CN114015197A - Matrix resin suitable for non-autoclave molding and preparation method thereof - Google Patents
Matrix resin suitable for non-autoclave molding and preparation method thereof Download PDFInfo
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- CN114015197A CN114015197A CN202111382009.XA CN202111382009A CN114015197A CN 114015197 A CN114015197 A CN 114015197A CN 202111382009 A CN202111382009 A CN 202111382009A CN 114015197 A CN114015197 A CN 114015197A
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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
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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
- C08L63/04—Epoxynovolacs
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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
Abstract
The invention relates to a matrix resin suitable for non-autoclave molding and a preparation method thereof, which is mainly characterized in that a low-melting-point blend with a lower melting point and viscosity sensitive to temperature is prepared by mixing solid epoxy resins with similar structures but different softening points and then rapidly cooling the mixture. The low-melting-point blend is matched with a latent curing agent, so that the matrix resin with low viscosity (less than or equal to 1000mPa & s) and a longer process window (more than or equal to 30min) before curing can be prepared. The resin can be fully infiltrated and gas can be led out under the low molding pressure (less than or equal to 0.1MPa) of a non-autoclave, and the low-cost high-quality manufacturing requirements of advanced high-performance composite materials are met. The performance of the composite material manufactured by the resin is equivalent to that of an autoclave molding composite material, the manufacturing cost and difficulty can be greatly reduced, and the resin has good market application prospect.
Description
Technical Field
The invention relates to a matrix resin suitable for non-autoclave molding and a preparation method thereof, belonging to the technical field of polymer composite materials.
Background
The fiber reinforced resin matrix composite material has the characteristics of high specific strength, high specific modulus, fatigue resistance, corrosion resistance and the like, and is widely applied to the fields of aerospace, wind power energy, ship industry and the like. In advanced civil aircraft, the proportion of the composite material in the structural material is over 50 percent. The high-quality molding of the composite material is mainly realized by a prepreg-autoclave process. Before molding, the matrix resin is presoaked with the reinforcing fibers to form a prepreg, and the prepreg is molded in a hot-pressing tank under the assistance of vacuum and negative pressure through high-temperature positive high-pressure molding to prepare a composite material part with excellent internal quality.
However, the prepreg-autoclave process requires the support of a high pressure gas source and a high power supply, while forming a closed high temperature and high pressure space within the equipment; the cost and the energy consumption of production units are improved, the management risk of high-temperature and high-pressure equipment on production sites is increased, the cost of the composite material is high compared with that of other advanced materials, and the popularization and the application of the composite material are seriously influenced.
Aiming at the problem of the use cost of the autoclave, the ideal solution is to realize the infiltration of resin to fibers under the vacuum negative pressure, discharge the gas mixed in the resin, simultaneously compact the fibers as much as possible, improve the volume ratio of the reinforced fibers in the composite material, and realize the production and the manufacture of the high-quality aviation-grade composite material under the non-high-temperature and high-pressure state so as to reduce the cost and the production difficulty.
When only vacuum negative pressure is adopted, the molding pressure of the product is only 1/7-1/3 of positive pressure in the autoclave, the resin viscosity before molding is required to be as low as possible, and a relatively long window period is provided at high temperature and low viscosity, so that gas mixed in the resin can be fully discharged, and fibers can be fully compacted; meanwhile, the prepreg lay-up process requires that the resin be a non-flowing viscous solid at room temperature operating conditions. Thus, the Out of Autoclave (OoA) molding process requires that the corresponding resin have high temperature sensitivity over a narrow temperature variation range (< 90 ℃), can be converted from a solid to a low viscosity liquid, and have good latency before the curing temperature.
Disclosure of Invention
The invention provides a method for preparing epoxy resin which has proper process performance at room temperature, but viscosity can be rapidly reduced to low-viscosity liquid along with temperature rise before curing and a longer process window is kept, aiming at preparing prepreg and composite material which can be formed by a non-autoclave and has forming quality and mechanical property equivalent to that of autoclave products. Meanwhile, the prepreg has the advantages of good construction performance and long storage period.
The purpose of the invention is realized by the following technical scheme:
the invention provides an epoxy resin suitable for high-quality molding by a non-autoclave process, which has high sensitivity to temperature in bulk viscosity and is characterized in that: the epoxy resin comprises the following chemical components in parts by weight:
the epoxy resin 1 is one or a mixture of more of bisphenol epoxy resin, phenolic epoxy resin and biphenyl epoxy resin;
the epoxy resin 2 is another solid epoxy resin which has a similar molecular structure to the epoxy resin 1, but has a softening point which is different from that of the epoxy resin 1 greatly by the difference of molecular weight (polymerization degree) and substituent (such as central substituent of bisphenol epoxy resin);
the liquid epoxy resin is one or a mixture of more of m-phenylenediamine diglycidyl amine type epoxy resin, diaminodiphenylmethane glycidyl amine type epoxy resin, aliphatic epoxy resin, alicyclic epoxy resin and other liquid epoxy resins with low viscosity and high epoxy value;
the curing agent is dihydrazide, dicyanodiamine and boron trifluoride-monoethylamine complex;
the toughening agent is one or a mixture of two of rubber or a core-shell microsphere toughening agent;
the accelerator is organic urea, tertiary amine or organic phosphorus accelerator.
In one embodiment, the epoxy resin 1 is a bisphenol A epoxy resin with a softening point of 115-125 ℃, a bisphenol S epoxy resin with a softening point of 90-100 ℃, a bisphenol A novolac epoxy resin with a softening point of 100-110 ℃, an o-cresol novolac epoxy resin with a softening point of 80-90 ℃ and a biphenyl epoxy resin with a softening point of 105-115 ℃.
In one implementation, the epoxy resin 2 is bisphenol A epoxy resin with a softening point of 65-75 ℃, bisphenol S epoxy resin with a softening point of 60-70 ℃, bisphenol A novolac epoxy resin with a softening point of 65-70 ℃, o-cresol novolac epoxy resin with a softening point of 55-65 ℃ and biphenyl epoxy resin with a softening point of 80-90 ℃.
In one embodiment, the liquid epoxy resin is m-phenylenediamine diglycidyl amine, diaminodiphenylmethane glycidylamine, epoxyhexanedicarboxylic acid diglycidyl ester, pentanediol diglycidyl ether.
In one implementation, the rubber toughening agent is nitrile rubber, carboxyl-terminated nitrile rubber, hydroxyl-terminated nitrile rubber, epoxy-terminated nitrile rubber, polysulfide rubber, natural rubber, styrene butadiene rubber, polyurethane, silicone rubber.
In one implementation, the core-shell microsphere toughening agent is a polymethylmethacrylate/butadiene rubber core-shell microsphere, a polymethylmethacrylate/styrene butadiene rubber core-shell microsphere, a polymethylmethacrylate/silicone rubber core-shell microsphere, or a polymethylmethacrylate/polyurethane core-shell microsphere.
In one implementation, the curing agent is a dihydrazide, dicyanodiamine, boron trifluoride-monoethylamine complex.
In one implementation, the accelerator is an organic urea accelerator, a tertiary amine accelerator, an organophosphorus accelerator.
The technical scheme of the invention also provides a method for preparing the composite material matrix resin suitable for non-autoclave molding, which is characterized by comprising the following steps: the method comprises the following steps:
(1) preparation of a low melting blend of epoxy resin 1 and epoxy resin 2: weighing epoxy resin 1 and epoxy resin 2 according to the mass part ratio of 1: 0.1-10, stirring and mixing for 0.1-5 h in a constant temperature environment at the temperature 20-35 ℃ higher than the maximum softening point of the epoxy resin 1 and the epoxy resin 2 to obtain a uniform blend, spreading the mixed resin at room temperature, wherein the stacking thickness of the spread resin is less than 30mm, and rapidly cooling the resin to obtain a low-melting-point blend of the epoxy resin 1 and the epoxy resin 2;
(2) weighing liquid epoxy resin, a toughening agent, an accelerant and a curing agent according to the proportion, and uniformly mixing by adopting a three-roller grinding, double-roller grinding or ball milling mode to obtain premixed resin;
(3) and (3) placing the low-melting-point blend and the premixed resin in a constant temperature environment which is 5-15 ℃ higher than the melting point of the low-melting-point blend, stirring and mixing for 0.1-2 h, and cooling at room temperature to obtain the composite material matrix resin suitable for non-autoclave molding.
The technical scheme of the invention has the following characteristics and beneficial effects:
the invention aims at the problems of high process cost and high difficulty caused by the fact that an autoclave curing process is required to be adopted for forming the high-performance composite material at present. By designing the prepreg matrix resin which has high sensitivity to temperature, can keep extremely low viscosity (less than or equal to 1000mPa & s) and longer process window (more than or equal to 30min) for a long time before curing, the resin can be kept in a colloid state at room temperature, the prepreg has good operability and repeated paving performance, and meanwhile, the composite material can fully infiltrate fibers, discharge contained gas, reduce pores in the material and realize higher internal quality of molding at room temperature and under low curing pressure (less than or equal to 0.1mPa & s). Meanwhile, the latent curing agent can also keep the low reactivity of the epoxy resin at room temperature, prolong the time for the low-viscosity resin to soak the reinforcing fiber and exhaust gas, and further ensure that the composite material achieves good molding quality.
The composite material matrix resin prepared by the technical scheme of the invention can be applied to the production of large-scale high-performance composite material products, such as large-scale aerospace bearing structures, including composite material wings and composite material cabins. The high cost caused by the manufacture and the use of a large autoclave can be avoided, the technical difficulty caused by large-area high-temperature and high-pressure resistant sealing is reduced, and the method has wide application prospect and popularization value.
Drawings
FIG. 1 is a comparison of the performance of a carbon fiber reinforced composite suitable for use in the preparation of a non-autoclave molding resin of example 1 with a conventional autoclave cured composite;
FIG. 2 is an appearance state of a carbon fiber reinforced composite material suitable for use in the preparation of a non-autoclave molding resin in example 3;
FIG. 3 is a viscosity-temperature curve for a non-autoclave molding resin as in example 5.
Detailed Description
The technical scheme of the invention is further detailed in the following by combining the drawings and the embodiment:
example 1
The method for preparing the composite material matrix resin suitable for non-autoclave molding comprises the following steps:
step one, weighing 10kg of bisphenol A type epoxy resin with the softening point of 115-125 ℃ and 7.5kg of bisphenol A type epoxy resin with the softening point of 65-75 ℃. Heating the mixture to 150 +/-5 ℃, stirring at a rotating speed of more than or equal to 240rpm for 60 +/-10 min, and quickly pouring out the low-melting-point blend to obtain the low-melting-point blend (melting point 50 ℃) of the bisphenol A type epoxy resin;
weighing 2kg of diaminodiphenylmethane glycidol ammonia and carboxyl-terminated butadiene-acrylonitrile rubber respectively, heating the mixture to 150 +/-5 ℃, adding 20g of triphenylphosphine, stirring for 300 +/-10 min, and taking out to obtain the toughened blend of the epoxy resin;
weighing 10kg of diaminodiphenylmethane glycidol ammonia, 7.5kg of adipic dihydrazide curing agent, 4kg of toughening blend of epoxy resin and 1kg of tertiary amine accelerator, adding into a three-roll grinder, and mixing for three times, wherein each time lasts for 5 +/-1 min to obtain premixed resin;
and step four, placing the low-melting-point blend and the premixed resin in a constant temperature environment of 60 +/-5 ℃ to be stirred and mixed for 120 +/-10 min, and cooling at room temperature after pouring out to obtain the composite material matrix resin suitable for non-autoclave molding.
The comparison of the performance of the carbon fiber reinforced composite material suitable for non-autoclave molding resin preparation in this example with that of a conventional autoclave cured composite material is shown in fig. 1.
Example 2
The method for preparing the composite material matrix resin suitable for non-autoclave molding comprises the following steps:
step one, weighing 2kg of bisphenol A novolac epoxy resin with a softening point of 100-110 ℃ and 6kg of bisphenol A novolac epoxy resin with a softening point of 65-70 ℃. Heating the mixture to 135 +/-5 ℃, stirring at a rotating speed of more than or equal to 120rpm for 180 +/-10 min, and quickly pouring out the low-melting-point blend to obtain the low-melting-point blend (melting point is 45 ℃) of the bisphenol A novolac epoxy resin;
weighing 6kg of m-phenylenediamine diglycidyl amine, 2kg of dicyanodiamide curing agent, 2kg of polymethyl methacrylate/styrene-butadiene rubber core-shell microsphere toughening agent and 1kg of organic urea accelerator, adding into a three-roll grinding machine, and mixing for three times, wherein each time lasts for 5 +/-1 min to obtain premixed resin;
and step three, placing the low-melting-point blend and the premixed resin in a constant temperature environment of 55 +/-5 ℃ to be stirred and mixed for 120 +/-10 min, and cooling at room temperature after pouring out to obtain the composite material matrix resin suitable for non-autoclave molding.
Example 3
The method for preparing the composite material matrix resin suitable for non-autoclave molding comprises the following steps:
step one, weighing 500kg of o-cresol formaldehyde epoxy resin with a softening point of 80-90 ℃ and 500kg of o-cresol formaldehyde epoxy resin with a softening point of 55-65 ℃. Heating the mixture to 115 +/-5 ℃, stirring at a rotating speed of more than or equal to 200rpm for 240 +/-10 min, and quickly pouring out the low-melting-point blend to obtain the low-melting-point blend (melting point 50 ℃) of the o-cresol formaldehyde epoxy resin;
weighing 150g of pentanediol diglycidyl ether and 50g of carboxyl-terminated butadiene-acrylonitrile rubber respectively, heating the mixture to 150 +/-5 ℃, adding 4g of triphenylphosphine, stirring for 300 +/-10 min, and taking out the mixture to obtain a toughened blend of the epoxy resin;
weighing 700g of pentanediol diglycidyl ether, 180g of dicyanodiamide curing agent, 200g of toughening blend of epoxy resin and 90g of organic urea accelerator, adding into a three-roll grinder, and mixing for three times, wherein each time lasts for 5 +/-1 min, so as to obtain premixed resin;
and step four, placing the low-melting-point blend and the premixed resin in a constant temperature environment of 60 +/-5 ℃ to be stirred and mixed for 60 +/-10 min, and cooling at room temperature after pouring out to obtain the composite material matrix resin suitable for non-autoclave molding.
The appearance of the carbon fiber-reinforced composite material suitable for the production of the non-autoclave molding resin in the present example is shown in fig. 2.
Example 4
The method for preparing the composite material matrix resin suitable for non-autoclave molding comprises the following steps:
step one, weighing 15kg of biphenyl type epoxy resin with a softening point of 105-115 ℃ and 5kg of biphenyl type epoxy resin with a softening point of 80-90 ℃. Heating the mixture to 145 +/-5 ℃, stirring at a rotating speed of more than or equal to 400rpm for 30 +/-10 min, and quickly pouring out the low-melting-point blend to obtain the low-melting-point blend (melting point 50 ℃) of the biphenyl epoxy resin;
weighing 16kg of epoxyhexane dicarboxylic acid diglycidyl ester, 10kg of boron trifluoride-monoethylamine curing agent, 3kg of polymethyl methacrylate/butadiene rubber core-shell microsphere toughening agent and 720g of organic phosphorus accelerator, adding into a three-roll grinding machine, and mixing for three times, wherein each time lasts for 5 +/-1 min, so as to obtain premixed resin;
and step three, placing the low-melting-point blend and the premixed resin in a constant temperature environment of 60 +/-5 ℃ to be stirred and mixed for 150 +/-10 min, and cooling at room temperature after pouring out to obtain the composite material matrix resin suitable for non-autoclave molding.
Example 5
The method for preparing the composite material matrix resin suitable for non-autoclave molding comprises the following steps:
step one, weighing 3kg of bisphenol S type epoxy resin with a softening point of 90-100 ℃ and 9kg of bisphenol S type epoxy resin with a softening point of 60-70 ℃. Heating the mixture to 125 +/-5 ℃, stirring at a rotating speed of more than or equal to 150rpm for 200 +/-10 min, and quickly pouring out the low-melting-point blend to obtain the low-melting-point blend (the melting point is 60 ℃) of the bisphenol S type epoxy resin;
weighing 10kg of pentanediol diglycidyl ether, 2.4kg of dicyanodiamide curing agent, 2kg of epoxy-terminated nitrile rubber toughening agent and 1.2kg of organic urea accelerator, adding into a three-roll grinder, and mixing for three times, wherein each time lasts for 5 +/-1 min, so as to obtain premixed resin;
and step three, placing the low-melting-point blend and the premixed resin in a constant temperature environment of 70 +/-5 ℃ to be stirred and mixed for 120 +/-10 min, and cooling at room temperature after pouring out to obtain the composite material matrix resin suitable for non-autoclave molding.
The viscosity-temperature curve for the non-autoclave molding resin of this example is shown in FIG. 3.
Claims (9)
1. The composite material matrix resin suitable for non-autoclave molding is characterized in that: the composite material matrix resin comprises the following chemical components in percentage by mass:
the solid epoxy resin A is one or a mixture of more of bisphenol epoxy resin, phenolic epoxy resin and biphenyl epoxy resin;
the solid epoxy resin B is another solid epoxy resin of which the softening point is different from that of the epoxy resin 1 greatly by the difference of molecular weight (polymerization degree) and substituent (such as central substituent of bisphenol epoxy resin) and the difference of the softening point and the epoxy resin 1, and the solid epoxy resin A and the epoxy resin 1 have similar molecular structures;
the liquid epoxy resin is one or a mixture of more of m-phenylenediamine diglycidyl amine type epoxy resin, diaminodiphenylmethane glycidyl amine type epoxy resin, aliphatic epoxy resin, alicyclic epoxy resin and other liquid epoxy resins with low viscosity and high epoxy value;
the curing agent is dihydrazide, dicyanodiamine and boron trifluoride-monoethylamine complex;
the toughening agent is one or a mixture of two of rubber or a core-shell microsphere toughening agent;
the accelerator is organic urea, tertiary amine or organic phosphorus accelerator.
2. The composite matrix resin suitable for non-autoclave molding according to claim 1, wherein: the bisphenol epoxy resin 1 is a specification that the state is solid at room temperature in resins such as bisphenol a epoxy resin, bisphenol B epoxy resin, bisphenol C epoxy resin, bisphenol E epoxy resin, bisphenol F epoxy resin, bisphenol P epoxy resin, bisphenol S epoxy resin, furyl bisphenol epoxy resin, or tetrachlorobisphenol epoxy resin.
3. The composite matrix resin suitable for non-autoclave molding according to claim 1, wherein: the bisphenol type epoxy resin 1 is a specification that the state is solid at room temperature in resins such as phenol type epoxy resin, bisphenol A type novolac epoxy resin, o-cresol novolac epoxy resin and the like.
4. The composite matrix resin suitable for non-autoclave molding according to claim 1, wherein: the epoxy resin 2 is one or a mixture of more of bisphenol type epoxy resin, phenolic aldehyde type epoxy resin and biphenyl type epoxy resin. The selected epoxy resin 1 has a similar molecular structure, but the softening point of the selected epoxy resin is different from that of the selected epoxy resin 1 by the difference of molecular weight and substituent (such as central substituent of bisphenol epoxy resin).
5. The composite matrix resin suitable for non-autoclave molding according to claim 1, wherein: the combination of the epoxy resin 1 and the epoxy resin 2 has good compatibility, and after the two epoxy resins are mixed, a low-melting-point blend can be formed, and the blend can be converted from a solid to a low-viscosity liquid within a temperature range of 15-20 ℃ below the curing temperature of the resin.
6. The composite matrix resin suitable for non-autoclave molding according to claim 1, wherein: the liquid epoxy resin is one or a mixture of more of m-phenylenediamine diglycidyl amine type epoxy resin, diaminodiphenylmethane glycidyl amine type epoxy resin, aliphatic epoxy resin, alicyclic epoxy resin and other liquid epoxy resins with low viscosity and high epoxy value. After the epoxy resin is further mixed with the mixture of the epoxy resin 1 and the epoxy resin 2, the curing crosslinking degree and the operation manufacturability of the mixed resin reach the state suitable for being used as a composite material matrix.
7. The composite matrix resin suitable for non-autoclave molding according to claim 1, wherein: the rubber toughening agent is nitrile rubber, carboxyl-terminated nitrile rubber, hydroxyl-terminated nitrile rubber, epoxy-terminated nitrile rubber, polysulfide rubber, natural rubber, styrene butadiene rubber, polyurethane and organic silicon rubber.
8. The composite matrix resin suitable for non-autoclave molding according to claim 1, wherein: the core-shell microsphere toughening agent is polymethyl methacrylate/butadiene rubber core-shell microsphere, polymethyl methacrylate/styrene butadiene rubber core-shell microsphere, polymethyl methacrylate/organic silicon rubber core-shell microsphere or polymethyl methacrylate/polyurethane core-shell microsphere.
9. A method of preparing the composite matrix resin suitable for non-autoclave molding according to claim 1, characterized by: the method comprises the following steps:
(1) preparation of a low melting blend of epoxy resin 1 and epoxy resin 2: weighing epoxy resin 1 and epoxy resin 2 according to the mass part ratio of 1: 0.1-10, stirring and mixing for 0.1-5 h in a constant temperature environment at the temperature 20-35 ℃ higher than the maximum softening point of the epoxy resin 1 and the epoxy resin 2 to obtain a uniform blend, spreading the mixed resin at room temperature, wherein the stacking thickness of the spread resin is less than 30mm, and rapidly cooling the resin to obtain a low-melting-point blend of the epoxy resin 1 and the epoxy resin 2;
(2) weighing liquid epoxy resin, a toughening agent, an accelerant and a curing agent according to the proportion, and uniformly mixing by adopting a three-roller grinding, double-roller grinding or ball milling mode to obtain premixed resin;
(3) and (3) placing the low-melting-point blend and the premixed resin in a constant temperature environment which is 5-15 ℃ higher than the melting point of the low-melting-point blend, stirring and mixing for 0.1-2 h, and cooling at room temperature to obtain the composite material matrix resin suitable for non-autoclave molding.
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