CN101062966A - Super water-absorbing resin and preparation method thereof - Google Patents
Super water-absorbing resin and preparation method thereof Download PDFInfo
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- CN101062966A CN101062966A CN 200610076693 CN200610076693A CN101062966A CN 101062966 A CN101062966 A CN 101062966A CN 200610076693 CN200610076693 CN 200610076693 CN 200610076693 A CN200610076693 A CN 200610076693A CN 101062966 A CN101062966 A CN 101062966A
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Abstract
The invention discloses a super water uptake resin and preparing method, which comprises the following steps: adding light initiating agent and sensitizer into rubber latex; irradiating with ultraviolet light; introducing into dormancy group on the surface of rubber gel particle; adding cross linker into rubber latex; heating; making dormancy group of rubber jel particle surface crack; generating surface free group; triggering rubber emulsion and cross linker to polymerize; getting the rubber emulsion of microcosmic stereoscopic network; adding hydrophilicity macromolecule polymer monomer water solution into the rubber emulsion; triggering hydrophilic monomer grafted polymerization reaction; getting the product with rubber gel particle as joint and microcosmic stereoscopic network structure. The specific absorption for pure water of this resin can reach 5000-13000 double.
Description
Technical field:
The present invention is a kind of super moisture absorbing resin and preparation method thereof, relates to by the technology of UV-light initiation at latex rubber micelle surface grafting polymerization.
Background technology:
Super moisture absorbing resin is meant the hydrophilic high molecular polymer that contains cross-linked network structure, and it can absorb hundred times and even up to ten thousand times to the water of own wt and keep gel state.The super water-absorbent resin can be divided into following two classes by its composition, the homopolymer super moisture absorbing resin: comprise polyacrylic acid (salt), polyacrylamide, polyoxyethylene glycol etc.; Multipolymer super moisture absorbing resin: comprise that starch system, cellulose-based, protein are grafts super water-absorbent resin etc.On microtexture, existing super moisture absorbing resin mainly is by cross-linker molecules the individual molecule chain to be coupled together, molecular chain is crosslinked and a little is divided into several parts (as Fig. 1), the short one by one hydrophilic molecule chain that water-absorbing resin really participates in absorbing water after just being separated, water-retaining capacity is very limited.Therefore soaking effect is also not really high, generally the water absorbent rate to pure water is about about 800～2000 times, water absorbent rate to salt solution (in 0.9% sodium-chlor (NaCl) weight solution), the highlyest be no more than 200 times, so an important content of super moisture absorbing resin preparation research is exactly the water absorbent rate that how to improve super moisture absorbing resin.The water-absorbing resin suction formula traditional according to Flory, the principal element that influences the super moisture absorbing resin water absorbent rate as can be known has three aspects: first, the monomeric wetting ability of this body structure of super moisture absorbing resin, promptly monomeric wetting ability is good more, and the water absorbent rate of gained super moisture absorbing resin is high more; The second, the electric density in the super moisture absorbing resin, electric density are high more, and the molecular chain of super moisture absorbing resin is discrete to be opened more, and water absorbent rate is also high more; The 3rd, the cross-linking density of super moisture absorbing resin system, cross-linking density is low, and the free active ability of molecular chain is strong, the water absorbent rate height.
At present the preparation method of super moisture absorbing resin generally is that monomer (or grafting main body), linking agent and initiator are added reactor, then polymerization and getting.The homopolymer super moisture absorbing resin is linking agent, initiator to be joined in the monomer solution obtain behind the polymerization certain hour, and the multipolymer super moisture absorbing resin is pretreated starch (Mierocrystalline cellulose, protein etc.) is mixed, adds linking agent and initiator polymerization with monomer and to get.Difference with aforesaid method polymerization gained variant production is that choosing of monomer, linking agent is different with proportioning, and does not have controllability for the structure of product.
Very limited from the development space of monomer and electric density two aspects raising water absorbent rate, the water-retaining capacity of water-absorbing resin is mainly controlled by cross-linking density, can realize by two kinds of methods, the firstth, the consumption of adjustment linking agent, the secondth, the kind of selection linking agent.
The water absorbent rate of super moisture absorbing resin becomes reverse variation relation with dosage of crosslinking agent, dosage of crosslinking agent is many more, and cross-linking density is high more, and the water absorbent rate of water-absorbing resin is low more.Desire to make super moisture absorbing resin to have higher water absorbent rate, must reduce cross-linking density.If but cross-linking density is low excessively, the molecular chain of super moisture absorbing resin is to the enough binding forces of olighydria, and water-intake rate descends again on the contrary, and gel content also can reduce simultaneously.The low basic reason of this traditional just water-absorbing resin water-retaining capacity has restricted further developing of water-absorbing resin thus.
By selecting suitable linking agent, can when not changing the cross-linking set number, reduce cross-linking density, reach the purpose that improves water-retaining capacity.Disclose a kind of synthetic method of macromolecules cross-linking agent in the Chinese patent 01136626.5,, obtained the linking agent of different chain length the low polyoxyethylene glycol two ends acrylate chloride esterification of different molecular weight.Prepare super moisture absorbing resin with this linking agent, overcome that common cross-linker molecules is little, reaction is too fast, cause the crosslinked uneven problem of water-absorbing resin, obtain water absorbent rate and reach water-absorbing resin more than 4000 times.In addition, also can control the water absorbent rate of water-absorbing resin by the chain length of control linking agent, utilize the linking agent of long-chain, the crosslink density in the reduction resin is to improve water absorbent rate.Simultaneously, linking agent itself participates in suction, also helps the raising of water absorbent rate.However, the raising of this patent resin water absorbent rate is still in fact that cross-linking density realizes by reducing, and do not break through traditional water-absorbing resin structure, moreover cross-linking density can not reduce infinitely, otherwise cross-linking density is too low, certainly will cause intensity to reduce and water absorbent rate decline.
The applicant discloses a kind of preparation method of ultraviolet photo-initiated crosslinking ultra fine powder rubber in Chinese patent application 200410046163x, it is to carry out illumination under 30-100 watt/square metre the UV-light that the rubber latex of adding light trigger and crosslinking sensitizer is placed intensity, replaces the gamma-rays high-energy ray irradiation to cause rubber cross.
Summary of the invention:
The purpose of this invention is to provide a kind of super moisture absorbing resin with new microstructures, the hydrating structure of this resin can make water-absorbing resin have longer suction chain, enough degree of freedom bound water molecules are arranged, by crosslinking structure institute's bonded water molecules on the molecular chain is fixed up simultaneously, thereby has high water absorbent rate.The present invention also provides the preparation method of this water-absorbing resin, by hydrogen-capture-type light initiator under the condition of ultraviolet lighting, make rubber micelle surface form the dormancy group through initiation-coupling two-step reaction, utilize this dormancy group to cause the hydrophilic monomer polymerization then, grafting suction high molecular polymer, thus prepare have novel texture, the super moisture absorbing resin of high water absorbent rate.
Super moisture absorbing resin of the present invention is: be made of the rubber micelle grafting suction high molecular polymer that is the solid space network structure, with each the rubber micelle in the network structure is node, stretch out a plurality of can the suction and the high molecular polymer molecular chain of water storage to the space, form the suction unit that is star structure.
Above-mentioned suction high molecular polymer is or/and the high molecular polymer that other alkene classes monomer polymerization commonly used obtains by acrylic acid or the like, acrylic amide and derivative thereof, esters of acrylic acid.
The preparation method of super moisture absorbing resin of the present invention, may further comprise the steps successively: will add the rubber latex of light trigger and sensitizing agent under UV-light, under protection of inert gas, shine, reacted 15～90 minutes, introduce the dormancy group on rubber micelle surface by initiation-coupling two-step reaction; In postradiation rubber latex, add linking agent, being heated to 75～90 ℃ makes the dormancy base fracture on rubber micelle surface produce surface free radical, be 75～90 ℃ of following stirring reactions in temperature then, 0.5 hour～2 hours reaction times, cause rubber latex and linking agent polyreaction that the micelle surface has the dormancy group, obtain the cross-linked rubber emulsion of the microcosmic cubic network that is made of linking agent and rubber micelle, wherein network is that node, cross-linker molecules chain are netting twine with the micelle; Add the hydrophilic monomer aqueous solution in the rubber latex after crosslinked, under 75～90 ℃ of temperature, carry out graft reaction, the graft reaction time is 4～20 hours, produce elementary free radical by the unreacted dormancy group fracture in micelle surface and cause the hydrophilic monomer graft reaction, form many and stretch out the hydrophilic polymer molecules chain to the space from rubber micelle surface, constitute the suction unit of similar star structure, obtain the super moisture absorbing resin of novel texture.
Light trigger is with disclosed hydrogen-abstraction ultraviolet initiator among the patent application 200410046163x in the aforesaid method, as: benzophenone and derivative thereof, anthraquinone and derivative thereof, thioxanthone and derivative thereof or xanthone and derivative thereof; The light trigger consumption is 0.5～5%, preferred 3～5% of a rubber dry glue quality per-cent.
Disclosed among used sensitizing agent such as the patent application 200410046163x in the aforesaid method, be a kind of polymerisable monomer of single functionality, difunctionality or polyfunctionality or the mixture of multiple polymerisable monomer.Consumption is a rubber dry glue quality per-cent 1～5%.Single functionality mixes use with the polyfunctionality sensitizing agent can obtain effect preferably.
The exposure intensity of aforesaid method medium ultraviolet light is 30～100W/m
2, appropriate wavelength is 230～400nm.
The linking agent that adds in the rubber latex after irradiation in the aforesaid method is the water-soluble bifunctional vinyl compound of bisacrylamide class; The consumption of linking agent is 1～9% of a rubber dry glue quality per-cent, and better consumption is 1～5% of a rubber dry glue quality per-cent.
Used hydrophilic monomer is common in the aforesaid method: acrylic acid or the like and derivative thereof, acrylic amide and derivative thereof, esters of acrylic acid and derivative thereof are or/and other vinyl hydrophilic monomer; Amount of monomer is 15～60 times of the dried glue weight of rubber.
Effect of the present invention: the present invention is by the rubber micelle grafting suction high molecular polymer of solid space network structure, made up suction unit with microcosmic star novel texture, this hydrating structure has longer suction chain, there are enough degree of freedom can bound water molecule, the 3 D cross-linked structure of mesh space is fixed up institute's bonded water molecules on the molecular chain simultaneously, thereby improved the water absorbent rate of water-absorbing resin greatly, super moisture absorbing resin of the present invention, water absorbent rate to pure water can reach 5000～13000 times, more excellently reaches 5000～10000 times; To hardness is 10 tap water, and water absorbent rate can reach 350～650 times, more excellent 350～500 times; Water absorbent rate to salt solution (in 0.9%NaCl weight solution) can reach 100～320 times, and more excellent 100～250 times, far above the water absorbent rate of general water-absorbing resin.
Description of drawings:
Fig. 1 is the existing water-absorbing resin unitary microtexture synoptic diagram that absorbs water; Among the figure, 1 is the individual molecule chain, and 2 is cross-linker molecules.
Fig. 2 is the water-absorbing resin of the present invention unitary microcosmic star structure synoptic diagram that absorbs water; Among the figure, 3 represent rubber micelle node, the 4th, macromolecule water uptake chain
But Fig. 3, Fig. 4 are preparation method of the present invention introduces the dormancy base of re-initiation on rubber micelle surface initiation and coupling process synoptic diagram;
Fig. 5 is that preparation method of the present invention contains the rubber latex of dormancy group and the rubber latex process synoptic diagram that the linking agent prepared in reaction has microcosmic cubic network structure;
Fig. 6 is that preparation method of the present invention causes the hydrophilic monomer graft reaction and prepares super moisture absorbing resin reaction process synoptic diagram on emulsion microcosmos network node; Among the figure, 3 represent rubber micelle node, and the 4th, the macromolecule water uptake chain, 5 represent the 3 D cross-linked structure of mesh space.
Embodiment:
The present invention is from the microtexture of water-absorbing resin, at first make up the spatial network of rubber micelle, cause in aforesaid UV-light on the technical foundation of cross-linked rubber,, obtain the water-absorbing resin that has novel texture and show the superelevation water absorbent rate at rubber micelle surface grafting hydrophilic polymer.Implementation method is as follows:
The first step: but the dormancy base of re-initiation introduced on rubber micelle surface: the rubber latex of adding light trigger and sensitizing agent is shone under UV-light, introduce the dormancy group on rubber micelle surface.With hydrogen-capture-type light initiator benzophenone (BP) is example, can introduce which pure dormancy base of half Knit-the-brows on rubber micelle surface by initiation-coupling two-step reaction as shown in Figure 3, Figure 4.The weak bond that the dormancy base links to each other with rubber micelle surface under the effect of light or heat can take place to rupture and regenerate free radical polymerization.Specific practice is: earlier light trigger is dissolved in the mixing solutions of preparing light trigger and sensitizing agent in the sensitizing agent; In the reactor that a band stirs, add rubber latex, dropwise add the mixing solutions of light trigger and sensitizing agent in the time of stirring; After treating to dissolve fully, letting nitrogen in and deoxidizing at least 30 minutes continue to stir, and the above-mentioned reaction solution for preparing is placed under the UV-light irradiation to react then under nitrogen protection 15～90 minutes.
Used radiation source is a radiation source commonly used in the uv-light polymerization technology in the inventive method, and mercuryarc lamp (comprising low pressure mercury lamp, medium pressure mercury lamp and high voltage mercury lamp), electrodeless lamp or metal halide lamp are arranged.The appropriate wavelength of used UV-light is 230～400nm, and exposure intensity is 30～100W/m
2Reactor is an encloses container, and reactor, is generally made by transparent material, as hard glass, silica glass, resin film (as polyethylene film, polypropylene film or polyester film) etc. greater than 80% over against the light transmittance requirement of the Lights section.
The used rubber latex of the present invention can be the mixed rubber emulsion of a kind of rubber or multiple rubber; Rubber latex can be solution shape, emulsion form, thin suspension; Contained rubber can be conventional rubber, also can be specialty elastomer; The rubber latex solid content is 40～60% weight, is generally 50% weight, and the particle diameter of rubber micelle generally is about 50～500nm.
Used light trigger is the hydrogen-abstraction ultraviolet initiator, can be benzophenone (BP) and derivatives class, anthraquinone and derivative thereof, thioxanthone (commonly used as isopropyl thioxanthone-ITX etc.) or xanthone and derivative thereof etc.The consumption of light trigger is generally 0.5～5% (mass percent) of rubber dry glue quality, preferred 3～5%.
A kind of polymerisable monomer of disclosed single functionality, difunctionality or polyfunctionality or the mixture of multiple polymerisable monomer among used sensitizing agent such as the patent application 200410046163x.Single functionality mixes use with the polyfunctionality sensitizing agent can obtain effect preferably.The single functionality sensitizing agent is selected from butyl acrylate, Octyl methacrylate, Isooctyl methacrylate or glycidyl methacrylate etc.; The difunctionality sensitizing agent is selected from tetramethylene dimethacrylate, dimethacrylate hexylene glycol ester, dimethacrylate one condensed ethandiol ester or dimethacrylate triethyleneglycol ester etc.; The polyfunctionality sensitizing agent is selected from Viscoat 295 (TMPTA), trimethylolpropane trimethacrylate, pentaerythritol acrylate trimethyl or tetramethylolmethane tetramethyl-acrylate etc.Sensitizing agent mainly contains two kinds of effects: the light trigger that sensitizing agent can dissolved solids at first, so that take initiator to rubber micelle surface and inner; Secondly light trigger not only can be captured the reactive hydrogen generation dormancy group on latex rubber micelle surface in the illumination process, can also capture reactive hydrogen from emulsion particle inside by the bridging effect of sensitizing agent and produce the dormancy group.The existence of sensitizing agent has improved the content of emulsion particle surface and internal dormancy group, helps further crosslinked and graft reaction.
The sensitizing agent consumption is generally 1～5% (mass percent) of rubber dry glue quality, preferred 3～5%.
Preferably adopt the different light time for different light triggers in this step, to the BP photoinitiator, preferred 60～90 minutes of light application time; For the ITX photoinitiator, preferred 15～30 minutes of light application time.Light application time is too short, and light trigger can not fully be initiated, and does not reach the requirement that secondary causes.Light application time is long, and resulting dormancy group consumes under the effect of light to some extent, is unfavorable for subsequent reactions, also consumes the more energy simultaneously.
Second step: preparation has the rubber latex of microcosmic cubic network structure: promptly add linking agent in the first step gained rubber latex, be heated to certain temperature, make the dormancy base fracture on rubber micelle surface produce surface free radical, cause linking agent polyreaction (as Fig. 5) then, the emulsion that obtains is made up of the microcosmic cubic network that linking agent and rubber micelle constitute, and network is that node, cross-linker molecules chain are netting twine with the micelle.
Specific practice is: get the emulsion that a certain amount of above-mentioned the first step obtains, add a certain amount of cross-linking agent aqueous solution behind the dilute with water, logical nitrogen deoxygenation is reaction at a certain temperature after at least 30 minutes.Temperature of reaction is 75～90 ℃, 0.5 hour～2 hours reaction times.
The used linking agent of this step is water-soluble double vinyl compound, can be the bisacrylamide class, as N, and N-methylene radical-bisacrylamide (MBA), piperazine diacrylamine etc., the consumption of linking agent is generally 1～10% (mass percent) of the dried glue of rubber.
The 3rd step: on emulsion microcosmos network micelle node, cause the hydrophilic monomer graft reaction, preparation super moisture absorbing resin: as Fig. 6, on the second step gained microcosmos network node, prepare super moisture absorbing resin by the elementary free radical of micelle surface unreacted dormancy group fracture generation, initiation hydrophilic monomer graft reaction, the hydrophilic polymer molecules chain that forms stretches out the similar star structure (see figure 2) of structural unit to the space from rubber micelle surface.Finally obtaining by the rubber micelle is node, stretches out the super moisture absorbing resin of the 3 D cross-linked network structure of the star suction unit of a plurality of suction molecular chains forming of microcosmic to the space.
Specific practice is: the rubber latex of getting a certain amount of second step gained adds in the reaction flask, and it is even to add the hydrophilic monomer aqueous solution again, and letting nitrogen in and deoxidizing is warming up to graft reaction under the certain temperature at least after 30 minutes.The graft reaction time is 4～24 hours, and temperature of reaction is 75～90 ℃.
Used hydrophilic monomer is general known water-soluble vinyl monomer, vinylformic acid and derivative thereof, acrylamide and derivative thereof, its derivative of CALCIUM ACRYLATE be or/and other vinyl hydrophilic monomer, as: the N-alkyl derivative of acrylamide, 2-acrylamido-2-methyl isophthalic acid-propanesulfonic acid; Vinylformic acid 2-hydroxy methacrylate, 2-hydroxyethyl methacrylate, N-vinyl pyrrolidone, allylic phosphonic acid based, sulfuric acid based, sulfonic acid class etc.
Above-mentioned hydrophilic monomer can use separately, also can several mixing use, and used amount of monomer is 15～60 times of the dried glue weight of rubber.
The measuring method of monomer conversion and gel content is as follows in the inventive method:
Get three of the super moisture absorbing resins that make, be weighed as W respectively
1, W
2, W
3, to constant weight (drying process of the present invention is: at first in 50 ℃ of constant pressure and dries 24 hours, and then in 50 ℃ of vacuum-dryings 24 hours), it is W that weighing gets weight with first part's water-absorbing resin convection drying
4The second section water-absorbing resin was soaked in acetone 5 days, changed acetone once in per 12 hours, remove unreacted monomer and keep polymkeric substance, be dried to constant weight then, it is W that weighing gets weight
5The third part water-absorbing resin was soaked in water 72 hours, changed water once in per 6 hours, remove non-grafting part.Be dried to constant weight then, it is W that weighing gets weight
6Transformation efficiency and gel content are calculated as follows:
In the formula: W
4/ W
1Be the monomer total amount that adds in every gram sample; W
5/ W
2Total amount for polymkeric substance in every gram sample; W
6/ W
3Be the gel total amount.
The measuring method of water absorbent rate is as follows in the inventive method:
1. to the water absorbent rate of pure water: get super moisture absorbing resin that fritter makes and place three to steam level ultrapure waters and soak, changed water one time in per 12 hours, soaked 5 days, take out a certain amount of super moisture absorbing resin and be weighed as W
7, then with this super moisture absorbing resin in 50 ℃ of dryings 24 hours, place 50 ℃ of vacuum-dryings 24 hours again, W weighs
8Water absorbent rate is calculated as follows:
2. tap water and brinish water absorbent rate: get the super moisture absorbing resin that fritter makes and place the NaCl salt solution of tap water or 0.9% to soak, changed water one time in per 12 hours, soaked 5 days, take out a certain amount of super moisture absorbing resin W that weighs
9, place pure water to soak this gel then, changed water one time, soaked 5 days in 12 hours.Again in 50 ℃ of dryings 24 hours, the W that weighs is taken out in 50 ℃ of vacuum-drying 24 hours
10, inhale tap water (salt solution) multiplying power and be calculated as follows:
By the following examples enforcement of the present invention is further specified, but the present invention should not be limited to these embodiment, also should comprise: not depart under the scope of the invention condition, disclosed method is carried out the conspicuous various changes of those skilled in the art.
Embodiment 1
With 5g light trigger benzophenone (BP), be added in 4g sensitizing agent Viscoat 295 (TMPTA) and the 1g n-butyl acrylate (n-BA), TMPTA and n-BA are used with 4: 1 ratio of mass ratio; Initiator is added to makes it in the sensitizing agent to dissolve fully.
(the heavy 100g of dried glue, commercial disignation is: butyronitrile 26), place beaker, stir, dropwise add the mixed solution of above-mentioned light trigger for preparing and sensitizing agent, make its dissolving fully in rubber latex with the 200g acrylonitrile-butadiene rubber latex.
Get the above-mentioned acrylonitrile-butadiene rubber latex for preparing of 20ml and place the illumination reaction bottle, logical nitrogen placed illumination under the UV-light after 30 minutes.Light source is a high-pressure halogen lamp, and the predominant wavelength light intensity is 40 watts/square metre, initiator absorbing wavelength scope, and light application time is 90 minutes, obtains the pre-polymerization emulsion.
Get above-mentioned pre-polymerization emulsion 2g, 0.04g N,N methylene bis acrylamide (MBA) is dissolved in the 98g water, logical nitrogen 30 minutes, and reaction is 120 minutes in 85 ℃ of water-baths, obtains reacting emulsion.
Get above-mentioned reaction emulsion 10g, with 5g water, 9g 30% acrylamide (AM), 6g 5% vinylformic acid (AA) places reaction flask to mix, and total monomer concentration is 10% weight.Logical nitrogen 30 minutes, reaction is 10 hours in 85 ℃ of water-baths, gets the product super moisture absorbing resin.After measured, monomer conversion is 60%, and gel content is 87.2%, and inhaling the pure water multiplying power is 6900 times, and it is 650 times that tap water absorbs multiplying power, and it is 138 times that 0.9% salt solution absorbs multiplying power.
Embodiment 2
Preparation method such as embodiment 1, temperature of reaction is reduced to 80 ℃ during only with the final step polymerization, and the reaction times is extended for 20 hours.The product super moisture absorbing resin after measured, monomer conversion is 87.3%, gel content reaches 98.7%, is 6000 times to the absorption multiplying power of pure water, it is 500 times that tap water is absorbed multiplying power, it is 184 times that 0.9% salt solution is absorbed multiplying power.
Preparation method such as embodiment 1 only shorten to 4 hours with final step polymerization the reaction time.The product super moisture absorbing resin after measured, monomer conversion is 54.64%, is 12500 times of suctions to the absorption multiplying power of pure water, it is 610 times that tap water is absorbed multiplying power, it is 246 times that 0.9% salt solution is absorbed multiplying power.
Preparation method such as embodiment 1 still use the reaction emulsion of a kind of embodiment.Emulsion 10g is answered in negate, with 2.5g water, and 8.5g 30% acrylamide (AM), 9g 5% vinylformic acid (AA) places reaction flask to mix, and total monomer concentration is 10% weight.Logical nitrogen 30 minutes, reaction is 10 hours in 85 ℃ of water-baths, gets the product super moisture absorbing resin.Absorption multiplying power to pure water is 7500 times after measured.
Get the pre-polymerization emulsion 1g among the embodiment 1,0.02g N,N methylene bis acrylamide (MBA) is dissolved in the 98g water, logical nitrogen 30 minutes, and reaction is 60 minutes in 85 ℃ of water-baths, obtains reacting emulsion.
Get above-mentioned reaction emulsion 10g, with 5.35g water, 8.5g 30% acrylamide (AM), 6g 5% vinylformic acid (AA) and 0.15g N-vinyl pyrrolidone (NVP) place reaction flask to mix, and total monomer concentration is 10% weight.Logical nitrogen 30 minutes, reaction is 10 hours in 80 ℃ of water-baths, gets the product super moisture absorbing resin.Monomer conversion is 74.5% after measured, and gel content is 96.9%, is 5000 times to the absorption multiplying power of pure water, and it is 550 times that tap water is absorbed multiplying power, and it is 200 times that 0.9% salt solution is absorbed multiplying power.
Embodiment 6
Preparation method such as embodiment 5 are reduced to 0.01g with the consumption of N,N methylene bis acrylamide (MBA), logical nitrogen 30 minutes, and reaction is 60 minutes in 85 ℃ of water-baths, obtains reacting emulsion.
Get above-mentioned reaction emulsion 10g, 8g 30% acrylamide (AM), 12g 5% vinylformic acid (AA) places reaction flask to mix, and total monomer concentration is 10% weight.Logical nitrogen 30 minutes, reaction is 10 hours in 85 ℃ of water-baths, gets the product super moisture absorbing resin.Monomer conversion is 75.4% after measured, and gel content is 74.56%, is 6000 times to the absorption multiplying power of pure water, and it is 300 times that 0.9% salt solution is absorbed multiplying power.
Embodiment 7
With 5g light trigger benzophenone (BP), be added in 4g sensitizing agent TMPTA and the 1g n-butyl acrylate (n-BA), TMPTA and n-BA are used with 4: 1 ratio of mass ratio; Initiator is added to makes it in the sensitizing agent to dissolve fully.
With 200g carboxy nitrile rubber emulsion (the heavy 100g of dried glue), place beaker, stir, add the mixed solution of above-mentioned light trigger for preparing and sensitizing agent gradually, make its dissolving fully in rubber latex.
Get the above-mentioned acrylonitrile-butadiene rubber latex for preparing of 20ml and place the illumination reaction bottle, logical nitrogen placed illumination under the UV-light after 30 minutes.Light source is a high-pressure halogen lamp, and the predominant wavelength light intensity is 45 watts/square metre, initiator absorbing wavelength scope, and light application time is 60 minutes, obtains the pre-polymerization emulsion.
Get above-mentioned pre-polymerization emulsion 3g, 0.06g N,N methylene bis acrylamide (MBA) is dissolved in the 147g water, logical nitrogen 30 minutes, and reaction is 60 minutes in 85 ℃ of water-baths, obtains reacting emulsion.
Get above-mentioned reaction emulsion 10g, with 10g water, 9.3g 30% acrylamide (AM), 0.7g 30% vinylformic acid (AA) places reaction flask to mix, and total monomer concentration is 10% weight.Logical nitrogen 30 minutes, reaction is 10 hours in 85 ℃ of water-baths, gets the product super moisture absorbing resin.Transformation efficiency is 66.39% after measured, and gel content is 85.78%, is 8900 times to the absorption multiplying power of pure water, and it is 540 times that tap water absorbs multiplying power, and it is 164 times that 0.9% salt solution absorbs multiplying power.
Embodiment 8
Preparation method such as embodiment 7, it is 90 ℃ that the temperature of reaction during only with crosslinked and polymerization raises, the reaction times is 8 hours.The product super moisture absorbing resin after measured, monomer conversion is 64.74%, and the absorption multiplying power of pure water is reached 13000 times.
Embodiment 9
Implementation method is with embodiment 7, only with embodiment 7 resulting products after pure water soaks fully, sodium hydroxide solution with 0.5% soaks hydrolysis, after hydrolysis time is 18 hours, absorption multiplying power to pure water is increased to 8000 times, when hydrolysis time is 106 hours, the absorption multiplying power of pure water is reached 10060 times.
Embodiment 10
Implementation method only is reduced to 9g with 30% acrylamide (AM) among the embodiment 7 with embodiment 7, and 30% vinylformic acid (AA) increases to 1g, places reaction flask to mix, and total monomer concentration is 10% weight.Logical nitrogen 30 minutes, reaction is 10 hours in 85 ℃ of water-baths, gets the product super moisture absorbing resin.After measured, monomer conversion is 61.54%, and gel content is 88.36%, is 13000 times to the absorption multiplying power of pure water, and it is 560 times that tap water is absorbed multiplying power, and it is 204 times that 0.9% salt solution is absorbed multiplying power.
Embodiment 11
Implementation method only is reduced to 8.8g with 30% acrylamide (AM) among the embodiment 7 with embodiment 7, increases 0.15g 2-hydroxyethyl methacrylate (HEMA) simultaneously, places reaction flask to mix, and it is 10% weight that water is transferred total monomer concentration.Logical nitrogen 30 minutes, reaction is 10 hours in 85 ℃ of water-baths, gets the product super moisture absorbing resin.After measured, monomer conversion is 73.64%, and gel content is 88.41%, is 5000 times to the absorption multiplying power of pure water, and it is 350 times that tap water is absorbed multiplying power, and it is 129 times that 0.9% salt solution is absorbed multiplying power.
Embodiment 12
Get pre-polymerization emulsion 6g used among the embodiment 7,0.135g N,N methylene bis acrylamide (MBA) is dissolved in the 147g water, logical nitrogen 30 minutes, and reaction is 60 minutes in 85 ℃ of water-baths, obtains reacting emulsion.
Get above-mentioned reaction emulsion 10g, with 10g water, 9g 30% acrylamide (AM), 1g 30% vinylformic acid (AA) places reaction flask to mix, and total monomer concentration is 10% weight.Logical nitrogen 30 minutes, reaction is 10 hours in 85 ℃ of water-baths, gets the product super moisture absorbing resin.After measured, be 7000 times to the absorption multiplying power of pure water, it is 357 times that tap water is absorbed multiplying power, it is 161 times that 0.9% salt solution is absorbed multiplying power.
Embodiment 13
Implementation method only is cut into small pieces jel product among the embodiment 10 with embodiment 10, with solid sodium hydroxide hydrolysis 24 hours, obtains gel after the hydrolysis.After measured, be 10100 times to the absorption multiplying power of pure water, it is 321 times that 0.9% salt solution is absorbed multiplying power.
Embodiment 14
With 0.5g light trigger isopropyl thioxanthone (ITX), be added in 4g sensitizing agent TMPTA and the 1g n-butyl acrylate (n-BA), TMPTA and n-BA are used with 4: 1 ratio of mass ratio; Initiator is added to makes it in the sensitizing agent to dissolve fully.
With 200g carboxy nitrile rubber emulsion (the heavy 100g of dried glue), place beaker, stir, add the mixed solution of above-mentioned light trigger for preparing and sensitizing agent gradually, make its dissolving fully in rubber latex.
Get the above-mentioned acrylonitrile-butadiene rubber latex for preparing of 20ml and place the illumination reaction bottle, logical nitrogen placed illumination under the UV-light after 30 minutes.Light source is a high-pressure halogen lamp, and the predominant wavelength light intensity is 45 watts/square metre, initiator absorbing wavelength scope, and light application time is 15 minutes, obtains the pre-polymerization emulsion.
Get above-mentioned pre-polymerization emulsion 3g, 0.06g N,N methylene bis acrylamide (MBA) is dissolved in the 147g water, logical nitrogen 30 minutes, and reaction is 30 minutes in 75 ℃ of water-baths, obtains reacting emulsion.
Get above-mentioned reaction emulsion 10g, with 10g water, 9.3g 30% acrylamide (AM), 0.7g 30% vinylformic acid (AA) places reaction flask to mix, and total monomer concentration is 10% weight.Logical nitrogen 30 minutes, reaction is 10 hours in 75 ℃ of water-baths, gets the product super moisture absorbing resin.Transformation efficiency 55.28% after measured, is 8100 times to the absorption multiplying power of pure water, and it is 500 times that tap water is absorbed multiplying power, and it is 295 times that 0.9% salt solution is absorbed multiplying power.
Embodiment 15
With 0.5g light trigger isopropyl thioxanthone (ITX), be added in 4g sensitizing agent TMPTA and the 1g n-butyl acrylate (n-BA), TMPTA and n-BA are used with 4: 1 ratio of mass ratio; Initiator is added to makes it in the sensitizing agent to dissolve fully.
With 200g SBR emulsion (the heavy 100g of dried glue), place beaker, stir, add the mixed solution of above-mentioned light trigger for preparing and sensitizing agent gradually, make its dissolving fully in rubber latex.
Get the above-mentioned SBR emulsion for preparing of 50ml and place the illumination reaction bottle, logical nitrogen placed illumination under the UV-light after 30 minutes.Light source is a high-pressure halogen lamp, and the predominant wavelength light intensity is 45 watts/square metre, initiator absorbing wavelength scope, and light application time is 30 minutes, obtains the pre-polymerization emulsion.
Get above-mentioned pre-polymerization emulsion 2g, 0.04g N,N methylene bis acrylamide (MBA) is dissolved in the 98g water, logical nitrogen 30 minutes, and reaction is 60 minutes in 85 ℃ of water-baths, obtains reacting emulsion.
Get above-mentioned reaction emulsion 10g, with 10g water, 9g 30% acrylamide (AM), 1g 30% vinylformic acid (AA) places reaction flask to mix, and total monomer concentration is 10% weight.Logical nitrogen 30 minutes, reaction is 10 hours in 85 ℃ of water-baths, gets the product super moisture absorbing resin.Transformation efficiency 76.93% after measured, and gel content is 84.91%, is 9400 times to the absorption multiplying power of pure water, and it is 350 times that tap water is absorbed multiplying power, and it is 120 times that 0.9% salt solution is absorbed multiplying power.
Claims (10)
1, a kind of super moisture absorbing resin, it is characterized in that: constitute by the rubber micelle grafting suction high molecular polymer that is the solid space network structure, each rubber micelle in the network structure is a node, stretch out a plurality of can the suction and the suction high molecular polymer molecular chain of water storage to the space, form the suction unit that is star structure.
2, the preparation method of the described super moisture absorbing resin of a kind of claim 1, may further comprise the steps successively: will add the rubber latex of light trigger and sensitizing agent under UV-light, under protection of inert gas, shine, reacted 15～90 minutes, and introduced the dormancy group on rubber micelle surface by initiation-coupling two-step reaction; In postradiation rubber latex, add linking agent, being heated to 75～90 ℃ makes the dormancy base fracture on rubber micelle surface produce surface free radical, stirring reaction 0.5～2 hour, cause rubber latex and linking agent polyreaction that the micelle surface has the dormancy group, obtain the rubber latex of the microcosmic cubic network that constitutes by linking agent and rubber micelle; Add the hydrophilic monomer aqueous solution in the microcosmic cubic network rubber latex of gained, carry out graft reaction under 75～90 ℃ of temperature, the graft reaction time is 4～20 hours.
3, preparation method according to claim 2 is characterized in that, used light trigger is the hydrogen-abstraction ultraviolet initiator, and consumption is 0.5～5% of a rubber dry glue quality per-cent; Used sensitizing agent is a kind of polymerisable monomer of single functionality, difunctionality or polyfunctionality or the mixture of multiple polymerisable monomer, and consumption is 1～5% of a rubber dry glue quality per-cent.
4, preparation method according to claim 3 is characterized in that, the hydrogen-abstraction ultraviolet initiator is benzophenone and derivative thereof, anthraquinone and derivative thereof, thioxanthone and derivative thereof or xanthone and derivative thereof.
5, preparation method according to claim 2 is characterized in that, adding linking agent in postradiation rubber latex is water-soluble double vinyl compound.
6, preparation method according to claim 5 is characterized in that, water-soluble double vinyl compound is: N, N-methylene radical-bisacrylamide or piperazine diacrylamine.
7, preparation method according to claim 2 is characterized in that, the consumption of linking agent is the mass percent 1～9% of the dried glue of rubber.
8, preparation method according to claim 2 is characterized in that, used hydrophilic monomer is: vinylformic acid and derivative thereof, acrylamide and derivative thereof, its derivative of acrylate are or/and other vinyl hydrophilic monomer; Amount of monomer is 15～60 times of the dried glue weight of rubber.
9, preparation method according to claim 2, it is characterized in that used hydrophilic monomer is to be selected from one or more of following material: the N-alkyl derivative of (methyl) vinylformic acid, (methyl) acrylamide, (methyl) acrylamide, 2-acrylamido-2-methyl isophthalic acid-propanesulfonic acid; Vinylformic acid 2-hydroxy methacrylate, 2-hydroxyethyl methacrylate; The N-vinyl pyrrolidone, allylic phosphonic acid based, sulfuric acid based, sulfonic acid class.
10, preparation method according to claim 2 is characterized in that, for the benzophenone photoinitiator, and light application time 60～90 minutes; For thioxanthone photoinitiator, light application time 15～30 minutes.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103194177A (en) * | 2013-03-26 | 2013-07-10 | 杭州普济医药技术开发有限公司 | Manufacturing method of ice bag for preserving biological products |
| CN111902581A (en) * | 2018-03-27 | 2020-11-06 | 住友精化株式会社 | Sandbag and manufacturing method thereof |
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2006
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103194177A (en) * | 2013-03-26 | 2013-07-10 | 杭州普济医药技术开发有限公司 | Manufacturing method of ice bag for preserving biological products |
| CN103194177B (en) * | 2013-03-26 | 2016-01-06 | 杭州普济医药技术开发有限公司 | For the manufacture method of the ice bag of preservation biological products |
| CN111902581A (en) * | 2018-03-27 | 2020-11-06 | 住友精化株式会社 | Sandbag and manufacturing method thereof |
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