CN102466589A - Method for determining relation between swelling multiplying power and gel strength of composite water-absorbing material - Google Patents
Method for determining relation between swelling multiplying power and gel strength of composite water-absorbing material Download PDFInfo
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Abstract
The invention discloses a method for determining the relation between the swelling multiplying power and the gel strength of a composite water-absorbing material. The method for determining the relation between the swelling multiplying power and the gel strength of the composite water absorbent material comprises the following steps: the composite water-absorbing material is melted into the medium solution and reaches a certain expansion rate; measuring a cross-sectional area A and a tension value F by a spring tension meter; and calculating the gel strength through the cross section area A and the tension value F. The method can determine the relationship between the swelling multiplying power of the composite water-absorbing material and the gel strength, has high measurement precision and simple measurement steps, and reduces the measurement cost.
Description
Technical field
The present invention relates to a kind of method of measuring composite absorbent material swelling multiplying power and gel strength relation.
Background technology
High-hydroscopicity be a kind of have strong absorptive very can and the functional high molecule material of water retention property.It can absorb hundred times and even the thousands of times moisture to deadweight, and under the certain temperature and pressure of external environment, can keep moisture lastingly, and this is that traditional imbibition material such as sponge is incomparable.
In the sixties in last century, the water-absorbing resin that occurs the earliest is by United States Department of Agriculture starch-propylene cyanogen graft copolymer to be hydrolyzed and to make high hydroscopic resin, has drawn back the prelude of global broad research water absorbent polymer thus.Thereafter soon, " water-absorbing resin of starch derivative has the excellent water-absorbing ability, and suction back gel water-retaining property is very strong, and these characteristics have all exceeded macromolecular material in the past " reported in research.This type of high hydroscopic resin is realized suitability for industrialized production at first, obtains howling success, has drawn back the prelude of global range broad research high absorbency material thus.
Succeeded in developing starch-propylene cyanogen graft copolymer high hydroscopic resin from 1966 and begin, the industrialization progress is very rapid, according to statistics, and the initial stage eighties, ten thousand tons of yearly capacity less thaies.And be 260,000 tons to world's high hydroscopic resin output in 1989, wherein the U.S. 10.5 ten thousand, about 7.6 ten thousand tons of Japan, and by 2000, U.S.'s high hydroscopic resin output reached 500,000 tons, Japanese output reaches 400,000 tons.During this period, the water-absorbing-retaining material of all kinds of excellent performances obtains development in succession and produces.
See that from chemical constitution starch is to contain hydrophilic radicals such as carboxyl and hydroxyl on main chain and the graft side chain of high hydroscopic resin, the affinity interaction of these hydrophilic radicals and hydrone is the main internal cause of its possess hydrophilic property; See that from physical arrangement it has the tridimensional network of lower crosslink density.Because the peculiar performance of high hydroscopic resin has just caused the great interest of people since it comes out, obtain widespread use at aspects such as industry, agricultural, daily life, health cares.Be usually used in dewatering agent, accelerating chemicals, plugging material, water shutoff agent etc.And mainly use it for soil conditioner, water-loss reducer in agricultural sector, the bed base of growing seedlings.Because high hydroscopic resin is widely used, after United States Department of Agriculture's north experimental study was at first succeeded in developing, Japan had also carried out a large amount of development researches.Japan, Germany, France last century late nineteen seventies drop into suitability for industrialized production in succession.Ground enterprises such as China Guangdong, Shanghai introduce some wet diaper production lines in the eighties, have begun the industrialized paces of China's absorbent material.
The reaction of early stage research starch graft copolymer uses many initiating agents to be cerium salt.Make initiating agent with cerium salt, grafting efficiency is high, but costs an arm and a leg.People adopt initiating agents such as manganese salt, persulfate and redox system again subsequently.The graft copolymerization that radiation method causes starch can carry out at normal temperatures, compares with chemistry initiation method to have more advantage.Because starch and cellulose belong to carbohydrate together, people imagine again and use cellulose to prepare high hydroscopic resin as raw material.Because the cellulose graft rate is lower, the researchist handles its carboxymethylation earlier.Though but starch, this type of cellulose natural material wide material sources, biodegradability is good, and the problem that faces simultaneously is easy to putrid and deteriorated exactly, and heat resistance is poor, and gel strength is low, is difficult to standing storage.
For overcoming above-mentioned shortcoming, people shift sight to synthesizing to be super absorbent resin, to be raw material with acrylic acid, propylene cyanogen, acrylic amide, polyvinyl alcohol (PVA) etc. mainly that this has become the main development trend of high hydroscopic resin now gradually.
High hydroscopic resin is classified from synthetic raw material, can be divided into starch system, and cellulose-based and synthetic is the resin three major types.
The native starch class is studied morely owing to abundant raw material, cheapness, and research in this respect mainly concentrates on the grafting aspect of starch, and what be usually used in grafting with it has propylene cyanogen, acrylic acid, acrylic amide, an acrylic ester etc.Simultaneously can utilize agricultural product such as potato, corn to reduce production costs.Starch is that the disadvantage of product is exactly that heat resistance is poor, and long-term water holding capacity is not enough, perishable, is difficult to standing storage.
The cellulose family water-intake capacity is poor, need improve its water-intake capacity through the method for grafting, and common method comprises and hydrophilic monomer graft copolymerization or carboxymethylation.However, the product water-intake rate is still lower, and is easy to receive microorganism to decompose and loses water holding capacity.But it can be used for processing the high-hydroscopicity fabric, with the synthon blending, improves the final performance of product.
Synthetic resin is mainly propylene salt series and modified polyvinylalcohol series.Natural polymer graft copolymers such as the water-intake capacity of propylene salt and starch are suitable, but product is difficult for corruption, and water-intake rate is high, and the intensity of gel is big, Stability Analysis of Structures, and the product good combination property is studied more at present.Polyvinyl alcohol (PVA) is domestic to have only minority unit to develop; But polyvinyl alcohol (PVA) is owing to have the hydrophilic functional group (OH) in the polymkeric substance; Thereby except the performance of general water-absorbing resins, also has the not available premium properties of other water-absorbing resin, for example brine tolerance, high-gel strength etc.It is compared with other water-absorbing resin and is prone to discharge to soil, sand bed after the prime advantage that has is to absorb water, and keeps the moistening of soil, for solving global food problem and desert problem the possibility of solution is provided.
High hydroscopic resin is used for the keeping crop seedling from drought and the soil improvement aspect of agricultural and forestry at first.High hydroscopic resin possesses good suction, water retention property, can reduce the evaporation capacity of soil, in soil, can also absorb the moisture of capacity during precipitation, and when arid, discharge these moisture.People such as Abd El-Rehim use radiation method to prepare serial polyacrylic acid, polyacrylamide high hydroscopic resin; And it is added in the soil; Result of study shows: polyacrylamide/potassium acrylate high hydroscopic resin is owing to can adsorb and keep the water of thousands of times of own wts; Improve the water retention property and the farming performance of sandy soil, thereby helped plant growth.
China at first with super absorbent resin be used for the crops water conservation be academy of sciences chemistry people such as yellow beautiful jade; They successively are used for grow seedlings of vegetable and fruit plantation with super absorbent resin; The result show high hydroscopic resin to the transplanting survival rate of apple with spend before the maturity stage obvious facilitation is all arranged; To grape growth also obvious facilitation, can promote grape precocity fruiting, and can make grape yield increasing.
The resin kind is on the increase at present; Product begins to intelligent, the high-level development of multifunctional material, and industries such as household chemicals industry, building material industry, health care industry, communications and transportation, oil-gas mining are widened in the agriculture aspect that application is kept a full stand of seedings by original soil improvement, water conservation drought resisting, breeding.Because high hydroscopic resin has very strong water-intake capacity; And do not absorb hydrophobicity hydro carbons material characteristics; Can it and inorganics or organic lipid be mixed and process compound substance, water injection well and producing well are handled, with the water-intake capacity that improves low permeability layer with reduce water rate.Surface as with the inorganic material powders particle coats with water-absorbing resins, obtains water-absorbing composite; Perhaps water-absorbing resin is worn into the particle of certain grain size scope, be suspended in the aqueous salt brine, process profile-controlling and plugging agent, water-swellable behind the injection most permeable zone stops up the effect that most permeable zone (water layer) plays profile control.When being squeezed into oil reservoir, because it does not possess oil absorption, thereby when exploitation, carry out easily, reach the selectively blocking off purpose.Super absorbent resin has lightly crosslinked three-dimensional net structure, contains a large amount of hydrophilic radicals in its structure and has guaranteed that water-absorbing resins has imbibition property, does not have imbedibility to oil.And the volumetric contraction phenomenon can take place in high hydroscopic resin in oil.
Super absorbent resin is a kind of flexible macromolecule, can guarantee under external force reversible deformation can take place after the suction.When using in the oil recovery field, high hydroscopic resin can drive the remaining oil in space, stratum under external force and migrate to producing well, plays oil displacement efficiency.In addition, the high hydroscopic resin particle also can be detained in formation pore, stops up hole, plays the effect of water blockoff, forces Groundwater Flow to turn to.Utilize this selection water shut-off of high hydroscopic resin, can improve oil recovery factor.Because the concentration of various inorganic ions is higher in the underground water, therefore be used for the high hydroscopic resin that recovers the oil in the oil field, should have brine tolerance preferably.
Clay be organic and inorganic composite high-water uptake property resin with traditional synthetic be that super absorbent resin is compared because the introducing of clay can reduce cost, improve the performances such as brine tolerance, gel strength of gel.In numerous kind clay minerals, the bentonitic clay of layer structure is because reserves are abundant, function admirable and have application promise in clinical practice.Bentonitic clay mainly contains two kinds of sodium bentonite and calcium-base bentonites, and the bentonitic clay that occurring in nature exists is the most general with the calcium base.Think that at present the performance of sodium bentonite is superior to calcium-base bentonite.The sodium bentonite water-intake rate is big, degree of expansion is big, cation exchange capacity is big; Good dispersion in aqueous medium, colloid index is big, and soliquid thixotropy, viscosity, lubricity are good, and pH value is high, Heat stability is good etc.The revert to take drugs research of water-base resin of swelling soil series organic-inorganic also mainly concentrates on and uses sodium bentonite to prepare negative ion or non-ionic super absorbent resin.
There are very big relation in the swelling multiplying power of composite absorbent material and gel strength, how to determine the swelling multiplying power of composite absorbent material and the relation of gel strength, and synthetic composite absorbent material is seemed most important.
Summary of the invention
The objective of the invention is to overcome the shortcoming and defect of above-mentioned prior art; The method of measuring composite absorbent material swelling multiplying power and gel strength relation is provided; The method of this mensuration composite absorbent material swelling multiplying power and gel strength relation can determine the relation of composite absorbent material swelling multiplying power and gel strength; And measuring accuracy is high, and measuring process is simple, has reduced the measurement cost.
The object of the invention is realized through following technical proposals: measure the method for composite absorbent material swelling multiplying power and gel strength relation, may further comprise the steps:
(a) composite absorbent material to be determined is added respectively in four kinds of medium solutions, make it in four kinds of medium solutions, reach certain swelling multiplying power respectively;
(b) the above-mentioned mixed solution that is the column gel of intercepting, the two ends clamping links to each other with the spring tension meter;
(c) measure gel middle part cross-sectional area A through the spring tension instrumentation, flashy value of thrust F before reading gel piece and under tension, rupturing;
(d) through cross-sectional area A and value of thrust F, calculate gel strength S.
Said four kinds of medium solutions are respectively deionized water, NaCl solution, KCl solution, CaCl
2Solution.
Said NaCl solution, KCl solution, CaCl
2The concentration of solution is 0.5%.
In the said step (a), the swelling multiplying power is 20 times.
In sum, the invention has the beneficial effects as follows: can determine the relation of composite absorbent material swelling multiplying power and gel strength, and measuring accuracy is high, measuring process is simple, has reduced the measurement cost.
Description of drawings
Fig. 1 is the influence synoptic diagram of different swelling multiplying power of the present invention to gel strength.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is done further detailed description, but embodiment of the present invention is not limited only to this.
Embodiment:
The mensuration composite absorbent material swelling multiplying power that the present invention relates to and the method for gel strength relation may further comprise the steps:
(a) composite absorbent material to be determined is added respectively in four kinds of medium solutions, make it in four kinds of medium solutions, reach certain swelling multiplying power respectively;
(b) the above-mentioned mixed solution that is the column gel of intercepting, the two ends clamping links to each other with the spring tension meter;
(c) measure gel middle part cross-sectional area A through the spring tension instrumentation, flashy value of thrust F before reading gel piece and under tension, rupturing;
(d) through cross-sectional area A and value of thrust F, calculate gel strength S.
Computing formula in the above-mentioned steps (d) is:
Said four kinds of medium solutions are respectively deionized water, NaCl solution, KCl solution, CaCl
2Solution.
Said NaCl solution, KCl solution, CaCl
2The concentration of solution is 0.5%.
In the said step (a), the swelling multiplying power is 20 times.
There are very big relation in the swelling multiplying power of above-mentioned composite absorbent material and gel strength, how to determine the swelling multiplying power of composite absorbent material and the relation of gel strength, and synthetic composite absorbent material is seemed most important.
In order to obtain best swelling multiplying power; The present invention has done the influence test of swelling multiplying power to gel strength; The result is as shown in Figure 1; Can be known by Fig. 1: in four kinds of media being investigated, it is consistent that the tensile strength during different swelling amount changes, and promptly all is that the increase pulling strengrth along with the gel swelling amount reduces.Be lower than at liquid absorbency rate under 20 the situation, gel tensile strength and media environment of living in relation are little, only relevant with gel network swelling multiplying power; Just gel tensile strength is high slightly in KCl solution, possibly be because K
+Na between the switching part bentonite bed
+, K
+Ion embeds between bentonite bed and more effectively peels off bentonitic lamellar structure, makes that bentonite lamella structural stress ball action scope is more even, and resin toughness increases, and tensile strength strengthens.
The method of measuring composite absorbent material swelling multiplying power and gel strength relation can determine the relation of composite absorbent material swelling multiplying power and gel strength, and measuring accuracy is high, and measuring process is simple, has reduced the measurement cost.
The above only is preferred embodiment of the present invention, is not the present invention is done any pro forma restriction, and every foundation technical spirit of the present invention, any simple modification, equivalent variations to above embodiment did all fall within protection scope of the present invention.
Claims (4)
1. measure the method for composite absorbent material swelling multiplying power and gel strength relation, it is characterized in that, may further comprise the steps:
(a) composite absorbent material to be determined is added respectively in four kinds of medium solutions, make it in four kinds of medium solutions, reach certain swelling multiplying power respectively;
(b) the above-mentioned mixed solution that is the column gel of intercepting, the two ends clamping links to each other with the spring tension meter;
(c) measure gel middle part cross-sectional area A through the spring tension instrumentation, flashy value of thrust F before reading gel piece and under tension, rupturing;
(d) through cross-sectional area A and value of thrust F, calculate gel strength S.
2. the method for mensuration composite absorbent material swelling multiplying power according to claim 1 and gel strength relation is characterized in that, said four kinds of medium solutions are respectively deionized water, NaCl solution, KCl solution, CaCl
2Solution.
3. the method for mensuration composite absorbent material swelling multiplying power according to claim 2 and gel strength relation is characterized in that, said NaCl solution, KCl solution, CaCl
2The concentration of solution is 0.5%.
4. the method for mensuration composite absorbent material swelling multiplying power according to claim 1 and gel strength relation is characterized in that, in the said step (a), the swelling multiplying power is 20 times.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103018125A (en) * | 2012-06-05 | 2013-04-03 | 济南吉利汽车有限公司 | Device and method for determining expansion rate of expansion damping sealant for automobile welding |
| CN113544164A (en) * | 2019-03-08 | 2021-10-22 | 住友精化株式会社 | Water-absorbent resin particles |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103018125A (en) * | 2012-06-05 | 2013-04-03 | 济南吉利汽车有限公司 | Device and method for determining expansion rate of expansion damping sealant for automobile welding |
| CN103018125B (en) * | 2012-06-05 | 2014-09-24 | 济南吉利汽车有限公司 | Device and method for determining expansion rate of expansion damping sealant for automobile welding |
| CN113544164A (en) * | 2019-03-08 | 2021-10-22 | 住友精化株式会社 | Water-absorbent resin particles |
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