CN101550261A - High oil absorption composite material containing cellulose waste filler and preparation method thereof - Google Patents
High oil absorption composite material containing cellulose waste filler and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a high oil absorption composite material containing cellulose waste filler and a preparation method thereof. The composite material takes acrylic ester multipolymer high oil absorption resin as base material, in which the cellulose waste in the shape of island is uniformly dispersed in the base material. The preparation includes the following steps of: the preparation of the base material, namely the acrylic ester multipolymer high oil absorption resin; the preparation of the cellulose waste filler; the blending of the high oil absorption resin and the cellulose waste filler to prepare the high oil absorption composite material. Compared with the prior art, the composite material has the following advantages of excellent oil absorption performance, the availability to absorb a plurality of oils, high oil absorption percentage and good fat-binding performance. The key technology of the invention lies in the acrylic ester multipolymer oil absorption resin, which has wide raw material source, takes water accounting for 60-80 percent as dispersing medium, and the technology is simple and easily controllable. The filler is natural cellulose waste with the particle diameter of 0.84-0.074mm. The waste can be bagasse, corn cob, peanut shells and sawdust powder, and has wide source, belongs to resource recycling area, conforms to the national policy of sustainable development and is simple, safe and environment-friendly in preparation process.
Description
Technical field:
The present invention relates to a kind of composite material for oil absortion, especially relate to high oil absorption composite material of a kind of cellulose waste filler and preparation method thereof.
Background technology:
High oil absorbing resin (High Oil-Absorbable Resin is called for short HOAR) is the new functional macromolecule material that a kind of energy substitutes traditional oil absorption material, removing pollution by oil, improves in the environment for human survival playing an important role.
At present, oil absorption material is divided into three phases from the development and change of material: the fs, and utilize porous materials such as cotton, sponge and clay to come oil suction, the oil suction principle absorbs according to kapillary, is a kind of physical adsorption.The result is unsatisfactory, and this oil absorption material has significant disadvantages: the oil suction multiplying power is less, a pressurization leakage of oil again slightly after the oil suction, and these shortcomings make their application be subjected to certain restriction.Subordinate phase is utilized hydrophobic polymer material polypropylene, polyethylene etc., and through melt-spun or melt and spray and wait the net felt make certain voidage, its oil absorbency and profit selectivity all have raising, still still has under the pressure condition problem of leakage of oil again.Phase III, high oil absorbing resin is a kind of new functional macromolecule material, intermolecular have a three-dimensional cross-linked reticulated structure, solvation by lipophilic group on the macromolecular chain and oil molecule makes resin swelling, the oil molecule that absorbs is kept in the network with Van der Waals force, thereby has solved the problem of leakage of oil.Japanese catalyst chemical industrial company was at document (Ayman M.Atta in 1992, K.F.Amdt, Journal of Applied PolymerScience, 2005.97:80-91) in put down in writing after the Product industrializations such as realizing comprising polyacrylic acid long-chain ester class oil-absorbing resin, high oil-absorbing resin becomes the focus of domestic and international research and development.People such as Keenan are at document (Keenan, et al., Hydrophobic oil absorbing polymers and process, USP, 6770285) put down in writing in and passed through emulsion polymerisation process, with methacrylic acid long-chain and short-chain ester is comonomer, has synthesized Tg=25 ℃ high oil-absorbing resin, and this material has the low characteristics of surface viscosity.Liu sends out to wait the people strong, and (high oil-absorbing resin and synthetic method thereof, CN1442438 have put down in writing that to have synthesized particle diameter by suspension polymerization be the polyacrylic ester high oil absorbing resin of 0.3～2mm in 2003.09.17) at document.People such as Cao Aili are at document (the synthetic and performance study of acrylic acid series high oil-absorbing resin, polymer material science and engineering, 1999,15 (2) 38-40) having put down in writing the employing letex polymerization in, to have synthesized polyacrylic ester be emulsion, method by breakdown of emulsion gets high oil absorbing resin, is applied to the rubber oiliness improver.Pass through domestic and international research, show such material except that having the characteristics that the oil suction kind is many, multiplying power is high and guarantor's oiliness is good, also has the slow deficiency of oil suction speed, at having addressed this problem a lot of reports, people such as Blaney are at document (et al., Hydrophobic oil absorbingpolymers and process, USP, 5834385) put down in writing employing physical package package method in, having prepared a kind of internal layer is cellulose materials, skin is the non-woven fabric compounded oil absorption material of PP of oil suction, and it has the fast and plain degradable advantage of inner fiber of oil suction.People such as Zhu Bin are in document (the synthetic and oil absorptiveness research of high oil absorbing resin fast, South China Science ﹠ Engineering University's journal, 1999,27 (12) 100-105) having put down in writing with the mixed methyl acrylate in is monomer, adopt dispersion polymerization processes, synthesized the fast oil-absorbing resin of oil suction speed.People such as Sun Hua are at document (a kind of oil absorption material that can be recycled, CN1978511,2007.06.13) in put down in writing by in synthetic alkene/olefin(e) acid ester copolymer, adding auxiliary agents such as comprising the whipping agent azodicarbonamide, through mixing, mold pressing and pulverize reusable material.People such as Ye Xianbang have put down in writing the employing suspension polymerization in document (study on the synthesis of quick high oil absorbency acrylate resin, plastics industry, 2004,32 (07)), adding ethyl acetate and primary isoamyl alcohol is agent of pore crack and expanding material, has improved oil suction speed.More than all methods its characteristic is respectively arranged, but reactions steps is many, the temperature height adds organic solvent to raising the efficiency, energy-conservation, safety and environmental protection is disadvantageous.
Summary of the invention:
The objective of the invention is to provide at the prior art weak point a kind of inhale multiple oils, that the oil suction multiplying power is high, protect oiliness good, that oil suction speed is fast, easily adsorb oil slick and the high oil absorption composite material cellulose waste filler that raw material sources are extensive, manufacture craft simply, does not produce new pollution, Environmental Safety and preparation method thereof.
The objective of the invention is to realize by following measure: high oil absorption composite material of a kind of cellulose waste filler and preparation method thereof, its special character is:
The composition of the high oil absorption composite material of cellulose waste filler: by the acrylate copolymer high oil absorbing resin is base material, and homodisperse is the cellulose castoff of island shape in the described base material;
Its preparation process the following step:
(1) composition of base material acrylate copolymer high oil absorbing resin and preparation method:
Form: in the multipolymer in soft segment monomer/multipolymer the rigid chain segment monomer be 95～50/5～50, emulsifying agent is that anionic and non-ionic type are composite, proportioning 3: 1～1: 4, account for 2～5% of polymerization single polymerization monomer, linking agent accounts for 2～6% of polymerization single polymerization monomer for the bifunctional monomer, initiator be persulphate account for polymerization single polymerization monomer 0.4～1.0%, deionized water is that disperse phase is 1.5～4 times of polymerization single polymerization monomer;
Its preparation method: 1. prepare burden according to the above ratio; 2. stirring and emulsifying, reinforced employing drips the part initiator in batches or drips the mode of partial monosomy and initiator in batches, and rate of addition is as the criterion with the temperature of reaction of keeping setting, churning time 0.75～1 hour; 3. connect the protection of nitrogen ball behind the logical nitrogen deoxygenation; 4. heated polymerizable reaction, temperature of reaction is controlled at 70～90 ℃, and the reaction times is 5～9 hours; 5. getting acrylate copolymer milk sap product (A) sealing keeps in Dark Place standby;
(2) the cellulose castoff filler is formed and the preparation method:
Form: comprise that particle diameter is that the natural cellulose waste of bagasse, corn ear, Pericarppium arachidis hypogaeae and sawdust of 0.25～0.035mm and HLB value are 1.8～5.0 tensio-active agent, its both blending ratios are 1/0.2～1;
Its preparation method: 1. choose the natural cellulose waste, drying, pulverizing, sub-sieve by above-mentioned composition; 2. tensio-active agent is handled, and aforementioned natural cellulose waste is added in the surfactant soln, and infiltration stirs; 3. get cellulose castoff filler (B) after the dry constant weight;
(3) high oil absorbing resin/cellulose castoff filler blend prepares the high oil absorption composite material method:
Step 1,1. extracting cellulose waste filler (B) and acrylate copolymer emulsion (A), both blending ratio B/A are 1/5～30, the mixing that 2. stirs at normal temperatures and pressures, 3. composite emulsion (C);
Step 2 by known technology spraying, brushing, casting, impregnating method, is made the different structure of film like, sheet, mesh skeleton, fibrous packing and the high oil absorption composite material of shape with composite emulsion (C).
Soft segment monomer/rigid chain segment monomer in the described base material acrylate copolymer can be chosen wantonly in following comonomer, and wherein polymer flexibility segment monomer has: the just own ester of ethyl propenoate, n-butyl acrylate, vinylformic acid, Isooctyl acrylate monomer, methacrylic dodecyl gallate, methacrylic acid 13 esters; Wherein polymkeric substance rigid chain segment monomer has: methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, vinyl acetate, acrylonitrile, vinylbenzene.
Emulsifying agent in the described base material acrylate copolymer is that anionic and non-ionic type are composite, and wherein anionic is optional in following: sodium laurylsulfonate (SAS), sodium lauryl sulphate (SDS), Sodium dodecylbenzene sulfonate (SDBS); Wherein non-ionic type is optional in following: polyoxyethylene 20 sorbitan monostearate (trade(brand)name Tween60), polyoxyethylene 20 sorbitan monooleate (Tween80), alkyl phenyl Soxylat A 25-7 (Op-10).
Linking agent bifunctional monomer in the described base material acrylate copolymer high oil absorbing resin is optional in following: N, N '-methylene diacrylamide, vinylformic acid, methacrylic acid, N hydroxymethyl acrylamide, epoxy chloropropane.
Initiator in the described base material acrylate copolymer high oil absorbing resin is Potassium Persulphate or ammonium persulphate.
Described tensio-active agent is got one by in the following material and is dissolved in the hexane solution, its both proportioning is 1: 100, and aforementioned following material is: Witconol AL 69-66 (trade(brand)name Span85), anhydrous sorbitol three stearic acid acid esters (Span65), sorbitan monooleate (Span80), sorbitan monostearate (Span60), alkyl phenyl Soxylat A 25-7 (Op-4).
Described high oil absorbing resin/cellulose castoff filler blend prepares the making method of high oil absorption composite material film like: 1. composite emulsion (C) is adopted knifing or brushing or spraying coating process system film on template; 2. heat 50-100 degree centigrade of drying; 3. take off film, preserve.
Described high oil absorbing resin/cellulose castoff filler blend prepares the flaky making method of high oil absorption composite material: 1. composite emulsion (C) is cast in the mould; 2. heat 70-100 degree centigrade of drying; 3. the sheet preservation is got in the demoulding.
Described high oil absorbing resin/cellulose castoff filler blend prepares the making method that high oil absorption composite material contains mesh skeleton or fibrous packing material: 1. get natural or synthetic macromolecule is a material, adopt the technology that stretches or melt and spray to make fiber, make Web materials by braiding or non-woven fabrics method; 2. the technology coated that composite emulsion is passed through dipping, sprays becomes netted high oil-absorbent material on the net.
Compared with prior art, the present invention has following advantage: 1) oil absorptiveness is good, and it is many to have the oil suction kind, oil suction multiplying power height, and guarantor's oiliness is good, and oil suction speed is fast, easily swims in the water surface, helps absorption and recovery to oil slick.2) one of gordian technique of the present invention is synthetic acrylate copolymer oil-absorbing resin with good oil absorptiveness, its raw material sources are extensive, to account for 60～80% water is dispersion medium, employing normal pressure, the emulsion polymerisation process that temperature of reaction is lower, its technology is simple, easily control, no fire and explosive hazard.3) preparation technology of matrix material is to be base-material with the synthetic acrylate copolymer emulsion, adds filler, through the simple physics blend; Filler is that particle diameter is a 0.84-0.074 millimeter natural cellulose waste, and waste bagasse, corn cob, Pericarppium arachidis hypogaeae and sawdust powder source are abundant, belong to resources circulation and utilize, meet the state basic policy of Sustainable development, the simple and safe environmental protection of preparation technology.
Embodiment:
The composition of the high oil absorption composite material of cellulose waste filler of the present invention: by the acrylate copolymer high oil absorbing resin is base material, and homodisperse is the cellulose castoff of island shape in the described base material.
Its preparation prepares through the following step:
(1) composition of base material acrylate copolymer high oil absorbing resin and preparation method:
Its composition:
Multipolymer soft segment monomer/multipolymer rigid chain segment monomer is 95～50/5～50;
Emulsifying agent is that negatively charged ion and non-ionic type are composite, proportioning 3: 1～1: 4, and it accounts for 2～5% of polymerization single polymerization monomer;
Linking agent accounts for 2～6% of polymerization single polymerization monomer for the bifunctional monomer;
Initiator be persulphate account for polymerization single polymerization monomer 0.4～1.0%;
Deionized water is that disperse phase is poly-and monomeric 1.5～4 times;
Wherein:
Described multipolymer soft segment monomer can be chosen wantonly from following material: the just own ester of ethyl propenoate, n-butyl acrylate, vinylformic acid, Isooctyl acrylate monomer, methacrylic dodecyl gallate, methacrylic acid 13 esters; Described multipolymer rigid chain segment monomer can be chosen wantonly from following material: methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, vinyl acetate, acrylonitrile, vinylbenzene.The multipolymer soft segment monomer of this formulation selection, the second-order transition temperature of its polymkeric substance (Tg) is a negative value, and under the condition that is higher than second-order transition temperature (Tg), molecule segment is flexible on the microcosmic, and macromolecular chain link and segment are all in kinestate.As the relevant physicals of polymer materials, have viscosity, tensile strength is low, the specific elongation rate is very big characteristic.The multipolymer rigid chain segment monomer of this formulation selection, its polymer glass temperature (Tg) be on the occasion of, under the condition that is higher than second-order transition temperature (Tg), on the microcosmic macromolecular chain link and segment all in kinestate, opposite as the relevant physicals of polymer materials with the soft segment polymkeric substance.Selecting the polymer flexibility segment monomer and the reaction of polymkeric substance rigid chain segment monomer copolymerizable of different ratios in this prescription for use, is the composition of optimizing macromolecular chain, favourable formation micro hole structure, favourable absorption to oil molecule.Ratio range is to optimize by experiment, and the performance synergy obtains.
Described emulsifying agent anionic can be chosen wantonly from following material: sodium laurylsulfonate (SAS), sodium lauryl sulphate (SDS), Sodium dodecylbenzene sulfonate (SDBS); Described emulsifying agent non-ionic type can be chosen wantonly from following material: polyoxyethylene 20 sorbitan monostearate (trade(brand)name Tween60), polyoxyethylene 20 sorbitan monooleate (Tween80), alkyl phenyl Soxylat A 25-7 (Op-10).Because it is stable that anionic emulsifier helps the emulsion system micellar, nonionic emulsifying agent has good anti-ionic nature, can improve the application performance of product, so adopt both composite, both proportionings are 3: 1～1: 4, and the monomer that letex polymerization is selected for use is insoluble basically or is slightly soluble in the organic molecule of water, by emulsifying agent and stirring, make it become emulsion state, implement letex polymerization
Described linking agent is optional in following: N, N-methylene diacrylamide, vinylformic acid, methacrylic acid, N hydroxymethyl acrylamide, epoxy chloropropane.The effect of linking agent is to make the suitable chemically crosslinked of acquisition between copolymer molecule in this prescription, form three-dimensional net structure, make oil-absorbing resin in oil product, can fully absorb and swelling but can not dissolve, guarantee that oil absorption material has higher saturated oil absorbency and protects oily rate.
Described initiator is Potassium Persulphate or ammonium persulphate, and selected monomer all contains two keys in this prescription, belongs to radical reaction mechanism, and action of evocating is initiation reaction under certain condition.
The preparation method of base material acrylate copolymer high oil absorbing resin is as follows:
1. prepare burden according to the above ratio;
2. stirring and emulsifying adds deionized water and emulsifying agent, stirring and emulsifying 15～20 minutes in reaction unit;
3. logical nitrogen deoxygenation connects the protection of nitrogen ball after 15～30 minutes;
4. add the mode of copolymerization monomer and part initiator or part copolymerization monomer and initiator again, rate of addition is as the criterion with the temperature of reaction of keeping setting, 0.75～1 hour dropping time;
5. drip remaining initiator and copolymerization monomer and initiator, temperature of reaction is controlled at 70～90 ℃, and the reaction times is 5～9 hours;
6. getting acrylate copolymer milk sap product (A) sealing keeps in Dark Place standby.
The detection index of acrylate copolymer milk sap product (A) is as follows:
Transformation efficiency: about 5 gram (be accurate to radix point after the four) emulsions of weighing are W
0, put into culture dish, be dried to constant weight, the weighing example weight is W
1
Transformation efficiency %=(W
1-emulsifying agent weight)/(W
0-water weight-emulsifying agent weight) * 100;
Gel fraction: weighing dry-eye disease (be accurate to radix point after four) is W
02, seal with stainless (steel) wire and to put into fatty extractor, with butanone extracting 48 hours, be dried to constant weight, example weight is W
2
Gel fraction %=W
2/ W
02* 100;
Latex particle size: adopt transmission electron microscope JEOL-2010 to check and characterize;
Oil absorbency: weighing dry-eye disease (be accurate to radix point after four) is W
03, put into port grinding bottle, add the oil of setting, soak at room temperature filtered 5 minutes with 60 eye mesh screens, and weighing oil suction gel weight is W
3
Oil absorbency (g.g
-1)=(W
3-W
03)/W
03
Machinery is protected oily rate: weighing oil suction gel sample (be accurate to radix point after four) is W
04, put into centrifuge tube, regulation and control 3000r/min, centrifugal 15 minutes, to filter, weighing gel weight is W
4
OR％＝W
4/W
04×100；
Oily rate is protected in absorption: the heavy W of weighing oil suction gel
05, being placed on open container, room temperature was placed 15 days, and the weighing gel heavily is W
5
OR％＝W
5/W
05×100；
Oil suction swelling kinetic constant K (h
-1): with reference to reference
[9]Calculate, the oil suction speed of cross-linked polymer can be described in order to following equation: dQ/dt=K (Q
Max-Q), Q in the formula
MaxBe maximum oil absorbency, Q is the oil absorbency of specified time, and the following formula indefinite integral gets formula: ln Q
Max/ Q
Max--Q=Kt, t are specified time (h), and K is oil suction swelling kinetic constant (h
-1).
Detect acrylate copolymer milk sap product (A) as stated above: its transformation efficiency 〉=99.5, gel fraction % 〉=65.00, latex particle size is 0.1～1 μ m.
(2) the cellulose castoff filler is formed and the preparation method:
Its composition: comprise that particle diameter is that the natural cellulose waste of bagasse, corn ear, Pericarppium arachidis hypogaeae and sawdust of 0.25～0.035mm and HLB value are 1.8～5.0 tensio-active agent, its both blending ratios are 1/0.2～1.Natural cellulose waste raw material is bagasse, corn cob, Pericarppium arachidis hypogaeae and sawdust powder, and its source is abundant, belongs to resources circulation and utilizes, meets the state basic policy of Sustainable development, the simple and safe environmental protection of preparation technology.
Cellulose castoff filler preparation method:
1. choose the natural cellulose waste by above-mentioned composition equal shares, drying, pulverizing, sub-sieve;
2. tensio-active agent is handled: at first prepare surfactant soln, getting one by in the following material is dissolved in the hexane solution, its both proportioning is 1: 100, and aforementioned following material is: Witconol AL 69-66 (trade(brand)name Span85), anhydrous sorbitol three stearic acid acid esters (Span65), sorbitan monooleate (Span80), sorbitan monostearate (Span60), alkyl phenyl Soxylat A 25-7 (Op-4).This is because tensio-active agent has affine, dispersion and solvation to lipophilic group on oil molecule and the acrylate copolymer molecular chain.
3. aforementioned natural cellulose waste is added in the surfactant soln, infiltration stirs, and through vacuum or heating recovery normal hexane.This is because cellulose castoff itself does not have affinity to oil, need through the tensio-active agent pre-treatment, when oil molecule enters composite material for oil absortion, tensio-active agent participates in solvation, gel volume increases, occur incompatible interface and defective between gel and the cellulose grain, be directed at the specific surface area that has increased gel, helped improving oil suction speed.Solved the slow problem of polyacrylic ester high oil absorbing resin oil suction speed to a certain extent.
4. after material is dried to constant weight, get cellulose castoff filler (B).
(3) high oil absorbing resin/cellulose castoff filler blend prepares the high oil absorption composite material method:
Step 1,1. extracting cellulose waste filler (B) and acrylate copolymer emulsion (A), both ratio B/A are 1/5～30, the mixing that 2. stirs at normal temperatures and pressures, 3. composite emulsion (C).
Step 2 by known technology spraying, brushing, casting, impregnating method, is made composite emulsion (C) film like, sheet, is contained the different structure of mesh skeleton or fibrous packing and the high oil absorption composite material of shape.
The high oil absorption composite material of described different structure and shape is film like, sheet, contain the high oil absorption composite material of mesh skeleton or fibrous packing.
The high oil absorption composite material making method of film like: 1. composite emulsion (C) is adopted knifing or brushing or spraying coating process system film on template; 2. heat 50-100 degree centigrade of drying; 3. take off film, preserve.
Flaky high oil absorption composite material making method: 1. composite emulsion (C) is cast in the mould; 2. heat 70-100 degree centigrade of drying; 3. the sheet preservation is got in the demoulding.
The high oil absorption composite material making method that contains mesh skeleton: 1. get natural or synthetic macromolecule is a material, adopt the technology that stretches or melt and spray to make fiber, make Web materials by braiding or non-woven fabrics method; 2. the technology coated that composite emulsion is passed through dipping, sprays becomes netted high oil-absorbent material on the net.
Make film like, sheet in view of the above, contain the high oil absorption composite material of mesh skeleton or fibrous packing.
The oil absorptiveness of the high oil absorption composite material of making according to the present invention survey following data:
Oil absorbency (g.g
-1): alkanes, 120# gasoline 29.00, white oil 25.71, kerosene 29.34, diesel oil 23.87,20# machine oil 11.97,40# machine oil 10.5, oil slick (15ml kerosene) 29.8, oil slick (15ml diesel oil) 28; Aromatic hydrocarbon, benzene 23.80, toluene 32.99, dimethylbenzene 38.9, bromobenzene 31.9 and oil of mirbane 20.24; Halohydrocarbon, trichloromethane 53.60,1,1,1 trichloroethane, 35.94,1,1,2,2 tetrachloroethane 51.31.The oil absorbency that more than provides is the maximum value of research range of the present invention.
Protect oily rate: the oil suction gel pressurization of acrylate copolymer high oil absorbing resin and novel high oil absorption composite material is oil-proof, and the machinery of kerosene and diesel oil is protected oily rate and is about 95.00% and 96.65% respectively; 15 days absorption is protected oily rate and is about 65.39% and 69.29% respectively.
Oil suction speed: the oil suction swelling kinetic constant K value of the suction kerosene oil slick of high oil absorption composite material, diesel oil oil slick has improved 100%, 25% (comparing with pure high oil absorbing resin) respectively.
Exemplify following specific embodiment and further specify the process that the present invention prepares novel high oil absorption composite material:
Embodiment 1
(1) acrylic acid synthesizing ester copolymer high oil absorbing resin
Filling a prescription by weight, the percentage ratio metering is respectively: deionized water=69.85, SDS+ polysorbate60=1.357, methacrylic dodecyl gallate+vinyl acetate=26.20, N-methylol acryloyl ammonium+vinylformic acid=0.94, Potassium Persulphate=0.22; In the four-hole reaction flask of preceding binomial adding with electronic stirring, prolong, dropping liquid balance funnel and thermometer, be warming up to 40～50 ℃ and stirred 15 minutes, add comonomer, stirred 30 minutes, logical nitrogen deoxygenation connects the protection of nitrogen ball after 15 minutes; Be warming up to 80 ± 2 ℃, add 1/4 persulfate aqueous solution, react after 40 minutes by dropping liquid balance funnel 3/4 persulfate aqueous solution is splashed into, rate of addition is stabilized in 85 ± 2 ℃ with temperature of reaction and is advisable; React after 7 hours, temperature rises to 90 ℃ and reacts cooling after 1 hour again, and product emulsion (A) sealing is kept in Dark Place standby.
(2) pre-treatment of natural cellulose waste
With 0.06 part of (weight) Span80 be dissolved in 6.00 parts of hexane solutions surfactant soln; Get selected particle diameter respectively and be each 0.15 part in bagasse, corn cob, Pericarppium arachidis hypogaeae and the sawdust of 0.25mm through super-dry, pulverizing and sub-sieve, it is joined in the corresponding surfactant soln, infiltration stirs, vacuum or heating recovery normal hexane, be dried to constant weight, get the waste filler (B) that can be dispersed in the emulsion (A).
(3) emulsion (A)/filler (B) blend prepares novel high oil absorption composite material
Get (A) 10ml of solid content 30%, add 0.15 gram (B), stirring is mixed, and gets composite emulsion (C).By casting, in a certain amount of (C) tetrafluoroethylene of falling people or glass mold, make certain thickness film or flaky material by design; In the mould of place mat Web materials, cast contain the network framework matrix material, in the mould of place mat fiber casting (C) the matrix material of fibre-bearing filler; Also can be by spraying, dipping and the method for brushing preparation.
Embodiment 2
(1) the synthetic acrylate copolymer high oil absorbing resin of emulsion copolymerization
Prescription: distilled water, OP-10, sodium laurylsulfonate, methacrylic acid, N hydroxymethyl acrylamide, Isooctyl acrylate monomer, butyl acrylate and ammonium persulphate, its proportioning percentage ratio by weight are respectively 69.66,1.00,0.37,046,0.54,13.9,13.9 and 0.17.Step: in glass cylinder, monomer, linking agent are mixed, logical nitrogen deoxygenation is (D), is (E) with less water with the initiator wiring solution-forming; Dispersion medium and emulsifying agent are added in the four-hole reaction flask with electronic stirring, prolong, balance dropping funnel and thermometer, and heated and stirred 15 minutes adds 1/4 (D) then, and logical nitrogen stirred 30 minutes, connects the protection of nitrogen ball after adding (E) deoxygenation of 1/4; , be warming up to 75 ± 2 ℃ of reactions 40 minutes; (D) that drip to reserve respectively and (E) then, rate of addition is stabilized in 80 ± 2 ℃ of standards with temperature of reaction, react after 7 hours, improves temperature to 85 ± 2 and ℃ reacts 1 hour again, and the cooling end is reacted; Product (A) sealing is kept in Dark Place.
(2) preprocessing part of natural cellulose waste is with embodiment 1.
(3) emulsion (A)/filler (B) blend prepares novel high oil absorption composite material part with embodiment 1.
Claims (9)
1. high oil absorption composite material of a cellulose waste filler and preparation method thereof is characterized in that:
The composition of the high oil absorption composite material of cellulose waste filler: by the acrylate copolymer high oil absorbing resin is base material, and homodisperse is the cellulose castoff of island shape in the described base material;
Its preparation prepares through the following step:
(1) composition of base material acrylate copolymer high oil absorbing resin and preparation method:
Form: in the multipolymer in soft segment monomer/multipolymer the rigid chain segment monomer be 95～50/5～50, emulsifying agent is that anionic and non-ionic type are composite, proportioning 3: 1～1: 4, account for 2～5% of polymerization single polymerization monomer, linking agent accounts for 2～6% of polymerization single polymerization monomer for the bifunctional monomer, initiator be persulphate account for polymerization single polymerization monomer 0.4～1.0%, deionized water is that disperse phase is 1.5～4 times of polymerization single polymerization monomer;
Its preparation method: 1. prepare burden according to the above ratio; 2. stirring and emulsifying, reinforced employing drips the part initiator in batches or drips the mode of partial monosomy and initiator in batches, and rate of addition is as the criterion with the temperature of reaction of keeping setting, churning time 0.75～1 hour; 3. connect the protection of nitrogen ball behind the logical nitrogen deoxygenation; 4. heated polymerizable reaction, temperature of reaction is controlled at 70～90 ℃, and the reaction times is 5～9 hours; 5. getting acrylate copolymer milk sap product (A) sealing keeps in Dark Place standby;
(2) the cellulose castoff filler is formed and the preparation method:
Form: comprise that particle diameter is that the natural cellulose waste of bagasse, corn ear, Pericarppium arachidis hypogaeae and sawdust of 0.25～0.035mm and HLB value are 1.8～5.0 tensio-active agent, its both blending ratios are 1/0.2～1;
Its preparation method: 1. choose the natural cellulose waste, drying, pulverizing, sub-sieve by above-mentioned composition; 2. tensio-active agent is handled, and aforementioned natural cellulose waste is added in the surfactant soln, and infiltration stirs; 3. get cellulose castoff filler (B) after the dry constant weight;
(3) high oil absorbing resin/cellulose castoff filler blend prepares the high oil absorption composite material method:
Step 1,1. extracting cellulose waste filler (B) and acrylate copolymer emulsion (A), both blending ratio B/A are 1/5～30, the mixing that 2. stirs at normal temperatures and pressures, 3. composite emulsion (C);
Step 2 by known technology spraying, brushing, casting, impregnating method, is made the different structure of film like, sheet, mesh skeleton, fibrous packing and the high oil absorption composite material of shape with composite emulsion (C).
2. high oil absorption composite material of cellulose waste filler according to claim 1 and preparation method thereof, it is characterized in that the soft segment monomer/rigid chain segment monomer in the described base material acrylate copolymer can choose wantonly in following comonomer, wherein polymer flexibility segment monomer has: the just own ester of ethyl propenoate, n-butyl acrylate, vinylformic acid, Isooctyl acrylate monomer, methacrylic dodecyl gallate, methacrylic acid 13 esters; Wherein polymkeric substance rigid chain segment monomer has: methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, vinyl acetate, acrylonitrile, vinylbenzene.
3. high oil absorption composite material of cellulose waste filler according to claim 1 and preparation method thereof, it is characterized in that the emulsifying agent in the described base material acrylate copolymer is that anionic and non-ionic type are composite, wherein anionic is optional in following: sodium laurylsulfonate (SAS), sodium lauryl sulphate (SDS), Sodium dodecylbenzene sulfonate (SDBS); Wherein non-ionic type is optional in following: polyoxyethylene 20 sorbitan monostearate (trade(brand)name Tween60), polyoxyethylene 20 sorbitan monooleate (Tween80), alkyl phenyl Soxylat A 25-7 (Op-10).
4. high oil absorption composite material of cellulose waste filler according to claim 1 and preparation method thereof, it is characterized in that the linking agent bifunctional monomer in the described base material acrylate copolymer high oil absorbing resin is optional in following: N, N '-methylene diacrylamide, vinylformic acid, methacrylic acid, N hydroxymethyl acrylamide, epoxy chloropropane.
5. high oil absorption composite material of cellulose waste filler according to claim 1 and preparation method thereof is characterized in that the initiator in the described base material acrylate copolymer high oil absorbing resin is Potassium Persulphate or ammonium persulphate.
6. high oil absorption composite material of cellulose waste filler according to claim 1 and preparation method thereof, it is characterized in that described tensio-active agent gets one and be dissolved in the hexane solution by appointing in the following material, its both proportioning is 1: 100, and aforementioned following material is: Witconol AL 69-66 (trade(brand)name Span85), anhydrous sorbitol three stearic acid acid esters (Span65), sorbitan monooleate (Span80), sorbitan monostearate (Span60), alkyl phenyl Soxylat A 25-7 (Op-4).
7. high oil absorption composite material of cellulose waste filler according to claim 1 and preparation method thereof is characterized in that described high oil absorbing resin/cellulose castoff filler blend prepares the making method of high oil absorption composite material film like: 1. composite emulsion (C) is adopted knifing or brushing or spraying coating process system film on template; 2. heat 50-100 degree centigrade of drying; 3. take off film, preserve.
8. high oil absorption composite material of cellulose waste filler according to claim 1 and preparation method thereof is characterized in that described high oil absorbing resin/cellulose castoff filler blend prepares the flaky making method of high oil absorption composite material: 1. composite emulsion (C) is cast in the mould; 2. heat 70-100 degree centigrade of drying; 3. the sheet preservation is got in the demoulding.
9. high oil absorption composite material of cellulose waste filler according to claim 1 and preparation method thereof, it is characterized in that described high oil absorbing resin/cellulose castoff filler blend prepares the making method that high oil absorption composite material contains mesh skeleton or fibrous packing material: 1. get natural or synthetic macromolecule is a material, adopt the technology that stretches or melt and spray to make fiber, make Web materials by braiding or non-woven fabrics method; 2. the technology coated that composite emulsion is passed through dipping, sprays becomes netted high oil-absorbent material on the net.
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