CN1107688C - Process for preparing solution of polyimid-base resin - Google Patents
Process for preparing solution of polyimid-base resin Download PDFInfo
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- CN1107688C CN1107688C CN 00128254 CN00128254A CN1107688C CN 1107688 C CN1107688 C CN 1107688C CN 00128254 CN00128254 CN 00128254 CN 00128254 A CN00128254 A CN 00128254A CN 1107688 C CN1107688 C CN 1107688C
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- tetracid
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- ethyl ester
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Abstract
The present invention provides a preparation method of a polyimide matrix resin solution. In the method, the resin solution which can be used for impregnating fibers is obtained by stirring biphenyl tetracid dimethyl ester, diamine and a blocking agent reacting in a mixture of ethanol and water under nitrogen protection at the temperature between the room temperature and 60DEG C for 4 hours. A solvent in use has the advantages of low price and nontoxicity. The present invention which can be suitable for monomers in a wide range can simultaneously reserve the inherent advantages, such as high solid content, low viscosity, etc., of a PMR technology.
Description
The invention belongs to the preparation method of solution of polyimid-base resin.
PMR (the polymerization of monomer reactant, Polymerization of monomer 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 carbon 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 the tetracid diester; diamines and end-capping reagent are in the mixing solutions of alcohol and water, and in room temperature 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 impregnation of carbon fibers/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) or diphenyl sulfide tetracid mono ethyl ester (TDPEE); Used diamines has the mixture of Ursol D (p-PDA), mphenylenediamine (m-PDA), diaminodiphenylmethane (MDA), diaminodiphenyl oxide (ODA) or these diamines; 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) or phthalic acid mono ethyl ester (PEE); Used solvent has methyl alcohol, ethanol or Virahol and water, and the ratio of alcohol and water is 8: 1-1: 4; With the tetracid diester, diamines and end-capping reagent are in the mixed solvent of alcohol and water, and in room temperature 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-PDA 4.055g, 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-PDA 4.055g, PEPE14.014g 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 isopropanol=3/2, gets PMR resin impregnation liquid.
Embodiment 5:
Take by weighing BPDEE 19.318g, m-PDA 8.110g, PEPE 14.014g 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, PEPE 14.014g 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-PDA 4.055g, 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-PDA 4.055g, 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 is characterized in that used tetracid diester has pyromellitic acid dimethyl ester, pyromellitic acid diethyl ester, biphenyl tetracid dimethyl ester, biphenyl tetracid diethyl ester, phenyl ether tetracid mono-methyl, phenyl ether tetracid mono ethyl ester, diphenyl sulfide tetracid mono-methyl or diphenyl sulfide tetracid mono ethyl ester; Used diamines has the mixture of Ursol D, mphenylenediamine, diaminodiphenylmethane, diaminodiphenyl oxide or these diamines; Used end-capping reagent has monomethyl maleate, ethyl maleate, nadic acid mono-methyl, nadic acid mono ethyl ester, phenylacetylene base phthalic acid mono-methyl, phenylacetylene base phthalic acid mono ethyl ester, phthalic acid mono-methyl or phthalic acid mono ethyl ester; Used solvent is methyl alcohol, ethanol or Virahol and water, and the ratio of alcohol and water is 8: 1-1: 4; With the tetracid diester, diamines and end-capping reagent are in the mixture of alcohol and water, and in room temperature to 60 ℃, stirring reaction just obtains being used for the resin solution of impregnation of fibers under the nitrogen protection.
2. the preparation method of solution of polyimid-base resin as claimed in claim 1 is characterized in that used diamines is the mixture of Ursol D and mphenylenediamine.
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 |
Applications Claiming Priority (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 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1306024A CN1306024A (en) | 2001-08-01 |
| CN1107688C true 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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Families Citing this family (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 |
| 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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| CN1306024A (en) | 2001-08-01 |
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