CN107892745B - Thermoplastic polybenzoxazole imide and preparation method thereof - Google Patents
Thermoplastic polybenzoxazole imide and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/22—Polybenzoxazoles
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
Abstract
The invention provides thermoplastic polybenzoxazole imide and a preparation method thereof, wherein the structural formula of the polybenzoxazole imide is shown in the following figure, m is an integer of 1-1000, n is an integer of 0-1000, and Ar is1Is the residue of a diamine compound, Ar2The thermoplastic polybenzoxazole imide is prepared by adopting a mode of homopolymerization of benzoxazole diamine and triphenyl diether dianhydride or copolymerization of the benzoxazole diamine and the triphenyl diether dianhydride and other common dianhydride and diamine through polycondensation reaction. The high-temperature-resistant polyester fiber has the characteristics of good mechanical property, high heat resistance, good processability and the like, is suitable for injection molding, extrusion, die pressing, dissolving coating, melt spinning and solution spinning processing, and has good application prospect in the related fields of high-temperature-resistant engineering plastics, films, fibers, adhesives, coatings, advanced composite materials and the like.
Description
Technical Field
The invention belongs to the technical field of polyimide and related preparation methods, and particularly relates to thermoplastic polybenzoxazole imide and a preparation method thereof.
Background
Polyimide is a resin material with excellent comprehensive performance, has the advantages of good thermal stability, excellent mechanical performance, good dimensional stability, excellent chemical stability, high breakdown voltage, low dielectric constant, high flame retardance, low expansion coefficient and the like, and is widely applied to the high-tech fields of electronic and electrical products, aerospace, automobiles, chemical machinery and the like. However, most of polyimide resins have a strong molecular chain rigidity, which makes it difficult to melt or dissolve, and easy-to-process polyimide resins can be obtained by introducing a flexible ether bond, such as thermoplastic polyimide, which is the most common worldwide, Ultem resin developed by GE, USA, which has a Tg of 217 ℃, crystalline thermoplastic polyimide Aurum developed by Sandongtong pressure, Japan, which has a Tg of 250 ℃, but too much introduction of a flexible group causes a significant decrease in the glass transition temperature (Tg), and it is difficult to find a polyimide resin that satisfies both high Tg and easy-to-process.
Polybenzoxazole is a kind of high-performance engineering plastics with excellent comprehensive performance, particularly has outstanding heat resistance and mechanical properties, is widely used in the fields of aerospace, electronic and electric appliances, fuel cell proton exchange membranes and the like, and is now an important material in national economy, advanced technology and high and new technology industries.
With the development of greening in the field of electronic packaging, the heat resistance of the base resin used in the packaging substrate is greatly challenged. In the packaging process, the peak temperature of reflow soldering reaches 260 ℃, and when the temperature of the thermoplastic material is higher than Tg, the deformation resistance of the thermoplastic material is rapidly reduced, so that the reliability of the packaging substrate is affected, and therefore, the development of the polyimide resin which has high Tg (Tg >260 ℃) and is easy to process is urgently needed. At present, many research institutes have conducted studies on polybenzoxazole imide materials obtained by combining benzoxazole units with imide units, such as U.S. Pat. No. 5, 005919892A, Toyo Boseki Kagaku Kogyo US20070272124A1, Korea Hanyang university US8087064B2, Toyo Boseki Kagaku Kogyo US008314203B2, US005317078A, Dow chemical Co., Ltd US005233821A, Toyo Boseki Kagaku Kogyo EP2380732A1, and Toyo Boseki Kagaku Kogyo EP1707590B 1. However, these polyoxazoleimides synthesized with benzoxazole as a diamine unit are mainly used in the field of high-strength and high-modulus fibers or films, and the processability thereof is not improved by introducing a flexible group, so that the processability thereof is still to be further improved.
Disclosure of Invention
The invention aims to provide a high-Tg (Tg >260 ℃) easily-processed thermoplastic polybenzoxazole imide, which combines an oxazole structural unit with stronger rigidity and a triphendiether dianhydride structural unit with relative flexibility and has the characteristics of high glass transition temperature (Tg) and easy processing.
The technical scheme adopted by the invention for realizing the technical purpose is as follows: a polybenzoxazole imide having the formula:
wherein Ar is1Is a residue of a diamine compound, Ar2 is a residue of a dianhydride compound, m is an integer of 1 to 1000, and n is an integer of 0 to 1000;
when n is 0, the structural formula of the polybenzoxazole imide is shown as follows:
the oxygen atom of the triphenyl diether dianhydride part in the molecular chain exists at the 3-position or the 4-position of the benzene ring, and the specific structure is as follows:
the oxygen atom of benzoxazole part in the molecular chain exists in 5-position or 6-position of benzene ring, and the specific structure is as follows:
ar is1May be one of the following groups:
preferably, Ar is1May be one of the following:
ar is2May be one of the following groups:
preferably, Ar is2May be one of the following groups:
when the concentration of the polybenzoxazole imide in N-methyl pyrrolidone is 0.5g/dL, the inherent viscosity of the polybenzoxazole imide is measured to be between 0.2dL/g and 1.5dL/g at the temperature of 30 ℃ by an Ubbelohde viscometer; preferably 0.3dL/g to 1.2dL/g, and more preferably 0.4 dL/g to 0.8 dL/g. The glass transition temperature is 260-400 ℃ through differential scanning calorimetry; preferably from 270 ℃ to 380 ℃ and more preferably from 280 ℃ to 350 ℃. The 5 percent thermal decomposition temperature is measured to be 400-580 ℃ by a thermal weight loss analyzer; preferably 420 to 550 ℃ and more preferably 450 to 540 ℃. The melt index measured by a melt index meter is 0.1-50 g/10min, preferably 1-30 g/10min, and more preferably 2-20 g/10 min.
The invention also provides two preparation methods of the polybenzoxazole imide resin material, wherein the preparation method can be one of the following two methods:
the method comprises the following steps: adding a dianhydride monomer, a diamine monomer and an organic solvent into a reaction container under the protection of inert gas, fully and uniformly mixing, heating to perform polycondensation reaction in the presence of an alkaline catalyst, then cooling a reaction product, pouring the cooled reaction product into a precipitator, filtering, collecting precipitates, fully washing and drying to obtain the polybenzoxazole imide.
The second method comprises the following steps: in a reactor, adding a diamine monomer into a polar aprotic solvent protected by inert gas, stirring to completely dissolve the diamine monomer, adding a dianhydride monomer, and stirring to react for 3-48 hours to obtain a polyamic acid solution; and then adding a mixed solution of acetic anhydride and pyridine or a mixed solution of acetic anhydride and triethylamine into the polyamic acid solution, stirring and reacting for 2-24 hours, carrying out chemical imidization reaction to obtain a polyimide solution, pouring the polyimide solution into a precipitator to precipitate, collecting precipitates, fully washing, and drying to obtain the polybenzoxazole imide.
In the first and second methods, the diamine monomer is one of the following: 2- (4-aminophenyl) -5-aminobenzoxazole monomer, 2- (4-aminophenyl) -6-aminobenzoxazole monomer, a mixture of the 2- (4-aminophenyl) -5-aminobenzoxazole monomer and one of the compounds shown in the following formula A, and a mixture of the 2- (4-aminophenyl) -6-aminobenzoxazole monomer and one of the compounds shown in the following formula A
H2N-Ar1-NH2
A
In the formula A, Ar1Is as defined above.
Further, the structural formula of the compound shown in the formula A is as follows:
the dianhydride monomer is triphenyl diether dianhydride or a mixture of triphenyl diether dianhydride and one of the compounds shown in the following formula B.
The triphenyl diether dianhydride is 3,3 ' -triphenyl diether dianhydride, 3,4 ' -triphenyl diether dianhydride or 4,4 ' -triphenyl diether dianhydride, and the specific structural formula is as follows:
the general formula of the compound shown in the formula B is shown as follows:
in the formula B, Ar2Is as defined above.
Further, the structural formula of the compound represented by the formula B is one of the following:
in the first method and the second method, when the diamine monomer is a 2- (4-aminophenyl) -5-aminobenzoxazole monomer or a 2- (4-aminophenyl) -6-aminobenzoxazole monomer and the dianhydride monomer is triphendiether dianhydride, the polybenzoxazole imide with n being 0 in the general formula is prepared.
The diamine monomer is a mixture of a 2- (4-aminophenyl) -5-aminobenzoxazole monomer and one of the compounds shown in the following formula A or a mixture of a 2- (4-aminophenyl) -6-aminobenzoxazole monomer and one of the compounds shown in the following formula A, and when the dianhydride monomer is triphenyl diether dianhydride, polybenzoxazole imide with n being more than 0 in the general formula is prepared; or the diamine monomer is 2- (4-aminophenyl) -5-aminobenzoxazole monomer or 2- (4-aminophenyl) -6-aminobenzoxazole monomer, and the dianhydride monomer is the mixture of triphenyl diether dianhydride and one of the compounds shown in the following formula B, so that the polybenzoxazole imide with n being more than 0 in the general formula is prepared.
In the first method or the second method, the ratio of the amounts of the diamine monomer and the dianhydride monomer is 1: 0.9 to 1.1, preferably 1: 0.9 to 1.
In the first method, the organic solvent may be N, N-dimethylformamide, N-dimethylacetamide, sulfolane, m-cresol, methyl sulfoxide, N-methylpyrrolidone, or diphenylsulfone, and the like, preferably m-cresol.
The volume usage of the organic solvent is generally 3-10 mL/mmol based on the amount of diamine monomer.
And a water-carrying agent can be added into the reaction system of the first method, wherein the water-carrying agent can be toluene, chlorobenzene, xylene or dichlorobenzene and the like.
In the first method, the basic catalyst can be selected from, but not limited to, carbonates, bicarbonates, hydroxides, organic bases, alkali metal salts of alcohols, metal hydrides, pyridine, isoquinoline, triethylamine and other basic compounds, preferably isoquinoline.
In the first method, the amount of the basic catalyst is generally 10 to 150% of the amount of the diamine monomer.
In the first method, the precipitating agent can be selected from, but is not limited to, ethanol, acetone, deionized water, and the like.
In the first method, the polycondensation reaction is carried out in a nitrogen or other inert gas protective atmosphere; in the reaction process, the temperature of the reaction system is between 130 and 250 ℃.
After the polycondensation reaction is finished, a blocking agent can be added for blocking, wherein the blocking agent is phthalic anhydride, and the structural formula of the blocking agent is as follows:
the ratio of the amount of the substance of the blocking agent to the amount of the substance of the diamine monomer is generally 0.05 to 0.5:1, preferably 0.1 to 0.3:1
Further, preferably, the reaction process of the first method comprises the steps of adding a dianhydride monomer, a diamine monomer and an organic solvent into a reaction container, fully mixing the materials, heating the materials to 130-150 ℃ (preferably 130-140 ℃) in the presence of an alkaline catalyst to react for 1-5 hours, heating the materials to 150-250 ℃ (preferably 180-200 ℃) for 8-10 hours, cooling the materials to 100-120 ℃, adding an end capping reagent, continuing to react for 1-3 hours, cooling the materials to room temperature, pouring the materials into a precipitator, filtering, collecting precipitates, fully washing and drying the precipitates to obtain the polybenzoxazole imide resin, and in the second method, the polar aprotic solvent is N, N-dimethylacetamide, N-methylpyrrolidone, N-dimethylformamide or dimethyl sulfoxide.
The total volume usage of the polar aprotic solvent is 1-5 mL/mmol based on the amount of diamine monomer, and the polar aprotic solvent is added in two steps, wherein one part is used for dissolving the diamine monomer, and the other part is added into the reaction system together with the dianhydride monomer.
In the second method, in the mixed solution of acetic anhydride and organic base, the volume ratio of acetic anhydride to organic base is 1.5-5: 1, preferably 2-3: 1.
In the second method, the volume of the mixed solution of acetic anhydride and organic base is generally 0.3-0.8 mL/mmol based on the amount of diamine monomer.
In conclusion, the thermoplastic polybenzoxazole imide resin material prepared by combining the oxazole structural unit with stronger rigidity and the relatively flexible triphenyl diether dianhydride structural unit has the characteristics of high glass transition temperature (Tg) and easiness in processing, and has the following advantages:
(1) due to the introduction of an oxazole structural unit, the oxazole polyimide resin can obviously improve the glass transition temperature and has better melt fluidity and thermal stability;
(2) the molecular weight can be regulated and controlled by the end capping agent, so that the oxazole type copolyimide resin with different grades such as fiber grade, injection molding grade, coating grade and the like can be conveniently prepared;
(3) the polyoxazoleimide structure can be changed by the structure and the proportion of common dianhydride and diamine monomers, so that the structure adjustable space is large.
Therefore, the polybenzoxazole imide resin provided by the invention has the characteristics of good mechanical property, good heat resistance, good processability and the like, is suitable for injection molding, extrusion, mould pressing, dissolving coating, melt spinning and solution spinning processing, and has good application prospect in the related fields of high-temperature-resistant engineering plastics, films, fibers, adhesives, coatings, advanced composite materials and the like.
Detailed Description
The present invention will be described in further detail with reference to specific examples, which should be noted that the present invention is only illustrative and should not be construed as limiting the scope of the present invention. Those skilled in the art may make insubstantial modifications and adaptations to the invention described above.
Example 1:
in this example, the polybenzoxazole imide has the following structural formula:
the preparation method of the polybenzoxazole imide comprises the following steps:
11.2625g (0.05mol) of 2- (4-aminophenyl) -5-aminobenzoxazole monomer and 19.3109g (0.048mol) of 3, 3' -triphendiether dianhydride monomer are added into a dry and clean 500-mL three-necked bottle, 270mL of m-cresol and 10 drops of isoquinoline are added, and the mixture reacts for 1 hour at 130 ℃ under the protection of nitrogen; then heating to 200 ℃ for reaction for 8 hours, cooling to 110 ℃, adding 1.1850g (0.008mol) of phthalic anhydride, continuing to react for 2 hours, cooling to room temperature, slowly pouring the reaction liquid into 1.5L of ethanol for precipitation, filtering, boiling and washing the obtained filter cake with ethanol for 2 times, and then placing in a vacuum oven at 120 ℃ for drying for 8 hours to obtain 27.13g of light yellow polybenzoxazole imide powder with the yield of 92.0 percent.
The polybenzoxazole imide was subjected to a performance test, and the results were as follows:
(1) an inherent viscosity of 0.52dL/g measured in N-methylpyrrolidone at a concentration of 0.5g/dL at 30 ℃;
(2) a glass transition temperature of 286 ℃ as determined by differential scanning calorimetry;
(3) the 5% thermal decomposition temperature measured by a thermogravimetric analyzer was 524 ℃.
(4) The melt index measured by a melt index meter is 1.2g/10min, the test conditions are that the pressure is 12.5Kg, the temperature is 340 ℃, and the plasticizing time is 2 minutes.
Example 2:
in this example, the polybenzoxazole imide has the following structural formula:
the preparation method of the polybenzoxazole imide comprises the following steps:
11.2625g (0.05mol) of 2- (4-aminophenyl) -5-aminobenzoxazole monomer, 9.2531g (0.023mol) of 3,3 '-triphendiether dianhydride monomer, 6.7670g (0.023mol) of 4, 4' -biphenyltetracarboxylic dianhydride monomer, 250mL of m-cresol and 8 drops of isoquinoline are added into a dry and clean 500mL three-necked bottle, and the mixture is reacted for 1 hour at 130 ℃ under the protection of nitrogen; then heating to 190 ℃ for reaction for 6 hours, cooling to 110 ℃, adding 1.1850g (0.008mol) of phthalic anhydride, continuing to react for 2 hours, cooling to room temperature, slowly pouring the reaction liquid into 1.5L of ethanol for precipitation, filtering, boiling and washing the obtained filter cake with ethanol for 2 times, and then placing in a vacuum oven at 140 ℃ for drying for 6 hours to obtain light yellow polybenzoxazole imide powder 26.64g with the yield of 92.2%.
The polybenzoxazole imide was subjected to a performance test, and the results were as follows:
(1) an inherent viscosity of 0.49dL/g measured in N-methylpyrrolidone at a concentration of 0.5g/dL at 30 ℃;
(2) a glass transition temperature of 289 ℃ as determined by differential scanning calorimetry;
(3) the 5% thermal decomposition temperature measured by a thermogravimetric analyzer was 553 ℃.
(4) The melt index measured by a melt index meter is 0.8g/10min, the test conditions are that the pressure is 12.5Kg, the temperature is 340 ℃, and the plasticizing time is 2 minutes.
Example 3:
in this example, the polybenzoxazole imide has the following structural formula:
the preparation method of the polybenzoxazole imide comprises the following steps:
9.0100g (0.04mol) of 2- (4-aminophenyl) -5-aminobenzoxazole monomer, 2.0023g (0.01mol) of 4,4 '-diaminodiphenyl ether monomer, 18.9090g (0.047mol) of 3, 3' -triphendiether dianhydride monomer, 270mL of m-cresol and 10 drops of isoquinoline are added into a dry and clean 500mL three-necked bottle and reacted for 1 hour at 140 ℃ under the protection of nitrogen; then heating to 195 ℃ for reaction for 10 hours, cooling to 120 ℃, adding 1.1850g (0.008mol) of phthalic anhydride, continuing to react for 2 hours, cooling to room temperature, slowly pouring the reaction liquid into 1.5L of acetone for precipitation, filtering, boiling and washing the obtained filter cake with ethanol for 2 times, and then placing in a vacuum oven at 160 ℃ for drying for 4 hours to obtain 25.61g of light yellow polybenzoxazole imide powder with the yield of 89.6 percent.
The polybenzoxazole imide was subjected to a performance test, and the results were as follows:
(1) an inherent viscosity of 0.54dL/g measured in N-methylpyrrolidone at a concentration of 0.5g/dL at 30 ℃;
(2) a glass transition temperature determined by differential scanning calorimetry of 272 ℃;
(3) the 5% thermal decomposition temperature measured by a thermogravimetric analyzer was 535 ℃.
(4) The melt index measured by a melt index meter is 3.6g/10min, the test conditions are that the pressure is 12.5Kg, the temperature is 340 ℃, and the plasticizing time is 2 minutes.
Example 4:
in this example, the polybenzoxazole imide has the following structural formula:
the preparation method of the polybenzoxazole imide comprises the following steps:
11.2625g (0.05mol) of 2- (4-aminophenyl) -5-aminobenzoxazole monomer, 14.4832g (0.036mol) of 3,3 '-triphendiether dianhydride monomer, 5.0289g (0.0125mol) of 4, 4' -triphendiether dianhydride monomer, 270mL of m-cresol and 12 drops of isoquinoline are added into a dry and clean 500mL three-necked bottle and reacted for 3 hours at 140 ℃ under the protection of nitrogen; then heating to 180 ℃ for reaction for 10 hours, cooling to 100 ℃, adding 1.1850g (0.008mol) of phthalic anhydride, continuing to react for 3 hours, cooling to room temperature, slowly pouring the reaction liquid into 2.0L of ethanol for precipitation, filtering, boiling and washing the obtained filter cake with ethanol for 2 times, and then placing in a vacuum oven at 140 ℃ for drying for 8 hours to obtain light yellow polybenzoxazole imide powder 26.96g with the yield of 93.5%.
The polybenzoxazole imide was subjected to a performance test, and the results were as follows:
(1) an inherent viscosity of 0.52dL/g measured in N-methylpyrrolidone at a concentration of 0.5g/dL at 30 ℃;
(2) a glass transition temperature of 279 ℃ by differential scanning calorimetry;
(3) the 5% thermal decomposition temperature measured by a thermogravimetric analyzer was 542 ℃.
(4) The melt index measured by a melt index meter is 1.8g/10min, the test conditions are that the pressure is 12.5Kg, the temperature is 340 ℃, and the plasticizing time is 2 minutes.
Example 5:
in this example, the polybenzoxazole imide has the following structural formula:
the preparation method of the polybenzoxazole imide comprises the following steps:
11.2625g (0.05mol) of 2- (4-aminophenyl) -5-aminobenzoxazole monomer and 100mL of N, N-dimethylacetamide are added into a dry and clean 250mL three-necked bottle, stirred at normal temperature under the protection of nitrogen, 16.0924g (0.04mol) of 4,4 ' -triphendiether dianhydride monomer, 3.1024g (0.01mol) of 3,3, ' 4,4 ' -diphenyl ether tetracarboxylic dianhydride monomer and 22mL of N, N-dimethylacetamide are added after diamine monomer is completely dissolved, reaction is carried out for 24 hours at normal temperature, 28mL of mixed solution of acetic anhydride and triethylamine (20 mL of acetic anhydride and 8mL of triethylamine) is added, reaction is carried out for 12 hours at normal temperature, reaction liquid is slowly poured into 1L of deionized water for precipitation, filtration is carried out, the obtained filter cake is boiled and washed for 2 times by ethanol, and then the filter cake is placed into a vacuum oven at 120 ℃ for drying for 8 hours, 26.50g of pale yellow polybenzoxazole imide powder was obtained in 92.5% yield.
The polybenzoxazole imide was subjected to a performance test, and the results were as follows:
(1) an inherent viscosity of 0.49dL/g measured in N-methylpyrrolidone at a concentration of 0.5g/dL at 30 ℃;
(2) a glass transition temperature of 270 ℃ as determined by differential scanning calorimetry;
(3) the 5% thermal decomposition temperature measured by a thermogravimetric analyzer was 556 ℃.
(4) The melt index measured by a melt index meter is 1.1g/10min, the test conditions are that the pressure is 12.5Kg, the temperature is 340 ℃, and the plasticizing time is 2 minutes.
Example 6:
in this example, the polybenzoxazole imide has the following structural formula:
the preparation method of the polybenzoxazole imide comprises the following steps:
11.2625g (0.05mol) of 2- (4-aminophenyl) -5-aminobenzoxazole monomer and 100mL of N-methylpyrrolidone are added into a dry and clean 250mL three-necked bottle, stirred at normal temperature under the protection of nitrogen, after diamine monomer is completely dissolved, 15.2878g (0.038mol) of 4,4 ' -triphendiether dianhydride monomer, 3.2222g (0.01mol) of 3,3 ', 4 ' -benzophenone tetracarboxylic dianhydride monomer and 20mL of N-methylpyrrolidone are added, reacted for 18 hours at normal temperature, 0.1850g (0.008mol) of phthalic anhydride is added, reacted for 3 hours at normal temperature, 28mL of mixed solution of acetic anhydride and pyridine (20 mL of acetic anhydride and 8mL of pyridine) is added, the reaction solution is continuously reacted for 15 hours at normal temperature, reaction liquid is slowly poured into 1.5L of ethanol for precipitation, filtered, the obtained filter cake is boiled and washed for 2 times by ethanol, and then the filter cake is placed in a vacuum oven at 140 ℃ for drying for 4 hours, this gave 25.93g of a pale yellow polybenzoxazole imide powder in a yield of 90.1%.
The polybenzoxazole imide was subjected to a performance test, and the results were as follows:
(1) an inherent viscosity of 0.45dL/g measured in N-methylpyrrolidone at a concentration of 0.5g/dL at 30 ℃;
(2) a glass transition temperature of 275 ℃ as determined by differential scanning calorimetry;
(3) the 5% thermal decomposition temperature measured by a thermogravimetric analyzer was 552 ℃.
(4) The melt index measured by a melt index meter is 0.6g/10min, the test conditions are that the pressure is 12.5Kg, the temperature is 340 ℃, and the plasticizing time is 2 minutes.
Example 7:
in this example, the polybenzoxazole imide has the following structural formula:
the preparation method of the polybenzoxazole imide comprises the following steps:
9.0100g (0.04mol) of 2- (4-aminophenyl) -5-aminobenzoxazole monomer, 1.9830g (0.01mmol) of 4,4 '-diaminodiphenylmethane monomer and 90mL of N, N-dimethylacetamide are added into a dry and clean 250mL three-necked bottle, stirred at normal temperature under the protection of nitrogen, 20.1155g (0.05mol) of 3, 3' -triphenyldiether dianhydride monomer and 35mL of N, N-dimethylacetamide are added after diamine monomer is completely dissolved, reaction is carried out at normal temperature for 18 hours, 30mL of mixed solution of acetic anhydride and triethylamine (22 mL of acetic anhydride and 8mL of triethylamine) is added, reaction is carried out at normal temperature for 10 hours, reaction liquid is slowly poured into 1L of ethanol for precipitation, filtered, the obtained filter cake is boiled and washed with ethanol for 2 times, and then the obtained product is placed into a vacuum oven at 180 ℃ for drying for 4 hours, thus obtaining 26.23g of light yellow polybenzoxazole imide powder, the yield was 89.5%.
The polybenzoxazole imide was subjected to a performance test, and the results were as follows:
(1) an inherent viscosity of 0.50dL/g measured in N-methylpyrrolidone at a concentration of 0.5g/dL at 30 ℃;
(2) a glass transition temperature as determined by differential scanning calorimetry of 530 ℃;
(3) the 5% thermal decomposition temperature measured by a thermogravimetric analyzer was 468 ℃.
(4) The melt index measured by a melt index meter is 2.6g/10min, the test conditions are that the pressure is 12.5Kg, the temperature is 340 ℃, and the plasticizing time is 2 minutes.
Example 8:
in this example, the polybenzoxazole imide has the following structural formula:
the preparation method of the polybenzoxazole imide comprises the following steps:
11.2625g (0.05mol) of 2- (4-aminophenyl) -5-aminobenzoxazole monomer and 80mL of N-methylpyrrolidone are added into a dry and clean 250mL three-necked bottle, stirred at normal temperature under the protection of nitrogen, 16.0924g (0.04mol) of 3,3 ' -triphendiether dianhydride monomer, 2.9422g (0.01mol) of 2,3 ', 3,4 ' -biphenyltetracarboxylic dianhydride monomer and 40mL of N-methylpyrrolidone are added after diamine monomer is completely dissolved, reaction is carried out at normal temperature for 18 hours, 32mL of mixed solution of acetic anhydride and pyridine (22 mL of acetic anhydride and 10mL of pyridine) is added, reaction is carried out at normal temperature for 10 hours, reaction liquid is slowly poured into 1.2L of deionized water for precipitation, filtration is carried out, obtained filter cake is boiled and washed with ethanol for 2 times, and then placed in a vacuum oven at 160 ℃ for drying for 5 hours, and light yellow polybenzoxazole imide powder 25.13g is obtained, the yield was 88.2%.
The polybenzoxazole imide was subjected to a performance test, and the results were as follows:
(1) an inherent viscosity of 0.46dL/g measured in N-methylpyrrolidone at a concentration of 0.5g/dL at 30 ℃;
(2) a glass transition temperature of 296 ℃ as determined by differential scanning calorimetry;
(3) the 5% thermal decomposition temperature measured by a thermogravimetric analyzer was 545 ℃.
(4) The melt index (MFI) determined by a melt index tester is 4.2g/10min, the test conditions are a pressure of 12.5Kg, a temperature of 380 ℃ and a plasticizing time of 2 minutes.
Comparative example 1:
in this comparative example, the polyimide has the following structural formula:
the preparation method of the polyimide comprises the following steps:
adding 0.05mol of 4, 4' -diaminodiphenyl ether monomer, 0.047mol of pyromellitic dianhydride monomer, 270mL of m-cresol and 8 drops of isoquinoline into a dry and clean 500mL three-necked bottle, and reacting for 1 hour at 130 ℃ under the protection of nitrogen; and then heating to 200 ℃ for reaction for 8 hours, cooling to 110 ℃, adding 0.009mol of phthalic anhydride, continuing to react for 2 hours, cooling to room temperature, slowly pouring the reaction liquid into 2L of ethanol for precipitation, filtering, boiling and washing the obtained filter cake with ethanol for 2 times, and then placing in a vacuum oven at 160 ℃ for drying for 8 hours to obtain light yellow polyimide powder. Although the glass transition temperature was high (367 ℃), there was no processability (melt index of 0).
Comparative example 2:
in this comparative example, the polyimide has the following structural formula:
the preparation method of the polyimide comprises the following steps:
adding 0.05mol of 4,4 '-diaminodiphenyl ether monomer, 0.047mol of 3, 3' -triphendiether dianhydride monomer, 270mL of m-cresol and 8 drops of isoquinoline into a dry and clean 500mL three-necked bottle, and reacting for 1 hour at 130 ℃ under the protection of nitrogen; and then heating to 200 ℃ for reaction for 8 hours, cooling to 110 ℃, adding 0.009mol of phthalic anhydride, continuing to react for 2 hours, cooling to room temperature, slowly pouring the reaction liquid into 2L of ethanol for precipitation, filtering, boiling and washing the obtained filter cake with ethanol for 2 times, and then placing in a vacuum oven at 160 ℃ for drying for 8 hours to obtain light yellow polyimide powder. Comparative example 2, although having processability (melt index >70g/10min), has a low glass transition temperature (245 ℃).
Claims (3)
1. A thermoplastic polybenzoxazole imide having the general structural formula:
wherein Ar is1Is the residue of a diamine compound, Ar2Is a residue of a dianhydride compound, m is an integer of 1 to 1000, and n is an integer of 0 to 1000; the oxygen atom of the triphenyl diether dianhydride moiety in the molecular chain is presentThe 3-position of the benzene ring has the following specific structure:
when the concentration of the polybenzoxazole imide in N-methyl pyrrolidone is 0.5g/dL, the inherent viscosity of the polybenzoxazole imide is 0.4-0.8 dL/g when the polybenzoxazole imide is measured at 30 ℃ by an Ubbelohde viscometer, and the melt index measured by a melt index meter is 1-30 g/10 min; the glass transition temperature is 260-400 ℃; the 5 percent thermal decomposition temperature is measured to be 400-600 ℃ by a thermal weight loss analyzer;
the thermoplastic polybenzoxazole imide is prepared by one of the following methods:
the method comprises the following steps: adding a dianhydride monomer, a diamine monomer and an organic solvent into a reaction container, fully mixing uniformly, heating to 130-150 ℃ in the presence of an alkaline catalyst, reacting for 1-5 hours, heating to 150-250 ℃ for reacting for 8-10 hours, cooling to 100-120 ℃, adding an end capping agent, continuing to react for 1-3 hours, cooling to room temperature, pouring into a precipitator, filtering, collecting precipitate, fully washing, and drying to obtain polybenzoxazole imide resin;
the end capping agent is phthalic anhydride, and the structural formula of the end capping agent is as follows:
the ratio of the amount of the end-capping agent to the amount of the diamine monomer is 0.05-0.5: 1;
the second method comprises the following steps: in a reactor, adding a diamine monomer into a polar aprotic solvent protected by inert gas, stirring to completely dissolve the diamine monomer, adding a dianhydride monomer and the polar aprotic solvent, and stirring at room temperature to react for 3-48 hours to obtain a polyamic acid solution; then adding mixed solution of acetic anhydride and organic base into the polyamic acid solution, wherein the organic base is pyridine or triethylamine, stirring and reacting for 2-24 hours at room temperature, carrying out chemical imidization reaction to obtain polyimide solution, pouring the polyimide solution into a precipitator for precipitation, collecting precipitate, fully washing and drying to obtain polybenzoxazole imide
In the first and second methods, the diamine monomer is one of the following: 2- (4-aminophenyl) -5-aminobenzoxazole monomer, 2- (4-aminophenyl) -6-aminobenzoxazole monomer, a mixture of the 2- (4-aminophenyl) -5-aminobenzoxazole monomer and one of the compounds shown in the following formula A, and a mixture of the 2- (4-aminophenyl) -6-aminobenzoxazole monomer and one of the compounds shown in the following formula A
H2N-Ar1-NH2
A
In the formula A, Ar1Is one of the following groups:
the dianhydride monomer is triphenyl diether dianhydride or a mixture of triphenyl diether dianhydride and one of the compounds shown in the following formula B; the triphenyl diether dianhydride is 3, 3' -triphenyl diether dianhydride;
the general formula of the compound shown in the formula B is shown as follows:
in the formula B, Ar2Is one of the following groups:
2. a process for preparing a thermoplastic polybenzoxazole imide according to claim 1 wherein said process is one of the following:
the method comprises the following steps: adding a dianhydride monomer, a diamine monomer and an organic solvent into a reaction container, fully mixing uniformly, heating to 130-150 ℃ in the presence of an alkaline catalyst, reacting for 1-5 hours, heating to 150-250 ℃ for reacting for 8-10 hours, cooling to 100-120 ℃, adding an end capping agent, continuing to react for 1-3 hours, cooling to room temperature, pouring into a precipitator, filtering, collecting precipitate, fully washing, and drying to obtain polybenzoxazole imide resin;
the second method comprises the following steps: in a reactor, adding a diamine monomer into a polar aprotic solvent protected by inert gas, stirring to completely dissolve the diamine monomer, adding a dianhydride monomer and the polar aprotic solvent, and stirring at room temperature to react for 3-48 hours to obtain a polyamic acid solution; adding a mixed solution of acetic anhydride and organic base into the polyamic acid solution, wherein the organic base is pyridine or triethylamine, stirring and reacting for 2-24 hours at room temperature, carrying out chemical imidization reaction to obtain a polyimide solution, pouring the polyimide solution into a precipitator for precipitation, collecting the precipitate, fully washing, and drying to obtain polybenzoxazole imide;
in the first and second methods, the diamine monomer is one of the following: 2- (4-aminophenyl) -5-aminobenzoxazole monomer, 2- (4-aminophenyl) -6-aminobenzoxazole monomer, a mixture of the 2- (4-aminophenyl) -5-aminobenzoxazole monomer and one of the compounds shown in the following formula A, and a mixture of the 2- (4-aminophenyl) -6-aminobenzoxazole monomer and one of the compounds shown in the following formula A
H2N-Ar1-NH2
A
In the formula A, Ar1Is one of the following groups:
the dianhydride monomer is triphenyl diether dianhydride or a mixture of triphenyl diether dianhydride and one of the compounds shown in the following formula B; the triphenyl diether dianhydride is 3, 3' -triphenyl diether dianhydride;
the general formula of the compound shown in the formula B is shown as follows:
in the formula B, Ar2Is one of the following groups:
3. the method of claim 2, wherein: in the first method or the second method, the ratio of the amounts of the diamine monomer and the dianhydride monomer is 1: 0.9 to 1.1.
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| CN109134861A (en) * | 2018-08-02 | 2019-01-04 | 王金桢 | A kind of preparation method of the fire-retardant polyimides new material of solubility |
| CN111019345B (en) * | 2019-12-17 | 2021-06-29 | 中国科学院化学研究所 | Poly (imide-benzoxazole) film and preparation method and application thereof |
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