CN107778398A - A kind of Novel super absorbent resin and preparation method thereof - Google Patents
A kind of Novel super absorbent resin and preparation method thereof Download PDFInfo
- Publication number
- CN107778398A CN107778398A CN201610738720.7A CN201610738720A CN107778398A CN 107778398 A CN107778398 A CN 107778398A CN 201610738720 A CN201610738720 A CN 201610738720A CN 107778398 A CN107778398 A CN 107778398A
- Authority
- CN
- China
- Prior art keywords
- preparation
- furfurylidene
- levulic acid
- water
- resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000011347 resin Substances 0.000 title claims abstract description 62
- 229920005989 resin Polymers 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000002250 absorbent Substances 0.000 title abstract description 14
- 230000002745 absorbent Effects 0.000 title abstract description 14
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 claims abstract description 76
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000011949 solid catalyst Substances 0.000 claims abstract description 27
- 238000005575 aldol reaction Methods 0.000 claims abstract description 25
- 239000000178 monomer Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000002270 dispersing agent Substances 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 14
- 239000003999 initiator Substances 0.000 claims description 12
- 229910052783 alkali metal Inorganic materials 0.000 claims description 9
- 150000001340 alkali metals Chemical class 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 9
- 238000012545 processing Methods 0.000 claims description 9
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 8
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 8
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 229910052593 corundum Inorganic materials 0.000 claims description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 6
- 229910021055 KNH2 Inorganic materials 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Inorganic materials [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 claims description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 2
- JYTNGEWJAZCVAN-UHFFFAOYSA-N 2-hexadecylbenzenesulfonic acid;sodium Chemical compound [Na].CCCCCCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O JYTNGEWJAZCVAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910018954 NaNH2 Inorganic materials 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 239000011575 calcium Substances 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 239000011574 phosphorus Substances 0.000 claims 1
- 229910052698 phosphorus Inorganic materials 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 50
- 239000000463 material Substances 0.000 abstract description 11
- 239000002028 Biomass Substances 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract description 2
- 230000036632 reaction speed Effects 0.000 abstract 1
- 239000000725 suspension Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 16
- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 12
- -1 propylene Acid amides Chemical class 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 239000004698 Polyethylene Substances 0.000 description 8
- 239000007795 chemical reaction product Substances 0.000 description 8
- 229920000573 polyethylene Polymers 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 239000002585 base Substances 0.000 description 6
- 238000010557 suspension polymerization reaction Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 239000002861 polymer material Substances 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 229940040102 levulinic acid Drugs 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229920002785 Croscarmellose sodium Polymers 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- 229920006167 biodegradable resin Polymers 0.000 description 2
- 239000001506 calcium phosphate Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000007667 floating Methods 0.000 description 2
- 239000006210 lotion Substances 0.000 description 2
- 230000000116 mitigating effect Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 2
- 229940078499 tricalcium phosphate Drugs 0.000 description 2
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 2
- 235000019731 tricalcium phosphate Nutrition 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- WXQDFOGZIYLEGP-UHFFFAOYSA-N C(C(C)C)#N.C(C(C)C)#N.[N] Chemical compound C(C(C)C)#N.C(C(C)C)#N.[N] WXQDFOGZIYLEGP-UHFFFAOYSA-N 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 238000005882 aldol condensation reaction Methods 0.000 description 1
- 229940125717 barbiturate Drugs 0.000 description 1
- 229920002988 biodegradable polymer Polymers 0.000 description 1
- 239000004621 biodegradable polymer Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000037237 body shape Effects 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000003670 easy-to-clean Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 238000005213 imbibition Methods 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 230000011987 methylation Effects 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920000247 superabsorbent polymer Polymers 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F134/00—Homopolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain and having one or more carbon-to-carbon double bonds in a heterocyclic ring
- C08F134/02—Homopolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain and having one or more carbon-to-carbon double bonds in a heterocyclic ring in a ring containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/54—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/20—Aqueous medium with the aid of macromolecular dispersing agents
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a kind of Novel super absorbent resin and preparation method thereof, including solid catalyst is prepared first, biomass material furfural and levulic acid then are carried out into aldol reaction under solid catalyst effect is made intermediate furfurylidene levulic acid monomer；Then intermediate carries out polymerisation.Prepare that high hydroscopic resin reaction speed is fast, mild condition using the inventive method, the catalyst later stage is disposable.Using furfurylidene levulic acid as raw material, the poly- strong water-absorbing resin of furfurylidene acetyl-propionic acid that is prepared using suspension polymerisation mode, there are good water absorbing properties, inhale salt performance and mechanical strength.
Description
Technical field
The invention belongs to strong absorptive resin material field, it is related to a kind of water-absorbing resins and preparation method thereof, especially relates to
A kind of and biological poly furfurylidene acetyl-propionic acid high hydroscopic resin and preparation method thereof.
Background technology
High hydroscopic resin is also known as strong water-absorbing resin (Super Absorbent Polymer, SAP), is a kind of new high score
Sub- material, there is hydrophilic radical, largely can absorb moisture and be swelled and can and maintain the synthetic resin that moisture does not outflow, such as starch
Grafted propylene Barbiturates, graft acrylamide, high substituted degree cross-linked carboxymethyl cellulose, cross-linked carboxymethyl cellulose grafted propylene
Acid amides, cross-linking type hydroxyethyl cellulose graft acrylamide polymer etc..
High hydroscopic resin has excellent water absorbing properties, and the water of hundreds of or thousands of times can be weighed with absorptance own wt,
And the gel formed after absorbing water, do not outflow, there is excellent water retention property.Thus in health, medical material, agriculture gardens, soil
Earth transformation, environmental protection etc. have broad application prospects.Application of the super absorbent resin in terms of physiological hygiene articles for use be
One field of comparative maturity, and market maximum at present.The wherein strong water-absorbing resin stable performance of polyacrylic, water imbibition
Can be strong, turn into the emphasis novel high polymer material of recent domestic research.In petroleum resources increasingly depleted and waste high polymer
Material endangered to caused by environment increasingly cause it is of concern simultaneously, the poly- furfurylidene acetyl-propionic acid of new bio base absorbs water by force
Resin is Biodegradable polymer material, and one side raw material sources are extensive, cheap, and on the other hand environment-friendly, it has
Preferable development prospect.
High hydroscopic resin is a kind of macromolecular containing hydrophilic radical and cross-linked structure, uses starch by Fanta etc. earliest
Graft polypropylene nitrile is made through saponification again.Divided by raw material, there is starch-series (graft, carboxy methylation etc.), cellulose-based (carboxylic first
Base, graft etc.), synthetic polymer system (polyacrylic, polyethenol series, polyoxyethylene system etc.) several major classes.It is wherein poly-
Acrylic Acid Superabsorbent Resins compared with starch-series and it is cellulose-based compare, have production cost is low, technique is simple, production efficiency is high,
The series of advantages such as water absorbing capacity is strong, shelf life of products length, turn into the study hotspot in the current field.World's super absorbent resin at present
In fat production, polyacrylic accounts for 80%.
With-COOH ,-OH ,-SO on strong water-absorbing resin3H and-CONH2Deng the one or more in group, using raw material and
Preparation method is varied.Chinese patent CN101486781 discloses one kind and prepares strong absorptive tree using reverse microemulsion process
The method of fat.Chinese patent CN103102443, which is disclosed, has invented a kind of water-absorbing resins for physiological hygiene.Chinese patent
CN101045773A discloses the preparation method invented using acrylic compounds water-absorbing resins.Though above-mentioned patented invention is using different
Method, but universal water absorbing properties are slightly worse, while the strong absorptive resin prepared can not be decomposed by biologically effective, be unfavorable for environment guarantor
Shield.
The content of the invention
The primary and foremost purpose of the present invention be for the above-mentioned problems of the prior art provide it is a kind of environment-friendly and it is biological can
Strong water-absorbing resin of biological poly furfurylidene acetyl-propionic acid of degraded and preparation method thereof, the inventive method is by biomass degradation thing
Matter levulic acid, furfural are prepared into high water absorption in the presence of solid catalyst by aldol reaction, suspension polymerization
Resin, the water absorption of high hydroscopic resin can reach 1120g/g；10% saline solution water absorption reaches 352g/g.
To realize the purpose of the present invention, one aspect of the present invention provides a kind of preparation method of high hydroscopic resin, present invention side
Method includes the step of order below is carried out：
1) solid catalyst is prepared
Solid carrier is soaked in alkali metal soln first, calcination processing is being carried out after drying, carrying alkali metal is made
Solid catalyst；
2) aldol reaction
Levulic acid, furfural and solid catalyst are well mixed, in temperature<It is anti-that aldol condensation is carried out under conditions of 10 DEG C
Should, furfurylidene levulic acid monomer is made；
3) polymerisation
Furfurylidene levulic acid monomer, dispersant are dissolved in solvent, after being well mixed, initiator is added, is polymerize
Reaction, is produced.
Wherein, solid carrier described in step 1) is alundum (Al2O3) (Al2O3), calcium oxide (CaO), zirconium oxide (ZrO2)
In one kind, preferably alundum (Al2O3) (Al2O3)。
Particularly, the selection of alkali metal soln described in step 1) KOH solution, KNH2Solution, KNO3Solution, NaOH solution,
NaNH2Solution or NaNO3One kind in solution, preferably KOH solution, KNH2Solution, KNO3Solution, more preferably KNH2It is molten
Liquid.
Especially, the mass percent concentration of the alkali metal soln is 7-15%, preferably 10%.
Particularly, soak time 24-48h, preferably 30-36h.
Wherein, the drying temperature in the drying course is 100-120 DEG C, preferably 110 DEG C；Drying time is 1.5-
2.5h, preferably 2h.
Particularly, the moisture content for being dried to solid carrier is preferably 5-10%, more preferably 5% less than 10%.
Wherein, the temperature of the calcination processing is 300-450 DEG C, preferably 400 DEG C.
Particularly, the calcination time is 4-12h, preferably 6-8h.
The solid catalyst of carrying alkali metal is used to be catalyzed aldol reaction.
Wherein, the temperature of aldol reaction described in step 2) is -10~10 DEG C, is preferably -5~0 DEG C, further excellent
Elect 0 DEG C as；Reaction time is 10-30min.
Particularly, levulic acid described in step 2) and furfural mole the ratio between be 1:0.9-1.5, preferably 1:1.1-
1.4。
Especially, the mass ratio of solid catalyst described in step 2) and levulic acid is 0.1-2:100, be preferably
0.5-1:100。
Particularly, the levulic acid, furfural are prepared by renewable resource biomass by hydrolyzation.
Especially, the biomass includes careless class, agricultural crop straw, corncob, fruit cot etc. and contains cellulosic material.
Particularly, in addition into the reaction system after aldol reaction acid solution, regulation reaction system pH are added
To 2-3.
Especially, the acid solution selection 1mol/L hydrochloric acid solutions.
Wherein, polymeric reaction temperature described in step 3) is 40-100 DEG C, preferably 60-80 DEG C；Polymerization reaction time is
6-10h, preferably 8h.
Particularly, one in the selection of dispersant described in step 3) polyvinyl alcohol, tricalcium phosphate, cetyl benzenesulfonic acid sodium
Kind, preferably polyvinyl alcohol；The initiator selection benzoyl peroxide, azodiisobutyronitrile, peroxidating are in benzoyl
One kind, preferably benzoyl peroxide.
Wherein, one kind in the selection of solvent described in step 3) water, ethanol, acetone, preferably water.
Particularly, the solvent selection deionized water.
Wherein, the mass ratio of the monomer of furfurylidene levulic acid described in step 3) and solvent is 1:0.9-1.5, it is preferably
1:1；The mass ratio of the dispersant and solvent is 7-15:100, preferably 10:100.
Particularly, the mass ratio of the furfurylidene levulic acid monomer and aqueous solvent is 1:0.9-1.5, preferably 1:1；
The mass ratio of the dispersant and aqueous solvent is 7-15:100, preferably 10:100.
Particularly, the mass ratio of initiator described in step 3) and furfurylidene levulic acid monomer is 0.5-1:100, it is excellent
Elect 1 as:100.
Particularly, with regard to also including to the reaction system after progress polymerisation is filtered, polymerizate enters in 50-60 DEG C
Row drying and processing.
Especially, water-absorbing resin moisture content rate≤10% after drying, preferably 5-10%.
Another aspect of the present invention provides a kind of high hydroscopic resin being prepared according to the method described above.
Relative to prior art, the present invention has advantages below：
1st, the present invention prepares the raw material of the strong water-absorbing resin of biological poly furfurylidene levulic acid by renewable resource biomass
Hydrolysis is made, and process efficient, cleaning, low-carbon, green, makes full use of biomass resource, has great economic value and society to imitate
Benefit.
2nd, supported solid catalyst is used in resin intermediate furfurylidene levulic acid preparation process in the present invention, be catalyzed
Effect is strong, later stage catalyst easy to clean, improves product qualities.
3rd, the strong water-absorbing resin of biological poly furfurylidene levulic acid prepared by the present invention is biodegradable resin, and environment is friendly
It is good, there is good mitigation to high polymer material pollution.
4th, the water absorbing properties of the strong water-absorbing resin of biological poly furfurylidene levulic acid prepared by the present invention are good, and its water absorption can
To reach 1120g/g；10% saline solution water absorption reaches 352g/g.
Embodiment
The invention will now be further described with reference to specific embodiments, advantages of the present invention and feature will be with description and
It is apparent.But these embodiments are only exemplary, do not form any restrictions to the scope of the present invention.People in the art
Member to the details and form of technical solution of the present invention it should be understood that can enter without departing from the spirit and scope of the invention
Row modifications or substitutions, but these modifications and replacement are each fallen within protection scope of the present invention.
Method in following embodiments, no special instruction, it is conventional method.
Embodiment 1
1st, solid catalyst is prepared
By carrier Al2O3Powder is immersed in the KOH aqueous solution that quality very concentration is 10% and taken out after 36h；Then in
Dried at 110 ± 1 DEG C 2 hours to moisture content be 10%, (it is 5-10% to be generally dried to moisture content)；Then in 400 DEG C of height
Calcination processing is carried out under the conditions of temperature, is calcined 6 hours, load KOH solid catalyst is made.
Carrier in the present invention is with Al2O3Exemplified by illustrate, other are also applied for the present invention such as calcium oxide, zirconium oxide；This
In inventive embodiments exemplified by 110 DEG C of drying temperature meaning during preparing the solid catalyst of carrying alkali metal, other drying
100-120 DEG C of temperature is applied to the present invention；For drying time by taking 2h as an example, other drying times 1.5-2.5h is applied to this hair
It is bright；Drying and processing of the present invention to carrier moisture content is less than 10%, is generally dried to moisture content as after 5-10%, then carry out at calcining
Reason.
2nd, aldol reaction
Under the conditions of 0 DEG C, the alkali solid catalyst for the load KOH that levulic acid, furfural are prepared with step 1) mixes
Uniformly, aldol reaction is carried out at 0 DEG C, the wherein mol ratio of levulic acid and furfural is 1:1.2；It is solid to load KOH alkalescence
The mass ratio of body catalyst and levulic acid is 0.1:20 (i.e. 0.5:100)；After reacting 30min, added into reaction system
1mol/L hydrochloric acid solutions, neutralization reaction system to pH are 2-3, and aldol reaction product furfurylidene levulic acid is analysed into solid-like
Go out, filter, aldol reaction product monomer furfurylidene levulic acid is made, wherein, levulic acid conversion ratio is 85%, sub- chaff
Base yield of levulinic acid is 89%.
3rd, polymerisation
Under 60 DEG C of water bath conditions, furfurylidene levulic acid, solvent deionized water, polyethylene of dispersing agent alcohol are mixed equal
It is even, polymerization initiator BPO (benzoyl peroxide) is subsequently added into, is well mixed, suspension polymerization is then carried out at 60 DEG C,
Wherein, furfurylidene levulic acid and the mass ratio of solvent deionized water are 1:1；Polyethylene of dispersing agent alcohol and solvent deionized water
Mass ratio is 10:100；The mass ratio of initiator B PO and furfurylidene levulic acid is 1：100；After suspension polymerization 8h,
Filtered, washed successively, 50 DEG C are dried to moisture content≤10% (being usually 5-10%), obtain biological poly furfurylidene acetyl
Propionic acid absorbing resin material.
Dispersant illustrates by taking polyvinyl alcohol as an example in the embodiment of the present invention, other dispersants such as tricalcium phosphate, ten
Six sodium alkyl benzene sulfonates are also applied for the present invention；Initiator illustrates by taking benzoyl peroxide as an example, and other initiators are as occasionally
Nitrogen bis-isobutyronitrile, peroxidating are also applied for the present invention to benzoyl；Solvent illustrates by taking deionized water as an example, and other are such as second
Alcohol, acetone are also applied for the present invention.
Embodiment 2
1st, solid catalyst is prepared
By carrier Al2O3Powder is immersed in the KNH that quality very concentration is 10%2Taken out in the aqueous solution after 36h；Then
Dried at 110 ± 1 DEG C 2 hours to moisture content be 5%；Then calcination processing, calcining 8 are carried out under 400 DEG C of hot conditions
Hour, load KNH is made2Solid catalyst.
2nd, aldol reaction
Under the conditions of 0 DEG C, by the load KNH of levulic acid, furfural and step 1) preparation2Alkali solid catalyst mixing
Uniformly, aldol reaction is carried out at 0 DEG C, the wherein mol ratio of levulic acid and furfural is 1:1.2；Load KNH2Alkalescence is solid
The mass ratio of body catalyst and levulic acid is 1:100；After reacting 30min, it is molten that 1mol/L hydrochloric acid is added into reaction system
Liquid, neutralization reaction system to pH are 2-3, and aldol reaction product furfurylidene levulic acid separates out into solid-like, filters, and is made
Aldol reaction product monomer furfurylidene levulic acid, wherein, levulic acid conversion ratio is 92%, and furfurylidene levulic acid is received
Rate is 95%.
3rd, polymerisation
Under 80 DEG C of water bath conditions, furfurylidene levulic acid, solvent deionized water, polyethylene of dispersing agent alcohol are stirred
Uniformly, and bath temperature is controlled as 80 DEG C；Polymerization initiator BPO is subsequently added into, is well mixed；Then suspended at 80 DEG C
Polymerisation, wherein, the mass ratio of furfurylidene levulic acid and solvent deionized water is 1:1；Polyethylene of dispersing agent alcohol and solvent
The mass ratio of deionized water is 10:100；The mass ratio of initiator B PO and furfurylidene levulic acid is 1：100；Suspend poly-
After closing reaction 8h, filtered, washed successively, 60 DEG C are dried to moisture content 5%, obtain the suction of biological poly furfurylidene levulic acid
Water-resin material.
Embodiment 3
1st, solid catalyst is prepared
By carrier Al2O3Powder is immersed in the KNO that quality very concentration is 15%3Taken out in the aqueous solution after 30h；Then
2 hours are dried at 110 ± 2 DEG C to moisture content 7%；Then the carrier after drying is placed under 450 DEG C of hot conditions and carried out
Calcination processing, calcine 4 hours, load KNO is made3Solid catalyst.
2nd, aldol reaction
Under the conditions of -2 DEG C, by the load KNO of levulic acid, furfural and step 1) preparation3Solid catalyst be placed in instead
Answer in device, be uniformly mixed, aldol reaction is carried out at -2 DEG C, the wherein mol ratio of levulic acid and furfural is 1:
1.1；Load KNO3The mass ratio of solid catalyst and levulic acid is 2:100；After reacting 30min, add into reaction system
Enter 1mol/L hydrochloric acid solutions, neutralization reaction system to pH is 2-3, and aldol reaction product furfurylidene levulic acid is into solid-like
Separate out, filtering, aldol reaction product monomer furfurylidene levulic acid is made, wherein, levulic acid conversion ratio is 81%, sub-
Furfuryl group yield of levulinic acid is 80%.
3rd, polymerisation
Furfurylidene levulic acid, solvent deionized water, polyethylene of dispersing agent alcohol are well mixed first；It is subsequently added into polymerization
Initiator B PO, it is well mixed；Then heat, suspension polymerization is carried out under 100 DEG C, stirring, wherein, furfurylidene second
Acyl propionic acid and the mass ratio of solvent deionized water are 1:0.9；The mass ratio of polyethylene of dispersing agent alcohol and solvent deionized water is
15:100；The mass ratio of initiator B PO and furfurylidene levulic acid is 1：100；After suspension polymerization 8, carried out successively
Filter, washing, 50 DEG C are dried to moisture content 10%, obtain biological poly furfurylidene levulic acid absorbing resin material.
Embodiment 4
1st, solid catalyst is prepared
By carrier Al2O3Powder is immersed in the KOH aqueous solution that quality very concentration is 7% and taken out after 48h；Then in
Dried at 110 ± 5 DEG C 2 hours to moisture content be 5%；Then the carrier after drying is forged under 300 DEG C of hot conditions
Burning processing, is calcined 12 hours, and load KOH solid catalyst is made.
2nd, aldol reaction
Under the conditions of -5 DEG C, load KOH prepared by levulic acid, furfural and step 1) solid catalyst is placed in reaction
In device, it is uniformly mixed, aldol reaction is carried out in -5 times, the wherein mol ratio of levulic acid and furfural is 1:1.4；It is negative
The mass ratio for carrying KOH solid catalysts and levulic acid is 0.1:15(0.667:100)；After reacting 10min, to reaction system
Middle addition 1mol/L hydrochloric acid solutions, neutralization reaction system to pH are 2-3, aldol reaction product furfurylidene levulic acid Cheng Gu
Body shape separates out, and filtering, aldol reaction product monomer furfurylidene levulic acid is made, wherein, levulic acid conversion ratio is
89%, furfurylidene yield of levulinic acid is 92%.
3rd, polymerisation
Under 60 DEG C of water bath conditions, it is mixed that furfurylidene levulic acid, solvent deionized water, polyethylene of dispersing agent alcohol are put into stirring
Close uniformly, and it is 60 DEG C to control bath temperature；Polymerization initiator BPO is subsequently added into, is well mixed；Then hanged at 60 DEG C
Floating polymerisation, wherein, the mass ratio of furfurylidene levulic acid and solvent deionized water is 1:1.5；Polyethylene of dispersing agent alcohol with
The mass ratio of solvent deionized water is 7:100；The mass ratio of initiator B PO and furfurylidene levulic acid is 0.5：100；It is outstanding
After floating polymerisation 10h, filtered, washed successively, 50 DEG C be dried to moisture content 7% (, obtain biological poly furfurylidene acetyl
Propionic acid absorbing resin material.
The water absorbing properties of test example 1 are tested
The poly- each 10g of furfurylidene levulic acid absorbing resin material of new bio base of embodiment 1-4 preparations is weighed respectively
(m1) high hydroscopic resin then, is soaked in more than 15min in running water respectively, after high hydroscopic resin washing lotion saturation, will be inhaled
Water-resin is transferred in the nylon net bag of 100 mesh, is hung to remove the water not exhausted；Then weigh respectively and inhale water saturated resin
Weight (m2), the water absorbent rate (q) of high hydroscopic resin of the present invention is calculated according to formula (II), wherein water absorbent rate formula is as follows
Q=(m2-m1)/m1 (II)
In formula：Q---- water absorbent rates g/g；
M1---- water-absorbing resin weight (g)；
The weight (g) of water-absorbing resin after m2---- water suctions
Test result is as shown in table 1.
The salt water absorption properties of test example 2 are tested
The poly- each 10g of furfurylidene levulic acid absorbing resin material of new bio base of embodiment 1-4 preparations is weighed respectively
(M1), high hydroscopic resin is then soaked in more than 15min in the saline solution that quality very concentration is 10% respectively, treat high suction
After water-resin washing lotion saturation, water-absorbing resin is transferred in the nylon net bag of 100 mesh, hung to remove the saline solution not exhausted；
Then weigh respectively and absorb saline solution to the weight (M2) of the resin of saturation, high hydroscopic resin of the present invention is calculated according to formula (III)
Absorption saline solution multiplying power (Q), wherein inhale absorb saline solution multiplying power formula it is as follows
Q=(M2-M1)/M1 (III)
In formula：Q---- absorbs saline solution multiplying power g/g；
M1---- water-absorbing resin weight (g)；
M2---- absorbs the weight (g) of water-absorbing resin after saline solution
Test result is as shown in table 1.
The water absorbing properties result of the test of the Novel super absorbent resin of table 1
| Water absorbing properties (g/g) | 10% saline solution water absorbing properties (g/g) | |
| Embodiment 1 | 1020 | 312 |
| Embodiment 2 | 1120 | 352 |
| Embodiment 3 | 980 | 295 |
| Embodiment 4 | 1050 | 322 |
It was found from the result of the test of table 1：
1st, the water absorbing properties of Novel super absorbent resin prepared by the present invention are good, and water absorbent rate is high, reaches more than 980g/g, this
The high hydroscopic resin of invention can absorb water of more than 980 times equivalent to resin own wt, can reach 1120 times；
2nd, the water suction saline solution performance of Novel super absorbent resin prepared by the present invention is good, and water absorbent rate is high, reaches 295g/g
More than, the quality very concentration that high hydroscopic resin of the invention can absorb more than 295 times equivalent to resin own wt is
10% saline solution, 352 times can be reached；
3rd, super absorbent resin prepared by the present invention is made up of furfurylidene levulic acid monomer of suspension polymerization, raw
The poly- strong water-absorbing resin of furfurylidene levulic acid of thing base is biodegradable resin, environment-friendly, is had very to high polymer material pollution
Good mitigation.
Claims (10)
1. a kind of preparation method of high hydroscopic resin, it is characterized in that, including the step of order below progress：
1) solid catalyst is prepared
Solid carrier is soaked in alkali metal soln first, calcination processing is being carried out after drying, consolidating for carrying alkali metal is made
Body catalyst；
2) aldol reaction
Levulic acid, furfural and solid catalyst are well mixed, in temperature<Aldol reaction is carried out under conditions of 10 DEG C,
Furfurylidene levulic acid monomer is made；
3) polymerisation
Furfurylidene levulic acid monomer, dispersant are dissolved in solvent, after being well mixed, initiator is added, carries out polymerisation,
Produce.
2. preparation method as claimed in claim 1, it is characterized in that, solid carrier described in step 1) is alundum (Al2O3), oxygen
Change one kind in calcium or zirconium oxide.
3. preparation method as claimed in claim 1 or 2, it is characterized in that, the selection of alkali metal soln described in step 1) KOH is molten
Liquid, KNH2Solution, KNO3Solution, NaOH solution, NaNH2Solution or NaNO3One kind in solution.
4. preparation method as claimed in claim 1 or 2, it is characterized in that, the temperature of aldol reaction described in step 2) for-
10~10 DEG C；Reaction time is 10-30min.
5. preparation method as claimed in claim 1 or 2, it is characterized in that, mole of levulic acid described in step 2) and furfural
The ratio between be 1:0.9-1.5.
6. preparation method as claimed in claim 1 or 2, it is characterized in that, solid catalyst described in step 2) and levulic acid
Mass ratio be 0.1-2:100.
7. preparation method as claimed in claim 1 or 2, it is characterized in that, polymeric reaction temperature described in step 3) is 40-100
℃；Polymerization reaction time is 6-10h.
8. preparation method as claimed in claim 1 or 2, it is characterized in that, the selection of dispersant described in step 3) polyvinyl alcohol, phosphorus
One kind in sour DFP or cetyl benzenesulfonic acid sodium；Initiator selection benzoyl peroxide, azodiisobutyronitrile or the mistake
Oxidation is to one kind in benzoyl.
9. preparation method as claimed in claim 1 or 2, it is characterized in that, initiator described in step 3) and furfurylidene levulinic
The mass ratio of acid monomers is 0.5-1:100.
10. a kind of high hydroscopic resin, it is characterized in that, it is prepared according to such as any methods describeds of claim 1-9.
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| CN116813829A (en) * | 2023-07-10 | 2023-09-29 | 山东诺尔生物科技有限公司 | Composition for preparing super absorbent resin, super absorbent resin and preparation method of super absorbent resin |
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|---|---|---|---|---|
| WO2012006278A3 (en) * | 2010-07-05 | 2012-07-26 | Reluceo, Inc. | Degradable superabsorbent polymers |
| CN103122049A (en) * | 2013-03-04 | 2013-05-29 | 太原理工大学 | Preparation method of cellulose ultra-strong water-absorbent resin |
| CN105779036A (en) * | 2016-05-10 | 2016-07-20 | 中国科学院广州能源研究所 | Method for producing oil for traffic fuel by using straws |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012006278A3 (en) * | 2010-07-05 | 2012-07-26 | Reluceo, Inc. | Degradable superabsorbent polymers |
| CN103122049A (en) * | 2013-03-04 | 2013-05-29 | 太原理工大学 | Preparation method of cellulose ultra-strong water-absorbent resin |
| CN105779036A (en) * | 2016-05-10 | 2016-07-20 | 中国科学院广州能源研究所 | Method for producing oil for traffic fuel by using straws |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116813829A (en) * | 2023-07-10 | 2023-09-29 | 山东诺尔生物科技有限公司 | Composition for preparing super absorbent resin, super absorbent resin and preparation method of super absorbent resin |
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