CN102585211B - Continuous production method for amino end-capped polyether - Google Patents
Continuous production method for amino end-capped polyether Download PDFInfo
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Abstract
The invention relates to a continuous production method for amino end-capped polyether. The method comprises the following three continuous phases of: (1) a pre-treatment phase: dehydrating and drying a polyether raw material, proportionally mixing with hydrogen and liquid ammonia to form a mixed material, and heating to a reaction temperature; (2) a reaction phase: putting the mixed material into a tubular reactor, contacting with a porous nickel-based catalyst filled into the tubular reactor, and undergoing a hydro-ammoniation reaction under the action of the catalyst; and (3) a post-treatment phase: cooling a product generated in the reaction phase, introducing into a gas-liquid separating device, separating ammonia gas and hydrogen gas from a liquid product, filtering the separated liquid, and drying to obtain a finished product. The continuous production method has the advantages of realization of continuous production of aminopolyether, high mass transfer and heat transfer efficiencies, high reaction speed, mild reaction condition, reduction in side reactions, safety and reliability. The catalyzing efficiency of the catalyst is high, and the production efficiency and the conversion rate of the product are effectively increased.
Description
Technical field
The continuous production method that the present invention relates to a kind of amino-terminated type polyethers, belongs to field of chemical technology.
Background technology
Amino-terminated type polyethers is the polyoxyalkylene compounds that a class end is comprised of primary amine groups or secondary amine, belongs to the derivative of polyether glycol or polyoxyethylene glycol series.The polyethers of amino-terminated type has higher reactive behavior compared with the polyethers of C-terminal type, fast with speed of response such as isocyanate groups, epoxide group, hydroxy-acid groups, transformation efficiency is high, with the obvious advantage, it is mainly used in lubricating oil additive, the synthesis material of high-performance polyureas material, solidifying agent, tensio-active agent and the medical material etc. of epoxy resin.
The synthetic method of the amino-terminated type polyethers of report mainly contains three kinds both at home and abroad: 1, face hydrogen ammoniation process, adopt hydrogen, ammonia, end hydroxy polyether under the catalyst based effect of solid nickel, amino-polyether is produced in reaction.Whole reaction process mainly comprises that the dehydrogenation of end hydroxy polyether terminal hydroxyl generates polyethers aldehyde, and it is the polyethers of alkene imine structure that ammonia and polyethers aldehyde addition amination reaction are produced end, and last alkene imines obtains Amino Terminated polyether(ATPE) through catalytic hydrogenation reaction again.2, amino-butenate method, first with dienone or by the transesterification reaction of methyl aceto acetate and Aethoxy Sklerol, end at polyethers connects acetoacetate groups, and then polyethers and unary primary amine, alkyl alcoholamine or binary primary amine are carried out to amination, thereby obtain the group with imine moiety that end group is amino-butenate.3, leavings group method, the method is generally divided into two steps, the first step is esterification, uses with easy leavings group or the compound (as acid chloride group, methylsulfonyl chloro, halogen radical, aldehyde radical etc.) of unsaturated group and the active hydrogen reaction of hydroxy polyethers end, carries out end-blocking; Second step is amination reaction, and the product directly the first step being obtained reacts and obtains amino-terminated polyethers with monoamine or polyamine.Three kinds of synthetic methods respectively have relative merits, and the method that suitability for industrialized production is taked is at present mainly the first operational path, but mostly be intermittently tank reactor, produce.Intermittently tank reactor is a large reaction chamber that comprises agitator and muff, reactant adds reactor under pressure in batch, reaction is carried out a few hours or a couple of days, reaction product needs off-response device to take out, greatly reduce production efficiency, safe reliability is poor, and by-products content is high, unstable product quality.
Patent 200310112615.5 has been reported a kind of production method of aliphatics Amino Terminated polyether(ATPE), first adopt the metallic nickel, aluminium, the Chrome metal powder that form by a certain percentage to prepare nickel-base catalyst, then adopt intermittently autoclave reaction process, in autoclave, by polyether glycol, face the synthetic Amino Terminated polyether(ATPE) of hydrogen ammonification.Wherein, prepare in the metal alloy of nickel-base catalyst, metallic nickel content reaches 60 ~ 80%, and facing hydrogen aminating reaction temperature is 180 ~ 280 ℃, and reaction pressure is 13 ~ 21MPa, and in 2 ~ 8 hours reaction times, reaction conversion ratio can reach 96%.
Patent 200780036903 has been reported a kind of preparation method of polyetheramine, adopt the cobalt of at least 80% quality or under Raney catalyzer exists, the catalyzer that the copper that comprises at least 80% quality cobalt or aluminium and at least 5% quality forms, respectively in autoclave and fixed-bed reactor, take Aethoxy Sklerol as initiator, carried out catalytic ammoniation reaction, 50 ~ 250 ℃ of temperature of reaction, reaction pressure 1 ~ 300 bar, the transformation efficiency of product is 85 ~ 98%.
Patent 201010525067 has been reported and has been adopted amorphous alloy catalyst to prepare the method for polyetheramine.It is main component that catalyzer be take 40 ~ 50% Ni and 40 ~ 50% Al, one or more of take in Mo, La, Cr and Mn are ancillary component, in autoclave, the polyether glycol of take carries out catalyzed reaction as raw material, temperature of reaction is 180 ~ 200 ℃, reaction pressure is 13 ~ 15MPa, and prepared polyetheramine transformation efficiency is greater than 97%.
Yet these still reactions all belong to intermittent type preparation method, production process can not be carried out continuously, has strengthened the difficulty of production operation, has reduced production efficiency.
Summary of the invention
The object of the present invention is to provide a kind of continuous production method of amino-terminated type polyethers, the deficiency such as solve that the reaction medium Contact area that gap tank reactor exists is little, mass-and heat-transfer efficiency is low, reaction pressure is high, side reaction is many, production efficiency is low, quality is unstable and safe reliability is poor, the polyethers serialization production realizing by C-terminal obtains amino-terminated polyethers.
The technical solution adopted in the present invention is: a kind of method that continous way is produced amino-terminated polyethers is realized by a set of complete pipe reaction Processes and apparatus.
1) pretreatment stage: polyethers raw material, through dehydrating, is mixed in proportion rear formation mixture and is warming up to temperature of reaction with hydrogen and liquefied ammonia; The blending ratio of aforementioned polyethers raw material and hydrogen and liquefied ammonia is as follows: in ammonia and pfpe molecule, the ratio of the mole number of hydroxyl is 5 ~ 50, and in hydrogen and pfpe molecule, the ratio of the mole number of hydroxyl is 0.05 ~ 5;
2) step of reaction: mixture enters in tubular reactor, contacts with the large hole nickel-based catalyst of filling in tubular reactor, under catalyst action, faces hydrogen aminating reaction;
3) post-processing stages: the product that step of reaction generates enters gas-liquid separation device after cooling, ammonia and hydrogen and product liquid are carried out separated, isolated liquid after filtration, dry, make finished product.
Polyethers raw material of the present invention is that end is the aliphatic polyether of primary hydroxyl, comprise monohydroxy alkyl, polyether, two hydroxy polyethers and polyether glycol, as polyalkylene glycol monoalkyl ether, polyoxyethylene glycol/propylene-glycol monoalky lether, polypropylene glycol monoalky lether, ethylene glycol or propylene glycol and oxyethane or/and the affixture of propylene oxide, aliphatic amide and oxyethane or/and the affixture of propylene oxide, polyvalent alcohol and oxyethane or/and the affixture of propylene oxide etc.Because the molecular weight of the aliphatic polyether of above-mentioned primary hydroxyl is preferably 200 ~ 5000, to avoid because of the too high reaction efficiency that reduces of molecular weight.
Pretreatment stage of the present invention adopts the heating and continuous mode vacuumizing to dehydrate polyethers raw material, and dehydration temperaturre is 120 ℃ ~ 150 ℃, the pressure vacuumizing-more than 0.085MPa, dewatering time is 4 ~ 6h.Dehydrate and can reduce to greatest extent the water-content in polyethers raw material, thereby be conducive to reduce the generation of by product in reaction process, improve the quality of product.Polyethers raw material after dehydrating can be placed in the storage tank of sealing and preserve temporarily.
When dried polyethers raw material of the present invention mixes with hydrogen and liquefied ammonia, the charging first pressing of hydrogen is preferably 1 ~ 5MPa, and its reason is that hydrogen feed pressure is too low, and liquid ammonia gasification is too serious; Hypertonia, in the time of can causing temperature reaction, the integral pressure of system is higher, wayward rational reaction pressure.
The large hole nickel-based catalyst of filling in the tubular reactor that step of reaction adopts is loading type, solid support material is porous inert carrier, and the mass content of each component of nickel-base catalyst of institute's load is: Ni accounts for 75 ~ 80%, Cu and accounts for 15 ~ 20%, Cr accounts for 1 ~ 5%, Co and accounts for 0.5 ~ 2%.
For effectively guaranteeing fully carrying out of reaction, step of reaction of the present invention is to carry out in a continuous tubular reactor, tubular reactor adopts the tubular reactor of existing routine, the large hole nickel-based catalyst of wherein filling is loading type, solid support material is porous inert carrier, as: aluminum oxide, amorphous silica, diatomite, titanium dioxide, magnesium oxide, calcium oxide, activated carbon etc.The main component of the nickel-base catalyst of institute's load is metal Ni, Cu, Cr and Co, and the concrete mass content of each component is: Ni accounts for 75 ~ 80%, Cu and accounts for 15 ~ 20%, Cr and account for 1 ~ 5%, Co and account for 0.5 ~ 2%.Aforesaid loading type large hole nickel-based catalyst can be geometrical shape arbitrarily, for example rule or irregular spherical, sheet or bar-shaped, or the mixture of its various shape.
Because high-ratio surface and wide-aperture catalyzer are conducive to provide more catalytic site, there is higher catalytic activity and catalytic selectivity, thereby improve the catalytic efficiency of catalyzer, and then improved the transformation efficiency of production efficiency and raw material.Simultaneously, reasonably catalyst particle size is more conducive to catalyzer in the optimum filling of inside reactor, makes mass-and heat-transfer abundant, and local heat effect is very little, therefore side reaction is suppressed, and the specific surface area of the loading type large hole nickel-based catalyst that the present invention adopts is preferably 100 ~ 300m
2/ g, mean pore size is 50 ~ 100nm, median size is preferably 5 ~ 20mm.
The preparation method of above-mentioned loading type large hole nickel-based catalyst is well known to those skilled in the art, and therefore repeats no more.
Because reasonably temperature of reaction and pressure not only can guarantee production efficiency, also can significantly reduce the generation of side reaction, improved the quality of product, therefore, the air speed that step of reaction mixture of the present invention enters tubular reactor is 0.05 ~ 2h
-1, temperature of reaction is 180 ~ 260 ℃, reaction pressure is 10 ~ 14MPa.
In post-processing stages of the present invention, the product that step of reaction generates, after cooling to 100 ~ 120 ℃, enters in gas-liquid separation device and carries out gas-liquid separation, and the hydrogen of residual dissolving in material is carried out separated with ammonia with product.Mixed gas after separation further carries out separated to ammonia and hydrogen by ammonia absorption tower, and respectively the ammonia after separation and hydrogen are carried out to recycling, realizes and cleans production, reduces production costs simultaneously.Liquid product after separation removes through filtration unit the catalyst solid particle of taking out of in product again, finally product is fully dried, and obtains amino-terminated polyethers.
The transformation efficiency that continous way of the present invention is produced amino-terminated type polyethers is 95 ~ 99%, and wherein primary amine groups content is 97 ~ 99%.
The present invention has realized the continuous production of amino-polyether, and mass-and heat-transfer efficiency is high, and speed of response is fast, and reaction conditions is comparatively gentle, has reduced the generation of side reaction, safe and reliable.Catalyst efficiency is high, has effectively improved the transformation efficiency of production efficiency and product.
Accompanying drawing explanation
Fig. 1 is the reaction unit process flow diagram that continous way that the present invention adopts is produced amino-terminated type polyethers.
Wherein, equipment 1 is polyethers raw material drying treatment unit, and equipment 2 is polyethers material temporary storage tank after dry, NH
3liquefied ammonia, H
2hydrogen, equipment 3 is the mixing tank of polyethers raw material, hydrogen and liquefied ammonia, equipment 4 is heating unit, equipment 5 is tubular reactor, equipment 6 is cooling device, and equipment 7 is gas-liquid separation device, and equipment 8 is polyethers crude product filtration unit, equipment 9 is finished product drying and dehydrating device, and equipment 10 is ammonia and hydrogen separation device.Above equipment is this area existing installation.
Embodiment
To come by specific embodiment that the invention will be further described below.
Embodiment 1
With the continuous reaction apparatus shown in Fig. 1, proceed as follows process.To adding molecular weight in polyethers drying process device 1, be 1000 polyoxyethylene glycol, stir and be warming up to 120 ℃, continue to be evacuated to-more than 0.09MPa, continue, after dehydration 4h, material to be transferred in temporary storage tank 2.From every batch of polyethers temporary storage tank 2 minutes, to mixing tank 3, inject 200kg polyethers, 34kg liquefied ammonia, with the first pressing of 2MPa, inject 0.08kg hydrogen.Then by mixture with air speed 1.8h
-1charging enters in the tubular reactor 5 that is filled with large hole nickel-based catalyst carrier after heating unit 4 heating, maintains 180 ~ 200 ℃ of temperature of reaction, reaction pressure 10 ~ 11MPa, successive reaction 80h.Material, after the continuous catalytic reaction of tubular reactor, is cooled to 110 ℃ through cooling device 6, then enters in gas-liquid separation device 7, by air lift, vacuum mode, the liquids and gases in mix products are separated.Isolated gas is access to plant 10 again, further separated with hydrogen to ammonia, and carries out respectively recycling.Isolated product liquid enters in filtration unit 8, and catalyzer residual in product is carried out to filtering separation.Separated rear catalyst is reused after reclaiming activation, the product introduction drying and dehydrating device 9 after separation, and discharging after drying dehydration, obtains final finished.Products obtained therefrom transformation efficiency is 98.4%, and the primary amine groups polyethers selection rate by titration measuring is 98.6%.
With the continuous reaction apparatus shown in Fig. 1, proceed as follows process.To adding molecular weight in polyethers drying process device 1, be 400 polypropylene glycol, stir and be warming up to 140 ℃, continue to be evacuated to-more than 0.09MPa, continue, after dehydration 5h, material to be transferred in temporary storage tank 2.From every batch of polyethers temporary storage tank 2 minutes, to mixing tank 3, inject 100kg polyethers, 85kg liquefied ammonia, with the first pressing of 5MPa, inject 2kg hydrogen.Then by mixture with air speed 0.08h
-1charging enters in the tubular reactor 5 that is filled with large hole nickel-based catalyst carrier after heating unit 4 heating, maintains 240 ~ 260 ℃ of temperature of reaction, reaction pressure 12 ~ 13MPa, successive reaction 50h.Material, after the continuous catalytic reaction of tubular reactor, is cooled to 100 ℃ through cooling device 6, then enters in gas-liquid separation device 7, by air lift, vacuum mode, the liquids and gases in mix products are separated.Isolated gas is access to plant 10 again, further separated with hydrogen to ammonia, and carries out respectively recycling.Isolated product liquid enters in filtration unit 8, and catalyzer residual in product is carried out to filtering separation.Separated rear catalyst is reused after reclaiming activation, the product introduction drying and dehydrating device 9 after separation, and discharging after drying dehydration, obtains final finished.Products obtained therefrom transformation efficiency is 98.1%, and the primary amine groups polyethers selection rate by titration measuring is 97.5%.
With the continuous reaction apparatus shown in Fig. 1, proceed as follows process.To adding molecular weight in polyethers drying process device 1, be 3000 polyoxytrimethylene triol, stir and be warming up to 130 ℃, continue to be evacuated to-more than 0.09MPa, continue, after dehydration 6h, material to be transferred in temporary storage tank 2.From every batch of polyethers temporary storage tank 2 minutes, to mixing tank 3, inject 300kg polyethers, 255kg liquefied ammonia, with the first pressing of 3MPa, inject 3kg hydrogen.Then by mixture with air speed 1.1h
-1charging enters in the tubular reactor 5 that is filled with large hole nickel-based catalyst carrier after heating unit 4 heating, maintains 200 ~ 220 ℃ of temperature of reaction, reaction pressure 11 ~ 12MPa, successive reaction 80h.Material, after the continuous catalytic reaction of tubular reactor, is cooled to 100 ℃ through cooling device 6, then enters in gas-liquid separation device 7, by air lift, vacuum mode, the liquids and gases in mix products are separated.Isolated gas is access to plant 10 again, further separated with hydrogen to ammonia, and carries out respectively recycling.Isolated product liquid enters in filtration unit 8, and catalyzer residual in product is carried out to filtering separation.Separated rear catalyst is reused after reclaiming activation, the product introduction drying and dehydrating device 9 after separation, and discharging after drying dehydration, obtains final finished.Products obtained therefrom transformation efficiency is 96.6%, and the primary amine groups polyethers selection rate by titration measuring is 98.2%.
Embodiment 4
With the continuous reaction apparatus shown in Fig. 1, proceed as follows process.To adding molecular weight in polyethers drying process device 1, be 5000 polypropylene glycol, stir and be warming up to 120 ℃, continue to be evacuated to-more than 0.09MPa, continue, after dehydration 6h, material to be transferred in temporary storage tank 2.From every batch of polyethers temporary storage tank 2 minutes, to mixing tank 3, inject 200kg polyethers, 34kg liquefied ammonia, with the first pressing of 1MPa, inject 0.192kg hydrogen.Then by mixture with air speed 0.05h
-1charging enters in the tubular reactor 5 that is filled with large hole nickel-based catalyst carrier after heating unit 4 heating, maintains 230 ~ 250 ℃ of temperature of reaction, reaction pressure 13 ~ 14MPa, successive reaction 80h.Material, after the continuous catalytic reaction of tubular reactor, is cooled to 100 ℃ through cooling device 6, then enters in gas-liquid separation device 7, by air lift, vacuum mode, the liquids and gases in mix products are separated.Isolated gas is access to plant 10 again, further separated with hydrogen to ammonia, and carries out respectively recycling.Isolated product liquid enters in filtration unit 8, and catalyzer residual in product is carried out to filtering separation.Separated rear catalyst is reused after reclaiming activation, the product introduction drying and dehydrating device 9 after separation, and discharging after drying dehydration, obtains final finished.Products obtained therefrom transformation efficiency is 95.7%, and the primary amine groups polyethers selection rate by titration measuring is 97.2%.
With proceeding as follows process to continuous reaction apparatus similar shown in Fig. 1.To adding molecular weight in polyethers drying process device 1, be polyoxyethylene/propylene oxide glycol of 2000, stir and be warming up to 130 ℃, continue to be evacuated to-more than 0.09MPa, continue, after dehydration 4h, material to be transferred in temporary storage tank 2.From every batch of polyethers temporary storage tank 2 minutes, to mixing tank 3, inject 300kg polyethers, 214.2kg liquefied ammonia, with the first pressing of 4MPa, inject 2.1kg hydrogen.Then by mixture with air speed 0.5h
-1charging enters in the tubular reactor 5 that is filled with large hole nickel-based catalyst carrier after heating unit 4 heating, maintains 210 ~ 230 ℃ of temperature of reaction, reaction pressure 11 ~ 12MPa, successive reaction 100h.Material, after the continuous catalytic reaction of tubular reactor, is cooled to 110 ℃ through cooling device 6, then enters in gas-liquid separation device 7, by air lift, vacuum mode, the liquids and gases in mix products are separated.Isolated gas is access to plant 10 again, further separated with hydrogen to ammonia, and carries out respectively recycling.Isolated product liquid enters in filtration unit 8, and catalyzer residual in product is carried out to filtering separation.Separated rear catalyst is reused after reclaiming activation, the product introduction drying and dehydrating device 9 after separation, and discharging after drying dehydration, obtains final finished.Products obtained therefrom transformation efficiency is 98.5%, and the primary amine groups polyethers selection rate by titration measuring is 98%.
Claims (6)
1. a continuous production method for amino-terminated polyethers, is characterized in that comprising following three continuous stages:
1) pretreatment stage: polyethers raw material, through dehydrating, is mixed in proportion rear formation mixture and is warming up to temperature of reaction with hydrogen and liquefied ammonia; The blending ratio of aforementioned polyethers raw material and hydrogen and liquefied ammonia is as follows: in ammonia and pfpe molecule, the ratio of the mole number of hydroxyl is 5～50, and in hydrogen and pfpe molecule, the ratio of the mole number of hydroxyl is 0.05～5;
2) step of reaction: mixture enters in tubular reactor, contacts with the large hole nickel-based catalyst of filling in tubular reactor, under catalyst action, faces hydrogen aminating reaction; Aforementioned large hole nickel-based catalyst is loading type, and solid support material is porous inert carrier, and the mass content of each component of nickel-base catalyst of institute's load is: Ni accounts for 75～80%, Cu and accounts for 15～20%, Cr and account for 1～5%, Co and account for 0.5～2%;
3) post-processing stages: the product that step of reaction generates enters gas-liquid separation device after cooling, ammonia and hydrogen and product liquid are carried out separated, isolated liquid after filtration, dry, make finished product;
Described polyethers raw material is that end is the aliphatic polyether of primary hydroxyl, is selected from monohydroxy alkyl, polyether, two hydroxy polyethers or polyether glycol, and its molecular weight is 200～5000.
2. the continuous production method of amino-terminated polyethers as claimed in claim 1, it is characterized in that pretreatment stage adopts the heating and continuous mode vacuumizing to dehydrate polyethers raw material, dehydration temperaturre is 120 ℃～150 ℃, the pressure vacuumizing-more than 0.085MPa, dewatering time is 4～6h.
3. the continuous production method of amino-terminated polyethers as claimed in claim 1, is characterized in that when pretreatment stage polyethers raw material mixes with hydrogen and liquefied ammonia, the charging first pressing of hydrogen is 1～5MPa.
4. the continuous production method of amino-terminated polyethers as claimed in claim 1, the specific surface area that it is characterized in that filled loading type large hole nickel-based catalyst is 100～300m
2/ g, mean pore size is 50～100nm, median size is 5～20mm.
5. the continuous production method of amino-terminated polyethers as claimed in claim 1, is characterized in that the air speed that step of reaction mixture enters tubular reactor is 0.05～2h
-1, temperature of reaction is 180～260 ℃, reaction pressure is 10～14MPa.
6. the continuous production method of amino-terminated polyethers as claimed in claim 1, is characterized in that in post-processing stages, and the mixed gas after gas-liquid separation device separation further carries out separated to ammonia with hydrogen by ammonia absorption tower.
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Families Citing this family (11)
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| CN103626988B (en) * | 2012-08-23 | 2016-03-02 | 中国石油化工股份有限公司 | A kind of continuous processing prepares the production method of Amino Terminated polyether(ATPE) |
| CN103059286B (en) * | 2013-01-05 | 2015-01-21 | 扬州晨化新材料股份有限公司 | Continuous hydrogenation ammoniation/amination reaction device |
| CN104419002B (en) * | 2013-08-20 | 2017-12-01 | 中国石油化工股份有限公司 | A kind of production method of amine terminated polyether |
| CN104231256B (en) * | 2014-10-13 | 2016-06-15 | 南京红宝丽股份有限公司 | A kind of continuous preparation method of amine terminated polyether |
| CN104693434B (en) * | 2015-03-04 | 2017-11-21 | 扬州晨化新材料股份有限公司 | A kind of fixed bed is continuously synthesizing to the production method of polyetheramine |
| CN105295021A (en) * | 2015-12-01 | 2016-02-03 | 王伟跃 | Process of continuously producing amine-terminated polyether and reactor design of process |
| CN106810683B (en) * | 2015-12-02 | 2019-07-05 | 中国科学院大连化学物理研究所 | A kind of method and device preparing polyetheramine |
| CN105713191B (en) * | 2016-03-01 | 2018-04-13 | 江苏清泉化学股份有限公司 | The technique that hydrogen ammonification production polyetheramine is faced in a kind of serialization |
| CN105860053B (en) * | 2016-04-20 | 2018-08-14 | 南京林业大学 | A kind of continuous method and its special-purpose catalyst for preparing end secondary amino group polyethers |
| CN109663467A (en) * | 2019-02-25 | 2019-04-23 | 临沂华毅医药股份有限公司 | A kind of aminating reaction object optimization device and method of ortho-aminobenzoic acid |
| CN112759758A (en) * | 2020-12-31 | 2021-05-07 | 淄博正大聚氨酯有限公司 | Method for preparing polyether amine by intermittent catalytic amination |
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| CN101347734A (en) * | 2007-07-18 | 2009-01-21 | 中国石油化工股份有限公司 | Large hole nickel-based catalyst |
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| US5003107A (en) * | 1989-12-18 | 1991-03-26 | Texaco Chemical Company | Catalytic method for the reductive amination of poly(oxytetramethyle) glycols |
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| CN101347734A (en) * | 2007-07-18 | 2009-01-21 | 中国石油化工股份有限公司 | Large hole nickel-based catalyst |
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Effective date of registration: 20140512 Address after: 211103, No. 59 West Wan An Road, Jiangning District, Jiangsu, Nanjing Patentee after: Jiangsu Subute New Materials Co., Ltd. Patentee after: Nanjing Bote Building Materials Co., Ltd. Address before: 211103, No. 59 West Wan An Road, Jiangning District, Jiangsu, Nanjing Patentee before: Jiangsu Subute New Materials Co., Ltd. Patentee before: Jiangsu Bote New Materials Co., Ltd. Patentee before: Nanjing Bote Building Materials Co., Ltd. Patentee before: Jiangsu Provincial Architectural Science Institute Ltd. |
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| CP02 | Change in the address of a patent holder | ||
| CP02 | Change in the address of a patent holder |
Address after: No.6 shuiyougang, Gulou District, Nanjing City, Jiangsu Province 210013 Patentee after: JIANGSU SUBOTE NEW MATERIALS Co.,Ltd. Patentee after: JIANGSU BOTE NEW MATERIALS Co.,Ltd. Address before: 211103, No. 59 West Wan An Road, Jiangning District, Jiangsu, Nanjing Patentee before: JIANGSU SUBOTE NEW MATERIALS Co.,Ltd. Patentee before: JIANGSU BOTE NEW MATERIALS Co.,Ltd. |