CN101456830B - Methods of making an antistatic agent - Google Patents
Methods of making an antistatic agent Download PDFInfo
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- CN101456830B CN101456830B CN200810185913XA CN200810185913A CN101456830B CN 101456830 B CN101456830 B CN 101456830B CN 200810185913X A CN200810185913X A CN 200810185913XA CN 200810185913 A CN200810185913 A CN 200810185913A CN 101456830 B CN101456830 B CN 101456830B
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Abstract
A method for preparing a phosphonium sulfonate salt of generic formula (1), wherein each X is independently a halogen or hydrogen, provided that the molar ratio of halogen to hydrogen is greater than about 0.90; p is 0 or 1, and q and r are integers of 0 to about 7 provided that q+r is less than 8 and that if p is not zero then r is greater than zero; and each R is the same or different hydrocarbon radical containing 1 to about 18 carbon atoms. The method comprises a step of mixing a compound of general formula (2) with a compound of general formula (3) chemically calculated to be excessive. In the general formula (2), M is Li or Na, and X, q, p and r are as defined above. In the general formula (3), Z is a halogen, R is as defined above. (R)4P-Z (3)
Description
The application is to be that April 7, application number in 2005 are that 200580012095.8 (PCT/US2005/011756), exercise question are divided an application for " a kind of preparing method's of static inhibitor " the applying date.
The cross reference of related application
The application requires the right of priority of the U.S. Provisional Application series number 60/562,010 of submission on April 13rd, 2004, and it is incorporated herein in full by reference.
Background of invention
The disclosure relates to a kind of method for preparing static inhibitor.
Thermoplastics is used to prepare article and the widespread use of assembly from auto parts to the electronic equipments.Because their extensive use especially aspect electrical equipment, is desirable to provide the thermoplastic resin that contains static inhibitor.Many polymkeric substance or mixture of polymers are relative insulating, and during handling and using said polymkeric substance, this can cause build-up of static charges.For example, charged moulded product can attract little grit, thereby possibly influence the outward appearance of smooth-flat-surface for example through the article transparency is descended.In addition, static charge can become this base polymer and prepares obstacle serious in the process.
Static inhibitor is to be added in the polymkeric substance, to reduce the trend that it obtains static charge, perhaps, when having electric charge, promotes the material of this type electric-charge-dissipating.Organic antistatic agents is hydrophilic or ionic in essence.When being present in polymeric materials surperficial, they promote electronic migration, thereby eliminate build-up of static charges.Before further being processed into article, static inhibitor being added to polymer compsn, thereby be known as " inside applies ".The useful static inhibitor that applies by this way is heat-staple in the course of processing and can moves to the surface.
Considered and tested a large amount of with the static inhibitor of tensio-active agent as its staple.Many one or more defectives that all run into, for example not have consistency (this influence is uniformly dispersed), poor heat stability and/or static resistance poor with said polymkeric substance.Especially, thermotolerance missionary society to the engineering thermoplasties for example the optical property of aromatic copolycarbonate have a negative impact.
Yet it is useful static inhibitor that the Te that has shown some sulfonic acid is Dinged phosphonium salt.U.S. Patent number 4,943,380 disclose the antistatic composition with the thermotolerance phosphonium sulfonates of the following general formula of polycarbonate that contains 90-99.9% weight and 0.1-10% weight, the electric charge on the minimizing polycarbonate resin:
Wherein R is the straight or branched alkyl with 1-18 carbon atom; R
1, R
2And R
3Identical, respectively be the aryl radical that has the aliphatic group of 1-8 carbon atom or have 6-12 carbon atom; And R
4It is alkyl with 1-18 carbon atom.
U.S. Patent number 6,194,497 disclose anti-static resin composition, are specially transparent resin composition, and it contains the halogenation medium chain or the short-chain alkyl sulphonate of thermoplastic compounds and four Qu Dai De phosphonium cations.IX through the haloalkyl potassium sulfonate produces corresponding acid, prepares wherein said static inhibitor.Said haloalkyl sulfonic acid generates said static inhibitor with the reaction of hydroxide 4-butyl-phosphonium again.
Advantage of this synthetic is that the employing ion-exchange step causes product very pure between synthesis phase, that is, what do not contain can finally not cause the for example halogenated compound of polycarbonate degraded of resin to not containing fully.Although this is applicable to its re-set target, this concrete synthetic a large amount of shortcoming that also has.For example, adopt ion-exchange step to increase processing charges, and needing possibly to cause the generation of the refuse of treatment procedures.Said synthesizing also adopted sylvite product to start with, and it is prepared by corresponding sulfonic acid fluoride.Because it is lower to cross the solubleness of alkylsulphonic acid potassium, for example, 20 ℃ down about 5%, so need water/alcohol mixture in the IX.The alcoholic acid inflammableness requires in synthetic, to carry out effective safe precaution measure.In addition, it also is important selecting suitable water/proportion of ethanol.Excess ethanol can make final product be dissolved in the reaction solvent, so that possibly need further extraction step separated product.
Therefore, this area still needs more efficient methods, and especially the method for a step prepares phosphonium sulfonates static inhibitor and the thermoplastic resin composition who has mixed these static inhibitor.Hope that also these class methods can generate the static inhibitor that security and/or said degree of purity of production to said method have no adverse effect with good yield.
The invention summary
The method of the sulfonic acid phosphonium salt of preparation formula (1) has solved the above-mentioned of this area and other defective:
Wherein each X independently is halogen or hydrogen, and prerequisite is that the mol ratio of halogen and hydrogen is greater than about 0.90; P is 0 or 1, and q and r are the integers of 0-about 7, if prerequisite be q+r less than 8 and p be not 0, then r is greater than 0; Independently for having the alkyl of about 18 carbon atoms of 1-, said method is included in the water medium each R, makes formula (2) compound:
Wherein M is Li or Na, and X, q, p and r as above define, and formula (3) compound:
(R)
4P-Z (3)
Wherein Z is a halogen, and R defines as above; Separate type (1) product from said water medium again.
In another embodiment, the method for the sulfonic acid phosphonium salt of preparation formula (1) comprises at first and in water medium, to make formula (4) compound:
Compound with the excessive general formula (5) of stoichiometric calculation:
(R)
4P-OH (5)
Identical in the meaning of X, p, q, r and R and the formula (1) wherein; Separate type (1) product from said water medium again.
In another embodiment, the method for the sulfonic acid phosphonium salt of preparation formula (1) comprises makes sodium hydroxide and/or Lithium Hydroxide MonoHydrate mix in water medium with the compound of above-mentioned general formula (4) and the compound of above-mentioned general formula (3), and wherein X, q, p, r and R as above define; The phosphonium sulfonates of separate type (1) from said water medium again.
Another embodiment comprises the static inhibitor by the formula (1) of one of preceding method preparation.
In yet another embodiment, provide and contain thermoplastic polymer and by the thermoplastic compounds of the static inhibitor of one of preceding method preparation.
The present invention includes:
1. method for preparing the sulfonic acid phosphonium salt of general formula (1):
Wherein each X independently is halogen or hydrogen, and prerequisite is that the mol ratio of halogen and hydrogen is greater than about 0.90; P is 0 or 1, and q and r are the integers of 0-about 7, prerequisite be q+r less than 8, and if p be not 0, then r is greater than 0; Each R is the identical or different alkyl that contains about 18 carbon atoms of 1-, and said method comprises:
In water medium, make the compound of general formula (2):
Wherein M is Li or Na, and X, q, p and r as above define, and excessive general formula (3) compound of stoichiometric calculation:
(R)
4P-Z (3)
Wherein Z is a halogen, and R defines as above; With
Phosphonium sulfonates from said water medium separate type (1).
2. 1 method, wherein X is a fluorine; Z is bromine or chlorine; That three R groups can be is identical, contain the aliphatic group of about 8 carbon atoms of 1-or contain the aryl of about 12 carbon atoms of 6-, and the 4th R group is the alkyl that contains about 18 carbon atoms of 1-.
3. 2 method, wherein p is 0.
4. 1 method; Wherein said sulfonate radical is perfluor methanesulfonate, perfluor ethyl sulfonic acid root, perfluor propanesulfonic acid root, perfluor fourth sulfonate radical, perfluor penta sulfonate radical, the own sulfonate radical of perfluor, perfluor sulfonate radical in heptan, perfluorooctane sulfonate root, or contains the combination of at least a aforementioned sulfonate radical; And Phosphonium of stating is tetramethyl phosphonium, four second base Phosphonium, 4-butyl-phosphonium, triethyl first base Phosphonium, tributyl first base Phosphonium, tributyl second base Phosphonium, three hot basic first base Phosphonium, trimethylammonium fourth base Phosphonium, the hot basic Phosphonium of trimethylammonium, trimethyldodecane base Phosphonium, the hard fat base of trimethylammonium Phosphonium, the hot basic Phosphonium of triethyl and fragrant family Phosphonium for example tetraphenylphosphoniphenolate, three phenyl methyl Phosphonium, triphenyl benzyl base Phosphonium, tributyl benzyl base Phosphonium in it, or comprises the combination of at least before stating one of Phosphonium.
5. 4 method, wherein sulfonate radical is perfluor methanesulfonate, perfluor fourth sulfonate radical, the own sulfonate radical of perfluor, perfluor sulfonate radical in heptan, perfluorooctane sulfonate root or comprises the anionic combination of at least a aforementioned organic sulfonic acid root, Suo Shu Phosphonium is a 4-butyl-phosphonium.
6. 1 method, the mol ratio of its Chinese style (2) compound and formula (3) compound is the about 1:1.5 of about 1:1.001-.
7. 1 method, the mol ratio of its Chinese style (2) compound and formula (3) compound is the about 1.5:1 of about 1.001:1-.
8. 1 method, wherein said water medium comprises the non-aqueous media that is less than about 1 volume percent.
9. 1 method, phosphonium sulfonates product wherein is settled out from said water medium.
10. method for preparing the sulfonic acid phosphonium salt of general formula (1):
Wherein each X independently is halogen or hydrogen, and prerequisite is that the mol ratio of halogen and hydrogen is greater than about 0.90; P is 0 or 1, and q and r are the integers of 0-about 7, prerequisite be q+r less than 8, and if p be not 0, then r is greater than 0; Each R is the identical or different alkyl that contains about 18 carbon atoms of 1-, and said method comprises:
In water medium, make the compound of general formula (4)
Identical in the meaning of X, p, q and r and the formula (1) wherein, and the compound of general formula (5):
(R)
4P-OH (5)
Identical in the meaning of R and the formula (1) wherein; With
Separate type (1) phosphonium sulfonates product.
11. the method for item 10, wherein X is a fluorine; Z bromine or chlorine; Three R groups are identical aliphatic group that contains about 8 carbon atoms of 1-or the aryl that contains about 12 carbon atoms of 6-, and the 4th R group is the alkyl that contains about 18 carbon atoms of 1-.
12. the method for item 11, wherein p is 0.
13. the method for item 10; Sulfonate radical wherein is perfluor methanesulfonate, perfluor ethyl sulfonic acid root, perfluor propanesulfonic acid root, perfluor fourth sulfonate radical, perfluor penta sulfonate radical, the own sulfonate radical of perfluor, perfluor sulfonate radical in heptan, perfluorooctane sulfonate root, or contains the combination of at least a aforementioned sulfonate radical; Phosphonium of stating is the hot basic Phosphonium of tetramethyl phosphonium, four second base Phosphonium, 4-butyl-phosphonium, triethyl first base Phosphonium, tributyl first base Phosphonium, tributyl second base Phosphonium, three hot basic first base Phosphonium, trimethylammonium fourth base Phosphonium, trimethylammonium, trimethyldodecane base Phosphonium, the hard fat base of trimethylammonium Phosphonium, the hot basic Phosphonium of triethyl and fragrant family Phosphonium for example tetraphenylphosphoniphenolate, three phenyl methyl Phosphonium, triphenyl benzyl base Phosphonium, tributyl benzyl base Phosphonium or comprise the combination of stating Phosphonium before at least a in it.
14. the method for item 13, sulfonate radical wherein is perfluor methanesulfonate, perfluor fourth sulfonate radical, the own sulfonate radical of perfluor, perfluor sulfonate radical in heptan, perfluorooctane sulfonate root or comprises the anionic combination of at least a aforementioned organic sulfonic acid root that Suo Shu Phosphonium is a 4-butyl-phosphonium.
15. the method for item 14, the mol ratio of its Chinese style (4) compound and formula (3) compound is the about 1:3 of about 1:2.01-.
16. the method for item 10, wherein said water medium comprises the non-aqueous media that is less than about 1 volume percent.
17. the method for item 10, wherein the phosphonium sulfonates product is settled out from said water medium.
18. sulfonic acid phosphonium salt method for preparing general formula (1):
Wherein each X independently is halogen or hydrogen, and prerequisite is that the mol ratio of halogen and hydrogen is greater than about 0.90; P is 0 or 1, and q and r are the integers of 0-about 7, prerequisite be q+r less than 8, and if p be not 0, then r is greater than 0; Each R is the identical or different alkyl that contains about 18 carbon atoms of 1-, and said method comprises:
In water medium, make sodium hydroxide and/or Lithium Hydroxide MonoHydrate;
The compound of general formula (4)
Identical in the meaning of X, p, q and r and the formula (1) wherein; With
The compound of general formula (3):
(R)
4P-Z (3)
Wherein Z is a halogen, and the definition of R as above; With
The phosphonium sulfonates of separate type (1).
19. the method for item 18, the mol ratio of its Chinese style (4) compound and formula (3) compound is the about 1:3 of about 1:2.01-.
20. the method for item 18, wherein X is a fluorine; Z is bromine or chlorine; Three R groups are identical aliphatic group that contains about 8 carbon atoms of 1-or the aryl that contains about 12 carbon atoms of 6-, and the 4th R group is the alkyl that contains about 18 carbon atoms of 1-.
21. the method for item 18, wherein p is 0.
22. the method for item 18; Wherein sulfonate radical is perfluor methanesulfonate, perfluor ethyl sulfonic acid root, perfluor propanesulfonic acid root, perfluor fourth sulfonate radical, perfluor penta sulfonate radical, the own sulfonate radical of perfluor, perfluor sulfonate radical in heptan, perfluorooctane sulfonate root, or contains the combination of at least a aforementioned sulfonate radical; Phosphonium of stating is the hot basic Phosphonium of tetramethyl phosphonium, four second base Phosphonium, 4-butyl-phosphonium, triethyl first base Phosphonium, tributyl first base Phosphonium, tributyl second base Phosphonium, three hot basic first base Phosphonium, trimethylammonium fourth base Phosphonium, trimethylammonium, trimethyldodecane base Phosphonium, the hard fat base of trimethylammonium Phosphonium, the hot basic Phosphonium of triethyl and fragrant family Phosphonium for example tetraphenylphosphoniphenolate, three phenyl methyl Phosphonium, triphenyl benzyl base Phosphonium, tributyl benzyl base Phosphonium or comprise the combination of stating Phosphonium before at least a in it.
23. the method for item 22, wherein sulfonate radical is perfluor methanesulfonate, perfluor fourth sulfonate radical, the own sulfonate radical of perfluor, perfluor sulfonate radical in heptan, perfluorooctane sulfonate root or comprises the anionic combination of at least a aforementioned organic sulfonic acid root, and Suo Shu Phosphonium is a 4-butyl-phosphonium.
24. the method for item 18, wherein said water medium comprises the non-aqueous media that is less than about 1 volume percent.
25. the method for item 18, phosphonium sulfonates product wherein is settled out from said water medium.
26. the method for item 18, wherein Lithium Hydroxide MonoHydrate and/or sodium hydroxide add to formula (4) compound prior to formula (5) compound.
27. 26 method, the product that wherein adds behind Lithium Hydroxide MonoHydrate and/or the sodium hydroxide is corresponding alkaline sulfonate (2).
28. the method for item 25, this method also are included in the preceding separated salt (2) of adding formula (5) compound.
Detailed Description Of The Invention
The inventor finds unexpectedly, by corresponding halogenation four alkane base Phosphonium and haloalkyl sulfonic acid lithium or sodium salt, can easily in water medium, obtain being suitable for the haloalkyl sulfonic acid phosphonium salt as static inhibitor with a step.As selection, can in water medium, obtain said haloalkyl sulfonic acid phosphonium salt with a step by corresponding halogenation or hydroxide four alkane base Phosphonium and haloalkyl sulfonic acid fluoride.Reactant is easy to obtain, and adopts water to quicken the separation of product as reaction solvent.Therefore, rely on wonderful extremely useful characteristic, the inventor to have been found that to make reactant simply the mixing antistatic molecule that can cause being used as target precipitate with high yield.
Generally speaking, said haloalkyl sulfonic acid phosphonium salt has general formula (1):
Wherein X independently is selected from halogen or hydrogen, and prerequisite is that the mol ratio of halogen and hydrogen is greater than about 0.90.Halogen can be independently selected from bromine, chlorine, fluorine and iodine.Especially, halogen is a fluorine.
In addition, in formula (1), p is 0 or 1, and q and r are the integers of 0-about 7, prerequisite be q+r less than 8, and if p be not 0, then r is greater than 0.In one embodiment, p is 0.
Independently for containing the alkyl of about 18 carbon atoms of 1-, that is, each R is identical or different, can be the straight or branched aliphatic group that contains about 18 carbon atoms of 1-, or contains the aryl of about 18 carbon atoms of 6-for each R in the formula (1)." aromatics " base that is used for this paper comprises full aromatic yl group, aralkyl and alkylaryl.In one embodiment, three R groups in You Ji phosphonium cation can be the identical aliphatic group that contains about 8 carbon atoms of 1-or contain the aryl of about 12 carbon atoms of 6-, and the 4th R group can be the alkyl that contains about 18 carbon atoms of 1-.
Therefore, said static inhibitor can be and contains organic sulfonic acid root negatively charged ion and the quaternary halogenated sulfonic acid phosphonium salt of height that the machine phosphonium cation is arranged.Specific examples is a perfluoride, but because preparing method's (electrolysis) of fluorization generates only partially fluorinated compound sometimes.
The anionic specific examples of organic sulfonic acid root that is suitable for comprises: perfluor methanesulfonate, perfluor ethyl sulfonic acid root, perfluor propanesulfonic acid root, perfluor fourth sulfonate radical, perfluor penta sulfonate radical, the own sulfonate radical of perfluor, perfluor sulfonate radical in heptan and perfluorooctane sulfonate root.Also has aforesaid combination.
The instance of tool body phosphonium cation comprises such as following positively charged ion: tetramethyl phosphonium, four second base Phosphonium, four positive third basic Phosphonium, four different third basic Phosphonium, 4-butyl-phosphonium, triethyl first base Phosphonium, tributyl first base Phosphonium, tributyl second base Phosphonium, three hot basic first base Phosphonium, trimethylammonium fourth base Phosphonium, the hot basic Phosphonium of trimethylammonium, trimethyldodecane base Phosphonium, the hard fat base of trimethylammonium Phosphonium, the hot basic Phosphonium of triethyl, tetraphenylphosphoniphenolate, three phenyl methyl Phosphonium, triphenyl benzyl base Phosphonium and tributyl benzyl base Phosphonium.Also has above-mentioned combination.
In one embodiment, the phosphonium sulfonates method of a kind of preparation formula (1) is provided, it is included in and makes formula (2) compound in the water medium:
Wherein M is the basic metal that is selected from lithium (Li) or sodium (Na), and X, q, p and r as above define, and excessive formula (3) compound of stoichiometric calculation:
(R)
4P-Z (3)
Wherein Z is a halogen, and R defines as above; Separate type (1) product again.Z specifically can be bromine or chlorine.
In one embodiment, said method can comprise the whole haloalkyl sodium sulfonate or the lithium salts of formula (2) are dissolved in the water medium.For example, said water medium can not contain for example ethanol of solubility promoter basically." water medium " that be used for this paper refers to solution, dispersion-s or the suspension of water.In addition, the water medium that is used for this paper " not containing solubility promoter basically " refers to, contains to be less than approximately 1, especially is less than approximately 0.5, is more especially the water medium of the solubility promoter that is less than about 0.1 volume percent.Although under the situation of sylvite, adopt solubility promoter maybe and necessity, adopt the water that does not contain solubility promoter basically can generate more highly purified product, avoid safety concerns because of adopting solvent flashing to cause.During employing, suitable solubility promoter helps to dissolve sulfonic acid alkali metal salts, comprises for example methyl alcohol, acetate etc. and chlorinated solvent methylene dichloride etc. for example of lower alcohol.Can adopt the mixture of solubility promoter.
The water medium that contains the whole haloalkyl sulfonic acid alkali metal salts can react with halogenation four Qu Dai Phosphonium again.Interpolation it seems unimportant in proper order,, also can be dissolved in water medium through for example making halogenation four Qu Dai Phosphonium that is, adds the whole haloalkyl sulfonic acid alkali metal salts again; Through dissolving simultaneously and mixing said reactant; Accomplish reaction through dissolving methods such as the said reactant of remix respectively.Can obtain the resulting sulfonic acid phosphonium salt of this paper through the mixture that adopts whole haloalkyl sulfonic acid alkali metal salts and halogenation four to get for Phosphonium.
Said method can and be carried out under the reaction times in the temperature of broad range, and will depend on used concrete reactant, solubility promoter (if any), desirable yield, desirable purity, cost, convenience, is easy to factors such as preparation and considers.For example, the temperature of the whole bag of tricks generally can be about 10 ℃-Yue 100 ℃, particularly about 20 ℃-Yue 95 ℃, is more especially about 30 ℃-Yue 90 ℃.In one embodiment, under general about 20 ℃-Yue 25 ℃ room temperature or envrionment temperature, carry out said reaction.Equally, the reaction times can be different, but generally can be about 5 minutes-Yue 1 day, and particularly about 30 minutes-Yue 12 hours, or be more particularly about 60 minutes-Yue 4 hours.These temperature and times can differ widely, and can be confirmed by those of ordinary skill in the art.
Can with respect to whole haloalkyl sulphonate at least equimolar amount use halogenation four Qu Dai Phosphonium; More particularly; The mol ratio of the halogenation four Qu Dai Phosphonium of the whole haloalkyl sulphonate of formula (2) and formula (3) can be the about 1:1.5 of about 1:1.001-; Especially the about 1:1.1 of about 1:1.002-, the about 1:1.015 of more about 1:1.005-.According to concrete reactant, temperature, solubility promoter (if any) and time, optimum ratio is different, and is easy to confirmed by those of ordinary skill in the art.
In another embodiment, the mol ratio of the halogenation four Qu Dai Phosphonium of the whole haloalkyl sulphonate of formula (2) and formula (3) can be the about 1.5:1 of about 1.001:1-, the about 1.1:1 of especially about 1.002:1-, the more particularly about 1.015:1 of the about 1.005:1-of amount.According to concrete reactant, temperature, solubility promoter (if any) and time, optimum ratio is different, and is easy to confirmed by those of ordinary skill in the art.
According to very favorable characteristics, select said reactant and water medium, so that sulfonic acid phosphonium salt (1) precipitates from said water medium with high purity, and can pass through simple filtering and washing, from the especially halogen-containing impurity of impurity, separate.Especially need remove halogen-containing impurity (for example bromination halogenation four Qu Dai Phosphonium and/or chlorination four Qu Dai Phosphonium), since known these impurity are understood for example polycarbonate of degradative resins.Therefore because said impurity is water-soluble, and required product is water insoluble, through can be easily with water washing and remove impurity effectively.
In yet another embodiment, provide a kind of prepare formula (method of 1) phosphonium sulfonates, it is included in the sulfonic acid fluoride that makes general formula (4) in the water medium:
Wherein the meaning of X, p, q and r as above, and the hydroxide four Qu Dai Phosphonium chemical combination of the excessive formula (5) of stoichiometric calculation:
(R)
4P-OH (5)
Wherein the R definition as above; Again from said water medium separate type (1) product.In one embodiment, selective reaction thing and water medium are so that be settled out the sulfonic acid phosphonium salt from said water medium.
In this embodiment, available single stage method prepares the sulfonic acid phosphonium salt of formula (1), and it can be included in and sulfonic acid fluoride (4) and hydroxide four got for Phosphonium (5) react.Therefore, compound (4) can be dispersed or dissolved in and contains in the water medium that solubility promoter or aforesaid do not contain solubility promoter basically, again to wherein adding hydroxide four Qu Dai Phosphonium (5).Interpolation it seems unimportant in proper order,, also can be dissolved in water medium through for example making said hydroxide four Qu Dai Phosphonium (5) that is, adds sulfonic acid fluoride (4) again, or through dissolution and the said reactant of mixing are accomplished reaction simultaneously.The combination of different sulfonic acid fluoride (4) and/or different hydro oxidation four Qu Dai Phosphonium (5) is reacted.
As stated, can adopt large-scale reaction times, temperature and other processing condition, but for being easy to prepare preferred room temperature.Generally use hydroxide four Qu Dai Phosphonium (5) at least about 2 moles amount with every mole of sulfonic acid fluoride (4); More particularly; The mol ratio of the phosphonium hydroxides of formula (4) compound and formula (5) can be the about 1:3 of about 1:2.01-, and the about 1:2.7 of particularly about 1:2.1-is more particularly the about 1:2.6 of about 1:2.2-.According to concrete reactant, temperature, solubility promoter (if any) and time, optimum ratio can be different, and be easy to confirmed by those of ordinary skill in the art.
In yet another embodiment, the method for the sulfonic acid phosphonium salt of a kind of preparation formula (1) is provided, it is included in the water medium, and the halogenation four of formula (4) sulfonic acid fluoride, formula (3) is got for Phosphonium and basic metal or alkaline earth metal alkali mixing; Again from the phosphonium sulfonates of said water medium separate type (1).The alkali that is suitable for for example comprises alkaline hydrated oxide for example Pottasium Hydroxide, sodium hydroxide, Lithium Hydroxide MonoHydrate, Marinco H etc.Also can adopt mixture.Preferred Pottasium Hydroxide, sodium hydroxide and/or Lithium Hydroxide MonoHydrate.In one embodiment, selective reaction thing and water medium are so that be settled out the sulfonic acid phosphonium salt from said water medium.
In addition, interpolation it seems unimportant in proper order, therefore, can mix said each component simultaneously, or halogenation four Qu Dai Phosphonium (3) can add to the aqueous solution/dispersion-s of said alkali, this medium/dispersion-s is added to the solution/dispersion of sulfonic acid fluoride (4) again.In yet another embodiment, sulfonic acid fluoride (4) and said alkali are mixed, reaction for some time is with effective formation alkaline sulfonate (2).Then, need not separate alkaline sulfonate (2), phosphonium halide (3) is added to form product in the medium.This method is simple, effectively and with time and raw material minimize.As selection, adding phosphonium halide (3) before, separable alkaline sulfonate (2) and with or dissolve again without solubility promoter.Can adopt large-scale reaction times, temperature and other processing condition, but for being easy to preparation preferred about 25 ℃ (room temperatures)-Yue 100 ℃.Optimum response thing ratio is easy to confirmed by those of ordinary skill in the art, for example can be above-mentioned those ratios.
Can comprise have general formula those salt of (6) through the sulfonic acid phosphonium salt of methods described herein preparations:
Wherein F is a fluorine; N is the integer of 0-about 7, and S is a sulphur; Each R be identical or different, contain the aliphatic group of about 18 carbon atoms of 1-or contain the aryl of 6-Yue 18 carbon atoms.In one embodiment, have three R groups in the machine phosphonium cation can be identical, contain the aliphatic group of about 8 carbon atoms of 1-or contain the aryl of 6-Yue 12 carbon atoms, and the 4th R group can be the alkyl that contains about 18 carbon atoms of 1-.Available many different modes adopt the antistatic composition of the fluorine phosphonium sulfonates that contains the formula (6) as its main ingredient, to utilize its static resistance, consistency and thermotolerance, for example, to thermoplastic resin this type antistatic property are provided.The thermoplastic resin that is suitable for includes but not limited to; Polycarbonate, polyetherimide, polyester, polyphenylene ether/polystyrene blends, polymeric amide, polyketone, acrylonitrile-butadiene-styrene copolymer (ABS), or comprise the mixture of at least a aforementioned polymer.The sulfonic acid phosphonium salt is the semisolid material of eutectic, so they can be used as the fusing fluid processing.Under some embodiment room temperature of the present disclosure (about 25 ℃ of about 15-) is the solid crystal material, is easy to weigh, handles and adds to above-mentioned thermoplastic resin.
Except that thermoplastic resin, said thermoplastic compounds also can contain the various additives that mix this based resin composition usually.Can adopt the mixture of additive.Can form in the said compsn process in the said component of mixing and sneak into this type additive in appropriate time.The instance of useful additives has, impact modifier, filler, thermo-stabilizer, inhibitor, photostabilizer, softening agent, releasing agent, UV light absorber, lubricant, pigment, dyestuff, tinting material, whipping agent, dripping inhibitor and fire retardant.
The usual way of implementing this method is when polymkeric substance generates or constitute, directly to add said additive to said thermoplastic resin, and makes it to mix.This can carry out through traditional way, comprise extrude, injection, moulding, compression molding or casting.Can prepare thermoplastic compounds through the common available method in this area; For example; In a kind of embodiment in one embodiment; At first make thermoplastic resin, static inhibitor and/or other optional component of powdering, choose wantonly and in the Henschel super mixer, mix with glass cullet silk or other filler.Other low shear is handled and is included but not limited to that manual stirring also can realize this mixing.Through hopper mixture is fed the inlet of twin screw extruder machine again.As selection, one or more components can be mixed in the said compsn through in the ingress and/or feeder (sidestuffer) directly feeds tube machine through the side in downstream.This type additive also can be mixed into master batch with required polymer resin, is fed in the tube machine.Generally said compsn is flowed operate tube machine under the required temperature being higher than.Quencher extrudate and process the ball shape in water-bath immediately.When the said extrudate of cutting, so the ball material of preparation can be 1/4th inches long or littler as required.This type ball material can be used for follow-up mold pressing, moulding or formation.
The amount that is added to the sulfonic acid phosphonium salt of thermoplastic resin is the amount that effectively reduces or eliminates static charge, and can in certain scope, change.Have been found that if adding to the anlistatig of resin gets for the sulfonic acid phosphonium salt very little then on the article that said resin is processed, to also have the trend of build-up of static charges.If the addition of anti static additive is too high, then the interpolation of this tittle is uneconomic, and when certain level, it can begin other character of said resin is had a negative impact.Gross weight with respect to static inhibitor and polymkeric substance; Adopt about 10% weight of about 0.01-; Especially about 2.0% weight of about 0.2-, static inhibitor that is more especially about 1.5% weight of about 0.5-and about 99.99% weight of about 90-, about 99.8% weight of especially about 99-; Be more especially the polymkeric substance of about 99.5% weight of about 98.5-, can obtain anti-static function enhanced thermoplastic compounds.In one embodiment; For obtaining good result aspect the clear polycarbonate rank through the inner applying method of this type; The amount of used static inhibitor is generally about 3.0% weight of about 0.01-of moulding compound; About 1.5% weight of particularly about 0.1-, or be in particular about 0.8% weight of about 0.4-.The static inhibitor that this paper provided has stronger thermotolerance, its addition than traditional ionogenic surfactant for example Wan base phosphonium sulfonates lack, said resin combination has the good transparency and mechanical property.
Shang Shu phosphonium salt also can be used for preparing the thermoplastic polymer composition that has through improved thermal stability.In one embodiment, 130 ℃ down aging after 936 hours, contains yellowness index through the polycarbonate compositions of the static inhibitor of one of aforesaid method preparation and be lower than approximately 15, particularly is lower than approximately 10, more particularly is lower than approximately 8, even more particularly is lower than about 6.
For example; The thermoplastic compounds that contains said static inhibitor can be used for making article, for example computingmachine and business machine housings for example the carrying band, auto parts etc. of mobile phone, terminal box and illuminating equipment part shell, ornament, home appliances, roof, greenhouse, sun-room, swimming pool fence, package semiconductor material of watch-dog shell, hand-hold electronic device shell for example.
Adopting process for example the extruding of film and thin slice, jet molding, gas helps jet molding, extrusion molding, compression molding and blowing, can make thermoplastic compounds be converted into article.The expressing technique of film and thin slice can include but not limited to that fusion-cast, blown film extrude and roll.Coextrusion and laminating technology can be used for forming composite multi-layer film or thin slice.Also can further apply one or more layers coating to one or more layers substrate, to give extra performance, for example resistance to marring, uviolresistance, aesthstic attractive force etc.Can the for example spreading of coated technology, spraying, dipping, brushing or flow coat, apply coating.As selection, can pass through to remove said solvent subsequently, preparation film or thin slice on suspension to substrate, travelling belt or the roller of the said thermoplastic compounds in the casting suitable solvents.
Can adopt conventional stretching technique, near heat-drawn wire, extrude or drawn casting or film the preparation oriented film through blown film through rolling.For example, can be to the multiaxis application of radiation stretching pantograph that stretches simultaneously; Can use x-y to the stretching pantograph so that the x-y direction is simultaneously or continuous mutually the stretching on the plane.Also can use the device of band uniaxial drawing parts, for example be equipped with to along machine direction tensile differential speed roll parts with to the machine of the tentering frame parts of cross directional stretch, with realize single shaft to and biaxial stretching.
Thermoplastic compounds of the present invention also can be converted to composite wafer; It comprises first thin slice and second thin slice; First thin slice has first and second first thin slice; Wherein first thin slice contains thermoplastic polymer, and wherein first face of first thin slice is placed on first of a plurality of floors (rib); Second thin slice has first and second, and wherein second thin slice contains thermoplastic polymer, and wherein first face of second thin slice is placed on second of said a plurality of floors, and first of wherein said a plurality of floors with second of said a plurality of floors relatively.
Through being shaped and moulding technology, comprise for example thermoforming, vacuum forming and pressure forming, jet molding and compression molding, can further above-mentioned film and thin slice thermoplastic be processed into formed article.Also can be through on jet molding thermoplastic resin to single or multiple lift film or the thin slice substrate, for example through providing the surface optional list or the multi-layer thermoplastic substrate (for example adopting silk screen printing or transfer dyeing) that one or more colors are arranged; Make the shape-consistent of substrate and mould, for example moulding and moulding substrate become 3D shape, and substrate is packed in its surface and the mould that the 3D shape of substrate conforms to; Thermoplastic resin is sprayed into the die cavity after the substrate; Process the multilevel shaping article,, or (ii) transmit pattern or aesthetic effect to spraying into resin from printed substrate so that (i) form the three-dimensional article of a permanent bond; And remove printed substrate, thereby give the moulding resin aesthetic effect.
Those skilled in the art also can be appreciated that; Known curing and surface modification technology; Include but not limited to; Thermal-setting, decorative pattern, embossing, corona treatment, flame treating, plasma treatment and/or vacuum moulding machine meeting further are applied to above-mentioned article, to change appearance and to give article extra function.
Therefore, another embodiment of the present invention relates to article, thin slice and the film by above-mentioned thermoplastic compounds preparation.
Can give birth to into phosphonium salt (1) with high purity ground fast with aforesaid method.In one embodiment, the total amount of ionic impurity is less than per approximately 1,000,000 parts (ppm), more particularly less than about 500ppm, even more particularly less than about 100ppm, more particularly less than about 50ppm, the most especially less than about 10ppm.In yet another embodiment, said product contains the basic metal less than about 5ppm, preferably is less than the basic metal of about 4ppm.In yet another embodiment, said product contains less than about 500ppm, preferably less than about 100ppm, is more preferably less than about 50ppm, most preferably less than the halogenide of about 10ppm.Other ionic impurity, for example phosphoric acid salt or vitriol are individually with less than about 100ppm, preferably less than about 50ppm, most preferably existing less than measuring of about 10ppm.
Further specify present method through following non-limiting examples.
Embodiment
, carry out dsc (DSC) and measure from 50 ℃ of-100 ℃ of scanning samples with the sweep velocity of 10 ℃/min.From 50 ℃ of-600 ℃ of scanning samples, carry out thermogravimetric analysis (TGA) with the sweep velocity of 10 ℃/min.Confirm the ion content of said salt through ion chromatography.Gretag McBeth Color-Eye 7000A through adopting Propalette software confirms yellowness index (YI).
In the following example, " MQ water " refers to de-ionized and through the water (MilliQ
is the trade mark of Millipore company) of MilliQ
system handles." TBPBr " refers to the Xiuization 4-butyl-phosphonium.
Embodiment 1
At first, (MW 302, and 16.55mmol) perfluorination fourth sulfonic acid fluoride (" A ") stirs and in 85 ℃ of oil baths, refluxes with magnetic stirrer in 100-mL2-neck round bottom beaker to claim 5.00 grams.
Then, add (24.83mmol) the also dissolving of 0.95 gram Lithium Hydroxide MonoHydrate (LiOH), slowly add to A again to 25mL MQ water.Said mixture was refluxed about one hour, add 25mL MQ water and stirring again.Resistates is not dissolved in elimination again, is collected in another 100-mL 2-neck round bottom beaker, and reheat once in 85 ℃ of oil baths.Then 8.43 gram TBPBr (24.83mmol) are dissolved in the 25mL MQ water, and slowly are added to said filtrating, generate the static inhibitor product.After all dissolving TBPBr adds, the said mixture of restir 15 minutes.Then preferably in ice/water-bath, cool off said mixture, decantation water again.Then, add 100mL MQ water, stirred 15 minutes when being to heat in 85 ℃ of oil baths., also wash to room temperature with the said mixture of postcooling through filtering separated product with 25mL MQ water.In 50 ℃ of dry said products in vacuum drying oven.Theoretical yield is 9.24 gram static inhibitor; Obtain 3.8g.
Embodiment 2
At first, under the room temperature, make 54.8 gram (180.837mmol) perfluorination fourth sulfonic acid lithiums (" Li Rimar ") add and be dissolved in 300mL MQ water, 60.8 gram (179.062mmol) TBPBr are added and be dissolved in 200mL MQ water.Filter TBPBr solution, stir with spiral stirrer on the limit again, and the limit in the impouring Li Rimar salts solution, generates the static inhibitor product gradually.After adding whole TBPBr, restir reaction mixture 15 minutes.Reaction is last, separates the static inhibitor product through filtering, and with the flushing of 50mL MQ water, to remove most of impurity.Through making the static inhibitor product be suspended in MQ water and being heated to 80 ℃, stir several minutes, cooling mixture makes static inhibitor product recrystallize again, accomplishes further purifying.Then can be through filter separating the static inhibitor product, in 50 ℃ at the vacuum drying oven inner drying.Theoretical yield is 100.0 gram static inhibitor; Obtain 87.1 grams.
Embodiment 3
At first, (MW 302, and 16.55mmol) perfluorination fourth sulfonic acid fluoride (" A ") stirs with magnetic stirrer in 100-mL 2-neck round bottom beaker, in 85 ℃ of oil baths, refluxes to take by weighing 5.00 grams.
Then slowly adding 32% weight NaOH solution, is 2.4 times of amount of A.That is, 39.72mmol is corresponding to 1.58 gram NaOH (4.94 grams, 32% weight solution).Reflux then mixture 1 hour adds 50mL MQ water again, is stirred to whole dissolvings.Then, make 5.62 gram TBPBr (16.55mmol) be dissolved in 25mL MQ water, slowly be added to said solution, generate the static inhibitor product.After adding whole dissolving TBPBr, restir mixture 15 minutes.Then, the cooling cooling mixture preferably cools off in ice/water-bath, decantation water again.Add 100mL MQ water then, heat in 85 ℃ of oil baths on the limit, and stirred 15 minutes on the limit.Cooling mixture separates the static inhibitor product to room temperature through filtering, and washes with 25mL MQ water.The static inhibitor product is again through 50 ℃ of vacuum drying oven dryings.Theoretical yield is 9.24 gram static inhibitor; Obtain 5.8 grams.
Embodiment 4
At first, under the room temperature, 5.77 gram (18.083mmol) perfluorination fourth sodium sulfonates (" Na Rimar ") are added and are dissolved in 50mL MQ water, under the room temperature, 6.08 gram (17.906mmol) TBPBr are added and are dissolved in 20mL MQ water.Filter TBPBr solution, strong magnetic stirrer use on the limit again, and the limit is gradually in the impouring Na Rimar salts solution, generation static inhibitor product.After adding whole TBPBr, the said reaction mixture of restir 15 minutes.When reaction finishes, separate the static inhibitor product through filtering, and with the flushing of 50mL MQ water, to remove most of impurity.Through the static inhibitor product in the stirring MQ water, and be heated to 80 ℃, the restir several minutes, cooling mixture makes static inhibitor product recrystallize again, can realize further purifying.Again through filter separating the static inhibitor product, in 50 ℃ at the vacuum drying oven inner drying.Theoretical yield is 10.0 gram static inhibitor; Obtain 8.10 grams.
At first, (MW 302, and 16.55mmol) perfluorination fourth sulfonic acid fluoride (" A ") stirs with magnetic stirrer in 100-mL 2-neck round bottom beaker, in 85 ℃ of oil baths, refluxes to take by weighing 5.00 grams.Then, slowly add 4.46g50% weight KOH solution, obtain 2.4 normal KOH (2.23g, 39.72mmol) (4.46 grams, 50% weight solution).Backflow mixture 1 hour adds 75mL ethanol/MQ (volume ratio is 3/4) again, is stirred to whole dissolvings.Then, make 5.56 gram TBPBr (16.38mmol) be dissolved in 25mL MQ water, slowly be added to said solution again, generate the static inhibitor product.After adding all dissolving TBPBr, make mixture be cooled to room temperature before, restir mixture 15 minutes.Extract the static inhibitor product with the 75mL methylene dichloride through separating funnel, with 50mL MQ water washing 3 times.Vacuum (50 ℃, p
Initial=475mbar and p
Finish=125mbar) remove organic layer.Through the static inhibitor product in the stirring MQ water, and be heated to 80 ℃, stir several minutes, cooling mixture makes static inhibitor product recrystallize again, can realize further purifying.Separate the static inhibitor product through filtering again, at 50 ℃ of vacuum drying oven inner dryings.Theoretical yield is 9.24 gram static inhibitor; Obtain 6.04 grams.
Comparing embodiment 6
At first, under the room temperature, 6.06 gram (17.9mrnol) perfluorination fourth potassium sulfonates (" K Rimar ") are added and are dissolved in 75mL ethanol/MQ volume ratio is in 3/4 the aqueous solution, and 6.01 gram (17.7mmol) TBPBr are added and are dissolved in 25mL MQ water.With TBPBr solution impouring KRimar salts solution gradually, generate the static inhibitor product while stirring.After adding whole TBPBr, restir reaction mixture 15 minutes.Extract the static inhibitor product with the 75mL methylene dichloride through separating funnel again, with 50mLMQ water washing 3 times.Vacuum (50 ℃, p
Initial=475mbar and p
Finish=125mbar) remove organic layer.Through the static inhibitor product in the stirring MQ water, and be heated to 80 ℃, stir several minutes, cooling mixture makes static inhibitor product recrystallize again, can realize further purifying.Separate the static inhibitor product through filtering again, at 50 ℃ of vacuum drying oven inner dryings.Theoretical yield is 10.0 gram static inhibitor; Obtain 8.91 grams.
Embodiment 7
At first, (MW 302, and 16.55mmol) A stirs with magnetic stirrer in 100-mL 2-neck round bottom beaker, in 85 ℃ of oil baths, refluxes to claim 5.00 grams.Then, add 10.98 gram (39.72mmol) 40% weight hydroxide 4-butyl-phosphoniums.Mixture 1 hour again refluxes.Then add 50mL MQ water, restir 15 minutes.Then cooling mixture preferably cools off in ice/water-bath, decantation water again.Add 100mL MQ water then, heat in 85 ℃ of oil baths on the limit, and stirred 15 minutes on the limit.Then cooling mixture is to room temperature, and filtering separation static inhibitor product washes with 25mL MQ water.Then, dry static inhibitor product in 50 ℃ of vacuum drying ovens.Its theoretical yield is 9.24 gram static inhibitor; Obtain 7.4 grams.
Table 1 provides the characteristic through the prepared static inhibitor of the various synthetic routes of the foregoing description 1-7 detailed description.Authentic specimen is the perfluorination fourth sulphonate static inhibitor that derives from commodity Zonyl
FASP-I by name of Dupont.(DSC) confirms fusing point through dsc.Confirm the thermal destruction of static inhibitor through thermogravimetric analysis (TGA), under this temperature, measure, wherein measure degraded earlier.
Table 1.
Visible from last table 1, the method for embodiment 3 is because of the high particularly advantageous of yield.In addition, synthesis step is simple.
Table 2 shows, the static inhibitor that the different synthetic routes that detail through embodiment 1-2 make, and after with 80 ℃ of water washings, contained ionic impurity is few.
Table 2
Some by product in the static inhibitor of known common discovery can be harmful to the for example character of polycarbonate of mixture heat thermoplastic polymer.For example, shown in Figure 1, the existence of the bromine of raising amount can result in the polycarbonate yellowing increase after 936 hours of 130 ℃ of heat agings.Table 3 is further behind the expression heat aging, contains the variation of YI (Δ YI) of polycarbonate of the ionic impurity of specified amount.In the polycarbonate of heat aging, observing spot, it possibly cause because of potassium and sodium impurity.
Table 3.
Be definite effect of washing the static inhibitor of the foregoing description, the not washing static inhibitor that takes by weighing 2 preparations of 10.02 gram the foregoing descriptions adds 100mL MQ water in the 150mL beaker.To its stirring, so that static inhibitor homodisperse in water continues under the room temperature to stir 15 minutes.Refilter, dry static inhibitor and test its ionic impurity.
In second test, the not washing static inhibitor that takes by weighing 2 preparations of 10.06 gram the foregoing descriptions is in the 150mL beaker, to wherein adding 100mL MQ water.Fully stir so that static inhibitor is dispersed in the water, 80 ℃ are continued to stir 15 minutes down.The static inhibitor of embodiment 2 melts under this temperature, forms emulsion while stirring.Cooling mixture leaches solid, dry and test ion purity.Table 4 shows the yield after the washing, and table 5 shows the chromatography of ions result.
Table 4
Table 5
Can synthesize static inhibitor according to above-mentioned all embodiment.But under room temperature or 80 ℃ with any ionic impurity of this static inhibitor flush away of water washing.
Singulative " one ", " a kind of " and " being somebody's turn to do " comprise plural, only if context clearly refers else.Term among this paper " first ", " second " etc. are not represented any order, quantity or importance, and are used to make a kind of key element to distinguish mutually with another key element.The end points of enumerating the entire area of same characteristic can combine and comprise listed end points.The modifier of the amount of being used for " pact " comprises said value, and has the said meaning of context (for example, comprising and the concrete relevant error degree of measuring of measurement).By reference, all reference are incorporated herein.
Although for purposes of illustration, illustrated typical embodiment, above stated specification should not be considered to the restriction to this paper scope.Therefore, for a person skilled in the art, it is possible not breaking away from the spirit of this paper and various modifications, modification and the replacement of scope.
Claims (21)
1. method for preparing the sulfonic acid phosphonium salt of general formula (1):
Wherein each X independently is halogen or hydrogen, and prerequisite is that the mol ratio of halogen and hydrogen is greater than 0.90; P is 0 or 1, and q and r are the integers of 0-7, prerequisite be q+r less than 8, and if p be not 0, then r is greater than 0; Each R is the identical or different alkyl that contains 1-18 carbon atom, and said method comprises:
In water medium, make the compound of the compound and the general formula (5) of general formula (4):
Identical in the meaning of X, p, q and r and the formula (1) wherein,
(R)
4P-OH (5)
Identical in the meaning of R and the formula (1) wherein; With,
Separate type (1) phosphonium sulfonates product.
2. the process of claim 1 wherein that X is a fluorine; Z bromine or chlorine; Three R groups are identical aliphatic group that contains 1-8 carbon atom or the aryl that contains 6-12 carbon atom, and the 4th R group is the alkyl that contains 1-18 carbon atom.
3. the method for claim 2, wherein p is 0.
4. the method for claim 1; Sulfonate radical wherein is perfluor methanesulfonate, perfluor ethyl sulfonic acid root, perfluor propanesulfonic acid root, perfluor fourth sulfonate radical, perfluor penta sulfonate radical, the own sulfonate radical of perfluor, perfluor sulfonate radical in heptan, perfluorooctane sulfonate root, or contains the combination of at least a aforementioned sulfonate radical; Qi Zhong Suo Shu Phosphonium is tetramethyl phosphonium, Si Yi Ji Phosphonium, 4-butyl-phosphonium, triethyl Jia Ji Phosphonium, tributyl Jia Ji Phosphonium, tributyl Yi Ji Phosphonium, San Xin base Jia Ji Phosphonium, trimethyl Ding Ji Phosphonium, trimethylammonium Xin Ji Phosphonium, trimethyldodecane Ji Phosphonium, trimethylammonium Ying Zhi Ji Phosphonium, triethyl Xin Ji Phosphonium; Tetraphenylphosphoniphenolate, three phenyl methyl Phosphonium, triphenyl benzyl base Phosphonium and tributyl benzyl base Phosphonium, or comprise the combination of stating Phosphonium before at least a.
5. the method for claim 4, sulfonate radical wherein is perfluor methanesulfonate, perfluor fourth sulfonate radical, the own sulfonate radical of perfluor, perfluor sulfonate radical in heptan, perfluorooctane sulfonate root or comprises the anionic combination of at least a aforementioned organic sulfonic acid root that Suo Shu Phosphonium is a 4-butyl-phosphonium.
6. the method for claim 5, the mol ratio of its Chinese style (4) compound and formula (3) compound is 1: 2.01-1: 3.
7. the process of claim 1 wherein that said water medium comprises the non-aqueous media that is less than 1 volume percent.
8. the process of claim 1 wherein that the phosphonium sulfonates product is settled out from said water medium.
9. the method for claim 4, Phosphonium of stating is selected from tetraphenylphosphoniphenolate, three phenyl methyl Phosphonium, triphenyl benzyl base Phosphonium and tributyl benzyl base Phosphonium in it.
10. sulfonic acid phosphonium salt method for preparing general formula (1):
Wherein each X independently is halogen or hydrogen, and prerequisite is that the mol ratio of halogen and hydrogen is greater than 0.90; P is 0 or 1, and q and r are the integers of 0-7, prerequisite be q+r less than 8, and if p be not 0, then r is greater than 0; Each R is the identical or different alkyl that contains 1-18 carbon atom, and said method comprises:
In water medium, make sodium hydroxide and/or Lithium Hydroxide MonoHydrate;
The compound of the compound of general formula (4) and general formula (3):
Identical in the meaning of X, p, q and r and the formula (1) wherein;
(R)
4P-Z (3)
Wherein Z is a halogen, and the definition of R as above; With
The phosphonium sulfonates of separate type (1).
11. the method for claim 10, the mol ratio of its Chinese style (4) compound and formula (3) compound is 1: 2.01-1: 3.
12. the method for claim 10, wherein X is a fluorine; Z is bromine or chlorine; Three R groups are identical aliphatic group that contains 1-8 carbon atom or the aryl that contains 6-12 carbon atom, and the 4th R group is the alkyl that contains 1-18 carbon atom.
13. the method for claim 10, wherein p is 0.
14. the method for claim 10; Wherein sulfonate radical is perfluor methanesulfonate, perfluor ethyl sulfonic acid root, perfluor propanesulfonic acid root, perfluor fourth sulfonate radical, perfluor penta sulfonate radical, the own sulfonate radical of perfluor, perfluor sulfonate radical in heptan, perfluorooctane sulfonate root, or contains the combination of at least a aforementioned sulfonate radical; Qi Zhong Suo Shu Phosphonium is tetramethyl phosphonium, Si Yi Ji Phosphonium, 4-butyl-phosphonium, triethyl Jia Ji Phosphonium, tributyl Jia Ji Phosphonium, tributyl Yi Ji Phosphonium, San Xin base Jia Ji Phosphonium, trimethyl Ding Ji Phosphonium, trimethylammonium Xin Ji Phosphonium, trimethyldodecane Ji Phosphonium, trimethylammonium Ying Zhi Ji Phosphonium, triethyl Xin Ji Phosphonium; Tetraphenylphosphoniphenolate, three phenyl methyl Phosphonium, triphenyl benzyl base Phosphonium and tributyl benzyl base Phosphonium, or comprise the combination of stating Phosphonium before at least a.
15. the method for claim 14, wherein sulfonate radical is perfluor methanesulfonate, perfluor fourth sulfonate radical, the own sulfonate radical of perfluor, perfluor sulfonate radical in heptan, perfluorooctane sulfonate root or comprises the anionic combination of at least a aforementioned organic sulfonic acid root, and Suo Shu Phosphonium is a 4-butyl-phosphonium.
16. the method for claim 10, wherein said water medium comprises the non-aqueous media that is less than 1 volume percent.
17. the method for claim 10, phosphonium sulfonates product wherein is settled out from said water medium.
18. the method for claim 10, wherein Lithium Hydroxide MonoHydrate and/or sodium hydroxide add to formula (4) compound prior to formula (3) compound.
19. the method for claim 18, the product that wherein adds behind Lithium Hydroxide MonoHydrate and/or the sodium hydroxide is corresponding alkaline sulfonate (2)
Wherein M is Li or Na, and each X independently is halogen or hydrogen, and prerequisite is that the mol ratio of halogen and hydrogen is greater than 0.90; P is 0 or 1, and q and r are the integers of 0-7, prerequisite be q+r less than 8, and if p be not 0, then r is greater than 0.
20. the method for claim 19, this method also are included in the preceding separated salt (2) of adding formula (3) compound.
21. the method for claim 14, Phosphonium of stating is selected from tetraphenylphosphoniphenolate, three phenyl methyl Phosphonium, triphenyl benzyl base Phosphonium and tributyl benzyl base Phosphonium in it.
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| US60/562,010 | 2004-04-13 | ||
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| US10/966,774 US7211690B2 (en) | 2004-04-13 | 2004-10-15 | Methods of making an antistatic agent |
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