CN1709943A - Polybenzodithiazole containing fatty-group lateral group and preparation method thereof - Google Patents
Polybenzodithiazole containing fatty-group lateral group and preparation method thereof Download PDFInfo
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Abstract
The present invention discloses polybenzothiadiazole containing fatty group pendent groups and its preparation method. This series of polymers makes substituted di(amino mercapto) hydrochloride and aromatic binary carboxylic acid as raw materials, and polyphosphoric acid (PPA) as solvent and condensing agent , and polyesterifies to prepare. The introduction of alicyclic large pendent groups can improve the solubility of this series of polymers and keep various good properties as high thermostability and chemical stability, so it can widen the application bound of this series of polymers in various aspects.
Description
Technical field:
The present invention relates to a base polymer and preparation method, the polyphenyl of particularly fatty family side group and dithiazole and preparation method thereof.
Background technology:
The people such as Wolfe of SRI (Stanford Research International) material laboratory in 1981 on the long-term basis of exploring, having released has 2 on the main chain, the two heterocyclic contraposition aromatic polymers of 6-benzo, the research and development success of this base polymer material, make the research of high-temperature polymer obtain progress and success greatly, be considered to the pioneer and the representative of high strength of new generation, high-modulus, high temperature polymeric materials, through R and D for many years, formed a series of polymers that is commonly referred to as polyhenylene benzo benzo two heterocycles (PBZ).As: polyphenylene benzo dithiazole (PBZT), polyphenylene benzo dioxazole (PBO), polyphenylene benzo diimidazole (PBI).Initial research finds that PBZ family polymkeric substance only can be dissolved in the strong protonic acids such as methanesulfonic (MSA), polyphosphoric acid (PPA), chlorsulfonic acid (CSA), trifluoracetic acid (TFA), the vitriol oil, and is mesomorphic phase in the finite concentration scope.Because they are difficult to be dissolved in organic solvent, so the processing treatment difficulty.It is good but do not sacrifice the macromolecular compound of its every excellent properties that many researchs all are devoted to develop solubility property.At present main method be introduce on the main polymer chain ehter bond or fluorinated groups improve the PBZ compounds in organic solvent solvability and make it have thermoplasticity.
Summary of the invention:
The present invention is from Molecular Structure Design and point of practical use, big side group is introduced in replacement two (amino mercapto) benzene hydrochloride, again with this monomer with a series of di-carboxylic acid polycondensations after, prepared a series of high temperature resistant, high strength and the better polyphenyl and the dithiazole base polymer of deliquescent fatty family side group are arranged has application prospect at aspects such as space materials.
The polyphenyl of the fatty family of the present invention side group and the segment repeated structural unit of dithiazole are as follows:
Wherein the scope of n value is between 20-45;
X is:
Y is:
Wherein have: poly-2,2 '-to penylene-6,6 '-cyclohexyl benzo dithiazole, poly-2,2 '-penylene-6,6 '-cyclohexyl benzo dithiazole, poly-2,2 '-biphenylene-6,6 '-cyclohexyl benzo dithiazole, poly-2,2 '-Ya hexichol ether-6,6 '-cyclohexyl benzo dithiazole, poly-2,2 '-Ya benzophenone base-6,6 '-cyclohexyl benzo dithiazole, poly-2,2 '-Ya diphenyl sulfone-6,6 '-cyclohexyl benzo dithiazole, poly-2,2 '-Ya hexichol hexafluoro different propyl-6,6 '-cyclohexyl benzo dithiazole, poly-2,2 '-to penylene-6,6 '-(3-methyl) cyclohexyl benzo dithiazole, poly-2,2 '-penylene-6,6 '-(3-methyl) cyclohexyl benzo dithiazole, poly-2,2 '-biphenylene-6,6 '-(3-methyl) cyclohexyl benzo dithiazole, poly-2,2 '-Ya hexichol ether-6,6 '-(3-methyl) cyclohexyl benzo dithiazole, poly-2,2 '-Ya benzophenone base-6,6 '-(3-methyl) cyclohexyl benzo dithiazole, poly-2,2 '-Ya diphenyl sulfone-6,6 '-(3-methyl) cyclohexyl benzo dithiazole, poly-2,2 '-Ya hexichol hexafluoro different propyl-6,6 '-(3-methyl) cyclohexyl benzo dithiazole, poly-2,2 '-to penylene-6,6 '-(4-methyl) cyclohexyl benzo dithiazole, poly-2,2 '-penylene-6,6 '-(4-methyl) cyclohexyl benzo dithiazole, poly-2,2 '-biphenylene-6,6 '-(4-methyl) cyclohexyl benzo dithiazole, poly-2,2 '-Ya hexichol ether-6,6 '-(4-methyl) cyclohexyl benzo dithiazole, poly-2,2 '-Ya benzophenone base-6,6 '-(4-methyl) cyclohexyl benzo dithiazole, poly-2,2 '-Ya diphenyl sulfone-6,6 '-(4-methyl) cyclohexyl benzo dithiazole, poly-2,2 '-Ya hexichol hexafluoro different propyl-6,6 '-(4-methyl) cyclohexyl benzo dithiazole, poly-2,2 '-to penylene-6,6 '-(the 4-tertiary butyl) cyclohexyl benzo dithiazole, poly-2,2 '-penylene-6,6 '-(the 4-tertiary butyl) cyclohexyl benzo dithiazole, poly-2,2 '-biphenylene-6,6 '-(the 4-tertiary butyl) cyclohexyl benzo dithiazole, poly-2,2 '-Ya hexichol ether-6,6 '-(the 4-tertiary butyl) cyclohexyl benzo dithiazole, poly-2,2 '-Ya benzophenone base-6,6 '-(the 4-tertiary butyl) cyclohexyl benzo dithiazole, poly-2,2 '-Ya diphenyl sulfone-6,6 '-(the 4-tertiary butyl) cyclohexyl benzo dithiazole or poly-2,2 '-Ya hexichol hexafluoro different propyl-6,6 '-(the 4-tertiary butyl) cyclohexyl benzo dithiazole.
The polyphenyl of the fatty family of the present invention side group and dithiazole are that starting raw material polycondensation in polyphosphoric acid (PPA) prepares to replace two (amino mercapto) benzene hydrochlorides and aromatic dicarboxylic acids, polyphosphoric acid promptly is that solvent is again a condensing agent in reaction, and its polyreaction equation can be expressed as follows:
The polyphenyl of the fatty family of the present invention side group and the concrete preparation method of dithiazole are as follows:
In the three-necked bottle that mechanical stirring and argon gas gangway are housed, add polyphosphoric acid and replace two (amino mercapto) benzene hydrochloride; polyphosphoric acid is 10: 1～16: 1 with the mass ratio that replaces two (amino mercapto) benzene hydrochloride; the stirring at room reaction is 24 hours under argon shield; 70 ℃ of following stirring reactions 36 hours; intermittence vacuumizes during this time; to eliminate the HCl gas of generation; add aromatic dicarboxylic acids and Vanadium Pentoxide in FLAKES then; the aromatic dicarboxylic acids is 1: 1 with the mol ratio that replaces two (amino mercapto) benzene hydrochloride; Vanadium Pentoxide in FLAKES is 3: 1～6: 1 with the mass ratio that replaces two (amino mercapto) benzene hydrochloride; be heated to 110 ℃ rapidly; in 3～5 hours, be warming up to 165 ℃ of stirring reactions 5～24 hours; 180 ℃ of stirring reactions 12～24 hours; 190 ℃ of stirring reactions 6～24 hours; 200 ℃ of stirring reactions 4～10 hours; reaction is poured heavy-gravity solution in the big water gaging into after finishing; sedimentation and filtration; weak caustic solution washing with 5wt%; be washed to neutrality; methanol eddy 10 hours; filter, drying obtains the polyphenyl and the dithiazole of fatty family side group.
Replacement two (amino mercapto) benzene hydrochloride that the present invention uses is selected from 1,1-two (4-amino-3-sulfydryl phenyl) hexanaphthene dihydrochloride, 1,1-two (4-amino-3-sulfydryl phenyl)-3-methylcyclohexane dihydrochloride, 1,1-two (4-amino-3-sulfydryl phenyl)-4-methylcyclohexane dihydrochloride or 1, a kind of in 1-two (4-amino-3-sulfydryl phenyl)-4-tertiary butyl hexanaphthene dihydrochloride.
The aromatic dicarboxylic acids that the present invention uses is selected from terephthalic acid, m-phthalic acid, 2,2 '-biphenyl dicarboxylic acid, 4,4 '-dicarboxyl phenyl ether, 4,4 '-benzophenonedicarboxylic acid, 4,4 '-Dicarboxy diphenylsulfone or 4, a kind of in the different propane of 4 '-dicarboxyl hexichol hexafluoro.
The weak base that the present invention uses is selected from a kind of in yellow soda ash, sodium bicarbonate, salt of wormwood or the saleratus.
The concrete preparation method who replaces two (amino mercapto) benzene hydrochloride is as follows:
(a) under protection of inert gas and stirring, will add in the reactor in aniline and the hydrochloric acid adding reactor or with aniline and anilinechloride, wherein the mol ratio of aniline and hydrochloric acid is 1: 1～1: 8; The mol ratio of aniline and anilinechloride is 1: 1～10: 1, behind the two thorough mixing, again alicyclic carbonyl compound is added, the mol ratio of wherein alicyclic carbonyl compound and aniline is 1: 4～1: 16, then mixture was reacted 12～36 hours at 120～160 ℃, reaction is cooled to room temperature with reaction solution after finishing, in reaction solution, add the aqueous solution of sodium hydroxide to pH=10, oil reservoir is separated, and wash with water to neutrality, dry filter, underpressure distillation are removed excessive aniline, obtain containing the aromatic diamines of cycloaliphatic big lateral base behind recrystallization;
(b) under protection of inert gas and stirring, the aromatic diamines that will contain cycloaliphatic big lateral base is dissolved in the Glacial acetic acid fully, containing the aromatic diamines of cycloaliphatic big lateral base and the mass ratio of Glacial acetic acid is 1: 10～1: 20, in solution, add potassium sulfocyanate or Sodium Thiocyanate 99 after the stirring and dissolving, stirring makes its dissolving, wherein containing the aromatic diamines of cycloaliphatic big lateral base and the mol ratio of potassium sulfocyanate or Sodium Thiocyanate 99 is 1: 3～1: 12, under stirring and ice bath cooling, the glacial acetic acid solution of dripping bromine in reaction solution, bromine is 2: 1～5: 1 with the mol ratio that contains the aromatic diamines of cycloaliphatic big lateral base, the mass ratio of bromine and Glacial acetic acid is 1: 1～5: 1, dropwised the back stirring at room 12～36 hours, in reaction solution, add water and refluxed 2～5 hours, be cooled to room temperature, filter, filtrate is poured in the big water gaging, produce precipitation, solid filtering is also extremely neutral with ammonia scrubbing, obtains containing the aminobenzothiazole of cycloaliphatic big lateral base behind recrystallization;
(c) under protection of inert gas and stirring; potassium hydroxide is soluble in water; the mass ratio of potassium hydroxide and water is 1: 1～1: 4; solution is heated to 100 ℃; add the aminobenzothiazole that contains cycloaliphatic big lateral base; the mol ratio of it and potassium hydroxide is 1: 15～1: 25; be warming up to 140～180 ℃; reflux and stopped to produce to carbonic acid gas and ammonia in 5～8 hours; solution is chilled to stirred overnight at room temperature; in reaction solution, add entry; the mass ratio of water and potassium hydroxide is 2: 3～3: 1; be heated to 100 ℃ to solution becomes clarification, after the cooling, under protection of inert gas, solution poured in 6～12mol/L hydrochloric acid and precipitate; solid filtering; obtain replacing the crude product of two (amino mercapto) benzene hydrochloride, obtain replacing two (amino mercapto) benzene hydrochloride behind the recrystallization in being added with the 10wt% hydrochloric acid soln of antioxidant, the concentration of antioxidant in hydrochloric acid soln is 1wt%.Replace the alicyclic carbonyl compound that uses among two (amino mercapto) benzene hydrochloride preparation method and be selected from a kind of in pimelinketone, 3-methylcyclohexanone, 4-methylcyclohexanone or the 4-tertiary butyl pimelinketone, the antioxidant of use is selected from a kind of in zinc or the tin protochloride.
The present invention is from Molecular Structure Design and point of practical use, to replace two (amino mercapto) benzene hydrochlorides and aromatic dicarboxylic acids's polycondensation, prepared a series of high comprehensive performances and the better polyphenyl and the dithiazole base polymer material of deliquescent fatty family side group have been arranged, compare with the polyphenylene benzo dithiazole (PBZT) of no side group, they are except dissolving in strong protonic acids such as methanesulfonic, wherein great majority can also be dissolved in various organic solvents wholly or in part, as: 1-methyl 2-Pyrrolidone, N,N-dimethylacetamide etc.Their heat decomposition temperatures in nitrogen are at 482-534 ℃, and X-ray diffraction shows that the polyphenyl and the dithiazole of all fatty family side groups are amorphous state.
Description of drawings:
Fig. 1 gathers 2 in the example 1,2 '-Ya hexichol ether-6, the infrared spectra of 6 '-cyclohexyl benzo dithiazole.
Fig. 2 gathers 2 in the example 1,2 '-Ya hexichol ether-6, the proton nmr spectra of 6 '-cyclohexyl benzo dithiazole.
Fig. 3 gathers 2 in the example 2,2 '-Ya hexichol hexafluoro different propyl-6, the carbon-13 nmr spectra of 6 '-cyclohexyl benzo dithiazole.
Fig. 4 gathers 2 in the example 3,2 '-Ya hexichol hexafluoro different propyl-6, the infrared spectra of 6 '-(the 4-tertiary butyl) cyclohexyl benzo dithiazole.
Fig. 5 gathers 2 in the example 3,2 '-Ya hexichol hexafluoro different propyl-6, the proton nmr spectra of 6 '-(the 4-tertiary butyl) cyclohexyl benzo dithiazole.
Embodiment:
The following examples are to further specify of the present invention, rather than limit the scope of the invention.
Example 1:
With 0.5g (1.24mmol) 1; 1-two (4-amino-3-sulfydryl phenyl) hexanaphthene dihydrochloride and 6.11g polyphosphoric acid (PPA) join mechanical stirring are housed; in the three-necked bottle of argon gas gangway; the stirring at room reaction is 24 hours under argon shield; 70 ℃ of following stirring reactions 36 hours; intermittently container is vacuumized during this time; to eliminate the HCl gas of generation; add 0.32g (1.24mmol) 4 then; 4 '-dicarboxyl phenyl ether and 1.69g Vanadium Pentoxide in FLAKES; be rapidly heated to 110 ℃; in 3 hours, progressively be warming up to 165 ℃; 165 ℃ of stirring reactions 12 hours; be warming up to 180 ℃ of stirring reactions 16 hours, be warming up to 190 ℃ of stirring reactions 12 hours, at last 200 ℃ of stirring reactions 6 hours.Reaction soln is along with the rising of temperature of reaction and the prolongation of time, and color deepens gradually, and viscosity becomes greatly gradually, is Vandyke brown at last, and viscous solution is poured in the big water gaging, and sedimentation and filtration is used 5wt%NaHCO
3Solution washing is washed to neutrality, and methanol eddy 10 hours filters, washing, and 120 ℃ of dryings are 2 days in vacuum drying oven, obtain 2,2 '-Ya hexichol ether-6, the infrared spectra 0.608g of 6 '-cyclohexyl benzo dithiazole (productive rate 94.8%).Fig. 1 represents to gather 2,2 '-Ya hexichol ether-6, and the infrared spectra IR (KBr) of 6 '-cyclohexyl benzo dithiazole: 2930,2856 (m,
), 1595 (C=N), 1241em
-1(C-O-C).Fig. 2 represents to gather 2,2 '-Ya hexichol ether-6, the proton nmr spectra of 6 '-cyclohexyl benzo dithiazole
1H NMR (D
2SO
4): δ (ppm)=1.08-2.28 (br m, 10H, hexanaphthene), 7.18-7.89 (m, 14H, phenyl ring).Molecular weight is measured as 10300gmol by viscosimetry
-1
Example 2:
With 0.5g (1.24mmol) 1; 1-two (4-amino-3-sulfydryl phenyl) hexanaphthene dihydrochloride and 7.59g polyphosphoric acid (PPA) join mechanical stirring are housed; in the three-necked bottle of argon gas gangway; the stirring at room reaction is 24 hours under argon shield; 70 ℃ of following stirring reactions 36 hours; intermittently container is vacuumized during this time; to eliminate the HCl gas of generation; add 0.486g (1.24mmol) 4 then; different propane of 4 '-dicarboxyl hexichol hexafluoro and 2.35g Vanadium Pentoxide in FLAKES; be rapidly heated to 110 ℃; in 3 hours, progressively be warming up to 165 ℃; 165 ℃ of stirring reactions 12 hours; be warming up to 180 ℃ of stirring reactions 18 hours, be warming up to 190 ℃ of stirring reactions 6 hours, at last 200 ℃ of stirring reactions 4 hours.Reaction soln is along with the rising of temperature of reaction and the prolongation of time, and color deepens gradually, and the very fast change of viscosity is big, is tawny at last, and viscous solution is poured in the big water gaging, and sedimentation and filtration is used 5wt%NaHCO
3Solution washing is washed to neutrality, and methanol eddy 10 hours filters, washing, 120 ℃ of dryings are 2 days in vacuum drying oven, obtain poly-2,2 '-Ya hexichol hexafluoro different propyl-6,6 '-cyclohexyl benzo dithiazole 0.793g (productive rate 98.3%).IR(KBr)：2933，2860(m，
)，1593(C＝N)，1240cm
-1(C-O-C)。
1H NMR (THF-d
8): δ (ppm)=1.28-2.49 (br m, 10H, hexanaphthene), 7.56-8.15 (m, 14H, phenyl ring).Fig. 3 represents to gather 2,2 '-Ya hexichol hexafluoro different propyl-6, the carbon-13 nmr spectra of 6 '-cyclohexyl benzo dithiazole
13C NMR (THF-d
8): δ (ppm)=25.00,26.61,39.32,48.82,66.73,121.98,125.11,122.28,124.87,127.61,130.98,128.45,129.20 132.84,136.84,137.14,137.70,148.51,154.45,167.58.Molecular weight is measured as 13000gmol by viscosimetry
-1
Example 3:
With 0.5g (1.09mmol) 1; 1-two (4-amino-3-sulfydryl phenyl)-4-tertiary butyl hexanaphthene dihydrochloride and 7.20g polyphosphoric acid (PPA) join mechanical stirring are housed; in the three-necked bottle of argon gas gangway; stirring at room is 24 hours under argon shield; 70 ℃ of following stirring reactions 36 hours; intermittently container is vacuumized during this time; to eliminate the HCl gas of generation; add 0.427g (1.09mmol) 4 then; different propane of 4 '-dicarboxyl hexichol hexafluoro and 2.21g Vanadium Pentoxide in FLAKES; temperature rapidly increases to 110 ℃; in 3 hours, progressively be warming up to 165 ℃ then; 165 ℃ of stirring reactions 12 hours; be warming up to 180 ℃ of stirring reactions 18 hours, be warming up to 190 ℃ of stirring reactions 12 hours, at last 200 ℃ of stirring reactions 4 hours.Reaction soln is along with the rising of temperature of reaction and the prolongation of time, and color deepens gradually, and the very fast change of viscosity is big, is brown at last, and viscous solution is poured in the big water gaging, and sedimentation and filtration is used 5wt%NaCO
3Solution washing is washed to neutrality, and methanol eddy 10 hours filters, washing, 120 ℃ of dryings are 2 days in vacuum drying oven, obtain poly-2,2 '-Ya hexichol hexafluoro different propyl-6,6 '-(the 4-tertiary butyl) cyclohexyl benzo dithiazole 0.730g (productive rate 94.8%).Fig. 4 represents to gather 2,2 '-Ya hexichol hexafluoro different propyl-6, and the infrared spectra IR (KBr) of 6 '-(the 4-tertiary butyl) cyclohexyl benzo dithiazole: 2941,2865 (m,
), 1598 (C=N), 1256cm
-1(C-O-C).Fig. 5 represents to gather 2,2 '-Ya hexichol hexafluoro different propyl-6, the proton nmr spectra 1 of 6 '-(the 4-tertiary butyl) cyclohexyl benzo dithiazole
HNMR (THF-d
8): δ (ppm)=0.785 (s, 3H, CH
3), 1.28-3.04 (br m, 9H, hexanaphthene), 7.42-8.18 (m, 14H, phenyl ring).Molecular weight is measured as 14800gmol by viscosimetry
-1
Claims (5)
1. the polyphenyl and the dithiazole of fatty family side group is characterized in that the segment repeated structural unit is:
Wherein the scope of n value is between 20-45;
X is:
Or
Y is:
Wherein have: poly-2,2 '-to penylene-6,6 '-cyclohexyl benzo dithiazole, poly-2,2 '-penylene-6,6 '-cyclohexyl benzo dithiazole, poly-2,2 '-biphenylene-6,6 '-cyclohexyl benzo dithiazole, poly-2,2 '-Ya hexichol ether-6,6 '-cyclohexyl benzo dithiazole, poly-2,2 '-Ya benzophenone base-6,6 '-cyclohexyl benzo dithiazole, poly-2,2 '-Ya diphenyl sulfone-6,6 '-cyclohexyl benzo dithiazole, poly-2,2 '-Ya hexichol hexafluoro different propyl-6,6 '-cyclohexyl benzo dithiazole, poly-2,2 '-to penylene-6,6 '-(3-methyl) cyclohexyl benzo dithiazole, poly-2,2 '-penylene-6,6 '-(3-methyl) cyclohexyl benzo dithiazole, poly-2,2 '-biphenylene-6,6 '-(3-methyl) cyclohexyl benzo dithiazole, poly-2,2 '-Ya hexichol ether-6,6 '-(3-methyl) cyclohexyl benzo dithiazole, poly-2,2 '-Ya benzophenone base-6,6 '-(3-methyl) cyclohexyl benzo dithiazole, poly-2,2 '-Ya diphenyl sulfone-6,6 '-(3-methyl) cyclohexyl benzo dithiazole, poly-2,2 '-Ya hexichol hexafluoro different propyl-6,6 '-(3-methyl) cyclohexyl benzo dithiazole, poly-2,2 '-to penylene-6,6 '-(4-methyl) cyclohexyl benzo dithiazole, poly-2,2 '-penylene-6,6 '-(4-methyl) cyclohexyl benzo dithiazole, poly-2,2 '-biphenylene-6,6 '-(4-methyl) cyclohexyl benzo dithiazole, poly-2,2 '-Ya hexichol ether-6,6 '-(4-methyl) cyclohexyl benzo dithiazole, poly-2,2 '-Ya benzophenone base-6,6 '-(4-methyl) cyclohexyl benzo dithiazole, poly-2,2 '-Ya diphenyl sulfone-6,6 '-(4-methyl) cyclohexyl benzo dithiazole, poly-2,2 '-Ya hexichol hexafluoro different propyl-6,6 '-(4-methyl) cyclohexyl benzo dithiazole, poly-2,2 '-to penylene-6,6 '-(the 4-tertiary butyl) cyclohexyl benzo dithiazole, poly-2,2 '-penylene-6,6 '-(the 4-tertiary butyl) cyclohexyl benzo dithiazole, poly-2,2 '-biphenylene-6,6 '-(the 4-tertiary butyl) cyclohexyl benzo dithiazole, poly-2,2 '-Ya hexichol ether-6,6 '-(the 4-tertiary butyl) cyclohexyl benzo dithiazole, poly-2,2 '-Ya benzophenone base-6,6 '-(the 4-tertiary butyl) cyclohexyl benzo dithiazole, poly-2,2 '-Ya diphenyl sulfone-6,6 '-(the 4-tertiary butyl) cyclohexyl benzo dithiazole or poly-2,2 '-Ya hexichol hexafluoro different propyl-6,6 '-(the 4-tertiary butyl) cyclohexyl benzo dithiazole.
2. the polyphenyl of fatty according to claim 1 family side group and the preparation method of dithiazole is characterized in that the preparation method is as follows:
In the three-necked bottle that mechanical stirring and argon gas gangway are housed, add polyphosphoric acid and replace two (amino mercapto) benzene hydrochloride; polyphosphoric acid is 10: 1～16: 1 with the mass ratio that replaces two (amino mercapto) benzene hydrochloride; the stirring at room reaction is 24 hours under argon shield; 70 ℃ of following stirring reactions 36 hours; intermittence vacuumizes during this time; to eliminate the HCl gas of generation; add aromatic dicarboxylic acids and Vanadium Pentoxide in FLAKES then; the aromatic dicarboxylic acids is 1: 1 with the mol ratio that replaces two (amino mercapto) benzene hydrochloride; Vanadium Pentoxide in FLAKES is 3: 1～6: 1 with the mass ratio that replaces two (amino mercapto) benzene hydrochloride; be heated to 110 ℃ rapidly; in 3～5 hours, be warming up to 165 ℃ of stirring reactions 5～24 hours; 180 ℃ of stirring reactions 12～24 hours; 190 ℃ of stirring reactions 6～24 hours; 200 ℃ of stirring reactions 4～10 hours; reaction is poured heavy-gravity solution in the big water gaging into after finishing; sedimentation and filtration; weak caustic solution washing with 5wt%; be washed to neutrality; methanol eddy 10 hours; filter, drying obtains the polyphenyl and the dithiazole of fatty family side group.
3. the polyphenyl and the dithiazole preparation method of fatty family according to claim 2 side group, it is characterized in that replacing two (amino mercapto) benzene hydrochloride and be selected from 1,1-two (4-amino-3-sulfydryl phenyl) hexanaphthene dihydrochloride, 1,1-two (4-amino-3-sulfydryl phenyl)-3-methylcyclohexane dihydrochloride, 1,1-two (4-amino-3-sulfydryl phenyl)-4-methylcyclohexane dihydrochloride or 1, a kind of in 1-two (4-amino-3-sulfydryl phenyl)-4-tertiary butyl hexanaphthene dihydrochloride.
4. the polyphenyl and the dithiazole preparation method of fatty family according to claim 2 side group, it is characterized in that the aromatic dicarboxylic acids is selected from terephthalic acid, m-phthalic acid, 2,2 '-biphenyl dicarboxylic acid, 4,4 '-dicarboxyl phenyl ether, 4,4 '-benzophenonedicarboxylic acid, 4,4 '-Dicarboxy diphenylsulfone or 4, a kind of in the different propane of 4 '-dicarboxyl hexichol hexafluoro.
5. the polyphenyl and the dithiazole preparation method of fatty family according to claim 2 side group is characterized in that weak base is selected from a kind of in yellow soda ash, sodium bicarbonate, salt of wormwood or the saleratus.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100387636C (en) * | 2005-12-22 | 2008-05-14 | 上海交通大学 | Benzothiazole-carbamide polymer containing aliphatics lateral group and method for preparing the same |
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Cited By (1)
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|---|---|---|---|---|
| CN100387636C (en) * | 2005-12-22 | 2008-05-14 | 上海交通大学 | Benzothiazole-carbamide polymer containing aliphatics lateral group and method for preparing the same |
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