HK1196389A - Fluorochemical composition and use thereof - Google Patents
Fluorochemical composition and use thereof Download PDFInfo
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Abstract
The instant invention relates to the Fluorochemical composition comprising a dispersion or a solution of a fluorinated compound, wherein said fluorinated compound comprises the reaction product of at least two reactants A and B wherein reactant A being a compound of formula (I); Rf-O-(CF(CF3)CF2O)mCF(CF3)-X-Y-Z (I) with Rf being a perfluorinated alkyl group, m being from 3 to 25; X being a carbonyl group or CH2; Y being a chemical bond or an organic divalent or trivalent linking group bearing a functional or difunctional isocyanate reactive group; Z being an organic group bearing at least one cationic group, reactant B being a polyfunctional isocyanate or a mixture thereof and optionally one or more isocyanate-reactive co-reactants C.
Description
Fluorochemical composition obtainable by reacting a polyisocyanate compound with at least one isocyanate-reactive fluorinated polyether compound having at least one cationic group and its use to provide oil repellents for substrates such as paper, textiles and leather.
Commercially available oil-and/or water repellent compositions are generally based on fluorinated compounds having perfluorinated aliphatic groups. Such compositions are also described, for example, in U.S. Pat. No. 5,276,175 and EP-A-435641. The commercial success of this type of composition can be attributed to its high efficiency.
Fluorinated compounds based on perfluorinated ether moieties have also been described in the prior art for use in providing fiber matrix oil-and water repellents. Perfluorinated polyether compounds are disclosed, for example, in EP-A-1-038919, EP-A-273499, U.S. Pat. No. 3,553,179 and U.S. Pat. No. 3,446,761. It has been found that previously disclosed compositions based on perfluorinated polyether compounds may not be very effective in providing matrix oil-and/or water repellents.
In order to make it suitable for use in contact with food, an important requirement for the treatment of paper is to minimize any risk of contamination of the packaged food by any substance that is harmful or potentially harmful to human or animal health. The optimum situation is that the paper is completely free of any harmful substances or at least does not release harmful substances during its use.
The fluoride should impart the desired oleophobic properties to the paper being treated.
Perfluoroalkyl derivatives are typically mixtures of molecules of different chain lengths containing four to twenty carbon atoms. The disadvantage of these chemicals is the difficulty in completely eliminating the undesirable, persistent and bioaccumulating contaminants perfluorooctanoic acid (PFOA) and perfluorooctylsulfonic acid (PFOS). The challenge was to find PFOA/PFOS free fluorides with the same or similar application properties compared to existing products.
The compounds disclosed in WO-03/100158 attempt to overcome the obstacles of the prior art and describe fluorochemical compositions comprising dispersions or solutions of fluorinated compounds which are the reaction product of a fluorinated polyether and a polyisocyanate. The compositions described herein are useful for providing fiber materials with oil-and water-repellents.
However, the composition described by WO03/100158 has been shown to be insufficiently soluble or dispersible in glycols or glycol/water mixtures, which is necessary in order to uniformly apply the fluorochemical composition on fibrous substrates, especially on paper.
Surprisingly, it was found that when isocyanate-reactive fluorochemical polyethers having at least one cationic group react with polyfunctional isocyanates, PFOA/PFOS-free fluorochemical compounds are provided which dissolve or disperse very well in diols or diol/water mixtures and which can therefore be applied homogeneously on fibrous substrates and which subsequently show unexpectedly good properties with respect to oil-and/or water repellency, especially when used on paper.
The present invention thus relates to a fluorochemical composition comprising a dispersion or solution of a fluorinated compound wherein said fluorinated compound comprises the reaction product of at least two reactants a and B wherein reactant a is a compound of formula (I);
Rf-O-(CF(CF3)CF2O)mCF(CF3)-X-Y-Z (I)
wherein
RfIs a perfluorinated alkyl group, and is a fluorinated alkyl group,
m is from 3 to 25;
x is a carbonyl group or CH2；
Y is a chemical bond or an organic divalent or trivalent linking group having a functional or difunctional isocyanate-reactive group;
z is an organic group having at least one cationic group,
the reactant B is a multifunctional isocyanate or a mixture thereof
And optionally one or more isocyanate-reactive coreactants C.
Preferably, reactant a is a mixture of compounds of formula (I) wherein m is from 4 to 22.
Reactant A has an average molecular weight of from 750 to 4000g/mol, more preferably from 1000 to 3000g/mol, and even more preferably from 1500 to 2500 g/mol.
In a preferred embodiment, the reactants a further contain from 0 to 10% by weight, more preferably from 0 to 5% by weight, even more preferably from 0 to 1% by weight, particularly preferably from 0 to 0.1% by weight, of compounds having a molecular weight of less than 750g/mol, the% by weight being based on the total weight of the reactants a.
Preferably, reactant a is a compound of formula (I) wherein X is a carbonyl group.
In one embodiment, reactant a is a compound of formula (I) wherein Y is a linking group comprising one or two isocyanate reactive groups including thiol, hydroxyl and amino groups, more particularly amino groups such as secondary amino groups.
Reactant a may be a compound of formula (I) wherein Z is a linking group having at least one cationic group, including a tertiary amine, N-oxide, or ammonium group.
The N-oxide or ammonium group may also be obtained by treating the tertiary amine group with a suitable reagent after the reaction between the reactants a and B. The presence of at least one cationic group is an essential requirement for easy dispersion of the composition in a glycol or glycol/water mixture without the use of any dispersing agent. In compositions that do not contain a compound having at least one cationic group, the use of a compound within the spirit of the present invention results in a fluoride composition that is not sufficiently soluble or dispersible in the glycol or water/glycol mixture.
The presence of cationic groups furthermore provides a high affinity of the polymer for the anionic cellulose of the preferred substrate paper. This is important for the application of the fluorochemical compounds of the present invention on paper, not only in the size press, but also in wet end applications.
Particularly preferred reactants a are compounds of formula (II):
Rf-O-(CF(CF3)CF2O)mCF(CF3)-CON(R1)-R2-NH-R3-N(R4)2 (II)
wherein
RfAnd m is as defined above for all of its preferred embodiments,
R1is hydrogen or, for example, 1 to 4An alkyl group of a carbon atom, or a substituted or unsubstituted alkyl group,
R2and R3Independently an alkylene group of 1 to 15 carbon atoms, and
R4is an alkyl group of 1 to 4 carbon atoms.
Even more preferably, reactant A is a compound of formula (II) wherein R1Is hydrogen, R2And R3Is alkylene of 2 or 3 carbon atoms, and R4Is a methyl group. Examples include
Rf-O-(CF(CF3)CF2O)mCF(CF3)-CONH-CH2-CH2-NH-CH2-CH2-N(CH3)2,
Rf-O-(CF(CF3)CF2O)mCF(CF3)-CONH-CH2-CH2-CH2-NH-CH2-CH2-N(CH3)2,
Rf-O-(CF(CF3)CF2O)mCF(CF3)-CONH-CH2-CH2-CH2-NH-CH2-CH2-CH2-N(CH3)2，
Rf-O-(CF(CF3)CF2O)mCF(CF3)-CONH-CH2-CH2-NH-CH2-CH2-CH2-N(CH3)2
The polyfunctional isocyanate compound B may be aliphatic or aromatic and is conveniently a non-fluorinated compound. The molecular weight of the polyisocyanate will generally not exceed 1500 g/mol.
Preferably, the reactant B is a polyisocyanate having at least 3 isocyanate groups, or a mixture of polyisocyanate compounds having an average of more than 2 isocyanate groups per molecule, such as for example a mixture of a diisocyanate compound and a polyisocyanate compound having at least 3 isocyanate groups. The polyisocyanate may be aliphatic or aromatic. Examples include hexamethylene diisocyanate, 2, 4-trimethyl-1, 6-hexamethylene diisocyanate, 1, 2-ethylene diisocyanate, dicyclohexylmethane-4, 4 '-diisocyanate, 1,3, 6-hexamethylene triisocyanate, cyclic trimer of hexamethylene diisocyanate, cyclic trimer of isophorone diisocyanate, 4' -methylenediphenylene diisocyanate, 4, 6-bis- (trifluoromethyl) -1, 3-phenylene diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, o-, m-and p-xylene diisocyanate, 4 '-diisocyanatodiphenyl ether, 3' -dichloro-4, 4 '-diisocyanatodiphenylmethane, 4, 5' -diphenyldiisocyanate, 4 '-diisocyanatobenzyl, 3' -dimethoxy-4, 4 '-diisocyanatodiphenyl, 3' -dimethyl-4, 4 '-diisocyanatodiphenyl, 2' -dichloro-5, 5 '-dimethoxy-4, 4' -diisocyanatodiphenyl, 1, 3-diisocyanatobenzene, 1, 2-naphthalene diisocyanate, 4-chloro-1, 2-naphthalene diisocyanate, 1, 3-naphthalene diisocyanate, 1, 8-dinitro-2, 7-naphthalene diisocyanate, polyphenylenepolyphenylenepolyphenylisocyanate, 3-isocyanatomethyl-3, 5, 5-trimethylcyclohexyl isocyanate, polymethylene polyphenyl isocyanates, isocyanates containing self-condensate moieties such as biuret or isocyanurate containing polyisocyanates, or azetidinedione containing diisocyanates.
More preferably, reactant B is an isocyanate containing an internal isocyanate-derived moiety such as a biuret-containing tri-isocyanate, such as that available from Bayer as DESMODURTMAnd N-type.
In a particularly preferred embodiment, reactant B is DESMODURTM N100、DESMODURTM N3200、DESMODURTM N3300、DESMODURTMN3400 and DESMODURTM N3600。
The optional co-reactant C is a fluorinated organic compound having one or more isocyanate reactive groups.
In detail, the coreactant C is a compound of formula (III)
(Rf-O-(CF(CF3)CF2O)mCF(CF3)-X)n-Q (III)
Wherein
RfAnd m is as defined above,
x is a carbonyl group, and X is a carbonyl group,
q is an organic group or an organic divalent or trivalent linking group having a functional or difunctional isocyanate-reactive group;
n is 1 or 2.
Preferably, the co-reactant C is a compound of formula (III) wherein Q is an organic group containing one or two isocyanate reactive groups including thiol, hydroxyl and amino groups, more preferably amino groups, even more preferably dialkylamino groups.
In a particularly preferred embodiment, the co-reactant C is a compound of formula (IV):
(Rf-O-(CF(CF3)CF2O)mCF(CF3)-CON(R1)-R2)n-N(R5)H (IV)
wherein R isf、R1、R2M and n are as defined above for all preferred embodiments, R5Is (if n is 1) hydrogen or an alkyl group of 1 to 4 carbon atoms.
Preferably, the total stoichiometric amount of isocyanate-reactive groups of reactant a and co-reactant C is less than or equal to the total stoichiometric amount of isocyanate groups of reactant B; more preferably, the total stoichiometric amount of isocyanate-reactive groups of reactant a and co-reactant C is from a factor of 0.8 to 1 of the total stoichiometric amount of isocyanate groups of reactant B.
In an even more preferred embodiment, the total stoichiometric amount of isocyanate-reactive groups of reactant a and co-reactant C is from a factor of 0.9 to 1 of the total stoichiometric amount of isocyanate groups of reactant B.
Preferably, the total stoichiometric amount of isocyanate-reactive groups of co-reactant C is from a factor of 0 to 10, more preferably from 0 to 7 and even more preferably from 0 to 4, even more preferably from 0 to 1 of the total stoichiometric amount of isocyanate-reactive groups of reactant a.
If the total stoichiometric amount of isocyanate-reactive groups of reactant A and co-reactant C is less than or equal to the total stoichiometric amount of isocyanate groups of reactant B, the excess isocyanate groups are preferably further polymerized by autopolymerization, or reaction with a polyfunctional isocyanate-reactive compound comprising, for example, water, a polyol or a polyamine.
Another subject of the invention is a process for the production of a fluorochemical composition characterized by reacting a reactant B with said reactant a and optionally a co-reactant C, wherein said reactants A, B and C have the meaning as described above.
Any order of addition of the reactants may be used.
Preferably, both reactant a and co-reactant C are added to reactant B simultaneously.
Preferably, the stoichiometric amounts of reactants A, B and C are as described above.
Preferably, the reactants are reacted at a temperature in the range of from 0 to 120 ℃, and more preferably from 20 to 80 ℃; this pressure is between atmospheric pressure and 2bar and more preferably between atmospheric pressure and 1.2 bar; wherein the reaction time is in the range of 1 minute to 48 hours and preferably from 1 hour to 12 hours.
The reaction may be carried out in the presence or absence of a catalyst. Suitable catalysts include amines, tin salts such as dibutyltin dilaurate, dibutyltin diacetate, dibutyltin di (2-ethylhexanoate), stannous octoate, stannous oleate, stannous chloride; bismuth salts such as and others known to those skilled in the art. Generally, the preferred concentration of catalyst is from 0.001 to 10% and more preferably from 0.1 to 5% by weight based on the total weight of the reactants.
Preferably, the reaction is carried out in the absence of any catalyst, especially if the coated article is used in the food industry.
In another preferred embodiment, the reaction is carried out in an aprotic solvent or a mixture of aprotic solvents. Preferred solvents are acetone, ethyl acetate, methyl isobutyl ketone, cyclohexanone, tetrahydrofuran, diethyl ether, tert-butyl methyl ether, hydrofluoroethers such as methoxynonafluorobutane, trifluorotoluene, 1, 3-bis (trifluoromethyl) benzene, and mixtures thereof.
Unreacted reactant B can be removed by washing with a non-fluorinated organic solvent in which the fluoride composition is insoluble.
A further subject of the invention is an aqueous dispersion or solution of said fluorochemical composition.
Preferably, the dispersion or solution comprises from 0.5 to 40% by weight, said% by weight being based on the total weight of the dispersion or solution of the fluorochemical composition, more preferably from 5 to 30%.
Thus, the fluoride composition is preferably dispersed or dissolved in water, wherein the dispersion or solution may comprise additional co-solvents.
The co-solvent used in the dispersion or solution is preferably water soluble or at least partially water soluble, more preferably the co-solvent has at least one hydroxyl group, even more preferably the co-solvent is a glycol. In a preferred embodiment, the co-solvent is selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, hexamethylene glycol, hexylene glycol, polytetrahydrofuran, monoalkyl ethers of these glycols, and mixtures of these solvents.
In the example using co-solvents, when any solvents used during the preparation of the compounds are distilled, they are slowly added to the reaction mixture, followed by neutralization of the resulting product with acid and then addition of water.
The distillation of the reaction solvent is preferably done under vacuum.
The acid used for neutralization is preferably selected from the group consisting of acetic and lactic acid, adipic acid, benzoic acid, caprylic acid, citric acid, formic acid, azelaic acid, boric acid, isophthalic acid, itaconic acid, lauric acid, maleic acid, malic acid, oxalic acid, phosphoric acid, phthalic acid, pyromellitic acid, succinic acid, terephthalic acid, ascorbic acid, hypophosphorous acid, propionic acid, sulfonic acid, sodium bisulfate, or p-toluenesulfonic acid, glutaric acid, p-hydroxybenzoic acid, resin acids, and abietic acid, salicylic acid, sebacic acid.
Optionally, the fluorochemical composition of the present invention can be dispersed or dissolved in an anhydrous co-solvent or mixture, wherein the co-solvent is as defined above.
The composition is dispersed or dissolved at a temperature in the range of from 25 to 200 ℃, preferably from 25 to 150 ℃, especially from 25 to 100 ℃.
A further subject-matter of the invention is the use of said fluorochemical composition, preferably in the form of a dispersion or solution, for the treatment of paper, textiles and leather to provide an oil repellent agent for said substrate.
Furthermore, the invention relates to paper treated with a solution or dispersion comprising said fluorochemical composition. The fluorochemical compositions of the present invention can be used for paper sizing by using application methods known in the art. For example, it can be obtained by surface treatment of already formed paper: size press and/or coating. Another method is the wet end, which is the use in pulp slurry.
For such applications, paper, cardboard, etc. are treated with a dispersion or solution of the fluorochemical composition in a suitable vehicle, water, or a mixture of water and solvent.
In the case of surface treatment, the fluorochemical composition can be applied by spreading, dipping, coating, or size pressing. In a typical application by coating, the fluorochemical composition is used in an amount of 0.2 to 2% by weight relative to the coating suspension used, which may contain mineral fillers such as calcium carbonate, kaolin, titanium dioxide and binders such as pigments based on styrene-butadiene copolymers, acrylic copolymers or copolymers containing vinyl acetate. In a typical application by paper sizing in the size press, the fluorochemical composition is used in an amount of 0.2 to 2% by weight relative to the paper, in the form of an aqueous suspension fed into the cylinder of the size press equipment at a temperature of from 20 to 90 ℃. Other additives such as starch, functionalized starch, polyvinyl alcohol, carboxymethyl cellulose, melamine resin, urea resin, aldehyde group-containing compounds, acrylic resin, styrene-butadiene copolymer may be added to the suspension. Defoamers are often added to improve machine runnability.
Drying may take place at a temperature in the range from 90 to 130 ℃ according to techniques commonly used in the paper industry.
The dispersion or the solution of the fluorochemical composition may also contain other products such as known additives as described above necessary to maintain, improve or modify the properties of the paper.
It has been found that when an isocyanate-reactive fluorochemical polyether having at least one cationic group is reacted with a polyfunctional isocyanate, PFOA/PFOS-free fluorochemical compounds are provided which exhibit unexpectedly good performance when used on paper. In addition, the resulting polymer has good thermal stability.
Examples
The test method comprises the following steps:
kit test
The kit test is a procedure to characterize paper resistance to lipids. The kit test involves applying test solutions numbered from 1 to 16 to the sample to be evaluated. The test was conducted under the direction of the Tappi test method for lipid resistance to paper and paperboard T559. When composing the kit solution, weight measurements were used for castor oil because its high viscosity makes volume measurements less accurate.
The kit test uses dark plates in a well-lit fume hood to show penetration as a darker spot.
1. Place each test specimen on the selected surface, which must be clean and dry, with the test side facing up.
2. Select the middle kit test solution and carefully touch the sample without a drip tube, apply a stripe of approximately 2cm length to the sample, and start a timer
3. After 15s the excess test solution was quickly removed using a clean paper towel, a minimum pressure was applied to the paper surface, and the test area was inspected immediately.
Failure is indicated by a dark background of the test sample if used, or by a bright light spot if a bright box is used.
The change in staining resulted from wetting of the sample due to penetration of the test solution on the paper.
If the area to be tested is not immediately examined, evaporation of volatile components of the test solution will occur and the sample can regain its original appearance and be scored as passing.
4. If the sample failed its first test, the untested area of the same paper is selected and repeated with a lower numbered solution.
Repeat until the highest numbered kit solution determined to stay on the surface for 15 seconds did not cause failure.
5. If the sample passes its first test, the test is repeated in the untested areas of the sample using the higher numbered kit solution.
Repeat until the highest numbered kit solution determined to stay on the surface for 15 seconds did not cause failure.
The highest numbered kit solution passed is the kit rating for the sample.
The test was repeated at least twice.
Oil absorption test:
a 15 x 15cm square sample of paper was cut using a template. The test samples were conditioned (23 ℃/50% relative humidity) and weighed on a balance, the weight being recorded for calculation of oil pick-up after completion of the test. The test oil was dispersed into the test cylinder, which required an amount of 7 to 8 ml. The oil was rapidly poured onto the surface of the test sample in a spiral/square pattern of approximately 10 x 10 cm. A 12 x 12cm filter paper was then quickly placed over the oil so that the oil was completely covered. The oil immediately penetrated onto the filter paper and rapidly extended to expose the entire test area of 12X 12cm to the oil. The timer is started simultaneously.
The test was run for 10 minutes. The filter paper is then removed from the test sample. The remaining oil on the test sample was then blotted immediately and then wiped off with an absorbent paper towel until the sample was free of surface oil. After the test the sample was re-weighed and the gravity uptake of the oil-this is called "corn oil absorption":
w1-weight of sample before test
W2-weight of sample after test
S-surface area in contact with oil
The corn oil absorbency value is given in g/m2A description is given. The test can be repeated to ensure that statistically significant results are obtained.
Example 1
Prepared according to WO/2009/118348, Mw1947g/mol, 194.7g of polyhexafluoropropylene oxide methyl ester (poly-HFPO-methyl ester) without oligomers having an Mw of less than 1000g/mol are charged into a glass reactor equipped with a thermometer, a mechanical stirrer and a vacuum distillation apparatus and cooled to-10 ℃. 16.0g of N' - (3-aminopropyl) -N, N-dimethylpropane-1, 3-diamine are slowly added with stirring and by maintaining the temperature at-10 ℃ to 0 ℃. The mixture was then further stirred overnight. The resulting methanol is removed under vacuum and the compound of formula (1) is obtained:
CF3CF2CF2O(CF(CF3)CF2O)nCF(CF3)CONHCH2CH2CH2NHCH2CH2CH2N(CH3)2 (1)
example 2
Prepared according to WO/2009/118348, Mw1905g/mol, 40.0g of polyhexafluoropropylene oxide methyl ester (poly-HFPO-methyl ester) without oligomers having an Mw of less than 1000g/mol are charged into a glass reactor equipped with a thermometer, a mechanical stirrer and a vacuum distillation apparatus and are cooled to-10 ℃. 3.36g of N' - (3-aminopropyl) -N, N-dimethylpropane-1, 3-diamine are slowly added with stirring and by maintaining the temperature at-10 ℃ to 0 ℃. The mixture was then further stirred overnight. The resulting methanol was removed under vacuum and an amide similar to that described in formula (1) was obtained, but with a lower molecular weight.
Examples 3 to 9
Table 1 contains compounds that can be used as either reactant a or co-reactant C. It can be prepared analogously to the method described in example 1 or 2 by using the corresponding starting materials.
Table 2: synthesis of polyhexafluoropropyleneoxide amide (poly-HFPO-amide)
| Examples | Ri | Rii | Riii |
| 3 | H | -CH2CH2CH2- | -CH3 |
| 4 | -CH3 | -CH2CH2CH2- | -CH3 |
| 5 | H | -CH2CH2- | -CH2CH2NH2 |
| 6 | H | -CH2CH2- | -CH2CH2N(CH3)2 |
| 7 | H | -CH2CH2CH2- | -CH2CH2N(CH3)2 |
| 8 | -CH3 | -CH2CH2CH2- | -CH2CH2CH2N(CH3)2 |
| 9 | H | -CH2CH2- | -CH2CH2CH2N(CH3)2 |
Example 10
Prepared according to WO/2009/118348, Mw1947g/mol, 58.41g of polyhexafluoropropylene oxide methyl ester (poly-HFPO-methyl ester) without oligomers having a Mw of less than 1000g/mol were charged into a glass reactor equipped with a thermometer, a mechanical stirrer and a vacuum distillation apparatus and cooled to-10 ℃. A mixture of 3.20g of N' - (3-aminopropyl) -N, N-dimethylpropane-1, 3-diamine and 0.89g of 3-amino-1-methylaminopropane was slowly added with stirring and by maintaining the temperature at-10 ℃ to 0 ℃. The mixture was then further stirred overnight. The resulting methanol is removed under vacuum and a mixture of compounds of formulae (10a) and (10b) is obtained in a ratio of 2: 1:
CF3CF2CF2O(CF(CF3)CF2O)nCF(CF3)CONHCH2CH2CH2NHCH2CH2CH2N(CH3)2
(10a)
CF3CF2CF2O(CF(CF3)CF2O)nCF(CF3)CONHCH2CH2CH2NH(CH3)
(10b)
examples 11 to 26
Table 2 below contains a mixture of reactant a and co-reactant C. It can be prepared similarly to the method described in example 10 by using the corresponding starting materials. It can also be obtained by mixing the single components prepared by the method described in example 1 or 2.
Table 2: synthesis of a mixture of polyhexafluoropropyleneoxide amides (poly-HFPO-amides)
| Examples | x | y | Amine A | Amine B |
| 11 | 3 | 1 | H2NCH2CH2CH2NHCH2CH2CH2N(CH3)2 | H2NCH2CH2CH2NH(CH3) |
| 12 | 1.7 | 1 | Same as above | Same as above |
| 13 | 3 | 1 | Same as above | H2NCH2CH2NHCH2CH2NH2 |
| 14 | 2 | 1 | Same as above | Same as above |
| 15 | 2 | 1 | H2NCH2CH2NHCH2CH2N(CH3)2 | H2NCH2CH2CH2NH(CH3) |
| 16 | 1.5 | 1 | Same as above | Same as above |
| 17 | 3 | 1 | Same as above | Same as above |
| 18 | 2 | 1 | H2NCH2CH2CH2NHCH2CH2N(CH3)2 | Same as above |
| 19 | 3 | 1 | Same as above | Same as above |
| 20 | 2 | 1 | H2NCH2CH2NHCH2CH2CH2N(CH3)2 | Same as above |
| 21 | 3 | 1 | Same as above | Same as above |
| 22 | 1.7 | 1 | Same as above | H2NCH2CH2NHCH2CH2NH2 |
| 23 | 2 | 1 | Same as above | Same as above |
| 24 | 3 | 1 | Same as above | Same as above |
| 25 | 4 | 1 | H2NCH2CH2CH2NHCH2CH2CH2N(CH3)2 | Same as above |
| 26 | 4 | 1 | Same as above | H2NCH2CH2CH2NH(CH3) |
Example 27
62.0g of the reaction product from example 10 are diluted with 70g of tert-butyl methyl ether (TBME). 6.4g Desmodur N3300 (from BAYER, polyfunctionalized isocyanate resin based on hexamethylene diisocyanate; eq.wt.. 197) were then added and the polycondensation reaction and postcrosslinking reaction were carried out at 20-40 ℃. After completion of the reaction, the TBME phase was withdrawn and the polymer phase was washed a second time with 70g TBME. After removal of the TBME phase, 1.0g of acetic acid was added. The remaining TBME is then distilled off under reduced pressure (400 to 100 mbar/. about.50-60 ℃). During the distillation, 102g of propylene glycol were added. Then 0.8g of a second portion of acetic acid and finally 228g of water were slowly added. The mixture was stirred for an additional 1h until homogenization was complete. The pH was then adjusted to 4-5 using acetic acid. The resulting polymer dispersions can be used directly for the surface treatment of textile fibers and leather, especially on paper or cardboard. In the case of paper, for example, it can be applied by spreading, dipping, coating or size pressing of the paper that has been formed. Another method for paper is wet end application, which is an application in pulp slurry. In all examples, the substrates treated with the described compositions exhibit excellent lipid and oil release properties.
Examples 28 to 78
The following table 3 contains compositions prepared similarly to the method described in claim 27 by using the corresponding starting materials.
| Examples | Poly-HFPO-amides | Isocyanates |
| 28 | Example 11 | DESMODURTM N3300 |
| 29 | Example 11 | DESMODURTM N3200 |
| 30 | Example 11 | DESMODURTM N100 |
| 31 | Example 12 | DESMODURTM N3300 |
| 32 | Example 12 | DESMODURTM N3200 |
| 33 | Example 13 | DESMODURTM N3400 |
| 34 | Example 14 | DESMODURTM N3400 |
| 35 | Example 14 | DESMODURTM N3600 |
| 36 | Example 15 | DESMODURTM N3200 |
| 37 | Example 15 | DESMODURTM N3300 |
| 38 | Example 16 | DESMODURTM N3600 |
| 39 | Example 16 | DESMODURTM N3300 |
| 40 | Example 16 | DESMODURTM N3200 |
| 41 | Example 17 | DESMODURTM N3300 |
| 42 | Example 17 | DESMODURTM N3600 |
| 43 | Example 18 | DESMODURTM N3300 |
| 44 | Example 18 | DESMODURTM N3200 |
| 45 | Example 19 | DESMODURTM N3300 |
| 46 | Example 19 | DESMODURTM N3200 |
| 47 | Example 20 | DESMODURTM N3600 |
| 48 | Example 20 | DESMODURTM N3300 |
| 49 | Example 21 | DESMODURTM N3600 |
| 50 | Example 21 | DESMODURTM N3200 |
| 51 | Example 21 | DESMODURTM N3300 |
| 52 | Example 22 | DESMODURTM N3300 |
| 53 | Example 22 | DESMODURTM N3600 |
| 54 | Example 23 | DESMODURTM N3200 |
| 55 | Example 24 | DESMODURTM N3300 |
| 56 | Example 24 | DESMODURTM N3200 |
| 57 | Example 25 | DESMODURTM N3300 |
| 58 | Example 26 | DESMODURTM N3300 |
| 59 | Example 2 | DESMODURTM N3300 |
| 60 | Example 2 | DESMODURTM N3200 |
| 61 | Example 2 | DESMODURTM N3600 |
| 62 | Example 2 | DESMODURTM N100 |
| 63 | Example 3 | DESMODURTM N3600 |
| 64 | Example 3 | DESMODURTM N3300 |
| 65 | Example 3 | DESMODURTM N3400 |
| 66 | Example 4 | DESMODURTM N3300 |
| 67 | Example 4 | DESMODURTM N100 |
| 68 | Example 6 | DESMODURTM N3300 |
| 69 | Example 6 | DESMODURTM N3300 |
| 70 | Example 7 | DESMODURTM N3200 |
| 71 | Example 7 | DESMODURTM N3400 |
| 72 | Example 7 | DESMODURTM N3600 |
| 73 | Example 7 | DESMODURTM N100 |
| 74 | Example 8 | DESMODURTM N3300 |
| 75 | Example 8 | DESMODURTM N3300 |
| 76 | Example 9 | DESMODURTM N3300 |
| 77 | Example 9 | DESMODURTM N3200 |
| 78 | Example 9 | DESMODURTM N3600 |
Comparative example C1:
this example shows a fluorochemical composition as prepared in example 1 or 2 but which does not contain cationic groups when reacted with a polyfunctional isocyanate.
200.0g of the reaction product from example 3 are diluted with 200g of tert-butyl methyl ether (TBME). Then 21.1g Desmodur N3300 (from BAYER, poly-functional isocyanate resin based on hexamethylene diisocyanate; eq.wt.. 197) was added and the polycondensation reaction and the postcrosslinking reaction were carried out at 20 to 40 ℃. After completion of the reaction, the TBME phase was withdrawn and the polymer phase was washed a second time with 70g TBME. After removal of the TBME phase, 1.0g of acetic acid was added. The remaining TBME is then distilled off under reduced pressure (400 to 100 mbar/. about.50-60 ℃). During distillation, 102g of propylene glycol was added, but the resulting fluoride compound was insoluble and non-dispersible in propylene glycol or propylene glycol/water mixtures or other glycols or other glycol/water mixtures listed above.
Dispersibility in the glycol or glycol/water mixture is critical for use on the substrates listed above.
Table 4 shows compositions prepared similarly to the method described in comparative example C1 by using poly-HFPO-amide derived from examples 3,4, so the resulting fluorochemical composition also did not contain cationic groups. These compositions are therefore insoluble or dispersible in the diol or diol/water mixture used.
| Examples | Poly-HFPO-amides | Isocyanates | Solvent(s) |
| C2 | Example 4 | DESMODURTM N3300 | Propylene glycol |
| C3 | Example 5 | DESMODURTM N3300 | Propylene glycol/water (1:2) |
| C4 | Example 3 | DESMODURTM N3300 | Diethylene glycol/water (1:1) |
| C5 | Example 3 | DESMODURTM N3200 | Propylene glycol/water (1:2) |
| C6 | Example 5 | DESMODURTM N3200 | Propylene glycol |
| C7 | Example 4 | DESMODURTM N3300 | Propylene glycol/water (1:2) |
| C8 | Example 4 | DESMODURTM N3200 | Propylene glycol/water (1:1) |
| C9 | Example 4 | DESMODURTM N3200 | Diethylene glycol |
Claims (19)
1. Fluorochemical composition comprising a dispersion or solution of a fluorinated compound wherein said fluorinated compound comprises the reaction product of at least two reactants a and B wherein reactant a is a compound of formula (I);
Rf-O-(CF(CF3)CF2O)mCF(CF3)-X-Y-Z (I)
wherein
RfIs a perfluorinated alkyl group, and is a fluorinated alkyl group,
m is from 3 to 25;
x is a carbonyl group or CH2；
Y is a chemical bond or an organic divalent or trivalent linking group having a functional or difunctional isocyanate-reactive group;
z is an organic group having at least one cationic group,
the reactant B is a multifunctional isocyanate or a mixture thereof
And optionally one or more isocyanate-reactive coreactants C.
2. Fluorochemical composition according to claim 1 wherein a is a mixture of compounds of formula (I) wherein m is from 4 to 22 and has an average molecular weight of from 750 to 4000 g/mol.
3. Fluorochemical composition according to claim 1 and/or 2 wherein reactant a further contains 0 to 10% by weight, more preferably 0 to 5% by weight, even more preferably 0 to 1% by weight, especially preferably 0 to 0.1% by weight of a compound having a molecular weight of less than 750g/mol, said% by weight being based on the total weight of reactant a.
4. Fluorochemical composition according to at least one of the preceding claims wherein reactant a can be a compound of formula (I) wherein Z is a linking group having at least one cationic group comprising a tertiary amine, N-oxide or ammonium group; n-oxide or ammonium groups, which are also obtainable by treatment of the tertiary amine groups with suitable reactants after the reaction between reactants a and B.
5. Fluorochemical composition according to at least one of the preceding claims wherein reagent a is a compound of formula (II):
Rf-O-(CF(CF3)CF2O)mCF(CF3)-CON(R1)-R2-NH-R3-N(R4)2 (II)
wherein
RfAnd m is as defined above for all of its preferred embodiments,
R1is hydrogen or an alkyl group of for example 1 to 4 carbon atoms,
R2and R3Independently an alkylene group of 1 to 15 carbon atoms, and
R4is an alkyl group of 1 to 4 carbon atoms.
6. Fluorochemical composition according to at least one of the preceding claims wherein said polyfunctional isocyanate compound B can be aliphatic or aromatic and is a non-fluorinated compound having a molecular weight not exceeding 1500 g/mol.
7. Fluorochemical composition according to at least one of the preceding claims wherein said reactant B is an isocyanate containing an internal isocyanate-derived moiety such as a biuret containing tri-isocyanate.
8. Fluorochemical composition according to at least one of the preceding claims wherein said coreactant C is a compound of formula (III)
(Rf-O-(CF(CF3)CF2O)mCF(CF3)-X)n-Q (III)
Wherein
RfAnd m is as defined above,
x is a carbonyl group, and X is a carbonyl group,
q is an organic group or an organic divalent or trivalent linking group having a functional or difunctional isocyanate-reactive group;
n is 1 or 2.
9. Fluorochemical composition according to at least one of the preceding claims wherein the co-reactant C is a compound of formula (III) wherein Q is an organic group containing one or two isocyanate reactive groups comprising thiol, hydroxyl and amino groups, more preferably amino groups.
10. Fluorochemical composition according to at least one of the preceding claims wherein co-reactant C is a compound of formula (IV):
(Rf-O-(CF(CF3)CF2O)mCF(CF3)-CON(R1)-R2)n-N(R5)H (IV)
wherein R isf、R1、R2M and n are as defined above for all preferred embodiments, R5Is (if n is 1) hydrogen or an alkyl group of 1 to 4 carbon atoms.
11. Fluorochemical composition according to at least one of the preceding claims wherein the total stoichiometric amount of isocyanate reactive groups of reactant a and co-reactant C is from a factor of 0.9 to 1 of the total stoichiometric amount of isocyanate groups of reactant B.
12. Process for the production of a fluorochemical composition according to at least one of claims 1 to 11 characterized in that a reactant B is reacted with said reactant a and optionally a co-reactant C at a temperature in the range of from 0 to 120 ℃ and a pressure between atmospheric pressure and 2 bar.
13. The process according to claim 12, wherein the reaction is carried out in an aprotic solvent or a mixture of aprotic solvents.
14. Dispersion or solution comprising 0.5 to 40% by weight of a fluorochemical composition according to at least one of claims 1 to 11.
15. The dispersion or solution of claim 14, comprising an additional co-solvent.
16. The dispersion or solution of claim 15, wherein the co-solvent is water soluble or at least partially water soluble, more preferably the co-solvent has at least one hydroxyl group, even more preferably the co-solvent is a glycol.
17. Paper treated with a solution or dispersion comprising a fluorochemical composition according to at least one of claims 1 to 11.
18. Use of a fluorochemical composition according to at least one of claims 1 to 11 for the surface treatment of a fibrous material to render it oil and water repellent.
19. Use of a fluorochemical composition according to claim 18 for already formed paper such as size press and/or coating or wet end applications.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP11010033.6 | 2011-12-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| HK1196389A true HK1196389A (en) | 2014-12-12 |
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