CN109503839B - Bismaleimide resin prepolymer and preparation method thereof - Google Patents
Bismaleimide resin prepolymer and preparation method thereof Download PDFInfo
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- CN109503839B CN109503839B CN201811289962.8A CN201811289962A CN109503839B CN 109503839 B CN109503839 B CN 109503839B CN 201811289962 A CN201811289962 A CN 201811289962A CN 109503839 B CN109503839 B CN 109503839B
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- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/12—Unsaturated polyimide precursors
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- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/12—Unsaturated polyimide precursors
- C08G73/126—Unsaturated polyimide precursors the unsaturated precursors being wholly aromatic
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Abstract
The invention discloses a bismaleimide resin prepolymer and a preparation method thereof, wherein the bismaleimide resin prepolymer is prepared by Diels-Alder reaction of bismaleimide and diallyl bisphenol A in a double-screw extruder reactor; or is prepared by Michael addition reaction of bismaleimide and diamine in a double screw extruder reactor; wherein the bismaleimide comprises a bismaleimide monomer or a bismaleimide low-melting mixture; the diallyl bisphenol A comprises the existing diallyl bisphenol A and the modified diallyl bisphenol A; diamines include diamine monomers and diamine mixtures. According to the preparation method, a double-screw extruder is used as a reaction container, so that the temperature can be accurately controlled, the inside and outside of the resin are uniform, and the temperature gradient is zero; in addition, continuous production can be realized, and the product quality stability and the production efficiency are greatly improved; the bismaleimide resin prepolymer of the present invention has higher quality.
Description
Technical Field
The invention belongs to the technical field of bismaleimide resin preparation, and particularly relates to a bismaleimide resin prepolymer and a preparation method thereof.
Background
The bismaleimide resin prepolymer powder can be used as a resin binder and molding powder of a diamond grinding wheel for manufacturing high-temperature resistant mechanical parts; after being dissolved by an organic solvent, the high-temperature-resistant adhesive can be used as a high-temperature-resistant adhesive for manufacturing polyimide laminated plates and polyimide copper clad plates; bismaleimide resin prepolymers are used in a wide variety of applications.
The bismaleimide resin prepolymer is a linear chain-extended bismaleimide resin prepolymer which is generated by Michael addition reaction of a bismaleimide monomer and a diamine compound under a melting condition; or linear chain-extended bismaleimide resin prepolymer which is generated by Diels-Alder reaction of bismaleimide monomer and diallyl bisphenol A under the melting condition. Generally, the softening point of the bismaleimide resin prepolymer is controlled to be 95-100 ℃, and the particle size is controlled to be larger than 400 meshes.
The present melt-process bismaleimide resin prepolymer adopts the following synthesis process:
(1) designing a bismaleimide resin formula according to the heat resistance index requirement of the bismaleimide resin prepolymer, and determining the proportion of each component;
(2) uniformly mixing the determined component materials, and putting the mixture into a reactor; the reactor is usually a small reactor with a stirring paddle;
(3) controlling the temperature of the reactor to be 130-160 ℃;
(4) under the condition of stirring, the reaction materials are gradually melted from a powder state;
(5) as the reaction proceeds, the whole material is melted completely to gradually increase the viscosity of the system from small;
(6) when the viscosity of the system reaches the index (3000-5000 mpa.s), the resin is quickly taken out of the reactor and is quickly cooled to room temperature, at the moment, the resin prepolymer is changed from a viscous and flowable liquid state to a solid state, and the softening point of the resin prepolymer is 90-100 ℃.
Analysis of problems in the preparation of bismaleimide resin prepolymers by melt Process:
(1) in the process of heating, melting and reacting materials, due to the influence of a stirring form and the nonuniformity of temperature distribution, the materials are difficult to reach a very uniform state, so that the nonuniformity of Michael addition reaction is caused, and the molecular weight distribution of resin is seriously influenced;
(2) as the viscosity of the system becomes larger and larger along with the progress of the reaction, the heat transfer in the resin is poorer and poorer, and the resin system is difficult to be in a uniform state even under stirring conditions, so the feeding amount of each batch of resin synthesis needs to be small, the thickness of the resin layer is generally not more than 20mm, and the nonuniformity of the Michael addition reaction is reduced as much as possible;
(3) the batch-to-batch process, i.e., one-pot-to-one-pot production, also results in stability and variability in the quality of each batch of resin.
Disclosure of Invention
In order to solve the above problems in the prior art, the present invention provides a bismaleimide resin prepolymer and a method for preparing the same. The technical problem to be solved by the invention is realized by the following technical scheme:
a bismaleimide resin prepolymer is prepared by the Diels-Alder reaction of bismaleimide and diallyl bisphenol A in a double-screw extruder reactor;
wherein the bismaleimide comprises a bismaleimide monomer or a bismaleimide low-melting mixture;
the bismaleimide low-eutectic-ratio mixture is prepared by the synthetic reaction of maleic anhydride and a diamine mixture; the diamine mixture comprises two or more diamine compounds, and at least one aromatic diamine is contained in the two or more diamine compounds; the diamine compounds in the diamine mixture have different molecular structures;
the diallyl bisphenol A comprises the existing diallyl bisphenol A and the modified diallyl bisphenol A; the improved diallyl bisphenol A is prepared by carrying out Claisen rearrangement reaction on bisphenol A diallyl ether in an inert solvent system; the inert solvent and the bisphenol A diallyl ether are mutually soluble, and the boiling point of the inert solvent is 200-205 ℃.
A bismaleimide resin prepolymer is prepared by the Michael addition reaction of bismaleimide and diamine in a double-screw extruder reactor;
wherein the bismaleimide comprises a bismaleimide monomer or a bismaleimide low-melting mixture;
the bismaleimide low-eutectic-ratio mixture is prepared by the synthetic reaction of maleic anhydride and a diamine mixture; the diamine mixture comprises two or more diamine compounds, and at least one aromatic diamine is contained in the two or more diamine compounds; the diamine compounds in the diamine mixture have different molecular structures;
the diamine includes a diamine monomer and a diamine mixture.
A preparation method of bismaleimide resin prepolymer comprises the following steps:
step 1, uniformly mixing bismaleimide and diallyl bisphenol A or diamine to obtain a mixed reactant;
step 2, continuously and uniformly feeding the mixed reactants into a double-screw extruding machine, and controlling the temperature of the double-screw extruding machine to be 180-200 ℃; controlling the extrusion speed of the double-screw extruder to keep the time from feeding the mixed reactants into the double-screw extruder to extruding the mixed reactants from the outlet of the double-screw extruder within 1-10 min;
and 3, cooling the molten resin extruded from the outlet of the double-screw extruder into solid resin.
In an embodiment of the present invention, after the step 3, the method further includes:
and 4, crushing the solid resin to 400-800 meshes by using an air flow crusher.
In one embodiment of the invention, the bismaleimide comprises a bismaleimide monomer or a bismaleimide eutectic mixture;
the bismaleimide low-eutectic-ratio mixture is prepared by the synthetic reaction of maleic anhydride and a diamine mixture; the diamine mixture comprises two or more diamine compounds, and at least one aromatic diamine is contained in the two or more diamine compounds; the diamine compounds in the diamine mixture have different molecular structures.
In one embodiment of the present invention, the diamine compound further comprises an aliphatic diamine and an alicyclic diamine.
In one embodiment of the present invention, the diallyl bisphenol a comprises existing diallyl bisphenol a and modified diallyl bisphenol a;
the improved diallyl bisphenol A is prepared by carrying out Claisen rearrangement reaction on bisphenol A diallyl ether in an inert solvent system; the inert solvent and the bisphenol A diallyl ether are mutually soluble, and the boiling point of the inert solvent is 200-205 ℃.
In one embodiment of the present invention, the inert solvent includes gamma-butyrolactone and N-methyl pyrrolidone.
In one embodiment of the present invention, the diamine comprises a diamine monomer and a diamine mixture.
In one embodiment of the present invention, the bismaleimide and diallyl bisphenol A or diamine (0.8 to 10): 1.
compared with the prior art, the invention has the beneficial effects that:
1. according to the preparation method of the bismaleimide resin prepolymer, a double-screw extruder is used as a reaction container, so that the temperature can be accurately controlled, the inside and outside of the resin are uniform, and the temperature gradient is zero; in addition, continuous production can be realized, and the product quality stability and the production efficiency are greatly improved.
2. The bismaleimide resin prepolymer of the present invention uses a bismaleimide eutectic mixture which is an improved bismaleimide eutectic mixture having a melting point lower than that of the respective pure compound; the structural regularity of the formed eutectic mixture is reduced, the solubility in the bismaleimide resin prepolymer is increased, no precipitate is separated out from the bismaleimide resin prepolymer along with the standing time, and the service life is longer.
3. The improved diallyl bisphenol A used in the bismaleimide resin prepolymer has the viscosity lower than that of diallyl bisphenol A prepared by the traditional process and lower than that of diallyl bisphenol A prepared by the traditional process, and has consistent color with standard color and higher quality; therefore, the bismaleimide resin prepolymer prepared by using the bismaleimide resin prepolymer also has higher quality.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto.
Before the description of the specific embodiments of the present invention, the bismaleimide low-melting blend and the modified diallyl bisphenol A of the present invention are described separately.
The bismaleimide low-melting mixture is prepared by the synthetic reaction of maleic anhydride and a diamine mixture; the diamine mixture comprises two or more diamine compounds, and at least one aromatic diamine is contained in the two or more diamine compounds; the diamine compounds in the diamine mixture have different molecular structures; the diamine compound may include aliphatic diamines and alicyclic diamines in addition to the aromatic diamines.
The bismaleimide low eutectic mixture can be prepared by an acetone method or a thermal closed-loop homogeneous phase method.
The method for preparing the bismaleimide low eutectic mixture by the acetone method comprises the following steps:
step 1, adding acetone and water into a first container provided with a stirring device, a temperature measuring device and a reflux condensing device, then adding maleic anhydride into the first container, and stirring and dissolving at room temperature to obtain a maleic anhydride solution; the molar ratio of the maleic anhydride to the diamine mixture is (2.1-2.3): 1; the amount of each diamine compound in the diamine mixture is determined according to the specification requirements of the bismaleimide low-melting mixture.
Step 2, adding acetone into a second container, then adding the diamine mixture into the second container, and stirring and dissolving at room temperature to obtain a diamine dissolved solution;
step 3, dropwise adding the diamine dissolved solution into the maleic anhydride dissolved solution under stirring at room temperature to react for 0.8-1.5 h; a solution system containing a bismaleamic acid mixture was obtained.
Step 4, adding a chemical dehydrating agent, namely acetic anhydride, a cocatalyst, namely triethylamine and a catalyst, namely nickel acetate into the solution system containing the bismaleamic acid mixture, heating to a system reflux state, and reacting for 1.5-3 hours under stirring until the reaction system is completely transparent; the molar ratio of the added chemical dehydrating agent acetic anhydride, the added cocatalyst triethylamine and the added catalyst nickel acetate to the diamine mixture is respectively 2.9: 1. 0.3:1 and 0.02: 1.
and 5, reducing the temperature of the reaction system to 3-10 ℃, then dripping water within 15-30 min under the stirring condition, continuously stirring for 0.5-1 h, and filtering to obtain the crude bismaleimide low-eutectic-ratio mixture.
And 6, washing the crude bismaleimide low-melting-point mixture product with weak alkali liquor and water to be neutral, filtering and drying to obtain the bismaleimide low-melting-point mixture.
(II) a method for preparing a bismaleimide low eutectic mixture by a hot closed-loop homogeneous method, which comprises the following steps:
adding toluene and p-catalyst toluenesulfonic acid into a first container provided with a stirring device, a temperature measuring device and a reflux condensing device, and stirring and dissolving maleic anhydride in the first container at room temperature to obtain a maleic anhydride solution; wherein the molar ratio of the maleic anhydride to the diamine mixture is (2.1-2.3): 1; the amount of each diamine compound in the diamine mixture is determined according to the specification requirements of the bismaleimide low-melting mixture.
And (2) adding toluene and N, N-dimethylformamide into a second container, then adding the diamine mixture into the second container, and stirring and dissolving at the temperature of 40-50 ℃ to obtain a diamine dissolved solution.
And (3) heating the maleic anhydride solution to a reflux temperature under a stirring condition, then dripping the diamine solution into the maleic anhydride solution for reaction, and continuously discharging water generated by the reaction from the bottom of a reflux condenser for 4-8 hours.
And (4) cooling the system after the reaction is finished to 70-85 ℃, and then adding water to wash for 3-5 times under the stirring condition, so that the solution phase keeps a neutral state, and the solution containing the bismaleimide low eutectic mixture is obtained.
And (5) putting the solution containing the low eutectic mixture of bismaleimide into a crystallizer, and crystallizing at the temperature of 5-15 ℃ to separate out a crude low eutectic mixture of bismaleimide.
And (6) filtering and drying the crude bismaleimide low-melting-point mixture to obtain the bismaleimide low-melting-point mixture.
The improved diallyl bisphenol A is prepared by performing a Claisen rearrangement reaction on bisphenol A diallyl ether in an inert solvent system; the inert solvent and the bisphenol A diallyl ether are mutually soluble, and the boiling point of the inert solvent is 200-205 ℃. The inert solvent includes gamma-butyrolactone and N-methylpyrrolidone.
The invention relates to an improved preparation method of diallyl bisphenol A, which comprises the following steps:
step 1, respectively adding an inert solvent and bisphenol A diallyl ether into a reactor provided with a stirring device, a temperature measuring device and a reflux condensing device; wherein the mass ratio of the inert solvent to the bisphenol A diallyl ether is 4: 1.
And 2, heating to the reflux temperature (200-205 ℃) of the system under the stirring condition, and reacting for 3-5 hours at the reflux temperature.
And 3, cooling the reaction system to 140-160 ℃, evaporating the inert solvent under the vacuum condition, and condensing and recycling.
And 4, collecting the residue in the reactor to obtain the improved diallyl bisphenol A.
The bismaleimide resin prepolymer of the present invention and the method for preparing the same are specifically exemplified below.
Example 1:
the bismaleimide resin prepolymer of this example was prepared from a bismaleimide low eutectic mixture and diallyl bisphenol A by Diels-Alder reaction in a twin screw extruder reactor.
Wherein, the bismaleimide low-melting mixture is prepared by the synthetic reaction of maleic anhydride and a diamine mixture; the diamine mixture comprises two or more diamine compounds, and at least one aromatic diamine is contained in the two or more diamine compounds; the diamine compounds in the diamine mixture have different molecular structures; the diamine compound may include aliphatic diamines and alicyclic diamines in addition to the aromatic diamines.
The diallyl bisphenol A of this example was prepared by a conventional process.
The preparation method of bismaleimide resin prepolymer of this example includes the following steps:
step 1, uniformly mixing a bismaleimide low eutectic mixture and diallyl bisphenol A to obtain a mixed reactant; the molar ratio of the bismaleimide low eutectic mixture to the diallyl bisphenol A is 1: 1.
Step 2, continuously and uniformly feeding the mixed reactants into a double-screw extruder, and controlling the temperature of the double-screw extruder to be 180 ℃; the extrusion rate of the twin-screw extruder was controlled so that the time from feeding the mixed reactants to extrusion from the outlet of the twin-screw extruder was kept at 10 min.
And 3, cooling the molten resin extruded from the outlet of the double-screw extruder into solid resin.
According to the requirements of the final product, the method also comprises the following crushing steps:
and 4, crushing the solid resin to 400-800 meshes by using an air flow crusher.
This example prepared bismaleimide low-melt blend the diamine mixture used was two aromatic diamine compounds: 4, 4 '-diaminodiphenylmethane and 2, 2' -bis [ 4- (4-aminophenoxy) phenyl ] propane in a molar ratio of 1: 1; synthesizing the bismaleimide low-melting mixture by adopting an acetone method.
The bismaleimide eutectic mixture used in this example is an improved bismaleimide eutectic mixture having a melting point lower than that of the respective pure compound; the structural regularity of the formed eutectic mixture is reduced, the solubility in the bismaleimide resin prepolymer is increased, no precipitate is separated out from the bismaleimide resin prepolymer along with the standing time, and the service life of the bismaleimide resin prepolymer is prolonged.
In addition, in the embodiment, a double-screw extruder is used as a reaction container, so that the temperature can be accurately controlled, the inside and the outside of the resin are uniform, and the temperature gradient is zero; in addition, continuous production can be realized, and the product quality stability and the production efficiency are greatly improved.
Example 2:
the bismaleimide resin prepolymer of this example was prepared from bismaleimide monomer and modified diallyl bisphenol A by Diels-Alder reaction in a twin screw extruder reactor.
The preparation method of bismaleimide resin prepolymer of this example includes the following steps:
step 1, uniformly mixing a bismaleimide monomer and improved diallyl bisphenol A to obtain a mixed reactant; the molar ratio of bismaleimide monomer to modified diallyl bisphenol A was 0.8: 1.
Step 2, continuously and uniformly feeding the mixed reactants into a double-screw extruder, and controlling the temperature of the double-screw extruder to be 185 ℃; the extrusion rate of the twin-screw extruder was controlled so that the time from feeding the mixed reactants to extrusion from the outlet of the twin-screw extruder was maintained at 8 min.
And 3, cooling the molten resin extruded from the outlet of the double-screw extruder into solid resin.
According to the requirements of the final product, the method also comprises the following crushing steps:
and 4, crushing the solid resin to 400-800 meshes by using an air flow crusher.
In the improved diallyl bisphenol a used in this embodiment, the inert solvent with the boiling point consistent with the reaction temperature of the diallyl bisphenol a is adopted, the heat released by the reaction vaporizes the inert solvent, and then the inert solvent is condensed and refluxed by a condensing device, so that the reaction heat of the whole reaction system is constantly vaporized and condensed and refluxed to realize the constant temperature state of the reaction system, and the viscosity index of the prepared diallyl bisphenol a is lower than that of the diallyl bisphenol a prepared by the traditional process because the reaction system is always in the constant temperature state; the rearrangement reaction of bisphenol A diallyl ether Claisen is more thorough, the hydroxyl equivalent of the prepared diallyl bisphenol A is higher than that of the diallyl bisphenol A prepared by the traditional process and is closer to a theoretical value, namely, the rearrangement reaction of bisphenol A diallyl ether is more complete; in addition, because the inert solvent which is compatible with bisphenol A diallyl ether is used as a reaction system, the system hardly contains air (oxygen), so that the prepared diallyl bisphenol A has light yellow color and is consistent with the color of a standard product. Overall, the improved diallyl bisphenol a used in this example was of higher quality.
In addition, in the embodiment, a double-screw extruder is used as a reaction container, so that the temperature can be accurately controlled, the inside and the outside of the resin are uniform, and the temperature gradient is zero; in addition, continuous production can be realized, and the product quality stability and the production efficiency are greatly improved.
Example 3:
the bismaleimide resin prepolymer of this example was prepared from a bismaleimide low eutectic mixture and modified diallyl bisphenol A by Diels-Alder reaction in a twin screw extruder reactor.
Wherein, the bismaleimide low-melting mixture is prepared by the synthetic reaction of maleic anhydride and a diamine mixture; the diamine mixture comprises two or more diamine compounds, and at least one aromatic diamine is contained in the two or more diamine compounds; the diamine compounds in the diamine mixture have different molecular structures; the diamine compound may include aliphatic diamines and alicyclic diamines in addition to the aromatic diamines.
The modified diallyl bisphenol A of this example was prepared by the Claisen rearrangement of bisphenol A bis allyl ether in an inert solvent system; the inert solvent and the bisphenol A diallyl ether are mutually soluble, and the boiling point of the inert solvent is 200-205 ℃; the inert solvent includes gamma-butyrolactone and N-methylpyrrolidone.
The preparation method of bismaleimide resin prepolymer of this example includes the following steps:
step 1, uniformly mixing a bismaleimide low eutectic mixture and diallyl bisphenol A to obtain a mixed reactant; the molar ratio of the bismaleimide low eutectic mixture to the diallyl bisphenol A is 1: 1.
Step 2, continuously and uniformly feeding the mixed reactants into a double-screw extruder, and controlling the temperature of the double-screw extruder to be 180 ℃; the extrusion rate of the twin-screw extruder was controlled so that the time from feeding the mixed reactants to extrusion from the outlet of the twin-screw extruder was kept at 10 min.
And 3, cooling the molten resin extruded from the outlet of the double-screw extruder into solid resin.
According to the requirements of the final product, the method also comprises the following crushing steps:
and 4, crushing the solid resin to 400-800 meshes by using an air flow crusher.
This example prepared bismaleimide low-melt mixture the diamine mixture used was an aromatic diamine compound and an alicyclic diamine compound: the preparation method comprises the following steps of preparing a mixture of 4, 4 '-diaminodiphenylmethane and 4, 4' -diaminodicyclohexylmethane according to a molar ratio of 2:1 by adopting a thermal closed-loop homogeneous phase method.
The bismaleimide eutectic mixture used in this example is an improved bismaleimide eutectic mixture having a melting point lower than that of the respective pure compound; the structural regularity of the formed eutectic mixture is reduced, the solubility in the bismaleimide resin prepolymer is increased, no precipitate is separated out from the bismaleimide resin prepolymer along with the standing time, and the service life of the bismaleimide resin prepolymer is prolonged.
In the improved diallyl bisphenol a used in this embodiment, the inert solvent with the boiling point consistent with the reaction temperature of the diallyl bisphenol a is adopted, the heat released by the reaction vaporizes the inert solvent, and then the inert solvent is condensed and refluxed by a condensing device, so that the reaction heat of the whole reaction system is constantly vaporized and condensed and refluxed to realize the constant temperature state of the reaction system, and the viscosity index of the prepared diallyl bisphenol a is lower than that of the diallyl bisphenol a prepared by the traditional process because the reaction system is always in the constant temperature state; the rearrangement reaction of bisphenol A diallyl ether Claisen is more thorough, the hydroxyl equivalent of the prepared diallyl bisphenol A is higher than that of the diallyl bisphenol A prepared by the traditional process and is closer to a theoretical value, namely, the rearrangement reaction of bisphenol A diallyl ether is more complete; in addition, because the inert solvent which is compatible with bisphenol A diallyl ether is used as a reaction system, the system hardly contains air (oxygen), so that the prepared diallyl bisphenol A has light yellow color and is consistent with the color of a standard product. Overall, the improved diallyl bisphenol a used in this example was of higher quality.
In addition, in the embodiment, a double-screw extruder is used as a reaction container, so that the temperature can be accurately controlled, the inside and the outside of the resin are uniform, and the temperature gradient is zero; in addition, continuous production can be realized, and the product quality stability and the production efficiency are greatly improved.
Example 4:
the composition of this example was prepared from bismaleimide monomer and diallyl bisphenol A by Diels-Alder reaction in a twin screw extruder reactor.
The preparation method of bismaleimide resin prepolymer of this example includes the following steps:
step 1, uniformly mixing a bismaleimide low eutectic mixture and diallyl bisphenol A to obtain a mixed reactant; the molar ratio of the bismaleimide low eutectic mixture to the diallyl bisphenol A was 10: 1.
Step 2, continuously and uniformly feeding the mixed reactants into a double-screw extruder, and controlling the temperature of the double-screw extruder to be 200 ℃; the extrusion rate of the twin-screw extruder was controlled so that the time from feeding the mixed reactants to extrusion from the outlet of the twin-screw extruder was kept at 1 min.
And 3, cooling the molten resin extruded from the outlet of the double-screw extruder into solid resin.
According to the requirements of the final product, the method also comprises the following crushing steps:
and 4, crushing the solid resin to 400-800 meshes by using an air flow crusher.
In the embodiment, a double-screw extruder is used as a reaction container, so that the temperature can be accurately controlled, the inside and outside of the resin are uniform, and the temperature gradient is zero; in addition, continuous production can be realized, and the product quality stability and the production efficiency are greatly improved.
Example 5:
the bismaleimide resin prepolymer of this example was prepared by Michael addition of a bismaleimide low-melt blend and diamine monomers in a twin screw extruder reactor.
The bismaleimide low-melting mixture in the embodiment is prepared by the synthetic reaction of a mixture of maleic anhydride and diamine; the diamine mixture comprises two or more diamine compounds, and at least one aromatic diamine is contained in the two or more diamine compounds; the diamine compounds in the diamine mixture have different molecular structures; the diamine compound may include aliphatic diamines and alicyclic diamines in addition to the aromatic diamines.
The diamine monomer in this embodiment includes an aromatic diamine, an aliphatic diamine, or an alicyclic diamine.
The preparation method of bismaleimide resin prepolymer of this embodiment includes the following steps:
step 1, uniformly mixing a bismaleimide low-eutectic mixture and a diamine monomer to obtain a mixed reactant; the molar ratio of the bismaleimide low eutectic mixture to the diamine monomer is 5: 1.
Step 2, continuously and uniformly feeding the mixed reactants into a double-screw extruder, and controlling the temperature of the double-screw extruder to be 190 ℃; the extrusion rate of the twin-screw extruder was controlled so that the time from feeding the mixed reactants to extrusion from the outlet of the twin-screw extruder was kept at 5 min.
And 3, cooling the molten resin extruded from the outlet of the double-screw extruder into solid resin.
According to the requirements of the final product, the method also comprises the following crushing steps:
and 4, crushing the solid resin to 400-800 meshes by using an air flow crusher.
This example prepared bismaleimide low-melt blend the diamine mixture used for the preparation of the aromatic diamine compound and the aliphatic diamine compound: the compound of 4, 4' -diaminodiphenylmethane and 2, 2, 4-trimethylhexamethylene diamine according to the molar ratio of 2:1 is prepared by adopting a thermal closed-loop homogeneous phase method.
The bismaleimide eutectic mixture used in this example is an improved bismaleimide eutectic mixture having a melting point lower than that of the respective pure compound; the structural regularity of the formed eutectic mixture is reduced, the solubility in the bismaleimide resin prepolymer is increased, no precipitate is separated out from the bismaleimide resin prepolymer along with the standing time, and the service life of the bismaleimide resin prepolymer is prolonged.
In addition, in the embodiment, a double-screw extruder is used as a reaction container, so that the temperature can be accurately controlled, the inside and the outside of the resin are uniform, and the temperature gradient is zero; in addition, continuous production can be realized, and the product quality stability and the production efficiency are greatly improved.
Example 6:
the bismaleimide resin prepolymer of this example was prepared by the Michael addition of a bismaleimide low-melt blend and a diamine blend in a twin screw extruder reactor.
The bismaleimide low-melting mixture in the embodiment is prepared by the synthetic reaction of a mixture of maleic anhydride and diamine; the diamine mixture comprises two or more diamine compounds, and at least one aromatic diamine is contained in the two or more diamine compounds; the diamine compounds in the diamine mixture have different molecular structures; the diamine compound may include aliphatic diamines and alicyclic diamines in addition to the aromatic diamines.
The diamine mixture reacted with the bismaleimide low-melting mixture in this embodiment includes at least two of an aromatic diamine, an aliphatic diamine, or an alicyclic diamine.
The preparation method of bismaleimide resin prepolymer of this embodiment includes the following steps:
step 1, uniformly mixing a bismaleimide low-eutectic mixture and a diamine mixture to obtain a mixed reactant; the molar ratio of the bismaleimide low eutectic mixture to the diamine mixture was 3: 1.
Step 2, continuously and uniformly feeding the mixed reactants into a double-screw extruder, and controlling the temperature of the double-screw extruder to be 200 ℃; the extrusion rate of the twin-screw extruder was controlled so that the time from feeding the mixed reactants to extrusion from the outlet of the twin-screw extruder was kept at 4 min.
And 3, cooling the molten resin extruded from the outlet of the double-screw extruder into solid resin.
According to the requirements of the final product, the method also comprises the following crushing steps:
and 4, crushing the solid resin to 400-800 meshes by using an air flow crusher.
This example prepared bismaleimide low-melt blend the diamine mixture used was two aromatic diamine compounds: the preparation method comprises the steps of preparing a mixture of 4, 4 '-diaminodiphenylmethane and 3, 3' -dimethyl-5, 5 '-diethyl-4, 4' -diaminodiphenylmethane according to a molar ratio of 1:1 by an acetone method.
The bismaleimide eutectic mixture used in this example is an improved bismaleimide eutectic mixture having a melting point lower than that of the respective pure compound; the structural regularity of the formed eutectic mixture is reduced, the solubility in the bismaleimide resin prepolymer is increased, no precipitate is separated out from the bismaleimide resin prepolymer along with the standing time, and the service life of the bismaleimide resin prepolymer is prolonged.
In addition, in the embodiment, a double-screw extruder is used as a reaction container, so that the temperature can be accurately controlled, the inside and the outside of the resin are uniform, and the temperature gradient is zero; in addition, continuous production can be realized, and the product quality stability and the production efficiency are greatly improved.
Example 7:
the bismaleimide resin prepolymer of this example was prepared by the Michael addition of a mixture of bismaleimide monomers and diamines in a twin screw extruder reactor.
The diamine mixture in this embodiment includes at least two of an aromatic diamine, an aliphatic diamine, or an alicyclic diamine.
The preparation method of bismaleimide resin prepolymer of this embodiment includes the following steps:
step 1, uniformly mixing a bismaleimide low-eutectic mixture and a diamine mixture to obtain a mixed reactant; the molar ratio of the bismaleimide low eutectic mixture to the diamine mixture was 7: 1.
Step 2, continuously and uniformly feeding the mixed reactants into a double-screw extruder, and controlling the temperature of the double-screw extruder to be 195 ℃; the extrusion rate of the twin-screw extruder was controlled so that the time from feeding the mixed reactants to extrusion from the outlet of the twin-screw extruder was kept at 2 min.
And 3, cooling the molten resin extruded from the outlet of the double-screw extruder into solid resin.
According to the requirements of the final product, the method also comprises the following crushing steps:
and 4, crushing the solid resin to 400-800 meshes by using an air flow crusher.
In the embodiment, a double-screw extruder is used as a reaction container, so that the temperature can be accurately controlled, the inside and outside of the resin are uniform, and the temperature gradient is zero; in addition, continuous production can be realized, and the product quality stability and the production efficiency are greatly improved.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.
Claims (6)
1. A bismaleimide resin prepolymer is characterized in that bismaleimide and diallyl bisphenol A are subjected to Diels-Alder reaction in a double-screw extruder reactor to form the bismaleimide resin prepolymer;
wherein the bismaleimide comprises a bismaleimide monomer or a bismaleimide low-melting mixture;
the bismaleimide low-eutectic-ratio mixture is prepared by the synthetic reaction of maleic anhydride and a diamine mixture; the diamine mixture comprises two or more diamine compounds, and at least one aromatic diamine is contained in the two or more diamine compounds; the diamine compounds in the diamine mixture have different molecular structures;
the diallyl bisphenol A comprises modified diallyl bisphenol A; the improved diallyl bisphenol A is prepared by performing a Claisen rearrangement reaction on bisphenol A diallyl ether in an inert solvent system in a reflux and condensation manner; the inert solvent and the bisphenol A diallyl ether are mutually soluble, the boiling point of the inert solvent is consistent with the reaction temperature of the bisphenol A diallyl ether, the boiling point of the inert solvent is 200-205 ℃, and the inert solvent comprises gamma-butyrolactone and N-methyl pyrrolidone;
wherein the preparation method of the bismaleimide resin prepolymer comprises the following steps:
step 1, uniformly mixing bismaleimide and diallyl bisphenol A to obtain a mixed reactant;
step 2, continuously and uniformly feeding the mixed reactants into a double-screw extruding machine, and controlling the temperature of the double-screw extruding machine to be 180-200 ℃; controlling the extrusion speed of the double-screw extruder to keep the time from feeding the mixed reactants into the double-screw extruder to extruding the mixed reactants from the outlet of the double-screw extruder within 1-10 min;
step 3, cooling the molten resin extruded from the outlet of the double-screw extruder into solid resin;
and 4, crushing the solid resin to 400-800 meshes by using an air flow crusher.
2. A preparation method of bismaleimide resin prepolymer is characterized by comprising the following steps:
step 1, uniformly mixing bismaleimide and diallyl bisphenol A to obtain a mixed reactant;
step 2, continuously and uniformly feeding the mixed reactants into a double-screw extruding machine, and controlling the temperature of the double-screw extruding machine to be 180-200 ℃; controlling the extrusion speed of the double-screw extruder to keep the time from feeding the mixed reactants into the double-screw extruder to extruding the mixed reactants from the outlet of the double-screw extruder within 1-10 min;
step 3, cooling the molten resin extruded from the outlet of the double-screw extruder into solid resin;
the diallyl bisphenol A comprises modified diallyl bisphenol A; the improved diallyl bisphenol A is prepared by performing a Claisen rearrangement reaction on bisphenol A diallyl ether in an inert solvent system in a reflux and condensation manner; the inert solvent and the bisphenol A diallyl ether are mutually soluble, the boiling point of the inert solvent is 200-205 ℃, the boiling point of the inert solvent is consistent with the reaction temperature of the bisphenol A diallyl ether, and the inert solvent comprises gamma-butyrolactone and N-methyl pyrrolidone;
wherein the preparation steps of the improved diallyl bisphenol A comprise:
step a, respectively adding an inert solvent and bisphenol A diallyl ether into a reactor provided with a stirring device, a temperature measuring device and a reflux condensing device; wherein the mass ratio of the inert solvent to the bisphenol A diallyl ether is 4: 1;
b, heating to the reflux temperature of the system of 200-205 ℃ under the stirring condition, and reacting for 3-5 hours at the reflux temperature in a timing manner;
step c, cooling the reaction system to 140-160 ℃, evaporating the inert solvent under the vacuum condition, and condensing and recycling;
and d, collecting the residue in the reactor to obtain the improved diallyl bisphenol A.
3. The method for preparing bismaleimide resin prepolymer as claimed in claim 2 further comprising, after step 3:
and 4, crushing the solid resin to 400-800 meshes by using an air flow crusher.
4. The method of preparing a bismaleimide resin prepolymer as claimed in claim 2 wherein said bismaleimide comprises a bismaleimide monomer or a bismaleimide eutectic mixture;
the bismaleimide low-eutectic-ratio mixture is prepared by the synthetic reaction of maleic anhydride and a diamine mixture; the diamine mixture comprises two or more diamine compounds, and at least one aromatic diamine is contained in the two or more diamine compounds; the diamine compounds in the diamine mixture have different molecular structures.
5. The method for producing a bismaleimide resin prepolymer as claimed in claim 4 wherein said diamine compound further comprises an aliphatic diamine and an alicyclic diamine.
6. The method for producing a bismaleimide resin prepolymer according to claim 2, wherein the molar ratio of bismaleimide to diallyl bisphenol a is (0.8 to 10): 1.
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