CN115895257A - Method for improving surface quality of bismaleimide resin cured product - Google Patents
Method for improving surface quality of bismaleimide resin cured product Download PDFInfo
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- CN115895257A CN115895257A CN202211548878.XA CN202211548878A CN115895257A CN 115895257 A CN115895257 A CN 115895257A CN 202211548878 A CN202211548878 A CN 202211548878A CN 115895257 A CN115895257 A CN 115895257A
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- 229920005989 resin Polymers 0.000 title claims abstract description 133
- 239000011347 resin Substances 0.000 title claims abstract description 133
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 title claims abstract description 118
- 229920003192 poly(bis maleimide) Polymers 0.000 title claims abstract description 111
- 238000000034 method Methods 0.000 title claims abstract description 42
- 239000000654 additive Substances 0.000 claims abstract description 31
- 230000000996 additive effect Effects 0.000 claims abstract description 31
- 238000001723 curing Methods 0.000 claims description 31
- 238000002156 mixing Methods 0.000 claims description 16
- -1 diallyl phenyl compound Chemical class 0.000 claims description 11
- WOCGGVRGNIEDSZ-UHFFFAOYSA-N 4-[2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical compound C=1C=C(O)C(CC=C)=CC=1C(C)(C)C1=CC=C(O)C(CC=C)=C1 WOCGGVRGNIEDSZ-UHFFFAOYSA-N 0.000 claims description 9
- IPJGAEWUPXWFPL-UHFFFAOYSA-N 1-[3-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC(N2C(C=CC2=O)=O)=C1 IPJGAEWUPXWFPL-UHFFFAOYSA-N 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 6
- SJLLJZNSZJHXQN-UHFFFAOYSA-N 1-dodecylpyrrole-2,5-dione Chemical compound CCCCCCCCCCCCN1C(=O)C=CC1=O SJLLJZNSZJHXQN-UHFFFAOYSA-N 0.000 claims description 5
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 claims description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 4
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims description 4
- AQGZJQNZNONGKY-UHFFFAOYSA-N 1-[4-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=C(N2C(C=CC2=O)=O)C=C1 AQGZJQNZNONGKY-UHFFFAOYSA-N 0.000 claims description 3
- IKFPAKYBSYICFK-UHFFFAOYSA-N 1-[4-(4-propylphenoxy)phenyl]pyrrole-2,5-dione Chemical compound C1=CC(CCC)=CC=C1OC1=CC=C(N2C(C=CC2=O)=O)C=C1 IKFPAKYBSYICFK-UHFFFAOYSA-N 0.000 claims description 3
- KIKBJYQCJJXCBZ-UHFFFAOYSA-N 1-octylpyrrole-2,5-dione Chemical compound CCCCCCCCN1C(=O)C=CC1=O KIKBJYQCJJXCBZ-UHFFFAOYSA-N 0.000 claims description 3
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 claims description 3
- VMSIYTPWZLSMOH-UHFFFAOYSA-N 2-(dodecoxymethyl)oxirane Chemical compound CCCCCCCCCCCCOCC1CO1 VMSIYTPWZLSMOH-UHFFFAOYSA-N 0.000 claims description 3
- BLHDYAXSQWGYSM-UHFFFAOYSA-N 3-octadecylpyrrole-2,5-dione Chemical compound CCCCCCCCCCCCCCCCCCC1=CC(=O)NC1=O BLHDYAXSQWGYSM-UHFFFAOYSA-N 0.000 claims description 3
- VEPKQEUBKLEPRA-UHFFFAOYSA-N VX-745 Chemical compound FC1=CC(F)=CC=C1SC1=NN2C=NC(=O)C(C=3C(=CC=CC=3Cl)Cl)=C2C=C1 VEPKQEUBKLEPRA-UHFFFAOYSA-N 0.000 claims description 3
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 claims description 3
- 229940065472 octyl acrylate Drugs 0.000 claims description 3
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 claims description 3
- PSGSIXPTLRADTD-UHFFFAOYSA-N prop-2-enyl undecanoate Chemical compound CCCCCCCCCCC(=O)OCC=C PSGSIXPTLRADTD-UHFFFAOYSA-N 0.000 claims description 3
- LQZUVUANAHQVJU-UHFFFAOYSA-N 4-nonan-5-yl-1-oxidopyridin-1-ium Chemical compound CCCCC(CCCC)C1=CC=[N+]([O-])C=C1 LQZUVUANAHQVJU-UHFFFAOYSA-N 0.000 claims description 2
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 230000037303 wrinkles Effects 0.000 abstract description 22
- 239000011159 matrix material Substances 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 6
- 238000005266 casting Methods 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 229920001187 thermosetting polymer Polymers 0.000 abstract description 2
- 239000011248 coating agent Substances 0.000 abstract 1
- 125000001931 aliphatic group Chemical group 0.000 description 22
- 238000010438 heat treatment Methods 0.000 description 21
- 239000002344 surface layer Substances 0.000 description 13
- 230000001590 oxidative effect Effects 0.000 description 8
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- FZENGILVLUJGJX-NSCUHMNNSA-N (E)-acetaldehyde oxime Chemical compound C\C=N\O FZENGILVLUJGJX-NSCUHMNNSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000003384 small molecules Chemical group 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000011241 protective layer Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical group O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 1
- BEQQRHFABVAUTH-UHFFFAOYSA-N 2-methylidenepentadecanoic acid Chemical compound CCCCCCCCCCCCCC(=C)C(O)=O BEQQRHFABVAUTH-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000011157 advanced composite material Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
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- 239000002131 composite material Substances 0.000 description 1
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- 238000002715 modification method Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920000090 poly(aryl ether) Polymers 0.000 description 1
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Abstract
The invention provides a method for improving the surface quality of a bismaleimide resin cured substance, belonging to the technical field of thermosetting resins. According to the invention, the active additive containing the flexible fatty chain is added into the bismaleimide resin matrix, so that the surface wrinkle phenomenon caused by uneven curing shrinkage of the bismaleimide resin is effectively eliminated, the surface quality of the bismaleimide resin cured product is improved, and the application of the bismaleimide resin in a high-temperature resistant coating and a high-temperature resistant casting body is facilitated.
Description
Technical Field
The invention belongs to the technical field of thermosetting resin, and particularly relates to a method for improving the surface quality of a bismaleimide resin cured product.
Background
The allyl compound copolymerization modified bismaleimide resin is the most successful modification method at present, and a cured product of the resin has the characteristics of excellent heat resistance, radiation resistance, humidity resistance and the like, has excellent processing property similar to that of epoxy resin, and can be widely applied to the fields of aerospace, machinery, electronics and the like as advanced composite material matrix resin and high-temperature adhesive. However, most of allyl compound modified bismaleimide resins have a surface layer that rapidly gels to form a film during the curing process, and then wrinkles are generated on the surface of a cured resin due to uneven shrinkage during the curing process of the resin, which is extremely unfavorable for the application of bismaleimide resins to high temperature resistant coatings and high temperature resistant castings. The reason why the surface wrinkles of the allyl compound-modified bismaleimide resin are generated is hardly reported in the literature, and it is likely that the oxidative polymerization of the surface layer of the resin promotes the curing reaction of the surface layer, resulting in uneven internal and external curing shrinkage.
At present, researches on bismaleimide resin are mainly focused on synthesis of novel bismaleimide resin, toughening modification of bismaleimide resin and performance research of composite material thereof, and few researches on surface quality of bismaleimide resin are solved. Chinese invention patent CN103193990A discloses a method for eliminating skinning during bismaleimide resin curing and a resin compound, wherein the problem of surface wrinkles of the bismaleimide resin is effectively eliminated by adding polyarylether thermoplastic resin rich in allyl reactive groups into the bismaleimide resin, but the thermoplastic additive has high melting point and high viscosity, and the addition amount is too large (the mass fraction is more than or equal to 10%), which can cause the viscosity of the bismaleimide resin to be increased violently, and increase the difficulty in the molding process. Chinese patent No. 103554912A discloses a method for reducing the curing temperature of bismaleimide resin and preventing skinning and modified resin, wherein a small amount of ketoxime or aldoxime substance is added into the bismaleimide resin as an antioxidant to inhibit the oxidative polymerization of a surface layer, so that the surface unevenness phenomenon during curing of the bismaleimide resin can be effectively improved, but the ketoxime or aldoxime substance additive cannot be connected into a cross-linking network of the bismaleimide resin to form impurities in the cross-linking network, so that the mechanical property of a resin system is influenced, the bismaleimide resin is high-temperature resistant resin, the ketoxime or aldoxime substance additive is small molecule, and the ketoxime or aldoxime substance additive is easy to generate thermal decomposition at a higher temperature, so that the thermal stability of the resin is reduced.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a method for improving the surface quality of a cured bismaleimide resin, which can eliminate the surface wrinkle phenomenon caused by the uneven curing shrinkage of the bismaleimide resin and improve the surface quality of the cured bismaleimide resin by adding a reactive additive containing a flexible aliphatic chain to a bismaleimide resin matrix.
The invention provides a method for improving the surface quality of a bismaleimide resin condensate, which comprises the following steps:
the reactive additive containing flexible fatty chains is mixed with the bismaleimide resin.
Preferably, the bismaleimide resin includes:
bismaleimides and diallylphenyl compounds.
Preferably, the weight content of the bismaleimide in the bismaleimide resin is 30-65%;
the mass content of the diallyl phenyl compound in the bismaleimide resin is 35-70%.
Preferably, the reactive additive containing flexible fatty chains is selected from one or more of 2, 3-epoxypropyl butyl ether, 1-butylamine, octyl acrylate, 1-octylamine, N-N-octylmaleimide, allyl undecanoate, 1-dodecylamine, N-dodecylmaleimide, 2-tridecylacrylate, hexadecyl acrylate, octadecylmaleimide, N-octadecylglycidyl ether, stearyl amine and lauryl glycidyl ether.
Preferably, the mass of the flexible fatty chain-containing active additive is 0.5-7% of that of the bismaleimide resin.
Preferably, the bismaleimide is one or more selected from 4,4' -methylenebis (N-phenylmaleimide), N, N- (4-methyl-1, 3-phenylene) bismaleimide, N, N ' - (1, 3-phenylene) bismaleimide, 2-bis [4- (4-maleimidophenoxy) phenyl ] propane and N, N ' - (1, 4-phenylene) bismaleimide.
Preferably, the diallyl phenyl compound is one or more selected from 2,2 '-diallyl bisphenol A, bisphenol A bis-diallyl ether and 3,3' -diallyl bisphenol S.
Preferably, the mixing temperature is 90-140 ℃; the mixing time is 5 min-30 min.
Preferably, the resin further comprises, after mixing:
the resin is cured.
Preferably, the method of curing the resin comprises:
raising the temperature to 150-170 ℃ at a heating rate of 0.1-5 ℃/min, keeping the temperature for 0.5-3 h, raising the temperature to 180-200 ℃ at a heating rate of 0.1-5 ℃/min, keeping the temperature for 0.5-4 h, raising the temperature to 230-260 ℃ at a heating rate of 0.1-5 ℃/min, keeping the temperature for 0-8 h, and lowering the temperature to below 60 ℃ at a cooling rate of 0.1-5 ℃/min after curing.
The invention provides a method for improving the surface quality of a bismaleimide resin condensate, which can effectively inhibit the oxidative polymerization of a bismaleimide resin surface layer by adding a flexible aliphatic chain-containing active additive, prevent the surface layer from gelling and filming in advance and further eliminate the surface wrinkle phenomenon caused by uneven curing shrinkage of the bismaleimide resin. Because the solubility parameters of benzene rings and strong polar succinimide skeleton of the aliphatic chain and the bismaleimide resin are greatly different, the compatibility is poor, the structure of the aliphatic chain is regular and flexible, and the aliphatic chain has high activity, and can spontaneously gather at the interface of a resin matrix and air thermodynamically to form a protective layer of a flexible aliphatic chain, so that the contact of oxygen and the bismaleimide resin is blocked, and the oxidative polymerization of the surface layer of the bismaleimide resin is inhibited. The method provided by the invention has high universality and is suitable for modification of various bismaleimide resins. In addition, the active additive containing the flexible aliphatic chain is a small molecule, has low viscosity, can be dissolved in the bismaleimide resin system, does not increase the viscosity of the bismaleimide resin system, and does not cause the process performance change of the bismaleimide resin system. The reactive additive containing flexible fatty chains has reactive groups that can react with the bismaleimide resin matrix, thus enabling the grafting of flexible fatty chains into the host cross-linked network. The mass fraction of the active additive containing the flexible fatty chain in the bismaleimide resin system is not more than 7 percent, so that the active additive has little influence on the heat resistance, the heat stability and other properties of the bismaleimide resin.
Drawings
FIG. 1 is a schematic surface view of a cured product prepared in examples of the present invention and comparative examples.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a method for improving the surface quality of a bismaleimide resin condensate, which comprises the following steps:
the reactive additive containing flexible fatty chains is mixed with the bismaleimide resin.
In the present invention, the reactive additive containing a flexible fatty chain is preferably selected from one or more of 2, 3-epoxypropylbutyl ether, 1-butylamine, octyl acrylate, 1-octylamine, N-N-octylmaleimide, allylundecanoate, 1-dodecylamine, N-dodecylmaleimide, tridecyl 2-acrylate, hexadecyl acrylate, octadecylmaleimide, N-octadecylglycidyl ether, stearyl amine, lauryl glycidyl ether.
In the present invention, the bismaleimide resin preferably includes:
bismaleimides and diallylphenyl compounds.
In the present invention, the bismaleimide is preferably one or more selected from 4,4' -methylenebis (N-phenylmaleimide), N- (4-methyl-1, 3-phenylene) bismaleimide, N ' - (1, 3-phenylene) bismaleimide, 2-bis [4- (4-maleimidophenoxy) phenyl ] propane, and N, N ' - (1, 4-phenylene) bismaleimide.
In the present invention, the diallylphenyl compound is preferably selected from one or more of 2,2 '-diallylbisphenol a, bisphenol a bis-diallylether, and 3,3' -diallylbisphenol S.
In the invention, the weight content of the bismaleimide in the bismaleimide resin is preferably 30-65%, and more preferably 40-60%; the mass content of the diallylphenyl compound in the bismaleimide resin is preferably 35% to 70%, more preferably 40% to 60%.
In the present invention, the mass of the reactive additive containing a flexible aliphatic chain is preferably 0.5 to 7% of the mass of the bismaleimide resin, and more preferably 2 to 5%.
In the present invention, the mixing is preferably mixed to a homogeneous phase; the mixing is preferably carried out under stirring; the mixing temperature is preferably 90-140 ℃, and more preferably 100-130 ℃; the mixing time is preferably 5 to 30min, more preferably 10 to 25min.
In the present invention, the method of mixing preferably comprises:
carrying out first mixing on bismaleimide and a diallyl phenyl compound to obtain resin;
and carrying out second mixing on the resin and the active additive containing the flexible fatty chain to obtain the modified resin.
In the present invention, it is preferable that the resin mixture further includes:
the resin is cured.
In the present invention, it is preferable that the modified resin is cured; the method of curing the resin preferably comprises:
after the temperature is raised to the first temperature at the first speed and is kept constant for the first time, the temperature is raised to the second temperature at the second speed and is kept constant for the second time, then the temperature is raised to the third temperature at the third speed and is kept constant for the third time, and then the temperature is lowered to the fourth temperature at the fourth speed.
In the present invention, the first speed is preferably 0.1 ℃/min to 5 ℃/min, more preferably 0.5 ℃/min to 4 ℃/min, more preferably 1 ℃/min to 3 ℃/min, and most preferably 2 ℃/min; the first temperature is preferably 150 ℃ to 170 ℃, more preferably 155 ℃ to 165 ℃, and most preferably 160 ℃; the first time is preferably 0.5 to 3 hours, more preferably 1 to 2.5 hours, and most preferably 1.5 to 2 hours.
In the present invention, the second speed is preferably 0.1 ℃/min to 5 ℃/min, more preferably 0.5 ℃/min to 4 ℃/min, more preferably 1 ℃/min to 3 ℃/min, and most preferably 2 ℃/min; the second temperature is preferably 180 ℃ to 200 ℃, more preferably 185 ℃ to 195 ℃, and most preferably 190 ℃; the second time is preferably 0.5h to 4h, more preferably 1h to 3h, most preferably 2h.
In the present invention, the third speed is preferably 0.1 ℃/min to 5 ℃/min, more preferably 0.5 ℃/min to 4 ℃/min, more preferably 1 ℃/min to 3 ℃/min, and most preferably 2 ℃/min; the third temperature is preferably 230 ℃/min to 260 ℃, more preferably 240 ℃/min to 250 ℃, and most preferably 245 ℃; the third time is preferably 0 to 8 hours, more preferably 1 to 7 hours, more preferably 2 to 6 hours, more preferably 3 to 5 hours, and most preferably 4 hours.
In the present invention, the fourth speed is preferably 0.1 ℃/min to 5 ℃/min, more preferably 0.5 ℃/min to 4 ℃/min, more preferably 1 ℃/min to 3 ℃/min, and most preferably 2 ℃/min; the fourth temperature is preferably below 60 ℃.
The invention provides a method for improving the surface quality of a bismaleimide resin condensate, which can effectively inhibit the oxidative polymerization of a bismaleimide resin surface layer by adding a flexible aliphatic chain-containing active additive, prevent the surface layer from gelling and filming in advance and further eliminate the surface wrinkle phenomenon caused by uneven curing shrinkage of the bismaleimide resin. Because the solubility parameters of the benzene ring and the strong polar succinimide skeleton of the aliphatic chain and the bismaleimide resin are different greatly, the compatibility is poor, the structure of the aliphatic chain is regular and flexible, the aliphatic chain has high activity, and can be spontaneously gathered at the interface of a resin matrix and air thermodynamically to form a protective layer of a flexible aliphatic chain, so that the contact of oxygen and the bismaleimide resin is blocked, and the oxidative polymerization of the surface layer of the bismaleimide resin is inhibited. The method provided by the invention has high universality and is suitable for modification of various bismaleimide resins. In addition, the active additive containing the flexible aliphatic chain is a small molecule, has low viscosity, can be dissolved in the bismaleimide resin system, does not increase the viscosity of the bismaleimide resin system, and does not cause the process performance change of the bismaleimide resin system. The reactive additive containing flexible fatty chains has reactive groups that can react with the bismaleimide resin matrix, thus enabling the grafting of flexible fatty chains into the host cross-linked network. The mass fraction of the active additive containing the flexible aliphatic chain in the bismaleimide resin system is not more than 7 percent, so that the active additive has little influence on the heat resistance, the heat stability and other properties of the bismaleimide resin.
Example 1
The bismaleimide adopts 4,4 '-methylene bis (N-phenyl maleimide), the diallyl phenyl compound adopts 2,2' -diallyl bisphenol A, and the mass ratio of the bismaleimide to the diallyl phenyl compound is 65:35, weighing; adding 252g 2,2 '-diallyl bisphenol A into a three-neck flask, heating to 130 ℃, adding 468g 4,4' -methylene bis (N-phenyl maleimide) under the stirring state, preserving the temperature for 20min until the materials are dissolved into a homogeneous phase to obtain bismaleimide resin I, and detecting the viscosity of 678mPa & s at 110 ℃ by a rheometer; and finally, adding 7.2g of 1-dodecylamine into the bismaleimide resin I, wherein the addition amount is 1 percent of the weight of the bismaleimide resin, stirring and mixing for 15min at 110 ℃ to obtain the modified resin I, and detecting the viscosity of 707mPa & s at 110 ℃ by adopting a rheometer.
Curing the modified resin I: heating to 150 ℃ at a heating rate of 3 ℃/min, keeping the temperature for 1h, heating to 200 ℃ at a heating rate of 3 ℃/min, keeping the temperature for 2h, heating to 243 ℃ at a heating rate of 3 ℃/min, keeping the temperature for 6h, cooling to below 60 ℃ at a cooling rate of 5 ℃/min after curing is finished, and obtaining a cured product, wherein as shown in figure 1, the wrinkle phenomenon generated by surface curing shrinkage can be obviously improved, and the surface wrinkle depth is detected by a depth measuring instrument, and the maximum wrinkle depth is 1.13mm.
Example 2
The bismaleimide adopts 4,4' -methylene bis (N-phenyl maleimide) and N, N ' - (1, 3-phenylene) bismaleimide, and is combined according to the mass ratio of 70, and the diallyl phenyl compound adopts 2,2' -diallyl bisphenol A; adding 204g of 2,2' -diallyl bisphenol A into a three-neck flask, heating to 130 ℃, adding 80g of N, N ' - (1, 3-phenylene) bismaleimide under the stirring state, keeping the temperature until the N, N ' - (1, 3-phenylene) bismaleimide is dissolved into a homogeneous phase, then adding 250g of 4,4' -methylenebis (N-phenylmaleimide), keeping the temperature for 20min until the N, N ' -methylenebis (N-phenylmaleimide) is dissolved into the homogeneous phase to obtain bismaleimide resin II, and detecting the viscosity of 433 mPas at 110 ℃ by adopting a rheometer; and finally, adding 13.3g of N-dodecyl maleimide into the bismaleimide resin II, wherein the addition amount of the N-dodecyl maleimide is 2.5 percent of the mass of the bismaleimide resin, stirring and mixing for 20min at 110 ℃ to obtain the modified resin II, and detecting the viscosity of 590mPa & s at 110 ℃ by adopting a rheometer.
Curing the modified resin II: heating to 150 ℃ at a heating rate of 3 ℃/min, keeping the temperature for 1h, heating to 200 ℃ at a heating rate of 3 ℃/min, keeping the temperature for 2h, heating to 243 ℃ at a heating rate of 3 ℃/min, keeping the temperature for 6h, cooling to below 60 ℃ at a cooling rate of 5 ℃/min after curing is finished, and obtaining a cured product, wherein as shown in figure 1, the phenomenon of shrinkage and wrinkling of the surface during curing can be obviously eliminated, the surface is smooth and flat, and the depth of the surface wrinkles is detected by a depth measuring instrument, and the maximum wrinkle depth is 0.57mm.
Example 3
The bismaleimide adopts 4,4' -methylene bis (N-phenyl maleimide) and N, N ' - (1, 3-phenylene) bismaleimide, and is combined according to the mass ratio of 80, and the diallyl phenyl compound adopts 2,2' -diallyl bisphenol A; adding 430g of 2,2' -diallyl bisphenol A into a flask, heating to 130 ℃, adding 106g of N, N ' - (1, 3-phenylene) bismaleimide under the stirring state, preserving the temperature until the bismaleimide is dissolved into a homogeneous phase, then adding 424g of 4,4' -methylenebis (N-phenylmaleimide), preserving the temperature for 20min until the bismaleimide is dissolved into the homogeneous phase to obtain bismaleimide resin III, and detecting the viscosity to be 471mPa & s at 110 ℃ by adopting a rheometer; and finally, adding 48g of stearylamine into the bismaleimide resin III, wherein the addition amount of the stearylamine is 5% of the mass of the bismaleimide resin, stirring and mixing for 20min at 110 ℃ to obtain the modified resin III, and detecting the viscosity of 692mPa & s at 110 ℃ by adopting a rheometer.
Curing the modified resin III: the temperature is raised to 150 ℃ at the heating rate of 3 ℃/min, the temperature is maintained for 1h, then the temperature is raised to 200 ℃ at the heating rate of 3 ℃/min, the temperature is maintained for 2h, then the temperature is raised to 243 ℃ at the heating rate of 3 ℃/min, the temperature is maintained for 6h, after curing is completed, the temperature is lowered to below 60 ℃ at the cooling rate of 5 ℃/min, a cured product is obtained, as shown in figure 1, the phenomenon of surface curing shrinkage wrinkle can be observed to be obviously eliminated, the surface is flat and smooth, the surface has mirror surface gloss, and the surface wrinkle depth is detected by a depth measuring instrument, wherein the maximum wrinkle depth is 0.06mm.
Comparative example 1
The bismaleimide resin II prepared according to the method of example 2, as shown in fig. 1 after curing the bismaleimide resin II according to the conventional curing process (the curing method is the same as example 2), the surface wrinkle phenomenon caused by the curing shrinkage of the resin can be observed, and the surface wrinkle depth is detected by a depth measuring instrument, and the maximum wrinkle depth is 5.37mm.
Comparative example 2
The bismaleimide resin III prepared according to the method of the comparative document 2 is cured according to a conventional curing process (the curing method is the same as that of the example 3), as shown in fig. 1, a surface wrinkle phenomenon caused by the curing shrinkage of the resin can be observed, and a depth measuring instrument is used to detect the depth of the surface wrinkle, wherein the maximum wrinkle depth is 9.69mm.
The invention provides a method for improving the surface quality of a bismaleimide resin condensate, which can effectively inhibit the oxidative polymerization of a bismaleimide resin surface layer by adding a flexible aliphatic chain-containing active additive, prevent the surface layer from gelling and filming in advance and further eliminate the surface wrinkle phenomenon caused by uneven curing shrinkage of the bismaleimide resin. Because the solubility parameters of the benzene ring and the strong polar succinimide skeleton of the aliphatic chain and the bismaleimide resin are different greatly, the compatibility is poor, the structure of the aliphatic chain is regular and flexible, the aliphatic chain has high activity, and can be spontaneously gathered at the interface of a resin matrix and air thermodynamically to form a protective layer of a flexible aliphatic chain, so that the contact of oxygen and the bismaleimide resin is blocked, and the oxidative polymerization of the surface layer of the bismaleimide resin is inhibited. The method provided by the invention has high universality and is suitable for modification of various bismaleimide resins. In addition, the active additive containing the flexible aliphatic chain is a small molecule, has low viscosity, can be dissolved in the bismaleimide resin system, does not increase the viscosity of the bismaleimide resin system, and does not cause the process performance change of the bismaleimide resin system. The reactive additive containing flexible fatty chains has reactive groups that can react with the bismaleimide resin matrix, thus enabling the grafting of flexible fatty chains into the host cross-linked network. The mass fraction of the active additive containing the flexible aliphatic chain in the bismaleimide resin system is not more than 7 percent, so that the active additive has little influence on the heat resistance, the heat stability and other properties of the bismaleimide resin.
While the invention has been described and illustrated with reference to specific embodiments thereof, such description and illustration are not intended to limit the invention. It will be clearly understood by those skilled in the art that various changes in form and details may be made therein without departing from the true spirit and scope of the invention as defined by the appended claims, to adapt a particular situation, material, composition of matter, substance, method or process to the objective, spirit and scope of this application. All such modifications are intended to be within the scope of the claims appended hereto. Although the methods disclosed herein have been described with reference to particular operations performed in a particular order, it should be understood that these operations may be combined, sub-divided, or reordered to form equivalent methods without departing from the teachings of the present disclosure. Accordingly, unless specifically indicated herein, the order and grouping of the operations is not a limitation of the present application.
Claims (10)
1. A method for improving the surface quality of a bismaleimide resin condensate comprises the following steps:
the reactive additive containing flexible fatty chains is mixed with the bismaleimide resin.
2. The method of claim 1, wherein the bismaleimide resin comprises:
bismaleimides and diallylphenyl compounds.
3. The method according to claim 2, wherein the weight content of the bismaleimide in the bismaleimide resin is 30-65%;
the mass content of the diallyl phenyl compound in the bismaleimide resin is 35-70%.
4. The method according to claim 1, wherein the reactive additive containing flexible fatty chains is selected from one or more of 2, 3-epoxypropylbutyl ether, 1-butylamine, octyl acrylate, 1-octylamine, N-octylmaleimide, allylundecanoate, 1-dodecylamine, N-dodecylmaleimide, tridecyl 2-acrylate, hexadecyl acrylate, octadecylmaleimide, N-octadecylglycidyl ether, stearyl amine, lauryl glycidyl ether.
5. The method according to claim 1, wherein the mass of the additive containing a flexible fatty chain reactive agent is 0.5 to 7% of the mass of the bismaleimide resin.
6. The method according to claim 2, wherein the bismaleimide is selected from one or more of 4,4' -methylenebis (N-phenylmaleimide), N, N- (4-methyl-1, 3-phenylene) bismaleimide, N, N ' - (1, 3-phenylene) bismaleimide, 2-bis [4- (4-maleimidophenoxy) phenyl ] propane, and N, N ' - (1, 4-phenylene) bismaleimide.
7. The method according to claim 2, wherein the diallylphenyl compound is selected from one or more of 2,2 '-diallylbisphenol A, bisphenol A bis-diallyl ether, and 3,3' -diallylbisphenol S.
8. The method according to claim 1, wherein the temperature of the mixing is 90 ℃ to 140 ℃ and the time of the mixing is 5min to 30min.
9. The method of claim 1, further comprising, after said mixing:
the resin is cured.
10. The method of claim 9, wherein the resin curing method comprises:
after the temperature is raised to a first temperature at a first speed and is kept constant for a first time, the temperature is raised to a second temperature at a second speed and is kept constant for a second time, the temperature is raised to a third temperature at a third speed and is kept constant for a third time, and then the temperature is lowered to a fourth temperature at a fourth speed;
the first temperature is 150-170 ℃, the second temperature is 180-200 ℃, the third temperature is 230-260 ℃, and the fourth temperature is below 60 ℃.
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| US5003018A (en) * | 1988-04-29 | 1991-03-26 | Basf Aktiengesellschaft | Slurry mixing of bismaleimide resins |
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| CN104327667A (en) * | 2014-10-16 | 2015-02-04 | 宜兴市巨人涂料有限公司 | Preparation method of solvent-free self-leveling iron core covering paint used for wet and dry transformer |
| CN109096442A (en) * | 2018-07-20 | 2018-12-28 | 中国航发北京航空材料研究院 | A kind of method of primary reconstruction toughening modifying bimaleimide resin |
| US20220348718A1 (en) * | 2019-07-30 | 2022-11-03 | Soochow University | Remoldable bismaleimide resin and application thereof |
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| US5003018A (en) * | 1988-04-29 | 1991-03-26 | Basf Aktiengesellschaft | Slurry mixing of bismaleimide resins |
| CN101120027A (en) * | 2005-02-16 | 2008-02-06 | Cytec技术有限公司 | Bismaleimide resin with high temperature thermal stability |
| CN103193990A (en) * | 2013-04-03 | 2013-07-10 | 中国航空工业集团公司北京航空材料研究院 | Method for eliminating surface crust during curing of bismaleimide resin and resin complex |
| CN103554912A (en) * | 2013-11-05 | 2014-02-05 | 中航复合材料有限责任公司 | Method for lowering curing temperature and preventing skinning of bismaleimide resin and modified resin |
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