CN87103106A - Water dispersion and preparation method thereof - Google Patents
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- CN87103106A CN87103106A CN87103106.XA CN87103106A CN87103106A CN 87103106 A CN87103106 A CN 87103106A CN 87103106 A CN87103106 A CN 87103106A CN 87103106 A CN87103106 A CN 87103106A
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Abstract
The present invention has disclosed a kind of water dispersion and preparation method thereof.This water dispersion comprises (i) hydrophobic thermoplastic polymer; (ii) contain concentration and be 0.1-5 milligramequivalent/grams (in-COO-) the water-insoluble thermoplastic polymer of carboxylate groups; (iii) water; (essential words) (iv) are at least following a kind of material: negatively charged ion or nonionic surface active agent, organic solvent and oil.It is solid-state that said water dispersion is from the surface, and water-content is 0.5-3% (weight percentage), and resistance is less than 10
6Ω cm, and after water was added in this dispersion, solid was dispersed in aqueous phase with fine-grained form immediately equably.
Description
The present invention relates to water dispersion of resin and preparation method thereof.Especially, the present invention relates to a kind of resin and be evenly dispersed in this class water dispersion (though this dispersion is solid-state shape composition from the surface, water content is very low) of aqueous phase with fine-grained form, and preparation method thereof.
Various aqueous polymer dispersion was known already.For example, water content is higher than 30% flowable water dispersion (but hereinafter referred to as mobile moisture prose style free from parallelism) coated on molded plastic product, woodwork and metal products, and carries out drying, to form resin molding, make matrix can be water-fast, the invasion and attack of oil and chemicals, or as heat-seal adhesive.But owing to adopt water as the water dispersion medium in these mobile moisture prose style free from parallelisms, thereby cause in minimizing and to catch fire or the tendency of environmental pollution and be convenient to operating aspect etc. and all be better than the solvent-borne type dispersion that they are widely used in the various fields for this reason.
In addition, do not have mobile, be solid-state water dispersion (hereinafter referred to as the solid water dispersion) by the look of it but also known by people as an above-mentioned mobile moisture prose style free from parallelism.That is these solid water dispersions are Powdered, are referred to as powder emulsion, if water is added in these solid water dispersions, then they will be dispersed in the water, and form flowable water dispersion.These solid water dispersions are moisture hardly, if contain water, then water content is at most the 2-3%(weight percentage).Therefore, even the danger of also not freezing at low temperatures, its superior part is that also packing or transportation are simplified, and can dwindle storage space.In addition, solid water disperse physical efficiency directly with avoid powder or the particle that water contacts, directly mix (though but this being blended in the mobile moisture prose style free from parallelism is very difficult) as cement, mortar and gypsum, therefore can prepare composite prod with height processing treatment degree.
The solid water dispersion can be by the preparation of following method: promptly once form the water dispersion of high-moisture according to currently known methods, with atomizer water dispersion is sprayed in the stove in the warm air then, to steam moisture, obtain powder.
The inventor has recommended a kind of water dispersion that comprises following component in Japanese patent application No. 153039/84, that is:
(ⅰ) hydrophobic thermoplastic resin;
(ⅱ) water-insoluble and water-insoluble thermoplastic polymer, it contains the carboxylate groups that is connected on the polymer chain, its concentration be every gram polymkeric substance contain the 0.1-5 milligramequivalent (with
The form meter) and
(ⅲ) water, this water dispersion are solid-state by the look of it, and water content is the 3-25%(weight percentage) and have such specific character, promptly after water added, solid was evenly dispersed in aqueous phase thereupon.This kind solid water dispersion prepares by said components or its precursor are melted to knead in extrusion machine.
Owing in the drying means of preparation solid water dispersion, can cause the polymer beads caking in the spraying stage, perhaps formed powder emulsion was assembled under heat or pressure effect, and formed macrobead in the past.Make it to carry out redispersion in this powder emulsion as if water is added to, often can not reach good dispersion state, or degenerate because of viscosity increases the coating physical properties that makes shaping.The additive of release agent or protection colloid and so on need be added in preceding water dispersion of spraying or the dry preceding powder for this reason.Yet, if additive capacity is big inadequately, can not reach significant effect, but if a large amount of additive that adds can cause again then the coating physical properties to be degenerated.And because contained large quantity of moisture need evaporate, power loss also increases thereupon, and therefore from the economic point of view, this method is not favourable.For this reason, people expect to develop a kind of processing method that is used to prepare the solid water dispersion such as powder formulation, and this method energy waste is low, and needn't use additive.
The back method advantage that the inventor recommended is that the solid water dispersion can directly prepare with more a spot of water, needn't carry out the operation of drying and so on, but this method still has weak point, and its reason is that the particle diameter of dispersive resin groups branch is bigger, is about micrometer level.
Therefore the people in this technical field wish to develop a kind of like this solid water dispersion urgently, and its water content is low as much as possible, and after adding water, resin particle is the even aqueous phase that is dispersed in finely as far as possible all.And also serious hope works out a kind of preparation method of novelty, and above-mentioned solid water dispersion can directly be prepared, and need not the processing of concentrated and drying and so on.
The inventor finds, as (ⅰ) hydrophobic thermoplastic polymer, (ⅱ) contain the not thermoplastic polymer of swelling property of the water-insoluble of the carboxylic acid that is connected on the polymer chain or carboxylate groups and water, (ⅲ) water, when kneading according to the method fusing one that the aforementioned inventor recommended, if in advance polymkeric substance (ⅰ) and polymkeric substance (ⅱ) are melted-knead, then water (or together with alkaline matter) is added to the screw rod that is full of melt in the extrusion machine basically and the space between the cylindrical shell, continue to make mixture melt one to knead, thus in the water dispersion of gained, water exists as external phase, and polymkeric substance is the discrete particles phase, the low 3%(weight percentage that reaches of water content) or littler.The inventor has now finished the present invention on the basis of this discovery.
More precisely, according to a basic sides of the present invention, provide a kind of water dispersion that comprises following ingredients: (ⅰ) hydrophobic thermoplastic polymer, (ⅱ) contain be connected on the polymer chain (concentration be every gram polymkeric substance contain 0.1-5 millinormal-COO-) the water-insoluble thermoplastic polymer of carboxylate groups, (ⅲ) water, be selected from by aniorfic surfactant and also can comprise (ⅳ) in case of necessity, nonionic surface active agent, at least one member in this group that organic solvent and oil are formed, said water dispersion begin it seems resemble solid-state, water content is the 0.5-3%(weight percent), resistance is lower than 10
6Ohm-cm, and it also has a kind of like this character, and promptly after water added in the dispersion, solid will be dispersed in aqueous phase with fine-grannular equably.
According to another basic sides of the present invention, provide a kind of preparation method of water dispersion, this method comprises following component:
(ⅰ) hydrophobic thermoplastic polymer;
(ⅱ) water-insoluble thermoplastic polymer, it contains carboxylic acid or the carboxylate groups that is connected on its polymer chain, concentration is that every gram polymkeric substance contains 0.1-5 milligramequivalent (in the form of-COO-), or contains the carboxylic acid derivatives group that can produce the said group under the said concentration by alkaline purification; (if necessary words)
(ⅲ) be selected from, can change at least one member in the organic compound, nonionic surface active agent, organic solvent of aniorfic surfactant and this group that oil is formed by alkaline purification by aniorfic surfactant, formed mixed melting thing with
(ⅳ) water and
(ⅴ) alkaline matter when having the thermoplastic polymer (ⅱ) need carry out alkaline purification or organic compound (if),
In extrusion machine, mix, and apply counterpressure to melt constantly, then melt-knead said mixture, causing inversion of phases, thereby form a kind of water dispersion of polymer solids.
Brief Description Of Drawings:
Fig. 1 is the side-view of kneading unit that is used to realize the present invention's method, has shown the decoration form of this device.
With reference to digital 1 expression extrusion machine, the digital 2 expression cylindrical shells of reference are represented screw rod respectively with reference to digital 3a and 3b among the figure, and with reference to number 4 expression funnels, with reference to digital 5 expression inlets, refrigerating unit is then represented with reference to digital 7 in the digital 6 expression feed water inlets of reference.
The present invention system is based on this discovery, namely melt when kneading when hydrophobic polymer (ⅰ) and the polymer (ⅱ) that contains carboxyl, add water (or together with alkaline matter) to the melt that is full of substantially space between extruder inner screw and the cylindrical shell, and proceed to melt and knead, even water content is extremely low, reach 0.5-3%(by the mixture total weight amount) also be like this, inversion of phases takes place thus, and obtain a kind of with water as continuous phase, polymer is as the aqueous dispersion of discrete particles phase.
According to above-mentioned conventional method, for form a kind of with water as continuous phase, and resin is as the aqueous dispersion of discrete particles phase, then water content should be the 3%(percetage by weight at least), be generally 5%(by weight) or higher, if water content is lower than this value, then can not form aqueous dispersion. Its reason is, in conventional method, because the fusing one twin shaft screw extruder of kneading and being Carry out under the state that outlet is opened wide, thereby molten resin is not applied any pressure, and melt the resin of kneading and in the situation that really is not full of space between screw rod and the cylindrical shell, be extruded.
And among the present invention, water is to add under the screw rod of extruder and the space between the cylindrical shell are full of the situation of molten resin composition basically, and proceed to melt the operation of kneading, shearing force between screw rod and cylindrical shell and the power of kneading are able to directly and effectively be applied in water-melt system thus, water is dispersed in earlier in the melt as a result, and inversion of phases takes place then effectively. In composition of the present invention, the carboxylate groups of thermoplastic polymer (ⅱ) demonstrates the strong affinity to water (ⅲ), and the polymer chain of thermoplastic polymer (ⅱ) demonstrates the affinity to hydrophobic thermoplastic polymer (ⅰ). Therefore, if said composition is kneaded under condition is kneaded in fusing one of the present invention, then water is absorbed by the hydroxy-acid group of thermoplastic polymer, and be dispersed in the resin, and by the capillary effect of molten resin, carboxylate groups in the resin is in resin outer surface orientation, and in the particle that forms thus, water is attached on these directed carboxylate groups with unimolecule rete or similar thin layer form.
According to the present invention, resin solid becomes the solid water dispersion and takes place under aforesaid way by inversion of phases. If need to take out the solid water dispersion, then must be lower than in temperature the boiling point of water, generally under 70-90 ℃ condition, carry out. In view of the temperature of the mixture that melts-knead is much higher than the boiling point of water, if formed solid water dispersion directly is extruded, then water is overflowed flash distillation, thereby the solid water dispersion that can not obtain expecting. If cooler is arranged in the top of extruder, extrude after making aqueous dispersion be cooled to below the boiling point of water by this cooler, then can prevent the flash distillation of sealing, even in the low situation of water content, also can stably obtain the solid water dispersion. And if aqueous dispersion is cooled off on the extruder top, then the flowability of melt reduces, and pressure (for instance) can be elevated to the 5-20 kilograms per centimeter2(gauge pressure), molten resin have been full of the space between cylindrical shell and the screw rod basically. According to the present invention, make aqueous dispersion in the cooling of extruder top, can reach simultaneously by this effect of anti-sealing flash distillation and basically make melt be filled in the effect in space between screw rod and the cylindrical shell.
In composition of the present invention, contain the thermoplastic polymer (ⅱ) of carboxylate to causing The hydrophobic thermoplastic polymer inversion of phases becomes the oil-in-water type discrete particles to play Main Function, if select as required by anionic surfactant, nonionic surface active agent, at least one member (ⅳ) in formed this group of organic solvent and oil, then can further promote this inversion of phases process, by the water content in the fusion mixture of each component and water being adjusted to the level that is lower than conventional method, that is 0.5-3%(percetage by weight), and melt under these conditions-knead, can make the dispersion particle diameter of resin solid thinner, also can be less than 0.5 micron.
In addition, in the present invention, disperse particle diameter to be defined as the particle diameter of the resin solid that forms, when water being added in the solid water dispersion, there is no any special shearing or suchlike variation.
In solid water dispersion of the present invention, water exists with the form of continuous phase, resin solid then occurs as particulate decentralized photo independently, even water content is low to moderate the 3%(percentage by weight) or lower also be that so this point is confirmed by following truth: namely resistance is lower than 105Ω-cm generally is lower than 105Ω-cm, and when Jiang Shui added in this class solid water dispersion, solid then was evenly dispersed in aqueous phase.
Below will describe the present invention.
Component
The thermoplastic polymer (ⅰ) that constitutes one of the component of solid water dispersion of the present invention is a not swelling property resin of water-insoluble and water, it does not have water dispersible, do not contain carboxyl in fact, for example, the disconnected multipolymer of random and embedding of polyolefine such as new LDPE (film grade), high density polyethylene(HDPE), polypropylene, polybutene-1, poly-(4-methyl-1-pentene) and the alpha-olefins such as ethene, propylene, butene-1 and 4-methyl-1-pentene; The multipolymer of the ethylene/vinyl based compound such as ethylene, ethylene/vinyl alcohol copolymer and ethene/vinyl chloride copolymer; Styrene type resin such as polystyrene, vinyl cyanide/styrol copolymer, alkylbenzene sulfonate and Alpha-Methyl-vinylbenzene/styrol copolymer; Such as polyvinyl chloride, polyvinylidene dichloride, vinylchlorid/1, the polyvinyl compound of the inferior ethylene copolymer of 1-dichloro, polymethylmethacrylate and polymethyl acrylate and so on; Polymeric amide such as nylon 6 nylon 6-6, nylon 6-10, Ni Long11 and nylon 12; Thermoplastic polyester such as poly terephthalic acid vinyl acetate and poly terephthalic acid butene esters; And polycarbonate and polyphenylene oxide.Can use the mixture that this base polymer is formed more than two or two.
In these thermoplastic polymers, preferably adopt the chain type olefinic resin, that is the homopolymer and the multipolymer of the α alkene such as ethene, propylene, butene-1,3-methyl-1-butene, 4-methyl-1-pentene, 3-Methyl-1-pentene, 1=heptene, 1=hexene, 1=decene and 1=dodecylene, and can polyethylene, polypropylene, poly-1-butylene, poly--3-methyl-1-butene, poly--4-methyl-1-pentene, poly--the 3-Methyl-1-pentene, ethylene/propene copolymer, ethene/butene-1 copolymer and propylene/1-butene multipolymer be representative; Alpha-olefins copolymers with conjugation or non-conjugated diene, can ethene/butadienecopolymer and ethene/ethylene norbornene copolymer be representative; And at least two multipolymers with alpha-olefins of conjugation or non-conjugated diene, can ethylene/propene/butadiene trimer, ethylene/propene/Dicyclopentadiene (DCPD) trimer, ethylene/propylene/ethylidene norbornene trimer and ethylene/propene/1,5-hexadiene trimer is representative.Be good with the homopolymer or the multipolymer of alpha-olefins especially wherein.
The melt flow of thermoplastic polymer (according to ASTM D-1238) was at least 1 gram/10 minutes, preferably was at least 5 grams/10 minutes.If melt flow (MFR) is lower than 1 gram/10 minutes, then the viscosity of melt is difficult to melt and kneads too high, thereby is difficult to obtain preferable water dispersion.
According to a preferred embodiment of the present invention, be to adopt ethylene/propene copolymer elastomerics or ethylene/propylene/diene trimer elastomerics.
Among another embodiment according to the present invention described below, utilize aniorfic surfactant and/or nonionic surface active agent and organic solvent to match, might obtain the resin solid water dispersion that the melting solid flow is substantially zero, that is average molecular wt (MW) is at least a kind of ultra-high molecular weight chain olefine resin of 500,000.
As the thermoplastic polymer (ⅱ) of another component of solid water dispersion of the present invention can by will have neutralization or not in and carboxylic acid group's monomer, or the monomer with saponification or unsaponified carboxylate group is introduced in the above-mentioned thermoplastic polymer (ⅰ), or adopt graft copolymerization, block copolymerization or these class means of random copolymerization and introduce in its constituent monomers, the necessary also available alkaline matter of words neutralizes or saponification, so that the carboxylate salt content that forms in polymkeric substance is that every gram polymkeric substance contains 0.1～5 milligramequivalent, especially with the 0.2-4 milligramequivalent be advisable (with
The form meter).The said polymer can partly be neutralized or saponification, has hydroxy-acid group or carboxylate group in interior.Thermoplastic polymer (ⅱ) should have the not character of swelling property of water-insoluble and water.If carboxylic acid group who is neutralized and/or saponification carboxylate group's content exceed outside the above-mentioned scope, then thermoplastic polymer (ⅱ) will can not be brought into play and promote the effect of thermoplastic polymer (ⅰ) dispersive, can not the good solid dispersion of preparation.If polymkeric substance (ⅱ) is water-soluble or water-swellable, then the physical properties of coating will be degenerated.
If thermoplastic polymer (ⅱ), the method by post neutralization or after saponification obtains, and then starting polymer is the multipolymer of the monomer polymerization identical with the compositing monomer of the thermoplastic polymer with alkene chain unsaturated carboxylic acid or its ester (ⅰ).And that unsaturated carboxylic acid can be vinylformic acid, methylacrylic acid, toxilic acid, fumaric acid, tetrahydrophthalic acid, methylene-succinic acid, citraconic acid, Ba Dousuan, iso-crotonic acid, Nadic acid is (interior-cis two rings (2,2,1)-heptan-5-alkene-2, the 3-dicarboxylic acid), maleic anhydride and citraconic anhydride.And undersaturated carboxylicesters can be the monoesters and the dibasic acid esters of methyl, ethyl and the propyl group of above-mentioned carboxylic acid.Certainly, can pass through the method for the monomer-grafted thermoplastic polymer (ⅱ) (as the chain olefine resin) of usefulness ethylene linkage unsaturated carboxylic acid or acid anhydride or its ester and so on for the thermoplastic polymer of post neutralization or back esterification, replace a large amount of monomer copolymerizations and obtain, this point is apparent for the people of this field ordinary skill level.
Desire is introduced ethylene linkage unsaturated carboxylic acid on the monomer or the amount of acid anhydride or its ester should be enough to provide above-mentioned carboxylate salt concentration, and its numerical value is to contain 0.1 milligramequivalent at least in every gram polymkeric substance, be preferably the 0.1-5 milligramequivalent (with
The form meter).
Be used for neutralizing or the saponified alkaline matter can be this class play the material of alkali at water, as basic metal; Alkaline-earth metal; Ammonia and amine; Alkali-metal oxide compound, oxyhydroxide, salt of weak acid and hydride; The oxide compound of alkaline-earth metal, oxyhydroxide, salt of weak acid and hydride; And the alkoxide of these metals.The object lesson of these materials is described below:
(1) basic metal can be sodium and potassium etc.; And alkaline-earth metal can be calcium, strontium and barium etc.
(2) amine can be inorganic amine of azanol, hydrazine and so on and the organic amine of methylamine, ethamine, thanomin and hexahydroaniline and so on.
(3) oxide compound of basic metal and alkaline-earth metal, oxyhydroxide and hydride can be sodium oxide, sodium peroxide, potassium oxide, Potassium peroxide, calcium oxide, strontium oxide, barium oxide, hydrated barta, potassium hydroxide, calcium hydroxide, strontium hydroxide, hydrated barta, sodium hydride, potassium hydride KH and hydrolith.
(4) salt of weak acid of basic metal or alkaline-earth metal can be yellow soda ash, salt of wormwood, sodium bicarbonate, saleratus, Calcium hydrogen carbonate, sodium acetate, potassium acetate and lime acetate.
(5) compound of ammonia and amine can be the quaternary ammonium compound and the hydrazine hydrate of ammonium hydroxide, tetramethylphosphonihydroxide hydroxide amine and so on.
In alkaline matter neutralization or saponified carboxylic acid group or carboxylate group, be good with carboxy acid alkali's metal-salt of carboxylic acid sodium, carboxylic acid potassium and carboxylic acid ammonium and so on, wherein especially with carboxylic acid potassium for better.
Preferably use and have the polymkeric substance of good affinity as thermoplastic polymer (ⅱ) with thermoplastic polymer (ⅰ).That is when attempting to obtain a kind of solid water dispersion of alkene type resin, should select for use and contain the ethylene linkage polymer of monomers in the main chain as polymkeric substance (ⅱ).For example, when polyolefine that uses polyethylene and so on or ethylene/vinyl acetate copolymer, preferably adopt this base polymer, perhaps neutralization or saponified ethene/(methyl)-acrylic copolymer or ethene/(toxilic acid graft product of methylmethacrylate copolymer.For a parameter selecting suitable thermoplastic polymer is solubility parameter (SP value).In other words, the neutralization or saponification before starting polymer and the poor solubility between the thermoplastic polymer (ⅰ) should the 2(card/centimetre
3)
1/2In, especially with the 1(card/centimetre
3)
1/2For good.
Herein, solubility parameter is defined as having common meaning, that is is the square root of internal cohesive energy.This solubility parameter system is according to D.W.Van Klevelen; The following formula that polymer property (Elsevier, 1972) is disclosed, utilize former under an influence molecular volume Vi value and the internal cohesive energy En of atomic group calculate:
SP=((∑ Eni)/(∑ Vi)) (card/centimetre
3)
1/2
If (ⅳ-a) is as optional component with aniorfic surfactant, then can use and alkali substance reaction and any anion surfactant of forming, as generation higher fatty acid salt, two generation higher fatty acid salt, the high grade primary alcohol sulfuric acid, senior secondary alcohol sulfuric acid, the higher primary alkylsulfonate, senior secondary alkyl sulfonate, the senior alkyl stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate, the sulfonation higher fatty acid salt, the higher fatty acid sulfuric acid, higher fatty acid sulphonate salt, higher alcohol sulfate salt, the higher alcohols ether sulfonate, the alkanol sulfuric acid of higher fatty acid amides, alkylbenzene-sulfonate, alkylphenol vitriol, alkylnaphthalene-sulfonate and alkyl benzimidazole sulfonate.The particular compound title of these tensio-active agents is disclosed in " synthetic surfactant " documents such as (Sanky Shuppan, 1986) at Hiroshi Horiguchi.Wherein with an alkali metal salt of higher fatty acid, particularly better with saturated and undersaturated higher fatty acid, more particularly, the saturated fatty acid alkali metal salt of capric acid, undecanoic acid, lauric acid, tetradecanoic acid, palmitinic acid, margaric acid, stearic acid, eicosanoic acid (arachic acid) and so on; Such as linderic acid, tsuzuic acid, petroselinic acid, oleic acid, linolic acid (Linolic acid), linolic acid (Linoleic acid) and arachidonic acid, and their mixture.
If (ⅳ-b), then its hydrophile-lipophile balance value (HLB value) should be 10 at least, preferably is not less than 13 as optional component with nonionic surface active agent.Nonionic surface active agent can use separately, also the form of mixtures that contains two or more this class promoting agent can be used.Under one situation of back, if the HLB value of mixture then is enough to meet the demands in above-mentioned scope.For example can use Voranol EP 2001, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, polyoxyethylene fatty acid amide ether, polyhydric alcohol fatty acid ester, polyoxyethylene polyols fatty acid ester, fatty acid cane sugar ester, alcohol amide and polyoxyethylene block copolymer, the HLB value of these materials is all in above-mentioned scope.In above nonionogenic tenside, the increase of polyoxyethylene unit content often causes the HLB value to rise.Therefore, by the molar weight that the regulating ring oxidative ethane adds, the nonionogenic tenside that can obtain having required HLB value.
Any organic solvent that can dissolving (swelling) thermoplastic polymer (ⅰ) and thermoplastic polymer (ⅱ) all can (ⅳ-c) be used as organic solvent as optional components, for example, the aromatic hydrocarbon such as benzene,toluene,xylene, vinylbenzene, alpha-methyl styrene and Vinylstyrene; Aliphatic hydrocrbon such as hexane, heptane; And the halohydrocarbon such as trieline.Organic solvent can be contained in the final solid water dispersion, also can remove from final solid water dispersion by distillation or component distillation.For example, under the situation that organic solvent is removed by distillation, then this solvent boiling point should be lower than 100 ℃.
This kind organic solvent can swelling or is partly dissolved thermoplastic polymer (ⅰ), and its addition can be much lower than the consumption of usual vehicle method.
(during ⅳ-d), then can select following material for use: the mineral lubricating oils such as spindle oil and machine oil if natural or synthetic is oily as optional components; Mineral oil such as whiteruss, electric insulation oil and process oil; Synthetic oil such as alkylbenzene oil, diolefinic oil, dibasic acid esters oil and naphthenic acid alkyl ester oil; And the vegetables oil of Viscotrol C, Toenol 1140, dish (seed) oil, Oleum Cocois and Yatall MA and so on.For oil is stably remained in the resin solid, the molecular-weight average of oil must be not less than 200.
The composition of solid water dispersion and preparation
Above-mentioned thermoplastic polymer (ⅰ) and (ⅱ) between weight ratio be preferably 100: (1 to 60), wherein especially with 100: (2 to 50) are good.If the amount of thermoplastic polymer (ⅱ) very little, be lower than above-mentioned scope, then cause the dispersion of thermoplastic polymer (ⅰ) abundant inadequately, but if the amount of polymkeric substance (ⅱ) is too big, surpass above-mentioned scope, then the different in kind of the dispersion of Xing Chenging is in the character of the expection dispersion of thermoplastic polymer (ⅰ).
Except said components, solid water dispersion of the present invention also comprises water (ⅲ).The content of water is 0.5-3%, is preferably 1.0-2.5%(and is weight percentage).No doubt in solid water dispersion of the present invention, also can add some water yields.Even but must be noted that like this, in the presence of above-mentioned less water, be effective to the inversion of phases of solid water dispersion.
Solid water dispersion of the present invention comprises above-mentioned three kinds of requisite components.If need, can add at least one member who is selected from this group of being formed by aniorfic surfactant, nonionic surface active agent, by agent solvent and oil in the preparation.
With regard to per 100 parts of organic polymers (ⅰ), ((addition of ⅳ-b) is 0.1-40 part to aniorfic surfactant, especially with 0.2-20 part be advisable (above all by weight) for ⅳ-a) and/or nonionic surface active agent.(amount of ⅳ-c) is 10-1000 part, especially with 20-700 part be advisable (above all by weight) and with respect to the organic solvent of 100 parts of polymkeric substance (ⅰ).The oily 10-500 part that is equivalent to same umber polymkeric substance (ⅰ) is especially from 20-300 part be advisable (above all by weight).
If comprise the thermoplastic polymer (ⅱ) or the anion surfactant precursor that need carry out alkaline purification, then must add reaction necessary alkaline matter (ⅴ).
With reference to Fig. 1, this chart is understood the preferred means of the method be used to implement the present invention, and extrusion machine 1 comprises cylindrical shell 2, is installed in twin shaft screw rod 3a and 3b in this cylindrical shell 2.Be used to supply with thermoplastic polymer (ⅰ) and (ⅱ), also simultaneously the funnel 4 of supply schedule surface-active agent is disposed in an end of extrusion machine 1, and supplied water or alkaline substance solution, and the inlet of tensio-active agent (liquid) or oil is installed in the centre of extrusion machine 1.In addition, refrigerating unit 7 is the other end that is positioned at extrusion machine 1, that is on the mouth of extrusion machine.Refrigerating unit can be to be equipped with to supply with the static mixer of heat-eliminating medium circulation with chuck.
When preparation solid water dispersion of the present invention, at first add hydrophobic thermoplastic polymers (ⅰ) and contain the thermoplastic polymer (ⅱ) of carboxylic acid derivative group from funnel 4, also can add together together with anion surfactant, nonionogenic tenside (, then needing) from mouth 5 feed if tensio-active agent is a liquid.And these component fusings one are kneaded.Fusing one temperature of kneading is higher than the fusing point of the polymkeric substance with higher melt, but is preferably lower than melt viscosity less than 10
6Temperature during pool is especially to be lower than dissolved matter viscosity less than 10
5Temperature during pool is good.Using component (ⅳ-c) or (under the situation of ⅳ-d), fusing one temperature of kneading needn't be higher than the resin fusing point, if the viscosity of composition in above-mentioned scope, then is enough to meet the demands.
The aqueous solution of water or alkaline matter is added in the melt of hole between the cylindrical shell 2 that is filled in extrusion machine 1 and screw rod 3a and the 3b.Be applied to the counterpressure on the melt in the said hole by mensuration, can prove conclusively melt and whether the space is full of basically.Although counterpressure is along with the flow characteristics of resin melt or melt and knead temperature and change, if its numerical value is in the 0.5-300 kilograms per centimeter
2(be preferably 1.0～200 kilograms per centimeter in the scope of (gauge pressure)
2), then can conclude to be full of resin melt in the said hole basically.In addition, term " counterpressure " means by the water supply or the aqueous solution and is applied to pressure on the melt.
In addition, the space (water adds from here) between cylindrical shell 2 and screw rod 3a and the 3b is full of under the situation of melt, and by the extrusion machine power increase of unit resin extruded amount, specific energy is higher than 0.3 kilowatt-hour/kilogram.Herein specific energy be defined as in the given time power consumption with the motor of continuous kneading unit divided by the amount of resin of being pushed value.
For making resin melt be full of space between the cylindrical shell of water supply part and the screw rod basically, can adopt following method: be about to the cold device 7 that goes and be installed in the extrusion machine top, and sieve plate (screen pack) or similar parts are set connecting this top end, to produce above-mentioned resin pressure.In a word, can take any means, as long as the counterpressure of melt that acts on the water supply position is in above-mentioned scope.
After adding the aqueous solution of water or alkaline matter, mixture is melted knead, become water dispersion with phase inversion.Formed water dispersion is cooled to the boiling point that temperature is lower than water through water cooler, takes out with the form of stable, solid water dispersion then.By the way, only when taking out water dispersion from system, just must cool off by need; If it needn't take out, and be directly used in aftertreatment, chemical reaction or other similar processing, then needn't cool off.
Certainly, in resulting solid water dispersion, can add some water yields again.
Then, the water dispersion that makes thus is cooled to room temperature naturally or artificially.By cooling, discrete particles is hardened, and forms stable solid water dispersion.Under the situation of using solvent, can remove by the means of distillation and so in case of necessity and desolvate.
When preparing this kind solid water dispersion or being added with the dispersion of water, can use the auxiliary substance that is generally used for water dispersion, for example, dispersion agent (as anionic or nonionic surface active agent), emulsifying agent, stablizer, swelling agent, tackifier, pore forming material, defoamer, setting accelerator, jelling agent, antiaging agent, tenderizer, flexibility agent, weighting agent, tinting material, spices, release agent and releasing agent.
Water dispersion
Though water dispersion of the present invention is solid-state by the look of it, it has oil-in-water-type dispersion structure, and wherein water forms external phase, and resin formation particles dispersed phase.From the electron microscopic mirror image sheets of this solid water dispersion as can be seen, the secondary granule of the present invention's solid water dispersion comprises the tiny primary granule of distortion a little, and the latter assembles quite densely.By the various facts described below, prove that primary granule has oil-in-water discrete form.
A characteristic of the present invention's solid water dispersion is that resistance is lower than 10
6Ω-cm generally is lower than 10
5Ω-cm.Can infer this low resistance owing to the following fact causes, promptly the external phase of dispersion is made up of water, and discontinuous phase then is made of resin.As being made up of resin for external phase, or toner contains the weight percentage until 3%() dispersion of water, then resistance is that the characteristic value of resin is (generally 10
10The order of magnitude of Ω-cm).
By the way, related herein resistance system records according to following method: it is on 1 centimetre the relative inner edge of square container that the electrode that also is about to 1 cm long is attached to the length of side, dispersion is contained in this container then, and press tight simultaneously, then under 60 hertz, measure resistance between two electrodes with the alternating current resistance time meter.
Can determine by following method by adding the dispersion state that water forms; The solid water dispersion is poured in the cold water, and stirred this mixture, make the dispersion that is produced by being roughly 100 purpose nets thereafter, to filter, at last with the particle in the dispersion that microscopic examination produced with the general mixer that has the turbine type blade.
When by adding water the solid water dispersion being dispersed in the water, then it presents the form that is roughly spherical particle, and median size is less than 0.5 μ.Wherein particle diameter can be measured with micro-track instrument.
The water content of the present invention's solid water dispersion is extremely low, is solid-state by the look of it, if add water to it, then solid dispersion can easily change into flowable water dispersion.And the characteristics of the present invention's solid water dispersion are: needn't worry to freeze; Storage space dwindles; And transportation or packaged convenience.In addition, the present invention's solid water dispersion can directly be added to and avoid in the powder or particle that contacts with water, as cement, mortar or gypsum.Add that but a mobile moisture prose style free from parallelism that forms behind the water can be used on various materials forming that one deck is water-fast, the film of oil resistant and the invasion and attack of anti-chemicals, or can be used as the heated sealant material.According to the present invention's Another Application embodiment, very little shearing force is applied in the present invention's the solid water solution, or under temperature condition as mild as a dove dry solid water dispersion, then this solid water dispersion can be got very carefully, or water content can be minimized.In addition, the present invention's solid water dispersion can be used as the binding agent of new ceramics or as polymer modifiers.
Now describe the present invention, but this is limited scope of the present invention with reference to the following example.In addition, unless indicate separately, what occur among the embodiment owns " umbers " and " % " all by weight.
(the PCM-30 type that Ikegai Tekko produces adds the mixture that comprises following component: 100 parts of (density=0.915 gram per centimeter of the new LDPE (film grade) as thermoplastic polymer (ⅰ) in funnel L/D=20) from unidirectional rotation meshing-type two-axis screw extruder shown in Figure 1
3, MFR(melt flow)=70 Grams Per Minutes, SP value=7.80(card/centimetre
3)
1/2, (maleic anhydride content is 3.3% to 10 parts of maleic anhydride-grafted polyethylenes as thermoplastic polymer (ⅱ), and-COO-radical concentration is 0.67 milligramequivalent/gram (polymkeric substance), and density is 0.94 gram per centimeter
3, the SP value be the 8.06(card/centimetre
3)
1/2] and 2 parts of oleic acid, the latter is as can be by forming the material of aniorfic surfactant with alkali substance reaction, feeding rate be 112 parts/time, at extrusion machine intermediary inlet, with 3.5 parts/time flow supply with continuously 23% potassium hydroxide aqueous solution, and mixture pushes under 160 ℃ of Heating temperatures continuously.Resin compound after the extruding is through being installed in extruder outlet, and the static mixer that has a chuck is cooled to 90 ℃, and discharges from device.Products therefrom is a white solid.Counterpressure during aqueous solution feed is 0.6 kilograms per centimeter
2(gauge pressure), and the vertical pressure of extruder screw is 10.0 kilograms per centimeter
2(gauge pressure).From the specific energy of amount of compression and power consumption calculations gained is 0.32 kilowatt-hour/kilogram.It is in 1 centimetre the cubitainer that white solid is filled in the length of side, and measures its resistance, and institute's value is 8 * 10
3Ω-cm.By with solid dispersed in water, and use the microscopic examination deployment conditions, find that it disperses with spherical fine-grained form.Show that through the mensuration of micro-track instrument the particle median size is 0.45 μ to the discrete particles particle diameter.
From the funnel of the used identical unidirectional rotation meshing-type two-axis screw extruder of embodiment 1, add the mixture that comprises following component: 100 parts of ethylene/vinyl acetate resin copolymer resin (vinyl acetate content=19%, density=0.97 gram per centimeter as thermoplastic polymer (ⅰ)
3, MFR=150 gram/10 minutes, SP value=8.06(card/centimetre
3)
1/2; 10 parts as the maleic anhydride-grafted polyethylene of thermoplastic polymer (ⅱ) (with used identical of embodiment 1); With 3 parts of potassium oleates as aniorfic surfactant, feeding rate be 113 parts/time, at extrusion machine intermediary inlet, with 2.9 parts/time flow supply with 13% potassium hydroxide aqueous solution continuously, and mixture pushes under 140 ℃ of Heating temperatures continuously.The static mixer that have chuck of mixture after the extruding through being installed in extruder outlet is cooled to 90 ℃, and discharges from device.Products therefrom is a white solid.Counterpressure during aqueous solution feed is 5.0 kilograms per centimeter
2(gauge pressure), and the vertical pressure of extruder screw is 8.0 kilograms per centimeter
2(gauge pressure).From the specific energy of amount of compression and power consumption calculating gained is 0.31 kilowatt-hour/kilogram.The resistance value that records by example 1 described the same manner is 8 * 10
3Ω-cm.By with this solid dispersed in water, and use the microscopic examination deployment conditions, find that it disperses with spherical fine-grained form.Show that through the mensuration of micro-track instrument the particle median size is 0.48 μ to the discrete particles particle diameter.
Reference example 1
In barometric point type kneading machine, pack into and embodiment 1 used 100 parts of identical maleic anhydride one grafted polyethylenes, and make resin under 140 ℃ of temperature, melt-knead.Drip 40 parts of alkaline aqueous solutions that are dissolved with 3.76 parts of potassium hydroxide (counting 1.0 chemical equivalents with-COO-group) then gradually, after the water evaporates of waiting, resin continued to knead 30 minutes again, was cooled off then.
Embodiment 3
From the funnel of the used identical unidirectional rotation meshing-type two-axis screw extruder of embodiment 1, add the mixture that comprises following component: 100 parts of ethylene/propene terpolymer (ethylene content=65 mole %, density=0.87 gram per centimeter as thermoplastic polymer (ⅰ)
3, MFR=0.4 gram/10 minutes, SP value=8.03(card/centimetre
3)
1/2; An alkali metal salt of 10 parts of thermoplastic polymers (ⅱ) (from reference example 1, obtaining); With 3 parts of potassium oleates as aniorfic surfactant, for section's speed be 113 parts/time, distilled water with 1.2 parts/time flow supply with continuously from extrusion machine intermediary inlet, and mixture pushes under 200 ℃ of Heating temperatures continuously.The static mixer that have chuck of mixture after the extruding through being installed in extruder outlet is cooled to 90 ℃, and discharges from device.Products therefrom is a white solid.Counterpressure during the distilled water feed is 20.0 kilograms per centimeter
2(gauge pressure), and the vertical pressure of extruder screw is 20 kilograms per centimeter
2(gauge pressure).From the specific energy of amount of compression and power consumption calculating gained is 0.39 kilowatt-hour/kilogram.By the example 1 described resistance value that records with quadrat method is 8 * 10
4Ω-cm.By with the gained solid dispersed in water, and use the microscopic examination deployment conditions, find that it disperses with spherical fine-grained form.Show that through the mensuration of microscope track instrument the particle median size is 0.37 micron (μ) to the discrete particles particle diameter.
Embodiment 4
From the funnel of the used identical unidirectional rotation meshing-type two-axis screw extruder of embodiment 1, with 4.5 parts/time speed supply with the mixture that comprises following component continuously: 100 parts of ethylene/vinyl acetate copolymer (with used identical of embodiment 2): 10 parts of maleic anhydride-grafted polyethylenes (with used identical of embodiment 1) as thermoplastic polymer (ⅰ); With 10 parts of (A-C polyethylene 5120 that Allied chemical company produces of the ethylene/acrylic acid copolymer resin as thermoplastic polymer (ⅱ), acrylic acid content=15%,-COO-radical concentration=2.14 mmoles equivalent/gram (polymkeric substance), viscosity (140 ℃)=650 centipoises, density=0.93 gram per centimeter
3, SP value 8.58(card/centimetre
3)
1/2, 35% potassium hydroxide aqueous solution with 4.5 parts/time flow, supply with continuously from extrusion machine intermediary inlet, and mixture pushes under 160 ℃ of Heating temperatures continuously.The static mixer that have chuck of mixture after the extruding through being installed in extruder outlet is cooled to 90 ℃, and discharges from device.Products therefrom is a white solid.Counterpressure during aqueous solution feed is 7.0 kilograms per centimeter
2(gauge pressure), and the vertical pressure of extruder screw is 10.0 kilograms per centimeter
2(gauge pressure).From the specific energy of amount of compression and power consumption calculating gained is 0.33 kilowatt-hour/kilogram.By the embodiment 1 described solid resistance value that records with quadrat method is 9 * 10
3Ω-cm.By with the gained solid dispersed in water, and use the microscopic examination deployment conditions, find that it disperses with spherical fine-grained form.Show that through the mensuration of micro-track instrument the particle median size is 0.47 micron (μ) to the discrete particles particle diameter.
From the funnel of the used identical unidirectional rotation meshing-type two-axis screw extruder of embodiment 1, with 110 parts/time speed supply with the mixture that comprises following component: 100 parts of ethylene/propene terpolymers as thermoplastic polymer (ⅰ) (with used identical of embodiment 3) and 10 parts are used as the maleic anhydride-grafted polyethylene (with used identical of embodiment 1) of thermoplastic polymer (ⅱ).Oleic acid that can be by generating aniorfic surfactant with alkali substance reaction with 2 parts/time speed, from the inlet at position between the funnel that is arranged on extrusion machine and venting port feed continuously, and 23% potassium hydroxide aqueous solution with 3.5 parts/time flow, from the inlet of the venting port that is arranged on extrusion machine and middle part, top feed continuously.Said mixture is extruding continuously under 140 ℃ of Heating temperatures.The static mixer of resin compound after the extruding through having chuck is cooled to 90 ℃, and discharges from device.Products therefrom is a white solid.Counterpressure during aqueous solution feed is 5.0 kilograms per centimeter
2(gauge pressure), extruder screw top pressure is 8.0 kilograms per centimeter
2(gauge pressure).From the specific energy of amount of compression and power consumption calculating gained is 0.38 kilowatt-hour/kilogram.By the embodiment 1 described solid resistance value that records with quadrat method is 8 * 10
3Ω-cm.By with above-mentioned solid dispersed in water, and use the microscopic examination deployment conditions, find that it disperses with spherical fine-grained form.Show that through the mensuration of micro-track instrument the particle median size is 0.48 μ to the discrete particles particle diameter.
Embodiment 6
From the funnel of the used identical unidirectional rotation meshing-type two-axis screw extruder of embodiment 1, with 115 parts/time speed supply with the mixture that comprises following component: 100 parts of new LDPE (film grade)s (with used identical of embodiment 1) as thermoplastic polymer (ⅰ); 10 parts as the maleic anhydride-grafted polyethylene of thermoplastic polymer (ⅱ) (with used identical of embodiment 1); Supply by Kao with 5 parts of Emulgen 430() as nonionic surface active agent, from the inlet that is arranged on the extrusion machine middle part with 2.3 parts/time flow supply with 17% potassium hydroxide aqueous solution continuously, then extruding continuously under 160 ℃ of Heating temperatures of mixture.The static mixer that have chuck of resin compound after the extruding through being installed in extruder outlet is cooled to 90 ℃, and discharges from device.Products therefrom is a white solid.Counterpressure during above-mentioned aqueous solution feed is 6.0 kilograms per centimeter
2(gauge pressure), and the vertical pressure of extrusion machine is 10.0 kilograms per centimeter
2(gauge pressure).From the specific energy of amount of compression and power consumption calculating gained is 0.35 kilowatt-hour/kilogram.By the embodiment 1 described solid resistance value that records with quadrat method is 9 * 10
3Ω-cm.By with solid dispersed in water, and use the microscopic examination deployment conditions, find that it disperses with spherical fine-grained form.Show that through the mensuration of micro-track instrument the particle median size is 0.40 micron (μ) to the discrete particles particle diameter.
From the funnel of the used identical unidirectional rotation meshing-type two-axis screw extruder of embodiment 1, with 120 parts/time speed supply with mixture with following composition: 100 parts of new LDPE (film grade)s (with used identical of embodiment 1) as thermoplastic polymer (ⅰ); 10 parts of polymkeric substance an alkali metal salts (from reference example 1, obtaining) as thermoplastic polymer (ⅱ); Supply by Kao with 10 parts of Emulgen 430(); And distilled water with 2.7 parts/time flow from the inlet that is arranged on extrusion machine middle part feed continuously, said mixture pushes under 160 ℃ of Heating temperatures continuously.The static mixer that have chuck of resin compound after the extruding through being installed in extruder outlet is cooled to 90 ℃, and is discharged from device.Products therefrom is a white solid.Counterpressure during above-mentioned water feed is 13.5 kilograms per centimeter
2(gauge pressure), and extruder screw top pressure is 12.5 kilograms per centimeter
2(gauge pressure).From the specific energy of amount of compression and power consumption calculating gained is 0.34 kilowatt-hour/kilogram.By the example 1 described solid resistance that records with quadrat method is 1 * 10
4Ω-cm.By with above-mentioned solid dispersed in water, and use the microscopic examination deployment conditions, find that it disperses with spherical fine-grained form.Show that through the mensuration of micro-track instrument average grain directly is 0.43 micron (μ) to the discrete particles particle diameter.
Embodiment 8
From the funnel of the used identical unidirectional rotation meshing-type two-axis screw extruder of embodiment 1, with 112 parts/time speed supply with mixture with following composition: 100 parts of ethylene/propene ter-polymers (with used identical of embodiment 3) as thermoplastic polymer (ⅰ); 10 parts as the maleic anhydride-modified poly ethylene of thermoplastic polymer (ⅱ) (with used identical of embodiment 1); With 2 parts of potassium oleates as aniorfic surfactant, as the tetrachloroethylene of organic solvent with 10 parts/time flow supply with from the inlet that is arranged on extrusion machine funnel and venting port middle part, and 18% potassium hydroxide aqueous solution with 2.2 parts/time flow supply with continuously from the inlet that is positioned at extrusion machine venting port and middle part, top.Said mixture pushes under 200 ℃ of Heating temperatures continuously.The static mixer that have chuck of resin compound after the extruding through being installed in extruder outlet is cooled to 90 ℃, and discharges from device.Products therefrom is a white solid.Counterpressure during above-mentioned aqueous solution feed is 12.0 kilograms per centimeter
2(gauge pressure), and the vertical pressure of extrusion machine is 12.5 kilograms per centimeter
2(gauge pressure).From the specific energy of amount of compression and power consumption calculating gained is 0.32 kilowatt-hour/kilogram, is 9 * 10 by the example 1 described solid resistance that records with quadrat method
3Ω-cm.By with solid dispersed in water, and use the microscopic examination deployment conditions, find that it disperses with spherical fine-grained form.Show that through the mensuration of micro-track instrument the particle median size is 0.30 micron (μ) to the discrete particles particle diameter.
Comparative example 1
With the operation steps of the same manner repetition embodiment 1, but the concentration of the potassium hydroxide aqueous solution of supplying with from the extrusion machine middle part changes into 8%, and its feed flow is then changed into 10 parts/hour (by weight).Products therefrom is a white solid, is 2 * 10 by the embodiment 1 described solid resistance that records with quadrat method
3Ω-cm.Counterpressure during above-mentioned aqueous solution feed is 6.0 kilograms per centimeter
2(gauge pressure).And extruder screw top pressure is 8.0 kilograms per centimeter
2(gauge pressure).By with solid dispersed in water, and use the microscopic examination deployment conditions, find that it disperses with spherical fine-grained form.Show that through the mensuration of micro-track instrument the particle median size is 1.21 microns (μ) to the discrete particles particle diameter.
Embodiment 9
From the funnel of the used identical unidirectional rotation meshing-type two-axis screw extruder of embodiment 1, with 112 parts/time speed supply with mixture with following composition: 100 parts of styrene/ethylene/butylene/styrene multipolymers as thermoplastic polymer (ⅰ) are (by the Kranton G-1657 of the Shell supply of material, density=0.90 gram per centimeter
3, SP value=8.33(card/centimetre
3)
1/2; 10 parts of maleic anhydride-grafted polyethylene [maleic anhydride content=3.3% ,-COO-radical concentration=0.67 mmole equivalent/gram (polymkeric substance), density=0.94 gram per centimeter as thermoplastic polymer (ⅱ)
3, and SP value=8.06(card/centimetre
3)
1/2]; With 2 parts of potassium oleates, the latter is as the organic substance that can form aniorfic surfactant with alkali substance reaction, and 19% potassium hydroxide aqueous solution with 3.0 parts/time flow supply with continuously from the inlet (charging pump) that is arranged on the extrusion machine middle part, said mixture pushes under 200 ℃ of Heating temperatures continuously.Counterpressure during above aqueous solution feed is 14.0 kilograms per centimeter
2(gauge pressure), and the vertical pressure of extruder screw is 12.5 kilograms per centimeter
2(gauge pressure).The static mixer that have chuck of resin compound after the extruding through being arranged on extruder outlet is cooled to 90 ℃, and discharges from device.Products therefrom is a white solid.The specific energy that calculates from amount of compression and power consumption is 0.35 kilowatt-hour/kilogram.By the embodiment 1 described solid resistance that records with quadrat method is 5 * 10
3Ω-cm.By with above-mentioned solid dispersed in water, and use the microscopic examination deployment conditions, find that it disperses with spherical fine-grained form.Show that through the mensuration of micro-track instrument median size is 0.45 micron (μ) to the discrete particles particle diameter.
Claims (23)
1, a kind of water dispersion, it comprises:
(i) hydrophobic thermoplastic polymer;
(ii) water-insoluble thermoplastic polymer, it contains and is connected with its polymer chain, and concentration is the 0.1-5 milligramequivalent, the carboxylate groups of (in-COO-form)/gram (polymkeric substance);
(iii) water; (if necessary words)
(iv) be selected from least one member in this group of being formed by aniorfic surfactant, nonionic surface active agent, organic solvent and oil; It is solid-state that said water dispersion is by the look of it, and water content is 0.5-3% (by weight), and resistance is less than 10
6Ω-cm, and after water joined in this dispersion, solid promptly was dispersed in aqueous phase with fine-grained form equably.
2, water dispersion according to claim 1 wherein makes it dispersive particulate particle diameter less than 0.5 micron (μ) by adding water.
3, water dispersion according to claim 1, wherein thermoplastic polymer (ⅰ) is the homopolymer or the multipolymer of alpha-olefins.
4, water dispersion according to claim 1, wherein thermoplastic polymer (ⅰ) is the multipolymer of ethylene/vinyl based compound.
5, water dispersion according to claim 1, wherein thermoplastic polymer (ⅰ) is the ter-polymers elastomerics of ethylene/propene copolymer elastomerics or ethylene/propylene/diene.
6, water dispersion according to claim 1, wherein the melt flow of thermoplastic polymer (ⅰ) (ASTM D1238) was at least 1 gram/10 minutes.
7, water dispersion according to claim 1, wherein thermoplastic polymer (ⅰ) is the chain olefine resin of ultra-high molecular weight, molecular-weight average (MW) is at least 500,000.
8, water dispersion according to claim 1, wherein thermoplastic polymer (ⅱ) is a kind of multipolymer that comprises the salt unsaturated carboxylic acid of monomer (as major portion) identical with the monomer that constitutes thermoplastic polymer (ⅰ) and band ethylene linkage.
9, water dispersion according to claim 1, wherein thermoplastic polymer (ⅱ) is the salt of the multipolymer of α alkene and the unsaturated carboxylic acid of being with ethylene linkage.
10, water dispersion according to claim 1, wherein the difference of the solubility parameter between thermoplastic polymer (ⅰ) and the thermoplastic polymer (ⅱ) before the neutralization can reach the 2(card/centimetre
3)
1/2
11, water dispersion according to claim 1, wherein the consumption of thermoplastic polymer (ⅱ) is 1-60 part/100 part thermoplastic polymers (ⅰ) (all by weight).
12, water dispersion according to claim 1, wherein water content is the 1.0-2.5%(weight percentage).
13, water dispersion according to claim 1, wherein the content of aniorfic surfactant and/or nonionic surface active agent is 0.1-40 part/100 part thermoplastic polymers (ⅰ) (all by weight).
14, water dispersion according to claim 1, wherein the content of organic solvent is 10-1000 part/100 part thermoplastic polymers (ⅰ) (all by weight).
15, water dispersion according to claim 1, wherein You content is 10-500 part/100 part thermoplastic polymers (ⅰ) (all by weight).
16, water dispersion according to claim 1, wherein the resistance of water dispersion is lower than 10
5Ω-cm.
17, a kind of method for preparing water dispersion, this method is included in the melt that will have following composition in the extrusion machine:
(ⅰ) hydrophobic thermoplastic polymer;
(ⅱ) water-insoluble thermoplastic polymer, it comprises with its polymer chain and being connected, concentration is the carboxylic acid or the carboxylate groups of 0.1-5 milligramequivalent (in-COO-form)/gram (polymkeric substance), perhaps comprises the carboxylic acid derivatives group that can produce the said group of said concentration by alkaline purification; (if essential words).
(ⅲ) be selected from, can be converted at least one member in the organic compound, nonionic surface active agent, organic solvent of aniorfic surfactant and this group that oil is formed by alkaline purification by aniorfic surfactant;
With
(ⅳ) water and
(ⅴ) alkaline matter (if having the thermoplastic polymer (ⅱ) or the organic compound that need carry out alkaline purification)
Mix continuously, and on melt, apply counterpressure, continue fusing this mixture of kneading, causing inversion of phases, thereby form the water dispersion of polymer solids.
18, method according to claim 17, wherein the addition of water is that 0.5-3%(is in composition total weight).
19, method according to claim 17, the water dispersion that is wherein formed by inversion of phases are lower than in temperature under the state of water boiling point and are extruded away.
20, method according to claim 17, wherein melting-kneading is to carry out under specific energy is at least 0.3 kilowatt-hour/kilogram condition.
21, method according to claim 17, wherein the counterpressure that is applied on the melt when adding water is the 0.5-300 kilograms per centimeter
2(gauge pressure) is preferably the 1.0-200 kilograms per centimeter
2(gauge pressure) is especially with the 5.0-100 kilograms per centimeter
2(gauge pressure) is for better.
22, method according to claim 17, wherein the extruding of water dispersion is to utilize the extrusion machine that has the water cooler that is arranged on the top to carry out.
23, method according to claim 17, wherein material (ⅳ) and (ⅴ) be added to the screw rod of extrusion machine and cylindrical shell between, and be full of in the gap of material (ⅰ), (ⅱ) and fusion mixture (ⅲ).
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9337486 | 1986-04-24 | ||
| JP93374/86 | 1986-04-24 | ||
| JP69178/87 | 1987-03-25 | ||
| JP62069178A JPH0796647B2 (en) | 1986-04-24 | 1987-03-25 | Aqueous dispersion and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN87103106A true CN87103106A (en) | 1987-12-16 |
| CN1011590B CN1011590B (en) | 1991-02-13 |
Family
ID=26410373
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 87103106 Expired CN1011590B (en) | 1986-04-24 | 1987-04-24 | Aqueous dispersion and process for preparation thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1011590B (en) |
-
1987
- 1987-04-24 CN CN 87103106 patent/CN1011590B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CN1011590B (en) | 1991-02-13 |
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