CN1006846B - Interpenetrating polymeric network foams comprising cross linked polyelectrolytes - Google Patents
Interpenetrating polymeric network foams comprising cross linked polyelectrolytesInfo
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- CN1006846B CN1006846B CN 85103792 CN85103792A CN1006846B CN 1006846 B CN1006846 B CN 1006846B CN 85103792 CN85103792 CN 85103792 CN 85103792 A CN85103792 A CN 85103792A CN 1006846 B CN1006846 B CN 1006846B
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- absorber
- polymer
- acrylic acid
- copolymer
- acid
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Abstract
The present invention relates to an absorber which absorbs body fluid and has high liquid-retaining property. The absorber includes microporous polymer absorbing material and microvesicle interpenetrating polymeric networks containing cross-linking polyelectrolyte.
Description
The invention relates to provides a kind of microvesicle polymer that is applicable to absorb body fluids, sanitary towel for example, menopad, diaper, binder, surgical dressing etc.These materials are commonly referred to as the foamed materials that is used for these products.What suggestion was adopted is urethane foam material and cellulose foam material etc.
Although these foamed materialss are absorb body fluids to some extent substantially, their character is not enough to as diaper, products such as sanitary towel.A shortcoming is that these foamed materialss are hydrophilic, has absorbed a large amount of water when therefore beginning, and these liquid are easy to be extruded and when being under pressure, and promptly the liquid retention of these foamed materialss is very poor.Its reason is: most liquid is mechanically to remain in the space of microvesicle in foamed materials because the deformation that causes of ambient pressure, thereby the wall that destroyed microvesicle reduced can receiving fluids volume, so liquid just has been extruded.Need not illustrate that these cause that the pressure of deformation is to be produced by the user of dressing these g. absorbent products.
Suggestion once infiltrates in the foamed materials other polymer absorbing agent to improve its liquid retention.Usually it is water-fast that these that are referred to as hydrocolloid or superabsorbents add polymer, the polyelectrolyte of swellable, this polyelectrolyte can inspiration itself weight manyfold liquid, and under pressure, retaining these liquid, this insoluble polyelectrolyte is sneaked into foaming mixture with the solid particle state in the foamable reaction process.This foaming mixture generates foamed materials, so polyelectrolyte just is distributed in the last foamed materials matrix.In British patent 1,550, set forth this technology in 614.Regrettably when generation material during by liquid wets, some the swollen and superabsorbents glue sample are easy to deviate from from the foamed materials matrix, so just reduced the ability of the liquid hold-up of foamed materials microvesicle.Find also that in addition the major part of superabsorbents is encapsulated in the high molecular foamed materials matrix, therefore stoped to contact, thereby limited its swelling and the probability of maintenance liquid with liquid.
Therefore need the microcellular polymer material absorbing material that better approach provides the energy liquid hold-up.
According to explanation of the present invention, it is that foamed materials is used for absorbent product that a kind of microcellular polymer material material is provided.This microcellular polymer material material has the water retentivity that has improved greatly, does not have a defective on those former microcellular polymer material material liquid retainabilities.The present invention provides specially and has been the absorber of absorb body fluids.This is the network polymers of crosslinked polyelectrolyte of containing of a kind of microvesicle interpenetration.
In technology in the past, known mutually saturating polymer network (IPN ' S), for example in following article:
Sperling L.H.J.Poly.Sci，Macronol Re V.，12，141，（1977），
Frisch H.L.，Frisch，K.C.，Klempner，D.，Chemtech，7，188，1977;
Lipatov，Yu，s.，Sergeva，L.M.，Russ.Chem.，Rev，45，63（1976）;
Jerome，R.，Desreux，V.，J.Appl，Poly.Sci.，15，199（1971）。
They can be defined as the poly-polymeric mixture of being made up of two or more mutual synthetic polymer network.From molecular level, they can be counted as two kinds of molecules that lock mutually, are not chemical bond between them, but physically inseparable.In other words, polymeric blends often is unsettled on the thermodynamics, therefore causes being separated, and on the other hand, under the situation of IPN, thereby has avoided being separated with the molecular level interlocking.
Reported the different routes of producing IPN ' S, three main routes are:
(1) synthesize a kind of polymer network, suck the monomer of second polymer then, then polymerization and crosslinked, product is the IPN that a kind of substep generates.
(2) mix two kinds of different types of prepolymers, then carry out polymerization and crosslinked by the mechanism that it doesn't matter mutually, therefore avoided the chemical bond of two individual system, product is a kind of IPN of synchronous generation.
(3) earlier synthetic a kind of polymer network, the monomer with second kind of polymer not containing cross-linking agent absorbs it then, so obtain a kind of line polymer during polymerization, it is not interlocking and obviously be and first kind of polymer network twines that product is called as false IPN.
The present invention considers all these methods of producing IPN ' S of three types, is included in to have at least a kind of network polymers to foam in the system, i.e. and microcellular polymer material, another kind of then be crosslinked poly-electric matter.Foamed polymer can be from various parents, and as polymer, the oligomer of responding property, monomer or other component that generates microcellular polymer material that can foam prepares.
Applicable polymer should with water-based latex form provide, as the aqueous latex of styrene-butadiene, the aqueous latex of styrene-butadiene-acrylonitrile, the aqueous latex of polyurethane, the aqueous latex of epoxy or acrylic acid latex.
The oligomer of available responding property is for example: the polyurethane of isocyanate end has the polyester of unsaturated carbon carbon bond, epoxy oligomer, aminoplast (for example melamino-formaldehyde, the plain formaldehyde of urea) or phenolic resins.
Useful monomer is isocyanates or epoxide for example.
Polyelectrolyte and cross-linking agent and foamable prepolymer mix, in the process of foaming or foaming back crosslinked.But it is never crosslinked before foaming.They only are crosslinked by carboxyl functional group, and not with foamable polymer reaction.Consequently: the microvesicle material is the physical blending thing of the polymer of an interlocking, thereby is IPN.
At one preferably in the example, make a kind of softness and be imbued with the foamed materials of flexural properties by the prescription of foaming, the water that promptly comprises q.s to be to keep solution state, the water miscible polyelectrolyte of q.s arranged and be used for the cross-linking agent of this polyelectrolyte.For example system is: the polyether polyol of isocyanate end, the ratio of it and water is 1: 1(weight), be proposed in recent years and be used for producing the Hdyrophilic polyurethane foamed materials.W.R.Grace company sells the foamable polymeric system of this class with commodity Hypol by name.
The invention provides a kind of absorbent that is used for absorb body fluids, it is a kind of mutually saturating polymer network of crosslinked electrolytical microvesicle that contains.One of component of network polymer is a microcellular polymer material, and they can be produced from parent, as polymer, and the monomer of responding property or oligomer.These parents can foam when gas is arranged.Second component of this system is polyelectrolyte, and be preferably water miscible, and it can carry out crosslinked to generate mutually saturating polymer network with first component in foaming process or after the foaming.
The polymers compositions that is used to foam can be one of aqueous dispersion of many known polymer or oligomer, can generate solid foamed materials with foaming agent or the continuous bubble that produces down that stirs.The example of this latex has polyurethane, SB, and styrene-butadiene-acrylonitrile is the nitrile polymers altogether, epoxy, acrylic acid aqueous dispersion latex.Ethyl acrylate is for example arranged, acrylic acid methyl ester., methyl methacrylate, the polymer of butenoate and their copolymer.Also can adopt synthetic rubber or even natural rubber latex.In addition, can polymerization in the presence of gas in the foaming process and the monomer and the oligomer of the responding property of foaming be suitable for.As: epoxy-terminated oligomer such as epoxy-terminated polyether, epoxy-terminated polyalkylene oxides (as poly(ethylene oxide), poly(propylene oxide) and their common polymers), they can be in polymerization in the presence of the catalyst, as tertiary amine or boron trifluoride.Perhaps with the chain growth polymerization of primary amine or secondary amine.Carrying out the oligomer of the unsaturated polyester (UP) of radical polymerization in the presence of catalyst, mix with foaming agent, also is suitable.In addition, the amido plastics are to share as melamino-formaldehyde or urea-formaldehyde and phenolic resins.These oligomers can carry out polymerization in the presence of acid catalyst.
The system of selecting for use comprises the polyurethane oligomer of isocyanate end, polymerization and emit carbon dioxide during the reaction of it and water, thus generated solid polyurethane foamed material.The polyether polyol of the isocyanate end of the commodity that W.R.Grace company sells Hypol by name is this system.
The carboxylic acid electrolyte components that generates foam IPN of the present invention is known on technology, as in US Patent No 4,310, sets forth in 593, and this patent is incorporated this paper into by quoting as proof.The main points of feasible polyelectrolyte are: they contain at least the enough carboxylate groups with the form of salt, make the polyelectrolyte can be water-soluble, thereby can be sucked into the matrix of foamed polymer before crosslinked.If the polymer that share can prepare and it can be changed salify for deliquescent needs from very facile monomer, as acrylic acid and acrylic ester copolymers, acrylic acid-acrylamide copolymer, acrylic acid-olefin copolymer, polyacrylic acid, acrylic acid-ethylene base aromatics composition copolymer, acrylic acid-styrene sulfonic acid copolymer, acrylic acid-ethylene base ether copolymer, acrylic acid-vinyl acetate co-polymer, acrylic acid-ethylene alcohol copolymer, methacrylic acid and top all monomeric copolymers, maleic acid, fumaric acid and their ester and top all monomeric copolymers, maleic anhydride and top all monomeric copolymers.
According to the present invention, a lot of suitable crosslinking agent are suitable for, certainly these cross-linking agent can with the acid-base reaction on the poly-electrolyte, obtain IPN of the present invention but can not react with foamable matrix polymer matrix.In US Patent No, set forth these cross-linking agent in 4,008,353, as many fontanels substituted alkyl alcohol, as 1,3 dichloroisopropanol, 1,3 dibromo isopropyl alcohol; Sulfonic acid amphion, for example the Tetramethylene sulfide adduct of phenolic resins; Fontanel is for epoxide such as epoxychloropropane, epoxy bromopropane, 2-methyl epichlorohydrin and epoxy iodopropane; Polyglycidyl ether such as glycerin diglycidyl ether, Ethylene glycol diglycidyl ether, propylene glycol diglycidylether, the mixture of a condensed ethandiol diglycidyl ether and above-mentioned these chemical compounds.
I about the United States Patent (USP) of crosslinked carboxylic polyelectrolyte and preparation method thereof in set forth best cross-linking agent, this cross-linking agent is low-molecular-weight in general, water soluble compound.At least the functional group of containing two bondings, the general formula of this group is:
R can select hydrogen for use separately herein, has the alkyl of 1 to 3 carbon atom or has the alkenyl group of 1 to 3 carbon atom.These functional groups preferably are connected on the aliphatic chain of aliphatic chain or replacement, and main is that this chain will be small enough to guarantee soluble in water.Preferably the molecule of chemical compound is less than less than 1000.This fat or replacement aliphatic chain can be the alkylidenes of 2 to 12 carbon atoms, the alkylidene of replacement such as alkylidene hydroxide: butylidene alcohol, butylidene glycol.The mercaptan of hydrocarbon such as butylidene mercaptan.The ether of aliphatic compound is as a condensed ethandiol or tirethylene glycol, the fat of the ester of fatty compound such as triglyceride or trimethylolpropane.
These several chemical compounds are commercial to be provided, and those skilled in the art is all understood, and according to above-mentioned general introduction, can synthesize wherein chemical compound lot.Effective especially group is the addition compound product of aziridine on the trimethylolpropane tris propionic ester in these chemical compounds, and molecular formula is:
Sell with trade name TAZ by Aceto chemical company.
Another compounds effective is based on the addition product of pentaerythritol triacrylate, and molecular formula is:
Sell with trade name TAZO by Aceto chemical company.Similar chemicals described above is also sold with trade name XAMA by Cordoba chemical company.Also available other polynitrogen heterocycle propane functional compounds is as being skeleton with triazine or phosphate ester, as three (1-azacyclopropane base) phosphine oxide, three (1-azacyclopropane bases), phosphine sulfide, 2,4,6-three aziridine base-S-triazine.
Below room temperature to 150 ℃, the carboxyl reaction on aziridine base functional group and the carboxylic polyelectrolyte is carried out very soon.Certainly reaction temperature improves response speed just increases.By open loop, course of reaction carry out as shown in the formula:
As mentioned above, when the carboxyl of multi-functional aziridine molecule and adjacent polyelectrolyte takes place when crosslinked, at these intermolecular bridges that just formed.
The general synthetic route of microvesicle IPN of the present invention is: the aqueous solution that at first generates polyelectrolyte and cross-linking agent and an optional surfactant.The size of these surfactant may command bubble or provide and have higher wettable final products.In the ordinary course of things, cross-linking agent must guarantee at least that to the ratio of polyelectrolyte polyelectrolyte does not dissolve, and can not arrive the swelling behavior that influences cross-linking products greatly again.Usually use and be not more than the polyelectrolyte of the cross-linking agent of 30 parts of weight, most preferably less than the cross-linking agent of 20 parts of weight to 100 parts of weight.
When cross-linking agent is preferably during the polyfunctional group aziridine, its concentration in solution approximately is 0.2% to 20% concerning the electrolytical weight of carboxylic acid.More suitable is 0.5% to allusion quotation 5%.Is best from 1% to 10%.For a kind of polyelectrolyte, the concentration of aziridine is too low can not to guarantee that polyelectrolyte does not dissolve.On the other hand, the concentration of too high aziridine will make crosslinked have lower swelling behavior and low absorptive capacity.These character also change with the molecular weight of uncrosslinked polymer.Low-molecular-weight polyelectrolyte needs the cross-linking agent of higher concentration.The polyelectrolyte of higher molecular weight then uses more a spot of cross-linking agent.In general, in order to obtain best absorbent properties, must make the undissolved minimum cross-linking agent of polyelectrolyte.
According to of the present invention, the solution and the foamable parent that contain polyelectrolyte, cross-linking agent and optional a kind of surfactant mix.Crosslinked polyelectrolyte will be high enough to improve effectively the water retentivity of foamed polymer to the ratio of foamable parent.Under the situation of the polyurethane oligomer parent of the best, if use too high ratio, the foam IPN of gained is hard, and no resilience also causes producing out of contior bulla.Generally must be between 3% to 50% based on the percetage by weight of the polyelectrolyte of the parent that can foam, preferably from 5% to 20%.
In the production of foam mixture, must be to the foaming parent, polyelectrolyte, the water that adds q.s in cross-linking agent and the surfactant mixtures is with the quality problems that solve foregoing polyelectrolyte and cross-linking agent and foaming process can be carried out.When the latex that uses each manufacturer to sell is aqueous dispersions,, usually need to add again in addition water in order to keep other component in solution.
Following Example has been narrated the manufacture method of product of the present invention and product and the method for improving product property.
Example 1:
With 100 gram water, 12.5 (Rohn and Haas company produce the gram polyacrylic acid, trade name Acrysol A-5) and 6.5 the gram sodium hydroxide make solution, the cross-linking agent (Aceto chemical company produces, trade name TAZO) of the solution of the sodium polyacrylate that generates and 0.2 gram, three aziridine functional groups mixes.This aqueous solution and 100 gram Hypol4000 polyurethane are given polymers (W.R.Grace company product) to be mixed.In high shear mixer, fully mix.Mixture at room temperature foams, and inserts in one 65 ℃ the air circulation case 12 hours after 1 hour again up to drying.The foamed materials softness that generates, density is 3.3 pounds/foot
3
Diameter of weighing is 2 inches, and thickness is 3/8 inch disk shape dried foam material sample, immerses then in the beaker fill the 1%Nacl aqueous solution 1 hour.Wet foamed materials is suspended on 15 seconds in the air.And then weighing.Every gram foamed materials has absorbed the sodium-chloride water solution of 31 grams.
Under static pressure and dynamic pressure, measure the liquid retainability of foamed materials.Static pressure test, wet foamed materials wafer sample be placed on one hard sieve plate on, a polyacrylate cylindrical tube has covered the limit of disk, a heavy plunger of 2 jin inserts in the cylinder exerts pressure to disk, and stopper is placed on sample last 15 minute till not having more liquid to flow out by sieve plate from sample.The weighing sample is to measure liquid holdup then.This routine foam sample of every gram has kept 8 gram Nacl aqueous solutions under static pressure test.
Dynamic pressure test: at short notice, apply higher pressure to estimate extruding at the liquid under pressure that happens suddenly.Wet foam sample places between two filter paper, and the cylinder average rate of one 10 pound weight is rolled so that pressure to be provided, and repeats after twice of this operation weighing again with the mensuration liquid holdup.This routine sample, every gram foamed materials have kept 19 gram Nacl solution.
Example 2(comparative example):
Except not adding the polyacrylic acid polyelectrolyte, repeat the step of example 1.The foamed materials softness that generates, density is 3.1 pounds/foot
3The absorptive capacity of foamed materials is the Nacl aqueous solution of 29 grams 1%.The same with example 1 haply.But the foamed materials of example 2 is in static pressure and dynamic pressure test, and every gram foamed materials only is detained 4.7 gram Nacl aqueous solutions.
Example 3:
Except in foam mixture, adding outside the 1 gram organic silicon surfactant (Union Carbide Corp produces, trade name L-562), repeat the operating procedure of example 1.The foamed materials that generates is except because of having used this surfactant to produce the bigger hole bubble, and its character is identical with example 1.This structure has been accelerated the defeated diffusing of foam interior liquid, has increased absorption rate.Should be noted that this wet foam material is because the polyelectrolyte polymers swelling, thereby increased by 75% volume.
Claims (11)
1, a kind of absorber of absorb body fluids, this absorber comprise the mutually saturating polymer network of the microvesicle that contains crosslinked polyelectrolyte.
2, the absorber of claim 1, the mutually saturating polymer network of wherein said microvesicle comprises a kind of foamed materials, this foamed polymer and crosslinked polyelectrolyte are crosslinked shape, generate the mutually saturating polymer network of IPN(completely).
3, network polymers absorber, this absorber comprises a kind of foamed polymer, said foamed polymer and crosslinked polyelectrolyte are linear, generate false IPN.
4, the absorber of claim 1, wherein said foamed polymer generates from foamable matrix polymer.
5, the absorber of claim 4, wherein foamable matrix polymer is selected styrene-butadiene for use, styrene-butadiene-acrylonitrile, polyurethane, epoxy polymer or acrylate copolymer.
6, the absorber of claim 1, wherein said foamed polymer is generated by a kind of oligomer parent of foamable responding property.
7, the absorber of claim 6, wherein the oligomerisation parent of said foamable responding property is selected the polyurethane of isocyanate end for use, has polyester, epoxy oligomer, aminoplast or the phenolic resins of unsaturated carbon carbon bond.
8, the absorber of claim 1, wherein said foamed polymer are to be generated by a foamable monomer precursor.
9, the absorber of claim 8, wherein said foamable monomer is selected isocyanates or epoxide for use.
10, the absorber of claim 1, wherein said crosslinked polyelectrolyte are a kind of water miscible carboxylic polyelectrolytes.
11, the absorber of claim 10, wherein said water-soluble carboxylic acid's polyelectrolyte is selected acrylic acid and acrylic ester copolymers for use, acrylic acid-acrylamide copolymer, acrylic acid-olefin copolymer, polyacrylic acid, acrylic acid-ethylene base aromatics composition copolymer, acrylic acid-styrene sulfonic acid copolymer, acrylic acid-ethylene base ether copolymer, acrylic acid-vinyl acetate co-polymer, the rare alcohol copolymer of acrylic acid-second, methacrylic acid and top all monomeric copolymers, maleic acid, fumaric acid and their ester and top used monomeric copolymer, the salt of br dilute anhydride and top all monomeric copolymers and top all polymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 85103792 CN1006846B (en) | 1984-04-27 | 1985-05-13 | Interpenetrating polymeric network foams comprising cross linked polyelectrolytes |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/604,710 US4613543A (en) | 1984-04-27 | 1984-04-27 | Interpenetrating polymeric network foams comprising crosslinked polyelectrolytes |
| CN 85103792 CN1006846B (en) | 1984-04-27 | 1985-05-13 | Interpenetrating polymeric network foams comprising cross linked polyelectrolytes |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85103792A CN85103792A (en) | 1986-12-10 |
| CN1006846B true CN1006846B (en) | 1990-02-21 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 85103792 Expired CN1006846B (en) | 1984-04-27 | 1985-05-13 | Interpenetrating polymeric network foams comprising cross linked polyelectrolytes |
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| Country | Link |
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| CN (1) | CN1006846B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| PL1931397T3 (en) * | 2005-10-05 | 2009-08-31 | Essity Hygiene & Health Ab | Absorbent article comprising hydrophilic and hydrophobic regions |
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1985
- 1985-05-13 CN CN 85103792 patent/CN1006846B/en not_active Expired
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| Publication number | Publication date |
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| CN85103792A (en) | 1986-12-10 |
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