CN1036140C - Vegetable fibre film product and its process - Google Patents
Vegetable fibre film product and its process Download PDFInfo
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- CN1036140C CN1036140C CN92114514A CN92114514A CN1036140C CN 1036140 C CN1036140 C CN 1036140C CN 92114514 A CN92114514 A CN 92114514A CN 92114514 A CN92114514 A CN 92114514A CN 1036140 C CN1036140 C CN 1036140C
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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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B9/00—Cellulose xanthate; Viscose
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/02—Cellulose; Modified cellulose
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- C—CHEMISTRY; METALLURGY
- 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
- C09K17/52—Mulches
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2001/00—Use of cellulose, modified cellulose or cellulose derivatives, e.g. viscose, as moulding material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
- B29K2105/0011—Biocides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
- B29K2105/0052—Tracing elements, e.g. to detect the origin of articles
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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
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/02—Cellulose; Modified cellulose
Abstract
The present invention relates to a plant cellulose film which is prepared from 50 to 90 wt% of plant cellulose, 0.2 to 40 wt% of modifying agent and 5 to 20 wt% of moisture. The plant cellulose film can also comprise a weed killer, an insecticide, a bactericidal agent, N, P and K fertilizers, trace elements and rare earth elements. The plant cellulose film is used as a degradable agricultural mulching film, a packing material for commodities, food, such as meat sausages, fruit, vegetables, candies and pastries, medicines and garbage, and a green growing zone of artificial greensward; the plant cellulose and hemicellulose can also be used for manufacturing disposable cups, tableware, food containers, etc. A method for preparing the plant cellulose film comprises the extraction, the extrusion, the pulverization, the degradation, the polymerization, the sulfonation, the dissolving, the filtration and the ripening of plant cellulose to obtain an adhesive, film spraying, solidification, regeneration, desulphurization, bleaching, plasticization, rolling, drying, coating and the rolling of a finished film.
Description
The present invention relates to vegetable fibre film product and technology thereof.This cellulosefilm can be used as mulch film, commodity packaging, especially food such as meat intestines, fruit, vegetables, candy and cake class, pharmaceutical packing.It can also be used for green zone, refuse bag and dialysis tubing material.The invention still further relates to degraded cellulose mulch film, the sterilizing pesticide of the plain mulch film of biodegradable fiber, weeding the plain mulch film of biodegradable fiber, contain the plain mulch film of biodegradable fiber of N.P.K and rare earth element and contain trace element and plain mulch film of the biodegradable fiber of rare earth element and technology thereof.
As everyone knows, existing all kinds of synthetic macromolecule films and goods and develop rapidly in the world wide from the beginning of the sixties.Polyethylene agricultural mulching and other synthesized polymer material various product almost are penetrated into all industries.China's polyethylene plastic film for agricultural use its raw material consumption at the beginning of the nineties surpasses 500,000 tons, and area coverage reaches more than 5,000 ten thousand mu, and enlarge consumption with 15%～20% speed every year, estimates to reach 7000～10,000 ten thousand mu to nineteen ninety-five, and the raw material consumption reaches 70～1,000,000 tons.
Along with people's Environmental awareness increases and the environmental pollution problem is concerned about day by day, the countries in the world scientific worker seriously pay close attention to usage quantity big, reclaim difficulty, the place into the soil Polymer Synthesizing plastics that can not be degraded and polyethylene agricultural mulching etc. are grown the detrimentally affect that is produced to environment and farm crop normal growth for a long time; And think and go down to cause major disaster in the world wide for a long time.West Europe part country, Japan and the U.S. made laws in succession from the beginning of the nineties, begin to forbid or limit and use until all kinds of synthetic macromolecule plastics that all can not use non-degraded, and develop degradable package material and new bio degraded agricultural mulching one after another as various wrapping material.
How to utilize the film that to be degraded to replace synthetic high polymer to be paid close attention to by people for a long time.Starch (20～150 μ m) and polyethylene blowing under certain temperature (170～200 ℃) after machinery is mixed (starch content is greater than 30% in the mixture).Because of starch granules and melt material move with friction-motion speed, so formed the easily crisp low thin-film material of intensity with holes.This starch film is owing to thickness, and the intensity low transparency is low, poor for applicability simultaneously.Though this film starch small grain is because of having than poly-hydroxy, parent not performance is good, but be degraded by microorganisms, but still can not degrade with its blended polyethylene.The somebody manages to allow starch granules introduce the mixing of chemical chain promotion synthetic polymer.Such film is existing the introduction in patent documentation U.S.4337181, GB1487050 and GB1485833.Though these films can be degraded, this technical sophistication, cost are very high, tensile strength is poor, and making thickness and film can not stretch.
Light ?lysis Film is a synthetic high polymer, adds a certain amount of photaesthesia agent (EP230143) when wherein making film, blowing under the hot melt situation (calendering) film forming.This film is degradable under action of ultraviolet radiation.But this membrane degradation is not thorough, can not make the synthetic high polymer degraded become CO fully
2And water.And imbed to can not see in the soil under the sunlight conditions and just can't degrade at all when these superpolymer.When particularly using Light ?lysis Film as mulch film, the season of growth of they and crop is difficult to synchronously, and in other words, when crop did not need to cover, covering with plastic film should be degraded exactly, otherwise, when crop also need cover, should not degrade.But, present photolyzed film, because various condition influence, the photodissociation mulch film is difficult to have the degraded of control, (sometimes because degraded period and crop growing season " asynchronous ") usually caused crop failure on the contrary.Therefore photolyzed film must be accomplished " controlled ".But accomplish quite difficulty of this point, even on producing, bring about great losses.
A kind of degradable composite membrane and method for making thereof have been introduced in CN90109135.9 (Finland Biodata Oy) application, and adopting synthetic polymer (polyethylene or polyacrylic olefines) and Biodegradable polymeric (as starch or Mierocrystalline cellulose) is the Biodegradable film of base-material.But this film still will be used synthetic high polymer, and technology is complicated.Even superpolymer degraded, but degradation time is long is the longest 2 years, and whether the degraded back is nontoxic, harmless to the farmland, still remain to be proved.
CN90109250.9 has introduced and has utilized cotton stalk and Pericarppium arachidis hypogaeae to prepare regenerated cellulose film, though this method is without synthetic high polymer, but " agricultural byproducts ", cuprammonia solvent legal system viscose glue problem of environmental pollution is many, wastewater treatment is difficulty quite, and 50% above non-cellulose yield is less in the raw material.
According to the problem that in exploitation preparation degradable membrane, exists both at home and abroad, patent applicant of the present invention is from the super straw fiber agricultural film that begins one's study and utilize cheapness can be degraded by microorganisms fully of in May, 1988, and to Patent Office of the People's Republic of China patent application " a kind of straw fiber agricultural with film and manufacture method thereof " is proposed June nineteen ninety, application number is 90103061.9, and publication number is CN10580284.This application for a patent for invention is incorporated reference at this.This straw fiber plastic sheeting for farm use has overcome domestic and international researchist of for some time and has developed the existing problem of degradative membrane.Its feature is that raw material sources are extensive, and the film of making can be swashed biological degradation by soil, can be incubated water conservation, can replace polyethylene commodity plastic sheeting for farm use and other starch film and photolyzed film in the market fully.Simultaneously, it can substitute a lot of plastics of making of synthetic high polymer on the market, has solved because synthetic high polymer down can the pollution degradation problem of environment.In recent years, the present patent application people by further investigation, has made a lot of substantial improvements to original straw fiber film on former patent application basis.The vegetable fibre film of the present patent application all has substantial improvements and significant technical progress on materials, kind, performance and technology.
The purpose of the present patent application provides a kind of vegetable fibre film and preparation technology thereof.This film can be used as mulch film, commodity packaging, especially food product pack, can also be used for green zone and dialysis tubing material and rubbish wrapping material.This plant cellulose is made up of plant cellulose, properties-correcting agent and moisture, and it consists of (by weight):
Plant cellulose 50-90%
Properties-correcting agent 0.2-40%
Moisture 5-20%
The plant cellulose raw material that vegetable fibre film of the present invention adopted comprises crop stalk such as straw, wheat straw, cotton stalk, vegetable seed bar, sunflower bar, corn stalk, sorghum rod and soybean bar etc., crop seeds cot class such as Pericarppium arachidis hypogaeae, sunflower shell, natural plant fibre class such as velveteen, fiber crops etc., timber is like birch, China fir, pine, shrub etc., plant screenings class such as wood pulp, bagasse etc., grass class such as Herba Poae Sphondylodis, alfa etc., bamboo class etc.
The kind of properties-correcting agent that is used for vegetable fibre film of the present invention is a lot, comprising: aromatic esters class such as dibutyl phthalate, di-sec-octyl phthalate, dioctyl phthalate (DOP), diisononyl phthalate, diheptyl phthalate, butyl benzyl phthalate, Di Iso Decyl Phthalate, phthalic acid C
4～C
10Ester, phthalic acid fourth (ethyl glycollate) ester, 4,5-epoxy tetrahydrophthalic acid two (the 2-ethyl is own) ester, terephthalic acid C
4～C
10Ester, fatty acid ester such as Methyl glutarate, pentanedioic acid dibutylester, C
5～C
9Mixed fatty acid glycol ester, bis(pentaerythritolester), Diethylene Glycol C
7～C
9Acid esters, glycol butyl, dioctyl sebacate, the sebacic acid di-sec-octyl, the motor dioctyl phthalate, butyl ester of epoxy fatty acid, epoxyfatty acid 2-ethylhexyl,, sorbitan monopalmitate, polyoxyethylene sorbitol acid anhydride trioleate, Tween-20, sorbitan trioleate etc., paraffinic hydrocarbon and substituent thereof such as emulsified olefin hydrocarbon, the clorafin hydrocarbon, the mixture of chlorination phenyl alkylsulf and clorafin etc., phosphoric acid ester such as dibutyl phenyl phosphate, Sodium hexametaphosphate 99, diphenyl octyl phosphate, three cresols phosphoric acid salts etc., polyvalent alcohol and derivative thereof such as ethylene glycol, glycol ether, Diethylene Glycol, glycerine, Sorbitol Powder etc., ethanolamines such as Monoethanolamine MEA BASF, diethanolamine, trolamine etc.; Plant oil such as soya-bean oil, peanut oil, rapeseed oil, plam oil, tung oil, castor-oil plant wet goods; Polyethenoxy ether class such as alkyl phenyl polyoxyethylene, fatty alcohol-polyoxyethylene ether, high fatty alcohol Soxylat A 25-7 etc., the copolymer analog of vinylformic acid and derivative thereof such as polyacrylic acid, poly-Class C acid amides, polyacrylic acid C
1～C
5Ester, vinylformic acid and acrylamide copolymer, vinylformic acid and vinylformic acid C
1～C
5The multipolymer of ester, poly-alkyl acrylic, poly-alkyl acrylamide, poly-alkyl acrylic C
1～C
5Ester, alkyl acrylic one alkyl acrylic C
1～C
5The multipolymer of ester etc., polyvinyl alcohol and acetals thereof such as polyvinyl alcohol, the polyvinyl alcohol C that contracts
1～C
4Aldehyde, the polyvinyl alcohol aromatic aldehyde etc. that contracts, Vinyl Acetate Copolymer and multipolymer thereof such as Vinyl Acetate Copolymer, vinyl acetate between to for plastic and C
2～C
5Olefin copolymer, the multipolymer of vinyl acetate between to for plastic and vinylformic acid and derivative thereof, vinyl acetate between to for plastic and fragrant olefin copolymer etc., polyolefine and multipolymer thereof such as polyethylene wax, oxidic polyethylene, emulsifiable polyethylene, polyvinylidene dichloride, vinyl chloride-vinylidene chloride copolymer, polyvinyl chloride etc., polyaromatic and multipolymer thereof such as butylbenzene copolymer, carboxyl butylbenzene copolymer etc., Mierocrystalline cellulose and starch based such as carboxymethyl cellulose, Natvosol, modified starch etc., Synolac such as water soluble alkyd resin, Resins, epoxy such as water-soluble epoxy resin, other properties-correcting agent also has: the aminoresin melamine formaldehyde resin, silicone, sodium alginate etc.
In the above properties-correcting agent even more preferably: aromatic esters class such as dibutyl phthalate, di-sec-octyl phthalate, dioctyl phthalate (DOP), diisononyl phthalate, butyl benzyl phthalate, phthalic acid fourth (ethyl glycollate), terephthalic acid C
4～C
10Ester, fatty acid ester such as Uniflex DBS, dioctyl sebacate, sebacic acid di-sec-octyl, C
5～C
9The mixed fatty acid glycol ester,, sorbitan monopalmitate, the motor dioctyl phthalate, epoxyfatty acid 2-ethylhexyl, paraffinic hydrocarbon and substituent thereof such as emulsified olefin hydrocarbon, the clorafin hydrocarbon, phosphoric acid ester such as dibutyl phenyl phosphate, Sodium hexametaphosphate 99, diphenyl octyl phosphate, polyvalent alcohol and derivative thereof such as ethylene glycol, glycol ether, Diethylene Glycol, glycerine, plant oil such as Viscotrol C, the polyoxyalkylene Viscotrol C, polyethenoxy ether class such as fatty alcohol-polyoxyethylene ether, the high fatty alcohol Soxylat A 25-7, copolymer analog such as polyacrylic ester and multipolymer thereof, the vinyl acetate between to for plastic acrylate copolymer, ethylene vinyl acetate, the styrene-acrylate multipolymer, polyolefine and multipolymer thereof such as polyethylene wax; butylbenzene copolymer; carboxyl butylbenzene copolymer; polyvinylidene dichloride; vinylchlorid vinylidene resin and carboxymethyl cellulose; water-soluble alcohol acid resin; water-soluble epoxy resin; terpolycyantoamino-formaldehyde resin.
The above-mentioned all kinds of properties-correcting agent kind difference that requirement adds according to the made film performance can be used separately also some properties-correcting agent can be mixed and use.Its consumption is generally 0.2%～40% by vegetable fibre film weight, better is 0.5～20%, is preferably 1～15%.The properties-correcting agent use-pattern also can be multiple, can mix film forming in the viscose glue by a certain percentage with above-mentioned relevant properties-correcting agent; Adopt after the regenerated cellulose film moulding and method such as spray, be coated with, soak and regenerated cellulose film is made composite membrane.The degradable plant cellulose film thickness of making is 8～20 μ.Measure its biology, optics, mechanical property and the not land for growing field crops application of 11 experimental points of same-action, different weather, different soils, test-results proves that its performance is an ideal.
(1) mechanical property: longitudinal stretching 17.3～49.2MPa
Cross directional stretch 13.3～30.4MPa
(2) optical property: transmittance 83.2～91.1%
(3) biology performance: film is imbedded in the 15cm moisture soil, and beginning in 40 days is decomposed slightly, degrades in 80 days; Cover on the ground 60 days beginning microcracks, the degraded rapidly that begins to split in 100 days; Film floods 15 days simulation laboratory tests of continuous degradation with the soil water, and total degradation rate is 3～4.69%.
(4) field experiment: test all has obvious effect of increasing production on crops such as peanut, cotton, soybean, corn, watermelon, and general amount of increase in production is all more than 20%, and corn reaches as high as 50%.
Another free-revving engine of the present invention provide have weeding, desinsection, sterilization and contain the vegetable fibre film of the compound nutriment in a fertilizer of N.P.K and trace element/rare earth element.These multi-function membrane compositions and making method are identical with aforementioned vegetable fibre film, just add the chemical substance with specific function therein, and the adding mode of these materials generally is to spray, be coated with, all can soak.
Weeding Mierocrystalline cellulose agricultural mulching
Contain weedicide in the weeding Mierocrystalline cellulose agricultural mulching of the present invention, it all is water miscible, its consumption be 0.05～1 the gram/square metre.According to crop and weeding object difference, adopt following weedicide usually: careless fourth phosphorus, Paraquat, difenzoquat, dalapon, bialaphos, alloxydim, weeds are burnt, a kind of or its mixture in the sodium pentachlorophenate.
Desinsection Mierocrystalline cellulose agricultural mulching
Contain sterilant in this film, said sterilant all is water miscible.The sterilant that adds has: a kind of or its mixture in monocrotophos, phosphamidon, Phosdrin, omethoate, phosfolan_methyl, acephatemet, acephate, first sulphur ring, desinsection grass, thiocyclam, disosultap, Padan and the cyhexatin.Their consumption is controlled at 50～2000PPm/ square metre.
The plain agricultural mulching of sterilizing fiber
Contain sterilant in this film, it is water-soluble, nontoxic.Sterilant has: a kind of or its mixture in sterilization pellet-AM, sodium paminobenzensulfonate, phosethyl Al, the phthalic acid, its consumption is generally 50～2000PPm/ square metre.
Contain element N, P, the plant cellulose plastic sheeting for farm use of the compound nutriment in a fertilizer of K
Can contain single nutriment in a fertilizer such as N in this film, P, K also can contain compound manure.By the solution spray that contains nutriment in a fertilizer, be coated with or the mode of soaking is fixed on the film surface, in membrane degradation or the shower of face aqueous vapor splash into, reach the purpose of increase crop alimentary nutriment in a fertilizer.At first solid fertilizer is dissolved in the water during use, sprays, be coated with or soak, be fixed in table body (surface).In film body degraded or the process of crop growth, impose on soil and the crop blade face reaches the purpose that increases crop nutrition content and increase production by the steam leaching of film.Said nutriment in a fertilizer has: a kind of or its mixture in urea, thiamines, bicarbonate of ammonia, ammonium nitrate, ammonium chloride, calcium superphosphate, fused(calcium magnesium)phosphate, secondary calcium phosphate, diammonium phosphate, Repone K, the potassium primary phosphate.They all are water miscible.The effective nutriment in a fertilizer concentration of face (N: P: K=6: 3: 1) is generally 2001000PPm/ square metre.
The plant cellulose plastic sheeting for farm use that contains trace element and rare earth element
Trace element is a kind of or its mixture salt that utilizes in iron, manganese, zinc, magnesium, nickel, cobalt, copper, the tin, makes its dissolving back extract the solution that contains above-mentioned each element, by soak, be coated with, the spray mode imposes on face.Rare earth element is to adopt mixed rare-earth elements, and profit uses the same method and is fixed on the film.Trace element and ree content can be controlled in 0.05～10PPm/ square metre by film size.
The above-mentioned vegetable fibre film technology of preparation provided by the invention comprises making of plant cellulose viscose glue and film forming.
Specifically, this technology may further comprise the steps:
(1) plant cellulose that concentrates in the purification plant cellulose raw material becomes dry pulp or wet loosing to starch, and with alkali lye its dipping is stirred the back and leaches hemicellulose, the soda cellulose after the pulverizing extruding;
(2) soda cellulose of heating impels its chain-scission degradation;
(3) be 0.074～0.093MPa in vacuum tightness, in the poly-soda cellulose of falling of stirring, add CS
2, make its sulfonation, add alkaline solution again, after stirring at low speed makes its dissolving fully, add properties-correcting agent and stir, make faint yellow viscose glue;
(4) viscose glue is filtered to remove impurity;
(5) carry out maturation with vacuumizing after making evacuation of viscose;
(6) viscose glue after the maturation is sprayed film;
(7) solidify with precipitation bath;
(8) bathe sulphuric acid soln with regeneration and make the cellulose membrane regeneration and the washing of solidifying;
(9) with alkali lye regeneration membrane is carried out desulfurization and washing;
(10) film after the desulfurization is bleached and washed;
(11) film after the bleaching is plastified, to improve its plasticity;
(12) the plasticizing film is rolled,, and increase film toughness with minimizing moisture and film thickness;
(13) with hot blast the film that rolled is carried out drying;
(14) coated surface properties-correcting agent on dried film surface makes vegetable fibre film;
(15) rolling.
Fig. 1 is that the plant cellulose viscose glue is made and the film forming schema.
Fig. 2 is that another kind of plant cellulose viscose glue is made and the film forming schema.
Below in conjunction with above-mentioned flow chart technology of the present invention is carried out in detail Describe.
The plant cellulose viscose glue is made
(1) alkali soaks the extruding pulverizing
According to different material, cellulose in the raw material is concentrated carry earlier Pure, make cellulose dry pulp (or pulp) or the wet slurry that looses. If press The aobvious slurry that looses, moisture is controlled at 10-60%, is 14-with concentration 25% bases such as NaOH dipping stir 40-140 rev/min to 40-120 minutes, unnecessary alkali is extruded, and therefrom extracted half fiber Element is used for making disposable container (such as cup, food box, mess-tin Deng), alkali lye recycles behind the extraction hemicellulose. Alkali fibre after the extruding Dimension is plain to enter experienced drum degraded through pulverizing.
(2) the alkali cellulose temperature control falls poly-
The alkali cellulose that will push in experienced drum after pulverizing is warmed to 20-100 ℃, be preferably 40-80 ℃, be preferably 45-65 ℃ About 1-3 hour, make cellulosic degree of polymerization approximately be controlled at 200-600, prevent that cellulose continues degraded under the high temperature, under 10-30 ℃ Kept 0.5-2 hour.
(3) sulfonation-dissolving
Alkali cellulose is put into sealing stirring in the retort after degrading, and is keeping adding the CS that counts 15-45% (WT) by cellulose amount in the vacuum 600mmHg situation2, reacted 1-2.5 hour, when The r value of cellulose xanthic acid fat 20-40 hour adds 10-15% The aqueous slkali dissolving stirring at low speed 1.5-4 hour, adds behind the dissolve complete Modifier stirs, and makes faint yellow cellulose viscose glue. The viscose glue fibre The dimension cellulose content is controlled at 5-9%, and alkali content is at 4-7.5%, with falling The ball method is measured viscose riscosity and is got final product second for 30-90.
(4) viscose filtration
Impurity does not take film formation process in the viscose glue manufacturing process in order to make, and carries High film quality filters viscose glue. Filtration can be carried out twice.
(5) evacuation of viscose maturation
A large amount of bubble vacuumizing and defoaming in the viscose glue, the vacuum defoamation process In, the hydrolysis saponification takes place in the glue, xanthic acid comes off. Use salt The measured in solution xanthic acid degree that comes off. It is sticking after degree of ripeness is 4-8 But glue film forming. The maturation time is generally 30-80 hour, and temperature is 8-30 ℃.
In viscose glue manufacturing process of the present invention, also can be with the plant fibre Tie up that plain alkali soaks, poly-, sulfonation falls in pulverizing, chain rupture, a synthetic step of dissolving Carry out, make viscose glue by batch viscose machine. Viscose glue forms and above-mentioned technology It is identical that process makes. Making adhesive means for two kinds determines according to main To decide according to the plant cellulose quality.
Film forming
Referring to Fig. 1,2, plant cellulose viscose glue film forming of the present invention is Carry out continuously on film-forming machine, the film-forming machine linear velocity is 10-60M/ second, film forming thickness is 8-20 μ, is preferably 12-14 μ. The film forming width is about 1.5M.
(1) spray film
The spray film is relevant with quality of forming film, and the spray seam is controlled at during operation 0.15-0.25mm chamber pressure is 0.05-0.2MPa.
(2) solidify
Coagulating bath is by sulfuric acid 90-180 grams per liter and sodium sulphate 180-240 grams per liters and part froth breaking stabilizing agent form, and content is 20-80 Fill/liter, temperature is to solidify under 40-60 ℃.
(3) regeneration
Regeneration bathe be sulfuric acid solution, content be the 50-130 gram/ Rising, is 40-70 ℃ of regeneration in temperature.
(4) desulfurization
Cellulose membrane is containing the 0.15-0.80 grams per liter after will regenerating Under 60-90 ℃, carry out desulfurization in the desulfurizer of alkali lye.
(5) bleaching
Film after the desulfurization is floated under 20-30 ℃ in bleaching cistern In vain, bleaching cistern includes calcium hypochlorite, clorox or takes place with ozone Device. Effectively Cl and O content are the 0.3-1.2 grams per liter.
(6) plasticizing
With 8-17% one diethyl acetal or glycerine and 0.5-2.0% silicon Colloidal sol plastifies the film of bleaching, improves film feel and plasticity.
(7) by means of two different hardness rubber rolls plasticizing after with The cellulose membrane of large quantity of moisture rolls, reduce moisture, reduce thick Degree; The packing of gaining in strength and increasing film. Thereby minimizing back Film drying process transpiring moisture energy consume.
In the above film forming procedure, after the viscose glue film forming from regeneration until float In vain, for preventing that solution mixes mutually in per step operation groove, guarantee concentration Change not quite, so per step inter process has rinsing bowl, its temperature is 40-60 ℃.
(8) drying
Drying be film by means of hot blast, make film roll that cylinder walks about the time Between in, moisture evaporation in the film body. The linear velocity of drying cylinder and film-forming machine Linear velocity is identical. The temperature of hot blast is unsuitable too high, the temperature of drying line Be low-high-low-cold. Film body keeps 5-20% water after the oven dry Divide.
(9) membrane surface modification
On dried film surface, be coated with the table of 2-5 μ with coating machine Face modifier, a kind of in Insecticides (tech) ﹠ Herbicides (tech), the bactericide or More than kind, also can apply N.P.K nutriment in a fertilizer, trace element and rare Earth elements.
Below be the embodiment of vegetable fibre film of the present invention, it is to specify of the present invention, rather than protection scope of the present invention is limited.Should be appreciated that the various modifications and changes of carrying out all belong to protection scope of the present invention in spirit of the present invention.
Embodiment 1
1000 gram wheat straw oven dry stocks (cellulose 70%) are extracted with extrusion machine, moisture reaches 35%, stirs with 20 liters of 20%NaOH and soaks 60 minutes, by the congee pump is squeezed into the aperture squeezing machine, NaOH content is about 14% in the soda cellulose after pressing dry, and content of cellulose is about 30%.Soda cellulose is by pulverizing on the thickness pulverizer, then adds 50 ℃ experienced 1.5 hours of experienced drum, with tap water constant temperature 1 hour, sends into the airtight 600mmHg of the being evacuated to post in sulfonation jar stirring at low speed (12 rev/mins) back, adds the 160mlCS of cellulose amount 30%
2React 1.5 hours to cellulosic r value be more than 30.Add 11%NaOH solution dissolving cellulos xanthate, faster rotational speed is 24 rev/mins.Make the Mierocrystalline cellulose viscose glue become NaOH5%, Mierocrystalline cellulose 8% above viscose glue, viscosity is 40 seconds (falling ball method), mixes the dioctyl terephthalate that accounts for cellulose amount 8% simultaneously in viscose glue, stirs about 2 hours.The back dissolving vessel is got to toothed gear pump in the basic evenly back of dissolving, continues stirring and dissolving 2 hours with 150 rev/mins, with cold water cooling back dissolving vessel, when the sampling observation does not have little micelle substantially, squeezes into tundish with toothed gear pump and filters.Enter deaeration storage glue jar calymma after the filtration, it is experienced under 20 ℃ of constant temperature to vacuumize 600mmHg, measures degree of ripeness after 40 hours and is about 6 and get final product film forming.
With film former engine speed 30 meter per seconds, spray lip spray seam is that 0.20mm enters in the coagulating pan viscose glue, H in the precipitation bath
2SO
4Concentration is about 145 grams per liters, Na
2SO
4Concentration is about 210 grams per liters, and temperature is 45 ℃, and viscose glue is rapid freezing film in coagulating pan, and film then enters and contains H
2SO
480 grams per liters, temperature is that 55 ℃ regeneration tank is regenerated, and wash, the desulfurizer that to enter temperature then be 75 ℃, contain the NaOH0.5 grams per liter carries out desulfurization, and face washed, film after the washing enters the bleaching tank that contains clorox 0.5 grams per liter and bleaches, and bleaching temperature is 25 ℃, enters in the plasticizing groove that contains 12% glycol ether and 1% silicon bath glue to plastify after washing.Film body moisture is heavy 2.5 times of film after rolling, and film is 50-90-50 ℃ through temperature variation, and the drying system of a room temperature is dried to that moisture content is 9% in the film.Make the vegetable fibre film of 630 grams at last at the Diethylene Glycol of coated cellulose amount on the face about 5%, yield is 87%, moisture content 10%, thickness 14.4 μ, transmittance 86%, permeable gas is 3.50 gram/square metre hour (20 ℃), and longitudinal tensile strength is 19.5MPa, and transverse tensile strength is 15.4MPa.
Embodiment 2
Operate by embodiment 1 identical process, different just replaces straw with wheat straw, and properties-correcting agent replaces dioctyl terephthalate with.Make film 600 grams, yield 85.7%, water content 9%, thickness 13.60 μ, transmittance 86.3%, permeable gas 3.6 gram/square metre hour (20 ℃), longitudinal tensile strength 18.6MPa, transverse tensile strength 16.2MPa.
Embodiment 3
Operating process is identical with embodiment 1, and different is to replace straw with wood pulp, and properties-correcting agent replaces dioctyl terephthalate with dibutyl phenyl phosphate.Make film 610 gram, yield 89.0%, water content 9%, thickness 12.80 μ, transmittance 90.2%, permeable gas 3.8 grams/square metre hour, longitudinal tensile strength 23.9MPa, transverse tensile strength 18.5MPa.
Embodiment 4
Make film earlier by embodiment (1) operating process.
Get 1000 gram urea, 2000 gram monocalcium phosphates and 1000 gram potassium primary phosphates, soaking and stirring is 15 minutes in 10 premium on currency, gets 2 liters of leach liquors and mixes 20 liters of Diethylene Glycols.Get 2 liters of these mixed solutions and be coated onto on 20 square metres of faces, the about 1000PPm/ of N.P.K coating concentration square metre, N: P: the K ratio is 6: 3: 1.Thickness is 16 μ, longitudinal tensile strength 19.2MPa, and transverse tensile strength 15.1MPa, transmittance are 85%.
Embodiment 5
Make film earlier by embodiment 1 operating process
Make 10 liters of effective monocrotophos solution of 200PPm, in 2 liters of these liquid, add water soluble alkyd resin, it is coated onto on 20 square metres of faces.This film contains effective monocrotophos 100PPm/ square metre, and thickness 16 μ, transmittance are 85%, and longitudinal tensile strength 18.4MPa, transverse tensile strength are 14.8MPa.
Claims (28)
1. vegetable fibre film, it consists of by weight:
Plant cellulose 50-90%
Properties-correcting agent 0.2-40%
Moisture 5-20%
Said properties-correcting agent is selected from the vegetable fibre film: the multipolymer of aromatic esters, fatty acid ester, paraffinic hydrocarbon and derivative thereof, phosphoric acid ester, polyvalent alcohol and derivative thereof, vegetables oil, Soxylat A 25-7, acrylic acid and derivative thereof, polyvinyl alcohol and acetal thereof, polyolefine and multipolymer thereof, Mierocrystalline cellulose and starch, Synolac, Resins, epoxy, aminoresin and sodium alginate.
2. according to the vegetable fibre film of claim 1, wherein said plant cellulose is selected from: crop stalk, crop seeds cot, natural plant fibre, timber, careless class or bamboo.
3, according to the vegetable fibre film of claim 1, wherein said plant cellulose is selected from: straw, wheat straw, bagasse, Herba Poae Sphondylodis, wood pulp, velveteen, reed.
4. according to the vegetable fibre film of claim 1, wherein said properties-correcting agent is selected from: dibutyl phthalate, di-sec-octyl phthalate, dioctyl phthalate (DOP), diisononyl phthalate, butyl benzyl phthalate, phthalic acid fourth (ethyl glycollate), terephthalic acid C
4-C
10Ester, Uniflex DBS, dioctyl sebacate, sebacic acid di-sec-octyl, C
5-C
9The mixed fatty acid glycol ester,, sorbitan monopalmitate, dioctyl maleate, epoxyfatty acid 2-ethylhexyl, the emulsified olefin hydrocarbon, the clorafin hydrocarbon, dibutyl phenyl phosphate, Sodium hexametaphosphate 99, diphenyl octyl phosphate, glycol ether, Diethylene Glycol, ethylene glycol, glycerine, Viscotrol C, the polyoxyalkylene Viscotrol C, fatty alcohol-polyoxyethylene ether, the high fatty alcohol Soxylat A 25-7, acrylate copolymer, vinyl acetate between to for plastic and acrylate copolymer, ethene and acetate ethylene copolymer, vinylbenzene and acrylate copolymer, polyethylene wax; butylbenzene copolymer; carboxyl butylbenzene copolymer; polyvinylidene dichloride; vinylchlorid vinylidene chloride copolymer; carboxymethyl cellulose; water soluble alkyd resin; water-soluble epoxy resin or terpolycyantoamino-formaldehyde resin.
5. according to the film of claim 1, wherein said properties-correcting agent consumption is counted 0.5-20% by film weight.
6. according to the film of claim 1, wherein said properties-correcting agent consumption is counted 1-15% by film weight.
7. according to the film of claim 1, its longitudinal tensile strength is 17.3-49.2MPa, and transverse tensile strength is 13.3-30.4MPa.
8. one kind prepares vegetable fibre film technology, comprising:
(1) concentrates dry pulp or the wet diffusing slurry that the plant cellulose in the purification plant cellulose raw material is made, with alkali lye it is flooded and stir back proposition hemicellulose, pulverize the Mierocrystalline cellulose after pushing;
(2) that its chain rupture is fallen is poly-for the heating soda cellulose;
(3) in being the soda cellulose that is stirred of 0.079-0.093MPa, vacuum tightness adds CS
2, make its sulfonation, add alkaline solution again, after stirring at low speed makes its dissolving fully, add properties-correcting agent and stir, make faint yellow viscose glue;
(4) viscose glue is filtered to remove impurity;
(5) carry out maturation with vacuumizing after making evacuation of viscose;
(6) viscose glue after the maturation is sprayed film;
(7) solidify with precipitation bath;
(8) bathe sulphuric acid soln with regeneration and make the film regeneration of solidifying
(9) with alkali lye regeneration membrane is carried out desulfurization;
(10) film after the desulfurization is bleached;
(11) film after the bleaching is plastified, to improve its plasticity;
(12) the plasticizing film is rolled,, and increase film toughness with minimizing moisture and film thickness;
(13) with hot blast the film that rolled is carried out drying;
(14) coated surface properties-correcting agent on dried film surface makes vegetable fibre film;
(15) rolling.
9. technology according to Claim 8, wherein said properties-correcting agent is made film by mixing in the viscose glue
10. technology according to Claim 8, wherein said properties-correcting agent are by spray, are coated with or the method for soaking is coated on the film surface and forms.
11. technology according to Claim 8, alkali are wherein soaked, push, pulverize, fall poly-and the sulfonation dissolving can be combined into a step and carries out.
12. technology according to Claim 8, wherein the wet pulp-water branch that looses in the step (1) is 14-25% at the 10-60% alkali concn.
13. technology according to Claim 8, wherein the Heating temperature in the step (2) is 20-100 ℃, and cellulosic degree of polymerization is 200-600.
14. technology according to Claim 8, the wherein CS in the step (3)
2Consumption is counted 15-45% (WT) by cellulose amount, and the viscose fiber cellulose content is 5.0-9.0%, and viscosity is 30-90 second.
15. technology according to Claim 8, wherein the maturation temperature in the step (5) is 8-30 ℃, and the time is 30-80 hour.
16. technology according to Claim 8, wherein spray lip spray seam is 0.15-0.25mm in the step (6), and chamber pressure is 0.05-0.2MPa.
17. technology according to Claim 8, wherein temperature of solidification is 40-60 ℃ in the step (7).
18. technology according to Claim 8, wherein regeneration temperature is 40-70 ℃ in the step (8).
19. technology according to Claim 8, wherein desulfurization temperature is 60-90 ℃ in the step (9).
20. technology according to Claim 8, wherein bleaching temperature is 20-30 ℃ in the step (10).
21. technology according to Claim 8 wherein keeps 5-20% moisture with film body after the warm air drying in the step (13).
22. the vegetable fibre film of claim 1 is as agricultural mulching.
23. the vegetable fibre film of claim 1 is as the commodity packaging material.
24. the vegetable fibre film of claim 1 is as diet product and drug packing material.
25. the vegetable fibre film of claim 1 is as meat intestines, fruit, vegetables and candy, cake packaging material.
26. the vegetable fibre film of claim 1 is as the rubbish wrapping material.
27. the vegetable fibre film of claim 1 is as green zone.
28. the vegetable fibre film of claim 1 is as dialysis tubing.
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN92114514A CN1036140C (en) | 1992-12-18 | 1992-12-18 | Vegetable fibre film product and its process |
| JP5342322A JPH0770366A (en) | 1992-12-18 | 1993-12-15 | Plant-derived cellulose film product and its production |
| DE4342723A DE4342723A1 (en) | 1992-12-18 | 1993-12-15 | Vegetable cellulose film and process for its production |
| AU52513/93A AU677243B2 (en) | 1992-12-18 | 1993-12-17 | Plant cellulose film products and process of preparing the same |
| CA002111732A CA2111732A1 (en) | 1992-12-18 | 1993-12-17 | Plant cellulose film and process of preparing the same |
| BR9305113A BR9305113A (en) | 1992-12-18 | 1993-12-17 | Plant cellulose film and process for preparing the same |
| KR1019930028486A KR940014563A (en) | 1992-12-18 | 1993-12-18 | Plant cellulose film and its manufacturing method |
| GB9325981A GB2273458B (en) | 1992-12-18 | 1993-12-20 | Vegetable cellulose films |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN92114514A CN1036140C (en) | 1992-12-18 | 1992-12-18 | Vegetable fibre film product and its process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1088225A CN1088225A (en) | 1994-06-22 |
| CN1036140C true CN1036140C (en) | 1997-10-15 |
Family
ID=4946971
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN92114514A Expired - Fee Related CN1036140C (en) | 1992-12-18 | 1992-12-18 | Vegetable fibre film product and its process |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JPH0770366A (en) |
| KR (1) | KR940014563A (en) |
| CN (1) | CN1036140C (en) |
| AU (1) | AU677243B2 (en) |
| BR (1) | BR9305113A (en) |
| CA (1) | CA2111732A1 (en) |
| DE (1) | DE4342723A1 (en) |
| GB (1) | GB2273458B (en) |
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-
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- 1992-12-18 CN CN92114514A patent/CN1036140C/en not_active Expired - Fee Related
-
1993
- 1993-12-15 JP JP5342322A patent/JPH0770366A/en active Pending
- 1993-12-15 DE DE4342723A patent/DE4342723A1/en not_active Withdrawn
- 1993-12-17 BR BR9305113A patent/BR9305113A/en not_active Application Discontinuation
- 1993-12-17 CA CA002111732A patent/CA2111732A1/en not_active Abandoned
- 1993-12-17 AU AU52513/93A patent/AU677243B2/en not_active Ceased
- 1993-12-18 KR KR1019930028486A patent/KR940014563A/en not_active Application Discontinuation
- 1993-12-20 GB GB9325981A patent/GB2273458B/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100460596C (en) * | 2000-03-31 | 2009-02-11 | 永丰余造纸股份有限公司 | A nulti-functional paper and a method of making the same |
| CN109197283A (en) * | 2018-09-08 | 2019-01-15 | 佛山市森昂生物科技有限公司 | A kind of preparation method of degradable water conservation mulch |
| CN110330804A (en) * | 2019-07-02 | 2019-10-15 | 大庆正和能源科技开发有限公司 | A kind of full degradable mulch of addition biomass fiber controllable biological base |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0770366A (en) | 1995-03-14 |
| AU677243B2 (en) | 1997-04-17 |
| KR940014563A (en) | 1994-07-18 |
| GB9325981D0 (en) | 1994-02-23 |
| GB2273458A (en) | 1994-06-22 |
| CA2111732A1 (en) | 1994-06-19 |
| GB2273458B (en) | 1997-06-04 |
| DE4342723A1 (en) | 1994-06-23 |
| BR9305113A (en) | 1994-07-05 |
| CN1088225A (en) | 1994-06-22 |
| AU5251393A (en) | 1994-06-30 |
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