CN103484054A - High-temperature resistant adhesive used for polyether ether ketone bonding - Google Patents
High-temperature resistant adhesive used for polyether ether ketone bonding Download PDFInfo
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- CN103484054A CN103484054A CN201310418927.2A CN201310418927A CN103484054A CN 103484054 A CN103484054 A CN 103484054A CN 201310418927 A CN201310418927 A CN 201310418927A CN 103484054 A CN103484054 A CN 103484054A
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Abstract
The invention discloses high-temperature resistant adhesive used for polyether ether ketone bonding, and belongs to the technical field of high-molecular polymer. The formula of the adhesive includes the steps of enabling bismaleimide resin, thermoplasticity polyimide and aromatic diamine to be blended in an organic solvent according to a certain proportion, obtaining evenly jointly blended resin, then coating the cleaned surfaces of polyether ether ketone bonding pieces with the adhesive resin to enable the bonding pieces to be connected together in a lap joint mode, and completing solidification of the adhesive under the conditions of the 160-240DEG C temperature and the 1-5MPa pressure. The adhesive is moderate in resin viscosity and low in solidification temperature, and has the good usability. Meanwhile, the solidified adhesive has the excellent heat resistance, the bonding pieces can keep the high shearing intensity at the temperature of 250DEG C, and the high-temperature resistant adhesive is suitable for polyether ether ketone bonding.
Description
Technical field
The invention belongs to the high molecular polymer technical field, be specifically related to a kind of high-temperature resistance adhesive for bonding polyether-ether-ketone.
Background technology
Polyether-ether-ketone (Poly ether ether ketone, PEEK) is a kind of new special engineering plastics, has excellent over-all properties, comprises high-temperature stability, good mechanical property, self lubricity, chemical proofing, flame retardant resistance and resistance to fatigue.Because PEEK has excellent physical and chemical performance, and can adopt traditional thermoplastic plastics shaping working method to be processed, it is applied in high-tech sectors such as aerospace, nuclear energy, information communication, electronic apparatus, petrochemical complex and machinofacture, thereby makes the traditional product of many industries realize update.
Tackiness agent is to connect two kinds of identical or different materials by bonding effect, and can possess a class material of certain mechanical property, physicals and chemical property.The application of tackiness agent is extensive all the more along with the development of modern technologies, and adhesive bonding technique has become one of the large interconnection technique in the present age three that comprises splicing, welding and mechanical connection.Especially at adhesive applications maximum topmost aircraft industry the earliest, tackiness agent is mainly used in the bonding of metal construction, metal and plastics, metal and rubber, honeycomb sandwich construction and wallboard etc., can replace gradually part rivet and welding.This is mainly owing to adopting adhesive technology can obviously alleviate the weight of structure, improving fatigue lifetime, process simplification.
Along with the increasing of PEEK in the high-tech sector range of application, to the exploitation of the tackiness agent that is applicable to bonding PEEK, also become inevitable.But the PEEK goods have the material surface density and slickness is high, the characteristic that surface can be low, therefore general tackiness agent adhesive effect is poor; In addition, the use temperature of PEEK goods is higher, and the use temperature of some matrix materials based on PEEK, up to 300 ℃, therefore, need to be developed the high-temperature resistance adhesive that is applicable to bonding PEEK.
Summary of the invention
The purpose of this invention is to provide a kind of high-temperature Resistance Adhesives that is applicable to bonding polyether-ether-ketone.
A kind of high-temperature Resistance Adhesives for bonding polyether-ether-ketone, calculate by quality and 100%, and the bimaleimide resin by 30%～85%, 10%～30% aromatic diamine and 5%～40% thermoplastic polyimide form.
Wherein, the general structure of bimaleimide resin is:
R is
(N, N '-ditane type),
The number-average molecular weight of thermoplastic polyimide is preferably 25000～30000 at 5000～60000(), the molecular formula of structural unit is as follows:
The application of the high-temperature Resistance Adhesives for bonding polyether-ether-ketone of the present invention, its step is as follows:
1) the rectangle PEEK thin slice that uses injection moulding to obtain, as bond, is of a size of 50mm*15mm*3mm, to bonding piece, first uses acetone supersound process 15min with degreasing, rinses with clear water, then uses the distilled water cleaning, drying stand-by;
2) preparation of tackiness agent: the bimaleimide resin of aforementioned proportion, aromatic diamine and thermoplastic polyimide are dissolved in organic solvent, and solid content is that 10%～30%, 40 ℃ of heating steam partial solvent, obtains the resin viscous fluid of homogeneous;
3) preparation of glue joint: according to GB7124-2008, the tackiness agent made is applied on bonding piece after treatment, then overlap, by the Temperature Setting of thermocompressor, it is 160 ℃～240 ℃, apply the pressure of 1MPa～5MPa, heating is cured, and obtains testing the glue joint of shearing resistance.
The 2nd) organic solvent in step can be methylene dichloride, trichloromethane or dimethyl formamide.
Tackiness agent provided by the invention has the following advantages: the PEEK that can effectively bond, and under room temperature, the shearing resistance of bonding piece reaches 16MPa; Have excellent high-temperature stability, still keep very high cohesive force under 250 ℃, shearing resistance is 12.8MPa.The preparation method of tackiness agent is fairly simple simultaneously, and solidification value is lower, is easy to moulding.
The accompanying drawing explanation
Fig. 1: the DSC scanning curve that a curve is the bimaleimide resin that adopts of embodiment 1, the DSC scanning curve that the b curve is the adhesive resin for preparing of embodiment 1.Bimaleimide resin has lower fusing point, is 76 ℃, at 220 ℃, crosslinked peak occurs; Sizing agent resin after modification, because aromatic diamine plays the effect of solidifying agent, therefore crosslinked peaks occur at 180 ℃;
The room temperature down cut intensity curve of the glue joint that Fig. 2: embodiment 1 prepares.The sizing agent made according to this formula at room temperature has higher shearing resistance, reaches 16MPa;
The shearing resistance curve of the glue joint that Fig. 3: embodiment 1 prepares under 250 ℃.The sizing agent made according to this formula still keeps higher shearing resistance at 250 ℃, reaches 12.8MPa.
Embodiment
Embodiment 1
Add 5.4g N in the 40mL dichloromethane solvent, N '-m-phenoxy diphenyl ketone type bimaleimide resin, 1.8g1,4-(p-aminophenyl oxygen base) the thermoplastic polyimide resin A that-2-phenyl benzene and 0.8g molecular weight are 25000, after material dissolution is even, be heated to 40 ℃ of solvents that steam half amount, obtain the resin viscous fluid of homogeneous.The resin viscous fluid made is applied on PEEK thin slice bonding piece after treatment, then overlaps.The baking oven that bond is placed in to 80 ℃ keeps 10min to dry neat solvent, to transfer to Temperature Setting in the thermocompressor that is 200 ℃, and the pressure that applies 2MPa keeps 3h, obtains testing the glue joint of shearing resistance.
Under room temperature and 250 ℃, to this bond test shearing resistance, room temperature down cut intensity is 16MPa, is 12.8MPa under 250 ℃.
Add 6.8g N in the 40mL dichloromethane solvent, N '-m-phenoxy diphenyl ketone type bimaleimide resin, 0.8g1,4-(p-aminophenyl oxygen base) the thermoplastic polyimide resin A that-2-phenyl benzene and 0.4g molecular weight are 25000, after material dissolution is even, be heated to 40 ℃ of solvents that steam half amount, obtain the resin viscous fluid of homogeneous.The resin viscous fluid made is applied on PEEK thin slice bonding piece after treatment, then overlaps.The baking oven that bond is placed in to 80 ℃ keeps 10min to dry neat solvent, to transfer to Temperature Setting in the thermocompressor that is 200 ℃, and the pressure that applies 2MPa keeps 3h, obtains testing the glue joint of shearing resistance.
Under room temperature and 250 ℃, to this bond test shearing resistance, room temperature down cut intensity is 13.1MPa, is 11.5MPa under 250 ℃.
Embodiment 3
Add 5.4g N in the 40mL dichloromethane solvent, N '-m-phenoxy diphenyl ketone type bimaleimide resin, 1.8g1,4-(p-aminophenyl oxygen base) the thermoplastic polyimide resin A that-2-phenyl benzene and 1.6g molecular weight are 25000, after material dissolution is even, be heated to 40 ℃ of solvents that steam half amount, obtain the resin viscous fluid of homogeneous.The resin viscous fluid made is applied on PEEK thin slice bonding piece after treatment, then overlaps.The baking oven that bond is placed in to 80 ℃ keeps 10min to dry neat solvent, to transfer to Temperature Setting in the thermocompressor that is 200 ℃, and the pressure that applies 2MPa keeps 3h, obtains testing the glue joint of shearing resistance.
Under room temperature and 250 ℃, to this bond test shearing resistance, room temperature down cut intensity is 14.3MPa, is 9.8MPa under 250 ℃.
Embodiment 4
Add 2.4g N in the 40mL dichloromethane solvent, N '-m-phenoxy diphenyl ketone type bimaleimide resin, 2.4g1,4-(p-aminophenyl oxygen base) the thermoplastic polyimide resin A that-2-phenyl benzene and 3.2g molecular weight are 25000, after material dissolution is even, be heated to 40 ℃ of solvents that steam half amount, obtain the resin viscous fluid of homogeneous.The resin viscous fluid made is applied on PEEK thin slice bonding piece after treatment, then overlaps.The baking oven that bond is placed in to 80 ℃ keeps 10min to dry neat solvent, to transfer to Temperature Setting in the thermocompressor that is 200 ℃, and the pressure that applies 2MPa keeps 3h, obtains testing the glue joint of shearing resistance.
Under room temperature and 250 ℃, to this bond test shearing resistance, room temperature down cut intensity is 8.6MPa, is 6.1MPa under 250 ℃.
Add 4.5g N in the 40mL dichloromethane solvent, N '-m-phenoxy diphenyl ketone type bimaleimide resin, 2.5g1,4-(p-aminophenyl oxygen base) the thermoplastic polyimide resin A that-2-phenyl benzene and 0.8g molecular weight are 27000, after material dissolution is even, be heated to 40 ℃ of solvents that steam half amount, obtain the resin viscous fluid of homogeneous.The resin viscous fluid made is applied on PEEK thin slice bonding piece after treatment, then overlaps.The baking oven that bond is placed in to 80 ℃ keeps 10min to dry neat solvent, to transfer to Temperature Setting in the thermocompressor that is 200 ℃, and the pressure that applies 2MPa keeps 3h, obtains testing the glue joint of shearing resistance.
Under room temperature and 250 ℃, to this bond test shearing resistance, room temperature down cut intensity is 12.1MPa, is 9.2MPa under 250 ℃.
Add 5.4g N in the 40mL dichloromethane solvent, N '-m-phenoxy hexichol diketone metaphenylene bimaleimide resin, 1.8g4, the thermoplastic polyimide resin C that 4 '-diaminodiphenylmethane and 0.8g molecular weight are 25000, after material dissolution is even, be heated to 40 ℃ of solvents that steam half amount, obtain the resin viscous fluid of homogeneous.The resin viscous fluid made is applied on PEEK thin slice bonding piece after treatment, then overlaps.The baking oven that bond is placed in to 80 ℃ keeps 10min to dry neat solvent, to transfer to Temperature Setting in the thermocompressor that is 200 ℃, and the pressure that applies 2MPa keeps 3h, obtains testing the glue joint of shearing resistance.
Under room temperature and 250 ℃, to this bond test shearing resistance, room temperature down cut intensity is 12.5MPa, is 8.2MPa under 250 ℃.
Add 5.4g N in the 40mL dichloromethane solvent, N '-m-phenoxy hexichol diketone metaphenylene bimaleimide resin, 1.8g4, the thermoplastic polyimide resin C that 4 '-diaminodiphenylmethane and 0.8g molecular weight are 27000, after material dissolution is even, be heated to 40 ℃ of solvents that steam half amount, obtain the resin viscous fluid of homogeneous.The resin viscous fluid made is applied on PEEK thin slice bonding piece after treatment, then overlaps.The baking oven that bond is placed in to 80 ℃ keeps 10min to dry neat solvent, to transfer to Temperature Setting in the thermocompressor that is 200 ℃, and the pressure that applies 4MPa keeps 3h, obtains testing the glue joint of shearing resistance.
Under room temperature and 250 ℃, to this bond test shearing resistance, room temperature down cut intensity is 11.2MPa, is 7.9MPa under 250 ℃.
Add 4.6g N in the 40mL dichloromethane solvent, N '-m-phenoxy hexichol diketone metaphenylene bimaleimide resin, 2.4g4, the thermoplastic polyimide resin C that 4 '-diaminodiphenylmethane and 0.8g molecular weight are 25000, after material dissolution is even, be heated to 40 ℃ of solvents that steam half amount, obtain the resin viscous fluid of homogeneous.The resin viscous fluid made is applied on PEEK thin slice bonding piece after treatment, then overlaps.The baking oven that bond is placed in to 80 ℃ keeps 10min to dry neat solvent, to transfer to Temperature Setting in the thermocompressor that is 200 ℃, and the pressure that applies 2MPa keeps 3h, obtains testing the glue joint of shearing resistance.
Under room temperature and 250 ℃, to this bond test shearing resistance, room temperature down cut intensity is 11.5MPa, is 9.2MPa under 250 ℃.
Claims (5)
1. the high-temperature Resistance Adhesives for bonding polyether-ether-ketone is characterized in that: by quality and 100%, calculate, the bimaleimide resin by 30%～85%, 10%～30% aromatic diamine and 5%～40% thermoplastic polyimide form.
2. a kind of high-temperature Resistance Adhesives for bonding polyether-ether-ketone as claimed in claim 1, it is characterized in that: the general structure of bimaleimide resin is:
Wherein, R is
3. a kind of high-temperature Resistance Adhesives for bonding polyether-ether-ketone as claimed in claim 1 is characterized in that:
Aromatic diamine is
4. a kind of high-temperature Resistance Adhesives for bonding polyether-ether-ketone as claimed in claim 1, it is characterized in that: the number-average molecular weight of thermoplastic polyimide is 5000～60000, and the molecular formula of structural unit is as follows,
5. a kind of high-temperature Resistance Adhesives for bonding polyether-ether-ketone as claimed in claim 4, it is characterized in that: the number-average molecular weight of thermoplastic polyimide is 25000～30000.
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| CN201310418927.2A CN103484054A (en) | 2013-09-14 | 2013-09-14 | High-temperature resistant adhesive used for polyether ether ketone bonding |
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| CN201310418927.2A CN103484054A (en) | 2013-09-14 | 2013-09-14 | High-temperature resistant adhesive used for polyether ether ketone bonding |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110728078A (en) * | 2019-11-14 | 2020-01-24 | 吉林大学 | Method for predicting mechanical property of bonding structure in full-service temperature interval based on chemical characteristics of adhesive |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020193541A1 (en) * | 1994-09-02 | 2002-12-19 | Loctite | Thermosetting resin compositions containing maleimide and/or vinyl compounds |
| CN102112568A (en) * | 2008-08-04 | 2011-06-29 | 日立化成工业株式会社 | Adhesive composition, film-like adhesive, adhesive sheet and semiconductor device |
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- 2013-09-14 CN CN201310418927.2A patent/CN103484054A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020193541A1 (en) * | 1994-09-02 | 2002-12-19 | Loctite | Thermosetting resin compositions containing maleimide and/or vinyl compounds |
| CN102112568A (en) * | 2008-08-04 | 2011-06-29 | 日立化成工业株式会社 | Adhesive composition, film-like adhesive, adhesive sheet and semiconductor device |
Non-Patent Citations (5)
| Title |
|---|
| 刘俊宁: "双马来酰亚胺树脂的改性及应用", 《热固性树脂》, vol. 23, no. 4, 30 July 2008 (2008-07-30), pages 46 - 49 * |
| 吴建元等: "双马来酰亚胺增韧改性研究进展", 《化工新型材料》, vol. 37, no. 3, 31 March 2009 (2009-03-31) * |
| 张丽娟等: "热塑性树脂增韧改性双马来酰亚胺树脂的研究进展", 《绝缘材料》, vol. 41, no. 5, 20 October 2008 (2008-10-20), pages 34 - 39 * |
| 张斌等: "一种双马来酰亚胺耐高温胶粘剂的研制", 《复合材料学报》, vol. 16, no. 1, 28 February 1999 (1999-02-28), pages 58 - 62 * |
| 李四红等: "双马来酰亚胺树脂增韧改性研究进展", 《粘结》, vol. 25, no. 2, 10 April 2004 (2004-04-10), pages 33 - 36 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110728078A (en) * | 2019-11-14 | 2020-01-24 | 吉林大学 | Method for predicting mechanical property of bonding structure in full-service temperature interval based on chemical characteristics of adhesive |
| CN110728078B (en) * | 2019-11-14 | 2022-11-25 | 吉林大学 | Method for predicting mechanical property of bonding structure in full-service temperature interval based on chemical characteristics of adhesive |
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Application publication date: 20140101 |