阅读说明：本技术 一种基于2,5-二烯丙氧基对苯二胺单体的新型聚酰胺高分子材料及其制备方法 (Novel polyamide 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：本发明公开了一种含烯丙氧基芳香族聚酰胺和含羟基和烯丙基芳香族聚酰胺制备方法与应用。该类新型高分子化合物,为由式I-1或式I-2所示重复结构单元构成的聚合物。本发明选用二烯丙氧基二胺单体为基本单体,通过与二元芳香伯胺、二元芳香酰卤按比例进行共缩聚,得到不同侧基含量的一系列新型芳香族聚酰胺。所制备的聚合物的热稳定性优异,侧基带有丰富官能团,可提高不同材料间界面结合强度。利用直接成型法制备出新型含羟基和烯丙基的芳纶浆粕,可提高浆粕与基体材料间的结合强度,如橡胶、酚醛树脂等,进而发展出界面复合良好的高分子材料。<Image he="594" wi="700" file="DDA0001694512180000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(The invention discloses a preparation method and application of aromatic polyamide containing allyloxy and aromatic polyamide containing hydroxyl and allyl. The novel macromolecular compound is a polymer formed by a repeating structural unit shown in a formula I-1 or a formula I-2. The invention selects the diene propoxy diamine monomer as the basic monomer, and the diene propoxy diamine monomer, the binary aromatic primary amine and the binary aromatic acyl halide are subjected to copolycondensation according to the proportion to obtain a series of novel aromatic polyamides with different side group contents. The prepared polymer has excellent thermal stability, and the side group has rich functional groups, so that the interface bonding strength of different materials can be improved. The novel aramid pulp containing hydroxyl and allyl is prepared by a direct forming method, the bonding strength between the pulp and a base material, such as rubber, phenolic resin and the like, can be improved, and a high polymer material with good interface composition is developed.)

1. The polyamide high polymer material based on the 2, 5-diallyl-oxy-p-phenylenediamine monomer is a polymer consisting of a repeating structural unit shown in a formula I-1 or a formula I-2:

in the formula I-1 and the formula I-2, x is 0-1;

Ar₂represents the residue of a primary diamine,

Ar₃denotes the residue of a dicarboxylic acid,

and Ar₂、Ar₃All are groups substituted by any two hydrogens on the aromatic ring in the following compounds:

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

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

3. the polyamide polymer material according to claim 1, characterized in that: the weight average molecular weight of the polymer is not less than 1000, and specifically can be 4000-1,000,000, 4000-500,000 or 4000-20,000.

4. A method for preparing a polymer of claim 1 consisting of repeating structural units of formula I-1, comprising:

in the presence of a cosolvent and an acid-binding agent, 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 carrying out a polycondensation reaction to obtain a polymer formed by a repeating structural unit shown in a formula I-1 in claim 1, wherein x is not 0 or 1;

alternatively, the first and second electrodes may be,

in the presence of a cosolvent and an acid-binding agent, 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 a polycondensation reaction to obtain a polymer formed by a repeated structural unit shown in a formula I-1 in claim 1, wherein x is 1;

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

in the formula IV, Ar₃Is as defined in claim 1 for Ar in formula I-1 or formula I-2₃The definition of (1).

5. The method of claim 4, wherein: the molar ratio of the binary aromatic acyl chloride monomer shown in the formula IV to the diallyloxy diamino monomer shown in the formula II and the binary aromatic primary amine monomer shown in the formula III is 1:0-1:1-0 in sequence; or the like, or, alternatively,

the molar ratio of the binary aromatic acyl chloride monomer shown in the formula IV to the diallyloxy diamino monomer shown in the formula II is 1: 1;

the cosolvent is CaCl₂The dosage of the solvent is 3-12% of the mass of the used solvent;

the acid-binding agent is pyridine, and the using amount of the acid-binding agent is 2-6 times of the total molar amount of the diallyloxy diamino monomer shown in the formula II and the binary aromatic primary amine monomer shown in the formula III;

or the dosage of the monomer is 2 to 6 times of the molar weight of the diallyloxy diamino monomer shown in the formula II;

the solvent is at least one selected from N-methyl pyrrolidone, N-dimethyl acetamide and hexamethyl phosphoric triamide.

6. The method according to claim 4 or 5, characterized in that: the polycondensation reaction comprises the following steps: firstly reacting for 0.1-10h at-10 ℃ to-5 ℃, then heating to the middle temperature of 25-30 ℃ and reacting for 1-24 h.

7. The method according to any one of claims 4-6, wherein: the method further comprises the steps of: after the polycondensation reaction is finished, precipitating the reaction system in water, collecting the precipitate, washing the precipitate with water, ethanol and acetone for three times respectively, and drying the precipitate at 80 ℃ for 24 hours to obtain a purified polymer which is composed of the repeating structural unit shown in the formula I-1 and is claimed in claim 1;

or the like, or, alternatively,

after the polycondensation reaction is completed, the obtained polymer jelly is directly subjected to aging, beating and aging, neutralization and water washing, and drying to obtain the pulp of the polymer composed of the repeating structural unit represented by the formula I-1 in claim 1.

8. A process for producing the polymer resin of claim 1 composed of the repeating structural unit represented by the formula I-2 or a pulp thereof, which comprises: subjecting the polymer resin or pulp thereof composed of the repeating structural unit represented by the formula I-1 in claim 1 to a claisen rearrangement reaction under vacuum or an inert atmosphere to obtain the polymer resin or pulp thereof composed of the repeating structural unit represented by the formula I-2 in claim 1;

alternatively, the first and second electrodes may be,

and (2) uniformly mixing the polymer resin consisting of the repeating structural unit shown in the formula I-1 in the claim 1 and a solvent under vacuum or inert atmosphere to carry out the claisen rearrangement reaction to obtain the polymer resin consisting of the repeating structural unit shown in the formula I-2 in the claim 1.

9. The method of claim 8, wherein: the operation of the claisen rearrangement reaction is as follows:

adding the polymer resin or pulp thereof composed of the repeating structural unit shown in the formula I-1 in the claim 1 into a polymerization tube, vacuumizing and introducing nitrogen for three times, sealing the tube under vacuum condition, reacting at 190 ℃ for 6-8h, cooling, breaking the polymerization tube to obtain a product;

alternatively, the first and second electrodes may be,

adding polymer resin consisting of the repeating structural unit shown as the formula I-1 in the claim 1 and a solvent into a polymerization tube, freezing and pumping the polymer resin and the solvent for three times by liquid nitrogen, sealing the tube under the vacuum condition, reacting for 6-8h at 190 ℃, cooling, breaking the polymerization tube to obtain a product,

the solvent is at least one selected from N-methyl pyrrolidone, N-dimethyl acetamide, N-dimethyl formamide and m-cresol.

10. A polymer pulp obtained from a polymer consisting of repeating structural units represented by the formula I-1 or the formula I-2 in claim 1.

11. Use of a polymer resin consisting of repeating structural units of the formula I-1 or the formula I-2 according to claim 1 or a pulp thereof for the preparation of a polyaramid composite.

Technical Field

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

Background

Polyamide is a polymer with a main chain formed by amido bonds, and when more than 85% of amido bonds of the main chain are directly connected with benzene rings, the polyamide is called wholly aromatic polyamide, namely aramid; the main chain of the aramid fiber molecule is a structure with benzene rings and amido bonds alternating, the covalent bond energy is large, the rigid benzene rings and the amido bonds enable the internal rotation energy barrier of the system to be high, the rigidity of the molecular chain is strong, no substituent is arranged on the main chain of the molecule, the symmetry is high, and the formation of hydrogen bonds and the pi-pi accumulation of the benzene rings between the molecular chains is facilitated. Therefore, the material has the advantages of high modulus, high strength, high heat resistance and the like, and is widely applied to the aspects of aerospace, military, trains, automobiles, communication cables, reinforced composite materials and the like.

The aramid fiber is generally prepared by performing low-temperature solution polycondensation on phthaloyl chloride and phenylenediamine, and can be divided into para-aramid fiber (aramid fiber 1414 or PPTA) and meta-aramid fiber (aramid fiber 1313) according to different occupation positions of monomer substituent groups used for polymerization. PPTA is an aramid fiber material with higher strength, but the solubility is very poor due to the strong hydrogen bond action between a rigid main chain and a chain, and the aramid fiber is mainly prepared by sulfuric acid liquid crystal spinning at present. On the other hand, PPTA molecular chains are arranged closely and have high crystallinity, and active reaction groups are lacked in the structure, so that the surface chemical activity is extremely low, the compatibility with other matrix materials is limited, and the introduced active groups can be damaged in the sulfuric acid liquid crystal spinning process. Therefore, development of an aramid-like structure with rich active groups and good solubility is urgently needed. After many years of modification attempts, scientists find that the effect of improving the solubility by introducing polar substituents into the molecular structure is better than that by introducing non-polar substituents.

Disclosure of Invention

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

The polyamide high polymer material based on the 2, 5-diallyl-oxy-p-phenylenediamine monomer is a polymer formed by a repeating structural unit shown in a formula I-1 or a formula I-2:

in the above formula I-1 and formula I-2, x may be 0 to 1 (endpoint 0 is not preferable), and x may be specifically 0.05, 0.1, 0.25, 0.5, 0.75 or 1; ar (Ar)₂Denotes the residue of a diprimary amine, Ar₃Represents a residue of a dicarboxylic acid, and Ar₂、Ar₃Each independently is a group substituted by any two 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:

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

the weight average molecular weight of the polymer is not less than 1000, specifically 4000 to 1,000,000, 4000 to 500,000, or 4000 to 20,000, and more specifically 4800, 5800, 11900, 13100, or 14925.

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:

in the presence of a cosolvent and an acid-binding agent, 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 carrying out a polycondensation reaction to obtain a polymer formed by a repeating structural unit shown in a formula I-1, wherein x is not 0 or 1;

alternatively, the first and second electrodes may be,

in the presence of a cosolvent and an acid-binding agent, 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 a polycondensation reaction to obtain a polymer consisting of a repeating structural unit shown in a formula I-1, wherein x is 1;

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

In the above formula IV, Ar₃Is as defined for Ar in formula I-1 or formula I-2₃The definition of (1).

Specifically, the binary aromatic primary amine monomer shown in the formula III is any one of the following monomers: 1, 3-phenylenediamine, 1, 4-naphthalenediamine, 1, 5-naphthalenediamine, 2, 6-naphthalenediamine, 2, 7-naphthalenediamine, 3 '-diaminobiphenyl, 4' -diaminobiphenyl, 3 '-diaminodiphenylmethane, 4' -diaminodiphenylmethane, 3,3' -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.

Specifically, the binary aromatic acyl chloride monomer shown in the formula IV is any one of the following monomers: 1, 3-benzenedicarboxylic acid dichloride, 1, 4-benzenedicarboxylic acid dichloride, 1, 3-naphthalenedicarboxylic acid dichloride, 1, 4-naphthalenedicarboxylic acid dichloride, 1, 5-naphthalenedicarboxylic acid dichloride, 2, 6-naphthalenedicarboxylic acid dichloride, 2, 7-naphthalenedicarboxylic acid dichloride, 4 '-dichloroformyl biphenyl, diphenylmethane 4,4' -dicarboxylic acid dichloride, 4 '-diphenyletherdicarboxylic acid dichloride 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-bis (4-benzoyl chloride-4-oxo-phenyl) trifluoroethane, 4,4- (9-fluorenylidene) -dibenzoyl chloride, 1, 3-trimethyl-3-phenylindane-4, 5-diformylchloride.

In the method, the molar ratio of the binary aromatic acyl chloride monomer shown in the formula IV to the diallyloxy diamino monomer shown in the formula II and the binary aromatic primary amine monomer shown in the formula III can be 1:0-1:1-0 (both endpoints 0 and 1 are not preferred), and specifically: 1:0.05-0.75: 0.95-0.25, 1:0.05:0.95, 1:0.10:0.90, 1:0.25:0.75, 1:0.50:0.50, 1:0.75: 0.25;

or the like, or, alternatively,

the molar ratio of the binary aromatic acyl chloride monomer shown in the formula IV to the diallyloxy diamino monomer shown in the formula II can be 1: 1;

the cosolvent may be CaCl₂The amount of the solvent used can be 3-12% by mass, preferably 5-8% by mass of the solvent used.

The acid-binding agent can be pyridine, and the dosage of the acid-binding agent is 2-6 times of the total molar quantity of the diallyloxy diamino monomer shown in the formula II and the binary aromatic primary amine monomer shown in the formula III;

or the amount of the diallyloxy diamino monomer is 2 to 6 times of the molar amount of the diallyloxy diamino monomer shown in the formula II.

The solvent is at least one selected from N-methyl pyrrolidone, N-dimethyl acetamide and hexamethyl phosphoric triamide.

The polycondensation reaction comprises the following steps: firstly reacting at-10 ℃ to-5 ℃ for 0.1-10h, then heating to the middle temperature of 25-30 ℃ for 1-24h, and specifically, reacting at-10 ℃ to-5 ℃ for 0.5h, and then heating to the middle temperature of 25-30 ℃ for 6 h.

The method also comprises the following steps: after the polycondensation reaction is finished, precipitating the reaction system in water, collecting the precipitate, washing the precipitate with water, ethanol and acetone for three times respectively, and drying the precipitate for 24 hours at 80 ℃ to obtain a purified polymer consisting of the repeating structural unit shown in the formula I-1;

or the like, or, alternatively,

after the polycondensation reaction is finished, directly curing the obtained polymer jelly, pulping, aging, neutralizing, washing with water and drying to obtain the pulp of the polymer consisting of the repeating structural unit shown in the formula I-1.

Wherein the curing temperature can be 60-90 ℃, particularly 80 ℃, the curing time can be 6-10 hours, particularly 8 hours, and the curing operation can be 80 ℃ for 8 hours.

The pulping time can be 5-10 min.

The invention also provides a method for preparing the polymer or the pulp thereof consisting of the repeating structural unit shown in the formula I-2.

The invention provides a method for preparing a polymer or pulp thereof consisting of a repeating structural unit shown in a formula I-2 (prepared according to a reaction equation shown in a figure 2), which comprises the following steps:

subjecting the polymer resin or the pulp thereof consisting of the repeating structural unit shown in the formula I-1 to a claisen rearrangement reaction in vacuum or inert atmosphere to obtain the polymer resin or the pulp thereof consisting of the repeating structural unit shown in the formula I-2;

alternatively, the first and second electrodes may be,

and (2) uniformly mixing the polymer resin consisting of the repeating structural unit shown in the formula I-1 and a solvent in vacuum or inert atmosphere to carry out a claisen rearrangement reaction to obtain the polymer resin consisting of the repeating structural unit shown in the formula I-2.

The operation of the claisen rearrangement reaction is as follows:

adding polymer resin or pulp thereof consisting of the repeating structural unit shown in the formula I-1 into a polymerization tube, vacuumizing and introducing nitrogen for three times, sealing the tube under a vacuum condition, reacting at 190 ℃ for 6-8h, cooling, and breaking the polymerization tube to obtain a product;

alternatively, the first and second electrodes may be,

adding polymer resin consisting of the repeating structural unit shown in the formula I-1 and a solvent into a polymerization tube, freezing and pumping the polymer resin and the solvent for three times by using liquid nitrogen, sealing the tube under a vacuum condition, reacting for 6-8h at 190 ℃, cooling, and breaking the polymerization tube to obtain a product.

The solvent can be at least one selected from N-methyl pyrrolidone, N-dimethyl acetamide, N-dimethyl formamide and m-cresol.

The method further comprises the steps of:

after the rearrangement reaction is finished, precipitating the reaction system in methanol, collecting the precipitate, washing the precipitate for three times by using the methanol, and drying the precipitate for 24 hours at the temperature of 80 ℃.

Pulp obtained from polymers consisting of repeating structural units of the formula I-1 or I-2 also falls within the scope of the present invention.

The application of the polymer composed of the repeating structural unit shown in the formula I-1 or the formula I-2 or the pulp thereof in preparing the polyaromatic amide composite material also belongs to the protection scope of the invention.

The invention selects diallyl oxydiamino monomer as basic monomer, and the diallyl oxydiamino monomer is copolycondensed with binary aromatic primary amine and binary aromatic acyl chloride according to a certain proportion to obtain a series of novel aromatic polyamide macromolecules with different allyloxy contents. The prepared polymer has excellent thermal stability, and the side group has rich functional groups, so that the interface bonding strength of different materials can be improved, and a high polymer material with good interface composition can be developed.

The invention uses a novel p-phenylenediamine monomer which is independently researched and developed to prepare the polyamide polymer modified by allyloxy, and hydroxyl and allyl can be obtained through claisen rearrangement so as to achieve the purposes of enriching surface functional groups, improving polymer solubility and the like. The polymer is prepared into aramid pulp by a direct molding process, and the introduction of polar groups such as hydroxyl groups and the like can greatly improve the interface bonding strength between the polymer pulp and other materials and prepare the high-molecular composite material with excellent performance.

Drawings

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

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

FIG. 3 is an IR spectrum of a novel aromatic polyamide containing an allyloxy group (ANPPTA-25, ANPPTA-50, ANPPTA-75, ANPPTA-100) prepared in examples 1 to 4 of the present invention;

FIG. 4 is an IR spectrum of a novel aromatic polyamide containing allyl and hydroxyl groups (CRNPPTA-25, CRNPPTA-50, CRNPPTA-75, CRNPPTA-100) prepared in examples 1 to 4 of the present invention;

FIG. 5 is a NMR chart of a butylated product of a novel aromatic polyamide containing allyloxy groups (ANPPTA-25, ANPPTA-50, ANPPTA-75, APPTA-100) prepared by examples 1 to 4 of the present invention;

FIG. 6 is a DSC plot of allyloxy-containing novel aromatic polyamides (ANPPTA-25, ANPPTA-50, ANPPTA-75, ANPPTA-100) prepared in examples 1-4 of the present invention;

FIG. 7 is a scanning electron micrograph of novel aromatic polyamide Pulp (ANPPTA-5-Pulp, ANPPTA-10-Pulp, CRNPPTA-10-Pulp) produced in examples 7 to 9 of the present invention; wherein, the pictures a and b are scanning electron micrographs of ANPPTA-5-Pulp; c, d is a scanning electron microscope image of ANPPTA-10-Pulp; e and f are scanning electron micrographs of CRNPPTA-10-Pulp.

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 molecular weight of the polymers in the examples described below was determined by Gel Permeation Chromatography (GPC) using polystyrene standards as a comparison, according to the method of the literature N.Ogata, K.Sanui, S.Kitayama J.Polym.Sci.Polym.Chem.Ed.1984, 22, 865-.

The 2, 5-diallyloxy p-phenylenediamine used in the following examples was prepared according to a process comprising the steps of:

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, extracted with dichloromethane, rotary evaporated to remove dichloromethane, and the crude product was purified by neutral alumina column chromatography (30: 1 by volume petroleum ether/ethyl acetate as eluent) to give 3.77g of product in 80% yield.