CN1560167A - Epoxy resin adhesive containing dimalea mic and preparation process thereof - Google Patents
Epoxy resin adhesive containing dimalea mic and preparation process thereof Download PDFInfo
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- CN1560167A CN1560167A CNA2004100219871A CN200410021987A CN1560167A CN 1560167 A CN1560167 A CN 1560167A CN A2004100219871 A CNA2004100219871 A CN A2004100219871A CN 200410021987 A CN200410021987 A CN 200410021987A CN 1560167 A CN1560167 A CN 1560167A
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Abstract
The invention is a bismaleimide-containing epoxy resin adhesive and its preparing method, and its character: adding diphenyl methane bismaleimide with fully meta-aromatic ether diamine by Micheal to prepare bismaleimide modified aromatic amine curing agent, which is viscoelastic at room temperature and can flow at 50 deg.C. Then, it commixes the curing agent in 20-40 weight shares, low-viscosity diphenol F epoxy resin resin in 80-120 weight share, core-shell rubber flexibilizer in 1-4 weight shares and liquid imidazole accelerant in 1-4 weight shares to prepare epoxy resin adhesive. The adhesive is liquid at room temperature and curable at medium temperature and used at high temperature. It is mainly used in advanced composite structure repairing filed.
Description
One, technical field
The present invention relates to a kind of epoxyn that contains bismaleimides and preparation method thereof, belong to the synthetic field of speciality polymer material.
Two, background technology
Except the requirement of mechanical property aspect, the tackiness agent that is used for the advanced composite structure repairing is also had special condition of cure requirement, can under boiling temperature that is lower than water and vacuum pressure, curing reaction be proceeded to higher degree; Also can under middle temperature, carry out post curing treatment; And the manufacturability of tackiness agent will be got well.
Bisphenol f type epoxy resin has excellent adhesiveproperties, and the resin chemical resistance after the curing is good, and intensity is higher; And viscosity is low, and good manufacturability relatively is suitable as advanced composite structure and repairs the matrix resin that sticks with glue agent.But the bisphenol f type epoxy resin thermotolerance is low, and for reaching service requirements, the thermotolerance of improving its curing system is very necessary, and the solidifying agent that uses good heat resistance is to improve the simple and the most feasible approach of epoxy resin solidifying system thermotolerance.
Can improve thermotolerance, make cured article satisfy in the epoxy curing agent of the warm service requirements imidazole curing agent that mainly contains aromatic amine and anhydrides and follow anionic reactive mechanism.During adhesive solidification, because aromatic amine produces than poly-hydroxy, helping improving bonding property in solidification process, is that ideal is selected.But under lower solidifying pressure (as vacuum pressure), the normal temperature tensile shear strength of Resins, epoxy/aromatic amine solidifying agent is generally not high, and its intensity is relatively more responsive to adhesive components proportioning and curing process, and this is very disadvantageous when carrying out the outfield repairing.
Bismaleimides (BMI) is a kind of intermediate of addition polyimide, and the molecule two ends are active end group with the unsaturated maleimide ring, and structure can be expressed as:
The BMI resin has good high temperature resistant, moisture-resistance, also has advantages such as starting material wide material sources, cost are lower simultaneously.Since 1969 were succeeded in developing by French Rhone Poulenc company, countries such as the U.S., Britain, Germany, Japan, China researched and developed in succession.As a class ideal advanced composite material matrix resin, the BMI resin is in department's widespread uses such as space flight and aviation, mechano-electronic, communications and transportation.But general general BMI fusing point is higher, and needs hot setting, is unsuitable for directly as the matrix resin of repairing tackiness agent or matrix resin.
Adopt bi-maleimide modified Resins, epoxy/aromatic diamine system to improve the existing bibliographical information of tackiness agent bonding strength and thermotolerance.Zhao Shilin etc. with diphenyl methane dimaleimide and two amido sulfobenzide copolymerization after, with bisphenol A type epoxy resin and rubber toughening agent blend, prepared the good tackiness agent of resistance toheat, (" chemistry is with bonding ", No.2,61～63,2000), but this tackiness agent needs hot setting, is not suitable for advanced composite structure and repairs the field.Liu Runshan is main solvent with toluene, diphenyl methane dimaleimide and diphenylmethane diamine are heated prepolymerization in advance, again with bisphenol A type epoxy resin and solubility promoter blend, made highly filled single-component solvent-based adhesive, (" bonding ", No.5,1～3,1998), this tackiness agent also needs hot setting, and requires to be cured adding to depress owing to containing solvent.
In addition, main dimaleimide/epoxy resin/two amine systems that also had some bibliographical informations as composite matrix resin.The people such as Hasmukh S.Patel of Sardar Patel university have synthesized the diamines of several new textures, with bismaleimides according to 2: 1 molar ratio reaction after products therefrom can be as the solidifying agent (Polymers﹠amp of bisphenol A type epoxy resin; Polymer Composites, v4, n3,1996, p173-180; High PerformancePolymers, v8, n2, Jun, 1996, p233-242).The Kim Dae Su of Korea Research Inst. of Chemical Technology etc. has synthesized a kind of new bismaleimides, with solidify (Polymers for Advanced Technologies with diphenylmethane diamine after a kind of four glycidyl amine type epoxy resins (TGDDM) copolymerization, v5, n5, May, 1994, p287-291).The breadboard A.Vanaja of Indian country aerospace etc. adopt a kind of cycloaliphatic epoxy resin of diphenyl methane dimaleimide modification, solidify with aromatic amine curing agent then, the second-order transition temperature of gained cured product and thermostability are all than unmodified epoxy-resin systems (the European Polymer Journal that is significantly improved, v38, n1, January, 2002, p187-193).
The used diamines of above-mentioned research work mostly is the contraposition aromatic diamine, and adhesive system all needs hot setting.
Three, summary of the invention
The objective of the invention is provides a kind of epoxyn that contains the bismaleimide amine component and preparation method thereof at the deficiencies in the prior art, be characterized in diphenyl methane dimaleimide and complete between a position aromatic oxide diamines prepare bi-maleimide modified aromatic amine curing agent by the Micheal addition reaction, this solidifying agent at room temperature is the viscoelastic attitude, can flow in the time of 50 ℃.With solidifying agent and low viscosity bisphenol f type epoxy resin and nucleocapsid type rubber toughner and the blend of liquid imidazole curing catalyst, prepare epoxyn again.Be liquid under this tackiness agent room temperature, have higher tensile shear strength and hot tensile shear strength after the curing, but intermediate temperature setting high temperature uses.
Purpose of the present invention is realized that by following technical measures wherein said raw material umber is parts by weight except that specified otherwise.
The composition of raw materials component that contains the epoxyn of bismaleimides is:
80～120 parts of low viscosity bisphenol f type epoxy resins
20～40 parts in solidifying agent
1～4 part of liquid imidazole promotor
1～4 part of nucleocapsid type rubber toughner
Wherein solidifying agent be bi-maleimide modified complete between position aromatic oxide diamines.
The manufacture method that contains the epoxyn of bismaleimides:
(1) bi-maleimide modified complete between the preparation of position aromatic oxide diamine curing agent
With mol ratio be 1: 2～1: 4 diphenyl methane dimaleimide and complete between a position aromatic oxide diamines join and have agitator, thermometer and logical N
2In the reactor of device, at N
2Protection down heated and stirred to the system fusion, 130 ℃～150 ℃ reactions of temperature 2～6 hours, obtain bi-maleimide modified complete between position aromatic oxide diamine curing agent.This solidifying agent is a red-brown, at room temperature is the viscoelastic attitude, can flow in the time of 50 ℃, and is good with epoxy resin compatibility.
(2) contain the preparation of the epoxyn of bismaleimides
80～120 parts of low viscosity bisphenol f type epoxy resins and 1～4 part of adding of nucleocapsid type rubber toughner are had in the reactor of agitator and thermometer, stirred 0.5～2 hour.Add 20～40 parts in solidifying agent then, mixed 0.5～2 hour for 20 ℃～80 ℃ in temperature.After the temperature of said mixture is reduced to 10 ℃～60 ℃, add 1～4 part of imidazoles promotor again, continue to stir 0.5～1 hour, obtain the epoxyn that contains bismaleimides of brown sticking shape.
In the solidifying agent of the present invention preparation bismaleimides and complete between the weight ratio of position aromatic oxide diamines the melt temperature of solidifying agent and the adhesiveproperties of epoxyn are all had considerable influence.Along with the increase of position aromatic oxide diamines weight between complete in the component, the melt temperature of solidifying agent is reduced to 50 ℃ by 80 ℃ gradually, and the tensile shear strength of tackiness agent and stripping strength then present increases the variation that reduces again earlier.The epoxyn that contains bismaleimides can be at 93 ℃ of curing of temperature, 120 ℃ of after fixing.Cured adhesive can keep the strength level under the room temperature at hot (130 ℃) tensile shear strength.This tackiness agent is mainly used in advanced composite structure and repairs the field.
The present invention has following advantage:
1. adopt bismaleimides that full meta-aromatic ether diamine solidifying agent is carried out modification, both can increase the polarity of solidifying agent, improve the cohesive strength of tackiness agent, improve the tackiness agent adhesiveproperties, again because of the prolongation of molecular chain, reduced the cross-linking density of cured article, residual solidified stress is reduced, can also reduce the susceptibility of tackiness agent performance simultaneously the set of dispense ratio.
Bismaleimides to full meta-aromatic ether diamine curing agent modified after, gained modified firming agent melt temperature is lower, can be even with epoxy blend at a lower temperature, the working life of adhesive system is longer.
3. the rigidity owing to BMI chain link in the molecular chain is very strong, gives cured article better heat-resisting performance.
4. because BMI does not participate in curing reaction directly, can realize at a lower temperature solidifying.
5. the adding of nucleocapsid type rubber toughner makes the toughness raising of tackiness agent and can not reduce its thermotolerance simultaneously, and toughening effect is not subjected to the influence of condition of cure.
Four, embodiment
Below by embodiment the present invention is carried out concrete description.Be necessary to be pointed out that at this present embodiment only is used for the present invention is further specified that can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of foregoing invention.
Embodiment 1
(1) bi-maleimide modified complete between the preparation of position aromatic oxide diamine curing agent
With mol ratio be 1: 2.2 diphenyl methane dimaleimide and complete between position triphen two ether diamines join and have agitator, thermometer and logical N
2In the reactor of device, at N
2Protection down heated and stirred to the system fusion, 135 ℃ ± 5 ℃ reactions of temperature 5 hours, obtain henna bi-maleimide modified complete between position aromatic oxide diamine curing agent.
(2) contain the preparation of the epoxyn of bismaleimides
With low viscosity bisphenol f type epoxy resin 90 grams and nucleocapsid type rubber toughner 2 grams, add in the reactor that has agitator and thermometer and stirred 2 hours.Mix with 20 gram modified firming agents then, mixed 2 hours 50 ℃ of temperature.After the temperature of said mixture reduced to room temperature, in mixture, add 1 gram liquid imidazole promotor, continue to stir 0.5 hour, obtain the epoxyn that contains the bismaleimide amine component of brown sticking shape.
Embodiment 2
(1) bi-maleimide modified complete between the preparation of position aromatic oxide diamine curing agent
With mol ratio be 1: 3 diphenyl methane dimaleimide and complete between position triphen two ether diamines join and have agitator, thermometer and logical N
2In the reactor of device, at N
2Protection down heated and stirred to the system fusion, 140 ℃ ± 5 ℃ reactions of temperature 4 hours, obtain henna bi-maleimide modified complete between position aromatic oxide diamine curing agent.
(2) contain the preparation of the epoxyn of bismaleimides
With low viscosity bisphenol f type epoxy resin 100 grams and nucleocapsid type rubber toughner 3 grams, add in the reactor that has agitator and thermometer and stirred 1 hour.Mix with 25 gram solidifying agent then, mixed 0.8 hour 50 ℃ of temperature.After the temperature of said mixture reduced to room temperature, in mixture, add 2 gram liquid imidazole promotor, continue to stir 1 hour, obtain the epoxyn that contains bismaleimides of brown sticking shape.
Embodiment 3
(1) bi-maleimide modified complete between the preparation of position aromatic oxide diamine curing agent
With mol ratio be 1: 4 diphenyl methane dimaleimide and complete between position triphen two ether diamines join and have agitator, thermometer and logical N
2In the reactor of device, at N
2Protection down heated and stirred to the system fusion, 145 ℃ ± 5 ℃ reactions of temperature 3 hours, obtain henna bi-maleimide modified complete between position aromatic oxide diamine curing agent.
(2) contain the preparation of the epoxyn of bismaleimides
With low viscosity bisphenol f type epoxy resin 120 grams and nucleocapsid type rubber toughner 4 grams, add in the reactor that has agitator and thermometer and stirred 1 hour.Mix with 35 gram solidifying agent then, mixed 1 hour 50 ℃ of temperature.After the temperature of said mixture reduced to room temperature, in mixture, add 3 gram liquid imidazole promotor, continue to stir 1 hour, obtain the epoxyn that contains the bismaleimide amine component of brown sticking shape.
Diphenyl methane dimaleimide among the embodiment is industrial goods, is produced by east, Mianyang, Sichuan insulating material limited-liability company; Position aromatic diamines purity is 95% between complete, and 107～108 ℃ of fusing points are produced by Shanghai organic chemistry institute; Bisphenol f type epoxy resin is industrial goods, oxirane value 0.60, and Dutch Shell Co. Ltd produces; Nucleocapsid type rubber toughner is industrial goods, and Singapore Wu Yu chemical company produces; The liquid modifying imidazoles, chemical pure, synthetic materials institute in Tianjin produces.
Claims (3)
1. the epoxyn that contains bismaleimides is characterized in that the composition of raw materials component of this tackiness agent is by weight:
80～120 parts of low viscosity bisphenol f type epoxy resins
20～40 parts in solidifying agent
1～4 part of liquid imidazole promotor
1～4 part of nucleocapsid type rubber toughner
Wherein solidifying agent be bi-maleimide modified complete between position aromatic oxide diamines.
2. according to the described manufacture method that contains the epoxyn of bismaleimides of claim 1, it is characterized in that:
(1) bi-maleimide modified complete between the preparation of position aromatic oxide diamine curing agent
With mol ratio be 1: 2～1: 4 diphenyl methane dimaleimide and complete between a position aromatic oxide diamines join and have agitator, thermometer and logical N
2In the reactor of device, at N
2Protection down heated and stirred to the system fusion, 130 ℃～150 ℃ reactions of temperature 2～6 hours, obtain bi-maleimide modified complete between position aromatic oxide diamine curing agent.
(2) contain the preparation of the epoxyn of bismaleimides
With low viscosity bisphenol f type epoxy resin 80～120 weight parts and nucleocapsid type rubber toughner 1～4 weight part, add and have in the reactor of agitator and thermometer, stirred 0.5～2 hour, then solidifying agent 20～40 weight parts are added, mixed 0.5～2 hour for 20 ℃～80 ℃ in temperature, after the temperature of said mixture is reduced to 10 ℃～60 ℃, add imidazoles promotor 1～4 weight part again, continue to stir 0.5～1 hour, obtain the epoxyn that contains bismaleimides of brown sticking shape.
3. according to claim 1 or the 2 described purposes that contain the epoxyn of bismaleimides, it is characterized in that this tackiness agent is mainly used in advanced composite structure and repairs the field.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200410021987 CN1233768C (en) | 2004-03-10 | 2004-03-10 | Epoxy resin adhesive containing dimalea mic and preparation process thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200410021987 CN1233768C (en) | 2004-03-10 | 2004-03-10 | Epoxy resin adhesive containing dimalea mic and preparation process thereof |
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| CN1560167A true CN1560167A (en) | 2005-01-05 |
| CN1233768C CN1233768C (en) | 2005-12-28 |
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| CN 200410021987 Expired - Fee Related CN1233768C (en) | 2004-03-10 | 2004-03-10 | Epoxy resin adhesive containing dimalea mic and preparation process thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102191004A (en) * | 2010-12-31 | 2011-09-21 | 莱芜金鼎电子材料有限公司 | Thermosetting adhesive for flexible basic material and preparation method thereof |
| CN103833958A (en) * | 2014-03-11 | 2014-06-04 | 吴江固德电材系统股份有限公司 | Preparation method of environment-friendly single-component solvent-free epoxy impregnating resin |
| CN104745133B (en) * | 2015-03-24 | 2016-08-24 | 王传广 | A kind of have the quick capillary flow of room temperature and can the flip-chip underfill of quick prosthetic |
| CN110951432A (en) * | 2019-12-24 | 2020-04-03 | 黄光来 | Epoxy resin building structural adhesive and preparation method thereof |
| CN114015398A (en) * | 2021-11-24 | 2022-02-08 | 浙江荣泰科技企业有限公司 | Heat-resistant epoxy adhesive for metal bonding and preparation method thereof |
| CN116875243A (en) * | 2023-07-17 | 2023-10-13 | 韦尔通科技股份有限公司 | High-flexibility, impact-resistant and low-temperature quick-curing underfill and preparation method thereof |
-
2004
- 2004-03-10 CN CN 200410021987 patent/CN1233768C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102191004A (en) * | 2010-12-31 | 2011-09-21 | 莱芜金鼎电子材料有限公司 | Thermosetting adhesive for flexible basic material and preparation method thereof |
| CN102191004B (en) * | 2010-12-31 | 2014-02-05 | 莱芜金鼎电子材料有限公司 | Thermosetting adhesive for flexible basic material and preparation method thereof |
| CN103833958A (en) * | 2014-03-11 | 2014-06-04 | 吴江固德电材系统股份有限公司 | Preparation method of environment-friendly single-component solvent-free epoxy impregnating resin |
| CN103833958B (en) * | 2014-03-11 | 2016-08-17 | 固德电材系统（苏州）股份有限公司 | The preparation method of environment-friendly type one-component solvent-free epoxy impregnation resin |
| CN104745133B (en) * | 2015-03-24 | 2016-08-24 | 王传广 | A kind of have the quick capillary flow of room temperature and can the flip-chip underfill of quick prosthetic |
| CN110951432A (en) * | 2019-12-24 | 2020-04-03 | 黄光来 | Epoxy resin building structural adhesive and preparation method thereof |
| CN110951432B (en) * | 2019-12-24 | 2021-11-23 | 杭州格鹭科技有限公司 | Epoxy resin building structural adhesive and preparation method thereof |
| CN114015398A (en) * | 2021-11-24 | 2022-02-08 | 浙江荣泰科技企业有限公司 | Heat-resistant epoxy adhesive for metal bonding and preparation method thereof |
| CN116875243A (en) * | 2023-07-17 | 2023-10-13 | 韦尔通科技股份有限公司 | High-flexibility, impact-resistant and low-temperature quick-curing underfill and preparation method thereof |
| CN116875243B (en) * | 2023-07-17 | 2024-01-23 | 韦尔通科技股份有限公司 | High-flexibility, impact-resistant and low-temperature quick-curing underfill and preparation method thereof |
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| CN1233768C (en) | 2005-12-28 |
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