CA1309795C - Water soluble polymers - Google Patents
Water soluble polymersInfo
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- CA1309795C CA1309795C CA000601181A CA601181A CA1309795C CA 1309795 C CA1309795 C CA 1309795C CA 000601181 A CA000601181 A CA 000601181A CA 601181 A CA601181 A CA 601181A CA 1309795 C CA1309795 C CA 1309795C
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Abstract
ABSTRACT
WATER SOLUBLE POLYMERS
A water soluble polymer containing acid groups can be fractionated into higher and lower molecular weight fractions by partial neutralisation of the polymer as a solution in a blend of water and a low molecular weight alcohol and separating the resultant aqueous and organic phases.
Pigment dispersions contain, as dispersing agent novel water soluble polymers containing acid groups, preferably polyacrylic acid or copolymers of polyacrylic acid with AMPS, having polydispersity below 1.5 and molecular weight in the range about 1,000 to about 5,000.
WATER SOLUBLE POLYMERS
A water soluble polymer containing acid groups can be fractionated into higher and lower molecular weight fractions by partial neutralisation of the polymer as a solution in a blend of water and a low molecular weight alcohol and separating the resultant aqueous and organic phases.
Pigment dispersions contain, as dispersing agent novel water soluble polymers containing acid groups, preferably polyacrylic acid or copolymers of polyacrylic acid with AMPS, having polydispersity below 1.5 and molecular weight in the range about 1,000 to about 5,000.
Description
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This application is a divisional of S.N. 454,568 filed 17 May 1984 and has claims directed to a dispersion of pigment, an aqueous dispersion point and a polymeric dispersing agent. The parent application contains claims directPd to a process of separating a water soluble polymer into higher and lower molecular weight fractions.
It is well known that low molecular weight water soluble polymers, and especially such polymers containing acidic groups that may have been partially or completely neutralised, are of value as pigment dispersants (including grinding aids). The pol~ers generally have a molecular weight (weight average molecular weight, Mw) of 1,000 to 10,000. However, the polymer will always consist of a blend of molecules of differing molecular weights, according to the number of momomeric units in each molecule. In practice, each commercial polymer is a mixture of molecules having a very wide variation in chain length. For instance a polymer having Mw = 5,000 will generally contain significant amounts of molecules of molecular weight below 1,000 and above 6,000. The extent to which any particular product is formed of molecules of a range of chain lengths is measured by its polydispersity. The polydispersity (PD) of a product is the weight average molecular weight (Mw) divided by the number average molecular weight (Nn). If PD = 1 then the polymer consists entirely of molecules of a single chain length. In practice PD is always much higher, generally above 2.
British Specification No. 1414964 describes certain vinyl acetate copolymers for dispersing chalk. In example 2, the polymers are described as having a number average molecular weight of 1,200 to 2,300 and fractional precipitation of the polymer is said to give fractions having number average molecular weight of 150 to 4,000. Slightly different process conditions in Example 3 are said to give a narrower molecular weight distribution and fractions of from 960 to 3,000. The range of molecular weight within each fraction is not quoted. The specification does not disclose the use or properties of 7 ~ ~
any of these fractions but it does attempt to show the poly~er of Example 3 (that is a blend of fractions having average molecular weights of 960 to 3,000) has better properties than the product of Example 2 and attributes S this to the ~effect o~ optimising the molecular weight distributionn. Since the polymers of Examples 2 and 3 could be split into polymer fractions having such a wide range of molecular weights, it is clear that the polymers of Examples 2 and 3 ~oth had high polydispersity values, probably of the order of 2. It is impossible to predict what the polydispersity values would have been of the polymer fractions, as this can vary according to the method of fractionisation, but it was probably in excess of 1.7. There is no suggestion to use the polymer lS fractions for any purpose.
The products that commercially are most successful as dispersants are polyacrylic acid and acrylic acid -2-acrylamido 2-methyl propane s^-tphonic acid (AMPS) copolymers. A widely used polyacrylic acid is our product Dispex N40 (Dispex is a trade mark). The products we sell generally have polydispersity values above 1.8 and indeed most products that are commercially available have polydispersity values above 2. We have regarded it as uneconomic and unnecessary to strive for lower polydispersity values and although batches of polymer having polydispersity slightly below 1.8 are sometimes made by us, during storage they always become blended with batches having higher polydispersity.
It is standard practice to make water soluble acidic polymers, such as polyacrylic ac-id, by solution polymerisation in which event the solvent may be a blend of water and an organic liquid such as isopropanol. The product of the polymerisation is a solution of polymer together with some oligomer and unreacted monomer~
One process that we have used for removing the unwanted low molecular weight components, i.e. the oligomers and monomer, has involved adding excess sodium hydroxide to the solution so as to neutralise all the acidic groups, and allowing the mixture to separate into an upper isopropanol fraction containing the unwanted low molecular weight components and a lower aqueous fraction containing the desired polymer. This fractionation has been regarded merely as a way of separating the useful polymer from the unwanted by-products. The useful polymer is a blend of molecules of various molecular weights and the PD values quoted above are of the purified polymer.
A particular process for separating unwanted by-products is described in European Patent Publication 46573. In this it is said that an aqueous solution of polyacrylic acid may be neutralised and that the neutralised polymerisate may then be treated in the usual way with polar solvents, methanol, ethanol, propanol, isopropanol, acetone and tetrahydrofuran being mentioned.
In the examples 80 grams fully neutralised sodium polyacrylate is fractionated in solution in 500 grams water with 400 grams methanol or 40 grams isopropanol.
In each instance the lighter, organic, phase is rejected.
This therefore seems to be a conventional fractionation to remove oligomers and the product would therefore be a conventional blend of molecular weights. If the starting polymer mixture is conventional the Mw, Mn and PD values of the extracted polymer will also be conventional, e.g.
PD above 1.8.
Certain ~ulphide, sulphone or sulphoxide terminated oligomers are described in US Patent Specifi~ation 3759860 for use as, for instance, emulsifiers. There is no suggestion that they should be used for dispersing pig~ents. It is said that they may have PD less than 2 ~and frequently as low as 1~4 to 1.5~. Apart from this disclosure, we are unaware of anyone ever having prop~sed the commercial use of low polydispersi~y water soluble polymers for any purpose and in particular there has been no suggestion that they would be of use in pigment dispersions. Indeed since it is much easier to make polymers having high PD values than low PD values the possibility of trying to make them on a commercial scale has probably never occurred to anyone previously as no one has ever previously recognised that there is any particular value in them.
Insoluble low molecular weight polymers having low polydispersity values are described in European Patent Specification 68887 but since such polymers are insoluble they cannot be used as pigment dispersants.
We have now found that low molecular weight water soluble polymeric dispersants have greatly improved pigment dispersing properties if the polymer has a much narrower range of molecular weight than has previously been used, that is to say if PD is reduced substantially below the conventional values of 1.8 and above to a value below 1.5. Thus we have found that for any particular purpose optLmum results are obtained if the polymer consists of lecules of very limited range of chain lengths. The presence of molecules of other chain lengths is disadvantageous for two reasons. First, and most important, these other molecules counteract the ~eneficial effects of the preferred molecules, presumably - because of preferential absorption of some other deleterious or antagonistic mechanism. Secondly, these other molecules dilute the polymer so tha~ it contains less than the theoretical maximum of the preferred molecules.
The present invention provides a new way of making polymers having improved properties, as well as particular uses of certain polymers. In the invention a ~ J ,~ ~
solution is formed in a blend of water and a polar solvent of a water soluble polymer containing neutralised acid groups and the ~olution is separa~ed into an aqueous phase containing a higher molecular weight fraction of the polymer and an organic phase containing a lower molecular weight fraction of the polymer, and in this process the polar solvent is a Cl to C5 alcohol, the acid groups are neutralised with cations selected from sodium, potassium, lithium and ammonium and the molar proportion of neutralised acid groups is 10 to 55~ when the cation is selected from sodium and potassium, 10 to 70~ when the cation is ammonium and 30 to 90~ when the cation is lithium.
The precise split between the lower and higher molecular weight fractions can be selected by altering the process conditions, and in particular the degree of neutralisation, and so the invention provides, for the first time, a simple process by which an acidic, water soluble, polymer can be fractionated into preselected molecular weight fractions. Unlike prior processes where the organic fraction is usually rejected, in the invention both fractions of polymer are commercially useful and so are recovered and used, the fraction in the organic phase being useful where lower molecular weights are desired and the fraction in the aqueous phase being useul where higher molecular weights are desired.
Additionally we have surprisingly found that the polymer in each fraction generally has at least one activity that is very much improved compared to the activity of the starting polymer. Of~en the polymer of one fraction has one type of greatly improved activity (for instance as a viscosifier) while the polymer in the other fraction may have a different type of greatly improved activity (for instance as a dispersant).
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The polymer in each fraction will have lower polydispersity (weight average molecular weight divided by number average molecular weight) than the starting polymer. For instance the initial value is almost always above 1.6, and often is above 2, but the fractions obtained in the invention often have values of below 1.5.
often 1.1 to 1.45 and most preferably 1.1 to 1.4.
Each of the polymer solutions can be used in the form in which it is obtained by phase separation, for instance simply by mixing the solution into the water or other liquor to be treated, or the polymer can be recovered from the solution by evaporation, precipitation or other conventional recovery techniques. The polymer in each of the separated solutions is generally in a partially neutralised state and can be acidified or fully neutralised in conventional manner if desired.
In the invention a dispersion of pigment in an aqueous medium contains a dispersing agent for the pigment which is a water soluble polymer formed from one or more ethylenically unsaturated monomers and contains acid groups selected from carboxyl and sulphonic groups, or is a water soluble salt thereof, and has a polydispersity of below 1.5 but at least l.1 and has a low molecular weight. Mw is normally at least about 1,ooo and can be up to about 6,000 but preferably it is up to about 5,000.
Particularly preferred products are those having PD below 1.4 and Mw 1,000 to 4,000.
Generally PD = 1.1 to 1.45 and in particular from l.l to 1.4. The best results are obtained with PD below 1.4 and preferably below 1.35. Although it is desirable for the value to be as close to 1 as possible but at least 1.1 it is generally preferred for it to be above 1.25.
The polymer is preferably acrylic acid or copolymer thereof with AMPS (2-acrylamido-2-methyl propane sulphonic acid). Throughout this specification it must ~ 3 be understood that any acid polymer can be present in the form of a partial or complete salt with an alkali metal, often sodium, or ammonia or an amine or other cation that yields a water soluble salt. For instance the polymer S may be a copolymer of acrylic acid with a salt of AMPS or it may be a complete salt of acrylic acid AMPS copolymer or a partial or complete salt of acrylic acid. All molecular weights herein are measured as the full sodium salt.
Although these are the preferred polymers, other water soluble polymers can be used in the invention, generally being polymers obtained by polymerisation of an ethylenically unsaturated monomer that contains acid groups either alone or with other ethylenically unsaturated monomeric material. Oligomers formed from the corresponding monomers may be used in place of the monomers. The acid groups are generally carboxylic acid or sulphonic acid groups. The monomers are often acrylic monomers and therefore preferred acidic monomers include one or more of methacrylic acid or, especially, acrylic acid or 2-acrylamido-2-methyl propane sulphonic acid, but a wide range of other polymerisable acidic monomers can be used, for instance maleic acid or vinyl sulphonic acid. Any comonomers that can be copolymerised, in the amounts present, with the acidic monomer or monomers to form a water soluble polymer can be used and include monomers such as acrylamide, acrylonitrile and acrylic esters. - Generally at least 50% by weight and often at least 80% by weight of the - 30 monomers from which the polymer is formed are acidic monomers. The polymer is generally a linear polymer.
Within the broad inventive concept defined above there are certain areas of particular value~
As mentioned above certain low molecular weight vinyl acetate copolymers are mentioned in British Specification ~ J~
No. 1414964 for dispersing pigments and as grinding dispe~sants for pigments. In practice however these have not made any significant commercial impact and the dispersants normally used are the low molecular weight polyacrylic acids havin~ PD generally above 1.8.
According to one aspect of the invention a disper~ion in water of a pigment includes, as dispersing agent, a polyacrylic acid having PD below 1.5 but at least 1.1 and Mw in the range about l,OOO to about 3,300, preferably 1,O00 to 3,000 and most preferably in the range about 1,800 to about 2,200, with best results generally being achieved at values of around 2,000. PD preferably is in the range 1.1 to 1.4, most preferably 1.1 to 1.3 or 1.35.
These dispersions can conveniently be made simply by blending particulate pigment with water in the presence of the dispersing agent, the amounts of pigment and dispersing agent being conventional. For instance the amount of dispersing agent is often from 0.05 to 0.3~ by weight dry polymer based on dry pigment. The amount of pigment is often from 10 to 90% by weight of the dispersion, most preferably 50 or 60 up to 80% by weight.
The pigment will be chosen having regard to the intended use of the dispersion. Often the dispersion is used in the paper industry, for instance for paper coating, and suitable pigments include china clay, talc, titanium dioxide and precipitated calcium carbonate. The particle size is generally in the range 0.5 to 100 microns, preferably 1 to 50 microns.
It is well recognised that there is a particular problem in making concentrated pigment dispersions by grinding calcium carbonate in water, particularly if very fine particle sizes are required. This is discussed in our European Patent Specification 108842 and in the literature to which that refers. We describe in that how sodium polyacrylate Mw 2,800 is conventionally used but 3~ S ~ J ~ !~
that improved results can be obtained using acrylic acid-AMPS copolymers, the best result (lowest viscosity) being shown at Mw around 5,700.
According to a second aspect of the invention a dispersion of calcium carbonate in water is made by grinding calcium carbonate in water in the presence of a dispersing agent that is a polyacrylic acid having PD
below 1.5 but at least 1.1 and Mw in the range about 2,500 to about 4,500, most preferably in the range 3,300 to 3,900.
According to a third aspect of the invention a dispersion of calcium carbonate in water is made by grinding calcium carbonate in water in the presence of a dispersing agent that is a copolymer of acrylic acid and AMPS having PD below 1.5 but at least 1.1 and Mw in the range about 1,500 to about 3,500, most preferably about 2,250 to about 2,750.
The preferred molecular weight for the homopolymer is about 3,600 and the preferred molecular weight for the copolymer is about 2,500. The proportions by weight of acrylic acid to AMPS are preferably 99:1 to~50:50.
When grinding calcium carbonate in accordance with either of these aspects of the invention PD is preferably from 1.1 to 1.4, most preferably 1.1 to 1.3.
The grinding is preferably by sand grinding and the -resultant particle size of the calcium carbonate (marble)is preferably mainly below 2 microns. The amount of pigment in the resultant dispersion is preferably above 70% and most preferably is above 75%. For more description of suitable grinding techniques, particle sizes and concentrations reference should be made to European Patent Publication 108842 and to the literature referred to therein.
In US Patent Specification 3840487 and in British Patent Specification 1505555 various aqueous dispersion paints comprising of pigment and a low molecular weight ~ ~ 3 J '~
polymeric dispersing agent are described. For the purposes described in those specifications particular polyacrylic acid-ester copolymers are used but in many other instances polyacrylic acid homopolymer, and in particular Dispex N40 is generally regarded as entirely satisfactory. We now find better results are obtained using the novel polymer defined herein. In particular, according to a fourth aspect of the invention an aqueous dispersion paint comprises a pigment, a binder for the paint and a dispersing agent for the pigment, the dispersing agent being polyacrylic acid having PD below 1.5 but at least 1.1 and Mw in the range about 1,500 to about 6,000. PD is preferably from 1.1 to 1.4, most preferably 1.1 to 1.3 and the molecular weight is preferably in the range 1,500 to 4,500. The aqueous medium of the paint may be water or a mixture of water with a polar solvent, generally a glycol.
The pigment generally is titanium dioxide, china clay, or calcium carbonate and generally has a particle size of 0.1 to 50 microns, preferably 0.2 to 25 microns.
The amount of pigment in the paint may be conventional, typically from 5 to 50% by weight of the paint. The binders and other components in the paint may be conventi~nal, for instance as described in US Patent Specification 3840487 and British 1505555.
The low polydispersity values required in the invention can be obtained by various techniques. For instance, a polymer can be made by a conventional polymerisation technique, for instance, solution polymerisation, to obtain a product having a high polydispersity value (typically 2 or higher) and may then be subjected to careful fractional precipitation so as to obtain fractions each having a polydispersity below 1.5.
The conditions for conducting the fractional precipitation must be such as to give this low ~ ;~ u~
polydispersity and so must consist of isothermal non ~olvent addition as detailed in Chapter Bl of ~Polymer Fractionation" Ed. Manfred Cantow.
Another way of obtaining the desired polymer is to conduct its synthesis under conditions that lead to its formation. For instance the polymer may be made by solution polymerisation in the presence of isopropanol as chain regulator. The process must be carried out under very uniform and closely monitored conditions, for instance controlled feeds of monomer, and initiator and uniform temperature throughout. If the product that is obtained has a polydispersity above the desired value it must be rejected or treated in such a manner as to reduce its polydispersity.
Another way of obtaining the desired polymer is to make an insoluble acrylate polymer having the desired PD
and Mw values, for instance as described in Example 40 of European Patent Specification 6~887 and then to hydrolyse the acrylate to the free acid, for instance by reaction with sodium hydroxide at 85C for 6 hours or as long as is necessary to achieve hydrolysis, the reaction generally being conducted in the presence of methanol as a diluent.
The preferred method is the method described above.
This may be conducted on any of the polymers discussed above.
The average molecular weight of the polymer that is to be fractionated can vary widely provided the value is not so high that the polymer is insoluble. Generally it is 500 to 1 million and ~he most valuable advantages are found when the average molecular weight is below 100,000, generally below 30,000 and especially between 1,000 and 10,000 for instance around 1,500 to 4,500.
The polymer may have been made by any conventional pol~merisation process and may have then been isolated, for instance as a solid, from any liquid phase in which it was formed, and then redissolved in the aqueous organic alkaline solution used in the invention.
Generally however the process of the invention is S conducted on a solution of the polymer obtained by solution polymerisation of the appropriate monomers.
The preferred solution polymerisation medium is an aqueous solution containing appropriate initiators or other polymerisation promotors, for instance water soluble peroxides and persulphates, or redox catalysts or catalysts for photopolymerisation and will generally include an organic solvent, for instance as a molecular weight regulator. Other known molecular weight regulators may be included in the solution if desired.
When the solution of polymer is made by polymerisation in a mixture of water and organic solvent this organic solvent may serve as the organic liquid for use in the invention. A very common solvent in solution polymerisations is isopropanol and blends of water and isopropanol are suitable for many processes accor~ing to the invention.
Irrespective of whether the solution is made by blending preformed polymer, water, organic solvent and alkali or by adding alkali to the reaction product of polymerisation in aqueous organic liquid, or in any other manner, the process of the invention requires that phase separation should be brought about between aqueous and organic phase in the presence of the ~pecified solvents and the specified amounts of the specified cations. If other solve~nts, other cations or other amounts of the specified cations are used the process generally will not give the variable fractionation of the invention but instead will either give no useful results or will merely strip oligomer and monomer from the product. For instance it is not possible to select the degree of ,~ C~ f ~ 3 ~
fractionation if the organic solvent is acetone or tetrahydrofuran or if the cation is provided by an amine such as ethylamine.
The degree of neutralisation of the acid groups controls the fractionation. ~he results obtained in any particular process will depend upon, inter alia, the concentrations, the polymer type and the solvent but there is a minimum degree of neutralisation below which substantially no fractionation occurs and the system may instead remain as a homogeneous solution. When the cation is sodium, potassium or lithium the degree of neutralisation will normally be at least 10%, often at least 15% and preferably at least 25% whilst if the cation is lithium the degree of neutralisation will normally have to be at least about 30%, preferably at least 40% and generally at least 50~. If the degree of neutralisation is too high the size of the lower molecular weight fraction is unacceptably low. When the cation is sodium or potassium the degree of neutralisation will normally be below 55%, preferably below 50~ and most preferably below 40%. When the cation is ammonium the degree of neutralisation will normally be below 70~, preferably below 60% and most prefera~ly below 50~ When the cation is lithium the degree of neutralisation will normally be below 90%, and preferably below 70%.
In any particular process the size of, for instance, the higher molecular weight fraction can be increased (with consequential reduction in its average molecular wei~ht and consequential reduction in the size and the average molecular weight of the lower molecular weight fraction) by increasing the amount of alkali and conversely the size of the low molecular weight fractivn can be increased by reducing ~he amount of alkali.
The process conditions are preferably selected such that each fraction contains from 20 to 80%, and most preferably 30 to 70%, by weight of the starting polymer.
The partial neutralisation of the acidic polymer is normally achieved by adding a compound that will provide the chose~ cation, the compound usually being a hydroxide, in the selectea amount to the dissolved polymer. Mixtures of two or more of the four cations may be utilised, in which event the proportions will be selected such that they have the same effect as the amounts specified for the individual cations.
For any particular polymer, the degree of fractionation is dependent not only on the degree of neutralisation and the type of cation but also upon the concentration of the polymer and the choice and amount of the alcohol. The alcohol is preferably isopropanol but propanol and other alcohols, especially C2 to C5 alcohols, may be used. The proportion water:alcohol by weight is preferably from 1:0.2 to 1:5, most preferably 1:0.5 to 1:2 with best results generally being achieved, especially when the alcohol is isopropanol and the cation is sodium, when the proportion is about 1:1. The proportions should be selected such that, having regard to the degree and nature of neutralisation, each of the phases will have a polymer concentration of at least 5%, generally at least 10% and preferably at least 15% by weight of the phase.
The amount of the polymer (measured as the acid polymer) is normaliy at least 5% by weight based on the 3Q weight of polymer, alcohol and water (including wa~er introduced with the alkali) and preferably is at least 10~. The concentration must not be so high that the system is so viscous that mixing and phase separation is significantly impeded and so is generally below 30%.
Preferably the concentration is 15 to 25~ by weight.
The phase separation may also be affected by the temperature at which the process is conducted. This may be between 15 and 80C but preferahly is between 30 and 70C.
The process may be conducted by combining the essential components of the solution in any convenient manner, for instance by adding aqueous alkali to the aqueous organic reaction product obtained by polymerisation of the monomer or monomers in aqueous organic solution. The process may be conducted continuously or batchwise. Depending upon the degree of neutralisation, and type and strength of base, the concentration of the polymer, the amount of solvent and the temperature the phase separation may occur rapidly or slowly. For instance it may occur substantially instantaneously or it may be necessary to leave the system to stand for periods of, for instance, S minutes to 2 hours, typically 30 minutes to I hour. The separation may be conducted batchwise or continuously, with the mix being fed through a conventional separation column or separation reactor.
The two phases are kept separate, may be fully neutralised with the same or different alkali and organic solvent may be stripped from the organic phase by distillation.
Each of the polymer fractions is recovered for subsequent commercial use.
The very low molecular weight fractions obtained by this technique have a particular value as agents for inhibiting the build-up of ~scale, and settlement of scale, and in particular as desalination aids. For instance we have established that the maxLmum level of alkalinity that can be maintained in solution is increased if PD is reduced. Thus best results are L ~ ii d ~ .~
achieved if Mw is from 350 to 1,000 and PD is below 1.5, most preferably 1.05 to 1.3.
In the following examples, Example 1 demonstrates how a polymer may he made to the desired PD and ~w values ~y careful polymerisation, and Examples 2 and 3 demonstrate how the polymer may be obtained by partial neutralisation and fractionation.
To a 700 cm3 resin pot equipped with thermometer, stirrer and external heating, three separate mixtures were continuously added over a 6 hour period.
Feed 1 consisted of: 340 g glacial acrylic acid in 226 g water Feed 2 10.5 g 100 vol. hydrogen peroxide and 57.1 g water Feed 3 28 g thioglycollic acid and 38.6 g water.
The pot contents were maintained at reflux temperature throughout the addition and then for a further hour before being cooled. The percentage unpolymerised acrylic acid was determined by Gas Liquid Chromatrography and shown to be 0.3% of the amount added.
The remaining polymer was fully neutralised by the addition of 46.6% sodium hydroxide and the final product diluted to give a 40% w/w sodium polyacrylate solution.
The viscosity of the product at 25% was 12.1 cS
(suspended level viscometer, No. 2, 25C). GPC analysis showed Mw = 1740, Mn = 1321, Polydispersity = 1.32.
A 23~ by weight solution of polyacrylic acid in a bl~nd of equal parts by weight isopropanol and water was prepared by pol~merisation of acrylic acid using ammonium persulphate as initiator, in conventional manner~
Samples of the product were extracted while other sa~ples were neutralised by the addition of varying amounts of J~3 sodium hydroxide, introduced as a 46% by weight aqueous ~olution. Each of the sa~ples, after the addition of sodium hydroxide, was allowea to stand for sufficient time for an aqueous phase to separate from an organic phase (that probably contained some water) and these phases were then separated from one another in conventional manner. Each phase was then fully neutralised with sodium hydroxide and the residual alcohol was removed by distillation. The yield of polymer in each of the phases was recorded.
A 20~ solution of polyacrylic a~id having Mw of 3131 and PD ~polydispersity) of 1.677 was dissolved in 50/50 w/w isopropanol/water was neutralised with various basic compounds and the two layers separated. The amount and molecular weight of the polymer in each layer was determined. The results are shown in Table 1.
TABLE l A~x~us layer o~nic layer nase % ~ %
Neutr~l;sation Extra ~ d~ Mw P.D. Extrac~ MW P.D.
NaQH 25 75.2 3833 1.30 24.8 1452 1.402 2 NH4oH 25 55.6 4025 1.30 44.4 1689 1.34 S LioH 25 NO.~PA~CN
lioH So 50.2 3957 1.427 49.8 1783 1.44 ROH 25 63.5 3649 1.56 36.5 1402 1.49 Nao~ 15 20.6 3976 1.49 - ~9.4 2027 1.63 ~ NaoH 50 95.7 3688 1.51 4.3 Vey low -- 30NaOH 75 99.3 3376-1.53- 0.7 Very low _XAMPLE 4 The products obtained in Example 2 were adjusted to 40~ active solids and compared as marble grinding aids as 1~
describea in Example 11 of sritish Patent Specification No. 1,414,964. The results are set out in Table 2.
5 P~xxn ~~~- - Yield PenY~t ~q~us Layer Neut~isat~ o~ c Aq~x~s MiL~ index 0* 0.25 87.2 12.8 79.3 20.7 23.1 76.9 1.94 4.0 96.0 2.33 0.7 99.3 1.22 100 0.5 99.5 0.37 *This product is made in conventional manner by full neutralisation followed by removal of the organic phase by distillation, and so there is no fractionation.
In the described test a milling index value of around 0.5 is generally satisfactory as it indicates commercially acceptable properties for preventing gelation of the marble dispersion.
It is apparent from the table that after full neutralisation almost all the polymer is in the aqueous phase but that substantial amounts of polymer go into the organic phase at low degrees of neutralisation. It is also very notable that the milling index is greatly improved even when the amount of polymer that is in the organic phase, instead of the aqueous phase, is quite low. For instance at 50% neutralisàtion the amount of polymer in the organic phase is low but the milling index is about 5 times what would be considered to be commercially adequate. At higher degress of neutralisat~on only a very low amount of poly~er goes into the organic phase.
.
A polymer was prepared by conventional polymerisation technique as a 23% solution of acrylic acid in equal amounts of isopropanol and water was neutralised to 25%
S with aqueous sodium hydroxide after polymerisation. This caused the reaction mixture to separate into two phases.
These were ~eparated and the poly~er present in such phase was recovered after removal of the isopropanol by distillation. The samples were fully neutralised with sodium hydroxide solution and adjusted to 40% active as sodium polyacrylate.
An unfractionated control polymer was also prepared from the original unneutralised polymer in isopropanol/water by removing the isopropanol by distillation and fully neutralising with sodium hydroxide and adjusting to 40~ active as sodium polyacrylate.
The products were evaluated as dispersants for titanium dioxide, having particle size 97% below 2 ~m, at 75% w/w slurry solids content by recording the slurry viscosity (cP) at 0.6, 0.8 and 1~ dry polymer based on dry pigment. The results are given in Table 3.
Neu~x~isa- ~__ PD Slurry Visoosity (cP) 25tion % l0.60.8 1.0 100 CbntDDl 3161 2019 1.565 _ 1320 1380 ph~æ 4236 2795 1.515 _ - } 26~0 30 ` ~ ic 1795 1367 1 314 3500 700 340 - Samples of narrow polydispersity sodium polyacrylates of aecreasing molecular weight were evaluated as ~ 3 ~ vi ~
dispersant for china clay at 64% w/w slurry solids content at p~ 6.8-7~0 and at various dosages, as in Example 4. The result~ are gi~en in Table 4 __ , Mw Mn El) Slurry vi~;oositY (cl?l 0.10 0.12 O.U 0.16 0.16 0.20 0.2 5543 4817 1.15 _ _ 1567 359 2gO 321 376 487~ 3907 1.25 _ 1483 643 285 296 330 405 4447 3592 1.24 _ 933 423 255 269 312 361 4053 3273 1.24 _ 703 263 225 249 284 _ 3202 2709 1.18 _ 234 198 211 233 271 _ 2144 1901 1.13 533 183 190 207 231 266 _ ~065 934 1.28 637 226 196 201 213 230 _ The results show that the most effective sodium polyacrylates for china clay dispersants lie between a molecular weight of 1000-3000. Preference been given to a molecular weight of approximately 2000.
EXAMæLE 7 Foue samples of sodium eolyacrylate of similar molecular weigh~ but varying eolydiseersity were evaluated as marble millinq aids. -Each of the molecular weights tand all the other molecularweights quoted herein) were determined by GPC (gel eermea~ion chromotoqraehy). It involves permeation of the polyme~ under test 'through a GPC column (Ultcagel~AcA 54, 5cm diameter and 31cm length) when being eluted with O.lM sodium chloride at 3ml/min at a temperature of 30C. the eluate being analysed with a W
detector. The column will 2reviously have been calibrated betwee~
upper and lower molecular weights by use of fractions of a polymer of the same chemical tyee (i.e., ~olyacrylic acid) but in w~ich ~ T~Q~ee~ k ~ ~ lv ~
, each fraction is a laboratory reagent grade of that eolymer having a different molecular weight. The uppe~ and lower limits of the calibration range are defined by markers of known molecular weight, ~or instance 10,000 at the upper end and below 1.900 at the lower end.
Mw and Mn values foc each polymer that is being tested can thus be determined in conventional manner and PD can then be calculated as described above. The results expre~sed as Milling Index using a test method as described in Example llo British Patent No. 1,414,964 are shown in Table 5.
Mw PD Milling Index 3225 1.38 2.54 3105 1.52 1~23 3229 1.63 0.29 3358 2.01 <0.20 The results show that the effectiveness of sodium polyacrylate on marble milling is dependent on polydispersity. The lower the polydispersity the more effective the product.
It can be shown that the interrelationship between molecular weight and polydispersity of a sodium AMPS/sodium acrylate l20/80 w/w) copolymer has a crucial effect when the product is evaluated as a marble grinding aid according to Example 11 of. British Patent Specification No. . 1,414,964. The interrelationship between these parameters is shown in Table 6.
; ri ~
g .
I~w m:~leal~arweigllt lawpoly~i~ersity 2351 1.26 2.6 2630 1.34 2.4 Low mDleo~rweight high polydispersity 2834 1.6 0.38 3151 1.55 0.44 High m~l~o~rweight low polyd~xrsity 7193 -1.40 0.67 4625 1.47 0.81 High m~ lar weight high polydispersity 6265 1.64 0.64 ~836 1.53 0.77 _ The results show that polymers of low molecular weight with narrow polydispersity are the most effective marble grinding aids. The optimum molecular-weight lies between 1500 and 3500 with preference given to polymers with a molecular weight of 2500.
Samples of sodium polyacrylate of similar molecular weight but varying polydispersity were evaluated as in Example 4 as dispersants for precipitated calcium carbonate at 70% w~w slurry solids content. The results are given in Table 7.
TABL~E 7 . _ _ . ' Mw PD _Bnx~ield Visoosity ~ O lSO 0.175 0.200 0.~25 0.250 0.275 0.300 _ 3æ~ 1.38 117114 ~ 130 177 114 107 1n4 3105 1.52 120 134 167 D8 164 130 127
This application is a divisional of S.N. 454,568 filed 17 May 1984 and has claims directed to a dispersion of pigment, an aqueous dispersion point and a polymeric dispersing agent. The parent application contains claims directPd to a process of separating a water soluble polymer into higher and lower molecular weight fractions.
It is well known that low molecular weight water soluble polymers, and especially such polymers containing acidic groups that may have been partially or completely neutralised, are of value as pigment dispersants (including grinding aids). The pol~ers generally have a molecular weight (weight average molecular weight, Mw) of 1,000 to 10,000. However, the polymer will always consist of a blend of molecules of differing molecular weights, according to the number of momomeric units in each molecule. In practice, each commercial polymer is a mixture of molecules having a very wide variation in chain length. For instance a polymer having Mw = 5,000 will generally contain significant amounts of molecules of molecular weight below 1,000 and above 6,000. The extent to which any particular product is formed of molecules of a range of chain lengths is measured by its polydispersity. The polydispersity (PD) of a product is the weight average molecular weight (Mw) divided by the number average molecular weight (Nn). If PD = 1 then the polymer consists entirely of molecules of a single chain length. In practice PD is always much higher, generally above 2.
British Specification No. 1414964 describes certain vinyl acetate copolymers for dispersing chalk. In example 2, the polymers are described as having a number average molecular weight of 1,200 to 2,300 and fractional precipitation of the polymer is said to give fractions having number average molecular weight of 150 to 4,000. Slightly different process conditions in Example 3 are said to give a narrower molecular weight distribution and fractions of from 960 to 3,000. The range of molecular weight within each fraction is not quoted. The specification does not disclose the use or properties of 7 ~ ~
any of these fractions but it does attempt to show the poly~er of Example 3 (that is a blend of fractions having average molecular weights of 960 to 3,000) has better properties than the product of Example 2 and attributes S this to the ~effect o~ optimising the molecular weight distributionn. Since the polymers of Examples 2 and 3 could be split into polymer fractions having such a wide range of molecular weights, it is clear that the polymers of Examples 2 and 3 ~oth had high polydispersity values, probably of the order of 2. It is impossible to predict what the polydispersity values would have been of the polymer fractions, as this can vary according to the method of fractionisation, but it was probably in excess of 1.7. There is no suggestion to use the polymer lS fractions for any purpose.
The products that commercially are most successful as dispersants are polyacrylic acid and acrylic acid -2-acrylamido 2-methyl propane s^-tphonic acid (AMPS) copolymers. A widely used polyacrylic acid is our product Dispex N40 (Dispex is a trade mark). The products we sell generally have polydispersity values above 1.8 and indeed most products that are commercially available have polydispersity values above 2. We have regarded it as uneconomic and unnecessary to strive for lower polydispersity values and although batches of polymer having polydispersity slightly below 1.8 are sometimes made by us, during storage they always become blended with batches having higher polydispersity.
It is standard practice to make water soluble acidic polymers, such as polyacrylic ac-id, by solution polymerisation in which event the solvent may be a blend of water and an organic liquid such as isopropanol. The product of the polymerisation is a solution of polymer together with some oligomer and unreacted monomer~
One process that we have used for removing the unwanted low molecular weight components, i.e. the oligomers and monomer, has involved adding excess sodium hydroxide to the solution so as to neutralise all the acidic groups, and allowing the mixture to separate into an upper isopropanol fraction containing the unwanted low molecular weight components and a lower aqueous fraction containing the desired polymer. This fractionation has been regarded merely as a way of separating the useful polymer from the unwanted by-products. The useful polymer is a blend of molecules of various molecular weights and the PD values quoted above are of the purified polymer.
A particular process for separating unwanted by-products is described in European Patent Publication 46573. In this it is said that an aqueous solution of polyacrylic acid may be neutralised and that the neutralised polymerisate may then be treated in the usual way with polar solvents, methanol, ethanol, propanol, isopropanol, acetone and tetrahydrofuran being mentioned.
In the examples 80 grams fully neutralised sodium polyacrylate is fractionated in solution in 500 grams water with 400 grams methanol or 40 grams isopropanol.
In each instance the lighter, organic, phase is rejected.
This therefore seems to be a conventional fractionation to remove oligomers and the product would therefore be a conventional blend of molecular weights. If the starting polymer mixture is conventional the Mw, Mn and PD values of the extracted polymer will also be conventional, e.g.
PD above 1.8.
Certain ~ulphide, sulphone or sulphoxide terminated oligomers are described in US Patent Specifi~ation 3759860 for use as, for instance, emulsifiers. There is no suggestion that they should be used for dispersing pig~ents. It is said that they may have PD less than 2 ~and frequently as low as 1~4 to 1.5~. Apart from this disclosure, we are unaware of anyone ever having prop~sed the commercial use of low polydispersi~y water soluble polymers for any purpose and in particular there has been no suggestion that they would be of use in pigment dispersions. Indeed since it is much easier to make polymers having high PD values than low PD values the possibility of trying to make them on a commercial scale has probably never occurred to anyone previously as no one has ever previously recognised that there is any particular value in them.
Insoluble low molecular weight polymers having low polydispersity values are described in European Patent Specification 68887 but since such polymers are insoluble they cannot be used as pigment dispersants.
We have now found that low molecular weight water soluble polymeric dispersants have greatly improved pigment dispersing properties if the polymer has a much narrower range of molecular weight than has previously been used, that is to say if PD is reduced substantially below the conventional values of 1.8 and above to a value below 1.5. Thus we have found that for any particular purpose optLmum results are obtained if the polymer consists of lecules of very limited range of chain lengths. The presence of molecules of other chain lengths is disadvantageous for two reasons. First, and most important, these other molecules counteract the ~eneficial effects of the preferred molecules, presumably - because of preferential absorption of some other deleterious or antagonistic mechanism. Secondly, these other molecules dilute the polymer so tha~ it contains less than the theoretical maximum of the preferred molecules.
The present invention provides a new way of making polymers having improved properties, as well as particular uses of certain polymers. In the invention a ~ J ,~ ~
solution is formed in a blend of water and a polar solvent of a water soluble polymer containing neutralised acid groups and the ~olution is separa~ed into an aqueous phase containing a higher molecular weight fraction of the polymer and an organic phase containing a lower molecular weight fraction of the polymer, and in this process the polar solvent is a Cl to C5 alcohol, the acid groups are neutralised with cations selected from sodium, potassium, lithium and ammonium and the molar proportion of neutralised acid groups is 10 to 55~ when the cation is selected from sodium and potassium, 10 to 70~ when the cation is ammonium and 30 to 90~ when the cation is lithium.
The precise split between the lower and higher molecular weight fractions can be selected by altering the process conditions, and in particular the degree of neutralisation, and so the invention provides, for the first time, a simple process by which an acidic, water soluble, polymer can be fractionated into preselected molecular weight fractions. Unlike prior processes where the organic fraction is usually rejected, in the invention both fractions of polymer are commercially useful and so are recovered and used, the fraction in the organic phase being useful where lower molecular weights are desired and the fraction in the aqueous phase being useul where higher molecular weights are desired.
Additionally we have surprisingly found that the polymer in each fraction generally has at least one activity that is very much improved compared to the activity of the starting polymer. Of~en the polymer of one fraction has one type of greatly improved activity (for instance as a viscosifier) while the polymer in the other fraction may have a different type of greatly improved activity (for instance as a dispersant).
~ JJ~ I
The polymer in each fraction will have lower polydispersity (weight average molecular weight divided by number average molecular weight) than the starting polymer. For instance the initial value is almost always above 1.6, and often is above 2, but the fractions obtained in the invention often have values of below 1.5.
often 1.1 to 1.45 and most preferably 1.1 to 1.4.
Each of the polymer solutions can be used in the form in which it is obtained by phase separation, for instance simply by mixing the solution into the water or other liquor to be treated, or the polymer can be recovered from the solution by evaporation, precipitation or other conventional recovery techniques. The polymer in each of the separated solutions is generally in a partially neutralised state and can be acidified or fully neutralised in conventional manner if desired.
In the invention a dispersion of pigment in an aqueous medium contains a dispersing agent for the pigment which is a water soluble polymer formed from one or more ethylenically unsaturated monomers and contains acid groups selected from carboxyl and sulphonic groups, or is a water soluble salt thereof, and has a polydispersity of below 1.5 but at least l.1 and has a low molecular weight. Mw is normally at least about 1,ooo and can be up to about 6,000 but preferably it is up to about 5,000.
Particularly preferred products are those having PD below 1.4 and Mw 1,000 to 4,000.
Generally PD = 1.1 to 1.45 and in particular from l.l to 1.4. The best results are obtained with PD below 1.4 and preferably below 1.35. Although it is desirable for the value to be as close to 1 as possible but at least 1.1 it is generally preferred for it to be above 1.25.
The polymer is preferably acrylic acid or copolymer thereof with AMPS (2-acrylamido-2-methyl propane sulphonic acid). Throughout this specification it must ~ 3 be understood that any acid polymer can be present in the form of a partial or complete salt with an alkali metal, often sodium, or ammonia or an amine or other cation that yields a water soluble salt. For instance the polymer S may be a copolymer of acrylic acid with a salt of AMPS or it may be a complete salt of acrylic acid AMPS copolymer or a partial or complete salt of acrylic acid. All molecular weights herein are measured as the full sodium salt.
Although these are the preferred polymers, other water soluble polymers can be used in the invention, generally being polymers obtained by polymerisation of an ethylenically unsaturated monomer that contains acid groups either alone or with other ethylenically unsaturated monomeric material. Oligomers formed from the corresponding monomers may be used in place of the monomers. The acid groups are generally carboxylic acid or sulphonic acid groups. The monomers are often acrylic monomers and therefore preferred acidic monomers include one or more of methacrylic acid or, especially, acrylic acid or 2-acrylamido-2-methyl propane sulphonic acid, but a wide range of other polymerisable acidic monomers can be used, for instance maleic acid or vinyl sulphonic acid. Any comonomers that can be copolymerised, in the amounts present, with the acidic monomer or monomers to form a water soluble polymer can be used and include monomers such as acrylamide, acrylonitrile and acrylic esters. - Generally at least 50% by weight and often at least 80% by weight of the - 30 monomers from which the polymer is formed are acidic monomers. The polymer is generally a linear polymer.
Within the broad inventive concept defined above there are certain areas of particular value~
As mentioned above certain low molecular weight vinyl acetate copolymers are mentioned in British Specification ~ J~
No. 1414964 for dispersing pigments and as grinding dispe~sants for pigments. In practice however these have not made any significant commercial impact and the dispersants normally used are the low molecular weight polyacrylic acids havin~ PD generally above 1.8.
According to one aspect of the invention a disper~ion in water of a pigment includes, as dispersing agent, a polyacrylic acid having PD below 1.5 but at least 1.1 and Mw in the range about l,OOO to about 3,300, preferably 1,O00 to 3,000 and most preferably in the range about 1,800 to about 2,200, with best results generally being achieved at values of around 2,000. PD preferably is in the range 1.1 to 1.4, most preferably 1.1 to 1.3 or 1.35.
These dispersions can conveniently be made simply by blending particulate pigment with water in the presence of the dispersing agent, the amounts of pigment and dispersing agent being conventional. For instance the amount of dispersing agent is often from 0.05 to 0.3~ by weight dry polymer based on dry pigment. The amount of pigment is often from 10 to 90% by weight of the dispersion, most preferably 50 or 60 up to 80% by weight.
The pigment will be chosen having regard to the intended use of the dispersion. Often the dispersion is used in the paper industry, for instance for paper coating, and suitable pigments include china clay, talc, titanium dioxide and precipitated calcium carbonate. The particle size is generally in the range 0.5 to 100 microns, preferably 1 to 50 microns.
It is well recognised that there is a particular problem in making concentrated pigment dispersions by grinding calcium carbonate in water, particularly if very fine particle sizes are required. This is discussed in our European Patent Specification 108842 and in the literature to which that refers. We describe in that how sodium polyacrylate Mw 2,800 is conventionally used but 3~ S ~ J ~ !~
that improved results can be obtained using acrylic acid-AMPS copolymers, the best result (lowest viscosity) being shown at Mw around 5,700.
According to a second aspect of the invention a dispersion of calcium carbonate in water is made by grinding calcium carbonate in water in the presence of a dispersing agent that is a polyacrylic acid having PD
below 1.5 but at least 1.1 and Mw in the range about 2,500 to about 4,500, most preferably in the range 3,300 to 3,900.
According to a third aspect of the invention a dispersion of calcium carbonate in water is made by grinding calcium carbonate in water in the presence of a dispersing agent that is a copolymer of acrylic acid and AMPS having PD below 1.5 but at least 1.1 and Mw in the range about 1,500 to about 3,500, most preferably about 2,250 to about 2,750.
The preferred molecular weight for the homopolymer is about 3,600 and the preferred molecular weight for the copolymer is about 2,500. The proportions by weight of acrylic acid to AMPS are preferably 99:1 to~50:50.
When grinding calcium carbonate in accordance with either of these aspects of the invention PD is preferably from 1.1 to 1.4, most preferably 1.1 to 1.3.
The grinding is preferably by sand grinding and the -resultant particle size of the calcium carbonate (marble)is preferably mainly below 2 microns. The amount of pigment in the resultant dispersion is preferably above 70% and most preferably is above 75%. For more description of suitable grinding techniques, particle sizes and concentrations reference should be made to European Patent Publication 108842 and to the literature referred to therein.
In US Patent Specification 3840487 and in British Patent Specification 1505555 various aqueous dispersion paints comprising of pigment and a low molecular weight ~ ~ 3 J '~
polymeric dispersing agent are described. For the purposes described in those specifications particular polyacrylic acid-ester copolymers are used but in many other instances polyacrylic acid homopolymer, and in particular Dispex N40 is generally regarded as entirely satisfactory. We now find better results are obtained using the novel polymer defined herein. In particular, according to a fourth aspect of the invention an aqueous dispersion paint comprises a pigment, a binder for the paint and a dispersing agent for the pigment, the dispersing agent being polyacrylic acid having PD below 1.5 but at least 1.1 and Mw in the range about 1,500 to about 6,000. PD is preferably from 1.1 to 1.4, most preferably 1.1 to 1.3 and the molecular weight is preferably in the range 1,500 to 4,500. The aqueous medium of the paint may be water or a mixture of water with a polar solvent, generally a glycol.
The pigment generally is titanium dioxide, china clay, or calcium carbonate and generally has a particle size of 0.1 to 50 microns, preferably 0.2 to 25 microns.
The amount of pigment in the paint may be conventional, typically from 5 to 50% by weight of the paint. The binders and other components in the paint may be conventi~nal, for instance as described in US Patent Specification 3840487 and British 1505555.
The low polydispersity values required in the invention can be obtained by various techniques. For instance, a polymer can be made by a conventional polymerisation technique, for instance, solution polymerisation, to obtain a product having a high polydispersity value (typically 2 or higher) and may then be subjected to careful fractional precipitation so as to obtain fractions each having a polydispersity below 1.5.
The conditions for conducting the fractional precipitation must be such as to give this low ~ ;~ u~
polydispersity and so must consist of isothermal non ~olvent addition as detailed in Chapter Bl of ~Polymer Fractionation" Ed. Manfred Cantow.
Another way of obtaining the desired polymer is to conduct its synthesis under conditions that lead to its formation. For instance the polymer may be made by solution polymerisation in the presence of isopropanol as chain regulator. The process must be carried out under very uniform and closely monitored conditions, for instance controlled feeds of monomer, and initiator and uniform temperature throughout. If the product that is obtained has a polydispersity above the desired value it must be rejected or treated in such a manner as to reduce its polydispersity.
Another way of obtaining the desired polymer is to make an insoluble acrylate polymer having the desired PD
and Mw values, for instance as described in Example 40 of European Patent Specification 6~887 and then to hydrolyse the acrylate to the free acid, for instance by reaction with sodium hydroxide at 85C for 6 hours or as long as is necessary to achieve hydrolysis, the reaction generally being conducted in the presence of methanol as a diluent.
The preferred method is the method described above.
This may be conducted on any of the polymers discussed above.
The average molecular weight of the polymer that is to be fractionated can vary widely provided the value is not so high that the polymer is insoluble. Generally it is 500 to 1 million and ~he most valuable advantages are found when the average molecular weight is below 100,000, generally below 30,000 and especially between 1,000 and 10,000 for instance around 1,500 to 4,500.
The polymer may have been made by any conventional pol~merisation process and may have then been isolated, for instance as a solid, from any liquid phase in which it was formed, and then redissolved in the aqueous organic alkaline solution used in the invention.
Generally however the process of the invention is S conducted on a solution of the polymer obtained by solution polymerisation of the appropriate monomers.
The preferred solution polymerisation medium is an aqueous solution containing appropriate initiators or other polymerisation promotors, for instance water soluble peroxides and persulphates, or redox catalysts or catalysts for photopolymerisation and will generally include an organic solvent, for instance as a molecular weight regulator. Other known molecular weight regulators may be included in the solution if desired.
When the solution of polymer is made by polymerisation in a mixture of water and organic solvent this organic solvent may serve as the organic liquid for use in the invention. A very common solvent in solution polymerisations is isopropanol and blends of water and isopropanol are suitable for many processes accor~ing to the invention.
Irrespective of whether the solution is made by blending preformed polymer, water, organic solvent and alkali or by adding alkali to the reaction product of polymerisation in aqueous organic liquid, or in any other manner, the process of the invention requires that phase separation should be brought about between aqueous and organic phase in the presence of the ~pecified solvents and the specified amounts of the specified cations. If other solve~nts, other cations or other amounts of the specified cations are used the process generally will not give the variable fractionation of the invention but instead will either give no useful results or will merely strip oligomer and monomer from the product. For instance it is not possible to select the degree of ,~ C~ f ~ 3 ~
fractionation if the organic solvent is acetone or tetrahydrofuran or if the cation is provided by an amine such as ethylamine.
The degree of neutralisation of the acid groups controls the fractionation. ~he results obtained in any particular process will depend upon, inter alia, the concentrations, the polymer type and the solvent but there is a minimum degree of neutralisation below which substantially no fractionation occurs and the system may instead remain as a homogeneous solution. When the cation is sodium, potassium or lithium the degree of neutralisation will normally be at least 10%, often at least 15% and preferably at least 25% whilst if the cation is lithium the degree of neutralisation will normally have to be at least about 30%, preferably at least 40% and generally at least 50~. If the degree of neutralisation is too high the size of the lower molecular weight fraction is unacceptably low. When the cation is sodium or potassium the degree of neutralisation will normally be below 55%, preferably below 50~ and most preferably below 40%. When the cation is ammonium the degree of neutralisation will normally be below 70~, preferably below 60% and most prefera~ly below 50~ When the cation is lithium the degree of neutralisation will normally be below 90%, and preferably below 70%.
In any particular process the size of, for instance, the higher molecular weight fraction can be increased (with consequential reduction in its average molecular wei~ht and consequential reduction in the size and the average molecular weight of the lower molecular weight fraction) by increasing the amount of alkali and conversely the size of the low molecular weight fractivn can be increased by reducing ~he amount of alkali.
The process conditions are preferably selected such that each fraction contains from 20 to 80%, and most preferably 30 to 70%, by weight of the starting polymer.
The partial neutralisation of the acidic polymer is normally achieved by adding a compound that will provide the chose~ cation, the compound usually being a hydroxide, in the selectea amount to the dissolved polymer. Mixtures of two or more of the four cations may be utilised, in which event the proportions will be selected such that they have the same effect as the amounts specified for the individual cations.
For any particular polymer, the degree of fractionation is dependent not only on the degree of neutralisation and the type of cation but also upon the concentration of the polymer and the choice and amount of the alcohol. The alcohol is preferably isopropanol but propanol and other alcohols, especially C2 to C5 alcohols, may be used. The proportion water:alcohol by weight is preferably from 1:0.2 to 1:5, most preferably 1:0.5 to 1:2 with best results generally being achieved, especially when the alcohol is isopropanol and the cation is sodium, when the proportion is about 1:1. The proportions should be selected such that, having regard to the degree and nature of neutralisation, each of the phases will have a polymer concentration of at least 5%, generally at least 10% and preferably at least 15% by weight of the phase.
The amount of the polymer (measured as the acid polymer) is normaliy at least 5% by weight based on the 3Q weight of polymer, alcohol and water (including wa~er introduced with the alkali) and preferably is at least 10~. The concentration must not be so high that the system is so viscous that mixing and phase separation is significantly impeded and so is generally below 30%.
Preferably the concentration is 15 to 25~ by weight.
The phase separation may also be affected by the temperature at which the process is conducted. This may be between 15 and 80C but preferahly is between 30 and 70C.
The process may be conducted by combining the essential components of the solution in any convenient manner, for instance by adding aqueous alkali to the aqueous organic reaction product obtained by polymerisation of the monomer or monomers in aqueous organic solution. The process may be conducted continuously or batchwise. Depending upon the degree of neutralisation, and type and strength of base, the concentration of the polymer, the amount of solvent and the temperature the phase separation may occur rapidly or slowly. For instance it may occur substantially instantaneously or it may be necessary to leave the system to stand for periods of, for instance, S minutes to 2 hours, typically 30 minutes to I hour. The separation may be conducted batchwise or continuously, with the mix being fed through a conventional separation column or separation reactor.
The two phases are kept separate, may be fully neutralised with the same or different alkali and organic solvent may be stripped from the organic phase by distillation.
Each of the polymer fractions is recovered for subsequent commercial use.
The very low molecular weight fractions obtained by this technique have a particular value as agents for inhibiting the build-up of ~scale, and settlement of scale, and in particular as desalination aids. For instance we have established that the maxLmum level of alkalinity that can be maintained in solution is increased if PD is reduced. Thus best results are L ~ ii d ~ .~
achieved if Mw is from 350 to 1,000 and PD is below 1.5, most preferably 1.05 to 1.3.
In the following examples, Example 1 demonstrates how a polymer may he made to the desired PD and ~w values ~y careful polymerisation, and Examples 2 and 3 demonstrate how the polymer may be obtained by partial neutralisation and fractionation.
To a 700 cm3 resin pot equipped with thermometer, stirrer and external heating, three separate mixtures were continuously added over a 6 hour period.
Feed 1 consisted of: 340 g glacial acrylic acid in 226 g water Feed 2 10.5 g 100 vol. hydrogen peroxide and 57.1 g water Feed 3 28 g thioglycollic acid and 38.6 g water.
The pot contents were maintained at reflux temperature throughout the addition and then for a further hour before being cooled. The percentage unpolymerised acrylic acid was determined by Gas Liquid Chromatrography and shown to be 0.3% of the amount added.
The remaining polymer was fully neutralised by the addition of 46.6% sodium hydroxide and the final product diluted to give a 40% w/w sodium polyacrylate solution.
The viscosity of the product at 25% was 12.1 cS
(suspended level viscometer, No. 2, 25C). GPC analysis showed Mw = 1740, Mn = 1321, Polydispersity = 1.32.
A 23~ by weight solution of polyacrylic acid in a bl~nd of equal parts by weight isopropanol and water was prepared by pol~merisation of acrylic acid using ammonium persulphate as initiator, in conventional manner~
Samples of the product were extracted while other sa~ples were neutralised by the addition of varying amounts of J~3 sodium hydroxide, introduced as a 46% by weight aqueous ~olution. Each of the sa~ples, after the addition of sodium hydroxide, was allowea to stand for sufficient time for an aqueous phase to separate from an organic phase (that probably contained some water) and these phases were then separated from one another in conventional manner. Each phase was then fully neutralised with sodium hydroxide and the residual alcohol was removed by distillation. The yield of polymer in each of the phases was recorded.
A 20~ solution of polyacrylic a~id having Mw of 3131 and PD ~polydispersity) of 1.677 was dissolved in 50/50 w/w isopropanol/water was neutralised with various basic compounds and the two layers separated. The amount and molecular weight of the polymer in each layer was determined. The results are shown in Table 1.
TABLE l A~x~us layer o~nic layer nase % ~ %
Neutr~l;sation Extra ~ d~ Mw P.D. Extrac~ MW P.D.
NaQH 25 75.2 3833 1.30 24.8 1452 1.402 2 NH4oH 25 55.6 4025 1.30 44.4 1689 1.34 S LioH 25 NO.~PA~CN
lioH So 50.2 3957 1.427 49.8 1783 1.44 ROH 25 63.5 3649 1.56 36.5 1402 1.49 Nao~ 15 20.6 3976 1.49 - ~9.4 2027 1.63 ~ NaoH 50 95.7 3688 1.51 4.3 Vey low -- 30NaOH 75 99.3 3376-1.53- 0.7 Very low _XAMPLE 4 The products obtained in Example 2 were adjusted to 40~ active solids and compared as marble grinding aids as 1~
describea in Example 11 of sritish Patent Specification No. 1,414,964. The results are set out in Table 2.
5 P~xxn ~~~- - Yield PenY~t ~q~us Layer Neut~isat~ o~ c Aq~x~s MiL~ index 0* 0.25 87.2 12.8 79.3 20.7 23.1 76.9 1.94 4.0 96.0 2.33 0.7 99.3 1.22 100 0.5 99.5 0.37 *This product is made in conventional manner by full neutralisation followed by removal of the organic phase by distillation, and so there is no fractionation.
In the described test a milling index value of around 0.5 is generally satisfactory as it indicates commercially acceptable properties for preventing gelation of the marble dispersion.
It is apparent from the table that after full neutralisation almost all the polymer is in the aqueous phase but that substantial amounts of polymer go into the organic phase at low degrees of neutralisation. It is also very notable that the milling index is greatly improved even when the amount of polymer that is in the organic phase, instead of the aqueous phase, is quite low. For instance at 50% neutralisàtion the amount of polymer in the organic phase is low but the milling index is about 5 times what would be considered to be commercially adequate. At higher degress of neutralisat~on only a very low amount of poly~er goes into the organic phase.
.
A polymer was prepared by conventional polymerisation technique as a 23% solution of acrylic acid in equal amounts of isopropanol and water was neutralised to 25%
S with aqueous sodium hydroxide after polymerisation. This caused the reaction mixture to separate into two phases.
These were ~eparated and the poly~er present in such phase was recovered after removal of the isopropanol by distillation. The samples were fully neutralised with sodium hydroxide solution and adjusted to 40% active as sodium polyacrylate.
An unfractionated control polymer was also prepared from the original unneutralised polymer in isopropanol/water by removing the isopropanol by distillation and fully neutralising with sodium hydroxide and adjusting to 40~ active as sodium polyacrylate.
The products were evaluated as dispersants for titanium dioxide, having particle size 97% below 2 ~m, at 75% w/w slurry solids content by recording the slurry viscosity (cP) at 0.6, 0.8 and 1~ dry polymer based on dry pigment. The results are given in Table 3.
Neu~x~isa- ~__ PD Slurry Visoosity (cP) 25tion % l0.60.8 1.0 100 CbntDDl 3161 2019 1.565 _ 1320 1380 ph~æ 4236 2795 1.515 _ - } 26~0 30 ` ~ ic 1795 1367 1 314 3500 700 340 - Samples of narrow polydispersity sodium polyacrylates of aecreasing molecular weight were evaluated as ~ 3 ~ vi ~
dispersant for china clay at 64% w/w slurry solids content at p~ 6.8-7~0 and at various dosages, as in Example 4. The result~ are gi~en in Table 4 __ , Mw Mn El) Slurry vi~;oositY (cl?l 0.10 0.12 O.U 0.16 0.16 0.20 0.2 5543 4817 1.15 _ _ 1567 359 2gO 321 376 487~ 3907 1.25 _ 1483 643 285 296 330 405 4447 3592 1.24 _ 933 423 255 269 312 361 4053 3273 1.24 _ 703 263 225 249 284 _ 3202 2709 1.18 _ 234 198 211 233 271 _ 2144 1901 1.13 533 183 190 207 231 266 _ ~065 934 1.28 637 226 196 201 213 230 _ The results show that the most effective sodium polyacrylates for china clay dispersants lie between a molecular weight of 1000-3000. Preference been given to a molecular weight of approximately 2000.
EXAMæLE 7 Foue samples of sodium eolyacrylate of similar molecular weigh~ but varying eolydiseersity were evaluated as marble millinq aids. -Each of the molecular weights tand all the other molecularweights quoted herein) were determined by GPC (gel eermea~ion chromotoqraehy). It involves permeation of the polyme~ under test 'through a GPC column (Ultcagel~AcA 54, 5cm diameter and 31cm length) when being eluted with O.lM sodium chloride at 3ml/min at a temperature of 30C. the eluate being analysed with a W
detector. The column will 2reviously have been calibrated betwee~
upper and lower molecular weights by use of fractions of a polymer of the same chemical tyee (i.e., ~olyacrylic acid) but in w~ich ~ T~Q~ee~ k ~ ~ lv ~
, each fraction is a laboratory reagent grade of that eolymer having a different molecular weight. The uppe~ and lower limits of the calibration range are defined by markers of known molecular weight, ~or instance 10,000 at the upper end and below 1.900 at the lower end.
Mw and Mn values foc each polymer that is being tested can thus be determined in conventional manner and PD can then be calculated as described above. The results expre~sed as Milling Index using a test method as described in Example llo British Patent No. 1,414,964 are shown in Table 5.
Mw PD Milling Index 3225 1.38 2.54 3105 1.52 1~23 3229 1.63 0.29 3358 2.01 <0.20 The results show that the effectiveness of sodium polyacrylate on marble milling is dependent on polydispersity. The lower the polydispersity the more effective the product.
It can be shown that the interrelationship between molecular weight and polydispersity of a sodium AMPS/sodium acrylate l20/80 w/w) copolymer has a crucial effect when the product is evaluated as a marble grinding aid according to Example 11 of. British Patent Specification No. . 1,414,964. The interrelationship between these parameters is shown in Table 6.
; ri ~
g .
I~w m:~leal~arweigllt lawpoly~i~ersity 2351 1.26 2.6 2630 1.34 2.4 Low mDleo~rweight high polydispersity 2834 1.6 0.38 3151 1.55 0.44 High m~l~o~rweight low polyd~xrsity 7193 -1.40 0.67 4625 1.47 0.81 High m~ lar weight high polydispersity 6265 1.64 0.64 ~836 1.53 0.77 _ The results show that polymers of low molecular weight with narrow polydispersity are the most effective marble grinding aids. The optimum molecular-weight lies between 1500 and 3500 with preference given to polymers with a molecular weight of 2500.
Samples of sodium polyacrylate of similar molecular weight but varying polydispersity were evaluated as in Example 4 as dispersants for precipitated calcium carbonate at 70% w~w slurry solids content. The results are given in Table 7.
TABL~E 7 . _ _ . ' Mw PD _Bnx~ield Visoosity ~ O lSO 0.175 0.200 0.~25 0.250 0.275 0.300 _ 3æ~ 1.38 117114 ~ 130 177 114 107 1n4 3105 1.52 120 134 167 D8 164 130 127
Claims
THE EMBDIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE PROPERTY OR
PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A dispersion of pigment in an aqueous medium containing a dispersing agent for the pigment and in which the dispersing agent is introduced as a water soluble polymer formed from one or more ethylenically unsaturated monomers and containing acid groups selected from carboxyl and sulphonic groups derived from acrylic acid, methacrylic acid, maleic acid, vinyl sulphonic acid or 2-acrylamido-2-methylpropane sulphonic acid or a mixture of acrylic acid and 2-acrylamido-2-methylpropane sulphonic acid, or a water soluble salt thereof, characterised in that the polymer has PD below 1.5 but at least 1.1 and Mw (measured as the sodium salt) of from about 1,500 to below 6,000.
2. A dispersion according to claim 1 in which PD is 1.05 to 1.4 and Mw is below 4,000.
3. A dispersion according to claim 1 in which the polymer is polyacrylic acid or a copolymer of acrylic acid and 2-acrylamido-2-methylpropane sulphonic acid, or a water soluble salt thereof.
4. A dispersion according to claim 1 in which the polymer is polyacrylic acid, or a water soluble salt thereof, having Mw, measured as the sodium salt, of below about 3,300.
5. A dispersion according to claim 2 in which the polymer is polyacrylic acid, or a water soluble salt thereof, having Mw, measured as the sodium salt, of below about 3,300.
6. A dispersion according to claim 4 in which Mw is in the range 1,800 to 2,200.
7. A dispersion of pigment in an aqueous medium containing a dispersinq agent for the pigment and in which the dispersing agent is introduced as a water soluble polymer formed from one or more ethylenically unsaturated monomers and containing acid groups selected from carboxyl and sulphonic groups, or a water soluble salt thereof, characterised in that the polymer has PD below 1.5 and Mw (measured as the sodium salt) of from about 1,500 to about 6,000, wherein the pigment is selected from china clay, talc, titanium dioxide and precipitated calcium carbonate and has a particle size in the range 1 to 50 microns.
8, A dispersion according to claim 6 in which the pigment is selected from china clay, talc, titanium dioxide and precipitated calcium carbonate and has a particle size in the range 1 tp 50 microns.
9. A dispersion according to claim 7 or 8 and which is a paper coating dispersion having a pigment concentration of 50 to 80% by weight.
10. A dispersion of pigment in an aqueous medium containing a dispersing agent for the pigment and in which the dispersing agent is introduced as a water soluble polymer formed from one or more ethylenically unsaturated monomers and containing acid groups selected from carboxyl and sulphonic groups, or a water soluble salt thereof characterised in that the polymer has PD below 1.5 and Mw (measured as the sodium salt) of from about 1,500 to about 6,000, wherein said dispersion is made by grinding calcium carbonate in water containing said polymer.
11. A dispersion according to claim 10 in which the polymer is selected from (a) polyacrylic acid, or a water soluble salt thereof, having Mw, measured as the sodium salt, in the range about 2,500 to about 4,500 and (b) a copolymer of acrylic acid and 2-acrylamino-2-methylpropane sulphonic aicd, or a salt thereof, having Mw, measured on the sodium salt, in the range about 1,500 to about 3,500.
12. A dispersion according to claim 11 in which the polymer is polyacrylic acid, or a water soluble salt thereof, and Mw is in the range about 3,300 to about 3,900.
13. A dispersion according to claim 11 in which the polymer is a copolymer of acrylic acid and 2-acrylamido-2-methylpropane sulphonic acid in the weight ratio 99:1 to 50:50 and Mw is in the range about 2,250 to about 2,750.
14. An aqueous dispersion according to claim 1 or claim 2 in which the polymer is polyacrylic acid.
15. A dispersion according to claim 14 in which the pigment is selected from titanium dioxide, china clay and calcium carbonate and has a particle size of 0.2 to 25 microns.
16. A water soluble polymeric dispersing agent suitable for use as the dispersing agent in an aqueous pigment dispersion and formed from one or more ethylenically unsaturated monomers and containing acid groups selected from carboxyl and sulphonic acid groups derived from acrylic acid, methacrylic acid, maleic acid, vinyl sulphonic acid or 2-acrylamido-2-methylpropane sulphonic acid or a mixutre of acrylic acid and 2-acrylamido-2-methylpropane sulphonic acid, or a water soluble salt thereof, characterised in that the polymer has PD below 1.5 but at least 1.1 and Mw, measured on the sodium salt, of from about 1,500 to below 6,000.
17. A polymeric dispersing agent according to claim 16 which has PD up to 1.4.
18. A polymeric dispersing agent according to claim 16 or claim 17 and that is polyacrylic acid or a copolymer of acrylic acid and 2-acrylamido-2-methylpropane sulphonic acid.
PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A dispersion of pigment in an aqueous medium containing a dispersing agent for the pigment and in which the dispersing agent is introduced as a water soluble polymer formed from one or more ethylenically unsaturated monomers and containing acid groups selected from carboxyl and sulphonic groups derived from acrylic acid, methacrylic acid, maleic acid, vinyl sulphonic acid or 2-acrylamido-2-methylpropane sulphonic acid or a mixture of acrylic acid and 2-acrylamido-2-methylpropane sulphonic acid, or a water soluble salt thereof, characterised in that the polymer has PD below 1.5 but at least 1.1 and Mw (measured as the sodium salt) of from about 1,500 to below 6,000.
2. A dispersion according to claim 1 in which PD is 1.05 to 1.4 and Mw is below 4,000.
3. A dispersion according to claim 1 in which the polymer is polyacrylic acid or a copolymer of acrylic acid and 2-acrylamido-2-methylpropane sulphonic acid, or a water soluble salt thereof.
4. A dispersion according to claim 1 in which the polymer is polyacrylic acid, or a water soluble salt thereof, having Mw, measured as the sodium salt, of below about 3,300.
5. A dispersion according to claim 2 in which the polymer is polyacrylic acid, or a water soluble salt thereof, having Mw, measured as the sodium salt, of below about 3,300.
6. A dispersion according to claim 4 in which Mw is in the range 1,800 to 2,200.
7. A dispersion of pigment in an aqueous medium containing a dispersinq agent for the pigment and in which the dispersing agent is introduced as a water soluble polymer formed from one or more ethylenically unsaturated monomers and containing acid groups selected from carboxyl and sulphonic groups, or a water soluble salt thereof, characterised in that the polymer has PD below 1.5 and Mw (measured as the sodium salt) of from about 1,500 to about 6,000, wherein the pigment is selected from china clay, talc, titanium dioxide and precipitated calcium carbonate and has a particle size in the range 1 to 50 microns.
8, A dispersion according to claim 6 in which the pigment is selected from china clay, talc, titanium dioxide and precipitated calcium carbonate and has a particle size in the range 1 tp 50 microns.
9. A dispersion according to claim 7 or 8 and which is a paper coating dispersion having a pigment concentration of 50 to 80% by weight.
10. A dispersion of pigment in an aqueous medium containing a dispersing agent for the pigment and in which the dispersing agent is introduced as a water soluble polymer formed from one or more ethylenically unsaturated monomers and containing acid groups selected from carboxyl and sulphonic groups, or a water soluble salt thereof characterised in that the polymer has PD below 1.5 and Mw (measured as the sodium salt) of from about 1,500 to about 6,000, wherein said dispersion is made by grinding calcium carbonate in water containing said polymer.
11. A dispersion according to claim 10 in which the polymer is selected from (a) polyacrylic acid, or a water soluble salt thereof, having Mw, measured as the sodium salt, in the range about 2,500 to about 4,500 and (b) a copolymer of acrylic acid and 2-acrylamino-2-methylpropane sulphonic aicd, or a salt thereof, having Mw, measured on the sodium salt, in the range about 1,500 to about 3,500.
12. A dispersion according to claim 11 in which the polymer is polyacrylic acid, or a water soluble salt thereof, and Mw is in the range about 3,300 to about 3,900.
13. A dispersion according to claim 11 in which the polymer is a copolymer of acrylic acid and 2-acrylamido-2-methylpropane sulphonic acid in the weight ratio 99:1 to 50:50 and Mw is in the range about 2,250 to about 2,750.
14. An aqueous dispersion according to claim 1 or claim 2 in which the polymer is polyacrylic acid.
15. A dispersion according to claim 14 in which the pigment is selected from titanium dioxide, china clay and calcium carbonate and has a particle size of 0.2 to 25 microns.
16. A water soluble polymeric dispersing agent suitable for use as the dispersing agent in an aqueous pigment dispersion and formed from one or more ethylenically unsaturated monomers and containing acid groups selected from carboxyl and sulphonic acid groups derived from acrylic acid, methacrylic acid, maleic acid, vinyl sulphonic acid or 2-acrylamido-2-methylpropane sulphonic acid or a mixutre of acrylic acid and 2-acrylamido-2-methylpropane sulphonic acid, or a water soluble salt thereof, characterised in that the polymer has PD below 1.5 but at least 1.1 and Mw, measured on the sodium salt, of from about 1,500 to below 6,000.
17. A polymeric dispersing agent according to claim 16 which has PD up to 1.4.
18. A polymeric dispersing agent according to claim 16 or claim 17 and that is polyacrylic acid or a copolymer of acrylic acid and 2-acrylamido-2-methylpropane sulphonic acid.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB838313976A GB8313976D0 (en) | 1983-05-20 | 1983-05-20 | Water soluble polymers |
| GB8313976 | 1983-05-20 | ||
| GB838321731A GB8321731D0 (en) | 1983-08-12 | 1983-08-12 | Water soluble polymers |
| GB8321731 | 1983-08-12 | ||
| CA000454568A CA1265635A (en) | 1983-05-20 | 1984-05-17 | Water soluble polymers |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000454568A Division CA1265635A (en) | 1983-05-20 | 1984-05-17 | Water soluble polymers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1309795C true CA1309795C (en) | 1992-11-03 |
Family
ID=27167440
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000601181A Expired - Lifetime CA1309795C (en) | 1983-05-20 | 1989-05-30 | Water soluble polymers |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1309795C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114716595A (en) * | 2022-03-23 | 2022-07-08 | 佳化化学科技发展（上海）有限公司 | Ultra-low molecular weight polyacrylic acid and preparation method and application thereof |
-
1989
- 1989-05-30 CA CA000601181A patent/CA1309795C/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114716595A (en) * | 2022-03-23 | 2022-07-08 | 佳化化学科技发展（上海）有限公司 | Ultra-low molecular weight polyacrylic acid and preparation method and application thereof |
| CN114716595B (en) * | 2022-03-23 | 2023-11-03 | 佳化化学科技发展（上海）有限公司 | Ultra-low molecular weight polyacrylic acid and preparation method and application thereof |
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