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US4954562A
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Water absorbent resins
Assignee: BASF SE
•
Filing: 1989-01-30
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Granted: 1990-09-04
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Expires: 2009-01-30
Abstract
Abstract Improved water-absorbing, crosslinked acrylate resins are prepared by aqueous polymerization of (A) acrylic acid neutralized 70 to 100 mole percent for example with ammonia and/or caustic alkali and/or an amine; with (B) acrylamide in a mole ratio of 70 to 100 mole percent (A) to 30:0 mole percent (B); (C) styrene, in an amount of 0% to 25% based on the weight of acrylic acid or acrylate; and (D) a water miscible or a water soluble polyvinyl monomer in the presence of (E) a metal oxide, such as titanium dioxide, in an amount of 0.001% to 5% based on the total weight of (A), (B), (C), (D) and (E), such that the amount of (D) is 0.001 to 0.6 weight percent based on the total weight of (A), (B), (C), (D) and (E). In addition, surface treating the water-absorbing crosslinked acrylate resins with a polyquaternary amine substantially further increases both the rate of water absorption and the quantity of water absorbed and retained by the metal oxide-containing resin. The untreated and the surface-treated resins also maintain the necessary "dry feel" required for most applications.
Inventors
- 👤 Mark Anderson
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-09 04:17
CPC Classifications
C; C08; C08F; C08F220/00; C08F220/02; C08F220/04; C08F220/06; A; A61; A61L; A61L15/00; A61L15/16; A61L15/42; A61L15/60; B; B01; B01J; B01J20/00; B01J20/22; B01J20/26; C08F8/00; C08F8/44; C08F2800/00; C08F2800/20; C08F2810/00; C08F2810/20
Claims Analysis
Total Claims: 48
Claim 1
Independent Claim
144 words
A process for preparing a solid water absorbing resin comprising mixing a solution of (A) acrylic acid neutralized 70-100 mole percent; (B) a non-reactive and water-insoluble metal oxide in an amount of about 0.001% to about 5% based on the total weight of the solution; and (C) a water-miscible to water-soluble polyvinyl monomer in a combined concentration of (A), (B) and (C) of at least 30 wt. %; with water to form a mixed solution wherein the monomers of the mixed solution consist essentially of (A) and (C) and initiating polymerization of monomers (A) and (C) such that during polymerization, the exothermic heat of reaction is substantially the only heat energy used to accomplish polymerization, crosslinking and to drive off sufficient water to obtain a solid crosslinked resin including metal oxide (B) and having a water content of 15 percent by weight or less.
Claim 2
Dependent Claim
144 words
A process for preparing a solid water absorbing resin comprising mixing a solution of (A) acrylic acid neutralized 70-100 mole percent; (B) a non-reactive and water-insoluble metal oxide in an amount of about 0.001% to about 5% based on the total weight of the solution; and (C) a water-miscible to water-soluble polyvinyl monomer in a combined concentration of (A), (B) and (C) of at least 30 wt. %; with water to form a mixed solution wherein the monomers of the mixed solution consist essentially of (A) and (C) and initiating polymerization of monomers (A) and (C) such that during polymerization, the exothermic heat of reaction is substantially the only heat energy used to accomplish polymerization, crosslinking and to drive off sufficient water to obtain a solid crosslinked resin including metal oxide (B) and having a water content of 15 percent by weight or less.
Claim 3
Dependent Claim
21 words
A process as defined in claim 1 wherein the metal oxide (B) is essentially homogeneously distributed throughout the solid crosslinked resin.
Claim 4
Dependent Claim
33 words
A process as defined in claim 1 wherein the combined concentration of the monomers (A) and (C) and metal oxide (B) is at least 30 wt. % and less than 80 wt. %.
Claim 5
Dependent Claim
30 words
A process as defined in claim 1 wherein the metal oxide (B) is present in an amount of about 0.75% to about 3% based on the weight of acrylic acid.
Claim 6
Dependent Claim
22 words
A process as defined in claim 1 wherein the mixed solution has a temperature of 20 to 85° C. prior to polymerization.
Claim 7
Dependent Claim
20 words
A process as defined in claim 1 wherein monomer (C) is selected from the group consisting of N,N-methylenebisacrylamide and N,N-methylenebismethacrylamide.
Claim 8
Dependent Claim
30 words
A process as defined in claim 1 wherein the mixed solution contains 1 to 10 wt. % of an organic solvent based on the weight of (A), (B) and (C).
Claim 9
Dependent Claim
25 words
A process as defined in claim 1 wherein the mixed solution further contains an organic solvent having a boiling point of 40 to 150° C.
Claim 10
Dependent Claim
82 words
A process as defined in claim 1 wherein the metal oxide is selected from a group consisting of titanium dioxide, magnesium oxide, zinc oxide, barium oxide, zirconium oxide, calcium oxide, silicon dioxide, aluminum oxide, selenium dioxide, tin oxide, bismuth oxychloride, antimony trioxide, antimony pentioxide, beryllium oxide, cadmium oxide, cerium oxide, iron oxide, lead oxide, bismuth oxide, vanadium oxide, cobalt oxide, magnesium aluminum oxide, zinc aluminum oxide, magnesium titantium oxide, iron titanium oxide, calcium titanium oxide, and beryllium aluminum oxide; or mixtures thereof.
Claim 11
Dependent Claim
67 words
A process as defined in claim 1 wherein the metal oxide is selected from a group consisting of titanium dioxide, magnesium oxide, zinc oxide, barium oxide, calcium oxide, silicon dioxide, aluminum oxide, tin oxide, bismuth oxychloride, antimony trioxide, iron oxide, lead oxide, bismuth oxide, vanadium oxide, cobalt oxide, magnesium aluminum oxide, zinc aluminum oxide, magnesium titantium oxide, iron titanium oxide, and calcium titanium oxide; or mixtures thereof.
Claim 12
Dependent Claim
24 words
A process as defined in claim 1 wherein the metal oxide has a particle size ranging from about 10 microns to about 200 microns.
Claim 13
Dependent Claim
24 words
A process as defined in claim 1 wherein the metal oxide has a particle size ranging from about 50 microns to about 125 microns.
Claim 14
Dependent Claim
34 words
A process as defined in claim 1 further comprising surface treating the solid crosslinked resin with a sufficient amount of a polyquaternary amine to substantially increase the water absorption of the solid crosslinked resin.
Claim 15
Dependent Claim
26 words
A process as defined in claim 13 wherein the resin is treated with from about 0.1% to about 5.0% by dry weight of a polyquaternary amine.
Claim 16
Dependent Claim
26 words
A process as defined in claim 13 wherein the resin is treated with from about 0.25% to about 2% by dry weight of a polyquaternary amine.
Claim 17
Dependent Claim
21 words
A process as defined in claim 13 wherein the polyquaternary amine has a molecular weight from about 200 to about 5000.
Claim 18
Dependent Claim
21 words
A process as defined in claim 13 wherein the polyquaternary amine has a molecular weight from about 300 to about 4000.
Claim 19
Dependent Claim
170 words
A process for preparing a solid, water absorbing, crosslinked resin comprising: combining a mixture of (A) potassium and/or ammonium acrylate; (B) a non-reactive and water-insoluble metal oxide in an amount of 0.0001% to 5% by weight based on the total amount of the mixture; and (C) a polyvinyl monomer, with water in an amount of at least 30 combined weight percent of (A) plus (B) plus (C) based on the total weight of (A) plus (B) plus (C) plus water to form a mixture wherein the monomers of the the mixture consist essentially of (A) and (C); adding a polymerization initiator to said mixture capable of initiating, and in an amount sufficient to initiate polymerization of said mixture; copolymerizing said mixture while utilizing the exothermic heat of reaction as substantially the only non-ambient energy source to drive water away from said polyacrylate resin copolymer to form said crosslinked resin copolymer, including the metal oxide (B) and having a water content sufficiently low to be powdered without an intermediate drying step.
Claim 20
Dependent Claim
170 words
A process for preparing a solid, water absorbing, crosslinked resin comprising: combining a mixture of (A) potassium and/or ammonium acrylate; (B) a non-reactive and water-insoluble metal oxide in an amount of 0.0001% to 5% by weight based on the total amount of the mixture; and (C) a polyvinyl monomer, with water in an amount of at least 30 combined weight percent of (A) plus (B) plus (C) based on the total weight of (A) plus (B) plus (C) plus water to form a mixture wherein the monomers of the the mixture consist essentially of (A) and (C); adding a polymerization initiator to said mixture capable of initiating, and in an amount sufficient to initiate polymerization of said mixture; copolymerizing said mixture while utilizing the exothermic heat of reaction as substantially the only non-ambient energy source to drive water away from said polyacrylate resin copolymer to form said crosslinked resin copolymer, including the metal oxide (B) and having a water content sufficiently low to be powdered without an intermediate drying step.
Claim 21
Dependent Claim
21 words
A process as defined in claim 18 wherein the metal oxide (B) is essentially homogenously distributed throughout the crosslinked resin copolymer.
Claim 22
Dependent Claim
34 words
The process of claim 18 further including the step of adjusting the temperature of the mixture to a temperature of 25 to 85° C. prior to adding said polymerization initiator to said monomer mixture.
Claim 23
Dependent Claim
25 words
The process of claim 18 wherein said polymerization initiator is added in an amount of at least 0.5% total by weight of (A) and (C).
Claim 24
Dependent Claim
37 words
The process of claim 18 wherein the water content of said crosslinked resin copolymer incorporating the metal oxide is not greater than about 10% by weight as recovered from the polymerized mixture, without an additional drying step.
Claim 25
Dependent Claim
29 words
The process of claim 18 further including combining a non-aqueous solvent having a boiling point of 40-150° C. with said (A), (B) and (C) to form a porous resin.
Claim 26
Dependent Claim
21 words
The process of claim 18 including the step of pulverizing said crosslinked resin including the metal oxide to form a powder.
Claim 27
Dependent Claim
31 words
The process of claim 18 wherein the combined concentration of the monomers (A) and (C) and metal oxide (B) is at least 30 wt. % and less than 80 wt. %.
Claim 28
Dependent Claim
80 words
The process of claim 18 wherein the metal oxide is selected from the group consisting of titanium dioxide, magnesium oxide, zinc oxide, barium oxide, zirconium oxide, calcium oxide, silicon dioxide, aluminum oxide, selenium dioxide, tin oxide, bismuth oxychloride, antimony trioxide, antimony pentoxide, beryllium oxide, cadmium oxide, cerium oxide, iron oxide, lead oxide, bismuth oxide, vanadium oxide, cobalt oxide, magnesium aluminum oxide, zinc aluminum oxide, magnesium titanium oxide, iron titanium oxide, calcium titanium oxide, and beryllium aluminum oxide; or mixtures thereof.
Claim 29
Dependent Claim
65 words
The process of claim 18 wherein the metal oxide is selected from the group consisting of titanium dioxide, magnesium oxide, zinc oxide, barium oxide, calcium oxide, silicon dioxide, aluminum oxide, tin oxide, bismuth oxychloride, antimony trioxide, iron oxide, lead oxide, bismuth oxide, vanadium oxide, cobalt oxide, magnesium aluminum oxide, zinc aluminum oxide, magnesium titanium oxide, iron titanium oxide, and calcium titanium oxide; or mixtures thereof.
Claim 30
Dependent Claim
22 words
The process of claim 18 wherein the metal oxide has a particle size of from about 10 microns to about 200 microns.
Claim 31
Dependent Claim
22 words
The process of claim 18 wherein the metal oxide has a particle size of from about 50 microns to about 125 microns.
Claim 32
Dependent Claim
35 words
The process of claim 18 further comprising contacting the crosslinked resin copolymer with a polyquaternary amine in an amount of from about 0.1% to about 5.0% based on the weight of the crosslinked resin copolymer.
Claim 33
Dependent Claim
44 words
The process of claim 18 including the step of pulverizing the crosslinked resin copolymer to form a powder prior to contacting said powder with a polyquaternary amine in an amount of about 0.1% to 5.0% based on the weight of said crosslinked resin copolymer.
Claim 34
Dependent Claim
32 words
The process of claim 18 wherein the crosslinked resin copolymer is treated with from about 0.25% to about 2.0% of a polyquaternary amine based on the weight of the crosslinked resin copolymer.
Claim 35
Dependent Claim
32 words
The process of claim 31 wherein the crosslinked resin copolymer is treated with from about 0.25% to about 2.0% of a polyquaternary amine based on the weight of said crosslinked resin copolymer.
Claim 36
Dependent Claim
19 words
The process of claim 18 wherein the polyquaternary amine has a molecular weight from about 200 to about 5000.
Claim 37
Dependent Claim
19 words
The process of claim 18 wherein the polyquaternary amine has a molecular weight from about 500 to about 3000.
Claim 38
Dependent Claim
28 words
The process of claim 18 wherein the polyquaternary amine is a condensation product of hexamethylenediamine, dimethylamine and epichlorohydrin; a condensation product of dimethylamine and epichlorohydrin; or quaternized polyethylenimine.
Claim 39
Dependent Claim
27 words
The process of claim 18 wherein the polyquaternary amine is dispersed in methanol from about 0.1% to about 20% by weight before contacting the crosslinked resin copolymer.
Claim 40
Independent Claim
169 words
A method of manufacturing a resin composition comprising mixing a solution of (A) acrylic acid, neutralized 70 to 100 mole percent, (B) a nonreactive and water-insoluble metal oxide in an amount of 0.001% to 5% based on the total weight of the solution; and (C) acrylamide in a mole ratio of (A):(C) in the range of 70:30 to 100:0; (D) a water soluble or water miscible polyvinyl monomer crosslinking agent in an amount of 0.001 to 0.6 percent by weight of (A) plus (B) plus (C); and water to form a mixed solution, wherein the monomers of the mixed solution consist essentially of (A), (C) and (D); and initiating polymerization of monomers (A), (C) and (D) such that during polymerization, the exothermic heat of reaction is substantially the only heat energy used to accomplish polymerization, crosslinking and to drive off sufficient water to form a water absorbing crosslinked polyacrylate resin composition including the metal oxide resin (B) and having a water content of 15 percent by weight or less.
Claim 41
Independent Claim
169 words
A method of manufacturing a resin composition comprising mixing a solution of (A) acrylic acid, neutralized 70 to 100 mole percent, (B) a nonreactive and water-insoluble metal oxide in an amount of 0.001% to 5% based on the total weight of the solution; and (C) acrylamide in a mole ratio of (A):(C) in the range of 70:30 to 100:0; (D) a water soluble or water miscible polyvinyl monomer crosslinking agent in an amount of 0.001 to 0.6 percent by weight of (A) plus (B) plus (C); and water to form a mixed solution, wherein the monomers of the mixed solution consist essentially of (A), (C) and (D); and initiating polymerization of monomers (A), (C) and (D) such that during polymerization, the exothermic heat of reaction is substantially the only heat energy used to accomplish polymerization, crosslinking and to drive off sufficient water to form a water absorbing crosslinked polyacrylate resin composition including the metal oxide resin (B) and having a water content of 15 percent by weight or less.
Claim 42
Dependent Claim
21 words
The method of claim 38 wherein the metal oxide is essentially homogenously distributed throughout the water absorbing crosslinked polyacrylate resin composition.
Claim 43
Dependent Claim
28 words
The method of claim 38 wherein the metal oxide (B) is present in an amount of about 0.75% to about 3% based on the weight of acrylic acid.
Claim 44
Dependent Claim
40 words
The method of claim 38 wherein the water content of said crosslinked polyacrylate resin composition including the metal oxide is not greater than about 10% by weight as recovered from the mixed solution after polymerization, without an additional drying step.
Claim 45
Dependent Claim
66 words
The method of claim 38 including depositing said solution including the monomer mixture, the metal oxide and said initiator onto a support surface in sheet form for polymerization and crosslinking, followed by pulverizing the resultant crosslinked resin to form a powder, and thereafter contacting said powder with a polyquaternary amine in an amount of from about 0.1% to 5.0% based on the weight of said powder.
Claim 46
Independent Claim
207 words
A method of absorbing aqueous liquids comprising mixing a solution of (A) acrylic acid, neutralized 70 to 100 mole percent; (B) a non-reactive and water-insoluble metal oxide in an amount of 0.001% to 5% based on the total weight of the solution; and (C) acrylamide in a mole ratio of acrylic acid:acrylamide in the range of 70:30 to 100:0; (D) a water soluble or water miscible polyvinyl monomer crosslinking agent in an amount of 0.001 to 0.6 percent by weight of (A) plus (B) plus (C); and water to form a mixed solution, wherein the monomers of the mixed solution consist essentially of (A), (C) and (D) and the concentration of (A), (B), (C) and (D) is below 70 percent by weight of the monomer solution prior to polymerization initiation; and initiating polymerization of monomers (A), (C) and (D) such that during polymerization, the exothermic heat of reaction is substantially the only heat energy used to accomplish polymerization, crosslinking and to drive off sufficient water to form a water absorbing crosslinked polyacrylate resin including the metal oxide (B) and having a water content of 15 percent by weight or less, and thereafter contacting said resin with an aqueous liquid to absorb said aqueous liquid into said resin.
Claim 47
Independent Claim
207 words
A method of absorbing aqueous liquids comprising mixing a solution of (A) acrylic acid, neutralized 70 to 100 mole percent; (B) a non-reactive and water-insoluble metal oxide in an amount of 0.001% to 5% based on the total weight of the solution; and (C) acrylamide in a mole ratio of acrylic acid:acrylamide in the range of 70:30 to 100:0; (D) a water soluble or water miscible polyvinyl monomer crosslinking agent in an amount of 0.001 to 0.6 percent by weight of (A) plus (B) plus (C); and water to form a mixed solution, wherein the monomers of the mixed solution consist essentially of (A), (C) and (D) and the concentration of (A), (B), (C) and (D) is below 70 percent by weight of the monomer solution prior to polymerization initiation; and initiating polymerization of monomers (A), (C) and (D) such that during polymerization, the exothermic heat of reaction is substantially the only heat energy used to accomplish polymerization, crosslinking and to drive off sufficient water to form a water absorbing crosslinked polyacrylate resin including the metal oxide (B) and having a water content of 15 percent by weight or less, and thereafter contacting said resin with an aqueous liquid to absorb said aqueous liquid into said resin.
Claim 48
Dependent Claim
58 words
The method of claim 40 further comprising contacting the crosslinked polyacrylate resin with a polyquaternary amine in an amount of from about 0.1% to about 5.0% based on the weight of said resin after forming the polyacrylate resin, and thereafter contacting said polyquaternary amine treated resin with an aqueous liquid to absorb said aqueous liquid into said resin.
References Cited (Backward Citations)
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