CN1167745C - Polyester imide modified epoxy resin - Google Patents
Polyester imide modified epoxy resin Download PDFInfo
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- CN1167745C CN1167745C CNB021111154A CN02111115A CN1167745C CN 1167745 C CN1167745 C CN 1167745C CN B021111154 A CNB021111154 A CN B021111154A CN 02111115 A CN02111115 A CN 02111115A CN 1167745 C CN1167745 C CN 1167745C
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- epoxy resin
- polyester
- modified epoxy
- imide
- resins
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Abstract
The present invention relates to thermoplastic polyester imide modified epoxy resin. General epoxy resin has crisp and hard texture, poor cracking resistance and poor shock resistance; rubber modified epoxy resin has low vitrification temperature and low bending modulus. In the present invention, epoxy resin is modified by polyester imide in the method of blending, and 5 to 50 pbw of the polyester imide and 50 to 100 pbw of a curing agent are added in the epoxy resin for blending and dissolving. Under the condition that the vitrification temperature of the system of the solidified modified epoxy resin is not reduced, the adhesive property of the modified epoxy resin is increased for over 1.4 times, and the shearing strength of the modified epoxy resin is enhanced for over 1.7 times.
Description
Technical field
The present invention relates to the thermoplastic polyester imide modified epoxy resin, be used for tackiness agent, coating, moulding compound and performance of composites to improve Resins, epoxy.
Background technology
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 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.From the mid-1960s, people begin with fluid rubber epoxy resin toughened, but the glass epoxy temperature of modified rubber is lower.For realize epoxy toughening under the prerequisite that does not reduce mechanical property and thermal characteristics, people are epoxy resin toughened at the thermoplastics of seeking thermotolerance height and good mechanical properties all the time in recent years.
Summary of the invention
The objective of the invention is to seek the method for modifying of the simple Resins, epoxy of a kind of method, to improve the over-all properties of Resins, epoxy.
The objective of the invention is modification, improve it as tackiness agent, coating, moulding compound and performance of composites by Resins, epoxy.
The inventive method is to form by add polyester-imide (PEsI) blend in Resins, epoxy, blend can be undertaken by common blend method, for example blend stirs in 120-160 ℃ oil bath, transparent to solution, be cooled to 100-110 ℃ then, stir the stoichiometric solidifying agent of adding down, solidifying agent dissolves postcooling fully, and is stand-by.The add-on 5-50pbw of polyester-imide during above-mentioned blend, (pbw is parts by weight).The add-on of solidifying agent is 40-100pbw.Resins, epoxy can be the bisphenol A epoxide resin of different molecular weight, as EPON-828, and E-51, CYD-128, DER-331 etc.; Solidifying agent can be phthalic anhydride (PA), methyl tetrahydro phthalic anhydride (MTHPA), tetrahydrophthalic anhydride (THPA), methyl Na Dike acid anhydrides (MDA), Na Dike acid anhydrides (NA) etc.
Polyester-imide of the present invention can be polymerized by dihydroxyphenyl propane diester acid anhydride and aromatic diamines, for example following six kinds:
PEsI viscosity of the present invention is 0.25-1.00dl/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 polyester-imide is dissolved in the appropriate solvent, as methylene dichloride, trichloromethane, tetrahydrofuran (THF), dioxane, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, N-N-methyl-2-2-pyrrolidone N-s 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 present invention also can implement with melt-mixing method; in being furnished with the container of stirring; the Resins, epoxy of the certain proportioning of weighing and polyester-imide; stirring and dissolving is to clear solution in 120-160 ℃ of oil bath; be cooled to 100-110 ℃ then; the solidifying agent that adds said ratio dissolves fully to solidifying agent, moulding or be cooled to room temperature and pulverize standby.Should be noted that blend refrigerated storage the best of making, and the moulding materials need vacuum defoamation.
Polyester-imide add-on of the present invention is better with 10-50pbw, both reduces cost, and the modified epoxy performance is improved.Solidifying agent add-on of the present invention is better with 50-80pbw.
Condition of cure of the present invention can be used the normal condition of prior art, and condition of cure is 80-120 ℃ of curing 1-8 hour preferably, and 130-160 ℃ solidified 1-8 hour, the modified epoxy that availability is good.
The used solidifying agent of the present invention can be a phthalic anhydride, methyl tetrahydro phthalic anhydride, tetrahydrophthalic anhydride, HHPA, methyl Na Dike acid anhydrides, fragrant acid anhydride type curing agents such as Na Dike acid anhydrides.
Because Resins, epoxy is the principal item of construction adhesive, unmodified epoxy resin binder unit elongation is low, and fragility 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 blend solution 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.
The present invention's thermoplastic polyester imide modified epoxy resin can improve the adhesive property that high cross-linked thermal set gonosome is under the situation of the advantages such as second-order transition temperature that do not reduce system.Phase structure to modified system studies show that, in polyreaction induction phase separating process, system can form " co-continuous phase " structure, and can form " counter-rotating phase " 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 is to constitute external phase by a spot of thermoplastics to constitute, and the mechanical property of system and heat, electrical property is 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 can prepare moulding compound or high performance composite matrix resin effectively.
The present invention uses polyester-imide, has excellent mechanical property and good solubility energy, can be dissolved in various conventional solvents and Resins, epoxy.Just can obtain co-continuous phase or counter-rotating phase structure with polyester imide modified epoxy resin system of the present invention, the adhesive property of the polyester imide modified epoxy resin of acquisition is increased substantially.The inventive method is simple, and processing condition realize having excellent industrial application foreground easily.
Embodiment
Example 1 is in being furnished with the container of stirring, earlier with 40pbw ODA type polyester-imide (PEsI, η=0.71dl/g) be dissolved in trichloromethane, after the dissolving fully, room temperature drops into the HHPA of 100pbw E51 Resins, epoxy and metering, and stirring and dissolving to clear solution can be standby.Program curing is: 120 ℃ solidify 3h, and 160 ℃ solidify 4h.The shearing resistance 13.6MPa of sample, (contrast: 3.45MPa); Cohesive force 102.3N, (contrast: 29.0N).102 ℃ of Tg (contrast: 90 ℃).
Example 2 is in being furnished with the container of stirring, accurate weighing 15pbw BISM type polyester-imide (η=0.65dl/g) and 100pbwE51 Resins, epoxy, be dissolved in trichloromethane, after the dissolving fully, room temperature drops into the methyl Na Dike acid anhydrides of 100pbw E51 Resins, epoxy and metering, and stirring and dissolving to clear solution can be standby.Program curing is: 130 ℃ solidify 3h, and 160 ℃ solidify 4h.The shearing resistance 9.28MPa of sample, (contrast: 3.45MPa); Cohesive force 70.6N, (contrast: 29.0N) 100 ℃ of Tg (contrast: 90 ℃).
Example 3 is in being furnished with the container of stirring, with 35pbw BISP type polyester-imide (η=0.58dl/g) and 100pbw E51 Resins, epoxy, in 150 ℃ of oil baths, stirring and dissolving is cooled to about 100 ℃ then to clear solution, the methyl tetrahydro phthalic anhydride that adds metering, dissolving while stirring, de-bubbled under the vital qi of limit is to transparent and homogeneous solution moulding, program curing is: 120 ℃ solidify 4h, and 160 ℃ solidify 4h.
Claims (6)
1, a kind of method of polyester imide modified epoxy resin, form by in Resins, epoxy, adding the polyester-imide blend, it is characterized in that in Resins, epoxy, adding polyester-imide stirred solution or the melt blending of 5-50pbw, cooling adds the 40-100pbw solidifying agent then, be stirred to dissolving fully, the add-on of solidifying agent is 50-80pbw.
2, the method for polyester imide modified epoxy resin according to claim 1 is characterized in that polyester-imide is polymerized with dihydroxyphenyl propane diester acid anhydride and aromatic diamines.
3, the method for polyester imide modified epoxy resin according to claim 1 is characterized in that adding polyester-imide in the Resins, epoxy is melt blending in 120-160 ℃ of oil bath.
4, the method for polyester imide modified epoxy resin according to claim 1, the add-on that it is characterized in that polyester-imide is 10-50pbw.
5, the method for polyester imide modified epoxy resin according to claim 1, its feature condition of cure is: 80-120 ℃ solidified 1-8 hour, and 130-160 ℃ solidified 1-8 hour.
6, the method for polyester imide modified epoxy resin according to claim 1 is characterized in that used solidifying agent is the fragrant acid anhydride type curing agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021111154A CN1167745C (en) | 2002-03-21 | 2002-03-21 | Polyester imide modified epoxy resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021111154A CN1167745C (en) | 2002-03-21 | 2002-03-21 | Polyester imide modified epoxy resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1374344A CN1374344A (en) | 2002-10-16 |
| CN1167745C true CN1167745C (en) | 2004-09-22 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021111154A Expired - Fee Related CN1167745C (en) | 2002-03-21 | 2002-03-21 | Polyester imide modified epoxy resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1167745C (en) |
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2002
- 2002-03-21 CN CNB021111154A patent/CN1167745C/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| CN1374344A (en) | 2002-10-16 |
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