CN1306024A - Process for preparing solution of polyimid-base resin - Google Patents
Process for preparing solution of polyimid-base resin Download PDFInfo
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- CN1306024A CN1306024A CN 00128254 CN00128254A CN1306024A CN 1306024 A CN1306024 A CN 1306024A CN 00128254 CN00128254 CN 00128254 CN 00128254 A CN00128254 A CN 00128254A CN 1306024 A CN1306024 A CN 1306024A
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Abstract
A polyimide-base resin solution used for dipping fibres is prepared from dimethyl diphenylbutyrate, diamine and terminating agent through reaction while stirring in the mixture of alcohol and water at ordinary time -60 deg.C under the protection of nitrogen gas for 4 hrs. Its advantages are non-toxic solvent, high content of solid and low viscosity.
Description
The invention belongs to the preparation method of solution of polyimid-base resin.
PMR (the polymerization of monomer reactant, Polymerization ofmonomer reactants) method is the method that be used to prepare polyimide advanced composite material matrix resin (United States Patent (USP) 3 528 950) of NASA (NASA) invention in 1970, this method is a raw material with the dimethyl ester of benzophenone tetracarboxylic dianhydride and diaminodiphenylmethane and nadic acid mono-methyl, the dipping that is used for the charcoal fiber in methyl alcohol after mixing is used for the manufacturing of matrix material with the preparation single-layer sheet.Its advantage is that polyreaction scene in the matrix material pressing process is carried out, and utilizes preceding low melting point of the complete polymerization of monomer and low melt viscosity, and to obtain high performance matrix material, typical kind is PMR-15.Yet this method also is not suitable for the polyimide of other kind, for example is the resin of raw material with the biphenyl dianhydride, because this raw material precipitation will occur in methyl alcohol with after other raw material mixes.Chinese patent 951002392 once improved the PMR method, made it be suitable for the preparation of biphenyl dianhydride polyimide type resin.
The preparation method who the purpose of this invention is to provide a kind of solution of polyimid-base resin; this method is with biphenyl tetracid dimethyl ester; diamines and end-capping reagent are in the mixture of second alcohol and water, and in chamber to 60 ℃, stirring reaction just obtained being used for the resin solution of impregnation of fibers in 4 hours under the nitrogen protection.
The present invention utilizes the high polarity of water and the good solubility combination of alcohol, in certain proportion, reactant is fully dissolved, and is able to satisfy the purpose of impregnated carbon fiber/glass fibre toughener.
The used tetracid diester of the present invention has pyromellitic acid dimethyl ester (PMDE), pyromellitic acid diethyl ester (PMDEE) biphenyl tetracid dimethyl ester (BPDE), biphenyl tetracid diethyl ester (BPDEE), phenyl ether tetracid mono-methyl (ODPE), phenyl ether tetracid mono ethyl ester (ODPEE), diphenyl sulfide tetracid mono-methyl (TDPE), diphenyl sulfide tetracid mono ethyl ester (TDPEE); Used diamines has Ursol D (p-PDA), mphenylenediamine (m-PDA), diaminodiphenylmethane (MDA), diaminodiphenyl oxide (ODA) and composition thereof; Used end-capping reagent has monomethyl maleate (ME), ethyl maleate (MEE), nadic acid mono-methyl (NE), nadic acid mono ethyl ester (NEE), phenylacetylene base phthalic acid mono-methyl (PEPE), phenylacetylene base phthalic acid mono ethyl ester (PEPEE), phthalic acid mono-methyl (PE), phthalic acid mono ethyl ester (PEE); Used solvent has methyl alcohol, ethanol, and Virahol, water, the ratio of alcohol and water is 8: 1-1: 4; With biphenyl tetracid diester, diamines and end-capping reagent are in the mixture of second alcohol and water, and in chamber to 60 ℃, stirring reaction just obtained being used for the resin solution of impregnation of fibers in 4 hours under the nitrogen protection.
Solvent for use cheapness of the present invention, nontoxic, can the wider monomer of the scope of application, also can keep PMR technology institute inherent advantage simultaneously, as high solids content, low-viscosity etc.
Embodiment provided by the invention is as follows:
Embodiment 1:
Take by weighing BPDE 17.912g, p-PDA 4.055g, m-PDA4.055g, PEPE 14.014g in reaction flask, add mixed solvent 45mL, ethanol/water=3/2, N
2Protection was stirred after 8 hours, was warming up to 60 ℃ and continued reaction 4 hours, got orange red PMR resin impregnation liquid after the reflux.
Embodiment 2:
Take by weighing BPDE 17.912g, ODA 15.017g, PEPE 14.014g in reaction flask, add mixed solvent 45mL, ethanol/water=8/1, N
2Protection was stirred after 8 hours, was warming up to 60 ℃ and continued reaction 4 hours, got PMR resin impregnation liquid after the reflux.
Embodiment 3:
Take by weighing PMDE 14.108g, p-PDA 4.055g, m-PDA4.055g, PEPE 14.014g in the single port bottle, add mixed solvent 60mL, methanol=1/4, N
2Stirred 8 hours under the protection room temperature, get orange-red solution.
Embodiment 4:
Take by weighing BTDA 19.617g, MDA 14.870g, PEPE 14.014g in the single port bottle, add mixed solvent 45mL, stirred 6 hours under the room temperature Virahol alcohol/water=3/2, gets PMR resin impregnation liquid.
Embodiment 5:
Take by weighing BPDEE 19.318g, m-PDA 8.110g, PEPE14.014g in the single port bottle, add mixed solvent 45mL, methanol=2/3, N
2Protection was stirred after 8 hours, was warming up to 60 ℃ and continued reaction 4 hours, got orange red PMR resin impregnation liquid after the reflux.
Embodiment 6:
Take by weighing TDPEE 20.922g, m-PDA 8.110g, PEPE14.014g in the single port bottle, add mixed solvent 40mL, ethanol/water=3/2, N
2Protection stirring at room down got PMR resin impregnation liquid in 8 hours.
Embodiment 7:
Take by weighing PMDEE 15.513g, MDA 14.871g, PEPE 14.014g in the single port bottle, add mixed solvent 55mL, ethanol/water=3/2, N
2Protection was stirred after 8 hours, was warming up to 40 ℃ and continued reaction 4 hours, got PMR resin impregnation liquid.
Embodiment 8:
Take by weighing BPDE 17.912g, p-PDA 4.055g, m-PDA4.055g, NE 8.210g in the single port bottle, add mixed solvent 45mL, ethanol/water=3/2, N
2The protection stirring was warming up to 60 ℃ and continues reaction 4 hours after 8 hours, and reheat gets PMR resin impregnation liquid to refluxing.
Embodiment 9:
Take by weighing BTDE 19.316g, p-PDA 4.055g, m-PDA4.055g, NE 8.210g in the single port bottle, add mixed solvent 45mL, ethanol/water=8/1, N
2Protect and stir after 8 hours, be warming up to 60 ℃ and continue reaction 4 hours, when getting orange-red solution after the reflux, get PMR resin impregnation liquid.
Embodiment 10:
Take by weighing BPDE 17.912g, m-PDA 8.110g, NE 8.210g in the single port bottle, add mixed solvent 45mL, ethanol/water=3/2, N
2Protect and stir after 8 hours, be warming up to 60 ℃ and continue reaction 4 hours, when getting orange-red solution after the reflux, get PMR resin impregnation liquid.
Embodiment 11:
Take by weighing BPDE 17.912g, m-PDA 8.110, NEE 8.797g in the single port bottle, add mixed solvent 40mL, ethanol/water=4/1, N
2Protect and stir after 8 hours, be warming up to 60 ℃ and continue reaction 4 hours, when getting orange-red solution after the reflux, get PMR resin impregnation liquid.
Embodiment 12:
Take by weighing BPDE 17.912g, MDA 14.871g, PEPEE 12.302g in the single port bottle, add mixed solvent 60mL, ethanol/water=3/2, N
2Protect and stir after 8 hours, be warming up to 60 ℃ and continue reaction 4 hours, when getting orange-red solution after the reflux, get PMR resin impregnation liquid.
Claims (2)
1. the preparation method of a solution of polyimid-base resin, it is characterized in that used tetracid diester has pyromellitic acid dimethyl ester (PMDE), pyromellitic acid diethyl ester (PMDEE), biphenyl tetracid dimethyl ester (BPDE), biphenyl tetracid diethyl ester (BPDEE), phenyl ether tetracid mono-methyl (ODPE), phenyl ether tetracid mono ethyl ester (ODPEE), diphenyl sulfide tetracid mono-methyl (TDPE), diphenyl sulfide tetracid mono ethyl ester (TDPEE); Used diamines has Ursol D (p-PDA), mphenylenediamine (m-PDA), diaminodiphenylmethane (MDA), diaminodiphenyl oxide (ODA) and composition thereof; Used end-capping reagent has monomethyl maleate (ME), ethyl maleate (MEE), nadic acid mono-methyl (NE), nadic acid mono ethyl ester (NEE), phenylacetylene base phthalic acid mono-methyl (PEPE), phenylacetylene base phthalic acid mono ethyl ester (PEPEE), phthalic acid mono-methyl (PE), phthalic acid mono ethyl ester (PEE); Used solvent is a methyl alcohol, ethanol, and Virahol, water, the ratio of alcohol and water is 8: 1-1: 4; With biphenyl tetracid diester, diamines and end-capping reagent are in the mixture of second alcohol and water, and in chamber to 60 ℃, stirring reaction just obtained being used for the resin solution of impregnation of fibers in 4 hours under the nitrogen protection.
2. the preparation method of solution of polyimid-base resin as claimed in claim 1 is characterized in that used mixture is Ursol D (p-PDA), mphenylenediamine (m-PDA).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00128254 CN1107688C (en) | 2000-12-14 | 2000-12-14 | Process for preparing solution of polyimid-base resin |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00128254 CN1107688C (en) | 2000-12-14 | 2000-12-14 | Process for preparing solution of polyimid-base resin |
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| Publication Number | Publication Date |
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| CN1306024A true CN1306024A (en) | 2001-08-01 |
| CN1107688C CN1107688C (en) | 2003-05-07 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 00128254 Expired - Fee Related CN1107688C (en) | 2000-12-14 | 2000-12-14 | Process for preparing solution of polyimid-base resin |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1298766C (en) * | 2005-06-20 | 2007-02-07 | 四川大学 | Polyarylene imide sulfide sulfone and its preparation method |
| CN102199290A (en) * | 2011-04-12 | 2011-09-28 | 中国科学院化学研究所 | Thermoplastic polyimide adhesive film as well as preparation method and application thereof |
| CN106866964A (en) * | 2015-12-14 | 2017-06-20 | 清华大学 | A kind of polyimide foam and preparation method thereof |
-
2000
- 2000-12-14 CN CN 00128254 patent/CN1107688C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1298766C (en) * | 2005-06-20 | 2007-02-07 | 四川大学 | Polyarylene imide sulfide sulfone and its preparation method |
| CN102199290A (en) * | 2011-04-12 | 2011-09-28 | 中国科学院化学研究所 | Thermoplastic polyimide adhesive film as well as preparation method and application thereof |
| CN102199290B (en) * | 2011-04-12 | 2013-06-12 | 中国科学院化学研究所 | Thermoplastic polyimide adhesive film as well as preparation method and application thereof |
| CN106866964A (en) * | 2015-12-14 | 2017-06-20 | 清华大学 | A kind of polyimide foam and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN1107688C (en) | 2003-05-07 |
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