CN1544497A - Water-absorbent starch resins and synthesis method thereof - Google Patents
Water-absorbent starch resins and synthesis method thereof Download PDFInfo
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- CN1544497A CN1544497A CNA2003101064498A CN200310106449A CN1544497A CN 1544497 A CN1544497 A CN 1544497A CN A2003101064498 A CNA2003101064498 A CN A2003101064498A CN 200310106449 A CN200310106449 A CN 200310106449A CN 1544497 A CN1544497 A CN 1544497A
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Abstract
The invention relates to a starch type absorbent resin which is oxidized starch alkene monomer, prepared through the yield of graft copolymerization and composite clay, in the presence of both initiating agent which can make starch molecule develop free radicals and can graft with monomers, and cross linking agent having multiple reaction functional groups, wherein the quantity of oxidized starch amounts to 3.00-50.00% of the total alkene monomers, the quantity of cross linking agent amounts to 1.00-50.00% of the total alkene monomers, the quantity of clay amounts to 0.001-50.00% of the total alkene monomers, the quantity of initiating agent amounts to 0.05-5.00% of the total alkene monomers. The invention also discloses the method for synthesis.
Description
One, technical field
The present invention relates to a kind of water-absorbing resin and synthetic method thereof, relate in particular to a kind of starch water-absorbing resin and synthetic method thereof of high-hydroscopicity energy.
Two, background technology
Aspect super absorbent resin, carried out a lot of research work both at home and abroad.Mainly contain synthetic resins and semi-synthetic resin two class super absorbent resins at present.Synthetic resin is by method synthetic such as graft copolymerizations, such as crosslinking sodium polyacrylate from the petroleum industry raw material.This synthetic resins production cost is higher, and the life-span is longer, but is difficult for degraded.And semi-synthetic resene is instigated natural polymer raw materials such as starch or Mierocrystalline cellulose, obtains with monomer-grafted copolymerization such as vinyl cyanide, vinylformic acid, acrylamide and acrylate.The synthetic class production cost of this semi-synthetic resinoid is low, can biological degradation in environment.The synthetic method of CN 1075488A is to be initiator with the ammonium peroxydisulfate, and epoxy chloropropane is a linking agent, and the prepolymerization under nitrogen earlier of vinylformic acid and acrylamide adds starch again and carries out the two step method polymerization.Adopt this method starch gelatinization temperature higher.CN1299836A increases clay composition in vinylformic acid starch graft copolymer system, add the single component initiator and cause, and adopts Repone K hierarchy of control viscosity, has improved solid content, reduced cost, but salt tolerance is not high.CN1224028A, makes through graft copolymerization with initiator system and the linking agent that persulphate and reductive agent are formed with clay and vinyl monomer grafting.Though can improve resistance to pressure, biological degradability is not strong.
Three, technology contents
Technical problem: the invention provides a kind of starch based water-absorbing resin and synthetic method thereof that can reduce cost, have biodegradable and institute's synthetic super absorbent resin can be used repeatedly, and water-absorbent, salt tolerance, the controlled characteristics of resistance to pressure.
Technical scheme: the present invention is a kind of starch based water-absorbing resin, it is Sumstar 190, vinyl monomer, making starch molecule produce free radical and can and being to have under the linking agent effect of many reactive functionality, make through gains and compound clay behind the graft copolymerization with monomer-grafted initiator.Wherein the Sumstar 190 consumption is 3.00～50.00% of a vinyl monomer total amount, dosage of crosslinking agent is 1.00～50.00% of a vinyl monomer total amount, the clay consumption is 0.001～50.00% of a vinyl monomer total amount, initiator amount is 0.05～5.00% of a vinyl monomer total amount, above-mentioned vinyl monomer comprises alkene class ionic comonomer and alkene class nonionic monomers, and the consumption of non-ionic type vinyl monomer accounts for 0～100% of ionic vinyl monomer consumption.
The synthetic method of water-absorbing resin of the present invention, with Sumstar 190 40～90 ℃ of following gelatinizations, be cooled to room temperature, logical nitrogen, add initiator more successively and by linking agent, ionic vinyl monomer and non-ionic type vinyl monomer, and the mixed solution that is mixed with of clay, stir, in 10～60min, control the degree of neutralization of reaction system between 30%～90% then to the strong base solution of reaction system dropping 25%, after waiting to drip strong base solution, control reaction temperature is in 30～90 ℃, reaction times is 1～6h, obtain the multipolymer of Sumstar 190 binary grafting compound clay, through soaking, washing, section, oven dry, bulk or granular product are made in pulverizing.
Technique effect: 1, the polynary monomer of the formed employing of the present invention is than adopting monobasic monomer and starch graft copolymer synthesizing high-hydroscopicity resin to have better water-retaining capacity and salt tolerance.This mainly is because the synergy of multiple group in the polynary monomer, and makes on the molecular backbone chain of institute's synthetic STARCH GRAFT POLYMER SUPER ABSORBENT RESIN and have multiple hydrophilic radical, thereby the water absorbing properties of super absorbent resin is improved.In cited several combination of monomers, the binary monomer of forming with vinylformic acid and acrylamide has best water absorbing properties.This is that acrylamide has non-ionic hydrophilic group (CONH because vinylformic acid has ionic hydrophilic group group (COOH, carboxyl)
2, amide group), they the two act synergistically mutually, improve the water absorbing properties and the salt tolerance of super absorbent resin, simultaneously, the acrylamide hydrophilic radical (CONH that is with itself
2), have very strong water-absorbent.Compare with starch-grafted vinyl cyanide super absorbent resin, it does not need saponification is exactly absorbent resin.If its saponification hydrolysis is also become the absorbent resin of being with carboxyl and amide group, and ionogen and pH value are less to the water absorbing properties influence of this resin.Starch and modified starch itself have biodegradability, and they can be resolved into micromolecular sugar by certain micro-organisms at occurring in nature, and are finally digested by environment, do not cause environmental pollution.By starch or modified starch is raw material synthetic super absorbent resin, and starch role in structure provides the cross-linked network skeleton.Therefore still can be degraded by microorganisms.This is the advantage that synthetic class super absorbent resin is not had.This advantage has friendly to environment.Sumstar 190 is the widest, the low-cost a kind of modified starch of purposes.It is that starch prepares with the oxygenant effect under acid, alkali or neutrallty condition, has introduced carboxyl and aldehyde radical in molecule.It and native starch relatively have that look shallow, gelatinization point is low, good fluidity, the paste fluid viscosity is low and stable height, transparency height, film forming properties is good, adhesive power is strong characteristics.
2, clay is by external sedimentation, or felsic parent rock forms through long-term weathering, and some then is to form owing to the influence that is subjected to hydrothermal alteration, mainly the earthy thing of being made up of less than the clay mineral of 0.004mm particle diameter.Clay has characteristics such as cohesiveness, plasticity-, adsorptivity, swelling property, resistivity against fire and coking property, China's clay resource is very abundant, therefore, clay is applied in synthesizing of super absorbent resin as matrix material, can reduce production costs widely, improve the performance of super absorbent resin effectively.
Because water-fast well as clay fines end as dispersion agent, is adsorbed on the surface of drop, plays isolated effect, make the reaction drop be not easy to bond together.Moreover clay itself has certain suction swelling and certain mechanical strength, can improve the water-absorbent and the colloid intensity of absorbent resin.
3, the present invention has the high-hydroscopicity energy:
A plurality of reactive functionality are arranged on the linking agent, and these reactive functionality energy and vinyl monomer and starch skeleton are lightly crosslinked, generate to have certain network strength, but water-insoluble super absorbent resin.This structure also plays a very important role to improving super absorbent resin water absorbing properties tool.
We find to adopt N in the linking agent, and the N-methylene diacrylamine has water absorbing properties preferably.Pass through graft reaction, carboxyl of on the Sumstar 190 molecular skeleton, introducing and amide group, and hydrophilic radicals such as all carboxyl of Sumstar 190 molecule itself and hydroxyl produce electrostatic repulsion and cause network to expand, because the network rigidity that is cross-linked to form obstruction network further expands, both can reach balance under certain condition simultaneously.This moment, the water-retaining capacity of super absorbent resin reached maximum.
4, mainly to adopt Sumstar 190 be raw material synthetic starch class super absorbent resin in the present invention.Its advantage is:
● adopting Sumstar 190 is that raw material can reduce gelatinization point effectively, improves reaction safety, effectively saves heat energy, reduces cost.
● institute's synthetic super absorbent resin is of light color and even
● institute's synthetic super absorbent resin water retention property at room temperature is superior, anti-enzyme raising, and long-time placement still keeps good gel state and has higher water content.
5, the uniqueness of manufacture method of the present invention is:
● adopt to add mixed solution earlier, and then slowly drip alkali neutralization, polymeric feed way simultaneously.Be characterized in to emit the temperature that neutralization heat is controlled reaction with vinylformic acid owing to utilizing in the sodium hydroxide in initial reaction stage.Can effectively utilize reaction heat, cut down the consumption of energy, reduce cost simultaneously, make reaction more stable, be easy to control.
Four, specific embodiments
Realize that technical scheme of the present invention is:
1, composition of raw materials: (wt%)
Acrylamide or acrylate consumption are 0.00～100.00% of vinylformic acid consumption
Below for being benchmark with ionic vinyl monomer and non-ionic type vinyl monomer consumption:
Sumstar 190: 3.00～50.00%
Initiator amount is 0.05～5.00% of a vinyl monomer total amount, initiator is by persulphate and forming with persulfate oxidation reductive salt, its proportioning is (0: 1)～(1: 0), that is: initiator both can adopt persulphate, also can adopt and can redox salt or both combinations take place with persulphate, can be ferrous salt, thiosulphate, sulphite, hydrosulphite,-sulfinate, hydrazine etc. with persulfate oxidation reductive salt.
Linking agent is N, N-methylene diacrylamine: 0.01～50.00%.
Clay: 0.001～50.00%
2, production technique
With Sumstar 190 40～90 ℃ of following gelatinizations, be cooled to room temperature, logical nitrogen, the mixed solution that adds initiator more successively and be mixed with by linking agent, vinylformic acid, acrylamide (or acrylate) and clay, stir, in 10～60min, drip 25%NaOH solution control degree of neutralization between 30%～90% then to reaction system, improve temperature of reaction and be controlled at 30～90 ℃, reaction times is 1～6h, obtain Sumstar 190 binary grafting compound clay multipolymer, make bulk or granular product through soaking, wash, cut into slices, dry, pulverizing.
3, performance measurement
Accurately take by weighing 0.020g resin dry sample in the 150mL beaker, the deionized water that adds 100mL respectively leaves standstill, it is saturated back with the accurate sub-sieve filtration of 200 targets to wait to absorb water, make water absorbent gel on screen cloth, leave standstill 5min, do not drip to there being free water, take by weighing the quality of sieve and water absorbent gel then, be calculated as follows suction multiple (representing) with WRV:
In the formula: W
1---the quality of sieve and suction back gel, g
W
2---the quality of sieve, g
W
3---the quality of resin dry sample, g
It is the same to inhale salt solution multiple measuring method.Just deionized water is changed into the 0.9%NaCl aqueous solution.A kind of Sumstar 190 binary provided by the invention connects copolymerized clay super absorbent resin of skill and synthetic method thereof, reduced the gelatinization point of starch, simultaneously, in initial reaction stage, utilize the neutralization heat control reaction temperature of emitting with vinylformic acid in the sodium hydroxide solution, help saving the energy.Make Sumstar 190 and two monomer systems carry out graft copolymerization, and compound clay, reduced cost, prepared products molecule structure and stable performance, be convenient to control, it is become obtain the product that water-absorbent, salt tolerance, resistance to pressure can be controlled, can be widely used in many aspects such as agroforestry.
The present invention is a kind of starch based water-absorbing resin, it is a Sumstar 190, vinyl monomer, can make starch molecule produce free radical and can and be to have under the linking agent effect of many reactive functionality with monomer-grafted initiator, make through gains and compound clay behind the graft copolymerization, wherein the Sumstar 190 consumption is 3.00～50.00% of a vinyl monomer total amount, dosage of crosslinking agent is 1.00～50.00% of a vinyl monomer total amount, the clay consumption is 0.001～50.00% of a vinyl monomer total amount, initiator amount is 0.05～5.00% of a vinyl monomer total amount, above-mentioned vinyl monomer comprises alkene class ionic comonomer and alkene class nonionic monomers, and the consumption of non-ionic type vinyl monomer accounts for 0～100% of ionic vinyl monomer consumption.
Embodiment 1: the present invention is a kind of starch based water-absorbing resin, it is a Sumstar 190, vinyl monomer, can make starch molecule produce free radical and can with monomer-grafted initiator and linking agent effect under, make through gains and compound clay behind the graft copolymerization, wherein the Sumstar 190 consumption is 3.00～50.00% of a vinyl monomer total amount (being the sum of alkene class ionic comonomer and alkene class nonionic monomers add-on), dosage of crosslinking agent is 1.00～50.00% of a vinyl monomer total amount, the clay consumption is 0.001～50.00% of a vinyl monomer total amount, above-mentioned vinyl monomer comprises alkene class ionic comonomer and alkene class nonionic monomers, the consumption of non-ionic type vinyl monomer accounts for 0～100% of ionic vinyl monomer consumption, wherein, alkene class ionic comonomer comprises vinylformic acid, alkene class ionic comonomer comprises propene sulfonic acid, alkene class nonionic monomers comprises acrylamide, alkene class nonionic monomers also comprises acrylate, as: methyl acrylate, ethyl propenoate, methyl methacrylate, initiator amount is 0.05～5.00% of a vinyl monomer total amount, initiator is by persulphate and forming with persulfate oxidation reductive salt, its proportioning is (0: 1)～(1: 0), the consumption of non-ionic type vinyl monomer accounts for 0～100% of ionic vinyl monomer consumption, linking agent comprises N, N-methylene diacrylamine, linking agent also comprise glycerine and epoxy chloropropane.
Embodiment 2: a kind of synthetic method that is used for above-mentioned water-absorbing resin, 3.00～50.00% Sumstar 190 is 40～90 ℃ of following gelatinizations, be cooled to room temperature, logical nitrogen, add initiator more successively and by linking agent, ionic vinyl monomer and non-ionic type vinyl monomer, and the mixed solution that is mixed with of clay, stir, in 10～60min, drip the degree of neutralization of 25% strong base solution control reaction system between 30%～90% then to reaction system, after waiting to drip strong base solution, control reaction temperature is in 30～90 ℃, reaction times is 1～6h, obtain Sumstar 190 binary grafting compound clay multipolymer, through soaking, washing, section, oven dry, bulk or granular product are made in pulverizing.
Embodiment 3: 30.0～20.00g Sumstar 190 is stirred gelatinization down at 60～90 ℃, be cooled to room temperature, logical nitrogen, add 0.05～1.00gN more successively, the N-methylene diacrylamine, 62.50～83.34g vinylformic acid 16.67～37.50g acrylamide, 0.01 the mixed solution that～20.00g wilkinite is mixed with, stir, in 10～60min, in reaction system dropping 25%NaOH solution, improve temperature of reaction then and be controlled at 30～90 ℃ with vinylformic acid, reaction times is 3h, obtain Sumstar 190 binary grafting composite earth swelling multipolymer, through soaking, washing, section, oven dry, pulverize, sieving obtains granular product.Inhaling the deionized water multiple is the 1359g/g polymkeric substance.Inhaling 0.9%NaCl aqueous solution multiple is the poly-same compound of 158g/g.
Embodiment 4: adopting vinylformic acid and methyl acrylate with embodiment 3 different being is the binary monomer, and clay adopts kaolin.It is the 1148g/g polymkeric substance that products obtained therefrom is inhaled the deionized water multiple.Inhaling 0.9%NaCl aqueous solution multiple is the 132g/g polymkeric substance.
Embodiment 5: adopting vinylformic acid and ethyl propenoate with 3 different being of example example is the binary monomer.It is the 1068g/g polymkeric substance that products obtained therefrom is inhaled the deionized water multiple, and inhaling 0.9%NaCl aqueous solution multiple is the 100g/g polymkeric substance.
Embodiment 6: the present invention is a kind of starch based water-absorbing resin, it is characterized in that it is Sumstar 190, alkene class ionic comonomer and alkene class nonionic monomers, can make starch molecule produce free radical and can and have under the multi-functional linking agent effect with monomer-grafted initiator, make through gains and compound clay behind the graft copolymerization, wherein the Sumstar 190 consumption is 10% of a vinyl monomer total amount, dosage of crosslinking agent is 1.00% of a vinyl monomer total amount, and the clay consumption is 5% of a vinyl monomer total amount.
Embodiment 7: the present invention is a kind of starch based water-absorbing resin, it is characterized in that it is Sumstar 190, alkene class ionic comonomer and alkene class nonionic monomers, can make starch molecule produce free radical and can and have under the multi-functional linking agent effect with monomer-grafted initiator, make through gains and compound clay behind the graft copolymerization, wherein the Sumstar 190 consumption is 20% of a vinyl monomer total amount, dosage of crosslinking agent is 10% of a vinyl monomer total amount, and the clay consumption is 10% of a vinyl monomer total amount.
Embodiment 8: the present invention is a kind of starch based water-absorbing resin, it is characterized in that it is Sumstar 190, alkene class ionic comonomer and alkene class nonionic monomers, can make starch molecule produce free radical and can and have under the multi-functional linking agent effect with monomer-grafted initiator, make through gains and compound clay behind the graft copolymerization, wherein the Sumstar 190 consumption is 50% of a vinyl monomer total amount, dosage of crosslinking agent is 5% of a vinyl monomer total amount, and the clay consumption is 30% of a vinyl monomer total amount.
Claims (10)
1, a kind of starch based water-absorbing resin, it is characterized in that it is Sumstar 190, vinyl monomer, can make starch molecule produce free radical and can and be to have under the linking agent effect of many reactive functionality with monomer-grafted initiator, make through gains and compound clay behind the graft copolymerization, wherein the Sumstar 190 consumption is 3.00～50.00% of a vinyl monomer total amount, dosage of crosslinking agent is 1.00～50.00% of a vinyl monomer total amount, the clay consumption is 0.001～50.00% of a vinyl monomer total amount, and initiator amount is 0.05～5.00% of a vinyl monomer total amount.
2, starch based water-absorbing resin according to claim 1 is characterized in that vinyl monomer comprises alkene class ionic comonomer and alkene class nonionic monomers, and the consumption of non-ionic type vinyl monomer accounts for 0～100% of ionic vinyl monomer consumption.
3, starch based water-absorbing resin according to claim 2 is characterized in that alkene class ionic comonomer comprises vinylformic acid.
4,, it is characterized in that alkene class ionic comonomer comprises propene sulfonic acid according to claim 2 or 3 described starch based water-absorbing resins.
5, starch based water-absorbing resin according to claim 4 is characterized in that alkene class nonionic monomers comprises acrylamide.
6, starch based water-absorbing resin according to claim 5 is characterized in that alkene class nonionic monomers comprises acrylate.
7, starch based water-absorbing resin according to claim 1 and 2 is characterized in that initiator by persulphate and forming with persulfate oxidation reductive salt, and its proportioning is (0: 1)～(1: 0).
8, starch based water-absorbing resin according to claim 1 is characterized in that linking agent comprises N, N-methylene diacrylamine.
9, starch based water-absorbing resin according to claim 8 is characterized in that linking agent comprises glycerine.
10, a kind of synthetic method that is used to make the described water-absorbing resin of claim 1, it is characterized in that Sumstar 190 40～90 ℃ of following gelatinizations, be cooled to room temperature, logical nitrogen, add initiator more successively and by linking agent, ionic vinyl monomer and non-ionic type vinyl monomer, and the mixed solution that is mixed with of clay, stir, in 10～60min, control the degree of neutralization of reaction system between 30%～90% then to the strong base solution of reaction system dropping 25%, after waiting to drip strong base solution, control reaction temperature is in 30～90 ℃, reaction times is 1～6h, obtain the multipolymer of Sumstar 190 binary grafting compound clay, through soaking, washing, section, oven dry, bulk or granular product are made in pulverizing.
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| CN101143912B (en) * | 2006-09-14 | 2010-09-29 | 台湾塑胶工业股份有限公司 | Method for producing high-performance high water absorption resin |
| WO2012001707A1 (en) * | 2010-07-02 | 2012-01-05 | Indian Council Of Agricultural Research | Novel superabsorbents and the method(s) of obtaining the same |
| CN103719656A (en) * | 2013-12-31 | 2014-04-16 | 楚雄长青科技有限公司 | Drying, sterilizing, impurity removal and screening device implemented by using circulating airflow and processing method of pollen pini |
| CN103819614A (en) * | 2014-02-20 | 2014-05-28 | 桂林理工大学 | Preparation method for alkali capacitive and high water-holding concrete internal curing material |
| CN104496685A (en) * | 2014-12-24 | 2015-04-08 | 金正大生态工程集团股份有限公司 | Preparation method of water retention type controlled-release urea formaldehyde compound fertilizer |
| CN106008821A (en) * | 2016-05-31 | 2016-10-12 | 山东胜伟园林科技有限公司 | Method for carrying out raw soil greening on slight saline and alkaline land by using halophilic microorganism-containing water retaining agent |
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| CN107245127A (en) * | 2017-04-12 | 2017-10-13 | 广西民族大学 | A kind of preparation method of starch base composite high water absorption resin |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101143912B (en) * | 2006-09-14 | 2010-09-29 | 台湾塑胶工业股份有限公司 | Method for producing high-performance high water absorption resin |
| WO2012001707A1 (en) * | 2010-07-02 | 2012-01-05 | Indian Council Of Agricultural Research | Novel superabsorbents and the method(s) of obtaining the same |
| US9833767B2 (en) | 2010-07-02 | 2017-12-05 | Indian Council Of Agricultural Research | Superabsorbents and the method(s) of obtaining the same |
| CN103719656A (en) * | 2013-12-31 | 2014-04-16 | 楚雄长青科技有限公司 | Drying, sterilizing, impurity removal and screening device implemented by using circulating airflow and processing method of pollen pini |
| CN103819614A (en) * | 2014-02-20 | 2014-05-28 | 桂林理工大学 | Preparation method for alkali capacitive and high water-holding concrete internal curing material |
| CN103819614B (en) * | 2014-02-20 | 2016-08-17 | 桂林理工大学 | The preparation method of conserving material in alkali capacitive high moisture retention concrete |
| CN104496685B (en) * | 2014-12-24 | 2017-10-17 | 金正大生态工程集团股份有限公司 | A kind of preparation method of water-retaining type ureaformaldehyde slow-release compound fertilizer |
| CN104496685A (en) * | 2014-12-24 | 2015-04-08 | 金正大生态工程集团股份有限公司 | Preparation method of water retention type controlled-release urea formaldehyde compound fertilizer |
| CN106008821A (en) * | 2016-05-31 | 2016-10-12 | 山东胜伟园林科技有限公司 | Method for carrying out raw soil greening on slight saline and alkaline land by using halophilic microorganism-containing water retaining agent |
| CN106046257A (en) * | 2016-05-31 | 2016-10-26 | 山东胜伟园林科技有限公司 | Water-retaining agent used for saline-alkali soil corn and containing fly ash and preparation method thereof |
| CN106010548A (en) * | 2016-05-31 | 2016-10-12 | 山东胜伟园林科技有限公司 | Seaweed meal raw material-containing water retaining agent used for wheat in saline and alkaline land, and preparation method thereof |
| CN107245127A (en) * | 2017-04-12 | 2017-10-13 | 广西民族大学 | A kind of preparation method of starch base composite high water absorption resin |
| CN107245127B (en) * | 2017-04-12 | 2019-07-02 | 广西民族大学 | A kind of preparation method of starch base composite high water absorption resin |
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