CN101735631A - Preparation of oxide anion antifoaming agent - Google Patents

Abstract

The invention discloses a master batch antifoaming agent added to materials in the production process of plastic products, which is formed by using calcined calcium oxide or calcined magnesia as an activated body and matching with resin and other auxiliary agents. The antifoaming agent releases anions and is characterized by consisting of the following prescriptions and is prepared by the following process; the master batch antifoaming agent is prepared by the prescription as follows: 10-60 parts of oxide, 30-60 parts of carrier resin, 3-10 parts of auxiliary agent and 0.5-30 parts of anion additive; the process is as follows: a solid matrix is a particulate, such as, inorganic oxide, resin, starch, and the like, the antifoaming agent and the solid matrix are sufficiently mixed, dried and pulverized to prepare a solid antifoaming agent. The prepared master batch antifoaming agent can be used in the material additive of various plastic products. The antifoaming agent also has the function of releasing anion and is good for the health of a human body. The invention can be widely used in the production of various plastic products in life, such as, the products of various plastic water supply pipes, extrusion plates, various plastic injection moulding parts, and the like.

Description

The preparation of oxide anion antifoaming agent

Technical field: the invention belongs to fields such as material preparation, chemical, chemical assistant, polymer modification.

Background technology: in most production processes, foam can result in hand cramps to production, eliminates deleterious foam and can utilize leave standstill, reduce pressure (vacuumizing), heat or way such as pressurization.Need at short notice but work as, when eliminating foam rapidly and effectively, just need be by means of adding defoamer.Defoamer is widely used in papermaking, coating, weaving, food, medical science, pharmacy and the petrochemical complex industry at present, and consumption also constantly increasing, selects suitable defoamer more and more to be subjected to the attention in each field.Since German experimental physics scholar Quincke at first proposes to come froth breaking with chemical process, four updates have up to the present been experienced.

First-generation defoamer is organism such as mineral oil, lipid acid and fatty acid ester, fatty amide, lower alcohols.Mineral oil such as kerosene, turps, whiteruss etc.Can be used for industries such as printing paste, papermaking.Lipid acid and fatty acid ester such as butter, lard, soya-bean oil, Viscotrol C, glycol stearate, sorbitan mono-laurate etc.This defoamer can be used for papermaking, paper pulp, dyeing, building coating, fermentation etc.Alcohols such as coconut alcohol, hexanol, hexalin.Can be used for sugaring, fermentation petroleum refinement etc.Amides such as ethylenedistearamide, two palmityl quadrols etc.

Organic defoamer is cheap, in the market still in a large amount of uses.It is suitable in liquid shear power less, use under the relatively mild condition of contained tensio-active agent foaming power, but it is relatively poor that the dense form foamy is eliminated ability.Because the Application Areas of organic defoamer has diversity and singularity, it often has specificity, and therefore constantly atrophy of the market share has limitation on using.But the industry that some is special such as strong acid, highly basic etc. just need be as organic defoamers of this class acid and alkali-resistance of tetrafluoroethylene.In recent years, for the attention to environment protection, the status of natural fats and oils defoamer has had raising again.It is low that organic defoamer and type siloxane defoamer are compared production cost, thereby Ying Zaineng uses the occasion of organic defoamer to use it as far as possible, and in this sense organic defoamer is rising.

S-generation defoamer is the polyethers defoamer.Polyethers is the segmented copolymer of the lower polyoxyethylene of molecular weight 2 polyoxypropylenes.It is a kind of water soluble nonionic surfactant of excellent property, when contacting with water, Sauerstoffatom in the ehter bond can combine with faint chemical force with the hydrogen atom in the water, form hydrogen bond, building block becomes indentation, hydrophobic group places the molecule inboard, becoming around the chain combines with water easily, when the temperature rising, when molecular motion is comparatively violent, zigzag chain can become zig-zag, lost the associativity with water, be warmed up to by the dissolution in low temperature state and present muddy temperature, the cloud point of Here it is polyethers, have only when the temperature of foaming system surpasses cloud point temperature, polyether antifoam agent is just brought into play the froth breaking effect.In preparation process,, just can change its cloud point, thereby be applicable to different occasions by regulating the ratio and the molecular weight of feed oxygen ethene, oxypropylene.

Polyether antifoam agent is developed rapidly after at first being gone into operation by U.S. Wyandot t company in 1954, and particularly along with the developing rapidly of polyethers industry, the development of polyethers defoamer is more rapid.China succeeded in developing in 1967 and puts into production.Polyether type defoamer mainly contain straight-chain polyether and by alcohol, ammonia is the polyethers of initiator or the polyether derivative of end group esterification.

1. straight-chain polyether: polyoxypropylene (PO) n and polyoxyethylene (EO) m segmented copolymer with (PO) n as hydrophobic chain, with (EO) m as hydrophilic chain.It has two types: promptly molecular end is that EO and molecular end are PO, and molecular structure is HO (EO) l (PO) m (EO) nH and HO (PO) l (EO) m (PO) nH.The defoamer cloud point of this type is lower, can be used for froth breaking in the lower system of temperature.

2. be the polyethers of initiator or the polyether derivative of end group esterification by alcohol, ammonia

2.1 with ammonia is that initiator is the molecular structure of the defoamer of initiator with ammonia

2.2 with alcohol is that initiator is mainly the polyethers of making initiator with monohydroxy-alcohol, dibasic alcohol, glycerol.

2.3 glycerin polyether fatty acid ester

Silicone based defoamer is to use a defoamer more widely in present dyeing and finishing, food, fermentation, papermaking, Chemical Manufacture, tackiness agent, latex, the lubricated wet goods industry.China is since the development seventies in 20th century and use silicone antifoam agent, in recent years, has obtained effect preferably.But on the whole, class is lower, and kind is also simpler, and has compared big gap abroad.The also main dependence on import [3] of the silicone antifoaming agent of using on more present imported units.Silicone antifoam agent is owing to the popularity of its application scenario, and not following tens kinds of its domestic and international marque is generally polydimethylsiloxane, and some occasion also needs siloxanes such as ethyl, hydroxyl, phenyl.Dimethyl silicone oil belongs to the line style polymethyl siloxane of MDnM type, it in the molecule easy " it " print train around song, molecular structure has determined it that following characteristic is arranged: surface tension is low: the surface tension of polydimethylsiloxane is all lower than water, water phase surfactant mixture and general oils, thereby the very suitable defoamer of doing; Low and the active height of solubleness in water and general oil: the polysiloxane molecule structure is special, and main chain is a siloxane bond, is non-polar molecule, and is not affine with polar solvent water, also very little with general oil product affinity; Volatility is low and have unreactiveness: the dimethyl silicone oil volatility is extremely low, and also has low surface tension, and the two combination makes defoamer play the froth breaking effect in the temperature widely; No physiology toxicity: generally higher as the dimethyl silicone oil polymerization degree of defoamer.The dimethyl silicone oil that has removed oligopolymer then is that no physiology is toxic.Because these advantages, the range of goods of this defoamer is more, and usage quantity is also bigger, has become the principal item in the defoamer.Domestic commercially available silicone antifoam agent can be divided into oily, solution-type, emulsion-type, solid type four classes by physical behavior at present.

1. oily silicone antifoam agent

The oily silicone antifoam agent can be divided into oil type and oil composite type.Oil type dimethyl silicone oil generally commonly used is as defoamer, and the silicone oil with low viscosity defoaming effect is fast, but persistence is poor; The viscous silicone fluid defoaming effect is slow, but persistence is good.Universal law is that foaming liquid viscosity is low more, and the silicon oil viscosity of selecting for use should be high more, otherwise foaming liquid viscosity is high more, and the silicon oil viscosity of selecting for use is low more.The oil type defoamer is gratifying to the defoaming effect of oil-soluble solution, but pure silicon oil does not have the froth breaking effect to the foam of the aqueous solution.In silicone oil, sneak into the silicon-dioxide auxiliary agent of crossing through hydrophobic treatment, form the oil composite type defoamer, because the silica sphere hydroxyl helps the dispersion of silicone oil, thereby has improved the antifoam performance of silicone oil and reduced cost, has enlarged the range of application of silicone oil type defoamer.

2. silicon oil solution

In order to make silicone antifoam agent can reach good froth breaking effect, it must be become very small particle, be evenly dispersed in the froth breaking object.Silicone oil can be dissolved in and make silicon oil solution in the solvent, organic solvent should both dissolve silicone oil, itself was easy to dissolving in the foaming system again, disperseed.The organic solvent that is used for the selection of non-aqueous system froth breaking has many monochloroethane, toluene, dimethylbenzene etc.; The organic solvent that is used for the selection of aqueous systems froth breaking has ethylene glycol, glycerine, other alcohol etc.The silicon oil solution defoamer is to carry silicone oil and be dispersed in the foaming liquid by solvent, solvent diffusion, and silicone oil is condensed into droplet, thus the effect of performance froth breaking.This simple mode is not widely used, and one is to use a large amount of solvents to improve cost; The 2nd, if there is not violent stirring, though easily diffusion of solvent, organosilicon is condensed in the original place does not have the oil droplet that froth breaking is active, granularity is excessive.

3. emulsion-type

The organosilicon breast is the thick liquid of white thickness, and chemical stability, thermotolerance and oxidation-resistance are all higher, and be harmless, applied widely, both can be applicable to nonaqueous phase, can be applicable to water again.Because the interfacial tension of water/silicone oil is higher, silicone oil is difficult with emulsification, and the stability of emulsion is the important indicator of defoamer quality, so the selection of emulsifying agent is crucial.Emulsifying agent belongs to tensio-active agent, and it can form film or electrostatic double layer on the surface of dispersed phase drop, stop these droplet phase mutual coagulations, helps to form stable emulsion.The hydrophile-lipophile balance value of emulsifying agent is that the HLB value must be moderate, it is generally acknowledged at 7-9.Most prescriptions also add white carbon black in silicone oil, white carbon black provides water to enter the polarity interface of silicone oil drop inside, helps the dispersion of silicone oil, hinder emulsification in addition in addition the effect that merges of silicone oil small droplets, thereby improved the froth breaking ability of silicone oil emulsion.In silicone emulsion, because silicone oil is difficult to emulsification than other oils, need a large amount of use emulsifying agents, though stability makes moderate progress, viscosity raises, antifoam performance reduces.From using, organic silicon emulsion exist poor stability, easily layering, perishable, easily be sunken to the shortcoming of bottom.But since organic silicon emulsion have easy to use, defoaming effect is obvious, moderate, also certain market will be arranged in the recent period, and, believe that organosilicon emulsion defoaming agents has bigger progress along with " composite " continuous advancement in technology.

4. solid type

Preparation technology is simple for the SOLID ORGANIC silicon defoaming agent, and excellent storage stability is convenient to transportation.By changing its carrier or auxiliary agent, can be used for water, can be used for oil phase again, and medium dispersiveness is preferably arranged.Therefore, the SOLID ORGANIC silicon defoaming agent is still except that being used for, the low sudsing detergent powder production, also use the field infiltration of liquid defoamer to other.Based on the good application performance of type siloxane defoamer with and versatility, it in industrial production application surface extensively be that other defoamer kind is incomparable.Along with the success of continually developing of new type siloxane material, the continuous progress of de-foaming process and perfect, must make it will be the main body of industrial defoamer in the quite a long time.The silicone antifoam agent defoaming effectiveness is very high, but it is barely satisfactory sometimes to press down the bubble effect.Thereby, organosilicon can be with fatty acid amide, polyethers etc. other have froth breaking, press down the active surfactant compound of bubble and become compound defoamer, so both can improve silicone antifoam agent but the bubble ability can reduce the cost of product again.Along with the surfactant compound development of technology, silicone antifoam agent is strong because of its froth breaking ability, working concentration is low and to the mankind and the nontoxic substantially characteristics of environment, will demonstrate wide application prospect and huge market potential.

The 4th generation defoamer be polyether-modified polysiloxane defoamer, it is to introduce polyether segment by modification on the polysiloxane segment.In the molecule of silicon ether copolymer, the siloxanes segment has lipophilicity, and polyether segment has wetting ability.Energy-conservation wetting ability and the whipability of providing of polyethylene oxide chain in the polyether segment, energy-conservation hydrophobicity and the seepage force of providing of poly(propylene oxide) chain.Polyether-modified polysiloxane defoamer not only has polysiloxane defoamer froth breaking and renders a service strong, characteristics such as surface tension is low, the bullet property sent out is low, nontoxic, pollution-free, physiology inertia, but also has the characteristics such as high temperature resistant, strong basicity resisting of polyethers defoamer.The organic silicon modified by polyether defoamer is a kind of new and effective defoamer that both advantage is combined, and in addition also has the characteristic of many excellences.Froth breaking is renderd a service strong: both polysiloxane institute inherent low surface tension, advantage of high activity have polyethers easy dispersive advantage in water again.Therefore, not only render a service by force, and under some occasion, can solve the problem that conventional defoamer cann't be solved than conventional silicone antifoam agent.

Contrary solvability: polyether-modified polysiloxane at low temperatures, polyether chain and water formation hydrogen bond portability polysiloxane chain equably diffusion profile in water, be similar to dissolved state; And when temperature raise, along with the destruction of hydrogen bond, polyether chain wetting ability variation when cloud point, had lost wetting ability, when making whole silicone polyether chain become not dissolved state, just brought into play the froth breaking effect.Silicone polyether type multipolymer has dissolution in low temperature, and the high temperature insoluble has effectively improved the polysiloxane application performance.

According to above-mentioned characteristic, the silicone polyether type defoamer that can select to have corresponding cloud point easily according to the temperature of the required froth breaking of system.In addition, contrary deliquescent convenience, can also be used in low temperature _ _ be not dissolved in the system of water, with the cold water that is lower than its cloud point, the defoamer of dissolved state is rinsed well.From milkiness: silicone polyether type multipolymer adds it and can form spontaneously in entry that the polysiloxane segment is crimped onto inside, the polyethers section extends in outside dispersion state under suitable temperature, forms micelle in water.This character is called " from milkiness ".From milkiness make silicone polyether type defoamer can be in foaming liquid homodisperse, help to give full play to the froth breaking effect.Stability: therefore the silicone polyether defoamer has good dispersion stabilization owing to have well in milkiness in water.The multipolymer that-Si-O-C-key connects is easy to hydrolysis, and chemical stability is relatively poor, but does not influence the froth breaking effect.The multipolymer that-Si-C-key connects is then more stable, and the thermostability of all kinds of silicone polyether type defoamers is all relatively good.Before the deadline, all can be used for the aqueous systems of boiling state, even can be used for the foaming aqueous systems of 130 ℃ of high temperature.Nontoxic: the silicone polyether defoamer allows to add in the wrapping paper of food as indirect foodstuff additive.Donalds etc. at first synthesize this analog copolymer at early fifties, and the defoamer of this type development in recent years is very fast, has been derivatized to a series of products, with polyether type defoamer, polysiloxane type defoamer, form three big synthetic defoamers of tripartite confrontation.The structure and the type of silicone polyether type defoamer are multifarious, according to the classification of the bridging mode of polysiloxane and polyethers, roughly have with-Si-C-key to be connected and to be connected two classes with-Si-O-C-key.

Because thermotolerance, shear resistant and the acid and alkali-resistance salt performance of polyether silicone oil are good, also have nonpoisonous and tasteless, storage-stable and advantage such as easy to use in addition, thereby extensively be used in the froth breaking of various occasions, also can be used for the froth breaking under many severe condition, is a kind of very representative, excellent property, broad-spectrum silicone antifoam agent [5].In the polyester piece good high-temperature dyeing process, general silicone antifoam agent can produce the film like precipitation and make pollutant produce spot under high temperature, high pressure.Use polyether-modified polysiloxane defoamers just can overcome these shortcomings, because these component of antifoam agent can be dissolved in cold water, and be insoluble to hot water, so can play the froth breaking effect.The effect of polyether modified polysiloxan defoaming agent in zymotechnique is even more important, and each kind, each operation all need froth breaking.The use of tradition defoamer is unsatisfactory.The defoamer that is applicable to zymotechnique must satisfy following requirement: to the microorganism nontoxicity; Not by microbial metabolism; Supply to oxygen does not have influence; Can stand the heat treated of sterilizing.Because polyether modified polysiloxan defoaming agent has characteristics such as nontoxic, harmless, efficient, multipotency and physiology inertia, more and more be subjected to the favor of producer, polyether modified polysiloxan defoaming agent is existing abroad produces, at present, this product also is in the development stage at home, and its product extremely is short of [6].It can be soluble in water rapidly, can use separately, also can be used with other treatment agent.Breakdown of emulsion floating oil phenomenon does not take place in good stability, and also sediment-free produces; Also effective to non-aqueous system equally.Polyether modified polysiloxan defoaming agent is optimal new variety in the organosilicon, is the developing direction of defoamer.

China's defoamer begins to enter evolution period through vicennial development, and technology reaches its maturity, and the development of carrying out novel defoamer to us provides feasible condition.Continuous discovery along with new high reactivity froth breaking component, deepening continuously of composite component synergistic effect research, those component structures are single, economic benefit is relatively poor, and low-grade defoamer will be replaced by multi-functional, high efficiency Compositional type defoamer gradually, composite such as composite, the polyethers of silicoorganic compound and tensio-active agent and organosilyl composite, water-soluble or oil soluble polyethers and silicon-containing polyether.Suitability is strong, and consumption is little, can improve the quality of products and plant factor new and effective

Defoamer will be the developing direction of current defoamer.Along with reducing year by year and the optimization of synthetic route of silicone oil synthesis material price, be furnished with the compound defoamer of polyether modified silicon oil component will be on the market in future dominate.

Summary of the invention:

The defoamer that the method that the present invention adopts calcining metal oxide, resin, negative ion etc. to combine is prepared.Defoamer on the market is mainly at aspects such as textile industry, coating and printing ink now, and the defoamer that relates to the plastics forming aspect is also few.And the present invention proposed to add the design of anionic additive in defoamer, and this at home and abroad also is rare.Described masterbatch defoamer comprises following component, is mass percent: oxide compound: 10-60; Vector resin: 30-60; Auxiliary agent 3-10; Anionic additive: 0.5-30.

This product froth breaking principle is: CaO+H2O → Ca (OH) 2

Invented technology and purposes:

Solid substrate mainly is particulates such as inorganic oxide, resin and starch.The solid substrate thorough mixing is bonded together, and drying and crushing makes solid defoamer then.

The masterbatch defoamer that makes can be used for the material additive of various plastic prods.The function that this defoamer discharges negative ion in addition has very big benefit to body-care.Can widespread use and various life with in the production of plastics, in the product as various plastic water pipes, extrusion board and various plastic injection pieces etc.

Embodiment:

The masterbatch defoamer comprises following component, is mass percent: oxide compound: 45; Vector resin: 40; Auxiliary agent 5; Anionic additive: 10.

Claims (7)

1. one kind is antifoam composition with calcined oxide calcium or magnesia calcined, cooperates resin and other auxiliary agent and masterbatch defoamer that being used for of forming adds in raw material production process of plastic products.It is characterized in that being made up of and prepared following invention prescription, invention is filled a prescription as follows: oxide compound: 10-60; Vector resin: 30-60; Auxiliary agent: 3-10: anionic additive 0.5-30.

According to claims 1 described oxide compound be can with the calcined material of water vigorous reaction, as magnesia calcined or calcined oxide calcium etc.

3. be PE, PP, PS, PMMA, PVC, DPVC, PC, PA, EVA, PU, CPE, ABS, SBS according to claims 1 described vector resin.

4. mainly be effects such as bonding, film forming, parcel according to claims 1 described auxiliary agent, as starch, carboxymethyl cellulose, water glass, Fatty Alcohol(C12-C14 and C12-C18), fatty acid ester etc.

5. according to claims 1 described anionic additive, be by the interpolation negative ion, make this masterbatch defoamer by negative ion-releasing function, the product of being produced when this defoamer is used for the plastics additive also has negative ion-releasing function.He has just played the dual function of froth breaking and release negative ion like this.

6. mainly be particulates such as inorganic oxide, resin and starch according to claims 1 described solid substrate.The solid substrate thorough mixing is bonded together, and drying and crushing makes solid defoamer then.

7. according to claims 1, the masterbatch defoamer that makes can be used for the material additive of various plastic prods.The function that this defoamer discharges negative ion in addition has very big benefit to body-care.Can widespread use and various life with in the production of plastics, in the product as various plastic water pipes, extrusion board and various plastic injection pieces etc.