CN111763323A - Polysiloxane modified tetraallyl compound, thermal-repair bismaleimide resin composition and preparation method - Google Patents
Polysiloxane modified tetraallyl compound, thermal-repair bismaleimide resin composition and preparation method Download PDFInfo
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- 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 68
- 229920003192 poly(bis maleimide) Polymers 0.000 title claims abstract description 61
- -1 Polysiloxane Polymers 0.000 title claims abstract description 39
- 239000011342 resin composition Substances 0.000 title claims abstract description 27
- 150000001875 compounds Chemical class 0.000 title claims abstract description 26
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000178 monomer Substances 0.000 claims description 20
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 14
- 238000005303 weighing Methods 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 claims description 8
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000002390 rotary evaporation Methods 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 claims description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N S-phenyl benzenesulfonothioate Natural products C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims description 2
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 230000035876 healing Effects 0.000 claims 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims 2
- 229920005989 resin Polymers 0.000 abstract description 20
- 239000011347 resin Substances 0.000 abstract description 20
- 229920001187 thermosetting polymer Polymers 0.000 abstract description 4
- 230000035484 reaction time Effects 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 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 description 2
- LSEBTZWHCPGKEF-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)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=C1 LSEBTZWHCPGKEF-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 125000001989 1,3-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([H])C([*:2])=C1[H] 0.000 description 1
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/188—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-O linkages
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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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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5425—Silicon-containing compounds containing oxygen containing at least one C=C bond
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08L79/085—Unsaturated polyimide precursors
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Abstract
The invention provides a polysiloxane modified tetraallyl compound, a thermal repair bismaleimide resin composition and a preparation method thereof, belonging to the technical field of functional thermosetting resins.
Description
Technical Field
The invention belongs to the technical field of functional thermosetting resin, and particularly relates to a polysiloxane modified tetraallyl compound, a thermal repair bismaleimide resin composition and a preparation method thereof.
Background
Bismaleimide (BMI for short in English) belongs to one of thermosetting resins, two ends of the bismaleimide are terminated by active maleimide, and the bismaleimide has an excellent molding process similar to that of epoxy resin, but the temperature resistance of the bismaleimide is far higher than that of epoxy resin, so that the bismaleimide has excellent processing performance and excellent heat resistance, and is widely applied to the fields of aerospace and mechanical electronics. However, since it has a disadvantage that the material exhibits brittleness due to its high crosslinking density as in the case of an epoxy resin cured product, it is likely to cause microcracks in the bismaleimide resin when it is subjected to a continuous load. Further microcracking will eventually lead to structural failure of the material. Thermosetting resins also have the characteristic of being infusible and insoluble, and therefore, are difficult to recycle, and cause great environmental pollution. If the material can be repaired in time at the initial stage of microcrack generation, the use safety and the service life of the material can be improved, and simultaneously, the resources are saved and the environmental pollution is reduced.
Thus, there are two main ways to solve the problems faced by bismaleimide resins. One approach is to toughen bismaleimide resin systems to reduce the likelihood of cracking during use. The other method is to realize self-repairing of the bismaleimide resin system, and the bismaleimide resin system mainly comprises intrinsic self-repairing and external self-repairing. Meanwhile, the research on the bismaleimide toughening and self-repairing system is less, and the bismaleimide resin toughening can cause the heat resistance to be greatly reduced, thereby seriously influencing the use of the bismaleimide resin.
Disclosure of Invention
Aiming at the defects that the existing bismaleimide resin is high in brittleness and cannot realize self-repairing, the invention provides a polysiloxane modified tetraallyl compound, a thermal-repairing bismaleimide resin composition and a preparation method thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a polysiloxane modified tetraallyl compound has the following structural formula:
wherein R is1And R2Is C1-C10 alkyl or aryl; r3Is one of C1-C6 straight-chain alkyl, substituted or unsubstituted C1-C6 branched-chain alkyl and O, S; n is 1 to 30.
A preparation method of a polysiloxane modified tetraallyl compound comprises the following steps: dissolving a diallyl compound in a solvent, adding chlorine-terminated polysiloxane, adding an alkaline substance to absorb HCl, reacting for a period of time at a certain temperature, and performing rotary evaporation by using a rotary evaporator to obtain a polysiloxane modified tetraallyl compound.
Further, the structural formula of the chlorine-terminated polysiloxane is as follows:
wherein R is1And R2Is C1-C10 alkyl or aryl; n is 1 to 30.
Further, the diallyl compound has the following structural formula:
wherein R is3Is one of C1-C6 straight-chain alkyl, substituted or unsubstituted C1-C6 branched-chain alkyl and O, S.
Furthermore, the mol ratio of the chlorine-terminated polysiloxane to the diallyl compound is 1 (2-2.5).
Further, the solvent is one or more of toluene, xylene and tetrahydrofuran, and toluene is preferred.
Further, the alkaline substance is one or more of pyridine and triethylamine.
Further, the reaction temperature is 80-120 ℃, and the reaction time is 2-4 h.
The thermal repair bismaleimide resin composition comprises, by mass, 100 parts of bismaleimide monomers, 60-100 parts of tetraallyl compounds and 1-5 parts of alkaline catalysts.
Further, the bismaleimide monomer is one or more of diphenylmethane diamine type, diphenyl ether diamine type, diphenyl sulfone diamine type, m-phenylene and p-phenylene type.
Further, the basic catalyst is one or more of tetramethylammonium hydroxide, lithium hydroxide, sodium hydroxide, potassium hydroxide and cesium hydroxide.
A preparation method of a thermal-repair bismaleimide resin composition comprises the following steps:
(1) weighing 100 parts of bismaleimide monomer and 60-100 parts of tetraallyl compound according to the mass parts, mixing the bismaleimide monomer and the tetraallyl compound, carrying out prepolymerization for 15-40 min at the temperature of 110-130 ℃, and cooling to room temperature to obtain a prepolymer;
(2) and weighing 1-5 parts of an alkaline catalyst, and adding the alkaline catalyst into the prepolymer in a three-roll grinder to obtain the bismaleimide resin composition.
The bismaleimide cured product with the thermal self-repairing function is prepared by curing the thermal repairing bismaleimide resin composition.
Compared with the prior art, the invention has the following advantages:
(1) the siloxane modified tetraallyl compound provided by the invention has the advantages of wide raw material source, low cost and simple preparation process, and is suitable for large-scale preparation;
(2) according to the invention, as the polysiloxane is introduced to realize the tetraallyl and the alkaline catalyst, the flexibility of the polysiloxane chain is high, and the toughness of the bismaleimide resin can be improved; meanwhile, the crosslinking density is greatly improved due to the tetraallyl compound, and the heat resistance is basically kept unchanged. In addition, the silicon-oxygen bond can generate reversible reaction under alkaline condition, is a dynamic covalent bond, can realize the thermal self-repair of the bismaleimide resin, can keep a certain mechanical property, can realize the self-repair, and can improve the toughness and the heat resistance of the bismaleimide resin. Compared with the traditional toughening, the self-repairing can be realized; compared with the common self-repairing resin, the toughness of the bismaleimide resin is greatly improved, and meanwhile, the heat resistance is not reduced.
Drawings
FIG. 1 is a graph representing self-repair performance.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be noted that these examples are only for describing the present invention and are not intended to limit the scope of the present invention. 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.
Example 1 Synthesis of polysiloxane modified bismaleimide monomer
1mol of diallyl bisphenol A was charged into a 1L three-necked flask equipped with a mechanical stirrer, a thermometer and a reflux condenser and dissolved in toluene, and 0.5mol of a chlorine-terminated polysiloxane (wherein R is1And R2Methyl n ═ 1), adding alkaline substance pyridine, stirring and reacting for 2h at 100 ℃, and performing rotary evaporation by a rotary evaporator to obtain the polysiloxane modified tetraallyl compound.
Example 2 Synthesis of polysiloxane modified bismaleimide monomers
The procedure of example 1 was followed except that the number of linkages n in the chlorine-terminated polysiloxane was 40, pyridine and triethylamine were added as basic substances, and the other proportions, temperatures and reaction times were the same.
Example 3 Synthesis of polysiloxane modified bismaleimide monomers
The proportions, temperatures and reaction times in this example were the same as in the preparation of example 1, except that the number of linkages n in the chlorine-terminated polysiloxane was chosen to be 5.
Example 4 Synthesis of polysiloxane-modified bismaleimide monomers
In this example except that R is selected from the group consisting of chlorine-terminated polysiloxanes3The structure is-O-, the solvent is changed into a mixture of toluene and xylene, and other proportions, temperatures and reaction times are the same as those of the preparation method of example 3.
Example 5 Synthesis of polysiloxane-modified bismaleimide monomer
In this example, the proportions, temperatures and reaction times were the same as those in the production method of example 3 except that the amount of allyl bisphenol A used was changed to 1.25 mol.
Example 6 Synthesis of polysiloxane-modified bismaleimide monomer
In this example, the proportions, temperatures and reaction times were the same as those in example 3 except that the amount of allyl bisphenol A used was changed to 1.1mol, the reaction temperature was changed to 120 ℃ and the reaction time was changed to 3 hours.
Example 7 Synthesis of polysiloxane-modified bismaleimide monomer
In this example, the proportions, temperatures and reaction times were the same as in the preparation method of example 3, except that the reaction temperature was changed to 80 ℃ and the reaction time was changed to 4 hours.
EXAMPLE 8 preparation of Heat-recoverable bismaleimide resin composition
(1) 100g of diphenylmethane diamine bismaleimide monomer and 80g of the tetraallyl compound prepared in example 3 were weighed, mixed, prepolymerized at 110 ℃ for 40min, and cooled to room temperature to obtain a prepolymer.
(2) Weighing 1g of potassium hydroxide, and adding an alkaline catalyst into the prepolymer in the step (1) in a three-roll grinder to obtain the bismaleimide resin composition.
Example 9 preparation of a Heat-curable bismaleimide resin composition
(1) 100g of diphenylmethane diamine bismaleimide monomer and 60g of the tetraallyl compound prepared in example 3 were weighed, mixed, prepolymerized at 130 ℃ for 15min, and cooled to room temperature to obtain a prepolymer.
(2) Weighing 3g of potassium hydroxide, and adding an alkaline catalyst into the prepolymer in the step (1) in a three-roll grinder to obtain the bismaleimide resin composition.
Example 10 preparation of a Heat-curable bismaleimide resin composition
(1) 100g of diphenylmethane diamine bismaleimide monomer and 100g of the tetraallyl compound prepared in example 3 were weighed, mixed, prepolymerized at 120 ℃ for 25min, and cooled to room temperature to obtain a prepolymer.
(2) Weighing 5g of potassium hydroxide, and adding an alkaline catalyst into the prepolymer in the step (1) in a three-roll grinder to obtain the bismaleimide resin composition.
EXAMPLE 11 preparation of Heat-recoverable bismaleimide resin composition
(1) 100g of diphenylmethane diamine bismaleimide monomer and 80g of the tetraallyl compound prepared in example 3 were weighed, mixed, prepolymerized at 110 ℃ for 15min, and cooled to room temperature to obtain a prepolymer.
(2) Weighing 1g of sodium hydroxide, and adding an alkaline catalyst into the prepolymer in the step (1) in a three-roll grinder to obtain the bismaleimide resin composition.
Comparative example 1
(1) Weighing 100g of diphenylmethane diamine bismaleimide monomer and 80g of diallyl bisphenol A, mixing the two, carrying out prepolymerization for 15min at the temperature of 110 ℃, and cooling to room temperature to obtain the prepolymer.
(2) Weighing 1g of potassium hydroxide, and adding an alkaline catalyst into the prepolymer in the step (1) in a three-roll grinder to obtain the bismaleimide resin composition.
Comparative example 2
100g of diphenylmethane diamine bismaleimide monomer and 80g of the tetraallyl compound prepared in example 3 were weighed, mixed, prepolymerized at 110 ℃ for 15min, and cooled to room temperature to obtain a prepolymer. The composition is obtained directly.
Curing process of bismaleimide resin composition: 180 ℃/1h +200 ℃/2h +250 ℃/3 h.
Characterization of cured product performance of bismaleimide resin, namely, the toughness of the cured product of the resin is characterized by impact strength, the impact strength is selected from a simple beam impact tester to carry out a non-notch impact test, the size of a sample is 80mm × 10mm × 4mm, and the characterization of self-repairing performance is shown in figure 1According to GB7124-2008 "adhesive tensile shear strength test method (metal to metal)", the adhesive strength of resin is measured by an instrument, the self-repairing performance is shown in the figure, a mechanical performance test is carried out by using single lap shearing, the repairing rate is calculated by the ratio of the shear strength before and after repairing, wherein u represents the tensile force. The parameters are set as the loading speed of 2mm/min, each group of samples is 5, the lapping length of the samples is 12.5 +/-0.5 mm, and the lapping width is 25 +/-1 mm. The tensile shear strength of the bismaleimide resin composition measured by a universal tester is S0Continuously lapping the damaged samples together, carrying out heat treatment at 250 ℃ for 6-10h, carrying out 1 single lapping shearing experiment on the treated samples, wherein the strength is S1Self repair efficiency η1＝S1/S0The efficiency of the subsequent four-time repair is ηx＝Sx/S0. The compositions prepared in examples 13 to 17 and comparative examples 1 to 2 were tested and compared in their properties as shown in the following tables 1 to 2:
TABLE 1
TABLE 2
| Example 8 | Example 10 | Comparative example 1 | Comparative example 2 | |
| η1(％) | 93 | 94 | 1.3 | 1.6 |
| η2(％) | 91 | 96 | 1.0 | 1.3 |
| η3(％) | 94 | 93 | 1.4 | 1.1 |
| η4(％) | 90 | 95 | 1.2 | 1.0 |
As can be seen from tables 1-2, the thermal-repair bismaleimide resin composition prepared by the invention has high impact strength and shear strength S1Obviously high self-repairing efficiency η1High performance.
Claims (10)
1. A polysiloxane modified tetraallyl compound is characterized in that the structural formula is as follows:
wherein R is1And R2Is C1-C10 alkyl or aryl; r3Is C1-C6 straight-chain alkyl, substituted or unsubstituted C1-C6 branched-chain alkyl,O, S; n is 1 to 30.
2. A preparation method of a polysiloxane modified tetraallyl compound is characterized by comprising the following steps: dissolving a diallyl compound in a solvent, adding chlorine-terminated polysiloxane, adding an alkaline substance to absorb HCl, heating to 80-120 ℃, reacting for 2-4 h, and performing rotary evaporation to obtain a polysiloxane modified tetraallyl compound;
the structural formula of the chlorine-terminated polysiloxane is as follows:
wherein R is1And R2Is C1-C10 alkyl or aryl; n is 1-30;
the diallyl compound has the following structural formula:
wherein R is3Is one of C1-C6 straight-chain alkyl, substituted or unsubstituted C1-C6 branched-chain alkyl and O, S.
3. The method for producing a polysiloxane-modified tetraallyl compound according to claim 2, wherein the molar ratio of the chlorine-terminated polysiloxane to the diallyl compound is 1 (2 to 2.5).
4. The method of claim 2, wherein the solvent is at least one of toluene, xylene, and tetrahydrofuran.
5. The method for producing a polysiloxane-modified tetraallyl compound according to claim 2, wherein the basic substance is at least one of pyridine and triethylamine.
6. A thermal-repair bismaleimide resin composition which comprises, by mass, 60 to 100 parts of the polysiloxane-modified tetraallyl compound according to claim 1, 100 parts of a bismaleimide monomer, and 1 to 5 parts of a basic catalyst.
7. The heat-recoverable bismaleimide resin composition of claim 6 wherein the bismaleimide monomer is at least one of a diphenylmethane diamine type, a diphenyloxide diamine type, a diphenylsulfone diamine type, a meta phenylene type, and a para phenylene type.
8. The thermally healing bismaleimide resin composition of claim 6 wherein the basic catalyst is at least one of tetramethylammonium hydroxide, lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide.
9. The preparation method of the thermal-repair bismaleimide resin composition is characterized by comprising the following steps:
(1) weighing 60-100 parts of the polysiloxane modified tetraallyl compound and 100 parts of bismaleimide monomer according to the claim 1 in parts by weight, mixing the two, carrying out prepolymerization for 15-40 min at the temperature of 110-130 ℃, and cooling to room temperature to obtain a prepolymer;
(2) and weighing 1-5 parts of an alkaline catalyst, and adding the alkaline catalyst into the prepolymer in a grinder to obtain the thermal-repair bismaleimide resin composition.
10. A cured bismaleimide product having a thermal self-healing function, which is obtained by curing the thermally healing bismaleimide resin composition according to any one of claims 6 to 8.
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