CN109776741A - The manufacturing method of super absorbent resin - Google Patents
The manufacturing method of super absorbent resin Download PDFInfo
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- CN109776741A CN109776741A CN201910063022.5A CN201910063022A CN109776741A CN 109776741 A CN109776741 A CN 109776741A CN 201910063022 A CN201910063022 A CN 201910063022A CN 109776741 A CN109776741 A CN 109776741A
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Abstract
Disclose a kind of manufacturing method of super absorbent resin.Described method includes following steps: (i) provides acrylic acid and internal crosslinking agent, and the absorbent resin powder as intermediate base-material is formed after polymerization；(ii) based on the weight of the intermediate base-material, the SiO of 0.1~5wt% is added2Particle, and measure the intermediate base-material and SiO2Water absorbent rate (BAAP) under the 2kPa pressure of granulate mixture；(iii) stops subsequent handling if the BAAP measured is less than 18g/g；If BAAP is 18g/g or more, the following steps (iv) is carried out；(iv) in the intermediate base-material, surface crosslinking agent is added, obtains surface-crosslinked Super Absorbent Polymer Particles after heating reaction.
Description
Technical field
The present invention relates to a kind of manufacturing method of super absorbent resin, manufacturing method of the present invention being capable of On-line Control high water absorption
Property naval stores quality, improve yield rate.
Background technique
Super absorbent resin (SAP, Super Absorbent Polymer) is a kind of to meet water-swellable but not soluble in water height
Molecular gel agent can absorb the aqueous solution of own wt several times or even hundreds times, and be based on the property, extensive
Used in the amenities such as paper diaper, sanitary napkin, incontinence protection and the various uses such as agriculture garden water-retaining agent or industrial water-stop
In.
In most cases, these super absorbent resins have been widely used for hygienic material field such as diaper or health
In towel.For these applications, high-hydroscopicity should be shown, even if under external pressure its should not discharge and absorbed
Water (i.e. pressurizing absorption performance), even and if in addition it should also be as in the state of making volume expansion (swelling) by absorbing water
Shape is kept well, and therefore shows excellent permeability for liquids.
In particular, recently as having been studied to provide performance while with relatively thin thickness and light weight
The diaper of excellent properties out, many attentions, which have been concentrated on to provide, has the high load water absorbing capacity and liquid further increased
Infiltrative super absorbent resin.
For example, Chinese patent CN104684969B discloses a kind of high hydroscopic resin, it include powdered basis resin and
The surface graft layer being formed on the powdered basis resin, the powdered basis resin includes cross-linked polymer,
By using internal crosslinking agent to comprising acidic-group and the water-soluble vinyl unsaturated monomer that is neutralized of at least part into
Row polymerize and is made；And the surface graft layer includes surface crosslinked polymer, by the powdered basis resin
Cross-linked polymer be further crosslinked and be made.Its to the centrifuge separation water retention property (CRC) of physiological saline be 28g/g with
On, it is 22g/g or more, solution permeability to water absorbent rate (AAP0.7) under the high pressure 4.8kPa (0.7psi) of physiological saline
It (SFC) is 20 × 10-7·cm3S/g or more, gel strength are 7000 to 11000Pa.
The prior art proposes the manufacturing method of a variety of high hydroscopic resins.For example, Chinese patent CN105848776A is disclosed
A kind of manufacturing method of water-absorbing resins, it includes by acrylic acid, polyethyleneglycol diacrylate internal crosslinking agent, chelating
Agent, sodium hydrate aqueous solution mixing, nitrogen are bubbled, are then polymerize under the action of sodium peroxydisulfate initiator, crushing obtains
Aqueous gel shape cross-linked polymer, drying are crushed and are sieved again, obtained absorbent resin powder.To the water-absorbing resins
Powder uniformly spray surface-crosslinker solution and carry out it is surface-crosslinked, then screening obtain water-absorbing resins, test the resin
Performance.The water-absorbing resins made from this method are able to satisfy: (a) free swell absorption speed is 0.28g/gs or more；(b) high
Water absorbent rate (AAP0.7) is 20g/g or more under pressure 4.8kPa；(c) " salt tolerance index=CRCdw/CRCs " (CRCdw be pair
The water absorbent rate of pure water, unit g/g；CRCs is to the water absorbent rate of 0.9wt% saline solution, unit g/g), shown in salt tolerance
Index meets " salt tolerance index≤0.49 × CRCs-7.47 ".
Usual viewpoint thinks that surface cross-linking process step can get water absorbent rate and the good high-hydroscopicity of liquid permeability under pressure
Resin." influence of the surface-crosslinked post-processing to super absorbent resin performance " (" fine chemistry industry " volume 30 the 11st of Zhang little Lei etc.
Phase, in November, 2013) describe the effect of the surface-crosslinked post-processing in the manufacturing process of water-absorbing resins.It, which is mentioned, does not carry out
The super absorbent resin of surface-crosslinked post-processing not can be used directly in feminine hygiene articles and baby paper diaper, because of resin
It is agglomerating that it is easy connection after particle contact liq, causes gel blocking, hinders penetrating further into for hydrone, and resin particle gel
Intensity difference, pressurizing absorption amount is low, is not able to satisfy the needs of amenities application.
In addition, keeping the consistency of product quality to be an important issue in industrial production.With regard to super absorbent resin
Production for, any fluctuation of process conditions can all react in the quality of final products.Therefore it needs to develop a kind of online
Detection method, it can determine the variation of process conditions in time, so that timely adjusting process parameter in process of production, avoids making
It is different just to find that the quality of finished product has when obtaining super absorbent resin finished product, to improve production efficiency, avoids meaningless loss.
Summary of the invention
A goal of the invention of the invention is that a kind of online test method is provided in the production process of super absorbent resin,
It can determine the variation of process conditions in time, so that timely adjusting process parameter in process of production, avoids in obtained water imbibition
It is different just to find that the quality of finished product has when resin finished product, to improve production efficiency, avoids meaningless loss.
It is a further object to provide a kind of production method of super absorbent resin, the height made from this method is inhaled
Water-base resin has stable quality.
Therefore, one aspect of the present invention provides the online test method in a kind of super absorbent resin production process, it
Include:
(i) absorbent resin powder of the preparation as intermediate base-material；With
(ii) based on the weight of the intermediate base-material, the SiO of 0.1~5wt% is added2Particle, and measure the intermediate base-material with
SiO2Water absorbent rate (BAAP) under the 2kPa pressure of granulate mixture.
Another aspect of the present invention provides a kind of manufacturing method of super absorbent resin, it includes the following steps:
(i) acrylic acid and internal crosslinking agent are provided, form the absorbent resin powder as intermediate base-material after polymerization；
(ii) based on the weight of the intermediate base-material, the SiO of 0.1~5wt% is added2Particle, and measure the intermediate base-material with
SiO2Water absorbent rate (BAAP) under the 2kPa pressure of granulate mixture；With
(iii) if measuring this base-material water absorption under pressure multiplying power (BAAP) less than 18g/g, stop subsequent handling；If BAAP is
18g/g or more then carries out the following steps (iv)；
(iv) in the intermediate base-material, surface crosslinking agent is added, to obtain surface-crosslinked Super Absorbent Polymer Particles.
Further aspect of the present invention is related to the test method of the pressurization water imbibition of base-material among super absorbent resin, it includes making
The intermediate base-material with, based on the weight of intermediate base-material, the SiO of 0.1~5wt%2Particle mixing then measures mixture pressurization
The step of water imbibition.
Specific embodiment
Preparing as the absorbent resin powder of intermediate base-material is the intermediate steps for preparing super absorbent resin finished product.As opened
Small equal " influence of the surface-crosslinked post-processing to super absorbent resin performance " Wen Suoshu of heap of stone, the pressurizing absorption of the intermediate base-material
It measures low, it is generally recognized that be difficult to as the index for judging super absorbent resin performance.
The present inventor has found after studying, if can improve the pressurizing absorption amount of the intermediate base-material to certain
Degree, then the quality trend correlation of the pressurizing absorption amount and final high exhaustion.The present invention is exactly on the basis of the discovery
Upper completion.
Therefore, the present invention relates to the test methods of the pressurization water imbibition of base-material among super absorbent resin, it includes making this
Intermediate base-material with, based on the weight of intermediate base-material, the SiO of 0.1~5wt%2Particle mixing then measures mixture pressurization and inhales
Aqueous step.
In the present invention, term " base-material among water-absorbing resins " refers to the water imbibition before surface-crosslinked postprocessing working procedures
Toner.
The present invention relates to the online test methods in a kind of super absorbent resin production process.The present invention includes preparation conduct
The step of absorbent resin powder of intermediate base-material.
The step of absorbent resin powder of the preparation as intermediate base-material suitable for the method for the present invention, is without particular limitation,
It can be the conventional method of this field, for example, water suction of the disclosed preparation of Chinese patent CN105848776A as intermediate base-material
Property toner method (Chinese patent is inserted into the method quoted herein as a part of the invention).
In an example of the present invention, the step of base-material, includes: among the preparation
Acrylic monomer, internal crosslinking agent, chelating agent aqueous solution, aqueous alkali and water are added in the reaction vessel
And mixed, thus it is prepared for solution (A)；
It is passed through N2Polymerization initiator is added afterwards to be polymerize, aqueous gel shape cross-linked polymer is obtained；
The polymer that broken obtained water-setting glue cross-linked polymer, drying and crushing and classification is dried is solved, water imbibition is obtained
Toner.
In the present invention, term " acrylic monomer " includes acrylic monomers, methacrylic acid monomer, acrylates list
The mixture of two or more of body, methacrylic acid salt monomer or front.
When preparing intermediate base-material, the present invention is used containing the intermediate base-material for having internal cross-linked structure, the internal crosslinking knot
Structure is realized by the polymerization of water-soluble unsaturated monomer.The intermediate base-material can be polycarboxylic-acid water-absorbing resins, such as poly- third
Polymer, hydrolysate of starch-acrylonitrile graft polymer that olefin(e) acid is partially neutralized etc..
In an example of the present invention, the acrylic monomer includes the acrylic compounds list that concentration is 35wt% or more
The aqueous solution of body.Based on the acrylic monomer, the dosage of the internal crosslinking agent is 0.04mol% or more.The dosage of alkali
So that the acid group neutralization ratio of monomer reaches 40~90mol%, preferably reach 60~80mol%.
In an example of the present invention, the de-airing step includes that N is passed through into monomer solution2, such as pipeline drum
Steep deoxygenation.
Internal crosslinking agent suitable for the method for the present invention is without particular limitation, can be normal internal known in the art and hands over
Join agent.In an example of the present invention, the internal crosslinking agent is selected from N, N'- di-2-ethylhexylphosphine oxide (methyl) acrylamide, poly- second
Glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate or
The mixture of its two or more formation.
By the meter of acrylic monomer, in the method for the present invention the dosage of internal crosslinking agent be usually 0.04mol%~
0.5mol%, preferably 0.05mol%~0.4mol%, more preferably 0.06mol%~0.3mol%, preferably 0.06mol%~
0.2mol%.If the dosage of the internal crosslinking agent is lower than 0.04mol%, it is possible to water suction of the presently claimed invention can not be obtained
Agent.
When aqueous solution is made in monomer, the monomer concentration in the monomer solution be with aqueous temperature and monomeric species and
It is fixed, it is not particularly limited, but the concentration of the monomer solution in preferred polymeric step is 30wt% or more, preferably 32~
60wt%, more preferably 35~50wt%, preferably 38~45wt%.If being detached from above-mentioned range, if such as concentration of aqueous solution it is low
In 30wt%, it is possible to water absorbing agent of the presently claimed invention can not be obtained.
Starting polymerization initiator used when the polymerization, there is no particular restriction, and heat decomposition type polymerization initiator can be used,
Such as: the persulfates such as sodium peroxydisulfate, potassium peroxydisulfate；The peroxide such as hydrogen peroxide, tert-butyl peroxide；Azonitrile chemical combination
Object, azo amidine compound and photolysis type polymerization initiator.In addition, the reduction that can also and be decomposed with promotion polymerization initiator
Agent can constitute redox system polymerization initiator by the combination of polymerization initiator and the reducing agent.
Water solution polymerization process can be preferably used in the present invention, if such as to carry out heat dissipation type with double-arm kneading machine etc. poly-
It closes, then preferably by reducing agent and heat decomposition type polymerization initiator and for constituting redox system polymerization initiator.In addition, if will
The aqueous solution of monomer, which provides the transmission into defined container or being driven, to be brought up and carries out boiling polymerization, then it is preferable to use heat point
Solution type polymerization initiator.
N2Addition there is no particular restriction, N is preferably made in pipeline2After converging with reaction solution, then additional stirring is carried out, it is special
It is not action of forced stirring.It in this case, is preferably within 10 seconds more preferably 5 from the time for converging place to additional stirring
Within second.
The manufacturing method of intermediate base-material of the invention includes the steps that the aqueous gel obtained to polymerization is dried, dry
Degree (water content of dried object) can be degree of drying known in the art.In an example of the present invention, from what is obtained
Intermediate base material physical property is seen, preferably can express the powder of mobility at room temperature.In a preferable example of the invention
In, the moisture content of dried intermediate base-material is 0.2~15wt%, preferably 0.3~12wt%, more preferably 0.4~10wt%,
Preferably 0.5~8wt%, preferably 0.6~6wt%, the appearance of the intermediate base-material are in pulverulence.
In an example of the present invention, dried intermediate base-material is that centrifugation water absorbent rate (CRC) is 35~50g/g
Dried object.Water absorbent rate can be adjusted by the amount and concentration of crosslinking agent in the polymerization procedure, heat drying temperature.Especially
Its polymerization that relatively high crosslinking degree is preferably carried out with the amount (preferably 0.04mol% or more) of the internal crosslinking agent, and
The aqueous gel of acquisition is thermally dried in turn, water absorbent rate is increased in target zone.
The manufacturing method of intermediate base-material of the invention also includes further pulverising step and classification step.That is, to above-mentioned through dry
Dry obtained dry intermediate base-material is further crushed, then to the step that intermediate base materials powder is classified obtained by being crushed
Suddenly.By these steps obtain intermediate base-material be carried out it is surface-crosslinked before, with following physical property characteristic:
(a) ratio of 180 μm of the partial size particles more than or lower than 600 μm is 80wt% or more, and
(b) weight average particle diameter (D50) is 300 μm~500 μm.
The present invention carries out specifically polymerizeing control and water absorbent rate control by setting accordingly, and on this basis,
The particle that makes 80wt% or more in intermediate base-material of the invention, fall into a manner of standard sieve classification as defined in 180 μm to 600 μm
This range.Further, it was found that the setting is very for the water absorption under pressure multiplying power (BAAP) under the weight bearing of 2kPa of the invention
Useful.
It is of the invention it is surface-crosslinked before the weight average particle diameter (D50) of intermediate base-material be 300~500 μm, preferably for 350~
450 μm, more preferably 380~420 μm.If weight average particle diameter, less than 300 μm, operability is deteriorated, dust increases, liquid transitivity becomes
Difference.
Online test method of the present invention further includes, and based on the weight of the intermediate base-material, the SiO of 0.1~5wt% is added2?
Grain, and measure the intermediate base-material and SiO2The step of 2kPa water absorption under pressure multiplying power of granulate mixture.
Test for the water absorbing capacity of intermediate base-material, usual method have normal pressure water absorbent rate, centrifugation water absorbent rate.But work as
When it carries out that water absorbing properties are tested under conventional pressure, due to do not carry out it is surface-crosslinked before intermediate base-material, in water absorbent gel
After change, lack enough gaps, easily generation gel blocking phenomenon.So water absorbing properties test cannot be used under normal pressures
Evaluate the performance of intermediate base-material.The present inventor is by sharp study, by the water-insoluble for mixing sufficient amount into intermediate base-material
SiO2Particle, to solve the problems, such as that intermediate base-material cannot carry out water absorbing capacity under pressure and examine or check.
In an example of the present invention, SiO2Particle loads be 0.1~5wt%, preferably 0.5~4wt%, more preferably
For 0.8~3wt%, preferably 0.9~2wt%, preferably 0.9~1.2wt%.When content is less than 0.1wt%, to intermediate base-material
Sepage raising effect it is insufficient；And when content is greater than 5wt%, the water absorbent rate under higher cost and pressure declines instead.
In an example of the present invention, the SiO2Particle is preferably vapor phase method SiO2, obtained by primary particles aggregate
It arrives.It can be commercial prod such as REOLOSIL (manufacture of day Bender mountain).The average grain diameter of primary particle is preferably 5~100nm,
More preferably 10~50nm.Aggregate particle size after aggregation is preferably 50 μm hereinafter, more preferably 10 μm or less.
The inventors discovered that when water absorbent rate BAAP is 18g/g or more under the 2kPa pressure of intermediate base-material, suction obtained
Water-base resin has excellent performance.
Therefore, online test method of the present invention measures water absorbent rate BAAP under the 2kPa pressure of base-material obtained intermediate.If
Water absorbent rate BAAP is 18g/g or more, it is necessary to carry out surface cross-linking step to intermediate base-material obtained, to be made final
Super absorbent resin finished product.If the intermediate base-material cannot meet the item that its 2kPa water absorption under pressure multiplying power BAAP is 18g/g or more
Part, then predicting its water-absorbing resins obtained cannot meet the requirements, further surface-crosslinked without carrying out.
As the manufacturing method of water-absorbing resins of the present invention, except base-material among above-mentioned manufacture and on-line checking qualification with
Outside, it further includes surface cross-linking step.
It is without particular limitation in the crosslinking agent that the surface cross-linking step uses, it can be various friendships known in the art
Join agent.From the viewpoint of physical property, polyol compound, epoxide, polyamine compounds or polyamines chemical combination are generally used
Object and halogenated epoxy close inorganic surfaces crosslinking agents such as organic surface crosslinking agent or multivalent metal salt such as the condensation polymer of object etc..
To obtain graininess super absorbent resin of the invention, surface friendship preferably is carried out with a variety of organic surface crosslinking agents
Connection, and at least a kind of surface crosslinking agent contains multi-hydroxy in surface crosslinking agent used.It can be also crosslinked according to different surfaces
Permeability and reactivity of the agent relative to water-absorbing resins, form optimal cross-linked layer using a variety of organic surface crosslinking agents,
To provide graininess super absorbent resin of the invention.
The dosage of surface crosslinking agent and specifically used crosslinker compound and combinations thereof etc. are related.At of the invention one
In example, based on the weight of intermediate base-material, the dosage of the surface crosslinking agent is 0.1~10wt%, preferably 0.5~8wt%,
More preferably 1~6wt%, preferably 1.5~5wt%, preferably 2~4.5wt%.
The method of administration of surface crosslinking agent is without particular limitation, can be conventional method known in the art.Such as it can incite somebody to action
Surface-crosslinker solution is sprayed on intermediate base-material surface, and is allowed to uniformly mixed.
The water-absorbing resins after being mixed surface crosslinking agent preferably receive heat treatment.Carry out the heat treatment
When, it has been mixed the temperature of the water-absorbing resins of surface crosslinking agent, that is, the water-absorbing resins and surface crosslinking agent
The temperature of the mixture mixed is usually 100~250 DEG C, preferably 120-240 DEG C, more preferably 150~210 DEG C.Heating
Time is usually 10min~70min, preferably 20min~60min, more preferably 30min~50min.
In an example of the present invention, the manufacturing method of the graininess super absorbent resin the following steps are included:
(i) using acrylic compounds as the polymerization procedure of the monomer solution of principal component, implementation condition are as follows: monomer
Concentration of aqueous solution is 35wt% or more, and is 0.04mol% or more relative to the internal crosslinking dosage of the monomer；The monomer water
Solution is passed through N2Deoxygenation；
(ii) drying steps are dried to through aqueous gel obtained by the polymerization procedure, obtain water content be 3~
The dried object of 6wt%；
(iii) pulverising step and classification step, and obtain the intermediate base-material with following physical property characteristic (a)~(c)
Super absorbent resin powder；
(a) ratio of 180 μm of the partial size particles more than or lower than 600 μm is 80wt% or more,
(b) weight average particle diameter (D50) is 300 μm~500 μm,
(c) water absorbent rate BAAP is 18g/g or more under intermediate base-material pressure.
Wherein, (c) water absorbent rate BAAP refers under base-material pressure: to the SiO of intermediate base-material addition 1wt%2Particle, and
Water absorbent rate under the pressure surveyed under the weight bearing of 2kPa.
(iv) surface cross-linking step, the absorbent resin powder obtained by through the pulverising step and classification step
In, the surface crosslinking agent of the compound of hydroxyl and/or the derivative base of hydroxyl is added, to obtain surface-crosslinked super absorbent resin
Particle.
Even if the super absorbent resin water-absorbing resins made from the method for the present invention are used under high loads, nor affect on
The particulate water-absorbing agent of the basic absorption performance of the absorbent commodities such as paper nappy, pressurize lower water absorbent rate and liquid permeability.
The present invention is further illustrated below with reference to embodiment.
Embodiment
Test method
" ENANA " is the abbreviation of European non-woven fabrics Industry Association." ERT " is the measurement of the super absorbent resin of European standard
The abbreviation of method.It is to come according to standard in ERT original (change within 2002 and determine version/known document) unless there are particularly pointing out in the present invention
Measure the physical property of super absorbent resin.
(1) centrifuge retention capacity (CRC)
The centrifuge retention capacity (CRC) of super absorbent resin is measured according to EDANA method (ERT441.2-02).
Specifically, super absorbent resin 0.2g to be equably put into tea envelope (60mm × 85mm) and heat seal
Afterwards, it is immersed at 23 (± 2) DEG C in the 0.90wt%NaCl aqueous solution of remote excessive (usual 500ml or so).By 30min
Afterwards, lift sack, using centrifugal separator (Japanese Kokusan limited liability company manufacture, model H-122), with 250G from
After mental and physical efforts remove water 3min, the weight W of sack is measured1g.In addition, not using super absorbent resin and carrying out identical operation, measure
Weight W at this time2G calculates CRC g/g according to the following formula.
(2) high to pressurize lower water absorbent rate (AAP0.7)
Water absorbent rate (AAP) of the super absorbent resin under 4.8kPa pressure is surveyed according to EDANA method (ERT442.2-02)
It is fixed.
(3) base-material pressurizes lower water absorbent rate (BAAP)
The test device of water absorbent rate is carried out according to according to EDANA method (ERT442.2-02) under base-material pressurizes, and to base
Material is added to the SiO2 particle (day Bender mountain, QS-102) of 1wt% content, surveys and applies pressure as 2kPa.
(4) moisture content
The moisture content of super absorbent resin is measured according to EDANA (ERT430.2-02).
(5) weight average particle diameter D50
The weight average particle diameter D50 of super absorbent resin is surveyed according to measuring method disclosed in U.S. Patent No. 7638570
It is fixed.
Specifically, under conditions of room temperature (23 ± 2 DEG C), humidity 50RH%, by super absorbent resin 100g with mesh
It is sieved, will be remained for 850 μm, 710 μm, 600 μm, 500 μm, 425 μm, 300 μm, 212 μm, 150 μm of ASTM standard
Weight percent R is drawn on logarithmic probability paper.Pulp classifier used is Germany Retsch vibrosieve instrument AS200.
The partial size for being equivalent to R=50% is read as a result, as weight average particle diameter (D50).
(6) Saline Flow rate (SFC)
The SFC of super absorbent resin of the invention is surveyed based on measuring method disclosed in U.S. Patent No. 5669894
It is fixed.
(7) free swell rate (FSR)
The FSR of super absorbent resin of the invention is based on measuring method disclosed in international publication the 2009/016055th
To measure.Specifically, indigo of the addition as food additives in previously prepared 1000 parts by weight of 0.90wt%NaCl aqueous solution
Blue 0.02 parts by weight, fluid temperature is adjusted to 23 DEG C.1.000 ± 0.01g of sample is weighed in 25ml beaker, then weighs coloring
For the 0.90wt%NaCl aqueous solution 20g of blue, it is poured into sample beaker.Start timing after solution is all added, when
Stop stopwatch when liquid level is all covered by resin, records the time.
FSR is sample expansion rate, W in formulaFFor the weight of 0.9%NaCl solution, tsFor Bulking Time, WDIt is net for sample
Weight.
Production Example 1
In the rustless steel container of volume 20L, the NaOH water of investment acrylic acid 5kg, deionized water 4345g and 50wt%
Solution 4159g, the investment speed of NaOH solution are 832g/min.In NaOH solution during adding, it can be observed that being precipitated
Object, but gradually dissolution forms transparent homogeneous solution.When being added dropwise, because the temperature of the heat of neutralization neutralizer rises to 91 DEG C.
Then, polyethylene glycol 400 diacrylate (the Taiwan Changxing material share work for the internal crosslinking agent for being 4% as concentration is added
Industry Co., Ltd) 686g, five sodium water solution of diethyl pentetic acid (BASF) 14g that concentration is 5wt%, and in container
Under the action of the circulator bath of collet, the temperature of reaction solution is down to 88 DEG C.
This reaction solution is got with the speed of 4735g/min through stainless steel pipes under the action of constant displacement pump, apart from pipeline
It exports at about 50mm, continuous on-line mixing flow is 110g/min, the Na that concentration is 3%2S2O8Aqueous solution, and crossing
Place is passed through the N that flow is 0.75L/min2。
Above-mentioned monomer solution is with the continous way polymerization machine of the continuous condensation zone of 4845g/min.Reaction solution enters in polymerization machine
Temperature at mouthful is 82 DEG C.Through having started polymerization reaction after a period of time.During the polymerization reaction, water is generated on one side and is steamed
Gas on one side it is to all the winds expanded foamed, after-contraction collapse to the size more somewhat larger than condensation zone width.Record will oxidation
The time that agent is added to sizing material blistering is 40s.And this time is defined as cream time.It has passed through when since polymerization reaction
After 3min, is taken out from the tail end of condensation zone and contain band-like water-setting glue cross-linked polymer.
Using meat grinder (Nanjing nine be full of mechanical equipment Co., Ltd, model JY-22M, aperture 8mm) to through above-mentioned
Aqueous gel obtained from polymerization reaction solve broken, has obtained granular aqueous gel (1).During gel solution is broken,
The input amount of gel is 1453g/min, and sprinkling input amount is the deionization that 161.5g/min temperature is heated to 75 DEG C parallel
Water.
It is layered on 850 μm of mesh of stainless steel wire mesh, puts down through graininess aqueous gel obtained from aforesaid operations
Paving is passed through 180 DEG C of hot wind with average speed 1m/s, hold time 30min, is thus dried with a thickness of 45mm.Then,
Using roller mill 600 μm and 180 μm of standard screen of mesh will be used after the crushing of dry polymer obtained from the drying process
It is classified.By above-mentioned a series of operation, the intermediate base-material (1) of random broken shape has been obtained.
The performance of the intermediate base-material is tested in aforementioned manners, is as a result listed in table 1.
Production Example 2
The dosage of polyethyleneglycol diacrylate aqueous solution in embodiment 1 is changed into as 369g (its opposite acrylic acid list
The mol ratio of body is 0.04mol%), operation same as Example 1 has been carried out in addition to this, while obtaining intermediate base
Expect (2).
The performance of the intermediate base-material is tested in aforementioned manners, is as a result listed in table 1.
Production Example 3
By the N in embodiment 12It is passed through flow and is set as 0, carried out operation same as Example 1 in addition to this, simultaneously
Obtain intermediate base-material (3).
The performance of the intermediate base-material is tested in aforementioned manners, is as a result listed in table 1.
Production Example 4
Temperature of the neutralizer in embodiment 1 in kettle is adjusted to 81 DEG C, and reaction solution is in the temperature of polymerization machine inlet
Degree is 75 DEG C.Operation same as Example 1 has been carried out in addition to this, while obtaining intermediate base-material (4).
The performance of the intermediate base-material is tested in aforementioned manners, is as a result listed in table 1.
Embodiment 1
Intermediate base-material (1) 1kg of above-mentioned acquisition is put into 10L vertical V-shaped stirred tank, it then, will be well prepared in advance
Surface-crosslinker solution 40g be added in the mixing machine and mix by spraying, to obtain coating wet feed.Herein, table used
Face crosslinker solution is relative to intermediate 100 parts by weight of base materials powder, by 0.6 parts by weight ethylene glycol, 0.4 parts by weight of ethylene carbonate
And the solution that 3 parts by weight of deionized water mix.And the revolving speed of mixing of mixing machine is 500rpm, the spray of surface cross-linking solution accelerates
Degree is 40g/min.Then, which is put into 8L vertical V-shaped stirred tank, this kettle whipped form is helical-ribbon type, is stirred
Mixing revolving speed is 250rpm.The collet oil temperature of heating kettle is 200 DEG C herein, and material temperature reaches 190 DEG C, heating treatment time 60min,
Thus it has carried out surface-crosslinked, has obtained super absorbent resin.Then, which is cooled to 60 DEG C, use net
The standard screen of 850 μm and 150 μm of eye is classified, and super absorbent resin finished product (1) has been obtained.
The end properties is tested in aforementioned manners, is as a result listed in table 2.
Comparative example 1
In comparative example 1, intermediate base-material (1) is changed into intermediate base-material (2), carried out in addition to this same with embodiment 1
The operation of sample, to obtain super absorbent resin finished product (2).
The end properties is tested in aforementioned manners, is as a result listed in table 2.
Comparative example 2
In comparative example 2, intermediate base-material (1) is changed into intermediate base-material (3), carried out in addition to this same with embodiment 1
The operation of sample, to obtain super absorbent resin finished product (3).
The end properties is tested in aforementioned manners, is as a result listed in table 2.
Comparative example 3
In comparative example 1, intermediate base-material (1) is changed into intermediate base-material (4), carried out in addition to this same with embodiment 1
The operation of sample, to obtain super absorbent resin finished product (4).
The end properties is tested in aforementioned manners, is as a result listed in table 2.
Polymerization parameter shown in 1 Production Example 1~4 of table and intermediate base-material performance
CRC, AAP0.7 of the intermediate base-material and gained finished product used of 2 embodiment of table and comparative example, free swell speed
Rate, the test result of SFC
| Project | Base-material used | CRC | AAP0.7 | FSR | SFC |
| Unit | / | g/g | g/g | g/(g·s) | 10-7cm3·s/g |
| Embodiment 1 | Production Example 1 | 31 | 27 | 0.29 | 52 |
| Comparative example 1 | Production Example 2 | 33 | 23 | 0.27 | 23 |
| Comparative example 2 | Production Example 3 | 34 | 22 | 0.3 | 10 |
| Comparative example 3 | Production Example 4 | 36 | 21 | 0.29 | 7 |
As it can be seen from table 1 i.e. for the intermediate base-material (1) used in the embodiment of the present invention 1,1~3 institute of comparative example
Intermediate base-material (2)~(4), although intermediate base-material CRC, in terms of do not embody poor performance,
Water absorbing properties BAAP is very low under its base-material pressure.Caused by it the result is that after surface-crosslinked, gained AAP0.7 and SFC
Energy poor (comparative example 1~3 for being shown in Table 2).It can be seen that super absorbent resin of the invention is presented with superior performance.
Specifically, comparative example 1 is carried out surface-crosslinked and is obtained using the intermediate base-material in Production Example 2.Its polymerization used
Internal crosslinking agent content is 0.4mol%, and opposite Production Example 1 is lower, when it passes through acquisition comparative example 1 after surface-crosslinked, property
Energy AAP0.7 and SFC is relatively undesirable.This may be that the decrease of internal crosslinking degree leads to that enough intensity cannot be obtained.
And comparative example 2 is not passed through N2With the lower reacting liquid temperature of comparative example 3, this results in the exception of polymerization blistering, rises
The bubble time is longer, and reaction crack is also larger.It can be seen that its CRC content with higher, but institute from respective intermediate base-material
The BAAP performance of survey is significant lower, and the comparative example 2 and the end properties of comparative example 3 after further surface-crosslinked are found out,
AAP0.7 and SFC are also undesirable.BAAP can be in this stage of intermediate base-material with regard to the basic performance of reaction mass.The present invention about
The new evaluating method BAAP of intermediate base-material is critically important for controlling in formulating and production.
Polyacrylic acid (salt) of the invention is that super absorbent resin has water absorbent rate height and liquid permeability under high pressurize excellent
Etc. performances, be applicable to the purposes of the amenities absorber such as paper diaper.
Claims (10)
1. the online test method in a kind of super absorbent resin production process, it includes:
(i) absorbent resin powder of the preparation as intermediate base-material；With
(ii) based on the weight of the intermediate base-material, the SiO of 0.1~5wt% is added2Particle, and measure the intermediate base-material and SiO2?
The 2kPa water absorption under pressure multiplying power of grain mixture.
2. online test method as described in claim 1, it is characterised in that in the intermediate base-material
(a) ratio of 180 μm of the partial size particles more than or lower than 600 μm is 80wt% or more；
(b) weight average particle diameter D50 is 300 μm~500 μm.
3. online test method as claimed in claim 1 or 2, which is characterized in that based on the weight of intermediate base-material, the SiO2
The additional amount of particle is 0.1~5wt%；The SiO2Particle is vapor phase method SiO2。
4. a kind of manufacturing method of super absorbent resin, it includes the following steps:
(i) acrylic acid and internal crosslinking agent are provided, form the absorbent resin powder as intermediate base-material after polymerization；
(ii) based on the weight of the intermediate base-material, the SiO of 0.1~5wt% is added2Particle, and measure the intermediate base-material and SiO2?
The 2kPa water absorption under pressure multiplying power BAAP of grain mixture；With
(iii) if the BAAP measured is less than 18g/g, stop reacting；If BAAP is 18g/g or more, the following steps are carried out
(iv)；
(iv) in the intermediate base-material, surface crosslinking agent is added, to obtain surface-crosslinked Super Absorbent Polymer Particles.
5. the manufacturing method of super absorbent resin as claimed in claim 4, it is characterised in that in the intermediate base-material
(a) ratio of 180 μm of the partial size particles more than or lower than 600 μm is 80wt% or more；
(b) weight average particle diameter D50 is 300 μm~500 μm.
6. the manufacturing method of super absorbent resin as described in claim 4 or 5, which is characterized in that by the weight of intermediate base-material
Meter, the SiO2The additional amount of particle is 0.1~5wt%；The SiO2Particle is vapor phase method SiO2。
7. the test method of the intermediate base-material pressurization water absorbent rate of super absorbent resin, it includes making the intermediate base-material and pressing
Between base-material poidometer, the SiO with 0.1~5wt%2Particle mixing then measures the 2kPa pressurization water absorbent rate of the mixture
The step of BAAP.
8. test method as claimed in claim 7, it is characterised in that in the intermediate base-material
(a) ratio of 180 μm of the partial size particles more than or lower than 600 μm is 80wt% or more；
(b) weight average particle diameter D50 is 300 μm~500 μm.
9. test method as claimed in claim 7 or 8, which is characterized in that based on the weight of intermediate base-material, the SiO2Particle
Additional amount be 0.1~5wt%.
10. test method as claimed in claim 7 or 8, it is characterised in that the SiO2Particle is vapor phase method SiO2。
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| CN115181205A (en) * | 2022-07-20 | 2022-10-14 | 浙江卫星新材料科技有限公司 | Preparation method of light-smell high-absorptivity resin |
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|---|---|---|---|---|
| CN102712712A (en) * | 2009-12-24 | 2012-10-03 | 株式会社日本触媒 | Water-absorbable polyacrylic acid resin powder, and process for production thereof |
| CN104822740A (en) * | 2012-12-03 | 2015-08-05 | 株式会社日本触媒 | Polyacrylate water-absorbent polymer and manufacturing method therefor |
| US20150217270A1 (en) * | 2012-08-30 | 2015-08-06 | Nippon Shokubai Co., Ltd. | Particulate water absorbing agent and method for manufacturing same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102712712A (en) * | 2009-12-24 | 2012-10-03 | 株式会社日本触媒 | Water-absorbable polyacrylic acid resin powder, and process for production thereof |
| US20150217270A1 (en) * | 2012-08-30 | 2015-08-06 | Nippon Shokubai Co., Ltd. | Particulate water absorbing agent and method for manufacturing same |
| CN104822740A (en) * | 2012-12-03 | 2015-08-05 | 株式会社日本触媒 | Polyacrylate water-absorbent polymer and manufacturing method therefor |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115181205A (en) * | 2022-07-20 | 2022-10-14 | 浙江卫星新材料科技有限公司 | Preparation method of light-smell high-absorptivity resin |
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