CN102466670A - Method for testing influence produced by neutralization degree on composite water-absorbent resin volume phase transition - Google Patents
Method for testing influence produced by neutralization degree on composite water-absorbent resin volume phase transition Download PDFInfo
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- CN102466670A CN102466670A CN201010541391XA CN201010541391A CN102466670A CN 102466670 A CN102466670 A CN 102466670A CN 201010541391X A CN201010541391X A CN 201010541391XA CN 201010541391 A CN201010541391 A CN 201010541391A CN 102466670 A CN102466670 A CN 102466670A
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Abstract
The invention discloses a method for testing the influence produced by a neutralization degree on composite water-absorbent resin volume phase transition. The method provided by the invention comprises the following steps of preparing composite water-absorbent resin powder for the next use through a hydrophobic high-strength resin synthesis technology capable of controlling a cross-linking agent use amount, putting the composite water-absorbent resin powder into multiple beakers, adding absorbed solutions having different neutralization degrees into the beakers, removing free water by filtration when the composite water-absorbent resin powder is fully swelled, respectively calculating volume phase transition values under different neutralization degree conditions according to liquid level lifting heights, and comparing the volume phase transition values to determine the influence produced by a neutralization degree on composite water-absorbent resin volume phase transition. The method provided by the invention can realize the testing of the influence produced by a neutralization degree on composite water-absorbent resin volume phase transition, has high testing accuracy, simple testing processes and a low testing cost, and provides a good theoretical basis for hydrophobic high-strength resin use.
Description
Technical field
The present invention relates to the method for testing of a kind of degree of neutralization to the influence of composite water absorbing resin volume phase transition.
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.
In the application of some water-absorbing resin, be not high especially to the requirement of its water absorbent rate; And, when gel acquired a certain degree in water absorbing capacity, the phenomenon of embrittlement appearred.If control the resin water absorbing capacity through improving cross-linking density, the phenomenon of polymkeric substance embrittlement also can appear, and tensile strength reduces.
The volume phase transition of composite water absorbing resin mainly is to be caused by the interaction between external solution and the resin matrix, changes the acidic-group degree of neutralization, has been equivalent to change the character and the quantity of hydrophilic radical, thereby can have caused the generation of volume phase transition.
Summary of the invention
The objective of the invention is to overcome the shortcoming and defect of above-mentioned prior art; The method of testing of a kind of degree of neutralization to the influence of composite water absorbing resin volume phase transition is provided; This method of testing can record degree of neutralization to the influence of composite water absorbing resin volume phase transition, and measuring accuracy is high, and measuring process is simple; Reduced the measurement cost, for the use of hydrophobic type high-intensity resin provides better theoretical foundation.
The object of the invention is realized through following technical proposals: degree of neutralization may further comprise the steps the method for testing of composite water absorbing resin volume phase transition influence:
(a) preparation composite water absorbing resin powder is subsequent use;
(b) composite water absorbing resin powder is placed a plurality of beakers respectively, in beaker, add the liquid that is absorbed of different degree of neutralization respectively;
(c) treat the suction of the abundant swelling of resin after, with mesh screen free water is filtered out;
(d) then water absorbent gel is placed identical liquid to be measured, calculate water absorbent gel volume V under the different degree of neutralization conditions respectively by the liquid level lifting height.
(e) calculate expansivity through water absorbent gel volume V, the expansivity under the more different degree of neutralization conditions promptly gets degree of neutralization to composite water absorbing resin volume effects of phase transition.
In the said step (a), composite water absorbing resin powder is a dry composite water-absorbing resin powder.
In the said step (b), the beaker volume is 1000ml.
In the said step (b), adding be absorbed that liquid is long-pending to be 500ml.
In the said step (c), mesh screen is 100 order mesh screens.
In sum, the invention has the beneficial effects as follows: can record degree of neutralization to composite water absorbing resin volume phase transition influence, and measuring accuracy is high, measuring process is simple, has reduced the measurement cost, for the use of hydrophobic type high-intensity resin provides better theoretical foundation.
Description of drawings
Fig. 1 is that degree of neutralization is to composite water absorbing resin volume effects of phase transition curve map.
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 degree of neutralization that the present invention relates to may further comprise the steps the method for testing of composite water absorbing resin volume phase transition influence:
(a) preparation composite water absorbing resin powder is subsequent use;
(b) composite water absorbing resin powder is placed a plurality of beakers respectively, in beaker, add the liquid that is absorbed of different degree of neutralization respectively;
(c) treat the suction of the abundant swelling of resin after, with mesh screen free water is filtered out;
(d) then water absorbent gel is placed identical liquid to be measured, calculate water absorbent gel volume V under the different degree of neutralization conditions respectively by the liquid level lifting height.
(e) calculate expansivity through water absorbent gel volume V, the expansivity under the more different degree of neutralization conditions promptly gets degree of neutralization to composite water absorbing resin volume effects of phase transition.
In the above-mentioned steps (e), the formula that calculates expansivity through water absorbent gel volume V is following:
In the following formula: V～water absorbent gel swelling equilibrium volume; V0～dry resin powder initial volume
In the said step (a), composite water absorbing resin powder is a dry composite water-absorbing resin powder.
In the said step (b), the beaker volume is 1000ml.
In the said step (b), adding be absorbed that liquid is long-pending to be 500ml.
In the said step (c), mesh screen is 100 order mesh screens.
Result through said method records is as shown in Figure 1.Can know that from Fig. 1 the composite water absorbing resin is the volume phase transition trend basically identical under the different degree of neutralization conditions in pure water, just the peak value appearance point is different.The volume phase transition of water-absorbing resin increases afterwards earlier and reduces.This mainly is because the water sorption of resin is to be formed with hydrone by a large amount of hydrophilic radicals on the network structure to cause, these hydrophilic radicals comprise-COOH ,-COO-,-SO
3H ,-OH etc.These groups are not simple stack to the contribution of resin imbibition ability.Under different degree of neutralization conditions, what in fact regulate is-COO
-,-SO3
-Ion and-COOH ,-ratio of unionized groups such as OH, only when reaching some optimal proportions, its superposition to imbibition ability is only the strongest.Along with the increase of degree of neutralization, ionic group increases ,-COO
-,-SO3
-Deng hydrophilicity very strong; If but these ionizing groups too much exist, electrostatic repulsion increases between strand, and strand can not fully freely be unfolded and come, and is disadvantageous to the resin absorbent on the contrary.
Above-mentioned method of testing can record degree of neutralization to composite water absorbing resin volume phase transition influence, and measuring accuracy is high, and measuring process is simple, has reduced the measurement cost, for the use of hydrophobic type high-intensity resin provides better theoretical foundation.
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 (5)
1. degree of neutralization is characterized in that the method for testing of composite water absorbing resin volume phase transition influence, may further comprise the steps:
(a) preparation composite water absorbing resin powder is subsequent use;
(b) composite water absorbing resin powder is placed a plurality of beakers respectively, in beaker, add the liquid that is absorbed of different degree of neutralization respectively;
(c) treat the suction of the abundant swelling of resin after, with mesh screen free water is filtered out;
(d) then water absorbent gel is placed identical liquid to be measured, calculate water absorbent gel volume V under the different degree of neutralization conditions respectively by the liquid level lifting height.
(e) calculate expansivity through water absorbent gel volume V, the expansivity under the more different degree of neutralization conditions promptly gets degree of neutralization to composite water absorbing resin volume effects of phase transition.
2. degree of neutralization according to claim 1 is characterized in that to the method for testing of composite water absorbing resin volume phase transition influence in the said step (a), composite water absorbing resin powder is a dry composite water-absorbing resin powder.
3. degree of neutralization according to claim 1 is characterized in that to the method for testing of composite water absorbing resin volume phase transition influence in the said step (b), the beaker volume is 1000ml.
4. degree of neutralization according to claim 1 is characterized in that the method for testing of composite water absorbing resin volume phase transition influence, in the said step (b), adding be absorbed that liquid is long-pending to be 500ml.
5. degree of neutralization according to claim 1 is characterized in that to the method for testing of composite water absorbing resin volume phase transition influence in the said step (c), mesh screen is 100 order mesh screens.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109444391A (en) * | 2018-12-18 | 2019-03-08 | 北京科技大学 | The measurement method of super absorbent resin reflation rate in a kind of hydrated cement paste |
| CN109444390A (en) * | 2018-12-18 | 2019-03-08 | 北京科技大学 | The measurement method of super absorbent resin reflation rate in simulation fracture |
| CN115993427A (en) * | 2023-02-16 | 2023-04-21 | 江苏亨通高压海缆有限公司 | Water-blocking tape testing device, system and testing method |
-
2010
- 2010-11-01 CN CN201010541391XA patent/CN102466670A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109444391A (en) * | 2018-12-18 | 2019-03-08 | 北京科技大学 | The measurement method of super absorbent resin reflation rate in a kind of hydrated cement paste |
| CN109444390A (en) * | 2018-12-18 | 2019-03-08 | 北京科技大学 | The measurement method of super absorbent resin reflation rate in simulation fracture |
| CN115993427A (en) * | 2023-02-16 | 2023-04-21 | 江苏亨通高压海缆有限公司 | Water-blocking tape testing device, system and testing method |
| CN115993427B (en) * | 2023-02-16 | 2024-04-26 | 江苏亨通高压海缆有限公司 | Water-blocking tape testing device, system and testing method |
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Application publication date: 20120523 |