CN109280169A - Low mixture of bismaleimide and preparation method thereof, Bismaleimides resin pre-polymer - Google Patents
Low mixture of bismaleimide and preparation method thereof, Bismaleimides resin pre-polymer Download PDFInfo
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- CN109280169A CN109280169A CN201811291551.2A CN201811291551A CN109280169A CN 109280169 A CN109280169 A CN 109280169A CN 201811291551 A CN201811291551 A CN 201811291551A CN 109280169 A CN109280169 A CN 109280169A
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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
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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
Abstract
The present invention relates to low mixture of a kind of bismaleimide and preparation method thereof, Bismaleimides resin pre-polymer, the low mixture of the bismaleimide is made by maleic anhydride and diamine mixture by synthetic reaction；Wherein the diamine mixture includes two or more diamine compound, and at least contains a kind of aromatic diamine in two or more diamine compound；The molecular structure of each diamine compound is different in diamine mixture；Diamine compound further includes aliphatic diamine and alicyclic diamine.The fusing point of the low mixture of bismaleimide prepared by the present invention is lower than the fusing point of respective pure compound；The eutectic mixture structural regularity of formation reduces, and the dissolubility in Bismaleimides resin pre-polymer increases；The service life of Bismaleimides resin pre-polymer is extended without Precipitation with standing time in Bismaleimides resin pre-polymer prepared by the present invention.
Description
Technical field
The invention belongs to bismaleimide synthetic method technical fields, and in particular to a kind of bismaleimide is low co-melting
Mixture and preparation method thereof, Bismaleimides resin pre-polymer.
Background technique
Bismaleimide monomer general formula of molecular structure is as follows:
Wherein: R1、R2For identical or different substituent group, they are generally-H, or-CnH2n+1Group or its
His substituent group, R are aliphatic, alicyclic or aromatic substituents group.
Under normal circumstances, the bismaleimide monomer of different structure is by maleic anhydride and aliphatic diamine, rouge
Ring race diamines or aromatic diamine are obtained by imidization reaction.When R is benzene ring structure, monomer has high fusing point,
Solidfied material has excellent heat resistance, glass transition temperature Tg≥250℃；When R is alicyclic structure, solidfied material color
It is shallower, glass transition temperature (Tg) lower；When R is aliphatic structure, monomer has compared with low melting point or is liquid condition.
Due to containing C=C unsaturated double-bond in bismaleimide monomer, as span polyimide type resin
Principal monomer and diamine carry out Michael addition reaction generate line style chain elongation polymer, then on maleimide ring
Double bond open and carry out free radical (anion) type curing reaction and form cross-linked network, while being formed after Michael addition reaction
Linear polymer in secondary amine can also further be reacted with remaining double bond on chain elongation polymer；Or with allyl phenyl
Close object and carry out the intermediate that ene addition reaction generates 1:1, then at relatively high temperatures the double bond in imide ring and intermediate into
Row Diels-Alder reaction and anion imide oligomer react the resinite to form the high crosslink density with trapezium structure
System.
Since the performance of different bismaleimide monomers is different, it is formed by bismaleimide resin polymer performance then not
Together, such as: the bismaleimide monomer of aromatic structure fusing point with higher, dissolubility in organic solvent is smaller,
But polymer has very high resistance to high (low) warm nature energy, and has good electrical insulation capability；The bismaleimide of aliphatic structure
The fusing point of monomer is low, in organic solvent have good dissolubility, dielectric properties are excellent, but the mechanical property of polymer and
Heat resistance is very poor；The property of the bismaleimide of alicyclic structure is therebetween.Under normal circumstances, in order to improve span
The performance of resin is with the bismaleimide monomer of one or more kinds of aromatic structures in bismaleimide resin system formula
It is main, then be aided with the bismaleimide monomer of aliphatic structure or/and the bismaleimide monomer of alicyclic structure, with this into
One-step optimization balances resin system curing network structure, while so that the polymeric acceptor obtained is tied up to holding high heat resistance, tool
There are excellent mechanical property and electrical property.
However, by the bismaleimide monomer of one or more kinds of aromatic structures, or it is aided with aliphatic structure
The bismaleimide monomer of bismaleimide monomer or/and alicyclic structure prepares Bismaleimides resin pre-polymer
When, solvent system or solvent-free system are either used, it is single all to have span in Bismaleimides resin pre-polymer
The problem of body is precipitated, and then influence stability and the validity period of Bismaleimides resin pre-polymer.
Summary of the invention
It is easy to solve bismaleimide monomer in Bismaleimides resin pre-polymer existing in the prior art
The problem of influencing its stability and validity period is precipitated, the present invention provides a kind of low mixture of bismaleimide and its systems
Preparation Method, Bismaleimides resin pre-polymer.The technical problem to be solved in the present invention is achieved through the following technical solutions:
A kind of preparation method of the low mixture of bismaleimide, the low mixture of the bismaleimide by
Maleic anhydride and diamine mixture are made by synthetic reaction；Wherein the diamine mixture includes two or more
Diamine compound, and at least contain a kind of aromatic diamine in two or more diamine compound；The diamine mixture
In each diamine compound molecular structure it is different.
Further, the diamine compound further includes aliphatic diamine and alicyclic diamine.
Further, the method for the synthetic reaction is hot closed loop homogeneous method.
Further, the synthetic reaction method specifically includes the following steps:
Step (1) is added to by toluene and to catalyst toluenesulfonic acid equipped with agitating device, temperature measuring equipment and reflux condensation mode
In the first container of device, then the maleic anhydride in the first container, dissolution is stirred at room temperature, obtains maleic two
Acid anhydrides lysate；
Toluene and n,N-Dimethylformamide are added in second container step (2), then add in the second container
Enter the diamine mixture, stirring and dissolving at a temperature of 40~50 DEG C obtains two amine solutions；
The maleic anhydride lysate is warming up to reflux temperature (~110 DEG C) by step (3) under agitation,
Then it instills two amine solution to be reacted, the water for reacting generation is constantly excluded from reflux condenser bottom, the reaction time
For 4~8h；
System after reaction is cooled to 70~85 DEG C by step (4), then adds water washing 3~5 under agitation
It is secondary, so that solution is mutually kept neutral state, obtains the solution containing the low mixture of bismaleimide；
The solution containing the low mixture of bismaleimide is put into crystallizer, 5~15 by step (5)
The low mixture crude product of bismaleimide is precipitated in crystallization at a temperature of DEG C；
Step (6) will obtain the span after the low mixture crude product filtering of the bismaleimide, drying
The low mixture of acid imide.
Further, the molar ratio of the maleic anhydride and the diamine mixture is (2.1~2.3): 1.
Further, the amount of each diamine compound is low co-melting mixed according to the bismaleimide in the diamine mixture
The technical requirement for closing object determines.
The invention further relates to a kind of low mixture of bismaleimide, the low mixture of the bismaleimide
The preparation method described in any of the above item is prepared.
The invention further relates to a kind of Bismaleimides resin pre-polymer, the Bismaleimides resin pre-polymer is by mixing
Bonding solvent, diallyl bisphenol and the low mixture of above-mentioned bismaleimide are prepared by solvent method.
Further, the mixed solvent is made of propylene glycol monomethyl ether and dioxane by the mass ratio of 3:1.
The invention further relates to a kind of Bismaleimides resin pre-polymer, the Bismaleimides resin pre-polymer is by two
Allyl bisphenol-A and the low mixture of above-mentioned bismaleimide are prepared by fusion method.
Compared with prior art, beneficial effects of the present invention:
1. the present invention (at least contains two kinds of a kind of aromatic diamine by using maleic anhydride and diamine mixture
Or two or more diamine compounds) reaction, it can directly prepare the low mixture of bismaleimide, the bismaleimide
The fusing point of the low mixture of amine is lower than the fusing point of respective pure compound；The eutectic mixture structural regularity of formation reduces,
Dissolubility in Bismaleimides resin pre-polymer increases, with standing time without precipitating in Bismaleimides resin pre-polymer
It is precipitated, extends the service life of Bismaleimides resin pre-polymer.
2. the Bismaleimides resin pre-polymer present invention can be according to the bismaleimide of final required different performance
The requirement of polyimide resin prepolymer performance indicator, and then determine that target product --- the technology of the low mixture of bismaleimide refers to
Mark requires, and sets the amount of each diamine compound monomer in diamine mixture, is passed through according to the performance indicator demand of target product
The control of aromatic diamine and aliphatic diamine or/and alicyclic diamine additional amount, prepares the bismaleimide of different performance
The low mixture of amine.
3. the preparation method of the low mixture of bismaleimide of the present invention, by being added to each reactant of reaction process
The control of amount, and to operating procedure, reaction temperature and the control in reaction time, temperature control uniformly, reaction thoroughly, and side reaction compared with
It is few.
4. the bimaleimide resin that the present invention is prepared in turn by the low mixture of the bismaleimide prepared
Prepolymer greatly strengthens the stability of Bismaleimides resin pre-polymer with standing time without Precipitation, extends double
The effective life of maleimide resin prepolymer.
Specific embodiment
Further detailed description is done to the present invention combined with specific embodiments below, but embodiments of the present invention are not limited to
This.
Embodiment 1:
A kind of preparation method of the low mixture of bismaleimide, the low mixture of the bismaleimide by
Maleic anhydride and diamine mixture are made by synthetic reaction；Wherein the diamine mixture includes two or more
Diamine compound, and at least contain a kind of aromatic diamine in two or more diamine compound；The diamine mixture
In each diamine compound molecular structure it is different.The diamine compound further includes aliphatic diamine and alicyclic diamine.
The principles of chemistry that it is synthesized are as follows:
By cis-butenedioic anhydride (also known as maleic anhydride, maleic anhydride, 2,5- furasndiones etc.) and two or more diamines
A kind of compound (at least containing aromatic diamines) reaction generates intermediate:
It is low total to carry out dehydration closed-loop reaction formation bismaleimide under catalyst (p-methyl benzenesulfonic acid) effect for intermediate
Melt mixture.
The synthetic method that the low mixture of the bismaleimide of the present embodiment uses is hot closed loop homogeneous method, hot closed loop
Homogeneous method can also be specifically included according to disclosed existing hot closed loop homogeneous method with hot closed loop homogeneous method according to the invention
Following steps:
Toluene and catalyst p-methyl benzenesulfonic acid are added to and divide water equipped with agitating device, temperature measuring equipment and condensation by step (1)
In the first container of device, then the maleic anhydride in the first container, dissolution is stirred at room temperature, obtains maleic acid
Acid anhydride lysate；Wherein, the molar ratio of maleic anhydride and diamine mixture is (2.1~2.3): 1；Catalyst p-methyl benzenesulfonic acid
Molar ratio with diamine mixture is 0.2:1；
Toluene and n,N-Dimethylformamide are added in second container step (2), then add in the second container
Enter the diamine mixture, stirring and dissolving at a temperature of 40~50 DEG C obtains two amine solutions；Wherein, each in diamine mixture
The amount of diamine compound is determined according to the technical requirement of the low mixture of the bismaleimide；
The maleic anhydride lysate is warming up to reflux temperature (~110 DEG C) by step (3) under agitation,
Then it instills two amine solution to be reacted, the water for reacting generation is constantly excluded from reflux condenser bottom, the reaction time
For 4~8h；
System after reaction is cooled to 70~85 DEG C, 3~5 is then washed with water under agitation by step (4)
It is secondary, so that solution is mutually kept neutral state, obtains the solution containing the low mixture of bismaleimide；
The solution containing the low mixture of bismaleimide is put into crystallizer, 5~15 by step (5)
The low mixture crude product of bismaleimide is precipitated in crystallization at a temperature of DEG C；
Step (6) will obtain the span after the low mixture crude product filtering of the bismaleimide, drying
The low mixture of acid imide.
In above-mentioned steps, the volume ratio of toluene additional amount and toluene additional amount in step 2 is 2:1 in rapid 1；In step (2)
Toluene additional amount and n,N-Dimethylformamide additional amount volume ratio are (4~5): 1.
The preparation of the low mixture of bismaleimide of the present invention using hot closed loop homogeneous method synthesis technology, by right
The control of each reactant additive amount of reaction process, and to operating procedure, reaction temperature and the control in reaction time, two methods
Equal temperature control is uniform, reaction is thorough, and side reaction is less.
Embodiment 2:
In the present embodiment diamine mixture be two kinds of aromatic diamine compounds: 4,4 '-diaminodiphenyl-methanes and 2,2 '-
Bis- [4- (4- amino-benzene oxygen) phenyl] propane, the in molar ratio mixture of 1:1；The present embodiment uses the system of hot closed loop homogeneous method
Preparation Method synthesizes the low mixture of bismaleimide in conjunction with specific reaction condition, and low to the bismaleimide of synthesis
The technical indicator of mixture is tested.
The preparation method of the low mixture of the bismaleimide of the present embodiment specifically includes the following steps:
(1) 120ml toluene and 0.02mol p-methyl benzenesulfonic acid are added to equipped with blender, thermometer and condensation water segregator
500ml there-necked flask in, add 0.21mol maleic anhydride, dissolution be stirred at room temperature；
(2) 60ml toluene and 14mlDMF (n,N-Dimethylformamide) are added in dropping funel, add diamines mixing
Object 0.1mol, the stirring and dissolving at 40-50 DEG C；Diamine mixture presses 4,4 '-diaminodiphenyl-methanes and 2,2 '-bis- [4- (4-
Amino-benzene oxygen) phenyl] propane molar ratio 1:1 ratio mixing.
(3) (1) system is warming up to reflux temperature (~110 DEG C) under agitation, it is molten that (2) solution is added drop-wise to (1)
It is reacted in liquid, the control reaction time is 6.0h, and the water generated in entire reaction process is constantly from condensation pipeline bottom
It excludes, homogeneous state is presented in system always；
(4) it is cooled to 80 DEG C or so after reaction, then adds water washing 3-5 times under agitation, protects solution mutually
Hold neutral state；
(5) (4) solution is put into crystallizer, the low mixture of knot precipitation bismaleimide is under the conditions of 10 DEG C
Yellow crystal particle；
(6) the low mixture product of bismaleimide is obtained after filtering drying.
(diamine mixture presses 4,4 '-diamino-diphenyls to the low mixture of bismaleimide manufactured in the present embodiment
Methane and 2, the ratio mixing of 2 '-bis- [4- (4- amino-benzene oxygen) phenyl] propane molar ratio 1:1) (hereinafter referred to as A1), warp
It is as follows to test its technical indicator:
Fusing point: 80~90 DEG C
Dissolubility (room temperature): 50g/100g methyl ethyl ketone, 50g/100g toluene
Appearance: yellow crystal sprills
Embodiment 3:
In the present embodiment diamine mixture be two kinds of aromatic diamine compounds: 4,4 '-diaminodiphenyl-methanes and 3,3 '-
5,5 '-diethyl -4 of dimethyl -, 4 '-diaminodiphenyl-methanes, the in molar ratio mixture of 1:1；The present embodiment is closed using heat
The preparation method of ring homogeneous method synthesizes the low mixture of bismaleimide in conjunction with specific reaction condition, and to the double of synthesis
The technical indicator of the low mixture of maleimide is tested.
The preparation method of the low mixture of the bismaleimide of the present embodiment specifically includes the following steps:
(1) 120ml toluene and 0.02mol p-methyl benzenesulfonic acid are added to equipped with blender, thermometer and condensation water segregator
500ml there-necked flask in, add 0.22mol maleic anhydride, dissolution be stirred at room temperature；
(2) 60ml toluene and 14mlDMF (n,N-Dimethylformamide) are added in dropping funel, add diamines mixing
Object 0.1mol, the stirring and dissolving at 40-50 DEG C；Diamine mixture presses 4,4 '-diaminodiphenyl-methanes and 3,3 '-dimethyl-
5,5 '-diethyl -4, the ratio mixing of 4 '-diaminodiphenyl-methane molar ratio 1:1.
(3) (1) system is warming up to reflux temperature (~110 DEG C) under agitation, it is molten that (2) solution is added drop-wise to (1)
It is reacted in liquid, the control reaction time is 7.0h, and the water generated in entire reaction process is constantly from condensation pipeline bottom
It excludes, homogeneous state is presented in system always；
(4) it is cooled to 80 DEG C or so after reaction, is then washed with water 3-5 times under agitation, protects solution mutually
Hold neutral state；
(5) (4) solution is put into crystallizer, the low mixture of knot precipitation bismaleimide is under the conditions of 10 DEG C
Yellow crystal particle；
(6) the low mixture product of bismaleimide is obtained after filtering drying.
(diamine mixture presses 4,4 '-diamino-diphenyls to the low mixture of bismaleimide manufactured in the present embodiment
Methane and 3,3 '-dimethyl -5,5 '-diethyl -4, the ratio mixing of 4 '-diaminodiphenyl-methane molar ratio 1:1) it is (following
Referred to as A2), its technical indicator is as follows after tested:
Fusing point: 120~130 DEG C
Dissolubility (room temperature): 40g/100g methyl ethyl ketone, 40g/100g toluene
Appearance: yellow crystal sprills
Embodiment 4:
Diamine mixture is aromatic diamine compound and alicyclic diamine compound: 4,4 '-diamino hexichol in the present embodiment
Methylmethane and 4,4 '-diamino-dicyclohexyl methanes, the in molar ratio mixture of 2:1；The present embodiment uses hot closed loop homogeneous method
Preparation method synthesize the low mixture of bismaleimide, and to the bismaleimide of synthesis in conjunction with specific reaction condition
The technical indicator of the low mixture of amine is tested.
The preparation method of the low mixture of the bismaleimide of the present embodiment specifically includes the following steps:
(1) 120ml toluene and 0.02mol p-methyl benzenesulfonic acid are added to equipped with blender, thermometer and condensation water segregator
500ml there-necked flask in, add 0.22mol maleic anhydride, dissolution be stirred at room temperature；
(2) 60ml toluene and 14mlDMF (n,N-Dimethylformamide) are added in dropping funel, add diamines mixing
Object 0.1mol, the stirring and dissolving at 40~50 DEG C；Diamine mixture presses 4,4 '-diaminodiphenyl-methanes and 4,4 '-diamino
The ratio of dicyclohexyl methyl hydride molar ratio 2:1 mixes；
(3) (1) system is warming up to reflux temperature (~110 DEG C) under agitation, it is molten that (2) solution is added drop-wise to (1)
It is reacted in liquid, the control reaction time is 7.0h, and the water generated in entire reaction process is constantly from condensation pipeline bottom
It excludes, homogeneous state is presented in system always；
(4) it is cooled to 80 DEG C or so after reaction, is then washed with water 3-5 times under agitation, protects solution mutually
Hold neutral state；
(5) (4) solution is put into crystallizer, the low mixture of knot precipitation bismaleimide is under the conditions of 10 DEG C
Pale yellow crystals particle；
(6) the low mixture product of bismaleimide is obtained after filtering drying.
(diamine mixture presses 4,4 '-diamino-diphenyls to the low mixture of bismaleimide manufactured in the present embodiment
Methane and 4, the ratio mixing of 4 '-diamino-dicyclohexyl methane molar ratio 2:1) (hereinafter referred to as A3), its technology after tested
Index is as follows:
Fusing point: 110~120 DEG C
Dissolubility (room temperature): 40g/100g methyl ethyl ketone, 40g/100g toluene
Appearance: pale yellow crystals sprills
Embodiment 5:
Diamine mixture is aromatic diamine compound and alicyclic diamine compound: 4,4 '-diamino hexichol in the present embodiment
Methylmethane and 2,2,4- trimethylhexane diamines, the in molar ratio mixture of 2:1；The present embodiment uses the preparation of hot closed loop homogeneous method
Method synthesizes the low mixture of bismaleimide in conjunction with specific reaction condition, and low total to the bismaleimide of synthesis
The technical indicator for melting mixture is tested.
The preparation method of the low mixture of the bismaleimide of the present embodiment specifically includes the following steps:
(1) 120ml toluene and 0.02mol p-methyl benzenesulfonic acid are added to equipped with blender, thermometer and condensation water segregator
500ml there-necked flask in, add 0.22mol maleic anhydride, dissolution be stirred at room temperature；
(2) 60ml toluene and 14mlDMF (n,N-Dimethylformamide) are added in dropping funel, add diamines mixing
Object 0.1mol, the stirring and dissolving at 40~50 DEG C；Diamine mixture presses 4,4 '-diaminodiphenyl-methanes and 2,2,4- trimethyls
The ratio of hexamethylene diamine molar ratio 2:1 mixes；
(3) (1) system is warming up to reflux temperature (~110 DEG C) under agitation, it is molten that (2) solution is added drop-wise to (1)
It is reacted in liquid, the control reaction time is 7.0h, and the water generated in entire reaction process is constantly from condensation pipeline bottom
It excludes, homogeneous state is presented in system always；
(4) it is cooled to 80 DEG C or so after reaction, is then washed with water 3-5 times under agitation, protects solution mutually
Hold neutral state；
(5) (4) solution is put into crystallizer, the low mixture of knot precipitation bismaleimide is under the conditions of 10 DEG C
Pale yellow crystals particle；
(6) the low mixture product of bismaleimide is obtained after filtering drying.
(diamine mixture presses 4,4 '-diamino-diphenyls to the low mixture of bismaleimide manufactured in the present embodiment
Methane and 2, the ratio mixing of 2,4- trimethylhexane diamine molar ratio 2:1) (hereinafter referred to as A4), its technical indicator is such as after tested
Under:
Fusing point: 100~110 DEG C
Dissolubility (room temperature): 40g/100g methyl ethyl ketone, 40g/100g toluene
Appearance: yellow crystal sprills
Carry out further comparative analysis below by the technical indicator for providing bismaleimide monomer.
Comparative example 1:
Comparative example 1 is the technical indicator of aromatic diamine compound monomer.
Chemical name: 4,4 '-diaminodiphenyl-methane, 4,4 '-diaminodiphenyl-methane CAS:13676-54-5
Fusing point: 155~160 DEG C
Dissolubility: at room temperature, it is practically insoluble in any organic solvent
Appearance: yellow crystal sprills
Comparative example 2:
Comparative example 2 is the technical indicator of aromatic diamine compound monomer.
Chemical name: 2,2 '-bis- [4- (maleimide phenoxyl) phenyl] propane
CAS:79922-55-7
Fusing point: 135-140 DEG C
Dissolubility (room temperature): 50g/100g methyl ethyl ketone, 50g/100g toluene
Appearance: yellow needles
Comparative example 3:
Comparative example 3 is the technical indicator of aromatic diamine compound monomer.
Chemical name: bis- (3- ethyl -5- methyl -4- maleimidophenyl) methane
CAS:105391-33-1
Appearance: light yellow crystalline powder
Fusing point: 158~163 DEG C
Dissolubility (room temperature): 40g/100g methyl ethyl ketone, 40g/100g toluene
The technical indicator of A1, A2, A3 and A4 that embodiment 2, embodiment 3, embodiment 4, embodiment 5 are prepared respectively with than
Compared with the technical indicator comparative analysis of the bismaleimide monomer of example 1, comparative example 2 and comparative example 3, it can be seen that embodiment 2,
The fusing point of the low mixture of bismaleimide prepared by embodiment 3, embodiment 4, embodiment 5 is substantially reduced, dissolubility phase
Aromatic series bismaleimide monomer than comparative example 1 dramatically increases.
Comparative example 4:
Respectively take 4, the 4 '-diaminodiphenyl-methane of monomer of comparative example 1 and the monomer 2 of comparative example 2,2 '-bis- [(Malaysias 4-
Imide phenoxy group) phenyl] each 25g of propane, progress physical mixed is uniform, and 100g methyl ethyl ketone is taken to do solubility reality at room temperature
It tests, is 4,4 '-diaminodiphenyl-methanes through Structural Identification by insoluble matter quantitative analysis, about 25g insoluble matter.
Comparative example 5:
Bis- (3- ethyl -5- the first of the monomer of 4, the 4 '-diaminodiphenyl-methane of monomer and comparative example 3 that respectively take comparative example 1
Base -4- maleimidophenyl) each 20g of methane, progress physical mixed is uniform, and 100g methyl ethyl ketone is taken to do solubility at room temperature
Insoluble matter quantitative analysis, about 20g insoluble matter are 4,4 '-diaminodiphenyl-methanes through Structural Identification by experiment.
From comparative example 4 and comparative example 5 as can be seen that insoluble matter is 4,4 '-diaminodiphenyl-methanes, illustrate aromatic series
The bismaleimide monomer of structure is practically insoluble in any organic solvent.
Application examples 1~8 gives the low mixture of bismaleimide of the invention using different preparation methods below
The specific embodiment of the Bismaleimides resin pre-polymer of (solvent method and fusion method) preparation, and pass through observation bismaleimide
The placement form of polyimide resin prepolymer at room temperature analyzes the influence factor of Bismaleimides resin pre-polymer.
Application examples 1:
Take mixed solvent 50g (propylene glycol monomethyl ether and dioxane mass ratio be 3:1), diallyl bis-phenol 94.5g,
A1105.5g, 120 DEG C of reaction temperature, the Bismaleimides resin pre-polymer of reaction time 2.0h, preparation are placed at room temperature
30 days, no Precipitation.
Application examples 2:
Take diallyl bisphenol 94.5g, A1105.5g, 130 DEG C of reaction temperature, reaction time 2.0h, the span of preparation
Bismaleimide resin prepolymer is placed 30 days at room temperature, no Precipitation.
Application examples 3:
Take mixed solvent 50g (propylene glycol monomethyl ether and dioxane mass ratio be 3:1), diallyl bisphenol 94.5g,
A2105.5g, 120 DEG C of reaction temperature, the Bismaleimides resin pre-polymer of reaction time 2.0h, preparation are placed at room temperature
30 days, no Precipitation.
Application examples 4:
Take diallyl bisphenol 94.5g, A2 105.5g, 120 DEG C of reaction temperature, reaction time 2.0h, the span of preparation
Bismaleimide resin prepolymer is placed 30 days at room temperature, no Precipitation.
Application examples 5:
Take mixed solvent 50g (propylene glycol monomethyl ether and dioxane mass ratio be 3:1), diallyl bisphenol 94.5g,
A3 105.5g, 120 DEG C of reaction temperature, the Bismaleimides resin pre-polymer of reaction time 2.0h, preparation are placed at room temperature
30 days, no Precipitation.
Application examples 6:
Take diallyl bisphenol 94.5g, A3 105.5g, 120 DEG C of reaction temperature, reaction time 2.0h, the span of preparation
Bismaleimide resin prepolymer is placed 30 days at room temperature, no Precipitation.
Application examples 7:
Take mixed solvent 50g (propylene glycol monomethyl ether and dioxane mass ratio be 3:1), diallyl bisphenol 94.5g,
A4 105.5g, 120 DEG C of reaction temperature, the Bismaleimides resin pre-polymer of reaction time 2.0h, preparation are placed at room temperature
30 days, no Precipitation.
Application examples 8:
Take diallyl bisphenol 94.5g, A4 105.5g, 120 DEG C of reaction temperature, reaction time 2.0h, the span of preparation
Bismaleimide resin prepolymer is placed 30 days at room temperature, no Precipitation.
From application examples 1~8 as can be seen that since A1, A2, A3 and A4 have formed highly uniform low mixture, because
No matter this uses solvent method or fusion method prepares Bismaleimides resin pre-polymer, and the stability of system obtains greatly
Improve.
The low mixture of bismaleimide in order to better illustrate the present invention is further preparing bismaleimide
To the impact effect of Bismaleimides resin pre-polymer when polyimide resin prepolymer, acyl is come to the span of comparative example preparation again below
Imide resin prepolymer is analyzed.
Using comparative example 1:
Take mixed solvent (propylene glycol monomethyl ether and dioxane mass ratio be 3:1) 50g, diallyl bisphenol 94.5g,
Comparative example 1 and comparative example 2 press 1:1 mixture 105.5g, and 120 DEG C of reaction temperature, reaction time 2.0h, the bismaleimide of preparation
Polyimide resin prepolymer is placed 5 days at room temperature, there is precipitating (4,4 '-diaminodiphenyl-methane) precipitation.
Using comparative example 2:
Take mixed solvent 50g (propylene glycol monomethyl ether and dioxane mass ratio be 3:1), diallyl bisphenol 94.5g,
Comparative example 1 and comparative example 3 press 1:1 mixture 105.5g, and 120 DEG C of reaction temperature, reaction time 2.0h, the bismaleimide of preparation
Polyimide resin prepolymer is placed 6 days at room temperature, there is precipitating (4,4 '-diaminodiphenyl-methane) precipitation.
Using comparative example 3:
Take diallyl bisphenol 94.5g, comparative example 1 and comparative example 2 by 1:1 mixture 105.5g, reaction temperature 130
DEG C, reaction time 0.5h, the Bismaleimides resin pre-polymer of preparation is placed 10 days at room temperature, there is precipitating (4,4 '-diaminos
Base diphenyl methane) it is precipitated.
Using comparative example 4:
Take diallyl bisphenol 94.5g, comparative example 1 and comparative example 3 by 1:1 mixture 105.5g, reaction temperature 130
DEG C, reaction time 0.5h, the Bismaleimides resin pre-polymer of preparation is placed 12 days at room temperature, there is precipitating (4,4 '-diaminos
Base diphenyl methane) it is precipitated.
From application comparative example 1~4 as can be seen that by the monomer of comparative example 1 and comparative example 2 and comparative example 3 respectively with physics
Mixed form is combined, no matter double using solvent method or fusion method preparation because being not likely to form low mixture
Maleimide resin prepolymer will appear precipitating (4,4 '-diaminodiphenyl-methane) precipitation.
It is analyzed from the indices of above embodiments, comparative example, application examples, and application comparative example, it is sufficient to prove this hair
The fusing point of the low mixture of bismaleimide of bright preparation method preparation is lower than the fusing point of respective pure compound；It is formed
Eutectic mixture structural regularity reduces, and the dissolubility in Bismaleimides resin pre-polymer increases, bismaleimide
The service life of Bismaleimides resin pre-polymer is extended without Precipitation with standing time in resin prepolymer.In addition,
The present invention can be according to the Bismaleimides resin pre-polymer performance indicator requirement of final required different performance, and then determines
Target product --- the technical requirement of the low mixture of bismaleimide sets each two amination in diamine mixture
The amount of monomer adduct passes through aromatic diamine and aliphatic diamine or/and alicyclic according to the performance indicator demand of target product
The low mixture of bismaleimide of different performance is prepared in the control of diamines additional amount.
It should be noted that Bismaleimides resin pre-polymer of the invention, it can be by span prepared by the present invention come acyl
The low mixture of imines and diallyl bisphenol are prepared using solvent method or fusion method；It can also be by prepared by the present invention
The low mixture of bismaleimide and diamines or diamine compound are prepared using fusion method.
When fusion method prepares Bismaleimides resin pre-polymer, reaction vessel selects Bitruder, control reaction
Temperature and extruded velocity react more uniform, continuity method may be implemented and uninterruptedly produce, stable product quality and production efficiency
Significantly promoted.
Bismaleimides resin pre-polymer is by the low mixture of bismaleimide and diallyl bisphenol using molten
When prepared by agent method or fusion method, diallyl bisphenol can be the diallyl bisphenol of prior art preparation, be also possible to by
The diallyl bisphenol of improved technique preparation, the technique of improved diallyl bisphenol is by bisphenol a diallyl ether lazy
Property dicyandiamide solution in carry out Claisen rearrangement reaction preparation；Atent solvent dissolves each other with bisphenol a diallyl ether；Atent solvent
Boiling point is 200~205 DEG C；Atent solvent includes gamma-butyrolacton and N-Methyl pyrrolidone.Two allyls of improved technique preparation
Base bisphenol-A has higher quality.
Finally, being illustrated to mentality of designing of the invention:
Mentality of designing of the invention is to find bimaleimide resin pre-polymerization based on the research to bismaleimide resin polymer
The problem of object preparation process, and then synthetic method of the invention is designed, it is low total to obtain bismaleimide of the invention
Melt mixture.
It finds under study for action, the problem of Bismaleimides resin pre-polymer preparation process has:
(1) solvent system
Due to the bismaleimide monomer of aromatic structure fusing point with higher, dissolubility in organic solvent compared with
It is small, in Bismaleimides resin pre-polymer preparation process, reach the A stage (by the prepolymerization reaction under certain condition, resin
System forming transparency liquid or solid state with certain softening point, the stage are known as the A stage of resin) stability of resin is very
Difference, during resin storage, span monomer is easy to be precipitated from Bismaleimides resin pre-polymer, so that the prepolymer
It can not normal use.It is analyzed from reaction mechanism, span monomer becomes liquid from solid-state during the reaction, mainly due to monomer
Lattice structure variation is chemically reacted with motive powers such as hydrogen bonds between, prepolymer and prepolymer, between prepolymer and solvent
Between balance caused by, i.e., Bismaleimides resin pre-polymer itself is a be in relative equilibrium Unstable Systems,
When slight variation occurs for external condition, it is possible to break the balance between motive power, above-mentioned deposited phenomenon occurs.
This is one of the main technique reason that Bismaleimides resin pre-polymer application is restricted.
(2) solvent-free system
It is pre- in bimaleimide resin in order to keep Bismaleimides resin pre-polymer that there is lower melt viscosity
In polymers preparation process, the degree chemically reacted is more shallow, and A stage condition has not been reached yet, and maintains the saturating of prepolymer system
Bright homogeneous state is even more the i.e. shakiness of Bismaleimides resin pre-polymer based on the van der Waals interaction between each compound
It is qualitative more serious, it is higher to the storage condition requirement of resin prepolymer, generally placed at low temperature (0 DEG C of ﹤), it is double to prevent
The precipitation of horse monomer.Even so, it is also difficult to guarantee the stability of resin prepolymer, so the validity period of resin prepolymer is all non-
It is often short.
In conclusion it is double in system for causing the crucial factor that span monomer is precipitated in Bismaleimides resin pre-polymer
Motive power balance between horse monomer is caused by destroying, therefore a kind of bismaleimide according to the present invention is low total
Motive power between melting the low mixture of bismaleimide obtained by preparation method of mixture and making obtains very
It balances well.
The above content is a further detailed description of the present invention in conjunction with specific preferred embodiments, and it cannot be said that
Specific implementation of the invention is only limited to these instructions.For those of ordinary skill in the art to which the present invention belongs, exist
Under the premise of not departing from present inventive concept, a number of simple deductions or replacements can also be made, all shall be regarded as belonging to of the invention
Protection scope.
Claims (10)
1. a kind of preparation method of the low mixture of bismaleimide, which is characterized in that the bismaleimide is low total
Melt mixture and is made by maleic anhydride and diamine mixture by synthetic reaction；Wherein the diamine mixture includes two kinds
Or two or more diamine compounds, and at least contain a kind of aromatic diamine in two or more diamine compound；It is described
The molecular structure of each diamine compound is different in diamine mixture.
2. preparation method according to claim 1, which is characterized in that the diamine compound further include aliphatic diamine and
Alicyclic diamine.
3. preparation method according to claim 1, which is characterized in that the method for the synthetic reaction is that hot closed loop is homogeneous
Method.
4. preparation method according to claim 1, which is characterized in that specifically includes the following steps:
Step (1) is added to by toluene and to catalyst toluenesulfonic acid equipped with agitating device, temperature measuring equipment and reflux condensate device
The first container in, then the maleic anhydride in the first container is stirred at room temperature dissolution, obtains maleic anhydride
Lysate；
Toluene and n,N-Dimethylformamide are added in second container, institute are then added in the second container by step (2)
Diamine mixture is stated, stirring and dissolving at a temperature of 40~50 DEG C obtains two amine solutions；
The maleic anhydride lysate is warming up to reflux temperature under agitation, then instills described two by step (3)
Amine solution is reacted, and the water for reacting generation is constantly excluded from reflux condenser bottom, and the reaction time is 4~8h；
System after reaction is cooled to 70~85 DEG C by step (4), is then added water washing 3~5 times under agitation,
So that solution is mutually kept neutral state, obtains the solution containing the low mixture of bismaleimide；
The solution containing the low mixture of bismaleimide is put into crystallizer, in 5~15 DEG C of temperature by step (5)
The low mixture crude product of bismaleimide is precipitated in the lower crystallization of degree；
Step (6) will obtain the bismaleimide after the low mixture crude product filtering of the bismaleimide, drying
The low mixture of amine.
5. the preparation method according to claim 4, which is characterized in that the maleic anhydride and the diamine mixture
Molar ratio be (2.1~2.3): 1.
6. preparation method according to claim 5, which is characterized in that the amount of each diamine compound in the diamine mixture
It is determined according to the technical requirement of the low mixture of the bismaleimide.
7. a kind of low mixture of bismaleimide, which is characterized in that the low mixture of the bismaleimide by
Described in any item preparation methods of claim 1~6 are prepared.
8. a kind of Bismaleimides resin pre-polymer, which is characterized in that the Bismaleimides resin pre-polymer is by mixing
Solvent, diallyl bisphenol and the low mixture of bismaleimide as claimed in claim 7 are prepared by solvent method
At.
9. Bismaleimides resin pre-polymer according to claim 8, which is characterized in that the mixed solvent is by the third two
Alcohol monomethyl ether and dioxane are formed by the mass ratio of 3:1.
10. a kind of Bismaleimides resin pre-polymer, which is characterized in that the Bismaleimides resin pre-polymer is by diene
Propyl bisphenol-A and the low mixture of bismaleimide as claimed in claim 7 are prepared by fusion method.
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Cited By (1)
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| CN110894295A (en) * | 2019-10-23 | 2020-03-20 | 广东同宇新材料有限公司 | Polyether maleimide resin and synthetic method thereof |
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