CN103145969A - Perfluorinated polyether diol and polyester-polyether segmented copolymer - Google Patents
Perfluorinated polyether diol and polyester-polyether segmented copolymer Download PDFInfo
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Abstract
The invention provides perfluorinated polyether diol as shown in formula (I), wherein n is 1-20. The invention further provides a polyester-polyether segmented copolymer, as shown in formula (III), based on the perfluorinated polyether diol. Compared with the existing multifunctional finishing agent based on fluorocarbon telomere, a fluorocarbon chain in the polyester-polyether segmented copolymer with the structure of formula (III) is perfluorinated polyether diol, wherein the perfluorinated polyether diol contains a plurality of C-F bonds which are short, strong, stable and low in polarity, so that the hydrophobic part with the structure of the formula (IV) has lower surface tension, and is not only water-repellent, but also oil-repellent. Meanwhile, compared with the multifunctional fabric finishing agent based on the fluorocarbon telomere, the perfluorinated polyether chain has better flexibility due to the existence of C-O covalent bonds, and therefore, the fabric has a soft hand feeling when the perfluorinated polyether chain is used as the fabric finishing agent.
Description
Technical field
The invention belongs to organic compound and synthesize and preparing technical field, relate in particular to PFPE glycol, Polyester-polyether copolymer.
Background technology
Compare with general polymer, fluoropolymer has excellent thermostability and chemical stability, and due to the low Intermolecular Forces between fluorocarbon polymer, make it present the various surface property such as excellent water and oil repellant and didirtresistance, be widely used in the fields such as weaving, leather, coating and papermaking.
Generally not fluorine-containing on its main chain of fluorine-containing multifunction finishing agent that is used for weaving, but perfluorination or partially fluorinated side chain radical had, therefore have excellent surface property, thereby make oil, water and spot etc. be difficult to soak or penetrate.In this series products, fluorine-containing side chain is its key component, the fluorine content in product and structures shape its physicals and application characteristic.The raw material that is applied to fluorine-containing multifunction finishing agent or tensio-active agent of commercialization or bibliographical information is mainly fluorine carbon telomer intermediate, have straight chain type and the two kinds of structures of branched chain type that contain branch, as perfluoroalkyl ethanol or perfluor alkyl ethide (methyl) acrylate.This class fluorine carbon telomer intermediate is mainly prepared by the product that telomerizes of Fluorine containing olefine (as tetrafluoroethylene, R 1216, trifluorochloroethylene, vinylidene etc.).But, this type of based on the telomer intermediate contain fluorine multifunctional fabric finishing agent in the fluorocarbon chain flexing poor, second-order transition temperature is low, although the finishing composition that therefore causes containing the perfluor carbochain has good water and oil repellant performance, but it is antifouling not good with antistatic property, and makes the fabric feeling after arrangement relatively poor.
Publication number is the preparation method and application that the Chinese patent of CN1927894 discloses a kind of fluorine-containing carbon chain acrylate and multipolymer thereof, and it makes R take the perfluor haloalkane as raw material with the vinylidene polymerization
f(CH
2CF
2)
mThen the perfluor haloalkane is made R-X(perfluor haloalkane),
f(CH
2CF
2)
m(CH
2)
n-OH(fluorine-containing alcohol), then carry out esterification and obtain fluorine-containing carbon chain acrylate.
publication number is that the Chinese patent of CN101148825 discloses a kind of organic fluorine water-refusing oil-refusing finishing agent and preparation thereof, the important composition composition of this finishing composition is assorted oxygen perfluoroalkyl (methyl) acrylate monomer, (methyl) acrylic ester high molecular type has good film-forming property, the characteristics that the cured article snappiness is good, with it as finishing composition handler woven fabric, after leather etc., process the sample good permeability, good feel is arranged, but it does not possess oil preventing performance, with after itself and fluorochemical monomer polymerization, because the electronegativity of fluorine is very large, the C-F key is very stable, polymkeric substance perfluor side chain orientation outwardly simultaneously, main chain and interior molecules are formed " shielding protection ", therefore make it possess simultaneously the performance of waterproof and oilproof.But the fluorocarbon chain that contains of this finishing composition is similarly the perfluoroolefine chain, and flexing is relatively poor, and second-order transition temperature is lower.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of PFPE glycol and Polyester-polyether copolymer based on the PFPE glycol.This PFPE glycol flexing is better.
The invention provides a kind of PFPE glycol, as shown in the formula (I):
（I）
Wherein, n=1～20.
The invention provides a kind of preparation method of PFPE glycol, comprise the following steps:
A) under the effect of alkali metal alcoholate or alkali metal hydroxide, formula (II) structure PFPE methyl alcohol to be mixed with halogenated epoxy propane, reacting by heating in the multiethylene-glycol dme obtains propylene oxide base PFPE methyl ether;
B) described propylene oxide base PFPE methyl ether, dimethyline are mixed with acid solution, reacting by heating obtains the PFPE glycol of formula (I) structure;
（II）
Wherein, n=1～20.
Preferably, described alkali metal alcoholate or alkali metal hydroxide are selected from a kind of in sodium tert-butoxide, sodium ethylate, sodium methylate, sodium hydroxide, potassium tert.-butoxide, potassium ethylate, potassium methylate and potassium hydroxide.
Preferably, described multiethylene-glycol dme is selected from a kind of in glycol dimethyl ether, diethylene glycol dimethyl ether, TRIGLYME and tetraethyleneglycol dimethyl ether.
Preferably, described halogenated epoxy propane is epoxy chloropropane or epoxy bromopropane.
Preferably, described steps A) preferably also comprise: after reacting by heating, add alkali metal hydroxide, then extract with organic reagent, obtain propylene oxide base PFPE methyl ether.
The invention provides a kind of Polyester-polyether copolymer, as shown in the formula (III):
（III）
Wherein, R
f-be formula (IV) structure:
（IV）
Wherein, m:n
1=(0.2～5): 1, l=2～30, n=1～20.
The present invention also provides a kind of preparation method of Polyester-polyether copolymer, comprising:
The PFPE glycol of terephthalic acid ester compound, ethylene glycol, formula (I) structure is mixed with polyoxyethylene glycol, under the effect of the first catalyzer, transesterification reaction is carried out in heating, then add the second catalyzer and phosphorus-containing antioxidant, under the condition of protection of inert gas, reacting by heating obtains the Polyester-polyether copolymer of formula (III) structure;
（I）
（III）
Wherein, R
f-be formula (IV) structure:
（IV）
Wherein, m:n
1=(0.2～5): 1, l=2～30, n=1～20.
Preferably, described the first catalyzer is selected from a kind of in zinc acetate, Burow Solution, manganese acetate and calcium acetate.
Preferably, described the second catalyzer is selected from a kind of in antimonous oxide, antimony acetate and antimony glycol.
The invention provides a kind of PFPE glycol, as shown in the formula (I), n=1～20 wherein.The present invention also provides a kind of Polyester-polyether copolymer based on this PFPE glycol, as shown in the formula (III).Compare based on the multifunction finishing agent of fluorine carbon telomer with existing, the fluorocarbon chain of the Polyester-polyether copolymer of formula (III) structure is the PFPE glycol, contain more C-F key in the PFPE chain, it is short, strong, stable and have a very low polarity key, make the hydrophobic part of formula (IV) structure have lower surface tension, not only hydrophobic but also hate oil; Simultaneously, and compare based on the multifunctional fabric finishing agent of fluorine carbon telomer, the existence of the covalent linkage of C-O makes the PFPE chain have kindliness preferably, therefore uses it for when fabric finishing agent uses to make fabric have submissive feel.
Embodiment
The invention provides a kind of PFPE glycol, as shown in the formula (I):
（I）
Wherein, n=1～20 are preferably 5～10.
The present invention also provides a kind of preparation method of PFPE glycol, comprise the following steps: A) under the effect of alkali metal alcoholate or alkali metal hydroxide, the PFPE methyl alcohol of formula (II) structure is mixed with halogenated epoxy propane, reacting by heating in the multiethylene-glycol dme obtains propylene oxide base PFPE methyl ether; B) described propylene oxide base PFPE methyl ether, dimethyline are mixed with acid solution, reacting by heating obtains the PFPE glycol of formula (I) structure;
（II）
Wherein, n=1～20 are preferably 5～10.
All raw materials of the present invention do not have special restriction to its source, and that buys on market gets final product.
The present invention carries out substitution reaction take the PFPE methyl alcohol of formula (II) structure as raw material with itself and halogenated epoxy propane, the PFPE methyl alcohol of wherein said formula (II) structure does not have business-like product, be the laboratory self-control, preferably be prepared in accordance with the following methods in the present invention: S1) alkaline metal fluoride cpd or alkaline-earth metal fluoride, perfluoro propene oxid are mixed with organic solvent, stirring reaction, obtain liquid catalyst, then it is mixed with perfluoro propene oxid, isothermal reaction obtains the perfluoro polyether acyl fluorine; S2) described perfluoro polyether acyl fluorine, alcohol are mixed with acid binding agent, obtain the PFPE ester after reaction; S3) described PFPE ester, multiethylene-glycol dme are mixed with reductive agent, reaction obtains the PFPE methyl alcohol of formula (II) structure.
Step S1 of the present invention) need first prepare liquid catalyst, then itself and perfluoro propene oxid are reacted, the preparation process of described liquid catalyst is specially: alkaline metal fluoride cpd or alkaline-earth metal fluoride are first stirred 20～50min with organic solvent, be preferably 20～40min, fully passing into perfluoro propene oxid under stirring and pressure, then reaction obtains liquid catalyst.
Wherein, alkaline metal fluoride cpd or alkaline-earth metal fluoride are that alkaline metal fluoride cpd well known to those skilled in the art or alkaline-earth metal fluoride get final product, there is no special restriction, be preferably cesium fluoride, lithium fluoride, Sodium Fluoride, Potassium monofluoride or magnesium fluoride in the present invention, more preferably cesium fluoride or Potassium monofluoride.
Described organic solvent is as S1) middle reaction solvent, for organic solvent well known to those skilled in the art gets final product, there is no special restriction, be preferably the multiethylene-glycol dme in the present invention, more preferably diethylene glycol dimethyl ether or tetraethyleneglycol dimethyl ether.
After alkaline metal fluoride cpd or alkaline-earth metal fluoride and organic solvent are fully mixed, pass into perfluoro propene oxid, react, described reaction preferably under the condition of 25 ℃～40 ℃, more preferably 30 ℃～35 ℃, is reacted 5～7h, be preferably 5.5～6.5h, obtain liquid catalyst.
the present invention is used for the liquid catalyst that obtains to be prepared the perfluoro polyether acyl fluorine with the perfluoro propene oxid reaction, this reaction preferably is specially: first a part of liquid catalyst is added in reaction vessel, be preferably half of liquid catalyst, then when constantly passing into perfluoro propene oxid, drip another part liquid catalyst, in this process, system begins heat release, make the system isothermal reaction by exterior cooling, preferred constant temperature reacts at 25 ℃～40 ℃, more preferably 30 ℃～35 ℃, reaction 30～50h, be preferably 35～40h, obtain the perfluoro polyether acyl fluorine.The flow that passes into of perfluoro propene oxid gas is preferably 1.5～2.5L/min in this process.
With the perfluoro polyether acyl fluorine that the obtains reactions steps S2 for the preparation of the PFPE methyl esters) be specially: at first described perfluoro polyether acyl fluorine is mixed with alcohol, then add acid binding agent, react and obtain the PFPE ester; For reducing the generation of bubble in this reaction, described acid binding agent preferably adds in batches.
Raw alcohol in this reaction is that alcohol well known to those skilled in the art gets final product, and there is no special restriction, is preferably the alcohol of C1～C4 in the present invention, more preferably methyl alcohol or ethanol; Described acid binding agent is that acid binding agent well known to those skilled in the art gets final product, and can promote the carrying out that react to there is no special restriction, is preferably sodium carbonate, salt of wormwood, triethylamine or pyridine in the present invention.
Described step S2) reaction in can be carried out at ambient temperature, also can carry out under heating condition, and the temperature of its reaction is preferably 20 ℃～100 ℃, and more preferably 30 ℃～60 ℃, the reaction times is preferably 3～20h, more preferably 5～10h.
The present invention with described PFPE ester by step S3) reduce the PFPE methyl alcohol that obtains corresponding formula (II) structure, in this reaction, solvent for use is the multiethylene-glycol dme, it is that multiethylene-glycol dme well known to those skilled in the art gets final product, there is no special restriction, be preferably glycol dimethyl ether, diethylene glycol dimethyl ether.TRIGLYME or tetraethyleneglycol dimethyl ether; In this reaction, reductive agent used is that reductive agent well known to those skilled in the art gets final product, and there is no special restriction, is preferably Lithium Aluminium Hydride or sodium borohydride.
Described PFPE ester is mixed in the multiethylene-glycol dme with reductive agent, carry out reduction reaction, the temperature of described reduction reaction is preferably 0～30 ℃, more preferably reacts under condition of ice bath, and the reaction times is preferably 5～12h, more preferably 6～10h.
After reduction reaction of the present invention, preferably carry out following aftertreatment, obtain the PFPE methyl alcohol of formula (II) structure: after reduction reaction, add deionized water, sulphuric acid soln and 1,1,2-Freon 113 in reaction system, washing, remove water layer, organic solvent is removed in the organic phase decompression, obtains the PFPE methyl alcohol of formula (II) structure.
Steps A) under the effect of alkali metal alcoholate or alkali metal hydroxide, the PFPE methyl alcohol of formula (II) structure is mixed with halogenated epoxy propane, wherein, described alkali metal alcoholate or alkali metal hydroxide are that alkali metal alcoholate well known to those skilled in the art or alkali metal hydroxide get final product, there is no special restriction, be preferably sodium ethylate, sodium methylate, sodium hydroxide or potassium hydroxide in the present invention, it is as catalyst PFPE methyl alcohol and the reaction of halogenated epoxy propane; The quality optimization of described alkali metal alcoholate or alkali metal hydroxide is 1～2% of formula (II) structure PFPE methyl alcohol molar weight, more preferably 1.2～1.4%; Described halogenated epoxy propane is that halogenated epoxy propane well known to those skilled in the art gets final product, and there is no special restriction, preferred epoxy chloropropane or epoxy bromopropane, more preferably epoxy chloropropane in the present invention.
Steps A) reacting by heating in the multiethylene-glycol dme obtains propylene oxide base PFPE methyl ether, and the temperature of described reacting by heating is preferably 50 ℃～70 ℃, and the time of reacting by heating is preferably 10～15h.
Under the effect of alkali metal alcoholate or alkali metal hydroxide; the PFPE methyl alcohol of formula (II) structure is mixed with halogenated epoxy propane; reacting by heating in the multiethylene-glycol dme; this reaction preferably is specially: the PFPE methyl alcohol of formula (II) structure is mixed with the multiethylene-glycol dme, under the condition of protection of inert gas, add alkali metal alcoholate or alkali metal hydroxide; and stir; then drip halogenated epoxy propane, reacting by heating obtains propylene oxide base PFPE methyl ether.
Wherein, after adding catalyzer alkali metal alcoholate or alkali metal hydroxide, preferably stir 0.5～2h, then drip halogenated epoxy propane; And in the process that halogenated epoxy propane drips, the temperature of preferred reaction system is no more than 60 ℃, then after dropwising, and reacting by heating.
According to the present invention, when described steps A) under the effect of alkali metal alcoholate after reacting by heating, preferably add alkali metal hydroxide aqueous solution to carry out cancellation and catalyst-solvent, and extract with organic solvent, obtaining lower floor after layering is propylene oxide base PFPE methyl ether.The organic solvent of described extraction use is preferably Virahol or tetrahydrofuran (THF).
Steps A) in, the concentration of cancellation reaction alkali metal hydroxide aqueous solution used is preferably 30～60%, and more preferably 40～55%, its consumption is 5～10 times of catalyzer alkali metal alcoholate quality, is preferably 5～8 times; The quality optimization that extracts organic solvent used is 2～4 times of multiethylene-glycol dme quality.
Described propylene oxide base PFPE methyl ether, dimethyline are mixed with acid solution, wherein said dimethyline is that dimethyline well known to those skilled in the art gets final product, there is no special restriction, described dimethyline is as the solvent of propylene oxide base PFPE methyl ether, its consumption is preferably 0.2～2 times of propylene oxide base PFPE methyl ether quality, more preferably 0.5～2 times; Described acid solution is preferably sulphuric acid soln or hydrochloric acid soln, and more preferably concentration is 10～15% sulphuric acid soln or 10～15% hydrochloric acid soln, and its consumption is 2～10 times of propylene oxide base PFPE methyl ether molar weight, more preferably 2～8 times.
After above raw material was mixed, ring-opening reaction was carried out in heating,, described reacting by heating is preferably back flow reaction, and the reaction times is preferably 6～12h, and more preferably 6～10h obtains the PFPE glycol of formula (I) structure.
According to the present invention, described step B) after reacting by heating is completed, preferably with basic solution, reaction system is neutralized, then use organic solvent extraction, obtain the PFPE glycol of formula (I) structure; Wherein, the basic solution used that neutralizes is that basic solution well known to those skilled in the art gets final product, and there is no special restriction, and in the present invention, the preferred aqueous sodium hydroxide solution that adopts neutralizes, and more preferably adopting concentration is that 15～30% aqueous sodium hydroxide solution neutralizes; The organic solvent that described extraction is adopted is preferably Freon 113.
The present invention also provides a kind of Polyester-polyether copolymer, as shown in the formula (III):
（III）
Wherein, R
f-be formula (IV) structure:
（IV）
Wherein, m:n
1=(0.2～5): 1, be preferably (0.5～4): 1; L=2～30 are preferably 5～20; N=1～20 are preferably 5～10.
Compare based on the multifunction finishing agent of fluorine carbon telomer with existing, the fluorocarbon chain in the Polyester-polyether copolymer of formula (III) structure is the PFPE glycol.Therefore this Polyester-polyether copolymer has water and oil-resistant, static resistance owing to having introduced PFPE side chain block; Simultaneously, and compare based on the multifunctional fabric finishing agent of fluorine carbon telomer, the existence of the covalent linkage of C-O makes the PFPE chain have kindliness preferably, therefore uses it for when fabric finishing agent uses to make fabric have submissive feel.
The present invention also provides the preparation method of the Polyester-polyether copolymer of above-mentioned formula (III) structure; comprise: the PFPE glycol of terephthalic acid ester compound, ethylene glycol, formula (I) structure is mixed with polyoxyethylene glycol; under the effect of the first catalyzer; transesterification reaction is carried out in heating; then add the second catalyzer and phosphorus-containing antioxidant; under the condition of protection of inert gas, reacting by heating obtains the Polyester-polyether copolymer of formula (III) structure.
Wherein said terephthalic acid ester compound is that terephthalic acid ester compound well known to those skilled in the art gets final product, and there is no special restriction, is preferably dimethyl terephthalate (DMT) or diethyl terephthalate in the present invention; Described polyoxyethylene glycol is that polyoxyethylene glycol well known to those skilled in the art gets final product, and there is no special restriction, and in the present invention, the preferred molecular weight that adopts is 200～2000 polyoxyethylene glycol, more preferably 1000～1500; The mol ratio of the PFPE glycol of described terephthalic acid ester compound and formula (I) structure is preferably (1.2～6): 1, more preferably (1.5～5): 1.
In the present invention, above-mentioned raw materials is blended under the effect of the first catalyzer, transesterification reaction is carried out in heating, wherein said the first catalyzer is that the catalyzer for transesterification reaction well known to those skilled in the art gets final product, there is no special restriction, the acetate of preferable alloy in the present invention, more preferably zinc acetate, Burow Solution, manganese acetate or calcium acetate; The consumption of described the first catalyzer be preferably raw material formula (I) structure PFPE glycol quality 0.01～1%.Described the first catalyzer preferably at the PFPE glycol of raw material terephthalic acid ester compound, ethylene glycol, formula (I) structure with after polyoxyethylene glycol mixes, heat up, add again after the whole meltings of raw material.
The temperature of described transesterification reaction is preferably 150 ℃～180 ℃, till reaction extremely steams without cut.
After in the present invention, transesterification reaction is completed, add the second catalyzer and phosphorus-containing antioxidant, wherein, described the second catalyzer is that the catalyzer for polycondensation well known to those skilled in the art gets final product, there is no special restriction, be preferably the oxide compound of metallic antimony, the alcoholate of metallic antimony, the carboxylate salt of metallic antimony or the halogenide of metallic antimony, more preferably antimonous oxide, antimony acetate or antimony glycol; The consumption of described the second catalyzer be preferably raw material formula (I) structure PFPE glycol quality 0.01～2%; Described phosphorus-containing antioxidant is that phosphorus-containing antioxidant well known to those skilled in the art gets final product, and there is no special restriction, is preferably triphenyl phosphite or triphenylphosphate, and it plays stabilization in polyreaction, can reduce the generation of side reaction; The consumption of described phosphorus-containing antioxidant be preferably raw material formula (I) structure PFPE glycol quality 0.01～0.5%.
After adding the second catalyzer and phosphorus-containing antioxidant, under the condition of protection of inert gas, reacting by heating obtains the Polyester-polyether copolymer of formula (III) structure with mixed system.Wherein, described rare gas element is that rare gas element well known to those skilled in the art gets final product, and there is no special restriction, is preferably nitrogen in the present invention.
Under the condition of protection of inert gas; reacting by heating; the temperature of described reacting by heating is preferably 200 ℃～240 ℃; in the present invention, this reaction more preferably is heated to 200 ℃～210 ℃, vacuumizes; after underpressure distillation to absence of liquid distillates; continue again to be warming up to 230 ℃～240 ℃ underpressure distillation, after steaming without cut, obtain the Polyester-polyether copolymer of formula (III) structure.
In order to further illustrate the present invention, below in conjunction with embodiment, PFPE glycol provided by the invention, Polyester-polyether copolymer are described in detail.
In following examples, reagent used is commercially available.
Embodiment 1
1.1 the 50g cesium fluoride is mixed with the 80ml tetraethyleneglycol dimethyl ether, stir 30min, fully passing into the 130g perfluoro propene oxid under stirring and pressure, 35 ℃ of holding temperatures, reaction 6h makes liquid catalyst; Half of gained liquid catalyst added in the 2 liter steel autoclaves that agitator is housed; then when constantly passing into perfluoro propene oxid gas; slow dropping liquid body catalyst; internal temperature is controlled at 35 ℃ by exterior cooling; keeping perfluoro propene oxid to pass into flow is 2L/min; temperature is controlled at 35 ℃ of lasting 3h by exterior cooling, then continues reaction 40h, obtains the perfluoro polyether acyl fluorine.
1.2 perfluoro polyether acyl fluorine and 45g methanol mixed with obtaining in 30g1.1 remain 30 ℃ with temperature, add in batches 8g sodium carbonate as acid binding agent; reaction 5h is after reaction is completed, with twice of 30ml deionized water washing; remove the upper strata, obtain lower floor's product, be the PFPE ester.
1.3 the PFPE ester, the 100ml tetraethyleneglycol dimethyl ether that obtain in 30g1.2 are mixed with the 2g sodium borohydride, react 8h under the ice-water bath condition of 0 ℃, after reaction is completed, the sulphuric acid soln and the 120ml1 that add respectively 150ml deionized water, 75ml15% in the reaction soln, 1, the 2-Freon 113, washing, remove a water layer, organic phase reduces pressure away 1,1, the 2-Freon 113, remaining liquid is placed 4h under vacuum condition, obtain the PFPE methyl alcohol of formula (II) structure, its molecular-weight average is 1000.
1.4 the PFPE methyl alcohol that obtains in 100g1.3 is mixed with 50g glyceryl alcohol dme; add the 8.2g sodium ethylate under the condition of nitrogen protection; stir 2h; then be heated to 50 ℃; slowly drip the 11.2g epoxy chloropropane; after dripping; the temperature of reaction system is risen to 60 ℃; stirring reaction 12h, reaction solution are cooled to below 30 ℃, add the NaOH aqueous solution of 50g50% with slower speed; after mix and blend 1h; add Virahol, take off a layer fluorous carbon phase after layering, obtain the thick product of propylene oxide base PFPE methyl ether.
1.5 the thick product of propylene oxide base PFPE methyl ether that obtains in 100g1.4 is mixed with 50g glyceryl alcohol dme, the aqueous sulfuric acid that slowly adds 100g50% under the condition that stirs, be heated to reflux state, then reaction 8h neutralizes with 20% the NaOH aqueous solution, and Freon 113 extracts three times, merge organic phase, use the Rotary Evaporators desolventizing, obtain the PFPE glycol of the water white formula of 102g (I) structure, its hydroxyl value is 93.4mg KOH/g.
Utilize nucleus magnetic resonance that the PFPE glycol of formula (I) structure that obtains in 1.5 is analyzed, obtain its hydrogen spectrum, result is 1H-NMR(CDCl
3) δ: 1.9(2H, CH
2), 2.1 (H, OH), 2.3(H, CH
2OH), 3.3 (2H, CH
2), 3.68 (2H, CH
2OH).
Embodiment 2
2.1 100g PFPE methyl alcohol (molecular-weight average is 1324) is mixed with 50g glyceryl alcohol dme; add the 6.3g sodium ethylate under the condition of nitrogen protection; stir 2h; then be heated to 50 ℃; slowly drip the 8.9g epoxy chloropropane; after dripping; the temperature of reaction system is risen to 60 ℃; stirring reaction 12h, reaction solution are cooled to below 30 ℃, add the NaOH aqueous solution of 50g50% with slower speed; after mix and blend 1h; add Virahol, take off a layer fluorous carbon phase after layering, obtain the thick product of propylene oxide base PFPE methyl ether.
2.2 the thick product of propylene oxide base PFPE methyl ether that obtains in 100g2.1 is mixed with 50g glyceryl alcohol dme, the aqueous sulfuric acid that slowly adds 100g50% under the condition that stirs, be heated to reflux state, then reaction 8h neutralizes with 20% the NaOH aqueous solution, and Freon 113 extracts three times, merge organic phase, use the Rotary Evaporators desolventizing, obtain the PFPE glycol of the water white formula of 101g (I) structure, its hydroxyl value is 75.3mg KOH/g.
Embodiment 3
3.1 100g PFPE methyl alcohol (molecular-weight average is 2155) is mixed with 50g glyceryl alcohol dme; add the 3.8g sodium ethylate under the condition of nitrogen protection; stir 2h; then be heated to 50 ℃; slowly drip the 5.2g epoxy chloropropane; after dripping; the temperature of reaction system is risen to 60 ℃; stirring reaction 6h, reaction solution are cooled to below 30 ℃, add the NaOH aqueous solution of 50g50% with slower speed; after mix and blend 1h; add Virahol, take off a layer fluorous carbon phase after layering, obtain the thick product of propylene oxide base PFPE methyl ether.
3.2 the thick product of propylene oxide base PFPE methyl ether that obtains in 100g3.1 is mixed with 50g glyceryl alcohol dme, the aqueous sulfuric acid that slowly adds 100g50% under the condition that stirs, be heated to reflux state, then reaction 8h neutralizes with 20% the NaOH aqueous solution, and Freon 113 extracts three times, merge organic phase, use the Rotary Evaporators desolventizing, obtain the PFPE glycol of the water white formula of 95g (I) structure, its hydroxyl value is 48.3mg KOH/g.
Embodiment 4
4.1 100g PFPE methyl alcohol (molecular-weight average is 670) is mixed with 50g glyceryl alcohol dme; add the 12.2g sodium ethylate under the condition of nitrogen protection; stir 2h; then be heated to 50 ℃; slowly drip the 17.2g epoxy chloropropane; after dripping; the temperature of reaction system is risen to 60 ℃; stirring reaction 6h, reaction solution are cooled to below 30 ℃, add the NaOH aqueous solution of 50g50% with slower speed; after mix and blend 1h; add Virahol, take off a layer fluorous carbon phase after layering, obtain the thick product of propylene oxide base PFPE methyl ether.
4.2 the thick product of propylene oxide base PFPE methyl ether that obtains in 100g4.1 is mixed with 50g glyceryl alcohol dme, the aqueous sulfuric acid that slowly adds 100g50% under the condition that stirs, be heated to reflux state, then reaction 8h neutralizes with 20% the NaOH aqueous solution, and Freon 113 extracts three times, merge organic phase, use the Rotary Evaporators desolventizing, obtain the PFPE glycol of the water white formula of 99.0g (I) structure, its hydroxyl value is 135.5mg KOH/g.
Embodiment 5
300g dimethyl terephthalate (DMT), 58g ethylene glycol, 830g PFPE glycol (molecular-weight average is 1074) are mixed with 200g polyoxyethylene glycol (molecular-weight average is 800), be warming up to 150 ℃, add the 1.5g zinc acetate after the whole meltings of material, slowly be warming up to 180 ℃ of stirrings and carry out transesterification reaction, be distilled to absence of liquid and distillate stopped reaction; Then add 4g antimonous oxide and 1g triphenyl phosphite, logical nitrogen protection vacuumizes when being warming up to 210 ℃; underpressure distillation to absence of liquid distillates; be warming up to again 240 ℃ of underpressure distillation, after steaming without cut, obtain the Polyester-polyether copolymer that 1380g thickness product is formula (III) structure.
The Polyester-polyether copolymer that obtains in embodiment 5 is arranged fabric by pickling process: configuration process liquid, fabric is put into treatment solution by the bath raio of 1:20, flood 20min under normal temperature condition, dehydration 1min, then 110 ℃ of oven dry 1h test, and test result sees Table 1.
Utilize OCA20 video optics contact angle measurement that the surface tension that the Polyester-polyether copolymer that obtains in embodiment 5 carries out water and oil-resistant is tested, obtain the results are shown in Table 1.
According to FZ/T01042-1996 " measuring method of textile materials antistatic property static voltage transformation period ", the Polyester-polyether copolymer that obtains in embodiment 5 is carried out the antistatic property test, fabric face resistance is little, crest voltage is little, transformation period is short, antistatic property is good, otherwise, poor, obtain test result and see Table 1.
Adopt the Y561 fabric according to GB/T5453-1997 " mensuration of textile fabric ventilation property ", the Polyester-polyether copolymer that obtains in embodiment 5 to be carried out the ventilation property test, the Air permenbility that flows through the fabric unit surface under certain pressure reduction is larger, the permeability of fabric is better, and the test result that obtains sees Table 1.
Utilize double-blind method, by the assessment panel that 10 people form, the pliability that obtains the fabric after Polyester-polyether copolymer is processed in process embodiment 5 is estimated, and statistics, overall score is higher, illustrates that the feel of fabric is more soft, obtains the results are shown in Table 1.
Embodiment 6
300g dimethyl terephthalate (DMT), 35g ethylene glycol, 1162g PFPE glycol (molecular-weight average is 1074) are mixed with 200g polyoxyethylene glycol (molecular-weight average is 1400), be warming up to 150 ℃, add the 1.5g zinc acetate after the whole meltings of material, slowly be warming up to 160 ℃ of stirrings and carry out transesterification reaction, be distilled to absence of liquid and distillate stopped reaction; Then add 6g antimonous oxide and 1g triphenyl phosphite, logical nitrogen protection vacuumizes when being warming up to 210 ℃; underpressure distillation to absence of liquid distillates; be warming up to again 240 ℃ of underpressure distillation, after steaming without cut, obtain the Polyester-polyether copolymer that 1650g thickness product is formula (III) structure.
The Polyester-polyether copolymer that obtains in embodiment 6 is arranged fabric by pickling process: configuration process liquid, fabric is put into treatment solution by the bath raio of 1:20, flood 20min under normal temperature condition, dehydration 1min, then 110 ℃ of oven dry 1h test, and test result sees Table 1.
Utilize OCA20 video optics contact angle measurement that the surface tension that the Polyester-polyether copolymer that obtains in embodiment 6 carries out water and oil-resistant is tested, obtain the results are shown in Table 1.
According to FZ/T01042-1996 " measuring method of textile materials antistatic property static voltage transformation period ", the Polyester-polyether copolymer that obtains in embodiment 6 is carried out the antistatic property test, fabric face resistance is little, crest voltage is little, transformation period is short, antistatic property is good, otherwise, poor, obtain test result and see Table 1.
Adopt the Y561 fabric according to GB/T5453-1997 " mensuration of textile fabric ventilation property ", the Polyester-polyether copolymer that obtains in embodiment 6 to be carried out the ventilation property test, the Air permenbility that flows through the fabric unit surface under certain pressure reduction is larger, the permeability of fabric is better, and the test result that obtains sees Table 1.
Utilize double-blind method, by the assessment panel that 10 people form, the pliability that obtains the fabric after Polyester-polyether copolymer is processed in process embodiment 6 is estimated, and statistics, overall score is higher, illustrates that the feel of fabric is more soft, obtains the results are shown in Table 1.
Embodiment 7
250g dimethyl terephthalate (DMT), 28g ethylene glycol, 969g PFPE glycol (molecular-weight average is 1400) are mixed with 250g polyoxyethylene glycol (molecular-weight average is 1400), be warming up to 150 ℃, add the 1.5g zinc acetate after the whole meltings of material, slowly be warming up to 180 ℃ of stirrings and carry out transesterification reaction, be distilled to absence of liquid and distillate stopped reaction; Then add 4g antimonous oxide and 1g triphenyl phosphite, logical nitrogen protection vacuumizes when being warming up to 210 ℃; underpressure distillation to absence of liquid distillates; be warming up to again 240 ℃ of underpressure distillation, after steaming without cut, obtain the Polyester-polyether copolymer that 1495g thickness product is formula (III) structure.
The Polyester-polyether copolymer that obtains in embodiment 7 is arranged fabric by pickling process: configuration process liquid, fabric is put into treatment solution by the bath raio of 1:20, flood 20min under normal temperature condition, dehydration 1min, then 110 ℃ of oven dry 1h test, and test result sees Table 1.
Utilize OCA20 video optics contact angle measurement that the surface tension that the Polyester-polyether copolymer that obtains in embodiment 7 carries out water and oil-resistant is tested, obtain the results are shown in Table 1.
According to FZ/T01042-1996 " measuring method of textile materials antistatic property static voltage transformation period ", the Polyester-polyether copolymer that obtains in embodiment 7 is carried out the antistatic property test, fabric face resistance is little, crest voltage is little, transformation period is short, antistatic property is good, otherwise, poor, obtain test result and see Table 1.
Adopt the Y561 fabric according to GB/T5453-1997 " mensuration of textile fabric ventilation property ", the Polyester-polyether copolymer that obtains in embodiment 7 to be carried out the ventilation property test, the Air permenbility that flows through the fabric unit surface under certain pressure reduction is larger, the permeability of fabric is better, and the test result that obtains sees Table 1.
Utilize double-blind method, by the assessment panel that 10 people form, the pliability that obtains the fabric after Polyester-polyether copolymer is processed in process embodiment 7 is estimated, and statistics, overall score is higher, illustrates that the feel of fabric is more soft, obtains the results are shown in Table 1.
Embodiment 8
150g dimethyl terephthalate (DMT), 17g ethylene glycol, 580g PFPE glycol (molecular-weight average is 1074) are mixed with 350g polyoxyethylene glycol (molecular-weight average is 2000), be warming up to 150 ℃, add the 1.5g zinc acetate after the whole meltings of material, slowly be warming up to 180 ℃ of stirrings and carry out transesterification reaction, be distilled to absence of liquid and distillate stopped reaction; Then add 4g antimonous oxide and 1g triphenyl phosphite, logical nitrogen protection vacuumizes when being warming up to 210 ℃; underpressure distillation to absence of liquid distillates; be warming up to again 240 ℃ of underpressure distillation, after steaming without cut, obtain the Polyester-polyether copolymer that 1097g thickness product is formula (III) structure.
The Polyester-polyether copolymer that obtains in embodiment 8 is arranged fabric by pickling process: configuration process liquid, fabric is put into treatment solution by the bath raio of 1:20, flood 20min under normal temperature condition, dehydration 1min, then 110 ℃ of oven dry 1h test, and test result sees Table 1.
Utilize OCA20 video optics contact angle measurement that the surface tension that the Polyester-polyether copolymer that obtains in embodiment 8 carries out water and oil-resistant is tested, obtain the results are shown in Table 1.
According to FZ/T01042-1996 " measuring method of textile materials antistatic property static voltage transformation period ", the Polyester-polyether copolymer that obtains in embodiment 8 is carried out the antistatic property test, fabric face resistance is little, crest voltage is little, transformation period is short, antistatic property is good, otherwise, poor, obtain test result and see Table 1.
Adopt the Y561 fabric according to GB/T5453-1997 " mensuration of textile fabric ventilation property ", the Polyester-polyether copolymer that obtains in embodiment 8 to be carried out the ventilation property test, the Air permenbility that flows through the fabric unit surface under certain pressure reduction is larger, the permeability of fabric is better, and the test result that obtains sees Table 1.
Utilize double-blind method, by the assessment panel that 10 people form, the pliability that obtains the fabric after Polyester-polyether copolymer is processed in process embodiment 8 is estimated, and statistics, overall score is higher, illustrates that the feel of fabric is more soft, obtains the results are shown in Table 1.
Table 1 the performance test results
As can be seen from Table 1, after fabric arranges through Polyester-polyether copolymer of the present invention, have good water and oil-resistant, static resistance and ventilation property.Compare with untreated fabric, the contact angle of the fabric after processing and water, oil obviously increases, and waterproof oil-proof result is remarkable; Its surface resistivity is little, and crest voltage diminishes, and the transformation period is short, and static resistance is good; Fabric breathability and feel after processing all are improved, and illustrate that the Polyester-polyether copolymer of formula of the present invention (III) structure can be used as good functional finishing agent.
The above is only the preferred embodiment of the present invention; should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. PFPE glycol, as shown in the formula (I):
（I）
Wherein, n=1～20.
2. the preparation method of a PFPE glycol, is characterized in that, comprises the following steps:
A) under the effect of alkali metal alcoholate or alkali metal hydroxide, formula (II) structure PFPE methyl alcohol to be mixed with halogenated epoxy propane, reacting by heating in the multiethylene-glycol dme obtains propylene oxide base PFPE methyl ether;
B) described propylene oxide base PFPE methyl ether, dimethyline are mixed with acid solution, reacting by heating obtains the PFPE glycol of formula (I) structure;
（I）
（II）
Wherein, n=1～20.
3. preparation method according to claim 2, is characterized in that, described alkali metal alcoholate or alkali metal hydroxide are selected from a kind of in sodium tert-butoxide, sodium ethylate, sodium methylate, sodium hydroxide, potassium tert.-butoxide, potassium ethylate, potassium methylate and potassium hydroxide.
4. preparation method according to claim 2, is characterized in that, described multiethylene-glycol dme is selected from a kind of in glycol dimethyl ether, diethylene glycol dimethyl ether, TRIGLYME and tetraethyleneglycol dimethyl ether.
5. preparation method according to claim 2, is characterized in that, described halogenated epoxy propane is epoxy chloropropane or epoxy bromopropane.
6. preparation method according to claim 2, is characterized in that, described steps A) preferably also comprise: after reacting by heating, add alkali metal hydroxide, then extract with organic reagent, obtain propylene oxide base PFPE methyl ether.
7. Polyester-polyether copolymer, as shown in the formula (III):
（III）
Wherein, R
f-be formula (IV) structure:
（IV）
Wherein, m:n
1=(0.2～5): 1, l=2～30, n=1～20.
8. the preparation method of a Polyester-polyether copolymer, is characterized in that, comprising:
The PFPE glycol of terephthalic acid ester compound, ethylene glycol, formula (I) structure is mixed with polyoxyethylene glycol, under the effect of the first catalyzer, transesterification reaction is carried out in heating, then add the second catalyzer and phosphorus-containing antioxidant, under the condition of protection of inert gas, reacting by heating obtains the Polyester-polyether copolymer of formula (III) structure;
（I）
（III）
Wherein, R
f-be formula (IV) structure:
（IV）
Wherein, m:n
1=(0.2～5): 1, l=2～30, n=1～20.
9. preparation method according to claim 8, is characterized in that, described the first catalyzer is selected from a kind of in zinc acetate, Burow Solution, manganese acetate and calcium acetate.
10. preparation method according to claim 8, is characterized in that, described the second catalyzer is selected from a kind of in antimonous oxide, antimony acetate and antimony glycol.
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| CN104448277A (en) * | 2014-12-12 | 2015-03-25 | 东华大学 | Perfluoropolyether modified antifouling droplet-preventing copolyester and preparation method thereof |
| CN108239509A (en) * | 2016-12-23 | 2018-07-03 | 上海理日化工新材料有限公司 | Polyether ester hot melt adhesive with good heat resistance and preparation method thereof |
| CN110857263A (en) * | 2018-08-23 | 2020-03-03 | 乳源东阳光氟有限公司 | Preparation method of perfluoropolyether alcohol |
| CN111356714A (en) * | 2017-09-27 | 2020-06-30 | 阿科玛股份有限公司 | Addition and condensation polymers prepared from halogenated reactants |
| CN115536827A (en) * | 2022-09-23 | 2022-12-30 | 濮阳市盛通聚源新材料有限公司 | Bio-based fluorine-containing polycarbonate and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104448277A (en) * | 2014-12-12 | 2015-03-25 | 东华大学 | Perfluoropolyether modified antifouling droplet-preventing copolyester and preparation method thereof |
| CN108239509A (en) * | 2016-12-23 | 2018-07-03 | 上海理日化工新材料有限公司 | Polyether ester hot melt adhesive with good heat resistance and preparation method thereof |
| CN108239509B (en) * | 2016-12-23 | 2021-01-01 | 上海理日化工新材料有限公司 | Polyether ester hot melt adhesive with good heat resistance and preparation method thereof |
| CN111356714A (en) * | 2017-09-27 | 2020-06-30 | 阿科玛股份有限公司 | Addition and condensation polymers prepared from halogenated reactants |
| CN110857263A (en) * | 2018-08-23 | 2020-03-03 | 乳源东阳光氟有限公司 | Preparation method of perfluoropolyether alcohol |
| CN110857263B (en) * | 2018-08-23 | 2023-02-03 | 乳源东阳光氟有限公司 | Preparation method of perfluoropolyether alcohol |
| CN115536827A (en) * | 2022-09-23 | 2022-12-30 | 濮阳市盛通聚源新材料有限公司 | Bio-based fluorine-containing polycarbonate and preparation method thereof |
| CN115536827B (en) * | 2022-09-23 | 2023-12-19 | 濮阳市盛通聚源新材料有限公司 | Bio-based fluorine-containing polycarbonate and preparation method thereof |
| CN117025158A (en) * | 2023-10-09 | 2023-11-10 | 上海惊叹化学有限公司 | Anti-aging polyurethane adhesive and preparation method and application thereof |
| CN117025158B (en) * | 2023-10-09 | 2023-12-08 | 上海惊叹化学有限公司 | Anti-aging polyurethane adhesive and preparation method and application thereof |
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