CN1098879C - Polyetherimide modified bimalieimide resin - Google Patents
Polyetherimide modified bimalieimide resin Download PDFInfo
- Publication number
- CN1098879C CN1098879C CN00114943A CN00114943A CN1098879C CN 1098879 C CN1098879 C CN 1098879C CN 00114943 A CN00114943 A CN 00114943A CN 00114943 A CN00114943 A CN 00114943A CN 1098879 C CN1098879 C CN 1098879C
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- Prior art keywords
- polyetherimide
- modified
- resin
- bimalieimide
- bismaleimide resin
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Abstract
The present invention relates to bismaleimide resin modified by thermoplastic polyether imide. General bismaleimide resin has the disadvantages of crisp and hard texture, poor cracking resistance performance and poor shock resistance performance, and rubber modified bismaleimide resin has the disadvantages of low vitrification temperature and low bending modulus. The bismaleimide resin is modified by the polyether imide in a blend method, and 5 to 45 Phr of polyether imide is added in the bismaleimide resin for blend and dissolution. The prepared modified bismaleimide resin improves the toughness of high crosslink thermosetting systems under the condition that the advantages of high vitrification temperature, high strength, high hardness, etc. of the systems are not decreased, and the breaking energy of the modified bismaleimide resin is greatly increased.
Description
The present invention relates to the thermoplastic polyether modified bimalieimide resin, be used for tackiness agent, coating, molding powder or performance of composites to improve bimaleimide resin.
The carbon fiber reinforced plastics matrix material is subject to people's attention day by day as a kind of high performance structures matrix material, but the relatively poor weakness of impelling strength also influences its widespread use.The fragility of matrix resin has reduced the toughness of matrix material.With the bimaleimide resin is example, and matrix resin is carried out modification, increases the shortcoming that its toughness just can overcome the impact resistance difference, improves performance of composites greatly.The bimaleimide resin quality is crisp firmly, and resistance to cracking and shock resistance are relatively poor.People begin with fluid rubber toughness reinforcing bimaleimide resin, but the bimaleimide resin second-order transition temperature of modified rubber is lower, and when obtaining better toughness and breaking tenacity and improve rubber content, this phenomenon is particularly remarkable especially.For realizing that under the prerequisite that does not reduce mechanical property and thermal characteristics bismaleimides is toughness reinforcing, people seek the toughness reinforcing bimaleimide resin of thermoplastics of and good mechanical properties high with thermotolerance again in recent years.
The objective of the invention is to seek a kind of method of modifying of bimaleimide resin, to improve the over-all properties of bimaleimide resin.
The objective of the invention is modification, improve it as tackiness agent, coating, molding powder or performance of composites by bimaleimide resin.
The inventive method is to form by add polyetherimide (PEI) blend in bimaleimide resin, and blend can be undertaken by common blend method, and for example blend stirs in 130-160 ℃ oil bath, and is transparent to solution, solidifies then.The polyetherimide add-on is 5-45Phr during above-mentioned blend, and Phr is the umber that per 100 portions of spans come to add in the western imide properties-correcting agent.Bismaleimides (Bismaleimide is that the reaction of maleic anhydride and aromatic diamines makes BMI):
Polyetherimide of the present invention can be polymerized by dihydroxyphenyl propane diether acid anhydride and aromatic diamines, for example following four kinds:
Bismaleimides is after preliminary modification, and performance is better.Preliminary modification of the present invention is to add bismaleimides and O, and O '-diallyl bisphenol (DBA) mol ratio is the amount modification of 0.8-1.2.
Bismaleimides also can reach the purpose of preliminary modification by the aromatic diamines that adds 10-40Phr, and then through polyetherimide modified, it is better as tackiness agent, coating, molding powder or performance of composites.The aromatic diamines that adds is as 4,4 '-diaminodiphenylmethane, 4,4 '-diaminodiphenylsulfone(DDS) etc.
DBA and aromatic diamines all add simultaneously, also obtain good result.
PEI viscosity of the present invention is 0.25-1.0dl/g, and this viscosity is to test in 30 ℃, concentration are N-N-methyl-2-2-pyrrolidone N-(NMP) solution of 0.5g/dl.
The present invention can implement with solution blending process, earlier PEI is dissolved in the suitable solvent, as methylene dichloride, tetrahydrofuran (THF), dioxane, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone etc., wait fully dissolving after, add the ditane type bismaleimides (BDM) and the DBA dissolving of metering.DBA is used for preliminary modification.This solution can be used for the preimpregnation of the fiber or the fabric of high performance composite, also can be used for tackiness agent or coating.
The also available melt-mixing method of the present invention is implemented; the polyetherimide (PEI) and the O of accurate weighing institute expense; O '-diallyl bisphenol (DBA) is in being furnished with the container of stirring, in 160 ℃ of oil baths; earlier PEI is joined the DBA stirring and dissolving to homogeneous transparent solution; be cooled to 120-150 ℃ then, add the ditane type bismaleimides (BDM) of certain proportioning, be stirred to dissolving fully; solidify moulding or be cooled to room temperature to be ground into powder standby.
Should be noted that blend makes back refrigerated storage the best, and the moulding materials need vacuum defoamation.
Polyetherimide add-on of the present invention is better with 10-35Phr, both reduces cost, and the modified bismaleimide resin performance is improved.
Condition of cure of the present invention can be with the normal condition of prior art, and solidifies 1.5-2.0 hour when condition of cure is 120-160 ℃ preferably; Solidified 1.5-2.0 hour in the time of 175-190 ℃; Solidified 7.5-8.5 hour in the time of 200-230 ℃, raise with temperature and divide three sections progressively to solidify the modified bismaleimide resin that availability is good.
Because bimaleimide resin is the principal item of construction adhesive, the low fragility of unmodified bimaleimide resin tackiness agent unit elongation is big, and glued part is antifatigue not, so should not use at structure position.The bimaleimide resin of modification of the present invention is under its thermotolerance and the impregnable prerequisite of modulus in flexure, and its toughness is improved greatly, and the modified bismaleimide resin blended liquid that obtains with the solution method blend promptly can be used for tackiness agent.
Equally, the modified epoxy blended liquid that obtains with the solution method blend is used for coating and has also obtained good result.Blended liquid can be used as the presoak of matrix material.
De-bubbled can be used for the molding powder behind the melt blending.
The present invention's thermoplastic polyether modified bimalieimide resin, thereby under the situation of advantages such as the second-order transition temperature that does not reduce system, intensity and hardness, improve the toughness that high cross-linked thermal set gonosome is, phase structure to modified system studies show that, in polyreaction induction phase separating process, system can form " co-continuous phase " structure, and the phenomenon of what is called " phase reversion " can take place under certain condition, promptly become the external phase of system as the thermoplastics of a small amount of component.Owing to the counter-rotating phase structure constitutes netted external phase by a spot of thermoplastics and forms, and the mechanical property of system and heat, electrical property be often based on external phase, and therefore this structure helps increasing substantially of system performance.On this basis, the phase structure of the hierarchy of control just becomes the important means that prepare the high performance composite matrix resin effectively.
Polyetherimide of the present invention has excellent mechanical property and good solubility energy, can be dissolved in various conventional solvents and bimaleimide resin.With polyetherimide amount modified bismaleimide tree of the present invention is just to obtain bicontinuous structure and phase reversion structure, and the energy-to-break of the polyetherimide modified bimalieimide resin of acquisition improves greatly.
Embodiment:
Example 1, accurate weighing 15Phr polyetherimide (PIP) η=0.75dl/g and O, O '-diallyl bisphenol (DBA) in 150 ℃ of oil baths, is added to PIP among the DBA earlier, stirring and dissolving is to equal clear solution, oil bath is cooled to 130 ℃ then, adds two amido diphenyl methane dimaleimides (BDM) of certain proportioning, (BDM: DBA=57: 43 (Wt%), after treating that it dissolves fully, the vacuum outgas bubble is poured into rapidly in the mould of preheating, puts into curing oven.Program curing is: 130 ℃ of 2h, 165 ℃ of 2h, 210 ℃ of 8h.Sample mechanical property: fracture toughness property K
IC=1.62Mpam
1/2, (contrast: 0.97)
Energy-to-break G
IC=616J/m
2(contrast: 210),
Modulus in flexure E=3.43Gpa (contrast: 3.94)
Second-order transition temperature Tg=301 ℃ (contrast: 293 ℃)
Example 2, accurate weighing 20Phr polyetherimide (PIM, η=0.46) and O, O '-diallyl bisphenol (DBA), in 150 ℃ of oil baths, earlier PIM is added among the DBA, stirring and dissolving is to all transparent solution, oil bath is cooled to 130 ℃ then, add certain proportioning two amido diphenyl methane dimaleimides (BDM) (BDM: DBA=57: 43 (Wt%)), after treating to dissolve fully, vacuum outgas bubble, pour into rapidly in the mould of preheating, put into curing oven, program curing: 150 ℃ of 2h, 175 ℃ of 2h, 230 ℃ of 8h, mechanical property is as follows:
Fracture toughness property K
IC=1.64Mpam
1/2Energy-to-break G
IC=668J/m
2Tg=301 ℃ of modulus in flexure E=3.43Gpa second-order transition temperature
Claims (8)
1, a kind of method of polyetherimide modified bimalieimide resin, form by in bimaleimide resin, adding the polyetherimide blend, it is characterized in that in bimaleimide resin, adding the polyetherimide blended under agitation of 5-45 parts by weight/100 parts of weight bismaleimidess, be stirred to dissolving fully, solidify.
2, the method for polyetherimide modified bimalieimide resin according to claim 1 is characterized in that polyetherimide is to be polymerized with dihydroxyphenyl propane diether acid anhydride and aromatic diamines.
3, the method for polyetherimide modified bimalieimide resin according to claim 1, the preliminary modification that it is characterized in that bismaleimides is to add O, O '-diallyl bisphenol, add-on is that bismaleimides and diallyl bisphenol mol ratio are 0.8-1.2, or the adding aromatic diamines, add-on is 10-40 parts by weight/100 part weight bismaleimidess.
4, the method for polyetherimide modified bimalieimide resin according to claim 1 is characterized in that in the bimaleimide resin that adding polyetherimide is solution blending, or melt blending in 130-160 ℃ of oil bath.
5, the method for polyetherimide modified bimalieimide resin according to claim 1, the add-on that it is characterized in that polyetherimide are 10-35 parts by weight/100 part weight bismaleimidess.
6, the method for polyetherimide modified bimalieimide resin according to claim 1 is characterized in that condition of cure is: in the time of 120-160 ℃ 1.5-2.0 hour, and in the time of 175-190 ℃ 1.5-2.0 hour; In the time of 200-230 ℃ 7.5-8.5 hour.
7, the method for polyetherimide modified bimalieimide resin according to claim 1 is characterized in that the bimaleimide resin after the modification is used for tackiness agent or coating.
8, the method for polyetherimide modified bimalieimide resin according to claim 1 is characterized in that the bimaleimide resin after the modification is used for molding powder or matrix material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00114943A CN1098879C (en) | 2000-03-14 | 2000-03-14 | Polyetherimide modified bimalieimide resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00114943A CN1098879C (en) | 2000-03-14 | 2000-03-14 | Polyetherimide modified bimalieimide resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1263901A CN1263901A (en) | 2000-08-23 |
| CN1098879C true CN1098879C (en) | 2003-01-15 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN00114943A Expired - Fee Related CN1098879C (en) | 2000-03-14 | 2000-03-14 | Polyetherimide modified bimalieimide resin |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100482718C (en) * | 2006-01-26 | 2009-04-29 | 长春应化特种工程塑料有限公司 | Polyimide semi-interpenetrating network resin and its prepn. method |
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| CN101440175B (en) * | 2007-11-23 | 2011-07-20 | 颜立峰 | Cast nylon active heat resisting flexibilizer and preparation thereof |
| CN101845143B (en) * | 2010-05-19 | 2012-05-02 | 中国科学院化学研究所 | Modified bismaleimide resin as well as preparation method and application thereof |
| CN103242767B (en) * | 2013-05-20 | 2014-08-20 | 黑龙江省科学院石油化学研究院 | High-temperature-resistant bismaleimide resin carrier structure adhesive film and preparation method thereof |
| CN103804908B (en) * | 2014-02-25 | 2016-07-13 | 南京航空航天大学 | BMI/Polythioetherimide alloy and preparation method thereof |
| JP2020515402A (en) * | 2017-04-06 | 2020-05-28 | ダウ グローバル テクノロジーズ エルエルシー | Thin film composite membrane containing cross-linked Treger base polymer |
| CN110204875A (en) * | 2019-07-10 | 2019-09-06 | 浙江尚居环保科技股份有限公司 | A kind of poly-lactic acid material enhancing and heat-resisting method of modifying |
Citations (7)
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|---|---|---|---|---|
| JPS6172024A (en) * | 1984-09-18 | 1986-04-14 | Toshiba Chem Corp | Thermosetting resin composition |
| US4714642A (en) * | 1983-08-30 | 1987-12-22 | Basf Aktiengesellschaft | Carbon fiber multifilamentary tow which is particularly suited for weaving and/or resin impregnation |
| JPH01230680A (en) * | 1988-03-11 | 1989-09-14 | Furukawa Electric Co Ltd:The | Heat-resistant insulating paint |
| US4902752A (en) * | 1987-10-05 | 1990-02-20 | Hi-Tek Polymers, Inc. | Polycyanate esters of polyhydric phenols blended with thermoplastic polymers |
| US4956393A (en) * | 1988-08-29 | 1990-09-11 | Basf Aktiengesellschaft | Structures exhibiting improved transmission of ultrahigh frequency electromagnetic radiation and structural materials which allow their construction |
| US5134421A (en) * | 1988-08-29 | 1992-07-28 | Basf Aktiengesellschaft | Structures exhibiting improved transmission of ultrahigh frequency electromagnetic radiation and structural materials which allow their construction |
| US5278224A (en) * | 1989-02-16 | 1994-01-11 | Hexcel Corporation | Resin systems of improved toughness and high temperature performance and method therefor |
-
2000
- 2000-03-14 CN CN00114943A patent/CN1098879C/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4714642A (en) * | 1983-08-30 | 1987-12-22 | Basf Aktiengesellschaft | Carbon fiber multifilamentary tow which is particularly suited for weaving and/or resin impregnation |
| JPS6172024A (en) * | 1984-09-18 | 1986-04-14 | Toshiba Chem Corp | Thermosetting resin composition |
| US4902752A (en) * | 1987-10-05 | 1990-02-20 | Hi-Tek Polymers, Inc. | Polycyanate esters of polyhydric phenols blended with thermoplastic polymers |
| JPH01230680A (en) * | 1988-03-11 | 1989-09-14 | Furukawa Electric Co Ltd:The | Heat-resistant insulating paint |
| US4956393A (en) * | 1988-08-29 | 1990-09-11 | Basf Aktiengesellschaft | Structures exhibiting improved transmission of ultrahigh frequency electromagnetic radiation and structural materials which allow their construction |
| US5134421A (en) * | 1988-08-29 | 1992-07-28 | Basf Aktiengesellschaft | Structures exhibiting improved transmission of ultrahigh frequency electromagnetic radiation and structural materials which allow their construction |
| US5278224A (en) * | 1989-02-16 | 1994-01-11 | Hexcel Corporation | Resin systems of improved toughness and high temperature performance and method therefor |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100482718C (en) * | 2006-01-26 | 2009-04-29 | 长春应化特种工程塑料有限公司 | Polyimide semi-interpenetrating network resin and its prepn. method |
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|---|---|
| CN1263901A (en) | 2000-08-23 |
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