CN110402267A - The preparation method of water-absorbing resins - Google Patents
The preparation method of water-absorbing resins Download PDFInfo
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- CN110402267A CN110402267A CN201880019427.2A CN201880019427A CN110402267A CN 110402267 A CN110402267 A CN 110402267A CN 201880019427 A CN201880019427 A CN 201880019427A CN 110402267 A CN110402267 A CN 110402267A
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Abstract
The preparation method of water-absorbing resins is to include by the preparation method of the water-absorbing resins of the coarse crushing process of the aqueous gel progress coarse crushing of cross-linked polymer, wherein, the temperature of foregoing aqueous gel in coarse crushing process is 35 DEG C or less, by the preparation method of the water-absorbing resins, improve the reproducibility of the size distribution of gained water-absorbing resins.
Description
Technical field
The present invention relates to the preparation methods of water-absorbing resins.
Background technique
Water-absorbing resins are in recent years in agricultural such as the hygienic materials such as paper nappy or physiological articles, water-retaining agent or soil conditioners
It is widely used in the fields of various absorbent commodities such as the industry goods, materials and equipments such as horticultural materials, water-stop or resistive connection distillate medicinal water.Water imbibition tree
Rouge according to its purposes and it has been known that there is multiple types, but wherein main use by and making water-soluble olefinic polymerization of unsaturated monomers
Water-absorbing resins made of the obtained polymer (hereinafter referred to as cross-linked polymer) with cross-linked structure.As its preparation side
Method can enumerate the aqueous gel that cross-linked polymer is prepared by aqueous solution polymerization, suspension polymerisation etc., the side being then dried
Method etc..
In patent document 1, as preparation method, disclose for example by water solution polymerization process prepare it is described be crosslinked it is poly-
The aqueous gel (the hereinafter referred to as aqueous gel of cross-linked polymer) for closing object, by containing for the cross-linked polymer obtained as block
It after hydrogel is heated to 45~90 DEG C of temperature and coarse crushing, is dried, dried object is crushed, implement granularity adjustment as needed
With it is surface-crosslinked, thus obtain the water-absorbing resins as final products.
In patent document 2, it discloses in container, the aqueous gel shaped polymer application with cross-linked structure is cut
Shear force and the preparation method for being subdivided into granular graininess aqueous gel shaped polymer, which is characterized in that for temperature
It is heated to 40~110 DEG C of aqueous gel shaped polymer and applies 0.01~1.5kg/cm2Load, simultaneously repeatedly apply shearing
Power.
In patent document 3, the preparation method of graininess aqueous gel shaped polymer is disclosed, is by that there will be friendship
The aqueous gel shaped polymer for being coupled structure is squeezed out by the porous plate of the thickness in hole and 1~20mm with 3~20mm of aperture and is made
The method of standby graininess aqueous gel shaped polymer, wherein the temperature of the aqueous gel shaped polymer is 35~90 DEG C.
In patent document 4, it discloses using gel grinding device and prepares water-absorbing resins, the gel grinding device
It is the gel grinding device that there is screw rod, supply mouth, extrusion, porous plate and roller and be used to prepare water-absorbing resins, it is special
Sign is in gel pulverizing process to use at 40 DEG C~120 DEG C.
It in these methods, is all the temperature that the temperature of aqueous gel is set higher than to 35 DEG C or 40 DEG C, use is porous
The specific device such as plate or pressurization lid carries out the coarse crushing of aqueous gel.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 9-309916 bulletin
Patent document 2: Japanese Unexamined Patent Publication 5-112654 bulletin
Patent document 3: Japanese Unexamined Patent Publication 6-41319 bulletin
Patent document 4: No. 2015/030129 bulletin of International Publication.
Summary of the invention
Invent the project to be solved
Although also depending on the type of polymerizing reactor, as will be obtained from water-soluble olefinic polymerization of unsaturated monomers
The block that cross-linked polymer can be used as aqueous gel obtains.In general, the aqueous gel of resulting cross-linked polymer is after coarse crushing
For drying, then dried object is crushed, as needed carry out granularity adjustment and it is surface-crosslinked, thus obtain as final products
Water-absorbing resins.But present inventor has performed researchs, as a result known to resulting water-absorbing resins exist according to preparing item
Part, the reproducibility for being easy to generate deviation such problems, especially size distribution between preparation batch (ロ ッ ト) are low.
The object of the present invention is to provide the deviations between the reproducibility for the size distribution for improving water-absorbing resins, preparation batch
The preparation method of few water-absorbing resins.
Solution for solving the problem
The present inventor in order to solve the above problems, has untiringly carried out making great efforts research, as a result, it has been found that: in the preparation of water-absorbing resins
It is and including that the temperature of the aqueous gel of cross-linked polymer is set as to 35 DEG C or less that aqueous gel progress is thick in method
The reproducibility of broken process, the size distribution of resulting water-absorbing resins is got higher.
That is, the present invention provides the preparation method of water-absorbing resins, be include by the aqueous gel of cross-linked polymer into
The preparation method of the water-absorbing resins of the coarse crushing process of row coarse crushing, wherein the temperature of the above-mentioned aqueous gel in coarse crushing process is
35 DEG C or less.
The effect of invention
By using preparation method of the invention, the reproducibility of the size distribution of gained water-absorbing resins can be improved.
Specific embodiment
Hereinafter, suitable embodiment of the invention is described in detail.But the present invention is by embodiment party below
Formula is limited.
The aqueous gel preparation section > of < cross-linked polymer
The aqueous gel of cross-linked polymer in the present invention can be for example, by that will contain the water of water-soluble ethylenically unsaturated monomer
Water-soluble ethylenically unsaturated monomer in solution (hereinafter also referred to " monomer solution "), which is polymerize, to be obtained.
(water-soluble ethylenically unsaturated monomer)
As the water-soluble ethylenically unsaturated monomer being used in the present invention, such as (methyl) acrylic acid can be enumerated (in this theory
In bright book, " acrylic " and " methylpropenyl " is denoted as to " (methyl) acrylic " together.It is same below.), maleic acid, Malaysia
The carboxylic serials monomer of the α such as acid anhydrides, fumaric acid, beta-unsaturated carboxylic acid and its salt etc.；(methyl) acrylamide, N, N- dimethyl (first
Base) acrylamide, (methyl) acrylic acid 2- hydroxy methacrylate, N- methylol (methyl) acrylamide, polyethyleneglycol (methyl) third
The non-ionic monomers such as olefin(e) acid ester；(methyl) acrylic acid N, N- diethylamino ethyl ester, (methyl) acrylic acid N, N- diethyl amino
The amino-containing unsaturated monomers and its quaternary ammonium salt etc. such as base propyl ester, diethyl amino propyl (methyl) acrylamide；Vinyl sulphur
Acid, styrene sulfonic acid, 2- (methyl) acrylamide-2-methyl propane sulfonic, 2- (methyl) acryloyl group ethanesulfonic acid and they salt
Equal sulfonic acid system monomer etc..These water-soluble ethylenically unsaturated monomers may be used singly or in combination of two or more.
Specifically, water-soluble ethylenically unsaturated monomer is preferably selected from (methyl) at least one of acrylic acid and its salt.
(methyl) acrylic acid and its salt can be made to be copolymerized with other water-soluble ethylenically unsaturated monomers to use.In this case, in water
, it is preferable to use 70~100 moles of % in the total amount of dissolubility ethylenically unsaturated monomer, more preferably use 80~100 moles of %, more into
It is preferable to use 90~100 moles of % for one step.
Water-soluble ethylenically unsaturated monomer such as (methyl) acrylic acid, 2- (methyl) acrylamide-2-methyl propane sulfonic that
When sample has acidic group, the substance that its acidic group is neutralized by antalkali in advance can be used as needed.As in this way
Antalkali, it can be mentioned, for example the alkali metal salts such as sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide, potassium carbonate；Ammonia
Deng.These antalkalis in order to so that neutralization operation is become easy and can be made aqueous solution state come using.Above-mentioned alkalinity
Neutralizer may be used singly or in combination of two or more.It should be noted that the neutralization of acidic group can be as raw material
It carries out, can also be carried out in polymerization or after polymerization before water-soluble olefinic polymerization of unsaturated monomers.
By the degree of neutralization for the water-soluble ethylenically unsaturated monomer that antalkali generates, from the water imbibition tree as obtained by improving
The osmotic pressure of rouge come improve water absorbing properties and will not because of extra antalkali presence and in terms of generate
From the perspective of problem, it is often preferred that 10~100 moles of %, more preferably 30~90 moles of %, further preferably 40~85
It mole %, is still more preferably 50~80 moles of %.Wherein, degree of neutralization is is had relative to water-soluble ethylenically unsaturated monomer
Whole acidic groups degree of neutralization.
The concentration of aforementioned water-soluble ethylenically unsaturated monomer in aforementioned monomer aqueous solution be usually 20 mass % or more and
Below saturated concentration, preferably 25~70 mass %, more preferably 30~50 mass %.
(internal crosslinking agent)
In the method for the invention, cross-linked polymer is caused in addition to having by polymerization reaction preferably as its internal cross-linked structure
Self-crosslinking, also have as caused by internal crosslinking agent be crosslinked.As internal crosslinking agent, can be used for example with 2 or more
The compound of polymerism unsaturated group.It can enumerate for example that (poly-) ethylene glycol is (in the present specification, such as by " polyethylene glycol "
" ethylene glycol " is denoted as " (poly-) ethylene glycol " together.Below equally), (poly-) propylene glycol, trimethylolpropane, glycerol polyoxy Asia second
Two or three (methyl) esters of acrylic acid of the polyalcohols such as base glycol, polyoxypropylene glycol and (poly-) glycerol；Make above-mentioned more
Unsaturated polyester (UP) class obtained by first alcohol is reacted with the unsaturated acids such as maleic acid and fumaric acid；N, N '-di-2-ethylhexylphosphine oxide (methyl) third
The bisacrylamide class of acrylamide etc.；Two or three (methyl) acrylic acid obtained by reacting polyepoxide with (methyl) acrylic acid
Esters；React the polyisocyanates such as toluene di-isocyanate(TDI) or hexamethylene diisocyanate with (methyl) Hydroxyethyl Acrylate
Obtained by two (methyl) propenoic methyl carbamate classes；Allyl starch；Allylcellulose；Diallyl phthalate；
N, N ', N "-Triallyl isocyanurate；Divinylbenzene etc..In these substances, preferably foregoing polyols class two or
Three (methyl) esters of acrylic acid.
In addition, can be used other than the aforementioned compound with 2 or more polymerism unsaturated groups with 2
The compound of the above reactive functional groups is as internal crosslinking agent.Can enumerate such as (poly-) ethylene glycol diglycidyl base ether,
The compound containing glycidyl such as (poly-) propylene glycol diglycidyl ether and (poly-) diglycidyl ether；
(poly-) ethylene glycol, (poly-) propylene glycol, (poly-) glycerol, pentaerythrite, ethylenediamine, polyethyleneimine, (methyl) acrylic acid shrink sweet
Grease etc..In these substances, from low temperature under reactivity it is excellent from the viewpoint of, preferably (poly-) ethylene glycol diglycidyl
Base ether, (poly-) propylene glycol diglycidyl ether and (poly-) diglycidyl ether.These internal crosslinking agents can be independent
It uses, or can also be used in combination of two or more.
When using internal crosslinking agent, in order to sufficiently improve the water absorbing properties such as water holding capacity of gained water-absorbing resins, make
Dosage is relative to 100 moles of water-soluble ethylenically unsaturated monomer, preferably 0.0001 mole or more, more preferably 0.001 mole
More than, further preferably 0.003 mole or more, be still more preferably 0.01 mole or more.
The addition of internal crosslinking agent keeps cross-linked polymer insoluble, brings suitable water absorbing capacity, but internal crosslinking agent
The increase of additive amount is associated with the reduction of the water absorbing capacity of gained water-absorbing resins, therefore the amount of internal crosslinking agent is relative to water
100 moles of dissolubility ethylenically unsaturated monomer, for example be preferably 0.50 mole hereinafter, more preferably 0.25 mole hereinafter, further
Preferably 0.05 mole or less.
(other compositions)
In monomer solution, the additives such as chain-transferring agent, thickener, inorganic filler can also be contained as needed.As chain
Transfer agent can be enumerated such as thio-alcohol, thiol acids (チ オ ー Le acids), secondary alcohol class, hypophosphorous acid, phosphorous acid.As
Thickener can enumerate carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, methylcellulose, polyethylene glycol, gather
Acrylic acid, polyacrylic acid corrective, polyacrylamide etc..As inorganic filler, can enumerate for example metal oxide, ceramics,
Viscosity mineral etc..These substances can be used alone, and can also be used in combination of two or more.
(polymerization)
In aqueous gel preparation section of the invention, as needed in the presence of a crosslinking agent, make water using polymerization initiator
Water-soluble olefinic polymerization of unsaturated monomers in solution.It, can as the polymerization of the water-soluble ethylenically unsaturated monomer in the present invention
To use aqueous solution polymerization, emulsion polymerization, inverse suspension polymerization etc..In the present invention, it is preferred to be obtained by aqueous solution polymerization
The aqueous gel of cross-linked polymer.
As polymerization methods, it can be and polymerize under the state (such as static condition) for not stirring monomer solution
Stand polymerization methods, the stirring polymerization methods being polymerize while stirring monomer solution in reaction unit etc..At this
In invention, in aqueous solution polymerization, cross-linked polymeric is obtained preferably by polymerization is stood as the aqueous solution for standing polymerization methods
The aqueous gel of object.For stand polymerization methods, at the end of polymerization, the aqueous gel of cross-linked polymer can be used as with anti-
Monomer solution present in container is answered to occupy the single block-like aqueous gel of roughly the same volume and obtain.It should be noted that
The water-miscible organic solvent etc. that can also be suitably compounded in aforementioned monomer aqueous solution other than water.
The mode of preparation can be in batches, it is semicontinuous, continuous etc..For example, in aqueous solution polymerization, for poly- as standing
Conjunction mode and as continuation mode, aqueous solution stand continuous polymerization, can be continuously fed on one side in continuous polymerization unit
Monomer solution carries out polymerization reaction on one side, and obtains continuous (such as band-like) aqueous gel.
(polymerization initiator)
By in aforementioned monomer aqueous solution add polymerization initiator, as needed heated, light irradiation etc. ands cause polymerize.
It is preferable to use water-soluble radical polymerization initiators for polymerization initiator.
As the peroxide for being used as polymerization initiator, can enumerate such as potassium peroxydisulfate, ammonium persulfate, sodium peroxydisulfate
Persulfuric acid salt；Methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, di-t-butyl peroxide, tert-butyl peroxide isopropyl
The organic peroxide class of benzene, t-butyl peroxy-acetate, t-butyl peroxy-isobutylate, tert-Butyl peroxypivalate etc.；Hydrogen peroxide
Deng peroxide.In these peroxide, from the viewpoint of the water-absorbing resins for obtaining having good water absorbing properties,
It is preferable to use potassium peroxydisulfate, ammonium persulfate, sodium peroxydisulfate, hydrogen peroxide, even more preferably use potassium peroxydisulfate, persulfuric acid
Ammonium, sodium peroxydisulfate.These peroxide can be used alone, or can also be used in combination of two or more.For example, can incite somebody to action
Persulfate and hydrogen peroxide are applied in combination.
As the azo compound for being used as polymerization initiator, such as 2 can be enumerated, bis- [ the 2-(N- benzene carbon amidines of 2 '-azos
Base) propane dihydrochloride, 2,2 '-azos bis- { 2- [ N-(4- chlorphenyl) amidino groups ] propane } dihydrochlorides, 2,2 '-azos it is bis-
2- [ N-(4- hydroxy phenyl) amidino groups ] propane } dihydrochloride, 2, bis- [ 2-(N- benzyl amidino groups) propane ] dihydrochlorides of 2 '-azos,
2,2 '-azos bis- [ 2-(N- allyl amidino groups) propane ] dihydrochlorides, 2,2 '-azos bis- (2- amidine propane) dihydrochlorides, 2,
2 '-azos bis- { 2- [ N-(2- hydroxyethyl) amidino groups ] propane } dihydrochlorides, 2, the bis- [ 2-(5- methyl -2- imidazolines-of 2 '-azos
2- yl) propane ] dihydrochloride, 2,2 '-azos bis- [ 2-(2- imidazoline -2- base) propane ] dihydrochlorides, 2, the bis- [ 2- of 2 '-azos
(4,5,6,7- tetrahydro -1H-1,3- diaza -2- base) propane ] dihydrochloride, 2,2 '-azos it is bis- 2-(5- hydroxyl -3,4,
5,6- tetrahydropyrimidine -2- bases) propane ] dihydrochloride, 2, the bis- { 2- [ 1-(2- hydroxyethyl) -2- imidazoline -2- base ] of 2 '-azos
Propane } dihydrochloride, 2,2 '-azos bis- (2- methyl propanamide) dihydrochlorides, 2,2 '-azos it is bis- 2-(2- imidazoline -2- base)
Propane ] dithionate dihydrate, 2,2 '-azos bis- [ N-(2- carboxy ethyl) -2- methyl-prop amidine ] tetrahydrates, 2,2 '-is even
The water-soluble azo based compound etc. of nitrogen bis- [ 2- methyl-N-(2- hydroxyethyls) propionamide ] etc..Have well from readily available
From the viewpoint of the water-absorbing resins of water absorbing properties, preferably 2,2 '-azos bis- (2- amidine propane) dihydrochlorides, 2,2 '-is even
Bis- { 2- [ 1-(2- the hydroxyethyl) -2- imidazoline -2- base ] propane } dihydrochlorides and 2 of nitrogen, bis- [ the N-(2- carboxyl second of 2 '-azos
Base) -2- methyl-prop amidine ] tetrahydrate.These azo compounds can be used alone, or can also be by two or more combinations
It uses.
From the viewpoint of the readily available water-absorbing resins with good water absorbing properties, as polymerization initiator, preferably
Two or more polymerization initiator above-mentioned is applied in combination, wherein more preferably by peroxide and water-soluble azo system chemical combination
Object is applied in combination.Such as sodium peroxydisulfate and 2, the combination of bis- (2- amidine propane) dihydrochlorides of 2 '-azos or over cure can be enumerated
Sour sodium, hydrogen peroxide and 2, the combination etc. of bis- (2- amidine propane) dihydrochlorides of 2 '-azos.Alternatively, it is also possible to by aforementioned polymeric
Initiator is applied in combination with the reducing agent of sodium sulfite, sodium hydrogensulfite, ferrous sulfate and L-AA etc., as oxidation
Reductive polymerization initiator uses.
When a variety of polymerization initiators are applied in combination, azo compound relative to whole polymerization initiators usage amount from
Improve water absorbing properties from the viewpoint of, can be 10~100 moles of %, more preferably 25~90 moles of %, further preferably
30~85 moles of % are still more preferably 35~80 moles of %.
From the viewpoint of avoiding fierce polymerization reaction and shortening polymerization reaction time, total use of polymerization initiator
Amount is relative to 100 moles of water solubility ethylenically unsaturated monomer preferably 0.005~1 mole used in polymerization, more preferably
0.01~0.5 mole, further preferably 0.0125~0.1 mole are still more preferably 0.015~0.05 mole.
Polymerization temperature is different according to the polymerization initiator used, therefore cannot treat different things as the same, but from by making to gather
Close and carry out rapidly, shorten polymerization time, and improve productivity, at the same be easier to remove heat of polymerization and the sight swimmingly reacted
Point considers that polymerization temperature is preferably 0~130 DEG C, more preferably 10~110 DEG C.Polymerization time can cause according to the polymerization used
The type or amount of agent, reaction temperature etc. and suitably set, but preferably 1~200 minute, more preferably 5~100 minutes.
(aqueous gel of cross-linked polymer)
In the present invention, cross-linked polymer obtained by water-soluble ethylenically unsaturated monomer being polymerize is the shape of aqueous gel
State.The moisture content of the aqueous gel of cross-linked polymer is from the point of view of coarse crushing process easy to implement, preferably 30~80 matter
Measure %, more preferably 40~75 mass %, further preferably 50~70 mass %.Moisture content can pass through the water of monomer solution
The operation of drying or humidification etc. after component or polymerization adjusts.It should be noted that in the present invention, the polymerization of aqueous gel shape
The moisture content of object is the content that water shared in the gross mass of aqueous gel shaped polymer is indicated with quality %.
The coarse crushing process > of < aqueous gel
The preparation method of water-absorbing resins of the invention includes the coarse crushing process of the aqueous gel of cross-linked polymer.It is preferred that containing water-setting
The size of the coarse crushing of glue treated size is, for example, 0.1~10mm or so, the preferably size of 0.1~5mm or so.Herein,
Size refers to the full-size of each aqueous gel.
The temperature of aqueous gel in coarse crushing process be 35 DEG C hereinafter, preferably 33 DEG C hereinafter, more preferably 30 DEG C hereinafter,
Further preferably 25 DEG C or less.
The temperature of aqueous gel in coarse crushing process can be 0 DEG C or more, for example, 5 DEG C or more, preferably 10 DEG C or more,
More preferably 15 DEG C or more.
The temperature of aqueous gel in coarse crushing process can be changed if it is in aforementioned range in pulverizing process, be become
Temperature range when dynamic is relative to predetermined temperature, for example within ± 10 DEG C, within preferably ± 5 DEG C, within more preferably ± 3 DEG C.
As the method that the temperature of aqueous gel is adjusted to aforementioned temperature, it can enumerate and stand the aqueous gel of high temperature
The method of stipulated time；Make the method for the gas of aqueous gel and low temperature contact stipulated time；By the way that aqueous gel will be maintained
Container impregnate the stipulated time and the method etc. that is adjusted to aforementioned temperature in refrigerant bath etc..In general, containing water-setting after polymerization
Glue is high temperature, therefore is preferably adjusted by cooling temperature of completing.
As the coarse crushing device of aqueous gel, kneader can be used (for example, adding pressure type kneader, dual-arm kneader
Deng), masticator and shredding machine, pharmaceutical mill (フ ァ ー マ ミ Le) etc. coarse crushing device.Wherein, more preferably dual-arm is pinched
Conjunction machine, masticator, shredding machine.Coarse crushing device can also be identical kind with the grinding device of following aqueous gel dried objects
Class.
The drying process > of < aqueous gel coarse crushing object
The preparation method of water-absorbing resins of the invention include will the aqueous gel coarse crushing object obtained in aforementioned coarse crushing process into
The dry drying process of row.By being removed the solvent comprising water in coarse crushing object using heating or air blast, and coarse crushing object is done
It is dry.As dry method, as long as by the general method such as natural drying, heat drying, spray drying, freeze-drying from containing
Solvent is removed in hydrogel.Drying can under normal pressure, decompression under, in order to improve drying efficiency and under the air-flow of nitrogen etc.
Deng progress, these methods can also be applied in combination.Drying temperature when being dried under normal pressure is preferably 70~250 DEG C,
More preferably 80~200 DEG C.Process is dried, until the moisture content of cross-linked polymer becomes 20 mass % or less, preferably 10
Quality % or less, more preferable 5 mass % or less.
The pulverizing process > of < dried object
The preparation method of water-absorbing resins of the invention include will the dried object obtained in aforementioned drying process crushed and
Obtain the pulverizing process of crushed material.
Well known pulverizer can be used in the crushing of aforementioned dried object, and edge runner (rolls) can be used for example, smash to pieces
Machine, jet pulverizer, high speed rotation pulverizer (hammer crusher, needle mill, rotor beater type crusher (ロ ー タ ビ
ー タ ミ Le) etc.), the driving grinding mill of container (rotary grinder, vibration grinding mill, planetary mill etc.) etc..It is preferable to use
High speed rotation pulverizer.The maximum grain that pulverizer can have porous plate or sieve, grid etc. to control pulverized particles in outlet side
The opening portion of diameter.The shape of opening portion can be polygon, circle etc., and the maximum gauge of opening portion can be 0.1~5mm, excellent
It is selected as 0.3~3.0mm, more preferably 0.5~1.5mm.
Classification process, the table that preparation method of the invention may further include other processes, for example carry out granularity adjustment
Face cross-linking process step etc..
The classification process > of < crushed material
The preparation method of water-absorbing resins of the invention may include being classified the crushed material obtained in pulverizing process
It is classified process.It should be noted that pulverizing process and classification process etc. is repeated there may be the particle after classification is crushed again
, multiple fractionation process, or can also after following surface cross-linking process steps exist classification process.Herein, classification refers to certain
Particle group according to partial size is divided into 2 or its above number, the operation of particle group that size distribution is different.
The classification of crushed material can be used well known stage division, such as can be screen fractionation, air classification etc., preferably
For screen fractionation.As screen fractionation, vibrating screen, rotation sifter device, agitated cylinder sieve, air blast sifter device, rotation hammering can be enumerated
Formula screen vibrator etc..Screen fractionation refers to by vibrating sieve, and by the gradation on sieve at the mesh by sieve
Particle and not over particle method.Air classification refers to the flowing using air by the method for gradation.
In the present invention, the 90% of the preferred total weight of the partial size of water-absorbing resins is the above are 850 μm hereinafter, more preferably
700 μm hereinafter, further preferably 600 μm or less.It should be noted that in the present specification, partial size refers to be measured using sieve method
Value.
In the present invention, the preferred median particle diameter of water-absorbing resins be 100~800 μm, more preferably 150~600 μm, into one
Preferably 200~500 μm of step, be still more preferably 240~450 μm.Median particle diameter is according to the side recorded in following embodiments
Method measurement.
Even if preparation method of the invention is the number for the crushing that object is dried is few or the grinding time of dried object is short
In the case where, the crushed material of required size distribution can be also obtained with good reproducibility, be industrially advantageous.And then pass through
The number crushed or time are reduced, also can avoid the performance due to water-absorbing resins caused by being placed in mechanicalness load for a long time
Deteriorate.
< surface cross-linking process step >
In the preparation process in accordance with the present invention, it for cross-linked polymer, can further add containing 2 or more and derived from water solubility
The functional group of ethylenically unsaturated monomer has the crosslinking agent (being denoted as surface crosslinking agent) of reactive functional group and makes its reaction (note
Make surface-crosslinked processing).Surface-crosslinked processing is carried out by addition surface crosslinking agent, the crosslinking near the surface of water-absorbing resins
Density increases, therefore water absorbing capacity, gel strength or liquid passability etc. under the load of gained water-absorbing resins can be improved
Water absorbing properties.
Any period of the addition of aforementioned surfaces crosslinking agent after coarse crushing process carries out, can be for cross-linked polymer
Aqueous gel, the coarse crushing object of aqueous gel of cross-linked polymer, the dried object of coarse crushing object or dried object crushed material carry out
Addition, wherein the crushed material of dried object or dried object preferably for coarse crushing object is added.As adding for surface crosslinking agent
Adding method, such as surface-crosslinker solution can be added in water-absorbing resins, or can also be sprayed in water-absorbing resins
Add surface-crosslinker solution.As the addition manner of surface crosslinking agent, from the viewpoint of keeping surface crosslinking agent evenly dispersed,
It is preferred that surface crosslinking agent is dissolved in water or/and alcohol equal solvent, added as surface-crosslinker solution.In addition, surface is handed over
Connection process can be implemented 1 time or be divided into 2 times or more and repeatedly implements.
As aforementioned surfaces crosslinking agent, the compound with 2 or more reactive functional groups can be enumerated.Example can be enumerated
Such as ethylene glycol, propylene glycol, 1,4- butanediol, trimethylolpropane, glycerol, polyoxyethylene glycol, polyoxypropylene glycol, gather
The polyalcohols of glycerol etc.；(poly-) ethylene glycol diglycidyl base ether, (poly-) ethylene glycol triglycidyl group ether, (poly-) glycerol two
Glycidyl ether, (poly-) glycerol triglycidyl ether, the more glycidyl ethers of (poly-) propylene glycol, (poly-) glycerol shrink sweet more
The multi-shrinking glyceryl compound of oleyl ether etc.；The halogenated epoxy chemical combination of epichlorohydrin, bromopropylene oxide, Alpha-Methyl epichlorohydrin etc.
Object；The isocyanate compounds such as 2,4 toluene diisocyanate, hexamethylene diisocyanate etc. have 2 or more reactive officials
The compound that can be rolled into a ball；3- methyl -3- oxetane methanol, 3- ethyl -3- oxetane methanol, 3- butyl -3- oxa- ring
Butane methanol, 3- methyl -3- oxetanes ethyl alcohol, 3- ethyl -3- oxetanes ethyl alcohol, 3- butyl -3- oxetanes
The oxetane compound of ethyl alcohol etc.；The oxazoline compound of 1,2- ethylenebis oxazoline etc.；The carbon of ethylene carbonate etc.
Ester compound；The hydroxyalkylamide compound etc. of bis- [ N, N- bis- (beta-hydroxy ethyl) ] adipamides etc..In these changes
It closes in object, preferably (poly-) ethylene glycol diglycidyl base ether, (poly-) ethylene glycol triglycidyl group ether, (poly-) glycerol two shrink
Glyceryl ether, (poly-) glycerol triglycidyl ether, the more glycidyl ethers of (poly-) propylene glycol, the more glycidyls of (poly-) glycerol
Multi-shrinking glyceryl compound and/or ethylene glycol, propylene glycol, 1,4- butanediol, the trimethylolpropane, polyoxyethylene of ether etc.
The polyalcohols of glycol, polyoxypropylene glycol etc., more preferably multi-shrinking glyceryl compound.These surface crosslinking agents can be with
It is used alone, or can also be used in combination of two or more.Such as it can be by multi-shrinking glyceryl compound and polyalcohols
It is applied in combination.
From the viewpoint of the crosslink density that appropriateness increases near water-absorbing resins surface, the additive amount of surface crosslinking agent is logical
Often 100 moles of total amount preferably 0.0001~1 mole relative to the water solubility ethylenically unsaturated monomer used in polymerization, more
Preferably 0.001~0.5 mole.
Surface cross-linking process step is preferably being 1~200 mass parts relative to water-soluble 100 mass parts of ethylenically unsaturated monomer
It is carried out in the presence of the water of range.By suitably using the water-miscible organic solvent of water or/and alcohol etc., adjustable amount of moisture.
It should be noted that the water solubility olefinic insatiable hunger as used in polymerization reaction of the solid portion of the water-absorbing resins in aqueous gel
It is calculated with the feeding quantity of monomer, while also calculating the amount of moisture contained in monomer solution.That is, after aqueous gel preparation section
Each process in aqueous gel contained in amount of moisture can by subtracted from the amount of moisture contained in monomer solution by
Amount of moisture that aqueous gel after polymerization removes calculates.In this way, amount of moisture when by adjusting surface cross-linking process step, Ke Yigeng
The crosslinking being suitably carried out near the particle surface of water-absorbing resins.
The treatment temperature of surface crosslinking agent can be suitably set according to the surface crosslinking agent used, can be 20~250 DEG C,
Handling the time is preferably 1~200 minute, and more preferably 5~100 minutes.
Embodiment
Hereinafter, based on embodiment and comparative example and then explain the present invention in detail, but the present invention be not only limited to it is described
Embodiment.
The moisture content of the aqueous gel of cross-linked polymer in each embodiment and comparative example by method as shown below into
Row evaluation.
(moisture content)
Cross-linked polymer 2.0g is put into preparatory constant (Wa(g)) in the aluminium foil box (No. 8) changed, precision weighing (Wb(g)).Benefit
After being dried aforementioned sample 2 hours with the air drier (ADVANTEC corporation) that interior temperature is set as 105 DEG C, in drier
It lets cool, the quality (Wc(g) after measurement is dry).The moisture rate of cross-linked polymer is calculated by following formula.
Moisture content (quality %)=[(Wb-Wa)-(Wc-Wa)]/(Wb-Wa) × 100.
(size distribution of water-absorbing resins measures)
By JIS standard screen with 850 μm of mesh of sieve, 500 μm of mesh of sieve, 250 μm of mesh of sieve, 180 μm of mesh from upper
The sequence of sieve, 150 μm of mesh of sieve and reception ware is combined.
It is put into water-absorbing resins 50g into combined uppermost sieve, vibrates 20 minutes using Ro-Tap
It is classified.After classification, removes the water-absorbing resins on 850 μm of sieve and receive the water-absorbing resins on ware.Then, with residual
The quality of water-absorbing resins on each sieve is calculated relative to the form of the quality percentage of total amount, acquires size distribution.
(median particle diameter)
According to aforementioned the size distribution of water-absorbing resins (measure), with the quality of the water-absorbing resins remained on each sieve relative to
The form of the quality percentage of total amount calculates, and acquires size distribution.About the size distribution, from the big side of partial size successively
Quality percentage on each sieve is added up, to mark and draw the mesh of sieve on logarithmic probability paper and sieve upper remaining water suction
The relationship of the aggregate-value of the quality percentage of property resin.By linking the plot point straight line on probability paper, will be equivalent to tire out
The partial size of 50 mass % of quality percentage is counted as median particle diameter.
[ embodiment 1 ]
100% acrylic acid of 195.36g is packed into the separate type flask of 2L.Add while being stirred in separate type flask
Enter the ion exchange water of 135.13g, 30% sodium hydroxide of 357.93g is further added dropwise under ice bath.Then, it is added
100% acrylic acid of 104.73g makes acrylate moiety neutralizer.
In the polyethylene bottle of 2L capacity, make acrylate moiety neutralizer 780g above-mentioned, as internal crosslinking agent solution
The 2% polyethyleneglycol diacrylate (average repeat unit of ethylene oxide: 9) aqueous solution 43.78g, ion exchange water
180.7g mixing, prepares monomer solution.The monomer solution is packed into stainless steel round pallet (internal diameter 200mm, depth
In 60mm), after being sealed with film from top, it is blown into nitrogen, thus makes the dissolved oxygen 0.1ppm or less in solution.And then in nitrogen
The temperature of aforementioned monomer aqueous solution is adjusted to 18 DEG C under atmosphere, 5% sodium persulfate aqueous solution is then successively added dropwise under stiring
1.58g, 5%2, bis- (2- amidine propane) dihydrochloride aqueous solution 1.58g, 0.5%L- aqueous ascorbic acids of 2 '-azos
1.50g and 0.35% aqueous hydrogen peroxide solution 1.70g.After hydrogen peroxide is added dropwise, stop stirring.Cause immediately and polymerize, 9 minutes
Afterwards, the temperature of monomer solution reaches 86 DEG C of peak temperature.And then, pallet above-mentioned is immersed in 80 DEG C of hot bath
In, it is kept for 10 minutes, obtains the aqueous gel of cross-linked polymer.
Then, it is being inserted into thermometer from the foregoing aqueous gel that pallet takes out, indoor standing 50 minutes of 23 DEG C, adjusted
Save into defined temperature (30 DEG C).The moisture content of the aqueous gel of cross-linked polymer after cooling is 63%.By cross-linked polymer
Aqueous gel 1L volume dual-arm kneader coarse crushing after, it is 30 minutes dry at 180 DEG C, obtain dried object.Then, it uses
Pulverizer (rotor beater type crusher) crushes dried object in such a way that the pore size of sieve is 1mm.After crushing, pass through
850 μm or more of crushed material and the crushed material less than 150 μm are removed, the water-absorbing resins (1) that median particle diameter is 280 μm are obtained.
5 operations as hereinbefore are carried out, the average and variation of the size distribution of every sieve of water-absorbing resins (1) is acquired
Coefficient CV (standard deviation/size distribution of=size distribution average × 100).As a result shown in table 1 and table 2.
[ embodiment 2 ]
Similarly to Example 1, the aqueous gel of cross-linked polymer is obtained.By the aqueous gel of resulting cross-linked polymer 23
DEG C indoor standing 50 minutes after, further stand 5 minutes on ice-water bath, be adjusted to defined temperature (20 DEG C).After cooling
Cross-linked polymer aqueous gel moisture content be 63%.Then, coarse crushing, drying, crushing are carried out similarly to Example 1.
After crushing, 850 μm or more of crushed material and the crushed material less than 150 μm are removed, obtains the water imbibition tree that median particle diameter is 250 μm
Rouge (2).
5 operations as hereinbefore are carried out, the average and variation of the size distribution of every sieve of water-absorbing resins (2) is acquired
Coefficient CV.As a result shown in table 1 and table 2.
[ comparative example 1 ]
Similarly to Example 1, the aqueous gel of cross-linked polymer is obtained.By the aqueous gel of resulting cross-linked polymer 23
DEG C indoor standing 1 minute, be adjusted to defined temperature (70 DEG C).The moisture content of the aqueous gel of cross-linked polymer after cooling
It is 64%.Then, coarse crushing, drying, crushing are carried out similarly to Example 1.After crushing, remove 850 μm or more crushed material and
Crushed material less than 150 μm obtains the comparison water-absorbing resins (1) that median particle diameter is 330 μm.
Carry out 5 operations as hereinbefore, acquire the average of the size distribution for comparing every sieve of water-absorbing resins (1) and
Coefficient of variation CV.As a result shown in table 1 and table 2.
[ comparative example 2 ]
Similarly to Example 1, the aqueous gel of cross-linked polymer is obtained.By the aqueous gel of resulting cross-linked polymer 23
DEG C indoor standing 20 minutes, be adjusted to defined temperature (45 DEG C).The aqueous gel of cross-linked polymer after cooling it is aqueous
Rate is 64%.Then, coarse crushing, drying, crushing are carried out similarly to Example 1.After crushing, 850 μm or more of crushed material is removed
With the crushed material less than 150 μm, the comparison water-absorbing resins (2) that median particle diameter is 250 μm are obtained.
Carry out 5 times and aforementioned same operation, acquire the average of the size distribution for comparing every sieve of water-absorbing resins (2) and
Coefficient of variation CV.As a result shown in table 1 and table 2.
[table 1]
[table 2]
Industrial utilizability
Can suitable for the agricultural horticultural materials such as hygienic materials, water-retaining agent or the soil conditioner such as paper nappy or physiological articles,
The various absorbent commodities of the industry goods, materials and equipments such as water-stop or resistive connection distillate medicinal water etc..
Claims (4)
1. the preparation method of water-absorbing resins, being includes the coarse crushing process that the aqueous gel of cross-linked polymer is carried out to coarse crushing
The preparation method of water-absorbing resins, wherein the temperature of the foregoing aqueous gel in coarse crushing process is 35 DEG C or less.
2. the preparation method of water-absorbing resins according to claim 1, wherein including by water-soluble ethylenically unsaturated monomer
It polymerize and obtains the aqueous gel preparation section of the aqueous gel of aforementioned cross-linked polymer,
70~100 moles of % in the total amount of aforementioned water solubility ethylenically unsaturated monomer are in (methyl) acrylic acid and its salt
At least one.
3. the preparation method of water-absorbing resins according to claim 1 or 2, wherein the moisture content of foregoing aqueous gel is
30~70 mass %.
4. the preparation method of water-absorbing resins described in any one of claim 1 to 3, wherein including will be by aforementioned
The powder for obtaining the drying process of dried object and crushing aforementioned dried object is dried in the resulting coarse crushing object of coarse crushing process
Broken process.
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| JP2017059805 | 2017-03-24 | ||
| PCT/JP2018/011453 WO2018174175A1 (en) | 2017-03-24 | 2018-03-22 | Method for producing water-absorbing resin |
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| WO2021246243A1 (en) * | 2020-06-04 | 2021-12-09 | 住友精化株式会社 | Method for producing cross-linked polymer particles and method for producing water-absorbent resin particles |
| JPWO2022024787A1 (en) * | 2020-07-28 | 2022-02-03 | ||
| JPWO2022071503A1 (en) * | 2020-10-02 | 2022-04-07 | ||
| WO2022265466A1 (en) * | 2021-06-18 | 2022-12-22 | 주식회사 엘지화학 | Method for preparing super absorbent polymer |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11188727A (en) * | 1997-12-25 | 1999-07-13 | Nippon Shokubai Co Ltd | Production of hydrophilic resin |
| JP2012041439A (en) * | 2010-08-19 | 2012-03-01 | San-Dia Polymer Ltd | Absorbing resin particle and absorbent article |
| CN102378778A (en) * | 2009-03-31 | 2012-03-14 | 株式会社日本触媒 | Process for producing particulate water-absorbing resin |
| CN102482435A (en) * | 2009-08-28 | 2012-05-30 | 株式会社日本触媒 | Process for production of water-absorbable resin |
| JP2015048386A (en) * | 2013-08-30 | 2015-03-16 | 株式会社日本触媒 | Method for pulverizing water-absorbing resin, and water-absorbing resin having excellent salt resistance |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61110510A (en) * | 1984-11-06 | 1986-05-28 | Dai Ichi Kogyo Seiyaku Co Ltd | Crushing method of water-soluble polymer gel |
| JP3851915B2 (en) | 1994-06-08 | 2006-11-29 | 株式会社日本触媒 | Water absorbent resin and method for producing the same |
| JP4244084B2 (en) * | 1998-03-26 | 2009-03-25 | 株式会社日本触媒 | Water-absorbing agent, method for producing the same, and body fluid-absorbing article |
| JP4198265B2 (en) | 1998-04-15 | 2008-12-17 | 株式会社日本触媒 | Method for producing water absorbent resin |
| JP4676625B2 (en) | 2000-02-29 | 2011-04-27 | 株式会社日本触媒 | Method for producing water absorbent resin powder |
| JP3795431B2 (en) | 2002-05-31 | 2006-07-12 | 株式会社日本触媒 | Method for crushing (meth) acrylic acid water-soluble polymer hydrogel |
| JP2005036035A (en) | 2003-07-16 | 2005-02-10 | Sanyo Chem Ind Ltd | Colored water-absorbing resin |
| JP5042674B2 (en) | 2006-03-29 | 2012-10-03 | 株式会社日本触媒 | Method for producing polyacrylic acid (salt) water-absorbing resin |
| JP5935601B2 (en) * | 2012-08-30 | 2016-06-15 | 三菱レイヨン株式会社 | Method for producing water-soluble polymer |
| KR20170132800A (en) | 2015-03-30 | 2017-12-04 | 가부시키가이샤 닛폰 쇼쿠바이 | Particulate absorbent |
-
2018
- 2018-03-22 CN CN201880019427.2A patent/CN110402267A/en active Pending
- 2018-03-22 JP JP2019506978A patent/JP7355646B2/en active Active
- 2018-03-22 WO PCT/JP2018/011453 patent/WO2018174175A1/en active Application Filing
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11188727A (en) * | 1997-12-25 | 1999-07-13 | Nippon Shokubai Co Ltd | Production of hydrophilic resin |
| CN102378778A (en) * | 2009-03-31 | 2012-03-14 | 株式会社日本触媒 | Process for producing particulate water-absorbing resin |
| CN104974358A (en) * | 2009-03-31 | 2015-10-14 | 株式会社日本触媒 | Producing method for particulate water-absorbing resin |
| CN102482435A (en) * | 2009-08-28 | 2012-05-30 | 株式会社日本触媒 | Process for production of water-absorbable resin |
| JP2012041439A (en) * | 2010-08-19 | 2012-03-01 | San-Dia Polymer Ltd | Absorbing resin particle and absorbent article |
| JP2015048386A (en) * | 2013-08-30 | 2015-03-16 | 株式会社日本触媒 | Method for pulverizing water-absorbing resin, and water-absorbing resin having excellent salt resistance |
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| WO2018174175A1 (en) | 2018-09-27 |
| JPWO2018174175A1 (en) | 2020-01-23 |
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