CN116731288A - Epoxy glass polymer containing dynamic ester bonds, glass fiber cloth laminated board and preparation method and application thereof - Google Patents

Epoxy glass polymer containing dynamic ester bonds, glass fiber cloth laminated board and preparation method and application thereof Download PDF

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Publication number
CN116731288A
CN116731288A CN202310882462.XA CN202310882462A CN116731288A CN 116731288 A CN116731288 A CN 116731288A CN 202310882462 A CN202310882462 A CN 202310882462A CN 116731288 A CN116731288 A CN 116731288A
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epoxy
fiber cloth
glass fiber
polymer containing
glass
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毕曙光
黄亮
冉建华
郭庆峰
杨应奎
唐加功
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Wuhan Textile University
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Wuhan Textile University
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Priority to CN202310882462.XA priority Critical patent/CN116731288A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • 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
    • C08G59/20—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 epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • C08G59/245—Di-epoxy compounds carbocyclic aromatic
    • 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
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C08G59/4215—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof cycloaliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F03—MACHINES OR ENGINES FOR LIQUIDS; WIND, SPRING, OR WEIGHT MOTORS; PRODUCING MECHANICAL POWER OR A REACTIVE PROPULSIVE THRUST, NOT OTHERWISE PROVIDED FOR
    • F03D—WIND MOTORS
    • F03D3/00—Wind motors with rotation axis substantially perpendicular to the air flow entering the rotor 
    • F03D3/06—Rotors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • B32B2260/023—Two or more layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—Synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/762—Self-repairing, self-healing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C08J2363/02—Polyglycidyl ethers of bis-phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Combustion & Propulsion (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Reinforced Plastic Materials (AREA)

Abstract

The invention belongs to the technical field of high polymer materials, and particularly relates to an epoxy glass polymer containing dynamic ester bonds, a glass fiber cloth laminated board, a preparation method and application thereof. Epoxy resin, epoxy reactive diluent and methyl tetrahydrophthalic anhydride are used as monomers, and epoxy glass polymer containing dynamic ester bonds is synthesized under the action of an ester exchange catalyst. The epoxy glass polymer containing the dynamic ester bonds has the characteristics of self-repairing, welding and reworkability at high temperature. The epoxy glass polymer containing the dynamic ester bonds is coated and soaked on the glass fiber cloth, and the glass fiber cloth laminated board also has reworkability. The method for preparing the glass fiber cloth laminated board is simple, the glass fiber cloth laminated board is prepared from two or more glass fiber cloth prepregs through a hot pressing process, each glass fiber cloth prepreg is prepared from one glass fiber cloth and is coated and soaked on two sides of the glass fiber cloth, and the prepared glass fiber cloth laminated board can be applied to preparing wind blades.

Description

Epoxy glass polymer containing dynamic ester bonds, glass fiber cloth laminated board and preparation method and application thereof
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to an epoxy glass polymer containing dynamic ester bonds, a glass fiber cloth laminated board, a preparation method and application thereof.
Background
Wind blades are typically made from continuous glass fiber reinforced polymer (e.g., epoxy, polyester, or vinyl ester) composites. Epoxy resins are an important class of thermosets, similar to other traditional thermosets, are insoluble, infusible, have irreversible covalent networks, and prevent reprocessing, recycling and remodeling of the epoxy resins. Therefore, the recovery and reprocessing of most aged, damaged and discarded epoxy-based fiberglass wind blades is challenging. In recent years, epoxy glass polymers have been prepared by introducing reversible covalent bonds into an epoxy resin crosslinked network, so that the epoxy resin combines the excellent mechanical properties of thermosetting plastics and the reworkability of thermoplastics, and imparts excellent reworkability, self-healing, welding, remodeling and recycling properties to the epoxy glass polymers. No document has been found for the use of epoxy glass polymers for the production of wind blades.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides an epoxy glass polymer containing dynamic ester bonds, a glass fiber cloth laminated board, a preparation method and application thereof.
The aim of the invention is achieved by the following technical scheme:
the preparation process of epoxy glass polymer with dynamic ester bond includes synthesizing epoxy glass polymer with dynamic ester bond in the presence of ester exchange catalyst with epoxy resin, epoxy reactive diluent and methyltetrahydrophthalic anhydride as monomer.
Further, the epoxy resin comprises any one of bisphenol a type epoxy resin or bisphenol F type epoxy resin.
Further, the epoxy reactive diluent is at least one of benzyl glycidyl ether or 1, 4-butanediol diglycidyl ether.
Further, the transesterification catalyst is at least one of zinc acetylacetonate or 1, 5, 7-triazabicyclo [4, 4, 0] dec-5-ene.
Further, the mass ratio of the epoxy resin to the epoxy reactive diluent is 2-9:1, the mass ratio of the methyltetrahydrophthalic anhydride to the epoxy group is 0.5-0.8:1, and the mass ratio of the transesterification catalyst to the epoxy group is 1:5-15. The epoxy group is the sum of epoxy groups in the epoxy resin and the epoxy reactive diluent.
Further, the epoxy resin and the epoxy reactive diluent are mixed and stirred uniformly, then the transesterification catalyst is added into the mixed resin at the temperature of 85-95 ℃, the mixed resin is stirred and mixed for 25-35 min, and after the mixture is cooled to room temperature, the methyl tetrahydrophthalic anhydride is added, and the mixed mixture is continuously stirred and stirred uniformly.
The epoxy glass polymer containing dynamic ester bonds prepared by the method.
The glass fiber cloth laminated board is prepared from two or more glass fiber cloth prepregs through a hot pressing process, wherein each glass fiber cloth prepreg is composed of one layer of glass fiber cloth and resin compositions coated and infiltrated on two sides of the glass fiber cloth, and the resin compositions are the epoxy glass polymers containing dynamic ester bonds.
Further, the hot pressing process comprises the following steps: curing at 85-95 deg.c to 1.5-2.5-h and at 115-125 deg.c to 1.5-2.5-h under 1-5 MPa, and cooling to room temperature.
The epoxy glass polymer containing the dynamic ester bonds is applied to the preparation of wind blades.
The invention has the following advantages: the epoxy glass polymer containing the dynamic ester bonds has the characteristics of self-repairing, welding and reworkability at high temperature. The epoxy glass polymer containing the dynamic ester bonds is coated and soaked on the glass fiber cloth, and the glass fiber cloth laminated board also has reworkability. The method for preparing the glass fiber cloth laminated board is simple, the glass fiber cloth laminated board is prepared from two or more glass fiber cloth prepregs through a hot pressing process, each glass fiber cloth prepreg is prepared from one glass fiber cloth and is coated and soaked on two sides of the glass fiber cloth, and the prepared glass fiber cloth laminated board can be applied to preparing wind blades.
Drawings
FIG. 1 is a FTIR chart of an epoxy glass polymer containing dynamic ester bonds prepared in example 1.
FIG. 2 is a DSC of an epoxy-based glass polymer containing a dynamic ester bond prepared in example 1.
FIG. 3 is a graph showing the storage modulus and loss tangent of the epoxy-based glass polymer containing a dynamic ester bond prepared in example 1.
FIG. 4 is a self-repairing diagram of the epoxy glass polymer containing dynamic ester bonds prepared in example 1.
FIG. 5 is a diagram showing the welding and reworking of the epoxy glass polymer containing dynamic ester bonds prepared in example 1.
FIG. 6 is a reworkable drawing of the epoxy glass fiber cloth laminate of example 2 containing dynamic ester bonds.
Detailed Description
The invention will be further described with reference to the accompanying drawings and examples, to which the scope of the invention is not limited:
example 1: the preparation process of epoxy glass polymer containing dynamic ester bond includes mixing epoxy resin and epoxy reactive diluent, stirring, adding ester exchange catalyst into the mixed resin at 85 deg.c, stirring and mixing for 25min, cooling to room temperature, adding methyl tetrahydrophthalic anhydride, stirring and mixing to obtain epoxy glass polymer containing dynamic ester bond.
Wherein the mass ratio of the epoxy resin to the epoxy reactive diluent is 2:1, and the mass ratio of the methyltetrahydrophthalic anhydride to the epoxy group is 0.5:1; the mass ratio of the transesterification catalyst to the epoxy group is 1:5; the epoxy resin is bisphenol A type epoxy resin; the epoxy reactive diluent is benzyl glycidyl ether; the transesterification catalyst is zinc acetylacetonate.
Example 2: the preparation process of epoxy glass polymer containing dynamic ester bond includes mixing epoxy resin and epoxy reactive diluent, stirring, adding ester exchange catalyst into the mixed resin at 95 deg.c, stirring and mixing for 35 min, cooling to room temperature, adding methyl tetrahydrophthalic anhydride, stirring and mixing to obtain the epoxy glass polymer containing dynamic ester bond.
Wherein the mass ratio of the epoxy resin to the epoxy reactive diluent is 9:1, the mass ratio of the methyltetrahydrophthalic anhydride to the epoxy group is 0.8:1, and the mass ratio of the transesterification catalyst to the epoxy group is 1:15; the epoxy resin is bisphenol F type epoxy; the epoxy reactive diluent is 1, 4-butanediol diglycidyl ether; the transesterification catalyst is 1, 5, 7-triazabicyclo [4, 4, 0] dec-5-ene.
Example 3: the preparation process of epoxy glass polymer containing dynamic ester bond includes mixing epoxy resin and epoxy reactive diluent, stirring, adding ester exchange catalyst into the mixed resin at 90 deg.c, stirring for 30 min, cooling to room temperature, adding methyl tetrahydrophthalic anhydride, stirring and mixing to obtain epoxy glass polymer containing dynamic ester bond.
Wherein the mass ratio of the epoxy resin to the epoxy reactive diluent is 5:1, the mass ratio of the methyltetrahydrophthalic anhydride to the epoxy group is 0.6:1, and the mass ratio of the transesterification catalyst to the epoxy group is 1:10; the epoxy resin comprises bisphenol A type epoxy resin; the epoxy reactive diluent is a mixture of benzyl glycidyl ether and 1, 4-butanediol diglycidyl ether, and the volume ratio of the epoxy reactive diluent to the mixture is 1:2; the transesterification catalyst is a mixture of zinc acetylacetonate and 1, 5, 7-triazabicyclo [4, 4, 0] dec-5-ene, and the weight ratio is 1:1.
Example 4: the glass fiber cloth laminated board is prepared from two layers of glass fiber cloth prepregs through a hot pressing process, wherein the hot pressing process comprises the following steps: curing at 85 ℃ to 1.5 h and at 115 ℃ to 1.5 h, controlling the pressure to 1 MPa, taking out and cooling to room temperature after hot pressing is finished, wherein each layer of glass fiber cloth prepreg consists of one layer of glass fiber cloth and resin compositions coated and infiltrated on two sides of the glass fiber cloth, and the resin compositions are the epoxy glass polymer containing the dynamic ester bonds, which is prepared in the embodiment 1.
Example 5: the glass fiber cloth laminated board is prepared from three layers of glass fiber cloth prepreg through a hot pressing process, wherein the hot pressing process comprises the following steps: curing at 95 ℃ to 2.5 h and at 125 ℃ to 2.5 h, controlling the pressure to 5MPa, taking out and cooling to room temperature after hot pressing, wherein each layer of glass fiber cloth prepreg consists of one layer of glass fiber cloth and resin compositions coated and infiltrated on two sides of the glass fiber cloth, and the resin compositions are the epoxy glass polymers containing dynamic ester bonds prepared in the embodiment 2.
Example 6: the glass fiber cloth laminated board is prepared from three layers of glass fiber cloth prepreg through a hot pressing process, wherein the hot pressing process comprises the following steps: curing at 90 ℃ 2h and 120 ℃ 2h, controlling the pressure to be 3 MPa, taking out and cooling to room temperature after hot pressing is finished, wherein each layer of glass fiber cloth prepreg consists of one layer of glass fiber cloth and resin compositions coated and infiltrated on two sides of the glass fiber cloth, and the resin compositions are the epoxy glass polymers containing dynamic ester bonds prepared in the embodiment 3.
The beneficial effects of the invention are illustrated by the following experiments:
example 1:
preparation of epoxy glass polymer containing ester bonds: weighing 8 g BPF-170 bisphenol F epoxy resin and 2 g benzyl glycidyl ether, mixing and stirring uniformly to obtain diluted mixed epoxy resin; then adding 0.73 g zinc acetylacetonate into the mixed epoxy resin, mixing and magnetically stirring for half an hour at 90 ℃, adding 4.6 g methyl tetrahydrophthalic anhydride after cooling to room temperature, mixing and stirring uniformly, then pouring the mixture into a polytetrafluoroethylene mould, solidifying for 2 hours at 90 ℃ and 2 hours at 120 ℃, and taking out a sample after the solidifying procedure is finished to obtain the epoxy glass polymer containing ester bonds.
Through infrared testing, as can be seen in FIG. 1, the epoxy resin was found to be in 915 cm -1 The absorption peak of epoxy group disappears, which indicates that the epoxy resin is completely cured; the glass transition temperature of the epoxy glass polymer containing ester bonds is about 67 ℃ as measured by DSC (differential scanning calorimetry) test in figure 2; by dynamic thermo-mechanical analysis, the glass transition temperature of the epoxy glass polymer containing ester bonds is about 64 ℃ and the glass state storage modulus is about 5.6 GPa as measured in FIG. 3; as shown in fig. 4, after the epoxy glass polymer containing ester bonds is thermally repaired for 80 minutes at 160 ℃, scratches can be obviously reduced; as shown in figure 5, the epoxy glass polymer containing ester bonds can be reprocessed at 100 ℃, and has weldability under the action of external force.
Example 2:
preparing a glass fiber cloth laminated board: weighing 24 g BPF-170 bisphenol F epoxy resin and 6 g benzyl glycidyl ether, mixing and stirring uniformly to obtain diluted mixed epoxy resin; then adding 2.19 g zinc acetylacetonate into the mixed epoxy resin, mixing and magnetically stirring for half an hour at 90 ℃, cooling to room temperature, then adding 13.8 g methyl tetrahydrophthalic anhydride, mixing and stirring uniformly, and standing for later use;
the resin mixture is manually dip-coated on glass fiber cloth to prepare prepreg, then three layers of prepreg are paved between two steel plates, the steel plates and the prepreg are separated by a layer of polytetrafluoroethylene film, and the steel plates and the prepreg are placed into a hot press under the hot press process conditions that: and (3) carrying out hot press solidification at 90 ℃ for 2 hours, carrying out hot press solidification at 120 ℃ for 2 hours, controlling the pressure to be 5MPa, taking out and cooling to room temperature after hot press is finished, and obtaining the glass fiber cloth laminated board. As shown in fig. 5, the laminate produced had reworkability.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art who is skilled in the art to which the present invention pertains will appreciate that the technical scheme and the inventive concept according to the present invention are equally substituted or changed within the scope of the present invention.

Claims (10)

1. The preparation process of epoxy glass polymer with dynamic ester bond features that epoxy resin, epoxy reactive diluent and methyltetrahydrophthalic anhydride are used as monomer and the epoxy glass polymer with dynamic ester bond is synthesized under the action of ester exchange catalyst.
2. The method for producing a glass polymer containing a dynamic ester bond according to claim 1, wherein the epoxy resin comprises any one of bisphenol a type epoxy resin and bisphenol F type epoxy resin.
3. The method for preparing the epoxy glass polymer containing the dynamic ester bonds, which is disclosed in claim 1, is characterized in that the epoxy reactive diluent is at least one of benzyl glycidyl ether or 1, 4-butanediol diglycidyl ether.
4. The method for preparing an epoxy glass polymer containing dynamic ester bonds according to claim 1, wherein the transesterification catalyst is at least one of zinc acetylacetonate or 1, 5, 7-triazabicyclo [4, 4, 0] dec-5-ene.
5. The method for preparing the epoxy glass polymer containing the dynamic ester bonds, which is disclosed in claim 1, is characterized in that the mass ratio of the epoxy resin to the epoxy reactive diluent is 2-9:1, the mass ratio of the methyltetrahydrophthalic anhydride to the epoxy group is 0.5-0.8:1, and the mass ratio of the transesterification catalyst to the epoxy group is 1:5-15.
6. The method for preparing the epoxy glass polymer containing the dynamic ester bonds, which is characterized in that epoxy resin and epoxy reactive diluent are mixed and stirred uniformly, then ester exchange catalyst is added into the mixed resin at the temperature of 85-95 ℃, and stirred and mixed for 25-35 min, and methyl tetrahydrophthalic anhydride is added after the mixture is cooled to room temperature, and the mixture is stirred and mixed uniformly continuously.
7. An epoxy-based glass polymer containing a dynamic ester bond prepared according to the method of any one of claims 1 to 6.
8. The glass fiber cloth laminated board is characterized by being prepared from two or more glass fiber cloth prepregs through a hot pressing process, wherein each glass fiber cloth prepreg is composed of one glass fiber cloth layer and a resin composition coated and infiltrated on two sides of the glass fiber cloth layer, and the resin composition is the epoxy glass polymer containing the dynamic ester bonds according to claim 7.
9. The fiberglass cloth laminated board according to claim 1, wherein the hot pressing process is: curing at 85-95 deg.c to 1.5-2.5-h and at 115-125 deg.c to 1.5-2.5-h under 1-5 MPa, and cooling to room temperature.
10. The use of the glass fiber laminated board of claim 8 or 9 for preparing wind blades, wherein the glass polymer comprises a dynamic ester bond epoxy glass polymer of claim 7.
CN202310882462.XA 2023-07-19 2023-07-19 Epoxy glass polymer containing dynamic ester bonds, glass fiber cloth laminated board and preparation method and application thereof Pending CN116731288A (en)

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CN112979925A (en) * 2021-02-24 2021-06-18 中国工程物理研究院化工材料研究所 Medium-low temperature curing type epoxy glass polymer
CN113150500A (en) * 2021-04-30 2021-07-23 中国工程物理研究院化工材料研究所 Winding-formed fiber-reinforced epoxy glass polymer composite material
CN114891249A (en) * 2022-05-07 2022-08-12 重庆国际复合材料股份有限公司 Preparation method of glass fiber reinforced epoxy resin composite material
CN115651165A (en) * 2022-11-29 2023-01-31 新创碳谷集团有限公司 Recyclable epoxy resin and preparation method and recycling method thereof
CN115678204A (en) * 2022-07-26 2023-02-03 西南科技大学 Epoxy fiber composite material for wind power blade and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112979925A (en) * 2021-02-24 2021-06-18 中国工程物理研究院化工材料研究所 Medium-low temperature curing type epoxy glass polymer
CN113150500A (en) * 2021-04-30 2021-07-23 中国工程物理研究院化工材料研究所 Winding-formed fiber-reinforced epoxy glass polymer composite material
CN114891249A (en) * 2022-05-07 2022-08-12 重庆国际复合材料股份有限公司 Preparation method of glass fiber reinforced epoxy resin composite material
CN115678204A (en) * 2022-07-26 2023-02-03 西南科技大学 Epoxy fiber composite material for wind power blade and preparation method thereof
CN115651165A (en) * 2022-11-29 2023-01-31 新创碳谷集团有限公司 Recyclable epoxy resin and preparation method and recycling method thereof

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