CN108727201A - A kind of diethyl toluene diamine synthetic method based on zinc oxide catalyst - Google Patents
A kind of diethyl toluene diamine synthetic method based on zinc oxide catalyst Download PDFInfo
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Abstract
The diethyl toluene diamine synthetic method based on zinc oxide catalyst that the present invention relates to a kind of, belongs to technical field of fine.The present invention is for catalyst during the catalyzing and synthesizing of diethyl toluene diamine the problem of reaction impurities content is more, catalyst easy in inactivation, a kind of catalyst based on nano zine oxide loaded Ag and Y is proposed, which has the advantages that reactivity is high, impurity content is low, catalyst is with long service life.
Description
Technical field
The diethyl toluene diamine synthetic method based on zinc oxide catalyst that the present invention relates to a kind of, belongs to fining
Work technical field.
Background technology
Diethyl toluene diamine（English name Diethyltoluenediamine）Refer to that two kinds of diethyl toluene diamines are different
Structure body mixture, that is, two kinds of isomer mixtures being commercialized：3,5- diethyl -2,4- diaminotoluenes（3,5-Diethyl-
Toluene-2,4-diamine）76% and 3,5- diethyl -2,6- diaminotoluene（3,5-Diethyl-toluene-2,6-
diamine）24%, vehicle economy TDA.Diethyl toluene diamine is used as the chain extender of reaction injection molding polyurethane, and polyurethane applies
Material, epoxy resin, alkyd resin curing agent.Pesticide, dyestuff intermediate, plastics, rubber, oils antioxidant.Diethyltoluene two
Amine is the aromatic diamine curing agent of polyurethane elastomer and epoxy resin, for pouring into a mould, coating, adhesive and poly- ammonia
The chain extender of ester and polyurea elastomer.It is fast with the reaction speed of base polyurethane prepolymer for use as, is mainly used for reacting the poly- ammonia of moulding by casting
Ester system and spraying polyurethane (urea) elastic coating system have reaction speed fast, and demoulding time is short, initial strength is high, system
Product hydrolysis, it is heat-resisting the advantages that.In addition the product also act as the antioxidant of elastomer, lubricant and commercial grease, and chemistry
Synthetic intermediate.
Traditional diethyl toluene diamine (DETDA) synthetic method：Toluenediamine（TDA）It is raw material with ethylene, is being catalyzed
Under the existence condition of agent, alkylated reaction occurs for high temperature and pressure, is formed through refined.Synthesis diethyl toluene diamine (DETDA) is urged
Agent includes mainly：Aluminium powder, alchlor, alkylation aluminium, alumin(i)um zinc alloy-alchlor mixed system, alumin(i)um zinc alloy-tri-chlorination
Aluminium-alkylation aluminium mixed system.But above-mentioned catalyst the problem of that all there is reactivities is not high, short life.
Invention content
The present invention for catalyst during the catalyzing and synthesizing of diethyl toluene diamine reaction impurities content is more, catalyst
The problem of easy in inactivation, it is proposed that a kind of catalyst based on nano zine oxide loaded Ag and Y, the catalytic reaction process have reaction
Activity is high, impurity content is low, catalyst advantage with long service life.
Technical solution is：
A kind of diethyl toluene diamine synthetic method based on zinc oxide catalyst, includes the following steps：
Catalyst is added into autoclave, and is passed through N for 1st step2Toluenediamine is added after air in replacement reaction kettle
It is warming up to 120~160 DEG C；N is used again2It carries ethylene to be added into reaction kettle, and is forced into 2.0~2.5MPa, 250~290
1~4h is reacted under the conditions of DEG C；
Reactant is pressed into rectifying column after reaction and carries out rectification process by the 2nd step, and rectifying uses rectification under vacuum, steams light
After component, bottom of tower obtains diethyl toluene diamine；
The preparation method of the catalyst, includes the following steps：
S1, the preparation of nano zine oxide carrier：Urea and zinc chloride are dissolved in ethanol water, be warming up to 85~90 DEG C it
After carry out being stirred to react 1~3h, after reactant is precipitated again, sediment is dried in vacuo under the conditions of 70~80 DEG C to 2~
After 4h, 1~3h is roasted under the conditions of 200~220 DEG C in Muffle furnace, obtains carrier；
S2, the positive charge of carrier surface：According to weight ratio 6~10：4~5：100~120：3~6 by carrier, deionized water,
Toluene, Silane coupling agent KH550 mixing, at 50~55 DEG C react 2~4h, after reaction, solid product successively with acetone, go
It is dried after ion water washing, using grinding, obtains silicane coupling agent surface grafted carrier；It will be silicane coupling agent surface grafted
Carrier, acetonitrile, [BsAIm] [HSO4] ionic liquid, azodiisobutyronitrile is according to weight ratio 3~6：80~90：2~4：0.6
~0.8 is uniformly mixed in a nitrogen atmosphere, then 8~10h is reacted under the conditions of 70~75 DEG C, and after reaction, solid product is successively
It is dried after acetone, deionized water washing, using grinding, obtains the carrier of positive surface charge；
S3, AgI bear the preparation of colloidal sol：It is added dropwise 0.01 under agitation in the KI solution of 0.01~0.05mol/L~
The AgNO of 0.03mol/L3Y (the NO of solution and 0.01~0.02mol/L3)3Solution is to get negative colloidal sol；
S4, by the support dispersion of the positive surface charge obtained in step S2 in negative colloidal sol, the addition of carrier is negative colloidal sol
The 5~10% of weight remove solvent under reduced pressure after standing 3~6h, solid after roasting 2~4h under the conditions of 750~780 DEG C,
Obtain catalyst.
In 1st step, the molar ratio of toluenediamine and ethylene is 1：1.9~2.3；The weight of catalyst is toluene two
The 0.2~0.5% of amine weight.
In 2nd step, the vacuum degree during rectification under vacuum is 0.094~0.098MPa；Recovered (distilled) temperature 140~
170 DEG C, reflux ratio 2~4：1.
In step S1, concentration of alcohol is 40~60vol.% in ethanol water, and urea and zinc chloride are in ethanol water
Concentration is respectively 4~6mol/L and 1~1.8mol/L.
In step S2, KI solution, AgNO3Solution, Y (NO3)3The volume ratio of solution is：1：1.0~1.2：0.2~0.25.
Advantageous effect
The present invention is in the building-up process of diethyl toluene diamine, and catalytic efficiency is not high, the short problem of catalyst life, proposes
It is a kind of using sheet zinc oxide as carrier, using Ag and Y as the catalyst of Active sites, sheet zinc oxide carrier has than table
The big advantage of area, by after the modification of its surface ion liquid, making it carry positive charge, while bearing colloidal sol using Ag can be with
It is coated on positive charge carrier by the effect of electrostatic, cladding of the preferable activated centre on carrier can be formed, be prepared into
To catalyst compared with the existing technology in catalyst for, have the advantages that excellent catalytic effect, long lifespan.
Description of the drawings
Fig. 1 is the electron microscope of catalyst prepared by the present invention.
Fig. 2 is the XRD figures of catalyst prepared by the present invention.
Fig. 3 is the nonexpondable reaction yield comparison diagram of catalyst.
Specific implementation mode
Embodiment 1
Catalyst is added into autoclave, and is passed through N for 1st step2Toluenediamine is added after air in replacement reaction kettle
It is warming up to 120 DEG C；N is used again2It carries ethylene to be added into reaction kettle, and is forced into 2.0MPa, react 1h under the conditions of 250 DEG C,
The molar ratio of toluenediamine and ethylene is 1：1.9；The weight of catalyst is the 0.2% of toluenediamine weight；
Reactant is pressed into rectifying column after reaction and carries out rectification process by the 2nd step, and rectifying uses rectification under vacuum, steams light
After component, bottom of tower obtains diethyl toluene diamine, and the vacuum degree during rectification under vacuum is 0.094MPa；140 DEG C of recovered (distilled) temperature,
Reflux ratio 2：1；
The preparation method of the catalyst, includes the following steps：
S1, the preparation of nano zine oxide carrier：Urea and zinc chloride are dissolved in ethanol water, ethyl alcohol in ethanol water
Concentration is 40vol.%, and urea and the zinc chloride concentration in ethanol water are respectively 4mol/L and 1mol/L, are warming up to 85 DEG C
Be stirred later reaction 1h, after reactant is precipitated again, after sediment is dried in vacuo 2h under the conditions of 70 DEG C, in horse
1h not is roasted under the conditions of 200 DEG C in stove, obtains carrier；
S2, the positive charge of carrier surface：According to weight ratio 6：4：100：3 by carrier, deionized water, toluene, silane coupling agent
KH550 is mixed, and 2h is reacted at 50 DEG C, after reaction, solid product is dried after being washed successively with acetone, deionized water, then is passed through
Grinding is crossed, silicane coupling agent surface grafted carrier is obtained；By silicane coupling agent surface grafted carrier, acetonitrile, [BsAIm]
[HSO4] ionic liquid, azodiisobutyronitrile is according to weight ratio 3：80：2：0.6 is uniformly mixed in a nitrogen atmosphere, then 70 DEG C of items
8h is reacted under part, after reaction, solid product is dried after acetone, deionized water washing successively, using grinding, is obtained
The carrier of positive surface charge；
S3, AgI bear the preparation of colloidal sol：The AgNO of 0.01mol/L is added dropwise under agitation in the KI solution of 0.01mol/L3
Y (the NO of solution and 0.01mol/L3)3Solution, KI solution, AgNO3Solution, Y (NO3)3The volume ratio of solution is：1：1.0：0.2,
Up to negative colloidal sol；
S4, by the support dispersion of the positive surface charge obtained in step S2 in negative colloidal sol, the addition of carrier is negative colloidal sol
The 5% of weight after standing 3h, removes solvent under reduced pressure, and solid obtains catalyst after roasting 2h under the conditions of 750 DEG C.
Embodiment 2
Catalyst is added into autoclave, and is passed through N for 1st step2Toluenediamine is added after air in replacement reaction kettle
It is warming up to 160 DEG C；N is used again2It carries ethylene to be added into reaction kettle, and is forced into 2.5MPa, react 4h under the conditions of 290 DEG C,
The molar ratio of toluenediamine and ethylene is 1： 2.3；The weight of catalyst is the 0.5% of toluenediamine weight；
Reactant is pressed into rectifying column after reaction and carries out rectification process by the 2nd step, and rectifying uses rectification under vacuum, steams light
After component, bottom of tower obtains diethyl toluene diamine, and the vacuum degree during rectification under vacuum is 0.098MPa；170 DEG C of recovered (distilled) temperature,
Reflux ratio 4：1；
The preparation method of the catalyst, includes the following steps：
S1, the preparation of nano zine oxide carrier：Urea and zinc chloride are dissolved in ethanol water, ethyl alcohol in ethanol water
Concentration is 60vol.%, and urea and the zinc chloride concentration in ethanol water are respectively 6mol/L and 1.8mol/L, are warming up to 90
DEG C after be stirred reaction 3h, after reactant is precipitated again, after sediment is dried in vacuo 4h under the conditions of 80 DEG C,
3h is roasted under the conditions of 220 DEG C in Muffle furnace, obtains carrier；
S2, the positive charge of carrier surface：According to weight ratio 10： 5： 120：6 is even by carrier, deionized water, toluene, silane
Join agent KH550 mixing, 4h is reacted at 55 DEG C, after reaction, solid product is dried after being washed successively with acetone, deionized water,
Using grinding, silicane coupling agent surface grafted carrier is obtained；By silicane coupling agent surface grafted carrier, acetonitrile,
[BsAIm][HSO4] ionic liquid, azodiisobutyronitrile is according to weight ratio 6： 90： 4：0.8 mixes in a nitrogen atmosphere
It is even, then 10h is reacted under the conditions of 75 DEG C, after reaction, solid product is dried after acetone, deionized water washing successively, then
By grinding, the carrier of positive surface charge is obtained；
S3, AgI bear the preparation of colloidal sol：The AgNO of 0.03mol/L is added dropwise under agitation in the KI solution of 0.05mol/L3
Y (the NO of solution and 0.02mol/L3)3Solution, KI solution, AgNO3Solution, Y (NO3)3The volume ratio of solution is：1： 1.2：
0.25 to get negative colloidal sol；
S4, by the support dispersion of the positive surface charge obtained in step S2 in negative colloidal sol, the addition of carrier is negative colloidal sol
The 10% of weight after standing 6h, removes solvent under reduced pressure, and solid obtains catalyst after roasting 4h under the conditions of 780 DEG C.
Embodiment 3
Catalyst is added into autoclave, and is passed through N for 1st step2Toluenediamine is added after air in replacement reaction kettle
It is warming up to 130 DEG C；N is used again2It carries ethylene to be added into reaction kettle, and is forced into 2.2MPa, react 3h under the conditions of 280 DEG C,
The molar ratio of toluenediamine and ethylene is 1：2.2；The weight of catalyst is the 0.4% of toluenediamine weight；
Reactant is pressed into rectifying column after reaction and carries out rectification process by the 2nd step, and rectifying uses rectification under vacuum, steams light
After component, bottom of tower obtains diethyl toluene diamine, and the vacuum degree during rectification under vacuum is 0.094~0.098MPa；Distillate temperature
150 DEG C of degree, reflux ratio 3：1；
The preparation method of the catalyst, includes the following steps：
S1, the preparation of nano zine oxide carrier：Urea and zinc chloride are dissolved in ethanol water, ethyl alcohol in ethanol water
Concentration is 40~60vol.%, and urea and the zinc chloride concentration in ethanol water are respectively 5mol/L and 1.5mol/L, heating
To being stirred reaction 2h after 88 DEG C, after reactant is precipitated again, sediment is dried in vacuo 3h under the conditions of 75 DEG C
Afterwards, 2h is roasted under the conditions of 210 DEG C in Muffle furnace, obtains carrier；
S2, the positive charge of carrier surface：According to weight ratio 8：6：110：5 by carrier, deionized water, toluene, silane coupling agent
KH550 is mixed, and 3h is reacted at 52 DEG C, after reaction, solid product is dried after being washed successively with acetone, deionized water, then is passed through
Grinding is crossed, silicane coupling agent surface grafted carrier is obtained；By silicane coupling agent surface grafted carrier, acetonitrile, [BsAIm]
[HSO4] ionic liquid, azodiisobutyronitrile is according to weight ratio 5：85：3：0.7 is uniformly mixed in a nitrogen atmosphere, then 72 DEG C of items
9h is reacted under part, after reaction, solid product is dried after acetone, deionized water washing successively, using grinding, is obtained
The carrier of positive surface charge；
S3, AgI bear the preparation of colloidal sol：The AgNO of 0.02mol/L is added dropwise under agitation in the KI solution of 0.02mol/L3
Y (the NO of solution and 0.02mol/L3)3Solution, KI solution, AgNO3Solution, Y (NO3)3The volume ratio of solution is：1：1.1：
0.22 to get negative colloidal sol；
S4, by the support dispersion of the positive surface charge obtained in step S2 in negative colloidal sol, the addition of carrier is negative colloidal sol
The 6% of weight after standing 5h, removes solvent under reduced pressure, and solid obtains catalyst after roasting 3h under the conditions of 760 DEG C.
Reference examples 1
Difference with embodiment 3 is：The surface of sheet zinc oxide load is not modified using the positive chargeization of ionic liquid.
Catalyst is added into autoclave, and is passed through N for 1st step2Toluene is added after air in replacement reaction kettle
Diamines is warming up to 130 DEG C；N is used again2It carries ethylene to be added into reaction kettle, and is forced into 2.2MPa, reacted under the conditions of 280 DEG C
The molar ratio of 3h, toluenediamine and ethylene is 1：2.2；The weight of catalyst is the 0.4% of toluenediamine weight；
Reactant is pressed into rectifying column after reaction and carries out rectification process by the 2nd step, and rectifying uses rectification under vacuum, steams light
After component, bottom of tower obtains diethyl toluene diamine, and the vacuum degree during rectification under vacuum is 0.094~0.098MPa；Distillate temperature
150 DEG C of degree, reflux ratio 3：1；
The preparation method of the catalyst, includes the following steps：
S1, the preparation of nano zine oxide carrier：Urea and zinc chloride are dissolved in ethanol water, ethyl alcohol in ethanol water
Concentration is 40~60vol.%, and urea and the zinc chloride concentration in ethanol water are respectively 5mol/L and 1.5mol/L, heating
To being stirred reaction 2h after 88 DEG C, after reactant is precipitated again, sediment is dried in vacuo 3h under the conditions of 75 DEG C
Afterwards, 2h is roasted under the conditions of 210 DEG C in Muffle furnace, obtains carrier；
S2, AgI bear the preparation of colloidal sol：The AgNO of 0.02mol/L is added dropwise under agitation in the KI solution of 0.02mol/L3
Y (the NO of solution and 0.02mol/L3)3Solution, KI solution, AgNO3Solution, Y (NO3)3The volume ratio of solution is：1：1.1：
0.22 to get negative colloidal sol；
S3, by the support dispersion obtained in step S1 in negative colloidal sol, the addition of carrier is the 6% of negative sol weight, stands 5h
Afterwards, solvent is removed under reduced pressure, solid obtains catalyst after roasting 3h under the conditions of 760 DEG C.
Reference examples 2
Difference with embodiment 3 is：Y (NO are not added on the surface of catalyst3)3As activated centre presoma.
Catalyst is added into autoclave, and is passed through N for 1st step2Toluene is added after air in replacement reaction kettle
Diamines is warming up to 130 DEG C；N is used again2It carries ethylene to be added into reaction kettle, and is forced into 2.2MPa, reacted under the conditions of 280 DEG C
The molar ratio of 3h, toluenediamine and ethylene is 1：2.2；The weight of catalyst is the 0.4% of toluenediamine weight；
Reactant is pressed into rectifying column after reaction and carries out rectification process by the 2nd step, and rectifying uses rectification under vacuum, steams light
After component, bottom of tower obtains diethyl toluene diamine, and the vacuum degree during rectification under vacuum is 0.094~0.098MPa；Distillate temperature
150 DEG C of degree, reflux ratio 3：1；
The preparation method of the catalyst, includes the following steps：
S1, the preparation of nano zine oxide carrier：Urea and zinc chloride are dissolved in ethanol water, ethyl alcohol in ethanol water
Concentration is 40~60vol.%, and urea and the zinc chloride concentration in ethanol water are respectively 5mol/L and 1.5mol/L, heating
To being stirred reaction 2h after 88 DEG C, after reactant is precipitated again, sediment is dried in vacuo 3h under the conditions of 75 DEG C
Afterwards, 2h is roasted under the conditions of 210 DEG C in Muffle furnace, obtains carrier；
S2, the positive charge of carrier surface：According to weight ratio 8：6：110：5 by carrier, deionized water, toluene, silane coupling agent
KH550 is mixed, and 3h is reacted at 52 DEG C, after reaction, solid product is dried after being washed successively with acetone, deionized water, then is passed through
Grinding is crossed, silicane coupling agent surface grafted carrier is obtained；By silicane coupling agent surface grafted carrier, acetonitrile, [BsAIm]
[HSO4] ionic liquid, azodiisobutyronitrile is according to weight ratio 5：85：3：0.7 is uniformly mixed in a nitrogen atmosphere, then 72 DEG C of items
9h is reacted under part, after reaction, solid product is dried after acetone, deionized water washing successively, using grinding, is obtained
The carrier of positive surface charge；
S3, AgI bear the preparation of colloidal sol：The AgNO of 0.02mol/L is added dropwise under agitation in the KI solution of 0.02mol/L3
Solution, KI solution, AgNO3The volume ratio of solution is：1：1.1 to get negative colloidal sol；
S4, by the support dispersion of the positive surface charge obtained in step S2 in negative colloidal sol, the addition of carrier is negative colloidal sol
The 6% of weight after standing 5h, removes solvent under reduced pressure, and solid obtains catalyst after roasting 3h under the conditions of 760 DEG C.
Reference examples 3
Difference with embodiment 3 is：Using triethyl aluminum in the prior art（TEA）As catalyst.
The electron microscope for the catalyst that embodiment 3 is prepared is as shown in Figure 1, it can be seen that the activity of nano silver and nanometer yttrium
Center uniform load has the advantages that Load Balanced, large specific surface area in the surface of the zinc oxide carrier of sheet.
The XRD for the catalyst that embodiment 3 is prepared is as shown in Figure 3, it can be seen that, the diffraction maximum of zinc oxide is sharp, table
Bright crystallinity is good, compares its D value and JCDPS cards are almost the same.Illustrate that product is hexagonal system structure；Also have simultaneously and receives
The peak of meter Yin, peak position is consistent with data on JCPDS cards (JCPDSNO14-0781), illustrates that nano silver is preferably carried on oxidation
The surface of zinc carrier.
Catalysis reaction yield, product content in the above various embodiments is as shown in the table：
After after above-mentioned catalyst per is finished, being washed with deionized, drying, catalysis reaction is carried out again, is repeated 10 times
Afterwards, toluenediamine conversion ratio is as shown in the table.
Change curve curve is as shown in figure 3, it can be seen from the figure that during 10 secondary responses, catalysis provided by the invention
Agent has the advantages that with long service life for conventional catalyst.
Claims (5)
1. a kind of diethyl toluene diamine synthetic method based on zinc oxide catalyst, which is characterized in that including walking as follows
Suddenly：
Catalyst is added into autoclave, and is passed through N for 1st step2Toluenediamine is added after air in replacement reaction kettle
It is warming up to 120~160 DEG C；N is used again2It carries ethylene to be added into reaction kettle, and is forced into 2.0~2.5MPa, 250~290
1~4h is reacted under the conditions of DEG C；
Reactant is pressed into rectifying column after reaction and carries out rectification process by the 2nd step, and rectifying uses rectification under vacuum, steams light
After component, bottom of tower obtains diethyl toluene diamine；
The preparation method of the catalyst, includes the following steps：
S1, the preparation of nano zine oxide carrier：Urea and zinc chloride are dissolved in ethanol water, be warming up to 85~90 DEG C it
After carry out being stirred to react 1~3h, after reactant is precipitated again, sediment is dried in vacuo under the conditions of 70~80 DEG C to 2~
After 4h, 1~3h is roasted under the conditions of 200~220 DEG C in Muffle furnace, obtains carrier；
S2, the positive charge of carrier surface：According to weight ratio 6~10：4~5：100~120：3~6 by carrier, deionized water,
Toluene, Silane coupling agent KH550 mixing, at 50~55 DEG C react 2~4h, after reaction, solid product successively with acetone, go
It is dried after ion water washing, using grinding, obtains silicane coupling agent surface grafted carrier；It will be silicane coupling agent surface grafted
Carrier, acetonitrile, [BsAIm] [HSO4] ionic liquid, azodiisobutyronitrile is according to weight ratio 3~6：80~90：2~4：0.6
~0.8 is uniformly mixed in a nitrogen atmosphere, then 8~10h is reacted under the conditions of 70~75 DEG C, and after reaction, solid product is successively
It is dried after acetone, deionized water washing, using grinding, obtains the carrier of positive surface charge；
S3, AgI bear the preparation of colloidal sol：It is added dropwise 0.01 under agitation in the KI solution of 0.01~0.05mol/L~
The AgNO of 0.03mol/L3Y (the NO of solution and 0.01~0.02mol/L3)3Solution is to get negative colloidal sol；
S4, by the support dispersion of the positive surface charge obtained in step S2 in negative colloidal sol, the addition of carrier is negative colloidal sol
The 5~10% of weight remove solvent under reduced pressure after standing 3~6h, solid after roasting 2~4h under the conditions of 750~780 DEG C,
Obtain catalyst.
2. the diethyl toluene diamine synthetic method according to claim 1 based on zinc oxide catalyst, feature
It is, in the 1st step, the molar ratio of toluenediamine and ethylene is 1：1.9~2.3；The weight of catalyst is toluenediamine
The 0.2~0.5% of weight.
3. the diethyl toluene diamine synthetic method according to claim 1 based on zinc oxide catalyst, feature
It is, in the 2nd step, the vacuum degree during rectification under vacuum is 0.094~0.098MPa；Recovered (distilled) temperature 140~170
DEG C, reflux ratio 2~4：1.
4. the diethyl toluene diamine synthetic method according to claim 1 based on zinc oxide catalyst, feature
It is, in step S1, concentration of alcohol is 40~60vol.% in ethanol water, and urea and zinc chloride are dense in ethanol water
Degree is respectively 4~6mol/L and 1~1.8mol/L.
5. the diethyl toluene diamine synthetic method according to claim 1 based on zinc oxide catalyst, feature
It is, in step S2, KI solution, AgNO3Solution, Y (NO3)3The volume ratio of solution is：1：1.0~1.2：0.2~0.25.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1657415A (en) * | 2005-02-02 | 2005-08-24 | 苏州大学 | Preparation method of nanometer zinc oxide |
| CN106083605A (en) * | 2016-06-03 | 2016-11-09 | 山东崇舜化工有限公司 | A kind of method synthesizing diethyl toluene diamine |
| CN106946714A (en) * | 2017-03-16 | 2017-07-14 | 安阳工学院 | A kind of synthesis technique of diethyl toluene diamine |
-
2018
- 2018-04-24 CN CN201810370998.2A patent/CN108727201B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1657415A (en) * | 2005-02-02 | 2005-08-24 | 苏州大学 | Preparation method of nanometer zinc oxide |
| CN106083605A (en) * | 2016-06-03 | 2016-11-09 | 山东崇舜化工有限公司 | A kind of method synthesizing diethyl toluene diamine |
| CN106946714A (en) * | 2017-03-16 | 2017-07-14 | 安阳工学院 | A kind of synthesis technique of diethyl toluene diamine |
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| CN108727201B (en) | 2021-02-02 |
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