CN1935783B - A synthetic method of 3,3'-dimethyl-4, 4'-biphenyl diisocyanate - Google Patents
A synthetic method of 3,3'-dimethyl-4, 4'-biphenyl diisocyanate Download PDFInfo
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- CN1935783B CN1935783B CN200510060910XA CN200510060910A CN1935783B CN 1935783 B CN1935783 B CN 1935783B CN 200510060910X A CN200510060910X A CN 200510060910XA CN 200510060910 A CN200510060910 A CN 200510060910A CN 1935783 B CN1935783 B CN 1935783B
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- trichloromethyl
- benzidine
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- 238000010189 synthetic method Methods 0.000 title claims description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
- 239000007788 liquid Substances 0.000 claims abstract description 40
- NUIURNJTPRWVAP-UHFFFAOYSA-N 3,3'-Dimethylbenzidine Chemical compound C1=C(N)C(C)=CC(C=2C=C(C)C(N)=CC=2)=C1 NUIURNJTPRWVAP-UHFFFAOYSA-N 0.000 claims abstract description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 claims description 43
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 34
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 23
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 16
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 claims description 16
- 238000010992 reflux Methods 0.000 claims description 15
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 10
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- 230000000630 rising effect Effects 0.000 claims description 7
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- FZXRXKLUIMKDEL-UHFFFAOYSA-N 2-Methylpropyl propanoate Chemical compound CCC(=O)OCC(C)C FZXRXKLUIMKDEL-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims description 4
- PPXUHEORWJQRHJ-UHFFFAOYSA-N ethyl isovalerate Chemical compound CCOC(=O)CC(C)C PPXUHEORWJQRHJ-UHFFFAOYSA-N 0.000 claims description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 4
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- 238000002156 mixing Methods 0.000 claims description 4
- PGMYKACGEOXYJE-UHFFFAOYSA-N pentyl acetate Chemical compound CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical group CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- ZPQOPVIELGIULI-UHFFFAOYSA-N 1,3-dichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1 ZPQOPVIELGIULI-UHFFFAOYSA-N 0.000 claims description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 2
- HFZLSTDPRQSZCQ-UHFFFAOYSA-N 1-pyrrolidin-3-ylpyrrolidine Chemical compound C1CCCN1C1CNCC1 HFZLSTDPRQSZCQ-UHFFFAOYSA-N 0.000 claims description 2
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 claims description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 2
- YEJCDKJIEMIWRQ-UHFFFAOYSA-N Linopirdine Chemical compound O=C1N(C=2C=CC=CC=2)C2=CC=CC=C2C1(CC=1C=CN=CC=1)CC1=CC=NC=C1 YEJCDKJIEMIWRQ-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- CMEWLCATCRTSGF-UHFFFAOYSA-N N,N-dimethyl-4-nitrosoaniline Chemical compound CN(C)C1=CC=C(N=O)C=C1 CMEWLCATCRTSGF-UHFFFAOYSA-N 0.000 claims description 2
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- IPBVNPXQWQGGJP-UHFFFAOYSA-N acetic acid phenyl ester Natural products CC(=O)OC1=CC=CC=C1 IPBVNPXQWQGGJP-UHFFFAOYSA-N 0.000 claims description 2
- 229940043232 butyl acetate Drugs 0.000 claims description 2
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 claims description 2
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 claims description 2
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 claims description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 2
- 150000007530 organic bases Chemical class 0.000 claims description 2
- 229940049953 phenylacetate Drugs 0.000 claims description 2
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 claims description 2
- 229940090181 propyl acetate Drugs 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 2
- 230000037452 priming Effects 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 10
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000007787 solid Substances 0.000 abstract description 3
- 239000013078 crystal Substances 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract 2
- UCPYLLCMEDAXFR-UHFFFAOYSA-N triphosgene Chemical compound ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl UCPYLLCMEDAXFR-UHFFFAOYSA-N 0.000 abstract 2
- 150000002170 ethers Chemical class 0.000 description 10
- 150000008422 chlorobenzenes Chemical class 0.000 description 6
- LAYPMCGIWDGYKX-UHFFFAOYSA-N trichloromethyl hydrogen carbonate Chemical compound OC(=O)OC(Cl)(Cl)Cl LAYPMCGIWDGYKX-UHFFFAOYSA-N 0.000 description 6
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 5
- 150000004818 1,2-dichlorobenzenes Chemical class 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 238000009423 ventilation Methods 0.000 description 2
- YRSOHTBCCGDLSN-UHFFFAOYSA-N 4-(4-amino-3-methylphenyl)-2-methylaniline;hydron;chloride Chemical compound Cl.C1=C(N)C(C)=CC(C=2C=C(C)C(N)=CC=2)=C1 YRSOHTBCCGDLSN-UHFFFAOYSA-N 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
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- 230000007613 environmental effect Effects 0.000 description 1
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- 150000008282 halocarbons Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
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- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000011495 polyisocyanurate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
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- 231100000004 severe toxicity Toxicity 0.000 description 1
- -1 tetracol phenixin Chemical compound 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention is a 3,3'-dimethyl-4,4'-biphenyldiisocyanate synthesizing method, belonging to organic synthesis preparing process field, using 3,3'-dimethyl-4,4'-biphenyldiamine or its hydrochloride to react with bis(trichloromethyl)carbonate in inert liquid medium so as to synthesize 3,3'-dimethyl-4,4'-biphenyldiisocyanate, where the charged weight of bis(trichloromethyl) carbonate is 0.5-10 times as large as that of 3,3'-dimethyl- 4,4'- biphenyldiamine or its hydrochloride, and the synthesis temperature is -10DEG C-200DEG C. And the raw materials are stable solid crystals at normal temperature, convenient to storage and transport, safe in use and environment-friendly. And the synthesizing method accurately calculates the reaction and reduces consumption of raw materials; the operating process is simple and easy to control, the operation is low-cost and suitable for industrialized production.
Description
Technical field
The invention belongs to organic synthesis fabricating technology field, be specifically related to 3,3 '-dimethyl-4, the synthetic method of 4 '-biphenyl diisocyanate particularly uses 3,3 '-dimethyl-4,4 '-benzidine or its hydrochloride and two (trichloromethyl) carbonate reaction, synthesize 3,3 '-dimethyl-4, the method for 4 '-biphenyl diisocyanate.
Background technology
As everyone knows, 3,3 '-dimethyl-4,4 '-biphenyl diisocyanate is a kind of important vulcabond, is used to produce the raw material of materials such as polyurethanes, polyureas, polyurethane class, poly-isocyanurate class in industry such as coating, resin.
The phosgenation processes of prepared in reaction isocyanic ester in inert solvent is well known with organic primary amine and phosgene.3,3 '-dimethyl-4,4 '-biphenyl diisocyanate can be with 3,3 '-dimethyl-4,4 '-benzidine and phosgene reaction synthesize and prepare, though the light phosgenation technology maturation but need be used the phosgene of excessive severe toxicity.Phosgene all has bigger danger in preparation, accumulating and use, operation, facilities and administration are required high, and serious to environmental influence, potential safety hazard is big, the aftertreatment complexity.
Summary of the invention
In order to overcome existing 3,3 '-dimethyl-4,4 '-biphenyl diisocyanate synthesis technique complexity, the shortcoming that environmental pollution is big, the purpose of this invention is to provide a kind of reaction conditions gentleness, easy to control, simple to operate, production cost is low and can realize clean produce 3,3 '-dimethyl-4, the synthetic method of 4 '-biphenyl diisocyanate.
The technical solution adopted for the present invention to solve the technical problems is:
3,3 '-dimethyl-4,4 '-benzidine or its hydrochloride and two (trichloromethyl) carbonic ether react in inert liquid medium and synthesize 3,3 '-dimethyl-4,4 '-biphenyl diisocyanate.
Building-up reactions equation of the present invention is as follows:
According to method of the present invention employed two (trichloromethyl) carbonic ether is solid at normal temperatures, uses very conveniently, and reaction conditions is gentle and easy to control.
The charging capacity of two (trichloromethyl) carbonic ether is 3 by weight, 3 '-dimethyl-4, and 4 '-benzidine or its hydrochloride 0.5～10 times, comparatively suitable is 3,3 '-dimethyl-4,1～5 times of the weight of 4 '-benzidine or its salt.Synthesis reaction temperature is-10 ℃～200 ℃.The consumption of two (trichloromethyl) carbonic ether by weight.
3,3 '-dimethyl-4,4 '-benzidine can directly be used as and two (trichloromethyl) carbonate reaction as raw material, also can be with 3,3 '-dimethyl-4,4 '-benzidine and hydrogen chloride gas precursor reactant obtain 3,3 '-dimethyl-4,4 '-biphenyl diisocyanate with two (trichloromethyl) carbonate reactions after forming hydrochloride again.When 3,3 '-dimethyl-4,4 '-benzidine directly as the reaction raw material the time, in reaction process, also part is converted into hydrochloride, and then with two (trichloromethyl) carbonate reaction, generate corresponding vulcabond.
3,3 '-dimethyl-4, the hydrochloride of 4 '-benzidine also can be by 3,3 '-dimethyl-4, and the manufacturer of 4 '-benzidine directly provides.
Described 3,3 '-dimethyl-4, the synthetic method of 4 '-biphenyl diisocyanate, 3,3 '-dimethyl-4,4 '-benzidine are during directly as raw material, and its synthesis technique step is as follows:
Processing step is as follows:
(1) preparation 3,3 '-dimethyl-4, the inert liquid medium solution of 4 '-benzidine, inert liquid medium consumption are 3,3 '-dimethyl-4,5～40 times of 4 '-benzidine quality; The inert liquid medium solution of preparation two (trichloromethyl) carbonic ether, the inert liquid medium consumption is 0.5～20 times of two (trichloromethyl) carbonic ether quality, the consumption of two (trichloromethyl) carbonic ether is calculated by weight to 3,3 '-dimethyl-4,0.5～10 times of 4 '-benzidine.
(2) 3,3 '-dimethyl-4 under-10 ℃～100 ℃, the inert liquid medium drips of solution of 4 '-benzidine is added in the inert liquid medium solution of two (trichloromethyl) carbonic ether, stirs;
(3) dropwise temperature rising reflux reaction 0.5～5 hour;
(4) remove by filter insolubles, inert liquid medium is reclaimed in distillation, gets 3,3 '-dimethyl-4,4 '-biphenyl diisocyanate.
Synthetic method of the present invention, when with 3,3 '-dimethyl-4,4 '-benzidine hydrochloride be raw material and two (trichloromethyl) carbonate reaction the time, concrete processing step is as follows:
(1) with 3,3 '-dimethyl-4,4 '-benzidine is a raw material, 3, and 3 '-dimethyl-4, feed hydrogen chloride gas in the inert liquid medium solution of 4 '-benzidine, 60 ℃～130 ℃ of holding temperatures were reacted 1～4 hour, and the inert liquid medium consumption is 3,3 '-dimethyl-4,5～40 times of 4 '-benzidine quality;
(2) the inert liquid medium solution of preparation two (trichloromethyl) carbonic ether, the inert liquid medium consumption is 0.5～20 times of two (trichloromethyl) carbonic ether quality, under-10 ℃～160 ℃, be added drop-wise in the above-mentioned steps reaction solution, stir, the consumption of two (trichloromethyl) carbonic ether is calculated by weight to 3,3 '-dimethyl-4,0.5～10 times of 4 '-benzidine;
(3) dropwised back flow reaction 1～5 hour;
(4) remove by filter insolubles, distillating recovering solvent gets 3,3 '-dimethyl-4,4 '-biphenyl diisocyanate.
According to of the present invention 3,3 '-dimethyl-4, the synthetic method of 4 '-biphenyl diisocyanate adds carrying out fast that suitable catalyzer can promote to react.With suitable catalyzer two (trichloromethyl) carbonic ether is suitably activated, can also reduce the consumption of two (trichloromethyl) carbonic ether, industrial more economical.
Catalyzer is the material that can cause that under reaction conditions two (trichloromethyl) carbonate moiety decomposes, as has atlapulgite, the gac of many hollow structures; Organic bases, as Trimethylamine 99, triethylamine, N, accelerine, N, N-Diethyl Aniline, pyridine, dimethyl formamide, N,N-DIMETHYLACETAMIDE etc.Comparatively the addition of appropriate catalyst is 0%～10% of two (trichloromethyl) carbonic ether weight.
Described inert liquid medium consumption is 3,3 '-dimethyl-4,5～40 times of 4 '-benzidine quality, comparatively preferred 5～15 times; The inert liquid medium solution of preparation two (trichloromethyl) carbonic ether, the inert liquid medium consumption is 0.5～20 times of two (trichloromethyl) carbonic ether quality, comparatively preferred 1～5 times; The consumption of inert liquid medium is low excessively, and reaction mixture is difficult to fully mix, thereby reaction yield is reduced; And consumption is excessive, and then equipment efficiency of usage is low, and energy consumption is big, and is industrial uneconomical.
Of the present invention 3,3 '-dimethyl-4, in the synthetic method of 4 '-biphenyl diisocyanate, used inert liquid medium be meant under temperature of reaction, be in a liquid state and under reaction conditions not with 3,3 '-dimethyl-4,4 '-benzidine, 3,3 '-dimethyl-4, the organic solvent of 4 '-biphenyl diisocyanate, two (trichloromethyl) carbonic ether, hcl reaction.Specifically comprise hydro carbons, as: sherwood oil, cyclohexane, normal hexane, xylol, o-Xylol, m-xylene, p-Xylol, toluene, benzene etc.; Halogenated hydrocarbons, as: 1,2-ethylene dichloride, tetracol phenixin, chlorobenzene, orthodichlorobenzene, Meta Dichlorobenzene, santochlor, bromobenzene etc.; The ester class, as: ethyl acetate, propyl acetate, pentyl acetate, Isoamyl Acetate FCC, butylacetate, isobutyl acetate, phenylacetate, ethyl propionate, propyl propionate, amyl propionate, isoamyl propionate, butyl propionate, isobutyl propionate, pentyl formate, Ethylisovalerate etc.; Ethers, as: dibutyl ether, tetrahydrofuran (THF), glycol dimethyl ether, methyl-phenoxide etc.; Ketone, as: acetone, butanone, cyclohexanone etc.These media can use separately or several mixing is used, and from reclaiming the angle of using again, preferably use separately certainly.Wherein preferential especially use is dimethylbenzene, chlorobenzene, orthodichlorobenzene, Isoamyl Acetate FCC etc.
With existing 3,3 '-dimethyl-4, the synthetic method of 4 '-biphenyl diisocyanate is compared, and beneficial effect of the present invention is as follows:
1, the present invention uses raw material two (trichloromethyl) carbonic ether, and normal temperature is a kind of stable solid crystal body down, is convenient to store and transportation, and is safe in utilization, environmentally friendly;
2, synthetic method reaction accurate measurement of the present invention, raw material consumption reduces;
3, technology is used and has been saved the relevant device that phosgene takes place and uses, and adopts conventional conversion unit to produce, and simple and safe operation process is easy to control, and running cost is low, is suitable for suitability for industrialized production.
Embodiment
The present invention is further illustrated by the following examples
Specific embodiments of the invention are as follows, but the present invention not only is confined in following examples.
Embodiment 1
Be furnished with at one and add 750 milliliters of chlorobenzenes and 50 gram (0.236mol) 3 in reflux exchanger, airway, thermometer, liquid 2000 milliliters of reaction flasks with dropping funnel, efficient agitator, 3 '-dimethyl-4,4 '-benzidine, heated and stirred is even.Feed the exsiccant hydrogen chloride gas by airway, the speed of ventilation is 0.2L/min, and holding temperature is under 60 ℃～130 ℃, reacts to stop ventilation after 2 hours.
Under 80 ℃～130 ℃, drip 300 gram two (trichloromethyl) carbonic ethers and 300 milliliters of solution that chlorobenzene is formed, add the back and continued back flow reaction 3 hours, filter, boil off solvent, obtain 3,3 '-dimethyl-4,4 '-biphenyl diisocyanate, 57.5 grams, yield 92.4%.
Embodiment 2
Be furnished with in reflux exchanger, thermometer, 2000 milliliters of reaction flasks of liquid at one, add 750 milliliters of chlorobenzenes and 65 gram (0.228mol) 3 with dropping funnel, efficient agitator, 3 '-dimethyl-4,4 '-benzidine hydrochloride stirs.
256 gram two (trichloromethyl) carbonic ethers dissolve with 300 milliliters of chlorobenzenes, stir, under 120 ℃～130 ℃, in above-mentioned reaction flask, drip the chlorobenzene solution of two (trichloromethyl) carbonic ether, add the back and continued back flow reaction 3 hours, filter, boil off solvent, obtain 3,3 '-dimethyl-4,4 '-biphenyl diisocyanate, 52.5 grams, yield 87.2%.
Embodiment 3
Be furnished with in reflux exchanger, thermometer, 1000 milliliters of reaction flasks of liquid at one, add 350 milliliters of orthodichlorobenzenes and 35.1 gram (0.123mol) 3 with dropping funnel, efficient agitator, 3 '-dimethyl-4,4 '-benzidine hydrochloride stirs;
280 gram two (trichloromethyl) carbonic ethers dissolve with 300 milliliters of orthodichlorobenzenes, under 150 ℃～160 ℃, in above-mentioned reaction flask, drip the o-dichlorobenzene solution of two (trichloromethyl) carbonic ether, add the back and continued back flow reaction 3 hours, filter, boil off solvent, obtain 3,3 '-dimethyl-4,4 '-biphenyl diisocyanate, 32.1 grams, yield 98.7%.
Embodiment 4
Be furnished with in reflux exchanger, thermometer, 1000 milliliters of reaction flasks of liquid at one, add 350 milliliters of orthodichlorobenzenes and 25 gram two (trichloromethyl) carbonic ethers, stir with dropping funnel, efficient agitator;
42.5 gram (0.2mol) 3,3 '-dimethyl-4,4 '-benzidine dissolves with 300 milliliters of orthodichlorobenzenes;
Under 50 ℃～60 ℃, in above-mentioned reaction flask, drip 3,3 '-dimethyl-4, the o-dichlorobenzene solution of 4 '-benzidine, add back temperature rising reflux reaction 3 hours, filter, boil off solvent, obtain 3,3 '-dimethyl-4,4 '-biphenyl diisocyanate, 24.4 grams, yield 46.2%.
Embodiment 5
Press the same reaction unit among the embodiment 2, add 150 gram two (trichloromethyl) carbonic ethers and 600 milliliters of chlorobenzenes, stirring and dissolving.
50 gram (0.236mol) 3,3 '-dimethyl-4,4 '-benzidine are dissolved in 500 milliliters of chlorobenzenes.Under the vigorous stirring, be added drop-wise in above-mentioned two (trichloromethyl) carbonic ether chlorobenzene solution under keeping 80 ℃～100 ℃.
Add back temperature rising reflux reaction 3 hours, filter, boil off solvent, obtain 3,3 '-dimethyl-4,4 '-biphenyl diisocyanate, 60.6 grams, yield 97.5%.Embodiment 6
Be furnished with in reflux exchanger, thermometer, liquid 5000 milliliters of reaction flasks at one, add 750 gram two (trichloromethyl) carbonic ethers and 2500 milliliter 1,2-ethylene dichloride, stirring and dissolving with dropping funnel, efficient agitator.
212.3 gram (1.0mol) 3,3 '-dimethyl-4,4 '-benzidine are dissolved in 1000 milliliter 1, in the 2-ethylene dichloride.
Under the vigorous stirring, keep-10 ℃～0 ℃ in reaction flask, add 3,3 '-dimethyl-4,1 of 4 '-benzidine, the 2-dichloroethane solution adds back temperature rising reflux reaction 3 hours, filter, boil off solvent, obtain 3,3 '-dimethyl-4,4 '-biphenyl diisocyanate, 249.1 grams, yield 94.3%.
Embodiment 7
Be furnished with in reflux exchanger, thermometer, 5000 milliliters of reaction flasks of liquid at one, add 750 gram two (trichloromethyl) carbonic ethers and 2500 milliliters of Isoamyl Acetate FCCs, stirring and dissolving with dropping funnel, efficient agitator.Under the vigorous stirring, keep 20 ℃～40 ℃ to add 127.4 gram (0.6mol) 3,3 '-dimethyl-4,4 '-benzidine and 1000 milliliters of solution that Isoamyl Acetate FCC is formed add back temperature rising reflux reaction 3 hours, filter, boil off solvent, obtain 3,3 '-dimethyl-4,4 '-biphenyl diisocyanate, 155.5 grams, yield 98.2%.
Embodiment 8
Be furnished with in reflux exchanger, thermometer, 5000 milliliters of reaction flasks of liquid at one, add 250 gram two (trichloromethyl) carbonic ethers and 2500 milliliters of Isoamyl Acetate FCCs, stirring and dissolving with dropping funnel, efficient agitator; Added 15 gram gac stir-activatings 30 minutes.
Under the vigorous stirring, keep 20 ℃～40 ℃ to add 169.8 gram (0.8mol) 3,3 '-dimethyl-4,4 '-benzidine and 1000 milliliters of solution that Isoamyl Acetate FCC is formed.
Add back temperature rising reflux reaction 1 hour, filter, boil off solvent, obtain 3,3 '-dimethyl-4,4 '-biphenyl diisocyanate, 195.6 grams, yield 92.6%
Embodiment 9
Press the same step of example 8, different is not add gac, obtains 3,3 '-dimethyl-4,4 '-biphenyl diisocyanate, 163.5 grams, yield 77.5%
Embodiment 10
Be furnished with at one and add 1000 milliliters of chlorobenzenes and 300 gram two (trichloromethyl) carbonic ethers, stirring and dissolving in reflux exchanger, airway, thermometer, liquid 3000 milliliters of reaction flasks with dropping funnel, efficient agitator.The chlorobenzene solution of 30 ℃ of following Dropwise 50 gram triethylamines (containing triethylamine 10 grams), continue to stir 1 hour, cooling, drip under the vigorous stirring by 212.3 gram (1.0mol) 3,3 '-dimethyl-4,4 '-benzidine and 1200 milliliters of solution that chlorobenzene is formed add the back and continued stirring reaction 30 minutes, are warmed up to 130 ℃～135 ℃ reactions 1 hour.
Filter, boil off solvent, obtain 3,3 '-dimethyl-4,4 '-biphenyl diisocyanate, 245.3 grams, yield 92.9%.
Claims (9)
1. one kind 3,3 '-dimethyl-4, the synthetic method of 4 '-biphenyl diisocyanate is characterized in that processing step is as follows:
(1) preparation 3,3 '-dimethyl-4, the inert liquid medium solution of 4 '-benzidine, inert liquid medium consumption are 3,3 '-dimethyl-4,5～40 times of 4 '-benzidine quality; The inert liquid medium solution of preparation two (trichloromethyl) carbonic ether, the inert liquid medium consumption is 0.5～20 times of two (trichloromethyl) carbonic ether quality, the consumption of two (trichloromethyl) carbonic ether is calculated by weight to 3,3 '-dimethyl-4,0.5～10 times of 4 '-benzidine;
(2) 3,3 '-dimethyl-4 under-10 ℃～100 ℃, the inert liquid medium drips of solution of 4 '-benzidine is added in the inert liquid medium solution of two (trichloromethyl) carbonic ether, stirs;
(3) dropwise temperature rising reflux reaction 0.5～5 hour;
(4) remove by filter insolubles, inert liquid medium is reclaimed in distillation, gets 3,3 '-dimethyl-4,4 '-biphenyl diisocyanate.
2. one kind 3,3 '-dimethyl-4, the synthetic method of 4 '-biphenyl diisocyanate is characterized in that the processing step of synthetic method is as follows:
(1) with 3,3 '-dimethyl-4,4 '-benzidine is a raw material, 3, and 3 '-dimethyl-4, feed hydrogen chloride gas in the inert liquid medium solution of 4 '-benzidine, 60 ℃～130 ℃ of holding temperatures were reacted 1～4 hour, and the inert liquid medium consumption is 3,3 '-dimethyl-4,5～40 times of 4 '-benzidine quality;
(2) the inert liquid medium solution of preparation two (trichloromethyl) carbonic ether, the inert liquid medium consumption is 0.5～20 times of two (trichloromethyl) carbonic ether quality, under-10 ℃～160 ℃, be added drop-wise in the above-mentioned steps reaction solution, stir, the consumption of two (trichloromethyl) carbonic ether is calculated by weight to 3,3 '-dimethyl-4,0.5～10 times of 4 '-benzidine;
(3) dropwised back flow reaction 1～5 hour;
(4) remove by filter insolubles, distillating recovering solvent gets 3,3 '-dimethyl-4,4 '-biphenyl diisocyanate.
3. as claimed in claim 1 or 23,3 '-dimethyl-4, the synthetic method of 4 '-biphenyl diisocyanate, the charging capacity that it is characterized in that two (trichloromethyl) carbonic ether is 3 by weight, 3 '-dimethyl-4,4 '-benzidine or its hydrochloride 1～5 times.
4. as claimed in claim 1 or 23,3 '-dimethyl-4, the synthetic method of 4 '-biphenyl diisocyanate, it is characterized in that adding causes or partly causes two (trichloromethyl) carbonic ether activatory catalyzer in reaction soln, the addition of catalyzer is 0%～10% of two (trichloromethyl) carbonic ether weight.
5. as claimed in claim 43,3 '-dimethyl-4, the synthetic method of 4 '-biphenyl diisocyanate is characterized in that catalyzer is atlapulgite, the gac with many hollow structures; Organic bases.
6. as claimed in claim 53,3 '-dimethyl-4, the synthetic method of 4 '-biphenyl diisocyanate, it is characterized in that catalyzer is Trimethylamine 99, triethylamine, N, accelerine, N, one or more mixing in N-Diethyl Aniline, pyridine, dimethyl formamide, the N,N-DIMETHYLACETAMIDE, the addition of catalyzer are 1%～8% of two (trichloromethyl) carbonic ether weight.
7. as claim 1, one of 2 or 6 described 3,3 '-dimethyl-4, the synthetic method of 4 '-biphenyl diisocyanate, it is characterized in that inert liquid medium solution is selected from sherwood oil, hexanaphthene, normal hexane, xylol, o-Xylol, m-xylene, p-Xylol, toluene, benzene, 1, the 2-ethylene dichloride, tetracol phenixin, chlorobenzene, orthodichlorobenzene, Meta Dichlorobenzene, santochlor, bromobenzene, ethyl acetate, propyl acetate, pentyl acetate, Isoamyl Acetate FCC, butylacetate, isobutyl acetate, phenylacetate, ethyl propionate, propyl propionate, amyl propionate, isoamyl propionate, butyl propionate, isobutyl propionate, pentyl formate, Ethylisovalerate, dibutyl ether, tetrahydrofuran (THF), glycol dimethyl ether, methyl-phenoxide, acetone, butanone, pimelinketone a kind of or more than one mixing.
8. as claimed in claim 73,3 '-dimethyl-4, the synthetic method of 4 '-biphenyl diisocyanate is characterized in that inert liquid medium solution is a kind of in dimethylbenzene, chlorobenzene, orthodichlorobenzene, the Isoamyl Acetate FCC or more than one mixing.
9. as claimed in claim 13,3 '-dimethyl-4, the synthetic method of 4 '-biphenyl diisocyanate is characterized in that processing step is as follows:
(1) chlorobenzene solution of preparation two (trichloromethyl) carbonic ether, the chlorobenzene consumption is 0.5～20 times of two (trichloromethyl) carbonic ether quality, 20 ℃～30 ℃ chlorobenzene solutions that drip 20% triethylamine down, the consumption of triethylamine is 3,3 '-dimethyl-4,1%～5% of 4 '-benzidine weight stirs, priming reaction 1～3 hour is cooled to-10 ℃～20 ℃;
(2) preparation 3,3 '-dimethyl-4, the chlorobenzene solution of 4 '-benzidine, chlorobenzene consumption are 3,3 '-dimethyl-4,5～40 times of 4 '-benzidine quality; Under the vigorous stirring with 3,3 '-dimethyl-4, the chlorobenzene solution of 4 '-benzidine is added drop-wise in the above-mentioned reaction solution, drips continue to stir 15 minutes～60 minutes;
(3) be warmed up to 130 ℃～180 ℃ back flow reaction 0.5h～2h, remove by filter insolubles, chlorobenzene is reclaimed in distillation, purify 3,3 '-dimethyl-4,4 '-biphenyl diisocyanate.
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| CN102659631B (en) * | 2011-12-24 | 2014-05-07 | 德州绿邦化工有限公司 | One-step synthesis of ethyl isocyanate |
| CN103145586A (en) * | 2013-03-11 | 2013-06-12 | 黄河三角洲京博化工研究院有限公司 | Synthetic method of isophorone diisocyanate |
| CN104447412A (en) * | 2014-11-12 | 2015-03-25 | 上海朗亿新材料科技有限公司 | Preparation method of isocyanate |
| CN104861138B (en) * | 2015-05-18 | 2017-10-10 | 黑龙江大学 | A kind of polyurethane containing trianilino group and its preparation method and application |
| CN104861152B (en) * | 2015-05-22 | 2017-10-10 | 黑龙江大学 | A kind of polyurethane with memristor performance and its preparation method and application |
| CN106045882A (en) * | 2016-06-03 | 2016-10-26 | 山东崇舜化工有限公司 | Method for synthesizing pentamethylene diisocyanate |
| CN109305930A (en) * | 2018-05-28 | 2019-02-05 | 江阴市万丰化工物资有限公司 | The synthetic method of 3,3 '--4,4 '-biphenyl diisocyanates of dimethyl |
| CN110066229B (en) * | 2019-05-31 | 2021-07-20 | 上海应用技术大学 | Preparation method of dimethylbiphenyl diisocyanate |
| CN111349020A (en) * | 2020-05-06 | 2020-06-30 | 江苏快达农化股份有限公司 | Synthetic method for preparing 3, 3-dimethyl-4, 4-biphenyl diisocyanate by phosgene continuous method |
| CN114644575A (en) * | 2022-04-14 | 2022-06-21 | 山东崇舜新材料科技有限公司 | Preparation method of o-alkyl-MDI |
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