CN1263909A - Polyetherimide modified epoxy resin - Google Patents
Polyetherimide modified epoxy resin Download PDFInfo
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- CN1263909A CN1263909A CN 00114942 CN00114942A CN1263909A CN 1263909 A CN1263909 A CN 1263909A CN 00114942 CN00114942 CN 00114942 CN 00114942 A CN00114942 A CN 00114942A CN 1263909 A CN1263909 A CN 1263909A
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- polyetherimide
- epoxy resin
- modified epoxy
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Abstract
本发明是热塑性聚醚酰亚胺改性环氧树脂。通用型环氧树脂质地脆硬,耐开裂性和抗冲击性能差,橡胶改性的环氧树脂玻璃化温度低,弯曲模量低。本发明用聚醚酰亚胺改性环氧树脂,用共混方法改性,在环氧树脂中加入5—45Phr的聚醚酰亚胺和20—60Phr的固化剂共混溶解。制得的改性环氧树脂在未降低体系的玻璃化温度、强度和硬度等优点情况下改善了高交联热固性体系的韧性,使改性后的环氧树脂断裂能高达1200Jm－2以上。The invention is a thermoplastic polyetherimide modified epoxy resin. General-purpose epoxy resins are brittle and hard, have poor crack resistance and impact resistance, and rubber-modified epoxy resins have low glass transition temperature and low flexural modulus. The present invention uses polyetherimide to modify the epoxy resin, which is modified by a blending method, and 5-45 Phr of polyetherimide and 20-60 Phr of curing agent are added to the epoxy resin for blending and dissolving. The prepared modified epoxy resin improves the toughness of the highly cross-linked thermosetting system without reducing the glass transition temperature, strength and hardness of the system, and makes the fracture energy of the modified epoxy resin as high as 1200Jm -2 or more.
Description
The present invention relates to the thermoplastic polyether imide modified epoxy resin, be used for tackiness agent, coating, molding powder and performance of composites to improve Resins, epoxy.
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 Resins, epoxy 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.Begin with fluid rubber epoxy resin toughenedly from the mid-1960s people, but the glass epoxy 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 realize epoxy toughening under the prerequisite that does not reduce mechanical property and thermal characteristics, people seek with the thermoplastics of thermotolerance height and good mechanical properties epoxy resin toughened again in recent years.
The objective of the invention is to seek a kind of method of modifying of Resins, epoxy, to improve the over-all properties of Resins, epoxy.
The objective of the invention is modification, improve it as tackiness agent, coating, molding powder and performance of composites by Resins, epoxy.
The inventive method is to form by add polyetherimide (PEI) blend in Resins, epoxy, blend can be undertaken by common blend method, for example blend stirs in 130-160 ℃ oil bath, transparent to solution, be cooled to 100-130 ℃ then, stir the stoichiometric solidifying agent of adding down, solidifying agent dissolves postcooling fully, and is stand-by.The polyetherimide add-on is 5-45Phr during above-mentioned blend, and Phr is the properties-correcting agent umber that per 100 parts of Resins, epoxy need add, and the add-on of solidifying agent is 20-60Phr.Resins, epoxy can be bisphenol A epoxide resin such as EPON-828,4, and 4 '-diaminodiphenylmethane, four glycidyl ethers (TGDDM) etc.; Solidifying agent can be 4.4 '-diaminodiphenylsulfone(DDS) (DDS), 4.4 '-diaminodiphenylmethane (DDM), 4.4 '-diaminodiphenyl oxide (ODA), 4.4 '-methylene radical, two Ortho-Chloro anilines (MOCA) etc.
Polyetherimide of the present invention can be polymerized by dihydroxyphenyl propane diether acid anhydride and aromatic diamines, for example following four kinds:
PE1 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, promptly in being furnished with the container of stirring, earlier polyetherimide is dissolved in the appropriate solvent, as methylene dichloride, tetrahydrofuran (THF), dioxane, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone etc., dissolving also can reflux.After the dissolving fully, the Resins, epoxy and the solidifying agent of the metering of room temperature input, stirring and dissolving to clear solution can be standby.
The also available melt-mixing method of the present invention is implemented; in being furnished with the container of stirring; the Resins, epoxy of the certain proportioning of weighing and polyetherimide; stirring and dissolving is to clear solution in 130-150 ℃ of oil bath; be cooled to 100-130 ℃ then; the solidifying agent that adds said ratio continues to react to solidifying agent and dissolves fully, moulding or be cooled to room temperature and pulverize 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 epoxy performance is improved.
Solidifying agent add-on of the present invention is better with 25-55Phr.
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 100-150 ℃ preferably; Solidified 1.5-2.0 hour in the time of 170-180 ℃; Solidified 7.5-8.5 hour in the time of 200-220 ℃, raise with temperature and divide three sections progressively to solidify the modified epoxy that availability is good.
The used solidifying agent of the present invention can be anhydrides or fatty amine or aromatic amine curing agent, as 4.4 '-diaminodiphenylsulfone(DDS), and 4.4 '-diaminodiphenyl oxide, triethylene tetramine, tetrahydrochysene methyl phthalic anhydride, six hydrogen methyl phthalic anhydrides etc.
Because Resins, epoxy is the principal item of construction adhesive, the low fragility of unmodified epoxy resin binder unit elongation is big, and glued part is antifatigue not, so should not use at structure position.The Resins, epoxy 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 epoxy 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, pulverizes behind the melt blending to be used for the molding powder.
The present invention's thermoplastic polyether imide modified epoxy resin, thus the toughness that high cross-linked thermal set gonosome is under the situation of advantages such as the second-order transition temperature that does not reduce system, intensity and hardness, improved.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 becomes 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 Resins, epoxy.Just can obtain bicontinuous structure and phase reversion structure with polyetherimide amount modified epoxy system of the present invention, the energy-to-break of polyethers acyl five amine-modified epoxy resins of acquisition is up to 1200Jm
2More than.
Embodiment:
1, in being furnished with the container of stirring, (η-0.51dl/g) drops among the Epon-828, and in 150 ℃ of oil baths, stirring and dissolving is to clear solution with 20PhrPIP, be cooled to then about 120 ℃, add 31Phr DDS, limit stirring and dissolving, de-bubbled under the vacuum of limit, to transparent and homogeneous solution moulding, program curing: 130 ℃ of 2h, 180 ℃ of 2h, 200 ℃ of 8h.Sample mechanical property: fracture toughness property K
IC=1.68Mpam
1/2,
Energy-to-break G
IC=813J/m
2(contrast: 159),
Modulus in flexure 2.6Gpa,
Second-order transition temperature Tg=212 ℃ (contrast: 210 ℃).
This system also can be used as the preparation of molding powder.
2, in being furnished with the molten device of stirring, drop into four-functional group epoxy resin TGDDM, solidifying agent DDS40Phr and 30Phr PIP (η: 0.63dl/g).Add the DMF solvent, stirring and dissolving under the room temperature.Program curing is 110 ℃ of 2h, 160 ℃ of 2h, 210 ℃ of 8h.
Glued joint shearing resistance 260kg/cm
2(in time, shine: 142kg/cm
2)
The inhomogeneous exfoliation temperature 190N/cm of room temperature (contrast: 78N/cm)
256 ℃ of second-order transition temperatures (contrast: 238 ℃)
This blended liquid can be used for tackiness agent or coating.
Claims (10)
1, a kind of method of polyetherimide modified epoxy resin, form by in Resins, epoxy, adding the polyetherimide blend, it is characterized in that adding in Resins, epoxy the polyetherimide blended under agitation of 5-45Phr, cooling adds the 20-60Phr solidifying agent then, is stirred to dissolving fully.
2, the method for polyetherimide modified epoxy 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 epoxy resin according to claim 1 is characterized in that adding polyetherimide in the Resins, epoxy is solution blending, or adds polyetherimide melt blending in 130-160 ℃ of oil bath in the Resins, epoxy.
4, the method for polyetherimide modified epoxy resin according to claim 1, the add-on that it is characterized in that polyetherimide is 10-35Phr.
5, the method for polyetherimide modified epoxy resin according to claim 1, the add-on that it is characterized in that solidifying agent is 25-55Phr.
6, the method for polyetherimide modified epoxy resin according to claim 1 is characterized in that condition of cure is: in the time of 100-150 ℃ 1.5-2.0 hour, and in the time of 170-180 ℃ 1.5-2.0 hour; 200-220 ℃ 7.5-8.5 hour.
7, the method for polyetherimide modified epoxy resin according to claim 1 is characterized in that used solidifying agent is anhydrides or fatty amine or aromatic amine curing agent.
8, the method for polyetherimide modified epoxy resin according to claim 1 is characterized in that the Resins, epoxy after the modification is used for tackiness agent.
9, the method for polyetherimide modified epoxy resin according to claim 1 is characterized in that the Resins, epoxy after the modification is used for coating.
10, the method for polyetherimide modified epoxy resin according to claim 1 is characterized in that the Resins, epoxy after the modification is used for molding powder or matrix material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00114942 CN1263909A (en) | 2000-03-14 | 2000-03-14 | Polyetherimide modified epoxy resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00114942 CN1263909A (en) | 2000-03-14 | 2000-03-14 | Polyetherimide modified epoxy resin |
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| Publication Number | Publication Date |
|---|---|
| CN1263909A true CN1263909A (en) | 2000-08-23 |
Family
ID=4584413
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 00114942 Pending CN1263909A (en) | 2000-03-14 | 2000-03-14 | Polyetherimide modified epoxy resin |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101538399B (en) * | 2009-04-16 | 2011-05-11 | 华东理工大学 | Damping type epoxy resin material and preparation method thereof |
| CN105131288A (en) * | 2015-09-30 | 2015-12-09 | 华东理工大学华昌聚合物有限公司 | Method for synthesizing end-anhydride epoxy resin curing agent |
| CN113321976A (en) * | 2021-06-03 | 2021-08-31 | 泉州超能涂料有限公司 | Special paint with good weather resistance for advertisement sign and preparation method thereof |
| CN113755073A (en) * | 2020-06-05 | 2021-12-07 | 上海维凯光电新材料有限公司 | Electrolyte-resistant matte coating composition for colored aluminum plastic film |
| CN117986529A (en) * | 2024-04-03 | 2024-05-07 | 潍坊弘润石化科技有限公司 | Novel polyetherimide-based epoxy resin and preparation method thereof |
-
2000
- 2000-03-14 CN CN 00114942 patent/CN1263909A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101538399B (en) * | 2009-04-16 | 2011-05-11 | 华东理工大学 | Damping type epoxy resin material and preparation method thereof |
| CN105131288A (en) * | 2015-09-30 | 2015-12-09 | 华东理工大学华昌聚合物有限公司 | Method for synthesizing end-anhydride epoxy resin curing agent |
| CN113755073A (en) * | 2020-06-05 | 2021-12-07 | 上海维凯光电新材料有限公司 | Electrolyte-resistant matte coating composition for colored aluminum plastic film |
| CN113321976A (en) * | 2021-06-03 | 2021-08-31 | 泉州超能涂料有限公司 | Special paint with good weather resistance for advertisement sign and preparation method thereof |
| CN117986529A (en) * | 2024-04-03 | 2024-05-07 | 潍坊弘润石化科技有限公司 | Novel polyetherimide-based epoxy resin and preparation method thereof |
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