CN103145979B - A kind of nylon and preparation method thereof - Google Patents
A kind of nylon and preparation method thereof Download PDFInfo
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- CN103145979B CN103145979B CN201310060588.5A CN201310060588A CN103145979B CN 103145979 B CN103145979 B CN 103145979B CN 201310060588 A CN201310060588 A CN 201310060588A CN 103145979 B CN103145979 B CN 103145979B
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- nylon
- pentamethylene diamine
- dibasic acid
- aliphatic dibasic
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Abstract
The invention discloses a kind of nylon, comprise following structural formula :-NH-(CH
2)
5wherein, R is the alkylidene group of C2 ~ C18 or the sub-alkylene of C2 ~ C18 to-NH-CO-R-CO-.The raw material of nylon of the present invention is pentamethylene diamine and aliphatic dibasic acid, and one at least is wherein by Biological preparation, there is green reproducible advantage, and the performance such as mechanics is suitable with existing nylon, existing nylon can be substituted and be used in the fields such as injection moulding, film forming, melt-spinning, be with a wide range of applications.
Description
Technical field
The invention belongs to technical field of polymer materials, specifically, the present invention relates to pentamethylene diamine is nylon of raw material and preparation method thereof.
Background technology
Nylon is also called polymeric amide, refers to linear thermoplastic polymer main chain having amide group (-CONH-) repeated structural unit.The amide group of nylon has polarity, intermolecular formation hydrogen bond, so the good characteristics such as nylon has tough wear-resisting, shock-resistant, antifatigue, corrosion-resistant, oil resistant, solvent resistant, nontoxic, self-extinguishing good, electronic isolation is good, be mainly used in the aspects such as mechanical device instrument, automotive window.
Current nylon is all obtained using the derivative of oil as raw material substantially, two kind nylon 6 that such as nylon market share amount is maximum and nylon66 fiber, their raw material hexanolactam and hexanodioic acid are obtained through series reaction such as hydrogenation reoxidize by benzene class homologue, and hexanediamine is prepared by catalytic hydrogenation method by divinyl or the first Adiponitrile of vinyl cyanide again, whole synthesis technique is complicated, exists and necessarily pollutes.
For a long time, people are waited in expectation and use the plant resources grown by absorbing carbon dioxide from air as parent material, prepare the green nylon suitable with existing kind properties of nylons, solve the dependence to non-renewable energy, build Circular Society Construction.
Cadaverine is a polyamine species, namely 1,5-pentamethylene diamine (abbreviation pentamethylene diamine), have another name called 1,5-1,5-DAP, be extensively exist in organism there is bioactive nitrogenous base, can be separated in the corpse rotted with seminal fluid and obtain, for protein corrupt time Methionin under the effect of decarboxylase, there is decarboxylic reaction generate.Pentamethylene diamine can pass through chemical method, and after being boiled by the ethanol solution of trimethylene cyanide, add sodium Metal 99.5 with speed faster, add water after having reacted, steamed by ethanol, remaining reactant superheated vapour distills, then acidizing neutralization, and the method for distillation obtains.The biological process that the discovered in recent years pentamethylene diamine lysine decarboxylase (L-lysine decarboxylase, EC 4.1.1.18) that can pass through in hafnia alvei (Hafnia.Alvei) acts on Methionin obtains.
Summary of the invention
In order to solve the problem preparing nylon complex process and existence pollution using the derivative of oil as raw material, present inventor provides a kind of nylon prepared as raw material using the pentamethylene diamine of Biological preparation or aliphatic dibasic acid.
Therefore, first object of the present invention is to provide a kind of nylon.
Second object of the present invention is that providing package contains the nylon composite of above-mentioned nylon.
3rd object of the present invention is the preparation method providing a kind of above-mentioned nylon.
The invention discloses a kind of nylon, comprise following structural formula:
-NH-(CH
2)
5-NH-CO-R-CO-
Wherein, R is the alkylidene group of C2 ~ C18 or the sub-alkylene of C2 ~ C18.Preferably, R is the alkylidene group of C2 ~ C8 or the sub-alkylene of C2 ~ C8.Preferred, R is ethylidene.Preferably, R is the alkylidene group of C9 ~ C18 or the sub-alkylene of C9 ~ C18.
According to the present invention, described nylon is prepared from by pentamethylene diamine and aliphatic dibasic acid, and one at least is wherein by Biological preparation.
According to the present invention, described pentamethylene diamine comprises the organic carbon of the renewable source meeting ASTM D6866 standard.Preferred, aliphatic diacid comprises the organic carbon of the renewable source meeting ASTM D6866 standard.
According to the present invention, described pentamethylene diamine can be prepared by chemical method, also can adopt Biological preparation.Those skilled in the art can know, by Methionin (salt) under the effect of lysine decarboxylase (EC 4.1.1.18), sloughs two end carboxyl, generates pentamethylene diamine.Such as, disclose concrete Biological preparation pentamethylene diamine method in " 1B decarboxylase character and applied research " (Jiang Lili, Nanjing University, Master's thesis, 2007).Such as, disclose concrete Biological preparation pentamethylene diamine method in " microbial transformation L mono-Methionin is the research of cadaverine " (Zhu Jing, University Of Science and Technology Of Tianjin, Master's thesis, 2009.3).
According to the present invention, described aliphatic dibasic acid can be short chain diacid (in carbochain, carbonatoms is less than 10), comprises succinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, preferred hexanodioic acid, sebacic acid; Also can be long carbochain biatomic acid, comprise DC11, SL-AH, tridecanyldicarboxylic acid, DC14,15 carbon dicarboxylic acids, 16-dicarboxylic acid, DC17, DC18, toxilic acid, Δ
9-1,18 octadecylene diprotic acid, preferred SL-AH.Most preferred, described aliphatic dibasic acid is succinic acid, or carbonatoms is the diprotic acid of 11 ~ 20.
According to the present invention, described aliphatic dibasic acid can be prepared by chemical method, also can pass through Biological preparation.Such as, Chinese patent literature (application number: 201210392035.5) disclose the method preparing succinic acid.Such as, Chinese patent literature (patent No. ZL200410018255.7 and ZL200610029784.6) discloses the method preparing long-chain biatomic acid.
According to a preferred embodiment of the invention, described nylon viscosity number is 120-250ml/g.
The invention also discloses a kind of nylon composite, comprise nylon prepared by aforesaid method.Described nylon composite also comprises one or more auxiliary agents, comprises weather resisting agent, release agent, lubricant, pigment, dyestuff, crystallization nucleating agent, softening agent, static inhibitor, fire retardant, weighting agent, other polycondensates etc.Described weather resisting agent, comprises dihydroxy-benzene based compound, salicylate based compound, benzotriazole based compound, benzophenone based compound, hindered amine based compound etc.Described release agent or lubricant, comprise fatty alcohol, aliphatic amide, aliphatics bisamide, allophanamide, polyethylene wax etc.Described pigment, comprises Cadmium Sulfide, phthalocyanine, carbon black etc.Described dyestuff, comprises nigrosine, nigrosine etc.Described crystallization nucleating agent, comprises the inanimate matter particulates such as talcum, silicon-dioxide, kaolin, clay, boron nitride or metal oxide, high-melting-point nylon etc.Described softening agent, comprises P-hydroxybenzoic acid monooctyl ester, N-butylbenzenesulfonamide etc.Described static inhibitor, comprises nonionic system static inhibitor, the trimethyl-glycine system both sexes static inhibitor etc. such as alkyl sulphate type negatively charged ion system static inhibitor, quaternary ammonium salt cationic system static inhibitor, Tween-60.Described fire retardant, comprises the combination etc. of melamine cyanurate, oxyhydroxide (such as magnesium hydroxide, aluminium hydroxide etc.), ammonium polyphosphate, brominated Polystyrene, brominated polyphenylether, brominated polycarbonate, brominated epoxy resin or these bromide fire retardants and ANTIMONY TRIOXIDE SB 203 99.8 PCT.Described weighting agent, comprises particulate state, needle-like, the tabular packing materials such as glass fibre, carbon fiber, carbon black, tusche, barium sulfate, magnesium sulfate, calcium carbonate, magnesiumcarbonate, weisspiessglanz, titanium dioxide, aluminum oxide, zinc oxide, ferric oxide, zinc sulphide, zinc, lead, nickel, aluminium, copper, iron, stainless steel, wilkinite, polynite, manufacture mica.Other polycondensates described, comprise other polymeric amide, polyethylene, polypropylene, polyester, polycarbonate, polyphenylene oxide, polyphenylene sulfide, liquid crystalline polymers, polysulfones, polyethersulfone, ABS resin, AS resin, polystyrene etc.
The invention also discloses a kind of method preparing above-mentioned nylon, comprise the steps:
(1), under nitrogen protection that pentamethylene diamine is soluble in water, add aliphatic dibasic acid while stirring, the mol ratio of pentamethylene diamine and aliphatic dibasic acid is 1:1 ~ 1.05, and after stirring, obtained concentration is the nylon salt aqueous solution of 30 ~ 52%;
(2), the gained nylon salt aqueous solution is heated to reaction system internal pressure and rises to 1.3 ~ 2.0Mpa, start exhaust, when system temperature rises to 230 ~ 280 DEG C, vacuumize and make reaction system internal pressure be down to-0.01 ~-0.1MPa, and maintain 1 ~ 60min, obtain nylon.
Nylon of the present invention can adopt the people such as injection moulding, film forming, melt-spinning, blow molding, vacuum forming with forming method to be shaped to desired shape, can use in such as injection moulded products, film, sheet, monofilament, band silk, fiber etc., also can use in tackiness agent, coating etc.
Nylon of the present invention can as the intake manifold of vehicle associated components, hinged clasp, tired band, resonator, air cleaner, hood, rocker cover, cylinder cover hood, Timing Belt lid, car fuel tank, secondary pneumatic thickener, radiator case, side cooler case, oil tank groove, food tray, electric power steering controller, oil filter, respirator, engine mount, web member, relay1 block, terminal stud, corrugated tube, the automobile railway carriage or compartment inner parts such as backplate, door handle, mud guard, expansion valve gap, roof rail, automobile door mirror, vibroshock, spoiler, the automobile exterior members such as wheelhouse portions, cupholder, supervisory control desk case, gas pedal, clutch pedal, speed control lever pedestal, with dress parts in the automobiles such as variator knob.
Nylon of the present invention can also at silkworm gut, the relevant goods, materials and equipments of the fishery such as fishing net, Switch, subminiature slide switch, DIP switch, switch capsule, lamp socket, tired band, joint, joint case, joint shell, IC seat class, coil rack, skeleton lid, rly., relay box, condenser box, the internal part of motor, miniature motor case, gear, cam, regulating wheel, dividing plate, shackle, return pulley, terminal board, electric tool bracket, the insulated part of starter, fuse unit, timing register box, bearing retaining ring, loud speaker jolting plate, thermally resistant container, electronic measurement parts, cooking utensils parts, printer box, in the electrical equipment for representative, electronics associate components, family expenses, electric appliance in office article component, computer associated components, facsimile recorder, duplicating machine associated components, use in the various uses such as machinery associated components.
Beneficial effect of the present invention: the raw material of nylon of the present invention is pentamethylene diamine or the aliphatic dibasic acid of Biological preparation, there is green reproducible advantage, and the performance such as mechanics is suitable with existing nylon, existing nylon can be substituted and be used in the fields such as injection moulding, film forming, melt-spinning, be with a wide range of applications.
Accompanying drawing explanation
Fig. 1 is the proton magnetic chart of nylon 56.
Fig. 2 is the proton magnetic chart of nylon 510.
Fig. 3 is the proton magnetic chart of nylon 512.
Embodiment
Below in conjunction with specific embodiment, the present invention will be further described.Should be understood that following examples only for illustration of the present invention but not for limiting the scope of the invention.
Present invention uses following characterizing method and carry out performance characterization:
1, viscosity number
Ubbelohde viscometer sulphate method: the dried nylon samples 0.25 ± 0.0002g of precise, adds the 50mL vitriol oil (96%) and dissolves, measure and record vitriol oil flow time t in 25 DEG C of constant temperature water baths
0with nylon solution flow time t.
Viscosity number calculation formula: viscosity number VN=(t/t
0-1)/C
T--solution flow time
T
0--solvent flow time
The concentration (g/mL) of C--polymkeric substance
2, fusing point Tm
Adopt Perkin Elmer DSC-6 analytical instrument test sample fusing point, nitrogen atmosphere, flow velocity is 40mL/min.First be warming up to 290 DEG C with 10 DEG C/min during test, keep 3min at 290 DEG C, be then cooled to 30 DEG C with 10 DEG C/min, then be warming up to 290 DEG C with 10 DEG C/min, endotherm peak temperature is now set to fusing point Tm.
3, nmr analysis
BRUKER400 type UlstraShield TM nuclear magnetic resonance analyser is adopted to carry out testing nylon samples.With deuterated DMSO and deuterated trifluoroacetic acid for mixed solvent.
4, relative density
Measure by ASTM D792 method.
5, tensile strength, elongation at break
Measure by ASTM D638 method.
6, flexural strength
Measure by ASTM D790 method.
7, Izod notched impact strength
Measure by ASTM D256 method.
8, pentamethylene diamine gas phase purity check
Injector temperature: 230 DEG C of FID temperature: 260 DEG C
Carrier gas: the combustion-supporting gas of hydrogen 50kpa: air 50kpa
Combustion gas: hydrogen 60kpa
Chromatographic column: Agilent J & W DB-1 30m × 0.32mm × 1.0um
Column temperature: 70 DEG C keep 0.3min, are warming up to 230 DEG C with 15 DEG C/min, keep 1min.
embodiment 1, nylon 56 preparation
Salt oven is become by 50 liters of enamel to replace wherein air three times by the mode of vacuum nitrogen filling gas; and with nitrogen protection; 30kg pure water is added in one-tenth salt oven; then 12.69kg pentamethylene diamine is added (purchased from the triumphant match in Shandong; comprise the organic carbon of the renewable source meeting ASTM D6866 standard; gas phase normalization method purity 99.56%); start stirring; add 17.64kg hexanodioic acid (purchased from Liaoning petrochemical industry); add Brueggemann company of 6g oxidation inhibitor H10(Bruggolen H10 Germany again to produce), the obtained nylon salt aqueous solution.
100 liters of polymeric kettles (K/SY166-2007 type) are used nitrogen replacement air, and nylon salt solution is transferred in polymeric kettle, oil bath temperature rises to 230 DEG C, treat that still internal pressure rises to 1.73Mpa, start exhaust, when temperature in the kettle reaches 265 DEG C, be evacuated to-0.06Mpa(gauge pressure), keep this vacuum tightness 20min, obtained nylon 56.
In polymeric kettle, be filled with nitrogen to pressure 0.5Mpa, start melting discharging, and utilize dicing machine (electromagnetic variable speed motor 300 type cantilevered) granulation.80 DEG C of dry vacuum-dryings carried out each Performance Detection after 8 hours, and as shown in Figure 1, result is shown in table 1 to the proton magnetic chart of nylon 56.
embodiment 2, nylon 56 preparation
Except not adding the oxidation inhibitor H10 in embodiment 1, operate similarly to Example 1.Carry out each Performance Detection to obtained polyamide resin, result is shown in table 1.
embodiment 3, nylon 56 preparation
Except in adjustment embodiment 1, pentamethylene diamine add-on is except 12.41kg, operate similarly to Example 1.Carry out each Performance Detection to obtained polyamide resin, result is shown in table 1.
embodiment 4, nylon 510 preparation
Except the diacid in adjustment embodiment 1 be 19.93kg sebacic acid and pentamethylene diamine add-on is except 10.39kg, operate similarly to Example 1, carry out each Performance Detection to obtained polyamide resin, as shown in Figure 2, result is shown in table 1 to the proton magnetic chart of nylon 510.
embodiment 5, nylon 512 preparation
Except the diacid in adjustment embodiment 1 be 20.78kg SL-AH and pentamethylene diamine add-on is except 9.54kg, operate similarly to Example 1.Carry out each Performance Detection to obtained polyamide resin, as shown in Figure 3, result is shown in table 1 to the proton magnetic chart of nylon 512.
embodiment 6, unsaturated nylon preparation
Except the diacid in adjustment embodiment 1 is 22.61kg Δ
9-1,18 octadecylene diprotic acid and pentamethylene diamine add-on are outside 7.42kg, operate similarly to Example 1.Carry out each Performance Detection to obtained polyamide resin, result is shown in table 1.
Table 1, each polymeric amide performance data table
The explanation of above embodiment just to technical scheme, does not form the restriction to technical solution of the present invention.Those skilled in the art, can by the proportioning raw materials in adjustment preparation process according to the knowledge of existing nylon Preparation Method, and the temperature, pressure etc. of preparation process, realize the nylon of different viscosity number.
Although represented and discussed aspects more of the present invention, but those skilled in the art it is to be appreciated that, can change in above-mentioned under the condition not deviating from the principle of the invention and spirit, therefore scope of the present invention limited by claim and equivalent content.
Claims (10)
1. a nylon, the structural formula of described nylon is as follows:
-NH-(CH
2)
5-NH-CO-R-CO-
Wherein, R is the alkylidene group of C2 ~ C18 or the sub-alkylene of C2 ~ C18; .
Described nylon is prepared from by pentamethylene diamine and aliphatic dibasic acid;
The preparation method of described nylon, comprises the steps:
(1), under nitrogen protection that pentamethylene diamine is soluble in water, add aliphatic dibasic acid while stirring, the mol ratio of pentamethylene diamine and aliphatic dibasic acid is 1:1 ~ 1.05, and after stirring, obtained concentration is the nylon salt aqueous solution of 30 ~ 52%;
(2), the gained nylon salt aqueous solution is heated to reaction system internal pressure and rises to 1.3 ~ 2.0Mpa, start exhaust, when system temperature rises to 230 ~ 280 DEG C, vacuumize and make reaction system internal pressure be down to-0.01 ~-0.1Mpa (gauge pressure), and maintain 1 ~ 60min, obtain nylon.
2. nylon as claimed in claim 1, is characterized in that, in described pentamethylene diamine and aliphatic dibasic acid, at least one is by Biological preparation.
3. nylon as claimed in claim 2, it is characterized in that, described pentamethylene diamine comprises the organic carbon of the renewable source meeting ASTMD6866 standard.
4. nylon as claimed in claim 2, it is characterized in that, described aliphatic dibasic acid comprises the organic carbon of the renewable source meeting ASTM D6866 standard.
5. nylon as claimed in claim 1, it is characterized in that, R is the alkylidene group of C2 ~ C8 or the sub-alkylene of C2 ~ C8.
6. nylon as claimed in claim 5, it is characterized in that, R is ethylidene.
7. nylon as claimed in claim 1, it is characterized in that, R is the alkylidene group of C9 ~ C18 or the sub-alkylene of C9 ~ C18.
8. nylon as claimed in claim 1, it is characterized in that, described nylon viscosity number is 120-250mL/g.
9. a nylon composite, comprises the nylon according to any one of claim 1 ~ 8.
10. the preparation method of the nylon according to any one of claim 1 ~ 8, comprises the steps:
(1), under nitrogen protection that pentamethylene diamine is soluble in water, add aliphatic dibasic acid while stirring, the mol ratio of pentamethylene diamine and aliphatic dibasic acid is 1:1 ~ 1.05, and after stirring, obtained concentration is the nylon salt aqueous solution of 30 ~ 52%;
(2), the gained nylon salt aqueous solution is heated to reaction system internal pressure and rises to 1.3 ~ 2.0Mpa, start exhaust, when system temperature rises to 230 ~ 280 DEG C, vacuumize and make reaction system internal pressure be down to-0.01 ~-0.1Mpa (gauge pressure), and maintain 1 ~ 60min, obtain nylon.
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Families Citing this family (9)
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| CN106147047B (en) * | 2015-03-25 | 2019-05-31 | 上海凯赛生物技术研发中心有限公司 | Elastic composition and preparation method thereof |
| CN108239393B (en) * | 2016-12-27 | 2021-02-19 | 上海凯赛生物技术股份有限公司 | Light polyamide composition and preparation method thereof |
| CN108503826B (en) * | 2017-02-24 | 2022-02-15 | 上海凯赛生物技术股份有限公司 | Polyamide 5X with low water-soluble oligomer content and preparation method thereof |
| CN108503825B (en) * | 2017-02-24 | 2022-02-15 | 上海凯赛生物技术股份有限公司 | Preparation method of polyamide and prepared polyamide resin |
| CN110054773B (en) * | 2018-01-19 | 2022-03-11 | 上海凯赛生物技术股份有限公司 | Long-carbon-chain polyamide resin and preparation method thereof |
| CN110066393B (en) * | 2018-01-23 | 2022-08-02 | 凯赛(乌苏)生物技术有限公司 | Long-carbon-chain polyamide resin and preparation method thereof |
| CN110372521B (en) * | 2019-07-30 | 2020-11-24 | 南京工业大学 | Method for stripping and recovering pentanediamine from aqueous phase containing pentanediamine |
| CN110372522B (en) * | 2019-07-30 | 2020-10-02 | 南京工业大学 | Method for stripping and recovering pentamethylene diamine from pentamethylene diamine-containing solid phase |
| CN111019091A (en) * | 2019-12-10 | 2020-04-17 | 广东科德环保科技股份有限公司 | Bio-based modified epoxy resin, bio-based electrophoretic coating and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101443382A (en) * | 2006-05-16 | 2009-05-27 | 三菱化学株式会社 | Polyamide resin |
| CN102498086A (en) * | 2009-01-22 | 2012-06-13 | 阿迈瑞斯公司 | Methods for producing dodecanedioic acid and derivatives thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101443382A (en) * | 2006-05-16 | 2009-05-27 | 三菱化学株式会社 | Polyamide resin |
| CN102498086A (en) * | 2009-01-22 | 2012-06-13 | 阿迈瑞斯公司 | Methods for producing dodecanedioic acid and derivatives thereof |
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