CN102093550B - Preparation method of perfluoroalkylethyl polyoxyethylene ether - Google Patents

Abstract

The invention discloses a preparation method of perfluoroalkylethyl polyoxyethylene ether, comprises the following steps of: in terms of weight parts, adding 10-16 parts of solvent and 0.3-1.0 part of catalyst into 27-53 parts of perfluoroalkyl alcohol which is used as a main material, wherein the solvent is pyridine or isopropanol, and the catalyst is BF3 (Boron Trifluoride) or strong base; raising temperate to 120-180 DEG C, adding oxirane, reacting under the pressure of 0.1-1.5 MPa for 1-5h; and filtering and washing to obtain a target product. The method is simple to operate and has high yield. The obtained levelling agent containing fluorine has high purity, the addition number of the oxirane is more uniform, and the oxirane has better solubility. Meanwhile, the number of the autopolymer of the oxirane is small, the obtained levelling agent containing fluorine has a stable structure which is difficult to decompose and an excellent property, and the surface tension can reach 18mN/m at least.

Description

A kind of preparation method of perfluor alkyl ethide polyoxyethylene groups ether

Technical field

The present invention be more particularly directed to a kind of preparation method of perfluor alkyl ethide polyoxyethylene groups ether.

Background technology

In recent years along with the continuous development in fields such as application, chromatic spray painting, tackiness agent; Application, chromatic spray painting, tackiness agent are had higher requirement; Surface effect as after the application processing not only will have the levelling effect, also must have good weathering resistance, gloss retention and tint retention.Common hc-surfactant gloss retention and tint retention are poor, not ultraviolet resistance irradiation, and weathering resistance is poor, can't satisfy the requirement of application surface-treated.Perfluor alkyl ethide polyoxyethylene groups ether has excellent weathering resistance can satisfy above-mentioned requirements.But the compound method of perfluor alkyl ethide polyoxyethylene groups ether is the fluorine-containing alcohol that adopts electrolysis process to obtain, and cost is high, pollution is big, by product is many.

Summary of the invention

The technical problem that the present invention will solve is to propose a kind of ability and satisfy-request for utilization of 30-280 ℃, and consumption is few, the ultraviolet resistance irradiation, and surface tension is low, has the preparation method of the perfluor alkyl ethide polyoxyethylene groups ether of excellent weathering resistance and leveling characteristics.

Technical solution of the present invention is following:

A kind of preparation method of perfluor alkyl ethide polyoxyethylene groups ether; Is major ingredient according to the parts by weight meter with perfluoroalkyl ethanol 27-53 part; Add solvent 10-16 part, catalyzer 0.3-1.0 part, described solvent is pyridine or Virahol, and described catalyzer is boron trifluoride BF₃Or highly basic, being warming up to 120-180 ℃ and to add oxyethane be to react under the 0.1-1.5MPa at pressure, the reaction times is 1-5h, obtains title product behind the filtration washing.

Carbon-fluorine bond is the even number of 6-20 in the molecular structure of above-mentioned perfluoroalkyl ethanol.

Above-mentioned reaction response pressure is 0.6-1.0MPa, reaction times 2-3h.

It is raw material that the present invention adopts perfluoroalkyl ethyl alcohol, and described perfluoroalkyl ethanol also can react acquisition in 4-5 hour by perfluor alkyl ethide iodine, Pottasium Hydroxide and water under 150-170 ℃ condition.Raw material is easy to get, and does not produce by product, adopts process control, and entire reaction course is steady, on reaction process, has greater advantage, the final perfluor alkyl ethide polyoxyethylene groups ether excellent property that obtains, and yield can reach more than 95%.Present method is simple to operate, and productive rate is high, and the addition number of oxyethane is comparatively even, has solvability preferably.Make solvent with Virahol, safe, inexpensive, need not separate separately, can directly apply to the field of coating of water-based system; The autopolymer of oxyethane is few simultaneously, obtains fluorine-containing flow agent rock steady structure, is difficult for decomposition, superior performance, and surface tension is below 17.8mN/m.

Specific embodiment

Embodiment 1

In having electric mixer, thermopair, spiral coil cooling tube 0.5 rising pressure stainless steel cauldron, add the basic ethanol of perfluoroalkyl (structural formula: F (CF₂)₆CH₂CH₂OH) 364g adds the 100g pyridine, 5gBF₃, reaction kettle is airtight towards nitrogen displacement emptying agitator, charge into oxyethane (add-on) to 0.2MPa after finding time with vacuum pump.Slowly be warming up to 120 ℃ and keep this temperature, add to 0.8MPa with oxyethane, question response pressure carries out ftercompction after dropping to 0.4MPa, and back and forth constantly ftercompction is to 0.65MPa, and the weight 450g of the oxyethane that stoichiometric consumption is fallen behind the reaction 3h is cooled to 42 ℃ of dischargings.The product that obtains is carried out filtration washing, separate the back and obtain the basic ethyl polyoxyethylene groups of perfluor ether 787g, yield 98%.This material is used for coating and adds 0.1%, and surface tension is that 17.8mN/m has comparatively ideal levelling effect.

Embodiment 2

Repeat example 1 with perfluoroalkyl octyl group ethanol (structural formula: F (CF₂)₈CH₂CH₂OH) 464g adds the 160g pyridine, 3gBF₃, reaction kettle is airtight with nitrogen pressure testing displacement back emptying agitator, find time back adding oxyethane to 0.2MPa with vacuum pump.After slowly being warming up to 180 ℃ and keep this temperature and add to 1.5MPa with oxyethane, question response pressure carries out ftercompction after dropping to 0.6MPa, repeats ftercompction to 1.5MPa.The weight 500g of the oxyethane that stoichiometric consumption is fallen behind the reaction 1h is cooled to 40 ℃ of dischargings.The product that obtains is carried out filtration washing, separate the back and obtain perfluoro capryl ethyl polyoxyethylene groups ether 894g, yield 98.5%.This title product is used for coating and adds 0.5%, and surface tension is 16.8mN/m.

Embodiment 3

In having electric mixer, thermopair, spiral coil cooling tube 0.5 rising pressure stainless steel cauldron, add perfluoro octyl ethanol (structural formula: F (CF₂)₈CH₂CH₂OH) 232g, perfluor nonyl ethanol F (CF₂)₁₀CH₂CH₂OH 188g, perfluoroalkyl ethanol F (CF₂)₁₂CH₂CH₂OH 110g adds the 110g pyridine, and 10gKOH is airtight with emptying agitator behind the nitrogen replacement three times with reaction kettle, charges into oxyethane to 0.2MPa after finding time with vacuum pump.After slowly being warming up to 200 ℃ and keep this temperature and add to 0.1MPa with oxyethane, question response pressure carries out ftercompction after dropping to 0.05MPa, back and forth constantly ftercompction to 0.1MPa, the weight 460g of the oxyethane that stoichiometric consumption is fallen behind the reaction 5h, the 45 ℃ of dischargings of lowering the temperature.The product that obtains is carried out filtration washing, separate the back and obtain perfluor alkyl ethide polyoxyethylene groups ether 962g, yield 95.5%.This title product is used for printing ink and adds 0. 5%, and surface tension is 17 mN/m

Embodiment 4

In having electric mixer, thermopair, spiral coil cooling tube 0.5 rising pressure stainless steel cauldron, add perfluor nonyl ethanol (structural formula: F (CF₂)₁₀CH₂CH₂OH) 280g, 130g Virahol, 8gNaOH, reaction kettle is airtight with emptying agitator behind the nitrogen replacement, charge into oxyethane to 0.2MPa after finding time with vacuum pump.After slowly being warming up to 150 ℃ and keep this temperature and add to 1.0MPa with oxyethane, question response pressure carries out ftercompction after dropping to 0.6MPa, and constantly ftercompction is to 1.0MPa, and the weight 480g of the oxyethane that stoichiometric consumption is fallen behind the reaction 4h is cooled to 38 ℃ of dischargings.The product that obtains is carried out filtration washing, separate the back and obtain perfluor nonyl ethyl polyoxyethylene groups ether 491g, yield 96%.This title product is used for water-borne coatings and adds 0.05%, and surface tension is 17.8mN/m.

Embodiment 5

In the 500ml four-hole boiling flask of whisking appliance, prolong, TM, water trap, tap funnel, nitrogen conduit is housed, add perfluoro capryl iodoethane F (CF₂)₈CH₂CH₂The pure substance 270g of I, agitator adds KOH30g, temperature raises 160 ℃ gradually, begin to drip water 100 g with temperature maintenance at 150-170 ℃, reaction times 4h filters the back with the reaction mass cooling and obtains the 212g product.Add the 110g pyridine, 10gKOH charges into oxyethane to 0.2MPa.After slowly being warming up to 200 ℃ and keep this temperature and add to 0.1MPa with oxyethane; Question response pressure carries out ftercompction after dropping to 0.05MPa; Back and forth constantly ftercompction is to 0.1MPa, and the weight 400g of the oxyethane that stoichiometric consumption is fallen behind the reaction 5h is cooled to 45 ℃ of dischargings.The product that obtains is carried out filtration washing, separate the back and obtain mix products 394g, yield 95%.This title product is used for printing ink and adds 0. 5%, and surface tension is that 17.5mN/m has comparatively ideal levelling effect.

Claims (2)

1. the preparation method of a perfluor alkyl ethide polyoxyethylene groups ether; It is characterized in that: is major ingredient according to the parts by weight meter with perfluoroalkyl ethanol 27-53 part; Add solvent 10-16 part, catalyzer 0.3-1.0 part, described solvent is pyridine or Virahol, and described catalyzer is boron trifluoride BF₃Or highly basic, be warming up to 120-180 ℃ and to add oxyethane be to react under the 0.6-1.0MPa at pressure, the reaction times is 2-3h, behind the filtration washing title product.

2. the preparation method of perfluor alkyl ethide polyoxyethylene groups ether according to claim 1 is characterized in that: the number of carbon-fluorine bond is the even number of 6-20 in the molecular structure of perfluoroalkyl ethanol.