CN1467231A - Nanometer composite double maleimide resin and method for preparing the same - Google Patents
Nanometer composite double maleimide resin and method for preparing the same Download PDFInfo
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- CN1467231A CN1467231A CNA021236933A CN02123693A CN1467231A CN 1467231 A CN1467231 A CN 1467231A CN A021236933 A CNA021236933 A CN A021236933A CN 02123693 A CN02123693 A CN 02123693A CN 1467231 A CN1467231 A CN 1467231A
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Abstract
A bimaleimide resin suitable for nano compounding, a nano compounding technique for filling the nano material in said bimaleimide resin, and a process for preparing its composition are disclosed. Said process includes such steps as preparing the basic resin by mixing methane-type BMI monomer, diallyl biphenol A and allylphenol in mass ratio of (50-60):(30-40):(8-12), adding nanoparticles, pressurizing, heating, and constant-temp solidifying. Its advantages are low viscosity, high particle dispersity, and strong stability and long open time.
Description
Technical field: the present invention relates to a kind of modified bismaleimide resin that is used to fill nano material, and nano combined bimaleimide resin base composite material and preparation method thereof.
Background technology: bimaleimide resin (BMI) is the resinoid system that the polyimide resin system derives from.The BMI resin is widely used as electrical apparatus insulation material, emery wheel binding agent, a rubber crosslinker, plastics additive etc.The BMI resin of modification not only has the manufacturability with the similar excellence of Resins, epoxy, and has better mechanical and physical performance, electrical property and hydrothermal stability etc. than Resins, epoxy.
The Chinese patent " double maleie polyimide modified resin and manufacture method " (application number is 92104822.X) of Daxue Industrial ﹠ Commercial General Co. of Penglai City and Cheng Shuan silver co-applications discloses a kind of polyenoic acid and MALEIC ANHYDRIDE by 16-20 carbon atom and generated the polyphosphazene polymer amide polymer with the reaction of two amido ditanes in the organic amine solvent, comes the polyamine span of polyimide and two amido ditanes reaction generation to come the high molecular polymer of acid amides with span again.Use epoxy resin cross-linking agent, through polymerization, be cross-linked into the method for the synthetic resins of inierpeneirating network structure.The Chinese patent " a kind of Dimaleic type liquid crystal polyimide and preparation method thereof " (patent No. is 96117849.3) of Sichuan University application discloses a kind ofly will have 4 of liquid crystal characteristic, 4 '-diallyl oxygen base biphenyl, aromatic diamine and bismaleimides be under solvent and catalyzer existence condition, add and have in the reactor of agitator, thermometer and reflux exchanger, back flow reaction is 2-6 hour when 60～150 ℃ of temperature, obtain Dimaleic type liquid crystal polyimide, after aftertreatment, make the Dimaleic type liquid crystal polyimide product.These two patent disclosures all be the method for preparing the span polyimide resin, and all do not dose other any material.The Chinese patent " a kind of nanometer composite polyamide-clay material " (patent No. is 96105362.3) of Institute of Chemistry, Academia Sinica application disclose a kind of with clay through cation exchange reaction, allow the monomer of polyamide intercalation enter clay, and allow clay and monomer of polyamide behind the intercalation in reactor, once finish copolymerization again, clay of laminar silicate is combined with polyamide substrate by the Coulomb's force, and be dispersed in the polyamide substrate with nanoscale, be prepared into high performance nanometer composite polyamide-clay material.By another Chinese patent " a kind of polyester/phyllosilicate nano-composite material and preparation method thereof " (patent No. is 97104055.9) of Institute of Chemistry, Academia Sinica application disclose a kind of with layered silicate through behind the intercalation with polyester monocase copolycondensation in polymerization reactor, make layered silicate combine with polyester matrix and be dispersed in high-performance polyester/laminated nm-silicate composite material in the polyester matrix with nanoscale by chemical bond.These two patents are disclosed all to be that polyester or polymeric amide are combined with clay, finally obtains having nanoscale and disperses compound polymer composite product.These two patents do not relate to the bismaleimides material.
Generally speaking, for the resin-base nano matrix material, the viscosity of matrix resin, surface active, with the interaction of nanoparticle be not very desirable, therefore, prepare good, can be specifically designed to nano combined resin matrix be exactly vital.
Summary of the invention: the purpose of this invention is to provide a kind of nano combined matrix resin that is applicable to, and this resin and nanoparticle are compound, prepare the method for nano composite material.
The prescription of matrix resin of the present invention is three kinds of materials: methane type BMI monomer, diallyl bisphenol and chavicol.The component of these three kinds of materials is than (methane type BMI monomer: diallyl bisphenol: chavicol) be: 50～60: 30～40: 8～12.
These three kinds of materials are mixed by the ratio of component weighing, kept 20 minutes down at 130 ℃～140 ℃, add the 2 dimension flake nano particles (as organic montmorillonoid) that account for weight fraction 0.1～10% then, the nano inorganic nonmetal particle (as ferrite magnetic powder) that perhaps adds 0 dimension, ferromagnetic oxide powder: BMI resin=30: 70 (parts by weight), under 80 ℃～90 ℃ conditions, leniently stir, shear and mix, promptly mix by hand and get final product.Then, mix once more on three-roller, mixing time is not wait in 10～30 minutes again, and mixing time is directly proportional with the amount of material.Mix finish after, the bismaleimides material of having filled nano particle is put into shaping mould, under normal pressure, be warmed up to 130 ℃ with the heat-up rate of 1.5 ℃/min from room temperature, be incubated one hour, the while is with the 0.2MPa pressurize.Then, be warming up to 190 ℃ with same speed from 130 ℃ again, under this temperature, boost to 0.4MPa again, kept 3 hours from 0.2MPa.At last, with the speed cooling of 2 ℃/min, until reducing to room temperature, die sinking.
Dimaleoyl imino body material of the present invention is fit to mix with multiple nanoparticle, not only be fit to mix with the tens ferrimagnetism powder to the hundreds of nanometer, and adaptation mixes with several nanometers organic montmorillonoid at interval.Through the mixed resin of nanometer have that viscosity is low, the uniform characteristic of mix particles and the good advantage of dispersing characteristic, have very long stability and open hour, good interface is cohered character and splicing character good and metal, can be used for the functional electrode materials of co-curing etc. that directly bonds.
Mixing process energy consumption of the present invention is little, and mixing time is moderate, need not special mixing device.Curing process has guaranteed that no small molecules discharges, thereby does not have the bubble generation, goods zero defect, internal stress free, nothing distortion.The nano imvite that for example organises just can be realized intercalation very wellly or peel off.Because material of the present invention has good adhesive property, therefore co-curable heterogeneous object has good application prospects in fields such as electronics and communication informations.
Embodiment:
Embodiment one:
1. preparation BMI resin is chosen 60 parts of methane type BMI monomers, 35 parts of diallyl bisphenols, 12 parts of chavicols (60: 35: 12);
2. the material of three kinds of components is poured in the beaker, uniform mixing is warmed up to 130 ℃～140 ℃, keeps 20 minutes;
3. sneak into 2 parts of (Institute of Chemistry, Academia Sinica provides) 2 dimension sheet organic montmorillonoids, under 80 ℃～90 ℃, leniently stir, shear and mix by hand;
4. mix on three-roller, mixing time is directly proportional with the amount of material again, and mixing time is about 10 minutes;
5. the material that will fill nano particle is put into shaping mould, is warmed up to 130 ℃ from room temperature with the heat-up rate of 1.5 ℃/min under normal pressure, is incubated one hour, simultaneously with the 0.2MPa pressurize.Then, be warming up to 190 ℃ with same speed from 130 ℃ again, under this temperature, boost to 0.4MPa again, kept 3 hours from 0.2MPa.At last, with the cooling of the speed of 2 ℃/min, until reducing to room temperature, die sinking, thus finish whole solidification processs.
Analysis revealed before and after solidifying, the BMI resin can unusually successfully insert between montmorillonite layer in mixing process, and makes the stratiform polynite take place further to peel off in solidification process, and the interlamellar spacing of nanoparticle reaches more than the 40nm.
Embodiment two:
1. preparation BMI resin is chosen 60 parts of methane type BMI monomers, 35 parts of diallyl bisphenols, 8 parts of chavicols (60: 35: 8);
2. the material of three kinds of components is poured in the beaker, uniform mixing is warmed up to 130 ℃～140 ℃, keeps 20 minutes;
3. sneak into nanocrystalline magnetic (Inst. of Physics, CAS provides), nanocrystalline magnetic: BMI resin=30: 70 (weight fraction), under 80 ℃～90 ℃, leniently stir, shear, mix by hand;
4. mix on three-roller, mixing time is directly proportional with the amount of material again, and mixing time is 15 minutes;
5. the material that will fill nano particle is put into shaping mould, is warmed up to 130 ℃ from room temperature with the heat-up rate of 1.5 ℃/min under normal pressure, is incubated one hour, simultaneously with the 0.2MPa pressurize.Then, be warming up to 190 ℃ with same speed from 130 ℃ again, under this temperature, boost to 0.4MPa again, kept 3 hours from 0.2MPa.At last, with the cooling of the speed of 2 ℃/min, until reducing to room temperature, die sinking, thus finish whole solidification processs.
Analysis revealed before and after solidifying, the BMI resin can be unusually successfully compound with this nanoparticle homodisperse in mixing process, and its matrix material has excellent electromagnetic performance, can be used for the manufacturing of microstrip antenna.
Embodiment three:
1. preparation BMI resin is chosen 50 parts of methane type BMI monomers, 40 parts of diallyl bisphenols, 12 parts of chavicols (50: 40: 12);
2. the material of three kinds of components is poured in the beaker, uniform mixing is warmed up to 130 ℃～140 ℃, keeps 20 minutes;
3. sneak into 4 parts of the polynites that (Institute of Chemistry, Academia Sinica provides) 2 dimension sheets organise, under 80 ℃～90 ℃, leniently stir, shear, mix by hand;
4. mix on three-roller, mixing time is directly proportional with the amount of material again, and mixing time is 30 minutes;
5. the material that will fill nano particle is put into shaping mould, is warmed up to 130 ℃ from room temperature with the heat-up rate of 1.5 ℃/min under normal pressure, is incubated one hour, simultaneously with the 0.2MPa pressurize.Then, be warming up to 190 ℃ with same speed from 130 ℃ again, under this temperature, boost to 0.4MPa again, kept 3 hours from 0.2MPa.At last, with the cooling of the speed of 2 ℃/min, until reducing to room temperature, die sinking, thus finish whole solidification processs.
Embodiment four:
1. preparation BMI resin is chosen 50 parts of methane type BMI monomers, 30 parts of diallyl bisphenols, 8 parts of chavicols (50: 30: 8);
2. the material of three kinds of components is poured in the beaker, uniform mixing is warmed up to 130 ℃～140 ℃, keeps 20 minutes;
3. sneak into (Inst. of Physics, CAS provides) nanocrystalline magnetic, nanocrystalline magnetic: BMI resin=30: 70 (weight fraction), under 80 ℃～90 ℃, leniently stir, shear, mix by hand;
4. mix on three-roller, mixing time is directly proportional with the amount of material again, and mixing time is 20 minutes;
5. the material that will fill nano particle is put into shaping mould, is warmed up to 130 ℃ from room temperature with the heat-up rate of 1.5 ℃/min under normal pressure, is incubated one hour, simultaneously with the 0.2MPa pressurize.Then, be warming up to 190 ℃ with same speed from 130 ℃ again, under this temperature, boost to 0.4MPa again, kept 3 hours from 0.2MPa.At last, with the cooling of the speed of 2 ℃/min, until reducing to room temperature, die sinking, thus finish whole solidification processs.
Claims (2)
1. the nano combined bimaleimide resin of using is characterized in that, and is nano combined with contained component of bimaleimide resin and content (parts by weight):
Methane type BMI resin monomer 50～60
Diallyl bisphenol 30～40
Chavicol 8～12
A. carry out nano combinedly with 2 dimension sheet organic montmorillonoids, 2 dimension sheet organic montmorillonoids account for the content 0.1～10% of above-mentioned resin;
B. with 0 dimension ferrite nano magnetic powder carry out nano combined, ferrite magnetic powder: BMI resin (methane type BMI monomer+diallyl bisphenol+chavicol)=30: 70.
2. a nanometer composite double maleimide resin method for preparing is characterized in that,
(1). in the described ratio preparation of claim 1 BMI resin,
(2). the material of three kinds of components is poured in the beaker, and uniform mixing is warmed up to 130 ℃～140 ℃, keeps 20 minutes;
(3). sneak into the 2 dimension polynites that organise of sheets or ferrite nano magnetic powder under 80 ℃～90 ℃, leniently stir, shear, mix by hand;
(4). mix on three-roller, mixing time is directly proportional with the amount of material again, and mixing time is about 10～30 minutes;
(5). the material that will fill nano particle is put into shaping mould, is warmed up to 130 ℃ from room temperature with the heat-up rate of 1.5 ℃/min under normal pressure, is incubated one hour, simultaneously with the 0.2MPa pressurize.Then, be warming up to 190 ℃ with same speed from 130 ℃ again, under this temperature, boost to 0.4MPa again, kept 3 hours from 0.2MPa.At last, with the cooling of the speed of 2 ℃/min, until reducing to room temperature, die sinking, thus finish whole solidification processs.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02123693 CN1200015C (en) | 2002-07-09 | 2002-07-09 | Nanometer composite double maleimide resin and method for preparing the same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02123693 CN1200015C (en) | 2002-07-09 | 2002-07-09 | Nanometer composite double maleimide resin and method for preparing the same |
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| Publication Number | Publication Date |
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| CN1467231A true CN1467231A (en) | 2004-01-14 |
| CN1200015C CN1200015C (en) | 2005-05-04 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 02123693 Expired - Lifetime CN1200015C (en) | 2002-07-09 | 2002-07-09 | Nanometer composite double maleimide resin and method for preparing the same |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101906237A (en) * | 2010-07-20 | 2010-12-08 | 中国西电集团公司 | Formula of magnetic slot wedge |
| CN102327768A (en) * | 2011-08-16 | 2012-01-25 | 湖南大学 | Imido magnetic nano-adsorbent as well as preparation method and application thereof |
| CN102634208A (en) * | 2012-04-27 | 2012-08-15 | 沈阳航空航天大学 | Nanocomposite modification method applied to bismaleimide resin based composite |
| CN115366013A (en) * | 2022-04-02 | 2022-11-22 | 珠海市世创金刚石工具制造有限公司 | Bismaleimide resin grinding wheel for dry grinding |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2006240379B2 (en) * | 2005-04-28 | 2011-01-06 | Cytec Technology Corp. | Bismaleimide resin system with improved manufacturing properties |
-
2002
- 2002-07-09 CN CN 02123693 patent/CN1200015C/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101906237A (en) * | 2010-07-20 | 2010-12-08 | 中国西电集团公司 | Formula of magnetic slot wedge |
| CN102327768A (en) * | 2011-08-16 | 2012-01-25 | 湖南大学 | Imido magnetic nano-adsorbent as well as preparation method and application thereof |
| CN102634208A (en) * | 2012-04-27 | 2012-08-15 | 沈阳航空航天大学 | Nanocomposite modification method applied to bismaleimide resin based composite |
| CN102634208B (en) * | 2012-04-27 | 2014-01-01 | 沈阳航空航天大学 | Nanocomposite modification method applied to bismaleimide resin based composite |
| CN115366013A (en) * | 2022-04-02 | 2022-11-22 | 珠海市世创金刚石工具制造有限公司 | Bismaleimide resin grinding wheel for dry grinding |
| CN115366013B (en) * | 2022-04-02 | 2023-12-08 | 珠海市世创金刚石工具制造有限公司 | Double-horse polyimide resin grinding wheel for dry grinding |
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| Publication number | Publication date |
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| CN1200015C (en) | 2005-05-04 |
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Granted publication date: 20050504 |