CN103819674A - Synthesis method of direct-spinning polyamide-imide polymer - Google Patents
Synthesis method of direct-spinning polyamide-imide polymer Download PDFInfo
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- CN103819674A CN103819674A CN201410025876.1A CN201410025876A CN103819674A CN 103819674 A CN103819674 A CN 103819674A CN 201410025876 A CN201410025876 A CN 201410025876A CN 103819674 A CN103819674 A CN 103819674A
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- imide polymer
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Abstract
The invention provides a synthesis method of a direct-spinning polyamide-imide polymer. The synthesis method is characterized by specifically comprising the following steps: 1, dissolving a diamine compound into an aprotic polar solvent, adding an acyl chloride compound and an organic amine acid-binding agent, and reacting for 0.5 to 200 hours; 2, adding anhydride into a reaction system, reacting for more than 1 hour and diluting to prepare direct-spinning polyamide-imide polymer slurry. The synthesis method adopts an acyl chloride method for preparation, is flexible, simple and convenient to control and is low in preparation cost; polymerization by complex production equipment is effectively avoided; stock solution spinning can be directly performed after polymerization; the synthesis method is favorable for industrialized production.
Description
Technical field
The invention belongs to a kind of synthetic method that can directly spun poly amide imide polymer.
Background technology
Polyamidoimide (PAI) is as a kind of amorphous high temperature resistant engineering thermoplastic resin, in molecule, there is heat-resisting imide group and flexible amide group simultaneously, can gather the premium properties of acid amides and polyimide in one, there is good dimensional stability and creep resistant, good thermotolerance, radiation resistance, dielectricity, mechanical property and chemical stability.Polyamidoimide chemical structure of general formula is shown below:
Prepare fiber take PAI as raw material, can obtain the fiber with good mechanical properties and resistance toheat.Up to now, Kermel fiber is unique commercial polyamide-imide fiber.Polyamide-imide fiber is typical high-temperature fibre, and itself has flame retardant resistance, not molten drop, high temperature dimensional stability is good, can be under 280 ℃ of high temperature life-time service.And polyamide-imide fiber spinning, weaving performance are good, can with viscose fiber, wool or aramid fiber blending, be widely used in bunker clothing, protective clothing and special uniform etc.
Polyamidoimide generally has following several synthetic method: (1) vulcabond method: prepare take vulcabond and trimellitic acid 1,2-anhydride (TMA) as main raw material.(2) aromatic tetracarboxylic acid's acid anhydride method: the aromatic tetracarboxylic acid's dianhydride take pyromellitic acid anhydride (PMDA) as representative and the aromatic diamine that contains amide group are reacted; (3) chloride method: by trimellitic acid 1,2-anhydride (TMA), acyl chlorides or derivatives thereof and the reaction of aromatic diamine or derivatives thereof.
That in patent FR2079785 and FR2643084, mentions can be prepared from by vulcabond method by spun poly amide imide, but the fibre strength of its acquisition is on the low side, and cost of material is higher.
In patent FR8802328 and FR9116339, mention the aromatic diacid acid anhydride that uses different sorts vulcabond and mix different ratios is reacted, in necessary situation, add basic metal or alkaline-earth metal, to improve the properties that obtains fiber.
Summary of the invention
The object of this invention is to provide a kind of synthetic method that can directly spun poly amide imide polymer, adopt chloride method, by selecting the kind of monomer, regulate polymerizing condition, to obtaining the polymer slurries that there is good solubility, homogeneous transparent in aprotic polar solvent, can directly carry out stoste spinning, guarantee that polymerization solvent system used, with finally consistent for the solvent system of spinning, simplified production technique and production cost.
In order to achieve the above object, the invention provides a kind of synthetic method that can directly spun poly amide imide polymer, it is characterized in that, concrete steps comprise:
The first step: diamine compounds is dissolved in aprotic polar solvent, adds acyl chloride compound and organic amine acid binding agent, react 0.5～200 hour;
Second step: add acid anhydrides in reaction system, reaction more than 1 hour, is diluted, and making can directly spun poly amide imide polymer slurries.
In the structure of polyamidoimide polymkeric substance of the present invention, comprise following repeating unit:
Wherein, R can be aliphatics or aromatic substituents.
Preferably, described diamine compounds has H
2n-R-NH
2structure, wherein R can be aliphatics or aromatic substituents.
More preferably, described diamine compounds is aromatic diamine.
More preferably, described R is that mononuclear aromatics, polycyclic aromatic hydrocarbons and non-benzene aromatic hydrocarbons are as benzene, biphenyl, phenyl ether, diphenyl sulfide, sulfobenzide, two thioanisoles, naphthyl, santowax, two phenylene, two phenylene methane or two phenylene ether.
More preferably, described R is upper with sulphur, oxygen, halogen atom ,-SO
2-or-O-.
More preferably, described diamine compounds is Ursol D, mphenylenediamine, 3,4 '-diaminodiphenyl oxide, 4,4 '-diaminodiphenyl oxide, 4,4 '-diaminodiphenyl sulfide, 4,4 '-diaminodiphenyl-methane, 3,3 '-tolidine, 2,2 '-tolidine, 3,3 '-dichlorobenzidine, 2,2 '-dichlorobenzidine, 3,3 '-dihydroxybiphenyl amine, 3,3 '-dimethoxy benzidine, 2,4 di amino toluene, 2,6-diaminotoluene, 3,3 '-bis-is chloro-4,4 '-diaminodiphenyl-methane, two (3-aminophenyl) propane of 1,3-, two (4-aminocarbonyl phenyl) HFC-236fa of 2,2-, 2,2 '-bis-(trifluoromethyl)-4,4 '-benzidine, α, α-bis-(4-aminophenyl)-Isosorbide-5-Nitrae-diisopropyl benzene, 4,4 '-dithio pentanoic, 4,4 '-methylene dianiline (MDA), 4,4 '-diaminobenzophenone, 3,3 '-diaminobenzophenone, DDS, 4,4 '-diamino-4 " one or more mixture in-hydroxyl tritane.
Preferably, the reaction times of the described the first step is 20～40 hours, and the reaction times of described second step is more than 12 hours.
The temperature of reaction of the described the first step is-80～120 ℃, is preferably-10～20 ℃.
Preferably, the mol ratio of described diamine compounds and acyl chloride compound is 1: 0.9～1: 1.5.
Preferably, described acyl chloride compound is Trimellitic Anhydride Chloride.
Preferably, described aprotic polar solvent is DMF (DMF), N,N-dimethylacetamide (DMAc) or N-Methyl pyrrolidone (NMP).
Preferably, described organic amine acid binding agent is tertiary amine compounds.
More preferably, described tertiary amine compounds is triethylamine, pyridine, picoline, ethylpyridine, lutidine, parvoline, quinoline or isoquinoline 99.9.
Preferably, the mol ratio of described tertiary amine compounds and Trimellitic Anhydride Chloride is 0.5: 1～2: 1.
Preferably, described acid anhydrides is diacetyl oxide, and the mol ratio of diacetyl oxide and acyl chloride compound is 0.5: 1～2: 1.
Preferably, described mass concentration that can directly spun poly amide imide polymer is 5%～25%, is preferably 10%～20%.
Preferably, in described second step, adopt aprotic polar solvent dilution.
Preferably, the described the first step and second step carry out under protection of inert gas.
Compared with prior art, the invention has the beneficial effects as follows:
(1) the present invention adopts chloride method preparation, controls flexible, easyly, and manufacturing cost is lower, effectively avoids adopting complicated production unit to carry out polymerization, is conducive to suitability for industrialized production.
(2) polymkeric substance of the present invention has good solubility, and polymer solvent is consistent with spin solvent, after polymerization, can directly carry out stoste spinning, adopt single stage method to prepare polyamide-imide fiber, simplified greatly production technique, the fiber of acquisition has good physical strength.
Embodiment
Below in conjunction with embodiment, the present invention is further described in detail, but content of the present invention is not limited only to this.
Embodiment 1:
One can directly spun poly amide imide polymer, in its structure, comprises:
Wherein, R is
n is 30～50, its synthetic method is: in electric mixer being housed and passing into dry, the clean there-necked flask of nitrogen, add 196mLDMF, 24.03g3,4 '-diaminodiphenyl oxide, after stirring and dissolving, be cooled to-10～-5 ℃ and add at twice 25.52g Trimellitic Anhydride Chloride and 14.24g triethylamine, after reaction 20h, add 110mLDMF, be stirred to even, under rapid stirring, add 16.76g diacetyl oxide, 20 ℃ of stirring reactions 12 hours, and with DMF dilution, what to obtain concentration be 15% can directly spun poly amide imide polymer slurries.
Embodiment 2:
One can directly spun poly amide imide polymer, in its structure, comprises:
Wherein, R is
n is 30～50, its synthetic method is: electric mixer is being housed and is passing into the dry of nitrogen, in clean there-necked flask, add 192mL DMAC, 24.03g3, 4 ' diaminodiphenyl oxide, after stirring and dissolving, be cooled to-10～-5 ℃ of disposable 25.52g Trimellitic Anhydride Chloride and 11.37g pyridines of adding continuously, after reaction 25h, add 110mLDMAC, be stirred to even, under rapid stirring, add 16.76g diacetyl oxide (please replace with concrete chemical name), (20) ℃ stirring reaction 14 hours, and dilute with (please supplement concrete chemical name DMAC), what acquisition concentration was 11% can directly spun poly amide imide polymer slurries.
Embodiment 3:
One can directly spun poly amide imide polymer, in its structure, comprises:
Wherein, R is
or
n is 30～50, its synthetic method is: electric mixer is being housed and is passing into the dry of nitrogen, in clean there-necked flask, add 204mLNMP, 19.22g3, 4 '-diaminodiphenyl oxide and 4.8g4, 4 '-diaminodiphenyl oxide, after stirring and dissolving, be cooled to-5～0 ℃ of disposable 25.53g of adding Trimellitic Anhydride Chlorides, and 10.50g quinoline, after reaction 30h, add 116mLNMP, be stirred to even, under rapid stirring, add 16.76g diacetyl oxide, 20 ℃ of stirring reactions 16 hours, and dilute with NMP, what acquisition concentration was 12% can directly spun poly amide imide polymer slurries.
Embodiment 4:
One can directly spun poly amide imide polymer, in its structure, comprises:
Wherein, R is
n is 30～50, its synthetic method is: in electric mixer being housed and passing into dry, the clean there-necked flask of nitrogen, add 204mL DMAC, 25.68g3,4 '-diaminodiphenyl oxide, after stirring and dissolving, be cooled to 10～15 ℃ points and add 25.26g Trimellitic Anhydride Chloride three times, and 10.26g quinoline, after reaction 40h, add 116mLDMAC, be stirred to even, under rapid stirring, add 16.76g diacetyl oxide, 20 ℃ of stirring reactions 18 hours, and with DMAC dilution, what to obtain concentration be 11% can directly spun poly amide imide polymer slurries.
Use by can measuring for following items by directly spun poly amide imide polymer of obtaining in above-described embodiment.
(1) dynamic viscosity: the dynamic viscosity that uses rotary viscosity design determining polymkeric substance at 40 ± 0.2 ℃.
(2) directly use polyamidoimide polymer slurries to carry out wet-spinning, measure fibre strength.
The indices obtaining is as shown in the table:
Claims (10)
1. a synthetic method that can directly spun poly amide imide polymer, is characterized in that, concrete steps comprise:
The first step: diamine compounds is dissolved in aprotic polar solvent, adds acyl chloride compound and organic amine acid binding agent, react 0.5～200 hour;
Second step: add acid anhydrides in reaction system, reaction more than 1 hour, is diluted, and making can directly spun poly amide imide polymer slurries.
2. synthetic method that can directly spun poly amide imide polymer as claimed in claim 1, is characterized in that, described diamine compounds has H
2n-R-NH
2structure, wherein R can be aliphatics or aromatic substituents.
3. synthetic method that can directly spun poly amide imide polymer as claimed in claim 1, is characterized in that, described diamine compounds is Ursol D, mphenylenediamine, 3,4 '-diaminodiphenyl oxide, 4,4 '-diaminodiphenyl oxide, 4,4 '-diaminodiphenyl sulfide, 4,4 '-diaminodiphenyl-methane, 3,3 '-tolidine, 2,2 '-tolidine, 3,3 '-dichlorobenzidine, 2,2 '-dichlorobenzidine, 3,3 '-dihydroxybiphenyl amine, 3,3 '-dimethoxy benzidine, 2,4 di amino toluene, 2,6-diaminotoluene, 3,3 '-bis-is chloro-4,4'-diaminodiphenyl-methane, two (3-aminophenyl) propane of 1,3-, two (4-aminocarbonyl phenyl) HFC-236fa of 2,2-, 2,2 '-bis-(trifluoromethyl)-4,4 '-benzidine, α, α-bis-(4-aminophenyl)-Isosorbide-5-Nitrae-diisopropyl benzene, 4,4 '-dithio pentanoic, 4,4 '-methylene dianiline (MDA), 4,4 '-diaminobenzophenone, 3,3 '-diaminobenzophenone, DDS, 4,4 '-diamino-4 " one or more mixture in-hydroxyl tritane.
4. synthetic method that can directly spun poly amide imide polymer as claimed in claim 1, is characterized in that, the temperature of reaction of the described the first step is-80～120 ℃.
5. synthetic method that can directly spun poly amide imide polymer as claimed in claim 1, is characterized in that, the mol ratio of described diamine compounds and acyl chloride compound is 1: 0.9～1: 1.5.
6. synthetic method that can directly spun poly amide imide polymer as claimed in claim 1, is characterized in that, described acyl chloride compound is Trimellitic Anhydride Chloride.
7. synthetic method that can directly spun poly amide imide polymer as claimed in claim 1, is characterized in that, described aprotic polar solvent is DMF, N,N-dimethylacetamide or N-Methyl pyrrolidone.
8. synthetic method that can directly spun poly amide imide polymer as claimed in claim 1, is characterized in that, described organic amine acid binding agent is tertiary amine compounds.
9. synthetic method that can directly spun poly amide imide polymer as claimed in claim 1, is characterized in that, described tertiary amine compounds and the mol ratio of Trimellitic Anhydride Chloride are 0.5: 1～2: 1.
10. synthetic method that can directly spun poly amide imide polymer as claimed in claim 1, is characterized in that, the acid anhydrides of stating is diacetyl oxide, and the mol ratio of diacetyl oxide and acyl chloride compound is 0.5: 1～2: 1.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104098772A (en) * | 2014-07-29 | 2014-10-15 | 上海华谊（集团）公司 | Novel polyamide-imide preparation method |
| CN106748963A (en) * | 2016-12-01 | 2017-05-31 | 北京航空航天大学 | Polyamidoimide containing indane structural and preparation method thereof |
| CN109402761A (en) * | 2018-10-24 | 2019-03-01 | 株洲时代新材料科技股份有限公司 | A kind of preparation method of aramid fiber 1313 modified fibre |
| CN110508154A (en) * | 2018-05-22 | 2019-11-29 | 中国石油化工股份有限公司 | Nanofiltration membrane and its preparation method and application |
| 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 |
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| US4098775A (en) * | 1976-11-15 | 1978-07-04 | The Upjohn Company | Novel polyamideimides |
| US5458969A (en) * | 1991-05-31 | 1995-10-17 | Amoco Corporation | Amide-imide heat-resistant fiber |
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| JP2012007069A (en) * | 2010-06-24 | 2012-01-12 | Nippon Kodoshi Corp | Low boiling-point solvent soluble resin, ink material using the resin, and ink |
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2014
- 2014-01-20 CN CN201410025876.1A patent/CN103819674A/en active Pending
Patent Citations (5)
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| US4098775A (en) * | 1976-11-15 | 1978-07-04 | The Upjohn Company | Novel polyamideimides |
| US5458969A (en) * | 1991-05-31 | 1995-10-17 | Amoco Corporation | Amide-imide heat-resistant fiber |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104098772A (en) * | 2014-07-29 | 2014-10-15 | 上海华谊（集团）公司 | Novel polyamide-imide preparation method |
| CN104098772B (en) * | 2014-07-29 | 2016-08-24 | 上海华谊（集团）公司 | A kind of preparation method of polyamidoimide |
| CN106748963A (en) * | 2016-12-01 | 2017-05-31 | 北京航空航天大学 | Polyamidoimide containing indane structural and preparation method thereof |
| CN106748963B (en) * | 2016-12-01 | 2019-08-02 | 北京航空航天大学 | Polyamide-imides and preparation method thereof containing indane structural |
| CN110508154A (en) * | 2018-05-22 | 2019-11-29 | 中国石油化工股份有限公司 | Nanofiltration membrane and its preparation method and application |
| CN109402761A (en) * | 2018-10-24 | 2019-03-01 | 株洲时代新材料科技股份有限公司 | A kind of preparation method of aramid fiber 1313 modified fibre |
| 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 |
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Application publication date: 20140528 |