CN113278395A - Pre-forming glue spraying composition and preparation method thereof - Google Patents
Pre-forming glue spraying composition and preparation method thereof Download PDFInfo
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- CN113278395A CN113278395A CN202110389661.8A CN202110389661A CN113278395A CN 113278395 A CN113278395 A CN 113278395A CN 202110389661 A CN202110389661 A CN 202110389661A CN 113278395 A CN113278395 A CN 113278395A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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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
- 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
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- C—CHEMISTRY; METALLURGY
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- 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
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Abstract
The invention relates to the technical field of adhesives, in particular to a pre-setting glue-spraying composition and a preparation method thereof. The pre-setting glue-spraying composition comprises the following components in parts by weight: 35-50 parts of modified resin, 10-20 parts of bisphenol A liquid epoxy resin and 30-70 parts of bisphenol A solid epoxy resin. The modified resin comprises 88-90 parts by weight of bisphenol A epoxy resin and 8-10 parts by weight of nitrile rubber. The pre-forming glue-spraying composition has good adhesion with the encapsulating epoxy resin, does not influence the mechanical property of the encapsulated material, does not discharge voc in the using process and has good environmental protection effect.
Description
Technical Field
The invention relates to the technical field of adhesives, in particular to a pre-setting glue-spraying composition and a preparation method thereof.
Background
The epoxy composite material is widely applied to wind power generation blades. Often earlier when preparation wind power generation blade paves the layer with glass fiber cloth then pours into epoxy, when using glass fiber cloth when paving the layer operation, in order to prevent that glass fiber cloth from removing, guarantee the accuracy of laying the layer, often can spray the preshaping glue and prevent that glass fiber cloth from sliding on glass fiber cloth layer surface in the manufacturing process. In the related art, the sprayed pre-setting spray adhesive is a non-epoxy resin system spray adhesive with a volatile solvent, and the following problems are mainly existed: on one hand, the connectivity between the epoxy resin and the composite fiber cloth layer for subsequent encapsulation is influenced, and the interface performance of the epoxy resin and the composite fiber cloth layer is reduced, so that the mechanical property of the blade is influenced; on the other hand, the volatilization of the solvent can discharge voc, which does not meet the environmental protection standard.
Disclosure of Invention
The application discloses glue composition is spouted in presetting and preparation method thereof, uses this glue composition is spouted in presetting can not influence by the mechanical properties of embedment material, and this glue composition is spouted in presetting and embedment epoxy's adhesion is good, and the use does not have voc and discharges, and environmental protection effect is better.
In a first aspect, the pre-forming spray adhesive composition disclosed by the application comprises the following components in parts by weight:
35-50 parts of modified resin
10-20 parts of bisphenol A liquid epoxy resin
30-70 parts of bisphenol A solid epoxy resin
The modified resin comprises the following components in parts by weight: 88-90 parts of bisphenol A epoxy resin and 8-10 parts of nitrile rubber.
Further, the bisphenol A liquid epoxy resin is one or more of E-54 type bisphenol A liquid epoxy resin, E-51 type bisphenol A liquid epoxy resin and E-44 type bisphenol A liquid epoxy resin.
Further, the bisphenol A solid epoxy resin is one or more of E-03 type bisphenol A solid epoxy resin, E-06 type bisphenol A solid epoxy resin and E-12 type bisphenol A solid epoxy resin.
Further, the modified resin also comprises an accelerant, the accelerant is 1 part by weight, and the accelerant is one of benzyltriethylammonium chloride, benzyldimethylamine and DMP-30.
In a second aspect, the present application also discloses a method of preparing a pre-set spray composition according to the first aspect, the method comprising the steps of:
preparing modified resin: mixing and stirring bisphenol A epoxy resin and nitrile rubber to obtain modified resin;
mixing: mixing and stirring bisphenol A liquid epoxy resin and bisphenol A solid epoxy resin until the bisphenol A solid epoxy resin is dissolved in the bisphenol A liquid epoxy resin to obtain mixed resin;
modification: and adding the modified resin into the mixed resin, and stirring to obtain the pre-shaped glue spraying resin.
Further, in the step of preparing the modified resin, the bisphenol A epoxy resin and the nitrile rubber are reacted for 3-4 hours at the temperature of 110-130 ℃.
Further, in the step of preparing the modified resin, an accelerator is mixed and stirred with the bisphenol A epoxy resin and the nitrile rubber, and the accelerator is one of benzyltriethylammonium chloride, benzyldimethylamine and DMP-30.
Further, in the mixing step, the bisphenol a liquid epoxy resin and the bisphenol a solid epoxy resin are reacted at a temperature of 110 ℃ to 150 ℃.
Further, the mixed resin is cooled to 80-100 ℃ and then added with the modified resin, and the modified resin is preheated to 80 ℃ and then added into the mixed resin.
Further, the sum of the molecular weights of the bisphenol A liquid epoxy resin and the bisphenol A solid epoxy resin is 1500-2700.
Compared with the prior art, the invention has the following beneficial effects:
the pre-setting glue-spraying composition prepared by the invention has good adhesion with the encapsulating epoxy resin, does not influence the mechanical property of the encapsulated material, does not discharge voc in the using process and has good environmental protection effect. Specifically, the pre-shaping glue-spraying composition mainly comprises modified resin, bisphenol A liquid epoxy resin and bisphenol A epoxy resin, wherein the modified resin is obtained by modifying the bisphenol A epoxy resin with nitrile rubber. The pre-shaping glue-spraying composition has the advantages that the pre-shaping glue-spraying composition is endowed with the sticky property at normal temperature through the modified resin, and the cross-linking reaction does not occur among the resins, and the specific expression is that the surface of a glue layer is not dried, but a certain viscosity can be kept, so that the bonding shaping of the composite fiber cloth layer is realized on the premise that the resins do not need cross-linking curing. On one hand, as the main components of the pre-setting glue spraying composition are epoxy resin substances, the pre-setting glue spraying composition has good adhesion with the encapsulating epoxy resin, and the mechanical property of the encapsulated epoxy resin cannot be influenced. On the other hand, the presetting glue spraying composition does not contain volatile solvent, and no voc substance is discharged, so the environment is not polluted, and the cloth layer can be repeatedly pasted because the surface of the glue layer of the presetting glue spraying composition is not dry, and the convenience of construction is also ensured.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a flow chart of a method for preparing a pre-formed spray composition according to an embodiment of the present application;
FIG. 2 is a diagram of a pre-shaped glue-sprayed area of a fiberglass panel when tested for creep resistance;
FIG. 3 is a schematic view of the shear line of the triaxial fabric in the tack force test.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the present invention, the terms "upper", "lower", "left", "right", "front", "rear", "top", "bottom", "inner", "outer", "center", "vertical", "horizontal", "lateral", "longitudinal", and the like indicate an orientation or positional relationship based on the orientation or positional relationship shown in the drawings. These terms are used primarily to better describe the invention and its embodiments and are not intended to limit the indicated devices, elements or components to a particular orientation or to be constructed and operated in a particular orientation.
Moreover, some of the above terms may be used to indicate other meanings besides the orientation or positional relationship, for example, the term "on" may also be used to indicate some kind of attachment or connection relationship in some cases. The specific meanings of these terms in the present invention can be understood by those skilled in the art as appropriate.
Furthermore, the terms "mounted," "disposed," "provided," "connected," and "connected" are to be construed broadly. For example, it may be a fixed connection, a removable connection, or a unitary construction; can be a mechanical connection, or an electrical connection; may be directly connected, or indirectly connected through intervening media, or may be in internal communication between two devices, elements or components. The specific meanings of the above terms in the present invention can be understood by those of ordinary skill in the art according to specific situations.
Furthermore, the terms "first," "second," and the like, are used primarily to distinguish one device, element, or component from another (the specific nature and configuration may be the same or different), and are not used to indicate or imply the relative importance or number of the indicated devices, elements, or components. "plurality" means two or more unless otherwise specified.
The epoxy composite material is a novel material formed by an epoxy resin matrix and a composite fiber material, and is widely applied to the fields of wind power generation blades and the like. Taking the wind power generation blade as an example, when producing the wind power generation blade, need to spread 100 multilayer glass fiber cloth, spread cloth according to the design and lay the layer order in the shop cloth process, for guaranteeing that the fibre cloth layer does not slide in the layer in-process, guarantee the mechanical properties of design requirement, can use the preforming to spout the removal that the glue prevents the cloth layer usually, guarantee the accuracy of laying the layer. However, in the prior art, the pre-shaped spray glue used for preparing the epoxy-based composite material is generally a shaped spray glue with a volatile solvent, and the spray glue is incompatible with an epoxy resin matrix as long as the components of the spray glue are a non-epoxy resin system. The existing pre-setting glue spraying method mainly has the following problems: on one hand, the existing pre-setting spray adhesive is a spray adhesive of a non-epoxy resin system and is incompatible with an epoxy resin matrix for subsequent encapsulation, so that the connectivity between the epoxy resin matrix and a composite fiber cloth layer is influenced, and the mechanical property of an epoxy-based composite material is influenced. On the other hand, the volatilization of the existing pre-setting glue-spraying solvent can discharge voc, which does not meet the environmental safety standard.
The technical solution of the present application will be further described with reference to the following embodiments and accompanying drawings.
The embodiment of the application discloses a pre-forming glue spraying composition which comprises, by weight, 35-50 parts of modified resin, 10-20 parts of bisphenol A liquid epoxy resin and 30-70 parts of bisphenol A solid epoxy resin. The modified resin comprises 88-90 parts by weight of bisphenol A epoxy resin and 8-10 parts by weight of nitrile rubber.
The pre-shaped glue-spraying composition in the embodiment of the application has good connectivity with the encapsulating epoxy resin matrix, and the mechanical property of the epoxy composite material cannot be influenced; and the pre-setting glue-spraying composition has no voc emission in the using process and causes no pollution. Specifically, in the embodiment of the application, the bisphenol a epoxy resin is modified by mixing a certain proportion of nitrile rubber and the bisphenol a epoxy resin, so that certain adhesiveness is given to the bisphenol a epoxy resin. And then mixing the modified resin with adhesiveness with bisphenol A liquid epoxy resin and bisphenol A solid epoxy resin to obtain the preformed spray adhesive composition with adhesiveness. On one hand, the pre-setting spray glue has certain compatibility with an epoxy resin matrix because the pre-setting spray glue composition is an epoxy resin system. Therefore, the preshaped glue spraying composition is sprayed on the composite fiber cloth layer and then is encapsulated with the epoxy resin matrix, the interface performance between the epoxy resin matrix and the preshaped glue spraying is not influenced, and the connectivity between the epoxy resin matrix and the preshaped glue spraying is improved. On the other hand, the pre-shaping glue-spraying composition is sprayed on the composite fiber cloth layer to show that the surface glue layer is not dry, and volatile substances voc are not discharged, so that certain harm is not caused to the environment.
In the prior art, the liquid epoxy resin or the solid epoxy resin has no application value when used alone, and the liquid epoxy resin or the solid epoxy resin has the application value only after the curing agent is added into the liquid epoxy resin or the solid epoxy resin, mixed and heated to prepare the epoxy adhesive. In order to improve the toughness of the epoxy adhesive and avoid cracking of the epoxy adhesive, a toughening agent, namely nitrile rubber is often added into the epoxy adhesive, the nitrile rubber is mainly used as the toughening agent, and the problems of high brittleness and easiness in cracking of the epoxy adhesive are solved. It can thus be understood that: on the one hand, the traditional adhesive is a resin reinforcing agent which plays a role in bonding after being crosslinked and cured, and the traditional adhesive is not suitable for the epoxy composite material preforming process because the surface of the adhesive is not required to be dry and is similar to the effect of a double-sided adhesive in the epoxy composite material preforming process. On the other hand, in the traditional technology, nitrile rubber is added into epoxy resin mainly for improving the toughness of the epoxy adhesive and avoiding cracking of the epoxy adhesive.
In the embodiment of the application, the pre-shaped spray glue composition mainly comprises a modified resin, a bisphenol A liquid epoxy resin and a bisphenol A solid epoxy resin. The epoxy resin with high molecular weight is solid and blocky, has high surface glossiness, and can not be adhered together at normal temperature, and the liquid epoxy resin can not be adhered to the surface of the fiber layer to generate viscous adhesion and shaping, so that the pure epoxy resin can not be used as shaping spray glue. However, in the embodiments of the present application, the inventors have experimentally verified that a predetermined spray mixture with adhesiveness can be prepared by mixing a certain proportion of modified resin, bisphenol a solid epoxy resin, and bisphenol a liquid epoxy resin.
The embodiment of the application endows bisphenol A solid epoxy resin and bisphenol A liquid epoxy resin with adhesiveness through the modified resin. Specifically, the modified resin comprises 88-90 parts of bisphenol A epoxy resin and 8-10 parts of nitrile rubber. The nitrile butadiene rubber has the main function of solving the problem that the surface of the bisphenol A epoxy resin is smooth and has no adhesive force at normal temperature, and the bisphenol A epoxy resin is endowed with normal-temperature adhesiveness through modification. When 35-50 parts of modified resin, 30-70 parts of bisphenol A solid epoxy resin and 10-20 parts of bisphenol A liquid epoxy resin are mixed, a pre-setting glue spraying composition is prepared, the pre-setting glue spraying composition has normal-temperature adhesiveness at normal temperature, and is characterized in that the surface of a glue layer is not dry and can keep adhesiveness, so that the bonding and setting of a composite fiber cloth layer are realized on the premise that the epoxy resin does not need crosslinking and curing, and the cloth layer can be repeatedly paved and pasted due to the fact that the surface of the glue layer is not dry, and construction convenience is guaranteed.
Further, in the examples of the present application, the bisphenol a liquid epoxy resin is one or more of an E-54 type liquid bisphenol a epoxy resin, an E-51 type liquid bisphenol a resin, and an E-44 type liquid bisphenol a resin. The bisphenol A solid epoxy resin is one or more of E-03 type solid bisphenol A epoxy resin, E-06 type solid bisphenol A epoxy resin and E-12 type solid bisphenol A epoxy resin.
The polymerization degree and molecular weight of different types of epoxy resins are different, so that the type of epoxy resin selected when preparing the pre-setting spray-coating composition can determine the reaction conditions and the performance of the prepared product. The applicant proves through experimental data that bisphenol A liquid epoxy resin is selected from one or more of E-54 type liquid bisphenol A epoxy resin, E-51 type liquid bisphenol A resin and E-44 type liquid bisphenol A resin, bisphenol A solid epoxy resin is selected from one or more of E-03 type solid bisphenol A epoxy resin, E-06 type solid bisphenol A epoxy resin and E-12 type solid bisphenol A epoxy resin, and the molecular weight and the polymerization degree of the finally obtained pre-shaped spray glue composition are within an ideal range.
Further, in the embodiment of the application, the modified resin further comprises an accelerator, wherein the accelerator is 1 part by weight, and the accelerator is one of benzyltriethylammonium chloride, benzyldimethylamine and DMP-30. In order to promote the reaction of the nitrile rubber and the bisphenol A epoxy resin, an accelerant is added in the embodiment of the application, the reaction speed of the nitrile rubber and the bisphenol A epoxy resin is accelerated through the accelerant, and the reaction time is saved. The accelerator may be any one of commercially available benzyltriethylammonium chloride, benzyldimethylamine, and DMP-30, and is not particularly limited herein.
The embodiment of the application also discloses a preparation method of the pre-setting glue spraying composition, and specifically, the preparation method comprises the following steps:
preparing modified resin: mixing and stirring bisphenol A epoxy resin and nitrile rubber to obtain modified resin;
mixing: mixing and stirring bisphenol A liquid epoxy resin and bisphenol A solid epoxy resin until the bisphenol A solid epoxy resin is dissolved in the bisphenol A liquid epoxy resin to obtain mixed resin;
modification: and adding the modified resin into the mixed resin, and stirring to obtain the pre-shaped glue spraying resin.
The bisphenol A epoxy resin is modified after being mixed and stirred with the nitrile rubber, so that the obtained modified resin has certain viscosity. And then mixing and stirring the bisphenol A liquid epoxy resin and the bisphenol A solid epoxy resin until the bisphenol A solid epoxy resin is completely dissolved in the bisphenol A liquid epoxy resin, and specifically observing whether solid substances exist in the bisphenol A liquid epoxy resin or not, wherein if the solid substances do not exist in the bisphenol A liquid epoxy resin, the bisphenol A solid epoxy resin is completely dissolved in the bisphenol A liquid epoxy resin. This has the advantage that the fully dissolved resin improves the homogeneity of the mixed resin due to mixing with the modified resin in a subsequent step. And adding the modified resin into the obtained mixed resin, and uniformly mixing and stirring the mixed resin and the modified resin to endow the mixed resin with adhesiveness, so that the prepared pre-shaped glue-spraying resin has adhesiveness. The above operation may be performed in a reaction vessel or in another apparatus, and is not particularly limited herein.
Further, in order to better modify the bisphenol A epoxy resin and enable the modified resin to have better viscosity, in the step of preparing the modified resin, the bisphenol A epoxy resin and the nitrile rubber are reacted for 3-4 hours at the temperature of 110-130 ℃. The applicant proves through a large amount of experimental data that after bisphenol A epoxy resin and nitrile rubber react for 3-4 hours at the temperature of 110-130 ℃, the reaction degree of active groups is higher, and the epoxy value of the obtained modified resin is relatively lower, so that the finally prepared pre-shaping spray adhesive has good stability and can be stored for a long time.
It is understood that the reaction of the bisphenol A epoxy resin and the nitrile rubber at a temperature of 110 ℃ to 130 ℃ in the present embodiment means that the reaction temperature of the two can be any value within the temperature range, and can be, for example, 110 ℃, 115 ℃, 118 ℃, 120 ℃, 122 ℃, 125 ℃, 128 ℃ to 130 ℃. The bisphenol A epoxy resin and the nitrile rubber are reacted for 3-4 hours, namely the reaction time of the bisphenol A epoxy resin and the nitrile rubber can be 3 hours, 3.5 hours and 4 hours.
In the embodiment of the application, in order to accelerate the reaction speed of the modified resin, in the step of preparing the modified resin, an accelerator is mixed and stirred with the bisphenol A epoxy resin and the nitrile rubber, and the accelerator is one of benzyltriethylammonium chloride, benzyldimethylamine and DMP-30. Due to the addition of the accelerant, the reaction speed of the bisphenol A epoxy resin and the nitrile rubber is increased, the reaction time is reduced, and the production efficiency can be improved during large-scale production.
Further, in order to facilitate the bisphenol A solid epoxy resin to be dissolved in the bisphenol A liquid epoxy resin as quickly as possible, the bisphenol A liquid epoxy resin and the bisphenol A solid epoxy resin are reacted at a temperature of 110 to 150 ℃ in the mixing step. When the reaction is carried out in the temperature range, the bisphenol A solid epoxy resin can reach the melting point, so that the bisphenol A solid epoxy resin can be completely dissolved in the bisphenol A liquid epoxy resin, and the bisphenol A liquid epoxy resin can be prevented from being evaporated.
Furthermore, in order to facilitate the modified resin to be fully mixed in the mixed resin, the modified resin is added after the mixed resin is cooled to 80-100 ℃, and the modified resin is added into the mixed resin after being preheated to 80 ℃. When the mixed resin is fully and uniformly stirred, the mixed resin is cooled in advance, so that the mixed resin is prevented from discoloring at high temperature for a long time, the energy loss can be reduced, and the mixed resin can still be kept in a liquid state within the range of 80-100 ℃. When the modified resin preheated to 80 ℃ is added into the mixed resin within the range of 80 ℃ to 100 ℃, the modified resin can be rapidly fused with the mixed resin as the temperature of the modified resin and the mixed resin is approximately equivalent. In addition, the problem that the mixed resin is cooled and solidified due to the addition of the modified resin with the excessively low temperature into the mixed resin is also avoided.
In the embodiment of the application, in order to enable the prepared pre-forming spray glue composition to have good adhesion, the sum of the molecular weights of the bisphenol A liquid epoxy resin and the bisphenol A solid epoxy resin is 1500-2700. The applicant proves through a large number of experiments that when the sum of the molecular weights of the bisphenol A liquid epoxy resin and the bisphenol A solid epoxy resin is 1500-2700, the pre-setting glue-spraying composition prepared by the assembly with the molecular weights has good adhesive force and creep resistance at normal temperature, so that the adhesive setting effect of the pre-setting glue-spraying composition is ensured.
In order to explain the technical scheme and technical effect of the present application in more detail, the present application will be explained by more specific examples and comparative examples.
Example one
The embodiment provides a pre-setting glue-spraying composition, which comprises the following components in parts by weight:
50 parts of modified resin
20 parts of E-54 type bisphenol A liquid epoxy resin
30 parts of E-03 type bisphenol A solid epoxy resin
The modified resin comprises the following components in parts by weight: 89 parts of E-54 type bisphenol A epoxy resin, 10 parts of carboxyl-terminated butadiene-acrylonitrile rubber and 1 part of accelerator (DMP-30).
The preparation method of the pre-setting glue-spraying composition comprises the following steps:
preparing modified resin: adding 89 parts of E-54 type bisphenol A epoxy resin into a reaction kettle, heating to control the temperature to be 120 ℃, adding 10 parts of carboxyl-terminated butadiene-acrylonitrile rubber and 1 part of DMP-30, removing bubbles in vacuum, continuously stirring for reaction for 3-4 hours, standing for more than 0.5 hour, and filling the reacted modified resin into a product barrel for later use.
Mixing: adding 20 parts of E-54 type bisphenol A liquid epoxy resin into a reaction kettle, heating to 140 +/-10 ℃, and then adding 30 parts of E-03 type bisphenol A solid epoxy resin, and fully stirring until the mixture is dissolved to obtain the mixed resin.
Modification: standing the mixed resin for more than 0.5 hour, and then cooling to 80-100 ℃; and then preheating the modified resin to 80 ℃, adding 50 parts of preheated modified resin into the mixed resin, continuously stirring for 1-2 hours, and standing for more than 0.5 hour to obtain the pre-shaped glue-spraying resin.
Example two
The embodiment provides a pre-setting glue-spraying composition, which comprises the following components in parts by weight:
40 parts of modified resin
10 parts of E-51 type bisphenol A liquid epoxy resin
50 parts of E-06 type bisphenol A solid epoxy resin
The modified resin comprises the following components in parts by weight: 90 parts of E-51 type bisphenol A epoxy resin and 10 parts of amine-terminated butadiene-acrylonitrile rubber.
The preparation method of the pre-setting glue-spraying composition comprises the following steps:
preparing modified resin: adding 90 parts of E-51 type bisphenol A epoxy resin into a reaction kettle, heating to control the temperature to be 120 +/-10 ℃, adding 10 parts of terminal amino nitrile rubber, removing bubbles in vacuum, continuously stirring for reaction for 3-4 hours, standing for more than 0.5 hour, and filling the reacted modified resin into a product barrel for later use.
Mixing: adding 10 parts of E-51 type bisphenol A liquid epoxy resin into a reaction kettle, heating to 120 +/-10 ℃, then adding 50 parts of E-06 type bisphenol A solid epoxy resin, and fully stirring until the mixture is dissolved to obtain the mixed resin.
Modification: standing the mixed resin for more than 0.5 hour, and then cooling to 80-100 ℃; and then preheating the modified resin to 80 ℃, adding 40 parts of preheated modified resin into the mixed resin, continuously stirring for 1-2 hours, and standing for more than 0.5 hour to obtain the pre-shaped glue-spraying resin.
EXAMPLE III
The embodiment provides a pre-setting glue-spraying composition, which comprises the following components in parts by weight:
30 parts of modified resin
10 parts of E-44 type bisphenol A liquid epoxy resin
70 parts of E-12 type bisphenol A solid epoxy resin
The modified resin comprises the following components in parts by weight: 89 parts of E-44 type bisphenol A epoxy resin, 10 parts of carboxylated nitrile rubber and 1 part of accelerator (DMP-30).
The preparation method of the pre-setting glue-spraying composition comprises the following steps:
preparing modified resin: adding 89 parts of E-44 type bisphenol A epoxy resin into a reaction kettle, heating to control the temperature to be 120 +/-10 ℃, adding 10 parts of carboxylated nitrile rubber, removing bubbles in vacuum, continuously stirring for reacting for 3-4 hours, standing for more than 0.5 hour, and filling the reacted modified resin into a product barrel for later use.
Mixing: adding 10 parts of E-44 type bisphenol A liquid epoxy resin into a reaction kettle, heating to 120 +/-10 ℃, then adding 50 parts of E-12 type bisphenol A solid epoxy resin, and fully stirring until the mixture is dissolved to obtain the mixed resin.
Modification: standing the mixed resin for more than 0.5 hour, and then cooling to 80-100 ℃; and then preheating the modified resin to 80 ℃, adding 30 parts of preheated modified resin into the mixed resin, continuously stirring for 1-2 hours, and standing for more than 0.5 hour to obtain the pre-shaped glue-spraying resin.
Comparative example 1
The comparative example provides a pre-shaped spray-coating composition, and compared with the first example, the comparative example is different in that: the heating temperature in the step of preparing the modified resin was controlled to 80 ℃.
Comparative example No. two
The comparative example provides a pre-shaped spray-coating composition, and compared with the first example, the comparative example is different in that: the heating temperature was controlled to 100 ℃ in the step of preparing the modified resin.
Comparative example No. three
The comparative example provides a pre-shaped spray-coating composition, and compared with the first example, the comparative example is different in that: the components of the pre-setting spray glue composition comprise 30 parts of E-54 type bisphenol A liquid epoxy resin and 20 parts of E-03 type bisphenol A solid epoxy resin. The pre-shaped glue-spraying resin finally obtained by the comparative example has the average molecular weight of less than 1500.
Comparative example No. four
The comparative example provides a pre-shaped spray-coating composition, and compared with the first example, the comparative example is different in that: the components of the pre-setting glue spraying composition comprise 30 parts of modified resin, 10 parts of E-54 type bisphenol A liquid epoxy resin and 60 parts of E-03 type bisphenol A solid epoxy resin. The pre-shaped spray resin finally obtained in the comparative example has an average molecular weight of more than 2800.
Firstly, the epoxy-based composite material is prepared by using the pre-forming glue-spraying composition prepared in the first to third embodiments and the 3M wind power glue-spraying used in the prior art under the same conditions, and the mechanical properties of the finally obtained epoxy-based composite material are tested. The test methods are GB/T1447-.
Table 1 comparison of mechanical properties of epoxy-based composites made in the present application with those made in the prior art
| Test items | Example one | Example two | EXAMPLE III | Prior Art |
| 0 degree tensile Strength (MPa) | 754.49 | 750.47 | 748.48 | 738.78 |
| 0 degree tensile modulus (GPa) | 33.12 | 32.89 | 42.98 | 32.54 |
| Tensile strength at 90 ° (MPa) | 134.89 | 134.56 | 133.89 | 131.61 |
| Tensile modulus at 90 ° (GPa) | 14.38 | 14.25 | 14.09 | 13.07 |
| In-plane shear Strength (MPa) | 197.5 | 195.78 | 193.67 | 188.2 |
| In-plane shear modulus (GPa) | 7.30 | 7.27 | 7.25 | 7.23 |
The first to third examples are conducted according to the component content and the manufacturing method of the present application, and it can be seen from table 1 that the mechanical properties of the epoxy-based composite material prepared by using the pre-shaped glue-spraying composition prepared in the first to third examples are slightly higher than those of the epoxy-based composite material prepared by using 3M wind power glue-spraying. The preshaped glue spraying composition is an epoxy resin system, and the encapsulated epoxy resin matrix is also an epoxy resin system, so that the preshaped glue spraying composition and the epoxy resin matrix have certain compatibility. Therefore, the pre-shaped glue spraying composition is sprayed on the composite fiber cloth layer and then encapsulated with the epoxy resin matrix, the interface performance between the epoxy resin matrix and the pre-shaped glue spraying is not affected, the pre-shaped glue spraying composition can be cross-linked and fused with the epoxy resin matrix, the connectivity between the epoxy resin matrix and the pre-shaped glue spraying is improved, the bonding between the epoxy resin matrix and the pre-shaped glue spraying is more stable, and the overall structure of the epoxy-based composite material is more stable.
Next, the modified resins obtained in example one, comparative example one and comparative example two were tested for epoxy value at different times by GB/T1677-.
The gel state of the pre-formed spray compositions prepared in example one, comparative example one and comparative example two was observed after storing for different periods of time, respectively, to obtain comparative storage test data, and the results are shown in table 3.
TABLE 2 reaction epoxy value Change of modified resins at different temperatures
Table 3 comparative experimental data on storability
| Examples | 30 days | 60 days | 120 days |
| Comparative example 1 | Colloidal part turbid | Cloudiness of colloid | Hardening of the surface of the colloid |
| Comparative example No. two | Is normal | Is normal | Colloidal part turbid |
| Example one | Is normal | Is normal | Is normal |
As can be seen from an examination of Table 3, the gel of the one-time-set spray composition prepared in example one was kept normal at the time of storage for 30 days, 60 days and 120 days, but the one-time-set spray composition prepared in comparative example one had started to be partially cloudy at the time of storage for 30 days, cloudy at the time of storage for 60 days and hardened at the time of storage for 120 days. Similar problems exist in comparative example II, where the preformed spray composition produced in comparative example shows some cloudiness when stored for 120 days. This is because the temperature at which the modified resin was prepared was 120 ℃ in example one, and the degree of reaction of the reactive groups was high, whereas the temperatures at which the modified resins were prepared in comparative example one and comparative example two were 80 ℃ and 90 ℃ respectively, and the degree of reaction of the reactive groups was low, as shown in Table 2. As can be seen in Table 2, the epoxy value in example one is lower than the epoxy values in comparative examples one and two at the same time, which indicates that the reactive groups in example one are more reactive and the corresponding preformed spray compositions are more stable. The data in tables 2 and 3 show that the stability of the prepared pre-shaped spray glue can be improved by controlling the temperature to be 110-130 ℃ when preparing the modified resin.
Finally, the application also calculates the molecular weight and viscosity of the pre-shaped spray glue compositions prepared in the first to third examples, the third comparative example and the fourth comparative example. The adhesion force and creep resistance of the pre-shaped spray composition prepared in the first to third examples are also tested, and the specific test method is as follows:
creep resistance test: the preset size spray compositions prepared in examples one to three, comparative example three and comparative example four were respectively sprayed on a 50cm x100cm glass fiber board in the shape as shown in fig. 2 under the environment of 25 to 35 c, and the glass fiber board was placed vertically, then 5 layers of 50cm x40cm glass fiber cloth was sewn together with a weight of 2.4kg, and finally 2.4kg of cloth was spread on the glass fiber board sprayed with the preset size spray composition, and the time taken from spreading to complete slipping and the displacement of slipping were tested. Wherein, the shadow area in the upper half part in fig. 2 is the spraying presetting glue spraying area. The test results are shown in Table 4.
And (3) testing the adhesion force: spraying the pre-shaped glue spraying compositions prepared in the first to third examples, the third comparative example and the fourth comparative example on a glass fiber board, wherein the glue spraying amount is 20g/m2Then, the triaxial fabric is cut into strips according to the method shown in fig. 3 and then is adhered to a glass fiber board, the tail ends of the strips are clamped by a clamp, the tension meter is pulled out by vertical force, and the reading of the tension meter is read. Wherein, the lower half vertical line of the triaxial fabric in fig. 3 is the cutting line. The test results are shown in Table 4.
TABLE 4 adhesion and creep resistance tests
It can be seen from table 4 that the number average molecular weights of examples one to three gradually decrease and the viscosity values also gradually decrease, but the corresponding adhesive strengths gradually increase, the number average molecular weight of comparative example three is less than 1500, at which time the adhesive strength reaches 4kg, and the number average molecular weight of comparative example four is greater than 2800, at which the adhesive strength is only 2.5 kg. This is because the smaller the number average molecular weight of the pre-setting spray composition, the thinner the composition, and the greater the adhesion because the pre-setting spray composition is immersed in the triaxial fabric during the spreading and the long triaxial fabric is hardly torn off after the composition is solidified.
It can also be seen from the observation of Table 4 that the time taken for 2.4kg of cloth to completely slip off in examples one to three was shorter and shorter, the time taken was the shortest in comparative example 3, and the time taken was only 32 minutes in comparative example four. Correspondingly, the displacement of the example one to the comparative example three slips longer and longer before complete slip, but only 2cm of slip in the comparative example four. The liquid or solid epoxy resins with different molecular weights are combined and matched with each other to obtain a stable and proper molecular weight range, and the composition with the molecular weight has good adhesive force and creep resistance effect at normal temperature, so that the adhesive forming effect of the pre-forming glue-spraying composition is ensured, a cloth layer is not easy to slide, and the stability of the pre-forming glue-spraying composition during the laying operation is ensured.
The pre-forming spray glue and the preparation method thereof disclosed by the embodiment of the invention are described in detail, the principle and the embodiment of the invention are explained by applying specific examples, and the description of the embodiment is only used for helping to understand the pre-forming spray glue, the preparation method and the core idea of the pre-forming spray glue; meanwhile, for a person skilled in the art, according to the idea of the present invention, there may be variations in the specific embodiments and the application scope, and in summary, the content of the present specification should not be construed as a limitation to the present invention.
Claims (10)
1. The pre-shaping glue spraying composition is characterized by comprising the following components in parts by weight:
35-50 parts of modified resin
10-20 parts of bisphenol A liquid epoxy resin
30-70 parts of bisphenol A solid epoxy resin
The modified resin comprises the following components in parts by weight: 88-90 parts of bisphenol A epoxy resin and 8-10 parts of nitrile rubber.
2. The pre-shaping spray composition according to claim 1, wherein said bisphenol A liquid epoxy resin is one or more of E-54 type bisphenol A liquid epoxy resin, E-51 type bisphenol A liquid epoxy resin, and E-44 type bisphenol A liquid epoxy resin.
3. The spray adhesive composition according to claim 1, wherein the bisphenol A solid epoxy resin is one or more of E-03 type bisphenol A solid epoxy resin, E-06 type bisphenol A solid epoxy resin, and E-12 type bisphenol A solid epoxy resin.
4. The pre-shaping glue-spraying composition as claimed in claim 1, wherein the modified resin further comprises an accelerator, the accelerator is 1 part by weight, and the accelerator is one of benzyltriethylammonium chloride, benzyldimethylamine and DMP-30.
5. A process for the preparation of a pre-shaped spray composition according to any one of claims 1 to 4, comprising the steps of:
preparing modified resin: mixing and stirring bisphenol A epoxy resin and nitrile rubber to obtain modified resin;
mixing: mixing and stirring bisphenol A liquid epoxy resin and bisphenol A solid epoxy resin until the bisphenol A solid epoxy resin is dissolved in the bisphenol A liquid epoxy resin to obtain mixed resin;
modification: and adding the modified resin into the mixed resin, and stirring to obtain the pre-shaped glue spraying resin.
6. The preparation method according to claim 5, wherein in the step of preparing the modified resin, the bisphenol A epoxy resin and the nitrile rubber are reacted at a temperature of 110 ℃ to 130 ℃ for 3 to 4 hours.
7. The method according to claim 5, wherein in the step of preparing the modified resin, an accelerator is mixed and stirred with the bisphenol A epoxy resin and the nitrile rubber, and the accelerator is one of benzyltriethylammonium chloride, benzyldimethylamine and DMP-30.
8. The method of claim 5, wherein in the mixing step, the bisphenol A liquid epoxy resin and the bisphenol A solid epoxy resin are reacted at a temperature of 110 ℃ to 150 ℃.
9. The preparation method of claim 5, wherein the mixed resin is cooled to 80-100 ℃ and then added with the modified resin, and the modified resin is preheated to 80 ℃ and then added with the mixed resin.
10. The method according to any one of claims 5 to 9, wherein the sum of the molecular weights of the bisphenol a liquid epoxy resin and the bisphenol a solid epoxy resin is 1500 to 2700.
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| CN118325549A (en) * | 2024-06-17 | 2024-07-12 | 吉林成飞新材料有限公司 | Solvent-free spray adhesive and preparation method thereof |
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