CN109020843A - A kind of naphthalene sulfonate-alkylnaphthalene sulfonate-formaldehyde condensation products preparation method and applications - Google Patents
A kind of naphthalene sulfonate-alkylnaphthalene sulfonate-formaldehyde condensation products preparation method and applications Download PDFInfo
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- CN109020843A CN109020843A CN201811103099.2A CN201811103099A CN109020843A CN 109020843 A CN109020843 A CN 109020843A CN 201811103099 A CN201811103099 A CN 201811103099A CN 109020843 A CN109020843 A CN 109020843A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
- C07C2/862—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms
- C07C2/864—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms the non-hydrocarbon is an alcohol
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
- C07C303/04—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups
- C07C303/06—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups by reaction with sulfuric acid or sulfur trioxide
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
- C07C303/22—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof from sulfonic acids, by reactions not involving the formation of sulfo or halosulfonyl groups; from sulfonic halides by reactions not involving the formation of halosulfonyl groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
Abstract
The invention discloses a kind of naphthalene sulfonate-alkylnaphthalene sulfonate-formaldehyde condensation products preparation methods, firstly, naphthalene and alkylating reagent generate the mixed liquor of naphthalene and alkylnaphthalene under the catalysis of sulfuric acid；Then, sulfuric acid is added into the mixed liquor of naphthalene and alkylnaphthalene, carries out sulfonating reaction；It adds formaldehyde and naphthalene sulfonate-alkylnaphthalene sulfonate-formaldehyde condensation products is prepared by one kettle way condensation；It is not necessary that naphthalene sulfonic acids and alkyl naphthalene sulfonic acid, easy to operate is prepared separately；Without removing spent acid, not generating acid waste water, safety and environmental protection；Naphthalene sulfonate-alkylnaphthalene sulfonate-formaldehyde condensation products of preparation in pesticide water dispersible granules or suspending agent, have higher suspensibility, thermodynamic stability more preferable as application of dispersant.
Description
Technical field
The present invention relates to pesticide formulation process technology region, more particularly to a kind of naphthalene sulfonate-alkylnaphthalene sulphur
Hydrochlorate-formaldehyde condensation products preparation method and applications.
Background technique
Naphthalene sulfonic formaldehyde condensation compound is a kind of anionic surfactant, have it is good emulsification, dispersion, wetting and
The performances such as infiltration, are now widely used for the industries such as leather, dyestuff, pesticide, building concrete.Wherein, sodium naphthalene sulfonate-alkylnaphthalene
Sodium sulfonate-formaldehyde condensation species dispersing agent with single monomer naphthalene sulfonic acids or alkyl naphthalene sulfonic acid compared with formaldehyde condensation products dispersing agent,
More excellent performance is all shown in all respects.Currently, preparing sodium naphthalene sulfonate-Negel-formaldehyde condensation both at home and abroad
The method of object mainly has following steps: 1) naphthalene synthesizes naphthalene sulfonic acids with sulfonating agent；2) naphthalene, alkylating reagent and sulfonating agent synthesize alkane
Base naphthalene sulfonic acids；3) after above-mentioned naphthalene sulfonic acids being mixed according to a certain percentage with alkyl naphthalene sulfonic acid, then with system is neutralized after formaldehyde condensation again
Obtain condensation liquid.
But there are mainly two types of approach for decalin base, sulfonation in existing preparation method, there is apparent defect: 1)
Use alkylol as alkylating reagent, oleum is alkylated sulfonation and carries out simultaneously as sulfonating agent and alkylation catalyst,
Reaction terminates that stratification operation point is needed to remove spent acid, as the Chinese patent of Publication No. CN107602421A discloses a kind of naphthalene
Sulfuric acid and oleum is added dropwise in the preparation process of sulfonic acid and butyl naphthalene sulfonic acid-formaldehyde condensation product after wherein naphthalene is mixed with n-butanol
Nitration mixture, stratification point removes spent acid after insulation reaction, and butyl naphthalene sulfonic acids can be obtained；But this technique uses a large amount of acid, no
Only increase cost of material, and increase the workload for removing acid, while generating a large amount of acid waste waters, pollution environment, increases quiet
Stratification step is set, is made cumbersome.2) naphthalene is first completed to be alkylated with alkylating reagent, then isolates alkylnaphthalene and carry out sulfonation, this
Alkylated reaction report has solid acid and ionic liquid-catalyzed technique in technique, and available selectivity and purity are relatively high
Product；But catalyst is influenced vulnerable to raw material and is inactivated, and expensive, high to ingredient requirement, process complexity, is difficult to realize work
Industry.
Therefore it provides naphthalene sulfonate-alkylnaphthalene sulfonate-first that a kind of step is simple, cost of material is low, ingredient requirement is low
The problem of preparation method of aldehyde condensate is those skilled in the art's urgent need to resolve.
Summary of the invention
In view of this, the present invention provides a kind of naphthalene sulfonate-alkylnaphthalene sulfonate-formaldehyde condensation products preparation method,
It is not necessary that naphthalene sulfonic acids and alkyl naphthalene sulfonic acid, easy to operate is prepared separately；Without removing spent acid, not generating acid waste water, safety and environmental protection；
Naphthalene sulfonate-alkylnaphthalene sulfonate-formaldehyde condensation products of preparation are as application of dispersant in pesticide water dispersible granules or suspending agent
In, have higher suspensibility, thermodynamic stability more preferable.
To achieve the goals above, the present invention adopts the following technical scheme:
A kind of naphthalene sulfonate-alkylnaphthalene sulfonate-formaldehyde condensation products preparation method, which is characterized in that firstly, naphthalene and alkane
Base reagent generates the mixed liquor of naphthalene and alkylnaphthalene under the catalysis of sulfuric acid；Then, it is added into the mixed liquor of naphthalene and alkylnaphthalene
Sulfuric acid carries out sulfonating reaction；It adds formaldehyde and naphthalene sulfonate-alkylnaphthalene sulfonate-formaldehyde is prepared by one kettle way condensation
Condensation product.
The beneficial effect of above-mentioned optimal technical scheme is: the mixing of naphthalene and alkylating reagent that the present invention is directly prepared
Liquid, then the mixture of naphthalene sulfonic acids and alkyl naphthalene sulfonic acid can be obtained by sulfonation by mixed liquor, without prepare respectively naphthalene sulfonic acids and
Alkyl naphthalene sulfonic acid；It can reach catalytic effect using a small amount of concentrated sulfuric acid in alkylation process, reduce the dosage of acid, avoid sour wave
Take and without removing spent acid；Whole preparation flow is simple, efficient, safe, has excellent development prospect.
Preferably, specifically comprise the following steps:
(1) alkylated reaction: naphthalene, alkylating reagent and sulfuric acid being mixed, then increase temperature under stirring condition, kept the temperature
The mixed liquor of naphthalene and alkylnaphthalene is prepared in reaction；
(2) sulfonating reaction: to sulfuric acid is added in the mixed liquor of above-mentioned naphthalene and alkylnaphthalene, heating up under stirring condition, and heat preservation is anti-
Ying Hou adds water adjustment acidity, sulfonated liquid is prepared；
(3) condensation reaction: reducing the temperature of above-mentioned sulfonated liquid, adds formalin, and insulation reaction obtains condensation liquid；
(4) neutralization reaction: reducing the temperature of condensation liquid obtained above, neutralizer is added and carries out neutralization reaction, obtains
And reaction product；
(5) it post-processes: neutralized reaction product obtained above being dried, moisture is boiled off and obtains brown solid product i.e.
For naphthalene sulfonate-alkylnaphthalene sulfonate-formaldehyde condensation products.
Preferably, alkylating reagent includes alkylol in the step (1), and the mass concentration of sulfuric acid is 98%, neutralizer
Including alkali metal hydroxide.
Preferably, the alkylol includes ethyl group alcohol, propyl alcohol, butane group alcohol, pentyl alcohol, hexyl alcohol, heptan
Alkylol, octyl alcohol, nonyl alcohol or decyl alcohol.
Preferably, the alkylol includes propyl alcohol, butane group alcohol or pentyl alcohol.
The beneficial effect of above-mentioned optimal technical scheme is: the present invention propyl alcohol, butane group alcohol or pentane selected to use
Base alcohol, boiling point is relatively high, it can be ensured that alkylation temperature is higher, so as to improve alkylation efficiency；And carbochain phase
To compared with short, steric hindrance is small, it is ensured that do not influence to be alkylated efficiency, so as to obtain optimal naphthalene/alkylnaphthalene ratio.
Preferably, the alkali metal hydroxide includes sodium hydroxide or potassium hydroxide.
Preferably, the naphthalene includes refined naphthalene or crude naphthalene is one such or two kinds of mixtures.
Preferably, the molar ratio of naphthalene, alkylating reagent and sulfuric acid is 1.0:0.1-2.0:0.05- in the step (1)
0.2；Temperature is increased to 80-140 DEG C, insulation reaction 4-6h.
It preferably, is that sulfuric acid is added in 1.0:1.0-1.3 according to the molar ratio of naphthylene group and sulfuric acid in the step (2)；Temperature
Degree rises to 150-160 DEG C, and insulation reaction 3-5h, acidity is adjusted to 24-26%.
Preferably, it is 1.0:0.8-1.0 according to the molar ratio of naphthylene group and formaldehyde in the step (3), formaldehyde is added；It will
Temperature is adjusted to 80-90 DEG C, insulation reaction 2-4h.
Preferably, temperature is reduced to 30-50 DEG C in the step (4), and temperature is controlled at < 80 DEG C during neutralization reaction,
Obtained neutralization reaction product pH=7-9.
Preferably, be dried in the step (5) is specially to be spray-dried.
The present invention also provides a kind of naphthalene sulfonate-application of the alkylnaphthalene sulfonate-formaldehyde condensation products in pesticidal preparations,
It is characterized in that, naphthalene sulfonate-alkylnaphthalene sulfonate-the formaldehyde condensation products are prepared using method as described above.
The beneficial effect of above-mentioned optimal technical scheme is: naphthalene sulfonate-alkylnaphthalene sulfonate prepared by the present invention-formaldehyde contracting
Object is closed as application of dispersant in pesticide water dispersible granules or suspending agent, it is more preferable with higher suspensibility, thermodynamic stability,
So as to improve the drug effect of pesticide.
Preferably, the naphthalene sulfonate-alkylnaphthalene sulfonate-formaldehyde condensation products are as aqueous suspension agent, water dispersible granules, dry
Suspending agent or wettable powder are used for pesticidal preparations.
It can be seen via above technical scheme that compared with prior art, the present disclosure provides a kind of naphthalene sulfonate-alkane
The preparation method of base naphthalene sulfonate-formaldehyde condensation product is alkylated in sulfonation process it is not necessary that naphthalene sulfonic acids and alkylnaphthalene sulphur is prepared separately
Acid does not generate acid waste water, easy to operate, safety and environmental protection without separating spent acid；Naphthalene sulfonate-alkylnaphthalene sulfonate-of preparation
Formaldehyde condensation products as application of dispersant in pesticide water dispersible granules or suspending agent, by the electrostatic repulsion of sulfonic acid hydrophilic group,
Under the collective effect for the steric hindrance that naphthalene nucleus, the dispersion force of alkyl naphthalene nucleus hydrophobic group and itself macromolecular structure generate, guarantee
The smoothness of Pesticide formulation, higher suspension rate and storage stability；It can be applied to high concentration agricultural chemical water as dispersing agent
In dispersible granule, preparation has many advantages, such as that suspensibility is high, thermodynamic stability is good.
Specific embodiment
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
Technical staff's every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
A kind of naphthalene sulfonate-alkylnaphthalene sulfonate-formaldehyde condensation products preparation method, specifically comprises the following steps:
(1) alkylated reaction: naphthalene, alkylating reagent and sulfuric acid are mixed according to molar ratio for 1.0:0.1-2.0:0.05-0.2
It closes；Then 80-150 DEG C is raised the temperature under stirring condition, the mixed liquor of naphthalene and alkylnaphthalene is prepared in insulation reaction 4-6h；
(2) sulfonating reaction: being 1.0:1.0-1.3 to the mixed of above-mentioned naphthalene and alkylnaphthalene according to the molar ratio of naphthylene group and sulfuric acid
It closes in liquid and sulfuric acid is added, be warming up to 150-160 DEG C under stirring condition, after insulation reaction 3-5h, add water and adjust acidity to 24-
26%, sulfonated liquid is prepared；
(3) condensation reaction: the temperature of above-mentioned sulfonated liquid is reduced to 80-90 DEG C, according still further to the molar ratio of naphthylene group and formaldehyde
Formalin is added for 1.0:0.8-1.0, insulation reaction 2-4h obtains condensation liquid；
(4) neutralization reaction: reducing the temperature of condensation liquid obtained above to 30-50 DEG C, and neutralizer is added and neutralize instead
It answers and controls temperature at < 80 DEG C, obtain the neutralization reaction product of pH=7-9；
(5) it post-processes: neutralized reaction product obtained above being dried, moisture is boiled off and obtains brown solid product i.e.
For naphthalene sulfonate-alkylnaphthalene sulfonate-formaldehyde condensation products.
For further optimisation technique scheme, the alkylating reagent includes alkylol, and the sulfuric acid is mass concentration
For 98% concentrated sulfuric acid, the neutralizer includes alkali metal hydroxide.
For further optimisation technique scheme, the alkylating reagent is alkylol, the alkali metal hydroxide packet
Include sodium hydroxide or potassium hydroxide.
For further optimisation technique scheme, the alkylol includes ethyl group alcohol, propyl alcohol, butane group alcohol, penta
Alkylol, hexyl alcohol, alkylol in heptan, octyl alcohol, nonyl alcohol or decyl alcohol.
For further optimisation technique scheme, the alkylol includes propyl alcohol, butane group alcohol or pentyl alcohol.
For further optimisation technique scheme, the naphthalene includes refined naphthalene or crude naphthalene is one such or two kinds mix
Object.
Be dried for further optimisation technique scheme, in the step (5) is specially to be spray-dried.
The present invention also provides a kind of naphthalene sulfonate-application of the alkylnaphthalene sulfonate-formaldehyde condensation products in pesticidal preparations,
Naphthalene sulfonate-alkylnaphthalene sulfonate-formaldehyde condensation products are prepared using method as described above.
For further optimisation technique scheme, naphthalene sulfonic acids-alkyl naphthalene sulfonic acid-formaldehyde condensation products are as aqueous suspension agent, water
Dispersible granule, dry suspending agent or wettable powder are used for pesticidal preparations.
Embodiment 1
A kind of naphthalene sulfonate-alkylnaphthalene sulfonate-formaldehyde condensation products preparation method, specifically comprises the following steps:
(1) alkylated reaction: the dense sulphur that 64g refined naphthalene, 6.5g isopropanol and 2.5g mass concentration are 98% is first sequentially added
Acid；Then 90 DEG C are raised the temperature under stirring condition, the mixed liquor of naphthalene and alkylnaphthalene, efficient liquid is prepared in insulation reaction 6h
It is 80:20 that phase chromatography, which detects naphthalene and isopropyl naphthalene content ratio in mixed liquor,；
(2) sulfonating reaction: in the mixed liquor of above-mentioned naphthalene and alkylnaphthalene be added 50g mass concentration be 98% the concentrated sulfuric acid,
It is warming up to 160 DEG C under stirring condition, after insulation reaction 5h, adds water adjustment acidity to 26%, sulfonated liquid is prepared；
(3) condensation reaction: being reduced to 80 DEG C for the temperature of above-mentioned sulfonated liquid, adds the first that 40g mass concentration is 37%
Aldehyde aqueous solution, insulation reaction 4h obtain condensation liquid；
(4) neutralization reaction: reducing the temperature of condensation liquid obtained above to 50 DEG C, and sodium hydroxide is added and neutralize instead
It answers and controls temperature at < 80 DEG C, obtain the neutralization reaction product of pH=7.5；
(5) it post-processes: above-mentioned neutralized reaction product naphthalene sulfonic sodium formaldehyde condensation liquid is delivered to pneumatic spray drying through pump
Tower is spray-dried, and is contracted again through the isolated brown color sodium naphthalene sulfonate-isopropyl naphthalene sulfonate-formaldehyde of secondary cyclone later
Object finished product is closed, inlet air temperature is 165 DEG C in spray drying tower, and leaving air temp is 90 DEG C.
Embodiment 2
A kind of naphthalene sulfonate-alkylnaphthalene sulfonate-formaldehyde condensation products preparation method, specifically comprises the following steps:
(1) alkylated reaction: the dense sulphur that 64g refined naphthalene, 13g isopropanol and 5.0g mass concentration are 98% is first sequentially added
Acid；Then 85 DEG C are raised the temperature under stirring condition, the mixed liquor of naphthalene and alkylnaphthalene, efficient liquid is prepared in insulation reaction 4h
It is 60:40 that phase chromatography, which detects naphthalene and isopropyl naphthalene content ratio in mixed liquor,；
(2) sulfonating reaction: in the mixed liquor of above-mentioned naphthalene and alkylnaphthalene be added 55g mass concentration be 98% the concentrated sulfuric acid,
It is warming up to 155 DEG C under stirring condition, after insulation reaction 4h, adds water adjustment acidity to 25%, sulfonated liquid is prepared；
(3) condensation reaction: being reduced to 85 DEG C for the temperature of above-mentioned sulfonated liquid, adds the first that 40g mass concentration is 37%
Aldehyde aqueous solution, insulation reaction 3h obtain condensation liquid；
(4) neutralization reaction: reducing the temperature of condensation liquid obtained above to 40 DEG C, and sodium hydroxide is added and neutralize instead
It answers and controls temperature at < 80 DEG C, obtain the neutralization reaction product of pH=8.0；
(5) it post-processes: above-mentioned neutralized reaction product naphthalene sulfonic sodium formaldehyde condensation liquid is delivered to pneumatic spray drying through pump
Tower is spray-dried, and is contracted again through the isolated brown color sodium naphthalene sulfonate-isopropyl naphthalene sulfonate-formaldehyde of secondary cyclone later
Object finished product is closed, inlet air temperature is 165 DEG C in spray drying tower, and leaving air temp is 90 DEG C.
Embodiment 3
A kind of naphthalene sulfonate-alkylnaphthalene sulfonate-formaldehyde condensation products preparation method, specifically comprises the following steps:
(1) alkylated reaction: the dense sulphur that 64g refined naphthalene, 20g isopropanol and 6.5g mass concentration are 98% is first sequentially added
Acid；Then 90 DEG C are raised the temperature under stirring condition, the mixed liquor of naphthalene and alkylnaphthalene, efficient liquid is prepared in insulation reaction 6h
It is 40:60 that phase chromatography, which detects naphthalene and isopropyl naphthalene content ratio in mixed liquor,；
(2) sulfonating reaction: it is 98% concentrated sulfuric acid to 50g mass concentration is added in the mixed liquor of above-mentioned naphthalene and alkylnaphthalene, stirs
It is warming up to 155 DEG C under the conditions of mixing, after insulation reaction 4h, adds water adjustment acidity to 25%, sulfonated liquid is prepared；
(3) condensation reaction: being reduced to 90 DEG C for the temperature of above-mentioned sulfonated liquid, adds the first that 35g mass concentration is 37%
Aldehyde aqueous solution, insulation reaction 4h obtain condensation liquid；
(4) neutralization reaction: reducing the temperature of condensation liquid obtained above to 45 DEG C, and sodium hydroxide is added and neutralize instead
It answers and controls temperature at < 80 DEG C, obtain the neutralization reaction product of pH=7.0；
(5) it post-processes: above-mentioned neutralized reaction product naphthalene sulfonic sodium formaldehyde condensation liquid is delivered to pneumatic spray drying through pump
Tower is spray-dried, and is contracted again through the isolated brown color sodium naphthalene sulfonate-isopropyl naphthalene sulfonate-formaldehyde of secondary cyclone later
Object finished product is closed, inlet air temperature is 165 DEG C in spray drying tower, and leaving air temp is 90 DEG C.
Embodiment 4
A kind of naphthalene sulfonate-alkylnaphthalene sulfonate-formaldehyde condensation products preparation method, specifically comprises the following steps:
(1) alkylated reaction: the dense sulphur that 64g refined naphthalene, 26g isopropanol and 10.0g mass concentration are 98% is first sequentially added
Acid；Then 90 DEG C are raised the temperature under stirring condition, the mixed liquor of naphthalene and alkylnaphthalene, efficient liquid is prepared in insulation reaction 6h
It is 20:80 that phase chromatography, which detects naphthalene and isopropyl naphthalene content ratio in mixed liquor,；
(2) sulfonating reaction: it is 98% concentrated sulfuric acid to 50g mass concentration is added in the mixed liquor of above-mentioned naphthalene and alkylnaphthalene, stirs
It is warming up to 160 DEG C under the conditions of mixing, after insulation reaction 5h, adds water adjustment acidity to 25%, sulfonated liquid is prepared；
(3) condensation reaction: being reduced to 90 DEG C for the temperature of above-mentioned sulfonated liquid, adds the first that 32g mass concentration is 37%
Aldehyde aqueous solution, insulation reaction 4h obtain condensation liquid；
(4) neutralization reaction: reducing the temperature of condensation liquid obtained above to 50 DEG C, and sodium hydroxide is added and neutralize instead
It answers and controls temperature at < 80 DEG C, obtain the neutralization reaction product of pH=8.5；
(5) it post-processes: above-mentioned neutralized reaction product naphthalene sulfonic sodium formaldehyde condensation liquid is delivered to pneumatic spray drying through pump
Tower is spray-dried, and is contracted again through the isolated brown color sodium naphthalene sulfonate-isopropyl naphthalene sulfonate-formaldehyde of secondary cyclone later
Object finished product is closed, inlet air temperature is 165 DEG C in spray drying tower, and leaving air temp is 90 DEG C.
Embodiment 5
A kind of naphthalene sulfonate-alkylnaphthalene sulfonate-formaldehyde condensation products preparation method, specifically comprises the following steps:
(1) alkylated reaction: first sequentially adding 64g refined naphthalene, 34g isopropanol and 2.5g mass concentration is 98% concentrated sulfuric acid；
Then 90 DEG C are raised the temperature under stirring condition, the mixed liquor of naphthalene and alkylnaphthalene, efficient liquid phase is prepared in insulation reaction 6h
Naphthalene is almost completely converted into isopropyl naphthalene in chromatography detection mixed liquor；
(2) sulfonating reaction: it is 98% concentrated sulfuric acid to 65g mass concentration is added in the mixed liquor of above-mentioned naphthalene and alkylnaphthalene, stirs
It is warming up to 150 DEG C under the conditions of mixing, after insulation reaction 3h, adds water adjustment acidity to 26%, sulfonated liquid is prepared；
(3) condensation reaction: being reduced to 90 DEG C for the temperature of above-mentioned sulfonated liquid, adds the first that 40g mass concentration is 37%
Aldehyde aqueous solution, insulation reaction 4h obtain condensation liquid；
(4) neutralization reaction: reducing the temperature of condensation liquid obtained above to 50 DEG C, and sodium hydroxide is added and neutralize instead
It answers and controls temperature at < 80 DEG C, obtain the neutralization reaction product of pH=9.0；
(5) it post-processes: above-mentioned neutralized reaction product naphthalene sulfonic sodium formaldehyde condensation liquid is delivered to pneumatic spray drying through pump
Tower is spray-dried, and is contracted again through the isolated brown color sodium naphthalene sulfonate-isopropyl naphthalene sulfonate-formaldehyde of secondary cyclone later
Object finished product is closed, inlet air temperature is 165 DEG C in spray drying tower, and leaving air temp is 90 DEG C.
Embodiment 6
Refined naphthalene in embodiment 1 is replaced with into crude naphthalene, other operating conditions are constant；High performance liquid chromatography detection naphthalene and alkane
Naphthalene and isopropyl naphthalene content ratio are 82:18 in the mixed liquor of base naphthalene.
Embodiment 7
6.5g isopropanol in embodiment 1 is replaced with into 8g n-butanol, other operating conditions are constant；High performance liquid chromatography inspection
Surveying naphthalene and butyl naphthalene content ratio in the mixed liquor of naphthalene and alkylnaphthalene is 83:17.
Embodiment 8
6.5g isopropanol in embodiment 1 is replaced with into 8g isobutanol, alkylated reaction temperature is 110 DEG C, other operations
Condition is constant；Naphthalene and butyl naphthalene content ratio are 80:20 in the mixed liquor of high performance liquid chromatography detection naphthalene and alkylnaphthalene.
Embodiment 9
6.5g isopropanol in embodiment 1 is replaced with into 9.5g n-amyl alcohol, alkylated reaction temperature is 140 DEG C, other behaviour
It is constant to make condition；Naphthalene and amyl naphthalene content ratio are 85:15 in the mixed liquor of high performance liquid chromatography detection naphthalene and alkylnaphthalene.
Embodiment 10
Sodium hydroxide in embodiment 1 in step (4) is replaced with into potassium hydroxide, other operating conditions are constant；Efficient liquid
It is 80:20 that phase chromatography, which detects naphthalene and isopropyl naphthalene content ratio in the mixed liquor of naphthalene and alkylnaphthalene,.
Embodiment 11
6.5g isopropanol in embodiment 1 is replaced with into 5.0g ethyl alcohol, alkylated reaction temperature is 80 DEG C, other operation items
Part is constant；Naphthalene and ethyl naphthalene content ratio are 90:10 in the mixed liquor of high performance liquid chromatography detection naphthalene and alkylnaphthalene.
Embodiment 12
6.5g isopropanol in embodiment 1 is replaced with into 11.0g n-hexyl alcohol, alkylated reaction temperature is 140 DEG C, other behaviour
It is constant to make condition；Naphthalene and hexyl naphthalene content ratio are 80:20 in the mixed liquor of high performance liquid chromatography detection naphthalene and alkylnaphthalene.
Embodiment 13
6.5g isopropanol in embodiment 1 is replaced with into 12.5g n-heptanol, alkylated reaction temperature is 145 DEG C, other behaviour
It is constant to make condition；Naphthalene and heptyl naphthalene content ratio are 84:16 in the mixed liquor of high performance liquid chromatography detection naphthalene and alkylnaphthalene.
Embodiment 14
6.5g isopropanol in embodiment 1 is replaced with into 14g n-octyl alcohol, alkylated reaction temperature is 145 DEG C, other operations
Condition is constant；Naphthalene and octyl naphthalene content ratio are 81:19 in the mixed liquor of high performance liquid chromatography detection naphthalene and alkylnaphthalene.
Embodiment 15
6.5g isopropanol in embodiment 1 is replaced with into 15.5g n-nonyl alcohol, alkylated reaction temperature is 150 DEG C, other behaviour
It is constant to make condition；Naphthalene and nonyl naphthalene content ratio are 86:14 in the mixed liquor of high performance liquid chromatography detection naphthalene and alkylnaphthalene.
Embodiment 16
6.5g isopropanol in embodiment 1 is replaced with into 17.1g Decanol, alkylated reaction temperature is 150 DEG C, other behaviour
It is constant to make condition；Naphthalene and decyl naphthalene content ratio are 88:12 in the mixed liquor of high performance liquid chromatography detection naphthalene and alkylnaphthalene.
Comparative example 1
Step (1) in embodiment 1 is omitted, other operating conditions are constant.
Embodiment 17
Naphthalene sulfonate-the alkylnaphthalene sulfonate being prepared with the above embodiment of the present invention 1-16-formaldehyde condensation products difference
As test group, with comparative example 1 as a control group 1, with similar product D425 (AkzoNobel) as a control group 2, respectively as
Dispersing agent prepares 75% tribenuron-methyl WDG, corresponding test group 1~16 and control group 1~2 by extrusion granulation method.
Wherein include the component of following mass percent in 75% tribenuron-methyl WDG: purity is 95% tribenuron-methyl raw medicine
78.9%, dispersing agent 5%, wetting agent lauryl sodium sulfate 3%, disintegrating agent ammonium sulfate additive amount is 2%, kaolin
11.1%.
Suspensibility, disintegration, blistering are carried out to 75% tribenuron-methyl WDG and D425 (AkzoNobel) being prepared respectively
Highly, (54 ± 2 DEG C, 14 days) of suspensibility detections, specific detection method include:
One, suspensibility measures:
Suspensibility is measured according to GB/T14825 method.
Two, disintegration measures:
In 25 DEG C of thermostats, 100mL tool plug graduated cylinder (interior high 22.5cm, internal diameter 28mm) is taken, 90mL distilled water is added；To
0.5g water dispersible granules sample is added in graduated cylinder, clamps in the middle part of tool plug graduated cylinder, graduated cylinder mouth is clogged, with the speed of 8r/min around center
Rotation, until sample disintegration dispersion completely in graduated cylinder, records disintegration time, detect disintegration with disintegration time length, generally
Regulation is less than 3min.
Three, wettability determination:
25 DEG C are added 500mL standard hard water (calcium ions and magnesium ions concentration 342g/L) in 500mL measuring graduates, weigh 1.0g system
Agent is quickly poured into graduated cylinder, is not stirred, and records the time that 99% sample sinks to graduated cylinder bottom with stopwatch at once, when as soaking
Between, with the wetability of wetting time detection water dispersible granules.
Four, foaming characteristic measures:
25 DEG C have addition 95mL standard hard water in plug graduated cylinder, graduated cylinder 100mL scale and plug bottom to graduated 100mL
Between volume in 25~40mL；It weighs in 1.0g water dispersible granules sample introduction cylinder, then plus standard hard water is settled to 100mL
Graduation mark；Plug is covered, turns upside down 30 times, is completed in 2s every time；5min is stood, foam volume is recorded.
Five, heat storage stability measures:
WDG need to be surveyed and be packed into ampoule bottle, each bottled 5.0g is put into 54 DEG C of ± 2 DEG C of baking ovens after sealing, heat storage 14 days
Afterwards, the corresponding heat storage suspensibility of WDG is surveyed by the method for GB/T19136-2003.
Testing result is as shown in table 1 below:
Table 1
It can obviously be learnt by the data in upper table: the naphthalene system sulphur made by single naphthalene or alkylnaphthalene compared to comparative example 1
Sour sodium formaldehyde condensation product, naphthalene sulfonate-alkylnaphthalene sulfonate-first that the present invention is prepared using method disclosed in embodiment 1~16
Aldehyde condensate is used to prepare 75% tribenuron-methyl WDG, can make the evaluation indexes such as system stability, thermodynamic stability, disintegration rate
It significantly improves；And compared with the similar imported product D425 in market, properties of product reach respective horizontal and have part index number super
The imported product is crossed, illustrates that step is simplified, and can reduce the harm to environment using method disclosed by the invention,
The corresponding technical level in this field can be reached simultaneously, there are substantive distinguishing features outstanding.
Each embodiment in this specification is described in a progressive manner, the highlights of each of the examples are with other
The difference of embodiment, the same or similar parts in each embodiment may refer to each other.For device disclosed in embodiment
For, since it is corresponded to the methods disclosed in the examples, so being described relatively simple, related place is said referring to method part
It is bright.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention.
Various modifications to these embodiments will be readily apparent to those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, of the invention
It is not intended to be limited to the embodiments shown herein, and is to fit to and the principles and novel features disclosed herein phase one
The widest scope of cause.
Claims (10)
1. a kind of naphthalene sulfonate-alkylnaphthalene sulfonate-formaldehyde condensation products preparation method, which is characterized in that firstly, naphthalene and alkyl
Change the mixed liquor that reagent generates naphthalene and alkylnaphthalene under the catalysis of sulfuric acid；Then, sulphur is added into the mixed liquor of naphthalene and alkylnaphthalene
Acid carries out sulfonating reaction；It adds formaldehyde and naphthalene sulfonate-alkylnaphthalene sulfonate-formaldehyde contracting is prepared by one kettle way condensation
Close object.
2. a kind of naphthalene sulfonate-alkylnaphthalene sulfonate-formaldehyde condensation products preparation method according to claim 1, special
Sign is, specifically comprises the following steps:
(1) alkylated reaction: naphthalene, alkylating reagent and sulfuric acid are mixed, then increased temperature under stirring condition, insulation reaction
The mixed liquor of naphthalene and alkylnaphthalene is prepared；
(2) sulfonating reaction: to sulfuric acid is added in the mixed liquor of above-mentioned naphthalene and alkylnaphthalene, heating up under stirring condition, after insulation reaction,
Water adjustment acidity is added, sulfonated liquid is prepared；
(3) condensation reaction: reducing the temperature of above-mentioned sulfonated liquid, formalin is being added, insulation reaction obtains condensation liquid；
(4) neutralization reaction: reducing the temperature of condensation liquid obtained above, and neutralizer is added and carries out neutralization reaction, obtains neutralizing anti-
Answer product；
(5) it post-processes: neutralized reaction product obtained above being dried, boiling off moisture and obtaining brown solid product is naphthalene
Sulfonate-alkylnaphthalene sulfonate-formaldehyde condensation products.
3. it is according to claim 2 it is a kind of prepare naphthalene sulfonate-alkylnaphthalene sulfonate-formaldehyde condensation products method, it is special
Sign is that alkylating reagent includes alkylol in the step (1), and the mass concentration of sulfuric acid is 98%, and neutralizer includes alkali gold
Belong to hydroxide.
4. it is according to claim 2 it is a kind of prepare naphthalene sulfonate-alkylnaphthalene sulfonate-formaldehyde condensation products method, it is special
Sign is, the alkylol includes ethyl group alcohol, propyl alcohol, butane group alcohol, pentyl alcohol, hexyl alcohol, alkylol in heptan, pungent
Alkylol, nonyl alcohol or decyl alcohol.
5. it is according to claim 2 it is a kind of prepare naphthalene sulfonate-alkylnaphthalene sulfonate-formaldehyde condensation products method, it is special
Sign is that the alkylol includes propyl alcohol, butane group alcohol or pentyl alcohol.
6. it is according to claim 2 it is a kind of prepare naphthalene sulfonate-alkylnaphthalene sulfonate-formaldehyde condensation products method, it is special
Sign is that the molar ratio of naphthalene, alkylating reagent and sulfuric acid is 1.0:0.1-2.0:0.05-0.2 in the step (1)；Temperature liter
Up to 80-150 DEG C, insulation reaction 4-6h.
7. it is according to claim 2 it is a kind of prepare naphthalene sulfonate-alkylnaphthalene sulfonate-formaldehyde condensation products method, it is special
Sign is that the mass concentration of sulfuric acid is 98% in the step (2), is 1.0:1.0- according to the molar ratio of naphthylene group and sulfuric acid
1.3 are added sulfuric acid；Temperature rises to 150-160 DEG C, and insulation reaction 3-5h, acidity is adjusted to 24-26%.
8. it is according to claim 2 it is a kind of prepare naphthalene sulfonate-alkylnaphthalene sulfonate-formaldehyde condensation products method, it is special
Sign is, according to the molar ratio of naphthylene group and formaldehyde is 1.0:0.8-1.0 in the step (3), formaldehyde is added；Temperature is adjusted
To 80-90 DEG C, insulation reaction 2-4h.
9. it is according to claim 2 it is a kind of prepare naphthalene sulfonate-alkylnaphthalene sulfonate-formaldehyde condensation products method, it is special
Sign is that temperature is reduced to 30-50 DEG C in the step (4), and neutralization reaction temperature controls the neutralization reaction obtained at < 80 DEG C
Product pH=7-9.
10. a kind of naphthalene sulfonate-application of the alkylnaphthalene sulfonate-formaldehyde condensation products in pesticidal preparations, which is characterized in that described
Naphthalene sulfonate-alkylnaphthalene sulfonate-formaldehyde condensation products are prepared using method as described in any one of claims 1-9.
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| CN109503433A (en) * | 2018-12-20 | 2019-03-22 | 江苏精禾界面科技有限公司 | A kind of modified naphthalene series sulfonate and formaldehyde condensation product and its application |
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| CN109810542A (en) * | 2019-01-19 | 2019-05-28 | 浙江吉盛化学建材有限公司 | A kind of naphthalene system dispersing agent and preparation method thereof |
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| CN114230492A (en) * | 2021-12-29 | 2022-03-25 | 陈会江 | Preparation process of concrete modification additive |
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