linear shrinkage epoxy resin composition according to claim 6, wherein the mold has a preheating temperature of 90 to 180 ° C, and the curing molding time is not high. In 20 minutes.
  10. 如权利要求6所述的使用快速固化低线性收缩的环氧树脂组成物制备固化物的方法，其特征在于，所述固化物适用于汽车车体零组件，轨道交通工具零组件，建筑材料，宇宙航空工具零组件，电子电器材料，运动器材和医疗器具。 A method of preparing a cured product using a fast curing low linear shrinkage epoxy resin composition according to claim 6, wherein the cured product is suitable for automobile body components, rail vehicle components, building materials, Aerospace aerospace tools and components, electrical and electronic materials, sports equipment and medical equipment.
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CN113549302A (en) * 2021-08-14 2021-10-26 东莞市德鸿家居用品有限公司 Forming mold for bathroom product and preparation method thereof
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