CN1033523A - A kind of epoxy resin toughened compound method - Google Patents
A kind of epoxy resin toughened compound method Download PDFInfo
- Publication number
- CN1033523A CN1033523A CN 87105941 CN87105941A CN1033523A CN 1033523 A CN1033523 A CN 1033523A CN 87105941 CN87105941 CN 87105941 CN 87105941 A CN87105941 A CN 87105941A CN 1033523 A CN1033523 A CN 1033523A
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- CN
- China
- Prior art keywords
- epoxy resin
- epoxy
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- ctpu
- resins
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/675—Low-molecular-weight compounds
- C08G18/6755—Unsaturated carboxylic acids
Abstract
A kind of epoxy resin toughened compound method according to method of the present invention, is mixed and made into toughness reinforcing epoxy resin by Resins, epoxy and ending carboxy polyurethane (CTPU), the dihydroxyphenyl propane of oxirane value in 0.3500～0.5000 epoxy equivalent (weight)/100 gram range of resin.Ending carboxy polyurethane (CTPU) is synthesized by poly(propylene oxide) and toluene diisocyanate and MALEIC ANHYDRIDE.The epoxy resin toughened cost that adopts the present invention to make is low, and fracture toughness property and impelling strength are significantly improved.
Description
The present invention is a kind of Resins, epoxy and polar rubber preparation process of mixture, specifically a kind of epoxy resin toughened preparation method.
Advantages such as Resins, epoxy is a kind of thermosetting resin of excellent performance, and it has the physical strength height, and is corrosion-resistant, heat-resisting are mainly used in the matrix of matrix material, coating, aspects such as sealing material and structure-type tackiness agent.But the higher Resins, epoxy of cross-linking density is very crisp, and Application Areas is restricted.Therefore, improving toughness is Resins, epoxy urgent problem in actual applications.
At present, it is main toughner that developed country generally adopts nbr carboxyl terminal (CTBN), also adds a certain amount of dihydroxyphenyl propane sometimes for helping toughner, mixes with Resins, epoxy, and preparation is epoxy resin toughened under the solidifying agent effect.Adopt the epoxy resin toughened toughness of this kind method preparation to improve a lot, and the heat-drawn wire of material descend also not obvious.Domestic present employing active liquid rubber-toughened epoxy resin development is slow, going back of industrial employing is few, its major cause is because toughening effect fluid rubber such as CTBN synthesis technique complexity preferably, production efficiency is low, cost an arm and a leg, per kilogram is about 300 yuan, thereby seldom use at home.Some domestic producers are the fragility that overcomes Resins, epoxy, usually low molecule organic esters such as butyl phthalate are added in the Resins, epoxy to improve the plasticity of material, but do like this, the heat-drawn wire of material descends greatly, can not reach toughness reinforcing purpose.
Purpose of the present invention is to provide a kind of toughness epoxy resin toughened preferably, and this epoxy resin toughened heat-drawn wire descends seldom, and main toughner synthesis technique is simple, low price.
The epoxy resin toughened preparation method that the present invention proposes is to be that the Resins, epoxy of 0.3500～0.5000 epoxy equivalent (weight)/100 gram resins is with main toughner ending carboxy polyurethane (CTPU) and help the toughner dihydroxyphenyl propane to mix in the presence of solidifying agent with oxirane value.
By weight, get oxirane value and be 100 parts of Resins, epoxy in 0.3500～0.5000 epoxy equivalent (weight)/100 gram range of resin, be added in the reactor, add then and become owner of toughening agent C TPU5～20 part, best 8～15 parts; Add again and help 5～40 parts of toughner dihydroxyphenyl propanes, best 25～30 parts, be warming up to 120 ℃～160 ℃, continuously stirring is 1～2 hour routinely, adds 7～25 parts in solidifying agent, and best 10～20 parts, its standing and defoaming of stirred for several minute relief.Then this mixture is put into container or is poured into mould, temperature be controlled at 90～100 ℃ 2～5 hours, be warming up to again and kept about 120 ℃ 5～8 hours, slowly cool to room temperature, can obtain epoxy resin toughened.
The solidifying agent that the present invention uses is the solidifying agent of now common usefulness, as trolamine, and piperidines, MALEIC ANHYDRIDE, Dicyanodiamide etc.
The structural formula of main toughening agent C TPU among the present invention is:
The building-up process of CTPU is: the poly(propylene oxide) in 400～3000 scopes is mixed between Nco/OH=0.6～0.95 by equivalent specific weight with toluene diisocyanate (TDI), temperature of reaction is controlled at 55 ℃～85 ℃, about stirring reaction 1 hour, press COOH/OH=2～4 again and add MALEIC ANHYDRIDE, temperature was controlled between 120～150 ℃ stirring reaction about 4 hours.More than be reflected under the nitrogen protection and carry out.
In order to make poly(propylene oxide) and TDI reaction more complete, when reaction, can suitably add a spot of catalyzer, catalyzer is the dibutyl tin dilaurate of using always, stannous octoate, lead naphthenate, triethylenediamine or the like.
Epoxy resin toughened and the generally acknowledged epoxy resin toughened economical comparision of carrying out under the same conditions of CTBN preferably of the present invention's preparation is listed by following table.
| Fracture toughness property increases multiple | Impelling strength increases multiple | Heat-drawn wire variable quantity ℃ | Ten thousand yuan/ton of prices | |
| CTBN is epoxy resin toughened | 26 | 2.42 | +4 | 3.70 |
| CTPU is epoxy resin toughened | 11 | 7.2 | -1.7 | 1.73 |
Annotate: the CTPU price is calculated by 30 yuan/kg; Epoxy resin toughened to contain main toughner respectively be 10% with two kinds.
Find out that from last table CTPU is epoxy resin toughened more approaching with the epoxy resin toughened total performance of CTBN, but low price is a lot, the CTPU cost has only 20 yuan/kg.
Further specify below by embodiment, but the present invention is not subjected to the influence of this embodiment.
Get terminal hydroxy group poly(propylene oxide) (molecular weight Mn=1000) 100 grams; add 14 gram toluene diisocyanates; the n-butyl phthalate solution that adds 25% dibutyl tin dilaurate about 2ml; under nitrogen protection; temperature is controlled at 60 ℃; stirring reaction 1 hour; reaction finishes the back and adds 15.6 gram MALEIC ANHYDRIDE; temperature was controlled at 140 ℃ of continuation stirring reactions 4 hours under nitrogen protection; after reaction finishes; reactor is connected vacuum extractor, extract unreacted cis-butenedioic anhydride and just obtained CTPU in about 2 hours.
Get 100 kilograms of CTPU10 kilogram and Resins, epoxy (oxirane value is 0.4974 epoxy equivalent (weight)/100 gram resins), dihydroxyphenyl propane adds in the reactor for 30 kilograms, temperature rises to 140 ℃ and stirred 1 hour, adds 15 kilograms of trolamines then, stirs 10 minutes, it is mixed, mixture is poured in the mould, and temperature is controlled at 100 ℃ solidified 3 hours, temperature was risen to 120 ℃ again, kept 6 hours, and allowed it naturally cool to the room temperature demoulding afterwards.Just obtain of the present invention epoxy resin toughened after the demoulding.
Claims (3)
1, a kind of epoxy resin toughened compound method, it is characterized in that the Resins, epoxy employing ending carboxy polyurethane (CTPU) in oxirane value 0.3500～0.5000 epoxy equivalent (weight)/100 gram range of resin is main toughner, dihydroxyphenyl propane is for helping toughner, stir syntheticly under 120～160 ℃, the structural formula of ending carboxy polyurethane (CTPU) is:
2, compound method according to claim 1 is characterized in that 5～20 parts of per by weight 100 parts of used for epoxy resin ending carboxy polyurethanes (CTPU), 5～40 parts of dihydroxyphenyl propanes.
3,, it is characterized in that per by weight 100 parts of the most handy CTPU8 of Resins, epoxy～15 parts, 25～30 parts of dihydroxyphenyl propanes according to claim 1 and 2 described compound methods.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 87105941 CN1033523A (en) | 1987-12-17 | 1987-12-17 | A kind of epoxy resin toughened compound method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 87105941 CN1033523A (en) | 1987-12-17 | 1987-12-17 | A kind of epoxy resin toughened compound method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1033523A true CN1033523A (en) | 1989-06-28 |
Family
ID=4815520
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 87105941 Pending CN1033523A (en) | 1987-12-17 | 1987-12-17 | A kind of epoxy resin toughened compound method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1033523A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105566610A (en) * | 2016-01-15 | 2016-05-11 | 苏州珍展科技材料有限公司 | Impact toughness improver and preparation method of modified epoxy resin composition thereof |
| CN106479417A (en) * | 2016-11-08 | 2017-03-08 | 深圳市宝力新材料有限公司 | LED packaging plastic and preparation method thereof |
| CN107987767A (en) * | 2016-10-26 | 2018-05-04 | 北京天山新材料技术有限公司 | A kind of epoxy resin adhesive and application |
-
1987
- 1987-12-17 CN CN 87105941 patent/CN1033523A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105566610A (en) * | 2016-01-15 | 2016-05-11 | 苏州珍展科技材料有限公司 | Impact toughness improver and preparation method of modified epoxy resin composition thereof |
| CN107987767A (en) * | 2016-10-26 | 2018-05-04 | 北京天山新材料技术有限公司 | A kind of epoxy resin adhesive and application |
| CN106479417A (en) * | 2016-11-08 | 2017-03-08 | 深圳市宝力新材料有限公司 | LED packaging plastic and preparation method thereof |
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| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication |