CN110540468A - 笼型倍半硅氧烷改性原位反应成膜型包膜控释肥及其制备方法 - Google Patents
笼型倍半硅氧烷改性原位反应成膜型包膜控释肥及其制备方法 Download PDFInfo
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- CN110540468A CN110540468A CN201910938471.XA CN201910938471A CN110540468A CN 110540468 A CN110540468 A CN 110540468A CN 201910938471 A CN201910938471 A CN 201910938471A CN 110540468 A CN110540468 A CN 110540468A
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- polyol
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- 239000003337 fertilizer Substances 0.000 title claims abstract description 81
- 238000013270 controlled release Methods 0.000 title claims abstract description 59
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 33
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000011248 coating agent Substances 0.000 claims abstract description 39
- 238000000576 coating method Methods 0.000 claims abstract description 37
- 229920005862 polyol Polymers 0.000 claims abstract description 28
- 150000003077 polyols Chemical class 0.000 claims abstract description 28
- 239000002245 particle Substances 0.000 claims abstract description 23
- 239000012948 isocyanate Substances 0.000 claims abstract description 18
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 18
- 239000011247 coating layer Substances 0.000 claims abstract description 14
- 239000002114 nanocomposite Substances 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 17
- 239000004202 carbamide Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 16
- -1 bismuth carboxylate Chemical class 0.000 claims description 14
- 239000012752 auxiliary agent Substances 0.000 claims description 13
- 239000005056 polyisocyanate Substances 0.000 claims description 12
- 229920001228 polyisocyanate Polymers 0.000 claims description 12
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 12
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 10
- 229920000570 polyether Polymers 0.000 claims description 10
- 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 claims description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 8
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 8
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 8
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 7
- 239000004359 castor oil Substances 0.000 claims description 7
- 235000019438 castor oil Nutrition 0.000 claims description 7
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 150000002009 diols Chemical class 0.000 claims description 6
- 239000008187 granular material Substances 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- 229910021536 Zeolite Inorganic materials 0.000 claims description 4
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 4
- 235000011187 glycerol Nutrition 0.000 claims description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000002808 molecular sieve Substances 0.000 claims description 4
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 4
- 235000012424 soybean oil Nutrition 0.000 claims description 4
- 239000003549 soybean oil Substances 0.000 claims description 4
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 4
- 239000008158 vegetable oil Substances 0.000 claims description 4
- 239000010457 zeolite Substances 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 3
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 claims description 2
- VZXPHDGHQXLXJC-UHFFFAOYSA-N 1,6-diisocyanato-5,6-dimethylheptane Chemical compound O=C=NC(C)(C)C(C)CCCCN=C=O VZXPHDGHQXLXJC-UHFFFAOYSA-N 0.000 claims description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 2
- WUKNPIYSKBLCQI-UHFFFAOYSA-N CC(C=C1)=CC=C1C1=CC=C(C)C=C1.N=C=O.N=C=O Chemical compound CC(C=C1)=CC=C1C1=CC=C(C)C=C1.N=C=O.N=C=O WUKNPIYSKBLCQI-UHFFFAOYSA-N 0.000 claims description 2
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 claims description 2
- 239000005696 Diammonium phosphate Substances 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 claims description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- BVFSYZFXJYAPQJ-UHFFFAOYSA-N butyl(oxo)tin Chemical compound CCCC[Sn]=O BVFSYZFXJYAPQJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 2
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- 239000006012 monoammonium phosphate Substances 0.000 claims description 2
- 229960002446 octanoic acid Drugs 0.000 claims description 2
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 claims description 2
- 229920005906 polyester polyol Polymers 0.000 claims description 2
- 229920000098 polyolefin Polymers 0.000 claims description 2
- 235000011056 potassium acetate Nutrition 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 235000010333 potassium nitrate Nutrition 0.000 claims description 2
- 239000004323 potassium nitrate Substances 0.000 claims description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 2
- 235000011151 potassium sulphates Nutrition 0.000 claims description 2
- SXWZSWLBMCNOPC-UHFFFAOYSA-M potassium;6-methylheptanoate Chemical compound [K+].CC(C)CCCCC([O-])=O SXWZSWLBMCNOPC-UHFFFAOYSA-M 0.000 claims description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 2
- 239000013638 trimer Substances 0.000 claims description 2
- 150000004072 triols Chemical class 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims 2
- 239000000654 additive Substances 0.000 claims 1
- 235000019270 ammonium chloride Nutrition 0.000 claims 1
- 235000013877 carbamide Nutrition 0.000 claims 1
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- 239000000126 substance Substances 0.000 abstract description 5
- 125000000524 functional group Chemical group 0.000 abstract description 3
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- 238000002715 modification method Methods 0.000 abstract description 3
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 230000009471 action Effects 0.000 description 6
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- 238000007654 immersion Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000010907 mechanical stirring Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 235000015097 nutrients Nutrition 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
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- 239000002904 solvent Substances 0.000 description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 235000019482 Palm oil Nutrition 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 210000003746 feather Anatomy 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000021048 nutrient requirements Nutrition 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- 239000010893 paper waste Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
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- 239000002689 soil Substances 0.000 description 1
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- 239000010902 straw Substances 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229940100445 wheat starch Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C9/00—Fertilisers containing urea or urea compounds
-
- 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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
-
- 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
- C08G18/61—Polysiloxanes
-
- 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
- C08G18/6547—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/36 or hydroxylated esters of higher fatty acids of C08G18/38
-
- 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
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
-
- 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
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/778—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur silicon
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/08—Polyurethanes from polyethers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Fertilizers (AREA)
Abstract
本发明公开了一种笼型倍半硅氧烷改性原位反应成膜型包膜控释肥及其制备方法。该包膜肥料，由肥料颗粒和包裹在所述肥料颗粒表面的纳米复合包膜层组成；其中，所述纳米复合包膜层材料所用原料包括异氰酸酯、多元醇、含笼型倍半硅氧烷的助剂。本发明提供的包膜控释肥利用粒径约为1‑10nm的含笼型结构的纳米粒子表面的官能团类型和个数的不同，通过化学键合改性的方法制备包膜率低且控释性能优良的POSS改性原位反应成膜型包膜控释肥。
Description
技术领域
本发明属于控释肥料领域，涉及一种笼型倍半硅氧烷改性原位反应成膜型包膜控释肥及其制备方法。
背景技术
包膜控释肥是指能够根据植物不同生长阶段的营养需求特点，调节养分的释放速率及供应强度，使其养分释放模式与作物吸肥同步的新型肥料，不但提高了肥料的利用率，而且减少了化学肥料对环境造成的污染。
包膜的构成与性质直接影响养分释放的模式和时间，因此，在包膜控释肥料的研制中，核心之一是包膜材料的筛选与优化。根据介质的不同，聚合物包膜材料可分为有机溶剂型、水型及无溶剂型等三种主要类型。有机溶剂型是将热塑性树脂高温溶解在有机溶剂后，喷涂到肥料表面成膜制成。由于包膜液中含有大量溶剂，在制备过程中对设备密封和溶剂回收等有严格要求，所以其应用受到制约。
水型的生产虽然采用的是绿色生产工艺，但是水基聚合物包膜剂的研发尚存在一些不足。一方面，目前的包膜剂溶液形成膜层的水渗透性较强，控释效果不理想；另一方面，包膜过程中水分在颗粒表面容易形成高湿性环境，部分肥料溶解再结晶将导致聚合物膜层严重受损，从而破坏控释效果。
近十年来，国内外越来越多的研究单位将重点放在无溶剂原位反应成膜上，即将小分子单体直接在肥料表面反应成膜制备包膜控释肥，设备简单且易实现连续化。Bortoletto-Santos等采用蓖麻油制备了聚氨酯包膜控释肥，包膜率约为4％时，肥料释放期为40天。杨越超等采用废煎炸棕榈油为包膜原料制备包膜控释尿素，与常规生物基包膜控释尿素相比，其控释期从50天延长为80天；该团队采用玉米秸和羽毛粉的液化产物制备的保水控释双层包膜具有延缓氮素释放和增加保水性的双重功效。张民等研究了淀粉、小麦秸秆、废纸的液化产物与固化剂原位反应制备聚氨酯包膜或复合包膜控释肥，该类包膜在土壤中具有良好的降解性。
虽然研究者们已对原位反应成膜型包膜控释肥进行了大量的研究，但是在制备过程中仍存在一些难点：当包膜率(包膜在控释肥中的质量百分含量)低于5％时，膜层微观结构对包膜肥料性能的影响变得尤为突出。要想制备同时具备良好控释性和低包膜率的原位反应成膜型包膜控释肥仍存在一定的困难。
发明内容
本发明的目的是提供一种笼型倍半硅氧烷(polyhedral oligomericsilsesquioxane，POSS)改性原位反应成膜型包膜控释肥及其制备方法。针对现有技术中当包膜率低时，膜层质量差的问题，利用含笼型结构的纳米粒子表面的官能团类型和个数的不同，通过化学键合改性的方法制备成膜性优良的POSS改性原位反应成膜型包膜控释肥。
本发明要求保护笼型倍半硅氧烷或笼型倍半硅氧烷和助剂在制备肥料中的应用；
本发明还要求保护含有笼型倍半硅氧烷的肥料或含有笼型倍半硅氧烷和助剂的肥料。
具体的，所述肥料为包膜控释肥；具体为聚合物包膜控释肥；更具体为所述原位反应成膜型包膜控释肥；
所述笼型倍半硅氧烷(POSS)的分子式为(RSiO3/2)n，其中，n为7或8；R选自羟基、聚乙二醇基和异氰酸酯基中至少一种；所述笼型倍半硅氧烷具体选自三羟基-七异丁基POSS、三硅醇基异丁基POSS、聚乙二醇基POSS、异氰酸酯基POSS中至少一种；所述笼型倍半硅氧烷(POSS)的粒径为1-10nm；
所述助剂选自乙二醇、丁二醇、戊二醇、三羟甲基丙烷、双羟乙基苯胺、甘油、沸石分子筛、二月桂酸二丁基锡、二硫醇二烷基锡、辛酸亚锡、单丁基氧化锡、二甲基环己胺、三亚乙基二胺、三乙醇胺、异辛酸钾、醋酸钾和羧酸铋中至少一种；
所述笼型倍半硅氧烷与所述助剂的质量比为0.3-8：0.5-5；具体可为2:0.5、3.5:2、0.35:2.15、1:2.25或1:2；
本发明还要求保护一种原位反应成膜型包膜控释肥，该原位反应成膜型包膜控释肥由肥料颗粒和包裹在所述肥料颗粒表面的纳米复合包膜层组成；其中，制备所述纳米复合包膜层的原料包括异氰酸酯、多元醇和所述液态笼型倍半硅氧烷和/或助剂。
具体的，所述肥料颗粒为水溶性单质肥料或由所述水溶性单质肥料中的至少两种混合得到的复混肥；其中，所述水溶性单质肥料具体选自尿素、硫酸铵、氯化铵、硝酸铵、磷酸一铵、磷酸二铵、氯化钾、硫酸钾、硝酸钾、硫酸镁、硝酸镁、硫酸锌、硫酸铜和氯化锌中至少一种；
所述异氰酸酯选自多亚甲基多苯基多异氰酸酯、甲苯二异氰酸酯、六亚甲基二异氰酸酯、二苯基甲烷二异氰酸酯(MDI)、液化MDI、异佛尔酮二异氰酸酯、1,6-己二异氰酸酯(HDI)、HDI的三聚体、三甲基六亚甲基二异氰酸酯，苯二亚甲基二异氰酸酯和二甲基联苯二异氰酸酯中至少一种；
具体的，所述多亚甲基多苯基多异氰酸酯可为购于德国拜耳公司，牌号为Desmodur 44V20的产品或购于烟台万华公司，牌号为PM200；所述液化MDI可购于烟台万华，型号为PMM-10；
所述多元醇选自聚醚多元醇、植物油多元醇、聚酯多元醇和聚烯烃多元醇中至少一种，所述多元醇的相对分子质量为200-3000；所述多元醇具体选自聚四氢呋喃二醇、聚醚三醇、聚醚二醇、蓖麻油和大豆油多元醇中的至少一种。
所述纳米复合包膜层质量为所述肥料颗粒质量的1.5-5％；
所述助剂的质量为所述纳米复合包膜层质量的0.5-5％；
所述笼型倍半硅氧烷质量为所述纳米复合包膜层质量的0.3-8％；具体可为2.1％、0.5％、5％、2.6％或2％。
所述异氰酸酯质量为所述纳米复合包膜层质量的30-50％；
余量为所述多元醇。
具体的，所述原位反应成膜型包膜控释肥可由如下各种配比的原料制得：
1kg尿素、0.4g三硅醇基异丁基POSS、5.4g植物油多元醇蓖麻油、0.1g助剂甘油、3.5g多亚甲基多苯基多异氰酸酯；或，
1kg尿素、0.7g三羟基-七异辛基POSS、7.8g聚四氢呋喃二醇、0.3g助剂三乙醇胺、0.1g助剂辛酸亚锡、4.2g液化MDI；或，
1kg尿素、0.07g聚乙二醇基POSS、4.8g聚醚三醇、3g聚醚二醇、0.43g三亚乙基二胺、4.7g多亚甲基多苯基多异氰酸酯；或，
1kg尿素、4.3g蓖麻油、0.3g助剂丁二醇、0.15g助剂三乙醇胺、0.2g异氰酸酯基POSS、2.8g多亚甲基多苯基多异氰酸酯；或，
1kg撒克富复合肥(N-P-K：15-15-15)、0.2g氰酸酯基POSS、5.2g大豆油多元醇、0.3g助剂沸石分子筛、0.1g助剂三乙醇胺、4.3g多亚甲基多苯基多异氰酸酯；
本发明提供的制备上述原位反应成膜型包膜控释肥的方法，包括如下步骤：
1)将肥料颗粒预热；
2)按照配比，将所述笼型倍半硅氧烷、助剂和多元醇混匀，预热，得到包膜液a；
或者，按照配比，将所述多元醇和助剂混匀，预热，得到包膜液b；
3)将步骤2)所得包膜液a和所述异氰酸酯同时雾化于步骤1)所得肥料颗粒表面，得到所述原位反应成膜型包膜控释肥；
或者，将步骤2)所得包膜液b、所述异氰酸酯和所述笼型倍半硅氧烷同时雾化于步骤1)所得肥料颗粒表面，得到所述原位反应成膜型包膜控释肥。
上述方法的所述步骤1)预热步骤中，预热装置为转鼓或流化床；预热温度为60-80℃；
所述步骤2)中，预热步骤中，温度为80-100℃。
本发明提供的包膜控释肥利用粒径约为1-10nm的含笼型结构的纳米粒子表面的官能团类型和个数的不同，通过化学键合改性的方法制备得到了包膜率低且控释性能优良的POSS改性原位反应成膜型包膜控释肥。
具体实施方式
下面结合具体实施例对本发明作进一步阐述，但本发明并不限于以下实施例。所述方法如无特别说明均为常规方法。除异氰酸酯基POSS外所述POSS均为美国HybridPlastics公司的产品，所述原材料如无特别说明均能从公开商业途径而得。下述实施例所用所述多元醇的相对分子质量均为200-3000。所用所述笼型倍半硅氧烷(POSS)的粒径均为1-10nm。
实施例1、
称取1kg尿素颗粒，置于转鼓中，预热至70℃；将0.4g三硅醇基异丁基POSS(n为7，质量分数2.1％)加入装有5.4g植物油多元醇蓖麻油、0.1g助剂甘油的溶解罐中，恒温至80℃，并在机械力搅拌作用下混合均匀，获得包膜液。将包膜液与3.5g多亚甲基多苯基多异氰酸酯(购于德国拜耳公司，牌号为Desmodur 44V20)同时雾化于预热的尿素颗粒表面进行原位反应成膜，保温3-5分钟，该喷涂过程进行2次，包膜率为1.8％。喷涂完成后，先将热源取出，再慢慢冷却。采用水浸泡法测定其控释性能，初期溶出率为2％，控释期为60天。
实施例2、
称取1kg尿素颗粒，置于转鼓中，预热至70℃；将0.7g三羟基-七异辛基POSS(n为8，质量分数5％)加入装有7.8g聚四氢呋喃二醇(购于德国BASF公司，牌号为PolyTHF 1000)、0.3g助剂三乙醇胺、0.1g助剂辛酸亚锡的溶解罐中，恒温至80℃，并在机械力搅拌作用下混合均匀，获得包膜液。将包膜液与4.2g液化MDI(购于烟台万华，型号为PMM-10)同时雾化于预热的尿素颗粒表面进行原位反应成膜，保温3-5分钟，该喷涂过程进行2次，包膜率为2.5％。喷涂完成后，先将热源取出，再慢慢冷却。采用水浸泡法测定其控释性能，初期溶出率为2％，控释期为90天。
实施例3、
称取1kg尿素颗粒，置于转鼓中，预热至70℃；将0.07g聚乙二醇基POSS(n为8，质量分数0.5％)加入装有4.8g聚醚三醇和3g聚醚二醇(购于江苏钟山化工，牌号分别为N330和N220)、0.43g三亚乙基二胺的溶解罐中，恒温至80℃，并在机械力搅拌作用下混合均匀，获得包膜液。将包膜液与4.7g多亚甲基多苯基多异氰酸酯(购于德国拜耳公司，牌号为Desmodur 44V20)同时雾化于预热的尿素颗粒表面进行原位反应成膜，保温3-5分钟，该喷涂过程进行4次，包膜率为5％。喷涂完成后，先将热源取出，再慢慢冷却。采用水浸泡法测定其控释性能，初期溶出率为0.1％，控释期为180天。
实施例4、
异氰酸酯基POSS的合成：从11g八铵盐POSS出发，在50mLN,N-二甲基甲酰胺中与10mL多亚甲基多苯基多异氰酸酯(购于烟台万华公司，牌号为PM200)在室温下反应2h，然后旋蒸、干燥而得。
称取1kg尿素颗粒，置于转鼓中，预热至70℃；将装有4.3g蓖麻油、0.3g助剂丁二醇、0.15g助剂三乙醇胺的溶解罐恒温至80℃，在机械力搅拌作用下混合均匀，获得包膜液；将0.2g合成好的异氰酸酯基POSS(n为8，质量分数2.6％)加入装有2.8g多亚甲基多苯基多异氰酸酯(购于烟台万华公司，牌号为PM200)的溶解罐中恒温至80℃，并在机械力搅拌作用下混合均匀，获得固化剂；将所得的包膜液和固化剂同时雾化于预热的尿素颗粒表面进行原位反应成膜，保温3-5分钟，该喷涂过程进行2次，包膜率为1.5％。喷涂完成后，先将热源取出，再慢慢冷却。采用水浸泡法测定其控释性能，初期溶出率为0.1％，控释期为30天。
实施例5、
称取1kg撒克富复合肥(N-P-K：15-15-15)，置于转鼓中，预热至60℃；将0.2g合成好的异氰酸酯基POSS(n为8，质量分数2％)加入装有5.2g大豆油多元醇(购于美国USSC公司，牌号为Soyoyl R137)、0.3g助剂沸石分子筛(购于法国Atofina公司，牌号为SiliporiteSA1720)、0.1g助剂三乙醇胺的溶解罐中，恒温至80℃，并在机械力搅拌作用下混合均匀，获得包膜液。将所得的包膜液和4.3g多亚甲基多苯基多异氰酸酯(购于烟台万华公司，牌号为PM200)同时雾化于预热的尿素颗粒表面进行原位反应成膜，保温3-5分钟，该喷涂过程进行2次，包膜率为2％。喷涂完成后，先将热源取出，再慢慢冷却。采用水浸泡法测定其控释性能，初期溶出率为0.1％，控释期为90天。
对照例1、
与实施例1基本相同，不同之处为不含POSS。采用水浸泡法测定其控释性能，初期溶出率为6.2％，控释期为30天。
Claims (8)
1.笼型倍半硅氧烷或笼型倍半硅氧烷和助剂在制备肥料中的应用；
含有笼型倍半硅氧烷的肥料或含有笼型倍半硅氧烷和助剂的肥料。
2.根据权利要求1所述的应用或肥料，其特征在于：所述肥料为包膜控释肥；具体为聚合物包膜控释肥；更具体为权利要求3-5任一所述原位反应成膜型包膜控释肥；
所述笼型倍半硅氧烷的分子式为(RSiO3/2)n，其中，n为7或8；R选自羟基、聚乙二醇基和异氰酸酯基中至少一种；所述羟基具体选自三羟基-七异丁基和三硅醇基异丁基中至少一种；
所述助剂选自乙二醇、丁二醇、戊二醇、三羟甲基丙烷、双羟乙基苯胺、甘油、沸石分子筛、二月桂酸二丁基锡、二硫醇二烷基锡、辛酸亚锡、单丁基氧化锡、二甲基环己胺、三亚乙基二胺、三乙醇胺、异辛酸钾、醋酸钾和羧酸铋中至少一种；
所述笼型倍半硅氧烷与所述助剂的质量比为0.3-8：0.5-5。
3.一种原位反应成膜型包膜控释肥，由肥料颗粒和包裹在所述肥料颗粒表面的纳米复合包膜层组成；制备所述纳米复合包膜层的原料包括异氰酸酯、多元醇和权利要求1或2所述液态笼型倍半硅氧烷和/或助剂。
4.根据权利要求3所述的原位反应成膜型包膜控释肥，其特征在于：所述肥料颗粒为水溶性单质肥料或由所述水溶性单质肥料中的至少两种混合得到的复混肥；其中，所述水溶性单质肥料具体选自尿素、硫酸铵、氯化铵、硝酸铵、磷酸一铵、磷酸二铵、氯化钾、硫酸钾、硝酸钾、硫酸镁、硝酸镁、硫酸锌、硫酸铜和氯化锌中至少一种；
所述异氰酸酯选自多亚甲基多苯基多异氰酸酯、甲苯二异氰酸酯、六亚甲基二异氰酸酯、二苯基甲烷二异氰酸酯(MDI)、液化MDI、异佛尔酮二异氰酸酯、1,6-己二异氰酸酯(HDI)、HDI的三聚体、三甲基六亚甲基二异氰酸酯，苯二亚甲基二异氰酸酯和二甲基联苯二异氰酸酯中至少一种；
所述多元醇选自聚醚多元醇、植物油多元醇、聚酯多元醇和聚烯烃多元醇中至少一种，所述多元醇的相对分子质量为200-3000；所述多元醇具体选自聚四氢呋喃二醇、聚醚三醇、聚醚二醇、蓖麻油和大豆油多元醇中的至少一种。
5.根据权利要求3或4所述的原位反应成膜型包膜控释肥，其特征在于：所述纳米复合包膜层质量为所述肥料颗粒质量的1.5-5％；
所述助剂的质量为所述纳米复合包膜层质量的0.5-5％；
所述笼型倍半硅氧烷质量为所述纳米复合包膜层质量的0.3-8％；
所述异氰酸酯质量为所述纳米复合包膜层质量的30-50％；
余量为所述多元醇。
6.一种制备权利要求3-5任一所述原位反应成膜型包膜控释肥的方法，包括：
1)将肥料颗粒预热；
2)按照配比，将所述笼型倍半硅氧烷、助剂和多元醇混匀，预热，得到包膜液a；或者，按照配比，将所述多元醇和助剂混匀，预热，得到包膜液b；
3)将步骤2)所得包膜液a和所述异氰酸酯同时雾化于步骤1)所得肥料颗粒表面，得到所述原位反应成膜型包膜控释肥；
或者，将步骤2)所得包膜液b、所述异氰酸酯和所述笼型倍半硅氧烷同时雾化于步骤1)所得肥料颗粒表面，得到所述原位反应成膜型包膜控释肥。
7.根据权利要求6所述的方法，其特征在于：所述步骤1)预热步骤中，预热装置为转鼓或流化床；预热温度为60-80℃；
所述步骤2)中，预热步骤中，温度为80-100℃。
8.权利要求3-5中任一所述原位反应成膜型包膜控释肥在施肥中的应用；
含有权利要求3-5中任一所述原位反应成膜型包膜控释肥的肥料。
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