CN102482487A - Novel nonionic surfactant and fog-preventive agent - Google Patents
Novel nonionic surfactant and fog-preventive agent Download PDFInfo
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- CN102482487A CN102482487A CN2010800398061A CN201080039806A CN102482487A CN 102482487 A CN102482487 A CN 102482487A CN 2010800398061 A CN2010800398061 A CN 2010800398061A CN 201080039806 A CN201080039806 A CN 201080039806A CN 102482487 A CN102482487 A CN 102482487A
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- 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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- 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
- C08G65/04—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 only
- C08G65/22—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring
- C08G65/223—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring containing halogens
- C08G65/226—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring containing halogens containing fluorine
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- 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
- C08G65/2603—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 oxygen
- C08G65/2606—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 oxygen containing hydroxyl groups
- C08G65/2609—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 oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
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- 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
- C08G65/32—Polymers modified by chemical after-treatment
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- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/22—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the initiator used in polymerisation
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Abstract
Provided is a fluorine-containing polyether composition which comprises (a) an adduct formed by introducing a group (F1) represented by formula (I): C6F13(CH2)n-CH(OH)CH2- or a group (F2) represented by formula (II): C6F13(CH2)n-CH(CH2OH)- via addition reaction to one terminal of a polyethylene glycol (PEG) having an average molecular weight of 250 to 550, (b) an adduct formed by introducing groups (F1) or groups (F2) via addition reaction to both terminals of a PEG having an average molecular weight of 250 to 550, and (c) an unreacted PEG having an average molecular weight of 250 to 550 at a molar ratio of 50 to 90 : 3 to 30 : 0 to 30 (with the sum of (a), (b) and (c) being 100). In formulae (I) and (II), n is 1 to 10. The composition exhibits excellent fog-preventive effect (of preventing the occurrence of fog) and is useful as a low-environmental-load type fog-preventive agent for the film for agricultural use. Further, the composition exhibits an excellent surface-tension lowering effect, thus being also useful as a nonionic surfactant.
Description
Technical field
The present invention relates to fluorine-containing epoxide is the nonionic compound of raw material and the low surface tension agent that contains this compound, the particularly antifogging agent of film for agricultural use.
Background technology
, in the antifogging agent of the additive of coating etc., various penetrant, flow agent, film for agricultural use etc., using as tensio-active agent for the effective fluorochemicals of low surface tensionization of solution and various organic solvents all the time.Compare with hydrocarbon-surfactant, the advantage of fluorochemical surfactant is with the interpolation of minute quantity the surface tension of mother solution to be reduced.
At present, in these fluorine class tensio-active agents a large amount of use gather fluoroalkyl, generally contain carbonatoms and be perfluoroalkyl (Rf yl) more than 8 (with reference to japanese kokai publication sho 57-136534 communique etc.).
But; Recently; EPA (USEPA) discloses for the compound that carbonatoms is the perfluoroalkyl (Rf yl) more than 8 that contains that is obtained by telomerization, have through telomer decomposition or metabolism produce Perfluorocaprylic Acid (perfluoro-octanoic acid, below; Abbreviate " PFOA " as) possibility (with reference to EPA OPPT FACT SHEET April 14,2003 (http://www.epa.gov/opptintr/pfoa/pfoafacts.pdf)).
In addition; EPA has delivered PFOA reinforcement science investigation (with reference to EPA report " PRELIMINARY RISK AS SES SMENT OF THE DEVELOPMENTAL TOXICITY AS SOCIATED WITH EXPOSURE TO PERFLUOROOCTANOIC ACID AND ITS SALTS " (http://www.epa.gov/opptintr/pfoa/pfoara.pdf)), and PFOA is regarded as problem to the load of environment.
Therefore, in recent years,, studied the compound of attempting using short chain Rf base (with reference to TOHKEMY 2006-219586 communique etc.) from the purpose that reduces carrying capacity of environment, through make carbonatoms less than 8 suppress PFOA generation.
On the other hand,, and in plastic greenhouse, keep high humidity, therefore produce mist in order to ensure the indispensable humidity of growing of raise crop.This mist is considered to the disease and insect of raise crop or the quality of cutting confidential relation is arranged, and in greenhouse production, should avoid as far as possible.
The water vapour dewfall of mist in the greenhouse produces, and is mainly in inside and outside temperature difference autumn and winter jumpy of greenhouse and morning and evening.As nonionic class fluorochemical surfactant one big purposes, oriented film for agricultural use adds in carrying out, and is suppressed at the purposes (below, be called " antifogging agent ") of generation of the mist of the autumn and winter in the plastic greenhouse.Wherein, " in add " be meant in the material resin of film add, behind the mixed surfactant, the interpolation in resin when forming process is film like.In the purposes of this antifogging agent, use always at present that to contain carbonatoms be the basic compound of Rf 8 or more as tensio-active agent (with reference to japanese kokai publication sho 59-093739 communique etc.).Therefore, in the purposes of antifogging agent, the potential problems that produce PFOA are arranged also.
The prior art document
Patent documentation
Patent documentation 1: japanese kokai publication sho 57-136534 communique
Patent documentation 2: TOHKEMY 2006-219586 communique
Patent documentation 3: japanese kokai publication sho 59-093739 communique
Summary of the invention
Invent problem to be solved
Problem of the present invention is to provide the generation that has suppressed PFOA, the compsn little to carrying capacity of environment, and the antifogging agent of the film for agricultural use that contains said composition is provided, and the tensio-active agent that contains said composition is provided.
As stated, at present,, use as containing the fluorine-based compound that carbonatoms is the Rf base more than 8 that has as the compound that fluorine class tensio-active agent uses always.These Rf base is shown below, and usually, is derived by the telomer that the telomerization through tetrafluoroethylene produces, and advantage and the cost aspect made from it are the mixture of the compound of carbonatoms 8,10,12 etc. mostly.
CF
3CF
2-I+nCF
2＝CF
2→CF
3CF
2-(CF
2CF
2)
n-I
For fear of the PFOA problem, in the compound relevant with tensio-active agent, also must develop with the little Rf base of carbonatoms be the tensio-active agent of raw material.
Must develop equally that to contain with the little Rf base of carbonatoms be the antifogging agent of the tensio-active agent of raw material.
That is, in film for agricultural use, when adding antifogging agent in resin and being shaped to film like, need be on the surface through the time ooze out, can carry out modification to the surface.Fluorine cpd can not dissolve owing to do not have affinity with water or general hydrocarbon simply, therefore, when adding moulding in resin, have the character of oozing out on the surface gradually in time.Therefore, if in resin, add minute quantity, then there are fluorine cpd to occur and with the characteristic of surface-treated on the surface.
Surface-treated particularly, is meant water-repellent oil-repellent property or didirtresistance etc., but for film for agricultural use, it is said that the charging property of fluorine cpd (Rf yl) is influential.Mist is that the water vapour gathering obtains, and is dust as the material of examining, positively charged.Because the Rf base band negative electricity of the antifogging agent that on film, oozes out, therefore, because electricity is inhaled mutually, mist is adsorbed on the film.
On the other hand, in the film for agricultural use, cooperate anti-caking distillate medicinal water (sorbitan fatty acid esters, glycerol fatty acid ester, polyvalent alcohol, lipid acid and alkylene oxide deutero-nonionic class tensio-active agent) in addition, they make the film surface hydrophilization.Therefore, owing to fluorine class tensio-active agent is adsorbed on the mist on the film surface, flow down downwards along the film surface of hydrophilization.Through the anti-caking distillate medicinal water, the mist that is adsorbed in film surface can be with the film like dewfall.When dewfall, film surface is fuzzy, and sun optical transmission is insufficient, and problem takes place when the cultivation of crop.Agronomy, gardening with plastic greenhouse in, adopt following mode usually: through and with fluorine class tensio-active agent, hydro carbons anti-caking distillate medicinal water, prevent the generation of mist, prevent the fuzzy generation that causes by dewfall.
Therefore, as the desired performance of fluorine class tensio-active agent of antifogging agent, enumerate following project.
(1) have electronegative Rf base, and the amount of fluorine is many.
(2) do not suppress the wetting ability of film surface or itself yet help hydrophilization.
(3) solubleness is little in water.If the antifogging agent that the solvability height then oozes out in water runs off with agglutinative water droplet on film.
(4) to a certain degree thermotolerance (applying the heat about 150 ℃～250 ℃ during processing film) is arranged.
Be used to solve the method for problem
In order to develop the antifogging agent that does not have the PFOA problem, using carbonatoms is the Rf base below 6, and it is satisfied and the equal above performance of existing antifogging agent.Because with existing carbonatoms is that Rf base more than 8 is compared; Carbonatoms is that the amount of the Rf base fluorine below 6 is few, be considered to guarantee sufficient negative charging amount, but contriver of the present invention furthers investigate all the time; The result finds unexpectedly; When use contains the carbonatoms that satisfies certain conditions and is the antifogging agent of the Rf base below 6, it is satisfied and the equal above performance of existing antifogging agent, thereby accomplished the present invention.
That is, the present invention relates to contain the derive fluorochemical polyether compsn of the nonionic compound that obtains of the raw material that never produces PFOA.
The invention still further relates to the film for agricultural use that contains this fluorochemical polyether compsn and use antifogging agent.
The invention still further relates to the nonionic class tensio-active agent that contains this fluorochemical polyether compsn.
More specifically, the present invention through make as the raw material that does not produce PFOA have the epoxy compounds that carbonatoms is 6 a Rf base (below, abbreviate " fluorine-containing C6 epoxide " as.) with have the hydrophilic group of nonionic class polyoxyethylene glycol (below, abbreviate " PEG " as.) reaction, process the fluorochemical polyether compsn of fluorine-containing nonionic class, thereby solved this problem.
That is, the present invention relates to the fluorochemical polyether compsn, wherein,
(a), molecular-weight average adds single terminal addition thing of the group (F2 yl) shown in group shown in the accepted way of doing sth (I) (F1 yl) or the formula (II) on being single end of 250～550 polyoxyethylene glycol,
Formula (I): C
6F
13(CH
2)
n-CH (OH) CH
2-
Formula (II): C
6F
13(CH
2)
n-CH (CH
2OH)-
(in the formula, n representes 1～10.)
(b) two terminal addition things of addition F1 base or F2 base on two ends of polyoxyethylene glycol,
(c) two terminal hydroxyl type polyoxyethylene glycol,
(a) and (b) are 30～95: 2～40 with (c) the molar ratio that exists: 0～40 ((a) and (b) with (c) add up to 100).
Wherein, (a) and (b) can be preferably 50～90: 3～30 with (c) the molar ratio that exists: 0～30 ((a) and (b) with (c) add up to 100.)。
The invention still further relates to a kind of fluorochemical polyether compsn, is the reactant of fluorine-containing C6 epoxide shown in the formula (III) and two terminal hydroxyl type polyoxyethylene glycol,
Formula (III):
(in the formula, n and above-mentioned synonym.)
Single terminal addition thing (a) is 1: 1 mol ratio affixture of fluorine-containing C6 epoxide and polyoxyethylene glycol,
Two terminal addition things (b) be fluorine-containing C6 epoxide and polyoxyethylene glycol 2: 1 mol ratio affixtures and
Two terminal hydroxyl type polyoxyethylene glycol (c) are unreacted polyoxyethylene glycol.
The film for agricultural use that the present invention relates to contain this fluorochemical polyether compsn is used antifogging agent.
The invention still further relates to the film for agricultural use that contains this antifogging agent.
The invention still further relates to and contain nonionic class tensio-active agent this fluorochemical polyether compsn, low surface tension.
The invention still further relates to and make the fluorochemical polyether method for compositions, make above-mentioned fluorine-containing C6 epoxide and two terminal hydroxyl type polyoxyethylene glycol with mol ratio reaction in 0.7: 1～1.3: 1.
The effect of invention
The problem that fluorochemical polyether compsn of the present invention does not exist PFOA to produce is few to the load of environment.In addition, fluorochemical polyether compsn of the present invention through in film for agricultural use as adding (or outside add) in the antifogging agent, can suppress the generation of the mist in the plastic greenhouse of autumn and winter effectively.In addition, the capillary reduction ability of fluorochemical polyether compsn of the present invention is excellent, provides to be used for the nonionic class tensio-active agent of purposes widely.
Embodiment
Below, the present invention at length is described.
Fluorochemical polyether compsn of the present invention is can be through being the mixture of nonionic compound of the reaction manufacturing of 250～550 PEG for fluorine-containing C6 epoxide shown in the formula (III) and molecular-weight average,
Formula (III):
(in the formula, n and above-mentioned synonym.)。In addition, below, sometimes fluorine-containing C6 epoxide formula (III) is designated as C
6F
13(CH
2)
n-CH (O) CH
2
Reaction can be carried out with usual method, for example, uses boron trifluoride (BF
3-OEt
2) carry out as catalyzer.
Reaction can be represented through following formula:
AC
6F
13(CH
2)
n-CH (O) CH
2+ b HO-(CH
2CH
2O)
m-X → fluorochemical polyether compsn
(in the formula, a is the mole number of the fluorine-containing C6 epoxide of raw material, and b is the mole number of raw material PEG, and X is that Wasserstoffatoms or carbonatoms are 1～20 alkyl (being preferably methyl), and m representes 1～12.)。Wherein, X is preferably Wasserstoffatoms.
" single terminal addition thing (a) " of the present invention in order to obtain; The terminal X of PEG; When for example being methyl; If with a: b=1: 1 molar ratio reaction is till the fluorine-containing C6 epoxide of raw material disappears, and the compound that can access the single terminal base of addition Rf fully of PEG (is called " single terminal addition thing (a) ".)。(a) the other end of this moment is a methyl.
On the other hand; When the terminal X of PEG is Wasserstoffatoms (so-called two terminal hydroxyl type PEG); Since fluorine-containing C6 epoxide can with two of PEG terminal hydroxyl reactions; If therefore in above-mentioned reaction formula with a: b=2: 1 molar ratio reaction disappears up to the fluorine-containing C6 epoxide of raw material, and the compound that then can access at the two terminal bases of addition Rf fully of PEG (is called " two terminal addition things (b) ".)。
Fluorochemical polyether compsn of the present invention can be through existing above-mentioned resulting (a) and (b) and two terminal hydroxyl type polyoxyethylene glycol (c) molar ratio mix to make with regulation.
On the other hand; When the terminal X of PEG is Wasserstoffatoms, in above-mentioned reaction formula, make fluorine-containing C6 epoxide and two terminal hydroxyl type PEG with less than a: b=2: 1 mol ratio; For example; With a: b=1: 1 mol ratio, reaction are till the fluorine-containing C6 epoxide of raw material disappears the time, and (this moment, the other end was a Wasserstoffatoms can to obtain single terminal addition thing (a) randomly.), there is the fluorochemical polyether compsn of ratio in the regulation of two terminal addition things (b) and unreacted PEG (c).This embodiment is as compsn of the present invention and preferred, in addition, and as method of manufacture, owing to can obtain at one stroke containing the (a) and (b) and (c) the fluorochemical polyether compsn of composition with the molar ratio that exists of regulation, so preferred.
Here said single terminal addition thing is specially
C
6F
13(CH
2)
n-CH(OH)CH
2-O-(CH
2CH
2O)
m-X、
C
6F
13(CH
2)
n-CH(CH
2OH)-O-(CH
2CH
2O)
m-X
(n and X and above-mentioned synonym.)，
Two terminal addition things are specially
C
6F
13(CH
2)
n-CH(OH)CH
2-O-(CH
2CH
2O)
m-CH
2CH(OH)-(CH
2)
nC
6F
13
C
6F
13(CH
2)
n-CH(OH)CH
2-O-(CH
2CH
2O)
m-CH(CH
2OH)-(CH
2)
nC
6F
13
C
6F
13(CH
2)
n-CH(CH
2OH)-O-(CH
2CH
2O)
m-CH
2CH(OH)-(CH
2)
nC
6F
13
C
6F
13(CH
2)
n-CH(CH
2OH)-O-(CH
2CH
2O)
m-CH(CH
2OH)-(CH
2)
nC
6F
13。
Wherein, in above-mentioned formula, the situation of preferred especially n=1.As single terminal addition thing, the situation of preferred X=Wasserstoffatoms.
Single terminal addition thing (a) in the fluorochemical polyether compsn of the present invention: the molar ratio that exists of two terminal addition things (b): unreacted PEG (c) is 30～95: 2～40: 0～40 ((a) and (b) with (c) add up to 100.), 50～90: 3～30: 0～30 ((a) and (b) with (c) add up to 100.), be preferably 60～80: 10～20: 0～20 ((a) and (b) with (c) add up to 100.)。When this fluorochemical polyether compsn was used as antifogging agent, this molar ratio was the scope with excellent anti-mist characteristic.In addition, this to have molar ratio also be the scope of low surface tension of the excellence of this fluorochemical polyether composition exhibiting.In addition, the molar ratio that exists of fluorochemical polyether compsn can be confirmed through analyses such as LC-MS.
Fluorochemical polyether compsn of the present invention, as stated, can be through making single terminal addition thing and two terminal addition things respectively, add the PEG that is equivalent to non-reacted parts again, be adjusted at the mixture that has molar ratio of above-mentioned scope and make.
Preferred fluorochemical polyether compsn of the present invention; Through using the PEG of X as two terminal hydroxyl types of H atom, with fluorine-containing C6 epoxide reaction, the control reaction; Make the above-mentioned molar ratio that exists of consisting of of fluorochemical polyether compsn, can make the fluorochemical polyether compsn of the application's invention.The above-mentioned control that has a molar ratio can be carried out with respect to the charging mol ratio of PEG, catalytic amount, temperature of reaction, reaction times etc. through fluorine-containing C6 epoxide.Among these factors, the principal element that has molar ratio of decision fluorochemical polyether compsn is the charging mol ratio of fluorine-containing C6 epoxide with respect to PEG.Fluorine-containing C6 epoxide is 0.7～1.3 with respect to the charging mol ratio of PEG, is preferably 0.8～1.1, is preferably 1.0 especially.
The PEG that uses among the present invention has the effect as the hydrophilic group of fluorochemical polyether compsn of the present invention.As PEG, as stated, preferred especially two terminal hydroxyl types.
For PEG, in operation, be liquid preferably at normal temperature, therefore, molecular-weight average is preferably about 200～1000.If molecular-weight average is more than 1000, then PEG is a solid, and since the movability step-down in the polymeric film, the exudative reduction to the surface, and excessive with the solvability rising of reactant in water of fluorine-containing C6 epoxide, therefore be difficult to use as antifogging agent.If the molecular-weight average of PEG is below 200, then the content of the fluorine in the molecule becomes many relatively, shows water-repellancy when in film for agricultural use, adding, so not preferred.
More preferably the molecular-weight average of PEG is about 250～550.Molecular-weight average is less than 250 o'clock, in the thermogravimetric amount minimizing increase of the TR that resin forming is processed as film (150 ℃～250 ℃ usually).If molecular-weight average surpasses 550, then the solvability of reactant in water with fluorine-containing C6 epoxide increases, and weather resistance reduces.The special preferable range of the molecular-weight average of PEG is 300～500.
Catalyzer is used in the reaction of fluorine-containing C6 epoxide and two terminal hydroxyl type PEG, uses solvent as required, 30 ℃～150 ℃, preferably under the TR heating at 50 ℃～120 ℃, stir and implement.As suitable catalyzer, can use ZnCl
2, AlCl
3, SnCl
4, SbCl
5, FeCl
3Deng periodictable the 12nd family～15 families and the metal halide or the BF of the 8th family
3(with the coordination compound of ether or alcohol), sulfuric acid, NaHSO
4Deng acid catalyst.Big in speed of response, aspect by product is few, the catalyzer that especially preferably uses is BF
3(with the coordination compound of ether or alcohol).The usage quantity of catalyzer is 0.01～2 weight % with respect to the weight of fluorine-containing C6 epoxide usually, is preferably 0.5～1.0 weight %.Analyze reaction solution through gc, thin-layer chromatography or liquid chromatography etc., the moment that disappears with the fluorine-containing C6 epoxide of raw material is a terminal point, implements reaction with this standard.Not special restriction of reaction times, but the relation of removing etc. of consideration and reactivity and reaction heat is generally 1 hour～24 hours, is preferably 3 hours～12 hours scope.
Then, antifogging agent of the present invention is described.
Antifogging agent of the present invention contains above-mentioned fluorochemical polyether compsn of the present invention.Single terminal addition thing in this fluorochemical polyether compsn: two terminal addition things: there is molar ratio in unreacted PEG; As stated; Be 50～90: 3～30: 0～30 (adding up to 100); Be preferably 60～80: 10～20: 0～20 (adding up to 100), when this fluorochemical polyether compsn was used as antifogging agent, this molar ratio was the scope with excellent anti-mist characteristic.
This antifogging agent adds use in film for agricultural use.That is, can after after the interpolation in the film for agricultural use substrate resin of the PVC RESINS stated etc., mixing, this antifogging agent of fusion, be processed as film and process film for agricultural use according to usual method.
With respect to film for agricultural use substrate resin 100 weight parts, the addition of antifogging agent of the present invention is preferably 0.05～2 weight part, more preferably 0.1～0.5 weight part.If be less than 0.05 weight part, then can not bring into play fully anti-fog effect sometimes, if more than 2 weight parts, then white opacity appears in film, or owing to ooze out and surfaces of tacky, adheres to dust easily.
Antifogging agent of the present invention is preferably also used with the anti-caking distillate medicinal water.As the anti-caking distillate medicinal water that can use in the present invention; It can be the general anti-caking distillate medicinal water of using; For example, can enumerate sorbitan fatty acid esters, glycerol fatty acid ester, polyvalent alcohol, lipid acid and alkylene oxide deutero-nonionic class tensio-active agent etc.For example; Ester, glycerine and the carbonatoms that as sorbitan and carbonatoms is 12～22 higher fatty acid is the ester of 12～22 higher fatty acid or their alkylene oxide affixture, for example can enumerate the glycerols compound of sorbitan compounds, glyceryl monolaurate, glycerine monopalmitate, Zerol, glyceryl monooleate or their the T 46155 affixture etc. of sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, dehydrated sorbitol mono-fatty acid ester or their polyvinyl oxide compound affixture etc.With respect to film for agricultural use substrate resin 100 weight parts, the addition of these anti-caking distillate medicinal waters is 0.3～3 weight part, more preferably 0.5～2 weight part.
As the film for agricultural use material that can use in the present invention, be generally about 150～250 ℃ can melt molding the film that has form the material of ability, generally can get final product at the material that agricultural is used in coated material, can both use.For example; Enumerate vinyl resins, acrylic resin of the vinyl chloride resin, Vilaterm, ethane-acetic acid ethyenyl copolymer etc. of vinyl chloride resin etc. etc. as representative substances; Be preferably vinyl chloride resin and vinyl resins, be preferably vinyl chloride resin especially.But synthetic resins of the present invention is not limited to these resins.
In addition; In the film for agricultural use of the present invention; Can be as required cooperate normally used various resin to use additive with the addition of common usage degree; For example, lubricant, static inhibitor, weathering resistance rising agent (UV light absorber, hindered amine light stabilizer etc.), softening agent, inhibitor (comprising thermo-stabilizer), dyestuff, pigment.Can not damage effect of the present invention thus, can not damage various resins yet with the various functions of additive.
Film for agricultural use of the present invention can also pass through the known method manufacturing, and for example through manufacturings such as extrusion molding (the T mould is extruded, blow molding method etc.), rolling-molding methods, its thickness is adjusted into 20～1000 microns, preferably is adjusted into 50～300 microns.
Then, nonionic class tensio-active agent of the present invention is described.Nonionic class tensio-active agent of the present invention contains above-mentioned fluorochemical polyether compsn of the present invention, and capillary reduction ability is excellent.Therefore, for example, also can in the purposes of the additive in fire foam, the coating etc., various penetrant and flow agent etc., use.
Below, through embodiment the present invention is described particularly further, but the present invention is not limited thereto.
Embodiment
Following embodiment and the evaluation of physical property in the comparative example carry out according to the method shown in following.
< dissolubility test >
In transparent Glass Containers, the fluorochemical polyether compsn of the addition reaction of fluorine-containing C6 epoxide and PEG is dissolved in zero(ppm) water or the organic solvent its state of visual detection with normality (10wt% and 0.1wt%).
< measurement of surface tension >
The surface tension of the solution of water or organic solvent is through platinum plate method (Wilhelmy Method), 25 ℃ of mensuration.
< the thermogravimetric amount reduces test >
Use thermobalance, when under air atmosphere, heating up, be determined at 200 ℃ weight minimizing value with 10 ℃/minute speed.
< mist evaluation >
In the tunnel-shaped greenhouse of width 8m, height 4m, degree of depth 110m, lay film for agricultural use, visual observation in the morning mist situation occurred that the temperature head inside and outside the greenhouse is big, with following benchmark evaluation:
-1: do not have mist fully
+ 1: mist is arranged slightly
+ 2: mist is slightly many
+ 3: mist is very many
Reference example 1 < synthesizing of single terminal addition thing >
In the four-hole boiling flask of the 200ml that possesses TM, water cooler and whipping appts, add 37.6g C
6F
13-CH
2CH (O) CH
2Shown fluorine-containing C6 epoxide (0.1 mole), 40g molecular-weight average be single terminal polyoxyethylene glycol (Me-PEG) (0.1 mole) of 400 with methyl blocking (epoxide: PEG mol ratio=1: 1) and 0.2g as the BF of catalyzer
3Ether coordination compound (0.0013 mole) under agitation, carries out reaction in 3 hours at 70 ℃.The end of reaction is through carrying out the gas chromatographic analysis of reaction solution, and the peak of epoxide disappears and confirms.After reaction finishes, obtain the fluorochemical polyether compsn of heavy-gravity liquid.Said composition is the single terminal addition thing at single terminal addition Rf base of PEG.
When the water-soluble of the resulting fluorochemical polyether compsn of visual observation, discovery 10wt% and 0.1wt% dissolve fully becomes uniform solution.The surface tension of the aqueous solution is the value that is low to moderate 18.1mN/m.Thermogravimetric amount at 200 ℃ is reduced to 17%, and is bigger.These results of expression in table 1.
Reference example 2 < synthesizing of two terminal addition things >
In the four-hole boiling flask of the 200ml that possesses TM, water cooler and whipping appts, add 75.2g C
6F
13-CH
2CH (O) CH
2Shown fluorine-containing C6 epoxide (0.2 mole), 40g molecular-weight average be 400 two terminal hydroxyl types polyoxyethylene glycol (H-PEG) (0.1 mole) (epoxide: PEG mol ratio=2: 1) and 0.4g as the BF of catalyzer
3Ether coordination compound (0.0025 mole) under agitation, carries out reaction in 4 hours at 70 ℃.The end of reaction is through carrying out the gas chromatographic analysis of reaction solution, and the peak disappearance Lay of epoxide is confirmed.After reaction finishes, obtain the fluorochemical polyether compsn of heavy-gravity liquid.Said composition is two terminal addition things of addition Rf base on two ends of PEG.
When the water-soluble of the resulting fluorochemical polyether compsn of visual observation, find to be the gonorrhoea state when 10wt%, when 0.1wt%, be separated into two-layer.Therefore, fail to measure the surface tension of the aqueous solution.Thermogravimetric amount at 200 ℃ is reduced to 8%, and is less.These results of expression in table 1.
Embodiment 1 < synthesizing of the mixed type fluorochemical polyether compsn of single terminal addition thing, two terminal addition things and unreacted PEG >
In the four-hole boiling flask of the 200ml that possesses TM, water cooler and whipping appts, add 37.6g C
6F
13-CH
2CH (O) CH
2Shown fluorine-containing C6 epoxide (0.1 mole), 40g molecular-weight average be 400 two terminal hydroxyl types polyoxyethylene glycol (H-PEG) (0.1 mole) (epoxide: PEG mol ratio=1: 1) and 0.2g as the BF of catalyzer
3Ether coordination compound (0.0013 mole) under agitation, carries out reaction in 3 hours at 70 ℃.The end of reaction is through carrying out the gas chromatographic analysis of reaction solution, and the peak of epoxide disappears and confirms.After reaction finishes, obtain the fluorochemical polyether compsn of heavy-gravity liquid.Said composition is single terminal addition thing of containing on single end of PEG addition Rf base, at the fluorochemical polyether compsn of the mixed type of two terminal addition things of two terminal addition Rf base and unreacted PEG.Measure the single terminal addition thing in this fluorochemical polyether compsn with LC-MS: two terminal addition things: there is molar ratio in unreacted PEG, and the result is 64: 12: 12.
When the water-soluble of the resulting fluorochemical polyether compsn of visual observation, find to be the gonorrhoea state when 10wt%, when 0.1wt% uniform gonorrhoea state.Surface tension is 17.9mN/m, and is lower.Thermogravimetric amount at 200 ℃ is reduced to 11%, and is less.These results of expression in table 1.
Comparative example 1 < synthesizing of single terminal addition thing >
Except using 57.6g to contain average group, the fluorine-containing C6 epoxide in the replacement reference example 1 becomes C
10F
21-CH
2CH (O) CH
2Shown average carbon atom number be 10 Rf base fluorine-containing epoxide (0.1 mole) in addition, react equally and aftertreatment with reference example 1, obtain single tip type affixture.The 10wt% aqueous solution generation gonorrhoea of resulting affixture, gonorrhoea takes place in the 0.1wt% aqueous solution equably.Surface tension is 21.5mN/m.Compare with embodiment 1, surface tension is higher value.These results of expression in table 1.
Comparative example 2 < synthesizing of the mixed type fluorochemical polyether compsn of single terminal addition thing, two terminal addition things and unreacted PEG >
Except using 57.6g to contain average group, the fluorine-containing C6 epoxide among the replacement embodiment 1 becomes C
10F
21-CH
2CH (O) CH
2Shown average carbon atom number be 10 Rf base fluorine-containing epoxide (0.1 mole) in addition, react equally and aftertreatment with embodiment 1, obtain the mixed type addition reaction.The 10wt% aqueous solution generation gonorrhoea of resulting reaction mixture, gonorrhoea takes place in the 0.1wt% aqueous solution equably.Surface tension is 23.5mN/m.Compare with embodiment 1, surface tension is higher value.These results of expression in table 1.
[table 1] fluorine-containing (containing the Rf yl) epoxide, the reaction conditions of PEG and the analytical results of resulting reactant
Above result shows, uses the surface tension of the reactant of fluorine-containing C6 epoxide to be lower than the reactant (using as existing antifogging agent) for the fluorine-containing C10 epoxide of relatively estimating of use.This result's hint, fluorochemical polyether compsn of the present invention has excellent performance as antifogging agent, shows simultaneously as nonionic class tensio-active agent also to have excellent capillary reduction ability.
" point that the solvability in water can not be big (this is because after adding in film for agricultural use, thereby together flows down the cause that lacks weather resistance with water droplet) " and " not damaging hydrophilic point " as the desired characteristic of antifogging agent, are arranged in addition.Can judge that from the result of table 1 when making fluorine-containing C6 epoxide as raw material and PEG reaction, in single terminal addition thing excessive dissolution in water, on the other hand, two terminal addition things do not dissolve each other and damage antisweat property, and are all not preferred in water.
Therefore, as the preferred compound of film for agricultural use, be the mixture that makes fluorine-containing C6 epoxide and two terminal hydroxyl type PEG reaction single terminal addition thing that obtain, at random, two terminal addition things and unreacted PEG with antifogging agent.
In fact by the result of the compound of liquid-phase chromatographic analysis embodiment 1, the mixing molar ratio of single terminal addition thing, two terminal addition things and unreacted PEG is 64: 12: 12.
Embodiment 2～4
The molecular-weight average that has in replacing embodiment 1 is that 400 two terminal hydroxyl type PEG use that to have molecular-weight average be 200,300 and 600 the two terminal hydroxyl type PEG, to react equally and aftertreatment with embodiment 1.Result that will measure the rerum natura of resulting fluorochemical polyether compsn and the result of embodiment 1 are illustrated in the table 2 in the lump.
Comparative example 3
In replacing comparative example 2 have molecular-weight average be 400 two terminal hydroxyl type PEG use have molecular-weight average be 300 two terminal hydroxyl type PEG, react equally and the place, back with comparative example 2.The result that will measure the rerum natura of resulting response composite and the result of comparative example 2 are illustrated in the table 2 in the lump.
[table 2] fluorine-containing (containing the Rf yl) epoxide and the reaction conditions of PEG and the analytical results of resulting reactant
Can judge that from table 2 if the molecular-weight average of PEG is little, then the thermogravimetric amount reduces greatly, if molecular-weight average is big, then the solvability to water increases.
Therefore, use antifogging agent as film for agricultural use, the molecular-weight average of judging PEG is preferably 250～550 scope above 200 and less than 600, is preferably 300～500 scope.
Embodiment 5 < result in the real machine stretched film >
With adding in EVA resin manufacturing film for agricultural use as follows in the embodiment 1 resulting fluorochemical polyether compsn as base material.As the anti-caking distillate medicinal water, and with auxiliary chemicals system (HP-IV).The antifog property of the resulting film for agricultural use of expression in table 3.
< film manufacturing method >
To being used for the master batch of film production, use kneading machine, single screw rod, double-screw extruding pelletizing to make machine.Film is three-decker (thickness is 1: 1: 1), only in innermost layer or innermost layer and middle layer, adds the fluorochemical polyether compsn.Film-making machine uses SJ-90/30, makes film at 150 ℃～205 ℃, and thickness is 0.1mm.
The antifog property of [table 3] film for agricultural use
Notes 1) addition is the weight part with respect to each thin film layer 100 weight part.
Annotate 2) antifog evaluation
-1: do not have mist fully
+ 1: mist is arranged slightly
+ 2: mist is slightly many
+ 3: mist is very many.
Utilizability in the industry
The problem that fluorochemical polyether compsn of the present invention does not exist PFOA to produce, few to the load of environment, can be as film for agricultural use with adding utilization in the antifogging agent.And fluorochemical polyether compsn of the present invention can utilize in the purposes of the additive in fire foam, the coating etc., various penetrant and flow agent etc. as the excellent nonionic class tensio-active agent of capillary reduction ability.
Claims (13)
1. fluorochemical polyether compsn is characterized in that:
(a), molecular-weight average adds single terminal addition thing of the group (F2 yl) shown in group shown in the accepted way of doing sth (I) (F1 yl) or the formula (II) on being single end of 250～550 polyoxyethylene glycol,
Formula (I): C
6F
13(CH
2)
n-CH (OH) CH
2-
Formula (II): C
6F
13(CH
2)
n-CH (CH
2OH)-
In the formula, n representes 1～10,
(b) two terminal addition things of addition F1 base or F2 base on two ends of polyoxyethylene glycol,
(c) two terminal hydroxyl type polyoxyethylene glycol,
(a) and (b) are 30～95: 2～40 with (c) the molar ratio that exists: 0～40, wherein, (a) and (b) with (c) add up to 100.
2. fluorochemical polyether compsn as claimed in claim 1 is characterized in that:
Compsn is the reactant of fluorine-containing C6 epoxide shown in the formula (III) and two terminal hydroxyl type polyoxyethylene glycol,
Formula (III):
In the formula, n and above-mentioned synonym,
Single terminal addition thing (a) is 1: 1 mol ratio affixture of fluorine-containing C6 epoxide and polyoxyethylene glycol,
Two terminal addition things (b) be fluorine-containing C6 epoxide and polyoxyethylene glycol 2: 1 mol ratio affixtures and
Two terminal hydroxyl type polyoxyethylene glycol (c) are unreacted polyoxyethylene glycol.
3. fluorochemical polyether compsn as claimed in claim 2 is characterized in that:
It obtains with mol ratio reaction in 0.7: 1～1.3: 1 through making fluorine-containing C6 epoxide and two terminal hydroxyl type polyoxyethylene glycol.
4. fluorochemical polyether compsn as claimed in claim 2 is characterized in that:
It obtains with mol ratio reaction in 1: 1 through making fluorine-containing C6 epoxide and two terminal hydroxyl type polyoxyethylene glycol.
5. like each described fluorochemical polyether compsn in the claim 1～4; It is characterized in that: the molar ratio that exists of single terminal addition thing (a), two terminal addition things (b) and polyoxyethylene glycol (c) is 60～80: 10～20: 0～20; Wherein, (a) and (b) with (c) add up to 100.
6. like each described fluorochemical polyether compsn in the claim 1～5, it is characterized in that:
The molecular-weight average of polyoxyethylene glycol is 300～500.
7. a film for agricultural use is used antifogging agent, it is characterized in that:
Contain each described fluorochemical polyether compsn in the claim 1～6.
8. film for agricultural use as claimed in claim 7 is used antifogging agent, it is characterized in that:
Also contain the anti-caking distillate medicinal water.
9. film for agricultural use that contains claim 7 or 8 described antifogging agents.
10. nonionic class tensio-active agent that contains each described fluorochemical polyether compsn in the claim 1～6.
11. make the fluorochemical polyether method for compositions for one kind, be used to make claim 1 or 2 described fluorochemical polyether compsns, the method is characterized in that:
Make fluorine-containing C6 epoxide and two terminal hydroxyl type polyoxyethylene glycol with mol ratio reaction in 0.7: 1～1.3: 1.
12. method as claimed in claim 11 is characterized in that:
Make fluorine-containing C6 epoxide and two terminal hydroxyl type polyoxyethylene glycol with mol ratio reaction in 1: 1.
13., it is characterized in that like claim 11 or 12 described methods:
At BF
3Under the existence of coordination compound catalyzer, carry out the reaction of fluorine-containing C6 epoxide and two terminal hydroxyl type polyoxyethylene glycol.
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| CN110799679A (en) * | 2017-06-20 | 2020-02-14 | 10X基因组学有限公司 | Method and system for improving droplet stabilization |
| CN114890874A (en) * | 2022-04-02 | 2022-08-12 | 浙江大学衢州研究院 | Fluorine-containing surfactant and preparation method thereof |
| CN115216213A (en) * | 2022-06-09 | 2022-10-21 | 中国科学院长春应用化学研究所 | High-light-transmittance antifogging spray, coating material and preparation method |
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| US20050142505A1 (en) * | 2003-12-26 | 2005-06-30 | Fuji Photo Film Co., Ltd. | Silver halide photographic light-sensitive material and aqueous coating composition |
| WO2009020906A2 (en) * | 2007-08-06 | 2009-02-12 | E. I. Du Pont De Nemours And Company | Mixed fluoroalkyl-alkyl surfactants |
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| TW200720321A (en) * | 2005-09-16 | 2007-06-01 | Seimi Chem Kk | Fluorine-containing compound, method for producing thereof, its use, and method for reducing surface tension and method for modifying resin surface using thereof |
| JP2008037912A (en) | 2006-08-02 | 2008-02-21 | Konica Minolta Medical & Graphic Inc | Resin based body and method for modifying surface thereof |
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| US20050142505A1 (en) * | 2003-12-26 | 2005-06-30 | Fuji Photo Film Co., Ltd. | Silver halide photographic light-sensitive material and aqueous coating composition |
| WO2009020906A2 (en) * | 2007-08-06 | 2009-02-12 | E. I. Du Pont De Nemours And Company | Mixed fluoroalkyl-alkyl surfactants |
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| CN110799679A (en) * | 2017-06-20 | 2020-02-14 | 10X基因组学有限公司 | Method and system for improving droplet stabilization |
| CN114890874A (en) * | 2022-04-02 | 2022-08-12 | 浙江大学衢州研究院 | Fluorine-containing surfactant and preparation method thereof |
| CN114890874B (en) * | 2022-04-02 | 2024-07-16 | 浙江大学衢州研究院 | Fluorine-containing surfactant and preparation method thereof |
| CN115216213A (en) * | 2022-06-09 | 2022-10-21 | 中国科学院长春应用化学研究所 | High-light-transmittance antifogging spray, coating material and preparation method |
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| JPWO2011030725A1 (en) | 2013-02-07 |
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