CN1054441A - Azeotropic solvent composition - Google Patents

Abstract

A kind of azeotropic solvent composition that contains dichloro pentafluoropropane and fluorinated alcohols.At cleaning force, particularly remove aspect welding agent, uninflammability, chemical stability and the selective dissolution ability, said composition is very good, and the liquid with lower boiling, high-dissolvability and solvent easy to control is formed and easily reclaimed and reuse this solvent.Even composition of the present invention does not cause metallic corrosion containing under the wet condition yet, therefore, can be applicable to different working conditionss and various material to be cleaned.

Description

Azeotropic solvent composition

The present invention relates to a kind of azeotropic solvent composition that contains dichloro pentafluoropropane (below be called " HCFC-225 ") and fluorinated alcohols.

Refrigerant R 113 (below be called " CFC-113 ") is a kind of chlorine fluoroethane compound, it does not fire, to organism low toxicity and selective dissolution ability excellence, can dissolved fat and oils, Tallow, beef and paraffin etc., and can not corrode the polymer material of plastics and rubber and so on.So CFC-113 is widely used as solvent, clean-out system or the like separately or with mixture or with the form of the Azeotrope compositions of another organic solvent so far.

Recently, because the chlorofluoroethane compound [wherein whole hydrogen atoms of ethane are replaced (below be called perhalogeno ethane) by chlorine atom and fluorine atom], destroy the problem of environmental pollution that the ozonosphere around the earth causes as CFC-113 and mentioned global agenda.So eager the requirement reduced the consumption of this perhalogeno ethane or do not used perhalogeno ethane.

As one of method of the consumption that reduces perhalogeno ethane, proposed to adopt the mixed solvent of CFC-113 and organic solvent except that perhalogeno ethane.But according to this method, because the effect of mixed solvent descends, the consumption of CFC-113 reduces very little.Also have, when using CFC, require the liquid of solvent easy to control to form and easy the recovery and the repeated use solvent, but also require mixed solvent to can be applicable to steam flushing as mixed solvent.In order to satisfy above-mentioned requirements, mixed solvent must be an azeotropic mixture, but is difficult to find such mixture.So, do not find spendable surrogate as yet.

On the other hand, also carried out various researchs for the solvent that does not contain perhalogeno ethane, but do not found spendable surrogate equally.

Though in Japanese unexamined patent bulletin 12864/1971, known the mixed solvent of halogenated organic solvent and fluorinated alcohols, do not found the Azeotrope compositions of HCFC-225 and fluorine alcohol as yet.In addition, the mixed solvent of known so far halogenated organic solvent, particularly fluorinated solvents and hydrocarbon alcohol.But this class mixed solvent has a kind of defective, promptly containing generation acid (example hydrochloric acid) under the wet condition, metal is caused corrosion.Therefore, if use mixed solvent, require dehumidifying or limit working conditions or be washed the kind of material.

An object of the present invention is to provide a kind of azeotropic solvent composition that does not contain CFC-113, said composition has improved cleaning force to welding agent, damages the ozone layer hardly and does not fire.

From following explanation, can see above and other objects of the present invention.

The invention provides a kind of azeotropic solvent composition that contains dichloro penta fluoro-propane and fluorinated alcohols.Surprisingly, even composition of the present invention is containing under the wet condition also not attack metal, and also stable.

Be used for HCFC of the present invention and have isomer, as 1,1-two chloro-2,2,3,3,3-pentafluoropropane [boiling point (bp): 51 ℃], 1,2-two chloro-1,2,3,3,3-pentafluoropropane (bp:56 ℃), 1,3-two chloro-1,2,2,3,3-pentafluoropropane (bp:56.1 ℃), 2,2-two chloro-1,1,3,3,3-pentafluoropropane (bp:54 ℃), 2,3-two chloro-1,1,2,3,3-pentafluoropropane (bp:56 ℃), 3,3-two chloro-1,1,2,2,3-pentafluoropropane (bp:58 ℃), 1,1-two chloro-1,2,3,3,3-pentafluoropropane (bp:49 ℃), 1,3-two chloro-1,1,2,3,3-pentafluoropropane (bp:48 ℃) and 1,2-two chloro-1,1,3,3,3-pentafluoropropane (bp:50 ℃).

HCFC-225 does not fire, and is nontoxic and chemical stability good to organism, has the selective dissolution ability, can wash and remove fat and oils stain off, and plastics, rubber, metal or the like are exerted an influence hardly.And HCFC-225 damages the ozone layer unlike CFC-113.

In the present invention, with regard to fluorinated alcohols, example has the alcohol that has two fluorine atoms in the per molecule at least and be no less than two carbon atoms.More particularly, can mention fluorine alcohol with following formula structure:

A wherein, c, e, g and i are respectively integer 1-5 and b, d, f, h and j are respectively integer 1-3.

Wherein, preferred especially trifluoroethanol (bp:77 ℃), C3-Fluoroalcohol (bp:107 ℃) and five fluorine propyl alcohol (below be called " 5FP ", bp:81 ℃).More preferably 5FP is not because of it fires.Can use fluorinated alcohols separately or with the form of its adulterant.

Composition of the present invention comprises HCFC-225 and the fluorinated alcohols with above-mentioned characteristic.In addition, because composition is an azeotropic, the liquid of solvent is formed and recovery and repeated use solvent so control easily, so said composition can be applicable to steam flushing.Also have, said composition can be used as cleaning solvent very effectively in electronics and electrical equipment industry, removes the welding agent of welding use in printed circuit board.The said composition chemical stability is also fine, even contain wet and metal in the presence of also stable especially, and have the selective dissolution ability, can clean with only removing stain plastics, rubber, metal etc. are had no adverse effects.In addition, said composition damages the ozone layer unlike CFC-113, and does not fire.

The mixture of HCFC-225 and fluorinated alcohols is 99.5-88.0/0.5-12.0, has preferably constituted azeotropic mixture azeotropic shape composition in the scope of 99.5-91.0/0.5-9.0 in the weight ratio of HCFC-225 and fluorinated alcohols.The azeotropic temperature of this Azeotrope compositions is 47.5 ℃-57.5 ℃.For instance, the example of azeotropic mixture and azeotropic composition is: 93.5wt%1,1-two chloro-2,2,3,3, the azeotropic mixture (azeotropic point: 49.8 ℃) of 3-pentafluoropropane (bp:51 ℃) and 6.5wt% five fluorine propyl alcohol (5FP) (bp:81 ℃), 92.2wt%1,3-two chloro-1,2,2,3,3-pentafluoropropane (bp:56.1 ℃) and 7.8wt%5FP(bp:81 ℃) azeotropic mixture (azeotropic point: 54.5 ℃), 93.5-92.2wt%1,1-two chloro-2,2,3,3,3-pentafluoropropane and 1,3-two chloro-1,2,2,3, the azeotropic composition of the mixture of 3-pentafluoropropane and 6.5-7.8wt%5FP, 1,1-two chloro-2,2,3,3,3-pentafluoropropane and 1,3-two chloro-1,2,2,3, the weight ratio of 3-pentafluoropropane is 0.5-99.5/99.5-0.5,5-60/95-40 preferably, be more preferably 20-50/80-50, and other.The mixture that the present invention mainly contains HCFC-225 not only is suitable for to be made to remove the cleaning solvent that welding agent uses (described welding agent is used for printed circuit board (PCB), only be difficult to it is disposed) with a kind of composition, and be applicable to the various occasions of usually having used CFC-113, for example as removing paraffin, animal and plant oil and the processing degreasing solvent of oil; As removing at molding molded and processing with the cleaning solvent of releasing agent; Cleaning solvent with the paraffin that will remove temporary transient fixedly silicon wafer in the processing of cutting or polishing and so on (being used for semi-conductor, quartzy and pottery) usefulness, Pressuresensitive Tape, paint, printing ink or the like; Dispersion medium as pottery or metal powder; Be used as the siccative that drying and dehydrating is used; As dry cleaning solvent; Or the like.

Though composition of the present invention is better than chemical stability with the solvent phase that contains Fatty Alcohol(C12-C14 and C12-C18), also can comprise a kind of stablizer.

Best, stablizer distills with the mixture of Azeotrope compositions of the present invention or Azeotrope compositions, and stablizer also can form Azeotrope compositions except stable composition being had the very big effect.

For instance, the example of aforementioned stable agent has aliphatic nitro cpd, and as nitroethane, Nitromethane 99Min. and nitropropane, alkynol is as the pure and mild methylpentynol of 3-methyl isophthalic acid-butine-3-; Epoxide, as Racemic glycidol, methyl glycidyl ether, glycidyl allyl ether, phenyl glycidyl ether, 1,2-butylene oxide ring, epoxy hexane and Epicholorohydrin; Ether, as Methylal(dimethoxymethane), 1,2-glycol dimethyl ether, 1,4-dioxan and 1,3,5-trioxane; Unsaturated hydrocarbons, as hexene, heptene, octene, 2,4,4-trimethylammonium-1-amylene, pentadiene, octadiene, tetrahydrobenzene and cyclopentenes; Enol is as vinyl carbinol, the pure and mild 3-methyl-1-butene of 1-butylene-3--3-alcohol; Acrylate is as methyl acrylate, ethyl propenoate and butyl acrylate; Or the like.Stablizer can use separately, and form that also can its mixture is used.Wherein, preferred Nitromethane 99Min..In addition, also can use other compound.Under the situation that other compound uses, can obtain collaborative stabilising effect at stablizer.For instance, the example of other compound is a phenol, as phenol, pseudocuminol, cyclohexylphenol, thymol, 2, and the 6-tertiary butyl-4-methylphenol, fourth hydroxyanisol and isoeugenol; Amine, as hexylamine, amylamine, dipropyl amine, Diisopropylamine, diisobutylamine, triethylamine, Tributylamine, pyridine, N-methylmorpholine, hexahydroaniline, 2,2,6,6-tetramethyl piperidine and N, N '-diallyl-Ursol D, triazole, as benzotriazole, 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole and chlorobenzotriazole, or the like.

The consumption of stablizer depends on the kind of stablizer, so can determine its consumption easily according to the kind of used stablizer.In general, in Azeotrope compositions, consumption is 0.1-10wt%, preferably 0.5-5wt%.Under the situation of using Nitromethane 99Min., its consumption is about the 0.1-1.0% of Azeotrope compositions weight.

The consumption of stablizer should be as the criterion not lose Azeotrope compositions.In general, because the consumption of stablizer is very low,, Azeotrope compositions is not had much influences so add stablizer as not being higher than 1wt%.

At aspects such as welding agent cleaning force, uninflammability, chemical stabilities, composition of the present invention is equal to or is better than CFC-113, and has optionally solvent power, simultaneously plastics, rubber, particularly metal is not almost had influence.Also have, azeotropic solvent composition of the present invention contains HCFC-225 as main component, and it is littler than CFC-113 to the destructiveness of ozonosphere, and welding agent cleaning force excellence, be that it can remove the welding agent that only can not fully remove with one-component, keep the various good characteristics of HCFC-225 simultaneously.In addition, aspect the desired characteristic of azeotropic solvent composition, said composition is very excellent, that is to say, boiling point is low, solubleness is high, manageable liquid is formed and easily reclaim or reuse this solvent.

Particularly when using composition of the present invention, even there is also corroding metal not of water, the metallic corrosion when using common alcohol certainly with and can not avoid having water.Therefore, composition of the present invention can be used for various working conditionss and various material to be cleaned.

Mode by the following examples illustrates in greater detail and explains the present invention, and wherein, and outer, all % and umber are all by weight unless otherwise indicated.Much less, the present invention is not limited to these embodiment, under the situation that does not deviate from its spirit and scope, also can carry out various changes and modifications to it.

Embodiment 1

Pack in the matrass 200 the gram 1,1-two chloro-2,2,3,3, the mixture of 3-pentafluoropropane (225Ca) (bp:51 ℃) and five fluorine propyl alcohol (5FP, bp:81 ℃), the weight ratio of 225Ca and 5FP is 50/50.A theoretical plate number is distillating mixture under the normal pressure in 30 the rectifying tower, obtains azeotropic point and be 49.8 ℃ distillate, and azeotropic point is lower than the boiling point of each solvent.

The gas chromatographic analysis result confirms, this distillate is by 93.5%1,1-two chloro-2,2,3,3, and 3-pentafluoropropane and 6.5% 5 fluorine propyl alcohol are formed.

Make solvent with the gained azeotropic mixture,, assess welding agent respectively and remove power, the influence and the stability of plastics according to following test.

Welding agent is removed power

Welding agent (sold by Kabushiki Kaisha Tamura Seisakusho, the trade mark " MH-320V) is administered on the printed-wiring board (PWB) (10cm * 10cm), and in 110 ℃ of preheatings.Afterwards, with printed-wiring board (PWB) in 250 ℃ of weldings (63Sn) 5 seconds.Then, with a kind of solvent shown in 1 liter of table 1, dipping cleaning 1 minute and steam cleaning 1 minute.

The condition of surface of visual inspection printed-wiring board (PWB).Usefulness Omegameter 500(KENCO Industrial Co., Ltd sale again) measures the survivor ion on the printed-wiring board (PWB).

Table 1 shows the result of welding agent removing power test.

Influence to plastics

A kind of plastics test piece shown in the dipping table 1 in the solvent of 100 grams shown in the tables 1 (5mm * 50mm * 2mm), and it was placed 5 minutes in 50 ℃ of thermostat containers.Then, from solvent, take out test piece, weigh immediately and measure the test piece volume.Calculate the variation of the weight and volume of plastics test piece, according to of the influence of following criterion evaluation to plastics:

◎: the percentage that weight or meausurement increases is from 0-＜2%

Zero: the percentage that weight or meausurement increases is from 〉=2%-＜5%

△: percentage 〉=5% that weight or meausurement increases

*: plastic samples is dissolved in solvent.

Table 1 shows the result to the plastics influence.

Chemical stability

In 100ml has the vial of sealing plug, pack into the solvent shown in the 100 gram tables 1,0.1% water solvent [being 0.01% water solvent (only with 225Ca or 225Cb) in following Comparative Examples 1 or 4] and metallic aluminium or zinc, and vial sealed.Then bottle was placed 30 days in 50 ℃ of thermostat containers.

During bottle is placed on thermostat container and after 30 days, whether the method for the metal that detects by an unaided eye assessment metal is corroded.

Table 1 shows the test-results of chemical stability.

Comparative Examples 1,2 and 3

The same manner of pressing embodiment 1 measure welding agent remove power, to the influence and the chemical stability of plastics, the azeotropic mixture that different is without 225Ca/5FP, but make solvent (Comparative Examples 1), make solvent (Comparative Examples 2) with 5FP separately and make solvent with 225Ca separately, or make solvent with 225Ca and alcoholic acid mixture (225Ca/ ethanol=97%/3%) (Comparative Examples 3).

The results are shown in table 1.

Embodiment 2

Press the same distillation 1 of embodiment 1,3-two chloro-1,2,2,3,3-pentafluoropropane (225Cb, bp:56.1 ℃) and 5FP(bp:81 ℃) mixture (weight ratio is 50/50), obtain azeotropic point and be 54.7 ℃ distillate, this temperature is lower than the boiling point of each solvent.

The gas chromatographic analysis result confirms, distillate by 92.2% 1,3-two chloro-1,2,2,3,3-pentafluoropropane and 7.8%5FP form.

The welding agent that the same manner of pressing embodiment 1 is measured the gained azeotropic mixture removes power, to the influence and the stability of plastics.

The results are shown in table 1.

Embodiment 3

Press 1 of embodiment 1 the same manner distillation 55%, 1-two chloro-2,2,3,3,3-pentafluoropropane (bp:51 ℃) and 45%1,3-two chloro-1,2,2,3, the mixture of 3-pentafluoropropane (bp:56.1 ℃) and the composition of 5FP (weight ratio of mixture and 5FP is 50/50) obtain distillate.This distillate demonstrates the stable boiling point in 50 ℃ of-54.9 ℃ of very narrow temperature ranges.

The gas chromatographic analysis result confirms, distillate is by 1 of 93.4-92.4%, 1-two chloro-2,2,3,3, and 3-pentafluoropropane/1,3-two chloro-1,2,2,3, (60-4%/40-96%) and the 5FP of 6.6-7.6% form the mixture of 3-pentafluoropropane.

Embodiment 1 same mode measures the welding agent cleaning force of gained azeotropic mixture, to the influence and the stability of plastics.

The results are shown in table 1.

Comparative Examples 4

Press embodiment 1 the same manner measure welding agent remove power, to the influence and the chemical stability of plastics, the azeotropic mixture that different is without 225Ca/5FP, and only make solvent with 225Cb.

The results are shown in table 1.

Claims (9)

1, a kind of azeotropic solvent composition that contains dichloro pentafluoropropane and fluorinated alcohols.

2, the composition of claim 1, the weight ratio of wherein said dichloro pentafluoropropane and described fluorinated alcohols are 99.5-88.0/0.5-12.0.

3, a kind of azeotropic solvent composition that contains the azeotropic mixture of dichloro pentafluoropropane and fluorinated alcohols.

4, the composition of claim 3, wherein the weight ratio of pentafluoropropane of dichloro described in the mixture and described fluorinated alcohols is 99.5-88.0/0.5-12.0.

5, the composition of claim 3, wherein said mixture is 1,1-two chloro-2,2,3,3, the mixture of 3-pentafluoropropane and five fluorine propyl alcohol.

6, the composition of claim 3, wherein said mixture is 93.5wt%1,1-two chloro-2,2,3,3, the mixture of 3-pentafluoropropane and 6.5wt% five fluorine propyl alcohol.

7, the composition of claim 3, wherein said mixture is 1,3-two chloro-2,2,3, the mixture of 3-pentafluoropropane and five fluorine propyl alcohol.

8, the composition of claim 3, wherein said mixture is 9.22wt%1,3-two chloro-1,2,2,3, the mixture of 3-pentafluoropropane and 7.8wt% five fluorine propyl alcohol.

9, (A) 93.5-92.2wt% of a kind of containing by 0.5-99.5wt%1,1-two chloro-2,2,3,3,3-pentafluoropropane and 99.5-0.5wt%1,3-two chloro-1,2,2,3, the mixture that the 3-pentafluoropropane constitutes and (B) the azeotropic composition of 6.5-7.8wt% five fluorine propyl alcohol.