Process for producing fibers, films and moldings of polybenzazole polymer (P)

文档序号：1026628 发布日期：2020-10-27 浏览：35次中文

阅读说明：本技术 制备聚吲哚聚合物（p）的纤维、膜和模制品的方法 (Process for producing fibers, films and moldings of polybenzazole polymer (P) ) 是由 M·布里尔 I·德博韦斯德瓦斯康塞洛斯 M·诺瓦克 O·弗雷斯彻 M·莫格 A·斯坦默于 2019-03-01 设计创作，主要内容包括：本发明涉及一种制备聚吲哚聚合物(P)的纤维、膜和模制品的方法,所述方法通过使包含以下组分的反应混合物(RG)转化进行：(a)至少一种通式(I)的芳族二羧酸化合物,其中Ar1选自未取代的或至少单取代的亚苯基、萘二基、蒽二基、联苯二基、二苯甲烷二基、二苯醚二基、二苯硫醚二基、二苯砜二基、二苯甲酮二基、吡啶二基、嘧啶二基、呋喃二基和噻吩二基,取代基选自-F、-Cl、-Br、-OR1和-C1-C10-烷基,其中R1为-H或-C1-C10-烷基；X1、X2各自独立地选自-OR2、-F、-Cl和-Br,其中R2为-H、-C1-C10-烷基、-C1-C10-烯基或通式(Ia)的重复单元,其中m为1至50的自然数,并且R3为-H、-C1-C10-烷基或-C1-C10-烯基；(b)至少一种通式(IIa)、(IIb)、(IIc)和/或(IId)的芳族二氨基化合物,其中n为0或1,Y1、Y2、Y3、Y4各自独立地为-H、-OR4或-SR4,其中R4选自-H、-C1-C10-烷基、三甲基甲硅烷基、叔丁基二甲基甲硅烷基、乙酰基和叔丁氧羰基,其中基团Y1和Y2中的至多一个为-H,其中基团Y3和Y4中的至多一个为-H；并且Z1、Z2、Z3、Z4、Z5、Z6、Z7、Z8各自独立地为-NH2或-NH3+Q–,其中Q–为选自F–、Cl–、Br–、I–、HSO4–、SO42–、H3C-SO3–、p-H3C-C6H4-SO3–和NO3–的离子等价物；和(c)至少一种离子液体(IL)；其特征在于,反应混合物(RG)的所述转化在0至120℃的温度TR下进行,以获得产物混合物(PVG)。根据本发明,然后将所述产物混合物(PVG)在0至100℃的温度TV下加工以形成膜、纤维或模制品,并将如此获得的膜、纤维或模制品加热到250至500℃的温度TP。<Image he="394" wi="700" file="DDA0002673368690000021.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(The invention relates to a method for producing fibers, films and moldings of polybenzazole polymer (P) by reacting a reaction mixture (R) comprising G ) The transformation is carried out: (a) at least one aromatic dicarboxylic acid compound of the general formula (I) in which Ar 1 Selected from the group consisting of unsubstituted OR at least mono-substituted phenylene, naphthalenediyl, anthracenediyl, biphenyldiyl, diphenylmethanediyl, diphenyletherdiyl, diphenylthioether-diyl, diphenylsulfonediyl, benzophenondiyl, pyridinediyl, pyrimidinediyl, furandiyl and thiophenediyl, the substituents being selected from the group consisting of-F, -Cl, -Br, -OR 1 and-C 1 ‑C 10 -alkyl, wherein R 1 is-H or-C 1 ‑C 10 -an alkyl group; x 1 、X 2 Each independently selected from-OR 2 -F, -Cl and-Br, wherein R 2 is-H, -C 1 ‑C 10 -alkyl, -C 1 ‑C 10 -alkenyl or a repeating unit of the general formula (Ia) wherein m is a natural number from 1 to 50, and R 3 is-H, -C 1 ‑C 10 -alkyl or-C 1 ‑C 10 -an alkenyl group; (b) at least one aromatic diamino compound of the general formulae (IIa), (IIb), (IIc) and/or (IId) in which n is 0 or 1, Y 1 、Y 2 、Y 3 、Y 4 Each independently is-H, -OR 4 or-SR 4 Wherein R is 4 Is selected from-H, -C 1 ‑C 10 Alkyl, trimethylsilyl, tert-butyldimethylsilyl, acetyl and tert-butyloxycarbonyl, where the radical Y 1 And Y 2 At most one of which is-H, wherein the group Y 3 And Y 4 At most one of which is-H; and Z 1 、Z 2 、Z 3 、Z 4 、Z 5 、Z 6 、Z 7 、Z 8 Each independently is-NH 2 or-NH 3 + Q – Wherein Q is – Is selected from F – 、Cl – 、Br – 、I – 、HSO 4 – 、SO 4 2– 、H 3 C‑SO 3 – 、p‑H 3 C‑C 6 H 4 ‑SO 3 – And NO 3 – An ionic equivalent of (a); and (c) at least one Ionic Liquid (IL); characterized in that the reaction mixture (R) G ) At a temperature T of from 0 to 120 DEG C R To obtain a product mixture (P) VG ). According to the invention, the product mixture (P) is then mixed VG ) At a temperature T of 0 to 100 DEG C V Working down to form a film, fibre or moulding and heating the film, fibre or moulding thus obtained to a temperature T of 250 to 500 ℃ P 。)

1. A process for preparing fibers, films and moldings of polybenzazole polymer (P) by reacting a reaction mixture (R) comprising_G) Reaction:

(a) at least one aromatic dicarboxylic acid compound of the general formula (I):

wherein

Ar¹Selected from the group consisting of unsubstituted or at least mono-substituted phenylene, naphthalenediyl, anthracenediyl, biphenyldiyl, diphenylmethanediyl, diphenyletherdiyl, diphenylthioetherdiyl, diphenylsulfonediyl, benzophenondiyl, pyridinediyl, pyrimidinediyl, furandiyl and thiophenediyl,

wherein the substituents are selected from the group consisting of-F, -Cl, -Br, -OR¹and-C₁-C₁₀-an alkyl group,

wherein R is¹is-H or-C₁-C₁₀-an alkyl group;

X¹、X²each independently selected from-OR²-F, -Cl and-Br,

wherein R is²is-H, -C₁-C₁₀-alkyl, -C₁-C₁₀-alkenyl or recurring units of general formula (Ia):

wherein

m is a natural number of 1 to 50, and

R³is-H, -C₁-C₁₀-alkyl or-C₁-C₁₀-an alkenyl group;

(b) at least one aromatic diamino compound of the general formulae (IIa), (IIb), (IIc) and/or (IId):

wherein

n is 0 or 1

Y¹、Y²、Y³、Y⁴Each independently is-H, -OR⁴or-SR⁴，

Wherein R is⁴Selected from:

-H、-C₁-C₁₀-alkyl, trimethylsilyl, tert-butyldimethylsilyl, acetyl and tert-butyloxycarbonyl, and

wherein the radical Y¹And Y²At most one of which is-H, and

wherein the radical Y³And Y⁴At most one of which is-H;

Z¹、Z²、Z³、Z⁴、Z⁵、Z⁶、Z⁷、Z⁸each independently is-NH₂or-NH₃ ⁺Q^–，

Wherein Q^–Is selected from F^–、Cl^–、Br^–、I^–、HSO₄ ^–、SO₄ ^2–、H₃C-SO₃ ^–、p-H₃C-C₆H₄-SO₃ ^–And NO₃ ^–An anionic equivalent of (a);

and

wherein the reaction mixture (R)_G) At a temperature T of from 0 to 120 DEG C_RTo obtain a product mixture (P)_VG) At a temperature T of from 0 to 100 DEG C_VWorking up the product mixture (P)_VG) To give films, fibres or moldings and at a temperature T of from 250 to 500 DEG C_PThe film, fiber or molded article thus obtained is heated.

2. The method of claim 1, wherein Ar¹Selected from unsubstituted or at least mono-substituted 1, 3-phenylenesA group, a 1, 4-phenylene group, a naphthalene-1, 4-diyl group, a naphthalene-2, 6-diyl group, an anthracene-9, 10-diyl group, a biphenyl-4, 4 '-diyl group, a diphenylmethane-4, 4' -diyl group, a diphenyl ether-4, 4 '-diyl group, a diphenyl sulfide-4, 4' -diyl group, a diphenyl sulfone-4, 4 '-diyl group, a benzophenone-4, 4' -diyl group, a pyridine-2, 5-diyl group, a pyrimidine-4, 6-diyl group, a furan-2, 5-diyl group and a thiophene-2, 5-diyl group.

3. The method according to claim 1 or 2, wherein component (a) is selected from the group consisting of terephthalic acid, terephthalic anhydride, terephthaloyl fluoride, terephthaloyl chloride, terephthaloyl bromide, C of terephthalic acid₁-C₁₀Alkyl esters, terephthalic acid C₁-C₁₀Alkenyl esters, isophthalic acid, isophthalic anhydride, isophthaloyl fluoride, isophthaloyl chloride, isophthaloyl bromide, polyanhydrides of isophthalic acid, C of isophthalic acid₁-C₁₀C of alkyl esters and isophthalic acid₁-C₁₀-alkenyl esters.

4. The process of any one of claims 1 to 3, wherein component (b) is selected from 4, 6-diamino-1, 3-dihydroxybenzene, 4, 6-diamino-1, 3-dihydroxybenzene dihydrochloride, 2, 5-diamino-1, 4-dihydroxybenzene, and 2, 5-diamino-1, 4-dihydroxybenzene dihydrochloride.

5. The process according to any one of claims 1 to 4, wherein the reaction mixture (R)_G) Comprising 5 to 25% by weight of component (a), 5 to 25% by weight of component (b) and 50 to 90% by weight of component (c), based on the reaction mixture (R)_G) Total weight of (c).

6. The method according to any one of claims 1 to 5, wherein the at least one Ionic Liquid (IL) has the general formula (III):

[C]_n ⁺[A]^n–(III)

wherein

n is 1,2,3 or 4;

cation [ C ]]_n ⁺At least one ofA cation selected from the group consisting of: unsubstituted or at least mono-substituted imidazolium cation, imidazolinium cation, tetrahydroimidazolium cation, quaternary ammonium cation, quaternary phosphonium cation, pyrazolium cation, dihydropyrazolium cation, pyridinium cation, pyridazinium cation, pyrimidinium cation, pyrazinium cation, pyrrolidinium cation, guanidinium cation, thiazolium cation, oxazolium cation, triazolium cation, 1, 8-diazabicyclo [5.4.0]]Undec-7-enium cation, 1, 8-diazabicyclo [4.3.0]Non-5-alkenylonium cations, and oligomers or polymers containing these cations,

wherein the substituents are selected from straight or branched chain C₁-C₁₈-alkyl, -C₅-C₁₂-cycloalkyl and-C₆-C₁₄-an aryl group;

anion [ A ]]^n–Selected from the group consisting of halide anions, cyanide, thiocyanate, cyanate, isocyanate, nitrite, nitrate, unsubstituted or at least mono-substituted sulphate, sulphite, sulphonate, carboxylate, borate, carbonate, amide, forminate, sulphonylidate, bis (sulphonyl) imidate, alcoholate and aryl oxide,

wherein the substituents are selected from straight or branched chain C₁-C₁₈-alkyl, -C₅-C₁₂-cycloalkyl and-C₆-C₁₄-an aryl group.

7. The process according to claim 6, wherein the at least one Ionic Liquid (IL) comprises at least one imidazolium cation of general formula (IV) as cation [ C ™ ]]_n ⁺：

Wherein

R⁵、R⁶、R⁷、R⁸、R⁹Each independently selected from-H, linear or branched-C₁-C₁₈-alkyl-C₅-C₁₂-cycloalkyl and-C₆-C₁₄-an aryl group.

8. The method according to claim 6 or 7, characterized in that the cation [ C ]]_n ⁺Is at least one cation selected from the group consisting of: 1-methylimidazolium salt, 1-methyl-2-ethylimidazolium salt, 1-methyl-3-octylimidazolium salt, 1, 2-dimethylimidazolium salt, 1, 3-dimethylimidazolium salt, 2, 3-dimethylimidazolium salt, 3, 4-dimethylimidazolium salt, 1,2, 3-trimethylimidazolium salt, 1,3,4, 5-tetramethylimidazolium salt, 1-ethylimidazolium salt, 1-ethyl-2-methylimidazolium salt, 1-ethyl-3-methylimidazolium salt, 1-ethyl-2, 3-dimethylimidazolium salt, 2-ethyl-3, 4-dimethylimidazolium salt, 1-propylimidazolium salt, and mixtures thereof, 1-propyl-2-methylimidazolium salt, 1-propyl-3-methylimidazolium salt, 1-propyl-2, 3-dimethylimidazolium salt, 1, 3-dipropylimidazolium salt, 1-butylimidazolium salt, 1-butyl-2-methylimidazolium salt, 1-butyl-3-methylimidazolium salt, 1-butyl-4-methylimidazolium salt, 1-butyl-2, 3-dimethylimidazolium salt, 1-butyl-3, 4, 5-trimethylimidazolium salt, 1-butyl-2-ethylimidazolium salt, 1-butyl-3-ethylimidazolium salt, 1-propyl-2-methylimidazolium salt, 1-propyl-3-methylimidazolium salt, 1-butyl-3-, 1-butyl-2-ethyl-5-methylimidazolium salt, 1, 3-dibutylimidazolium salt, 1, 3-dibutyl-2-methylimidazolium salt, 1-pentylimidazolium salt, 1-pentyl-2-methylimidazolium salt, 1-pentyl-3-methylimidazolium salt, 1-pentyl-2, 3-dimethylimidazolium salt, 1-hexylimidazolium salt, 1-hexyl-2-methylimidazolium salt, 1-hexyl-3-methylimidazolium salt, 1-hexyl-2, 3-dimethylimidazolium salt, 1-octyl-2-methylimidazolium salt, 1-octyl-3-methylimidazolium salt, 1-decyl-2-methylimidazolium salt, 1-pentyl-, 1-dodecyl-3-methylimidazolium salt, 1-tetradecyl-3-methylimidazolium salt, 1-hexadecyl-3-methylimidazolium salt, and 1-benzyl-3-methylimidazolium salt.

9. The method according to any one of claims 1 to 8, wherein the at least one Ionic Liquid (IL) is selected from: 1-methylimidazolium chloride salt, 1-ethylimidazolium chloride salt, 1-ethyl-3-methylimidazolium chloride salt, 1-butylimidazolium chloride salt, 1-butyl-3-methylimidazolium chloride salt, 1, 3-diethylimidazolium chloride salt, 1, 3-dibutylimidazolium chloride salt, 1-methylimidazolium tetrachloroaluminate, 1-ethylimidazolium tetrachloroaluminate, 1-ethyl-3-methylimidazolium tetrachloroaluminate, 1, 3-diethylimidazolium tetrachloroaluminate, 1-butylimidazolium tetrachloroaluminate, 1-butyl-3-methylimidazolium tetrachloroaluminate, 1, 3-dibutylimidazolium tetrachloroaluminate.

10. The process according to any one of claims 1 to 9, wherein the reaction mixture (R) is allowed to react_G) The reaction is carried out in the presence of at least one basic compound selected from the group consisting of: trialkylamine, imidazole, pyridine, lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, magnesium carbonate, calcium carbonate, lithium hydride, sodium hydride, potassium hydride, magnesium hydride, and calcium hydride.

11. The process according to any one of claims 1 to 10, wherein the reaction mixture (R)_G) Components (a), (b) and (c) comprising the following combinations, wherein in addition to component (b) the corresponding dihydrochloride salt is protected:

12. fibers, films and moldings obtainable by the process of any of claims 1 to 11.

13. Use of a fiber obtainable by the process of any one of claims 1 to 11 for: for the production of cables, ropes, cords, for glass fibre sheathing, for the production of fibre-reinforced rubber materials, for the production of fibre-reinforced building materials, for the production of brake linings for disc brakes, for the production of nonwovens, for the production of textiles, such as bulletproof vests, high-temperature-resistant protective clothing, helmet layers, for the provision of cable sheathing, for textile-reinforced building materials, such as textile concrete for the repair and repair of buildings.

14. Use of a membrane obtainable by the process of any one of claims 1 to 11 in a thermally stable membrane for gas separation, in a proton conducting membrane, in an electro-optical device or a light emitting diode.

15. Use of a molded article obtainable by the process according to any one of claims 1 to 11 as a high temperature resistant polymeric material.

Examples

The following parameters were determined using the following method:

tensile strength and modulus of elasticity of the fibers according to DIN EN ISO 5079.

Viscosity values according to DIN EN ISO 1628-1 in methanesulfonic acid at 25 ℃.

The phosphorus determination (method MB 2018/05, BASF SE, Kompetenzzentrum Analytik) is as follows:

a portion of 0.2 to 0.3g of the phosphorus-containing sample was treated with a concentrated sulfuric acid solution (about 96 wt% H) at 320 deg.C₂SO₄) Concentrated nitric acid (about 65 wt.% HNO)₃) And cesium sulfate solution (50 g of cesium sulfate Cs₂SO₄(purity 99.9) dissolved with water to a volume of 1000 ml). The residue obtained is treated with a mixed acid (concentrated nitric acid + concentrated perchloric acid (about 70% by weight of HClO)₄) + concentrated sulfuric acid, volume ratio 2:1:1) at about 160 ℃. The excess acid was evaporated off, the residue was boiled and dissolved in 25Volume% hydrochloric acid (a 3:1 mixture of concentrated hydrochloric acid (about 36% HCl) + water by volume) and deionized water. The exact volume is determined by inverse weighing and density calculations.

In the resulting dissolved solution, phosphorus was measured by atomic emission spectrometry (ICP-OES).

Matrix dissolving solution and standard solution: c (HCl) about 0.6mol/L, about 0.2% (m/v) Cs₂SO₄。

The instrument comprises the following steps: ICP-OES Agilent 5100 spectrometer.

Measurement conditions were as follows: integration time 10 seconds, generator 1200W, cone nebulizer 1ml, spectral line (nm): p213.618; and (3) correction: sc 361.383nm (internal standard), calibration: and (3) an external part.

1. Preparation of the product mixture (P)_VG) General experimental method

A750 ml double jacketed glass reactor equipped with an anchor stirrer and a distillation head was filled with 1-butyl-3-methylimidazolium chloride ("BMIM-Cl"). While stirring (100rpm), the Ionic Liquid (IL) was dried at 130 ℃ under a nitrogen feed (60L/h) and low pressure (50 mbar absolute) until a water content of < 0.03% was reached (measured by Karl-Fischer titration of withdrawn aliquots). After adjusting the IL temperature to 75 ℃,4, 6-diaminoresorcinol dihydrochloride (IUPAC name 4, 6-diamino-1, 3-dihydroxybenzene dihydrochloride) ("DAR") was added and stirred overnight until a homogeneous solution was obtained (about 16 h). Subsequently, while stirring (100rpm), terephthaloyl chloride ("TC") in solid form was added in five portions with an interval of about 15min between successive metered additions. The total amount of these five metered additions was 50, 75, 88, 95, 98 mol% TC, based on the amount of DAR used. The reaction gases were discharged under negative pressure (about 50 mbar absolute) by means of a nitrogen stream (about 90L/h). After the fifth metered addition of the appropriate amount of TC (see above), the torque of the stirrer was slowly increased until a torque of about 80Ncm was reached, followed by a reduction of the stirring speed (to about 20 rpm). If the torque is not increased further, TC is added further (so the total of six metered additions corresponds to 100.1 to 100.6 mol% of the amount of DAR) and the torque therefore increases rapidly. The stirring speed was further reduced (about 10rpm) and the mixture was further stirred until the torque no longer increased. Finally, the mixture is kept at low pressure (about 50 mbar) without further stirring to reduce the amount of gaseous inclusions in the solution, thereby facilitating further processing (e.g. spinning) as a whole. After releasing the reaction vessel to standard pressure (about 1013 mbar), an aliquot of the solution was removed for rheological characterization (see characterization).

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Process for producing fibers, films and moldings of polybenzazole polymer (P)

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