CN1109076A

CN1109076A - Microdispersion of hydroxamated polymers

Info

Publication number: CN1109076A
Application number: CN 94117972
Authority: CN
Inventors: H·I·海特纳; R·G·赖尔斯
Original assignee: Cytec Technology Corp
Current assignee: Cytec Technology Corp
Priority date: 1993-12-17
Filing date: 1994-11-15
Publication date: 1995-09-27
Also published as: CO4410412A1

Abstract

Stable, gel-free, water-in-oil microdispersions comprising a continuous phase of an oil and an emulsifier and a discontinuous phase of an aqueous solution of a hydroxamated vinyl polymer are disclosed. Also disclosed is a method for the production of the above-described microdispersions wherein neutralized hydroxylamide and excess base are reacted with a microdispersion of the vinyl polymer.

Description

Microdispersion of hydroxamated polymers

The application is on May 23rd, 1991 application, and application number is that U.S. of 07/704,477 does not authorize the extendible portion of application.

As everyone knows, the polymkeric substance that contains hydroxylamino is particularly useful for the flocculation of the red soil that is generated in Bayer (Bayer) (refining alumina) method, sees U.S. Patent No. 4,767,540, these polymkeric substance are made by the aqueous solution and the hydroxylammonium salt reaction of polymkeric substance such as polyacrylamide usually.In the time being brought into play the value of its best effect for this polymkeric substance by the molecular weight of the polymkeric substance of oxyamination in flocculation is used, its form all is full-bodied gel so far.Handle full-bodied gel, no matter among the oxyamination process or afterwards, all cause big problem, because extremely difficult high viscosity liquid is transferred to another container from a container, for example be transferred to storage, be transferred to transport container and be transferred to from storage and make use from transport container from reactor.When the molecular weight of polymkeric substance up to promptly about 1,000,000 when above, the viscosity of this gel is high especially.

And, traditionally will be before use with this full-bodied polymkeric substance, usually water dilutes in advance, make them can more easily be mixed in the substrate that needs to be flocculated, full-bodied oxyamination the high viscosity of polymer gel this flocculation is become be difficult to the process of carrying out, and often need be with equipment special, that valency is expensive.These inherent limitations of this gellike must mean that the solids content of this gel product must keep low as much as possible, are the level of a certain practicality to keep viscosity, that is to say that solids content is low more, and viscosity is just low more.Yet because dilution, the freight charges of the polymers soln of low solid content are obviously higher.

With regard to conventional acrylamide polymer, the viscosity problem major part is resolved by the exploitation of highly filled water-in-oil droplet dispersion, promptly for example exploitation becomes emulsion droplets, emulsion, forms such as droplet suspension, and use herein, this term means and comprises described all forms, as little micella, high-viscosity polymer at them when being added in using, yet in fact, gel itself more is soluble in matrix, like this, when highly filled polymkeric substance is stiff gel, the more easy to operate and use of the differential prose style free from parallelism of same gel owing to its lower viscosity.

Past attempts had the many trials for the stable droplet dispersion of initiative oxyamination polymkeric substance, saw United States Patent(USP) Nos. 4,587,306; 4,767,546 and 4,868,248.Yet, because the complicacy of the oxyamination that is carried out in generating this product reaction all may not finished this purpose in the past satisfactorily.The problem in the reaction of this oxyamination of appearing at comprises the relatively poor associativity of hydroxylamino functionality, the relatively poor stability of emulsion, that is leave standstill being separated after the short period, polymkeric substance can not solvability, molecular weight degradation etc.

U.S. Patent No. 4,587,306 disclosed a kind of by lower molecular weight, for example 4000 or lower polyacrylamide main chain prepare the method for the polymer emulsified liquid of oxyamination, yet, do not have evidence to show, prepared material is really a kind of, superpolymer is in oil, or in fact, or even a kind of dispersion of oil-in-water-type.Know that when the molecular weight of polymkeric substance was high, it is more outstanding that the problem of main polymer chain and reagent react just becomes.Abide by U.S. Patent No. 4,587,306 method prepares low and high-molecular weight, stable, some trials that do not contain the polymer emulsified liquid of water-in-oil-type oxyamination of gel show that the combination of hydroxylamino functionality is significantly less than (and not remarkable) wherein said method that is used for low-molecular weight polymer.And, under its high temperature of reaction, for example 70 ℃, if, in fact, there is one can form, also be the extremely difficult stable emulsion that becomes.Really, following example shows, under the reaction conditions of this patent, all can't be stable in room temperature or 70 ℃ of formation, and do not contain the high-molecular weight oxyamination polymkeric substance emulsion of gel.Like this, method in ' 306 patents obviously is unsuitable for preparing desired droplet dispersion in this, another point that merits attention is, in U.S. Patent No. 4,587, the used KOH and the mol ratio of hydroxylamine hydrochloride only are 0.78 in 306 methods, that is, azanol is only partly neutralized, thereby reaction is carried out under acidic conditions, this has just limited the speed of reaction, and needs with the extreme temperature that can further cause generating unstable product.

In U.S. Patent No. 4,767, disclosed a kind of method for preparing the polyacrylamide of oxyamination in 540, the emulsion of the polyacrylamide that is a stable oxyamination that wherein makes.Yet it is unsuccessful repeating the trial of the preparation process in this patent verified, and its reason is that the product of gained is not the stable water-in-oil dispersion that contains gel, face embodiment 34 and 35 as follows.

U.S. Patent No. 4,868,248 Shens claim to prepare the emulsion of oxyamination polymkeric substance; Yet the contriver does not disclose the specific embodiment of this polymkeric substance of any preparation.The method that its two kinds of narrating prepare polymkeric substance all is to be basic with solution, and does not show water-in-oil droplet dispersion.

Therefore, still to continue to seek a kind of the stable of oxyamination vinyl polymer that prepare, the method that does not contain the droplet dispersion of gel, that is, the integrity for preparing a kind of structure of wherein droplet dispersion still keeps proper and is the method for flowable droplet dispersion.

The water-in-oil-type that has made the oxyamination vinyl polymer is stable, does not contain the droplet dispersion of gel, and the micella size of discontinuous phase is about the 0.02-50 micron, and molecular weight is approximately higher than 1,000, and 000.This droplet dispersion does not contain gel, and by easily being scattered in the water from the modification effect.

Term used herein " stable, do not contain gel " droplet dispersion is meant this droplet dispersion one period considerable time, after for example about 9 months, is still keeping two different phases, i.e. external phase and discontinuous phase, and be flowable or free-pouring.In other words, mentioned herein to " not containing gel " system be meant a kind of droplet dispersion, the micella of the discontinuous phase of this droplet dispersion never took place deleterious the droplet dispersion become can not free-pouring nodulizing.Although this droplet dispersion may contain the agglomerative polymkeric substance, during preventing that the agglomerative polymer micelle from agglomerating into big and deleterious agglomerate, this droplet dispersion is still flowable, and can be used for desired purposes.

The oxyamination vinyl polymerization system that is droplet dispersion form by will comprise an external phase and one contain the water-in-oil droplet dispersion of discontinuous phase of precursor vinyl polymer and neutral oxyamine and, preferably, excessive alkali reaction and making.Opposite with the operation in the prior art, this process does not need high temperature or long reaction times.

The present invention relates to comprise stable, the water-in-oil droplet dispersion that do not contain gel of the discontinuous phase of the external phase of a suitable hydrocarbon ils and an emulsifying agent and the about oxyamination vinyl polymer aqueous solution more than 1,000,000 of a part amount.

The present invention also relates to the preparation method who stablizes, do not contain the water-in-oil droplet dispersion of gel of oxyamination vinyl polymer, this method comprises 1) comprise a suitable hydrocarbon ils and the external phase of emulsifying agent and the water-in-oil droplet dispersion and 2 of a precursor vinyl polymer aqueous solution micellar discontinuous phase) oxyamine that neutralized, preferably react with excessive alkali one.

The example that can be used for vinyl polymer of the present invention is those polymkeric substance that contains the outstanding basic functional group of an energy and oxyamine reaction, i.e. those polymkeric substance that made by following substances: vinylformic acid, methacrylic acid, Ba Dousuan etc.; Ester class such as methyl acrylate, ethyl propenoate, tert-butyl acrylate and corresponding methacrylic ester, dimethylaminoethyl acrylate methyl nitrilo acetic acid; Vinylformic acid diformazan ammonia ethyl ester; And quaternary salt; Methyl crotonate or the like; The polymkeric substance of maleic anhydride and ester thereof, or the like; Nitrile polymer such as those polymkeric substance that makes by vinyl cyanide etc.; Amide polymer such as those are by acrylamide, the polymkeric substance that Methacrylamide etc. make.Also can use the carboxymethyl cellulose ester, starch ester, xanthate etc., described polymkeric substance also, for example with linking agent such as methylene-bisacrylamide, reaction such as divinyl glycol and being crosslinked.

Above-mentioned vinyl monomer also each other copolymerization or with other negatively charged ion, positively charged ion or nonionic monomers, or its mixture copolymerization.

Any effective emulsifying agent that deleterious nodulizing takes place all vinyl polymer micellas that suitable micella mean diameter can be provided and can prevent gained all can be used for preparing novel composition herein, the scope of described mean diameter is about about 50 microns of 0.02-usually, be about about 10 microns of 0.1-preferably, better be about about 5 microns of 0.2-.These emulsifying agents should be such some emulsifiers, they make the droplet of oxyamination vinyl polymer disperse physical efficiency to keep unrestricted flow, becoming and can not flow due to the gel polymer solution micellar nodulizing promptly can not taken place, and for example is solidified into gum material group under the worst case.

The suitable emulsifying agent that can be used for preparing the water-in-oil droplet dispersion of this vinyl polymer that remains oxyamination comprises the aliphatic amide of ethoxylation; The alkanolamide of lipid acid; Imidazoles-fatty acid response product; Alkanolamine-fatty acid condensation product; Sorbitan fatty esters, or the like.Should select for use and can form and keep the suitable emulsifying agent of size range for the about 50 microns polymer micelle of about 0.02-.

Desirable a bit is, suitably,, that is to say to keep its integrity in the oxyamination process remaining to be added in the emulsion of oxyamination the identical or different emulsifying agent of additional quantity, emulsion among the oxyamination reaction process and afterwards must keep stable and not contain gel.

Water-in-oil droplet dispersion, the molecular-weight average of the vinyl polymer of emulsion for example described herein is at least about 1,000,000, is 5,000 preferably, more than 000, is 10,000 better, more than 000.

Any known hydrocarbon ils all can be used for forming and remains the droplet dispersion of polymkeric substance of oxyamination, and they comprise isoparaffin, straight chain or cyclic hydrocarbon such as benzene, and dimethylbenzene, toluene, oil fuel, kerosene, the odorlessness solvent oil, and composition thereof.

Water in the droplet dispersion is about 0.5-3 with the ratio of hydrocarbon phase: 1, be about 2: 1 usually.

The method that forms precursor vinyl polymer droplet dispersion has been well-known in existing document, and can be by following arbitrary United States Patent (USP), promptly, United States Patent (USP) 4,521,317(Candau), 4,147,681(Lim) method of this droplet dispersion of preparation disclosed in the grade makes.

Can be by any suitable method, for example distillation method handle precursor droplet dispersion and/or final oxyamination the polymer droplets dispersion anhydrate and/or oil to remove, purpose is to improve polymer solids content.Before or after dehydration, polymer solids content is a benchmark with the gross weight of droplet dispersion, and it is about 70% to be about 5%-, is about 10%-about 60% preferably.

Method of the present invention is as described below handled precursor polymer droplet dispersion with oxyamine and is made the polymkeric substance oxyamination.Oxyamine uses with the form of salt usually, is neutralized with alkali before or in the process so be preferably in the oxyamination reaction.

Suitable hydroxyl amine salt comprises vitriol, sulphite, phosphoric acid salt, hydrochloride, acetate, propionic salt etc.The pH value of hydroxylamine solutions is adjusted to about 3-14, yet, be preferably by in solution, adding alkali, as NaOH, it is about 6.0 to keep the pH value to be higher than, and is more preferably to be higher than about 11.0.

The degree of oxyamination, the unitary concentration of oxyamination thing can be about 1-100mol% in the promptly useful herein polymkeric substance, is about 5-75mol% preferably, and that best is about 10-50mol%.

Be preferably alkali with hydroxyl amine salt and excessive (in mol), as potassium hydroxide, sodium hydroxide, ammonia, lime etc. use together.Alkali is sodium hydroxide preferably, and used amount is a benchmark with the reactive group of precursor polymer, is preferably to be higher than about 5mol%.

The oxyamination reaction can be in low temperature, and promptly about 10 ℃-90 ℃, be preferably about 15 ℃-60 ℃, be more preferably under about 15 ℃-40 ℃ and carry out.

In a preferable example, in the oxyamine reactant, add a kind of is suitable for making the stable stablizer of vinyl polymer to prevent since existing of oxyamine vinyl polymer is degraded.Suitable stabilizers comprises sodium byposulfite water-soluble alkali metal salts, alkaline earth salt or ammonium salt; 2-mercaptothiazole class; 2-mercaptothiazole quinoline class; Thiuram disulfide; Thiourea; The sulfydryl alkanol; Respectively referring to the U. S. application No.07/074 of on May 23rd, 1991 application, 475 and 07/704,479, and U.S. Patent No. 5,527,146 and 5,141,730 now.

With oxyamine or its salt, excessive alkali preferably also has stablizer, adds in the droplet dispersion of the precursor vinyl polymer that is the aqueous solution or emulsion form and makes it to react.Be preferably, these compounds use with the solution form.In the presence of as mentioned above an emulsifying agent, the aqueous solution that adds these compounds in any above-mentioned oily matter just can form emulsion, and the same emulsifying agent that is used to form the vinyl polymer droplet dispersion for the treatment of oxyamination also can be used for the formation of oxyamine emulsion material.Also can use different emulsifying agents or emulsifier mixture.Yet it is essential that the result of existence of emulsifying agent is, hydroxylamine solutions enter the water of precursor droplet dispersion and final oxyamination the vinyl polymer dispersion be stable, be not contain gel, just as discussed above.Be preferably, the aqueous solution and oil and emulsifying agent are carried out homogenizing; Yet, only described component is stirred a little and also can obtain useful thicker emulsion.Perhaps, the condition of being discussed all meets, can be with oxyamine, and the excessive alkali and the hydroxylamine solution of stablizer directly add in the precursor vinyl polymer droplet dispersion, therein also oiling and emulsifying agent and be stirred to the standard that reaches above-mentioned discussion again.Also have, also can be with each component, i.e. oxyamine, excessive alkali and stablizer are made emulsion respectively, and add after this manner in the precursor vinyl polymer droplet dispersion.

As known in the art, the oxyamination degree is controlled by the ratio of the oxyamine reagent that added and precursor vinyl polymer main chain reactive group, and method of the present invention can cause very high oxyamine transformation efficiency, and the oxyamination degree can be by C ¹³Nuclear magnetic resonance spectroscopy, this paper represented with mol%, oxyamination the molecular weight of vinyl polymer can be measured via the viscosity of determining to be dissolved in the dilute polymer solution in the volumetric molar concentration sodium chloride solution.Soltion viscosity (SV), person as used herein, by 25 ℃ the time, be 0.1% polymers soln of benchmark with the precursor polymer, the Brookfield viscometer determining that uses band UL to take over, at 30rpm, SV used following relation: SV=exp. { viscosity during 30rpm-0.162 }, at 60rpm greater than 10 o'clock, SV represented with mPa.s less than 10 o'clock.With method of the present invention can make soltion viscosity be higher than about 2.0 oxyamination vinyl polymer water-in-oil droplet dispersion.

Oxyamination of the present invention vinyl polymer water-in-oil droplet dispersion can the direct formation aqueous solution soluble in water, this aqueous solution can be used as for example flocculation agent, in addition, if the words that need must or be arranged, can in the droplet dispersion, add emulsion splitter or in the dilution water that the droplet dispersion will be added into, add emulsion splitter, reverse with help droplet dispersion, thereby improve solubility property.Have again, oxyamination vinyl polymer can be by for example precipitation or in non-solvent by dry and from the droplet dispersion, be separated with a kind of dry powder.

Except that the representor of institute in appended claims, state the just explanation for example of purpose of following embodiment, cut it to be interpreted as it is limitation of the present invention.Unless otherwise indicated, all umber and percentage ratios are all represented with weight.

Embodiment 1

(contrast)

According to U.S. Patent No. 4,587, method 306(Vio) is with the water-in-oil droplet dispersion of hydroxylamine hydrochloride (for 0.5 equivalent of polyacrylamide) and potassium hydroxide (0.35 equivalent) processing polyacrylamide (molecular weight is about 600 ten thousand).This droplet dispersion system makes by add 4.7 parts of paraffin oils in the polyacrylamide droplet dispersion made from the octyl phenol emulsifying agent of ethoxylation (13.5% solid), in adition process, keep temperature to be lower than 30 ℃, stir this mixture overnight then, then a sample of mixture is heated to 70 ℃ 6 hours.Whole emulsion system generation gelling is also isolated oil phase.The NMR analysis revealed of polymer gel has 5% oxyamination thing (10% transformation efficiency), and one places the sample of the mixture under the room temperature is stable.This sample did not have the oxyamination thing with the NMR analysis revealed after 5 days.Present embodiment shows that the keying action of any oxyamine at room temperature can not take place the method for Vio, and in the time of 70 ℃, have only 10%(generate the 5mol% oxyamination polymkeric substance), in the time of 70 ℃, the emulsion gelling, be it be not one stable, the dispersion that does not contain gel, but two-phase is isolating, deleterious agglomeration takes place in polymer micelle.The difference of this embodiment is, the molecular weight of the polymkeric substance that the molecular weight ratio Vio of precursor droplet dispersion is used is much bigger, is about 600 ten thousand, and the result shows, when doing experiment with the high-molecular weight vinyl polymer, people's such as Vio method can not generate useful product.

Embodiment 2

(contrast)

Under the room temperature, spend 20 fens clock times, 130 parts of routines that contain 45.5 parts of polyacrylamides, add 34.6 part of 30% sulfuric acid hydroxylamine solutions in the anti-polyacrylamide droplet of the high-molecular weight dispersion, stirred this mixture 1.5 hours, spend 20 fens clock times to add 13.4 parts of 50%NaOH, promptly be in excess in oxyamine, because the micellar agglomeration, mixture generation gelationization can get similar result when adding NaOH solution homogenizing droplet dispersion mixture.This embodiment shows, herein under the condition if the droplet dispersion is not by adding more or second kind of emulsifying agent keeps stable and gel-free, agglomeration promptly can take place in micella, causes generating useless product.

Embodiment 3

Remain below under 25 ℃ the temperature, 99 part of 30% sulfuric acid hydroxylamine solutions mixed with 20 parts of Sulfothiorine stablizers and with 160 parts of 50%NaOH this mixture that neutralizes.The mol ratio of free NaOH and oxyamine is 4.5: 1.Filter this solution.Be dissolved in 108 parts of hydrocarbon solvents (LOPS) by aliphatic amine emulsifying agent (ethoxylation degree=5) and make an oil phase 4 parts of ethoxylations, use suitable homogenizer, spend 1 fen clock time that the aqueous solution is added in the oil phase, carry out homogenizing contains 0.0009mol/ part oxyamine with generation emulsion.At room temperature, 52.5 parts of these emulsion are added to 50 parts of isopropanol amides by lipid acid make, contain 33.8%(weight as emulsifying agent) in the polyacrylamide droplet dispersion (m.w.=10.6 1,000,000) of polymkeric substance.The mol ratio of oxyamine and acid amides is 0.2: 1, and the mol ratio of excessive NaOH and acid amides is 0.9: 1.After 1 week, gained stable, the soltion viscosity that does not contain the droplet dispersion of gel is 8.6mPa.s.The NMR method records, and polymkeric substance contains 16.2% oxyamination thing (81% transformation efficiency), this embodiment show can make by the oxyamine reagent that adds emulsion form stable, do not contain gel the high-molecular weight oxyamination the polymer droplets dispersion.

Embodiment 4-11

50% sodium hydroxide is added in the solution of sulfur acid oxyamine and Sulfothiorine stablizer, acquisition contains the sulfur acid oxyamine that mol ratio is 9.0/2.25/49.5, the solution of Sulfothiorine and NaOH, the water that adds capacity is to dissolve all neutralized reaction product, various piece solution with various these solution of emulsifying agent emulsification, obtain the anti-emulsion of each hydroxyl amine and excessive NaOH, under the room temperature, these emulsions are mixed with the homo-polypropylene acid amides and the ammonium acrylate/acrylamide copolymer that make in the presence of cited various tensio-active agents equally.In all cases, the mol ratio of oxyamine and acid amides all is 0.2: 1.In each case, all be recovered to oxyamination polymkeric substance stable, do not contain the droplet of gel after, in 30 fens clock times, with the nonylphenol of 0.5 part of ethoxylation add to 50 parts of oxyaminations the aliquots containig of polymer droplets dispersion in, the droplet dispersion of gained is stable, do not contain gel, and can in water, (that is, not needing in addition can be easily soluble in water with tensio-active agent) take place self to transform by conversion.Its soltion viscosity is 10.8mPa.s, and the content of oxyamination thing is the 17.9%(90% transformation efficiency).

Embodiment 15

With 3.3 parts of hydroxy amine hydrochloric acid salts be dissolved in 7.45 parts of potassium hydroxide reaction in 18.1 parts of water (the excessive KOH and the mol ratio of oxyamine are 1.8: 1 in this solution).At room temperature be dissolved in the aliphatic amide emulsifying agent (ethoxylation degree=2) of 1.0 parts of ethoxylations in 10.2 parts of paraffin oils and this mixture is added in 50 parts of embodiment, the 1 described same polyacrylamide droplet dispersion.28.8 parts of oxyamines/KOH solution is added in the polyacrylamide, to cause the oxyamine identical and the mol ratio of acid amides with embodiment 1.Stir the mixture and spend the night.With gained droplet dispersion samples stable, that do not contain gel be heated to 70 ℃ 6 hours, this sample shows 38.9% oxyamination thing content (78% transformation efficiency).Same droplet dispersion is at room temperature aging after 5 days, shows 46.2% oxyamination thing (92% transformation efficiency).This embodiment shows, when having excessive potassium hydroxide and using suitable tensio-active agent, can obtain high-molecular weight oxyamination stable, that do not contain gel the micro polymer dispersion.

Embodiment 16

The aliphatic amide emulsifying agent (ethoxylation degree=2) of 4.7 parts of ethoxylations is dissolved in 65.1 parts of paraffin oils, gained solution is added in the polyacrylamide droplet dispersion of 169.7 parts of polymkeric substance that contain 33.8% embodiment 12.50% sodium hydroxide is added in the solution of sulfur acid oxyamine and Sulfothiorine stablizer, obtain as the solution among the embodiment 4-11.After adding NaOH, this aqueous solution was at room temperature placed 2 hours.Then, at room temperature, continue under agitation 21.5 parts of this drips of solution to be added in 28.5 parts of polyacrylamide droplet dispersion mixtures in 1 hour time.The mol ratio of oxyamine and acid amides is 0.2: 1.Final product is that oxyamination reaches the 21mol%(100% transformation efficiency) polymer droplets dispersion stable, that do not contain gel.At room temperature, promptly about 20 ℃, aging respectively after 1 day and 13 days, the soltion viscosity that records (SV) is respectively 12.6 and 11.3mPa.s, (90% reservation).This embodiment shows by using suitable stabilizers, is Sulfothiorine as used herein, can overcome the degraded of the polyacrylamide that is caused by oxyamine.In the present embodiment, oxyamine reagent is added into the solution form.Equally, present embodiment also clearly illustrates that, has shown that stablizer has also reduced the loss of molecular weight, and this point can be found out by the good retention value of soltion viscosity.

Embodiment 17

Make a solution in embodiment 14 similar modes, it contains NaOH and thiocarbamide.The mol ratio of oxyamine and NaOH and stablizer such as embodiment 4-11.At room temperature placed solution 2 hours.In embodiment 4 identical modes 21.5 parts of this solution are added in 28.5 parts of same polyacrylamide droplet dispersions then, products therefrom is one stable, do not contain in the polymer droplets dispersion of gel, products therefrom is one stable, the polymer droplets dispersion that does not contain gel, its oxyamination reaches the 20mol%(100% transformation efficiency), and can keep its S.V. a very long time.Present embodiment shows that thiocarbamide can be used as the stablizer of oxyamine.

Embodiment 18

The amount of preparation hydroxyl amine and NaOH is identical with embodiment 16 and 17, but do not contain stablizer solution and with its put 20 ℃ following 2 hours.The same as embodiment 16 with 17, with same ratio and same speed it is added in the same polymer droplets dispersion mixture.Product is stable, does not contain the polymer droplets dispersion of gel, and its oxyamination reaches the 9.1mol%(45% transformation efficiency).At 20 ℃ after aging 1 day and 13 days, the soltion viscosity of polymkeric substance be respectively 11.8 and the 7.7mPa.s(65% retention value), present embodiment shows, under the situation that does not have stablizer, when it being preserved in room temperature, the polymer degradation that generation is caused by oxyamine, cause transformation efficiency to descend, and, when not having stablizer, the molecular weight of polymkeric substance can descend, and this can be clearly illustrated by the minimizing of soltion viscosity.Yet the whole maintenance of droplet dispersion is stable and do not contain gel.

Embodiment 19

Dispersion, the result is as shown in table 1 below.These embodiment show, are used for can being prepared with various tensio-active agent with the oxyamine/basic cpd/stablizer emulsion of precursor polyacrylamide droplet dispersion reaction.Similarly, the also available different tensio-active agent of precursor polyacrylamide droplet dispersion is prepared.Similarly, the precursor acrylamide polymer also can be anionic copolymer.

Table 1

Embodiment Prim (%) Ha (%) oxyamination thing transformation efficiency

Surf Emul Mole% %

4 A 1% A 1% 17.4 87

5 A 1% B 2% 19.1 95

6 A 1% C 2% 15.5 77

7 A 1% D 2% 16.6 83

8 A 1% E 2% 18.1 90

9 A 1% D 2% 16.6 83

10 F 2.2% E 2% 17.2 86

11 F 2.2% B 1% 16.7 83

Among the embodiment 4-9, use polyacrylamide main chain (MW=10.6M).

Among the embodiment 10-11, use the anionic polymer main chain (MW=11.0M) that makes by ammonium acrylate (5mol%) and acrylamide (95mol%).

Prim.Surf.=is used to prepare the major surfaces promoting agent of precursor polymer droplet dispersion

Ha Emuls=is used to prepare the tensio-active agent of oxyamine reagent emulsion

The isopropanol amide of A=lipid acid

The aliphatic amide of B=ethoxylation (ethoxylation degree=5)

C=2-hydroxyethyl oil-based imidazoline

D=diethanolamine and oleic condensation product

The aliphatic amide of E=ethoxylation (ethoxylation degree=2)

The monoleate of F=anhydro sorbitol

Embodiment 12

With embodiment 4-11 similarly, in the presence of the thiosulfuric acid salt stabilizing agent, with excessive sodium hydroxide neutralisation of sulphuric acid oxyamine.The water that adds capacity is with the solubilizing reaction product.Do not use homogenizer, by this aqueous solution is mixed to make a water in oil emulsion with aliphatic amide emulsifying agent (ethoxylation degree=5) solution of ethoxylation in being dissolved in paraffin oil.The volume viscosity of gained emulsion is 73cps, shows that the micella size of this emulsion is big.Under the room temperature, the aliquots containig of 29.5 parts of this emulsion is added in 20 parts of polyacrylamide droplet dispersions containing 33.8% polymkeric substance and make with lipid acid isopropanol amide emulsifying agent (molecular weight be about 12.5 hundred ten thousand).The soltion viscosity of gained droplet dispersion stable, that do not contain gel is 11.7mPa.s, and the content of the oxyamination thing that is recorded by NMR is the 18%(90% transformation efficiency).

Embodiment 13

With embodiment 12 similarly, with the aliquots containig of homogenizer homogenizing reagent emulsion, the volume viscosity of this emulsion is 127cps, shows that the micellar size is little.The aliquots containig of 29.5 parts of this emulsions is added in the same polyacrylamide main chain droplet dispersion that is used for embodiment 12, gained droplet dispersion be stable, do not contain gel and soltion viscosity institute's tool is 13.2mPa.s, the content of the oxyamination thing that is recorded by NMR is the 17.5%(85% transformation efficiency).

Embodiment 14

Contain poly-third of 33.8% polymkeric substance with what the mixture of the aliphatic amide emulsifying agent (ethoxylation degree=2) of 2.5 parts of ethoxylations and 34.5 parts of paraffin oils added to 90 parts of embodiment 12

By with the described solution of ethoxylated fatty amine (ethoxylation degree=5) emulsification embodiment 4-11 that is dissolved in paraffin oil, make hydroxyl amine and NaOH, mol ratio is 6.4: 35.6 an anti-oxyamine emulsion.Under the room temperature, add to 30.0 parts of this emulsion that polyoxyethylene-sorbitan mono-oleate is made and contain in the droplet dispersion of anionic acrylamide polymer (multipolymer-molecular weight of 30: 70 of ammonium acrylate and acrylamide is about 2,000 ten thousand) of polymkeric substance 25.7%.The mol ratio of oxyamine and monomeric unit is 0.20: 1, and the mol ratio of free NaOH and monomeric unit is 0.9: 1.It is stable that product is 16.5% oxyamination (82% transformation efficiency), do not contain the droplet dispersion of gel.Soltion viscosity after 5 days is 9.7mPa.s.

Embodiment 20

At room temperature, will add in anionic acrylamide-polymer droplets dispersion as embodiment 19 described same oxyamine emulsion.Polymkeric substance is 2-acrylamide ylmethyl-2-propanesulfonic acid (Na salt) and acrylamide 30: 70(is in mole) multipolymer.The mol ratio of oxyamine and caustic alkali and embodiment 13 are same, and product does not contain the polymer droplets dispersion of gel for to contain the stable of 15.8% oxyamination thing (79% transformation efficiency).Soltion viscosity after 5 days is 7.0mPa.s.

Embodiment 21

Cationic-type polyacrylamide droplet suspensoid uses the polyreaction of standard oxidation reduction initiation and the isopropanol amide emulsifying agent of lipid acid to make by acrylamide (90mol%) and the monomeric mixture of chlorination dimethyldiallylammonium (10mol%).It only is 30.4% polymkeric substance of benchmark with the acrylamide that product contains.At room temperature, the aliphatic amide emulsifying agent (ethoxylation degree=2) of 1.5 parts of ethoxylations is dissolved in 17 parts of paraffin oils, this mixture is added in 50 parts of polymkeric substance emulsion in room temperature, in 30 fens clock times, with 47.5 parts with embodiment 16 in identical oxyamine-alkali-thiosulfate solution add in the polymer droplets dispersion.Product is that soltion viscosity is the stable of 2.8mPa.s, does not contain the droplet dispersion of gel, isolates a polymer samples by precipitation in methyl alcohol.The exsiccant polymkeric substance contains 14% oxyamination thing (70% transformation efficiency) and 2% quaternary ammonium group (20% transformation efficiency).

Embodiment 22

The polyacrylamide droplet dispersion that contains 33.8% polymkeric substance of 153.5 parts of embodiment 12 is anhydrated and oil partly to remove in heating under vacuum.Polymer solids increases to 47.4%, and the aliphatic amide emulsifying agent (ethoxylation degree=5) of 1.5 parts of ethoxylations is dissolved in 21.5 parts of paraffin oils.This mixture is added in the polymer droplets dispersion that 40 parts of partial dehydrations cross.Make oxyamine, the solution that excessive NaOH and sodium thiosulfate content and embodiment 16 are identical.Under the room temperature, 59.5 parts of this solution are added in the polymer droplets dispersion with 25 fens clock times, product is stable, the polymer droplets dispersion that does not contain gel, soltion viscosity behind the one sky is 11.3mPa.s,, and contain 16% oxyamination thing (80% transformation efficiency).Present embodiment showed before reacting with oxyamine, can make the dehydration of precursor droplet dispersion to increase polymer solids.

Embodiment 23

By being carried out polymerization with the isoparaffic solvent that contains the emulsifier mixture of polyoxyethylene sorbitan monooleate and polyoxyethylene-sorbitan mono-oleate, acrylamide solution makes an anti-microemulsification body methacrylamide homopolymer.This polyreaction system makes it to carry out with a redox initiation system.This droplet emulsoil contains 23%(weight) polyacrylamide, its average micella is of a size of 31nm.Stirring and keeping mixture under 25 ℃, aliphatic amide emulsifying agent (ethoxylation degree=5) with 10.0 parts of paraffin solvents and 2.0 parts of ethoxylations, 11.2 part 50% aqueous sodium hydroxide solution, the aqueous solution of 2 part of 30% Sulfothiorine stablizer aqueous solution and 5.2 part of 47% hydroxy amine hydrochloric acid salt.At room temperature stirred this solution 20 minutes, then it is added in 29.0 parts of polyacrylamide droplet emulsoils, the product of gained is a droplet emulsoil stable, that do not contain gel, and its soltion viscosity is 10.7mPa.s, and oxyamination thing content is the 27%(72% transformation efficiency).Present embodiment shows that precursor droplet dispersion can be the droplet emulsoil.

Embodiment 24

By with 251 part of 30% sulfuric acid hydroxylamine solutions with 37 parts of Sulfothiorine stablizers mix and an anti-emulsion is made in this solution and the mixture copolymerization that contains the isopropanol amide derivative (emulsifying agent) of 108 parts of paraffin oils and 4 parts of longer chain fatty acids.By being carried out emulsification, 50% aqueous sodium hydroxide solution and mixture by the aliphatic amide emulsifying agent (ethoxylation degree=5) of paraffin oil and ethoxylation make second emulsion again.In 1 hour time, 20.7 parts of sulfuric acid oxyamine emulsion are added in 29.1 parts of sodium hydroxide emulsion.The mole of oxyamine and NaOH is 5.5: 1.0.Then 22.5 parts of this mixtures are added in anti-polyacrylamide (5mol% is carboxylated) the droplet dispersion of 20 parts of anionics made from the polyoxyethylene-sorbitan mono-oleate emulsifying agent.Product is a droplet dispersion stable, that do not contain gel, and the soltion viscosity behind the one sky is 10.8mPa.s, and contains 16.2% oxyamination thing (81% transformation efficiency).

Embodiment 25

Press the process of embodiment 24, wherein 8.3 parts of same sulfuric acid oxyamine emulsion are added in the polyacrylamide droplet dispersion that contains 33.8% polymkeric substance of 40 parts of embodiment 12.With 1 hour time 42.3 parts are made with the aliphatic amide emulsifying agent of ethoxylation then, the anti-emulsion that contains sodium hydroxide and Sulfothiorine stablizer respectively adds in the mixture by 45: 0.16 ratio.Gained is stable, and the soltion viscosity of polymkeric substance emulsion after 7 days that does not contain gel is 5.4mPa.s, and the content of its oxyamination thing is the 6.4%(64% transformation efficiency).Embodiment 24 and 25 shows that the reagent emulsion can separately add.

Embodiment 26

Press embodiment 3, the mol ratio of making wherein excessive NaOH and oxyamine is 4.5: 1, the water in oil emulsion that contains the oxyamine that has neutralized, 21.7 parts of this emulsion are mixed mutually with 50.0 parts of same polyacrylamide droplet dispersions as described in example 1 above, so that the mol ratio of oxyamine and acid amides is 0.10: 1, the mol ratio of excess NaOH and acid amides is 0.45: 1.Product is stable, does not contain the droplet dispersion of gel, and the soltion viscosity behind the one sky is 7.3.The content that is recorded its oxyamination thing by NMR is the 7%(70% transformation efficiency).

Embodiment 27

58.3 parts of hydroxy amine hydrochloric acid salts are mixed with 116 parts of water and 13 parts of Sulfothiorine.Mixture neutralizes with 128 parts of 50%NaOH.Filtering solution with the aliphatic amide (ethoxylation degree=5) of 4 parts of ethoxylations and 288 parts of said mixtures of emulsifying soln of 108 parts of paraffin oils, obtains an emulsion.97.0 parts of this emulsion are mixed with the anionic acrylamide polymer droplet dispersion that contains 38% polymkeric substance of 35.0 parts of embodiment 19, and the mol ratio that reaches oxyamine and acid amides is 1: 1.Product is the stable droplet dispersion that does not contain gel.Record polymkeric substance by the NMR analysis and contain 73.4% oxyamination thing (73% transformation efficiency).Its soltion viscosity after 6 days is 2.9mPa.s.Embodiment 26 and 27 shows that this process can be respectively applied for the polymkeric substance that preparation contains few and a large amount of oxyamination things.

Embodiment 28

With the method that is similar to embodiment 4-11, in the presence of Sulfothiorine stablizer (25mol% of oxyamine), with excessive sodium hydrate neutralisation of sulphuric acid oxyamine.The product that the water that adds capacity has neutralized with dissolving.Change the excessive NaOH of this aqueous phase and the mol ratio of oxyamine.The aliphatic amide (ethoxylation degree=5) that uses ethoxylation then as emulsifying agent to prepare anti-water in oil emulsion, keep constant by adding the oxyamine concentration that entry makes the aqueous phase of these oxyamine emulsion, 29.5 parts of every kind of gained emulsion that contain 0.019 part of oxyamine are added in the polyacrylamide droplet dispersion that contains 33.8% polyacrylamide of 20 parts of embodiment 12, so that the mol ratio of oxyamine and acid amides reaches 0.20: 1.All products all are droplet dispersion stable, that do not contain gel, and contain the composition in the following table 2.Present embodiment shows that the various mol ratios that are higher than 1.0: 1.0 NaOH/ oxyamine all can be used to prepare droplet dispersion stable, that do not contain gel of the present invention.

Table 2

The excessive oxyamination thing of embodiment polymer solids transformation efficiency %

NaOH/ hydroxyl Mole%

The mole of base amine

Ratio

28a 13.7 4.5 18.0 90%

28b 13.7 3.0 15.6 78%

28c 13.7 2.0 14.4 72%

28d 13.7 0.5 12.7 63%

28e 13.7 0.25 10.6 53%

Embodiment 29

By embodiment 3 described steps prepare oxyamination stable, that do not contain gel the polymer droplets dispersion, it is made comparisons in the performance of flocculation from " red soil " suspension process that aluminum oxide source mill obtains and the performance of the polyacrylate flocculant of can commodity buying that is used for this purpose, the results are shown in the following table 3.

Table 3

The solid that the dosage subsidence rate suspends

Polymkeric substance gram/ton ft/hr m#/L

Commodity 134 37 134

Polyacrylate

Oxyamination 80 7 60

{。##.##1},

Polymkeric substance 107 32 40

Droplet divides 134 51 29

A prose style free from parallelism 160 62 35

188 108 20

Present embodiment shows, confirm from higher subsidence rate and lower suspended solid amount, with the polymer phase ratio that waits the dosage routine, prepared herein oxyamination stable, that do not contain gel polyacrylamide droplet dispersion in the flocculation of " red soil ", have preferable performance.

Embodiment 30

(contrast)

The aqueous solution by the polypropylene acid amides prepares polyacrylamide (molecular weight is about 4200), with this solution dilution to containing solid 46.1%.By octyl phenol, HLB=3.6(tensio-active agent G) is dissolved in 132 parts of kerosene and makes an oil phase 8 parts of ethoxylations.Use a suitable homogenizer, 260 parts of polymers solns are added in the oil phase lentamente, mix after 100 seconds, homogenizer is speeded to #5, in 30 seconds of homogenizing, two-phase is separated into significantly two-layer at once.Present embodiment shows, can not use specific emulsifying agent to prepare stable precursor droplet dispersion with polyacrylamide solution.

Embodiment 31

(contrast)

Except that octyl phenol (HLB=7.8 tensio-active agent H) substitution list surface-active agent G with 8 parts of ethoxylations, repeat the step of embodiment 30, form an emulsion, the latter was divided into tangible two-phase in 1.5 hours.Use 16 parts of tensio-active agent H then, the oil phase that 234 parts of kerosene is made repeats this step, the emulsion of Xing Chenging was divided into significantly two-layer in 2 hours like this, present embodiment shows once more, even can not be from the precursor droplet dispersion of its formulations prepared from solutions polyacrylamide under the situation of the hydrocarbon ils amount that has improved.

Embodiment 32

(contrast)

Except with 8 parts of ethoxylation octyl phenols (HBL=10.4-tensio-active agent I) substitution list surface-active agent G, repeat embodiment 30 processes.Form a stable polyacrylamide emulsion.This emulsion contains and U.S. Patent No. 4,587,306, the composition that the emulsion among the embodiment 27 is same.Conductivity measurement shows that this oil is external phase, 7.34 parts of hydrochloric acid oxyamines is dissolved in 22.5 parts of water makes a solution.This solution with in the polymkeric substance emulsion made from the tensio-active agent I that added to 50 parts of stirrings in about 25 minutes, is stirred the aliquots containig of 50 parts of this emulsions, add 8.07 parts of 36%KOH solution with about 30 minutes time.The mol ratio of KOH and hydrochloric acid oxyamine and U.S. Patent No. 4,587, identical in 306(Vio) is 0.78: 1, with the sample of this emulsion in baking oven in 70 ℃ of heating 7 hours.After the 6th hour, the complete layering of two-phase, the polymkeric substance water of the sample that heated contains 0% oxyamination thing.Embodiment 32 shows, the stable anti-droplet dispersion of the low-molecular weight polymer that the method for Vio can not be used for preparing oxyamination.Because Vio does not describe any specific degrees of ethoxylation degree or wherein used octyl phenol emulsifying agent, so it is low to comprising in embodiment 30-32, the scope of emulsifying agent of high HLB of neutralizing is tested, none provides gratifying result, that is, all emulsifying agents all are divided into tangible two-phase separately.

Embodiment 33

Except oil phase be constitute by 4 parts of oleic Yi Bingchunan acid amides emulsifying agents and 136 parts of kerosene, repeat the process of embodiment 30, form a stable anti-polymer droplets dispersion precursor that contains 30% polyacrylamide, use identical emulsifying agent, the mol ratio of making hydroxyl amine and NaOH is 0.65: 3.55 an anti-emulsion.32.6 parts of this emulsion are added in 25 parts of polymkeric substance missible oil liquid, and product is the anti-emulsion stable, that do not contain gel of oxyamination thing polymkeric substance.The oxyamination transformation efficiency is 100%.

Embodiment 34

(contrast)

Press the U.S. Patent No. 4 of Spitzer, 767, embodiment in 540, with 58.2 parts of commodity acrylic acid multipolymer droplet dispersion (anionization degree=3mol%, the about 12-15 1,000,000 of molecular weight) mix with 16.3 parts of solid sulphuric acid oxyamines, the mol ratio that makes sulfuric acid oxyamine/acid amides is 1: 1, adds 50% sodium hydroxide solution (15.9 parts) of equimolar amount, with mixture heating up to 90 ℃, and stirred 5 hours.Be placed on then in 90 ℃ the baking oven 16.5 hours.Not runny product is a kind of evenly, the stiff gel of micellar that an agglomeration is got up, and oil is disperseed therein, as same emulsion.This product is water-soluble, and its soltion viscosity only is 1.4mPa.s, (molecular weight is about 100 ten thousand).

Embodiment 35

(contrast)

External except the commodity acrylic acid-acrylamide copolymer dispersion of using anionization degree=30% as polyreaction, repeat the process of embodiment 34.Product is that the micellar that gets up of an agglomeration is not runny, and stiff gel, oil are disperseed therein, as same emulsion.It is water insoluble.

Embodiment 36

The isopropanol amide that uses lipid acid is as emulsifying agent, with acrylamide and 500ppm(with respect to acrylamide) copolymerization of divinyl glycol, crosslinked to prepare, anti-polyacrylamide amine precursor droplet dispersion (26% activity).At room temperature, 57.6 parts are made by above-mentioned fatty acid emulsifier, contain oxyamine as the emulsion same amount among the embodiment 4-11, the anti-emulsion of sodium hydroxide and thiosulphate adds in the aliquots containig of 50 parts of above-mentioned precursor emulsion, products therefrom contains 20% oxyamination thing (100% transformation efficiency), is a system stable, that do not contain gel.

Embodiment 37

Press embodiment 14 an oxyamination of step preparation the droplet dispersion of polyacrylamide.The nonyl phenol demulsifier surfactant of ethoxylation is saved.By precipitation in methyl alcohol with the oxyamination of isolating dry powder polymkeric substance.Its oxyamination degree is the 17%(85% transformation efficiency).Soltion viscosity is 4.3mPa.s.

Embodiment 38-43

Except using: 38) MAPTAC ^*(25%); 39) styrene sulfonic acid (20%); 40) methacrylic acid (48%); 41) carboxymethyl cellulose ester (5%); 42) vinylformic acid and methacrylic acid are respectively (35%) (5%); With 43) methacrylic acid and sodium acrylate, be respectively (20%) (80%) (without acrylamide) and replace repeating the step of embodiment 20 outside the sulfonic acid.In each case, all generate oxyamination stable, that do not contain gel the polymer droplets dispersion.

*=the methyl chloride acrylamidopropyl trimethyl ammonium.

Claims

1, a kind of stable, the water-in-oil droplet dispersion that does not contain gel, comprise 1) one can prevent effectively that polymer micelle from the external phase and 2 of the hydrocarbon ils and the emulsifying agent of deleterious nodulizing taking place) one comprise molecular weight and be higher than about 1,000,000 oxyamination the micellar discontinuous phase of the aqueous solution of vinyl polymer.

2, water-in-oil droplet dispersion as claimed in claim 1 is characterized in that, polymkeric substance is an acrylamide polymer.

3, water-in-oil droplet dispersion as claimed in claim 2 is characterized in that, comprises 3) a kind of energy stabilization of polymer, prevent the stablizer of degrading and using owing to the existence of oxyamine.

4, water-in-oil droplet dispersion as claimed in claim 1 is characterized in that, the hydroxylamino content of polymkeric substance wherein, and the monomeric unit in the polymkeric substance is at least 5mol%.

5, water-in-oil droplet dispersion as claimed in claim 1 is characterized in that, it is from transforming.

6, water-in-oil droplet dispersion as claimed in claim 1 is characterized in that wherein the aqueous solution contains at least, is benchmark with the polymkeric substance, the excess base of about 5mol%.

7, water-in-oil droplet dispersion as claimed in claim 1 is characterized in that wherein the soltion viscosity of aqueous solutions of polymers is at least 2.0mPa.S.

8, water-in-oil droplet dispersion as claimed in claim 2 is characterized in that, wherein polymkeric substance is the multipolymer of acrylamide and at least a other comonomer.

9, water-in-oil droplet dispersion as claimed in claim 8 is characterized in that, described other comonomer is selected from by the chlorination dimethyldiallylammonium, the group that 2-acrylamido methyl propane sulfonic acid or its salt and (methyl) vinylformic acid or its salt constitute.

10, a kind of method of producing water-in-oil droplet dispersion as claimed in claim 1, comprise A) a kind of water in oil emulsion, this emulsion contains 1) external phase and 2 of deleterious nodulizing emulsifying agent takes place in a kind of hydrocarbon ils and a kind of polymer micelle that can prevent effectively) one comprise molecular weight and be higher than about 1,000,000 vinyl polymer aqueous solution micellar discontinuous phase is with B) oxyamine that neutralized and excessive alkali reacts.

11, method as claimed in claim 10 is characterized in that, polymkeric substance is an acrylamide polymer.

12, method as claimed in claim 11 is characterized in that, B) contains a kind of energy stabilization of polymer, prevents that the existence owing to oxyamine from the stablizer of Degradation taking place.

13, method as claimed in claim 10 is characterized in that, alkali is sodium hydroxide.

14, method as claimed in claim 11 is characterized in that, polymkeric substance is the multipolymer of acrylamide and at least a other comonomer.

15, method as claimed in claim 14 is characterized in that, described other comonomer is selected from by the chlorination dimethyldiallylammonium, the group that 2-acrylamido methyl propane sulfonic acid and salt thereof and (methyl) vinylformic acid and salt thereof constitute.

16, method as claimed in claim 10 is characterized in that, B) oxyamine of the neutralization in and alkali exist with emulsion form.

17, a kind of be pulverous oxyamination vinyl polymer.

18, powder as claimed in claim 17 is characterized in that, polymkeric substance is an acrylamide polymer.