CN113667150B - Polymer soil improvement solid water polymerization reaction method - Google Patents
Polymer soil improvement solid water polymerization reaction method Download PDFInfo
- Publication number
- CN113667150B CN113667150B CN202110952708.7A CN202110952708A CN113667150B CN 113667150 B CN113667150 B CN 113667150B CN 202110952708 A CN202110952708 A CN 202110952708A CN 113667150 B CN113667150 B CN 113667150B
- Authority
- CN
- China
- Prior art keywords
- polylactic acid
- reaction
- solid water
- soil improvement
- stirring
- 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.)
- Active
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 239000007787 solid Substances 0.000 title claims abstract description 51
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 40
- 239000002689 soil Substances 0.000 title claims abstract description 30
- 230000006872 improvement Effects 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 20
- 229920000642 polymer Polymers 0.000 title claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 55
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 46
- 239000004626 polylactic acid Substances 0.000 claims abstract description 46
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000003756 stirring Methods 0.000 claims abstract description 36
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 31
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000843 powder Substances 0.000 claims abstract description 24
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 22
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 22
- 239000011707 mineral Substances 0.000 claims abstract description 22
- 239000003999 initiator Substances 0.000 claims abstract description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 18
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 239000000017 hydrogel Substances 0.000 claims abstract description 14
- 239000012948 isocyanate Substances 0.000 claims abstract description 10
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000005520 cutting process Methods 0.000 claims abstract description 6
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- 238000007865 diluting Methods 0.000 claims abstract description 6
- 238000000227 grinding Methods 0.000 claims abstract description 6
- 238000007873 sieving Methods 0.000 claims abstract description 6
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 claims description 22
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- 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 13
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 claims description 12
- 235000019766 L-Lysine Nutrition 0.000 claims description 11
- 239000004472 Lysine Substances 0.000 claims description 11
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical group [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 claims description 10
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- SHFJWMWCIHQNCP-UHFFFAOYSA-M hydron;tetrabutylazanium;sulfate Chemical compound OS([O-])(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC SHFJWMWCIHQNCP-UHFFFAOYSA-M 0.000 claims description 8
- 238000006386 neutralization reaction Methods 0.000 claims description 6
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical group [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 5
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 5
- 235000011152 sodium sulphate Nutrition 0.000 claims description 5
- 239000001119 stannous chloride Substances 0.000 claims description 5
- 235000011150 stannous chloride Nutrition 0.000 claims description 5
- 239000005995 Aluminium silicate Substances 0.000 claims description 4
- 235000012211 aluminium silicate Nutrition 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- 229960000892 attapulgite Drugs 0.000 claims description 4
- 239000004927 clay Substances 0.000 claims description 4
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 4
- 229910000514 dolomite Inorganic materials 0.000 claims description 4
- 239000010459 dolomite Substances 0.000 claims description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 4
- 229910052625 palygorskite Inorganic materials 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- WPLOVIFNBMNBPD-ATHMIXSHSA-N subtilin Chemical compound CC1SCC(NC2=O)C(=O)NC(CC(N)=O)C(=O)NC(C(=O)NC(CCCCN)C(=O)NC(C(C)CC)C(=O)NC(=C)C(=O)NC(CCCCN)C(O)=O)CSC(C)C2NC(=O)C(CC(C)C)NC(=O)C1NC(=O)C(CCC(N)=O)NC(=O)C(CC(C)C)NC(=O)C(NC(=O)C1NC(=O)C(=C/C)/NC(=O)C(CCC(N)=O)NC(=O)C(CC(C)C)NC(=O)C(C)NC(=O)CNC(=O)C(NC(=O)C(NC(=O)C2NC(=O)CNC(=O)C3CCCN3C(=O)C(NC(=O)C3NC(=O)C(CC(C)C)NC(=O)C(=C)NC(=O)C(CCC(O)=O)NC(=O)C(NC(=O)C(CCCCN)NC(=O)C(N)CC=4C5=CC=CC=C5NC=4)CSC3)C(C)SC2)C(C)C)C(C)SC1)CC1=CC=CC=C1 WPLOVIFNBMNBPD-ATHMIXSHSA-N 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 9
- 239000000178 monomer Substances 0.000 abstract description 7
- 238000004132 cross linking Methods 0.000 abstract description 5
- 230000003472 neutralizing effect Effects 0.000 abstract description 4
- 238000013329 compounding Methods 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 description 16
- 239000000499 gel Substances 0.000 description 14
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 9
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 8
- 238000007789 sealing Methods 0.000 description 7
- 238000001514 detection method Methods 0.000 description 6
- 230000009471 action Effects 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000002250 absorbent Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229920000578 graft copolymer Polymers 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000013558 reference substance Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010413 gardening Methods 0.000 description 1
- 238000001879 gelation Methods 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
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000003020 moisturizing effect Effects 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 238000003900 soil pollution Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229920003176 water-insoluble polymer Polymers 0.000 description 1
- 238000004260 weight control Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/246—Intercrosslinking of at least two polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/08—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles
- B01J8/10—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles moved by stirrers or by rotary drums or rotary receptacles or endless belts
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/428—Lactides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/40—Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2435/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
- C08J2475/06—Polyurethanes from polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Dispersion Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Soil Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Biological Depolymerization Polymers (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention relates to a polymer soil improvement solid water polymerization reaction method, which comprises the steps of placing polylactic acid, 1,4 butanediol and a catalyst in a polymerization device, stirring for reaction under microwaves, adding isocyanate for continuous reaction, and then leading out and cooling to obtain chain-extended polylactic acid; diluting NaOH and deionized water, adding acrylic acid, stirring, neutralizing, adding cross-linking agent, mineral powder, chain-extended polylactic acid, initiator and phase transfer catalyst, circularly reacting under microwave to obtain solid hydrogel, cutting the solid hydrogel, drying, grinding, sieving to obtain solid water product, and cross-linking and compounding the acrylic acid monomer, mineral material, chain-extended polylactic acid and self-made cross-linking agent under microwave to form interpenetrating cross-linked network structure.
Description
Technical Field
The invention relates to a polymer soil improvement solid water polymerization reaction method, and belongs to the technical field of solid water.
Background
The solid water is a biodegradable moisturizing polymer with super-absorbent property, has the characteristics of high water absorption, salt and alkali resistance, soil improvement and biodegradability, and can be widely applied to the fields of agriculture, forestry, gardening technology, medical treatment and health, desert control and the like. The existing solid water high water absorbability is generally prepared by grafting starch to acrylonitrile, acrylic acid, polyurethane and the like, cooling, graft copolymerization, pressurized hydrolysis, acidification, neutralization, drying and forming after starch gelatinization, wherein the polypropylene salt formed by a main chain of the high water absorbability resin through C-C bonds is subjected to cation influence ion strength increase and water absorption rate decrease, and is limited by biodegradation under low molar mass, so that the molecular weight control difficulty of the graft copolymer is increased, soil pollution is caused because the graft copolymer cannot be completely degraded, the reaction time is long when a single stirring polymerization reaction device is used for crosslinking polymerization under a jacket thermal environment, salt addition is needed to promote the reaction, and the synthesized polymer has fewer strong hydrophilic groups, so that the water absorption rate, the water retention property and the gel mechanical strength comprehensive performance are poor.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a polymer soil improvement solid water polymerization reaction method, which uses acrylic acid monomer, mineral separation, chain extension polylactic acid and self-made cross-linking agent to crosslink and compound under microwaves to form an interpenetrating cross-linked network structure to improve the comprehensive performance of water absorption, water retention, gel mechanical strength and salt and alkali resistance, simplifies the synthesis process and ensures that solid water is used for improving soil.
The invention is realized by the following technical scheme:
a polymer soil improvement solid water polymerization reaction method comprises the following steps:
s1, dissolving L-lysine in dichloromethane, adding acrylic acid for circulating dispersion, adding citraconic anhydride and azodiisobutyronitrile, and carrying out stirring and circulating polymerization reaction in a polymerization device under microwaves to obtain a cross-linking agent;
s2: placing polylactic acid, 1,4 butanediol and a catalyst into a polymerization device, stirring for reaction under microwaves, adding isocyanate, continuing to react, and then leading out and cooling to obtain chain-extended polylactic acid;
s3: diluting NaOH and deionized water, putting into a polymerization device, adding acrylic acid, stirring for neutralization, adding a cross-linking agent, mineral powder, chain-extended polylactic acid, an initiator and a phase transfer catalyst, performing cyclic reaction under microwaves to obtain solid hydrogel, and cutting, drying, grinding and sieving the solid hydrogel to obtain a solid water finished product.
Further, in the step S1, the mass ratio of the L-lysine, the acrylic acid, the citraconic anhydride and the azodiisobutyronitrile is 85-120:75-95:120-200:0.1-0.3, microwave power of 20-50W, temperature of 40-50deg.C, stirring rate of 80-100r/min, and reacting for 30-60min
Further, the mass ratio of the polylactic acid to the 1,4 butanediol to the isocyanate in the step S2 is 55-65:35-45:25-35, wherein the weight average molecular weight of the polylactic acid is less than or equal to 5000, the catalyst is sodium sulfate or stannous chloride accounting for 0.5 percent of the total mass of the polylactic acid and the 1,4 butanediol, the microwave power is 120-230W, the temperature is 120-130 ℃, the stirring speed is 50-60r/min, the reaction is carried out for 30-60min, and the temperature is raised to 140-150 ℃ after the isocyanate is added, and the reaction is continued for 1-2h;
further, in the step S3, the mineral powder is one or more of kaolin, dolomite powder, attapulgite clay and montmorillonite powder, the initiator is ammonium persulfate or potassium persulfate, and the phase transfer catalyst is benzyl triethyl ammonium chloride or tetrabutyl ammonium bisulfate;
the neutralization degree is 60-70%, and the mass ratio of the acrylic acid to the cross-linking agent to the mineral powder to the chain-extended polylactic acid to the initiator to the phase transfer catalyst is 20-30:0.05-0.1:6-11:5-9:0.05:0.1, the microwave power is 300-350W, the temperature is 160-170 ℃, and the stirring speed is 40-80r/min for reaction for 1-2h.
The polymer soil improvement solid water polymerization device comprises a microwave hearth and a reactor arranged in the microwave hearth, wherein a stirrer rotating in the reactor is connected with a circulating pipeline at the top and the bottom of the reactor, and the circulating pipeline is connected with a feed pipe, a discharge pipe and a circulating pump.
Further, the reactor is eccentrically arranged in the microwave oven chamber, one side of the microwave oven chamber is provided with a variable frequency transformer, a magnetron and a filter tube positioned at the top of the side of the reactor, and the end part of the filter tube is provided with a baffle plate.
Further, the reactor includes the reaction cover fixed with microwave oven top, with reaction cover and microwave oven relatively rotatable's reaction body, the reaction cover top is equipped with gear motor, and the reaction cover is inside to be equipped with the mount pad, be equipped with the drive shaft on the mount pad, with the continuous transmission shaft of agitator, the external tooth ring that links to each other with the reaction body, all be equipped with the belt pulley in gear motor and the drive shaft, be equipped with driving belt outward on the belt pulley, be equipped with the internal gear with external tooth internal engagement on the transmission shaft, be equipped with between drive shaft and the reaction cover, between transmission shaft and the mount pad, all be equipped with bearing housing and sealing washer between reaction body and reaction cover and the microwave oven, the slope of inlet pipe tip extends to the reaction body inside.
The beneficial effects of the invention are as follows:
(1) The L-lysine contains hydrophilic side amino groups, and is grafted, acidified and modified with acrylic acid/citraconic anhydride under the activation action of azo-diisobutyronitrile serving as an initiator, so that the hydrophilicity, swelling rate and biodegradability of the degradable solid water are improved, and the reactivity is increased; the polylactic acid with low molecular weight, the 1,4 butanediol and the catalyst are subjected to hydroxyl end sealing, and then are subjected to chain extension by reaction of trifunctional isocyanate under microwaves, and hetero atoms are introduced into a C-C framework, so that biodegradability is improved;
(2) The method has the advantages that partially neutralized acrylic acid is used as a monomer, mineral is used for separating and filling, chain-extended polylactic acid is used as a monomer raw material, and the partially neutralized acrylic acid is crosslinked and compounded with a self-made crosslinking agent and under the microwave of an initiator phase transfer catalyst to form an interpenetrating crosslinked network structure, so that the comprehensive performances of water absorption, water retention, gel mechanical strength and saline-alkali resistance are improved, the synthesis process is simplified by a polymerization device of microwave radiation, the large-scale production is facilitated, and the soil improvement effect of a solid water finished product is achieved.
Drawings
FIG. 1 is a structural view of a reaction apparatus according to the present invention.
The marks in the figure: the device comprises a microwave oven cavity 1, a reactor 2, a stirrer 3, a circulating pipeline 4, a feeding pipe 5, a discharging pipe 6, a circulating pump 7, a variable frequency transformer 8, a magnetron 9, a filter guide pipe 10, a baffle 11, a reaction cover 12, a reaction body 13, a reducing motor 14, a mounting seat 15, a driving shaft 16, a driving shaft 17, an outer gear ring 18, a belt pulley 19, a driving belt 20, an inner gear 21, driving teeth 22, a bearing sleeve 23 and a sealing ring 24.
Detailed Description
The following describes the embodiments of the present invention further with reference to the drawings.
Example 1:
a polymer soil improvement solid water polymerization reaction method comprises the following steps:
s1, dissolving L-lysine in dichloromethane, adding acrylic acid for circulating dispersion, adding citraconic anhydride and azodiisobutyronitrile, and carrying out stirring circulating polymerization reaction in a polymerization device under microwaves to obtain a cross-linking agent, wherein the mass ratio of the L-lysine to the acrylic acid to the citraconic anhydride to the azodiisobutyronitrile is 100:85:180:0.2, the microwave power is 45W, the temperature is 46 ℃, and the stirring speed is 90r/min for 30min to obtain the catalyst;
s2: placing polylactic acid, 1,4 butanediol and a catalyst into a polymerization device, stirring the materials under microwave to react, continuously reacting after adding Toluene Diisocyanate (TDI), and leading out and cooling the materials to obtain chain-extended polylactic acid, wherein the mass ratio of the polylactic acid to the 1,4 butanediol to the Toluene Diisocyanate (TDI) is 58:42:32, the weight average molecular weight of the polylactic acid is less than or equal to 5000, the catalyst is sodium sulfate or stannous chloride accounting for 0.5 percent of the total mass of the polylactic acid and the 1,4 butanediol, the microwave power is 180W, the temperature is 122 ℃, the stirring speed is 55r/min, the reaction is carried out for 40min, toluene Diisocyanate (TDI) is added, and the temperature is raised to 140 ℃ for continuous reaction for 2h;
s3: diluting NaOH and deionized water, putting into a polymerization device, adding acrylic acid, stirring and neutralizing, adding a cross-linking agent, mineral powder, chain-extended polylactic acid, an initiator and a phase transfer catalyst after the neutralization degree is 60%, and circularly reacting under microwaves to obtain solid hydrogel, wherein the mineral powder is prepared from kaolin and attapulgite clay according to the mass ratio of 1:1, wherein the initiator is ammonium persulfate, the phase transfer catalyst is benzyl triethyl ammonium chloride, and the mass ratio of the acrylic acid, the cross-linking agent, the mineral powder, the chain-extended polylactic acid, the initiator and the phase transfer catalyst is 25:0.05:8:6: and (3) reacting for 1h at a microwave power of 320W and a stirring speed of 65r/min at a temperature of 165 ℃ at a ratio of 0.05:0.1, and cutting, drying, grinding and sieving the solid hydrogel to obtain a solid water finished product.
Example 2
A polymer soil improvement solid water polymerization reaction method comprises the following steps:
s1, dissolving L-lysine in dichloromethane, adding acrylic acid for circulating dispersion, adding citraconic anhydride and azodiisobutyronitrile, and carrying out stirring circulating polymerization reaction in a polymerization device under microwaves to obtain a cross-linking agent, wherein the mass ratio of the L-lysine to the acrylic acid to the citraconic anhydride to the azodiisobutyronitrile is 105:80:150:0.2, the microwave power is 40W, the temperature is 48 ℃, and the stirring speed is 93r/min for 40min to obtain the catalyst;
s2: placing polylactic acid, 1,4 butanediol and a catalyst into a polymerization device, stirring the materials under microwave to react, adding Hexamethylene Diisocyanate (HDI), continuously reacting, and guiding out and cooling to obtain chain-extended polylactic acid, wherein the mass ratio of the polylactic acid to the 1,4 butanediol to the Hexamethylene Diisocyanate (HDI) is 63:42:29, the weight average molecular weight of the polylactic acid is less than or equal to 5000, the catalyst is stannous chloride accounting for 0.5 percent of the total mass of the polylactic acid and the 1,4 butanediol, the microwave power is 180W, the temperature is 125 ℃, the stirring speed is 55r/min, the reaction is carried out for 50min, and after Hexamethylene Diisocyanate (HDI) is added, the temperature is raised to 145 ℃ for continuous reaction for 2h;
s3: diluting NaOH and deionized water, adding acrylic acid, stirring and neutralizing, adding a cross-linking agent, mineral powder, chain-extended polylactic acid, an initiator and a phase transfer catalyst, and circularly reacting under microwaves to obtain solid hydrogel, wherein the mineral powder is dolomite powder, the initiator is potassium persulfate, the phase transfer catalyst is tetrabutylammonium bisulfate, and the mass ratio of the acrylic acid to the cross-linking agent to the mineral powder to the chain-extended polylactic acid to the initiator to the phase transfer catalyst is 28:0.08:10:8: and (2) reacting for 2 hours at the temperature of 166 ℃ and the stirring speed of 50r/min at the microwave power of 340W in a ratio of 0.05:0.1, taking the solid hydrogel, and cutting, drying, grinding and sieving the solid hydrogel to obtain a solid water finished product.
Example 3
A polymer soil improvement solid water polymerization reaction method comprises the following steps:
s1, dissolving L-lysine in dichloromethane, adding acrylic acid for circulating dispersion, adding citraconic anhydride and azodiisobutyronitrile, and carrying out stirring circulating polymerization reaction in a polymerization device under microwaves to obtain a cross-linking agent, wherein the mass ratio of the L-lysine to the acrylic acid to the citraconic anhydride to the azodiisobutyronitrile is 90:80:165:0.2, the microwave power is 40W, the temperature is 45 ℃, and the stirring speed is 90r/min for 40min to obtain the catalyst;
s2: placing polylactic acid, 1,4 butanediol and a catalyst into a polymerization device, stirring the materials under microwaves for reaction, adding isophorone diisocyanate (IPDI), continuously reacting, and then guiding out and cooling to obtain chain-extended polylactic acid, wherein the mass ratio of the polylactic acid to the 1,4 butanediol to the isophorone diisocyanate (IPDI) is 58:42:27, the weight average molecular weight of the polylactic acid is less than or equal to 5000, the catalyst is sodium sulfate accounting for 0.5 percent of the total mass of the polylactic acid and the 1,4 butanediol, the microwave power is 180W, the temperature is 122 ℃, the stirring speed is 60r/min, the reaction is carried out for 40min, after isophorone diisocyanate (IPDI) is added, the temperature is raised to 143 ℃ and the reaction is continued for 1h;
s3: diluting NaOH and deionized water, adding acrylic acid, stirring and neutralizing, adding a cross-linking agent, mineral powder, chain-extended polylactic acid, an initiator and a phase transfer catalyst, and circularly reacting under microwaves to obtain solid hydrogel, wherein the mineral powder is montmorillonite powder, the initiator is potassium persulfate, the phase transfer catalyst is benzyl triethyl ammonium chloride, and the mass ratio of the acrylic acid to the cross-linking agent to the mineral powder to the chain-extended polylactic acid to the initiator to the phase transfer catalyst is 28:0.07:8:7: and (3) reacting for 1h at the stirring speed of 60r/min at the temperature of 163 ℃ and the microwave power of 320W at the ratio of 0.05:0.1, and cutting, drying, grinding and sieving the solid hydrogel to obtain a solid water finished product.
The polymer soil improvement solid water polymerization device in the above embodiments 1-3 comprises a microwave hearth 1, a reactor 2 arranged in the microwave hearth 1, a stirrer 3 rotating in the reactor 2, a circulating pipeline 4 connected with the top and the bottom of the reactor 2, and a feed pipe 5, a discharge pipe 6 and a circulating pump 7 connected with the circulating pipeline 4;
the reactor 2 is eccentrically arranged in the microwave oven cavity 1, one side of the microwave oven cavity 1 is provided with a variable frequency transformer 8, a magnetron 9 and a filter tube 10 positioned at the side top of the reactor 2, and the end part of the filter tube 10 is provided with a baffle 11;
the reactor 2 comprises a reaction cover 12 fixed on the top of the microwave oven 1, a reaction body 13 which can rotate relative to the reaction cover 12 and the microwave oven 1, a speed reducing motor 14 is arranged on the top of the reaction cover 12, a mounting seat 15 is arranged in the reaction cover 12, a driving shaft 16, a driving shaft 17 connected with the stirrer 3 and an outer gear ring 18 connected with the reaction body 13 are arranged on the mounting seat 15, belt pulleys 19 are arranged on the speed reducing motor 14 and the driving shaft 16, a driving belt 20 is arranged outside the belt pulleys 19, an inner gear 21 meshed with the inner gear 18 is arranged on the driving shaft 17, driving teeth 22 meshed with the outer gear 21 are arranged on the driving shaft 17, a bearing sleeve 23 and a sealing ring 24 are arranged between the driving shaft 16 and the reaction cover 12, between the driving shaft 17 and the mounting seat 15, and between the reaction body 13 and the microwave oven 1, and the end part of the feeding pipe 5 extends to the inside of the reaction body 13 in an inclined manner.
The mechanism of the invention is as follows:
the upper end part of the circulating pipe is obliquely extended to the feeding pipe 5 in the reaction body 13 for feeding, the driving shaft 16 is driven to rotate under the decelerating transmission of the driving belt 20 and the belt pulley 19 by the decelerating motor 14, a bearing sleeve 23 and a sealing ring 24 are arranged between the driving shaft 16 and the reaction cover 12, between the driving shaft 17 and the mounting seat 15, and between the reaction body 13 and the reaction cover 12 and the microwave oven cavity 1, so that the sealing corrosion resistance can be improved, the reaction body 13 is driven to rotate relative to the reaction cover 12 and the microwave oven cavity by driving the outer gear ring 18 through the inner gear wheel 21 when the driving shaft 16 rotates, the microwave radiation uniformity is improved, and the driving shaft 17 on the mounting seat 15 is driven to rotate in the reactor 2 by meshing the inner gear wheel 21 and the driving gear wheel 22, and the reaction body 13 is driven to rotate relative to the abutting discharging pipe 6 in the microwave oven cavity 1;
the stirrer 3 rotates at a high speed, the reaction body 13 rotates in opposite directions at a reduced speed to increase the convection turbulence of a material system, the material of the discharging pipe 6 circulates the material to the top feeding pipe 5 through the circulating pump 7 and the circulating pipe, the material circulating mass transfer reaction efficiency is increased, and the circulating pipe can be connected with a valve and a sampling pipe for sampling and detection;
is converted by a frequency conversion transformer 8. The magnetron 9 generates microwaves under the excitation of a power supply, and the microwaves are supplied to the reactor 2 in the microwave oven cavity 1 through the microwave coupling of the filter tube and the baffle 11, and the microwave frequency is: 2450MHz + -50 Hz, detecting temperature by a temperature detector extending into the reactant 13, controlling reaction temperature and microwave frequency by frequency conversion;
the solid water prepared in examples 1-3 was compared with a commercially available water absorbent polymer SAP (Tongling-FMX-6) as a control, and the detection method and detection result were as follows:
and (3) water absorption detection: adding water into 0.3g of solid water or a reference substance, standing for 30min, filtering out excessive water by a wet screen, standing until the mass reduction per minute is less than 1g, weighing, wherein M3 is the total weight of the screen and the gel after water absorption, M2 is the weight of the screen, and M1 is the dry weight according to the water absorption= (M3-M2-M1)/M1;
and (3) water retention detection: placing the retained gel and the screen after the water absorption is detected in a drying oven at 90 ℃ for 1.5 hours, taking out, cooling, weighing, and calculating according to the water retention rate (%) = (M4-M2)/(M1-M2) ×100%, wherein M4 is the total weight of the screen and the gel after dehydration, M2 is the weight of the screen, and M1 is the total weight of the screen and the gel before dehydration;
salt absorption rate detection: taking 0.3g of solid water or a reference substance, adding 0.9% saline, standing for 30min, filtering the wet net to remove excessive moisture, standing again until the mass reduction per minute is less than 1g, weighing, wherein M3 is the total weight of the screen mesh and the gel after water absorption, M2 is the weight of the screen mesh, and M1 is the dry weight according to the water absorption= (M3-M2-M1)/M1;
degradation time: weighing 75mg of snailase, dissolving in 50nl of buffer solution of acetic acid and sodium acetate, and stirring at 40 ℃ to measure degradation rate;
gel strength: taking 1g of solid water or saturated gel after the water-absorbent resin is fully swelled, and recording compression deformation resistance after 5min = initial height-final height under 50g weight pressure by using a altimeter;
| sequence number/item | Water absorption rate | Water retention (%) | Salt absorption rate | Degradation time | Compression set (cm) |
| Example 1 | 633 | 65.4 | 87 | 55 | 1.7 |
| Example 2 | 602 | 79.5 | 98 | 48 | 1.9 |
| Example 3 | 615 | 63.9 | 95 | 51 | 1.5 |
| Comparative example | 365 | 45.1 | 73 | Cannot be completely degraded | 3.6 |
The L-lysine contains hydrophilic side amino, and is grafted, acidified and modified with acrylic acid/citraconic anhydride under the activation action of an initiator azodiisobutyronitrile, and is thermally activated through a microwave stirring reaction, so that a branched chain is grafted and added, vinyl and carboxyl unsaturated olefin monomers are introduced, and the L-lysine is used as a cross-linking agent to effectively improve the hydrophilicity, swelling rate and biodegradability of degradable solid water and increase the reactivity;
stirring polylactic acid with low molecular weight and weight average molecular weight less than or equal to 5000, 1,4 butanediol, a catalyst sodium sulfate or stannous chloride under microwave for reaction, wherein microwave power is 120-230W, temperature is 120-130 ℃, hydroxyl end sealing polylactic acid is carried out, and then trifunctional isocyanate is subjected to chain extension under microwave, wherein the isocyanate comprises Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI) and 1, 5-Naphthalene Diisocyanate (NDI) to generate a carbamate bond and an amide bond, and the temperature is raised to 140-150 ℃ to avoid the decrease of the molecular weight of the product or the widening of molecular weight distribution and reduce side reaction, so that hetero atoms are introduced on a C-C framework and are easy to be completely degraded by microorganisms;
the method is characterized in that partially neutralized acrylic acid is used as a monomer, one or more of mineral separation kaolin, dolomite powder, attapulgite clay and montmorillonite powder are used as a filler, chain-extended polylactic acid is used as a monomer raw material, and is crosslinked and compounded with self-made crosslinking agent, initiator ammonium persulfate or potassium persulfate and phase transfer catalyst benzyl triethyl ammonium chloride or tetrabutyl ammonium bisulfate under microwaves, so that polyvalent metal ions in mineral separation increase polymerization reaction speed, crosslinking degree and gelation, thereby increasing water absorption rate and gel strength, being cheap and easily available in raw materials, increasing salt-tolerant alkalinity and adapting to soil environments with different salt alkalinity;
the mineral separation and chain extension polylactic acid are compounded to control the crosslinking degree, the microwave power is 300-350W, the temperature is 160-170 ℃, the stirring speed is 40-80r/min, the yield is improved, an interpenetrating crosslinked network structure is formed, the water retention and the thermal stability are improved, the surface crosslinking density is higher than the center, the water absorption, the water retention, the gel mechanical strength and the salt and alkali resistance are improved, the solid hydrogel is taken to be chopped, dried, ground and screened to obtain a hydrophilic and water-insoluble polymer soil improvement solid water finished product, and the synthesis process is simplified by a polymerization device of microwave radiation, so that the large-scale production is facilitated;
when in use, the solid water is mixed with water to form gel, and then the gel is stirred into seeds or is sprayed into planting holes to cover soil, and then watering or rainfall is carried out, the solid water absorbs and stores redundant moisture in soil, including fertilizer dissolved in water, and slowly releases the water under the action of microbial degradation, so that the soil is kept moist, a large number of pores are formed for the soil under the action of repeated shrinkage and swelling, the air permeability and the water permeability of the soil are improved, the plant root planting environment is improved, the soil matrix is improved, the soil hardening and salinization are prevented, and the soil improvement effect is achieved.
In the description of the present invention, it should be understood that the terms "center", "longitudinal", "lateral", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", etc. indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, are merely for convenience in describing the present invention and simplifying the description, and do not indicate or imply that the devices or elements referred to must have a specific orientation, be configured and operated in a specific orientation, and thus should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first", "a second", etc. may explicitly or implicitly include one or more such feature. In the description of the invention, unless otherwise indicated, the meaning of "a number" is two or more.
In the description of the present invention, it should be noted that, unless explicitly specified and limited otherwise, the terms "mounted," "connected," and "connected" are to be construed broadly, and may be either fixedly connected, detachably connected, or integrally connected, for example; can be mechanically or electrically connected; can be directly connected or indirectly connected through an intermediate medium, and can be communication between two elements. The specific meaning of the above terms in the present invention can be understood by those of ordinary skill in the art in a specific case.
The present invention is not limited to the above-mentioned embodiments, and any changes or substitutions that can be easily understood by those skilled in the art within the technical scope of the present invention are intended to be included in the scope of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.
Claims (6)
1. The polymer soil improvement solid water polymerization reaction method is characterized in that polylactic acid, 1,4 butanediol and a catalyst are placed in a polymerization device to be stirred and reacted under microwaves, isocyanate is added to continue to react, and then the polylactic acid with chain extension is obtained after export and cooling; diluting NaOH and deionized water, putting into a polymerization device, adding acrylic acid, stirring for neutralization, adding a cross-linking agent, mineral powder, chain-extended polylactic acid, an initiator and a phase transfer catalyst, performing cyclic reaction under microwaves to obtain solid hydrogel, and cutting, drying, grinding and sieving the solid hydrogel to obtain a solid water finished product;
the cross-linking agent is prepared by dissolving L-lysine in dichloromethane, adding acrylic acid for circulating dispersion, adding citraconic anhydride and azodiisobutyronitrile, and carrying out stirring and circulating polymerization reaction in a polymerization device under microwaves.
2. The polymer soil improvement solid water polymerization reaction method according to claim 1, wherein the mass ratio of polylactic acid to 1,4 butanediol to isocyanate is 55-65:35-45:25-35, and the weight average molecular weight of the polylactic acid is less than or equal to 5000.
3. The polymer soil improvement solid water polymerization reaction method according to claim 1, wherein the catalyst is sodium sulfate or stannous chloride accounting for 0.5% of the total mass of polylactic acid and 1,4 butanediol, the microwave power is 120-230W, the temperature is 120-130 ℃, the stirring rate is 50-60r/min, the reaction is carried out for 30-60min, and the temperature is raised to 140-150 ℃ after the isocyanate is added, and the reaction is continued for 1-2h.
4. The polymer soil improvement solid water polymerization reaction method according to claim 1, wherein the mass ratio of the L-lysine, the acrylic acid, the citraconic anhydride and the azobisisobutyronitrile to the crosslinking agent is 85-120:75-95:120-200:0.1-0.3, microwave power of 20-50W, temperature of 40-50 ℃, stirring speed of 80-100r/min, and reacting for 30-60 min.
5. The method for polymerizing polymer soil improvement solid water according to claim 1, wherein the mineral powder is one or more of kaolin, dolomite powder, attapulgite clay and montmorillonite powder, the initiator is ammonium persulfate or potassium persulfate, and the phase transfer catalyst is benzyl triethyl ammonium chloride or tetrabutyl ammonium bisulfate.
6. The polymer soil improvement solid water polymerization reaction method according to claim 1, wherein the neutralization degree is 60-70%, and the mass ratio of the acrylic acid, the cross-linking agent, the mineral powder, the chain-extended polylactic acid, the initiator and the phase transfer catalyst is 20-30:0.05-0.1:6-11:5-9:0.05:0.1, the microwave power is 300-350W, the temperature is 160-170 ℃, and the stirring speed is 40-80r/min for reaction for 1-2h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110952708.7A CN113667150B (en) | 2021-08-19 | 2021-08-19 | Polymer soil improvement solid water polymerization reaction method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110952708.7A CN113667150B (en) | 2021-08-19 | 2021-08-19 | Polymer soil improvement solid water polymerization reaction method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113667150A CN113667150A (en) | 2021-11-19 |
| CN113667150B true CN113667150B (en) | 2024-04-16 |
Family
ID=78543788
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110952708.7A Active CN113667150B (en) | 2021-08-19 | 2021-08-19 | Polymer soil improvement solid water polymerization reaction method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113667150B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101134793A (en) * | 2007-08-17 | 2008-03-05 | 广东工业大学 | Method for synthesizing completely biological degradable high-absorbent resin by anti-phase suspension polymerization |
| CN102206319A (en) * | 2011-04-19 | 2011-10-05 | 华南农业大学 | Microwave-assisted synthesis method for polylactic acid material |
| WO2012006278A2 (en) * | 2010-07-05 | 2012-01-12 | Reluceo, Inc. | Degradable superabsorbent polymers |
| CN109824831A (en) * | 2019-01-29 | 2019-05-31 | 江苏常源新材料科技有限公司 | A kind of preparation method of degradable high-performance water-absorbing resin |
| CN112662152A (en) * | 2020-12-23 | 2021-04-16 | 山西生物质新材料产业研究院有限公司 | Polylactic acid-based degradable composite material, preparation method and application of polylactic acid-based degradable composite material as mulching film |
-
2021
- 2021-08-19 CN CN202110952708.7A patent/CN113667150B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101134793A (en) * | 2007-08-17 | 2008-03-05 | 广东工业大学 | Method for synthesizing completely biological degradable high-absorbent resin by anti-phase suspension polymerization |
| WO2012006278A2 (en) * | 2010-07-05 | 2012-01-12 | Reluceo, Inc. | Degradable superabsorbent polymers |
| CN102206319A (en) * | 2011-04-19 | 2011-10-05 | 华南农业大学 | Microwave-assisted synthesis method for polylactic acid material |
| CN109824831A (en) * | 2019-01-29 | 2019-05-31 | 江苏常源新材料科技有限公司 | A kind of preparation method of degradable high-performance water-absorbing resin |
| CN112662152A (en) * | 2020-12-23 | 2021-04-16 | 山西生物质新材料产业研究院有限公司 | Polylactic acid-based degradable composite material, preparation method and application of polylactic acid-based degradable composite material as mulching film |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113667150A (en) | 2021-11-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0195406B1 (en) | Process for producing highly water-absorbing polymer | |
| US6969750B2 (en) | Water absorbent material and absorbent article using same | |
| Li et al. | Synthesis, characterization and water absorbency properties of poly (acrylic acid)/sodium humate superabsorbent composite | |
| CN101638461B (en) | Method for synthesizing super absorbent resin containing phosphorus and nitrogen by graft copolymerization reaction of potato starch organic phosphate | |
| JPH0519563B2 (en) | ||
| CN113667150B (en) | Polymer soil improvement solid water polymerization reaction method | |
| CN108559035B (en) | Method for modifying super absorbent resin by using main components of papermaking black liquor and material thereof | |
| CN105111407A (en) | Method for preparing biodegradable ocean antifouling polyurethane hybrid materials and product thereof | |
| US6653399B2 (en) | Water absorbent material | |
| JP2023509980A (en) | Biodegradable Super Absorbent Resin and Method for Producing Same | |
| CN106632949A (en) | Oligochitosan or derivative-modified polyurethane fiber dressing and preparation method thereof | |
| CN109135757A (en) | A kind of preparation method of compound water retaining agent | |
| CN102526810A (en) | Artificial skin alternative material and preparation method thereof | |
| CN109824831A (en) | A kind of preparation method of degradable high-performance water-absorbing resin | |
| CN108715765A (en) | A method of hemicellulose group water-retaining agent being prepared by microchannel reaction unit using hemicellulose lotion | |
| Trirahayu et al. | Synthesis and Performance Evaluation of Cellulose-based Slow-release Fertilizer: A Review | |
| CN115215977B (en) | Multi-nutrient element functional water-retaining agent and preparation method thereof | |
| Hua et al. | Preparation and properties of superabsorbent containing starch and sodium humate | |
| KR20180119191A (en) | Super absorbent resin comprising biodegradable acrylic crosslinker and preparation method thereof | |
| CN105524283A (en) | Hemicellulose based water absorption and retention material and preparation method therefor | |
| CN1046738C (en) | Method for preparation of starch graft copolymer acrylic acid (acrylate) super water-absorbing agent | |
| CN112279979A (en) | Biodegradable sandy soil water and fertilizer retention agent | |
| JPS6236411A (en) | Production of highly water-absorptive polymer | |
| EP1236507A2 (en) | Water absorbent material comprising polysaccharide derivatives | |
| Vedaiyan et al. | Starch Modified Tough Biocompatible Polyurethane/Acrylamide Bio Composites: Physicochemical Properties and Biodegradation Studies |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20240129 Address after: Room A703, University Entrepreneurship Park, No. 99 Daxue Road, High tech Industrial Development Zone, Xuzhou City, Jiangsu Province, 221000 Applicant after: Jiangsu Qingke Mucheng New Materials Research Institute Co.,Ltd. Country or region after: China Address before: Room A705, 99 University Road, Tongshan District, Xuzhou City, Jiangsu Province, 221000 Applicant before: Xuzhou Moda New Material Technology Co.,Ltd. Country or region before: China |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |