CN101671280B - Perfluor-vinyl-containing amino-allyl formate as well as preparation method and application thereof - Google Patents
Perfluor-vinyl-containing amino-allyl formate as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a perfluor-vinyl-containing amino-allyl formate as well as a synthesizing method and an application thereof. The method is carried out according to the following steps of: (1) causing methylbenzene-2,4-diisocyanate shown by a formula (II) and propenol shown by a formula (III) to carry out primary addition reaction in a polar aprotic solvent by taking organotin as a catalyst, continuing the reaction till II substantially disappears, and obtaining a reaction liquid A of an intermediate shown by a formula (IV); and (2) directly adding the reaction liquid A into 2-methoxyl-3-perfluor-vinoxyl propanol shown by a formula (V) to realize secondary addition reaction, obtaining a reaction liquid B after the reaction is finished, and obtaining the perfluor-vinyl-containing amino-allyl formate shown by a formula (I) after the reaction liquid B is carried out by desolventizing and column chromatography separation. The invention has the advantage that a polymer monomer perfluor-vinyl-containing amino-allyl formate (I) which has an absolutely new structure and is waterproof and grease-proof is provided; in addition, one-pot synthesizing is adopted, the intermediate process is simple, and the operation is convenient.
Description
One. technical field
The present invention relates to a kind of new polymers monomer and contain the perfluor allyl carbamate, particularly relate to allyl carbamate that contains the perfluorinated nonene base and the allyl carbamate that contains the perfluor hexenyl.
Two. background technology
Fluoropolymer is meant that with the C-C chain be main chain, on side chain or side chain, is connected with one or more fluorine atom, all is even the polymkeric substance of fluorine atom, mainly comprises viton and Fluroplast-4.The outer minimum van der Waals radius of the strong negative of fluorine, high C-F bond energy (540kJ/mol), dehydrogenation and to the shielding protection effect of carbochain; Give the superior thermostability of fluoropolymer, weathering resistance and unreactiveness; And special electrical property (low conduction constant), water-and oil-repellency [New Chemical Materials; 2004,32 (8): 46], optical characteristics (low reflectivity), so [the Organic Coat Applied Polymer Science Progress that is with a wide range of applications in a plurality of fields such as building, electronics, boats and ships, aviation, transportation, printing, textile finishings; 1983,48:407.].
Copolymerization is one of important method of preparation novel fluoropolymers; Both can carry out modification to existing fluoropolymer, and also can adopt different fluorine-containing comonomers to carry out the synthetic new fluoropolymer of copolyreaction through molecular designing etc. through on polymer molecular chain, introducing side group.Comonomer commonly used has tetrafluoroethylene, R 1216, trifluorochloroethylene and perfluoroalkyl vinyl ether (PFVOE) etc., and wherein PFVE has between perfluoro methyl vinyl ether (methyl ether), perfluoro propyl vinyl ether (propyl ether) and perfluor dioxy ring the eleventh of the twelve Earthly Branches alkene etc.
Fluoropolymer and monomeric compound method thereof are constantly developed in recent years.Yun-xiangZhang etc. have reported synthetic [PolymerInternational, 2000, the 49:763-774] of fluorine-containing gathering (N-Isopropamide); Rattan field and man etc. have synthesized polymkeric substance fluorochemical surfactant [JP 2003221419,2003] by fluorine-containing acrylamide monomers; MichaelS.Terrazas etc. have reported that fluorochemical monomer is with non-fluorochemical monomer copolymerization synthetic polymer fluorochemical surfactant [US 20060149012,2006]; Gao Jinzhang etc. have reported the preparation [applied chemistry, 2006,23 (8): 924-926] of polymkeric substance fluorochemical surfactant monomer Perfluorocaprylic Acid methacryloxy ethyl ester.
Fluorine-containing alkyl acrylate is meant that the hydrogen major part that is connected with carbon atom on the alkyl in the propenoate is by the substituted compound of fluorine.Because fluorine atom has replaced Wasserstoffatoms, to compare with general propenoate, fluorine-containing alkyl acrylate has more excellent physics and chemical property, and added value is higher.It is starting raw material that synthetic route mainly adopts Perfluorocaprylic Acid, and at N, dinethylformamide (DMF) exists down, with sulfur oxychloride (SOCl
2) reaction, generate perfluorooctane chloride.Perfluorooctane chloride reacts with hydramine again, obtains N-hydroxyethyl perfluor decoylamide.Human N-hydroxyethyl perfluor decoylamide is arranged under the catalysis of dibutyl tin laurate; With the hexone is solvent, elder generation and Toluene-2,4-diisocyanate, 4-di-isocyanate reaction; Carry out condensation reaction with methylacrylic acid-beta-hydroxyethyl ester again and generate fluorine-containing alkyl acrylate ester monomer; Total recovery reaches 60% [fine chemistry industry, 2002,19 (11): 661-663].
Perfluoro octyl sulfonic acid (PFOS) and verivate thereof because high persistence and cumulative bad are arranged in environment, exist potential dangerous, thereby receive strict restriction in developed countries such as the U.S., European Union.The substitute of PFOS has become new research hot issue, is a kind of effective alternative route with oligomerization of hexafluoropropylene deutero-perfluoroolefine as the fluorine-containing part of fluoropolymer wherein.
Toluene-2,4-diisocyanate, the 4-vulcabond is a kind of important chemical material, is mainly used in synthesis of polyurethane.2006, Y.Dong etc. are with Toluene-2,4-diisocyanate, and the 4-vulcabond is a raw material, synthesized non-ionic polyurethane tensio-active agent [Journal of Applied Polymer Science, 2006,100:956-2962].With Toluene-2,4-diisocyanate, the verivate of 4-vulcabond, oligomerization of hexafluoropropylene body and vinyl carbinol are main raw material, and the synthetic monomeric report of fluoropolymer is few.
Three, summary of the invention
One of the object of the invention provides a kind of polymer monomer with water and oil repellant performance tensio-active agent that can be made into and contains the perfluor allyl carbamate.
Two of the object of the invention provides the preparation method that a kind of new polymers monomer contains the perfluor allyl carbamate.
The technical scheme that the present invention adopts is:
A kind of new polymers monomer contains the perfluor allyl carbamate, and general structure is suc as formula shown in (I):
In the formula, n is 6 or 9.
The present invention relates to the preparation method that said new polymers monomer contains the perfluor allyl carbamate, its preparation method comprises the steps: (1) with the Toluene-2,4-diisocyanate shown in the formula (II), and the 4-vulcabond is the vinyl carbinol shown in raw material and the formula (III); In polar aprotic solvent, be that catalyzer carries out the first step addition reaction with the organotin, detect with TLC usually; Follow the tracks of reaction process, react to the Toluene-2,4-diisocyanate shown in the formula (II), the 4-di-isocyanate reaction is complete; Be Toluene-2,4-diisocyanate, the 4-vulcabond disappears basically, and reaction finishes; Obtain containing the reaction solution A of midbody shown in the formula (IV); (2) described reaction solution A directly adds the 2-methoxyl group shown in the formula V-3-perfluoro alkene oxygen base propyl alcohol, and promptly the second step addition reaction takes place 2-methoxyl group-3-perfluorinated nonene oxygen base propyl alcohol or 2-methoxyl group-3-perfluor hexene oxygen base propyl alcohol; Usually detect with TLC; Follow the tracks of reaction process, reaction finish reaction solution B, reaction solution B obtains containing the perfluor allyl carbamate shown in the formula (I) through removing solvent and column chromatography for separation.Reaction process is following:
In formula V or the formula (I), n is 6 or 9.
In the first step and the second step addition reaction; Said Toluene-2,4-diisocyanate; 4-vulcabond (II), vinyl carbinol (III) are 1: 1～2: 1～2 with the ratio of 2-methoxyl group-3-perfluoro alkene oxygen base propyl alcohol or 2-methoxyl group-3-perfluor hexene oxygen base propyl alcohol (V) amount of substance; Proportioning is 1: 1～1.5: 1～1.5 preferably, and best proportioning is 1: 1～1.2: 1～1.2; The first step addition reaction or the second step addition reaction temperature are respectively done for oneself 70～150 ℃, and preferable temperature of reaction is 70～120 ℃, and optimal reaction temperature is 70～90 ℃; The first step reaction times is 3～6 hours, and second reaction times in step was 4～6 hours.
Toluene-2,4-diisocyanate; In the addition reaction of same vinyl carbinol of 4-vulcabond (II) (III) and 2-methoxyl group-3-perfluoro alkene oxygen base propyl alcohol (V); Catalyzer is an organo-tin compound, and described catalyzer is one of following or the combination of any several kinds of organotin arbitrary proportions: tin tetraphenyl, tin tetraethyl, tetrabutyl tin, fentin acetate, triethyl tin sulphate or dibutyl tin dilaurate.Toluene-2,4-diisocyanate, the ratio of the amount of 4-vulcabond and catalyst substance is 1: 0.01～0.1, and proportioning is 1: 0.05～0.1 preferably, and best proportioning is 1: 0.08.
Polar aprotic solvent of the present invention is one of following: acetonitrile, N; Dinethylformamide, N; N-N,N-DIMETHYLACETAMIDE, DMSO 99.8MIN., acetone, tetramethylene sulfone, 1,2-ethylene dichloride, chloroform, ETHYLE ACETATE, trichloroethane, methylene dichloride, chlorobenzene, dichlorobenzene, oil of mirbane, ether, isopropyl ether, THF or furans etc.Toluene-2,4-diisocyanate, the 4-vulcabond is 1: 5～20 with the ratio of the amount of substance of polar aprotic solvent, preferred 1: 5～10.
Described in the recommendation step of the present invention (2) separation method be: reaction solution B distillation removes and desolvates; Be that 4: 1 hexanaphthene and ETHYLE ACETATE is eluent with volume ratio behind the precipitation; Separate through silica gel column chromatography, decompression removes solvent, must contain the allyl carbamate of perfluor.
The present invention can also add in the first step addition reaction in the described reaction raw materials of step (1) and add stopper; Described Toluene-2,4-diisocyanate; The 4-vulcabond is 1: 0.01～0.05 with the ratio of stopper quality; Described stopper is one of following: Resorcinol, tert-butyl catechol, o-nitrophenol, MEHQ or 2 etc.More preferably Resorcinol is a stopper.
Comparatively concrete, the preparation method who contains the allyl carbamate of perfluor of the present invention carries out according to following steps: (1) with Toluene-2,4-diisocyanate, the 4-vulcabond is dissolved in polar aprotic solvent, and the adding organotin is a catalyzer; Stopper, mixing is warming up to 75 ℃～120 ℃, drips vinylcarbinol; Dropwise, keep temperature to stir and carry out the first step addition reaction, reaction 3～6h, TLC detects; Follow the tracks of reaction process, must contain the reaction solution A of midbody shown in the formula (IV), (2) described reaction solution A directly drips the 2-methoxyl group shown in the formula V-3-perfluoro alkene oxygen base propyl alcohol; Be 2-methoxyl group-3-perfluorinated nonene oxygen base propyl alcohol or 2-methoxyl group-3-perfluor hexene oxygen base propyl alcohol, dropwise, the second step addition reaction takes place; 75 ℃～120 ℃ reaction 4～6h, TLC detects, and follows the tracks of reaction process; Reaction finish reaction solution B, be that 4: 1 hexanaphthene and ETHYLE ACETATE is eluent with volume ratio behind the reaction solution B distillation precipitation, obtain containing the perfluor allyl carbamate shown in the formula (I) through the silica gel column chromatography separation; Described polar aprotic solvent is 1,2-ethylene dichloride, DMSO 99.8MIN. or DMAC N,N; Described organotin catalysts is tin tetraethyl, tin tetraphenyl or tetrabutyl tin; Described Toluene-2,4-diisocyanate, the 4-vulcabond is 1: 0.05～0.1 with the ratio of the amount of substance of catalyzer, said Toluene-2,4-diisocyanate; 4-vulcabond, vinyl carbinol are 1: 1～2: 1～2 with 2-methoxyl group-3-perfluorinated nonene oxygen base propyl alcohol or 2-methoxyl group-3-perfluor hexene oxygen base propyl alcohol amount of substance ratio; Described Toluene-2,4-diisocyanate, the 4-vulcabond is 1: 5～20 with the amount of substance ratio of polar aprotic solvent, described Toluene-2,4-diisocyanate; The 4-vulcabond is 1: 0.01～0.05 with the ratio of stopper quality; Described stopper is one of following: Resorcinol, tert-butyl catechol, o-nitrophenol, MEHQ or 2.
The application of allyl carbamate in the preparation Waterproof, grease proof treating compound that contains perfluor of the present invention; Monomer copolymerizations such as the said allyl carbamate that contains perfluor and (methyl) vinylformic acid; It is bigger to make the emulsion water contact angle with water and oil repellant performance, can be used as the waterproof and oilproof processing that Waterproof, grease proof treating compound is applied to surfaces such as fabric, paper, leather and glass.
Beneficial effect of the present invention is mainly reflected in: provide a kind of polymer monomer of brand new to contain perfluor allyl carbamate (I); Compound method of the present invention is an one kettle way, and pilot process is simple, and is easy to operate.Contain shown in the formula (I) perfluor allyl carbamate can with (methyl) acrylic acid copolymer, obtain a kind of emulsion with water and oil repellant performance, the waterproof and oilproof that can be used for surface such as fabric, paper, leather and glass is handled.
(4) embodiment
Below in conjunction with specific embodiment the present invention is described further, but protection scope of the present invention is not limited in this:
Embodiment 1
Add 1 at the 250mL four-hole boiling flask, 2-ethylene dichloride 50mL, Toluene-2,4-diisocyanate, 4-vulcabond 17.4g (2; 4-TDI, 0.1mol), tin tetraethyl 1.9g (0.008mol), 0.5g Resorcinol are stopper; Stir, be warming up to 75 ℃, drip vinylcarbinol 5.8g (0.1mol), dropwise; TLC detects, and follows the tracks of reaction process, keeps temperature stirring reaction 4h.Drip 2-methoxyl group-3-perfluorinated nonene oxygen base propyl alcohol 53.6g (0.1mol), dropwise, TLC detects, and follows the tracks of reaction process, keeps temperature stirring reaction 5h.Reaction finishes, the underpressure distillation precipitation, and silica gel column chromatography separates (V
Hexanaphthene: V
ETHYLE ACETATE=4: 1), remove behind the solvent yellow thickness paste I
1(n=9), yield 61.2%, purity 99.7%.
FT-IR(cm
-1)：3307，2957，2936，1714，1601，1534，1276，1198，1163，971，754，717；
1H?NMRδ(CDCl
3)：7.80(s，1H)，7.21(s，1H)，7.09(d，1H)，6.65(s，1H)，6.45(s，1H)，5.96(m，1H)，5.35(d，1H)，5.24(d，1H)，5.08(m，1H)，4.66(m，2H)，4.17(m，2H)，3.59(m，2H)，3.38(s，3H)，2.18(s，3H)
19F?NMRδ(CDCl
3)：-169.4(m，1F)，-167.4(m，1F)，-72.6(d，6F)，-71.5(s，6F)，-56.2(t，3F)。
Embodiment 2
React according to embodiment 1 method, but 2-methoxyl group-3-perfluorinated nonene oxygen base propyl alcohol changes 2-methoxyl group-3-perfluor hexene oxygen base propyl alcohol 38.6g (0.1mol) into, other condition is identical with embodiment 1, obtains faint yellow paste I
2(n=6), yield 65.3%, purity 99.5%.
19F?NMRδ(CDCl
3)：-129.4(t，3F)，-127.4(s，3F)，-121.6(m，2F)，-83.3(s，2F)，-78.1(t，1F)。
Embodiment 3
Add DMAC N,N 50mL, 2 at the 250mL four-hole boiling flask; 4-TDI 17.4g (0.1mol), tin tetraphenyl 4.27g (0.01mol), 0.5g dihydroxy-benzene are stopper; Stir, be warming up to 100 ℃, drip vinylcarbinol 8.13g (0.14mol) and dropwise; TLC detects, and follows the tracks of reaction process, keeps temperature to stir the first step reaction 4h.Drip 2-methoxyl group-3-perfluorinated nonene oxygen base propyl alcohol 75.04g (0.14mol), dropwise, TLC detects, and follows the tracks of reaction process, keeps temperature to stir second step reaction 5h.Reaction finishes, precipitation, and silica gel column chromatography separates (V
Hexamethylene Alkane: V
ETHYLE ACETATE=7: 3), remove behind the solvent yellow paste I
1(n=9), yield 67.7%, purity 99.5%.
Embodiment 4
React according to embodiment 3 methods, but solvent changes DMSO 99.8MIN. 70mL into, 90 ℃ of temperature of reaction, behind dropping 2-methoxyl group-3-perfluorinated nonene oxygen base propyl alcohol, the first step insulated and stirred 4h, the second step insulated and stirred 5h.Other reaction conditions is identical with embodiment 3.Get yellow paste I
1(n=9), yield 70.1%, purity 99.8%.
Embodiment 5
React according to embodiment 3 methods; But solvent changes DMSO 99.8MIN. 70mL into, and tin tetraethyl changes tetrabutyl tin 3.5g (0.008mol) into, 90 ℃ of temperature of reaction; After dripping 2-methoxyl group-3-perfluorinated nonene oxygen base propyl alcohol, the first step and each insulated and stirred 5h of second step reaction.Other reaction conditions is identical with embodiment 3.Get yellow paste I
1(n=9), yield 69.2%., purity 99.9%
Embodiment 6
According to embodiment 3, but do not add hydroquinone of polymerization retarder, but the first step insulation reaction time be 6h, second the step insulation reaction be 6h.Other reaction conditions is identical with embodiment 3.Get yellow paste I
1(n=9), yield 53.9%, purity 99.6%.
Embodiment 7
According to embodiment 3, but the first step temperature of reaction and the second step insulation reaction temperature are 150 ℃, get yellow paste I
1(n=9), yield 60.1%, purity 99.8%.
Embodiment 8
In the 250mL four-hole boiling flask, add 50mL toluene, stir, heat to 80 ℃.0.9g initiator Diisopropyl azodicarboxylate is dissolved in the 5mL toluene, 10.0g TEB 3K, 20.0g Bing Xisuandingzhi and 10.0g embodiment 1 method make suc as formula the allyl carbamate I that contains perfluor shown in (I)
1(n=9), mix, initiator solution and monomer mixture solution slowly are added drop-wise in the four-hole boiling flask respectively simultaneously, dropwise, be warming up to 90 ℃, insulation reaction 45min reduces to room temperature with reaction mass, obtains colourless transparent oil liquid, i.e. fluorine carbon resin.On the cleaning of a 5cm * 20cm, exsiccant sheet glass, with the prepared fluorine carbon resin of vaporific even spraying, after the drying at room temperature, at 80 ℃ of baking 2h.Take out, be cooled to room temperature, measuring water contact angle is 118 °.
Embodiment 9
In the 250mL four-hole boiling flask, add 50mL toluene, stir, heat to 80 ℃.0.9g initiator Diisopropyl azodicarboxylate is dissolved in the 5mL toluene, 10.0g TEB 3K, 20.0g Bing Xisuandingzhi and 10.0g embodiment 2 methods make suc as formula the allyl carbamate I that contains perfluor shown in (I)
2(n=6), mix, initiator solution and monomer mixture solution slowly are added drop-wise in the four-hole boiling flask respectively simultaneously, dropwise, be warming up to 90 ℃, insulation reaction 45min reduces to room temperature with reaction mass, obtains colourless transparent oil liquid, i.e. fluorine carbon resin.On the cleaning of a 5cm * 20cm, exsiccant sheet glass, with the prepared fluorine carbon resin of vaporific even spraying, after the drying at room temperature, at 80 ℃ of baking 2h.Take out, be cooled to room temperature, measuring water contact angle is 109 °.
Claims (10)
1. the allyl carbamate that contains perfluor, general structure is suc as formula shown in (I):
In the formula, n is 6 or 9.
2. the compound method that contains the allyl carbamate of perfluor as claimed in claim 1 is characterized in that said method comprises the steps: (1) with the Toluene-2,4-diisocyanate shown in the formula (II), and the 4-vulcabond is the vinyl carbinol shown in raw material and the formula (III); In polar aprotic solvent; With the organotin is that catalyzer carries out the first step addition reaction, and reaction finishes, and obtains containing the reaction solution A of midbody shown in the formula (IV); (2) described reaction solution A directly adds the 2-methoxyl group shown in the formula V-3-perfluorinated nonene oxygen base propyl alcohol or 2-methoxyl group-3-perfluor hexene oxygen base propyl alcohol; The second step addition reaction takes place, reaction finish reaction solution B, reaction solution B obtains containing the perfluor allyl carbamate shown in the formula (I) through removing solvent and column chromatography for separation; In the formula V, n is 6 or 9
3. the compound method that contains the allyl carbamate of perfluor as claimed in claim 2; It is characterized in that: said Toluene-2,4-diisocyanate, 4-vulcabond, vinyl carbinol and 2-methoxyl group-3-perfluorinated nonene oxygen base propyl alcohol or 2-methoxyl group-3-perfluor alkene oxygen base propyl alcohol amount of substance ratio are 1: 1～2: 1～2.
4. the compound method that contains the allyl carbamate of perfluor as claimed in claim 2; It is characterized in that described catalyzer is one of following or the combination of any several kinds of organotin arbitrary proportions: tin tetraphenyl, tin tetraethyl, tetrabutyl tin, fentin acetate, triethyl tin sulphate or dibutyl tin dilaurate; Described Toluene-2,4-diisocyanate, the 4-vulcabond is 1: 0.01～0.1 with the ratio of the amount of substance of catalyzer.
5. the compound method that contains the allyl carbamate of perfluor as claimed in claim 2 is characterized in that the temperature of the described the first step or the second step addition reaction is carried out under 70 ℃～150 ℃ conditions.
6. the compound method that contains the allyl carbamate of perfluor as claimed in claim 2; It is characterized in that described polar aprotic solvent is one of following: acetonitrile, N; Dinethylformamide, N; N-N,N-DIMETHYLACETAMIDE, DMSO 99.8MIN., acetone, tetramethylene sulfone, 1,2-ethylene dichloride, chloroform, ETHYLE ACETATE, trichloroethane, methylene dichloride, chlorobenzene, dichlorobenzene, oil of mirbane, ether, isopropyl ether, THF or furans; Toluene-2,4-diisocyanate, the 4-vulcabond is 1: 5～20 with the amount of substance ratio of described polar aprotic solvent.
7. the compound method that contains the allyl carbamate of perfluor as claimed in claim 2 is characterized in that adding stopper in the described reaction raw materials of step (1), described Toluene-2,4-diisocyanate, and the 4-vulcabond is 1: 0.01～0.05 with the ratio of stopper quality.
8. like the described compound method that contains the allyl carbamate of perfluor of one of claim 2～7; It is characterized in that the separation method in the described step (2) is: reaction solution B distillation removes desolvates; With volume ratio is that 4: 1 hexanaphthenes and ETHYLE ACETATE are eluent; Separate through silica gel column chromatography, decompression removes solvent, must contain the allyl carbamate of perfluor.
9. the compound method that contains the allyl carbamate of perfluor as claimed in claim 7 is characterized in that synthesis step is following: (1) with Toluene-2,4-diisocyanate, the 4-vulcabond is dissolved in polar aprotic solvent, and the adding organotin is a catalyzer; Add stopper, mixing is warming up to 75 ℃～120 ℃, drips vinyl carbinol; Dropwise, keep temperature to stir and carry out the first step addition reaction, reaction 3～6h; TLC detects, and follows the tracks of reaction process, and reaction finishes; The reaction solution A that must contain midbody shown in the formula (IV), (2) described reaction solution A directly drip the 2-methoxyl group shown in the formula V-3-perfluorinated nonene oxygen base propyl alcohol or 2-methoxyl group-3-perfluor hexene oxygen base propyl alcohol, dropwise; The second step addition reaction takes place; 75 ℃～120 ℃ reaction 4～6h, TLC detects, and follows the tracks of reaction process; The reaction finish reaction solution B; Reaction solution B distillation removes and desolvates, and is that 4: 1 hexanaphthenes are eluent with ETHYLE ACETATE with volume ratio, obtains containing the perfluor allyl carbamate shown in the formula (I) through the silica gel column chromatography separation; Described polar aprotic solvent is 1,2-ethylene dichloride, DMSO 99.8MIN. or DMAC N,N; Described catalyzer is tin tetraethyl, tin tetraphenyl or tetrabutyl tin; Described Toluene-2,4-diisocyanate, the 4-vulcabond is 1: 0.05～0.1 with the ratio of the amount of substance of catalyzer, said Toluene-2,4-diisocyanate; 4-vulcabond, vinyl carbinol are 1: 1～2: 1～2 with 2-methoxyl group-3-perfluorinated nonene oxygen base propyl alcohol or 2-methoxyl group-3-perfluor hexene oxygen base propyl alcohol amount of substance ratio; Described Toluene-2,4-diisocyanate, the 4-vulcabond is 1: 5～10 with the amount of substance ratio of polar aprotic solvent, described stopper is one of following: Resorcinol, tert-butyl catechol, MEHQ or 2; 4, the 6-trinitrophenol.
10. the application of allyl carbamate in the preparation Waterproof, grease proof treating compound that contains perfluor as claimed in claim 1.
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| CN101671280A (en) | 2010-03-17 |
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