CN114380999A - Easily-molded p-phenylene benzodioxazole copolymer and preparation method thereof - Google Patents

Easily-molded p-phenylene benzodioxazole copolymer and preparation method thereof Download PDF

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CN114380999A
CN114380999A CN202111546188.6A CN202111546188A CN114380999A CN 114380999 A CN114380999 A CN 114380999A CN 202111546188 A CN202111546188 A CN 202111546188A CN 114380999 A CN114380999 A CN 114380999A
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刘薇
陈湘栋
刘宗法
刘群
孟昭瑞
代勇
张殿波
郭程
朱晓琳
钟蔚华
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Shandong Non Metallic Material Research Institute
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Abstract

The invention belongs to the technical field of high-performance materials, and relates to a p-phenylene benzobisoxazole copolymer easy to mold and process and a preparation method thereof. The p-phenylene benzobisoxazole copolymer containing a flexible olefin chain segment is synthesized by carrying out polycondensation reaction on monomer 4, 6-diamino-1, 3-benzenediol hydrochloride, terephthalic acid, adipic acid and sebacic acid in a polyphosphoric acid system through gradually heating solution. The copolymer keeps the excellent properties of the poly (p-phenylene benzobisoxazole), namely high tensile strength, high modulus and high heat resistance, emphasizes on improving the forming processing property, has the characteristic of melting by heating, and provides a new method for forming processing of the poly (p-phenylene benzobisoxazole).

Description

Easily-molded p-phenylene benzodioxazole copolymer and preparation method thereof
Technical Field
The invention belongs to the technical field of high-performance materials, and relates to a p-phenylene benzobisoxazole copolymer easy to mold and process and a preparation method thereof.
Background
The poly-p-Phenylene Benzobisoxazole (PBO) (cis and trans conformations) benzene ring and oxazole ring are almost coplanar with a chain axis, and are bilaterally symmetrical rigid rod-shaped molecular structures which are one form with the lowest energy. Due to the use of liquid crystal spinning technology, macromolecular chains, crystals and microfibrils/fibrils are all arranged along the axial direction of the fiber in an almost completely oriented manner, and a highly oriented ordered structure is formed. Therefore, the unique structure of the PBO fiber determines the excellent and outstanding performance of the PBO fiber, has the characteristics of high strength, high modulus, high heat resistance and good flame retardance, has good dimensional stability and high chemical resistance stability, and is the best comprehensive performance in all the organic fibers at present.
In the preparation process of PBO, the monomer 4, 6-diamino resorcinol hydrochloride (DARHB) has active property, is easy to oxidize and is difficult to store due to the existence of binary amino and hydroxyl. The strong covalent bond force and the weak intermolecular force on the axis of the PBO molecule are easy to slide between molecular chains, so that the compression resistance of the PBO molecule is poor. PBO has poor solubility, is insoluble in most organic solvents and alkaline solutions, and can only be dissolved in concentrated sulfuric acid and methanesulfonic acid. Because the melting temperature is higher than the thermal decomposition temperature, the forming and processing method of PBO is relatively single, the most studied existing method is dry-jet wet spinning, and the whole polymerization and spinning process is long in time and high in requirement.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a p-Phenylene Benzobisoxazole (PBO) copolymer which is easy to form and process and a preparation method thereof. The PBO copolymer is prepared by the polycondensation reaction of 4, 6-diaminoresorcinol hydrochloride (DARHB) and mixed dicarboxylic acid in a polyphosphoric acid system through gradually heating solution to synthesize a p-phenylene benzobisoxazole copolymer containing a flexible chain segment; the mixed dicarboxylic acid comprises a first carboxylic acid terephthalic acid, and a second carboxylic acid adipic acid or sebacic acid or a mixture thereof. The copolymer keeps the excellent properties of the poly-p-phenylene benzobisoxazole, namely high tensile strength, high modulus and high heat resistance, emphasizes on improving the forming processing property, has the characteristic of being meltable by heating, and provides a new method for forming processing of the poly-p-phenylene benzobisoxazole.
The main chain of the p-phenylene benzobisoxazole copolymer containing the flexible chain segment contains a flexible group, and the flexible group is butylene or octylene or both.
According to the mol percentage content, the mol percentage of the flexible groups in the main chain of the copolymer is 5 to 45 percent; the mole percentage of the benzodioxazole ring is 50%; the mole percentage of the phenyl is 5-45%.
Preferably, the mole percentage of flexible groups in the copolymer backbone is 10% to 40%; the mole percentage of the benzodioxazole ring is 50%; the mole percentage of the phenyl is 10-40%.
More preferably, the mole percentage of flexible groups in the copolymer backbone is from 10% to 30%; the mole percentage of the benzodioxazole ring is 50%; the mole percentage of the phenyl is 20-40%.
The easily-formed and processed p-phenylene benzobisoxazole copolymer main chain structure containing the flexible chain segment comprises a structure shown in a formula I:
Figure BDA0003414779090000011
in the formula I, R is
Figure BDA0003414779090000012
Or a flexible group (butylene or octylene); n is a positive integer.
Further, the structure of formula I may specifically be:
Figure BDA0003414779090000021
in the formula II R1The flexible group is formed by the following steps of x, y and z which are all 0 or positive integers, y and z are not 0 at the same time, and x and z are not 0 at the same time.
The invention discloses a preparation method of easy-to-mold and easy-to-process p-phenylene benzobisoxazole copolymer, which comprises the following steps: introducing nitrogen into a reaction device filled with polyphosphoric acid for a period of time, adding 4, 6-diaminoresorcinol hydrochloride, then heating in an oil bath to 60 ℃, stirring and reacting for 12 hours to exhaust hydrogen chloride (introducing the exhausted hydrogen chloride into a sodium hydroxide solution through a gas guide pipe); after the hydrogen chloride is exhausted, adding mixed dicarboxylic acid, carrying out gradient heating reaction after the addition is finished, stopping heating after the addition is finished, and adding distilled water to separate out a solid after cooling.
The nitrogen gas is preferably introduced for 0.5 h.
The gradient temperature-rising reaction is preferably carried out in the following way:
heating to 120 ℃ and stirring for reaction for 3h, heating to 140 ℃ and stirring for reaction for 3h, heating to 160 ℃ and stirring for reaction for 3h, and finally heating to 190 ℃ and stirring for reaction for 3 h.
In the reaction process, the molar ratio of the 4, 6-diaminoresorcinol hydrochloride to the mixed dicarboxylic acid is controlled to be 1: 1; the molar ratio of the first carboxylic acid to the second carboxylic acid in the mixed dicarboxylic acid is 0.1-0.9: 0.9-0.1.
After the reaction is finished, repeatedly stirring, washing and filtering the solid with distilled water to remove phosphoric acid and polyphosphoric acid, then pulverizing into powder with a high-speed universal pulverizer, transferring to a funnel, repeatedly stirring, washing and filtering with distilled water, testing with a pH test paper, washing and filtering with absolute ethyl alcohol after the neutral state is achieved, finally washing and filtering with normal hexane, placing the product in a vacuum drying oven for drying, taking out after drying, and weighing to obtain the solid.
Preferably, the vacuum drying oven temperature is set at 45 ℃.
The p-phenylene benzo dioxazole copolymer containing the flexible chain segment and easy to mold and process and the preparation method thereof have the following characteristics: in the preparation process of the PBO copolymer, a second dicarboxylic acid adipic acid or sebacic acid or a mixture thereof is adopted, so that the main chain of the PBO copolymer contains flexible butylene/octylene, the introduction of flexible alkylene obviously improves the formability and processability, the PBO copolymer can be melted by heating, and the copolymer can be dissolved in concentrated sulfuric acid and methanesulfonic acid and also can be dissolved in trifluoroacetic acid. Has good thermal stability and stronger tensile strength and modulus. In addition, the preparation method provided by the invention has the advantages of direct polymerization, simplified complicated polymerization steps in the conventional process, simplified procedure and convenient operation. The PBO copolymer obtained by the direct polymerization method can be prepared into particle materials which are convenient to store, and then the modified PBO fiber can be prepared by melt spinning. Compared with the prior art, the method not only maintains the excellent performance of the PBO fiber, but also solves the defect that the conventional PBO polymer is difficult to spin, provides a new method and a new way for the synthesis and application of the PBO in the field, reduces the difficulty and the cost of the technology, and has very wide application significance.
Drawings
FIG. 1 is a reaction scheme of a prior art terephthalic acid process for the preparation of PBO homopolymer;
FIG. 2 is a reaction scheme for preparing PBO copolymer by the method of the present invention;
wherein R in FIG. 2 is
Figure BDA0003414779090000022
Or a flexible group (butylene or octylene); n is a positive integer.
Detailed Description
The following examples are presented as further illustrations and are not intended to limit the scope of the claims. Using an infrared analyzer (FT-IR) (KBr pellet as test condition), and a nuclear magnetic resonance apparatus (1H NMR) (room temperature) analysis of the molecular structure of the polymer, Differential Scanning Calorimeter (DSC) (nitrogen atmosphere, temperature rise/drop rate of 10 ℃/min), thermogravimetric analyzer (TG) (nitrogen atmosphere, temperature rise rate of 10 ℃/min)10 ℃/min) the melting temperature and the thermal decomposition temperature of the polymer are measured.
Comparative example, preparation of PBO homopolymer by terephthalic acid Process (as shown in FIG. 1)
Introducing nitrogen into a reaction vessel filled with polyphosphoric acid for 0.5h, adding 3.422g of 4, 6-diaminoresorcinol hydrochloride, heating to 60 ℃ by using an oil bath, stirring and reacting for 12h to remove hydrogen chloride (the discharged hydrogen chloride is introduced into a beaker filled with sodium hydroxide solution by using a gas guide pipe), adding 2.668g of terephthalic acid (the molar ratio of 4, 6-diaminoresorcinol hydrochloride to terephthalic acid is 1:1) after removing the hydrogen chloride, heating to 120 ℃ after adding, stirring and reacting for 3h, heating to 140 ℃ again, stirring and reacting for 3h, heating to 160 ℃ again, stirring and reacting for 3h, heating to 190 ℃ finally, stirring and reacting for 3h, stopping heating, cooling, and adding distilled water to precipitate a solid. Taking out the mixture from a three-neck flask, putting the mixture into a funnel, repeatedly stirring, washing and filtering the mixture by using distilled water to remove phosphoric acid and polyphosphoric acid, taking out the mixture, pulverizing the mixture into powder by using a high-speed universal pulverizer, moving the powder to the funnel, repeatedly stirring, washing and filtering the powder by using the distilled water, testing the powder by using a pH test paper, washing and filtering the powder by using absolute ethyl alcohol after the powder is neutral, finally washing and filtering the powder by using normal hexane, putting a product into a vacuum drying oven for drying, setting the temperature of the vacuum drying oven to be 45 ℃, vacuumizing, taking out the product after drying, and weighing the product to obtain a solid.
The product structure and performance were analyzed as follows: infrared test shows that the copolymer generated by the reaction contains benzoxazole ring structure; by means of a nuclear magnetic resonance hydrogen spectrogram, the synthetic PBO homopolymer can be determined, the characteristic peak is integrated, and the integrated area conforms to the theory; DSC tests show that TA tests show that the thermal weight loss of the homopolymer is accelerated at 650 ℃, the homopolymer has no melting temperature, and the sample residual rate is 94.3% at 700 ℃.
Example 1 preparation of 20% adipic acid modified PBO copolymer (as shown in FIG. 2)
Introducing nitrogen into a reaction vessel filled with polyphosphoric acid for 0.5h, adding 3.422g of 4, 6-diaminoresorcinol hydrochloride, heating the reaction vessel to 60 ℃ by a rear oil bath, stirring and reacting for 12h to remove hydrogen chloride (the discharged hydrogen chloride is introduced into a beaker filled with sodium hydroxide solution by a gas guide tube), adding 2.134g of terephthalic acid and 0.471g of adipic acid (the molar ratio of the 4, 6-diaminoresorcinol hydrochloride to the terephthalic acid to the adipic acid is 1:0.8:0.2) after removing the hydrogen chloride, heating to 120 ℃ again, stirring and reacting for 3h, heating to 140 ℃ again, stirring and reacting for 3h, heating to 160 ℃ again, stirring and reacting for 3h, finally heating to 190 ℃ again, distilling and stopping heating, cooling, and adding water to precipitate a solid. Taking out the product from the three-neck flask, putting the product into a funnel, repeatedly stirring, washing and filtering the product by using distilled water to remove phosphoric acid and polyphosphoric acid, taking out the product, pulverizing the product into powder by using a high-speed universal pulverizer, moving the powder to the funnel, repeatedly stirring, washing and filtering the powder by using the distilled water, testing the powder by using a pH test paper, washing and filtering the neutral product by using absolute ethyl alcohol, finally washing and filtering the neutral product by using normal hexane, placing the product into a vacuum drying oven for drying, setting the temperature of the vacuum drying oven to be 45 ℃, vacuumizing, taking out the product after drying, and weighing the solid to obtain the product.
The product structure and performance were analyzed as follows: infrared test shows that the copolymer generated by the reaction contains benzoxazole ring structure; by means of a nuclear magnetic resonance hydrogen spectrogram, the synthetic PBO copolymer can be determined to be a random copolymer and integrates a characteristic peak, and the integrated area conforms to the theory; DSC test shows that the melting peak temperature T of the copolymerm433.5 ℃ and TA test showed that the copolymer started to accelerate the weight loss at 595 ℃ and that the sample residual rate was 60% at 700 ℃.
Example 2, 40% preparation of adipic acid modified PBO copolymer (as shown in FIG. 2)
Introducing nitrogen into a reaction vessel filled with polyphosphoric acid for 0.5h, adding 3.422g of 4, 6-diaminoresorcinol hydrochloride, heating the reaction vessel to 60 ℃ by a rear oil bath, stirring and reacting for 12h to remove hydrogen chloride (the discharged hydrogen chloride is introduced into a beaker filled with sodium hydroxide solution by a gas guide tube), adding 1.600g of terephthalic acid and 0.942g of adipic acid (the molar ratio of the 4, 6-diaminoresorcinol hydrochloride to the terephthalic acid to the adipic acid is 1:0.6:0.4) after removing the hydrogen chloride, heating to 120 ℃ again, stirring and reacting for 3h, heating to 140 ℃ again, stirring and reacting for 3h, heating to 160 ℃ again, heating to 190 ℃ finally, stirring and reacting for 3h, distilling and stopping heating, cooling, and adding water to precipitate a solid. Taking out the product from the three-neck flask, putting the product into a funnel, repeatedly stirring, washing and filtering the product by using distilled water to remove phosphoric acid and polyphosphoric acid, taking out the product, pulverizing the product into powder by using a high-speed universal pulverizer, moving the powder to the funnel, repeatedly stirring, washing and filtering the powder by using the distilled water, testing the powder by using a pH test paper, washing and filtering the neutral product by using absolute ethyl alcohol, finally washing and filtering the neutral product by using normal hexane, placing the product into a vacuum drying oven for drying, setting the temperature of the vacuum drying oven to be 45 ℃, vacuumizing, taking out the product after drying, and weighing the solid to obtain the product.
The product structure and performance were analyzed as follows: infrared test shows that the copolymer generated by the reaction contains benzoxazole ring structure; by means of a nuclear magnetic resonance hydrogen spectrogram, the synthetic PBO copolymer can be determined to be a random copolymer and integrates a characteristic peak, and the integrated area conforms to the theory; DSC test shows that the melting peak temperature T of the copolymermAt 329.7 c, TA testing indicated that the copolymer began to experience an increase in weight loss on heating at 510 c, and a sample retention of 58.9% at 700 c.
Example 3 preparation of 60% adipic acid modified PBO copolymer (as shown in FIG. 2)
Introducing nitrogen into a reaction vessel filled with polyphosphoric acid for 0.5h, adding 3.422g of 4, 6-diaminoresorcinol hydrochloride, heating the reaction vessel to 60 ℃ by a rear oil bath, stirring and reacting for 12h to exhaust hydrogen chloride (the exhausted hydrogen chloride is introduced into a beaker filled with sodium hydroxide solution by a gas guide tube), adding 1.067g of terephthalic acid and 1.414g of adipic acid (the molar ratio of the 4, 6-diaminoresorcinol hydrochloride to the terephthalic acid to the adipic acid is 1:0.4:0.6) after the hydrogen chloride is exhausted, heating the reaction vessel to 120 ℃ again, stirring and reacting for 3h, heating the reaction vessel to 140 ℃ again, stirring and reacting for 3h, heating the reaction vessel to 160 ℃ again, heating the reaction vessel to 190 ℃ finally, stirring and reacting for 3h, distilling and stopping heating, cooling, and adding water to precipitate a solid. Taking out the product from the three-neck flask, putting the product into a funnel, repeatedly stirring, washing and filtering the product by using distilled water to remove phosphoric acid and polyphosphoric acid, taking out the product, pulverizing the product into powder by using a high-speed universal pulverizer, moving the powder to the funnel, repeatedly stirring, washing and filtering the powder by using the distilled water, testing the powder by using a pH test paper, washing and filtering the neutral product by using absolute ethyl alcohol, finally washing and filtering the neutral product by using normal hexane, placing the product into a vacuum drying oven for drying, setting the temperature of the vacuum drying oven to be 45 ℃, vacuumizing, taking out the product after drying, and weighing the solid to obtain the product.
The product structure and performance were analyzed as follows: infrared test shows that the copolymer generated by the reaction contains benzoxazole ring structure; by means of a nuclear magnetic resonance hydrogen spectrogram, the synthetic PBO copolymer can be determined to be a random copolymer and integrates a characteristic peak, and the integrated area conforms to the theory; DSC test shows that the melting peak temperature T of the copolymermAt 263.5 deg.C, TA test showed that the copolymer began to lose weight faster at 457 deg.C, and at 700 deg.C, the sample retention was 54.94%.
Example 4, 80% preparation of adipic acid modified PBO copolymer (as shown in FIG. 2)
Introducing nitrogen into a reaction vessel filled with polyphosphoric acid for 0.5h, adding 3.422g of 4, 6-diaminoresorcinol hydrochloride, heating the reaction vessel to 60 ℃ by a rear oil bath, stirring and reacting for 12h to exhaust hydrogen chloride (the exhausted hydrogen chloride is introduced into a beaker filled with sodium hydroxide solution by a gas guide tube), adding 0.533g of terephthalic acid and 1.885g of adipic acid (the molar ratio of the 4, 6-diaminoresorcinol hydrochloride to the terephthalic acid to the adipic acid is 1:0.2:0.8) after the hydrogen chloride is exhausted, heating the reaction vessel to 120 ℃ after the hydrogen chloride is exhausted, stirring and reacting for 3h, heating the reaction vessel to 140 ℃ again, stirring and reacting for 3h, heating the reaction vessel to 160 ℃ again, heating the reaction vessel to 190 ℃ finally, stirring and reacting for 3h, distilling and stopping heating, cooling, and adding water to separate out a solid. Taking out the product from the three-neck flask, putting the product into a funnel, repeatedly stirring, washing and filtering the product by using distilled water to remove phosphoric acid and polyphosphoric acid, taking out the product, pulverizing the product into powder by using a high-speed universal pulverizer, moving the powder to the funnel, repeatedly stirring, washing and filtering the powder by using the distilled water, testing the powder by using a pH test paper, washing and filtering the neutral product by using absolute ethyl alcohol, finally washing and filtering the neutral product by using normal hexane, placing the product into a vacuum drying oven for drying, setting the temperature of the vacuum drying oven to be 45 ℃, vacuumizing, taking out the product after drying, and weighing the solid to obtain the product.
The product structure and performance were analyzed as follows: infrared test shows that the copolymer generated by the reaction contains benzoxazole ring structure; by means of nuclear magnetic resonance hydrogen spectrogram, the synthetic PBO copolymer is determined to be random copolymer and integrates the characteristic peak, the integrated area and the principleThe theory is consistent; DSC test shows that the melting peak temperature T of the copolymerm188.3 ℃ and TA test showed that the copolymer started to accelerate the weight loss on heating at 430 ℃ and the sample residual rate was 49.70% at 700 ℃.
Example 5 preparation of 20% sebacic acid modified PBO copolymer (as shown in FIG. 2)
Introducing nitrogen into a reaction vessel filled with polyphosphoric acid for 0.5h, adding 3.422g of 4, 6-diaminoresorcinol hydrochloride, heating the reaction vessel to 60 ℃ by a rear oil bath, stirring and reacting for 12h to remove hydrogen chloride (the discharged hydrogen chloride is introduced into a beaker filled with sodium hydroxide solution by a gas guide tube), adding 2.134g of terephthalic acid and 0.652g of sebacic acid (the molar ratio of the 4, 6-diaminoresorcinol hydrochloride to the terephthalic acid to the sebacic acid is 1:0.8:0.2) after removing the hydrogen chloride, heating the reaction vessel to 120 ℃ after adding the hydrogen chloride, stirring and reacting for 3h, heating the reaction vessel to 140 ℃ again, stirring and reacting for 3h, heating the reaction vessel to 160 ℃ again, stirring and reacting for 3h, heating the reaction vessel to 190 ℃ finally, distilling and stopping heating, cooling, and adding water to separate out a solid. Taking out the product from the three-neck flask, putting the product into a funnel, repeatedly stirring, washing and filtering the product by using distilled water to remove phosphoric acid and polyphosphoric acid, taking out the product, pulverizing the product into powder by using a high-speed universal pulverizer, moving the powder to the funnel, repeatedly stirring, washing and filtering the powder by using the distilled water, testing the powder by using a pH test paper, washing and filtering the neutral product by using absolute ethyl alcohol, finally washing and filtering the neutral product by using normal hexane, placing the product into a vacuum drying oven for drying, setting the temperature of the vacuum drying oven to be 45 ℃, vacuumizing, taking out the product after drying, and weighing the solid to obtain the product.
The product structure and performance were analyzed as follows: infrared test shows that the copolymer generated by the reaction contains benzoxazole ring structure; the synthesized PBO copolymer can be determined to be a random copolymer through a nuclear magnetic resonance hydrogen spectrogram, the characteristic peak is integrated, and the integrated area conforms to the theory; DSC test shows that the melting peak temperature T of the copolymerm330.7 ℃ and TA test showed that the copolymer started to accelerate the weight loss on heating at 505 ℃ and that the sample residual rate was 51.4% at 700 ℃.
Example 6, 40% preparation of sebacic acid modified PBO copolymer (as shown in FIG. 2)
Introducing nitrogen into a reaction vessel filled with polyphosphoric acid for 0.5h, adding 3.422g of 4, 6-diaminoresorcinol hydrochloride, heating the reaction vessel to 60 ℃ by a rear oil bath, stirring and reacting for 12h to remove hydrogen chloride (the discharged hydrogen chloride is introduced into a beaker filled with sodium hydroxide solution by a gas guide tube), adding 1.600g of terephthalic acid and 1.303g of sebacic acid (the molar ratio of the 4, 6-diaminoresorcinol hydrochloride to the terephthalic acid to the sebacic acid is 1:0.6:0.4) after removing the hydrogen chloride, heating the reaction vessel to 120 ℃ after adding the hydrogen chloride, stirring and reacting for 3h, heating the reaction vessel to 140 ℃ again, stirring and reacting for 3h, heating the reaction vessel to 160 ℃ again, stirring and reacting for 3h, heating the reaction vessel to 190 ℃ finally, distilling and stopping heating, cooling, and adding water to separate out a solid. Taking out the product from the three-neck flask, putting the product into a funnel, repeatedly stirring, washing and filtering the product by using distilled water to remove phosphoric acid and polyphosphoric acid, taking out the product, pulverizing the product into powder by using a high-speed universal pulverizer, moving the powder to the funnel, repeatedly stirring, washing and filtering the powder by using the distilled water, testing the powder by using a pH test paper, washing and filtering the neutral product by using absolute ethyl alcohol, finally washing and filtering the neutral product by using normal hexane, placing the product into a vacuum drying oven for drying, setting the temperature of the vacuum drying oven to be 45 ℃, vacuumizing, taking out the product after drying, and weighing the solid to obtain the product.
The product structure and performance were analyzed as follows: infrared test shows that the copolymer generated by the reaction contains benzoxazole ring structure; the synthesized PBO copolymer can be determined to be a random copolymer through a nuclear magnetic resonance hydrogen spectrogram, the characteristic peak is integrated, and the integrated area conforms to the theory; DSC test shows that the melting peak temperature T of the copolymerm290.9 ℃ and TA test showed that the copolymer started to accelerate the thermal weight loss at 478.1 ℃ and the sample residual rate was 43.7% at 700 ℃.
Example 7 preparation of 60% sebacic acid modified PBO copolymer (as shown in FIG. 2)
Introducing nitrogen into a reaction vessel filled with polyphosphoric acid for 0.5h, adding 3.422g of 4, 6-diaminoresorcinol hydrochloride, heating the reaction vessel to 60 ℃ in a rear oil bath, stirring and reacting for 12h to remove hydrogen chloride (the discharged hydrogen chloride is introduced into a beaker filled with sodium hydroxide solution by a gas guide tube), adding 1.067g of terephthalic acid and 1.956g of sebacic acid (the molar ratio of the 4, 6-diaminoresorcinol hydrochloride to the terephthalic acid to the sebacic acid is 1:0.4:0.6) after removing the hydrogen chloride, heating the reaction vessel to 120 ℃ after adding, stirring and reacting for 3h, heating the reaction vessel to 140 ℃ again, stirring and reacting for 3h, heating the reaction vessel to 160 ℃ again, stirring and reacting for 3h after heating the reaction vessel to 190 ℃, distilling and stopping heating, cooling, and adding water to separate out a solid. Taking out the product from the three-neck flask, putting the product into a funnel, repeatedly stirring, washing and filtering the product by using distilled water to remove phosphoric acid and polyphosphoric acid, taking out the product, pulverizing the product into powder by using a high-speed universal pulverizer, moving the powder to the funnel, repeatedly stirring, washing and filtering the powder by using the distilled water, testing the powder by using a pH test paper, washing and filtering the neutral product by using absolute ethyl alcohol, finally washing and filtering the neutral product by using normal hexane, placing the product into a vacuum drying oven for drying, setting the temperature of the vacuum drying oven to be 45 ℃, vacuumizing, taking out the product after drying, and weighing the solid to obtain the product.
The product structure and performance were analyzed as follows: infrared test shows that the copolymer generated by the reaction contains benzoxazole ring structure; the synthesized PBO copolymer can be determined to be a random copolymer through a nuclear magnetic resonance hydrogen spectrogram, the characteristic peak is integrated, and the integrated area conforms to the theory; DSC test shows that the melting peak temperature T of the copolymerm235.0 ℃ and TA test showed that the copolymer started to accelerate the thermal weight loss at 420.5 ℃ and the sample residual rate was 42.3% at 700 ℃.
Example 8, 80% preparation of sebacic acid modified PBO copolymer (as shown in FIG. 2)
Introducing nitrogen into a reaction vessel filled with polyphosphoric acid for 0.5h, adding 3.422g of 4, 6-diaminoresorcinol hydrochloride, heating the reaction vessel to 60 ℃ by a rear oil bath, stirring and reacting for 12h to remove hydrogen chloride (the discharged hydrogen chloride is introduced into a beaker filled with sodium hydroxide solution by a gas guide tube), adding 0.533g of terephthalic acid and 2.608g of sebacic acid (the molar ratio of the 4, 6-diaminoresorcinol hydrochloride to the terephthalic acid to the sebacic acid is 1:0.2:0.8) after removing the hydrogen chloride, heating the reaction vessel to 120 ℃ after adding the hydrogen chloride, stirring and reacting for 3h, heating the reaction vessel to 140 ℃ again, stirring and reacting for 3h, heating the reaction vessel to 160 ℃ again, stirring and reacting for 3h, stopping heating after heating the reaction vessel to 190 ℃, distilling and cooling, and adding water to separate out a solid. Taking out the product from the three-neck flask, putting the product into a funnel, repeatedly stirring, washing and filtering the product by using distilled water to remove phosphoric acid and polyphosphoric acid, taking out the product, pulverizing the product into powder by using a high-speed universal pulverizer, moving the powder to the funnel, repeatedly stirring, washing and filtering the powder by using the distilled water, testing the powder by using a pH test paper, washing and filtering the neutral product by using absolute ethyl alcohol, finally washing and filtering the neutral product by using normal hexane, placing the product into a vacuum drying oven for drying, setting the temperature of the vacuum drying oven to be 45 ℃, vacuumizing, taking out the product after drying, and weighing the solid to obtain the product.
The product structure and performance were analyzed as follows: infrared test shows that the copolymer generated by the reaction contains benzoxazole ring structure; the synthesized PBO copolymer can be determined to be a random copolymer through a nuclear magnetic resonance hydrogen spectrogram, the characteristic peak is integrated, and the integrated area conforms to the theory; DSC test shows that the melting peak temperature T of the copolymermAt 177.2 deg.C, TA test showed that the copolymer began to lose weight faster at 344.1 deg.C, and at 700 deg.C, the sample residual rate was 32.94%.
In conclusion, the PBO copolymer is a random copolymer, compared with the prior art, the PBO copolymer has the performance of ensuring equivalent thermal stability and stronger tensile strength and modulus, and overcomes the defect that the conventional PBO polymer is difficult to spin.

Claims (10)

1. An easy-to-mold processing p-phenylene benzo dioxazole copolymer is characterized in that,
the structure of the main chain of the copolymer is as shown in the formula I:
Figure FDA0003414779080000011
in the formula I, R is
Figure FDA0003414779080000012
Or a flexible group; n is a positive integer; the flexible group is butylene or octylene;
the main chain of the copolymer contains flexible groups, the flexible groups are butylene or octylene or both, and the mole percentage of the flexible groups in the main chain of the copolymer is 5 to 45 percent according to the mole percentage content; the mole percentage of the benzodioxazole ring is 50%; the mole percentage of the phenyl is 5-45%.
2. The easy-to-mold p-phenylene benzobisoxazole copolymer as recited in claim 1, wherein the mole percentage of the flexible group in the main chain of the copolymer is 10% -40%; the mole percentage of the benzodioxazole ring is 50%; the mole percentage of the phenyl is 10-40%.
3. The easy-to-mold p-phenylene benzobisoxazole copolymer as recited in claim 1, wherein the mole percentage of the flexible group in the main chain of the copolymer is 10% -30%; the mole percentage of the benzodioxazole ring is 50%; the mole percentage of the phenyl is 20-40%.
4. The p-phenylene benzobisoxazole copolymer easy to mold and process as claimed in claim 1, wherein the structure of formula I is specifically:
Figure FDA0003414779080000013
in the formula II R1The flexible group is formed by the following steps of x, y and z which are all 0 or positive integers, y and z are not 0 at the same time, and x and z are not 0 at the same time.
5. A preparation method of easy-to-mold-processing p-phenylene benzobisoxazole copolymer is characterized in that 4, 6-diaminoresorcinol hydrochloride and mixed dicarboxylic acid are subjected to a polycondensation reaction in a polyphosphoric acid system through a gradient heating solution to synthesize the p-phenylene benzobisoxazole copolymer containing a flexible chain segment; the mixed dicarboxylic acid comprises a first carboxylic acid terephthalic acid, and a second carboxylic acid adipic acid or sebacic acid or a mixture thereof.
6. The preparation method of the p-phenylene benzobisoxazole copolymer easy to mold and process as claimed in claim 5, which is characterized by comprising the following steps: introducing nitrogen into a reaction device filled with polyphosphoric acid, adding 4, 6-diaminoresorcinol hydrochloride, heating in an oil bath, stirring, and reacting to exhaust hydrogen chloride; after the hydrogen chloride is exhausted, adding mixed dicarboxylic acid, after the addition is finished, carrying out gradient heating reaction, stopping heating after the addition is finished, and adding distilled water to separate out a solid after cooling.
7. The preparation method of easy-to-mold p-phenylene benzobisoxazole copolymer as claimed in claim 5 or 6, wherein the gradient temperature rise reaction is as follows: heating to 120 ℃ and stirring for reaction for 3h, heating to 140 ℃ and stirring for reaction for 3h, heating to 160 ℃ and stirring for reaction for 3h, and finally heating to 190 ℃ and stirring for reaction for 3 h.
8. The method for preparing p-phenylene benzobisoxazole copolymer easy to mold and process according to claim 5 or 6, characterized in that the molar ratio of 4, 6-diaminoresorcinol hydrochloride to mixed dicarboxylic acid is 1: 1; the molar ratio of the first carboxylic acid to the second carboxylic acid in the mixed dicarboxylic acid is 0.1-0.9: 0.9-0.1.
9. The preparation method of easy-to-mold p-phenylene benzobisoxazole copolymer as claimed in claim 6, wherein the nitrogen gas is introduced for 0.5 h.
10. The method for preparing p-phenylene benzobisoxazole copolymer easy to mold and process as claimed in claim 6, wherein after the reaction is finished, the solid is repeatedly stirred with distilled water, washed and filtered to remove phosphoric acid and polyphosphoric acid, then the solid is pulverized into powder by a high-speed universal pulverizer, then the powder is moved to a funnel, repeatedly stirred with distilled water, washed, filtered and filtered, tested by a pH test paper, washed and filtered by absolute ethyl alcohol after the product is neutral, finally washed and filtered by n-hexane, the product is placed in a vacuum drying oven to be dried, and after the drying is finished, the solid is taken out and weighed, and the temperature of the vacuum drying oven is set to 45 ℃.
CN202111546188.6A 2021-12-16 2021-12-16 Easily-molded p-phenylene benzodioxazole copolymer and preparation method thereof Pending CN114380999A (en)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107417918A (en) * 2017-06-09 2017-12-01 郑州大学 Cross-linking PBO copolymers and its production and use

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107417918A (en) * 2017-06-09 2017-12-01 郑州大学 Cross-linking PBO copolymers and its production and use

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
SHANFENG WANG ET AL.: "Supramolecular Regulation of Photophysical Properties and Electron Paramagnetic Resonance Studies of Novel Rod-Coil Ordered Copolymers Based on Poly(p-phenylene benzobisoxazole)", 《MACROMOLECULES》, vol. 37, pages 3815 - 3822 *

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