阅读说明：本技术 基于2,5-二烯丙氧基对苯二胺单体的新型聚苯并噁唑高分子材料及其制备方法 (Novel polybenzoxazole high polymer material based on 2, 5-diallyloxy p-phenylenediamine monomer and preparation method thereof ) 是由 宛新华 齐翔 章斐 张�杰 于 2018-06-13 设计创作，主要内容包括：本发明公开了一种基于2,5-二烯丙氧基对苯二胺单体的聚苯并噁唑高分子材料及其制备方法。其重复结构单元如式I-1或式I-2所示。本发明选用不同烯丙氧基含量的一系列新型芳香族聚酰胺、聚酰亚胺高分子,经过克莱森重排和热转化重排的串联反应制备新型聚苯并噁唑高分子。此方法可开发出透过性能优良的聚苯并噁唑类气体分离膜。<Image he="726" wi="700" file="DDA0001694512410000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(The invention discloses a polybenzoxazole polymer material based on a 2, 5-diallyl-oxy-p-phenylenediamine monomer and a preparation method thereof. The repeating structural unit is shown as formula I-1 or formula I-2. The invention selects a series of novel aromatic polyamide and polyimide polymers with different allyloxy contents, and prepares the novel polybenzoxazole polymer through the series reaction of claisen rearrangement and thermal conversion rearrangement. The method can develop the polybenzoxazole gas separation membrane with excellent permeability.)

1. The polybenzoxazole high polymer material based on the 2, 5-diallyl oxy p-phenylenediamine monomer is as follows: a polymer consisting of a repeating structural unit represented by the formula I-1 or the formula I-2:

in the formula I-1, x is 0 to 1,

Ar₂denotes the residue of a divalent aromatic primary amine, Ar₃Is a residue of a dicarboxylic acid;

in the formula I-2, x is 0 to 1,

Ar₂denotes the residue of a divalent aromatic primary amine, Ar₄Is fourA residue of a meta-aromatic anhydride;

and Ar₂、Ar₃Independently a group obtained by replacing any two hydrogens on the aromatic ring in the following compound, Ar₄Is a group obtained by substituting any four hydrogens on the aromatic ring in the following compounds:

2. a polybenzoxazole polymer material according to claim 1, characterized in that: the repeated structural unit shown in the formula I-1 is any one of the following:

the repeated structural unit shown in the formula I-2 is any one of the following:

3. a polybenzoxazole polymer material according to claim 1 or 2, characterized in that: the weight average molecular weight of the polymer is not less than 1000, and specifically can be 4000-100,000.

4. A process for preparing a polymer consisting of recurring structural units of the formula I-1 according to any of claims 1 to 3, comprising: carrying out heat treatment on polyamide with ortho-hydroxyl substitution shown in the formula 2 to obtain polybenzoxazole shown in a formula I-1;

in the formula 2, x is 0-1;

Ar₂is as defined for Ar in formula I-1₂Definition of (A), Ar₃Is as defined for Ar in formula I-1₃The definition of (1).

5. The method of claim 4, wherein: the heat treatment is carried out under vacuum or inert gas conditions;

the polyamide having ortho-hydroxyl substitution represented by formula 2 exists in the form of a polymer film;

the heat treatment operation is as follows: treating at 200 deg.C for 6-8 hr, and treating at 350 deg.C for 8-10 hr.

6. A process for preparing a polymer consisting of recurring structural units of the formula I-2 according to any of claims 1 to 3, comprising: carrying out heat treatment on the polyimide substituted by the ortho-hydroxyl shown in the formula 3 to obtain polybenzoxazole shown in a formula I-2;

in the formula 3, x is 0-1;

Ar₂is as defined for Ar in formula I-2₂Definition of (A), Ar₄Is as defined for Ar in formula I-2₄The definition of (1).

7. The method of claim 6, wherein: the heat treatment is carried out under vacuum or inert gas conditions;

the ortho-hydroxyl substituted polyimide shown in the formula 3 exists in the form of a polymer film;

the heat treatment operation is as follows: first at 250 deg.C for 6-8h, and then at 500 deg.C for 8-10 h.

8. Use of a polymer consisting of repeating structural units of formula I-1 or formula I-2 according to claim 1 for the preparation of polybenzoxazole composites.

9. A polybenzoxazole composite comprising a polymer consisting of the repeating structural unit represented by formula I-1 or formula I-2 in claim 1.

10. Use of a polymer consisting of repeating structural units of the formula I-1 or I-2 according to claim 1 or of a polybenzoxazole composite according to claim 9 in the field of gas separation.

Technical Field

The invention belongs to the field of synthesis of high polymer materials, and particularly relates to a novel polybenzoxazole high polymer material based on a 2, 5-diallyloxy p-phenylenediamine monomer and a preparation method thereof.

Background

Polybenzoxazole, PBO, is a class of aromatic heterocyclic polymers whose backbone contains fused heterocyclic rings of benzoxazole. The high-rigidity fused heterocyclic structure enables the polymer to be a rod-shaped molecule, and the polymer has super heat resistance, super high tensile strength and good chemical stability. Therefore, polybenzoxazole is widely used in the fields of body armor, fire uniforms and thermal insulation composites.

As early as 1964, Kubota et al found that polyamide structures with ortho-hydroxyl substitution can be freed of H by high temperatures₂Conversion of O to polybenzoxazole PBO (kubota. tm. lett.,1964,2, 655); in 1999, Mathias et al discovered that polyimide structures with ortho-hydroxyl substitution can remove CO at high temperature in a thin film state₂Conversion to polybenzoxazole structure TR-PBO (l.j. mathias. macromolecules,1999,32, 3598).

After that, many researchers have made use of the conversion reaction of o-hydroxy substituted polyimide to prepare polybenzoxazole polymer materials, mainly represented by polybenzoxazole gas separation membranes. Lee et al investigated the effect of different glass transition temperatures Tg on the processing conditions required for such conversion reactions for such reactions and found that the lower the Tg, i.e. the stronger the mobility of the molecular chain, the lower the temperature required for its conversion (y.m. Lee., Macromolecules,2015,48, 2194). Furthermore, Lee et al also prepared polybenzoxazole having a crosslinked network by introducing crosslinking sites in the o-hydroxypolyimide copolymerized segment moiety, and obtained a gas separation membrane having high gas permeability and resistance to plasticization (y.m. Lee., Macromolecules,2015,48, 2603). McGrath et al utilized this reaction to convert polyimide into polybenzoxazole thin films by high temperature heating in a dry state and found that the gas permeability of the converted thin films was greatly improved with less loss of selectivity (j.e.mcgrath.j.mater.chem.a,2013,1, 262; j.e.mcgrath., j.mater.chem.a,2013,1, 6063). Recently, there have been reviews of relevant literature for systematic analysis and summary of such polybenzoxazole (TR-PBO) gas separation membranes prepared by thermal rearrangement, and when the o-hydroxypolyimide thin films are thermally rearranged and converted into polybenzoxazole, the polymer main chain structure is greatly chemically transformed in the solid state, the benzoxazole ring is more rigid and small molecules are released, and the obtained TR-PBO thin films have a larger interchain free volume fraction (FFV), so that the improvement in membrane permeability is significant (c.a. scholes, aust.j.chem.,2016,69, 601). As can be seen from the above studies, if a conversion pathway from polyimide to polybenzoxazole can be obtained by rational molecular design, a gas separation membrane material having high gas permeability and high gas selectivity and excellent overall performance can be prepared.

Disclosure of Invention

The invention aims to provide a polybenzoxazole high polymer material based on a 2, 5-diallyl-oxy-p-phenylenediamine monomer and a preparation method thereof.

The polybenzoxazole polymer material based on the 2, 5-diallyl-oxy-p-phenylenediamine monomer provided by the invention is as follows: a polymer consisting of a repeating structural unit represented by the formula I-1 or the formula I-2:

in the above formula I-1, x may be 0 to 1 (endpoint 0 is not preferable), and x may be specifically 0.1,0.25,0.5,0.75 or 1;

Ar₂denotes the residue of a divalent aromatic primary amine, Ar₃Is a residue of a dicarboxylic acid;

in the above formula I-2, x may be 0 to 1 (endpoint 0 is not preferable), and x may be specifically 0.1,0.25,0.5,0.75 or 1;

Ar₂denotes the residue of a divalent aromatic primary amine, Ar₄Is the residue of a quaternary aromatic anhydride;

and Ar₂、Ar₃Independently a group obtained by replacing any two hydrogens on the aromatic ring in the following compound, Ar₄Is a group obtained by substituting any four hydrogens on the aromatic ring in the following compounds:

specifically, the repeating structural unit shown in the formula I-1 is any one of the following:

specifically, the repeating structural unit shown in the formula I-2 is any one of the following:

the weight average molecular weight of the polymer is not less than 1000, and specifically can be 4000-100,000.

The above-mentioned polymer composed of the repeating structural unit represented by the formula I-1 is prepared according to the reaction equation shown in FIG. 1 by a method comprising the steps of:

carrying out heat treatment on polyamide with ortho-hydroxyl substitution shown in the formula 2 to obtain polybenzoxazole shown in a formula I-1;

in formula 2, x may be 0 to 1 (endpoint 0 is not preferable), and x may be specifically 0.1,0.25,0.5,0.75 or 1;

Ar₂is as defined for Ar in formula I-1₂Definition of (A), Ar₃Is as defined for Ar in formula I-1₃The definition of (1);

the heat treatment is performed under vacuum or inert gas (specifically, nitrogen).

The polyamide having ortho-hydroxyl substitution represented by formula 2 exists in the form of a polymer film.

The heat treatment operation is as follows: treating at 200 deg.C for 6-8 hr, and treating at 350 deg.C for 8-10 hr.

The polyamide having ortho-hydroxyl substitution represented by the above formula 2 is produced according to the reaction scheme shown in FIG. 2 by a method comprising the steps of:

uniformly mixing a diallyloxy diamino monomer shown in a formula II, a binary aromatic primary amine monomer shown in a formula III and a binary aromatic acyl chloride monomer shown in a formula IV in a solvent for polycondensation reaction, and performing claisen rearrangement reaction on the obtained polymer to obtain polyamide shown in a formula 2 and substituted by ortho-hydroxyl, wherein x is not 0 or 1;

alternatively, the first and second electrodes may be,

uniformly mixing a diallyloxy diamino monomer shown in a formula II and a binary aromatic acyl chloride monomer shown in a formula IV in a solvent for polycondensation reaction, and performing claisen rearrangement reaction on the obtained polymer to obtain polyamide shown in a formula 2 and substituted by ortho-hydroxyl, wherein x is 1;

in the above formula III, Ar₂Is as defined for Ar in formula I-1₂The definition of (1);

in the above formula IV, Ar₃Is as defined for Ar in formula I-1₃The definition of (1);

in the above method, the primary diarylamine monomer represented by formula III may be 1, 3-phenylenediamine, 1, 4-naphthalenediamine, 1, 5-naphthalenediamine, 2, 6-naphthalenediamine, 2, 7-naphthalenediamine, 3' -diaminobiphenyl, 4' -diaminobiphenyl, 3' -diaminodiphenylmethane, 4' -diaminodiphenylmethane, 3' -diaminodiphenyl ether, 3, 4' -diaminodiphenyl ether, 4' -diaminodiphenyl ether, 3' -diaminodiphenyl sulfone, 4' -diaminodiphenyl sulfone, 3' -diaminobenzophenone, 4' -diaminobenzophenone, 2-bis (3-aminophenyl) hexafluoropropane or 2, 2-bis (4-aminophenyl) hexafluoropropane;

the binary aromatic acyl chloride monomer shown in the formula IV can be 1, 3-phthaloyl chloride, 1, 4-phthaloyl chloride, 1, 3-naphthaloyl chloride, 1, 4-naphthaloyl chloride, 1, 5-naphthaloyl chloride, 2, 6-naphthaloyl chloride, 2, 7-naphthaloyl chloride, 4 '-dichloroformyl biphenyl, diphenylmethane 4,4' -diformyl chloride, 4 '-diphenyloxide diformyl chloride or 4,4' -dichloroformyl benzophenone, 1, 4-bis (4-oxo-1-benzoyl chloride) benzene, 1, 3-bis (4-oxo-1-benzoyl chloride) -4-adamantyl benzene, 1, 4-bis (4-oxo-1-benzoyl chloride) biphenyl, 1, 4-bis (4-oxo-3-trifluoromethyl-1-benzoyl chloride) biphenyl, 2-bis (4-benzoyl chloride-4-oxo-phenyl) hexafluoropropane, 2, 3-di-tert-butyl-1, 4-bis (4-oxo-1-benzoyl chloride) benzene, 2-bis (4-benzoyl chloride-4-oxo-3, 5-dimethyl-phenyl) hexafluoropropane, 2, 3-phenyl-1, 4-bis (4-oxo-3-trifluoromethyl-1-benzoyl chloride) benzene, 1, 4-bis (4-oxo-3-trifluoromethyl-1-benzoyl chloride) naphthalene, 1, 1-bis (4-benzoyl-chloride-4-oxy-phenyl) trifluoroethane, 4- (9-fluorenylidene) -dibenzoyl chloride, 1, 3-trimethyl-3-phenylindane-4, 5-diformylchloride.

The above-mentioned polymer composed of the repeating structural unit represented by the formula I-2 is prepared according to the reaction equation shown in FIG. 3 by a method comprising the steps of:

carrying out heat treatment on the polyimide substituted by the ortho-hydroxyl shown in the formula 3 to obtain polybenzoxazole shown in a formula I-2;

in formula 3, x may be 0 to 1 (endpoint 0 is not preferable), and x may be specifically 0.1,0.25,0.5,0.75 or 1;

Ar₂is as defined for Ar in formula I-2₂Definition of (A), Ar₄Is as defined for Ar in formula I-2₄The definition of (1);

the heat treatment is performed under vacuum or inert gas (specifically, nitrogen).

The ortho-hydroxy substituted polyimide represented by formula 3 exists in the form of a polymer film.

The heat treatment operation is as follows: first at 250 deg.C for 6-8h, and then at 500 deg.C for 8-10 h.

The o-hydroxy substituted polyimide represented by the above formula 3 is prepared according to the reaction scheme shown in FIG. 4 by a method comprising the steps of:

uniformly mixing a diallyloxy diamino monomer shown in a formula II, a binary aromatic primary amine monomer shown in a formula III and a quaternary aromatic anhydride monomer shown in a formula V in a solvent for polycondensation reaction, and performing claisen rearrangement reaction on the obtained polymer to obtain the o-hydroxy substituted polyimide shown in a formula 3, wherein x is not 0 or 1;

alternatively, the first and second electrodes may be,

uniformly mixing a diallyloxy diamino monomer shown in a formula II and a quaternary aromatic anhydride monomer shown in a formula V in a solvent for polycondensation reaction, and performing claisen rearrangement reaction on the obtained polymer to obtain the o-hydroxy substituted polyimide shown in a formula 3, wherein x is 1;

in the above formula III, Ar₂Is as defined for Ar in formula I-2₂The definition of (1);

in the above formula V, Ar₄Is as defined for Ar in formula I-2₄The definition of (1);

in the above method, the primary diarylamine monomer represented by formula III may be 1, 3-phenylenediamine, 1, 4-naphthalenediamine, 1, 5-naphthalenediamine, 2, 6-naphthalenediamine, 2, 7-naphthalenediamine, 3' -diaminobiphenyl, 4' -diaminobiphenyl, 3' -diaminodiphenylmethane, 4' -diaminodiphenylmethane, 3' -diaminodiphenyl ether, 3, 4' -diaminodiphenyl ether, 4' -diaminodiphenyl ether, 3' -diaminodiphenyl sulfone, 4' -diaminodiphenyl sulfone, 3' -diaminobenzophenone, 4' -diaminobenzophenone, 2-bis (3-aminophenyl) hexafluoropropane or 2, 2-bis (4-aminophenyl) hexafluoropropane;

the quaternary aromatic acid anhydride monomer represented by formula V may be pyromellitic anhydride, 1,4,5, 8-naphthalene tetracarboxylic anhydride, 4,4'- (hexafluoroisopropylene) diphthalic anhydride (6FDA), 3,3',4,4 '-Benzophenone Tetracarboxylic Dianhydride (BTDA), 3,3',4,4 '-diphenyl sulfide tetracarboxylic dianhydride (DTDA), 3,3',4,4 '-diphenyl sulfone tetracarboxylic dianhydride (DSDA), 4,4' -diphenyl ether dianhydride (OPDA), 2,3,3',4' -diphenyl ether tetracarboxylic dianhydride, 2,3,3',4' -biphenyl tetracarboxylic dianhydride, spirofluorene tetracarboxylic dianhydride (SBFDA), 5,6,11, 12-tetrahydro-5, 11-methanodiphenyl [ a, e ] [8] annulene-2, 3,8, 9-tetracarboxylic dianhydride (CTB1), 1, 1' -spirobisindanyl dianhydride (SBI).

The application of the polymer consisting of the repeating structural unit shown in the formula I-1 or the formula I-2 in preparing the polybenzoxazole composite material also belongs to the protection scope of the invention.

The application of the polybenzoxazole composite material made of the polymer consisting of the repeating structural units shown in the formula I-1 or the formula I-2 or the polymer consisting of the repeating structural units shown in the formula I-1 or the formula I-2 in the field of gas separation also belongs to the protection scope of the invention.

The invention selects a series of novel aromatic polyamide and polyimide polymers with different allyloxy contents to prepare the novel polybenzoxazole polymer through heat treatment. The method can develop the polybenzoxazole gas separation membrane with excellent permeability.

The invention uses a novel p-phenylenediamine monomer which is independently researched and developed to prepare the polyamide and polyimide macromolecules modified by allyloxy and obtain hydroxyl and allyl through claisen rearrangement. Further removing small molecules such as water and CO by thermal rearrangement₂To obtain polybenzoxazole polymer. The method is a novel series reaction which can be used for polymer molecular structure conversion, uses claisen rearrangement and thermal rearrangement as main paths, has simple reaction conditions, and can be carried out by heating treatment in a solid-phase inert atmosphere. The method can develop the polybenzoxazole gas separation membrane with excellent comprehensive performance.

Drawings

FIG. 1 is a reaction equation for preparing a polymer composed of the repeating structural unit represented by the formula I-1 in the present invention.

FIG. 2 is a reaction scheme of the present invention for preparing an ortho-hydroxy substituted polyamide represented by formula 2.

FIG. 3 is a reaction equation for preparing a polymer composed of the repeating structural unit represented by the formula I-2 in the present invention.

FIG. 4 is a reaction scheme for preparing an ortho-hydroxy substituted polyimide of formula 3 in accordance with the present invention.

FIG. 5 is a thermogravimetric plot (N.sub.w.) of the novel aromatic polyamide containing hydroxyl groups and allyl groups (CRNPPTA-34ODA-50/50) in example 1 of the present invention₂,10℃/min)；

FIG. 6 is a thermogram (N is N) of allyloxy-containing novel aromatic polyimide (ANPI-6FDA) in example 2 of the present invention₂,10℃/min)；

FIG. 7 is an ATR-IR spectrum of the conversion of the novel allyloxy containing aromatic polyimide (ANPI-6FDA) to polybenzoxazole according to example 2 of this invention.

Detailed Description

The present invention will be described below with reference to specific examples, but the present invention is not limited thereto.

The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.

The allyloxy-containing polyamide used in the following example 1 was prepared according to a method comprising the steps of:

preparation of 2, 5-Diallyloxyphenylenediamine:

500ml of acetone, 16.50g of 1, 4-hydroquinone, 51.00g of potassium carbonate and 61.70g of 3-bromopropylene are sequentially added into a 1L single-neck flask, and the mixture is stirred and refluxed for reaction for 6 to 8 hours. The obtained mixture is filtered to remove inorganic salts, the filtrate is rotated and evaporated to remove the solvent and residual bromopropene, and the crude product is purified by column chromatography (dichloromethane/petroleum ether with the volume ratio of 1: 5 is used as an eluent) to obtain 25.66g of the product (1, 4-diallyl-oxy-benzene) with the yield of 90%.

60ml of acetic anhydride and 15.00g of 1, 4-diallyloxybenzene are added into a 100ml three-neck flask, the temperature of the system is monitored by an alcohol thermometer, and dilute nitric acid is slowly added into the flask in multiple times under the temperature of 0-5 ℃ (ice bath), wherein the total volume of the mixture is 12.26ml, and the temperature of the system is not more than 20 ℃. After the reaction, the system was added to 400ml of ice water and filtered to obtain a yellow crude product. The crude product was purified by column chromatography (5: 1 by volume petroleum ether/ethyl acetate as eluent) to yield 11.49g of product (2, 5-diallyloxy p-dinitrobenzene) in 52% yield.

100ml of absolute ethyl alcohol, 6.00g of 2, 5-diallyl-oxy-p-dinitrobenzene and 90ml of concentrated hydrochloric acid are sequentially added into a 500ml three-neck flask, and 15.25g of tin powder is added in batches under stirring. The system is heated to 50 ℃ to react for 12 h. After the reaction, NaOH solution was added to the mixture to pH 10-12, and the mixture was extracted with dichloromethane, the dichloromethane was removed by rotary evaporation, and the crude product was purified by neutral alumina column chromatography (petroleum ether/ethyl acetate in a volume ratio of 30: 1 as eluent) to give 3.77g of product (2, 5-diallyloxy p-phenylenediamine) in 80% yield.

Is provided with a stirring paddle, a drying tube and N₂50ml of solvent N-methyl pyrrolidone and anhydrous CaCl serving as cosolvent are sequentially added into a four-neck flask with an introducing port₂4.12g, 8.32mmol (0.8997g) of diamino monomer p-phenylenediamine and 8.32mmol (1.8326g) of 2, 5-diallyloxy p-phenylenediamine are added successively and stirred to dissolve all the monomers, the mixture is cooled at-10 ℃ for 15min, 16.64mmol (3.3793g) of terephthaloyl chloride and 29.95mmol (2.4ml) of pyridine are added together in two portions under the conditions of-10 ℃ and rapid stirring, and stirring is accelerated, so that splashing is not generated. Keeping the temperature of the system at minus 10 ℃ and stirring for polycondensation reaction for 0.5h, then continuing stirring at 30 ℃ for polycondensation reaction for 6h, pouring the mixture into a large amount of water for precipitation, washing the mixture for three times respectively by hot water, ethanol and acetone, and then drying the mixture in vacuum at 80 ℃ for 24h to obtain the yellow polymer ANPPTA-50 of 4.88g with the yield of 99%.

The allyloxy-containing polyimide used in the following example 2 was prepared according to a method comprising the following steps:

is provided with a stirring paddle, a drying tube and N₂50ml of solvent N-methyl pyrrolidone, 2, 5-diallyl-oxy-p-phenylene-bis (p-phenylene-terephthalamide) is sequentially added into a three-neck flask with an inlet12.50mmol (2.7500g) of amine, stirring to dissolve it completely, adding 12.50mmol (5.5500g) of 6FDA anhydride under ice bath, stirring the mixture under ice bath for 1h, removing ice bath, stirring at room temperature for 12h, adding Et₃N and Ac₂O (1.25ml and 2.50ml), stirred at room temperature for 24h and at 80 ℃ for 3 h. The mixture was precipitated by pouring into 700ml of methanol, washed three times with methanol and dried under vacuum at 80 ℃ for 24h to give 6.72g of the polymer ANPI-6FDA as a white-yellow color in 86% yield.