CN1803885A - Benzothiazole-carbamide polymer containing aliphatics lateral group and method for preparing the same - Google Patents
Benzothiazole-carbamide polymer containing aliphatics lateral group and method for preparing the same Download PDFInfo
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- CN1803885A CN1803885A CN 200510111788 CN200510111788A CN1803885A CN 1803885 A CN1803885 A CN 1803885A CN 200510111788 CN200510111788 CN 200510111788 CN 200510111788 A CN200510111788 A CN 200510111788A CN 1803885 A CN1803885 A CN 1803885A
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- benzo thiazole
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- 125000001931 aliphatic group Chemical group 0.000 title abstract 3
- 238000000034 method Methods 0.000 title description 4
- 229920000642 polymer Polymers 0.000 title description 4
- LYASTVLDAJIXBL-UHFFFAOYSA-N 1,3-benzothiazole-2-carboxamide Chemical compound C1=CC=C2SC(C(=O)N)=NC2=C1 LYASTVLDAJIXBL-UHFFFAOYSA-N 0.000 title 1
- 239000004202 carbamide Substances 0.000 claims description 54
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical group NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 42
- 238000003756 stirring Methods 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- -1 washing is filtered Substances 0.000 claims description 19
- 238000002360 preparation method Methods 0.000 claims description 18
- CXUXSVRYIFBRSZ-UHFFFAOYSA-N 2-cyclohexyl-1,3-benzothiazole Chemical compound C1CCCCC1C1=NC2=CC=CC=C2S1 CXUXSVRYIFBRSZ-UHFFFAOYSA-N 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- JHRMJWGBGBDNJE-UHFFFAOYSA-N 1,3-benzothiazole-2,4-diamine Chemical compound C1=CC=C2SC(N)=NC2=C1N JHRMJWGBGBDNJE-UHFFFAOYSA-N 0.000 claims description 14
- 125000002723 alicyclic group Chemical group 0.000 claims description 14
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 claims description 13
- UHGULLIUJBCTEF-UHFFFAOYSA-N 2-aminobenzothiazole Chemical compound C1=CC=C2SC(N)=NC2=C1 UHGULLIUJBCTEF-UHFFFAOYSA-N 0.000 claims description 13
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000010907 mechanical stirring Methods 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- 239000003495 polar organic solvent Substances 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 108091064702 1 family Proteins 0.000 claims 1
- DQFBYFPFKXHELB-UHFFFAOYSA-N Chalcone Natural products C=1C=CC=CC=1C(=O)C=CC1=CC=CC=C1 DQFBYFPFKXHELB-UHFFFAOYSA-N 0.000 claims 1
- 235000005513 chalcones Nutrition 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims 1
- 229960002725 isoflurane Drugs 0.000 claims 1
- 125000005442 diisocyanate group Chemical group 0.000 abstract description 4
- 239000002861 polymer material Substances 0.000 abstract description 3
- KPYHKEZPEDJERZ-UHFFFAOYSA-N 10h-phenothiazine-1,2-diamine Chemical compound C1=CC=C2NC3=C(N)C(N)=CC=C3SC2=C1 KPYHKEZPEDJERZ-UHFFFAOYSA-N 0.000 abstract 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 16
- 239000002585 base Substances 0.000 description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 229960000583 acetic acid Drugs 0.000 description 8
- 239000012362 glacial acetic acid Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 6
- 239000012043 crude product Substances 0.000 description 6
- 238000001953 recrystallisation Methods 0.000 description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 5
- 150000004984 aromatic diamines Chemical class 0.000 description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 5
- 229910052794 bromium Inorganic materials 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 238000002329 infrared spectrum Methods 0.000 description 5
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 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
- 206010013786 Dry skin Diseases 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 241000220317 Rosa Species 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- MMCPOSDMTGQNKG-UHFFFAOYSA-N anilinium chloride Chemical compound Cl.NC1=CC=CC=C1 MMCPOSDMTGQNKG-UHFFFAOYSA-N 0.000 description 3
- 229920005601 base polymer Polymers 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000004900 laundering Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 238000005201 scrubbing Methods 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- VGVHNLRUAMRIEW-UHFFFAOYSA-N 4-methylcyclohexan-1-one Chemical compound CC1CCC(=O)CC1 VGVHNLRUAMRIEW-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 229920000137 polyphosphoric acid Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 2
- VUXREKGMWHNSLD-UHFFFAOYSA-N 1,3-thiazole;urea Chemical compound NC(N)=O.C1=CSC=N1 VUXREKGMWHNSLD-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical class [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- MQWCXKGKQLNYQG-UHFFFAOYSA-N methyl cyclohexan-4-ol Natural products CC1CCC(O)CC1 MQWCXKGKQLNYQG-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
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Abstract
The disclosed polybibenzothiazoleurea with aliphatic side group shown as following is polycondensed by the diaminophenothiazine with aliphatic side group and diisocyanate, and can be used as new polymer material with well solubility and thermal stability.
Description
Technical field:
The present invention relates to base polymer and preparation method thereof, poly-bisbenzothiazole-urea of particularly fatty family side group 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, 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: disclosed polyphenylene benzo dithiazole (PBZT) among the U.S. Pat Patent 4225700, 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 methylsulphonic acid (MSA), polyphosphoric acid (PPA), 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.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.And the polyureas polymkeric substance has many-sided premium propertiess such as good film-forming properties, but thermostability is relatively poor.People such as Unishi T has reported the preparation of polyimide-urea in Journal of Applied PolymerScience 1999,74,1719, finds that it is strong rigidity of a class and the base polymer with outstanding solubility property.
Summary of the invention:
The present invention is from Molecular Structure Design and point of practical use, the replacement diamino benzo thiazole that will contain alicyclic side group, after a series of diisocyanate resin polycondensations, a series of good solvabilities that have have been prepared, the poly-bisbenzothiazole-ureas polymkeric substance of the fatty family side group of thermostability and mechanical property.
The segment repeated structural unit of poly-two and thiazole-urea of the fatty family of the present invention side group is shown below:
Wherein the scope of n value is between 40-85;
X is
Or
Y is
Or
Wherein have poly-22,2 '-Ya hexichol, two urea groups-6,6 '-cyclohexyl benzo thiazole, poly-22,2 '-methylbenzene-(2,4) urea groups-6-two, 6 '-cyclohexyl benzo thiazole, poly-22,2 '-isophorone, two urea groups-6,6 '-cyclohexyl benzo thiazole, poly-22,2 '-oneself two urea groups-6,6 '-cyclohexyl benzo thiazole, poly-22,2 '-Ya hexichol, two urea groups-6,6 '-(4-methyl) cyclohexyl benzo thiazole, poly-22,2 '-methylbenzene-(2,4) urea groups-6-two, 6 '-(4-methyl) cyclohexyl benzo thiazole, gather 22,2 '-isophorone, two urea groups-6,6 '-(4-methyl) cyclohexyl benzo thiazole, poly-22,2 '-oneself two urea groups-6,6 '-(4-methyl) cyclohexyl benzo thiazole, gather 22,2 '-Ya hexichol, two urea groups-6,6 '-(the 4-tertiary butyl) cyclohexyl benzo thiazole, poly-22,2 '-methylbenzene-(2,4)-two urea groups-6,6 '-(the 4-tertiary butyl) cyclohexyl benzo thiazole, poly-22,2 '-isophorone, two urea groups-6,6 '-(the 4-tertiary butyl) cyclohexyl benzo thiazole, poly-22,2 '-oneself two urea groups-6,6 '-(the 4-tertiary butyl) cyclohexyl benzo thiazole.
Poly-bisbenzothiazole-the urea of the fatty family of the present invention side group is to be that the starting raw material polycondensation prepares with replacement diamino benzo thiazole that contains alicyclic side group and diisocyanate resin, and its polyreaction equation can be expressed as follows:
The concrete preparation method of the poly-bisbenzothiazole-urea of the fatty family of the present invention side group is as follows:
Be equipped with under mechanical stirring and the protection of inert gas; in three-necked flask, add the replacement diamino benzo thiazole that contains alicyclic side group; make it be dissolved in the anhydrous polar organic solvent of new distillatory; join in the three-necked flask vulcabond is disposable; containing the replacement diamino benzo thiazole of alicyclic side group and the mol ratio of vulcabond is 1: 1; the mass percentage concentration that contains the replacement diamino benzo thiazole of alicyclic side group and vulcabond in the solution is at 15～30wt%; 20～40 ℃ of vigorous stirring reactions 1～3 hour; progressively be warming up to 60～80 ℃, stirring reaction 5～12 hours.Reaction solution is poured in the big water gaging, be settled out fibrous white solid, washing is filtered, and solid filters with methanol eddy 3-6 hour, and drying obtains the poly-bisbenzothiazole-urea of fatty family side group.
The rare gas element that the present invention uses is selected from a kind of in nitrogen or the argon gas.
The replacement diamino benzo thiazole that contains alicyclic side group that the present invention uses is selected from 1,1-two (2-aminobenzothiazole base) hexanaphthene, 1,1-two (2-aminobenzothiazole base)-4-methylcyclohexane or 1, a kind of in 1-two (2-aminobenzothiazole base)-4-tertiary butyl hexanaphthene.
The vulcabond that the present invention uses is selected from inferior hexichol-4,4 '-vulcabond, Toluene-2,4-diisocyanate, a kind of in 4-vulcabond, isophorone diisocyanate or the hexamethylene diisocyanate.
The polar organic solvent that the present invention uses is selected from 1-Methyl-2-Pyrrolidone, N, N '-dimethyl formamide or N, a kind of in N '-N,N-DIMETHYLACETAMIDE.
The concrete preparation method of the replacement diamino benzo thiazole that contains alicyclic side group that uses among the present invention is as follows:
(a) under protection of inert gas, mechanical stirring condition, aniline and hydrochloric acid are added in the reactor, wherein the mol ratio of aniline and strong acid is 1: 1～1: 8; Or with in aniline and the anilinechloride adding reactor, 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 ℃, solution is cooled to room temperature, in reaction soln, add alkali lye to pH=10, oil reservoir is separated, and wash to neutrality dry filter with water, excessive aniline is removed in underpressure distillation, obtains containing the aromatic diamines of cycloaliphatic big lateral base behind the crude product recrystallization;
(b) at rare gas element, under the mechanical 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, in mechanical stirring, under the ice bath refrigerative condition, 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 replacement diamino benzo thiazole monomer of alicyclic side group behind the crude product recrystallization.
Contain the alkali that uses among the replacement diamino benzo thiazole preparation method of alicyclic side group and be selected from a kind of in sodium hydroxide, potassium hydroxide, yellow soda ash, sodium bicarbonate, salt of wormwood or the saleratus, the alicyclic carbonyl compound of use is selected from a kind of in pimelinketone, 4-methylcyclohexanone or the 4-tertiary butyl pimelinketone.
The present invention is from Molecular Structure Design and point of practical use, to contain the replacement diamino benzo thiazole and the diisocyanate resin polycondensation of alicyclic side group, prepared a series of high comprehensive performances and the poly-bisbenzothiazole-ureas polymer materials of good deliquescent fatty family side group has been arranged, they dissolve except being dissolved in the strong protonic acids such as methylsulphonic acid, and the great majority in them can both be dissolved in various organic solvents such as 1-methyl 2-Pyrrolidone fully, N, dinethylformamide, N, the N-N,N-DIMETHYLACETAMIDE, methyl-sulphoxide etc., heat decomposition temperature in nitrogen is greater than 300 ℃, X-ray diffraction shows that all polymkeric substance are amorphous state, have good film forming properties, tensile strength is greater than 70MP.
Description of drawings:
Fig. 1 is that example 2 gathers 22,2 '-Ya hexichol, two urea groups-6, the infrared spectra of 6 '-cyclohexyl benzo thiazole.
Fig. 2 is that example 2 gathers 22,2 '-Ya hexichol, two urea groups-6, the proton nmr spectra of 6 '-cyclohexyl benzo thiazole.
Fig. 3 is that example 3 gathers 22,2 '-methylbenzene-(2,4)-two urea groups-6, the infrared spectra of 6 '-cyclohexyl benzo thiazole.
Fig. 4 is that example 3 gathers 22,2 '-methylbenzene-(2,4)-two urea groups-6, the proton nmr spectra of 6 '-cyclohexyl benzo thiazole.
Fig. 5 is that example 2 gathers 22,2 '-Ya hexichol, two urea groups-6, the thermogravimetric analysis figure of 6 '-cyclohexyl benzo thiazole.
Embodiment:
The following examples are to further specify of the present invention, rather than limit the scope of the invention.
Example 1:1, the preparation of 1-two (2-aminobenzothiazole base) hexanaphthene
(a) with 37.3g (0.4mol) aniline, 37mL of 35wt%HCl solution joins magnetic agitation is housed, in the three-necked flask of nitrogen gangway and reflux condensing tube, 60 ℃ of following stirring and dissolving.Solution clarification back drips 9.8g (0.1mol) pimelinketone.Mixture was 120 ℃ of reactions 24 hours.Solution is cooled to room temperature, and the sodium hydroxide solution of adding 10% is to pH=10, and the organic layer separation also washes with water to neutrality.Anhydrous magnesium sulfate drying, underpressure distillation are removed excessive aniline, and crude product gets 1 with the toluene recrystallization, 1-two (4-aminophenyl) hexanaphthene 22.1g (productive rate 83.1%).
(b) with 26.6g (0.1mol) 1,1-two ((4-amino) phenyl) hexanaphthene, the 398mL Glacial acetic acid joins in the three-necked flask that mechanical stirring, nitrogen inlet and dropping funnel are housed, and adds 48.5g (0.51mol) potassium sulfocyanate after the stirring and dissolving.In the ice bath cooling, under the churned mechanically condition, drip the 10mL glacial acetic acid solution of 38.4g (0.24mol) bromine.There is the orange solid to produce in the dropping process.The mixture stirring at room adds 330mL water after 12 hours, mixture heating up refluxed 2 hours, was cooled to the room temperature after-filtration.Filtrate is poured in the big water gaging, filters and collects light yellow solid.Crude product 200mL ammonia scrubbing washes with water to neutrality again, and product gets 24.2g1,1-two (2-aminobenzothiazole base) hexanaphthene after using the tetrahydrofuran (THF) recrystallization.
Example 2: poly-22,2 '-Ya hexichol, two urea groups-6, the preparation of 6 '-cyclohexyl benzo thiazole is with 1g (2.63mmol) 1,1-two (2-aminobenzothiazole base) hexanaphthene and the new distillatory 1-Methyl-2-Pyrrolidone of 6.6mL (NMP) join in the three-necked flask that mechanical stirring, nitrogen inlet are housed, and stirring at room is to dissolving.Under argon shield, once add 0.658g (2.63mmol) diphenylmethanediisocyanate, 25 ℃ of vigorous stirring 1 hour, viscosity rises gradually, slowly is warming up to 60 ℃, stirs 5 hours, and this moment, viscosity substantially no longer rose.Viscous solution is poured in the big water gaging, white fiber shape sedimentation and filtration, and wash with massive laundering, methanol eddy 5 hours filters, and 120 ℃ of dryings are 2 days in vacuum drying oven, obtain gathering 22,2 '-Ya hexichol, two urea groups-6,6 '-cyclohexyl benzo thiazole 1.554g (productive rate 93.7%).Fig. 1 represents to gather 22,2 '-Ya hexichol, two urea groups-6, the infrared spectra IR (KBr) of 6 '-cyclohexyl benzo thiazole: 3189-3268,1604,1536 (O=CNH), 2859,2932
1705 (C=O), 1598 (C=N).Fig. 2 represents to gather 22,2 '-Ya hexichol, two urea groups-6, the proton nmr spectra of 6 '-cyclohexyl benzo thiazole
1H NMR (DMSO-d): δ (ppm)=1.47,2.31 (brm, 10H, hexanaphthene), 7.07-7.48 (m, 14H, phenyl ring), 7.90-10.63 (m, NH).Molecular weight is measured as 47000gmol by viscosimetry
-1Polymkeric substance can be dissolved in methylsulphonic acid, 1-methyl 2-Pyrrolidone, N, and dinethylformamide, N,N-dimethylacetamide, methyl-sulphoxide, heat decomposition temperature are 345 ℃, tensile strength 82MP.
Example 3: poly-22,2 '-methylbenzene-(2,4) urea groups-6-two, the preparation of 6 '-cyclohexyl benzo thiazole is with 1g (2.63mmol) 1,1-two (2-aminobenzothiazole base) hexanaphthene and the new distillatory N of 5.5mL, N '-N,N-DIMETHYLACETAMIDE (DMAc) joins in the three-necked flask that mechanical stirring, argon gas inlet are housed, and stirring at room is to dissolving.Under nitrogen protection, once add 0.458g (2.63mmol) Toluene-2,4-diisocyanate, the 4-vulcabond, 35 ℃ of vigorous stirring 1 hour, viscosity rises gradually, slowly is warming up to 60 ℃, stirs 6 hours, and this moment, viscosity substantially no longer rose.Viscous solution is poured in the big water gaging, white fiber shape sedimentation and filtration, and wash methanol eddy 4 hours with massive laundering, filter, 120 ℃ of dryings are 2 days in vacuum drying oven, obtain poly-22,2 '-methylbenzene-(2,4)-two urea groups-6,6 '-cyclohexyl benzo thiazole 1.329g (productive rate 91.2%).Fig. 3 represents to gather 22,2 '-methylbenzene-(2,4)-two urea groups-6, the infrared spectra IR (KBr) of 6 '-cyclohexyl benzo thiazole: 3323-3363,1537 (O=CNH), 2859,2932
1693 (C=O), 1598 (C=N).Fig. 4 represents to gather 22,2 '-methylbenzene-(2,4)-two urea groups-6, the proton nmr spectra of 6 '-cyclohexyl benzo thiazole
1H NMR (DMSO-d): δ (ppm)=1.47,2.34 (br m, 10H, hexanaphthene), 2.19 (s, 3H, CH
3), 7.13-7.90 (m, 14H, phenyl ring), (m, NH) molecular weight is measured as 38000gmol by viscosimetry to 8.02-11.05
-1Polymkeric substance can be dissolved in methylsulphonic acid, 1-methyl 2-Pyrrolidone, N, and dinethylformamide, N,N-dimethylacetamide, methyl-sulphoxide, heat decomposition temperature are 326 ℃, tensile strength 76MP.
Example 4:1, the preparation of 1-two (2-aminobenzothiazole base)-4-tertiary butyl hexamethylene
(a) with 15.4g (0.1mol) 4-tertiary butyl pimelinketone, 51.8g (0.4mol) anilinechloride and 102.3g (1.1mol) aniline joins in the three-necked flask of magnetic agitation, nitrogen inlet, mixture was 140 ℃ of stirring and refluxing 36 hours, solution is cooled to room temperature, the potassium hydroxide solution that adds 10wt% is to pH=10, mixture refluxed 10 minutes, and organic layer separates and washes with water to neutrality.Anhydrous magnesium sulfate drying, underpressure distillation are removed excessive aniline, and crude product gets 1 with the benzene recrystallization, 1-two (4-aminophenyl)-4-tertiary butyl hexanaphthene 20.6g (productive rate 63.9%).
(b) with 16.1g (0.05mol) 1,1-two (4-aminophenyl)-4-tertiary butyl hexanaphthene, the 240mL Glacial acetic acid joins in the three-necked flask that mechanical stirring, nitrogen inlet and dropping funnel are housed, and adds 29.1g (0.3mol) potassium sulfocyanate after the stirring and dissolving.In the ice bath cooling, under the churned mechanically condition, drip the 5mL glacial acetic acid solution of 19.2g (0.12mol) bromine.There is the orange solid to produce in the dropping process.The mixture stirring at room adds 170mL water after 12 hours, mixture heating up refluxed 4 hours, is cooled to room temperature and filters.Filtrate is poured in the big water gaging, filters and collects white solid.Crude product 120mL ammonia scrubbing washes with water to neutrality again, and product gets 15.7g 1,1-two (2-aminobenzothiazole base)-4-tertiary butyl hexanaphthene after using the tetrahydrofuran (THF) recrystallization.
Example 5: poly-22,2 '-methylbenzene. (2,4) urea groups-6-two, the preparation of 6 '-cyclohexyl benzo thiazole is with 1g (2.29mmol) 1,1-two (2-aminobenzothiazole base)-4-tertiary butyl hexanaphthene and the new distillatory 1-Methyl-2-Pyrrolidone of 5.0mL (NMP) join in the three-necked flask that mechanical stirring, nitrogen inlet are housed, and stirring at room is to dissolving.Under argon shield, once add 0.509g (2.29mmol) isophorone-vulcabond, 40 ℃ of vigorous stirring 2 hours, viscosity rises gradually, slowly is warming up to 80 ℃, stirs 8 hours, and this moment, viscosity substantially no longer rose.Viscous solution is poured in the big water gaging, white fiber shape sedimentation and filtration, and wash with massive laundering, methanol eddy 5 hours, filter, 120 ℃ of dryings are 2 days in vacuum drying oven, obtain poly-22,2 '-isophorone, two urea groups-6,6 '-(the 4-tertiary butyl) cyclohexyl benzo thiazole 1.360g (productive rate 90.1%).Gather 22,2 '-methylbenzene-(2,4)-two urea groups-6, the infrared spectra IR (KBr) of 6 '-cyclohexyl benzo thiazole: 3328-3367,1630,1540 (O=CNH), 2933,2860
1593 (C=N), 1463 (CH
3).Gather 22,2 '-methylbenzene-(2,4)-two urea groups-6, the proton nmr spectra of 6 '-cyclohexyl benzo thiazole
1H NMR (DMSO-d): δ (ppm)=0.92 (s, 3H, CH
3), 0.99 (s, 3H, CH
3), 1.00-1.86 (m, 6H, hexanaphthene), 3.15 (s, 2H, CH
2), 3.84 (m, 1H, hexanaphthenes), 7.09-7.61 (m, 6H, phenyl ring).Molecular weight is measured as 27000gmol by viscosimetry
-1Polymkeric substance can be dissolved in methylsulphonic acid, 1-methyl 2-Pyrrolidone, N, and dinethylformamide, N,N-dimethylacetamide, methyl-sulphoxide, heat decomposition temperature are 311 ℃, tensile strength 72MP.
Claims (6)
1. the poly-bisbenzothiazole-urea of fatty family side group is characterized in that the segment repeated structural unit is:
Wherein the scope of n value is between 40-85;
X is
Or
Y is
Or
Wherein have poly-22,2 '-Ya hexichol, two urea groups-6,6 '-cyclohexyl benzo thiazole, poly-22,2 '-methylbenzene-(2,4) urea groups-6-two, 6 '-cyclohexyl benzo thiazole, poly-22,2 '-isophorone, two urea groups-6,6 '-cyclohexyl benzo thiazole, poly-22,2 '-oneself two urea groups-6,6 '-cyclohexyl benzo thiazole, poly-22,2 '-Ya hexichol, two urea groups-6,6 '-(4-methyl) cyclohexyl benzo thiazole, poly-22,2 '-methylbenzene-(2,4) urea groups-6-two, 6 '-(4-methyl) cyclohexyl benzo thiazole, gather 22,2 '-isophorone, two urea groups-6,6 '-(4-methyl) cyclohexyl benzo thiazole, poly-22,2 '-oneself two urea groups-6,6 '-(4-methyl) cyclohexyl benzo thiazole, gather 22,2 '-Ya hexichol, two urea groups-6,6 '-(the 4-tertiary butyl) cyclohexyl benzo thiazole, poly-22,2 '-methylbenzene-(2,4)-two urea groups-6,6 '-(the 4-tertiary butyl) cyclohexyl benzo thiazole, poly-22,2 '-isophorone, two urea groups-6,6 '-(the 4-tertiary butyl) cyclohexyl benzo thiazole or poly-22,2 '-oneself two urea groups-6,6 '-(the 4-tertiary butyl) cyclohexyl benzo thiazole.
2. the preparation method of the poly-bisbenzothiazole-urea of fatty according to claim 1 family side group is characterized in that the preparation method is as follows:
Be equipped with under mechanical stirring and the protection of inert gas; in three-necked flask, add the replacement diamino benzo thiazole that contains alicyclic side group; make it be dissolved in the anhydrous polar organic solvent of new distillatory; join in the three-necked flask vulcabond is disposable; containing the replacement diamino benzo thiazole of alicyclic side group and the mol ratio of vulcabond is 1: 1; the mass percentage concentration that contains the replacement diamino benzo thiazole of alicyclic side group and vulcabond in the solution is at 15～30wt%; 20～40 ℃ of vigorous stirring reactions 1～3 hour; progressively be warming up to 60～80 ℃, stirring reaction 5～12 hours.Reaction solution is poured in the big water gaging, be settled out fibrous white solid, washing is filtered, and solid filters with methanol eddy 3-6 hour, and drying obtains the poly-bisbenzothiazole-urea of fatty family side group.
3. the preparation method of the poly-bisbenzothiazole-urea of fatty family according to claim 2 side group is characterized in that rare gas element is selected from a kind of in nitrogen or the argon gas.
4. the preparation method of the poly-bisbenzothiazole-urea of fatty family according to claim 2 side group, it is characterized in that the replacement diamino benzo thiazole that contains alicyclic side group is selected from 1,1-two (2-aminobenzothiazole base) hexanaphthene, 1,1-two (2-aminobenzothiazole base)-4-methylcyclohexane or 1, a kind of in 1-two (2-aminobenzothiazole base)-4-tertiary butyl hexanaphthene.
5. the preparation method of the poly-bisbenzothiazole-urea of fatty family according to claim 2 side group, it is characterized in that vulcabond is selected from diphenylmethanediisocyanate, Toluene-2,4-diisocyanate, a kind of in 4-vulcabond, isoflurane chalcone diisocyanate or the hexa-methylene isocyanic ester.
6. the preparation method of the poly-bisbenzothiazole-urea of fatty family according to claim 2 side group is characterized in that polar organic solvent is selected from 1-Methyl-2-Pyrrolidone, N, N '-dimethyl formamide or N, a kind of in N '-N,N-DIMETHYLACETAMIDE.
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| JPS60243126A (en) * | 1984-05-18 | 1985-12-03 | Asahi Chem Ind Co Ltd | Process for polymerizing polybenzobisthiazole |
| US4608427A (en) * | 1985-06-20 | 1986-08-26 | E. I. Du Pont De Nemours And Company | Method for making PBO and PBT polymers |
| CN1683348A (en) * | 2005-03-17 | 2005-10-19 | 上海交通大学 | Aminobenzothiazole monomer containing alicyclic macro side group and its preparing method |
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