CN100443553C - Method for preparing high water absorption and water retention composite materials containing amorphous silicate mineral - Google Patents
Method for preparing high water absorption and water retention composite materials containing amorphous silicate mineral Download PDFInfo
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- CN100443553C CN100443553C CNB2006100186167A CN200610018616A CN100443553C CN 100443553 C CN100443553 C CN 100443553C CN B2006100186167 A CNB2006100186167 A CN B2006100186167A CN 200610018616 A CN200610018616 A CN 200610018616A CN 100443553 C CN100443553 C CN 100443553C
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Abstract
The present invention relates to a preparation method of a composite material with good performance for water absorption and water retention, particularly to a preparation method of a composite material with good performance for high water absorption and water retention, wherein the composite material comprises amorphous silicate minerals. The preparation method is characterized in that the preparation method comprises: deep processing treatment of the amorphous silicate minerals; dispersing treatment: amorphous silicate mineral powder treated by deep processing is added into a water soluble ethylene unsaturated monomer solution containing a dissolved water soluble free radical polymerization initiating agent and a dissolved crosslinking agent to be dispersed and treated, and the weight concentration of the water soluble ethylene unsaturated monomer solution is from 10 to 50%; polymerization reaction: the dispersed and treated mixed material is slowly dropped into a hydrophobic organic dispersing medium dissolved with a surface active agent and/or polymer protective colloid to carry out water-in-oil type inverse suspension polymerization for 1 to 6 hours under the condition that the temperature is from 20 to 90DEG C; post treatment: after the polymerization reaction is completed and the temperature is lowered to the room temperature, the mixed material in the hydrophobic organic dispersing medium is dewatered with an added organic solvent or dewatered by azeotropic distillation, and then washed and filteredwith ethanol, and a polymerisate is dried in vacuum at the temperature of 40 to 110DEG C to obtain the product. The present invention has the characteristics of low preparation cost and good allround performance of the product.
Description
Technical field
The present invention relates to a kind of preparation method of composite materials with high water absorbing and retaining performances, be specifically related to a kind of high water absorbing and retaining preparation methods that contains amorphous silicate mineral.
Background technology
In recent years, the high water absorbing and retaining agent is widely used in various fields such as agricultural gardening, physiological hygiene articles for use, medicine, oil, chemical industry, environmental protection, building materials and food because of its good suction and water retention property.Traditional synthetic class super absorbent resin, as polyacrylonitrile based, polyacrylic, polyacrylamide system and polyethenol series.Toxicity is bigger, or production cost is higher, or water absorbing properties is not good, or salt resistance is relatively poor, thereby has limited their application.By interpolation non-metallic mineral powder and the compound over-all properties that can improve material of organic resin, and significantly reduce raw materials cost.Thereby obtained rapidly development, for the development and application of High hydrophilous resin provides wide prospect.
Present most of researchist adopts water solution polymerization process to prepare mineral/polymer composite materials with high water absorbing and retaining performances, and the characteristics of this method are: the characteristics of this method are: process is simple, both can be intermittently, but also continuous production, cost is low, and employing water is reaction solvent, and environmental pollution is less.Shortcomings such as the reaction heat difficulty is scattered and disappeared, easily implode but still exist, and will pass through mechanical disintegration after product instability and the product drying, and it is bigger to consume energy.
Inverse suspension polymerization method (being the ISP method) is a kind of novel method for preparing High hydrophilous resin that grows up the nearly more than ten years.Compare with aqua-solution method, the inverse suspension polymerization method has lot of advantages, as reacts easy control, and product is a fine granularity, convenient post-treatment, and product performance are preferable etc.The document that at present relevant inverse suspension polymerization legal system is equipped with mineral/polymer composite materials with high water absorbing and retaining performances is few, the non-metallic minerals of its interpolation also is a few layer silicate minerals such as wilkinite, sericite, kaolin and montmorillonite, and do not relate to pre-treatments such as the deep processing of mineral or purifications yet, and yet there are no open report so far about the document and the patent of adding amorphous silicate mineral.
Summary of the invention
The object of the present invention is to provide that a kind of preparation cost is low, the preparation method of the composite materials with high water absorbing and retaining performances that contains amorphous silicate mineral of product good combination property.
For achieving the above object, technical scheme of the present invention is: contain the preparation method of the composite materials with high water absorbing and retaining performances of amorphous silicate mineral, it is characterized in that it comprises the steps: 1) the amorphous silicate mineral deep processing handles: with amorphous silicate mineral original soil mechanical disintegration or superfine grinding to median size≤45um; 2) dispersing and mixing is handled: will join the weight concentration that is dissolved with water-soluble radical polymerization initiator and linking agent through the amorphous silicate mineral powder that deep processing was handled and be in 10～50% the water-soluble vinyl unsaturated monomer solution and carry out dispersion treatment; Decentralized approach is: the employing homogenizer carries out dispersed with stirring or disperses with colloidal mill, or adopts ultrasonic wave to carry out ultra-sonic dispersion; When adopting ultrasonic dispersion, the power of ultrasonic generator is 20～4000W, and frequency of ultrasonic is 10 kilo hertzs～300 megahertzes; The addition of amorphous silicate mineral is 2～200% of a water-soluble vinyl unsaturated monomer weight, the addition of water-soluble radical polymerization initiator is 0.001～10% of a water-soluble vinyl unsaturated monomer weight, and the addition of linking agent is 0～10% of a water-soluble vinyl unsaturated monomer weight; 3) polyreaction: through after the dispersing and mixing, the said mixture material is added drop-wise to lentamente and is dissolved with tensio-active agent or/and among the hydrophobicity organic dispersion medium of polymkeric substance protective colloid, carried out the water-in-oil-type inverse suspension polymerization 1～6 hour (preferred 2～5 hours) under 20～90 ℃ of (preferred 40～80 ℃) conditions; The hydrophobicity organic dispersion medium is 1～5 times of water-soluble vinyl unsaturated monomer solution volume, the addition of tensio-active agent is 0.1～20% of a water-soluble vinyl unsaturated monomer weight, and the addition of polymkeric substance protective colloid is 0.1～10% of a water-soluble vinyl unsaturated monomer weight; 4) aftertreatment: after above-mentioned polyreaction finishes, treat that temperature reduces to room temperature, add dehydration of organic solvent or carry out the component distillation dehydration, use washing with alcohol, filter, polymerisate gets particulate state or powder-like product through mechanical disintegration or without mechanical disintegration slightly in 40～110 ℃ of vacuum-dryings.(illustrate: when adopting tensio-active agent and polymkeric substance protective colloid; the addition of tensio-active agent is 0.1～20% of a water-soluble vinyl unsaturated monomer weight, and the addition of polymkeric substance protective colloid is 0.1～10% of a water-soluble vinyl unsaturated monomer weight.)
Organic solvent is methyl alcohol or acetone etc.
Introduce the present invention below in detail.
1. amorphous silicate mineral
Amorphous silicate mineral, the feature of this class silicate minerals is: its X ray collection of illustrative plates does not have the obvious characteristics diffraction peak, and does not have any optical characteristics.All amorphous silicate minerals with above-mentioned feature all can be used for the present invention.Typical amorphous silicate mineral has: malthacite (1-2SiO
2Al
2O
3NH
2O), (the essential mineral composition is an opal to diatomite, SiO
2NH
2O), quartz sand (mainly contains SiO
2, Al
2O
3, Fe
2O
3Deng) etc.These mineral can use separately, also can use than mixing with any by any several mineral.When being used alone mineral, its purity (or content) 〉=40%; For the mixed mineral powder, the purity of its main amorphous silicate mineral (or content) 〉=30%.(be generally the material of reductibility, for containing the poly-property material of resistance as Fe
2+, Cu
+Deng) the amorphous silicate mineral original soil also must be through overpickling, magnetic separation, the calcining or the roasting purification processes.Above-mentioned mineral before use must be through mechanical disintegration to median size≤45um.The addition of amorphous silicate mineral is 2～200% of a water-soluble vinyl unsaturated monomer weight, preferred 2～120% (weight).
2. water-soluble vinyl unsaturated monomer
Any satisfactory water-soluble vinyl unsaturated monomer all can be used for the present invention.Typical water-soluble ionic-type vinyl unsaturated monomer is: the ammonium salt of an alkali metal salt of vinylformic acid, methacrylic acid, acrylic acid an alkali metal salt, methacrylic acid, acrylic acid ammonium salt, methacrylic acid; An alkali metal salt of 2-(methyl) acrylamide-2-methyl propane sulfonic acid, 2-(methyl) acrylamide-2-methyl propane sulfonic acid.Typical nonionic monomers is: (methyl) acrylamide, N, N-dimethyl propylene acid amides, 2-hydroxyethyl (methyl) vinylformic acid, N-methylol (methyl) acrylamide.Wherein preferably vinylformic acid, acrylic acid an alkali metal salt, acrylic acid ammonium salt, acrylamide.These water-soluble vinyl unsaturated monomers can be used alone, but also also mix together, during any mixing more than two kinds: be any proportioning between the concrete monomer of each of ionic comonomer 1,, 2, be any proportioning between each concrete monomer of nonionic monomers; When 3, ionic comonomer and nonionic monomers are mixed, ionic comonomer: nonionic monomers=99: 1 or 1: 99 (mol ratio).
The weight concentration of water-soluble vinyl unsaturated monomer in aqueous solution is 10% to saturation concentration, preferred 20～50% (weight).Vinylformic acid can be partly or wholly to use with basic metal or ammonium compound neutral form.Degree of neutralization is 20～100% (moles).
If when water-soluble vinyl unsaturated monomer methacrylic acid or acrylamide and derivative thereof, its degree of neutralization is 20～100% (moles).
3. water-soluble radical polymerization initiator
Being fit to this type of polymeric water-soluble radical polymerization initiator is persulphate, as: Potassium Persulphate, Sodium Persulfate, ammonium persulphate, these water soluble starters can mix use, mix when using, and are any proportioning.Persulphate also can fit in redox system with reducing substances such as ferrous ion, sodium bisulfite, S-WAT etc. and use; Each proportioning components is determined by the quantitative relation of chemical equation when being used.
Water-soluble radical polymerization initiator is 0.001～10% (weight) with respect to the consumption of water-soluble vinyl unsaturated monomer, preferred 0.01～5% (weight).
4. linking agent
The linking agent per molecule that uses among the present invention contains two polymerisable unsaturated groups at least.Typical linking agent has: two of many alcohol-or three-(methyl) acrylate, said many alcohol are ethylene glycol, propylene glycol, glycerol polyoxyethylene glycol, polyoxy propylene glycol, polyglycerol for example; Typical linking agent also has: how pure unsaturated acid or acid anhydrides (for example toxilic acid, fumaric acid, maleic anhydride), the unsaturated polyester that fumaric acid or maleic anhydride and many alcohol reactions obtain; Bisacrylamide (as N, N '-methylene-bisacrylamide), two-or three-(methyl) acrylate that obtain by polyoxy compounds and methacrylic acid-respons; (methyl) acrylic-amino formyl fat that obtains by polymeric polyisocyanate (for example two isocyanic acid benzene methylene esters and two isocyanic acids inferior own ester) and hydroxyethyl (methyl) acrylate reactions; Polynary allylic cpd (for example allylation starch, allylation Mierocrystalline cellulose, O-phthalic allyl propionate etc.).In these linking agents, N preferably, N '-methylene-bisacrylamide, EGMa.
These linking agents make the high water absorbing and retaining agent form crosslinked or lightly crosslinked three-dimensional network to improve the gel-strength of high water absorbing and retaining agent at body in mutually.
With respect to the water-soluble vinyl unsaturated monomer, the consumption of linking agent is 0～10% (weight), preferred 0.01%～5% (weight).
5. hydrophobic solvent (being the hydrophobicity organic dispersion medium)
In the present invention, any satisfactory hydrophobic solvent can use, but the condition that must satisfy is water insoluble basically, and polymerization is inertia.Typical solvent is aliphatic hydrocarbon (for example Skellysolve A, normal hexane, normal heptane, octane, isomery paraffinic hydrocarbon, a gasoline etc.); Naphthenic hydrocarbon (as hexanaphthene, methylcyclohexane etc.); Arene (as toluene, dimethylbenzene, benzene etc.).From the viewpoint of quality and commercial operability, wherein preferred hexanaphthene.
The consumption of hydrophobic solvent generally is 1～5 times of water-soluble vinyl unsaturated monomer solution volume.Preferred 2～4 times.
6. tensio-active agent, polymkeric substance protective colloid (being antitack agent):
The dispersion agent major part that can adopt in suspension polymerization also can adopt in inverse suspension polymerization.Mainly be that HLB is 3～9 nonionogenic tenside often at this tensio-active agent that is suitable for.Typical nonionogenic tenside roughly has: sorbitol ester class (Span) (for example Span-60, Span-80 etc.); Polyoxyethylene (Tween) (as polyoxyethylene alkyl phenyl ether, Voranol EP 2001, polyoxyethylene fatty acid ester); Polyoxyethylene-polyoxypropylene block polymer; Phosphate monoester class (as hexadecyl phosphate monoester, octadecyl phosphate monoester); Fatty diglycollic amide, sucrose fatty ester, polyglycerol fatty acid ester; Polyvinyl alcohol, ethyl cellulose and derivative thereof.For improving dispersion effect, reduce caking phenomenon and take place.Two or more above-mentioned tensio-active agents can be used.In above-mentioned tensio-active agent, preferred Span-60, Span-80, its consumption is generally 0.1～20% (weight) of water-soluble vinyl unsaturated monomer, preferred 1～10% (weight).
In addition, be the gel particles that guarantees in reaction process, the to generate phenomenon that do not bond.Can add release agent, claim dispersing auxiliary again.It is nonionogenic tenside and the hydrocarbon-type oil or the grease etc. of (0.8～2.5) below 2.8 that antitack agent can adopt HLB.Nonionogenic tenside has Sorbitol Powder glycerol fatty acid ester, glycerose (aldehyde) oleic acid glyceride, glycerose stearate, propylene glycol Vinlub or their mixture.
Hydrocarbon-type oil and grease can use whiteruss, animals and plants wet goods.Polymeric surface active agent has ethyl cellulose, Natvosol etc.
Release agent can prevent organic solvent gel cementing, cohesion in dividing dried up process, and also is the antitack agent in the drying process.Preferred, ethyl in above-mentioned release agent, the addition of polymkeric substance protective colloid are 0.1～10% of water-soluble vinyl unsaturated monomer weight.
In the present invention, adopt following method to measure and calculate the liquid absorbency rate of inhaling distilled water, tap water and physiological saline:
Granular or the powder-like product that takes by weighing after 0.5～1.0g drying treatment places the 500-1000ml beaker, granular or powder-like product after adding 450～900ml distilled water or tap water or taking by weighing 0.5～1.0g drying treatment places the 150ml beaker to add 100ml 0.9%NaCl solution, after leaving standstill 24 hours, with 100 order mesh screens with unnecessary water elimination, weigh up gel quality affects, be calculated as follows water absorbent rate:
Liquid absorbency rate=(gel quality affects-xerogel quality)/xerogel quality.
The present invention adopts the anti-phase suspension technology that drips the water-soluble vinyl unsaturated monomer solution that contains mineral powder in hydrophobic solvent (oil phase), and preparation contains the composite materials with high water absorbing and retaining performances of layer silicate mineral.The present invention has that raw material sources are wide, cost is low, and organic dispersion medium is recyclable to be utilized again, and reaction process is controlled easily, the product cut size of gained is controlled, and (water-retaining capacity is strong, and rate of water absorption is fast for the product good combination property, water-retentivity and anti-salt property are good), the simple advantage of product aftertreatment.
The composite materials with high water absorbing and retaining performances of the layer silicate mineral that the present invention makes, material cost descends 20～50% than polyacrylic acid.The scope that experiment records the liquid absorbency rate of this serial high water absorbing and retaining agent is: the multiplying power of inhaling distilled water is 400～1600g/g, and the multiplying power of inhaling tap water is 250～650g/g, and the multiplying power of inhaling 0.9% physiological saline is 50～192g/g.Rate of water absorption is fast, and the water absorbent rate in 2～3min can reach more than 90% of its saturated water absorbent rate.
Embodiment
In order to understand the present invention better, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention not only is confined to the following examples.
Embodiment 1:
Hexanaphthene 230ml, Span-60 1.8g are added in the reactor, be warming up to 75 ℃, logical nitrogen flooding is removed oxygen wherein, opens to stir Span-60 is dissolved fully, forms oil phase.
Sodium hydroxide 13.4g is dissolved in the 40g deionized water, places for some time cooling or cooling fast in frozen water.Other takes by weighing 30g vinylformic acid, sodium hydroxide solution slowly is added drop-wise at ice-water bath and under stirring and makes it neutralization (being that degree of neutralization is 80%) in the vinylformic acid, making monomer is 25% in the weight concentration of aqueous phase, add malthacite powder (content 〉=40% after Potassium Persulphate 0.1g and the mechanical disintegration again, the 3g of particle diameter≤45um), carry out ultra-sonic dispersion with ultrasonic wave, after mixing, the mix monomer aqueous solution is slowly dripped in the above-mentioned oil phase,, treat that temperature reduces to room temperature at 75 ℃ of following polymerization 2h, add the methanol dehydration washing with alcohol, filter, polymerisate gets particulate state or Powdered finished product through mechanical disintegration or without mechanical disintegration slightly in 80 ℃ of vacuum-drying 3h.
Embodiment 2:
Hexanaphthene 300ml, Span-60 3g are added in the reactor, be warming up to 75 ℃, logical nitrogen flooding is removed oxygen wherein, opens to stir Span-60 is dissolved fully, forms oil phase.
In concentration is that 10% degree of neutralization is in 90% acrylic acid solution, 100 grams, stir and add N down, N '-methylene-bisacrylamide 0.007 gram, Potassium Persulphate 0.425 gram, dissolving, the diatomite that mechanical disintegration is crossed (content 〉=90% again, particle diameter≤45um) 50 grams add wherein ultra-sonic dispersion 20 minutes.Again the mix monomer aqueous solution slowly is added drop-wise in the above-mentioned oil phase, at 70 ℃ of following polymerization 2h, elevated temperature to 80 ℃ polymerization 1h again.Treat that temperature reduces to room temperature, add the methanol dehydration washing with alcohol, filtration, polymerisate gets particulate state or Powdered finished product through mechanical disintegration or without mechanical disintegration slightly in 120 ℃ of vacuum-drying 2h.
Embodiment 3:
Hexanaphthene 300ml, Span-60 4.5g are added in the reactor, be warming up to 75 ℃, logical nitrogen flooding is removed oxygen wherein, opens to stir Span-60 is dissolved fully, forms oil phase.
In concentration is that 10% degree of neutralization is in 90% acrylic acid solution, 100 grams, stir and add N down, N '-methylene-bisacrylamide 0.007 gram, Potassium Persulphate 0.425 gram, dissolving, diatomite that mechanical disintegration is crossed and malthacite mixed powder (weight ratio 1: 99 again, potash feldspar content 〉=30% wherein, the particle diameter of mixed mineral powder≤45um) 50 grams add wherein ultra-sonic dispersion 20 minutes.Again the mix monomer aqueous solution slowly is added drop-wise in the above-mentioned oil phase, at 70 ℃ of following polymerization 2h, elevated temperature to 80 ℃ polymerization 1h again.Treat that temperature reduces to room temperature, add the methanol dehydration washing with alcohol, filtration, polymerisate gets particulate state or Powdered finished product through mechanical disintegration or without mechanical disintegration slightly in 100 ℃ of vacuum-drying 4h.
Embodiment 4:
Hexanaphthene 300ml, Span-60 3g are added in the reactor, be warming up to 75 ℃, logical nitrogen flooding is removed oxygen wherein, opens to stir Span-60 is dissolved fully, forms oil phase.
In concentration is that 30% degree of neutralization is in 70% acrylic acid solution, 100 grams, stir and add N down, N '-methylene-bisacrylamide 0.007 gram, Potassium Persulphate 0.425 gram, dissolving, the quartz sand that mechanical disintegration is crossed (content 〉=90% again, particle diameter≤45um) 50 grams add wherein ultra-sonic dispersion 20 minutes.Again the mix monomer aqueous solution slowly is added drop-wise in the above-mentioned oil phase, at 70 ℃ of following polymerization 2h, elevated temperature to 80 ℃ polymerization 1h again.Treat that temperature reduces to room temperature, add the methanol dehydration washing with alcohol, filtration, polymerisate gets particulate state or Powdered finished product through mechanical disintegration or without mechanical disintegration slightly in 150 ℃ of vacuum-drying 1h.
Embodiment 5:
Adopt with embodiment 4 identical operations and step to prepare powdery or partical, just 1.8g span-60 and 0.9gtween-40 are used as tensio-active agent.
Embodiment 6:
Adopt with embodiment 4 identical operations and step to prepare powdery or partical, just 1.8g span-60 is used as tensio-active agent, the 2g ethyl cellulose is made release agent.
Embodiment 7:
Adopt with embodiment 4 identical operations and step to prepare powdery or partical, just 1.8g hexadecyl phosphate monoester is used as tensio-active agent.
Embodiment 8:
Adopt with embodiment 4 identical operations and step to prepare powdery or partical, just the 1.2g polyvinyl alcohol is used as tensio-active agent, the 0.03g sodium laurylsulfonate is as dispersing auxiliary.
Embodiment 9:
Toluene 300ml, Span-60 0.7g are added in the reactor, be warming up to 75 ℃, logical nitrogen flooding is removed oxygen wherein, opens to stir Span-60 is dissolved fully, forms oil phase.
In concentration is that 50% degree of neutralization is in 60% acrylic acid solution, 100 grams, stir and add acrylamide 20 grams down, N, N '-methylene-bisacrylamide 0.007 gram, ammonium persulphate 0.425 gram, dissolving, (content 〉=90%, particle diameter≤45um) 96 grams add wherein ultra-sonic dispersion 20 minutes with the malthacite of superfine grinding again.Under maintenance constant speed condition of stirring, the mix monomer aqueous solution slowly is added drop-wise in the container that above-mentioned oil phase is housed, in 70 ℃ of following polymerization 5h.Treat that temperature reduces to room temperature, add the methanol dehydration precipitation, use washing with alcohol, filtration, polymerisate gets particulate state or Powdered finished product through mechanical disintegration or without mechanical disintegration slightly in 80 ℃ of vacuum-drying 3h.
Embodiment 10:
Hexanaphthene 500ml, Span-60 3.6g are added in the reactor, be warming up to 75 ℃, logical nitrogen flooding is removed oxygen wherein, stirs Span-60 is dissolved fully, forms oil phase.
With concentration is that 30% degree of neutralization is in 40% acrylic acid solution, 280 grams, stir and add acrylamide 40 grams down, N, N '-methylene-bisacrylamide 0.05 gram, ammonium persulphate 0.225 gram, sodium bisulfite 0.200 gram, dissolving, malthacite (content 〉=60% that will cross through the pickling purification processes again, particle diameter≤45um) 50 grams add wherein ultra-sonic dispersion 20 minutes.Under maintenance constant speed condition of stirring, the mix monomer aqueous solution slowly is added drop-wise in the container that above-mentioned oil phase is housed, in 40 ℃ of following polymerization 4h.Treat that temperature reduces to room temperature, add methanol dehydration and use washing with alcohol, filtration, the gel of generation is in 140 ℃ of dryings 2 hours, then slightly through mechanical disintegration particulate state or powdery product.
Embodiment 11:
Hexanaphthene 600ml, Span-60 5.4g are added in the reactor, be warming up to 75 ℃, logical nitrogen flooding is removed oxygen wherein, stirs Span-60 is dissolved fully, forms oil phase.
In concentration is in 15% acrylamide soln, 300 grams, stir and add N down, N '-methylene-bisacrylamide 0.050 gram, Sodium Persulfate 0.115 and ammonium persulphate 0.110 gram, dissolving, diatomite (content 〉=60% that to cross through the magnetic separation purification processes again, particle diameter≤45um) 10 grams add wherein ultra-sonic dispersion 10 minutes.Under maintenance constant speed condition of stirring, the mix monomer aqueous solution slowly is added drop-wise in the container that above-mentioned oil phase is housed, in 75 ℃ of following polyase 13 h.Treat that temperature reduces to room temperature, add methanol dehydration and use washing with alcohol, filtration, the gel of generation gets particulate state or Powdered finished product through mechanical disintegration or without mechanical disintegration slightly in following 50 ℃ of dryings of vacuum condition 5 hours.
Embodiment 12:
Hexanaphthene 400ml, Span-60 1.8g are added in the reactor, be warming up to 75 ℃, logical nitrogen flooding is removed oxygen wherein, stirs Span-60 is dissolved fully, forms oil phase.
In concentration is that 25% degree of neutralization is to add acrylamide 20 grams in 90% acrylic acid solution, 200 grams, dissolving, stir and add N down, N '-methylene-bisacrylamide 0.031 gram, Sodium Persulfate 0.115 and ammonium persulphate 0.110 gram, dissolving, (content 〉=60%, particle diameter≤45um) 10 grams add wherein ultra-sonic dispersion 10 minutes to the diatomite that will cross through calcination process again.Under maintenance constant speed condition of stirring, the mix monomer aqueous solution slowly is added drop-wise in the container that above-mentioned oil phase is housed, in 75 ℃ of following polyase 13 h.Treat that temperature reduces to room temperature, add methanol dehydration and use washing with alcohol, filter that the gel of generation is in 150 ℃ of dryings 1 hour, slightly through mechanical disintegration or directly must particulate state or Powdered finished product without mechanical disintegration.
Embodiment 13:
Hexanaphthene 500ml, Span-60 2g are added in the reactor, be warming up to 75 ℃, logical nitrogen flooding is removed oxygen wherein, stirs Span-60 is dissolved fully, forms oil phase.
In concentration is that 5% degree of neutralization is to add acrylamide 40 grams in 90% acrylic acid solution, 200 grams, dissolving, stir and add N down, N '-methylene-bisacrylamide 0.027, Sodium Persulfate 0.115 and ammonium persulphate 0.110 gram, dissolving, again with the malthacite of high-temperature calcination (content 〉=60%, particle diameter≤45um) 40 grams add wherein, high-speed stirring was disperseed 30 minutes.Under maintenance constant speed condition of stirring, the mix monomer aqueous solution slowly is added drop-wise in the container that above-mentioned oil phase is housed, in 70 ℃ of following polymerization 6h.Treat that temperature reduces to room temperature, add methanol dehydration and use washing with alcohol, filter that the gel of generation is in 105 ℃ of dryings 4 hours, slightly through mechanical disintegration or directly must particulate state or Powdered finished product without mechanical disintegration.
Embodiment 14:
Hexanaphthene 480ml, Span-60 1.8g are added in the reactor, be warming up to 75 ℃, logical nitrogen flooding is removed oxygen wherein, stirs Span-60 is dissolved fully, forms oil phase.
In concentration is that 40% degree of neutralization is to add acrylamide 40 grams in 90% methacrylic acid solution, 200 grams, dissolving, stir and add N down, N '-methylene-bisacrylamide 0.024 gram, Sodium Persulfate 0.115 and ammonium persulphate 0.110 gram, dissolving, (content 〉=90%, particle diameter≤45um) 10 grams add wherein the diatomite that mechanical disintegration is crossed, the colloidal mill dispersion again.Under maintenance constant speed condition of stirring, the mix monomer aqueous solution slowly is added drop-wise in the container that above-mentioned oil phase is housed, in 75 ℃ of following polyase 13 h.Treat that temperature reduces to room temperature, add methanol dehydration and use washing with alcohol, filter that the gel of generation is in 140 ℃ of dryings 1 hour, slightly through mechanical disintegration or directly must particulate state or Powdered finished product without mechanical disintegration.
Embodiment 15:
Hexanaphthene 960ml, Span-60 1.8g are added in the reactor, be warming up to 75 ℃, logical nitrogen flooding is removed oxygen wherein, stirs Span-60 is dissolved fully, forms oil phase.
In concentration is that 40% degree of neutralization is to add acrylamide 40 grams in 90% methacrylic acid solution, 200 grams, dissolving, stir and add N down, N '-methylene-bisacrylamide 0.030 gram, Sodium Persulfate 0.110 and ammonium persulphate 0.115 gram, dissolving, (content 〉=60%, particle diameter≤45um) 2.4 grams add wherein the quartz sand that mechanical disintegration is crossed, high-speed stirring dispersion 10 minutes again.Under maintenance constant speed condition of stirring, the mix monomer aqueous solution slowly is added drop-wise in the container that above-mentioned oil phase is housed, in 75 ℃ of following polymerization 4h.Treat that temperature reduces to room temperature, add methanol dehydration and use washing with alcohol, filter that the gel of generation is in 140 ℃ of dryings 1 hour, slightly through mechanical disintegration or directly must particulate state or Powdered finished product without mechanical disintegration.
Embodiment 16:
Hexanaphthene 1000ml, Span-60 3.2g are added in the reactor, be warming up to 75 ℃, logical nitrogen flooding is removed oxygen wherein, stirs Span-60 is dissolved fully, forms oil phase.
In concentration is that 10% degree of neutralization is to add acrylamide 40 grams in 90% acrylic acid solution, 400 grams, dissolving, stir and add N down, N '-methylene-bisacrylamide 0.028 gram, Sodium Persulfate 0.120 and ammonium persulphate 0.114 gram, dissolving, (content 〉=60%, particle diameter≤45um) 240 grams add wherein the diatomite that mechanical disintegration is crossed, the colloidal mill dispersion again.Under maintenance constant speed condition of stirring, the mix monomer aqueous solution slowly is added drop-wise in the container that above-mentioned oil phase is housed, in 75 ℃ of following polyase 13 h.Treat that temperature reduces to room temperature, add methanol dehydration and use washing with alcohol, filter that the gel of generation is in 140 ℃ of dryings 1 hour, slightly through mechanical disintegration or directly must particulate state or Powdered finished product without mechanical disintegration.
Claims (9)
1. the preparation method who contains the composite materials with high water absorbing and retaining performances of amorphous silicate mineral is characterized in that it comprises the steps: 1) the amorphous silicate mineral deep processing handles: with amorphous silicate mineral original soil mechanical disintegration or superfine grinding to median size≤45um; Amorphous silicate mineral is any one or any mixing more than two kinds in malthacite, diatomite, the quartz sand; When a kind of, the purity of amorphous silicate mineral 〉=40% during any mixing more than two kinds, is any proportioning, the purity of amorphous silicate mineral 〉=30%; 2) dispersion treatment: will join the weight concentration that is dissolved with water-soluble radical polymerization initiator and linking agent through the amorphous silicate mineral powder that deep processing was handled and be in 10～50% the water-soluble vinyl unsaturated monomer solution and carry out dispersion treatment, the addition of amorphous silicate mineral is 2～200% of a water-soluble vinyl unsaturated monomer weight, the addition of water-soluble radical polymerization initiator is 0.001～10% of a water-soluble vinyl unsaturated monomer weight, and the addition of linking agent is 0～10% of a water-soluble vinyl unsaturated monomer weight; 3) polyreaction: through after the dispersing and mixing, the said mixture material is added drop-wise to lentamente and is dissolved with tensio-active agent or/and among the hydrophobicity organic dispersion medium of polymkeric substance protective colloid, carried out the water-in-oil-type inverse suspension polymerization 1～6 hour under 20～90 ℃ of conditions; The hydrophobicity organic dispersion medium is 1～5 times of water-soluble vinyl unsaturated monomer solution volume, the addition of tensio-active agent is 0.1～20% of a water-soluble vinyl unsaturated monomer weight, and the addition of polymkeric substance protective colloid is 0.1～10% of a water-soluble vinyl unsaturated monomer weight; 4) aftertreatment: after above-mentioned polyreaction finishes, treat that temperature reduces to room temperature, add dehydration of organic solvent or carry out the component distillation dehydration, use washing with alcohol, filter, polymerisate must product in 40～110 ℃ of vacuum-dryings.
2. the preparation method who contains the composite materials with high water absorbing and retaining performances of amorphous silicate mineral according to claim 1, it is characterized in that: also must be through overpickling for the amorphous silicate mineral original soil that contains the poly-property material of resistance, magnetic separation, calcining or roasting purification processes.
3. the preparation method who contains the composite materials with high water absorbing and retaining performances of amorphous silicate mineral according to claim 1, it is characterized in that: dispersion treatment is: the employing homogenizer carries out dispersed with stirring or disperses with colloidal mill, or adopts ultrasonic wave to carry out ultra-sonic dispersion; When adopting ultrasonic dispersion, the power of ultrasonic generator is 20～4000W, and frequency of ultrasonic is 10 kilo hertzs～300 megahertzes.
4. the preparation method who contains the composite materials with high water absorbing and retaining performances of amorphous silicate mineral according to claim 1 is characterized in that: organic solvent is methyl alcohol or acetone.
5. the preparation method who contains the composite materials with high water absorbing and retaining performances of amorphous silicate mineral according to claim 1 is characterized in that: the addition of amorphous silicate mineral is 2～120% of a water-soluble vinyl unsaturated monomer weight.
6. the preparation method who contains the composite materials with high water absorbing and retaining performances of amorphous silicate mineral according to claim 1 is characterized in that: the addition of water-soluble radical polymerization initiator is 0.01～5% of a water-soluble vinyl unsaturated monomer weight.
7. the preparation method who contains the composite materials with high water absorbing and retaining performances of amorphous silicate mineral according to claim 1 is characterized in that: the addition of linking agent is 0.01%～5% of a water-soluble vinyl unsaturated monomer weight.
8. the preparation method who contains the composite materials with high water absorbing and retaining performances of amorphous silicate mineral according to claim 1 is characterized in that: the hydrophobicity organic dispersion medium is 2～4 times of water-soluble vinyl unsaturated monomer solution volume.
9. the preparation method who contains the composite materials with high water absorbing and retaining performances of amorphous silicate mineral according to claim 1 is characterized in that: the addition of tensio-active agent is 1～10% of a water-soluble vinyl unsaturated monomer weight.
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| CN107057185A (en) * | 2017-03-09 | 2017-08-18 | 常州塑金高分子科技有限公司 | A kind of automobile-used low VOC regenerating polypropylenes composite and preparation method thereof |
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