CN1139639C - Agricultural synthetic resin covering material - Google Patents

Agricultural synthetic resin covering material Download PDF

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Publication number
CN1139639C
CN1139639C CNB998015938A CN99801593A CN1139639C CN 1139639 C CN1139639 C CN 1139639C CN B998015938 A CNB998015938 A CN B998015938A CN 99801593 A CN99801593 A CN 99801593A CN 1139639 C CN1139639 C CN 1139639C
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Prior art keywords
water smoke
fluorochemicals
smoke agent
acid
group
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CN1297326A (en
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盐治源市郎
树
福田博树
之
占野尚之
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AGC Inc
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Asahi Glass Co Ltd
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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
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G9/00—Cultivation in receptacles, forcing-frames or greenhouses; Edging for beds, lawn or the like
    • A01G9/14—Greenhouses
    • A01G9/1438—Covering materials therefor; Materials for protective coverings used for soil and plants, e.g. films, canopies, tunnels or cloches
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2639—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing elements other than oxygen, nitrogen or sulfur
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
    • Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
    • Y02A40/25—Greenhouse technology, e.g. cooling systems therefor

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  • Chemical & Material Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Soil Sciences (AREA)
  • Environmental Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)

Abstract

The present invention relates to agricultural synthetic resin covering materials which can inhibit the generation of water fog near the inner surfaces of the covering materials and has good continuity for preventing the water fog. The agricultural synthetic resin covering materials contain fluorochemicals (R<f>-Q-O-(A-O)n-R), water fog preventing agents B(the water fog preventing agents are derived from polyalcohol and the fatty acid of 10 to 22 carbon atoms)or water fog preventing agents C(the water fog preventing agents are derived from polyalcohol, the fatty acid of 10 to 22 carbon atoms and epoxides).

Description

Agricultural synthetic resin covering material
Technical field
The present invention relates to agricultural synthetic resin covering material, more particularly, relate to having and be suppressed at the water smoke that the cover material internal surface generates and be suppressed at the agricultural synthetic resin covering material that the ability (this ability be called prevent the water smoke persistence) of the excellent waterproof fog effect of the ability (this ability is called anti-water smoke) of water smoke phenomenon and long-time performance takes place near the cover material place.
Background technology
In recent years,, carry out the cultivation of greenhouse production and plastics tunnel widely, promptly under agricultural synthetic resin covering materials such as agricultural vinyl film cover, carry out promotion, half promotion of useful plant or suppress cultivation for improving productivity and the marketable value of useful plant.
In this greenhouse production and the cultivation of plastics tunnel, the major part of the synthetic resin covering material (as the polyvinyl chloride resin film) that uses is for promoting cover material internal surface (that is inside side surface in greenhouse and plastics tunnel, now.As follows) water droplet flow down, increase the sight amount of incident, contain the promptly anti-water smoke agent of a kind of tensio-active agent.Under the covering of the cover material that contains this type of anti-water smoke agent, it is big that the temperature difference of cover material inside and outside becomes, and therefore, usually can observe the water smoke phenomenon near cover material internal surface place.
This water smoke phenomenon mostly occur for facility cultivation such as greenhouse production and the cultivation of plastics tunnel most important late fall to winter.The reason that the water smoke phenomenon takes place it be unclear that, but the sight amount of incident in temperature, humidity, greenhouse or the tunnel in supposition greenhouse or the tunnel in temperature, water content, greenhouse or the tunnel of soil, the hydrophilicity of cover material wet side etc. influence each other knifeedge, make the moisture in greenhouse or the tunnel be difficult to carry out smoothly attached to the phenomenon under the cover material surface current along with temperature variation, the moisture of a part becomes vaporific near the cover material internal surface.
This water smoke phenomenon appears near the ground surface in greenhouse or the tunnel, near the cultivated plant and near the cover material internal surface.Promptly, cover material and cover material internal surface are owing to the decline of outside air temperature is cooled, and the greenhouse produces temperature head between the inside, warm-humid air in the greenhouse moves near the cover material internal surface owing to natural convection, become and to be taken place condensing by the water vapor that air comprised, it is promptly vaporific to become small water droplet, and natural convection is in the greenhouse or the tunnel internal diffusion.The vaporific minute water that forms drops in reevaporate in the natural convection way and when disappearing, and water smoke is or not the greenhouse or the tunnel internal diffusion, but evaporation disappearance speed is all covered by thick fog in greenhouse or the tunnel when slow.
This water smoke phenomenon makes in greenhouse or the tunnel leaf, stem, flower, fruit of the useful plant of cultivation etc. moistening, becomes the reason of generation disease, perhaps helps disease spread.In addition, for making moistening plant drying, need heating, thus, producing needs more fuel with problems such as temperature in raising greenhouse or the tunnel.In addition, also there is visibility meter variation in the greenhouse and causes problems such as farm work decrease in efficiency.
In the past, for reducing the temperature Change in greenhouse or the tunnel as much as possible, adopted the whole bag of tricks, as use painted agricultural synthetic resin film, perhaps with the soil in overlay film covering greenhouse or the tunnel, suppress the evaporation of water amount, perhaps improve sprinkling method (for example water after the dusk, regulate and water water section and water the water yield etc.), improve watering device etc.Yet these methods all can not suppress the generation of water smoke phenomenon fully.
As a kind of technology that overcomes above-mentioned shortcoming, the open communique of Japanese PCT special permission discloses for 1993 No. 72942 a kind of and has been used as the tensio-active agent of preventing the water smoke agent and the method for improving the fluorochemical surfactant of anti-water smoke.
Yet, according to present inventor's experiment, be not that all fluorochemical surfactants have anti-water smoke, even and have the compound of anti-water smoke, the anti-water smoke persistence to film produces detrimentally affect sometimes.
The objective of the invention is, provide to have to be suppressed near ability (anti-water smoke) that occurs the water smoke phenomenon cover material internal surface and agricultural synthetic resin covering material with excellent anti-water smoke persistence.
Summary of the invention
The invention provides the fluorochemicals that contains following formula 1 expression and the agricultural synthetic resin covering material of anti-water smoke agent,
R f-Q-O-(A-O) n-R ... in formula 1 formula,
R f: the polyfluoro aliphatic hydrocarbyl of 1-22 carbon atom,
The straight or branched alkylidene group of Q:3 or 4 carbon atoms,
The integer of n:1-100,
The alkylidene group of A:2-4 carbon atom, the hydrogen atom of this alkylidene group can be replaced by aromatic hydrocarbyl, alkoxyl group or phenoxy group.A when n is 2-100 can be identical or different,
R: the alkyl of hydrogen atom, a 1-18 carbon atom or the acyl group of 1-18 carbon atom.
Described anti-water smoke agent is following anti-water smoke agent B and/or anti-water smoke agent C,
Anti-water smoke agent B: the anti-water smoke agent that comes by the fatty acid derived of polyvalent alcohol and 10-22 carbon atom,
Anti-water smoke agent C: lipid acid and epoxide by polyvalent alcohol, a 10-22 carbon atom are derived and next anti-water smoke agent;
With respect to synthetic resins 100 weight parts, the amount of fluorochemicals is the 0.01-5.0 weight part, and the amount of anti-water smoke agent is the 1-5 weight part.
Embodiment
In the present invention, " alkyl " is meant the alkyl of only being made up of carbon atom and hydrogen atom in principle, comprise " aliphatic hydrocarbyl " and " aromatic hydrocarbyl " both.In aliphatic hydrocarbyl, preferred alkyl, alkenyl.The more than one hydrogen atom of aliphatic hydrocarbyl can be replaced by aromatic hydrocarbyl (as benzyl).In aromatic hydrocarbyl, preferred phenyl.
Fluorochemicals of the present invention is by following formula 1 expression.
R f-Q-O-(A-O) n-R ... formula 1
R in the formula 1 fExpression polyfluoro aliphatic hydrocarbyl is (to call R in the following text fGroup), 1-22 carbon atom arranged.R fGroup is 2 groups that above hydrogen atom is replaced by fluorine atom in the aliphatic hydrocarbyl.
R fThe carbonatoms of group is 1-22, and individual with 1-16 is good, is preferably 6-14.R fNumber of fluorine atoms in the group is by (R fThe number of fluorine atoms of group)/(with R fDuring (%) expression hydrogen atom in the aliphatic hydrocarbyl of the same carbon atoms number of group correspondence) * 100,, be preferably in more than 80% with being good more than 60%.In addition, R fGroup is good with linear chain structure or branched structure, preferably linear chain structure.When being branched structure, preferably component is that carbonatoms is the short chain about 1-3 and is present in R fThe terminal portions of group.
R fGroup preferably the perfluor aliphatic hydrocarbyl (to call R in the following text FGroup), has linear chain structure.R FGroup is actually R fThe group that hydrogen atom in the group is all replaced by fluorine atom.That is R, fGroup is preferably by F (CF 2) mThe group of-(m is the integer of 1-18) expression.M is 4-16 preferably, is preferably 6-14.
The R of linear chain structure FGroup is C 2F 5I and tetrafluoroethylene telomerize product, in addition, the alkyl of branched structure obtains by carrying out oligomerization with fluorochemical monomers such as catalyzer Paratetrafluoroethylene, R 1216 such as KF, CsF.
Fluorochemicals can be R fThe mixture of compound more than two kinds that the carbonatoms of group is different.Especially preferably with R fThe carbonatoms of group is that the fluorochemicals of 6-14 is main component, R fThe average carbon atom number of group is the mixture of 8-10.
Q in the fluorochemicals is that carbonatoms is the straight or branched alkylidene group of 1-5.The carbonatoms of Q is good with 2,3 or 4, preferably 3 or 4.
Q is C 3Or C 4The fluorochemicals of alkylidene group especially in the various environment when the synthetic resin covering material, still keeps good chemical stability and thermotolerance.
The example of Q has ethylidene, trimethylene, tetramethylene, propylidene (CH (CH 3) CH 2-), butylidene (CH (CH 3) CH 2CH 2-,-CH 2CH (CH 3) CH 2-,-CH (CH 3) CH (CH 3)-) etc.When Q has unsymmetric structure (for example propylidene), R fCan be connected with either party keyed jointing head.
N in the fluorochemicals is the integer of 1-100, is good with 2-50.When being the different mixture of compound more than two kinds of n number, the n mean value of fluorochemicals of the present invention is good with 1-50, is preferably 2-30.
A in the fluorochemicals is that carbonatoms is the alkylidene group of 2-4, and the hydrogen atom of this alkylidene group can be replaced by aromatic hydrocarbons or alkoxyl group.Its preferred example have ethylidene, tetramethylene, propylidene ,-CH (C 6H 5) CH 2-,-CH (CH 2OR 1) CH 2-etc.When A has unsymmetric structure (as propylidene), unqualified to its directivity.Wherein, R 1The alkyl of 1-10 carbon atom of expression, preferable methyl, butyl, 2-ethylhexyl.
When n is 2-100, can be identical or different between the A more than 2.When not simultaneously, A is 2 kinds or 3 kinds preferably, preferably 2 kinds.A in the fluorochemicals preferably has a kind or 2 kinds of existence, and these the 2 kinds of existence of ethylidene and propylidene are especially preferably arranged.
(A-O) nBe oxyalkylene, the polyoxy alkylidene that the opening by cyclic ethers obtains.
Cyclic ethers is preferably the compound that comprises the 3-5 unit ring-type ether that 1 Sauerstoffatom is arranged in the ring, preferably has the compound (monoepoxide) of 3 yuan of ring-type ethers.The epoxide of especially preferred 2,3 or 4 carbon atoms.
The example of cyclic ethers has oxyethane, propylene oxide, 1,2-butylene oxide ring, 2,3-butylene oxide ring, 1,1-dimethyl ethylene oxide, trimethylene oxide, methyl trimethylene oxide, phenyl glycidyl ether, tetrahydrofuran (THF), Styrene oxide 98min., alkyl glycidyl ether etc.The example of alkyl glycidyl ether has methyl glycidyl ether, butylglycidyl ether, 2-ethylhexyl glycidyl ether etc.
Preferable cyclic ethers is oxyethane, propylene oxide and tetrahydrofuran (THF).Tetrahydrofuran (THF) open loop and the A that forms is a tetramethylene.
Cyclic ethers can multiplely share, and preferably uses one or two or more kinds.When using the cyclic ethers more than two kinds, the mixture of the cyclic ethers more than two kinds can be used for reaction, also the cyclic ethers more than two kinds can be used for successively reaction.R in the fluorochemicals represents the alkyl of hydrogen atom, a 1-18 carbon atom or the acyl group of 1-18 carbon atom.
When R is the alkyl of 1-18 carbon atom, the alkyl of preferred 1-18 carbon atom, its example has ethyl, n-propyl, normal-butyl, the n-pentyl of methyl, linear chain structure.When R was the acyl group of 1-18 carbon atom, this acyl group is the acyl group of 1-10 carbon atom preferably, especially the acyl group of 1-6 carbon atom.
In above-mentioned group, R is hydrogen atom or methyl preferably, especially hydrogen atom.
The object lesson of fluorochemicals includes but not limited to following compound.In following compound, be equivalent to R FThe part of group can be a linear chain structure, also can be branched structure, is good with linear chain structure.In addition, when the polyalkylene chain that contains oxyalkylene more than two kinds existed, its mode of connection can be a block, also can be random.(C 3H 6O) part is represented the oxygen propylidene, that is, and and [CH (CH 3) CH 2O] or [CH 2CH (CH 3) O].In addition, (C 4H 8O) part is represented the ring-opening product (CH of tetrahydrofuran (THF) 2CH 2CH 2CH 2O).
In the present invention, fluorochemicals can be distinguished use separately, also can be used in combination more than two kinds.
C 8F 17C 2H 4O(C 3H 6O) 10H、
C 8F 17C 2H 4O(C 3H 6O) 4(C 2H 4O) 8H、
C 8F 17C 2H 4O(C 2H 4O) 13H、
C 8F 17C 2H 4O(C 4H 8O) 3(C 2H 4O) 10H、
C 8F 17C 3H 6O(C 3H 6O) 10H、
C 8F 17C 3H 6O(C 3H 6O) 4(C 2H 4O) 8H、
C 8F 17C 3H 6O(C 2H 4O) 13H、
C 8F 17C 3H 6O(C 4H 8O) 3(C 2H 4O) 10H、
C 8F 17C 4H 8O(C 3H 6O) 10H、
C 8F 17C 4H 8O(C 3H 6O) 4(C 2H 4O) 8H、
C 8F 17C 4H 8O(C 2H 4O) 13H、
C 8F 17C 4H 8O(C 4H 8O) 3(C 2H 4O) 10H、
C 8F 17C 4H 8O(CH(C 6H 5)CH 2) 2(CH(CH 2OCH 3)CH 2) 4H、
C 8F 17C 4H 8O(C 3H 6O) 4(C 2H 4O) 8CH 3、
C 8F 17C 4HC 8O(C 3H 6O) 4(C 2H 4O) 8COC 18H 37。
Fluorochemicals of the present invention passes through the cyclic ethers open loop then to R fQOH carries out addition and obtains.
R fThe synthetic method of QOH for example has: when Q is CH 2The time, with the ethene addition by the above-mentioned perfluoroalkyl iodides R that obtains that telomerizes FOn the I, obtain perfluoro alkyl ethylene R after the alkaline purification FCH=CH 2, with its oxidation, obtain perfluoro carboxylic acid then: R fCOOH uses NaBH again 4Deng with its reduction, obtain required R thus fCH 2OH.
Q is (CH 2) 2R fThe synthetic method of QOH for example has: at above-mentioned R FInsert ethylidene among the I, replace terminal iodine with hydroxyl then.
Q is (CH 2) 3R fThe synthetic method of QOH for example has: with the vinyl carbinol addition at above-mentioned R FOn the I, make hydrogen replace iodine with reductive agent then.
Q is (CH 2) 4R fThe synthetic method of QOH for example has: with 3-butene-1-pure addition at above-mentioned R FOn the I, make hydrogen replace iodine with reductive agent then.
In addition, as carbonatoms be the R of the isomer of 4 above-claimed cpd fCH 2CH 2CH 2(OH) CH 3Synthetic method for example have: with above-mentioned R FCH=CH 2Be dissolved in the ethanol, add radical initiator, heat while stirring, carry out the ethanol addition, obtain required product thus by the free radical addition reaction.
Q is (CH 2) 5R fThe synthetic method of QOH for example has: with the addition of 4-amylene-1-ol at above-mentioned R FOn the I, make hydrogen replace iodine with reductive agent then.
When cyclic ethers carries out opening more than two kinds, make its reaction after their can being mixed, they are reacted successively.When only using a kind of cyclic ethers and when using more than two kinds cyclic ethers, all can also they can be joined slowly in the reaction system in their disposable input reaction systems.
Fluorochemicals makes cyclic ethers and R usually in the presence of catalyzer fThe mixture reaction of QOH and generating.In addition, but also the limit cyclic ethers joined in the reaction system limit slowly react.Used catalyzer can be alkaline catalystss such as KOH, NaOH, CsOH generally, when being R fDuring QOH, preferred BF 3Deng metal complex catalysts such as acid catalyst, composition metal cyano compound title complexs.
When being R fDuring QOH, under strong alkaline condition, take off the side reaction of HF sometimes, therefore, preferably use NaBH 4/ NaI/I 2Alkaline catalysts that three-way catalyst etc. are gentle or above-mentioned acid catalyst, metal complex catalysts.When using acid catalyst, if the acidity of catalyzer is strong excessively, then may be with R fHydrogen on the ortho position carbon of the fluorine bonded carbon of group is sloughed, and therefore, takes off the HF reaction for suppressing this, optionally, can use diluting solvent.The example of diluting solvent has ether solvents such as glyme, diglyme, triglyme, methyl tertiary butyl ether.
The addition reaction temperature of cyclic ethers is-20 ℃ to 180 ℃, preferably 0-130 ℃.When using lower boiling diluting solvent, consider the rising of internal pressure, be preferably in than (boiling point of solvent+20) ℃ low thermotonus.
Terminal variations such as the further esterification of terminal hydroxyl by the polyoxy alkylidene chain that will obtain thus, alkylation can be regulated the various characteristics as fluorochemicals.
As the organic carboxyl acid that is used for esterification, can use ester, the acid anhydrides of monocarboxylic acids such as acetate, propionic acid, butyric acid, 2 ethyl hexanoic acid (sad), 3,5,5 Trimethylhexanoic acid (different n-nonanoic acid), oleic acid, stearic acid and these carboxylic acids and low-boiling point alcohol.In addition, also can use the acid anhydrides of di-carboxylic acid, carboxylicesters and diprotic acid such as oxalic acid, succsinic acid, toxilic acid, fumaric acid, phthalic acid.
Esterification is undertaken by following method: these carboxylic acids, carboxylicesters or acid anhydrides are joined in the fluorochemicals poly (oxyalkylene) based compound with C-terminal, do not heat while stirring dehydration then, dealcoholysis or unreacted acid heated up in a steamer having under the condition of catalyzer or in the presence of trace acid catalysts such as tosic acid, sulfuric acid or alkaline catalystss such as potassium hydroxide, sodium hydroxide.
Alkylating method has: react with single haloalkyl under strong alkaline condition; Use alkylsurfuric acid etc.For suppressing the reaction of sloughing of fluorine, be advisable with the reaction of using alkylating agents such as alkylsurfuric acid.
The fluorochemicals that obtains thus can optionally carry out purifying by the acid treatment of using sulfuric acid, phosphoric acid etc., the adsorption treatment of using synthetic magnesium, atlapulgite, gac etc. etc.
Join the initiator R in the reactor fThe amount of QOH is looked the addition amount of cyclic ether compounds of addition and is different, considers the agitation condition of reactor, preferably joins more than 1/10 of reactor inner capacities.Consider volumetric efficiency, after the cyclic ethers addition, plot ratio preferably can reach 80-95%, but this is not particularly limited.
The incorporation of the fluorochemicals in the synthetic resin covering material can change in big scope according to the kind of the fluorochemicals that mixes, the kind of synthetic resins etc.Usually, at 100 weight part synthetic resins (in softening agent is not included in.As follows) in, mix more than 0.01 weight part, the upper limit there be not strict the qualification, if but mix too much, then may occur oozing out, gonorrhoea, therefore, just enough below 2.0 weight parts usually.Be preferably in the 100 weight part synthetic resins and mix the 0.02-1.0 weight part.
In agricultural synthetic resin covering material of the present invention, mix anti-water smoke agent for increasing anti-water smoke.Anti-water smoke agent is used anti-water smoke agent in agricultural polychloroethylene resin film field so far preferably.In the present invention, anti-water smoke agent preferably be selected from anti-water smoke agent B (the anti-water smoke agent that comes by the fatty acid derived of polyvalent alcohol and 10-22 carbon atom) and anti-water smoke agent C (by the lipid acid of polyvalent alcohol, a 10-22 carbon atom and epoxide derive and anti-water smoke agent) at least a.They are the compounds that belong to the nonionogenic tenside category.
The example of polyvalent alcohol has Sorbitol Powder, N.F,USP MANNITOL, glycerol, polyglycerol, tetramethylolmethane, TriMethylolPropane(TMP) etc.
The lipid acid of 10-22 carbon atom can be straight chain, also can be ramose.Its object lesson also has fatty acid that tallow, plam oil, rapeseed oil, Semen Maydis oil, soya-bean oil, Oleum Gossypii semen, sesame oil, Semen Lini oil, these winterized stearins obtain and their mixed fatty acid except that lipid acid such as lauric acid, tetradecanoic acid, palmitinic acid, stearic acid, Unimac 5680, mountain Yu acid, oleic acid.
As epoxide, optimization ethylene oxide or oxyethane and propylene oxide, especially optimization ethylene oxide.As anti-water smoke agent C, preferably addition after the epoxide open loop is gone up and the product that obtains at the ester (ester with hydroxyl) of polyvalent alcohol and lipid acid.
Anti-water smoke agent preferably is selected from hypothermic phase in the winter time and also can brings into play anti-water smoke, also be difficult for being extracted, keeping for a long time the material of anti-water smoke in the summer high temperature phase from cover material.Object lesson with material of so anti-water smoke persistence has the anti-water smoke agent B or the anti-water smoke agent C of the nonionogenic tenside that comes as being derived by polyvalent alcohol (especially Sorbitol Powder, N.F,USP MANNITOL or condensation degree are the polyglycerol of 2-10), lipid acid (lipid acid of 16-18 carbon atom), epoxide (oxyethane).
In anti-water smoke agent B, anti-water smoke agent C, preferably the water molecule number of being sloughed by the intramolecular dehydration condensation reaction of polyvalent alcohol when the esterification of polyvalent alcohol and lipid acid is the material (, diester) of 2 molecules/molecular polylol.In addition, when generating the mixture of the ester more than two kinds by the reaction of polyvalent alcohol and lipid acid, wherein the content of diester preferably accounts for the 20-80% of gross weight.In addition, such diester preferably has hydroxyl, when making oxyethane or oxyethane and propylene oxide and its reaction, and their reacting weight adds up to the following nonionogenic tenside of 5 moles/mole polyvalent alcohols.
The anti-incorporation of water smoke agent in synthetic resins can be when being used for the agricultural synthetic resin film so far equal.Usually, in 100 weight part synthetic resins, mix 1-5 weight part (preferably 1.5-3.5 weight part).
Synthetic resins as constituting agricultural synthetic resin covering material of the present invention usually for example has the thermoplasticity synthetic resins with film-forming properties.The multipolymer, fluorine resin, polyester, polymeric amide etc. of more than one and other copolymerisable monomer (for example vinyl-acetic ester, vinylidene chloride etc.) in monomeric independent or their multipolymers between mutually or these monomers such as vinylchlorid, ethene, propylene, acrylate, methacrylic ester or the mixture of these multipolymers are arranged particularly.
Wherein, consider from the angle of weathering resistance, light transmission, economy, intensity, preferred vinyl chloride resin (promptly, polyvinyl chloride and the multipolymer of chloroethylene polymerization unit content more than 50 weight %) and ethenoid resin is (promptly, polyethylene and the multipolymer of vinyl polymerization unit content more than 50 weight %), preferred especially polyvinyl chloride.
In agricultural synthetic resin covering material of the present invention, amount that can be common adds common various resin additives, as softening agent, lubricant, thermo-stabilizer, static inhibitor, UV light absorber, pigment, dyestuff, moistening agent etc.
The example of the softening agent that is suitable for has dinoctyl phthalate, phthalic acid two (2-ethylhexyl), dibenzyl phthalate, Di Iso Decyl Phthalate, phthalic acid two (dodecyl ester), phthalic acid two phthalic acid derivatives such as (undecyl esters); Isophthalic acid derivatives such as dioctyl isophthalate; Hexanodioic acid such as Polycizer W 260, Octyl adipate derivative; Maleic acid derivatives such as n-butyl maleate; Citric acid derivants such as tri-n-butyl citrate; Derivatives from itaconic acid such as farming health acid mono; Oleic acid derivatives such as butyl oleate; Also have phosphoric acid (front three phenyl ester), tricresyl phosphate (diformazan phenyl ester), epoxidized soybean oil, epoxy resin softening agent in addition.
In the present invention, for example with regard to suitable flexible vinyl chloride resin, be about in the polyvinyl chloride of 600-2000, can mix about 30-70 weight part softening agent in the 100 weight part polymerization degree.
The example of lubricant or thermo-stabilizer has polyethylene wax, bisamide, stearic acid, Zinic stearas, barium stearate, calcium stearate, barium ricinoleate etc.
The example of UV light absorber has UV light absorber such as benzotriazole category, benzoate (ester) class, benzophenone, cyanoacrylate, salol class.
The example of pigment and dyestuff has titanium oxide, silicon-dioxide, ultramarine, phthalocyanine blue etc.
The example of moistening agent has hydrotalcite etc.
These resin additives can be common content add, for example, in 100 weight part synthetic resins, add the following a small amount of of 5 weight parts.
In synthetic resins, add fluorochemicals, anti-water smoke agent (and optionally as base material, add various resin additives again) time, adoptable method for example has: with common mix device, mixing device (as blending machine, mixing machines such as ribbon mixer, Banbury mixer, super mixing machines) and mix after, make film.
With the film forming method of synthetic resins system can be known method, for example extrusion by melting, solution casting method, rolling process etc.
If the thickness of agricultural synthetic resin covering material of the present invention is too thin, cover material intensity can be not enough, and if too thick, then can give into membranization operation and operation thereafter (comprising cutting film, the operation that engages with the greenhouse section bar, the operation of sprawling etc. in the greenhouse) etc. makes troubles, therefore, cover material thickness is preferably between the 0.01-0.5mm.
Agricultural synthetic resin covering material of the present invention as mentioned above, performance and anti-water smoke persistence that water smoke appears in its inboard that prevents that coated material from covering are improved, but also can be improved in the lump its cover material outside dirt resistance.For improving dirt resistance, useable solvents coating, water soluble paint, UV cured type coating etc. form dustproof overlay film.
Agricultural synthetic resin covering material of the present invention is same with the agricultural covering material that uses so far, can spread in the agriculture and garden facilities such as greenhouse, plastics tunnel, is used for the cultivation of useful plant.
Embodiment
Below by synthesis example (routine 1-7), embodiment (routine 8-15), comparative example (routine 16-24) the present invention is elaborated.Example 1: fluorochemicals D's is synthetic
Direct F (CF with 500g 2) 8(CH 2) 3The OH powder is put into the withstand voltage autoclave that stainless steel is made, and adds six cyano group cobalts acid Zn complex 0.25g again.Be warming up to 65 ℃, while stirring dissolving.Be warming up to 80 ℃, when maintaining 80 ℃ with importing continuously propylene oxide (to call PO in the following text) 546g ° in 3 hours
After reaction finishes, heat up in a steamer unreacted PO under the decompression, obtain thick resultant.Add sequestrant, remove the heavy metal as catalyzer, respectively with thick resultant: sorbent material is that the weight ratio of 100:1 adds sorbent material KW-1000 and KW-600 (trade(brand)name is Union Chemical Co., Ltd.'s product) successively, and mineral compound is adsorbed.Dehydration, filtration, dry then, obtain fluorochemicals D.The hydroxyl value of fluorochemicals D is 57.4mg KOH/g.NMR spectrum by resultant ( 1H-NMR, 19F-NMR and 13C-NMR) confirmed F (CF 2) 8(CH 2) 3O[CH 2CH (CH 3) O] nThe generation of H (wherein, the mean value of n is 8.6).Example 2: fluorochemicals E's is synthetic
Except that replacing the PO,, obtain fluorochemicals E by reacting with the same method of example 1 with the mixture of PO/ oxyethane (to call EO in the following text)=40/60 (weight ratio).The hydroxyl value of fluorochemicals E is 56.8mgKOH/g.NMR spectrum by resultant has been confirmed F (CF 2) 8(CH 2) 3O[CH 2CH (CH 3) O] p(CH 2CH 2O) q(wherein, the mode of connection of PO and EO is random to H.The mean value of p+q is 10, generation p:q=4.6).Example 3: fluorochemicals F's is synthetic
Direct F (CF with 500g 2) 8(CH 2) 3The OH powder is put into the withstand voltage autoclave that stainless steel is made, and adds ether and closes BF 30.5g with as the glyme 250g of thinner.Dissolving is warming up to 30 ℃ while stirring, is maintaining in 30 ℃ with the mixture 546g that imported tetrahydrofuran (THF) (to call THF in the following text)/EO=60/40 in 3 hours continuously.
After carrying out 5 hours slaking reactions again, heat up in a steamer unreacted THF/EO and solvent glyme under the decompression, obtain thick resultant.Add 10% aqueous sodium hydroxide solution, with in the acidic component and after, respectively with thick resultant: sorbent material is that the weight ratio of 100:1 adds sorbent material KW-1000 and KW-600 (the same) successively, and mineral compound is adsorbed.Dehydration, filtration, dry then, obtain fluorochemicals F.The hydroxyl value of fluorochemicals F is 59.2mg KOH/g.NMR spectrum by resultant has been confirmed F (CF 2) 8(CH 2) 3O[CH 2CH 2CH 2CH 2O] p(CH 2CH 2O) q(wherein, the mode of connection of THF and EO is random to H.The mean value of p+q is 7.7, generation p:q=6:4).Example 4: fluorochemicals G's is synthetic
Except that replacing the THF/EO,, obtain fluorochemicals G by reacting with the same method of example 3 with the PO of 573g.The hydroxyl value of fluorochemicals G is 56.5mgKOH/g.NMR spectrum by resultant has been confirmed F (CF 2) 8(CH 2) 3O[CH 2CH (CH 3) O] nThe generation of H (wherein, the mean value of n is 8.9).Example 5: fluorochemicals H's is synthetic
Except that replacing the THF/EO,, obtain fluorochemicals H by reacting with the same method of example 3 with the EO of 546g.The hydroxyl value of fluorochemicals H is 56.3mg KOH/g.NMR spectrum by resultant has been confirmed F (CF 2) 8(CH 2) 3O[CH 2CH 2O] nThe generation of H (wherein, the mean value of n is 11.8).Example 6: fluorochemicals I's is synthetic
Remove (CF with F 2) 8CH 2CH 2CH (CH 3) OH replaces the F (CF as initiator 2) 8(CH 2) 3Outside the OH,, obtain fluorochemicals I by reacting with the same method of example 3.The hydroxyl value of fluorochemicals I is 56.3mgKOH/g.NMR spectrum by resultant has been confirmed F (CF 2) 8CH 2CH 2CH (CH 3) O (CH 2CH 2O) nThe generation of H (wherein, the mean value of n is 11.5).The surface tension of 0.01% aqueous solution of fluorochemicals I is 17.6dyn/cm.Example 7: fluorochemicals M's is synthetic
Remove (CF with F 2) 8CH 2CH 2CH (CH 3) OH replaces the F (CF as initiator 2) 8(CH 2) 3Outside the OH,, obtain fluorochemicals M by reacting with the same method of example 2.The hydroxyl value of fluorochemicals M is 59.2mgKOH/g.NMR spectrum by resultant has been confirmed F (CF 2) 8CH 2CH 2CH (CH 3) O[CH 2CH (CH 3) O] p(CH 2CH 2O) q(wherein, the mode of connection of PO and EO is random to H.The mean value of p+q is 9, generation p:q=3:6).Example 8-23
With polyvinyl chloride (mean polymerisation degree=1300) 100 weight parts, dioctyl phthalate (DOP) 50 weight parts, Ba-Zn is that liquid stabilisers 2 weight parts, Ba-Zn are that powder stablizer 1 weight part is an essentially consist, and (unit: weight part) anti-water smoke agent and fluorochemicals mix with kind shown in table 1 and the table 2 and quantity with it.This mixture supplied to heat to 180 ℃ calendering formation machine, make film, make 16 kinds of the films (except the example 24) of thick 0.075mm with well-established law.Fluorochemicals J, K, L and anti-water smoke agent SP, SS see Table 3.
To above-mentioned 16 kinds of films and do not contain fluorochemicals commercially available thick 0.075mm anti-water smoke agricultural polychloroethylene film (example 24) totally 16 kinds estimate.
But experiment is applied film and is made by erecting the framework of high 0.5m, wide 0.8m, dark 0.4m on the tank of outdoor attemperation, repaving with the greenhouse.Prevent the evaluation of water smoke, water smoke situation occurred in order to following method.The results are shown in Table 1 and table 2.Anti-water smoke evaluation
Since September test, observe in during 8 months and spread over the anti-water smoke of experiment with the film internal surface around the greenhouse, prevent water smoke with following benchmark evaluation.
◎: do not observe adhering to of water droplet fully
Zero: only observe adhering to of a little water droplet
△: observe adhering to of water droplet
*: observe considerable water droplet
* *: is in the evaluation to water droplet water smoke situation occurred of the whole surface observation of film
In the time that descends with at dusk temperature, the tank water temperature is adjusted to 45 ℃ in the morning, during about 2 hours, observes spreading over the water smoke situation occurred of experiment with the film internal surface around the greenhouse.This observation was carried out 2 times in September, carried out 4 times to every month April after October.Estimate the situation occurred of water smoke with following basic Cui.
◎: do not observe water smoke fully and take place
Zero: only observe a little water smoke and take place
△: observe water smoke and take place
*: observed tangible water smoke and taken place
Table 1
Example 8 9 10 11 12 13 14 15 16
Anti-water smoke agent SP SS 2 2 2 2 2 2 2 2 2
Fluorochemicals D E F G H I J M 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2
The situation occurred of anti-water smoke water smoke ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ○ ○ ◎ ◎
Table 2
Example 17 18 19 20 21 22 23 24
Anti-water smoke agent SP SS 2 2 2 2 2 2 2 Not clear
Fluorochemicals J K L 0.2 0.2 0.2 0.2 0.2
The situation occurred of anti-water smoke water smoke ○ ○ △ △ ○ ○ ○ ○ △ △ ◎ × ◎ × × △
Table 3 fluorochemicals J:C 8F 17CH 2CH (OH) CH 2O (CH 2CH 2O) 10[CH 2CH (CH 3) O] CH 3Fluorochemicals K:C 9F 19CON (CH 3) (CH 2CH 2O) 12H fluorochemicals K:C 8F 17SO 2N (CH 2) (CH 2CH 2O) 10H prevents water smoke agent SP: sorbitan palmitate is prevented water smoke agent SS: the sorbitan stearate propylene oxide adduct
                        The possibility of industrial utilization
The greenhouse of sprawling with agricultural synthetic resin covering material of the present invention and plastics tunnel can suppress near the generation of the water smoke the cover material inner surface effectively. In addition, agricultural synthetic resin covering material of the present invention is owing to having mixed specific fluorochemical and surfactant, therefore, can not only effectively suppress the generation of water smoke, and, also have excellent water-mist-proof and water-mist-proof continuation, can be used for the facility cultivation of plant.

Claims (3)

1. contain the fluorochemicals of following formula 1 expression and the agricultural synthetic resin covering material of anti-water smoke agent,
R f-Q-O-(A-O) n-R ... in formula 1 formula,
R f: the polyfluoro aliphatic hydrocarbyl of 1-22 carbon atom,
The straight or branched alkylidene group of Q:3 or 4 carbon atoms,
The integer of n:1-100,
The alkylidene group of A:2-4 carbon atom, the hydrogen atom of this alkylidene group can be replaced by aromatic hydrocarbyl, alkoxyl group or phenoxy group, and the A when n is 2-100 can be identical or different,
R: the alkyl of hydrogen atom, a 1-18 carbon atom or the acyl group of 1-18 carbon atom;
Described anti-water smoke agent is following anti-water smoke agent B and/or anti-water smoke agent C,
Anti-water smoke agent B: the anti-water smoke agent that comes by the fatty acid derived of polyvalent alcohol and 10-22 carbon atom,
Anti-water smoke agent C: lipid acid and epoxide by polyvalent alcohol, a 10-22 carbon atom are derived and next anti-water smoke agent;
With respect to synthetic resins 100 weight parts, the amount of fluorochemicals is the 0.01-5.0 weight part, and the amount of anti-water smoke agent is the 1-5 weight part.
2. agricultural synthetic resin covering material as claimed in claim 1, wherein, R is a hydrogen atom.
3. agricultural synthetic resin covering material as claimed in claim 1 or 2, wherein, A is at least a group that is selected from ethylidene, propylidene and the tetramethylene.
CNB998015938A 1999-03-08 1999-03-08 Agricultural synthetic resin covering material Expired - Fee Related CN1139639C (en)

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