CN107674194A - A kind of polyether antifoam agent and preparation method thereof - Google Patents

A kind of polyether antifoam agent and preparation method thereof Download PDF

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CN107674194A
CN107674194A CN201710715909.9A CN201710715909A CN107674194A CN 107674194 A CN107674194 A CN 107674194A CN 201710715909 A CN201710715909 A CN 201710715909A CN 107674194 A CN107674194 A CN 107674194A
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defoamer
acid
initiator
agent
catalyst
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蔡政
万修倩
刘洋
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Shenyang Haobo Industrial Co Ltd
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Shenyang Haobo Industrial Co Ltd
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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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
    • C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
    • C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D19/00—Degasification of liquids
    • B01D19/02—Foam dispersion or prevention
    • B01D19/04—Foam dispersion or prevention by addition of chemical substances
    • B01D19/0404—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D19/00—Degasification of liquids
    • B01D19/02—Foam dispersion or prevention
    • B01D19/04—Foam dispersion or prevention by addition of chemical substances
    • B01D19/0404—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance
    • B01D19/0495—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance containing hetero rings
    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2618—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen
    • C08G65/2621—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups
    • C08G65/2624—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups containing aliphatic amine groups
    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2618—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen
    • C08G65/2621—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups
    • C08G65/263—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups containing heterocyclic amine groups
    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/30—Post-polymerisation treatment, e.g. recovery, purification, drying
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G5/00—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents
    • C23G5/02—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents
    • C23G5/032—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents containing oxygen-containing compounds
    • 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
    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
    • C08G2650/58—Ethylene oxide or propylene oxide copolymers, e.g. pluronics

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  • Polymers & Plastics (AREA)
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  • Degasification And Air Bubble Elimination (AREA)

Abstract

The invention discloses a kind of polyether antifoam agent, the defoamer carries out polymerisation as initiator and oxirane, expoxy propane, epoxy butane using polyfunctionality, with branched structure, the compound containing active hydrogen end group and hydrophobic end group in the presence of catalyst, and neutralized dose of reaction product forms through bleaching agent decolorization again after neutralizing；The preparation method of described defoamer, initiator and catalyst is put into autoclave, and reactor is sealed, be evacuated to 0.08MPa, inflated with nitrogen displacement, 3 times repeatedly；Then, oxirane, expoxy propane and epoxy butane is added dropwise respectively in order；Finally, 100 DEG C are cooled the temperature to, nertralizer is added, insulated and stirred 10min, adds decolorising agent, insulated and stirred 10min, be cooled to 60 DEG C, blowing obtains product.The short-term antifoaming speed of gained defoamer and the performance change i.e. resistance to ag(e)ing defoamed for a long time while it is guaranteed.

Description

A kind of polyether antifoam agent and preparation method thereof
Technical field
The invention belongs to field of fine chemical, in particular to a kind of polyether antifoam agent being used in metal degreasing agent and Its preparation method.
Background technology
Metal（Such as copper, zinc）And metal parts needs to make antirust treatment by smearing antirust oil when stored, antirust oil Main component is grease and mineral oil, and metal is using preceding needing to carry out ungrease treatment to its surface（Remove metal surface Antirust oil）.Degreasing metal processing typically using cleaning showers or swings two methods of cleaning, and metal is put into by cleaning showers to be contained Have in the spray groove of degreasing agent, the metal containing antirust oil is cleaned up by high-pressure spraying for a period of time；Swing cleaning be by Metal is put into the tank liquor containing degreasing agent, reaches the purpose cleaned up by swinging metal.
Degreasing agent is mainly by alkaline matter（Such as NaOH）, a variety of surfactants（Such as AEO）And disappear Infusion forms.In metal cleaning, because high-pressure spraying or strong swing act on, large quantity of air can be brought into tank liquor, air It can be scattered in liquid, form using air as dispersed phase, using liquid as decentralized medium system.Bubble in liquid rises to Liquid level, form the foaming aggregation that gas is separated with liquid film that big quantity of fluid is formed（That is foam）；Simultaneously as saponification Substantial amounts of foam can be produced, the generation of a large amount of foams will directly affect cleaning performance, the cleaning efficiency of metal, and cause degreasing agent Loss.Therefore, a small amount of defoamer need to be added in degreasing agent, reduces the generation with known foam, this requires defoamer With elimination and suppress effect caused by foam.
Defoamer is the relatively low material of a kind of surface tension, can be rapidly on vacuolar membrane surface after defoamer contacts with vacuolar membrane Sprawl, defoaming agent molecule instead of original foaming agent molecule on foam surface, and the new liquid film of formation is due to surface heterogeneity Property it is stronger, cause new Film strength very low, foam stability decline, be readily broken.Meanwhile defoamer is gone back in cleaning process Stronger foam-inhibiting effect need to be embodied, because defoamer has stronger surface-active compared with infusion, lower surface tension, preferentially Absorption is on the vacuolar membrane liquid film of air liquid interface, and defoamer its own face inhomogeneity is stronger, and the vacuolar membrane elasticity formed is poor, So the unstability of foam is higher, foam-inhibiting effect is generated.Also solubility size is related in water to defoamer for foam-inhibiting effect： General only to play disposable defoaming for the big defoamer of solubility, after defoamer is dissolved, defoaming effect may It is wholly absent, foam can regenerate again；The small or insoluble defoamer of solubility is after first time brokenly bubble, still with insoluble State be present in bubbling system, at this moment defoamer not only can inhibition system produce foam, and can to caused foam rise To defoaming effect again.
Defoamer is probably divided into containing silicon defoaming agent, fluorine-containing defoamer, polyether antifoam agent etc. by composition difference.Containing silicon defoaming agent Defoaming effect is good, but can form silicon spot in metal surface after use, is not suitable for using in metal degreasing agent；Fluorine-containing defoamer disappears Bubble, suds effect are good, but cost is too high, there is certain corrosivity to metal surface；Polyether antifoam agent defoaming effect is not as good as preceding two Class, but it has excellent suds, and therefore cleaning performance, is largely applied in metal degreasing agent without influence.
At present, polyether antifoam agent is mainly using straight chain alcohol or amine as initiator, with expoxy propane or the epoxy of different proportion The block polymer of the linear chain structure of ethane and expoxy propane.Polyether antifoam agent mainly has following a few classes：1) GP types defoamer, With binary or trihydroxylic alcohol（Glycerine or propane diols）For initiator, the PPOX formed by expoxy propane progress addition polymerization is sweet Oily ether is domestic to be referred to as GP, and such defoamer hydrophily is poor, and solubility is small in foaming system, influences defoaming, suds and degreasing effect Fruit, defoamer wall built-up phenomenon be present, so should not be used in spray degreasing agent；2) GPE types defoamer, the country are referred to as bubble enemy, GP type defoamers polypropylene glycol link latter end continue addition of ethylene oxide, make the end of the chain be hydrophilic group polyoxyethylene oxypropylene it is sweet Oily ether, GPE type defoamer hydrophilies are preferable, easily sprawled in foaming media, and defoaming capacity is strong, but solubility is also larger, defoaming Activity hold time it is short, initial stage suds still meet spray requirement, long-term suds are poor, can not meet spray scene Continuous production.
For these reasons, urgent need develops a kind of be used in metal degreasing agent completely newly, with the suppression efficient, steady in a long-term that disappears Bubble feature without silicon block polyether class defoamer.
The content of the invention
The present invention provides a kind of preparation method of synthesizing polyether defoamer, and prepared defoamer has that defoaming is strong, suppression Bubble property is stable, on the cleaning performance of degreasing agent without influence, it is environment-friendly many advantages, such as.
The present invention is achieved by the following scheme：A kind of polyether antifoam agent, the defoamer with polyfunctionality, have branch Change structure, the compound containing active hydrogen end group and hydrophobic end group exists for initiator and oxirane, expoxy propane, epoxy butane Polymerisation is carried out in the presence of catalyst, neutralized dose of reaction product forms through bleaching agent decolorization again after neutralizing；
In the defoamer, the mass fraction of each component is：
Initiator：10 parts；
Oxirane, expoxy propane, epoxy butane：800-2700 parts；
Catalyst：0.05-0.1 parts
Nertralizer：2.7-8.2 part
Bleaching agent：1.3-2.7 part
Preferably：Described polyfunctionality is three-functionality-degree, tetra functional or five degrees of functionality；
Described branched structure is isomery alcohol/ammonia or phenol；
Described active hydrogen end group is-OH ,-NH2；
Described hydrophobic end group is C1-C9Alkane or any isoparaffin with branched structure either with aromatic ring Alkane or isoparaffin.
Preferably：Described initiator structure is：
,
Wherein R1 is hydrophobic group, is C1-C13Alkane or the isoparaffin with branched structure or alkane with aromatic ring, R2, R3, R4 are alkane or the isoparaffin with branched structure, and X is alcoholic extract hydroxyl group or amino with reactive hydrogen atom.
Preferably：Described initiator is trimethylolpropane, melamine, pentaerythrite, diethylenetriamine, triethylene One or more in tetramine.
Preferably：Described catalyst is one in sodium hydroxide, potassium hydroxide, sodium methoxide, sodium tert-butoxide, potassium tert-butoxide Kind is several.
Preferably：Described nertralizer is in formic acid, acetic acid, propionic acid, butyric acid, isooctyl acid, oxalic acid, hydrochloric acid, phosphoric acid, sulfuric acid One or more.
Preferably：Described decolorising agent is hydrogen peroxide.
A kind of preparation method of defoamer：
First, initiator and catalyst are put into autoclave, reactor is sealed, be evacuated to -0.08MPa, fill Nitrogen displacement, 3 times repeatedly；
Then, it is evacuated to negative pressure -0.08MPa；Temperature in the kettle is risen to 80 DEG C, pressurize 30min sloughs moisture；It is warming up to 120 DEG C, start polymerisation, oxirane, expoxy propane and epoxy butane is added dropwise respectively in order；Reaction is extremely pressed after being added dropwise Power is stable, i.e., polymerisation terminates；
Finally, cooling the temperature to 100 DEG C, add nertralizer, insulated and stirred 10min adds decolorising agent, insulated and stirred 10min, 60 DEG C are cooled to, blowing obtains product.
Application of the above-mentioned defoamer in metal degreasing agent.
The structures shape of the initiator molecular chain structure of defoamer, initiator are branched structure, synthesized defoamer Strand is branched structure；The initiator degree of branching is more, and the strand of synthesized defoamer becomes network structure.Meanwhile Initiator at least one end connection need to be ensured is hydrophobic group, and R1 is hydrophobic group, can be C1-C13Alkane or any there is branch Change the isoparaffin either alkane or isoparaffin with aromatic ring of structure, R2, R3, R4 is alkane or arbitrarily has branch Change the isoparaffin of structure, end is alcoholic extract hydroxyl group or amino with reactive hydrogen atom.
Trimethylolpropane, melamine, pentaerythrite, diethylenetriamine, triethylene tetramine etc. have said structure Organic matter can be separately as initiator, or any several is mixed with arbitrary proportion as initiator.
Polyether structure and arrangement architecture in defoamer branched chain molecule by the HLB value for significantly affecting defoamer, cloud point, disappear Steep performance, suds suppressing properties.As three hydrophobic groups not in same plane, same direction, constitute it is irregular, interruption hate Water, hydrophilic-structure, cause foam surface the effect of the surface tension of different directions to be present, be easy to vanishing for foam.Using epoxy Ethane, expoxy propane and epoxy butane are primary raw material, defoam the scale effect defoaming agent molecule of EO, PO and BO in agent molecule Hydrophilic lipophilic balance.It is oil loving simultaneously to defoam agent molecule guarantee, also to there is preferable affinity with foaming system；Defoaming In agent molecule, EO is the hydrophilic segment of strand, and PO and BO constitute the oleophylic segment of strand, and PO and BO adduct number are got over It is more, defoam that the lipophile of agent molecule is stronger, EO adduct number is more, defoams that the hydrophily of agent molecule is stronger, the parent with expanding foam solution It is better with power, be so advantageous to defoam the surface that agent molecule enters foam, because defoamer is different from the surface tension of expanding foam solution, Play the effect of brokenly bubble.Both also contribute to the basic properties such as the cloud point of defoamer, and usual PO and BO adduct numbers are more, defoamer The cloud point of molecule is lower, and EO adduct number is more, defoams that the cloud point of agent molecule is higher, the suds of the lower product of cloud point of defoamer Property, defoaming are better.EO, PO and BO block order have large effect to its suds, antifoam performance in defoaming agent molecule.Point Contain EO segments in subchain, it is ensured that the affinity with expanding foam solution, but EO segments are not exposed to the end of strand again, point The front end and end of subchain are PO and BO oleophylic segment, can suppress the height of initial foam, and this kind of block structure can be protected Lipophile, the adhesion with expanding foam solution are demonstrate,proved, the initial foam height during use can be reduced again.Proportions are adjusted, and Insertion sequence can be controlled effectively, molecular weight, HLB value, antifoam performance and the suds suppressing properties of synthesizing polyether class defoamer.
Described different block structures are：Initiator is with oxirane, expoxy propane, epoxy butane with any insertion sequence Insertion, can be EO+PO+BO, PO+EO+BO, BO+EO+PO or multistage embedded structure EO+PO+EO+BO+PO etc..
It is wherein preferred：Initiator+PO+EO+BO+PO+EO+PO+BO structures, or initiator+BO+EO+BO+PO+EO+PO + BO structures.
Described expoxy propane and the ratio of oxirane can be：1:50 to 50:1；
Described epoxy butane and oxirane ratio can be：1:50 to 50:1；
Expoxy propane and the epoxy butane ratio can be：1:50 to 50:1；
It is wherein preferred：
The ratio 1 of expoxy propane and oxirane:10 to 10:1；
Epoxy butane and oxirane ratio 1:10 to 10:1；
Expoxy propane and epoxy butane ratio 1:10 to 10:1.The molecular weight of the front end polyethers of the synthesis is：500-20000；
Wherein preferred molecular weight 6000-12000
Described catalyst is base catalyst, including sodium hydroxide, potassium hydroxide, sodium methoxide, potassium tert-butoxide, sodium tert-butoxide etc. In one or more kinds of arbitrary proportions mixing；
Wherein preferred sodium tert-butoxide catalyst.
Contain base catalyst, unreacted monomer and its oligomer in defoamer after polymerization, after product returns to room temperature, Partial base catalyzed dose of crystallization separates out, and suspends in the product, defoamer outward appearance is cloudy state, and due to the presence of alkali, defoamer is Strong basicity, there is corrosivity to container and equipment while product is unstable.The organic acids such as glacial acetic acid, isooctyl acid, oxalic acid add Enter base catalyst that can effectively in neutralization system, product is reached neutral, can also eliminate the base catalyst to be suspended in defoamer, It is transparent to make product appearance.Nertralizer also selects inorganic acid, the strong acid in inorganic acid, such as sulfuric acid, can form bulky grain sodium potassium Salt is crystallized, and filtering is easier to, but its acidity is too strong, is easily caused defoaming agent molecule and is decomposed, big to equipment corrosion.Select intermediate acid Phosphoric acid of property etc. also has good effect in product appearance etc..
Described nertralizer includes：The organic acids such as formic acid, acetic acid, propionic acid, butyric acid, isooctyl acid, oxalic acid；Or hydrochloric acid, phosphorus The inorganic acids such as acid, sulfuric acid；Or above-mentioned organic-inorganic acid is mixed with arbitrary proportion；
Wherein preferred acetic acid or isooctyl acid.
The purpose of the nertralizer used is that reacted product is neutralized into neutrality, according to different reaction systems, The mass fraction for being computed obtaining the nertralizer is：2.7-8.2 part.
Because the polycondensation of expoxy propane, expoxy propane is strong exothermal reaction, local reaction overheats, and still has in reaction vessel few The presence of oxygen is measured, causes a small amount of oxidation of impurities in product and raw material to turn yellow, separately there is the generation of the materials such as accessory substance aldehydes.To ensure Product appearance color and luster hydrogen peroxide for decoloration technique, hydrogen peroxide carry peroxide bridge, easily because peroxide bridge is broken generation peroxide freedom Base, it is strong that the free radical takes electronic capability by force, there is strong oxidizing property.When the strong oxidizers such as hydrogen peroxide and pigment act on, coloring matter Molecule be oxidized so as to lose original color, the dosage of bleaching agent is so that the color of reaction product is colourless or faint yellow is Preferably, to reach above-mentioned purpose, bleaching agent mass fraction is：1.3-2.7 part.
Described nertralizer decolorization need to meet that the dosage of hydrogen peroxide should be not more than the dosage of organic acid or inorganic acid；
Described neutralization and decolorization need to meet first to add nertralizer, then add hydrogen peroxide.
It is an advantage of the invention that：Defoamer of the present invention, its structure are initiator+block structure, the block knot Structure is that oxirane, expoxy propane, epoxy butane are carried out obtained by graft reaction with the functional group in initiator in certain sequence, this Using the initiator of polyfunctionality in scheme, it can make that reaction speed is fast, and side reaction is few, so that the molecule of final product Measure narrow distribution range, comprising active hydrogen end group ensure that the quick progress of reaction, described hydrophobic end group and block structure In the mutual cooperation of hydrophilic radical the partial hydrophilicity of final product and partially hydrophobic is reasonably balanced so that The short-term antifoaming speed of gained defoamer and the performance change i.e. resistance to ag(e)ing defoamed for a long time while it is guaranteed.This project is with different Octanoic acid is nertralizer, neutralizes remaining base catalyst in product, while the product is reached neutrality, improves the transparent of product Degree；Bleaching agent uses hydrogen peroxide, the strong oxidizing property of hydrogen peroxide, can reduce the color of product, while the cost of hydrogen peroxide is relatively low；It is different Octanoic acid and hydrogen peroxide play a role jointly, obtain the anti-foam product of pale yellow transparent.
Specific embodiment
With reference to embodiment, the present invention is described further, as described below, is only the preferable implementation to the present invention Example, is not limited the present invention, any person skilled in the art is possibly also with the disclosure above Technology contents be changed to the equivalent embodiment changed on an equal basis.It is every of the invention without departing from the present invention program content, foundation Technical spirit any simple modification that following examples are made or equivalent variations, all fall within protection scope of the present invention.
Embodiment 1
Polyether antifoam agent, respectively with trimethylolpropane, melamine, pentaerythrite, diethylenetriamine, triethylene tetramine, three Hydroxymethyl-propane+melamine（1:1, quality parts ratio, similarly hereinafter）, trimethylolpropane+melamine（1:5）, trihydroxy methyl Propane+melamine（5:1）, trimethylolpropane+pentaerythrite（1:1）, trimethylolpropane+pentaerythrite（1:5）, three hydroxyls Methylpropane+pentaerythrite（5:1）, trimethylolpropane+diethylenetriamine（1:1）, trimethylolpropane+diethylenetriamine （1:5）, trimethylolpropane+diethylenetriamine（5:1）, diethylenetriamine+triethylene tetramine（1:1）, the second of diethylenetriamine+three Alkene tetramine（1:5）, diethylenetriamine+triethylene tetramine（5:1）, melamine+pentaerythrite（1:1）, melamine+Ji Wusi Alcohol（1:5）, melamine+pentaerythrite（5:1）For initiator, potassium hydroxide is catalyst, and molecular structure is initiator+BO+ EO+BO+PO+EO+PO+BO, molecular weight 8000, its ethylene oxide (EO), expoxy propane (PO), epoxy butane ( BO) mol ratio is EO：PO：BO=1:50:10, nertralizer isooctyl acid dosage is 3%, and dioxygen water consumption is 1%.
The preparation method of defoamer：Equipment is 10 L autoclaves；
First, a certain amount of initiator and catalyst are put into autoclave, reactor is sealed, vacuumized, nitrogen Displacement 3 times, is then evacuated to negative pressure；Treat that temperature in the kettle rises to 80 DEG C, negative pressure dehydration 30min；
120 DEG C are warming up to, starts polymerisation, oxirane, expoxy propane and epoxy butane is added dropwise respectively in order；Drip Aging reaction to negative pressure, i.e. polymerisation terminates after finishing；
100 DEG C are cooled to, isooctyl acid is added and is neutralized, and insulated and stirred 10min, add hydrogen peroxide for decoloration, insulated and stirred 10min, 60 DEG C are cooled to, blowing, obtains the anti-foam product, anti-foam product numbering is by different by initiator：1- 20#。
Embodiment 2
Polyether antifoam agent, respectively with sodium hydroxide, potassium hydroxide, sodium methoxide, sodium tert-butoxide, potassium tert-butoxide, potassium hydroxide+methanol Sodium（1:1）, potassium hydroxide+sodium methoxide（1:5）, potassium hydroxide+sodium methoxide（5:1）, potassium hydroxide+potassium tert-butoxide（1:1）, hydrogen-oxygen Change potassium+potassium tert-butoxide（1:5）, potassium hydroxide+potassium tert-butoxide（5:1）, potassium hydroxide+sodium tert-butoxide（1:1）, potassium hydroxide+uncle Sodium butoxide（1:5）, potassium hydroxide+sodium tert-butoxide（5:1）, sodium hydroxide+sodium methoxide（1:1）, sodium hydroxide+sodium methoxide（1:5）、 Sodium hydroxide+sodium methoxide（5:1）, sodium hydroxide+sodium tert-butoxide（1:1）, sodium hydroxide+sodium tert-butoxide（1:5）, sodium hydroxide+ Sodium tert-butoxide（5:1）, sodium hydroxide+potassium tert-butoxide（1:1）, sodium hydroxide+potassium tert-butoxide（1:5）, sodium hydroxide+potassium tert-butoxide （5:1）For catalyst, molecular structure is initiator+BO+EO+BO+PO+EO+PO+BO, and molecular weight is 1000, EO：PO：BO= 50:10:1, nertralizer isooctyl acid dosage is 3%, and dioxygen water consumption is 1%.Defoamer is synthesized as follows：Using 10 L high pressures Reactor.First, a certain amount of initiator and catalyst are put into autoclave, reactor is sealed, vacuumized, nitrogen Gas is replaced 3 times, is then evacuated to negative pressure；Treat that temperature in the kettle rises to 80 DEG C, negative pressure dehydration 30min；120 DEG C are warming up to, is started Polymerisation, a certain amount of oxirane, expoxy propane and epoxy butane is added dropwise respectively in order；Rear aging reaction is added dropwise To negative pressure, i.e. polymerisation terminates；100 DEG C are cooled to, the isooctyl acid of metering is added, insulated and stirred 10min, adds metering Hydrogen peroxide, insulated and stirred 10min, 60 DEG C are cooled to, blowing.The production code member for obtaining defoamer is：21-43#.
Embodiment 3
Polyether antifoam agent, it is respectively synthesized following structure defoamer：Initiator+EO+PO+BO, initiator+PO+EO+BO, initiator+ BO+EO+PO, initiator+EO+PO+EO+BO+PO, initiator+PO+EO+BO+PO+EO+PO+BO, initiator+BO+EO+BO+PO + EO+PO+BO, initiator are pentaerythrite, molecular weight 3500, EO：PO：BO=10:1:50, catalyst is potassium hydroxide, in It is 3% with agent isooctyl acid dosage, dioxygen water consumption is 1%.Defoamer is synthesized as follows：Using 10 L autoclaves.It is first First, a certain amount of initiator and catalyst are put into autoclave, reactor is sealed, is vacuumized, nitrogen displacement 3 It is secondary, then it is evacuated to negative pressure；Treat that temperature in the kettle rises to 80 DEG C, negative pressure dehydration 30min；120 DEG C are warming up to, it is anti-to start polymerization Should, a certain amount of oxirane, expoxy propane and epoxy butane is added dropwise respectively in order；Rear aging reaction is added dropwise to negative Pressure, i.e., polymerisation terminates；100 DEG C are cooled to, adds the isooctyl acid of metering, insulated and stirred 10min, adds the dioxygen of metering Water, insulated and stirred 10min, 60 DEG C are cooled to, blowing.The production code member for obtaining defoamer is：44-49#.
Embodiment 4
Polyether antifoam agent, synthesize the defoamer of following molecular weight：500th, 2000,3500,5000,8000,10000,20000, rise Beginning agent is trimethylolpropane, and molecular structure is initiator+BO+EO+BO+PO+EO+PO+BO, EO：PO：BO=1:50:10, urge Agent is potassium hydroxide, and nertralizer isooctyl acid dosage is 3%, and dioxygen water consumption is 1%.Defoamer is synthesized as follows：Using 10 L autoclaves.First, a certain amount of initiator and catalyst are put into autoclave, reactor are sealed, Vacuumize, nitrogen displacement 3 times, be then evacuated to negative pressure；Treat that temperature in the kettle rises to 80 DEG C, negative pressure dehydration 30min；It is warming up to 120 DEG C, start polymerisation, a certain amount of oxirane, expoxy propane and epoxy butane is added dropwise respectively in order；It is added dropwise Aging reaction to negative pressure, i.e. polymerisation terminates afterwards；100 DEG C are cooled to, adds the isooctyl acid of metering, insulated and stirred 10min, then The hydrogen peroxide of metering is added, insulated and stirred 10min, is cooled to 60 DEG C, blowing.The production code member for obtaining defoamer is：50-56#.
Embodiment 5
Polyether antifoam agent, synthesize the defoamer of following EO, PO, BO ratio, EO：PO：BO=1:50:10、EO：PO：BO=1:10: 50、EO：PO：BO=50:1:10、PO：EO=1:50、PO：EO=50:1、BO：EO=1:50、BO：EO=50:1、PO：EO=1:10、 PO：EO=10:1、BO：EO=1:10、BO：EO=10:1、PO：BO=1:10、PO：BO=10:1, initiator is trimethylolpropane, Molecular structure is initiator+BO+EO+BO+PO+EO+PO+BO, and molecular weight 5000, catalyst is potassium hydroxide, and nertralizer is different Sad dosage is 3%, and dioxygen water consumption is 1%.Defoamer is synthesized as follows：Using 10 L autoclaves.First, one Quantitative initiator and catalyst is put into autoclave, and reactor is sealed, and is vacuumized, nitrogen displacement 3 times, is then taken out Vacuum is to negative pressure；Treat that temperature in the kettle rises to 80 DEG C, negative pressure dehydration 30min；120 DEG C are warming up to, starts polymerisation, divides in order A certain amount of oxirane, expoxy propane and epoxy butane are not added dropwise；Rear aging reaction is added dropwise to negative pressure, i.e. polymerisation Terminate；100 DEG C are cooled to, adds the isooctyl acid of metering, insulated and stirred 10min, adds the hydrogen peroxide of metering, insulated and stirred 10min, 60 DEG C are cooled to, blowing.The production code member for obtaining defoamer is：57-69 #.
Embodiment 6
Polyether antifoam agent, defoamer is synthesized by nertralizer of following material：Formic acid, acetic acid, propionic acid, butyric acid, isooctyl acid, oxalic acid, Hydrochloric acid（80%）, phosphoric acid（100%）, sulfuric acid（50%）, formic acid：Acetic acid=1:1st, formic acid：Acetic acid=1:5th, formic acid：Acetic acid=5:1st, second Acid：Isooctyl acid=1:1st, acetic acid：Isooctyl acid=1:5th, acetic acid：Isooctyl acid=5:1st, isooctyl acid：Phosphoric acid=1:1st, isooctyl acid：Phosphoric acid=1: 5th, isooctyl acid：Phosphoric acid=5:1st, acetic acid：Isooctyl acid=1:1st, acetic acid：Isooctyl acid=1:5th, acetic acid：Isooctyl acid=5:1st, oxalic acid：Isooctyl acid =1:1st, oxalic acid：Isooctyl acid=1:5th, oxalic acid：Isooctyl acid=5:1st, oxalic acid：Phosphoric acid=1:1st, oxalic acid：Phosphoric acid=1:5th, oxalic acid：Phosphoric acid=5: 1, initiator is trimethylolpropane, and catalyst is potassium hydroxide, and molecular structure is initiator+BO+EO+BO+PO+EO+PO+ BO, EO：PO：BO=1:50:10, molecular weight 3500, nertralizer dosage is 3%, and dioxygen water consumption is 1%.Close as follows Into defoamer：Using 10 L autoclaves.First, a certain amount of initiator and catalyst are put into autoclave, Reactor is sealed, vacuumizes, nitrogen displacement 3 times, is then evacuated to negative pressure；Treat that temperature in the kettle rises to 80 DEG C, negative pressure dehydration 30min；120 DEG C are warming up to, starts polymerisation, a certain amount of oxirane, expoxy propane and epoxy is added dropwise respectively in order Butane；Rear aging reaction to negative pressure, i.e. polymerisation is added dropwise to terminate；100 DEG C are cooled to, adds the isooctyl acid of metering, is protected Temperature stirring 10min, adds the hydrogen peroxide of metering, insulated and stirred 10min, is cooled to 60 DEG C, blowing.Obtain the product of defoamer Numbering is：70-96#.
Embodiment 7
Polyether antifoam agent, nertralizer addition are respectively：1%th, 2%, 3%, initiator is trimethylolpropane, and catalyst is hydrogen-oxygen Change potassium, molecular structure is initiator+BO+EO+BO+PO+EO+PO+BO, EO：PO：BO=1:50:10, molecular weight 8000, in It is isooctyl acid with agent, dioxygen water consumption is 1%.Defoamer is synthesized as follows：Using 10 L autoclaves.First, one Quantitative initiator and catalyst is put into autoclave, and reactor is sealed, and is vacuumized, nitrogen displacement 3 times, is then taken out Vacuum is to negative pressure；Treat that temperature in the kettle rises to 80 DEG C, negative pressure dehydration 30min；120 DEG C are warming up to, starts polymerisation, divides in order A certain amount of oxirane, expoxy propane and epoxy butane are not added dropwise；Rear aging reaction is added dropwise to negative pressure, i.e. polymerisation Terminate；100 DEG C are cooled to, adds the isooctyl acid of metering, insulated and stirred 10min, adds the hydrogen peroxide of metering, insulated and stirred 10min, 60 DEG C are cooled to, blowing.The production code member for obtaining defoamer is：97-99#.
Embodiment 8
Polyether antifoam agent, dioxygen water consumption are respectively：0.1%th, 1%, 2%, 3%, initiator is trimethylolpropane, and catalyst is hydrogen Potassium oxide, molecular structure are initiator+BO+EO+BO+PO+EO+PO+BO, EO：PO：BO=1:50:10, molecular weight 5000, Nertralizer isooctyl acid dosage is 3%.Defoamer is synthesized as follows：Using 10 L autoclaves.First, a certain amount of Initiator and catalyst are put into autoclave, and reactor is sealed, and are vacuumized, nitrogen displacement 3 times, are then evacuated to Negative pressure；Treat that temperature in the kettle rises to 80 DEG C, negative pressure dehydration 30min；120 DEG C are warming up to, starts polymerisation, is added dropwise respectively in order A certain amount of oxirane, expoxy propane and epoxy butane；Rear aging reaction to negative pressure, i.e. polymerisation is added dropwise to terminate； 100 DEG C are cooled to, adds the isooctyl acid of metering, insulated and stirred 10min adds the hydrogen peroxide of metering, insulated and stirred 10min, 60 DEG C are cooled to, blowing.The production code member for obtaining defoamer is：100-103#.
Foaming properties test
According to degreasing agent prescription, the tank liquor of degreasing agent is prepared in the groove for simulating live spray thrower, under the conditions of 45 DEG C, normal pressure spray 1h, the foam height in tank liquor is observed after spray thrower stable circulation；It the results are shown in Table 1.
The different defoamer foaming properties of table 1
Defoamer Foam height/cm Defoamer Foam height/cm
1# 2 53# 2.5
2# 3 54# 2
3# 2.5 55# 1.5
4# 3.5 56# 1.5
5# 2 57# 2
6# 3 58# 2
7# 2 59# 7
8# 2.5 60# 7
9# 2.5 61# 3
10# 3 62# 7
11# 2.5 63# 3
12# 3 64# 5
13# 3 65# 3.5
14# 3.5 66# 5
15# 2.5 67# 3.5
16# 2 68# 3
17# 2 69# 3
18# 2.5 70# 3
19# 2.5 71# 2.5
20# 2 72# 2.5
21# 2.5 73# 2.5
22# 2 74# 2
23# 2.5 75# 2.5
24# 2 76# 3.5
25# 3 77# 2.5
26# 3 78# 3.5
27# 3 79# 2.5
28# 3 80# 2.5
29# 3 81# 3
30# 2.5 82# 3.5
31# 3 83# 2.5
32# 2.5 84# 3
33# 2.5 85# 3
34# 2.5 86# 3
35# 2 87# 3
36# 2.5 88# 2.5
37# 3 89# 3
38# 3.5 90# 3.5
39# 2.5 91# 3.5
40# 2.5 92# 3
41# 2.5 93# 2.5
42# 2.5 94# 2.5
43# 2.5 95# 3
44# 2.5 96# 3
45# 3 97# 2
46# 3 98# 2
47# 3 99# 2.5
48# 2.5 100# 2
49# 2 101# 2
50# 7 102# 2.5
51# 4.5 103# 3
52# 3
Remarks：1. overflow groove：Foam overflow work nest in working solution；Blank assay：Defoamer is not added in working solution；
2. the condition of this test is carried out with reference to actual operating conditions, the difference of test condition may cause the difference of result, but its The relative numerical value that bearing reaction goes out is constant, and therefore, this test condition is believable.This test can also be with reference to JB/ T4323.2 requirement is carried out, and cleaning agent can select general cleaning agent, and the SP403 types of such as Hao Yuan Chung Inc. are right As a result the meaning embodied is without influence.
As can be seen that blank assay is not due to adding defoamer from test result, foam caused by working solution is caused to overflow Work nest is gone out；After adding tri- sections of defoamers of L-61, GP-330, PPE in work nest respectively, the foam height of working solution obtains Eliminate and suppress, foam height is in 3-3.5cm；After the product for adding the present invention in working solution respectively, foam height obtains effectively Elimination and suppression, foam height maintains 2-2.5cm, it is clear that the defoamer synthesized with the initiator that the present invention uses produces Product, defoaming, the suds suppressing properties of defoamer are effectively raised, it is branched knot to be primarily due to the initiator that the present invention uses Structure, and be hydrophobic grouping with terminal groups, so as to get defoamer strand be branched or netted irregular segment, defoaming Agent molecule is irregular due to structure after the liquid film surface of foam is entered, can be by irregular, not Tongfang on the liquid film of foam To active force, foam can quickly vanish；And the molecular structure of domestic a few money anti-foam products is regular linear structure, defoaming Speed is relatively slow, so, the defoamer that the present invention obtains more domestic defoamer during metal cleaning showers has obvious Performance advantage；The foam height gap embodied on simulation spray thrower, can double to amplify in application process, have at the scene More obviously embody, in addition, the present invention uses oxirane, expoxy propane and epoxy butane as primary raw material, defoamer point The hydrophilic lipophilic balance of EO, PO and BO scale effect defoaming agent molecule in son.It is oil loving simultaneously to defoam agent molecule guarantee, Also there is preferable affinity with foaming system；Defoam in agent molecule, EO is the hydrophilic segment of strand, and PO and BO are constituted point The oleophylic segment of subchain, PO and BO adduct number are more, defoam that the lipophile of agent molecule is stronger, and EO adduct number is more, disappears The hydrophily of infusion molecule is stronger, better with the affinity of expanding foam solution, is so advantageous to defoam the surface that agent molecule enters foam, Because defoamer is different from the surface tension of expanding foam solution, the effect of brokenly bubble is played.Both also contribute to the bases such as the cloud point of defoamer Plinth performance, usual PO and BO adduct numbers are more, defoam that the cloud point of agent molecule is lower, and EO adduct number is more, defoams agent molecule Cloud point is higher, and suds, the defoaming of the lower product of cloud point of defoamer are better.Defoam the block of EO, PO and BO in agent molecule Order has large effect to its suds, antifoam performance.Contain EO segments in the strand of defoamer of the present invention, it is ensured that with The affinity of expanding foam solution, but EO segments are not exposed to the end of strand again, and the front end and end of strand are PO and BO parent Oily segment, the height of initial foam can be suppressed, this kind of block structure can ensure lipophile, the adhesion with expanding foam solution, again The initial foam height during use can be reduced.The present invention is by adjusting proportions, and insertion sequence can be controlled effectively Molecular weight, HLB value, antifoam performance and the suds suppressing properties of the synthesized polyethers defoamer of system.
Therefore the defoamer that the present invention obtains, has more superior defoaming and foam-inhibiting effect in metal cleaning showers.

Claims (9)

  1. A kind of 1. polyether antifoam agent, it is characterised in that：The defoamer with polyfunctionality, have branched structure, contain active hydrogen The compound of end group and hydrophobic end group is that initiator enters with oxirane, expoxy propane, epoxy butane in the presence of catalyst Row polymerisation, neutralized dose of reaction product form through bleaching agent decolorization again after neutralizing；
    In the defoamer, the mass fraction of each component is：
    Initiator：10 parts；
    Oxirane, expoxy propane, epoxy butane：800-2700 parts；
    Catalyst：0.05-0.1 parts；
    Nertralizer：2.7-8.2 part；
    Bleaching agent：1.3-2.7 part.
  2. 2. polyether antifoam agent according to claim 1, it is characterised in that：Described polyfunctionality is three-functionality-degree, four officials Energy degree or five degrees of functionality；
    Described branched structure is isomery alcohol/ammonia or phenol；
    Described active hydrogen end group is-OH ,-NH2；
    Described hydrophobic end group is C1-C9Alkane or any isoparaffin with branched structure either with aromatic ring Alkane or isoparaffin.
  3. 3. polyether antifoam agent according to claim 1, it is characterised in that：Described initiator structure is：
    ,
    Wherein R1 is hydrophobic group, is C1-C13Alkane or the isoparaffin with branched structure or alkane with aromatic ring, R2, R3, R4 are alkane or the isoparaffin with branched structure, and X is alcoholic extract hydroxyl group or amino with reactive hydrogen atom.
  4. 4. polyether antifoam agent according to claim 1, it is characterised in that：Described initiator is trimethylolpropane, three One or more in poly cyanamid, pentaerythrite, diethylenetriamine, triethylene tetramine.
  5. 5. polyether antifoam agent according to claim 1, it is characterised in that：Described catalyst is sodium hydroxide, hydroxide One or more in potassium, sodium methoxide, sodium tert-butoxide, potassium tert-butoxide.
  6. 6. polyether antifoam agent according to claim 1, it is characterised in that：Described nertralizer be formic acid, acetic acid, propionic acid, One or more in butyric acid, isooctyl acid, oxalic acid, hydrochloric acid, phosphoric acid, sulfuric acid.
  7. 7. polyether antifoam agent according to claim 1, it is characterised in that：Described decolorising agent is hydrogen peroxide.
  8. 8. the preparation method of the defoamer as described in claim 1-7 is any, it is characterised in that：
    First, initiator and catalyst are put into autoclave, reactor is sealed, be evacuated to -0.08MPa, fill Nitrogen displacement, 3 times repeatedly；
    Then, it is evacuated to negative pressure -0.08MPa；Temperature in the kettle is risen to 80 DEG C, pressurize 30min sloughs moisture；It is warming up to 120 DEG C, start polymerisation, oxirane, expoxy propane and epoxy butane is added dropwise respectively in order；Reaction is extremely pressed after being added dropwise Power is stable, i.e., polymerisation terminates；
    Finally, cooling the temperature to 100 DEG C, add nertralizer, insulated and stirred 10min adds decolorising agent, insulated and stirred 10min, 60 DEG C are cooled to, blowing obtains product.
  9. 9. application of any one of the claim 1-8 defoamers in metal degreasing agent.
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CN110540638A (en) * 2019-08-21 2019-12-06 佳化化学科技发展（上海）有限公司 Preparation method of emulsifier and application of emulsifier in preparation of pesticide emulsifiable concentrate
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CN113527654A (en) * 2021-04-28 2021-10-22 山东惠畅新材料有限公司 High-efficiency energy-saving polyether defoaming agent and preparation method thereof
CN113480726A (en) * 2021-06-09 2021-10-08 内蒙古科学技术研究院 Polyether defoaming agent for fermentation and preparation method thereof
CN113501951A (en) * 2021-06-09 2021-10-15 内蒙古科学技术研究院 Polyether defoaming agent and preparation method and application thereof
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Application publication date: 20180209