JPS6230125A - Production of water-swellable polymer electrolyte coating film or fiber - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to compositions useful in forming water-swellable articles of carboxyl-type synthetic cavity molecular electrolytes.

U.S. Patent Nos. 3,669,103 and 3,670,
It is known from No. 731 that it is possible to obtain disposable diapers or dressings by sandwiching cross-linked polymeric absorbent strips between strips of supporting material.

Furthermore, No. 2,988,539, No. 3,393,168
No. 5,514,419 and No. 3,357,067
It is known that a carboxyl copolymer with water-swelling cross-linking can be completely prepared from the 5-mer solution. However, these prior art colimers all cross-link during copolymerization or cross-link after polymerization in the subsequent formation of water-swellable polyelectrolytes that completely neutralize the carboxylic acid groups and thus these The prior art polyelectrolytes cannot be cross-linked in situ as a coating on a substrate or into a flexible film thereof.

The present invention comprises compositions useful for forming water-swellable articles of carboxyl-type synthetic polyelectrolytes comprising (1) 5 to 60% by weight (preferably 15 to 4% by weight, based on total solvent);
(0% by weight) of a carboxyl polyelectrolyte; (2) a cross-linking agent reactive with carboxylate groups of at least 1% by weight (preferably not more than 10% by weight) based on the polyelectrolyte; and (3) lower alcohol, water,
or a mixture thereof.

Examples of these cross-linking agents are haloalkanols, amphoteric sulfoniums, haloepoxy alkenes, &lJ glycidyl ethers, bisphenol A-ebichlorohydrin resins, and mixtures thereof.

In certain cases such as making films or fibers, plasticizers such as cellulose ethers, cellulose ethers, alkyne glycols, glycerin and mixtures thereof may be added in an amount of 10 to 50% by weight (preferably 15 to 50%) based on the polyelectrolyte. (25% by weight) is preferably included in the composition.

The present invention further provides that the compositions described above are deposited on separate films, absorbent articles, granules, fibers and various substrates at temperatures above 30°C, and desirably from 90" to about 150°C.
This includes methods for making acid products from these methods that can be heated to C. The use of these high temperatures is advantageous in promoting cross-linking and drying of the polyelectrolyte. However, if desired, it may be desirable to replace most of the water in the polyelectrolyte solution with a lower alcohol such as methanol or ethanol. This substitution results in a lower solution viscosity at a given percent solids and facilitates drying.

The final product of the invention is therefore water-swellable and useful whenever there is a need to absorb aqueous solutions. Examples of various uses include surgical sponges, menstrual tampons, diapers,
Meat trays, paper towels, disposable doorway mats, disposable bathroom mats, and disposable bedding for domestic pets.

Examples of carboxyl synthetic polyelectrolytes useful in the present invention are ammonium or alkali metal salts of acrylic or methacrylic acid homopolymers and one or more ethylenically unsaturated comonomers. The only limitation is
Any copolymer useful in the preparation of highly absorbent polymers according to the invention must be essentially water-soluble in its salt form. Alternatives to maleic anhydride and maleic acid and fumaric acid and esters (cobo+)
w- is useful when made water-soluble with a suitable base. One skilled in the art of free radical addition copolymerization will create any number of suitable heteropyrimers containing sufficient carboxylate functionality to render them water soluble and thus useful in the present invention.

A list of applicable carboxyl polymers which can be made from readily available monomers and which can be converted into their salt form is as follows: Niacrylic acid - acrylate - tocobirimer acrylic acid - Acrylamide Copolymer Acrylic Acid-Olefin Copolymer Polyacrylic Acid Acrylic Note-Aromatic Vinyl Cosmer Acrylic Acid-Styrene Sulfonic Acid Copolymer? Acrylic acid-vinyl ether copolymer Acrylic acid-vinyl acetate copolymer Acrylic acid-vinyl alcohol copolymer Copolymer of methacrylic acid and all of the above comonomers Maleic acid, 7-malic acid and their esters and all of the above comonomers Copolymers Copolymers of maleic anhydride and all of the comonomers mentioned above If desired, the polyelectrolytes mentioned above can be sulfonated by treatment with SO3, chlorosulfonic acid or fuming arsenic acid in an inert organic solvent. be.

As indicated above, in many cases it will be desirable to add a malleable agent to the polyelectrolyte solution to soften the film or cast. A disadvantage of using plasticizers is that many effective plasticizers are also wetting agents and make polyelectrolyte articles extremely sensitive to high temperature moldings through chill hydrolysis of the corresponding acrylates and acrylates. When converted to a remer, about 80% or more of the acrylate units (mar) must be converted before the polymer becomes water soluble. This is due to the alkali attack on the polymer particles from the outside, and in this case, the outside N I
The J mama-child is modified more by ester hydrolysis than in the interior of the particle. At the high degree of hydrolysis required to make all polymers soluble,
The resulting polymer is more similar to polyacrylates than to salts of polyacrylic acid. The flexibility of the original diacrylate has been replaced by the glassy brittleness of the salt. This brittleness is highly undesirable for water-swellable (absorbent) articles.

By pre-treating polyelectrolytes of the type disclosed above, namely polyacrylates, in the following manner, the formation of coatings and other highly water-absorbing articles which are flexible and therefore do not require the use of plasticizers is possible. It has further been found that it is possible.

A preferred type of polyelectrolyte is a polyacrylate that has been pretreated with a partial oxidation of the alkyl acrylate units in the polymeric chain. If this □ is left unattached, cross-linked articles formed from partially fused polyacrylate solutions may require the addition of special water-degradable desensitizers such as glycerin. In this preferred manner, the polyacrylates, which are also soft and flexible, are partially saponified with an alkali metal hydroxide solution before the final product is made. Generally, the method for preparing this polyacrylate is to prepare (1) an alkyl acrylate in which the alkyl group has 1 to 10 carbon atoms, carbon W in which the alkyl group has 4 to 10 carbon atoms, in an aqueous alkali metal hydroxide solution;
50 to 92 weight range of alkyl methacrylates with fjf<, or mixtures thereof.

(2) from 8i to 70% by weight of an olefinically unsaturated carboxylic acid; and (3) from Ot to 15% by weight of a ω-hydroxy-alkyl acrylate having 1 to 4 carbon atoms in all hydroxyalkyl groups. 30 to 70 by dissolving acrylate
It is characterized by the steps of forming a polyacrylate solution with % by weight of alkali metal carboxylate and heating this solution until saponification is complete. A crosslinker is then added to the polyacrylate as disclosed herein.

The alkali-soluble polyacrylates can be made by known techniques such as emulsion, clouding, bulk, or solution polymerization techniques. .

Most preferably, an alkali-soluble latex having 15 to 60 weight percent non-volatile polymer solids is used.

Examples of useful alkyl acrylates are methyl acrylate, ethyl acrylate, propyl acrylate, hexyl acrylate, and the like. Examples of useful alkyl methacrylates are butyl methacrylate,
Hexyl methacrylate, octyl methacrylate, decyl methacrylate and the like.

Examples of useful omega hydroxyalkyl acrylates are 2
-hydroxyethyl acrylate, hydroxymethyl acrylate, 3-hydroxypropyl acrylate and 4-hydroxybutyl acrylate.

The aforementioned polyacrylate is then dissolved in an aqueous alkali metal hydroxide solution. The equivalent weight of the hydroxide solution commonly used is 30 to 70 percent based on the molar concentration of the polymerized monomer, and the desired amount is about 40 to about 55 percent.

In any case, 1 of the hydroxide G solution added is alkali metal carboxyl-)KE
Y: Or was it sufficient to understand the alkali metal carboxylate by converting and using the polyacrylate's sword-bosyl group and thereby converting it? The reacrylate will have a weight capacity of 30 to 70 polyalkali metal carboxylates.

The olefinically unsaturated carboxylic acids used in this invention can be mono- or polycarboxylic acids.

Examples of mono-olefinic monocarzanoic acids are acrylic, methacrylic, croton, ink, azhicolic, tigrin, secondioic acids or mixtures thereof.

Examples of heptanoolefin polycarzanic acids are maleic, fumaric, itaconic, aconite, terraconic, citraconic, mesaconic, glutaconic acid.

A list of cross-contaminating agents useful in the present invention includes 1,3-dichloroinpropanol; polyhaloalkanols such as 113-dibromoinzolopanol; both ε nalunium (
114-butanediyl diglycidyl ether; Glycerin-1,3-diclycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, about 175 to about 3
Does it have an epoxy equivalent weight in the range of 80? There is a bisfuninol A epichlorohydrin epoxy resin having an epoxy equivalent weight ranging from about 182 to about 975 and a mixture of the foregoing.

Compounds containing two or more of the aforementioned staining agent functional groups would be expected to be useful as well, and under the conditions encountered in the heating or drying of molecular electrolyte solutions, these compounds would be expected to be useful as well. The same applies to the precursors that form the functional groups.

The cross-linking technique used in the present invention to convert polyelectrolytes into insoluble but water-swellable polymers is known as nucleophilic substitution on saturated carbons.

The carboxylate ions on the polyelectrolyte act as nucleophiles, regardless of whether the cross-linking agent is a substrate for the attack. Typical detachment (1eavi, nggroup
) groups and their corresponding substrates are shown in the table below.

A combination of any two or more of these leaving groups on the same substrate can be used as a polycarbonate compound (K) as a cross-linking agent.

Table 1 Ct-alkyl chloride R-CL Br-alkyl bromide R-Br Ni Iodide Arcel Co., Ltd. HO-alcohol R-〇H RO-ether ROR, R8R O0 , II.

RC-0-ester, R-button-R -oso R1 alkyl sulfonate R-○S○2R1
108OCt Alkyl chlorsulfide R
O3OCL-O? CL2 Alkyl chlorophosphite P, -○Pct2-OPBr2 Alkyl bromophosphite R-OPBr2-O8OR'
Alkylsulfinite RO8OR' Go table:'ζ
According to the present invention, several compounds of the present invention can be used as cross-linking agents. Once insolubility is reached, higher levels of the mixture will swell in the permanent medium to form a more elongated, less unstable gel, but less Actual absorption capacity &
IJ Mama - Give it.

1.3-dichloroinzolopanol 1-10%
Ebibromuhito1non O5-10
% Nipiepyrhydrin 1-10
e! 6 Glycerin diglycidyl ether oio-
4s% novolax sulfonium ion 1-
The rate of 10% cedar replacement is related to humidity and is a factor in this invention. If the zero degree of cross-linking agent in the composition is very low, the reaction rate will be quite slow (pot life of 10 to 43 hours) once the composition is applied to the substrate surface. When the bow powder evaporates quickly, the speed of cross-sliding is accelerated.

If heat is applied at this point, the reaction speed will be increased even more.

If the initial composition is overheated, aged, or exposed to excess diaphragm mixture, the absorbent article of the present invention will not be resistant to oxidation.

The composition becomes more viscous and viscous until it is spread, sprayed, or spun into a two-dimensional solution.
form a le.

Non-inventively useful plasticizers include heptalulose nitrates such as methylcellulose, nitylcellulone, and the like; cellulose esters such as cellulose acetate, cellulose butyrate, and the like; ethylene glycol, Alkylene glycols such as diethylene glycol, propylene glycol, and the like; glycerin, diglylene glycol (2,3
-zohydroxyderopyl ether), triglycerin,
and glycerin, such as tetraglycerin; polyethylene glycols having an average molecular weight of about 200 to about 400.

In a preferred method of making water-swellable films according to the present invention, the polyelectrolyte composition described above is spread on a flat sheet or roller of metal, plastic, or other impermeable substrate and heated to 30°C. 710 at high temperature
Heat to cross-link the polyelectrolytes and drive off excess water and/or alcohol. The film is then stripped from the plate or roller by a scraper to recover the salable film for storage or use.

In some cases, it may be desirable to add a small amount of a surfactant to the polyelectrolyte composition to aid in the removal of the webbing film from the water-impermeable substrate during flow and combing. A secondary benefit of using a surfactant is to enhance the wetting and tightness of the dry absorbent film final product. Either anionic or nonionic surfactants can be used. Examples of useful surfactants are alkyl sulfonic acids)
ethylene oxide derivatives of IJium and alkylated fininols and the like.

At the same time, when an absorbent article is made, the ester article is coated with this composition and the coating is cross-contaminated. It goes without saying that for the purpose of non-invention, there are two types of provisional five-stage stain complete coverage or cutting-edge covering, so is it suitable for ceramic, paper, woven or uncut? When fibrous substrates such as cloth and the like are used as substrates, the composition may be applied categorically, i.e., in large dots, squares, or grid lines. It is possible to retain the flexibility of the quality material and at the same time widely improve its non-absorbability. Plasticizers are not necessary in this case. The wood pulp can be ground into a slurry during polyelectrolyte formulation and swelled.

If desired, the water-swellable film prepared as described above can itself be used as the inner absorbent layer of baby diapers. This film can easily be broken down into flakes, strips or powder. This process is completed by crushing the film in a mill and crushing it into fine powder, although the compounding process is not as good as this.

If a long strip is required, it is possible to cut the film into wide slices using a suitable cutting machine.

In some cases, water resistance lines are desired. These can be made by extruding the polyelectrolytes described above into a C bath consisting of lower alkyl ketones such as acetone, -methyl ethyl ketone, diethyl ketone, and the like. The alcoholic composition can be extruded into chlorinated hydrocarbons, ie, non-aqueous detergents such as methylene chloride, perchlorethylene, and the like.

This soft extruded T7! The Usua is then removed from the bath by any convenient means such as 3 or 5 nerol clusters and heated to about 30°C.
The polyelectrolyte' is transported through a heated chamber to a temperature higher and preferably within the range of about 70' to about 150°C.
f! The J fibers are dried and bonded again.

Moreover, the absorption capacity of the combined polymer electrolyte (9 number of the solution made into a kelized solution of 7/1 material 19) is the combined urine (0,2
It is determined by the following method using 7N chloride).

Weigh 0.59 of a sample of the cross-contaminated polyelectrolyte and place it in a 250-cm beaker, pressurize 3-27N sodium chloride solution (150 ml) into the beaker, and let it cool to room temperature without stirring occasionally. Soak for 2 hours. Then, filter and collect the swollen polyelectrolyte, and report the volume as 9@ of the solution per 1 g of polymer salt.

The following English text is given for the purpose of explanation and does not limit the invention.

Example 1: Poly(imbutylene-col E-cumulative maleic acid)
A solution of IJ Umbu was made with deionized water, and 14.7.9 of this solution was spiked with 0.28.9 (8.7 weight range solid) of 1.3-dichloroimpropanol.
゛Sodium lauryl sulfonate 2-part solution 10
After allowing the c-side to cool for 40 minutes until all the bubbles disappeared, the solution was poured onto a clean polyethylene sheet using a 25 mil pull bar. When dry, the film separates from the golyethylene. - Even after overnight drying, the film is still under water. After 30 minutes at 060 DEG C., the film absorbs 64 times its own weight of 0.27 NNaO2 without dissolving it.

After 1 hour at 100'C, the absorption capacity (Kel capacity) was 0.0% for the film 11'@25 g of 0,27 N NaCL, indicating that the cross-linking reaction was qualitatively complete. (Imbutylene-disodium co-maleate) was made into a 25-width water C solution, and 10 g of this solution was added to 0.29 g of this solution.
(Part 8) of epibromohydrin, 1 part of water, and 2 parts of
4 liters of sodium lauryl sulfonate.

The film was stretched on Mylar, peeled the film from the Mylar sheet and cured for 2 hours at 100°C.
EXAMPLE 3 Example 2 was repeated using C1,059 (2%) shrimp bromohydrin in the wasca. This film absorbed 76 times its own weight of 0,27 N NaCt without dissolving it.

Example 4 Rokur+ and Haas Aku 1 Summer-Toru A-
5f' polyacrylic acid (25 solids in water) was neutralized with a stoichiometry of about 3 NaOH and treated with 10 tbsp of shrimp bromohydrin and the film was stretched onto Mylar.

After heating at 85℃ overnight, this film has a resistance of 0.27N.
It gave an absorption capacity of 5497ji in NaCL.

Example 5 Example 2 was repeated using 0.259 (10 weight solids) of epichlorohydrin as the cross-linking agent. 70°C
After drying overnight at 100 mL, the film gave an absorbency of 92979 in 0.27 N NaC4.

Example 6 1, OMffi% glycerin diglycidyl ether and 207J'fi% cQ Methocel
■ MC25 (?: methyl heptylulose having a viscosity of 25 cpB relative to the melt in S7) was used as a plasticizer, and Example 4 was repeated. After drying overnight at room temperature, the film was rough but sag h. After curing for 2 hours at 70°C, the film absorbed 33.69/9 of 0.27 N NaCL and 2269/9 of deionized water.

Example 7 Pyri (imptylene-co-ammonium-semi-amide diluted neat) in a 25-wide water 1'' (glycerin diglycidyl ether (1aMi% x glycerin (30% by weight of golimer) on a polymer basis), and The film was treated with 10 drops of sodium lauryl sulfonate.The film was stretched on a Mylar sheet and left overnight at room temperature.The film had an absorption capacity of 10.29 in 0.27 NNaCL.
The melt throat/g polymer.

Practical Example 8-14 A film was stretched on a sheet using various types of glycerin diglycidyl ether as a cross-linking agent in place of epibromohydrin, and -3-i conversion was carried out at rz +2. The results are shown in Table 1.

The 11A 26 m1 table shows the greater activity of glycerin diglycidyl ether (
efficiency). A smaller amount of molecule is required for curing, and curing occurs at room temperature.

Performance example 15 p ur 3- f 10 COx-17 8% 7K of acrylamide sodium acrylate copolymer
The melt was treated with 110% (by weight) glycerin diglycidyl ether, 25 gm of glycerin, 158 sides of two-width sodium lauryl sulfonate and a film was formed. Dry overnight at room temperature and store at 80"
This film was cured for 3σ in a Q furnace.
．． 27 N NaCtcP gave a gel volume of 159/i.

Experimental Example 16 An aqueous solution consisting of 25% solid poly(imbutylene-comaleate disodium) 109, 10 drops of two-width sodium lauryl sulfonate, and OJ 59 (2,0%) of shrimp bromohydrin. Covered with English paper towel. When dry, this removal σ becomes 36 bows of the full weight of the towel in Rl- in S, and this stone-covered boat is 153 in deionized rice fields! The untreated towel had an absorbency of 79 grams compared to 2.54979 grams.

Example 17 A foamed polystyrene inner plate was prepared using 209 22-linked adhesive (imbutylene-disodium maleate) and o, 1y
9 (4%) of dichloroimbupanol. - The weight of the coating after overnight drying is 0.7 g.
Atsushi. For a capacity of 19.9 bath liquid/g coating, the broken dish absorbed 5 g of IJ of 0.27>I HaCL W solution: ″l:.

Example 18 An ammonium semi-amide salt of ethylene-maleic anhydride copolymer (viscosity 82 al)s for 5% water solubility was made into a 25-g water solution. 8.0g saw and 10
A drop of 2% sodium lauryl sulfonate was formulated. The solution was spread onto a Mylar sheet using one 15 mil rod and allowed to cure for two days at room temperature. This film is 1
16E of O-27N Na':t(
D absorption'l giving Lri.

EXAMPLE 19 An ammonium-hemiamide salt of a styrene-maleic anhydride copolymer (175 ap8 to 5 water za) was treated as in Example 18 above. This film is 0.2'
It gave an absorption capacity of 5.4 g/g film in 7 N NaC2.

Example 20 Example 19 was repeated using only 1 weight percent glycerin diglycidyl ether.

After curing overnight at room temperature, this film weighed 13.2 g/g.
of 0.27 N N2LC6 was absorbed.

Implementation 121 Methyl vinyl ether Sakai 7 with maleinated copylimer (G
A film was prepared as in Example 18 using a disodium solution of AF Gantrez AN169) as a 15-width solid water-soluble α and using 3.3-glycerin diglycidyl ether as the cross-mixing agent.

After curing overnight at room temperature, this film cured itself (7
) it i noj 5.4 times 9.27 N Na0
Example 22 Inbutylene maleic anhydride copolymer (15,4,9
, 0.1 mol) in 200 g of methyl alcohol and added 1-g of pyridine to the sludge, and the mixture was stirred at SO'C for 24 hours until it became transparent. The polymer is precipitated in water, dried in water and diluted with caustic water. A 25% clear solution of the methyl half ester of the copolymer and IJ salt was obtained in rICK solution.

10 grams of this liquid was treated with 29 grams (1,16 grams) of glycerin diglycidyl ether and 10 drops of sodium 2-thirauryl sulfoate, and the solution was poured onto a Mylar sheet at 25 mils. I expanded it and made a film. After pregelatinization overnight at room temperature, the polymer became insoluble and 352g/9 of deionized water and 9f!
/9 of 0.27N NaCL was absorbed.

The cross-linking reaction was carried out at 17 m9 (0,68i3i%)
When the film was lowered to 5s, 69/! 9
of ionized salt solution and 7209/ji of deionized water. This same film absorbed the 279/9 salt solution after being placed in a 90° C. oven for 30 minutes, so the cross-linking reaction was not complete.

Ability level 23: Can you solve the Kohirima folding water object into the calculated amount of aqueous sodium and water? A 40% solids water bath was made of (imbutylene-disodium comaleate). 2
0 g of this solution was mixed with 0.4 g (51 wt% d-rimer) of glycerin diglycidyl ether. Extrusion room (departing)
× 2 “Pipe with ball valve at the bottom and extruded tip as an extrusion”
with the outlet of the tube) and fill the r-de (αopa
) was directly extruded into a 12" deep acetone bath.

A single gram of moxibustion was pumped onto the bottom of the bath and withdrawn at the end of the session. 2 to press the spinning dope through the extrusion top.
22 under a pressure of 5 psig was used.

After drying at 10° C. for 2 hours, the absorbent capacity of the piled fibers was examined. It is 2Bi/9 synthetic urine (0,27NNaC2)
and 1389g of deionized water were absorbed.

Example 24 Poly(°inbutylene-comaleate disodium)
25% of the polymer weight was formulated with 25% of glycerin and 2.5% of glycerin and 2.5% of the polymer weight.
ε-shaped Mylar sheet Kichi film from water-soluble j. The film was cured at 80'C for 1 hour and then flattened in SO width and humidity at the back of the room.The film was cut into strips of approximately 2 = width. When cut into flat sections, the stimulant rapidly absorbed 14 times its own weight of synthetic 92 and 55 times its own weight of deionized water.

Example 25 25% solid water of disodium salt of inbutylene hemihydrate maleic acid copolymer disclosed in Example 3B of patent @3,660,431 with a few drops of 2% sodium lauryl sulfonate 51% of an aryl ampholytic sulfonium copolymer.

A film was formed and dried at 100° C. for 13 hours. The cloudy film absorbed 58 times its weight in synthetic urine and 300 times its weight in deionized water.

Actual series 26 Making a film from 254-A/GQ, α of zonodium inbutylene/=nonmaleic acid copolymer and 0.75 gi % glycidyl ether:
After hardening for 3 hours at 0100°C, this film was
Absorbed 2g/g of synthetic urine. When this dry film was crushed into a small cylinder, it showed the same absorption, and when it was crushed in a crusher and produced in the Song Dynasty, it was 74f! It rapidly absorbed synthetic urine to the extent of 799 days.

Implementation ylJ27-32 Add sodium hydroxide from latex 7 of poly(methyl acrylate) and dilute with water to prepare poly(sodium acrylate-comethyl acrylate), 7.5 ratio 7X of 80% sodium acrylate. A film was spread on a glass plate using various amounts of glycidyl ether as a t0 cross-activating agent, and was fluorinated in an oven at 125° C. for 1 hour. The results are shown in Table 3.

Chapter ■ Dragon 27, 2, 5
172i3 1,0
1930 0j5
4131, 0.10
98, but in the absence of any of this polyelectrolyte, the film does not become swellable even after drying and heating. For an agitated water/dwelling cell, at least 0.12 quantity is required, the exact quantity depending on the polymer, cure, and end use.

Example 33 A 90/10 copoly7-25 water clear solution of sodium styrene sulfonate and sodium acrylate was added to 0.0
This monomer solution was prepared by boiling down the monomer solution overnight at 50°C in the presence of 4 parts by weight of 28208 (persulfuric acid processed). 8 g of this solution was mixed with 75 m9 (3 widths) of chrycerin diglycidyl ether and a film was ε-shaped on Mylar. After 2 hours of rough aging in nitrogen, the film was removed and placed in a 90°C oven for 1 hour. Gel capacity is 45
9/9 0.27N NaCt 1'Z Ri Example 34? Reacrylic acid (Rohm ana Eaas ACr
A 25-win solution of 7901 A-5) was treated to 1 part of sodium hydroxide and diluted to a 20-win solid. It can be mixed with Ro[F]736 of this daytime α. D, E-R
,■736. It is a diglycidyl ether of polypropylene glycol with a molecular weight of 250 and having E, E, and N of 75-205. Dry and cured film (0,59) of ε-shaped film on a chrome plate, air dried for 3 days and then cured in an oven at 1506C for 2 hours.
0,27 N NaC2 solution 7 Temporarily dispersed 2 and 1
After infiltration for 150 hours, this swollen 71Jmer
Collected on mesh sieve and weighed. This scale is 4
The absorption capacity was 82 g per 1 g of polymer 19.

Example 35 Mons (ethylene-motupyl comaleate) Mons
A 50ml solution of anto EMA 3122 was treated with 11ml of sodium hydroxide and diluted to 25% solids.

This capacity was adjusted as in Example 33 to 1. s C5D,
E.

R736 and films were made and tested. The absorption capacity was 39 g per gram of dIJ Mama.

Shoton Series 36-44 Three mixtures with the following composition were made: 75g TritonGR-s 77.2g 2.09i4FAe1-75.9'Sodium ÷ Dioxotyl Sodium -2 minutes for Ai
! Place in a reactor and warm to 40°C under a vigorous nitrogen flow. Part B of No. 18 was inserted into this reactor at 710 mm, and all parts of C part were inserted into this reactor. While maintaining the 2 rolls at 39-4' 1°C, the remaining portion of B was added over a further 2.5 hours. This latex was steamed in L4 at 60°C for 1.5 hours, cooled to 30°C and stored in bottles. This latex contains 40.6g of non-volatile content.

Gently stir a solution of 187.16 g of 50% NaOH dissolved in 99 deionized water for 5 days.The above latex 1125! After all of the ROBORIMER obtained at 71[+] was dissolved in a small stream over 25 minutes, the viscous bath was heated at 50° C. for 22 hours to completely transform it into Ω. The resulting solution (25.4% solids) has a Brookfield viscosity at 25°C of 16,200 cps (λ5 spindle, 1
0 rpm). This polymer is 50% in moles
of ethyl acrylate and the remainder were acrylic acid and sodium methacrylate.

Samples of the above 2 wholesalers D, 3, R0 ■ 736 Nibonshi Tora finger and polished; Ram version top: C25 mil bow 1
It was made into an ε shape. After air drying, the film was removed from the board and weighed in an oven at 150° for 2 hours. The 0.27 N Nacz cP absorption capacity (kel capacity) of various films is shown in Table V.

Chapter V Table 3.5 J15 0 57. d37
0.2' 0 36,238
0.25 0 3459 0.25
20 37. a40 0.5
20 28.2.11 1.0
20 19.542 5.0 ,,
20 6.4i13 5+0 0
10.444. 10.0 0 7
．． 2 Nari, E-R, o736 ha first method 2 IC) 7 Seton VcFJ power and then 8! Disperse 25g of 25c6 golimer in a 1" temporary S.

Table v lists the epoxies m A
In the case of W, E explains the need for a co-solvent or a carrier such as acetone to obtain sufficient crosslinking at high levels of developer. At extremely low wood rates, epoxy resin alone can be dispersed and react efficiently enough.

Examples 45-52 Using 20 amorphous dispersions of D, E, [, ■661' (bisphenol A-dibichlorohydrin epoxy resin having an ego capacity in the range of 475-575). Then, the method of Yihengaku 36-44 was repeated. The film thus produced was tested in a similar manner and the results are shown in Table V. Table 45 2.0 20
, '7846'' 2.5
20 40.647 3
．． 0' 2G 46.6
48 3.0 0
5.64?
20 68.450 5.0
Table 20 32.4 shows the performance of solid, water-insoluble epoxy resins. Without a co-agent, the resin and the polyelectrolyte react only on the surface of the blind fat granules, and the reaction is subtle and efficient. not good. After swelling in a co-solvent, the cross-linking capacity I is significantly improved.

Examples 53-61 The method of Examples 36-44 was repeated using diglycidyl ether of neopentyl glycol as the curing agent. The results are shown in Section 1).

Summary 111 -Table 53 0.15 0
8054 0+20 0
ao, 655, 0.25
0 47・656 0.5
20 31.457 1
．． 0 20 21.658
j5 20 11+8
59 5.0 20
9.260 5.0 0
1261, 1G, 0, ,
G 5+8* DGENG is the diglycidyl ether of neopentyl glycol.

Performance Example 62-6B The method of Examples 36-44 was repeated using diglycidyl ether of 1,4-butanediol (DGEBD) as the fecalizing agent. The results are shown in Table 1.

Chapter)] Dragon 62 0, i5 0
59 863 0+20
0 4. i664.
05 20 2186ε
1 20
drunk 66 5, o 2o
7.667 5.0
0 9.268 10 0
(] 6,
Example 69 Five mixtures were made with the following compositions.

Part A Part B Part C Ethyl 0.6g Surfactant* 37g Acrylic 2-2゜3
g Hydroxyethyl sodium bisulfite 2.19 Sodium persulfate 28p Methacrylic acid width
8. Reacrylic acid 3.19 Tertiary-dodecyl mercaptan* Dioctyl sodium sulfocinate (Trit
on GR-5).

Part A was placed in a 21 reactor and warmed to 4°C under vigorous nitrogen flushing. Part B of 18- was added to the reactor followed by the entirety of Part C. Temperature 159-41°
The remainder of Part B was added over an additional 2.5 hours while maintaining the temperature at C. The latex was then steamed at 40°C for 15 hours, cooled to 30°C and stored in bottles. This latex contained 39.5% non-volatile content.

The 400p latex prepared above was dissolved in 120g of deionized water with hydroxide (mixed with 20g of arsenium at 75°C to make a 30% polymer solution), which was 31.4
% acrylic acid and sodium methacrylate by weight. 10.9 g of the above solution and 50 μg of glycerin diglycidyl ether (i, 0% hardening agent based on the weight of the polymer) were mixed together.

Sheetra cast onto a mirror-finished chrome plate using a 25 mil drawbar, air dry, and heat at 70°C for 1 hour.
Furnace hardening was carried out for 5.5 hours and 0.5 hours at 90°. This remer sheet absorbed 23 times its own weight of synthetic urine (0.27N NaCl @17 ) in the absorption capacity test described above.

Examples 70-75 Example 6 with varying amounts of sodium hydroxide and hardening agent
'l method was repeated. The results are shown in Table 1 together with Example 69.

In these cases, there is an inverse relationship between softness and suction power, and the best quality of this product is that it has about 50% residual acrylic acid. ester and cross-linked with about 0.15% by weight glycerin dicrycidyl ether.

Example 76 Example 69 was repeated using the monomer mixture below and less initiator and without the marcabutane chain terminator to increase molecular weight.

Part A Part B Part C 600g deionized water 437.5 j! Acrylic 175g Deionized GR-5-acidium 1.75g
Sodium persulfate polymerization was carried out at 60°C and yielded a latex with 40.6% non-volatile content.

A solution of 187.16 g of 50% NaOHf in 547.9 jj deionized water was added to the above latex in one small stream over a period of 25 minutes while stirring gently. After all of the Hilimer has dissolved, the viscous solution is heated to 55°C for 22 hours to complete the molding. The resulting solution (25.4% solids) had a Brookfield viscosity of 16,200 Cps (No. 5 spindle, 10 revolutions per minute) at 25°C. This polymer has 50 moles
% ethyl acrylate and the remainder was acrylic acid and sodium methacrylate.

32.9% of the above solution was blended with 16 ml (0.2% by weight) of glycerine diglycidyl enitel and cast onto a chrome board loaded with a 25 mil draw bar. After air drying, the film was removed from the plate and placed in a 150°C oven. 0.27N Nact after 20 minutes of curing
The absorption capacity (gel capacity) of this film in 1 g of polymer Nikki 64I solution. The film was strong and flexible straight out of the oven and required a crease to be cut in order to tear.

8 g of the heated solution prepared in Example 76 was mixed with various amounts of 1,3-dichloroisozoropanol and films were cast from these mixtures in the manner of Example 76 and hardened ( The gel capacity of this film is shown in Table X.

Table
S number of 0,27 N NaCz per Billy r-1,j9 These examples are p, C, engineering,, P, 2. It shows that it is close to % by weight.

Example 81-8'8 Example 7 to change the content of sodium acrylate
The latex of Example 76 was prepared and heated by the method shown in Section 7, with varying amounts of hydroxide (hysodium).

Each solution was formulated with a different amount of 8g total glycerin diglycidyl ether. The film was then cast onto a polished chrome plate, air dried for 14 hours, and heated in an oven at 150'Q.
It made me hard for 2 hours. The absorbency was determined as described above and the softness at 45% relative humidity was recorded. These results are shown in Table V.

81 55 0.2 44.4 Soft 8
2 '52 0.2 48.8 Soft 63
50 0.2 49.6 Somewhat like a song 1
34 4(] 0.257.2 Brittle 85550.17552.4 Soft 86 52 0175 56.3 Soft 87
50 0175 56.4 Somewhat soft 88 40 0175 6o, o Brittle E, A, = Ethyl acrylate G, DJ = Glycerin diglycidyl ether It is shown that an increase of up to 52 mole % without significant loss results in a slenderable and desirable soft product.

Example 89 Three mixtures were made with the following compositions: Engineering 1E 230.9 Deionized Water 0.39 'l'riton GR-51, Og N
a2S208 (sodium persulfate) 10.09 itaconic acid part B 209 methacrylic acid 170 g ethyl acrylate part C 70 j J deionized water 1-25 ji N a HS O3 in part A 21 placed in reactor and heated to 60°C under vigorous nitrogen flow It was heated to Then part B of 20- was added followed by all of part C. 1 at 60°C for the remainder of 833 minutes.
Added continuously over time.

This latex was boiled at this temperature for 1 hour to yield a final latex with a total non-volatile content of 40.6%.

100.9 of the above latex was then mixed with 50% hydroxyl (aqueous sodium chloride solution) and 49.1 g of deionized water and heated at 55° C. for approximately 10 hours to form a polyelectrolyte containing 52 mole % ethyl acrylate. A total of 25% solution was given.

This polyelectrolyte was also calculated to have:

51% by weight ethyl acrylate 30% by weight sodium acrylate 2.0 g of the above polyelectrolyte F459 water and 7-5
g (0.15%) of glycerin diglycidyl ether. A 25 mil drawbar was used to cast the film onto a polished chrome plate and the film was air dried at room temperature for 6.5 hours and then heated in an oven at 150°C for 16 hours.
．． I was given a hard massage for 5 hours. The absorption capacity of the final feces (Hifilm) was found to be 41 g per 1 g of polymer in the above absorption test with synthetic urine.

Example 89 shows that the polymerization recipe and method can be varied significantly but still allow the production of superabsorbent polymers.

Claims (1)

Claims: a) 5 to 60% by weight, based on the amount of solvent, of a carboxylic polyelectrolyte or a mixture thereof, reactive with at least 0.1% by weight, based on the polyelectrolyte, of carboxylate groups; b) forming a coating or fiber from the solution, and c) heating such coating or fiber to dissolve the polyelectrolyte. A process for producing water-swellable polyelectrolyte-coated films or fibers, characterized by cross-linking and removing excess solvent.