CN110483795A - A kind of supermolecule sulfonated phenolic condensation polymer and its preparation method and application - Google Patents
A kind of supermolecule sulfonated phenolic condensation polymer and its preparation method and application Download PDFInfo
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- CN110483795A CN110483795A CN201910785313.5A CN201910785313A CN110483795A CN 110483795 A CN110483795 A CN 110483795A CN 201910785313 A CN201910785313 A CN 201910785313A CN 110483795 A CN110483795 A CN 110483795A
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- condensation polymer
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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
- A01N25/02—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 containing liquids as carriers, diluents or solvents
- A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
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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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
- C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
- C08G14/08—Ureas; Thioureas
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- Chemical & Material Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Dentistry (AREA)
- Medicinal Chemistry (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Wood Science & Technology (AREA)
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- Phenolic Resins Or Amino Resins (AREA)
Abstract
The present invention provides a kind of supermolecule sulfonated phenolic condensation polymers, and polymerization is derived from including following monomer, sulphur sylvan, formaldehyde, urea；The sulphur sylvan is the mixture of sulfomethylated phenol and sulfomethylated biphenol.Supermolecule sulfonated phenolic condensation polymer can rely on the steric hindrance of polymer itself, wetting and dispersing agricultural chemicals particle；Sulfonate radical is introduced in condensation polymer, not only enhances the water solubility of wetting dispersing agent, but also has widened the use scope of phenol-aldehyde condensation polyme, guarantees modified supermolecule sulfonated phenolic condensation polymer more resistant to high temperature；Creative introduces urea monomer in phenolic acid condensation polymer, ensure that agricultural chemicals particle more resistant to mechanical friction.
Description
Technical field
The present invention relates to novel high molecular polymer technical fields, more particularly to a kind of supermolecule sulfonated phenolic condensation polymer
And its preparation method and application.
Background technique
Due to the stronger activity of phenolic substances ortho para hydrogen atom, condensation reaction easily is modified with aldehyde material and is given birth to
At phenolic resin.Phenolic resin is a kind of important chemical products, can be used as coating, adhesive and plastics.
By resin modified, sulfonate radical is introduced in macromolecular, and to assign its water solubility, the water solubility of macromolecule can be obtained
Polymer.The purposes of phenolic resin is undoubtedly expanded, such as water-soluble polymer can be widely used in field of fine chemical, such as oil
Field inorganic agent, daily-use chemical industry, light industry and building etc..
With reference to Chinese periodical " Speciality Petrochemicals "-" preparation of sulfonated-pheno-formoldehyde resin ", with sodium hydrogensulfite/sulfurous acid
Sodium is that sulfonating agent, phenol and formaldehyde are raw material, prepares sulfonated-pheno-formoldehyde resin through phenol sulfomethylation and polycondensation reaction.Phenol
Urea formaldehyde condensation polymer wetting dispersing agent is mainly used for oil drilling solution additive, cement water reducing agent and agricultural chemicals dispersion
Agent." industrial building "-sulfonated phenol-formaldehyde condensation products type (SPF) high efficiency water reducing agent synthesis and dispersion performance research, disclose sulphur
The preparation method for changing phenol-formaldehyde condensation polymer type (SPF) high efficiency water reducing agent generates specifically after the concentrated sulfuric acid and phenol reactant to hydroxyl
Base benzene sulfonic acid generates sulphonated phenol-formaldehyde condensation products reacting with formaldehyde.High-performance water reducing agent, which is applied to mainly rise in concrete, to be changed
Kind concrete construction work property and the reduction ratio of mud and the intensity and durability that improve concrete, while cement consumption is also saved,
Reduce concrete initial imperfection.The study on the synthesis of Chinese periodical " Shandong chemical industry "-sulfonated-pheno-formoldehyde resin, discloses a kind of sulphur first
The synthesis of base phenolic resin is with phenol, formaldehyde, sodium hydrogensulfite, sodium sulfite etc. for primary raw material, under alkaline condition,
It is completed through a series of addition polymerization and condensation polymerization reaction.It declares with linear structure, through sodium sulfite sulfomethylation,
With good surface-active, wetting, emulsification, dispersion and anchorage, and there is good thermal stability.
But the crocking resistance of above-mentioned three kinds of water-reducing agents is poor.
Chinese patent application: 201510435180.0, the preparation method for disclosing sulfamate formaldehyde condensation products passes through
Raw water, sodium sulfanilate, phenol, acetone and lye is added, after reacting at a certain temperature, adds urea and propylene
Amide makes urea and formaldehyde and mixture carry out strand recombination, changes molecular weight, while grafting acrylamide as branch,
Amides acting factor is introduced, amino molecule structure is changed.The hardened phenomenon of concrete water bleeding can be improved, there is concrete
While more superior working performance, extend action time, the landslide face of guarantor is also improved.But due to joined branch
It is insufficient to will lead to its performance in aqueous solution as wetting, dispersing agent for chain acrylamide.
A kind of 201610136906 .5 title of Chinese Patent Application No.: papermaking black liquor modified sulfamate high-effective diminishing
Agent and preparation method thereof discloses, a kind of papermaking black liquor modified sulfamate high-effective water-reducing agent, the high efficiency water reducing agent by with
Lower component is formulated by weight: 130-140 parts of sodium sulfanilate, 30-60 parts of black liquid, sulfur dioxide 12-
30 parts, 50-70 parts of phenol, 150-180 parts of formaldehyde, 15-30 parts of 30% liquid alkaline, 9-13 parts of urea, 200-360 parts of water, preparation
Method is by after black liquid sulfur dioxide sulfonation, then to add it to sodium sulfanilate, urea, the alkalinity of phenol mixed
It closes in liquid, formaldehyde condensation is finally added dropwise and is made.High efficiency water reducing agent can be substantially reduced the loss of slump of concrete and bleeding shows
As improving and protecting collapsing property, improve workability, and production cost is low, reduces environmental pollution, and realizes the full benefit of black liquid
With reducing the cost of recycling.But due to must be added to black liquid, it will lead to it and generate in aqueous solution greatly
The foam of amount, in use process, automatic foam time is long, influences project progress, also general by actual measurement stability.
Summary of the invention
The object of the present invention is to provide a kind of supermolecule phenol-aldehyde condensation polymes, increase by two in segment by creative
Phenol, urea recombinate polymerized segment, make supermolecule phenol-aldehyde condensation polyme moisture dispersibility of the invention, stability (thermal stability,
Friction stability) it is more preferable.
Another object of the present invention is to provide the preparation method and application of above-mentioned supermolecule phenol-aldehyde condensation polyme.
The present invention is achieved by the following technical solutions:
A kind of supermolecule sulfonated phenolic condensation polymer, polymerization is derived from including following monomer, sulphur sylvan, formaldehyde, urea；Described
Sulphur sylvan is the mixture of sulfomethylated phenol and sulfomethylated biphenol.
The content range of each monomer is 40%-50% sulphur sylvan, 10%-40% formaldehyde, 10%-40% urea；The sulphur first
Base phenol is (6-2): 1 mixture of sulfomethylated phenol and sulfomethylated biphenol.
The molecular weight ranges of supermolecule sulfonated phenolic condensation polymer are 1000-10000.
Supermolecule sulfonated phenolic condensation polymer is comb shaped structure.
" comb polymer ", this quasi polymer include main chain and connect multiple branches on the main chain, and multiple branches are just
As the comb teeth of comb." in conjunction with " with solid is mainly the functional group by branch.
The fusing point of supermolecule sulfonated phenolic condensation polymer is between 280-320 DEG C.Dystectic supermolecule sulfonated phenolic polycondensation
Object high temperature resistance is good, can guarantee be denaturalized during the grinding process, be able to maintain efficient dispersibility after grinding.
The preparation method of above-mentioned supermolecule sulfonated phenolic condensation polymer, comprising the following steps: phenol and biphenol are added
Into methylol sulfonic acid saline solution, sulphur methyl phenol solution is prepared；Urea, formaldehyde are added, polycondensation reaction is carried out；It adjusts
PH obtains sulfonated phenolic condensation polymer.
The preparation of methylol sulfonic acid saline solution: sulfonating agent and water are added in container according to certain proportion, temperature control
Heating, makes it completely dissolved, when temperature is down to 30 DEG C ± 5 DEG C, formalin is added in container, and temperature has on slight
It rises, temperature control insulation reaction 2-4 hours, obtains methylol sulfonic acid saline solution to 60 DEG C ± 5 DEG C.
Sulfonating agent can be sodium sulfite and sodium hydrogensulfite, at least one therein.
The preparation of sulphur methyl phenol solution: phenol and biphenol are added in methylol sulfonic acid saline solution, adjust solution
PH 9-10 temperature reaction 4 hours, obtains sulphur methyl phenol solution.
Polycondensation reaction: being added urea, formaldehyde in sulphur methyl phenol solution, adjusts pH9-10, is heated to reflux, until reaction knot
Beam, then pH7-8 is adjusted after cooling down, obtain the aqueous solution of supermolecule sulfonated phenolic condensation polymer.
The application of above-mentioned supermolecule sulfonated phenolic condensation polymer, is used to prepare pyrazoles aqueous suspension, by weight percentage, pyrazoles
25%-30%；Supermolecule sulfonated phenolic condensation polymer 5%-10%；Thickener 6%-8%；Antifreezing agent 3%-8%；Stabilizer 1%-1.5%；Defoaming
Agent 0.1%-0.5%；Preservative 0.1%-0.2%；Water supplies 100%.
Compared with prior art, the present invention having the advantages that
The present invention not only enhances the water solubility of wetting dispersing agent by introducing sulfonate radical in condensation polymer, but also guarantees modified
Supermolecule sulfonated phenolic condensation polymer more resistant to high temperature；Meanwhile creative urea is introduced in supermolecule sulfonation phenolic acid condensation polymer
Monomer ensure that agricultural chemicals particle more resistant to mechanical friction, apply it preferably in the product for needing to grind；Sulphur methyl
Change phenol to deposit with compounding for sulfomethylated biphenol, ensure that the above two holding for introducing function.
Detailed description of the invention
Fig. 1: the test chart of the fusing point of 1 supermolecule sulfonated phenolic condensation polymer of embodiment.
Fig. 2: the infrared test figure of 1 supermolecule sulfonated phenolic condensation polymer of embodiment ,-OH:3393cm-1；-CH2-:1473cm-1 ；-C-O-:1176cm-1；-SO3 -:1039cm-1；.
Fig. 3: the number-average molecular weight examining report of 1 supermolecule sulfonated phenolic condensation polymer of embodiment.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection scope.
The raw materials used in the present invention source such as the following table 1:
The preparation method of embodiment and comparative example supermolecule sulfonated phenolic condensation polymer: by sulfonating agent and water according to certain proportion
(table 3) is added in container, and temperature control heating makes it completely dissolved, when temperature is down to 30 DEG C ± 5 DEG C, formalin is added
Into container, temperature has slight rising, and insulation reaction 2-4 hours, it is water-soluble to obtain methylol sulfonate to 60 DEG C ± 5 DEG C for temperature control
Liquid.Phenol and biphenol are added in methylol sulfonic acid saline solution again, adjust pH value of solution 9-10, temperature reaction 4 hours,
Obtain sulphur methyl phenol solution.Urea, formaldehyde are added in sulphur methyl phenol solution, adjusts pH 9-10, is heated to reflux, until reaction knot
Beam, then pH7-8 is adjusted after cooling down, obtain the aqueous solution of supermolecule sulfonated phenolic condensation polymer.
Table 2:25% pyrazoles aqueous suspension formula
25% pyrazoles aqueous suspension formula is specific the preparation method is as follows: by pyrazoles, embodiment or comparative example product, propylene glycol, defoaming
Agent, stabilizer and water are disposably uniformly mixed, and zirconium pearl is added after shearing, are then carried out grinding 1-2h to partial size D90 and are down to 5 microns
Left and right, filtering and discharging add xanthan gum and preservative, shear 2min, and point four samples carry out cold and hot storage and room temperature observation is steady
It is qualitative.
Properties test method:
(1) normal temperature storage stability: NYT1427-2007 pesticide storage at normal temperature stability test general rule, sample is in room temperature condition
Under, be precipitated after 3 months without solid or grease etc.；
(2) low-temperature storage stability: GB/T 19137-2003 pesticide low-temperature stability measuring method, sample under the conditions of 0 DEG C,
Be precipitated after 7 days without solid or grease etc.；
(3) high-temperature storage stability: GB/T 19136-2003 pesticide heat storage stability measuring method, sample is in 54 DEG C of conditions
Under, it is precipitated after 14 days without solid or grease, effective component resolution ratio≤10% etc.；
(4) grain diameter: operating, droplet measurement referring to LS-POPCP laser particle size analyzer, and heat storage front and back partial size growth rate≤
20%；
(5) it fusing point test method: is operated according to HS-DSC-101 MELTING POINT TESTER.
(6) infrared spectrum test method: match referring to FTIR-650(high) Fourier Transform Infrared Spectrometer measuring method.
(7) number-average molecular weight test method: referring to Waters1515 gel chromatography measuring method, (chromatographic column is SB-804
HQ).
(8) suspensibility test method: referring to GBT 14825-2006 agricultural-chemical suspension rate measuring method.
Table 3: embodiment and comparative example supermolecule sulfonated phenolic condensation polymer monomer dosage and properties test result
Continued 3
Fusing point height, the stability that can be seen that supermolecule sulfonated phenolic condensation polymer of the invention from embodiment 1-5 are good, are by it
Thermal stability makes its retention properties during the grinding process, non-agglomerate, suspensibility height.
It can be seen that not under formula of the invention from comparative example 1-5, even with whole monomers of the invention,
Stability is also bad, and dispersion performance is poor.
Claims (10)
1. a kind of supermolecule sulfonated phenolic condensation polymer, which is characterized in that polymerization is derived from including following monomer, sulphur sylvan, first
Aldehyde, urea；The sulphur sylvan is the mixture of sulfomethylated phenol and sulfomethylated biphenol.
2. supermolecule sulfonated phenolic condensation polymer according to claim 1, which is characterized in that the content range of each monomer is
40%-50% sulphur sylvan, 10%-40% formaldehyde, 10%-40% urea；The sulphur sylvan is sulfomethylated phenol and sulphur first
(6-2): 1 mixture of the biphenol of base.
3. supermolecule sulfonated phenolic condensation polymer according to claim 1, which is characterized in that supermolecule sulfonated phenolic condensation polymer
Molecular weight ranges be 1000-10000.
4. supermolecule sulfonated phenolic condensation polymer according to claim 1, which is characterized in that sulfonated phenolic condensation polymer is comb shape
Structure.
5. supermolecule sulfonated phenolic condensation polymer according to claim 1, which is characterized in that fusing point is between 280-320 DEG C.
6. the preparation method of the described in any item supermolecule sulfonated phenolic condensation polymers of claim 1-5, which is characterized in that including with
Lower step: phenol and biphenol are added in methylol sulfonic acid saline solution, and sulphur methyl phenol solution is prepared；Add urine
Element, formaldehyde carry out polycondensation reaction；It adjusts pH and obtains supermolecule sulfonated phenolic condensation polymer.
7. the preparation method of supermolecule sulfonated phenolic condensation polymer according to claim 6, which is characterized in that methylol sulfonic acid
The preparation of saline solution: sulfonating agent and water are added in container according to certain proportion, and temperature control heating makes it completely dissolved,
When temperature is down to 30 DEG C ± 5 DEG C, formalin is added in container, temperature has slight rising, temperature control to 60 DEG C ± 5 DEG C,
Insulation reaction 2-4 hours, obtain methylol sulfonic acid saline solution.
8. the preparation method of supermolecule sulfonated phenolic condensation polymer according to claim 6, which is characterized in that sulphur sylvan is molten
The preparation of liquid: phenol and biphenol are added in methylol sulfonic acid saline solution, adjust pH value of solution 9-10, and temperature reaction 4 is small
When, obtain sulphur methyl phenol solution.
9. the preparation method of supermolecule sulfonated phenolic condensation polymer according to claim 6, which is characterized in that polycondensation reaction:
Urea, formaldehyde are added in sulphur methyl phenol solution, adjusts pH9-10, is heated to reflux, until reaction terminates, then adjusts pH after cooling down
7-8 obtains the aqueous solution of supermolecule sulfonated phenolic condensation polymer.
10. the application of the described in any item supermolecule sulfonated phenolic condensation polymers of claim 1-5, which is characterized in that be used to prepare
Pyrazoles aqueous suspension, by weight percentage, pyrazoles 25%-30%；Supermolecule sulfonated phenolic condensation polymer 5%-10%；Thickener 6%-8%；
Antifreezing agent 3%-8%；Stabilizer 1%-1.5%；Defoaming agent 0.1%-0.5%；Preservative 0.1%-0.2%；Water supplies 100%.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102408882A (en) * | 2011-10-11 | 2012-04-11 | 山东轻工业学院 | Phenol-urea-formaldhyde resin modified lignite filtrate loss reducer with high temperature resistance and salt tolerance, and its preparation method |
| CN102775568A (en) * | 2012-07-27 | 2012-11-14 | 山东圣泉化工股份有限公司 | Preparation method of modified phenolic resin |
| CN103601401A (en) * | 2013-11-25 | 2014-02-26 | 金陵科技学院 | Preparation method of sulfonated bisphenol A-formaldehyde condensate superplasticizer |
| WO2018212651A1 (en) * | 2017-05-17 | 2018-11-22 | Stahl International B.V. | Tanning agent for leather production comprising a condensation poly mer of sulfonated phenol, urea, and formaldehyde |
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- 2019-08-23 CN CN201910785313.5A patent/CN110483795B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102408882A (en) * | 2011-10-11 | 2012-04-11 | 山东轻工业学院 | Phenol-urea-formaldhyde resin modified lignite filtrate loss reducer with high temperature resistance and salt tolerance, and its preparation method |
| CN102775568A (en) * | 2012-07-27 | 2012-11-14 | 山东圣泉化工股份有限公司 | Preparation method of modified phenolic resin |
| CN103601401A (en) * | 2013-11-25 | 2014-02-26 | 金陵科技学院 | Preparation method of sulfonated bisphenol A-formaldehyde condensate superplasticizer |
| WO2018212651A1 (en) * | 2017-05-17 | 2018-11-22 | Stahl International B.V. | Tanning agent for leather production comprising a condensation poly mer of sulfonated phenol, urea, and formaldehyde |
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