CN105017533A - Preparation method for polyamide imide coating - Google Patents
Preparation method for polyamide imide coating Download PDFInfo
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- CN105017533A CN105017533A CN201510390427.1A CN201510390427A CN105017533A CN 105017533 A CN105017533 A CN 105017533A CN 201510390427 A CN201510390427 A CN 201510390427A CN 105017533 A CN105017533 A CN 105017533A
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Abstract
The present invention relates to a preparation method for a polyamide imide coating. The preparation method comprises: dissolving pyromellitic dianhydride and trimellitic anhydride in an aprotic polar solvent, after stirring and dissolving the pyromellitic dianhydride and the trimellitic anhydride under protection of nitrogen gas, adding diphenylmethane diisocyanate and stirring the solution to obtain a polyamide imide solution; carrying out solvent exchange to obtain a yellowish-brown solid; and drying the obtained yellowish-brown solid to prepare the polyamide imide coating. The method is simple, short in polymerization process time and easy in treatment, and does not need secondary operation for carrying out imidization; and the obtained polyamide imide coating is strong in adsorption capacity and excellent in thermal oxidation resistance, so that the production cost of the polyamide imide is further lowered and the preparation method has a wide application prospect.
Description
Technical field
The invention belongs to the preparation field of coated material, particularly a kind of preparation method of polyamidoimide coating.
Background technology
Within 1961, E.I.Du Pont Company develops PMMI, has started the upsurge to polyimide research.As a kind of novel polyimide, the intensity of polyamidoimide is that in the world today, any industrial no reinforced plastics is incomparable, and its tensile strength is more than 172MPa, and under 1.8MPa load, heat-drawn wire is 274 DEG C.
Polyimide material has excellent chemical stability, excellent thermotolerance scale resistance, outstanding mechanical property, is widely used in space flight and aviation, fire-retardant material, filtration membrane etc.; But, due to polyimide molecule stiff backbone and the interaction of very strong molecular chain, cause the solubility property of polyimide poor, the processing characteristics of polyimide be restricted; Therefore, the emphasis of research is concentrated on the polyimide designing synthesizing new under the prerequisite keeping excellent properties by educational circles.The solvability of the polyimide utilizing flexible diamines to synthesize at Polymer Vol.42 (2001) 5175-5179 as people such as Been-YangLiaw obtains and significantly promotes and remain the thermal property of polyimide excellence; Polyimide not only containing amido linkage but also containing imide bond in the molecule that the people such as P.V.Prabhakaran synthesize at European PolymerJournal Vol.39 (2003) 401 – 405, X-ray diffractometer (XRD) is utilized to observe, the polyimide of synthesis is non-crystalline polymer, without obvious thermal weight loss at 400 DEG C of temperature;
Except synthesis pure component polyimide coating, some micromolecular additives are also apparent on the impact of polyimide coating performance.The people such as Sophie Costil join in polyimide coating with tetrafluoroethylene (PTFE) and silicon carbide (SiC) as additive at Surface & Coatings Technology Vol.235 (2013) 603 – 610, obtained compound coating, have studied its crocking resistance and thermal property.Adding of PTFE has a certain upgrade to the surface property of coating, but reduces the mechanical property of coating, and adding of SiC does not significantly promote the surface property of coating, but can improve mechanical property and the crocking resistance of coating.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of preparation method of polyamidoimide coating, and the inventive method is compared with traditional polyimide coating, and preparation is simple, and single stage method can directly be synthesized; Raw material is easy to get, and cost reduces further; Thermal property improves further.
The preparation method of a kind of polyamidoimide coating of the present invention, comprising:
Be that pyromellitic dianhydride and the trimellitic acid 1,2-anhydride of 2 ~ 10:90 ~ 98 is dissolved in aprotic polar solvent by mol ratio; under nitrogen protection; after 80 DEG C of stirring reaction 0.5h, add diphenylmethanediisocyanate, 80 DEG C keep 2.5-3h; be warming up to 140 DEG C subsequently and keep 5 ~ 6h; obtain dark red solution (polyamidoimide polymers soln), then cool, exchange of solvent obtains by yellow to the solid of brown; drying, preparation obtains polyamidoimide coating.
Described solvent is volume ratio is the N-Methyl pyrrolidone of 8 ~ 9:1 ~ 2 and the mixed solvent of dimethylbenzene.
Described N-Methyl pyrrolidone and dimethylbenzene all need to use molecular sieve process, except the moisture in desolventizing and impurity.
Described diphenylmethanediisocyanate is 1 ~ 1.05:1 with the amount of substance ratio of pyromellitic dianhydride, trimellitic acid 1,2-anhydride two kinds of acid anhydrides summations.
Described drying temperature is 120 DEG C, and time of drying is 24h.
Described solvent exchange procedure is slowly poured in deionized water by synthesized polyamidoimide polymers soln, and mutual permutoid reaction occurs for solvent and deionized water, outwells deionized water solution after certain hour, rejoins deionized water, repeatedly exchanges 5 times.In order to prevent the solid cracking of separating out, in exchange of solvent, add a small amount of N-Methyl pyrrolidone (deionized water containing 1%N-methyl-2-pyrrolidone) in deionized water, with the speed of the exchange of solvent that slows down.
Along with the increase of pyromellitic dianhydride content, the color burn of the polyamidoimide obtained, changes tawny into by yellow.Described drying temperature is 120 DEG C, and time of drying is 24h.
Described preparation obtains polyamidoimide coating: be that solvent is mixed with polyamidoimide coating with N-Methyl pyrrolidone.
Described N-Methyl pyrrolidone is the N-Methyl pyrrolidone after molecular sieve process.
The solid content of described polyamidoimide coating is 20% ~ 40%.
The chemical structural formula of described polyamidoimide:
Wherein n1:0.9-0.98, n2:0.02-0.1
beneficial effect
The present invention is simple to operate, and generated time is short; Gained polyamidoimide coating has excellent physics and chemical property, and thermal property significantly promotes, can standing storage, has widened the range of application of polyimide coating further, has had a good application prospect.
Accompanying drawing explanation
Fig. 1 is the FTIR photo of the polyamidoimide of synthesis;
Fig. 2 is the DSC photo of the polyamidoimide of synthesis;
Fig. 3 is the XRD photo of the polyamidoimide of synthesis;
Fig. 4 is the SEM comparison diagram of traditional polyamidoimide (PAI-0) and embodiment 1 synthesizing polyamides imide (PAI-5); Fig. 5 is the DSC comparison diagram of traditional polyamidoimide and synthesized polyamidoimide.
Embodiment
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Embodiment 1
By 0.01mol pyromellitic dianhydride; 0.09mol trimellitic acid 1,2-anhydride adds in there-necked flask; subsequently 75mlN-methyl-2-pyrrolidone and 10ml dimethylbenzene are added there-necked flask, when nitrogen protection, be heated to 80 DEG C, stir 30min; after pyromellitic dianhydride and trimellitic acid 1,2-anhydride dissolve completely; add 0.1mol diphenylmethanediisocyanate, continue to stir 2.5h at 80 DEG C, be warming up to 140 DEG C subsequently; stir 5h, take off there-necked flask subsequently and be cooled to room temperature.The polymers soln of gained is poured into uniformly in the deionized water containing 1%N-methyl-2-pyrrolidone, polymkeric substance is separated out, displacement lye 5 times.Subsequently the Tan solid obtained is positioned over dry 24h in 120 DEG C of vacuum drying ovens, obtains dry polymkeric substance.Fig. 1 is the FTIR collection of illustrative plates of polymkeric substance, can see 3353cm
-1for N – H vibration absorption peak, 1777cm
-1for the stretching, extension absorption peak of C=O asymmetric in imide bond, 1722cm
-1for the stretching, extension absorption peak of C=O symmetrical in imide bond, 1662cm
-1for C=O vibration absorption peak in amido linkage, 1378cm
-1for C-N in imide bond stretches absorption peak, 1118cm
-1, 725cm
-1for the deformation absorption peak of imide ring, can know that synthesized polymkeric substance is polyamidoimide by FTIR figure; 3g polyamidoimide is dissolved in the N-Methyl pyrrolidone of 7g molecular sieve process, after dissolving completely, obtained solid content is the polyamidoimide coating of 30%.
Fig. 2 is the DSC test pattern of polyamidoimide; Fig. 3 is the XRD test pattern of polyamidoimide, wherein PAI-5, PAI-4, PAI-3, PAI-2, PAI-1, PAI-0 represent that pyromellitic dianhydride molar weight accounts for 10%, 8%, 6%, 4%, 2%, 0% of pyromellitic dianhydride and trimellitic acid 1,2-anhydride mole summation respectively, the polyamidoimide obtained.
Fig. 4 is the SEM comparison diagram of traditional polyamidoimide and synthesized polyamidoimide, can be clearly seen that, novel polyamide imide film is more closely knit, smooth, even compared to traditional polyamidoimide film, in addition, also has higher hardness than traditional polyamidoimide.
The contrast of tradition polyamidoimide and the present embodiment polyamidoimide acid-proof alkaline: alkali resistance (50gL
-1naOH): conventional P AI-0 is 4h bubble, PAI-5 is that 12h bubbles; Acid resistance (10%H
2sO
4): conventional P AI is 3h bubble, and PAI-5 is that 7h bubbles.
Embodiment 2
By 8mmol pyromellitic dianhydride; 0.092mol trimellitic acid 1,2-anhydride adds in there-necked flask; subsequently 80mlN-methyl-2-pyrrolidone and 15ml dimethylbenzene are added there-necked flask, when nitrogen protection, be heated to 80 DEG C, stir 30min; after pyromellitic dianhydride and trimellitic acid 1,2-anhydride dissolve completely; add 0.1mol diphenylmethanediisocyanate, continue to stir 3h at 80 DEG C, be warming up to 140 DEG C subsequently; stir 5.5h, take off there-necked flask subsequently and be cooled to room temperature.The polymers soln of gained is poured into uniformly in the deionized water containing 1%N-methyl-2-pyrrolidone, polymkeric substance is separated out, displacement lye 7 times.Subsequently the Tan solid obtained is positioned over dry 24h in 120 DEG C of vacuum drying ovens, obtains dry polymkeric substance.4g polyamidoimide is dissolved in the N-Methyl pyrrolidone of 8g molecular sieve process, after dissolving completely, obtained solid content is the polyamidoimide coating of 35%.
Fig. 5 is traditional polyamidoimide and the comparing of novel polyamide imide thermal characteristics, can see, the imido second-order transition temperature of novel polyamide (Tg) increases along with the increase of PMDA, when PMDA content reaches 10% (Fig. 2), the imido Tg of novel polyamide has exceeded 300 DEG C, and thermal property has had significant lifting.
The contrast of tradition polyamidoimide and the present embodiment polyamidoimide acid-proof alkaline: alkali resistance (50gL
-1naOH): conventional P AI-0 is 4h bubble, PAI-4 is that 11h bubbles; Acid resistance (10%H
2sO
4): conventional P AI is 3h bubble, and PAI-5 is that 5h bubbles.
Embodiment 3
By 6mmol pyromellitic dianhydride; 0.094mol trimellitic acid 1,2-anhydride adds in there-necked flask; subsequently 70mlN-methyl-2-pyrrolidone and 15ml dimethylbenzene are added there-necked flask, when nitrogen protection, be heated to 80 DEG C, stir 30min; after pyromellitic dianhydride and trimellitic acid 1,2-anhydride dissolve completely; add 0.1mol diphenylmethanediisocyanate, continue to stir 3h at 80 DEG C, be warming up to 140 DEG C subsequently; stir 6h, take off there-necked flask subsequently and be cooled to room temperature.The polymers soln of gained is poured into uniformly in the deionized water containing 1%N-methyl-2-pyrrolidone, polymkeric substance is separated out, displacement lye.Subsequently the Tan solid obtained is positioned over dry 24h in 120 DEG C of vacuum drying ovens, obtains dry polymkeric substance.4g polyamidoimide is dissolved in the N-Methyl pyrrolidone of 4g molecular sieve process, after dissolving completely, obtained solid content is the polyamidoimide coating of 40%.
The contrast of tradition polyamidoimide and the present embodiment polyamidoimide acid-proof alkaline: alkali resistance (50gL
-1naOH): conventional P AI-0 is 4h bubble, PAI-3 is that 10h bubbles; Acid resistance (10%H
2sO
4): conventional P AI is 3h bubble, and PAI-5 is that 5h bubbles.
Can see, the imido resistance to acids and bases of novel polyamide has had obvious improvement than the acid-proof alkaline of traditional polyamidoimide, and adhesion property has had corresponding lifting.
Claims (10)
1. a preparation method for polyamidoimide coating, comprising:
Be that pyromellitic dianhydride and the trimellitic acid 1,2-anhydride of 2 ~ 10:90 ~ 98 is dissolved in solvent by mol ratio; under nitrogen protection; after 80 DEG C of stirring reaction 0.5h; add diphenylmethanediisocyanate, 80 DEG C keep 2.5-3h, are warming up to 140 DEG C subsequently and keep 5 ~ 6h; then cool; exchange of solvent, dry, preparation obtains polyamidoimide coating.
2. the preparation method of a kind of polyamidoimide coating according to claim 1, is characterized in that: described solvent is volume ratio is the N-Methyl pyrrolidone of 8 ~ 9:1 ~ 2 and the mixed solvent of dimethylbenzene.
3. the preparation method of a kind of polyamidoimide coating according to claim 2, is characterized in that: described N-Methyl pyrrolidone and dimethylbenzene all need to use molecular sieve process, except the moisture in desolventizing and impurity.
4. the preparation method of a kind of polyamidoimide coating according to claim 1, is characterized in that: described diphenylmethanediisocyanate is 1 ~ 1.05:1 with the amount of substance ratio of pyromellitic dianhydride, trimellitic acid 1,2-anhydride two kinds of acid anhydrides summations.
5. the preparation method of a kind of polyamidoimide coating according to claim 1, it is characterized in that: described drying temperature is 120 DEG C, time of drying is 24h.
6. the preparation method of a kind of polyamidoimide coating according to claim 1, it is characterized in that: described solvent exchange procedure is slowly poured in deionized water by synthesized polyamidoimide polymers soln, there is mutual permutoid reaction in solvent and deionized water, then deionized water solution is outwelled, rejoin deionized water, repeatedly exchange 5 times.
7. the preparation method of a kind of polyamidoimide coating according to claim 1, it is characterized in that: described drying temperature is 120 DEG C, time of drying is 24h.
8. the preparation method of a kind of polyamidoimide coating according to claim 1, is characterized in that: described preparation obtains polyamidoimide coating and is: be that solvent is mixed with polyamidoimide coating with N-Methyl pyrrolidone.
9. the preparation method of a kind of polyamidoimide coating according to claim 8, is characterized in that: described N-Methyl pyrrolidone is the N-Methyl pyrrolidone after molecular sieve process.
10. the preparation method of a kind of polyamidoimide coating according to claim 1, is characterized in that: the solid content of described polyamidoimide coating is 20% ~ 40%.
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Cited By (8)
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CN106336778A (en) * | 2016-09-01 | 2017-01-18 | 宁波群力紧固件制造有限公司 | Wear-resisting blade stud |
CN107936248A (en) * | 2017-11-27 | 2018-04-20 | 长沙新材料产业研究院有限公司 | A kind of preparation method of polyimide resin |
CN109071944A (en) * | 2016-11-17 | 2018-12-21 | 株式会社Lg化学 | Block copolymer film based on polyimides |
CN109206642A (en) * | 2018-07-26 | 2019-01-15 | 京东方科技集团股份有限公司 | Kapton, its forming method and the display device comprising it |
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Cited By (13)
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CN109071944A (en) * | 2016-11-17 | 2018-12-21 | 株式会社Lg化学 | Block copolymer film based on polyimides |
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CN109071944B (en) * | 2016-11-17 | 2020-12-22 | 株式会社Lg化学 | Polyimide-based block copolymer films |
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CN112480731A (en) * | 2019-09-12 | 2021-03-12 | 中国石油天然气股份有限公司 | High-temperature-resistant coating film-forming agent, preparation method and application thereof |
CN112251825A (en) * | 2020-10-12 | 2021-01-22 | 株洲时代新材料科技股份有限公司 | Preparation method of polyamide-imide copolymer fiber |
CN112251825B (en) * | 2020-10-12 | 2022-06-03 | 株洲时代新材料科技股份有限公司 | Preparation method of polyamide-imide copolymer fiber |
CN112679691A (en) * | 2020-12-28 | 2021-04-20 | 杭州吉华高分子材料股份有限公司 | Organic silicon modified polyamide imide for cooker coating and preparation method thereof |
CN112759988A (en) * | 2020-12-28 | 2021-05-07 | 杭州吉华高分子材料股份有限公司 | Water-based polyamideimide anti-corrosion non-stick coating and preparation method thereof |
CN112759988B (en) * | 2020-12-28 | 2022-02-18 | 杭州吉华高分子材料股份有限公司 | Water-based polyamideimide anti-corrosion non-stick coating and preparation method thereof |
CN112679691B (en) * | 2020-12-28 | 2022-04-08 | 杭州吉华高分子材料股份有限公司 | Organic silicon modified polyamide imide for cooker coating and preparation method thereof |
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