CN107417918B - Cross-linkable PBO copolymer and preparation method and application thereof - Google Patents
Cross-linkable PBO copolymer and preparation method and application thereof Download PDFInfo
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- 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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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
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- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
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Abstract
The invention discloses a cross-linkable PBO copolymer and a preparation method and application thereof, belonging to the field of high polymer materials. Relates to a crosslinkable PBO copolymer of formula (1) prepared by copolymerization of 2-methyl-4, 6-diaminoresorcinol dihydrochloride and aliphatic dicarboxylic acid and terephthalic acid in polyphosphoric acid, wherein m =1,2,3,4,5,6,7,8,9, 10. The polymer has a melting point lower than the thermal decomposition temperature, can be used as a photoelectric functional material and a mold pressing resin, is easy to carry out thermoplastic molding, forms a cross-linking structure after heat treatment, and further improves the heat resistance, solvent resistance and mechanical properties of products.
Description
Technical Field
The invention relates to a cross-linkable PBO copolymer and a preparation method and application thereof, belonging to the field of high polymer materials.
Background
The macromolecule containing the benzodioxazole structure has obvious chromophore effect, can generate strong fluorescence phenomenon, and is used for photochromic, photovoltaic cells, organic light emitting diodes and DNA fluorescence detection. The wholly aromatic benzodiazole polymer has excellent performances of high strength, high modulus, high temperature resistance and the like. However, the aromatic benzodiazole polymer has a melting point too high (higher than the decomposition temperature) and is insoluble in organic solvents, which makes the molding process difficult.
The introduction of flexible chain segments or side groups into the molecular main chain of the benzodiazole polymer can reduce the melting point and improve the solubility. Macromolecules 2004, 37, page 3815 describe that 4, 6-diaminoresorcinol dihydrochloride, terephthalic acid and sebacic acid are copolymerized in a polyphosphoric acid medium to synthesize a PBO copolymer with a main chain containing 8 methylene groups, and the PBO copolymer is used as a blue light material, but the copolymer is insoluble in common organic solvents, so that the application of the PBO copolymer is limited. CN2017100353026 describes that 2-methyl-4, 6-diaminoresorcinol dihydrochloride reacts with different aliphatic dicarboxylic acids in polyphosphoric acid medium to synthesize a series of crosslinkable polyalkylene benzodioxazole homopolymers for use as molding resins. At present, no relevant report is found on the cross-linkable PBO copolymer with low melting point.
Disclosure of Invention
The invention aims to provide a low-melting-point crosslinkable PBO copolymer.
It is another object of the present invention to provide a process for preparing the crosslinkable PBO copolymer.
The cross-linkable PBO copolymer has the following structure:
wherein m is 1,2,3,4,5,6,7,8,9, 10; x/y is 1/99-7/3
The synthesis method of the cross-linkable PBO copolymer is prepared by the copolymerization of 2-methyl-4, 6-diaminoresorcinol dihydrochloride shown in a formula (3), aliphatic dicarboxylic acid shown in a formula (4) and terephthalic acid in polyphosphoric acid.
The molar ratio of the 2-methyl-4, 6-diaminoresorcinol dihydrochloride to the aliphatic dicarboxylic acid is 0.8-1.2: 1, preferably 0.95 to 1.05: 1.
HOOC(CH2)mCOOH (4)
wherein m is 1,2,3,4,5,6,7,8,9, 10. The reaction temperature adopts a gradual heating method and is between room temperature and 200 ℃.
The specific method comprises the following steps: under the protection of nitrogen, 2-methyl-4, 6-diamino resorcinol dihydrochloride is firstly deprived of hydrogen chloride in polyphosphoric acid at the temperature of 30-130 ℃, and the preferable temperature is 60-90 ℃. Then adding terephthalic acid and aliphatic dicarboxylic acid, and gradually raising the reaction temperature to 200 ℃ for copolymerization reaction. Preferably, the reaction is carried out at 120 ℃ first, then at 150 ℃ and finally at 195 ℃.
The concentration of the polymerization reaction solution is 3 to 30 wt%, preferably 8 to 15 wt%.
The molar ratio of terephthalic acid to aliphatic dicarboxylic acid is 1: 99 to 7: 3.
the cross-linkable PBO copolymer prepared by the method is subjected to heat treatment to form the cross-linked polymer shown as the formula (2), wherein the heat treatment temperature is 200-400 ℃.
The invention has the advantages that: the cross-linkable PBO copolymer is dissolved in some common organic solvents (such as N-methyl pyrrolidone, dimethyl sulfoxide, formic acid and the like), can be formed into a film by a solution method, has a melting point (140-250 ℃) lower than the thermal decomposition temperature (400-500 ℃) and is easy to carry out thermoplastic forming. The PBO copolymer can form a cross-linked structure after heat treatment, and further improves the heat resistance, solvent resistance and mechanical properties of the product.
Drawings
Figure 1 is an FTIR spectrum of a crosslinkable PBO copolymer of the present invention (terephthalic acid: adipic acid molar ratio 2: 8).
Fig. 2 is an FTIR spectrum of a cross-linkable PBO copolymer of the present invention (terephthalic acid: sebacic acid molar ratio: 3: 7).
FIG. 3 is a cross-linkable PBO copolymer of the present invention (terephthalic acid: adipic acid molar ratio 2: 8)1HNMR spectrogram.
FIG. 4 is a cross-linkable PBO copolymer of the present invention (terephthalic acid: sebacic acid molar ratio: 3: 7)1HNMR spectrogram
Figure 5 is a DSC plot of a cross-linkable PBO copolymer of the present invention (terephthalic acid to adipic acid molar ratio of 2: 8).
Fig. 6 is a DSC profile of a cross-linkable PBO copolymer of the present invention (terephthalic acid: sebacic acid molar ratio of 3: 7).
Fig. 7 is a TG spectrum of a crosslinkable PBO copolymer of the present invention (terephthalic acid: adipic acid molar ratio of 2: 8).
Fig. 8 is a TG spectrum of a crosslinkable PBO copolymer of the present invention (terephthalic acid: sebacic acid molar ratio of 3: 7).
Detailed Description
Several examples are given below to further illustrate the preparation of the crosslinkable PBO copolymers of the present invention.
Example 1: synthesis of a crosslinkable PBO copolymer (terephthalic acid: adipic acid molar ratio 2: 8)
Adding 67.40g of polyphosphoric acid into a 250ml three-necked bottle under the protection of nitrogen, stirring at room temperature, adding 3.66g of 2-methyl-4, 6-diaminoresorcinol dihydrochloride, heating to 60 ℃, stirring to remove hydrogen chloride for 12 hours, adding 1.88g of adipic acid and 0.54g of terephthalic acid, reacting at 120 ℃ for 6 hours, reacting at 150 ℃ for 3 hours, reacting at 195 ℃ for 3 hours, cooling the reaction solution to 60 ℃, pouring into 300ml of water under stirring, filtering, washing with water to be neutral, and vacuum drying at 60 ℃ to obtain 3.69g of light yellow solid with the yield of 94.2%. The resulting polymer is soluble in N-methylpyrrolidone, dimethyl sulfoxide, m-cresol, formic acid, acetic acid, concentrated sulfuric acid and methanesulfonic acid.
The above synthesized crosslinkable PBO copolymer (terephthalic acid: adipic acid molar ratio ═ 2: 8) was subjected to IR and1HNMR detection, as target product, IR and1the results of HNMR analysis were as follows:
IR(KBr，cm-1)：2929，2853，1726，1627，1586，1403，1367，1152，1080；1H NMR(CF3COOD，400MHz，δ(ppm))：8.79-8.47(m，0.8H)，8.46-8.26(m，1H)，3.61(m，3.2H)，2.94(m，3H)，2.40(m，3.2H)。
the cross-linkable PBO copolymer synthesized above (terephthalic acid: adipic acid molar ratio 2: 8) had a melting peak-to-peak temperature of 186.6 ℃ and a cross-linking reaction endothermic peak-to-peak temperature of 256.6 ℃ in a DSC chart.
The resultant crosslinkable PBO copolymer (terephthalic acid: adipic acid molar ratio 2: 8) has an initial thermal decomposition temperature of 439.8 ℃ on the TG spectrum.
The cross-linkable PBO copolymer synthesized above (terephthalic acid: adipic acid molar ratio ═ 2: 8) was not dissolved in m-N-methylpyrrolidone, dimethyl sulfoxide, cresol, formic acid, acetic acid, concentrated sulfuric acid and methanesulfonic acid after treatment at 250 ℃ for 30 minutes under an air atmosphere.
Example 2: synthesis of a Cross-linkable PBO copolymer (terephthalic acid: sebacic acid molar ratio ═ 3: 7)
Adding 67.40g of polyphosphoric acid into a 250ml three-necked bottle under the protection of nitrogen, stirring at room temperature, adding 3.66g of 2-methyl-4, 6-diaminoresorcinol dihydrochloride, heating to 90 ℃, stirring to remove hydrogen chloride for 12 hours, adding 2.28g of sebacic acid and 0.80g of terephthalic acid, reacting at 120 ℃ for 6 hours, reacting at 150 ℃ for 3 hours, reacting at 195 ℃ for 3 hours, cooling the reaction solution to 60 ℃, pouring into 300ml of water under stirring, filtering, washing with water to be neutral, and vacuum drying at 60 ℃ to obtain 4.29g of light yellow solid with the yield of 97.5%. The resulting polymer is soluble in N-methylpyrrolidone, dimethyl sulfoxide, m-cresol, formic acid, acetic acid, concentrated sulfuric acid and methanesulfonic acid.
The cross-linkable PBO copolymer synthesized above (terephthalic acid: sebacic acid molar ratio ═ 3: 7) was IR-and1HNMR detection, as target product, IR and1the results of HNMR analysis were as follows:
IR(KBr，cm-1)：2929，2853，1726，1627，1586，1403，1367，1152，1080；1H NMR(CF3COOD，400MHz，δ(ppm))：8.79-8.47(m，1.2H)，8.47-8.31(m，1H)，3.51(m，2.8H)，2.97(m，3H)，2.17(m，2.8H)，1.65-1.54(m，5.6H)。
the above synthesized crosslinkable PBO copolymer (terephthalic acid: sebacic acid molar ratio: 3: 7) has a melting peak-to-peak temperature of 177.7 ℃ and a crosslinking reaction endothermic peak-to-peak temperature of 303.0 ℃ in a DSC chart.
The above synthesized crosslinkable PBO copolymer (terephthalic acid: sebacic acid molar ratio ═ 3: 7) has an initial thermal decomposition temperature of 454.3 ℃ on a TG spectrum.
The cross-linkable PBO copolymer synthesized above (terephthalic acid: sebacic acid molar ratio: 3: 7) was treated at 250 ℃ for 30 minutes under an air atmosphere and then was not dissolved in N-methylpyrrolidone, dimethyl sulfoxide, m-cresol, formic acid, acetic acid, concentrated sulfuric acid, and methanesulfonic acid.
The crosslinkable PBO copolymers can be used as molding resins, the use of which is illustrated below
In a diamond grinding wheel based on a double bevel maleimide-epoxy phenolic resin, the cross-linkable PBO copolymer (terephthalic acid: sebacic acid molar ratio is 3: 7) of the invention with the mass of 10 percent of the maleimide-epoxy phenolic resin is added, and under the same mould pressing process conditions, the performances of the obtained diamond grinding wheel are listed in Table 1
TABLE 1
The data in the table show that after the cross-linkable PBO copolymer is added, the breaking strength is improved by more than 40%, the toughness is improved, the holding force on diamond is enhanced, the sharp angle retentivity of the grinding wheel is improved, and the tooth number of the slotted manganese steel saw blade is improved by more than 2 times compared with that of the grinding wheel which is not added every time the grinding wheel is dressed.
Claims (5)
1. The cross-linkable PBO copolymer is characterized in that the structure is shown as the formula (1):
wherein m is 1,2,3,4,5,6,7,8,9, 10; 1/99-7/3 x/y,
the method is realized by the following steps: (1) under the protection of nitrogen, 2-methyl-4, 6-diamino resorcinol dihydrochloride shown in the formula (3) is firstly subjected to hydrogen chloride removal in polyphosphoric acid at the temperature of 30-130 ℃; (2) then adding terephthalic acid and aliphatic dicarboxylic acid shown in a formula (4), and gradually heating the reaction temperature to 200 ℃ for copolymerization reaction;
HOOC(CH2)mCOOH (4)
wherein m is 1,2,3,4,5,6,7,8,9, 10.
2. The crosslinkable PBO copolymer according to claim 1, wherein the reaction temperature in step (1) is selected from 60 ℃ to 90 ℃; the temperature of the step (2) is gradually increased, and the reaction is firstly carried out at 120 ℃, then the reaction is carried out at 150 ℃ and finally the reaction is carried out at 195 ℃.
3. A cross-linked PBO copolymer is characterized in that the structure is shown as formula (2):
wherein m is 1,2,3,4,5,6,7,8,9, 10; 1/99-7/3 x/y;
a method for synthesizing a cross-linked PBO copolymer, wherein the cross-linked PBO copolymer of formula (1) as defined in claim 1 is subjected to a heat treatment to obtain the cross-linked PBO copolymer of formula (2).
4. The crosslinkable PBO copolymer of claim 1 wherein the molar ratio of terephthalic acid to aliphatic dicarboxylic acid is 1: 99 to 7: 3; the molar ratio of the 2-methyl-4, 6-diaminoresorcinol dihydrochloride to the aliphatic dicarboxylic acid is 0.8-1.2: 1.
5. the crosslinked PBO copolymer of claim 3, wherein the heat treatment temperature is from 200 ℃ to 400 ℃.
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