CN113667150A - Polymer soil improvement solid water polymerization reaction method and device - Google Patents
Polymer soil improvement solid water polymerization reaction method and device Download PDFInfo
- Publication number
- CN113667150A CN113667150A CN202110952708.7A CN202110952708A CN113667150A CN 113667150 A CN113667150 A CN 113667150A CN 202110952708 A CN202110952708 A CN 202110952708A CN 113667150 A CN113667150 A CN 113667150A
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- reaction
- microwave
- polylactic acid
- solid water
- polymerization
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- 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
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- 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
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- 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
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Classifications
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
Abstract
The invention relates to a high molecular soil improvement solid water polymerization reaction method and a device, polylactic acid, 1,4 butanediol and a catalyst are placed in a polymerization device to be stirred and reacted under microwave, isocyanate is added to continue the reaction, and then the reaction is led out and cooled to obtain chain-extended polylactic acid; diluting NaOH and deionized water, putting the diluted NaOH and deionized water 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, performing cyclic reaction under microwave to prepare solid hydrogel, chopping, drying, grinding and screening the solid hydrogel to obtain a finished product of solid water, wherein the polymerization device comprises a microwave hearth and a reactor arranged in the microwave hearth, and an acrylic acid monomer, a mineral material, the chain-extended polylactic acid and a self-made cross-linking agent are subjected to cross-linking compounding under microwave to form an interpenetrating cross-linked network structure so as to improve the water absorption rate, the water retention property, the gel mechanical strength and the comprehensive performance of saline-alkali resistance, simplify the synthesis process, and enable the solid water to be used for improving soil.
Description
Technical Field
The invention relates to a polymerization reaction method and a polymerization reaction device for solid water for improving polymer soil, and belongs to the technical field of solid water.
Background
The solid water is a biodegradable moisturizing polymer with super-absorption performance, has the characteristics of high water absorption, saline-alkali resistance, soil improvement and biodegradability, and can be widely applied to the fields of agriculture, forestry, gardening technology, medical sanitation, desert control and the like. The existing solid water super-absorbent vertical method generally adopts starch grafted acrylonitrile, acrylic acid, polyurethane and the like, cooling, graft copolymerization, pressurized hydrolysis and acidification, neutralization and drying forming are carried out after starch gelatinization, polypropylene salt formed by a C-C bond of a super-absorbent resin main chain is influenced by cations, ionic strength is increased, water absorption rate is reduced, biodegradation can be limited under low molar mass, the difficulty of controlling molecular weight of a grafted copolymer is increased, soil pollution caused by complete degradation cannot be caused, a single stirring polymerization reaction device has long reaction time during cross-linking polymerization under a jacket thermal environment, salt needs to be added to promote reaction, and the synthesized polymer has poor comprehensive performance of water absorption, water retention and gel mechanical strength due to less strong hydrophilic groups.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a polymerization reaction method and a polymerization reaction device for solid water for improving polymer soil, which are characterized in that an acrylic monomer, a mineral material, chain-extended polylactic acid and a self-made cross-linking agent are subjected to cross-linking compounding under microwave to form an interpenetrating cross-linked 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, and the solid water is used for improving the soil.
The invention is realized by the following technical scheme:
a polymerization reaction method of solid water for improving polymer soil comprises the following steps:
s1, dissolving L-lysine in dichloromethane, adding acrylic acid for cyclic dispersion, adding citraconic anhydride and azobisisobutyronitrile, stirring in a polymerization device under microwave for cyclic polymerization to obtain a cross-linking agent;
s2: putting polylactic acid, 1,4 butanediol and a catalyst into a polymerization device, stirring and reacting under microwave, adding isocyanate, continuing to react, and then leading out and cooling to obtain chain-extended polylactic acid;
s3: diluting NaOH and deionized water, putting the diluted NaOH and the deionized water 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, carrying out cyclic reaction under microwave to obtain solid hydrogel, cutting the solid hydrogel, drying, grinding and screening to obtain a solid water finished product.
Further, in the step S1, the mass ratio of L-lysine, acrylic acid, citraconic anhydride and azobisisobutyronitrile is 85-120: 75-95: 120-200: 0.1-0.3, the microwave power is 20-50W, the temperature is 40-50 ℃, the stirring speed is 80-100r/min, and the reaction is carried out for 30-60min
Further, in the step S2, the mass ratio of the polylactic acid to the 1, 4-butanediol to the isocyanate is 55-65: 35-45: 25-35, the weight average molecular weight of the polylactic acid is less than or equal to 5000, the catalyst is sodium sulfate or stannous chloride with the mass 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, the temperature is raised to 140-150 ℃ after the isocyanate is added, and the reaction is continued for 1-2 h;
further, in 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 benzyltriethylammonium chloride or tetrabutylammonium hydrogen sulfate;
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 1-2 h.
The polymer soil improvement solid water polymerization device comprises a microwave hearth and a reactor arranged in the microwave hearth, wherein a stirrer rotates in the reactor, the top and the bottom of the reactor are connected with a circulating pipeline, and the circulating pipeline is connected with a feeding pipe, a discharging pipe and a circulating pump.
Furthermore, the reactor is eccentrically arranged in the microwave hearth, one side of the microwave hearth is provided with a frequency conversion transformer, a magnetron and a filter guide pipe positioned at the top of the reactor side, which are connected, and the end part of the filter guide pipe is provided with a baffle.
Further, the reactor includes with the fixed reaction cover in microwave furnace top, with the reaction body that reaction cover and microwave furnace can relative rotation, the reaction cover top is equipped with gear motor, the inside mount pad that is equipped with of reaction cover, be equipped with the drive shaft on the mount pad, with the transmission shaft that the agitator links to each other, with the outer ring gear that the reaction body links to each other, all be equipped with the belt pulley in gear motor and the drive shaft, be equipped with drive belt outside the belt pulley, be equipped with on the transmission shaft with outer ring gear inside meshing's internal gear, be equipped with the driving tooth with the outside meshing of internal gear on the transmission shaft, all be equipped with bearing housing and sealing washer between drive shaft and the reaction cover, between transmission shaft and the mount pad, between the reaction body and reaction cover and the microwave furnace, inlet pipe tip slope extends to the reaction body inside.
The invention has the beneficial effects that:
(1) l-lysine contains hydrophilic side amino, is grafted, acidified and modified with acrylic acid/citraconic anhydride under the activation action of an initiator azobisisobutyronitrile, is used as a cross-linking agent to improve the hydrophilicity, swelling rate and biodegradability of degradable solid water and increase the reaction activity; the low molecular weight polylactic acid, 1,4 butanediol and catalyst are used for sealing polylactic acid by hydroxyl end, then the reaction chain extension is carried out by isocyanate with three functional groups under microwave, and hetero atoms are introduced into a C-C skeleton, so that the biodegradability is improved;
(2) the method is characterized in that partially neutralized acrylic acid is used as a monomer, mineral material is filled, chain-extended polylactic acid is used as a monomer raw material, the monomer raw material and a self-made cross-linking agent are cross-linked and compounded under the microwave of an initiator phase transfer catalyst to form an interpenetrating cross-linked network structure, so that the water absorption rate, the water retention property, the gel mechanical strength and the salt and alkali resistance comprehensive performance are improved, a microwave radiation polymerization device is used for simplifying the synthesis process, the large-scale production is facilitated, and the solid water finished product achieves the effect of improving the soil.
Drawings
FIG. 1 is a schematic diagram of a reaction apparatus according to the present invention.
The labels in the figure are: the microwave oven comprises a microwave oven chamber 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 filtering guide pipe 10, a baffle plate 11, a reaction cover 12, a reaction body 13, a speed 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, a driving gear 22, a bearing sleeve 23 and a sealing ring 24.
Detailed Description
The following further describes embodiments of the present invention with reference to the drawings.
Example 1:
a polymerization reaction method of solid water for improving polymer soil comprises the following steps:
s1, dissolving L-lysine in dichloromethane, adding acrylic acid for cyclic dispersion, adding citraconic anhydride and azobisisobutyronitrile, stirring and cyclically polymerizing in a polymerization device under microwave to obtain the cross-linking agent, wherein the mass ratio of L-lysine to acrylic acid to citraconic anhydride to azobisisobutyronitrile is 100: 85: 180: 0.2, the microwave power is 45W, the temperature is 46 ℃, and the stirring speed is 90r/min for reaction for 30 min;
s2: putting polylactic acid, 1, 4-butanediol and a catalyst into a polymerization device, stirring and reacting under microwave, adding Toluene Diisocyanate (TDI), continuing to react, 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 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 2 h;
s3: diluting NaOH and deionized water, putting the diluted NaOH and the deionized water 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 performing a circulating reaction under microwave to obtain the solid hydrogel, wherein the mineral powder is prepared by mixing kaolin and attapulgite clay according to a mass ratio of 1: 1, the initiator is ammonium persulfate, the phase transfer catalyst is benzyltriethylammonium 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: 0.05:0.1, the microwave power is 320W, the temperature is 165 ℃, the stirring speed is 65r/min, the reaction is carried out for 1h, the solid hydrogel is taken, chopped, dried, ground and screened, and the finished product of the solid water is obtained.
Example 2
A polymerization reaction method of solid water for improving polymer soil comprises the following steps:
s1, dissolving L-lysine in dichloromethane, adding acrylic acid for cyclic dispersion, adding citraconic anhydride and azobisisobutyronitrile, stirring and cyclically polymerizing in a polymerization device under microwave to obtain the cross-linking agent, wherein the mass ratio of L-lysine to acrylic acid to citraconic anhydride to azobisisobutyronitrile is 105: 80: 150: 0.2, the microwave power is 40W, the temperature is 48 ℃, and the stirring speed is 93r/min for reaction for 40 min;
s2: putting polylactic acid, 1, 4-butanediol and a catalyst into a polymerization device, stirring and reacting under microwave, adding Hexamethylene Diisocyanate (HDI), continuing to react, guiding out, cooling and obtaining 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, Hexamethylene Diisocyanate (HDI) is added, and then the temperature is raised to 145 ℃ for continuous reaction for 2 h;
s3: diluting NaOH and deionized water, putting the diluted NaOH and deionized water 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 to perform a circulating reaction under microwave to prepare the solid hydrogel, wherein the mineral powder is dolomite powder, the initiator is potassium persulfate, the phase transfer catalyst is tetrabutylammonium hydrogen sulfate, 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: 0.05:0.1, the microwave power is 340W, the temperature is 166 ℃, the stirring speed is 50r/min, the reaction is carried out for 2h, the solid hydrogel is taken, chopped, dried, ground and screened, and the finished product of the solid water is obtained.
Example 3
A polymerization reaction method of solid water for improving polymer soil comprises the following steps:
s1, dissolving L-lysine in dichloromethane, adding acrylic acid for cyclic dispersion, adding citraconic anhydride and azobisisobutyronitrile, stirring and cyclically polymerizing in a polymerization device under microwave to obtain the cross-linking agent, wherein the mass ratio of L-lysine to acrylic acid to citraconic anhydride to azobisisobutyronitrile is 90: 80: 165: 0.2, the microwave power is 40W, the temperature is 45 ℃, and the stirring speed is 90r/min for reaction for 40 min;
s2: putting polylactic acid, 1,4 butanediol and a catalyst into a polymerization device, stirring for reaction under microwave, adding isophorone diisocyanate (IPDI), continuing the reaction, 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, isophorone diisocyanate (IPDI) is added, and the temperature is raised to 143 ℃ to continue the reaction for 1 h;
s3: diluting NaOH and deionized water, putting the diluted NaOH and deionized water 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 to perform a circulating reaction under microwave to prepare solid hydrogel, wherein the mineral powder is montmorillonite powder, the initiator is potassium persulfate, the phase transfer catalyst is benzyltriethylammonium 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 28:0.07:8: 7: 0.05:0.1, the microwave power is 320W, the temperature is 163 ℃, the stirring speed is 60r/min, the reaction is carried out for 1h, the solid hydrogel is taken, chopped, dried, ground and screened, and the finished product of the solid water is obtained.
The polymer soil improvement solid water polymerization device in the above embodiments 1 to 3, comprising a microwave oven chamber 1, a reactor 2 disposed in the microwave oven chamber 1, a stirrer 3 rotating in the reactor 2, a circulation pipeline 4 connected to the top and the bottom of the reactor 2, a feeding pipe 5, a discharging pipe 6 and a circulation pump 7 connected to the circulation pipeline 4;
the reactor 2 is eccentrically arranged in the microwave hearth 1, one side of the microwave hearth 1 is provided with a frequency conversion transformer 8, a magnetron 9 and a filter guide pipe 10 positioned at the top of the side of the reactor 2, which are connected, and the end part of the filter guide pipe 10 is provided with a baffle 11;
the reactor 2 comprises a reaction cover 12 fixed with the top of the microwave hearth 1, a reaction body 13 which can rotate relative to the reaction cover 12 and the microwave hearth 1, the top of the reaction hood 12 is provided with a speed reducing motor 14, the interior of the reaction hood 12 is provided with a mounting seat 15, the mounting seat 15 is provided with a driving shaft 16, a transmission shaft 17 connected with the stirrer 3 and an outer gear ring 18 connected with the reaction body 13, the speed reducing motor 14 and the driving shaft 16 are both provided with a belt pulley 19, a transmission belt 20 is arranged outside the belt pulley 19, the transmission shaft 17 is provided with an internal gear 21 engaged with the inside of the external gear ring 18, the transmission shaft 17 is provided with a transmission gear 22 engaged with the outside of the internal gear 21, bearing sleeves 23 and sealing rings 24 are arranged between the driving shaft 16 and the reaction cover 12, between the transmission shaft 17 and the mounting seat 15, and between the reaction body 13 and the reaction cover 12 and the microwave hearth 1, and the end part of the feeding pipe 5 obliquely extends into the reaction body 13.
The mechanism of the invention is as follows:
the feeding pipe 5 obliquely extending from the upper end part of the circulating pipe to the inside of the reaction body 13 feeds materials, the driving shaft 16 is driven to rotate by the speed reducing motor 14 under the speed reducing transmission of the driving belt 20 and the belt pulley 19, 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 hearth 1, so that the relative rotation can be realized, the sealing and corrosion resistance can be improved, when the driving shaft 16 rotates, the internal gear 21 drives the external gear ring 18 to drive the reaction body 13 to rotate relative to the reaction cover 12 and the microwave hearth, the microwave radiation uniformity is improved, the driving shaft 17 on the mounting seat 15 is driven to drive the stirrer 3 to rotate in the reactor 2 through the meshing of the internal gear 21 and the driving gear 22, and the reaction body 13 rotates relative to the butt joint discharging pipe 6 in the microwave hearth 1;
the stirrer 3 rotates at a high speed, the reaction body 13 rotates in opposite direction at a reduced speed to increase the convection turbulence of a material system, the material in the discharge pipe 6 circulates to the top feed pipe 5 through the circulating pump 7 and the circulating pipe to increase the reaction efficiency of material circulation mass transfer, and the circulating pipe is connected with a valve and a sampling pipe for sampling detection;
and the frequency is converted by a frequency conversion transformer 8. The magnetron 9 generates microwave under the excitation of a power supply, and the microwave energy is dispersed and provided to the reactor 2 in the microwave hearth 1 through the waveguide coupling of the filter tube and the baffle 11, wherein the microwave frequency is as follows: 2450MHz +/-50 Hz, and the temperature, the frequency conversion control reaction temperature and the microwave frequency are detected by a temperature detector extending into the reaction body 13;
the solid water prepared in examples 1-3 was compared with a commercially available polymer water absorbent resin SAP (Tonglingda FMX-6) as a control, and the detection method and detection result were as follows:
and (3) water absorption detection: taking 0.3g of solid water or a reference substance, adding water, standing for 30min, filtering excessive water by a wet net, standing until the mass reduction per minute is within 1g, and weighing, wherein according to the water absorption rate (M3-M2-M1)/M1, M3 is the total weight of a screen and gel after water absorption, M2 is the weight of the screen, and M1 is the dry weight;
and (3) water retention detection: placing the gel and the screen which are remained after the water absorption detection in a drying oven at 90 ℃ for 1.5h, taking out, cooling and weighing, wherein the weight is calculated according to the water retention rate (%) (M4-M2)/(M1-M2) × 100%, 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;
and (3) detecting the salt absorption rate: adding 0.9% saline water into 0.3g of solid water or a reference substance, standing for 30min, filtering out excessive water by a wet net, standing until the mass reduction per minute is within 1g, and weighing, wherein the water absorption rate is (M3-M2-M1)/M1, M3 is the total weight of a screen and gel after water absorption, M2 is the weight of the screen, and M1 is dry weight;
degradation time: weighing 75mg of helicase, dissolving the helicase in 50nl of acetic acid and sodium acetate buffer solution, and stirring the solution at the temperature of 40 ℃ to measure the degradation rate;
gel strength: taking 1g of solid water or saturated gel obtained after the water-absorbent resin is completely swelled, and recording the compression deformation resistance variable (initial height-final height) after 5min under the pressure of a 50g weight by a height gauge;
| sequence number/item | Water absorption rate | Water retention (%) | Salt absorption rate | Time of degradation | Resistance to compression deformation (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 | Can not be completely degraded | 3.6 |
L-lysine contains hydrophilic side amino, is grafted, acidified and modified with acrylic acid/citraconic anhydride under the activation action of an initiator azobisisobutyronitrile, is pyrolyzed and activated through microwave stirring reaction, is grafted to increase branched chains, introduces vinyl and carboxyl unsaturated olefin monomers, and is used as a crosslinking agent to effectively improve the hydrophilicity, swelling rate and biodegradability of degradable solid water and increase the reaction activity;
polylactic acid with low molecular weight and weight-average molecular weight less than or equal to 5000, 1, 4-butanediol, catalyst sodium sulfate or stannous chloride are stirred and reacted under microwave with the power of 120-230W and the temperature of 120-130 ℃, the polylactic acid is sealed by hydroxyl end, then the reaction chain extension is carried out by trifunctional isocyanate under microwave, the isocyanate comprises Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI) and 1, 5-Naphthalene Diisocyanate (NDI), thereby generating a carbamate bond and an amido bond, the temperature is increased to 140-150 ℃, the molecular weight reduction or the molecular weight distribution broadening of the product is avoided, the side reaction is reduced, so that the heteroatom is introduced into the C-C skeleton, and the C-C skeleton is easily and completely degraded by microorganism;
partially neutralized acrylic acid is used as a monomer, one or more of mineral material kaolin, dolomite powder, attapulgite clay and montmorillonite powder are used as a filling material, chain-extended polylactic acid is used as a monomer raw material and is in crosslinking compounding with a self-made crosslinking agent under the microwave by an initiator ammonium persulfate or potassium persulfate and a phase transfer catalyst benzyltriethylammonium chloride or tetrabutylammonium hydrogen sulfate, and polyvalent metal ions in the mineral material improve the polymerization reaction speed, the crosslinking degree and gelation, so that the water absorption rate and the gel strength are increased, the raw materials are cheap and easy to obtain, the saline-alkali resistance is increased, and the soil environment with different saline-alkali degrees is adapted;
the mineral material and the chain-extended polylactic acid compositely control the crosslinking degree, the yield is improved by the reaction at the microwave power of 300-;
when the soil conditioner is used, solid water is mixed with water and stirred to form gel, the gel is mixed with seeds or thrown into planting holes and covered with soil, and then the gel is watered or rained, the solid water absorbs and stores excessive moisture in the soil including fertilizer dissolved in water and slowly releases the moisture under the action of microbial degradation, so that the soil is kept moist, a large number of pores are formed in the soil under the actions of repeated contraction and expansion, 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 is prevented from being hardened and salinized, and the soil conditioning effect is achieved.
In the description of the present invention, it is to be understood that the terms "center", "longitudinal", "lateral", "up", "down", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", and the like, indicate orientations or positional relationships based on those shown in the drawings, and are used only for convenience in describing the present invention and for simplicity in description, and do not indicate or imply that the referenced devices or elements must have a particular orientation, be constructed and operated in a particular orientation, and thus, are not to be construed as limiting the present invention. Furthermore, the terms "first", "second", etc. are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first," "second," etc. may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless otherwise specified.
In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected 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 through specific situations.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are also included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. A high molecular soil improvement solid water polymerization reaction method is characterized in that the method comprises the following steps of putting polylactic acid, 1,4 butanediol and a catalyst into a polymerization device, stirring and reacting under microwave, adding isocyanate, continuing to react, leading out and cooling to obtain chain-extended polylactic acid; diluting NaOH and deionized water, putting the diluted NaOH and the deionized water 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, carrying out cyclic reaction under microwave to obtain solid hydrogel, cutting the solid hydrogel, drying, grinding and screening to obtain a solid water finished product.
2. The polymeric solid water polymerization reaction method for improving soil of high molecular weight according to claim 1, wherein the mass ratio of the polylactic acid, the 1, 4-butanediol and the 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 method as claimed in claim 1, wherein the catalyst is sodium sulfate or stannous chloride with a mass of 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 speed is 50-60r/min, the reaction is carried out for 30-60min, and after the isocyanate is added, the temperature is raised to 140-150 ℃ for further reaction for 1-2 h.
4. The method of claim 1, wherein the cross-linking agent is prepared by dissolving L-lysine in dichloromethane, adding acrylic acid for cyclic dispersion, adding citraconic anhydride and azobisisobutyronitrile, and subjecting to cyclic polymerization under microwave stirring in a polymerization apparatus.
5. The method for polymerization reaction of solid water for improving polymer soil according to claim 4, wherein the mass ratio of L-lysine, acrylic acid, citraconic anhydride and azobisisobutyronitrile in the preparation of the cross-linking agent is 85-120: 75-95: 120-200: 0.1-0.3, the microwave power is 20-50W, the temperature is 40-50 ℃, and the stirring speed is 80-100r/min for reaction for 30-60 min.
6. The method for polymerizing high molecular weight solid water for soil improvement 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 benzyltriethylammonium chloride or tetrabutylammonium hydrogen sulfate.
7. 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 crosslinking 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 1-2 h.
8. The polymer soil improvement solid water polymerization device according to any one of claims 1 to 7, comprising a microwave hearth and a reactor arranged in the microwave hearth, wherein a stirrer rotating in the reactor is arranged, the top and the bottom of the reactor are connected with a circulation pipeline, and the circulation pipeline is connected with a feeding pipe, a discharging pipe and a circulation pump.
9. The device for polymerizing high molecular soil improvement solid water according to claim 8, wherein the reactor is eccentrically arranged in a microwave oven chamber, a frequency conversion transformer, a magnetron and a filter conduit pipe are connected to one side of the microwave oven chamber, the filter conduit pipe is positioned at the top of the reactor side, and a baffle is arranged at the end part of the filter conduit pipe.
10. The polymeric solid water polymerization device for soil improvement of polymeric soil as claimed in claim 8, the reactor comprises a reaction cover fixed with the top of the microwave hearth and a reaction body which can rotate relative to the reaction cover and the microwave hearth, the top of the reaction cover is provided with a speed reducing motor, the interior of the reaction cover is provided with a mounting seat, the mounting seat is provided with a driving shaft, a transmission shaft connected with a stirrer and an outer gear ring connected with a reaction body, the speed reducing motor and the driving shaft are both provided with belt pulleys, a driving belt is arranged outside the belt pulleys, the driving shaft is provided with an internal gear meshed with the inside of the external gear ring, be equipped with on the transmission shaft with the external engaged's of internal gear driving tooth, all be equipped with bearing housing and sealing washer between drive shaft and the reaction cover, between transmission shaft and the mount pad, between reaction body and reaction cover and the microwave furnace, the slope of inlet pipe tip extends to the reaction body inside.
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| 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 |
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