CN110483795B - Supermolecule sulfonated phenolic polycondensate and preparation method and application thereof - Google Patents
Supermolecule sulfonated phenolic polycondensate and preparation method and application thereof Download PDFInfo
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- CN110483795B CN110483795B CN201910785313.5A CN201910785313A CN110483795B CN 110483795 B CN110483795 B CN 110483795B CN 201910785313 A CN201910785313 A CN 201910785313A CN 110483795 B CN110483795 B CN 110483795B
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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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Abstract
The invention provides a supermolecular sulfonated phenolic polycondensate, which is polymerized and derived from the following monomers, sulfomethyl phenol, formaldehyde and urea; the sulfomethylphenol is a mixture of sulfomethylated phenol and sulfomethylated diphenol. The supermolecule sulfonated phenolic aldehyde polycondensate can wet and disperse agricultural chemical particles by depending on the steric hindrance of the polymer; the sulfonic acid group is introduced into the polycondensate, so that the water solubility of the wetting dispersant is enhanced, the application range of the phenolic polycondensate is widened, and the modified supermolecule sulfonated phenolic polycondensate is ensured to be more resistant to high temperature; the urea monomer is creatively introduced into the phenolic acid polycondensate, so that the agricultural chemical particles are ensured to be more resistant to mechanical friction.
Description
Technical Field
The invention relates to the technical field of novel high molecular polymers, in particular to a supermolecular sulfonated phenolic polycondensate and a preparation method and application thereof.
Background
Because of the strong activity of the phenolic substance to the ortho-and para-hydrogen atoms, the phenolic substance is easy to be modified and condensed with the aldehyde substance to generate the phenolic resin. Phenolic resin is an important chemical product and can be used as coating, adhesive and plastics.
The resin is modified, and sulfonate groups are introduced into macromolecules to endow the macromolecules with water solubility, so that the water-soluble polymer with large molecular weight can be obtained. Undoubtedly expand the application of the phenolic resin, for example, the water-soluble polymer can be applied to the fields of fine chemical engineering such as oil field treating agents, daily chemical engineering, light industry, buildings and the like in a large quantity.
Referring to the fine petrochemical industry of China, the preparation of sulfomethyl phenolic resin, sodium bisulfite/sodium sulfite is used as a sulfonating agent, phenol and formaldehyde are used as raw materials, and the sulfomethyl phenolic resin is prepared through phenol sulfomethylation reaction and polycondensation reaction. The phenolic resin polycondensate wetting dispersant is mainly used as an oil field drilling fluid additive, a concrete water reducing agent and an agricultural chemical dispersant. The synthesis and dispersion performance research of sulfonated phenol-formaldehyde condensation polymer (SPF) superplasticizers in industrial buildings discloses a preparation method of the sulfonated phenol-formaldehyde condensation polymer (SPF) superplasticizer, and specifically comprises the steps of reacting concentrated sulfuric acid with phenol to generate p-hydroxybenzene sulfonic acid, and reacting with formaldehyde to generate a sulfonated phenol-formaldehyde condensation polymer. The high-performance water reducing agent is applied to concrete, and mainly has the effects of improving the workability of concrete construction, reducing the water-cement ratio, improving the strength and durability of the concrete, saving the using amount of cement and reducing the initial defects of the concrete. The synthesis of sulfomethyl phenolic resin is carried out by taking phenol, formaldehyde, sodium bisulfite, sodium sulfite and the like as main raw materials and carrying out a series of addition polymerization and condensation polymerization reactions under alkaline conditions. It is claimed to have a linear structure, is sulfomethylated by sodium sulfite, has good surface activity, wetting, emulsifying, dispersing and fixing properties, and has good thermal stability.
However, the three water reducing agents described above have poor friction resistance.
The Chinese patent application: 201510435180.0 discloses a method for preparing sulfamate formaldehyde condensate, which comprises adding raw materials of water, sodium sulfanilate, phenol, acetone and alkali liquor, reacting at a certain temperature, adding urea and acrylamide, recombining molecular chains of urea, formaldehyde and the mixture, changing molecular weight, grafting acrylamide as a branched chain, introducing amide function factors, and changing amino molecular structure. The concrete slump retaining agent can improve the phenomenon of bleeding and hardening of the concrete, so that the concrete has more excellent working performance, the action time is prolonged, and the slump retaining aspect is also improved. However, the addition of branched acrylamide results in insufficient wetting and dispersing properties in aqueous solutions.
Chinese patent application No. 201610136906.5 name: disclosed is a papermaking black liquor modified sulfamate high-efficiency water reducing agent and a preparation method thereof, wherein the papermaking black liquor modified sulfamate high-efficiency water reducing agent is prepared from the following components in parts by weight: 140 parts of sodium sulfanilate, 30-60 parts of papermaking black liquor, 12-30 parts of sulfur dioxide, 50-70 parts of phenol, 180 parts of formaldehyde 150, 15-30 parts of 30% liquid alkali, 9-13 parts of urea and 360 parts of water 200, and the preparation method comprises the steps of sulfonating the papermaking black liquor by using the sulfur dioxide, adding the sulfonated papermaking black liquor into an alkaline mixed solution of sodium sulfanilate, the urea and the phenol, and finally dropwise adding the formaldehyde for condensation to obtain the sodium sulfanilate. The high-efficiency water reducing agent can obviously reduce slump loss and bleeding phenomenon of concrete, improve slump retention and workability, has low production cost, reduces environmental pollution, realizes full utilization of papermaking black liquor and reduces recycling cost. However, because the papermaking black liquor must be added, a large amount of foam is generated in the aqueous solution, the automatic defoaming time is long in the using process, the engineering progress is influenced, and the stability is general after actual measurement.
Disclosure of Invention
The invention aims to provide a supramolecular phenolic polycondensate, which has better wetting dispersibility and stability (thermal stability and friction stability) by creatively adding diphenol and urea in a chain segment to recombine a polymerization chain segment.
The invention also aims to provide a preparation method and application of the supermolecular phenolic polycondensate.
The invention is realized by the following technical scheme:
a supramolecular sulfonated phenolic polycondensate polymerized from monomers comprising sulfomethylphenol, formaldehyde, urea; the sulfomethylphenol is a mixture of sulfomethylated phenol and sulfomethylated diphenol.
The content ranges of the monomers are 40-50% of sulfomethyl phenol, 10-40% of formaldehyde and 10-40% of urea; the sulfomethylphenol is (6-2) of sulfomethylated phenol and sulfomethylated diphenol: 1.
The molecular weight range of the supramolecular sulfonated phenolic polycondensate is 1000-10000.
The supermolecule sulfonated phenolic aldehyde polycondensate is of a comb-shaped structure.
"comb polymers" are polymers of this type comprising a main chain and a plurality of branches grafted to said main chain, the plurality of branches resembling the teeth of a comb. The "bonding" to the solid is primarily by virtue of the branched functional groups.
The melting point of the supramolecular sulfonated phenolic polycondensate is between 280 ℃ and 320 ℃. The supermolecule sulfonated phenolic aldehyde polycondensate with high melting point has good high-temperature resistance, can ensure that the supermolecule sulfonated phenolic aldehyde polycondensate is not denatured in the grinding process, and can keep high-efficiency dispersibility after grinding.
The preparation method of the supermolecular sulfonated phenolic polycondensate comprises the following steps: adding phenol and diphenol into a hydroxymethyl sulfonate aqueous solution to prepare a sulfomethyl phenol solution; then adding urea and formaldehyde for polycondensation reaction; adjusting the pH value to obtain the sulfonated phenolic polycondensate.
Preparation of an aqueous solution of a hydroxymethylsulfonate salt: adding a sulfonating agent and water into a container according to a certain proportion, controlling the temperature and heating to completely dissolve the sulfonating agent and the water, adding a formaldehyde solution into the container when the temperature is reduced to 30 +/-5 ℃, slightly increasing the temperature, controlling the temperature to 60 +/-5 ℃, and carrying out heat preservation reaction for 2-4 hours to obtain a hydroxymethyl sulfonate aqueous solution.
The sulfonating agent may be at least one of sodium sulfite and sodium bisulfite.
Preparation of sulfomethylphenol solution: adding phenol and diphenol into the aqueous solution of the hydroxymethylsulfonate, adjusting the pH of the solution to 9-10, and heating for reaction for 4 hours to obtain a sulfomethylphenol solution.
And (3) polycondensation reaction: adding urea and formaldehyde into the sulfomethylphenol solution, adjusting the pH value to 9-10, heating and refluxing until the reaction is finished, cooling and adjusting the pH value to 7-8 to obtain the aqueous solution of the supermolecule sulfonated phenolic aldehyde polycondensate.
The application of the supermolecule sulfonated phenolic aldehyde polycondensate is used for preparing a pyrazole water suspension agent, wherein the pyrazole accounts for 25-30% by weight; 5% -10% of supramolecular sulfonated phenolic polycondensate; 6 to 8 percent of thickening agent; 3% -8% of an antifreezing agent; 1% -1.5% of a stabilizer; 0.1 to 0.5 percent of defoaming agent; 0.1 to 0.2 percent of preservative; water makes up to 100%.
Compared with the prior art, the invention has the following beneficial effects
According to the invention, the sulfonic acid group is introduced into the polycondensate, so that the water solubility of the wetting dispersant is enhanced, and the modified supermolecule sulfonated phenolic polycondensate is ensured to be more resistant to high temperature; meanwhile, a urea monomer is creatively introduced into the supramolecular sulfonated phenolic acid polycondensate, so that the agricultural chemical particles are more resistant to mechanical friction, and the agricultural chemical particles are better applied to products needing to be ground; the sulfomethylated phenol and the sulfomethylated diphenol are compounded and stored, so that the maintenance of the two introduction functions is ensured.
Drawings
FIG. 1: example 1 test chart of melting point of supramolecular sulphonated phenolic polycondensate.
FIG. 2: example 1 infrared test chart of supramolecular sulfonated phenol polycondensate, -OH: 3393cm-1；-CH2-:1473cm-1 ；-C-O-:1176cm-1；-SO3 -:1039cm-1；。
FIG. 3: example 1 number average molecular weight measurement report of supramolecular sulfonated phenol condensation polymers.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
The sources of the raw materials used in the present invention are as follows in table 1:
examples and comparative examples the preparation of supramolecular sulphonated phenolic polycondensates was carried out: adding a sulfonating agent and water into a container according to a certain ratio (shown in table 3), controlling the temperature and heating to completely dissolve the sulfonating agent and water, adding a formaldehyde solution into the container when the temperature is reduced to 30 +/-5 ℃, slightly increasing the temperature, controlling the temperature to 60 +/-5 ℃, and carrying out heat preservation reaction for 2-4 hours to obtain the hydroxymethyl sulfonate aqueous solution. And adding phenol and diphenol into the aqueous solution of the hydroxymethyl sulfonate, adjusting the pH value of the solution to 9-10, and heating for reaction for 4 hours to obtain a sulfomethylphenol solution. Adding urea and formaldehyde into the sulfomethylphenol solution, adjusting the pH value to 9-10, heating and refluxing until the reaction is finished, cooling, and adjusting the pH value to 7-8 to obtain the aqueous solution of the supermolecule sulfonated phenolic aldehyde polycondensate.
Table 2: 25% pyrazole aqueous suspension formulation
The preparation method of the 25% pyrazole aqueous suspension formulation comprises the following steps: uniformly mixing pyrazole, the products of examples or comparative examples, propylene glycol, a defoaming agent, a stabilizing agent and water at one time, adding zirconium beads after shearing, then grinding for 1-2h until the particle diameter D90 is reduced to about 5 microns, filtering and discharging, adding xanthan gum and a preservative, shearing for 2min, and carrying out cold-hot storage and normal-temperature observation on the stability of four samples.
The performance test method comprises the following steps:
(1) normal temperature storage stability: the normal temperature storage stability test rule of the NYT1427-2007 pesticide is general, and no solid or oily substance is precipitated after 3 months under the room temperature condition of a sample;
(2) low-temperature storage stability: according to the method for measuring the low-temperature stability of the GB/T19137-2003 pesticide, no solid or oily substance is precipitated after 7 days when a sample is at the temperature of 0 ℃;
(3) high-temperature storage stability: according to the GB/T19136-;
(4) particle size of the particles: the particle size growth rate before and after heat storage is less than or equal to 20 percent by referring to the operation of an LS-POPCP laser particle size analyzer and particle size detection;
(5) melting point test method: the procedure was followed with an HS-DSC-101 melting point tester.
(6) The infrared spectrogram testing method comprises the following steps: reference is made to FTIR-650 (high-resolution) Fourier transform Infrared Spectroscopy assay.
(7) Number average molecular weight test method: reference is made to Waters1515 gel chromatography assay (SB-804 HQ as column).
(8) The suspension rate test method comprises the following steps: refer to GBT 14825-2006 pesticide suspension rate determination method.
Table 3: examples and comparative examples supramolecular sulfonated phenolic polycondensate monomer amount and performance test results
TABLE 3
As can be seen from examples 1-5, the supramolecular sulfonated phenolic polycondensate of the invention has high melting point and good stability, and due to the thermal stability, the supramolecular sulfonated phenolic polycondensate keeps properties during grinding, does not agglomerate and has high suspension rate.
As can be seen from comparative examples 1 to 5, the stability and the dispersibility were not good even if all the monomers of the present invention were used, not in the formulation of the present invention.
Claims (9)
1. A supramolecular sulfonated phenolic polycondensate characterized in that the polymerization is derived from monomers comprising in the range of 40% to 50% sulfomethylphenol, 10% to 40% formaldehyde, 10% to 40% urea; the sulfomethylphenol is (6-2) of sulfomethylated phenol and sulfomethylated diphenol: 1.
2. The supramolecular sulfonated phenol aldehyde polycondensate according to claim 1, characterized in that the molecular weight of the supramolecular sulfonated phenol aldehyde polycondensate ranges from 1000-10000.
3. The supramolecular phenolic polycondensate sulfonated according to claim 1, characterized in that the phenolic polycondensate sulfonated is of comb structure.
4. The supramolecular sulfonated phenol condensation polymer according to claim 1, characterized by a melting point between 280-320 ℃.
5. The process for the preparation of the supramolecular sulphonated phenolic polycondensate according to any of claims 1 to 4, characterized in that it comprises the following steps: adding phenol and diphenol into a hydroxymethyl sulfonate aqueous solution to prepare a sulfomethyl phenol solution; then adding urea and formaldehyde for polycondensation reaction; adjusting the pH value to obtain the supermolecular sulfonated phenolic polycondensate.
6. The method of producing supramolecular sulfonated phenol polycondensates according to claim 5, characterized in that the preparation of aqueous hydroxymethylsulfonate solution: adding a sulfonating agent and water into a container according to a certain proportion, controlling the temperature and heating to completely dissolve the sulfonating agent and the water, adding a formaldehyde solution into the container when the temperature is reduced to 30 +/-5 ℃, slightly increasing the temperature, controlling the temperature to 60 +/-5 ℃, and carrying out heat preservation reaction for 2-4 hours to obtain a hydroxymethyl sulfonate aqueous solution.
7. The method of producing supramolecular sulfonated phenol condensation polymers according to claim 5, characterized in that the preparation of the sulfomethylphenol solution: adding phenol and diphenol into the aqueous solution of the hydroxymethylsulfonate, adjusting the pH of the solution to 9-10, and heating for reaction for 4 hours to obtain a sulfomethylphenol solution.
8. The process for the preparation of the supramolecular sulphonated phenolic polycondensate according to claim 5, characterized in that the polycondensation reaction: adding urea and formaldehyde into the sulfomethylphenol solution, adjusting the pH value to 9-10, heating and refluxing until the reaction is finished, cooling and adjusting the pH value to 7-8 to obtain the aqueous solution of the supermolecule sulfonated phenolic aldehyde polycondensate.
9. Use of the supramolecular sulphonated phenolic polycondensate according to any of claims 1 to 4, characterized in that it is used for the preparation of aqueous pyrazole suspensions, in percentages by weight, between 25% and 30% pyrazole; 5% -10% of supramolecular sulfonated phenolic polycondensate; 6 to 8 percent of thickening agent; 3% -8% of an antifreezing agent; 1% -1.5% of a stabilizer; 0.1 to 0.5 percent of defoaming agent; 0.1 to 0.2 percent of preservative; water makes up to 100%.
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| CN102408882A (en) * | 2011-10-11 | 2012-04-11 | 山东轻工业学院 | Phenol urea-formaldehyde resin modified lignite high-temperature-resistant salt-resistant filtrate reducer and preparation method thereof |
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| CN103601401B (en) * | 2013-11-25 | 2015-07-15 | 金陵科技学院 | Preparation method of sulfonated bisphenol A-formaldehyde condensate superplasticizer |
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