CN1093139C - Cationic polymer - Google Patents
Cationic polymer Download PDFInfo
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- CN1093139C CN1093139C CN95197178A CN95197178A CN1093139C CN 1093139 C CN1093139 C CN 1093139C CN 95197178 A CN95197178 A CN 95197178A CN 95197178 A CN95197178 A CN 95197178A CN 1093139 C CN1093139 C CN 1093139C
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- Prior art keywords
- water
- polymkeric substance
- swellable
- radical
- insoluble
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- 229920006317 cationic polymer Polymers 0.000 title description 4
- -1 vinyl compound Chemical class 0.000 claims abstract description 39
- 239000000178 monomer Substances 0.000 claims abstract description 21
- 229920000642 polymer Polymers 0.000 claims abstract description 15
- 239000002250 absorbent Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 10
- 238000010521 absorption reaction Methods 0.000 claims abstract description 8
- 239000008346 aqueous phase Substances 0.000 claims abstract description 8
- 239000011953 free-radical catalyst Substances 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims description 59
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- 239000003513 alkali Substances 0.000 claims description 13
- 239000003999 initiator Substances 0.000 claims description 11
- 150000003254 radicals Chemical class 0.000 claims description 11
- 150000002500 ions Chemical class 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 7
- 238000010538 cationic polymerization reaction Methods 0.000 claims description 7
- 125000000524 functional group Chemical group 0.000 claims description 7
- 241000370738 Chlorion Species 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 239000004160 Ammonium persulphate Substances 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical group [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 claims description 4
- 230000005906 menstruation Effects 0.000 claims description 4
- 210000002700 urine Anatomy 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 3
- 125000004185 ester group Chemical group 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 229960003761 propamidine Drugs 0.000 claims description 3
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical group [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical group [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 0.000 claims description 2
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical group C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- YIOJGTBNHQAVBO-UHFFFAOYSA-N dimethyl-bis(prop-2-enyl)azanium Chemical compound C=CC[N+](C)(C)CC=C YIOJGTBNHQAVBO-UHFFFAOYSA-N 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 2
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical group [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 claims description 2
- 125000000962 organic group Chemical group 0.000 claims description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 claims 1
- 206010067482 No adverse event Diseases 0.000 claims 1
- 125000001033 ether group Chemical group 0.000 claims 1
- 125000001424 substituent group Chemical group 0.000 claims 1
- 150000003512 tertiary amines Chemical class 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 43
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract description 13
- 239000003431 cross linking reagent Substances 0.000 abstract description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 abstract 2
- 229920003176 water-insoluble polymer Polymers 0.000 abstract 2
- 230000002745 absorbent Effects 0.000 abstract 1
- 125000002091 cationic group Chemical group 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 235000002639 sodium chloride Nutrition 0.000 description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- 150000003839 salts Chemical class 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 239000012153 distilled water Substances 0.000 description 13
- 239000000499 gel Substances 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 206010042674 Swelling Diseases 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 230000008961 swelling Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000012266 salt solution Substances 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 241001122767 Theaceae Species 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 230000036541 health Effects 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000010557 suspension polymerization reaction Methods 0.000 description 4
- 210000001124 body fluid Anatomy 0.000 description 3
- 239000010839 body fluid Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 239000004745 nonwoven fabric Substances 0.000 description 3
- 231100000572 poisoning Toxicity 0.000 description 3
- 230000000607 poisoning effect Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 101710134784 Agnoprotein Proteins 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- NJSSICCENMLTKO-HRCBOCMUSA-N [(1r,2s,4r,5r)-3-hydroxy-4-(4-methylphenyl)sulfonyloxy-6,8-dioxabicyclo[3.2.1]octan-2-yl] 4-methylbenzenesulfonate Chemical group C1=CC(C)=CC=C1S(=O)(=O)O[C@H]1C(O)[C@@H](OS(=O)(=O)C=2C=CC(C)=CC=2)[C@@H]2OC[C@H]1O2 NJSSICCENMLTKO-HRCBOCMUSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical group CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 206010046543 Urinary incontinence Diseases 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000012458 free base Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 150000001261 hydroxy acids Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910001412 inorganic anion Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002891 organic anions Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- NIAGBSSWEZDNMT-UHFFFAOYSA-M tetraoxidosulfate(.1-) Chemical compound [O]S([O-])(=O)=O NIAGBSSWEZDNMT-UHFFFAOYSA-M 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000000207 volumetry Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen
- C08F226/04—Diallylamine
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/42—Use of materials characterised by their function or physical properties
- A61L15/60—Liquid-swellable gel-forming materials, e.g. super-absorbents
Abstract
The invention provides a water swellable, water-insoluble polymer comprising units derived from a diallylic quaternary ammonium salt monomer cross-linked by a suitable polyfunctional vinyl compound, at least a substantial proportion of the function groups being in basic form. The invention also provides a process for the production of a water-swellable, water-insoluble polymer which comprises polymerising a diallylic quaternary ammonium salt monomer and a suitable polyfunctional vinyl compound as cross-linking agent by cationic polymerisation in an aqueous phase using a free radical catalyst and polymers obtainable thereby. The water absorbent polymers are superabsorbents having improved water absorption properties particularly in respect of saline solution.
Description
The present invention relates to a kind of cationic polymers, more specifically, relate to the material of a kind of so-called " super-absorbent " type.
Be commonly referred to the normally lightly crosslinked hydrophilic polymer of material of " super-absorbent ".The chemical property of these polymkeric substance can be different, but they all have and can absorb and keep the aqueous fluid that equals their own wt manyfolds, even also like this under middle pressure.For example, super-absorbent can absorb usually and reach as high as the distilled water of himself weight more than 100 times or 100 times.
Advised super-absorbent is used for many different industrial application, can utilize the advantage of its water-absorbent and/or stand-up in these are used, example comprises the preparation of agricultural, construction industry, alkaline cell and strainer.Yet the primary application field of superabsorbent material is the health care and/or the preparation of health product, the disposable diaper of using as disposable sanitary napkin and child or adult's urinary incontinence.In these health cares and/or health product, usually super-absorbent and cellulosic fibre are used in combination absorbed body fluid (as menstruation or urine).Yet super-absorbent significantly is lower than receptivity to deionized water to the body fluid absorption ability.It has been generally acknowledged that this effect comes from the electrolyte content of body fluid, and this effect is called " salt poisoning ".
The performance of the water-absorbent of super-absorbent and reservation water is owing to there is ionogenic functional group in this polymer architecture.These groups are carboxylate radical normally, and when this polymkeric substance during in drying regime, high-load carboxylate radical is the form of salt, but when contacting with water, having produced disassociation turns into and solvation.When its disassociation state, this polymer chain has a series of functional groups that link on this chain, and these functional groups have identical electric charge, and are therefore mutually exclusive.This causes the expansion of this polymer architecture, allows further to absorb water molecules thereby should expand, though this expansion is subjected to the crosslinked restriction that causes in this polymer architecture, and must be full cross-linked in this polymkeric substance to prevent the dissolving of polymkeric substance.Think: the disassociation of these functional groups has been disturbed in the big electrolytical existence of concentration in water, and has produced " salt poisoning " effect.Though most commercially available superabsorbent agent are anionic, can make functional group equally and be positively charged ion superabsorbent agent as the quaternary ammonium root.This class material also must be the salt formula to be used as the influence that superabsorbent agent and its performance also are subjected to salt poisoning.
EP-A-0161762 relates at least a diallyl quaternary ammonium salt, the partial cross-linked multipolymer of poly (dially dialkyl) base ammonium halide preferably.By preparing this polymkeric substance as external phase, water as the contrary suspension polymerization of discontinuous phase with oil phase.Directly the polymkeric substance of the form that is salt of preparation is considered to the polymkeric substance of water-swellable, and the water-absorbent of this polymkeric substance can significantly not reduce when being used for absorbing salt solution.Yet the specific embodiment of EP-A-0161762 relates to a kind of material, according to this specification sheets results reported, the water-retaining capacity of this material in 0.9% (weight) NaCl solution only be in the deionized water water-retaining capacity 20%.
An object of the present invention is to provide a kind of positively charged ion water-absorbing polymer improved water absorbing properties, that particularly absorptive character are high in common salt aqueous solution that has.
On the one hand, the invention provides a kind of water-swellable, water-insoluble polymkeric substance, this polymkeric substance contain from diallyl ammonium salt monomer preparation, by the crosslinked unit of suitable polyfunctional vinyl compound, it is characterized in that this polymkeric substance prepares with cationic polymers at aqueous phase with free radical catalyst.
On the other hand, the invention provides a kind of water-swellable, water-insoluble polymkeric substance, this polymkeric substance contain from diallyl quaternary ammonium salt monomer preparation, by the unit of suitable polyfunctional vinyl compound crosslink, it is characterized in that at least quite most this functional group is the form of alkali.
Again on the one hand, the invention provides water-swellable, a water-insoluble polymkeric substance of preparation, this method comprises: use free radical catalyst, by the cationic polymerization at aqueous phase, polymerization diallyl quaternary ammonium salt monomer and as the suitable polyfunctional vinyl compound of linking agent.
Be surprised to find that: the polymer phase ratio with EP-A-0161762, come polymerization diallyl quaternary ammonium salt monomer and suitable linking agent at aqueous phase with cationic polymerization, prepared obvious water-swellable, the water-insoluble polymkeric substance that has improved performance.More specifically, in deionized water and/or salt solution, show improved water-absorbent at aqueous phase by the polymkeric substance that cationic polymerization prepares.
As already mentioned, the polymkeric substance of EP-A-0161762 is prepared by anti-suspension polymerization.Different polymerization process between expection, EP-A-0161762 and the present invention, the cationic polymerization of promptly anti-suspension polymerization and aqueous phase will cause the difference of the finished product.These differences are: for example crosslinked homogeneity and the homogeneity of molecular weight.When these differences can not be differentiated and be definite, the improvement performance of the difference of performance, particularly product of the present invention showed that these products itself are different between the product.
The present invention is applicable to any diallyl quaternary ammonium salt monomer that is suitable for preparing the water-swellable polymkeric substance.In fact, these monomers have following general formula:
R wherein
1And R
2, can be identical or different, each is the organic group that this polymer properties is not had disadvantageous effect, X is suitable negatively charged ion.
Preferred R
1And R
2Each independently is optional saturated hydrocarbyl or the aryl that replaces.For example this saturated hydrocarbyl can be straight or branched or cyclic alkyl.This aryl can comprise aralkyl.Preferred group R
1And R
2Have 1-20 carbon atom, more preferably have a 1-6 carbon atom.This saturated hydrocarbyl or aryl can be selected from following suitable substituting group and replace by one or more: carboxyl, ester group, hydroxyl, ether, sulfate radical, sulfonate radical, primary, the second month in a season or tertiary amine groups or quaternary ammonium root.At ester (CO
2R), (under situation O-R), the R base is the alkyl with 1-20, preferred 1-6 carbon atom to ether, and more preferably R is a methyl.As for aryl, suitable substituting group comprises definition saturated hydrocarbyl as above.R
1And R
2Preferred group be methyl.
But X can be any inorganic or organic suitable anion.Suitable inorganic anion comprises halogenide (being specially fluorochemical, muriate, bromide and iodide) ion, nitrate radical, phosphate radical, nitrite anions, carbonate, bicarbonate radical, borate, sulfate radical and hydroxide ion.Suitable organic anion comprises hydroxy-acid group, as acetate moiety, citrate, salicylate and propionate.
Preferred this negatively charged ion is chlorion or hydroxide ion.
Preferred monomer is diallyldimethylammonium chloride and dimethyl diallyl ammonium hydroxide.
Particularly preferred diallyl quaternary ammonium salt monomer is a dimethyl diallyl ammonium chloride.
In the presence of radical initiator, the polymerization of diallyl quaternary ammonium salt monomer generates following linear polymer:
Wherein n is the number of monomeric unit.Still insoluble when the water swelling in order to guarantee this polymkeric substance, be necessary in polyreaction, to come in polymkeric substance, to introduce enough degree of crosslinking by adding suitable crosslinking agent.
Suitable linking agent is generally the vinyl compound that has one or more polymerizable double bonds in molecule.The object lesson of linking agent comprises Vinylstyrene and N, the N-methylene diacrylamine.The linking agent of q.s should be used, make that the absorptivity gelatinous material (AGM) of preparation is insoluble when contacting with the aqueous solution, but the usage quantity of this linking agent the ability of the absorption aqueous solution of AGM must not be influenced.The usage quantity of this linking agent (mole %) is in the 0.01-20% scope with respect to monomeric mole number, preferably in the 0.05-5% scope.
Cationic polymerization of the present invention carries out in water-bearing media in the presence of suitable radical initiator.Can use any that type free base initiator that is generally used for cationoid polymerisation, comprise organo-peroxide, as hydrogen peroxide, persulphate (as ammonium persulphate) and azo-compound (as 2,2-azo two (2-methyl-prop amidine) dihydrochloride).Preferred radical initiator comprises azo-compound, particularly Diisopropyl azodicarboxylate (" AZBN ").
Polymerization process can as described belowly be carried out:
Prepare following solution: a) 60% monomer solution.B) cross-linking agent solution of about 230 grams per liters in the distilled water.C) the radical initiator solution of about 60 grams per liters in the distilled water.
For example a) solution is bled with vacuum pump.Then at the following b of continuously stirring) and c) add a).This mixture heating up is arrived about 60 ℃.Form solid product after about 4 hours.This product is cut into pieces, and come swelling to wherein adding 4 liters of distilled water.After about 2 hours, with filtering this swollen gel as nonwoven fabric thin paper filter cloth.In as ventilated drying oven under about 60 ℃ of temperature about 10 hours of dry this gel, obtain about 100g drying products.
Can change alkaligenous form by the product that following operation handlebar obtains: this product of swelling in distilled water adds alkaline solution (as NaOH), about 1 hour this gel of after-filtration under continuously stirring.Repeat with hydroxide treatment and filtration, till in washing water, no longer including chlorion, this available Silver Nitrate (AgNO
3) precipitation titration measures.Is 7 with this gel of distilled water wash up to the pH of washing water.Dry this product is for example in the airy baking oven.
Except the difference of the performance of this product, the method itself that relates to solution polymerization in the water-bearing media of the present invention is better than anti-suspension polymerization among the EP-A-0161762.Particularly, the monomer that the solution polymerization in the water-bearing media need add in this reaction medium is less, does not for example need to add emulsifying agent, and this just makes the impurity that produces in the finished product less.In addition, along with the formation of high molecular weight product, this polyreaction is carried out better.
Method of the present invention has formed and can be used as the absorption agent that is salt formula or alkali formula that absorbs water or salt solution.With alkali conversion as the aforementioned, can obtain the alkali formula of this polymkeric substance from the salt formula of this polymkeric substance.
Be used to absorb salt solution, for example be used for absorbing and contain the liquid (as urine or menstruation) that is the salt formula, the polymkeric substance that uses the present invention to be the form of alkali has tangible advantage.In this case, when absorbing liquid, owing to the conversion of this polymkeric substance to its salt formula, this polymkeric substance also has desalting to this liquid.When polymkeric substance of the present invention is strong ion-exchanger, the spontaneous salt formula that is transformed into this polymkeric substance when this polymkeric substance contacts with salt solution.
Absorption agent of the present invention is suitable for being used in especially to be wished to absorb in the liquid, aqueous application of saliniferous.The example of these liquid is particularly including menstruation and urine, and this absorbing material can with as the blend of the fibrous absorber of cellulose villus as the filler in menopad and the diaper.Alkali formula absorption agent of the present invention can use with the negatively charged ion super-absorbent of free acid or the cationite of acid, and negatively charged ion absorption agent and cationite are respectively at the patent application No. of our pending trial ... (internal reference DR 24) and ... introduce in (internal reference DR 26).
Further introduce the present invention by following embodiment.
Embodiment 1
In the vacuum flask of a 150ml, the diallyldimethylammonium chloride of the following 10g 60% of continuously stirring and 0.0172g N, N-methylene radical-diacrylamine (linking agent) mixes.Feed nitrogen after 15 minutes to this reaction vessel bubbling, add 0.015g ammonium persulphate (radical initiator), and this reaction mixture is heated to 70 ℃, and under this temperature, kept 3 hours, continue to stir till this rod can not move with magnetic bar.This polymer formation colloidal sol also becomes solid.
Add a large amount of deionized waters to this polymkeric substance then, and allow this polymers swell 24 hours, form the swollen gel.Then in a forced convection oven in 100 ℃ of down dry these swollen polymkeric substance 10 hours, and this exsiccant polymer machinery reconcile into powder.The polymkeric substance of this generation is the form of salt.The following processing with alkali (NaOH 0.01M) is Cl
-The polymkeric substance of form obtains being the polymkeric substance of the form of alkali.
The 20g polymkeric substance is placed one 10 liters beaker, and to wherein adding 4 liters of distilled water.After this polymers swell, under continuously stirring, add 500ml NaOH.After 1 hour, filter this gel with nonwoven fabric thin paper filter cloth.Repeat NaOH and handle and filtration step, till in washing water, not having chlorion (with agentometic (reagent) volumetry) to occur.With this gel of distilled water wash, be neutral (pH7) then up to this water.60 ℃ of down dry these gels obtain product in a ventilated drying oven.
According to the method (method that is equivalent to introduce among the EP-A-0161762) that embodiment below 2 introduces, test the absorptivity of this drying powder to deionized water and 0.9%NaCl solution.
Its result is as follows:
| Absorptivity g/g (tea bag test) | ||
| Deionized water | 0.9％ NaCl | |
| Embodiment 1 is the polymkeric substance of salt formula | 320 | 55 |
| Embodiment 1 is the polymkeric substance of alkali formula | 350 | 48 |
| The polymkeric substance of EP-A-0161762 | 160 | 31 |
The above results shows: polymkeric substance of the present invention in deionized water and 0.9%NaCl solution all the polymkeric substance than EP-A-0161762 have surprising high absorptivity.Polymkeric substance of the present invention can both absorb liquid no matter the form that it is salt still is the form of alkali.
The preparation of embodiment 2Fai 7 OH
60% aqueous solution of 133g dimethyl diallyl ammonium chloride (DMAC is available from fluka) weighed add in the 250ml flask.
Separately 0.2g bisacrylamide (BAC is available from fluka) being weighed adds in the 5ml test tube, and is dissolved in the distilled water of 2ml.
0.12g ammonium persulphate (radical initiator) is dissolved in the 2ml distilled water in the 5ml test tube.
With vacuum pump this monomer solution is vacuumized.
Afterwards, under continuously stirring, this cross-linking agent solution and radical initiator are added in this monomer solution, by this flask is placed a thermostatic bath come this temperature transfer to 60 ℃ four hours.
The solid product of this generation is with scraper cutting and transfer in 5 liters of beakers that 4 liters of distilled water are arranged, and filters this swollen gel with nonwoven flimsy material filter cloth after two hours.This gel in draft furnace 60 ℃ dry 12 hours down.Collect 60g exsiccant polymkeric substance and be called Fai 7 Cl.20g Fai 7 Cl are placed one 10 liters beaker, and under continuously stirring, add 4 liters of distilled water swellings.When this polymkeric substance swelling (after 2 hours), add 500ml 0.01M NaOH solution, and after 30 minutes, filter this gel with nonwoven fabric thin paper filter cloth.Repeat these operations (alkalization and filtration), (chlorion can be by AgNO not have chlorion in these washing water
3Reaction is checked) till.Up to this washing water in do not have the sign of alkali reaction till with this gel of distilled water wash this moment.
In ventilated drying oven, descended dry these gels 12 hours afterwards, collect 10g exsiccant polymkeric substance and also be called Fai 7 OH at 60 ℃.
According to following tea bag method of testing, test the absorptivity of this dried powder in deionized water and 1%NaCl solution:
0.3gAGM weighed to add in the tea bag envelope, and is allowed to condition in the 250ml beaker that contains 150ml 1%NaCl solution (or deionized water) swelling 1 hour.Remove this beaker afterwards, allow this envelope still suspend 10 minutes, and the unabsorbed water of therefrom draining.Then the envelope that contains swelling AGM is weighed, and its absorptivity of following calculating:
A=(W
Wet-W
Do)/G
Wherein:
The A=absorptivity
W
Wet=contain the envelope weight of wet AGM, g
W
Do=contain the envelope weight of doing AGM, g
The dried AGM weight that G=used in should testing, g.
| The test of absorptivity g/g tea bag | ||
| Deionized water | NaCl 1％ | |
| Fai 7 OH | 351 | 55 |
| Fai 7 Cl | 340 | 54 |
Claims (21)
1. a water-swellable, water-insoluble polymkeric substance, contain from diallyl quaternary ammonium salt monomer preparation, by the unit of suitable polyfunctional vinyl compound crosslink, it is characterized in that this polymkeric substance is to prepare by cationic polymerization at aqueous phase with free radical catalyst.
2. a water-swellable, water-insoluble polymkeric substance contain from diallyl quaternary ammonium salt monomer deutero-, by the unit of suitable polyfunctional vinyl compound crosslink, it is characterized in that at least suitable functional group of vast scale is the form of alkali.
3. claim 1 or 2 described water-swellables, water-insoluble polymkeric substance, wherein this monomer has general formula:
R in the formula
1And R
2, can be identical or different, each is the organic group that this polymer properties is had no adverse effects, and X is suitable negatively charged ion.
4. the described water-swellable of claim 3, water-insoluble polymkeric substance, wherein R
1And R
2Each independently is optional saturated hydrocarbyl or the aryl that replaces.
5. the described water-swellable of claim 4, water-insoluble polymkeric substance, wherein this saturated hydrocarbyl or aryl can be selected from following suitable substituent and replace by one or more: carboxyl, ester group, hydroxyl, ether, sulfate radical, sulfonate radical, primary, the second month in a season or tertiary amine or quaternary ammonium group.
6. each described water-swellable, water-insoluble polymkeric substance among the claim 3-5, the wherein radicals R in ester group and the ether substituting group
1, R
2And the R group has 1-20 carbon atom.
7. the described water-swellable of claim 6, water-insoluble polymkeric substance, wherein R
1, R
2With the R base be methyl.
8. the described water-swellable of claim 3, water-insoluble polymkeric substance, wherein X is halide ions, nitrate radical, phosphate radical, nitrite anions, carbonate, bicarbonate radical, borate, sulfate radical or carboxylate anion.
9. the described water-swellable of claim 8, water-insoluble polymkeric substance, wherein X is chlorion or hydroxide radical anion.
10. the described water-swellable of claim 3, water-insoluble polymkeric substance, wherein this monomer is dimethyl diallyl ammonium chloride or dimethyl diallyl ammonium hydroxide.
11. the described water-swellable of claim 10, water-insoluble polymkeric substance, wherein this monomer is a dimethyl diallyl ammonium chloride.
12. a method for preparing water-swellable, water-insoluble polymkeric substance, comprise with free radical catalyst, at aqueous phase by cationic polymerization polymerization diallyl quaternary ammonium salt monomer with as the vinyl compound of the suitable polyfunctionality of linking agent.
13. the method described in the claim 12, wherein this linking agent is the vinyl compound that has two or more polymerizable keys in its molecule.
14. the method described in the claim 13, wherein this linking agent is Vinylstyrene or N,N methylene bis acrylamide.
15. each described method among the claim 12-14, wherein should with mole % represent with respect to the amount of the linking agent of monomeric mole number in the 0.01-20% scope.
16. the described method of claim 15, wherein this radical initiator is organo-peroxide, persulphate or azo-compound.
17. the described method of claim 16, wherein this radical initiator is hydrogen peroxide, ammonium persulphate or 2,2-azo (2-methyl-prop amidine) dihydrochloride.
18. the described method of claim 17, wherein this radical initiator is 2,2-azo (2-methyl-prop amidine) dihydrochloride.
19. each described polymkeric substance contains electrolytical liquid, aqueous purposes in absorption among the claim 1-11.
20. the purposes described in the claim 19, wherein this liquid is menstruation or urine.
21. the purposes described in claim 19 or 20, wherein this polymkeric substance is the form of alkali, and is used in combination with negatively charged ion super-absorbent that is free acid form or the cationite that is sour form.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ITT094A000888 | 1994-11-10 | ||
| IT94TO000888A IT1267493B1 (en) | 1994-11-10 | 1994-11-10 | CATIONIC POLYMER, FOR EXAMPLE OF SUPER ABSORBENT TYPE, RELATIVE PROCEDURE AND USE. |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1171796A CN1171796A (en) | 1998-01-28 |
| CN1093139C true CN1093139C (en) | 2002-10-23 |
Family
ID=11412878
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95197178A Expired - Fee Related CN1093139C (en) | 1994-11-10 | 1995-11-13 | Cationic polymer |
Country Status (11)
| Country | Link |
|---|---|
| EP (1) | EP0791019A4 (en) |
| JP (1) | JPH10509471A (en) |
| KR (1) | KR970707182A (en) |
| CN (1) | CN1093139C (en) |
| AU (1) | AU4234896A (en) |
| BR (1) | BR9509638A (en) |
| CZ (1) | CZ291871B6 (en) |
| HU (1) | HU216321B (en) |
| IT (1) | IT1267493B1 (en) |
| MX (1) | MX213693B (en) |
| WO (1) | WO1996015162A1 (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6232520B1 (en) | 1997-02-19 | 2001-05-15 | The Procter & Gamble Company | Absorbent polymer compositions having high sorption capacities under an applied pressure |
| US6222091B1 (en) | 1997-11-19 | 2001-04-24 | Basf Aktiengesellschaft | Multicomponent superabsorbent gel particles |
| US5981689A (en) | 1997-11-19 | 1999-11-09 | Amcol International Corporation | Poly(vinylamine)-based superabsorbent gels and method of manufacturing the same |
| US6072101A (en) | 1997-11-19 | 2000-06-06 | Amcol International Corporation | Multicomponent superabsorbent gel particles |
| US6342298B1 (en) | 1997-11-19 | 2002-01-29 | Basf Aktiengesellschaft | Multicomponent superabsorbent fibers |
| US6623576B2 (en) | 1998-10-28 | 2003-09-23 | Basf Aktiengesellschaft | Continuous manufacture of superabsorbent/ion exchange sheet material |
| US6121509A (en) * | 1998-01-07 | 2000-09-19 | The Procter & Gamble Company | Absorbent polymer compositions having high sorption capacities under an applied pressure and improved integrity when wet |
| JP4428729B2 (en) * | 1998-08-13 | 2010-03-10 | 株式会社日本触媒 | Water-swellable crosslinked polymer composition and process for producing the same |
| US6534554B1 (en) | 1999-10-27 | 2003-03-18 | Basf Aktiengesellschaft | Multicomponent ion exchange resins |
| US6997327B2 (en) | 2003-09-24 | 2006-02-14 | Velcon Filters, Inc. | Salt-tolerant, water absorbing filter |
| CN102603956B (en) * | 2012-01-18 | 2014-04-16 | 朗盛（常州）有限公司 | 2-hydroxyethyl diallyl ammonium chloride derivative and preparation method and application of 2-hydroxyethyl diallyl ammonium chloride derivative to leather retanning and fat-liquoring agent |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0161762A2 (en) * | 1984-03-26 | 1985-11-21 | Pony Industries Incorporated | Water swellable polymers having high water absorbency |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3879447A (en) * | 1970-05-26 | 1975-04-22 | Kendall & Co | Monomeric emulsion stabilizers comprising a lipophilic diallyl or dimethallyl quaternary ammonium compound |
| US3968037A (en) * | 1972-09-01 | 1976-07-06 | Calgon Corporation | Emulsion polymerization of cationic monomers |
| US5330656A (en) * | 1993-03-05 | 1994-07-19 | Calgon Corporation | Polysalt compositions and the use thereof for treating an oil and water system |
-
1994
- 1994-11-10 IT IT94TO000888A patent/IT1267493B1/en active IP Right Grant
-
1995
- 1995-11-13 CN CN95197178A patent/CN1093139C/en not_active Expired - Fee Related
- 1995-11-13 EP EP95940680A patent/EP0791019A4/en not_active Withdrawn
- 1995-11-13 JP JP8516229A patent/JPH10509471A/en not_active Ceased
- 1995-11-13 WO PCT/US1995/014676 patent/WO1996015162A1/en active IP Right Grant
- 1995-11-13 KR KR1019970703146A patent/KR970707182A/en active IP Right Grant
- 1995-11-13 HU HU9801032A patent/HU216321B/en not_active IP Right Cessation
- 1995-11-13 CZ CZ19971407A patent/CZ291871B6/en not_active IP Right Cessation
- 1995-11-13 BR BR9509638A patent/BR9509638A/en not_active Application Discontinuation
- 1995-11-13 AU AU42348/96A patent/AU4234896A/en not_active Abandoned
-
1997
- 1997-05-09 MX MX9703449A patent/MX213693B/en not_active IP Right Cessation
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0161762A2 (en) * | 1984-03-26 | 1985-11-21 | Pony Industries Incorporated | Water swellable polymers having high water absorbency |
Also Published As
| Publication number | Publication date |
|---|---|
| CZ140797A3 (en) | 1997-10-15 |
| EP0791019A4 (en) | 1999-03-03 |
| WO1996015162A1 (en) | 1996-05-23 |
| JPH10509471A (en) | 1998-09-14 |
| HU216321B (en) | 1999-06-28 |
| ITTO940888A1 (en) | 1996-05-10 |
| CZ291871B6 (en) | 2003-06-18 |
| MX9703449A (en) | 1998-07-31 |
| HUT77804A (en) | 1998-08-28 |
| IT1267493B1 (en) | 1997-02-05 |
| AU4234896A (en) | 1996-06-06 |
| KR970707182A (en) | 1997-12-01 |
| BR9509638A (en) | 1997-10-14 |
| MX213693B (en) | 2003-04-11 |
| ITTO940888A0 (en) | 1994-11-10 |
| CN1171796A (en) | 1998-01-28 |
| EP0791019A1 (en) | 1997-08-27 |
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