JPH0516447B2 - - Google Patents

Description

[Detailed description of the invention]

BACKGROUND OF THE INVENTION Unsaturated, polymerizable carboxylic acids, such as carboxyl-containing polymers, homopolymers, such as acrylic acid, methacrylic acid, maleic acid, itaconic acid, etc.
or copolymers with other vinylidene monomers are useful thickening agents. These polymeric acids are often crosslinked using small amounts of crosslinking agents. These materials are usually prepared by free-radical catalyzed polymerization of acids in organic media in closed vessels under stirring. Immediately after the start of polymerization,
During such polymerization, the polymer begins to precipitate out of solution as it forms, aggregates and forms aggregates. The precipitated polymer forms a slurry in the solvent. This slurry often becomes extremely thick, rendering mixing ineffective and resulting in insufficient heat transfer, limiting the total solids content, and thus the polymer yield, obtained in the manufacturing equipment. The total solids content of such slurries typically ranges from about 8 to 17% by weight. High yields are desirable. U.S. Patent No. 4,375,533 reduces polymer accumulation and
Organic medium in the presence of a catalyst and a surfactant with an HLB value of 10 or less to improve heat transfer and give a product with improved drying properties and less residual solvent in the drying polymer. Discloses a method for polymerizing olefinically unsaturated carboxylic acids in. However, polymerization in benzene is usually limited to reducing the total solids content of the slurry to avoid high viscosity of the slurry due to excessive agglomeration. SUMMARY OF THE INVENTION Polymerization is carried out in an organic liquid in the presence of a block polymer of propylene oxide and ethylene oxide having a molecular weight in the range of about 1,500 to about 20,000, in an amount of not more than 10 parts by weight per 100 parts by weight of the monomers to be polymerized. ,
A new method of producing carboxy-containing hydrogel polymers provides increased reactor production capacity on a commercial scale with approximately 50% more product obtained per reactor. Effects and Configurations of the Invention According to the new and improved method of the present invention, the reactor product increases by 50% by weight when the increase in total solids content of the polymer slurry is measured, resulting in The production of carboxyl-containing polymer per unit can be increased. There is no adverse effect on the physical properties and properties of the carboxyl-containing polymer. The use of such block copolymers minimizes undesirable flocculation and agglomeration, thus allowing polymerizations to be carried out to substantially higher polymer solids levels. This effectively means that
It increases the plant capacity of current equipment and represents substantial cost savings. One unexpected benefit of the higher total solids content slurry of the present process is that the resulting carboxyl-containing Approximately 192 to 256 kg of polymer
m ³ (12-16 Lb/ft ³ ). This is the desired benefit. This is because a denser product yields packaging and transportation cost savings. A polymer slurry having a total solids content of about 50% by weight polymer in an organic liquid, such as benzene, is obtained by using sufficient block polymer during polymerization. Polymerization of the carboxyl-containing monomer, if desired with other vinylidene comonomers, is usually carried out in a closed vessel in an inert atmosphere at spontaneous or artificially induced pressure in the presence of a free radical catalyst. , or carried out in an open vessel with an inert atmosphere under reflux at atmospheric pressure. The temperature of polymerization may vary from about 0° to 125°C or lower or higher. using free radical catalysts
Polymerization at 25° to 90°C is typically 75% to 100%
It is effective for modifying monomers into polymers. In the practice of the invention, polymerization may be batch, semi-batch or continuous. The agitation may be any agitation sufficient to maintain the slurry and provide effective heat transfer, including, for example, helical agitation, pitched turbine agitation, and the like. Useful reaction temperature ranges range from 20°C to 90°C at about 1 atmosphere or more. Typical polymerization times are about 3 to 12 hours. Representative free radical forming catalysts include peroxy compounds such as sodium persulfate, potassium persulfate and ammonium persulfate, caprylyl peroxide, benzoyl peroxide, hydrogen peroxide, pelargonyl peroxide, cumene hydroperoxide, diisopropyl hydroperoxide, tertiary Butyl diperphthalate, tert-butyl perbenzoate, sodium peracetate, di(2-
ethylhexyl) peroxydicarbonate, etc.
and an azo catalyst, such as azodiisobutyrylnitrile. Other available catalysts are so-called "redox" type catalysts and activated heavy metal catalyst systems. Ultraviolet light may also be used as a source of free radicals. Although some systems polymerize by heating alone, a catalyst usually provides better control. The monomers may be added in batches, added continuously during the polymerization, or by any other commonly used polymerization technique. The polymerization reactions described herein typically have a solubilizing effect on one or more of the monomer components, but have substantially no solubilizing effect on the resulting polymer. It is done in no inert diluent. In other words, the medium used for polymerization is a non-polar organic fluid in which the monomer is preferably soluble but the polymer is substantially insoluble. Such materials are usually solvents for the monomers but non-solvents for the resulting polymers so that the polymer product is preferably obtained as a fine, friable or fuzzy precipitate. , organic liquids, and mixtures thereof.
Alkanes of 8 carbon atoms, such as hexane and heptane; cycloalkanes of 4 to 8, preferably 5 to 7 carbon atoms, such as cyclohexane; benzene and 1 to 2 lower alkyl substituents, preferably Alkyl-substituted benzenes containing methyl substituents, such as toluene and xylene; containing 1 to 6, preferably 1 to 4, carbon atoms in the alkyl group and 2 to 6, preferably 2 in the carboxylate moiety; Alkyl carboxylates containing ~4 carbon atoms, such as ethyl acetate, methyl acetate, and butyl acetate; haloalkanes, especially chlorofluoroalkanes, containing 1 to 2 carbon atoms and at least 2 halo groups, For example, methylene chloride, ethylene dichloride, and 1,1,
1-trichloroethane; and 0-2% aromatic hydrocarbons, 40-85% paraffin, and 15-50
% naphthenes and has a flash point above about 50°C. It has been found that methyl ethyl ketone, a polar solvent, is not suitable in the present invention. The amount of commonly used organic liquid solvents, such as benzene, is in excess to the monomers to be polymerized, and the ratio ranges from at least 1% by weight monomer and 99% solvent to about 50% by weight It may vary up to 50% by weight of monomer and solvent, more usually a concentration of about 10-35% organic monomer is used. A carboxyl-containing polymer is prepared from a vinylidene monomer containing at least one activated >C=C< group and a carboxyl group.
Such polymers include unsaturated polymerizable carboxyl monomers, such as homopolymers of acrylic acid, methacrylic acid, maleic acid, itaconic acid, etc.
or copolymers thereof. The carboxyl-containing polymer has a molecular weight from about 500 to several million, usually from about 10,000 to 900,000 or more. Representative materials are those described in US Pat. No. 2,798,053. For example, a copolymer is a gel-like polymer, especially a copolymer of acrylic acid with a small amount of a polyalkylenyl polyether crosslinker, which absorbs a large amount of water or solvent and then increases in amount substantially. Contains. Other useful carboxyl-containing polymers include the U.S. Pat. Described in No. 3940351. Other types of copolymers, in which the polymer described in U.S. Pat. It is described in Patent No. 4062817. As disclosed in U.S. Pat. Crosslinking may be performed using diester or the like. The carboxyl monomer has at least one activated olefinic carbon-carbon double bond;
and olefinically unsaturated carboxylic acids containing at least one carboxyl group, i.e.
It is an acid with an olefinic double bond that functions easily in polymerization. Here, in the polymerization, the double bond easily functions in the monomer molecule at the α-β position with respect to the carboxyl group, i.e. at -C=C-COOH, or as part of the terminal methylene group. That is, this is because CH ₂ =C<. This type of olefinic unsaturated acid includes substances such as acrylic acid represented by acrylic acid itself, α-cyanoacrylic acid, β-methylacrylic acid (crotonic acid), α-phenylacrylic acid,
β-acryloxypropionic acid, sorbic acid,
α-chlorosorbic acid, angelic acid, cinnamic acid,
p-chlorocinnamic acid, β-stearyl
acid (1-carboxy-4-phenylbutadiene-
1,3), itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, maleic acid,
Contains fumaric acid and tricarboxyethylene. As used herein, the term "carboxylic acid" refers to polycarboxylic acids and acids that are produced by the elimination of one molecule of water from two carboxyl groups located on the same polycarboxylic acid molecule. anhydrides of polycarboxylic acids, in which anhydride groups are formed;
For example, it contains maleic anhydride. Maleic anhydride and other acid anhydrides useful in the present invention have the general structure below. [In the above formula, R and R' are hydrogen, halogen and cyanogen (-C≡N) groups, and alkyl, aryl, alkaryl, aralkyl and cyanoalkyl groups, such as methyl, ethyl, propyl, octyl, decyl. , phenyl, tolyl, xylyl, benzyl, cyclohexyl, etc.]. Preferred carboxyl monomers have the general structure below: [In the above formula, R ² is hydrogen, halogen, cyanogen (-C≡N) group, monovalent alkyl group, monovalent aryl group, monovalent aralkyl group, monovalent alkaryl group, and monovalent is a substituent selected from the group consisting of alicyclic groups]. Among this group, acrylic acid and methacrylic acid are most preferred. Another useful carboxyl monomer is maleic acid or its anhydride. The polymer is a homopolymer of carboxylic acid or its anhydride and also has at least one terminal group>
It includes a copolymer of a carboxylic acid as defined above with one or more other vinylidene monomers containing CH ₂ . Such a monomer can be, for example, represented by the following formula: [In the above formula, R ³ is an alkyl group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, and R ² is, for example, an amount of about 1 to 40% by weight or more. acrylate ester monomers, such as derivatives of acrylic acid, represented by hydrogen, methyl or ethyl present in the copolymer. Representative acrylates include methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, methyl methacrylate, methyl ethacrylate, ethyl methacrylate, octyl acrylate, heptyl acrylate, octyl methacrylate, isopropyl methacrylate, and 2-ethylhexyl. Contains methacrylate, nonyl acrylate, hexyl acrylate, n-hexyl methacrylate, etc. Higher alkyl acrylates are decyl acrylate, isodecyl methacrylate, lauryl acrylate, stearyl acrylate, behenyl acrylate and merisyl acrylate and the corresponding methacrylates. Mixtures of two or three or more long chain acrylic esters may be successfully polymerized with one of the carboxyl monomers. Any polyfunctional vinylidene monomer containing at least two end groups CH ₂ <, including, for example, butadiene, isoprene, divinylbenzene, divinylnaphthalene, allyl acrylate, etc.
It may also be crosslinked with a polymer. Particularly useful crosslinking monomers for use in preparing copolymers are polyalkenyl polyethers having one or more alkenyl ether groups per molecule. The most useful have an alkenyl group CH ₂ =C< in which an olefinic double bond is present attached to the terminal methylene group. These are made by etherification of polyhydric alcohols containing at least 3 carbon atoms and at least 2 hydroxyl groups. Compounds of this type can be prepared by reacting an alkenyl halide, such as allyl chloride or allyl bromide, with a strongly alkaline aqueous solution of one or more polyhydric alcohols. This product is
It is a complex mixture of polyethers with varying numbers of ether groups. The analysis shows the average number of ether groups per each molecule. The capacity of polyether crosslinkers increases with the number of potentially polymerizable groups per molecule. It is preferred to use polyethers containing on average two or more alkenyl ether groups per molecule. Other crosslinking monomers include, for example, diallyl esters, dimethallyl ethers, allyl acrylate, allyl acrylamide, methalylacrylate, methalylacrylamide, tetraallyltin, tetravinylsilane, polyalkenylmethanes, diacrylates, and dimethacrylates, divinyl compounds. , for example, divinylbenzene, polyallyl phosphate, diallyloxy compounds, and phosphite esters. Typical reagents are:
Allyl pentaerythritol, allyl sucrose, trimethylolparowan triacrylate,
These include 1,6-hexanediol diacrylate, trimethylolpropane diallyl ether, pentaerythritol triacrylate, tetramethylene dimethacrylate, ethylene diacrylate, ethylene dimethacrylate, triethylene glycol dimethacrylate, and the like. Allyl pentaerythritol, trimethylolpropane diallyl ether and allyl sucrose provide excellent polymers. When a crosslinking agent is present, the mixture of polymers is typically crosslinked by up to about 5% by weight or more, based on the total carboxylic acid monomers plus other monomers, if present. and more preferably about 0.01 to 2.0% by weight of crosslinking monomer. Other vinylidene monomers containing acrylonitrile may also be used. Useful α,β-olefinically unsaturated nitriles are preferably monoolefinically unsaturated nitriles having from 3 to 10 carbon atoms, such as acrylonitrile, methacrylonitrile and the like. Most preferred are acrylonitrile and methacrylonitrile. The amount used is, for example, about 1 to 30% by weight of the total amount of monomers to be copolymerized. Acrylamide containing monoolefinically unsaturated amides may also be used.
They have at least one hydrogen on the amide nitrogen and the olefinic unsaturation is in the α-β position with respect to the carbonyl group. Typical amides are
Contains acrylamide, methacrylamide, N-t-butylacrylamide, N-cyclohexylacrylamide, etc. Acrylamide and methacrylamide are preferred. Other acrylamides include N-alkylolamides of α,β-olefinically unsaturated carboxylic acids, which range from 4 to 10
carbon atoms, such as N-methylol acrylamide, N-propanol acrylamide, N-methylol methacrylamide, N-
Methylolmaleamide, N-methylolmaleamide acid ester, N-alkylolamide of vinyl aromatic acids, such as N-methylol-p
-Contains vinylbenzamide, etc. α-olefins containing 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms; dienes containing 4 to 10 carbon atoms; vinyl and allyl esters, such as vinyl acetate; aromatics Vinyl, such as styrene, methylstyrene, chloro-styrene; vinyl ether, vinyl ketone,
Allyl ethers and allyl ketones, such as vinyl methyl ether and methyl vinyl ketone;
Chloroacrylate, cyanoalkyl acrylate, e.g. α-cyanomethyl acrylate, α
-, β- and γ-cyanopropyl acrylate; alkoxy acrylates, such as methoxyethyl acrylate, haloacrylates, such as chloroethyl acrylate; vinyl halides and vinyl chloride, vinylidene chloride, etc.;
Vinyl, diacrylates and other polyfunctional monomers such as divinyl ether, diethylene glycol diacrylate, ethylene glycol dimethacrylate, methylene-bis-acrylamide, allylpentaerythritol, etc.; and bis(β-haloalkyl)alkenyl phosphonates,
For example, bis(β-chloroethyl)vinylphosphonate and the like are known to those skilled in the art. Copolymers containing carboxy-containing monomers as minor components and other vinylidene monomers present as major components are readily prepared according to the method of the present invention. These copolymers can contain as little as 8% to as much as 100% by weight of carboxyl-containing monomers, based on the total weight of the polymer (ie, homopolymers). Particularly useful copolymers contain 40% or more acid, preferably 70% or more acid by weight. Block copolymers of propylene oxide and ethylene oxide are linear or branched. Linear copolymers are easily prepared by sequential addition of propylene oxide and ethylene oxide to a propylene glycol base. The substance has the following general structure: [where a, b and c are integers with respect to the molecular weight and the amount of propylene oxide and ethylene oxide in the molecule]. Branched block copolymers are usually prepared by the sequential addition of a triol, an aliphatic alcohol containing three hydroxyl groups, such as trimethylolpropane, with propylene oxide and ethylene oxide. Tetrafunctional materials are prepared by the sequential addition of propylene oxide and ethylene oxide to ethylene diamine. Block copolymers of propylene oxide and ethylene oxide are PLURONIC (trade name),
It is commercially available as PLURADOT (trade name) and TETRONIC polyol (trade name) (BASF Wyandotte). Pluronic(TM) material is a linear block copolymer, Pluronic(TM)
The material is a trifunctional liquid polyether based on accoxylated (polyoxyethylene and polyoxypropylene) triols, and Tetronic(TM) polyol, a trifunctional polyoxyethylene-polyoxypropylene polyol, is converted to ethylene diamine. prepared by sequential tetraaddition of propylene oxide and ethylene oxide. Block copolymers useful in the practice of this invention have molecular weights ranging from about 1,600 or greater, such as from 2,000 to about 20,000. Excellent results have been obtained using linear block copolymers having molecular weights ranging from about 2,500 to about 14,500. Approximately 3000~
Good results were also obtained using a branched block copolymer with a molecular weight of about 7500. The block copolymer polyoxyethylene content is approximately
10% to about 80% by weight. Excellent results have been observed when using block copolymers containing 10 to 80% by weight of polyoxyethylene units.
The amount of block copolymer used in the polymerization process is approximately 100% of the carboxyl-containing polymer formed.
About 0.5 parts by weight or more and 10 parts by weight or less per part by weight,
More preferably, from about 0.5 to about 5 parts by weight of block copolymer per 100 parts by weight of monomer polymerized. It was quite unexpected that while said block copolymers, which may be designated as polyoxyethylene-polyoxypropylene-block copolymers, provide the desired benefits of the present invention, so-called reverse block copolymers do not meet the requirements of the present invention. It was found to be ineffective for its purpose. That is, in the present invention, the copolymer represented by polyoxypropylene-polyoxyethylene-polyoxypropylene (POP-POE-POP) is
- Not as effective as POP-POE. moreover,
In solvents such as benzene, the HLB value of the block copolymer does not appear to be an effective factor according to the present invention. Block copolymers of propylene oxide and ethylene oxide with HLB values of 1 to 29, but without a defined critical molecular weight, are insufficient for the process of the invention, but have molecular weights in the required range. Block copolymers with HLB values of 1 to 29 are all sufficient. EXAMPLES The following examples are provided to illustrate certain features of the invention that are believed to provide significant benefits. EXAMPLE This example illustrates the preparation of a homopolymer of acrylic acid in methylene chloride solvent in the absence of a block copolymer of ethylene oxide and propylene oxide. This example does not constitute a part of the claimed invention. This is because in this example the preparation of polyacrylic acid is carried out in the absence of block copolymers. Following conventional procedures, 93 parts by weight of methylene chloride, 7 parts by weight of acrylic acid, 0.077 parts by weight of allylpentaerythritol, and 0.042 parts by weight of di(2-ethylhexyl) peroxydicarbonate were added to reactor 2. In addition, 6 at 40℃
Time polymerization was carried out. The resulting slurry was extremely thick, but the polymer could be barely recovered. 7% by weight monomer was considered to be the highest concentration to give a reasonably recoverable product with this polymerization method. Example This example shows a trifunctional block copolymer, polyoxyethylene-polyoxypropylene polyol and methylene chloride solvent, having a molecular weight of 3200 and identical to BASF's Pluradot HA-410. illustrates the polymerization of acrylic acid in the presence of Without said copolymer, this polymerization reaction cannot occur. In accordance with the invention disclosed herein, 90 parts by weight methylene chloride, 10 parts by weight acrylic acid, 0.11 parts by weight allylpentaerythritol, 0.06 parts by weight di(2-ethylhexyl)peroxydicarbonate, and 0.05 parts by weight Part of the trifunctional polyoxyethylene-polyoxypropylene polyol block copolymer was polymerized at 40°C for 6 hours. The resulting slurry was thick, but the product was recoverable. This polymerization could not be controlled without the presence of a block copolymer as a dispersant. EXAMPLE This example shows the analysis of polyoxyethylene-polyoxypropylene block copolymer in the absence and presence of a polyoxyethylene-polyoxypropylene block copolymer having a molecular weight of 2900 and identical to BASF's Pluronic L-64. , describes the preparation of polyacrylic acid in 1,1,1-trichloroethane solvent and shows the effect on slurry viscosity of block copolymers. In accordance with the invention disclosed herein, 8.13 parts by weight of acrylic acid, 91.87 parts by weight of 1,1,1-trichloroethane, 0.055 parts by weight of allylpentaerythritol, and 0.055 parts by weight of lauroyl peroxide were prepared at 74°C. Polymerization was carried out for 6 hours. The viscosity of the obtained slurry was measured using a 60 rpm LVT model B-type viscometer and was found to be 4.82 g/cm·s (482 cP) at 25°C. In the second polymerization, in addition to the above formulation, an additional 0.24 parts by weight of the same polyoxyethylene-polyoxypropylene polyol block copolymer was added. The viscosity of the obtained slurry was measured using the same method as above and was found to be 1.15 g/cm・s at 25°C.
(115cP). The reduction in slurry viscosity with the block copolymer indicates the effectiveness of the dispersant as a steric hindrance stabilizer for the polymerization of acrylic acid in 1,1,1-trichloroethane. Example Similar to the previous example, with a molecular weight of 2900,
in the absence and in the presence of a polyoxyethylene-polyoxypropylene block copolymer identical to BASF's Pluronic L-64.
Polymerizations of acrylic acid in 1,2-ethylene dichloride solvent were carried out to examine the effect of block copolymers on slurry viscosity. In accordance with the invention disclosed herein, 8.53 parts by weight of acrylic acid, 91.47 parts by weight of 1,2-ethylene dichloride, 0.055 parts by weight of allyl pentaerythritol and 0.055 parts by weight of lauroyl peroxide are polymerized for 6 hours at 80°C. I let it happen. The viscosity of the obtained slurry was 1.70 g/cm・s at 25°C.
(170cP). In addition to the above formulations, further
When 0.24 parts by weight of the same block copolymer was added to the above, 0.90 g/cm・s at 25°C
The slurry viscosity was (90cP). Furthermore, this indicates that in the wastewater dispersion polymerization of acrylic acid in 1,2-ethylene dichloride,
The effectiveness of block copolymers as steric hindrance stabilizers is demonstrated. To further illustrate the practice of the invention and the benefits of the invention, additional polymerizations to a total solids content of 25% by weight slurry were performed. The reactor used was a jacketed reactor equipped with a reflux condenser, a stirrer and heating-cooling means. The temperatures in the reactor, in the jacket outlet and in the heating bath were recorded by a striptease recorder. Temperature control was achieved by adjusting the bath temperature or circulating water through the reactor jacket. The following formulation was used. Polymerization Recipe Materials Parts by weight Acrylic acid 100.0 Benzene 300.0 Lauroyl peroxide 1st addition 0.11 2nd addition 0.07 Allylpentaerythritol 0.68 Block copolymer 1-3.0 Purge the reactor with nitrogen to control nitrogen flow to the reactor. The temperature was maintained constant throughout the reaction. 0.18 parts by weight of lauroyl peroxide was dissolved in 20 parts by weight of benzene and set aside. The remaining benzene, acrylic acid, allyl pentaerythritol and block copolymer were added to the reactor (1-3 parts by weight block copolymer in 20 parts by weight benzene).
The reaction contents were heated to 70°C under stirring. When the first addition of lauroyl peroxide is made and the temperature of the reaction mixture reaches 80.5°C, maintain this temperature for the remainder of the reaction unless the viscosity of the slurry exceeds the paste stage, at which point The temperature was lowered to 70-72°C. After 60 minutes, a second addition of lauroyl peroxide was made and the reaction continued for 4 hours. At 5 hours, the reactor was cooled to 25°C. 60 rpm type B viscometer with number 6 spindle, model
Samples were taken for measurement of slurry viscosity using LVT. The slurry was transferred to another container and heated at 110°C for 5 hours using a rotary evaporator.
It was dried under a vacuum of mmHg (27 inches Hg) to obtain a dry powder of crosslinked acrylic acid copolymer hydrogel. EXAMPLE A series of polymerization reactions were carried out using linear polyoxyethylene-polyoxypropylene-polyoxyethylene block copolymers of various molecular weights. Measurements of the viscosity of the resulting polymer slurry demonstrate the benefit of using block copolymers for the polymerization of carboxyl-containing monomers in benzene to form improved polymers that can then be further processed in the reactor. A slurry was obtained with a total solids content of 100%. All polymerizations were carried out to a polymer solids content of 25% by weight and the slurry viscosity was adjusted to cps.
It was described in (1) was performed using an alkoxylated (polyoxyethylene-polyoxypropylene) triol, and (2) to (12) were performed using a linear polyoxyethylene-polyoxypropylene-polyoxyethylene copolymer. did.

Table: In these examples, the desired agglomeration control and aggregation minimization were obtained and observed. When 5 parts by weight of the first block copolymer (1) is used, the slurry viscosity at the end of the polymerization reaction is
It was 230cps. In controls that do not contain either block copolymer, the reaction is not completed up to a total solids content of 25%, and the slurry becomes thick and viscous at total solids contents below 20% and cannot be stirred or temperature-controlled. It became impossible to do so. in benzene only when using block copolymers.
obtain a total solids content of 25% by weight or more;
And it was possible to maintain an operable reaction and slurry. Block copolymers with molecular weights of 1100 and 1630 are not very effective in this process. It is made by sequential addition of propylene oxide and ethylene oxide and has a molecular weight of 2700 or more. A block copolymer of ethylenediamine (Tetronic® polyol) was sufficient for the polymerization only at high levels. Reverse linear block copolymer POP-POE-
It has been found that POP cannot be used in place of the POE-POP-POE block copolymers of the present invention. This is because the former block copolymers are not effective at these concentrations. This block copolymer may not be completely sufficient at lower levels, but could be used at higher levels and/or at lower total polymer solids levels. EXAMPLES A series of polymerizations were carried out to demonstrate the properties of carboxyl-containing polymers obtained using various block copolymers at a total solids level of 25%.
The mucus viscosity in centipoise of various polymers prepared using various block polymers was determined by taking dry polymer samples of 0.2, 0.5 and 1.0.
Measured by weight percent mucus production. The polymer was dissolved in the indicated amount of water and the pH of the solution was adjusted to 7.2 and 7.8 using 18% aqueous sodium hydroxide. The viscosity of the obtained mucus is
Measured using a B-type viscometer model RVT at 20 rpm,
Written in centipoise (cps).

Table: These data demonstrate that desirably high bulk densities are obtained when each block copolymer is used. It has been found that the viscosity of the aqueous mucilage of the polymer prepared according to the method described above is not significantly affected by the use of block copolymers during the polymerization process. Although some foaming is observed in certain formulations when the amount of block copolymer is high, any such foaming is at manageable levels. When this example is repeated using a tetrafunctional polyoxypropylene-polyoxyethylene derivative of 5 parts of ethylenediamine containing 40% polyoxyethylene units, the obtained viscosity is 15000 at 0.2%. , 16000 when 0.5% and when 1.0%
It was 20,000. Carboxyl-containing polymers prepared by the method of the invention have many uses. Above all,
For example, bodying agents in various mucilage and colloidal gel-like coatings in cosmetics.
agent, thicking agent) and antisettling agent, for example, in pharmaceutical applications including toothpastes, surgical jellies, creams, ointments, and bulking laxatives, in food production, thickened latex, printing spaces, etc. Applications in formulations, oil well drainage, and other areas where ion-insensitive polymers are required.

Claims (1)

[Scope of Claims] 1. An olefinically unsaturated carboxylic acid containing at least one activated olefinic carbon-carbon double bond and at least one carboxyl group, wherein said carboxylic acid is at least partially soluble. and the resulting polymer is substantially insoluble, organic liquids and mixtures thereof;
50-90% by weight of a substantially non-polar solvent, a free radical forming catalyst, and a carboxyl-containing polymer formed
Approximately 0.5 parts by weight or more and 10 parts by weight or less per 100 parts by weight
having a molecular weight ranging from 2,000 to about 20,000 and from about 10 to
about 40 to 100% by weight polymerized in the presence of a hydroxyl-terminated polyoxyethylene-polyoxypropylene-polyoxyethylene block copolymer of propylene oxide and ethylene oxide containing about 80% by weight polyoxyethylene units. forming a polymer containing said unsaturated carboxylic acid. 2. The method according to claim 1, wherein in the carboxylic acid, the olefinic double bond is present in the α-β position with respect to the carboxyl group or is part of a terminal methylene group. 3. The method of claim 2, wherein the carboxylic acid is selected from the group consisting of acrylic acid, methacrylic acid and maleic acid. 4. said carboxylic acid is acrylic acid present in an amount of 40% or more by weight, and from 0 to 60% by weight of at least one other olefinic unsaturation containing at least one _CH2 =CH< group. 4. The method of claim 3, wherein a monomer is copolymerized with the acrylic acid. 5 The acrylic acid is present in an amount of 70% by weight or more and at least 5% by weight of at least two terminals.
5. The method of claim 4, wherein a polyfunctional crosslinking olefinically unsaturated monomer containing a _CH2 < group is present. 6. The block copolymer is a linear copolymer, the molecular weight is from about 2,500 to about 14,500, and the solvent is benzene, a haloalkane containing 1 to 2 carbon atoms and at least 2 halogens, and 6 to 8 halogens. 4. The method of claim 3, wherein the alkanes are selected from alkanes of carbon atoms. 7. The method of claim 5, wherein the block copolymer is a linear copolymer and has a molecular weight of from 2,500 to about 14,500. 8. The block copolymer is a trifunctional polyoxyethylene-polyoxypropylene triol copolymer, and has a molecular weight of about 3,000 to about 8,000.
The method according to claim 3, wherein: 9. The block copolymer is a trifunctional polyoxyethylene-polyoxypropylene triol copolymer, and has a molecular weight of about 3,000 to about 8,000.
The method according to claim 5, wherein the method is: 10. The method of claim 3, wherein the block copolymer is a tetrafunctional polyoxyethylene-polyoxypropylene copolymer having a molecular weight of from 3,000 to about 7,500. 11 The block copolymer is a tetrafunctional polyoxyethylene-polyoxypropylene ethylenediamine copolymer and has a molecular weight of about 3000 to
6. The method of claim 5, wherein the amount is approximately 7500. 12. The method of claim 7, wherein the crosslinking agent is selected from the group consisting of polyallyl pentaerythritol, polyallyl sucrose, and trimethylolpropane diallyl ether. 13 The following formula of 30% by weight or less 13. The acrylic acid ester of claim 12, wherein R' is hydrogen, methyl or ethyl and R is an alkyl group containing 1 to 30 carbon atoms. Method. 14 In the above formula, R' is hydrogen or methyl,
14. The method of claim 13, wherein and R is an alkyl group containing 2 to 20 carbon atoms. 15. The method of claim 8, wherein the crosslinking agent is selected from the group consisting of polyallyl pentaerythritol, polyallyl sucrose, and trimethylolpropane diallyl ether. 16. The method of claim 9, wherein the crosslinking agent is selected from the group consisting of polyallyl pentaerythritol, polyallyl sucrose, and trimethylolpropane diallyl ether. 17. The method of claim 10, wherein the crosslinking agent is selected from the group consisting of polyallyl pentaerythritol, polyallyl sucrose, and trimethylolpropane diallyl ether. 18. The method of claim 11, wherein the crosslinking agent is selected from the group consisting of polyallyl pentaerythritol, polyallyl sucrose, and trimethylolpropane diallyl ether.