CN102464757A - Synthesis process capable of enhancing resin performance for hydrophobic high-strength resin - Google Patents
Synthesis process capable of enhancing resin performance for hydrophobic high-strength resin Download PDFInfo
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- CN102464757A CN102464757A CN201010541377XA CN201010541377A CN102464757A CN 102464757 A CN102464757 A CN 102464757A CN 201010541377X A CN201010541377X A CN 201010541377XA CN 201010541377 A CN201010541377 A CN 201010541377A CN 102464757 A CN102464757 A CN 102464757A
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Abstract
The invention discloses a synthesis process capable of enhancing resin performance for a hydrophobic high-strength resin. The synthesis process capable of enhancing the resin performance for the hydrophobic high-strength resin comprises the following steps of: hydrating sodium bentonite; dissolving reaction substances; and adding acrylic acid, an initiator and a crosslinking agent, and undergoing a pre-reaction and a heating reaction to obtain a product, and the like. Due to the adoption of the synthesis process, the hydrophobic high-strength resin can be synthesized successfully, synthesis efficiency is high, synthesis steps are simple, and synthesis cost is reduced; and the adding amount of a hydrophobic monomer is controlled in the synthesis process, so that the resin performance of the synthesized hydrophobic high-strength resin is enhanced.
Description
Technical field
The present invention relates to a kind of synthesis technique that improves the hydrophobic type high-intensity resin of resin property.
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 USDA starch-propylene cyanogen graft copolymer to be hydrolyzed and to make High hydrophilous resin, has drawn back the prelude of global broad research water-absorbing polymer thus.Thereafter soon, " water-absorbing resin of starch derivative has the excellent water-absorbing ability, and suction back gel water-retentivity is very strong, and these characteristics have all exceeded macromolecular material in the past " reported in research.This type of High hydrophilous 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 hydrophilous resin from 1966 and begin, the industriallization 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 hydrophilous 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 hydrophilous 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 structure starch is to contain hydrophilic radicals such as carboxyl and hydroxyl on main chain and the graft side chain of High hydrophilous resin, the affinity interaction of these hydrophilic radicals and water molecules is the main internal cause of its possess hydrophilic property; See that from physical structure it has the tridimensional network of lower crosslink density.Because the peculiar performance of High hydrophilous 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, plugging agent etc.And mainly use it for soil improvement agent, water-holding agent in agricultural sector, the bed base of growing seedlings.Because High hydrophilous resin is widely used, after USDA'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 water-absorbing material.
The reaction of early stage research starch graft copolymer uses many initiators to be cerium salt.Make initiator with cerium salt, grafting efficiency is high, but costs an arm and a leg.People adopt initiators such as manganese salt, persulphate 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 Mierocrystalline cellulose belong to carbohydrate together, people imagine again and use Mierocrystalline cellulose to prepare High hydrophilous resin as raw material.Because the cellulose graft rate is lower, the researchist handles its carboxymethylation earlier.Though but starch, this type of Mierocrystalline cellulose natural materials wide material sources, biodegradability is good, and the problem that faces simultaneously is easy to putrid and deteriorated exactly, and resistance toheat 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 vinylformic acid, propylene cyanogen, acrylic amide, Z 150PH etc. mainly that this has become the main development trend of High hydrophilous resin now gradually.
High hydrophilous 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 being usually used in it, grafted has propylene cyanogen, vinylformic acid, acrylic amide, propenoate etc.Simultaneously can utilize agricultural-food such as potato, corn to reduce production costs.Starch is that the disadvantage of product is exactly that resistance toheat is poor, and long-term water retention capacity is not enough, perishable, is difficult to standing storage.
The cellulose family water-retaining capacity is poor, need improve its water-retaining capacity through the grafted method, and domestic method comprises and hydrophilic monomer graft copolymerization or carboxymethylation.However, the product water-intake rate is still lower, and is easy to receive microbiological degradation and loses water retention 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 polyvinyl alcohol series.Natural polymer graft copolymers such as the water-retaining 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.Z 150PH is domestic to have only minority unit to develop; But Z 150PH is owing to have the hydrophilic functional group (OH) in the polymkeric substance; Thereby except the performance of general absorbent resin, also has the not available premium properties of other water-absorbing resin, for example salt 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 hydrophilous resin is used for the keeping crop seedling from drought and the soil improvement aspect of agricultural and forestry at first.High hydrophilous resin possesses good suction, water retention property, can reduce the steam output 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 ROHM, SEPIGEL 305 High hydrophilous resin; And it is added in the soil; Result of study shows: SEPIGEL 305/potassium acrylate High hydrophilous 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 farm crop water conservation be AS 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 hydrophilous resin to the transplanting survival rate of apple with spend before the ripening 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 Areas is kept a full stand of seedings by original soil improvement, water conservation drought resisting, breeding.Because High hydrophilous resin has very strong water-retaining capacity; And do not absorb hydrophobicity hydro carbons material characteristics; Can it and inorganics or organic lipid be mixed and process matrix material, WIW and producing well are handled, with the water-retaining capacity that improves low permeability layer with reduce water rate.Surface as with the inorganic material powders particle coats with absorbent resin, 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 absorbent resin has water-swelling property, does not have imbedibility to oil.And the volumetric shrinkage phenomenon can take place in High hydrophilous 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 hydrophilous resin can drive the surplus oil in space, stratum under external force and migrate to recovery well, plays oil displacement efficiency.In addition, the High hydrophilous 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 hydrophilous resin, can improve oil recovery factor.Because the concentration of various mineral ions is higher in the underground water, therefore be used for the High hydrophilous resin that recovers the oil in the oil field, should have salt tolerance preferably.
In the Application Areas 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 regain, the phenomenon of embrittlement appearred.If control the resin water regain through improving cross-linking density, the phenomenon of polymkeric substance embrittlement also can appear, and tensile strength reduces.
Hydrophobic the forming with the most frequently used method of water-soluble polymers of preparation at present is to adopt to cause water-soluble monomer and hydrophobic monomer copolymerization, and copolymerization is divided into polymerization methodses such as cosolvent method, micell polymerization method, microemulsion polymerization method, conversed phase micro emulsion copolymerization method, supersonic method, radical interfacial polymerization.Wherein the product of cosolvent method is a random structure, this molecular structure help macromolecular chain in the aqueous solutions of polymers realize intramolecularly form with, be unfavorable for intermolecular form with.Adopt micellar free radical copolymerization to prepare multipolymer and can realize many little block hydrophobic structures, this block structure helps intermolecularly forming and acting on.And the block length of hydrophobic units can be by the decision of the mol ratio of hydrophobic grouping/tensio-active agent, and molecular chain structure is easy to control, so the micellar copolymerization mode is extensively adopted.Tensio-active agent forms micella in solution in this compound method, as solubilizing agent, hydrophobic monomer then by solubilising in micella.Hydrophobic monomer just can form homogeneous system in the aqueous solution like this, with water-soluble monomer generation polymerization.When hydrophobic monomer has amphiphilic structure, be polymerisable surfactant, himself can form micella in system, in aqueous phase system, accomplish polymerization.
In the technological process of hydrophobic synthetic type high-intensity resin, the content of hydrophobic monomer in resin is more significant to liquid absorbency rate and the influence of resin flexible.
Summary of the invention
The objective of the invention is to overcome the shortcoming and defect of above-mentioned prior art; A kind of synthesis technique that improves the hydrophobic type high-intensity resin of resin property is provided, the successful hydrophobic synthetic type high-intensity resin of this synthesis technique ability, and combined coefficient is high; Synthesis step is simple, has reduced synthetic cost; Through the hydrophobic monomer dosage in the control synthesis technique, thus the resin property of the hydrophobic type high-intensity resin that raising synthesizes.
The object of the invention is realized through following technical proposals: a kind of synthesis technique that improves the hydrophobic type high-intensity resin of resin property may further comprise the steps:
(a) with sodium bentonite in beaker, add water and be stirred well to the abundant aquation of wilkinite and disperse, leave standstill and make its aquation thorough;
(b) in reaction vessel, add acrylic amide, 2-acrylamido-2-methyl propane sulfonic acid, hydrophobic monomer, sodium bentonite and a small amount of zero(ppm) water, and control hydrophobic monomer dosage is 3.4%～3.6% of monomer total amount, low-grade fever stirs, and makes its whole dissolvings;
(c) the cooling back adds NaOH part neutral vinylformic acid, and logical nitrogen deoxygenation, adds initiator, cross-linking agent solution, heats up and carries out pre-reaction, and improve mixing speed;
(d) after the stirring pre-reaction liquid is moved into special container, sealed reactor behind the logical nitrogen 20min of continuation, constant temperature water bath is reacted into glue, promptly gets the hydrophobic type high-intensity resin.
In the said step (a), time of repose is 24h.
In the said step (b), reaction vessel is a there-necked flask.
In the said step (c), the deoxygenation time is 10min.
After said step (d) finished, through with pure water, ethanol wash products, oven dry also crushing screening made the different-grain diameter sample, places in the moisture eliminator subsequent use.
In the said step (b), the hydrophobic monomer dosage is 3.5% of a monomer total amount.
In sum, the invention has the beneficial effects as follows: the successful hydrophobic synthetic type high-intensity resin of ability, and combined coefficient is high, and synthesis step is simple, has reduced synthetic cost; Through the hydrophobic monomer dosage in the control synthesis technique, thus the resin property of the hydrophobic type high-intensity resin that raising synthesizes.
Description of drawings
Fig. 1 is the influence synoptic diagram of hydrophobic monomer dosage of the present invention to resin property.
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:
A kind of synthesis technique that improves the hydrophobic type high-intensity resin of resin property that the present invention relates to may further comprise the steps:
(a) with sodium bentonite in beaker, add water and be stirred well to the abundant aquation of wilkinite and disperse, leave standstill and make its aquation thorough;
(b) in reaction vessel, add acrylic amide, 2-acrylamido-2-methyl propane sulfonic acid, hydrophobic monomer, sodium bentonite and a small amount of zero(ppm) water, and control hydrophobic monomer dosage is 3.4%～3.6% of monomer total amount, low-grade fever stirs, and makes its whole dissolvings;
(c) the cooling back adds NaOH part neutral vinylformic acid, and logical nitrogen deoxygenation, adds initiator, cross-linking agent solution, heats up and carries out pre-reaction, and improve mixing speed;
(d) after the stirring pre-reaction liquid is moved into special container, sealed reactor behind the logical nitrogen 20min of continuation, constant temperature water bath is reacted into glue, promptly gets the hydrophobic type high-intensity resin.
In the said step (a), time of repose is 24h.
In the said step (b), reaction vessel is a there-necked flask.
In the said step (c), the deoxygenation time is 10min.
After said step (d) finished, through with pure water, ethanol wash products, oven dry also crushing screening made the different-grain diameter sample, places in the moisture eliminator subsequent use.
In the said step (b), the hydrophobic monomer dosage is 3.5% of a monomer total amount.
In the technological process of hydrophobic synthetic type high-intensity resin, the content of hydrophobic monomer in resin is more significant to liquid absorbency rate and the influence of resin flexible.
In order to obtain best hydrophobic monomer dosage, the present invention has done the influence test of hydrophobic monomer dosage to the resin property of the hydrophobic type high-intensity resin that synthesizes, and the result is as shown in Figure 1.Can know that from Fig. 1 the swelling multiplying power of resin in salt solution increases along with the add-on of hydrophobic monomer and rise earlier and afterwards reduce.The hydrophilic ability of long carbochain though this is, its hydrophobic in gel network forms and acts on formed reversible space grid structure and has stronger anti-inorganic salt performance.And tensile strength values is in rising trend always before hydrophobic monomer dosage 3.5 (wt) %.Liquid absorption is big more, and the double electrical layers compressive action of sodium bentonite is strong more, and hydration shell is thin more, the stress scope away from each other, this is disadvantageous to the water absorbent gel tension; Simultaneously the long carbochain flexibility in the hydrophobic monomer is good, and the physics existence forming and act on, is favourable to resin toughening.The variation of tensile strength is the result of this two aspects effect.After the hydrophobic monomer dosage was above 3.5%, downward trend appearred in the tensile strength of water-absorbing resin.This possibly be because the hydrophobic carbochain of length of toxilic acid monoesters too much is present among the hydrophilic network of resin, has influenced hydrophilic crosslinked effect, causes the cross-linked network polymer segment discontinuous, and the water absorbent gel degree of flexibility reduces.
To sum up can draw, control hydrophobic monomer dosage of the present invention is 3.4%～3.6% of a monomer total amount, and is preferably 3.5%.
The successful hydrophobic synthetic type high-intensity resin of above-mentioned synthesis technique ability, and combined coefficient is high, and synthesis step is simple, has reduced synthetic cost; Through the hydrophobic monomer dosage in the control synthesis technique, thus the resin property of the hydrophobic type high-intensity resin that raising synthesizes.
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 (6)
1. a synthesis technique that improves the hydrophobic type high-intensity resin of resin property is characterized in that, may further comprise the steps:
(a) with sodium bentonite in beaker, add water and be stirred well to the abundant aquation of wilkinite and disperse, leave standstill and make its aquation thorough;
(b) in reaction vessel, add acrylic amide, 2-acrylamido-2-methyl propane sulfonic acid, hydrophobic monomer, sodium bentonite and a small amount of zero(ppm) water, and control hydrophobic monomer dosage is 3.4%～3.6% of monomer total amount, low-grade fever stirs, and makes its whole dissolvings;
(c) the cooling back adds NaOH part neutral vinylformic acid, and logical nitrogen deoxygenation, adds initiator, cross-linking agent solution, heats up and carries out pre-reaction, and improve mixing speed;
(d) after the stirring pre-reaction liquid is moved into special container, sealed reactor behind the logical nitrogen 20min of continuation, constant temperature water bath is reacted into glue, promptly gets the hydrophobic type high-intensity resin.
2. a kind of synthesis technique that improves the hydrophobic type high-intensity resin of resin property according to claim 1 is characterized in that in the said step (a), time of repose is 24h.
3. a kind of synthesis technique that improves the hydrophobic type high-intensity resin of resin property according to claim 1 is characterized in that in the said step (b), reaction vessel is a there-necked flask.
4. a kind of synthesis technique that improves the hydrophobic type high-intensity resin of resin property according to claim 1 is characterized in that in the said step (c), the deoxygenation time is 10min.
5. a kind of synthesis technique that improves the hydrophobic type high-intensity resin of resin property according to claim 1; It is characterized in that, after said step (d) finishes, through with pure water, ethanol wash products; Oven dry and crushing screening make the different-grain diameter sample, place in the moisture eliminator subsequent use.
6. a kind of synthesis technique that improves the hydrophobic type high-intensity resin of resin property according to claim 1 is characterized in that in the said step (b), the hydrophobic monomer dosage is 3.5% of a monomer total amount.
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| CN112551944A (en) * | 2020-12-09 | 2021-03-26 | 蒲诃夫 | Modified bentonite anti-seepage material and preparation method and application thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112551944A (en) * | 2020-12-09 | 2021-03-26 | 蒲诃夫 | Modified bentonite anti-seepage material and preparation method and application thereof |
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Application publication date: 20120523 |