CN109180947A - One kind modified bismaleimide resin containing ethenyl cage model sesquialter siloxane and preparation method - Google Patents
One kind modified bismaleimide resin containing ethenyl cage model sesquialter siloxane and preparation method Download PDFInfo
- Publication number
- CN109180947A CN109180947A CN201810818834.1A CN201810818834A CN109180947A CN 109180947 A CN109180947 A CN 109180947A CN 201810818834 A CN201810818834 A CN 201810818834A CN 109180947 A CN109180947 A CN 109180947A
- Authority
- CN
- China
- Prior art keywords
- parts
- resin
- model sesquialter
- sesquialter siloxane
- bismaleimide resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/452—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences
- C08G77/455—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences containing polyamide, polyesteramide or polyimide sequences
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention relates to a kind of modified bismaleimide resin containing ethenyl cage model sesquialter siloxane and preparation methods, components by weight percent includes 40~100 parts of bimaleimide resin, 30~80 parts of diallyl bisphenol, 4~10 parts of methacryloxypropyl cage-type silsesquioxane.Bimaleimide resin is modified, its toughness is greatly improved on the basis of not reducing bimaleimide resin intensity.The invention has the beneficial effects that: used synthetic yield containing ethenyl cage model sesquialter siloxane is high, it is added in resin system and avoids inorganic nanoparticles bad dispersibility, the problem easy to reunite in resin system, while improving its toughness of bimaleimide resin, also its increased intensity.
Description
Technical field
The invention belongs to high-performance, function thermosetting resin field, are related to one kind and change containing ethenyl cage model sesquialter siloxane
Property bimaleimide resin and preparation method.
Background technique
Bimaleimide resin penetrated with its high temperature resistant, wet-heat resisting, resistance to good fortune, electrical insulating property, wave, good mechanical property
The excellent comprehensive performances such as energy are widely used in state as ideal resin matrix for advanced composite materials body and High-performance adhesive
The high-technology fields such as anti-military project, high-performance electronic equipment are however, since BMI curing system crosslink density is big, molecule chain rigidity
By force, cause resin that great brittleness is presented, and poor toughness is exactly the weight that BMI adapts to that high-tech requires and expands new opplication field
Big obstacle, therefore how to improve toughness just and become and determine one of BMI application and key technology of development.
Conventional toughening modifying method mainly has: interior chain extension method is modified, diamine is modified, allyl compound is modified, heat
Plasticity or thermosetting resin modification, the modification of rubber elastomer toughening modifying, inorganic functional material etc., but these can all sacrifice span
The intensity of bismaleimide resin, heat resistance, dielectric properties etc..
Cage-type silsesquioxane (POSS) is a kind of intramolecular hybrid inorganic-organic materials, cage type consisting of Si-O-Si
Inorganic nano kernel and the organic group R for passing through covalent bonding with silicon atom are formed, and inorganic Si-O-Si nanostructure has
Excellent mechanical property, thermal stability, low-dielectric and flame retardant property etc. have very strong with the bonded organic group of silicon atom
Designability and with the good compatibility of high molecular material etc., can pass through physical blending or chemical grafting method assigns material
Expect good toughness, intensity, thermal stability and dielectric properties etc., the modifying agent that can be used as high performance resin is widely used in boat
The high-tech areas such as sky, space flight, electronic device and medical material.
Summary of the invention
Technical problems to be solved
In order to avoid the shortcomings of the prior art, the present invention proposes that one kind is modified double containing ethenyl cage model sesquialter siloxane
Maleimide resin and preparation method, are modified bimaleimide resin, have obtained the span of excellent in mechanical performance
Bismaleimide resin composite material.
Technical solution
A kind of modified bismaleimide resin containing ethenyl cage model sesquialter siloxane, it is characterised in that composition by weight 40
~100 parts of bimaleimide resin, 30~80 parts of diallyl bisphenol and 4~10 parts of methacryloxypropyl
Cage-type silsesquioxane.
The bismaleimide is N, 4,4 '-diphenyl methane dimaleimide of N '-, 4,4 '-bismaleimide
Yl diphenyl ether, 4,4 '-dimaleoyl imino diphenyl sulfones, 2- methyl-1, one of 5- dimaleoyl imino benzene or it
Any combination.
A method of the modified bismaleimide resin containing ethenyl cage model sesquialter siloxane being prepared, feature exists
In steps are as follows:
Step 1: being 40~100 parts of bimaleimide resin and 30~80 parts of diallyl bisphenol by parts by weight
20~30min is stirred to react in 100 DEG C of oil bath pan after mixing；
Step 2: 4~10 parts of methacryloxypropyl cage-type silsesquioxane is added, is warming up to 135 under stirring condition
DEG C reaction 20~30min；
Step 3: 30~40min of de-bubbled in 140 DEG C of vacuum oven is poured into 140 DEG C of preheated glass molds
In tool；
Step 4: 20~30min of de-bubbled in 140 DEG C of vacuum oven, then press 150 DEG C/2h+180 DEG C/2h+220
DEG C/technique of 4h solidified, it is post-processed in 240 DEG C/4h；
Step 5: being cooled to room temperature demoulding, obtain modified bismaleimide resin containing ethenyl cage model sesquialter siloxane.
Beneficial effect
One kind modified bismaleimide resin containing ethenyl cage model sesquialter siloxane proposed by the present invention and preparation method,
Bimaleimide resin is modified, it is greatly improved on the basis of not reducing bimaleimide resin intensity
Toughness.This kind selects methacryloxypropyl cage-type silsesquioxane containing ethenyl cage model sesquialter siloxane, and addition difference contains
Influence of the methacryloxypropyl cage-type silsesquioxane of amount to bimaleimide resin impact strength and bending strength.
Methacryloxypropyl cage-type silsesquioxane synthetic yield used in the present invention is high, is added to resin system
In avoid inorganic nanoparticles bad dispersibility, the problem easy to reunite in resin system, improve bimaleimide resin its
While toughness, also its increased intensity.
Specific embodiment
Now in conjunction with embodiment, the invention will be further described:
Embodiment one:
The N of 40g is weighed, the diallyl bisphenol of 4,4 '-diphenyl methane dimaleimide of N '-, 30g is uniformly mixed,
It is stirred to react 20min in 100 DEG C of oil bath pan, is added 1g methacryloxypropyl cage-type silsesquioxane, under stirring condition
It is warming up to 135 DEG C of reactions 20min, the de-bubbled 30min in 140 DEG C of vacuum oven and is poured into 140 DEG C of preheated glass
In mold, the de-bubbled 20min in 140 DEG C of vacuum oven again, by 150 DEG C/2h+180 DEG C/2h+220 DEG C/4h technique
Solidified, 240 DEG C/4h post-processing.Demoulding is cooled to room temperature to get the bismaleimide resin composite material of high tenacity.
After tested, the impact strength of prepared bimaleimide resin is 10.49kJ/m2, bending strength is
122.16Mpa。
Embodiment two:
The N of 40g is weighed, the diallyl bisphenol of 4,4 '-diphenyl methane dimaleimide of N '-, 30g is uniformly mixed,
It is stirred to react 20min in 100 DEG C of oil bath pan, is added 3g methacryloxypropyl cage-type silsesquioxane, under stirring condition
It is warming up to 135 DEG C of reactions 20min, the de-bubbled 30min in 140 DEG C of vacuum oven and is poured into 140 DEG C of preheated glass
In mold, the de-bubbled 20min in 140 DEG C of vacuum oven again, by 150 DEG C/2h+180 DEG C/2h+220 DEG C/4h technique
Solidified, 240 DEG C/4h post-processing.Demoulding is cooled to room temperature to get the bismaleimide resin composite material of high tenacity.
After tested, the impact strength of prepared bimaleimide resin is 10.86kJ/m2, bending strength is
130.79Mpa。
Embodiment three:
The N of 40g is weighed, the diallyl bisphenol of 4,4 '-diphenyl methane dimaleimide of N '-, 30g is uniformly mixed,
It is stirred to react 20min in 100 DEG C of oil bath pan, is added 5g methacryloxypropyl cage-type silsesquioxane, under stirring condition
It is warming up to 135 DEG C of reactions 20min, the de-bubbled 30min in 140 DEG C of vacuum oven and is poured into 140 DEG C of preheated glass
In mold, the de-bubbled 20min in 140 DEG C of vacuum oven again, by 150 DEG C/2h+180 DEG C/2h+220 DEG C/4h technique
Solidified, 240 DEG C/4h post-processing.Demoulding is cooled to room temperature to get the bismaleimide resin composite material of high tenacity.
After tested, the impact strength of prepared bimaleimide resin is 19.10kJ/m2, bending strength is
147.62Mpa。
Example IV:
The 44BMIDPE of 50g is weighed, the diallyl bisphenol of 38g is uniformly mixed, at 100 DEG C
Oil bath pan in be stirred to react 25min, 7g methacryloxypropyl cage-type silsesquioxane is added, is warming up under stirring condition
135 DEG C of reactions 20min, the de-bubbled 30min in 140 DEG C of vacuum oven are poured into 140 DEG C of preheated glass molds
In, the de-bubbled 20min in 140 DEG C of vacuum oven, is carried out by 150 DEG C/2h+180 DEG C/2h+220 DEG C/4h technique again
Solidification, 240 DEG C/4h post-processing.Demoulding is cooled to room temperature to get the bismaleimide resin composite material of high tenacity.
After tested, the impact strength of prepared bimaleimide resin is 17.3kJ/m2, bending strength is
144.65Mpa。
Embodiment five:
The 4 of 50g are weighed, the diallyl bisphenol of 4 '-dimaleoyl imino diphenyl sulfones, 38g is uniformly mixed, 100
DEG C oil bath pan in be stirred to react 30min, 10g methacryloxypropyl cage-type silsesquioxane is added, is risen under stirring condition
Temperature is poured into 140 DEG C of preheated glass molds to 135 DEG C of reactions 20min, the de-bubbled 25min in 140 DEG C of vacuum oven
In tool, the de-bubbled 30min in 140 DEG C of vacuum oven again, by 150 DEG C/2h+180 DEG C/2h+220 DEG C/4h technique into
Row solidification, 240 DEG C/4h post-processing.Demoulding is cooled to room temperature to get the bismaleimide resin composite material of high tenacity.
After tested, the impact strength of prepared bimaleimide resin is 13.54kJ/m2, bending strength is
137.94Mpa。
Embodiment six:
The 4 of 50g are weighed, the diallyl bisphenol of 4 '-dimaleoyl imino diphenyl sulfones, 38g is uniformly mixed, 100
DEG C oil bath pan in be stirred to react 20min, 13g methacryloxypropyl cage-type silsesquioxane is added, is risen under stirring condition
Temperature is poured into 140 DEG C of preheated glass molds to 135 DEG C of reactions 20min, the de-bubbled 30min in 140 DEG C of vacuum oven
In tool, the de-bubbled 20min in 140 DEG C of vacuum oven again, by 150 DEG C/2h+180 DEG C/2h+220 DEG C/4h technique into
Row solidification, 240 DEG C/4h post-processing.Demoulding is cooled to room temperature to get the bismaleimide resin composite material of high tenacity.
After tested, the impact strength of prepared bimaleimide resin is 14.82kJ/m2, bending strength is
130.46Mpa。
Claims (3)
1. a kind of modified bismaleimide resin containing ethenyl cage model sesquialter siloxane, it is characterised in that composition by weight for 40~
100 parts of bimaleimide resin, 30~80 parts of diallyl bisphenol and 4~10 parts of methacryloxypropyl cage
Type silsesquioxane.
2. modified bismaleimide resin containing ethenyl cage model sesquialter siloxane according to claim 1, it is characterised in that:
The bismaleimide be N, 4,4 '-diphenyl methane dimaleimide of N '-, 44BMIDPE,
4,4 '-dimaleoyl imino diphenyl sulfones, 2- methyl-1, one of 5- dimaleoyl imino benzene or their any group
It closes.
3. a kind of side for preparing the modified bismaleimide resin as claimed in claim 1 or 2 containing ethenyl cage model sesquialter siloxane
Method, it is characterised in that steps are as follows:
Step 1: parts by weight are mixed for 40~100 parts of bimaleimide resin and 30~80 parts of diallyl bisphenol
20~30min is stirred to react in 100 DEG C of oil bath pan afterwards；
Step 2: 4~10 parts of methacryloxypropyl cage-type silsesquioxane is added, 135 DEG C are warming up under stirring condition instead
Answer 20~30min；
Step 3: 30~40min of de-bubbled in 140 DEG C of vacuum oven is poured into 140 DEG C of preheated glass molds；
Step 4: 20~30min of de-bubbled in 140 DEG C of vacuum oven, then press 150 DEG C/2h+180 DEG C/2h+220 DEG C/4h
Technique solidified, 240 DEG C/4h post-process；
Step 5: being cooled to room temperature demoulding, obtain modified bismaleimide resin containing ethenyl cage model sesquialter siloxane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810818834.1A CN109180947A (en) | 2018-07-24 | 2018-07-24 | One kind modified bismaleimide resin containing ethenyl cage model sesquialter siloxane and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810818834.1A CN109180947A (en) | 2018-07-24 | 2018-07-24 | One kind modified bismaleimide resin containing ethenyl cage model sesquialter siloxane and preparation method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109180947A true CN109180947A (en) | 2019-01-11 |
Family
ID=64936652
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810818834.1A Pending CN109180947A (en) | 2018-07-24 | 2018-07-24 | One kind modified bismaleimide resin containing ethenyl cage model sesquialter siloxane and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109180947A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114380947A (en) * | 2021-12-22 | 2022-04-22 | 苏州大学 | Halogen-free phosphorus-free flame-retardant shape memory bismaleimide resin and preparation method thereof |
| CN115521614A (en) * | 2021-06-24 | 2022-12-27 | 穗晔实业股份有限公司 | Thermosetting resin composition and prepreg |
| WO2022266951A1 (en) * | 2021-06-24 | 2022-12-29 | 穗晔实业股份有限公司 | Thermosetting resin composition and prepreg |
| CN115850710A (en) * | 2022-10-11 | 2023-03-28 | 苏州生益科技有限公司 | Modified bismaleimide prepolymer, resin composition and application of resin composition |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62246933A (en) * | 1986-04-18 | 1987-10-28 | Shin Etsu Chem Co Ltd | Production of imide group-containing organopolysiloxane |
| CN101070387A (en) * | 2007-06-06 | 2007-11-14 | 北京化工大学 | Low-dielectric resin containing low-poly-sesqui-silicone and its preparing method |
| CN101723968A (en) * | 2009-11-20 | 2010-06-09 | 苏州大学 | Maleimide with cage-type silsesquioxane structure and synthesis method thereof |
| CN102775605A (en) * | 2012-08-14 | 2012-11-14 | 西北工业大学 | Modified bismaleimide resin and preparation method thereof |
| CN105017771A (en) * | 2015-08-17 | 2015-11-04 | 中国航空工业集团公司西安飞机设计研究所 | Bismaleimide resin composite material and preparation method thereof |
-
2018
- 2018-07-24 CN CN201810818834.1A patent/CN109180947A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62246933A (en) * | 1986-04-18 | 1987-10-28 | Shin Etsu Chem Co Ltd | Production of imide group-containing organopolysiloxane |
| CN101070387A (en) * | 2007-06-06 | 2007-11-14 | 北京化工大学 | Low-dielectric resin containing low-poly-sesqui-silicone and its preparing method |
| CN101723968A (en) * | 2009-11-20 | 2010-06-09 | 苏州大学 | Maleimide with cage-type silsesquioxane structure and synthesis method thereof |
| CN102775605A (en) * | 2012-08-14 | 2012-11-14 | 西北工业大学 | Modified bismaleimide resin and preparation method thereof |
| CN105017771A (en) * | 2015-08-17 | 2015-11-04 | 中国航空工业集团公司西安飞机设计研究所 | Bismaleimide resin composite material and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| HU J. ET AL.: "High efficiency synthesis of octavinylsilsesquioxanes and its high performance hybrids based on bismaleimidetriazine resin", 《POLYMERS ADVANCED TECHNOLOGIES》 * |
| 吴建元等: "双马来酰亚胺增韧改性研究进展", 《化工新型材料》 * |
| 黄福伟: "含八氢基笼形倍半硅氧烷的双马来酰亚胺树脂", 《宇航材料工艺》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115521614A (en) * | 2021-06-24 | 2022-12-27 | 穗晔实业股份有限公司 | Thermosetting resin composition and prepreg |
| WO2022266951A1 (en) * | 2021-06-24 | 2022-12-29 | 穗晔实业股份有限公司 | Thermosetting resin composition and prepreg |
| US11639439B2 (en) | 2021-06-24 | 2023-05-02 | Prior Company Limited | Thermosetting resin composition and prepreg |
| CN115521614B (en) * | 2021-06-24 | 2023-09-26 | 穗晔实业股份有限公司 | Thermosetting resin composition and prepreg |
| CN114380947A (en) * | 2021-12-22 | 2022-04-22 | 苏州大学 | Halogen-free phosphorus-free flame-retardant shape memory bismaleimide resin and preparation method thereof |
| CN114380947B (en) * | 2021-12-22 | 2022-09-23 | 苏州大学 | Halogen-free phosphorus-free flame-retardant shape memory bismaleimide resin and preparation method thereof |
| CN115850710A (en) * | 2022-10-11 | 2023-03-28 | 苏州生益科技有限公司 | Modified bismaleimide prepolymer, resin composition and application of resin composition |
| CN115850710B (en) * | 2022-10-11 | 2023-09-15 | 苏州生益科技有限公司 | Modified bismaleimide prepolymer, resin composition and application of resin composition |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109180947A (en) | One kind modified bismaleimide resin containing ethenyl cage model sesquialter siloxane and preparation method | |
| CN105295792B (en) | A kind of cross-linking modified epoxy resin of high-performance polyimide and preparation method thereof | |
| Liu et al. | Promoted ablation resistance of polydimethylsiloxane via crosslinking with multi-ethoxy POSS | |
| CN102492116B (en) | Epoxy resin and polyhedral silsesquioxane nano hybrid material and its preparation method | |
| CN100523087C (en) | Thermostable benzoxazine resin compound and its preparation method and uses | |
| KR20160036566A (en) | Epoxy resin composition, prepreg, and fiber-reinforced composite material | |
| CN103408948B (en) | A kind of rubber combination and application thereof | |
| CN101070387A (en) | Low-dielectric resin containing low-poly-sesqui-silicone and its preparing method | |
| CN102079874A (en) | Preparation method of cage-type silsesquioxane-containing low-dielectric cyanate hybrid resin | |
| CN101974226A (en) | Flame-retardant bismaleimide resin and preparation method thereof | |
| CN113716557B (en) | Preparation method of modified graphene oxide and method for preparing epoxy resin composite material by using modified graphene oxide | |
| CN102634208B (en) | Nanocomposite modification method applied to bismaleimide resin based composite | |
| CN106566194B (en) | A kind of high-temperature-resistant epoxy resin | |
| CN110527300A (en) | A kind of high-strength epoxy with inierpeneirating network structure-silicon rubber modified material | |
| Zhang et al. | Cyanate ester composites containing surface functionalized BN particles with grafted hyperpolyarylamide exhibiting desirable thermal conductivities and a low dielectric constant | |
| CN101885901A (en) | Biphenyl-structure-contained epoxy resin/montmorillonite nano composite material | |
| CN108641356A (en) | Graphene/class graphene WS of three phosphonitrilic polymer of ring modification2/ Bismaleimide composites and preparation method | |
| CN101891936B (en) | Preparation method of composite material based on epoxy resin and phosphazene nanotubes | |
| CN104448820B (en) | Cyanate modified composition, cyanate prepreg, metamaterial substrate, its preparation method and the Meta Materials including it | |
| Niu et al. | Preparation, structures and properties of interpenetrating network structure-type Phosphate/PEEK composites with enhanced compressive strength and high temperature resistance | |
| JP2020524187A (en) | Epoxy resin system for manufacturing fiber reinforced composites | |
| CN111995861A (en) | GO/TPU composite powder for selective laser sintering of heat-resistant workpieces and preparation method thereof | |
| CN101845143A (en) | Modified bismaleimide resin as well as preparation method and application thereof | |
| CN106633642A (en) | Octadecylamine graft epoxy heat-conducting material and preparation method thereof | |
| CN114874443B (en) | Silicon rubber with low curing shrinkage and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20190111 |