CN105013510B - The solid catalyst for synthesizing of one plant growth regulators DA 6 - Google Patents
The solid catalyst for synthesizing of one plant growth regulators DA 6 Download PDFInfo
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- CN105013510B CN105013510B CN201510314840.XA CN201510314840A CN105013510B CN 105013510 B CN105013510 B CN 105013510B CN 201510314840 A CN201510314840 A CN 201510314840A CN 105013510 B CN105013510 B CN 105013510B
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Abstract
The invention discloses the solid catalyst for synthesizing of a plant growth regulators DA 6.The solid catalyst of the present invention, is to mix appropriate polyurethane foam microballoon and alumina powder, adds suitable quantity of water, be thoroughly mixed, in two times high-temperature process, prepare porous aluminum oxide carrier；Then carrier is soaked with the concentrated sulfuric acid and filtered；The solid matter that finally will filter out prepares solid catalyst in 5~8 hours in 200~300 DEG C of heat treatments.The solid catalyst of the present invention, is applied in plant growth regulator DA 6 synthesis, can greatly improve reaction rate and conversion ratio, and the yields of DA 6 that reaction is obtained can reach more than 96%, the products of DA 6 of higher degree are just can obtain without removal of impurities；Noxious material and pollution environment will not be discharged simultaneously, are met green and healthy agricultural and are required and trend.
Description
Technical field
Present invention relates particularly to a kind of solid catalyst and its application.
Background technology
DA-6（Caproic acid N, N- diethylaminoethanol ester）A kind of new plant growth regulator, it have auxin,
A variety of functions such as gibberellin and the basic element of cell division.DA-6 is widely used in cereal crops, industrial crops, fruit tree, vegetables, flower
On grass, promoting germination, improving seedlings root vigor, improving the activity of plant peroxidases and nitrate reductase, carry
In terms of the content of high chlorophyll, enhancing crop disease-resistant, cold tolerance, high physiologically active is shown.
In industry, DA-6 synthetic method is all to use amidatioon or chloride method mostly, and these methods are produced in processes
Raw a large amount of waste water and acyl chlorides discarded object, it is seriously polluted.Caproic acid and esterification route of the diethylaminoethanol for material are used, because of esterification
The invertibity of process, using traditional esterification catalyst, such as toluenesulfonic acid, the concentrated sulfuric acid and benzene sulfonic acid, the yield of acquisition is often
It is relatively low, generally also need to add toluene or hexamethylene equal solvent as water entrainer.In production, toluene or hexamethylene etc. are used as band water
Agent, is difficult that abjection is clean in DA-6 products, there is huge potential safety hazard and risk of environmental pollution in agricultural production application,
It is difficult after these solvents are mixed with water simultaneously to reclaim, it can also increase extra cost.Therefore, people seeking always new catalyst and
Synthetic method.
People are seeking new catalyst and synthetic method always, it is therefore intended that DA-6 yield is improved, while not polluting
Environment, it is often more important that do not have any harm to crops, meets pursuit of the modern for environment protection health.
In recent years, proton acid system, non-acid catalyst method and solid acid catalysis method have tremendous development.Bronsted acid catalyst
It is the acid centre by catalyst surface（Such as silica gel）Or it is ionizable go out H+The aobvious acidity of ion, carrys out catalytic esterification.
P-methyl benzenesulfonic acid is strong protonic acid, as catalyst it have the advantages that raw material be easy to get, it is with low cost；But it is molten to there is catalyst
The problem of can not being recycled in product or waste liquid.Some organo-metallic compounds as non-acid catalyst also serve as esterification and
The catalyst of ester exchange reaction, wherein organic titanium are exactly a class；Using such catalyst, reaction condition is gentle, yield is high, reaction
Speed is fast and catalyst and product are easily isolated, and makes product easy purification；But it is expensive, cost is higher.Solid acid catalysis
Method, there is also yield is not high, various catalyst preparations are cumbersome, it is expensive the problems such as.
Therefore, how higher DA-6 yields is obtained using economical and practical catalyst and the requirement of environment protection health is met
It is the problem of current research needs to solve.
The content of the invention
It is an object of the invention to provide a kind of solid catalyst；
Another object of the present invention is to provide the preparation method of a plant growth regulators DA-6.
The technical solution used in the present invention is：
1. a kind of solid catalyst, its preparation method comprises the following steps：
1) appropriate polyurethane foam microballoon and alumina powder are mixed, adds suitable quantity of water, be thoroughly mixed, 120
~180 DEG C are heat-treated 3 ~ 6 hours, continue to increase the temperature to 350~500 DEG C and are heat-treated 2~4 hours, prepare porous oxygen
Change alumina supporter；
2) the porous aluminum oxide carrier concentrated sulfuric acid prepared is soaked into 1~3h, wherein porous aluminum oxide carrier
Volume ratio with the concentrated sulfuric acid is 1：（1~4）；Then filtered；
3) solid matter that will filter out prepares solid catalyst in 5~8 hours in 200~300 DEG C of heat treatments.
For the further improvement of above-mentioned solid catalyst, a diameter of 1~3mm of polyurethane foam microballoon.
For the further improvement of above-mentioned solid catalyst, the granularity of alumina powder is 200~400 mesh.
For the further improvement of above-mentioned solid catalyst, step 1）The alumina powder of middle addition, polyurethane foam are micro-
The mass ratio of ball and water is 100：（0.2~0.6）：（10~20）.
For the further improvement of above-mentioned solid catalyst, step 1）Middle reaction condition is heat-treated 4 hours for 150 DEG C, after
It is continuous to increase the temperature to 400 DEG C and be heat-treated 3 hours, prepare porous aluminum oxide carrier.
For the further improvement of above-mentioned solid catalyst, step 2）Middle porous aluminum oxide carrier and mass percent are dense
The volume ratio for the concentrated sulfuric acid that degree is 98% is 1：（1~3）.
For the further improvement of above-mentioned solid catalyst, step 3）Middle reaction condition is 250 DEG C and is heat-treated 6 hours.
One plant growth regulators DA-6 preparation method, comprises the following steps：
1) n-caproic acid and diethylaminoethanol are put into reactor, then adds solid catalyst；Wherein add just oneself
Acid, the mass ratio of diethylaminoethanol and solid catalyst are（45~54）：（45~54）：（1~5）；
2) in the case where being passed through protection gas, 130~150 DEG C of 3~8h of reaction is heated to and crosses and filters out out catalyst, are planted
Thing growth adjustment DA-6；
Wherein solid catalyst is as described above.
For the further improvement of above-mentioned preparation method, step 1）Middle addition n-caproic acid, diethylaminoethanol and solid
The mass ratio of catalyst is 54:50:2.
For the further improvement of above-mentioned preparation method, step 2）In be heated to 150 DEG C reaction 6~8h filtering prepare
Plant growth adjustment DA-6.
The beneficial effects of the invention are as follows：
Of the invention used polyurethane foam microballoon and alumina powder are common materials, and inexpensive, are obtained
The solid catalyst processes obtained are simple, economical and practical, can Reusability.
The solid catalyst of the present invention, applies in plant growth regulator DA-6 synthesis, can greatly improve reaction
Speed and conversion ratio, the DA-6 yields that reaction is obtained can reach more than 96%, and higher degree is just can obtain without removal of impurities
DA-6 products.Will not give off noxious material pollution environment simultaneously, preparation-obtained DA-6 in agricultural can with safe to use,
Green and healthy agricultural is complied fully with to require and trend.
Plant growth regulators DA-6 disclosed by the invention preparation method, applies solid catalyst, while
N has been used in technique2Innovation of the gas with water and water knockout drum also solves environmental pollution and the cost that prior synthesizing method is brought
The problems such as increase.
Embodiment
Below in conjunction with specific embodiment, the present invention is further illustrated, but is not limited thereto.
Prepare plant growth regulator DA-6 solid catalyst for synthesizing：
The material of the polyurethane foam microballoon used in following examples is what polyisocyanates was obtained with polyol reaction
Foam microspheres, a diameter of 1~3mm.
Embodiment a
1) polyurethane foam 0.2~0.6g of microballoon is weighed, granularity is 200~400 mesh alumina powder 100g, and both are mixed
Close, add 10~20g water, be thoroughly mixed, 150 DEG C are heat-treated 4 hours, continue to increase the temperature to 400 DEG C of heat treatments 3
Hour, prepare porous aluminum oxide carrier；
2) by step 1）In the porous aluminum oxide carrier mass percent concentration for preparing soaked for 98% concentrated sulfuric acid
1~3h is steeped, the wherein volume ratio of alumina support and the concentrated sulfuric acid is 1:1~1:3；Then filtered；
3) solid matter that will filter out prepares solid catalyst in 6 hours in 250 DEG C of heat treatments.
Embodiment b
1) polyurethane foam 0.4~1.2g of microballoon is weighed, granularity is 200~400 mesh alumina powder 200g, and both are mixed
Close, add 30g water, be thoroughly mixed, 120~180 DEG C are heat-treated 3 ~ 6 hours, continue to increase the temperature to 350~500
DEG C heat treatment 2~4 hours, prepare porous aluminum oxide carrier；
2) by step 1）In the porous aluminum oxide carrier mass percent concentration for preparing soaked for 98% concentrated sulfuric acid
1~3h is steeped, the wherein volume ratio of alumina support and the concentrated sulfuric acid is 1:1~1:4；Then filtered；
3) solid matter that will filter out prepares solid catalyst in 5~8 hours in 200~300 DEG C of heat treatments.
Prepare plant growth regulator DA-6
Embodiment 1
54g n-caproic acids and 45g diethylaminoethanols are added in reactor, then adds and is prepared in 1g embodiments a
Solid catalyst.N is passed through with 20mL/min speed2, while accessing condenser pipe, reaction mass is heated to 130~150 DEG C
2~10h is reacted, crosses and filters out out catalyst, plant growth adjustment DA-6 is obtained；Every 2 hour sampling once, sample adds first
Benzene dilutes 10 times, and yield is analyzed with gas chromatograph.
Learnt by chromatography result, show good effect using the solid catalyst of the present invention, 2h yields are reachable
56.06%, 4h yield are that 75.75%, 6h yields are that 87.05%, 8h yields are 93.22%, and yield is not dramatically increased during 8~10h.
Consider from cost-effective, the reaction time is using 8h as benefit.Plant growth regulator DA-6 is prepared using this method environmentally safe
Any poisonous waste is not discharged, is complied fully with green and healthy agricultural and is required and trend.
Embodiment 2
54g n-caproic acids and 50g diethylaminoethanols are put into reactor, stood to after room temperature, 2g embodiments a is added
In the solid catalyst for preparing.N is passed through with 40mL/min speed2, while accessing condenser pipe, reactor is heated to 150
DEG C reaction 2~10h, cross filter out out catalyst, obtain plant growth adjust DA-6；Every 2 hour sampling once, sample is added
10 times of dilution with toluene, yield is analyzed with gas chromatograph.
Learnt by chromatography result, show good effect using the solid catalyst of the present invention, 2h yields are reachable
60.98%, 4h yield are that 75.44%, 6h yields are that 89.72%, 8h yields are 96.69%, reach more than 96%.Yield during 8~10h
Do not dramatically increase, so the reaction time is using 8h as benefit.Plant growth regulator DA-6 is prepared to environment without dirt using this method
Contaminate and do not discharge any poisonous waste, comply fully with green and healthy agricultural and require and trend.
Embodiment 3
N-caproic acid 54g and diethylaminoethanol 54g are put into reactor, stood to after room temperature, 3g embodiments b is added
In solid catalyst.N is passed through with 50mL/min speed2, while access condenser pipe, by reactor be heated to 150 DEG C reaction 2~
10h, crosses and filters out out catalyst, obtains plant growth adjustment DA-6；Every 2 hour sampling once, sample adds dilution with toluene
10 times, yield is analyzed with gas chromatograph.
Learnt by chromatography result, good effect is shown using the solid catalyst of the present invention, react 2h yields
It is that 73.44%, 6h yields are that 86.72%, 8h yields are 95.61% up to 60.81%, 4h yields, reaches more than 95%.
Result to embodiment 1~3 enters row-column list contrast, as a result as follows:
The table 1 not yield for the plant growth regulator DA-6 that be the same as Example is obtained and reaction time relation
As known from Table 1, the mass ratio that n-caproic acid, diethylaminoethanol and solid catalyst are added in embodiment 2 is 54:
50:When 2,8h yield highests reach more than 96%.
Comparative example
N-caproic acid 54 and diethylaminoethanol 50 are put into reactor, stood to after room temperature, 3g benzene sulfonic acids are added.With
50mL/min speed is passed through N2, while accessing condenser pipe, reactor is heated to 150 DEG C of 2~10h of reaction, crosses and filters out out catalysis
Agent, obtains plant growth adjustment DA-6；Sampled once every two hours, and add dilution with toluene sampling product, finally made
Yield is analyzed with gas chromatograph.
The chromatography result of embodiment 2 and comparative example is contrasted, table 2 is obtained, it is as follows：
The comparative analysis of the plant growth regulator DA-6 yields of table 2
It can be seen that by the result of table 2, in the case that other reaction conditions are the same, after the solid catalyst using the present invention, instead
It should be able to carry out rapidly, during reaction 2h, DA-6 yield reaches 60.9%.Using benzene sulfonic acid as catalyst, DA-6 yields are only
For 19.9%；React after 8h, the yield of embodiment 2 is 96.69%, and the yield of comparative example is only 51.40%, difference 45.29%.
To sum up, in plant growth regulator DA-6 building-up process, shown well using the solid catalyst of the present invention
Effect, not only need the amount of catalyst few using the catalyst, and reaction rate and DA-6 yield can be significantly improved, should
Technology path belongs to friendly process process, and product is free of any harmful substance, and process economy efficiently, is discharged almost without " three wastes ".
Claims (9)
1. a kind of solid catalyst, it is characterised in that its preparation method comprises the following steps：
1）By alumina powder, polyurethane foam microballoon and water according to mass ratio be 100：（0.2~0.6）：（10~20）Mixing,
It is thoroughly mixed, 120~180 DEG C are heat-treated 3 ~ 6 hours, continues to increase the temperature to 350~500 DEG C and be heat-treated 2~4 hours,
Prepare porous aluminum oxide carrier；
2）By the porous aluminum oxide carrier concentrated sulfuric acid prepared soak 1~3h, wherein porous aluminum oxide carrier with it is dense
The volume ratio of sulfuric acid is 1：（1~4）；Then filtered；
3）The solid matter that will filter out prepares solid catalyst in 5~8 hours in 200~300 DEG C of heat treatments.
2. a kind of solid catalyst according to claim 1, it is characterised in that：The polyurethane foam microballoon it is a diameter of
1~3mm.
3. a kind of solid catalyst according to claim 1, it is characterised in that：The granularity of the alumina powder is 200
~400 mesh.
4. a kind of solid catalyst according to claim 1, it is characterised in that：Step 1）Middle reaction condition is 150 DEG C of heat
Processing 4 hours, continues to increase the temperature to 400 DEG C and is heat-treated 3 hours, prepare porous aluminum oxide carrier.
5. a kind of solid catalyst according to claim 1, it is characterised in that：Step 2）Middle porous aluminum oxide carrier with
The volume ratio for the concentrated sulfuric acid that mass percent concentration is 98% is 1：（1~3）.
6. a kind of solid catalyst according to claim 1, it is characterised in that：Step 3）Middle reaction condition is 250 DEG C of heat
Processing 6 hours.
7. the preparation method of a plant growth regulators DA-6, comprises the following steps：
1）N-caproic acid and diethylaminoethanol are put into reactor, solid catalyst is then added；Wherein add n-caproic acid, two
The mass ratio of ethylaminoethanol and solid catalyst is（45~54）：（45~54）：（1~5）；
2）In the case where being passed through protection gas, it is heated to 130~150 DEG C of 3~8h of reaction and crosses and filter out out catalyst, obtain plant life
The long DA-6 that adjusts；
Wherein solid catalyst is as described in claim 1~6 any one.
8. preparation method according to claim 7, it is characterised in that：Step 1）Middle addition n-caproic acid, diethylaminoethanol
And the mass ratio of solid catalyst is 54:50:2.
9. the preparation method according to claim 7 or 8, it is characterised in that：Step 2）In be heated to 150 DEG C reaction 6~8h
Filtering prepares plant growth adjustment DA-6.
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