CN1224028A

CN1224028A - High hydroscopicity material of graft bentonite and its producing process

Info

Publication number: CN1224028A
Application number: CN 98110033
Authority: CN
Inventors: 巫拱生
Original assignee: Individual
Current assignee: Individual
Priority date: 1998-01-18
Filing date: 1998-01-18
Publication date: 1999-07-28
Anticipated expiration: 2018-01-18
Also published as: CN1073121C

Abstract

A graft bentone material with high water absorption in the form of plate, particle, or powder is prepared from bentone, vinyl monomers A and B, initiation system composed of persulfate and reducer and cross-linking agent through graft copolymerization. Its advantages are simple preparing process, high water absorption, reusing it cyclically, no environmental pollution, low cost and adjustable molecular structure and nature.

Description

High hydroscopicity material of graft bentonite and manufacture method thereof

What the present invention relates to is functional high molecule material and manufacture method thereof, more particularly is suction, water conservation, the high hydroscopicity material of graft bentonite of water storage and the manufacture method that is used to produce this product thereof that is used for aspects such as agricultural gardening, soil improvement, Water in Water Shutoff in Oil Field, environment protection and daily life.

As everyone knows, existent environment of people in global lack of water, arid, the positive serious threat of desertification, and particularly arid, the geographic agroforestry of massif and urban afforestation can be preserved water and soil effectively, keep natural rainwater and man-made irrigation water resources, make the soil obtain improvement, ecotope is improved.At present, the high-absorbent material of applying both at home and abroad mainly contains two kinds: a kind of is semi-synthetic resin, with natural polymer raw material and synthon graft copolymerization, wherein the natural polymer raw material refers to starch, cellulose, shitosan etc., and synthon is the monobasic monomers such as acrylonitrile, acrylicacidandesters class, obtain the natural polymer series of products through graft copolymerization, such as: the saponification resultant of starch and acrylonitrile graft copolymer, this semi-synthetic production of resins cost is higher, technology is complicated, also environment is had in various degree pollution; Another kind is synthetic resin, to get through crosslinked and polymerization with synthon fully, it is the synthetic high polymer series that makes from the petroleum industry raw material, as: crosslinking sodium polyacrylate, this synthetic resin production cost is higher, service life is longer, but be difficult for degraded, 4. 3. main material valency height, the graft crosslinking method of making the said goods mainly contain that the crosslinked 2. crosslinking agent that 1. caused by self causes crosslinkedly crosslinkedly imports the crosslinked action that hydrophobic group or crystalline texture produce by what radiation, heating, drying etc. caused; Compare with the present invention, existing number of patent application is that the synthetic method of 89101086.6 high-absorbent materials is as raw material take bentonite and acrylamide, adopt the synthetic method of redox initiation system, it is to adopt the acrylamide monomer system to carry out graft copolymerization take bentonite as primary raw material, uses NaOH (NaOH), ammonium persulfate ((NH ₄) ₂S ₂O ₈), potassium peroxydisulfate (K ₂S ₂O ₈) make oxidant, sodium thiosulfate (Na ₂S ₂O ₃), sodium sulfite (Na ₂SO ₃Make reducing agent, carry out under certain conditions redox initiate polymerization and make.The bentonite high water-absorbent material that this method is made, molecular structure controllability single and performance is relatively poor, and its water-absorbent, salt water resistance and resistance to pressure can not be regulated and control.Therefore do not satisfy the different demands that people use high-absorbent material.

The object of the present invention is to provide a kind of energy to eliminate above-mentioned shortcoming, it is simple to have technology, and product is stable, water-absorbent is strong, can use repeatedly, non-environmental-pollution, high hydroscopicity material of graft bentonite that cost is lower, molecular structure and performance are adjustable and the manufacture method that is used to produce this product thereof.Especially adopt reasonable molecular structural design, based on graft copolymerization, carry out grafting with binary monomer or polynary monomer system, be easy to control molecular structure and performance, make it become acquisition water-absorbent, salt water resistance, the controlled product of resistance to pressure, realized suitability for industrialized production.

High hydroscopicity material of graft bentonite of the present invention is natural macromolecular material and vinyl monomer A and the B such as bentonite, initiator system and crosslinking agent with persulfuric acid salt and reducing agent composition, make tabular through graft copolymerization, granular or powdery, wherein the weight ratio of bentonite and vinyl monomer (A+B) consumption is 1: 0.5 or 0.5～5: 1, also 1: 0.5,1: 1,1: 1.5,1: 2,1: 2.5,1: 3,1: 3.5,1: 4,1: 5 etc., select through accurately machined high-quality bentonite as the grafting skeleton, select the persulfuric acid salt preferably to select ammonium persulfate ((NH ₄) ₂S ₂O ₈) or sodium peroxydisulfate (Na ₂S ₂O ₈) and inferior hydracid hydrogen sodium (NaHSO ₃) forming redox initiation system, its consumption accounts for 0.1～3.0% of monomer consumption, and crosslinking agent is preferably selected N N '-methylene-bisacrylamide etc., and its consumption accounts for 0.01～2.00% of monomer consumption, and the weight ratio of NaOH and monomer consumption is 1: 1～5.Described vinyl monomer A is two kinds of different monomers with B, preferably select two kinds of monomers of acrylamide and acrylic acid to be grafted on the bentonite skeleton through copolyreaction, obtain the graft copolymer of bentonite and two monomers, molecular structure and stable performance, water imbibition, salt water resistance, the controlled product of resistance to pressure, the weight ratio of acrylamide and acrylic monomers consumption is 1: 9～9: 1.

The manufacture method of high hydroscopicity material of graft bentonite of the present invention, be to adopt the two graft copolymerization technologies of monomer under redox initiation system and linking agent effect of wilkinite and acrylamide and vinylformic acid, it is that the wilkinite of proportioning component is inserted in the reactor, stir into pulpous state with water, preferably deionized water or distilled water of water wherein, reactor are with the politef material or have polytetrafluorethylecoatings coatings and make.Add successively acrylamide aqueous solution, acrylic acid and N, N '-methylene-bisacrylamide, mixing time add persulfuric acid salt initiator system after 1--10 minute, and the persulfuric acid salt is preferably selected NaHSO ₃And (NH ₄) ₂S ₂O ₈) or K ₂S ₂O ₈Whipping temp is controlled on 20-45 ℃, preferably be controlled at 20～30 ℃ of upper stirrings, add again NaOH, stop after incorporation time 5-20 minute stirring, improve reaction temperature and be controlled on 50～85 ℃, reaction time is about 30-180 minute, obtain the resilient bentonite graft acrylamide of gel and acrylic copolymer, further deep processing is made bulk, powdery or granular product through section, oven dry, pulverizing.Description of drawings: Fig. 1: high hydroscopicity material of graft bentonite technological process of production figure

According to the high hydroscopicity material of graft bentonite technological process of production, describe manufacture process of the present invention in detail: the bentonite of aequum proportioning is inserted in the reactor that has been filled with water fully stir with water, be made into good aqueous dispersion pulpous state liquid, add monomer A such as acrylamide aqueous solution and monomers B such as acrylic acid, bentonite and monomer A+B weight ratio is 1: 1,1: 1.5,1: 2,1: 2.5,1: 3,1: 4,1: 5; Acrylamide and acrylic acid weight ratio are 9: 1-1: 9 scopes, add the N that consumption accounts for monomer weight 0.01-2.00%, and N '-methylene-bisacrylamide is done fully to stir after 1～10 minute, adds NaHSO ₃And (NH ₄) ₂S ₂O ₈) or K ₂S ₂O ₈, its consumption respectively accounts for monomer weight 0.1～3.0%, and the control temperature is under 20-45 ℃, add the NaOH aqueous solution, constantly stirring stops after 5-20 minute stirring, and improves temperature and is controlled at 50-85 ℃, graft copolymerization 30 minutes-3 hours, automatic cooling is to room temperature, obtain the graft copolymerization jello, also can after section, in 80-100 ℃ of baking oven, be dried to water content (3.00%, after the cooling, pulverize, sieving makes the high absorbency material of required form.Work in-process can be according to the different user requirement of agricultural, gardening, industry, aspect such as daily, the proportioning of conditioned reaction material, multiple and the different various model high-hydroscopicities energy materials of performance obtain absorbing water, it not only can absorb water but also can absorb liquid such as fertilizer, the imbibition multiple can be regulated proportioning with purposes and realize control, usually can be controlled in tens gram/grams, a few hectogram/gram, go up kilogram/gram, promptly be calculated as follows

Weight before imbibition multiple=(the preceding weight of weight-imbibition after the imbibition)/imbibition

Example 1: material proportion is: wilkinite 150 grams

300 milliliters of distilled water

Monomer A vinylformic acid 70 grams

Monomers B acrylamide 80 grams

Ammonium persulphate 0.4 gram is dissolved in 30 ml waters

Sodium bisulfite 0.3 gram is dissolved in 30 ml waters

NN '-methylene-bisacrylamide 0.15 gram is dissolved in 60 ml waters

The NaOH60 gram is dissolved in 200 ml waters.Example 2: material proportion: wilkinite 150 grams

Deionized water 500ML

Monomer A vinylformic acid 70mL

Monomers B vinyl cyanide 100mL

Potassium Persulphate 0.5 gram is dissolved in the 40ml water

Sodium bisulfite 0.4 gram is dissolved in the 35ml water

Sodium hydroxide 100 grams are dissolved in the 250ml water

Glycerine 5ml

With example 1, the material of example 2 is got ready by proportioning, earlier wilkinite is inserted according to technical process and to add water in the reactor and stir into pulpous state, add monomer A and B and reaction medium successively, stir and add primosome after 5 minutes, controlled temperature stirs in 20～45 ℃ of scopes and added behind the NaOH restir 3～20 minutes, stop to stir, temperature is controlled at 50～85 ℃, reaction times is promptly to obtain the two monomer copolymers of wilkinite grafting in 30～180 minutes, through section, dry, required high absorbency material is made in pulverizing, and the suction multiple can reach the 480g/1g product respectively, the product of 550g/1g.

High hydroscopicity material of graft bentonite of the present invention and manufacture method thereof, solved problem such as high absorbency material complex manufacturing, product stability is poor, work-ing life is short, cost is higher, salt tolerant, crushing resistance difference for a long time, especially adopt wilkinite and two monomer systems to carry out by the branch copolyreaction, control is convenient in made products molecule structure and stable performance, it is become obtain water-absorbent, salt water resistance, the controlled product of resistance to pressure, be widely used in agroforestry big area soil cultivating and use.This production technique is simple, facility investment is few, main raw material and initiator price are low, can use repeatedly, non-environmental-pollution, easily realize suitability for industrialized production, this product is good water absorption not only, but also can absorb liquid such as fertilizer by adjusting proportioning, according to different proportionings, its imbibition multiple can be controlled in tens gram/grams, a few hectogram/gram, goes up kilogram/gram, is specially adapted to fields such as industry, agricultural, environmental protection, oil, urban construction, daily life.Be that ideal is used for imbibition, liquid storage, improve the ecological environment, improve the soil, be easy to the natural high-absorbent material being accepted to use by the user.

Claims

1, a kind of high hydroscopicity material of graft bentonite, it is characterized in that it is that wilkinite and vinyl monomer A and B are arranged, initiator system and linking agent with persulphate and reductive agent composition, make tabular or granular or powdery through graft copolymerization, wherein the weight ratio of wilkinite and vinyl monomer consumption is 1: 0.5～5 or 0.5～5: 1.

2, high hydroscopicity material of graft bentonite as claimed in claim 1 is characterized in that described vinyl monomer A and B are respectively the two monomers of acrylamide and vinylformic acid; The weight ratio of its consumption is 9: 1-1: 9

3, high hydroscopicity material of graft bentonite as claimed in claim 1 is characterized in that described salt initiator system is (NH ₄) ₂S ₂O ₈-NaHSO ₃Or K ₂S ₂O ₈-NaHSO ₃, wherein: (NH ₄) ₂S ₂O ₈Or K ₂S ₂O ₈With NaHSO ₃Consumption respectively account for the 0.100-3.00% of monomer consumption.

4, high hydroscopicity material of graft bentonite as claimed in claim 1 is characterized in that the consumption of described linking agent N N '-methylene-bisacrylamide accounts for the 0.01-2.00% of two monomer consumptions, and NaOH is 1: 1～5 with the weight ratio of two monomer consumptions.

5, the manufacture method of high hydroscopicity material of graft bentonite as claimed in claim 1, it is characterized in that adopting the two monomers of bentonite and acrylamide and acrylic acid, graft copolymerization technology under the redox initiation system effect, bentonite inserted in the reactor stir into pulpous state with water, add successively acrylamide aqueous solution, acrylic acid and NN '-methylene-bisacrylamide, after mixing time is 1～10 minute, add NaHSO ₃And (NH ₄) ₂S ₂O ₈Perhaps K ₂S ₂O ₈Whipping temp is controlled at 20～45 ℃ of stirrings, add again NaOH, incorporation time stops after 5～20 minutes stirring, improve reaction temperature and be controlled at 50～85 ℃, reaction time is to obtain bentonite graft acrylamide and acrylic copolymer in 30～180 minutes, or through section, oven dry, pulverize and make bulk, powdery or granular product.

6, the manufacture method of high hydroscopicity material of graft bentonite as claimed in claim 4, it is characterized in that described mixing time is 4～5 minutes, mixing time is 5～10 minutes, and the reaction times is 60～120 minutes, whipping temp is 20～30 ℃, and temperature of reaction is 65～75 ℃.

7, require the manufacture method of 4 described high hydroscopicity material of graft bentonite as the power system, it is characterized in that described reactor is to make with polytetrafluoroethylmaterial material or its coating.