CN106749900A - A kind of water-soluble ter-polymers phosphate fertilizer synergist and its preparation method and application - Google Patents
A kind of water-soluble ter-polymers phosphate fertilizer synergist and its preparation method and application Download PDFInfo
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- CN106749900A CN106749900A CN201611184112.2A CN201611184112A CN106749900A CN 106749900 A CN106749900 A CN 106749900A CN 201611184112 A CN201611184112 A CN 201611184112A CN 106749900 A CN106749900 A CN 106749900A
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- 229920000642 polymer Polymers 0.000 title claims abstract description 73
- 239000002686 phosphate fertilizer Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000178 monomer Substances 0.000 claims abstract description 46
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims abstract description 44
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000003999 initiator Substances 0.000 claims abstract description 26
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 24
- JPZROSNLRWHSQQ-UHFFFAOYSA-N furan-2,5-dione;prop-2-enoic acid Chemical compound OC(=O)C=C.O=C1OC(=O)C=C1 JPZROSNLRWHSQQ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 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 20
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002689 soil Substances 0.000 claims abstract description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 5
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 4
- 238000009835 boiling Methods 0.000 claims abstract 2
- 239000000243 solution Substances 0.000 claims description 21
- 230000035484 reaction time Effects 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 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
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 5
- 239000012670 alkaline solution Substances 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000007603 infrared drying Methods 0.000 claims description 3
- 238000009413 insulation Methods 0.000 claims description 3
- 238000006386 neutralization reaction Methods 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 235000019394 potassium persulphate Nutrition 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 230000033228 biological regulation Effects 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims 1
- 238000011276 addition treatment Methods 0.000 abstract 1
- 238000007792 addition Methods 0.000 description 13
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 13
- 239000005696 Diammonium phosphate Substances 0.000 description 10
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 10
- 235000019838 diammonium phosphate Nutrition 0.000 description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 7
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- 239000003337 fertilizer Substances 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 235000010755 mineral Nutrition 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000004021 humic acid Substances 0.000 description 3
- 239000002054 inoculum Substances 0.000 description 3
- 238000005457 optimization Methods 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 235000015097 nutrients Nutrition 0.000 description 2
- 230000000050 nutritive effect Effects 0.000 description 2
- 230000037048 polymerization activity Effects 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000003900 soil pollution Methods 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 150000003431 steroids Chemical class 0.000 description 2
- 238000012916 structural analysis Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 241000040710 Chela Species 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 101710097943 Viral-enhancing factor Proteins 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 235000011148 calcium chloride Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000001955 cumulated effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 230000035764 nutrition Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003415 peat Substances 0.000 description 1
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000008055 phosphate buffer solution Substances 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—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; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/02—Acids; Metal salts or ammonium salts thereof, e.g. maleic acid or itaconic acid
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—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; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/04—Anhydrides, e.g. cyclic anhydrides
- C08F222/06—Maleic anhydride
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)
- Pest Control & Pesticides (AREA)
- Fertilizers (AREA)
Abstract
The invention discloses a kind of water-soluble ter-polymers phosphate fertilizer synergist and its preparation method and application.The polymer is polymerized prepared in aqueous by itaconic acid, maleic anhydride, acrylic acid and initiator.Its preparation method：The first itaconic acid after four-hole boiling flask addition treatment, maleic anhydride and appropriate amount of deionized water, it is passed through 7~15min of nitrogen, monomer is heated to be completely dissolved and reach reaction temperature, then in initiator that concentration is 25% and acrylic acid at the uniform velocity being dropped into reaction bulb by constant pressure funnel, completion of dropping, isothermal reaction certain hour, cooling discharge, is obtained IA/MA/AA ter-polymers.The polymer has good water solubility, biological degradability and chelating ability, can improve phosphate fertilizer utilization efficiency and adjust soil pH, has broad application prospects and economic worth.
Description
Technical field
The present invention relates to synergist of phosphate and binary polymerization technical field, a kind of water-soluble ter-polymers are related specifically to
Phosphate fertilizer synergist and its preparation method and application.
Background technology
Phosphorus is one of main nutrient elements necessary to growth and development of plants, and it is both many in plant important organises
The component of compound, while various metabolic processes in involved in plant body in many ways again.Therefore, phosphate fertilizer is played in agricultural production
Extremely important effect.
With industrial expansion, consumption of the phosphate fertilizer in agricultural is continuously increased, due to specific physicochemical character in soil and
Phosphatic chemical behavior, crop is very low to the utilization rate of phosphate fertilizer, this season utilization rate typically only 8%~25%, is not planted
The phosphate fertilizer that thing is utilized can be lost in being fixed on soil with the erosion of soil, cause water pollution, such as eutrophication of water body
Deng.
In recent years, fertilizer synergist was paid much attention to by researcher.Fertilizer synergist is by effectively facilitating plant
Thing improves chemical fertilizer utilization ratio to the absorption of nutrient.Synergistic factor mainly includes 4 major classes：It is humic acids, steroids, many
Element mineral class and high molecular polymerization species.Wherein steroids, multielement mineral class are metabolized by coordinate plant growth, and regulation is planted
Thing increases the absorption of fertilizer the fertilizer efficiency of composite fertilizer；Humic acids product is the extract of the mineral resource such as peat, with not
Renewable, resource-constrained, the shortcomings of amount of application is big；High molecular polymer, such as polyacrylic acid, with its addition it is few, promote plant
Thing biological effect substantially etc. advantage and be increasingly taken seriously.Existing high molecular polymer synergist species is less, biodegradable
Property it is not good, and with phosphate fertilizer be manured into soil in cause soil pollution, be unfavorable for long-run development.
Itaconic acid is nontoxic biological product, is the novel chemical raw material developed in recent years.Not only contain in itaconic acid molecule
Carbon-to-carbon double bond functional group, also containing two carboxyls of unsymmetric structure, the latter assigns itaconic acid copolymer excellent negative electricity dispersion
Performance.Maleic anhydride is a kind of conventional important basic organic chemical industry raw material.It is be only second to aceticanhydride and phthalic anhydride in the world the 3rd
Big anhydride starting material.It is relatively low that maleic anhydride compares price with other carboxylic acid type monomers.Maleic anhydride is hydrolyzed into maleic acid, and maleic acid is special
Some molecular structures increase polymer molecular chain carboxyl density.Substituted olefine has steric effect in two kinds of acid molecular structures causes
Reactivity is relatively low, and the acrylic acid higher with polymerization activity is combined, in polymer is increased on the premise of ensureing higher conversion
Carboxyl density.
The content of the invention
It is an object of the invention to provide a kind of water-soluble polymer phosphate fertilizer synergist and its preparation method and application, this three
Membered copolymer has good water solubility, biological degradability and sequestering, can improve phosphate fertilizer utilization efficiency and adjust soil pH, the conjunction
Easy to operate into Method And Principle reliability, conversion ratio is higher, and cost is relatively low, with wide market prospects.
In order to reach object above, the present invention uses following technical scheme：
Phosphate fertilizer synergist IA/MA/AA involved in the present invention is main from polymer molecule expansion service, intermolecular phase interaction
With etc. principle set out, with itaconic acid, maleic anhydride, acrylic acid as monomer, be prepared using radical copolymerization.
Itaconic acid (IA) is biological fermented product, nontoxic, wide material sources, and its molecule is：
Intramolecular contains two carboxyls, a carbon-carbon double bond, with active chemical property, can carry out poly- between itself
Close, can also be polymerized with other monomers, be dissolved in other solvents such as water, ethanol.
Maleic anhydride (MA) is the third-largest anhydride starting material for being only second to aceticanhydride and phthalic anhydride in the world, and its molecular formula is：
It is relatively low compared to other carboxylic acid type monomer's prices.It is easy to produce hydrogen bond with water, with temperature tolerance, the part of hydrolysis can be with
With calcium, magnesium ion chela and, can so make full use of acid anhydrides, while polymer molecular chain carboxyl density can be increased, improve poly-
The performance of compound.
Acrylic acid (AA), polymerization activity is higher, is a kind of monomer that can be copolymerized with IA, MA, to the greatest extent may be used for copolymer
Conversion ratio higher is ensure that while carboxyl can be introduced more.- COOH- is a kind of group of strong hydration capability, and negative electrical charge
Repulsive interaction contribute to polymer molecule extension improve polymer tackifying ability.
It is flexible with main chain that copolymer IA/MA/AA is, side base is the polymer of carboxyl, it is characterised in that with as follows
Structure：
The synthetic method of the new polymers phosphate fertilizer synergist is as follows：
A () weighs monomer IA, MA, AA, and the initiator ammonium persulfate or persulfuric acid for accounting for monomer gross mass 2%~10%
Potassium, half neutralisation treatment is carried out with alkaline solution NaOH or potassium hydroxide to monomer IA, and initiator is configured into concentration is
25% solution, it is standby；
B IA after MA and treatment is added reactor by (), it is the deionized water of 2.5~9 times of monomer gross mass to add quality,
7~15min of logical nitrogen, stirs and heats, after monomer is completely dissolved and temperature reaches 65~95 DEG C, initiator and acrylic acid is even
Speed drops to reactor, and time for adding controlled in 40~50min；
C 1~6h of () insulation reaction, stops heating and stirs, cooling discharge.IA/MA/AA ter-polymers are obtained；
(d) 40 DEG C of vacuum drying 5h, then 5h is dried with infrared drying oven, crushing obtains polymer powder.Or with solution
Form is preserved.
The present invention has advantages below：(1) biofermentation product itaconic acid IA can be improved into copolymer as monomer
Biological degradability has biological environmental production, reduces soil pollution；(2), used as monomer, price is compared with other carboxylic acids for maleic anhydride MA
Monomer is relatively low to reduce production cost, and increases the performance that polymer molecular chain carboxyl density improves copolymer；(3) polymer system
Preparation Method is simply easily achieved, synthetic yield is higher, cost is relatively low, economical and efficient；(4) compared with the existing humic acids in market, swash
Plain class, multielement mineral class synergist, the polymer has that addition is few, use cost is not high, it is economic and environment-friendly, promote plant to give birth to
Thing effect substantially etc. advantage.
Brief description of the drawings
Fig. 1 is the infrared spectrum of the present embodiment 2.
Specific embodiment
Embodiment 1
Preparing for ter-polymers IA/MA/AA is as follows
The preparation of polymer is as follows：A () weighs mol ratio for IA：MA：AA=1：1：1 (each 0.5mol), and
The initiator ammonium persulfate or potassium peroxydisulfate of monomer gross mass 2%~10% are accounted for, with alkaline solution NaOH or hydroxide
Potassium carries out half neutralisation treatment to monomer IA, and initiator is configured into the solution that concentration is 25%, standby；B () is by after MA and treatment
IA add reactor, it is the deionized water of 2.5~9 times of monomer gross mass to add quality, leads to nitrogen 7~15min, stirs and adds
Heat, after monomer is completely dissolved and temperature reaches 65~95 DEG C, by initiator and acrylic acid at the uniform velocity drop to reactor, be added dropwise
Time control is in 40~50min；C 1~6h of () insulation reaction, stops heating and stirs, cooling discharge.IA/MA/AA ternarys are obtained
Polymer；(d) 40 DEG C of vacuum drying 5h, then 5h is dried with infrared drying oven, crushing obtains polymer powder.Or with the shape of solution
Formula is preserved.
The principal element that influence prepares polymer IA/MA/AA has：Reaction temperature, reaction time, initiator addition, list
Body total concentration.To determine preferably synthesis condition, this example is adopted with the following method：By polymer obtained in different condition spend from
Sub- water is configured to the polymer solution of 100mg/mL, and the chelating ability of polymer is then determined with standard calcium volumetric soiutions, thus selects
Fixed more excellent formula.
First, reaction temperature
In monomer mole ratio IA：MA：AA=1：1：1 (each 0.5mol), securing unit mass concentration are that 15%, initiator adds
Enter amount be monomer mass 6%, reaction time 4h, change reaction temperature be 60~65 DEG C, 70~75 DEG C, 80~85 DEG C, 90~
95 DEG C, different polymer IA/MA/AA are prepared, obtained polymer solution chelating ability is as shown in table 1.
The chelating ability of polymer solution is obtained at a temperature of the differential responses of table 1
| Reaction temperature | 60~65 DEG C | 70~75 DEG C | 80~85 DEG C | 90~95 DEG C |
| Chelating ability/mgg-1 | 103.11 | 120.86 | 131.11 | 122.09 |
The result of table 1 shows：When temperature is 80~85 DEG C, obtained polymer solution chelating ability is maximum, higher than or it is low
In 80~85 DEG C, chelating ability has declined.Consider, optimal polymeric reaction temperature of the invention is 80~85 DEG C.
2nd, the reaction time
In monomer mole ratio IA：MA：AA=1：1：1 (each 0.5mol), fixed reaction temperature are 80~85 DEG C, monomer mass
Concentration is 6% that 15%, initiator addition is monomer mass, changes the reaction time for 2h, 4h, 6h, 8h, prepares different polymerizations
Thing IA/MA/AA, obtained polymer solution chelating ability is as shown in table 2.
The chelating ability of polymer solution is obtained under the differential responses time of table 2.
| Reaction time | 2h | 4h | 6h | 8h |
| Chelating ability/mgg-1 | 101.23 | 131.11 | 143.09 | 143.67 |
The result of table 2 shows：The optimal reaction time is 6h.Reaction time is too short, and polymerization imperfection can not be good, with
The extension in reaction time, chelating ability although increased but when reacted between it is unobvious more than 6h, chelating ability increase.Comprehensively examine
Consider, optimum reacting time of the invention is 6h.
3rd, initiator addition
In monomer mole ratio IA：MA：AA=1：1：1 (each 0.5mol), fixed reaction temperature are 80~85 DEG C, reaction time
For 6h, monomer mass concentration are 15%, change the percentage of monomer mass shared by the addition of initiator for 2%, 4%, 6%,
8%th, 10%, different polymer IA/MA/AA are prepared, obtained polymer solution chelating ability is as shown in table 3.
The chelating ability of polymer solution is obtained under the different initiator additions of table 3.
| Amount of initiator | 2% | 4% | 6% | 8% | 10% |
| Chelating ability/mgg-1 | 119.56 | 143.09 | 201.72 | 216.12 | 183.18 |
The result of table 3 shows：When initiator addition shared by monomer mass percentage be 8% polymer solution chelating
Power reaches maximum, and the addition of initiator is very few, and the free radical number of generation is less, causes reaction rate too low, cannot react completely
Entirely, initiator addition is excessive, produces number of free radicals mesh excessive, causes the degree of polymerization reduction molecular weight of polymer too low, chelating
Power is not good.Consider, the addition of optimum evocating agent of the invention is 8%.
4th, total monomer
In monomer mole ratio IA：MA：AA=1：1：1 (each 0.5mol), fixed reaction temperature are 80~85 DEG C, reaction time
6h, initiator addition are the 8% of monomer mass, and it is 10%, 15%, 20%, 25%, 30% to change total monomer, is prepared
Different polymer IA/MA/AA, obtained polymer solution chelating ability is as shown in table 4.
The chelating ability of polymer solution is obtained under the different polymeric monomer concentrations of table 4.
| Monomer concentration | 10% | 15% | 20% | 25% | 30% |
| Chelating ability/mgg-1 | 202.65 | 216.12 | 236.12 | 214.32 | 197.65 |
The result of table 4 shows：Optimal monomer concentration 20%, polymer monomer concentration can not be too high, concentration easy friendship high
Gel is given birth in coproduction, and concentration is too low, and reaction speed is slow, and reaction thoroughly, does not cause polymer performance bad.Consider, this hair
Bright optimal monomer concentration 20%.
The chelating ability of polymer IA/MA/AA prepared in cumulated volume example, determines the optimal bar for preparing the polymer
Part is：In monomer mole ratio IA：MA：AA=1：1：Under 1 (each 0.5mol), reaction temperature is 80~85 DEG C, and the reaction time is 6h,
The percentage of monomer mass shared by the addition of initiator is 6%, monomer concentration 20%.And polymerization is prepared with the optimal conditions
Thing IA/MA/AA, is investigated with polymer structure characterization later, polymer biodegradation and indoor application is investigated.
Embodiment 2
The structural analysis of ter-polymers IA/MA/AA
Structural analysis is carried out to obtained polymer IA/MA/AA under optimization formula in example 1, is carried out using KBr pressed disc methods
Infrared spectrum is characterized, as a result as shown in figure.As can be seen from Figure 1：3430cm-1 is O-H stretching vibration peaks in carboxyl,
1717.11cm-1 is C=O double bond stretching vibration peaks, and the absworption peak explanation monomer remnants for not occurring double bond in figure are very few, from red
The data of outer spectrogram may certify that synthetic product is IA, MA and AA ter-polymers.
Embodiment 3
The investigation of ter-polymers IA/MA/AA biodegradabilities
The investigation of biodegradability is carried out to obtained polymer IA/MA/AA under optimization formula in example 1.
A () claims 100g vegetable garden soils to be dissolved in one liter of distilled water, filtered after standing, and settled solution is standby as inoculum.(b)
Polymer IA/MA/AA distilled water is made into the solution 4 that mass fraction is 5%, adequate nutrition salt is added in every liter of solution
(the composition of nutritive salt：Calcium chloride, magnesium sulfate, ammonium sulfate, ferric trichloride, phosphate buffer solution), appropriate inoculum.C () separately takes
Distilled water replaces polymer IA/MA/AA solution to be measured, adds equivalent nutritive salt and inoculum, makees blank experiment.D () will
The above-mentioned mixed solution for preparing is sub-packed in 100ml conical flasks, every bottle of 50ml mixed liquor, is sealed with sealed membrane, is placed in after tightening
Vibrated on constant-temperature table.In 22 ± 0.1 DEG C of room temperature, cultivated under 120r/min speed conditions, the test period is 30d, every 7d (1,
7th, 14,21,28d) a pair of conical flasks are taken out, after mixed liquor is filtered with qualitative filter paper, according to GB11914-89 potassium dichromate methods
The biochemical oxygen demand value COD of filter liquor is determined, wherein content of organics is characterized with COD.E () subtracts blank with the COD of sample
COD, that is, obtain net COD, as follows according to the degradation rate that the net COD calculates sample:N-th day degradation rate=(original net COD- n-th day
Net COD)/original net COD.
Result shows that, when 30d is cultivated, the degradation rate of polymer IA/MA/AA reaches 64.83%
Embodiment 4
Ter-polymers IA/MA/AA applicating expeditions
Applicating expedition is carried out to obtained polymer IA/MA/AA under optimization formula in example 1.
The collection of pedotheque：Along " S " route, adopted according to the principle of " random ", " equivalent ", " multiple spot mixing "
Sample, the distribution of sampled point is uniform, each sampled point fetch earth depth and sampling quantity answers uniformity.The place of (b) pedotheque
Reason and storage：The soil sample that will be adopted back is placed in sample disc in time, spreads out into very thin one layer, is placed at the room ventilation of neat and tidy
Natural air drying, forbids to be exposed to the sun, and notes preventing the pollution of the gases such as acid, alkali and dust.Soil sample is often stirred in air drying process
And large clod is crumbed to accelerate drying.The debris such as stone in removal pedotheque, milled 2mm sieves are put into standby in sample bottle
With.C () pedotheque is analyzed：The Elemental characters of pedotheque are analyzed according to NY/T 1121, such as PH, the content of organic matter,
Available phosphorus content etc.；D () crushes granular Diammonium phosphate (DAP), be partly sufficiently mixed as synergy with appropriate copolymer powder
Diammonium phosphate (DAP) is standby, and Diammonium phosphate (DAP) or effective phosphoric acid diammonium containing P2O50.90g are added per 160g wind desiceted soils, is sufficiently mixed, each
Treatment is repeated 3 times, and is sub-packed in 200ml plastic cups, plus distilled water is to field capacity, is placed in semiclosed natural environment, often
Every a period of time supplement water, soil conservation is moistened, the content of available phosphorus is measured by sampling after culture 1,7,14,28,42d；(e)
Result of the test shows, common Diammonium phosphate (DAP) and effective phosphoric acid diammonium lab simulation under identical conditions, shows in soil effectively
Difference in phosphorus holding level.Within the observation cycle, effective phosphoric acid diammonium is significantly lower than common phosphoric acid in soil by fixed amount
Two ammoniums.The more common Diammonium phosphate (DAP) of the content of soil available phosphorus is about high by 8%~16% during this period.
Claims (10)
1. a kind of water-soluble ter-polymers phosphate fertilizer synergist, it is characterised in that：The ter-polymers phosphate fertilizer synergist is by clothing health
Prepared by tri- kinds of monomers of sour IA, maleic anhydride MA, acrylic acid AA, its structure is as follows：
2. the preparation method of a kind of water-soluble ter-polymers phosphate fertilizer synergist according to claim 1, it is characterised in that
Using following steps：
A () weighs IA, MA, AA and initiator, feed molar percentage is：Itaconic acid be 25~60%, maleic anhydride be 15~
35%, acrylic acid is 25~40%, and it is 4~6 to carry out half neutralisation treatment pH to monomer IA with alkaline solution, and initiator amount accounts for list
The 2%~10% of body gross weight, and initiator is configured to the solution that concentration is 25%, it is standby；
B IA after MA and treatment is added reactor by (), add deionized water 7~15min of logical nitrogen, is stirred and is heated, monomer
It is completely dissolved and after temperature reaches 65~95 DEG C, initiator and acrylic acid is at the uniform velocity dropped into reactor, time for adding control exists
40~50min；
C 1~6h of () insulation reaction, stops heating and stirs, cooling discharge, IA/MA/AA ter-polymers are obtained；
(d) 40 DEG C of vacuum drying 5h, then 5h is dried with infrared drying oven, crushing obtains polymer powder or enters as a solution
Row is preserved.
3. the preparation method of a kind of water-soluble ter-polymers phosphate fertilizer synergist according to claim 2, it is characterised in that：
The addition of deionized water makes monomer mass concentration be 10~30%.
4. the preparation method of a kind of water-soluble ter-polymers phosphate fertilizer synergist according to claim 2, it is characterised in that：
The feed molar percentage is：Itaconic acid be 25~60%, maleic anhydride be 15~35%, acrylic acid be 25~
40%.
5. the preparation method of a kind of water-soluble ter-polymers phosphate fertilizer synergist according to claim 2, it is characterised in that：
In step a, the initiator is ammonium persulfate or potassium peroxydisulfate, and its consumption accounts for the 2%~10% of total monomer weight, preparation it is poly-
Compound concentration is about 20%.
6. the preparation method of a kind of water-soluble ter-polymers phosphate fertilizer synergist according to claim 2, it is characterised in that：
In step a, the initiator is ammonium persulfate or potassium peroxydisulfate, and its consumption accounts for the 8% of total monomer weight.
7. the preparation method of a kind of water-soluble ter-polymers phosphate fertilizer synergist according to claim 2, it is characterised in that：
In step a, alkaline reagent used by described alkaline solution is NaOH or potassium hydroxide.
8. the preparation method of a kind of water-soluble ter-polymers phosphate fertilizer synergist according to claim 2, it is characterised in that：
In step b, reaction temperature is 80~85 DEG C；In step c, the reaction time is 6h.
9. the preparation method of a kind of water-soluble ter-polymers phosphate fertilizer synergist according to claim 2, it is characterised in that：
In step b, described reactor is the four-hole boiling flask equipped with flow back cool solidifying pipe, thermometer, constant pressure funnel and agitating device.
10. a kind of water-soluble ter-polymers phosphate fertilizer synergist according to claims 1, is improving phosphate fertilizer utilization efficiency simultaneously
Application in regulation soil pH.
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| CN107540441A (en) * | 2017-07-20 | 2018-01-05 | 青岛琅琊台集团股份有限公司 | A kind of solid phosphorus efficiency bio-feritlizer of fixed nitrogen that crop yield is improved using itaconic acid |
| CN112321353A (en) * | 2020-10-21 | 2021-02-05 | 郑州大学 | Forestry fertilizer prepared by pyrolysis of municipal sludge and solid waste and preparation method thereof |
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| CN102515959A (en) * | 2011-12-23 | 2012-06-27 | 北京瑞泰丰商务有限公司 | Water-soluble polymer synergist used for fertilizers, its preparation method and application |
| CN103351218A (en) * | 2013-06-19 | 2013-10-16 | 余丽 | Synergist for polyaspartic acid fertilizer and preparation method thereof |
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| CN112321353A (en) * | 2020-10-21 | 2021-02-05 | 郑州大学 | Forestry fertilizer prepared by pyrolysis of municipal sludge and solid waste and preparation method thereof |
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Effective date of registration: 20220711 Address after: 463000 room 511, floor 5, comprehensive service center of the administrative committee of Zhumadian Industrial Agglomeration District, Henan Province Patentee after: Henan Fulian Biotechnology Co.,Ltd. Address before: 450000 phosphate fertilizer research institute, North Campus of Zhengzhou University, No. 97, Wenhua Road, Zhengzhou, Henan Province Patentee before: ZHENGZHOU FUYILIAN TECHNOLOGY CO.,LTD. |
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Denomination of invention: A water-soluble ternary polymer phosphate fertilizer enhancer and its preparation method and application Granted publication date: 20190108 Pledgee: Bank of China Limited Zhumadian branch Pledgor: Henan Fulian Biotechnology Co.,Ltd. Registration number: Y2024980026447 |