CN1775830A - Hyperbranched polybenzimidazole and preparation method thereof - Google Patents
Hyperbranched polybenzimidazole and preparation method thereof Download PDFInfo
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- CN1775830A CN1775830A CN 200510111019 CN200510111019A CN1775830A CN 1775830 A CN1775830 A CN 1775830A CN 200510111019 CN200510111019 CN 200510111019 CN 200510111019 A CN200510111019 A CN 200510111019A CN 1775830 A CN1775830 A CN 1775830A
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- benzoglyoxaline
- hyperbranched poly
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- carboxyl
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- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000004693 Polybenzimidazole Substances 0.000 title abstract description 12
- 229920002480 polybenzimidazole Polymers 0.000 title abstract description 12
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229920000137 polyphosphoric acid Polymers 0.000 claims abstract description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- 125000003277 amino group Chemical group 0.000 claims abstract 7
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 45
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 16
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 15
- 239000004135 Bone phosphate Substances 0.000 claims description 10
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 238000010907 mechanical stirring Methods 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 4
- 230000001376 precipitating effect Effects 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 abstract description 18
- 239000002904 solvent Substances 0.000 abstract description 5
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 abstract description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 abstract description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract description 2
- KSSJBGNOJJETTC-UHFFFAOYSA-N COC1=C(C=CC=C1)N(C1=CC=2C3(C4=CC(=CC=C4C=2C=C1)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC(=CC=C1C=1C=CC(=CC=13)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC=C(C=C1)OC Chemical compound COC1=C(C=CC=C1)N(C1=CC=2C3(C4=CC(=CC=C4C=2C=C1)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC(=CC=C1C=1C=CC(=CC=13)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC=C(C=C1)OC KSSJBGNOJJETTC-UHFFFAOYSA-N 0.000 abstract 1
- 229940098779 methanesulfonic acid Drugs 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 239000012429 reaction media Substances 0.000 abstract 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract 1
- 150000003627 tricarboxylic acid derivatives Chemical class 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 10
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 8
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 150000001412 amines Chemical group 0.000 description 5
- 239000005711 Benzoic acid Substances 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 235000010233 benzoic acid Nutrition 0.000 description 4
- 229920000587 hyperbranched polymer Polymers 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 3
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- LMAQRGNIWKAAFR-UHFFFAOYSA-N benzene;dicarboxy carbonate Chemical compound C1=CC=CC=C1.OC(=O)OC(=O)OC(O)=O LMAQRGNIWKAAFR-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical group CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- PKXDNBNSQBZKFO-UHFFFAOYSA-N 4-(benzenesulfonyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1S(=O)(=O)C1=CC=CC=C1 PKXDNBNSQBZKFO-UHFFFAOYSA-N 0.000 description 1
- IFQUPKAISSPFTE-UHFFFAOYSA-N 4-benzoylbenzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C(=O)C1=CC=CC=C1 IFQUPKAISSPFTE-UHFFFAOYSA-N 0.000 description 1
- -1 4-carboxyl phenoxy Chemical group 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- PTUVQNJPCIBPIZ-UHFFFAOYSA-N SC1=C(C(=O)C2=CC=CC=C2)C=CC=C1.NC=1C=CC=CC1N Chemical compound SC1=C(C(=O)C2=CC=CC=C2)C=CC=C1.NC=1C=CC=CC1N PTUVQNJPCIBPIZ-UHFFFAOYSA-N 0.000 description 1
- DQBSBLHDMJMKCW-UHFFFAOYSA-N SC1=C(C=CC=C1)C1=CC=CC=C1.NC=1C=CC=CC1N Chemical group SC1=C(C=CC=C1)C1=CC=CC=C1.NC=1C=CC=CC1N DQBSBLHDMJMKCW-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 125000003983 fluorenyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
本发明公开了右式所示的一类超支化聚苯并咪唑及其制备方法，以三元羧酸及四元胺为原料，以多聚磷酸为反应介质，在150～220℃、氮气保护条件下反应5～30小时，制得以羧基或氨基为端基的超支化聚苯并咪唑，这类超支化聚苯并咪唑，具有较高的耐热性能及较好的溶解性能，可溶解在二甲基亚砜、N，N－二甲基乙酰胺以及磷酸、浓硫酸、甲磺酸等溶剂中，末端的羧基或氨基可以通过进一步官能化反应对聚合物进行改性。
The invention discloses a class of hyperbranched polybenzimidazole shown in the right formula and a preparation method thereof. Using tricarboxylic acid and tetraamine as raw materials and polyphosphoric acid as reaction medium, the polybenzimidazole is heated at 150-220°C under nitrogen protection. Under the conditions of reaction for 5 to 30 hours, the hyperbranched polybenzimidazole with carboxyl or amino group as the end group is prepared. This kind of hyperbranched polybenzimidazole has high heat resistance and good solubility, and can be dissolved in In dimethyl sulfoxide, N,N-dimethylacetamide, phosphoric acid, concentrated sulfuric acid, methanesulfonic acid and other solvents, the terminal carboxyl or amino groups can be further functionalized to modify the polymer.
Description
Technical field: the invention relates to class hyperbranched polymer and preparation method thereof, particularly hyperbranched poly benzoglyoxaline base polymer and preparation method thereof.
Background technology: the polybenzimidazole of full aromatic structure has outstanding mechanical property, dielectric properties, outstanding high temperature resistance and good fiber and film performance.Simultaneously, polybenzimidazole still is a kind of in the suitable equally hot-melt type adhesive that has potentiality of high temperature and cryogenic application scenario, still has under extreme temperature than better abrasion resistance properties of engineering plastics any filling or unfilled and weight bearing power.But polybenzimidazole is because its structural high degree of rigidity and chain and interchain intensive interact, and the general all very poor and infusibility of solvability causes its processing characteristics very poor, has limited its application in many aspects.The measure that improves this class material dissolves at present mainly comprises: introduce flexible group on the stiff backbone of polymkeric substance, improve the flowability of polymer molecular chain; Introduce the monomer of distortion and non-coplanar structure, closely pile up to prevent polymer molecular chain, thereby reduced Intermolecular Forces, improve solvability; Introduce a huge side group and can effectively reduce reactive force between molecular chain, but saboteur's chain rigidity not, thereby can when improving polymer dissolution, keep high temperature resistant character; By the symmetry and the repetition regularity of copolymerization saboteur structure, thus the interchain reactive force and the degree of crystallinity of reduction polymkeric substance, the solvability of raising polymkeric substance.
On the other hand, in the past decade people carry out extensive studies to hyperbranched polymer, find that hyperbranched polymer is owing to its special three-dimensional structure makes it have some unique physical propertiess, as good solubility and lower limiting viscosity, people have successfully prepared multiple hyperbranched polymer, but up to the present yet there are no the report of hyperbranched poly benzoglyoxaline.
Summary of the invention: the present invention seeks to the synthesis of super branched polybenzimidazole, polybenzimidazole is hyperbranched, its good solubility can be given and its outstanding pyro-oxidation resistance can be and kept, end group to the hyperbranched poly benzoglyoxaline carries out functional modification in addition, can further expand the application of polybenzimidazole.
Hyperbranched poly benzoglyoxaline of the present invention is that end group is that the hyperbranched poly benzoglyoxaline of carboxyl or end group are amino hyperbranched poly benzoglyoxaline, and its chemical structural formula is expressed as follows respectively:
Or
End group is that the hyperbranched poly benzoglyoxaline end group of carboxyl is amino hyperbranched poly benzoglyoxaline
Ar wherein
1Be selected from:
X is-O-,
Or
Ar
2For
Y is-,-O-,-S-,
The preparation method of hyperbranched poly benzoglyoxaline of the present invention is as follows:
(a) end group is the preparation of the hyperbranched poly benzoglyoxaline of carboxyl
Equimolar tribasic carboxylic acid and quaternary amine are at room temperature joined in the polyphosphoric acid that contains 70～90wt% Vanadium Pentoxide in FLAKES, wherein tribasic carboxylic acid and the quaternary amine concentration in polyphosphoric acid is 0.1～4wt%, under the nitrogen protection mechanical stirring condition in 50～220 ℃ the reaction 5～30 hours after, reduce to room temperature, precipitating with the alkali neutralization, is filtered in water then, in 100 ℃ of following vacuum-dryings, obtaining end group is the hyperbranched poly benzoglyoxaline of carboxyl;
Or (b) end group is the preparation of amino hyperbranched poly benzoglyoxaline
Quaternary amine is dissolved in earlier in the polyphosphoric acid that contains 70～90wt% Vanadium Pentoxide in FLAKES, tribasic carboxylic acid with 1/2 molar weight joins in the reaction solution in batches then, wherein tribasic carboxylic acid and the quaternary amine concentration in polyphosphoric acid is 0.1～1.5wt%, after 5～30 hours, reduce to room temperature 150～220 ℃ of reactions, precipitating is in water, neutralize with alkali then, filter,, obtain end group and be amino hyperbranched poly benzoglyoxaline in 100 ℃ of following vacuum-dryings.
The chemical structure of the tribasic carboxylic acid that the present invention is used is shown below:
Ar wherein
1Be selected from:
Or
X is-O-,
Or
Wherein have 1,3,5-three carboxyl benzene, 1,3,5-three (4-carboxyl phenoxy group) benzene, 1,3,5-three (4-carboxyl phenyl carbonyl) benzene or 1,3,5-three (4-carboxyl phenyl sulfuryl) benzene.
The chemical structure of the quaternary amine that the present invention is used is shown below:
Ar wherein
2For:
Y is-,-O-,-S-,
Wherein have 3,3 '-benzidine, 3,3 ', 4,4 '-tetramino phenyl ether, 3,3 ', 4,4 '-tetramino diphenyl sulfide, 2,2-two (3, the 4-diamino-phenyl) propane, 2,2-two (3, the 4-diamino-phenyl) HFC-236fa, 4,4 '-two (3, the 4-diamino phenoxy) biphenyl, 4,4 '-two (3,4-diaminobenzene sulfydryl) biphenyl, 4,4 '-two (3, the 4-diamino phenoxy) sulfobenzide, 4,4 '-two (3,4-diaminobenzene sulfydryl) sulfobenzide, 4,4 '-two (3, the 4-diamino phenoxy) benzophenone, 4,4 '-two (3,4-diaminobenzene sulfydryl) benzophenone or 9,9-two (3, the 4-diamino-phenyl) fluorenes.
The polyreaction equation of hyperbranched poly benzoglyoxaline of the present invention is as follows:
Wherein, m=n or n=2m.
The resulting hyperbranched poly benzoglyoxaline of the present invention is in many solvents such as dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone, and N,N-dimethylacetamide, methylsulfonic acid has good solubility in the phosphoric acid etc., kept good heat-resistant simultaneously.And the solvability of traditional line style polybenzimidazole is relatively poor, generally can only be dissolved in the strong acid medias such as the vitriol oil and methylsulfonic acid.Terminal carboxyl and amino can carry out modification to polymkeric substance by further functionalization.
The resulting end group of the present invention be the hyperbranched poly benzoglyoxaline of carboxyl can be further with contain the reaction of amino material such as monoamine or adjacent diamino aromatic hydrocarbons, obtain polymer-modified; The resulting end group of the present invention can be further and the substance reaction that contains carboxyl, aldehyde radical, epoxy group(ing) or acid chloride groups for amino hyperbranched poly benzoglyoxaline, obtains polymer-modified.
Description of drawings:
Fig. 1: end group is the infrared spectra IR (KBr) of the hyperbranched poly benzoglyoxaline of carboxyl
Fig. 2: the infrared spectra IR (KBr) of the hyperbranched poly benzoglyoxaline of O-Phenylene Diamine modification
Fig. 3: end group is the infrared spectra IR (KBr) of the hyperbranched poly benzoglyoxaline of amino
Fig. 4: the infrared spectra IR (KBr) of benzoic acid modified hyperbranched poly benzoglyoxaline
Fig. 5: end group is the hyperbranched poly benzoglyoxaline of carboxyl
1H NMR (DMSO-d
6)
Fig. 6: the hyperbranched poly benzoglyoxaline of O-Phenylene Diamine modification
1H NMR (DMSO-d
6)
Fig. 7: benzoic acid modified hyperbranched poly benzoglyoxaline
1H NMR (DMSO-d
6)
Concrete embodiment: following embodiment further specifies of the present invention, rather than limits the scope of the invention.
Embodiment 1: end group is the preparation of the hyperbranched poly benzoglyoxaline of carboxyl
With 3 of benzene tricarbonic acid between 1.5mmol (0.315g) and 1.5mmol (0.3214g); 3 '-benzidine diamines joins 31.6g and contains in the polyphosphoric acid of 85wt% Vanadium Pentoxide in FLAKES; under the nitrogen protection mechanical stirring condition; earlier 150 ℃ of reactions 2 hours; continue down reaction 20 hours at 190 ℃ then, reduce to during room temperature falls back.Earlier be neutralized to slightly acidic, be neutralized to neutrality with sodium bicarbonate again, filter then with sodium hydroxide, the polymkeric substance of collecting is added in the ammoniacal liquor in 80 ℃ stirred 12 hours, filter, after sample is washed till neutrality, 100 ℃ of vacuum-drying 24 hours, obtaining end group is the hyperbranched poly benzoglyoxaline of carboxyl.Fig. 1 is its infrared spectrogram; Fig. 5 is its nmr spectrum, and solvent for use is a deuterated dimethyl sulfoxide; Recording limiting viscosity in dimethyl sulfoxide (DMSO) under 35 ℃ is: 0.40dL/g.
Embodiment 2: the end group of O-Phenylene Diamine modification is the preparation of the hyperbranched poly benzoglyoxaline of carboxyl
The end group that embodiment 1 is obtained is that the hyperbranched poly benzoglyoxaline of carboxyl is dissolved in 31.6g and contains in the polyphosphoric acid of 85wt% Vanadium Pentoxide in FLAKES; under nitrogen protection mechanical stirring condition; the O-Phenylene Diamine that adds 0.1620g (1.5mmol); 150 ℃ of reactions 2 hours; continue down reaction 20 hours at 190 ℃ then, reduce to during room temperature falls back.Earlier be neutralized to slightly acidic with sodium hydroxide, be neutralized to neutrality with sodium bicarbonate again, filter then, the polymkeric substance of collecting is added to ammoniacal liquor to be stirred 12 hours in 80 ℃, filter, after sample is washed till neutrality, 100 ℃ of vacuum-drying 24 hours, the end group that obtains the O-Phenylene Diamine modification is the hyperbranched poly benzoglyoxaline of carboxyl.Fig. 2 is its infrared spectrogram; Fig. 6 is its nmr spectrum, and solvent for use is a deuterated dimethyl sulfoxide; Recording limiting viscosity in dimethyl sulfoxide (DMSO) under 35 ℃ is: 0.46dL/g.
Embodiment 3: end group is the preparation of the hyperbranched poly benzoglyoxaline of amino
With 2mmol (0.4285g) 3; 3 '-benzidine diamines joins 65g and contains in the polyphosphoric acid of 85wt% Vanadium Pentoxide in FLAKES; after 100 ℃ of abundant dissolvings; add benzene tricarbonic acid between 1mmol (0.21g) in two batches; under nitrogen protection mechanical stirring condition; 150 ℃ of reactions 2 hours continue down reaction 20 hours at 190 ℃ then, reduce to during room temperature falls back.Earlier be neutralized to slightly acidic, be neutralized to neutrality with sodium bicarbonate again, filter then with sodium hydroxide, the polymkeric substance of collecting is added to ammoniacal liquor in 80 ℃ of stirrings 12 hours, filters, after sample is washed till neutrality, 100 ℃ of vacuum-drying 24 hours, obtaining with amino is the hyperbranched poly benzoglyoxaline of end group.Fig. 3 is its infrared spectrogram.
Embodiment 4: benzoic acid modified end group is the preparation of the hyperbranched poly benzoglyoxaline of amino
The end group that embodiment 3 is obtained is that amino hyperbranched poly benzoglyoxaline is dissolved in 65g and contains in the polyphosphoric acid of 85wt% Vanadium Pentoxide in FLAKES; under nitrogen protection mechanical stirring condition; the phenylformic acid that adds 0.122g (1mmol); 150 ℃ of reactions 2 hours; continue reaction 20 hours down at 190 ℃ then; reduce to during room temperature falls back; earlier be neutralized to slightly acidic with sodium hydroxide; be neutralized to neutrality with sodium bicarbonate again, filter then, the polymkeric substance of collecting is added to ammoniacal liquor stirred 12 hours in 80 ℃; filter; after sample is washed till neutrality, 100 ℃ of vacuum-drying 24 hours, obtaining with benzoic acid modified end group is the hyperbranched poly benzoglyoxaline of amino.Fig. 4 is its infrared spectrogram; Fig. 7 is its nmr spectrum, and solvent for use is a deuterated dimethyl sulfoxide; Recording limiting viscosity in dimethyl sulfoxide (DMSO) under 35 ℃ is: 0.36dL/g.
Claims (4)
1. hyperbranched poly benzoglyoxaline is characterized in that its chemical structural formula is as follows:
End group is that the hyperbranched poly benzoglyoxaline end group of carboxyl is amino hyperbranched poly benzoglyoxaline
Ar wherein
1Be selected from:
X is-O-,
Or
Ar
2For:
Y is-,-O-,-S-,
2. the preparation method of hyperbranched poly benzoglyoxaline as claimed in claim 1 is characterized in that its preparation method is as follows:
(a) end group is the preparation of the hyperbranched poly benzoglyoxaline of carboxyl
Equimolar tribasic carboxylic acid and quaternary amine are at room temperature joined in the polyphosphoric acid that contains 70～90wt% Vanadium Pentoxide in FLAKES, wherein tribasic carboxylic acid and the quaternary amine concentration in polyphosphoric acid is 0.1～4wt%, under the nitrogen protection mechanical stirring condition in 50～220 ℃ the reaction 5～30 hours after, reduce to room temperature, precipitating with the alkali neutralization, is filtered in water then, in 100 ℃ of following vacuum-dryings, obtaining end group is the hyperbranched poly benzoglyoxaline of carboxyl;
Or (b) end group is the preparation of amino hyperbranched poly benzoglyoxaline
Quaternary amine is dissolved in earlier in the polyphosphoric acid that contains 70～90wt% Vanadium Pentoxide in FLAKES, tribasic carboxylic acid with 1/2 molar weight joins in the reaction solution in batches then, wherein tribasic carboxylic acid and the quaternary amine concentration in polyphosphoric acid is 0.1～1.5wt%, after 5～30 hours, reduce to room temperature 150～220 ℃ of reactions, precipitating is in water, neutralize with alkali then, filter,, obtain end group and be amino hyperbranched poly benzoglyoxaline in 100 ℃ of following vacuum-dryings.
3. hyperbranched poly benzoglyoxaline preparation method according to claim 2 is characterized in that the chemical structure of tribasic carboxylic acid is shown below:
Ar wherein
1Be selected from:
Or
X is-O-,
Or
4. hyperbranched poly benzoglyoxaline preparation method according to claim 2 is characterized in that the chemical structure of quaternary amine is shown below:
Ar wherein
2For:
Y is-,-O-,-S-
Or
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
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