CN1205692A - Fluorinated melt additives for thermoplastic polymers - Google Patents

Abstract

Fluorinated imides useful for imparting repellency of low surface tension fluids to thermoplastic polymers of formulae wherein R1 is F(CF2)x-(CH2)m, or F(CF2)xSO2N(R5) (CH2)p wherein x is from about 4 to about 20, m is from about 2 to about 6, p is from 1 to about 12, and R5 is an alkyl radical of from 1 to about 4 carbons; R2 is a linear, branched or cyclic alkylene or poly(oxyalkylene) hydrocarbon group having from about 2 to about 15 carbons; R3 is selected from the group consisting of F(CF2)x-(CH2)m, F(CF2)x-(CH2)m-OC(O)-(CH2)n, and F(CF2)xSO2N(R5)(CH2)pOC(O)(CH2)n wherein x is from about 4 to about 20, m is from about 2 to about 6, n is about 2 to about 12, p is from 1 to about 12, and R5 is an alkyl radical of from 1 to about 4 carbons; R4 is an alkyl or alkenyl group of from about 4 to about 20 carbons, and R6 is a linear or branched alkyl having from about 4 to about 20 carbons.

Description

The fluorinated melt additives of thermoplastic polymer

Invention field

The present invention relates to some new xenon fluoride imines and by in polymkeric substance, adding this class imide, thereby give thermoplastic polymer, especially fiber, fabric, non-woven, film and moulded parts be with the method to the repellency of low surface tension fluids of excellence.

Background of invention

Thermoplastic polymer fibers is handled through fluorochemicals commonly used, in the hope of influencing the surface characteristic of this fiber, for example improves repellency or gives stain resistance or dried pollution resistance.The most frequent is by spraying, pad or foaming, to use the fluorine-containing chemical dispersion liquid partly to the fabric of being made by these fibers, then by a drying step dehydration.

For example, known have a kind of method, can be used for by use partly from n be about 3～14 and m be 1～3 general formula C _nF _2n+1(CH ₂) _mThe perfluoroalkyl fatty alcohol of OH and contain 3～30 carbon and can contain other substituent monobasic or the aqueous dispersions of the various fluoroester of polycarboxylic acid deutero-, and make a kind of fabric fibre obtain dried pollution resistance and uninflammability conduction feature.These fluoroesters among others, also comprise the stearic acid perfluoroalkyl ester of " ZONYL " FTS of a kind of being equivalent to.

People are fully recognized that, add a kind of fluorine-containing chemical additive if this topical application replaces before this fiber is extruded in polymer melt, just can simplify the manufacturing process of thermoplastic polymer fibers, and can eliminate significant capital investment.Have difficulties aspect suitably stable and the effective fluorine-containing chemical additive seeking always.

Thermoplastic polymer among others, also comprises polyolefine, polyester, polymeric amide and polyacrylic ester.Polyolefine, polypropylene especially, through being usually used in the Disposable, nonwoven protective clothes, especially in medical/surgical field, some reasons are polyolefinic intrinsic repellency.Yet polyolefine is not intrinsic good repellents than low surface tension fluids such as blood and Virahol for other that often runs in the medical field.In order to remedy this defective, can use the fluorine-containing chemical dispersion liquid partly to these fabrics.

To being suitable for mixing the requirement of the additive in the polyolefin melt, repel the ability of low surface tension fluids during except that this additive lower concentration, also comprise the low volatility of gratifying thermostability and anti-processing conditions.Be preferably, this compound can be moved to the surface of fiber, reach the needed amount of additives of enough repellencies thereby be reduced to greatest extent.Though this migration tends to strengthen because of the post-heating of extruding of this fiber, be more preferably this migration and need not this heating steps and also can take place.Ambulant this requirement in the polymer fiber is tended to limit this fluorine-containing chemical bulk of molecule again, and effectively the fluorine-containing chemical additive of high-molecular weight polymer is got rid of outside considering.

The universal that fluorine-containing chemical additive is incorporated in the polyolefin fiber melt is known, but has limited the application of this notion in the difficulty aspect the effective additive that seek to be suitable for.Past is aim to improve this polyolefinic other performance for many effort of assessing this type of fluorine-containing chemical additive and doing always, and does not have to disclose the method for its improvement to the repellency of low surface tension fluids.

Nonwoven composite structure is known, partly form by two or more melt extrusion non-woven layers, wherein one deck comprises a kind of additive at least, and the feasible result who need not the shaping aftertreatment of any kind of and move to surperficial advantage owing to this additive just can give this surface at least a feature that is different from the surface characteristic of this polymkeric substance own.This example that contains additive layer comprises with the commercial additive agent modified polyacrylic polymer of fluorine-containing chemistry that gets, comprising above " ZONYL " FTS.

United States Patent (USP) 5,178,931 and United States Patent (USP) 5,178,932 disclose specific nonwoven laminate and the composite structure partly be made up of three melt extrusion non-woven layers respectively, wherein the second layer comprises a kind of shaping aftertreatment that need not any kind of and because additive just can be given the additive of scolding alcohol to the result of surperficial advantage migration, and in this case in the first layer and the 3rd layer at least one deck handled by a kind of medicament of topical application so that make its feature that certain change be arranged.This example that contains the second layer of additive comprises the commercial fluorine-containing chemical that gets, comprising " ZONYL " FTS.

The anti-soil polymer composition is known, and it is to prepare by the melt extrusion that has the non-polymer fluorine-containing chemical to be dispersed in the polymkeric substance.Used polymkeric substance comprises polypropylene, polyethylene, polymeric amide and polyester, and used fluorine-containing chemical is the full fluoroalkane ester of a kind of stearyl ester, especially " ZONYL " FTS.

Generally speaking, contain many examples of the polyolein fiber of the fluorine-containing chemical additive that mixes in melt stage though prior art discloses the surface characteristic of the fiber of extruding for a change, former work majority is for anti-contamination and painted or repellency.Disclose and given polyolefine fabric and adopted " ZONYL " FTS with those reference of scolding alcohol.Exist excellent repellency and the excellent product efficient so a kind of needs of realization at present to low surface tension fluids.Fluoric compound of the present invention has satisfied this needs.

Summary of the invention

The present invention includes the compound of a kind of formula A:

In the formula

R ₁Be F (CF ₂) _x-(CH ₂) _mOr F (CF ₂) _x-SO ₂N (R ₅)-(CH ₂) _p, wherein X is that about 4-is about 20, and m is that about 2-is about 6, and P is that 1-is about 12, R ₅It is the alkyl of about 4 carbon atoms of 1-;

R ₂Be straight chain, branching or cyclic alkylidene group or poly-(oxyalkylene) alkyl that contains about 15 carbon atoms of the 2-that has an appointment.

The present invention further comprises the compound of a kind of formula B

R in the formula ₁Definition as mentioned above, R ₆Be straight chain or the branched-alkyl that contains about 20 carbon atoms of the 4-that has an appointment.

The present invention further comprises the compound of a kind of formula C:

R in the formula ₃Be selected from F (CF ₂) _x-(CH ₂) _m, F (CF ₂) _x-(CH ₂) _m-OC (O)-(CH ₂) _nOr F (CF ₂) _x-SO ₂N (R ₅)-(CH ₂) _pOC (O)-(CH ₂) _n, wherein X is that about 4-is about 20, and m is that about 2-is about 6, and n is that about 2-is about 12, and p is that 1-is about 12, R ₅It is the alkyl of about 4 carbon atoms of 1-.

The present invention further comprises the compound of a kind of formula D:

R in the formula ₃Definition and top to R among the formula C ₃Definition identical.

The present invention further comprises the compound of a kind of formula E: R in the formula ₃Definition and top to R among the formula C ₃Definition identical, R ₄Be the alkyl or the alkenyl of about 20 carbon atoms of about 4-.

The present invention further comprises a kind of composition, wherein comprises at least a thermoplastic polymer and at least a compound of formula A, formula B, formula C, formula D or formula E as defined above that is selected from.

The present invention further comprises a kind of long filament of extruding, fiber, film, moulded product and non-woven webs or fabric, respectively comprises at least a thermoplastic polymer and at least a compound of formula A, formula B, formula C, formula D or formula E as defined above that is selected from.

The present invention comprises that further a kind of thermoplastic polymer articles that makes has method to the excellent repellency of low surface tension fluids, this method is included in and forms a kind of mixture before goods are shaped, the compound or its mixture that wherein contain a kind of as defined above formula A, B, C, D or the E of a kind of polymkeric substance and significant quantity, and this mixture melt extruded.This method is particularly suitable for being used for giving polyolefin articles with the low surface tension fluids repellency, and no matter adopts or be not adopted as and promote this additive to move and extrude after-heating step to what these goods carried out to product surface, can make in this way.Here used " goods " comprise long filament, fiber, non-woven webs or fabric, film and moulded parts.

Detailed description of the Invention is to the excellent repellency of low surface tension fluids, can form a kind of mixture by in a kind of polymkeric substance of goods shaping forward direction, adding some monomer xenon fluoride group with imine moiety, and melt extrude formed mixture, give thermoplastic polymer articles, for example long filament, fiber, non-woven webs or fabric, film and moulded parts.

" low surface tension fluids " this term is used to refer to surface tension less than 50 dyne/cm (50 * 10 at this ^-7Newton meter) fluid.This type of fluidic example comprises alcohols, oils and some body fluid such as blood.

Compound of the present invention comprises following xenon fluoride group with imine moiety: the formula A that respectively organizes:

Formula B Formula C

Formula D Formula E In the formula

R ₁Be F (CF ₂) _x-(CH ₂) _mOr F (CF ₂) _x-SO ₂N (R ₅)-(CH ₂) _p, wherein X is that about 4-is about 20, and m is that about 2-is about 6, and P is that 1-is about 12, R ₅It is the alkyl of about 4 carbon atoms of 1-;

R ₂Be straight chain, branching or cyclic alkylidene group or poly-(oxyalkylene) alkyl that contains about 15 carbon atoms of the 2-that has an appointment.

R ₃Be selected from F (CF ₂) _x-(CH ₂) _m, F (CF ₂) _x-(CH ₂) _m-OC (O)-(CH ₂) _nOr F (CF ₂) _x-SO ₂N (R ₅)-(CH ₂) _pOC (O)-(CH ₂) _n, wherein X is that about 4-is about 20, and m is that about 2-is about 6, and n is that about 2-is about 12, and p is that 1-is about 12, R ₅It is the alkyl of about 4 carbon atoms of 1-.

R ₄Be the alkyl or the alkenyl of about 20 carbon atoms of about 4-; And

R ₆Be straight chain or the branched-alkyl that contains about 20 carbon atoms of the 4-that has an appointment.

In compound of the present invention, R in general formula A and B ₁Definition in and in general formula C, D and E R ₃Definition in, the value of X is represented the length of fluorocarbons chain portion, its mean value is preferably about 7-about 10.Particularly preferably be following a kind of composition, the R among its formula of A and the B ₁Be F (CF ₂) _x-(CH ₂) _m, the R among general formula C, D and the E ₃Be F (CF ₂) _x-(CH ₂) _m-OC (O)-(CH ₂) _m, chain length distribution and weight percentage is as follows:

X=6 or following 0-10% (weight)

X=8 45-75% (weight)

X=10 20-40% (weight)

X=12 1-20% (weight)

X=14 or this range of compositions of above 0-5% (weight) when m=2, abbreviate Telomer BN as hereinafter.Formula R _fR among the-OH _fThis definition abbreviate Telomer BN alcohol as.

Have the whole bag of tricks can be used for preparing above compound, and method of the present invention is not limited to a certain specific preparation method.The personnel that are familiar with this gate technique follow the following method that is similar to, and just can easily prepare the compound in these several groups.

Formula A compound by following example 1-13 explanation is to adopt the preparation of 3 step procedure.At first, a kind of diamines and 2 normal trimellitic acid 1,2-anhydrides are reacted in the acetate that refluxes.At room temperature isolate product with vacuum filtration process.Then, make the reaction of trimellitic acid 1,2-anhydride/two amine adducts and thionyl chloride change into the intermediate acyl chlorides, react with Teolmer BN alcohol on the spot subsequently, generate fluoroester.

Formula B compound by following example 14-15 explanation is to adopt the preparation of 2 step procedure.At first, a kind of monoamine and 1 normal trimellitic acid 1,2-anhydride are reacted in the acetate that refluxes.After the separation, trimellitic acid 1,2-anhydride/monoamine adducts is only reacted at about 140 ℃ with Teolmer BN alcohol, generate fluoroester.

By the formula C of following example 16-21 explanation and formula D compound is by 1 normal 1,2,4,5-pyromellitic acid dianhydride (PMDA) or BPDA (BPDA) and 2 normal amine reaction and preparation in the acetate that refluxes.Double imide prepares by making 3-perfluoroalkyl propyl group amine and PMDA and BPDA carry out condensation.An alternative method of preparation formula C and formula D compound is at first to make a seed amino acid and PMDA and BPDA reaction, then, in second step, make the reaction of dianhydride/amino acid adducts and thionyl chloride change into corresponding acyl chlorides, react with TeolmerBN alcohol on the spot subsequently, generate fluoroester.

Formula E compound by following example 22-26 explanation is to adopt the preparation of 2 step reaction, and wherein, alkyl or alkenyl succinic anhydrides are at first reacted in the acetate that refluxes with a seed amino acid.The adducts of separating by 140 ℃ directly and Teolmer BN alcohol carry out esterification and change into ester.

Compound of the present invention is granular by it is added to, in the polymkeric substance of sheet, Powdered or other appropriate form and with this mixture backing, stirring or cooperation, and mix with thermoplastic polymer, obtains a kind of uniform mixture, carries out melt extruded then.Substituting can also be added compound of the present invention in a kind of polymer melt to, forms a kind of mixture, carries out melt extruded then.Thermoplastic polymer is a kind of polyolefine, polyester, polymeric amide or polyacrylic ester.Thermoplastic polymer better is a kind of polyolefine, multiple polyolefinic mixture, polyolefin copolymer, the mixture of multiple polyolefin copolymer, or the mixture of at least a polyolefine and at least a polyolefin copolymer.Thermoplastic polymer is more preferably a kind of polyolefin polymer or multipolymer, and wherein polymer unit or copolymer unit are ethene, propylene or butylene or its mixture.Therefore, polyolefine is polyethylene, polypropylene, polybutene or its blend or multipolymer.

Add the fluoric compound quantity in the thermoplastic polymer to, be preferably between 0.1 of this polymer weight～about 5%.The above quantity of this scope is operable, but is expensive for the benefit of being received, and is unnecessary.When being lower than this scope, for reality was used, its benefit was too little.Make this blend fusion then, be squeezed into long filament, fiber, non-woven webs or fabric, film or moulded parts with currently known methods.This fiber, long filament, from the supatex fabric of its preparation or the fluorine content of fibrous reticulum, film or moulded parts, be about 200 μ g/g～about 25,000 μ g/g.

Form various types of supatex fabric with extruding.Specifically, forming a kind of mean diameter with extruding is about 0.1～10 micron, the melt-blown non-woven fibrous reticulum of the continuous and random deposition primitive fiber in about 3～5 micrometer ranges more fortunately.This melt extruded is to be undertaken by the resin flow of mould with the every hole at least 0.1 of per minute～5 gram, these primitive fibers randomly are deposited on a kind of mobile supporter and form this fibrous reticulum.

In above-mentioned melt-blown process, in polymkeric substance and a kind of compound feeding to an extrusion machine of the present invention, this make it fusion and by one contain one row small orifice mould.When this polymkeric substance during from the ejection of this mould, make it to contact two strands of boundling high velocity, hot airs streams, the latter makes this polymkeric substance refinement, and becoming diameter is one air-flow of 0.1～10 micron fine discontinuous fibre.Available polymkeric substance throughput or flow range are the every hole of per minute 0.1～5 gram.Typical gas flow scope is per minute 2.5～100 pound (1.72 * 10 of a pneumatic outlet area per square inch ⁵～6.89 * 10 ⁵Pa).The air themperature scope is about 400 (204 ℃)～750 (399 ℃).Then, cooling air makes this fiber quenching, and (the online deposition of 15.2～30.5cm) diaphragms of locating becomes a kind of random interlacing fibrous reticulum to make them place 6～12 inches in this strand fibrous airstream the place ahead at one.

Melt-blown process has more detailed description: V.A.Wente in following article, " superfine thermoplastic fibre ", Industrial and Engineering Chemistry, Vol.48 (8), pp 1342-1346 (1956); R.R.Buntin and D.T.Lohkamp, " melt and spray the single stage method fibrous reticulum technology of a novel non-woven product ", Journal of the Technical Association ofthe Pulp and Paper Industry, Vol.56 (4), pp 74-77 (1973); And the United States Patent (USP) 3,972,759 of R.R.Buntin.The disclosure of these data is all classified this paper reference as.

The fibroreticulate peculiar property of being made up of the random assortment of fine crossed fiber of melt-blown non-woven comprises very large surface-area, very little aperture, medium tenacity and light weight structure.These character are particularly suitable for as the such application of medical textile this non-woven webs, and wherein, barrier property and ventilation property and drape are important.Following example further specifies the method that is used for test materials is carried out blending and melt extruded.

Extrusion process also is used for forming polymeric film.In film is used, a kind of film-forming polymer and compound of the present invention are together, when carrying by extrusion machine by one or more rotary screws, be forced to then when extruding by a slit or flat plate mold, be melted simultaneously and mix, wherein, make this film quenching with the known various technology of personnel of being familiar with this gate technique.This film randomly before quenching, by making this film at drawing by high temperature or stent, is orientated.

Moulded parts is by producing being pressed into or being expelled to from the molten polymer that contains The compounds of this invention of melt extrusion machine as described above in the mould that a meeting makes this polymer cure.That typical melt forming technology comprises is injection-molded, blowing, compression molding and extrusion molding, and is that to be familiar with the personnel of this gate technique well-known.This polymeric additive makes this moulded parts demoulding then, and randomly heat-treats, so that can be moved to the surface of these goods.

Can carry out an optional heating or annealing steps, but not require so.The goods that polymer melt is extruded fiber, long filament, non-woven webs or the fabric, film or the molding that form are heated to about 25 ℃～about 150 ℃ temperature.This heating can improve this fluorine-containing chemical additive in some cases and give the validity of scolding alcohol.

Compound of the present invention and composition can be used for various long filaments, fiber, non-woven webs or fabric, film and moulded parts.Example comprises the fiber that uses in fabric and the carpet, the moulded plastics articles of used supatex fabric and a lot of types in the protective clothing that uses in the medical/surgical field.Method of the present invention can be used for giving various thermoplastic polymer articles for example long filament, fiber, non-woven webs or fabric, film and moulded parts with the low surface tension fluids repellency.

Example 1

Step 1

Add 111g (1.48 moles) 1 toward being equipped with condenser and being equipped with in 5 liters of flasks of 2250ml Glacial acetic acid with about 1 hour time, 2-diaminopropanes (Aldrich company, 99%), then add 616g (3.06 moles) benzoic anhydride (Amoco company, at least 95.5%) and 375ml acetate partially again.Heating at room temperature leached reactive material after 14 hours under refluxing.Filter cake with the acetate washing, washes with water, till not containing acid earlier again.In 115 ℃ of vacuum drying ovens, obtain a kind of white solid after the drying, heavy 591g (93.4%); 323 ℃ of fusing points (DSC method).

Step 2 and 3

Advance QC and be connected to by drying tube in the 5 liters of four-hole boiling flasks of exsiccant of the condenser on the caustic scrubber to add 254g (0.6 mole) trimellitic acid 1,2-anhydride/1 adducts (step 1), 2500ml ethylene dichloride, 1.0g (0.004 mole) benzyltriethylammonium chloride and 87ml (1.19 moles) thionyl chloride successively toward being equipped with band nitrogen.Reflux after 28 hours mixture become transparent.In this yellow transparent solution, add the anhydrous TelomerBN alcohol of 660g (1.25 moles) at 60 ℃.After reactant is cooled to room temperature, with 1 hour dropping 140g (1.38 moles) triethylamine.Temperature rises to 70 ℃, keeps 1 hour.Observe some foam that forms owing to reactant is thick.At room temperature leach solid product, use washed with isopropyl alcohol, pulp in 60 ℃ of Virahols is filtered, and uses washed with isopropyl alcohol, washes with water at last.In 50 ℃ of vacuum drying ovens, after the drying, obtain 636g (74%) white solid; 148 ℃ of fusing points (DSC method).The product that makes is a kind of compound of formula A, wherein R ₂Equal

R ₁Equal Telomer BN alcohol.

Example 2-13

The compound of example 2-13 is with the program of example 1 and according to following listed R ₂Requirement with the preparation of suitable amine.Prepared compound is to have following R ₂The formula A compound of definition and fusing point, its R ₁Equal Telomer BN.

MP (℃, the DSC method)

Example 2 R ₂=(CH ₂) ₃141

Example 3 R ₂=(CH ₂) ₄151

Example 4 R ₂=(CH ₂) ₆135

Example 5 R ₂=(CH ₂) ₈126

Example 6 R ₂=(CH ₂) ₁₂123

Example 7

Example 8

Example 9 R ₂=C ₆H ₁₀-CH ₂-C ₆H ₁₀, 172

C ₆H ₁₀=cyclohexylidene

Example 10 R ₂=isophorone 115

Example 11 R ₂=(CH ₂-C (CH ₃) ₂-CH ₂) 164

Example 12 R ₂=(CH ₂) ₃-O-(CH ₂) ₄-O-(CH ₂) ₃102

Example 13 R ₂=1,3-encircles dihexyl 112

Example 14

Step 1

Program with example 1 step 1 has prepared trimellitic acid 1,2-anhydride/n-Laurylamine adducts, and different is to make 1 normal trimellitic acid 1,2-anhydride and n-Laurylamine reaction.

Step 2

Add 50.0g (0.125 mole) trimellitic acid 1,2-anhydride/n-Laurylamine adducts in the 250ml four-hole boiling flask of the dean stark trap that is equipped with mechanical stirrer, temperature regulator, band condenser and nitrogen inlet pipe and outlet pipe and (derive from step 1) and 74.0g (0.14 mole) TeolmerBN alcohol.This mixture heating up to fusion, is added 0.4g (0.0034 mole) phosphorous acid and 0.16g (0.0026 mole) boric acid then.With mixture heating up to 140 ℃, and kept about 5 days, till whole pure and mild acid-responss finish, analyze according to gas-chromatography and C-13 NMR respectively and determine.The compound that makes is R wherein ₆Be (CH ₂) ₁₁-CH ₃And R ₁It is the compound of the formula B of Teolmer BN.Output after the separation is 96.3g (yield 84.5%); Fluorine content: measured value 38.0%, calculated value 41.8%; 41.3 ℃ of fusing points (DSC method).

Example 15

The program preparation of example 15 usefulness examples 14, different is to make trimellitic acid 1,2-anhydride and the reaction of octadecane amine.Prepared is R wherein ₆Be (CH ₂) ₁₇-CH ₃And R ₁Be the compound of the formula B of Teolmer BN, the fusing point that records with the DSC method is 62.1 ℃.

Example 16

With 5.45g (0.025 mole) 1,2,4,5-pyromellitic acid dianhydride (PMDA) and 29.0g (0.06 mole) 3-(the perfluoroalkyl)-mixture of propylamine in the 150ml Glacial acetic acid be heated overnight under refluxing in being equipped with the 250ml flask of condenser.At room temperature leach isolated solid,, wash with water again till do not contain acid with acetate washing.In 100 ℃ of vacuum drying ovens, obtain 29.1g (98.7%) white solid after the drying, fusing point 209-214 ℃ (DSC method).Prepared compound is the compound of formula C, R in the formula ₃Be (CH ₂) ₃-(CF ₂) _xF, wherein X=6-18 is identical with the definition of Teolmer BN.

Example 17

Step 1

In the 1 liter of flask that is equipped with condenser, add 500ml Glacial acetic acid, 43.6g (0.20 mole) pyromellitic anhydride and 56.2g (0.42 mole) 6-aminocaprolc acid (98%).Heating at room temperature leached reactive material after 14 hours under refluxing.Filter cake washs with acetate, washes with water then till do not contain acid.In 100 ℃ of vacuum drying ovens, after the drying, obtain 81.4g (91.6%) white solid, 250 ℃ of fusing points (DSC method).

Step 2

Advance QC and be connected to by drying tube in the 1 liter of four-hole boiling flask of exsiccant of the condenser on the caustic scrubber to add 13.3g (0.03 mole) 1 successively toward being equipped with band nitrogen, 2,4,5-pyromellitic anhydride/6-aminocaprolc acid adducts (step 1), 300ml ethylene dichloride, 0.06g (0.00026 mole) benzyltriethylammonium chloride and 4.3ml (0.059 mole) thionyl chloride.Reflux after 28 hours mixture become transparent.In this clear solution, add the anhydrous TelomerBN alcohol of 33.0g (0.06 mole) at 70 ℃.After reactant is cooled to 50 ℃, drip 6.7g (1.38 moles) triethylamine.Temperature rises to 65 ℃, keeps 1.5 hours.At room temperature leach solid product, with 1,2-ethylene dichloride and washed with isopropyl alcohol, pulp in 60 ℃ of Virahols is filtered, and uses washed with isopropyl alcohol, washes with water at last.In 100 ℃ of vacuum drying ovens, after the drying, obtain 32.3g (73.6%) white solid; Fluorine content: measured value 44.6%, calculated value 49.3%; 172 ℃ of fusing points (DSC method).The compound that makes is a kind of compound of formula C, R in the formula ₃Be (CH ₂) ₅-C (O)-O-(CH ₂) ₂-(CF ₂) _xF, X=6-8 wherein is with identical to the definition of Telomer BN.

Example 18-21

Example 18 and 19 formula C compound are by 1,2,4, and 5-pyromellitic acid dianhydride makes the intermediate product of generation prepare with the reaction of Telomer BN alcohol with 4-aminobutyric acid and Beta-alanine reaction respectively again.Adopt the program of example 17 during with above-mentioned starting raw material.Example 20, i.e. the compound of a kind of formula D, be by the program of top example 16 with reactant 3,4,3 ', 4 '-biphenyl tetracarboxylic dianhydride (BPDA) and 3-(perfluoroalkyl) propylamine prepare.Example 21, i.e. the compound of a kind of formula D, be program by example 17 by making the reaction of BPDA and 6-aminocaprolc acid, the intermediate product of generation is prepared with the reaction of Telomer BN alcohol.The R of prepared these compounds ₃Below listing in.In all cases, on behalf of Telomer BN, X all distribute.

M.p. (℃, the DSC method) example 18 R ₃=(CH ₂) ₃-C (O)-O-(CH ₂) ₂-(CF ₂) _xF 166 examples 19 R ₃=(CH ₂) ₂-C (O)-O-(CH ₂) ₂-(CF ₂) _xF 182 examples 20 R ₃=(CH ₂) ₃-(CF ₂) _xF 161 examples 21 R ₃=(CH ₂) ₅-C (O)-O-(CH ₂) ₂-(CF ₂) _xF 171

Example 22

Step 1

In being equipped with 1 liter of flask of condenser, with 46.8g (0.35 mole) 6-aminocaprolc acid and 96.1g (0.35 mole) 2-dodecylene-mixture of 1-base succinyl oxide (97%) in 500ml Glacial acetic acid heated overnight under refluxing.Reaction mixture after the cooling, leaches isolated solid with cold water dilution and in ice bath, with the acetate washing, washes with water till do not contain acid again.In 50 ℃ of vacuum drying ovens, obtain 120.0g (90.4%) white solid after the drying.

Step 2

Add 45.50g (0.12 mole) dodecenyl succinic anhydride/caproic acid adducts in the 250ml four-hole boiling flask of the dean stark trap that is equipped with mechanical stirrer, temperature regulator, band condenser and nitrogen inlet pipe and outlet pipe and (derive from step 1) and 65.8g (0.125 mole) Teolmer BN alcohol.This mixture heating up to fusion, is added 0.2g (0.0017 mole) phosphorous acid and 0.08g (0.0013 mole) boric acid then.With mixture heating up to 140 ℃, and kept about 2 days, till the acid-respons of whole alcohol finishes, analyze according to gas-chromatography and C-13NMR respectively and determine.Make formula E compound, R in the formula ₄=CH ₂CH=CH-(CH ₂) ₉H, R ₃=(CH ₂) ₅-C (O)-O-(CF ₂) _xF, wherein X is that Teolmer BN distributes.Output after the separation is 98.4g (yield 92.4%); Fluorine content: measured value 41.0%, calculated value 41.0%; 40.4 ℃ of fusing points (DSC method).

Example 23-26

Example 23-26 is with following appropriate reaction thing preparation by the program of top example 22; Example 23: with 2-dodecylene-1-base succinyl oxide and Beta-alanine, example 24: with 2-vaccenic acid-1-base succinyl oxide and 6-aminocaprolc acid, example 25: make 2-vaccenic acid-1-base succinyl oxide and Beta-alanine, example 26: with 2-octadecyl succinyl oxide and 6-aminocaprolc acid.Made the compound of formula E, R in the formula ₄And R ₃Be defined as follows.In all cases, on behalf of TeolmerBN, X all distribute.Example R ₄R ₃M.p. (℃, the DSC method)

23?CH ₂CH=CH-(CH ₂) ₉H，?(CH ₂) ₂-C(O)-O-(CF ₂) _xF 42．9

24?CH ₂CH=CH-(CH ₂) ₁₅H，(CH ₂) ₅-C(O)-O-(CF ₂) _xF 65．3

25?CH ₂CH=CH-(CH ₂) ₁₅H，(CH ₂) ₂-C(O)-O-(CF ₂) _xF 67．8

26?(CH ₂) ₁₈H， (CH ₂) ₅-C(O)-O-(CF ₂) _xF 83．0

Example 27

Step 1: the preparation of polymer blend

The fluorine-containing chemical additive that produces among the example 1-26 is with a kind of uniform mixture of polyolefine, by making its merging and this mixture backing being prepared in about 24 hours.Used polyolefine is Escorene PD3745G or PD3746G (Exxon Chemical Americas, P.O.Box3272, Texas, Houston city 77001) acrylic resin, and its melt flow rate (MFR) is respectively about 800 and 1000.Use the comparative example of the described compound of prior art " ZONYL " FTS to prepare in a similar manner.

Specifically, compound for example 1,10.7g the fine pulverization compound and 1 of example 1,889g Escorene PD3746G (Exxon Chemical Americas, P.O.Box3273, Texas, Houston city 77001) uniform mixture of polypropylene (melt flow rate (MFR) about 1000) is by making this mixture backing preparation in 24 hours.Fluorine concentration calculated value in this mixture is the 3300ppm fluorine.Actual fluorine concentration in the non-woven webs is the 2660ppm fluorine.

Step 2: meltblown fiber web is shaped

The melt-blown non-woven fibrous reticulum is from above mixture, melts and sprays testing apparatus with the polymer feed rate preparation of about 0.4 gram in the every hole of per minute with 6 inches (15cm).It is in 175～250 ℃ the extrusion machine of three sleeve heating zone that blend polymer is fed to temperature range.Die temperature is 200 ℃～260 ℃, and the air themperature at mould place does not wait from 200 ℃ to 270 ℃.The preceding splaying of mould is 0.060 inch (0.15cm), and primary air pressure is 2.6psi (17.9 * 10 ³Pa).Fibrous reticulum is to form on the rotary drum that has been coated with " teflon ", and is collected on the wind up roll with 30 feet per minute clocks (914cm/ minute) runnings, forms unit weight and be the fabric of 1.0 ounce per square yard (34 grams/square metre).

Step 3: repellency test

The oiliness of scolding of meltblown fiber web can be with the oil droplet test determination, with scolding oiliness grade (ORT) expression.According to this test method, with several by standard test fluid drips with the selected a series of hydrocarbon compositions of different surfaces tensile on matrix, and observe wetting situation.Can not make the moistening test(ing) liquid of stromal surface in 30 seconds, it scolds the highest grade of oiliness.Standard test liquid and corresponding ORT list in table 1.

Table 1

Scold oiliness (ORT) grade

The ORT test(ing) liquid is formed

1 “NUJOL”

2 65/35 " NUJOL "/n-hexadecanes ^*

3 n-hexadecanes

4 n-tetradecanes

5 n-dodecanes

6 n-decanes

7 octanes

8 normal heptanes

^*By volume mixture when 70 (21 ℃)

" NUJOL " is the trade mark of a kind of mineral oil of Plough company, and the proportion when its Saybolt viscosity is 360/390,60 (15 ℃) when 100 (380 ℃) is 0.880/0.900.

The repellency of meltblown fiber web can be with the isopropanol test determination, represents with the percentage Virahol.Resist the fibrous reticulum that 100% Virahol/0% aqueous solution (lowest surface tension fluid) penetrates after 1～2 minute and be defined as highest level 100.The fibrous reticulum of only having resisted 100% water/0% aqueous isopropanol after 1～2 minute is defined as minimum rank 0.The middle rank of every increase by 10 is corresponding to the solution of solution to 90% Virahol/10% water of 20% Virahol/80% water among the 20-90, and is as shown in table 2.A kind of Virahol repellency rank of given fabric did not make the wetting lowest surface tension fluid of this fabric (maximum % isopropanol) after 1～2 minute.

Table 2

The IPA grade

Grade % Virahol/% water (volume ratio)

100 100／0

90 90／10

80 80／20

70 70／30

60 60／40

50 50／50

40 40／60

30 30／70

20 20／80

10 10／90

Table 3,4,5 and 6 has summed up that the polypropylene melt-blown that contains example 1-26 compound is fibroreticulate scolds oiliness and Virahol repellency data.Comparative examples A is " ZONYL " FTS.Be listed in the polypropylene control sample in addition in the table, be labeled as the PP contrast.ORT scolds the oiliness test grade.%IPA is the percentage Virahol.

Table 3

The fibroreticulate 0RT/ alcohol of the polypropylene melt-blown repellency that contains formula A fluorochemicals

The initial heating of ORT/%IPA grade example μ g/g fluorine, 220 °F ^*/ 10 minutes

ORT ％IPA ORT ％IPA

1 2660 0 30 4 100

2 2940 0 30 1 90

3 2810 0 30 1 80

4 3015 0 30 1 90

5 3060 0 30 1 90

6 2975 0 30 1 90

7 3015 0 30 0 90

8 2260 0 30 5 100

9 2800 0 30 0 80

10 2650 0 30 5 90

11 3390 0 30 1 40

12 2280 0 40 4 90

13 2,890 0 30 3 100 Comparative examples A 2,600 0 50 0 40 (1 minute) PP contrast 40 0 20 0 20 ^*104 ℃

Table 4

The fibroreticulate ORT/ alcohol of the polypropylene melt-blown repellency that contains formula B fluorochemicals

The initial heating of ORT/%IPA grade example μ g/g fluorine, 140 °F ^*/ 22 hours

ORT %IPA ORT %IPA 14 3,190 1 80 0 70-80 15 3,380 1 90 2 90 Comparative examples A 3,840 0 60-70 0 60PP contrasts 40 0 20 0 20 ^*60 ℃

Table 5

The fibroreticulate ORT/ alcohol of the polypropylene melt-blown repellency that contains formula C (example 16-19) and formula D (example 20-21) fluorochemicals

The ORT/%IPA grade

The initial heating of example μ g/g fluorine, 140 °F ^*/ 22 hours

ORT ％IPA ORT ％IPA

16 2650 0 30 0 80

17 2750 0 30 0 80

18 2880 0 30 0 90

19 2930 0 30 1 90

20 3050 0 30 1 90

21 3,050 0 30 0 90 Comparative examples A 2,600 0 50 0 40 (1 minute) PP contrast 40 0 20 0 20

^*60℃

Table 6

The fibroreticulate ORT/ alcohol of the polypropylene melt-blown repellency that contains formula E fluorochemicals

The ORT/%IPA grade

Example μ g/g fluorine has just been made the heating of 2 weeks, 140 ^*/ 22 hours

ORT ％IPA ORT ％IPA ORT ％IPA

22 2480 0 30 0 30-40 0 40-50

23 2760 0 40-50 0 80 0 60

24 2990 0 40 1 80 0 50

24 3370 - 80 - 70 - 70 ^**

25 1930 0 40 0 40-50 0 50

25 1920 - 60 80 - 60 ^**

26 3,450 0 50 1 90 2 100 Comparative examples A 2,600 0 50 0 40 (1 minute) PP contrast 40 0 20 0 20

^*60℃

^*220 (104 ℃) heating 1 minute

"-" expression can not get data

Claims (10)

1. the compound of a formula A: In the formula

R ₁Be F (CF ₂) _x-(CH ₂) _mOr F (CF ₂) _x-SO ₂N (R ₅)-(CH ₂) _p, wherein X is that about 4-is about 20, and m is that about 2-is about 6, and P is that 1-is about 12, R ₅It is the alkyl of about 4 carbon atoms of 1-;

R ₂Be straight chain, branching or cyclic alkylidene group or poly-(oxyalkylene) alkyl that contains about 15 carbon atoms of the 2-that has an appointment.

2. the compound of a formula B In the formula

R ₁Be F (CF ₂) _x-(CH ₂) _mOr F (CF ₂) _x-SO ₂N (R ₅)-(CH ₂) _p, wherein X is that about 4-is about 20, and m is that about 2-is about 6, and P is that 1-is about 12, R ₅It is the alkyl of about 4 carbon atoms of 1-;

R ₆Be straight chain or the branched chain alkyl that contains about 20 carbon atoms of the 4-that has an appointment.

3. the compound of a formula C:

In the formula

R ₃Be selected from F (CF ₂) _x-(CH ₂) _m, F (CF ₂) _x-(CH ₂) _m-OC (O)-(CH ₂) _nOr F (CF ₂) _x-SO ₂N (R ₅)-(CH ₂) _pOC (O)-(CH ₂) _n, wherein X is that about 4-is about 20, and m is that about 2-is about 6, and n is that about 2-is about 12, and p is that 1-is about 12, R ₅It is the alkyl of about 4 carbon atoms of 1-.

4. the compound of a formula D:

In the formula

R ₃Be selected from F (CF ₂) _x-(CH ₂) _m, F (CF ₂) _x-(CH ₂) _m-OC (O)-(CH ₂) _nOr F (CF ₂) _x-SO ₂N (R ₅)-(CH ₂) _pOC (O)-(CH ₂) _n, wherein X is that about 4-is about 20, and m is that about 2-is about 6, and n is that about 4-is about 20, and p is that 1-is about 12, R ₅It is the alkyl of about 4 carbon atoms of 1-.

5. the compound of a formula E:

In the formula

R ₃Be selected from F (CF ₂) _x-(CH ₂) _m, F (CF ₂) _x-(CH ₂) _m-OC (O)-(CH ₂) _nOr F (CF ₂) _x-SO ₂N (R ₅)-(CH ₂) _pOC (O)-(CH ₂) _n, wherein X is that about 4-is about 20, and m is that about 2-is about 4, and n is that about 4-is about 20, and p is that 1-is about 12, R ₅It is the alkyl of about 4 carbon atoms of 1-.

R ₄Be alkyl or the alkenyl that contains about 20 carbon atoms of about 4-.

6. composition wherein comprises at least a thermoplastic polymer that is selected from polyolefine, polyester, polymeric amide or polyacrylic ester and at least aly is selected from following compound:

1) compound of a kind of formula A: In the formula

R ₁Be F (CF ₂) _x-(CH ₂) _mOr F (CF ₂) _x-SO ₂N (R ₅)-(CH ₂) _p, wherein X is that about 4-is about 20, and m is that about 2-is about 6, and P is that 1-is about 12, R ₅It is the alkyl of about 4 carbon atoms of 1-;

R ₂Be straight chain, branching or cyclic alkylidene group or poly-(oxyalkylene) alkyl that contains about 15 carbon atoms of the 2-that has an appointment;

2) compound of a kind of formula B: In the formula

R ₁Definition identical with top definition to formula A,

R ₆Be straight chain or the branched chain alkyl that contains about 20 carbon atoms of the 4-that has an appointment;

3) compound of a kind of formula C:

In the formula

R ₃Be selected from F (CF ₂) _x-(CH ₂) _m, F (CF ₂) _x-(CH ₂) _m-OC (O)-(CH ₂) _nOr F (CF ₂) _x-SO ₂N (R ₅)-(CH ₂) _pOC (O)-(CH ₂) _n, wherein X is that about 4-is about 20, and m is that about 2-is about 6, and n is that about 2-is about 12, and p is that 1-is about 12, R ₅It is the alkyl of about 4 carbon atoms of 1-;

4) compound of a kind of formula D: In the formula

R ₃Definition identical with top definition to formula C;

5) compound of a kind of formula E:

In the formula

R ₃Definition identical with top definition to formula C;

R ₄Be contain the alkyl of about 20 carbon atoms of the 4-that has an appointment or alkenyl and

6) mixture of compd A-E.

7. the composition of claim 6, wherein this thermoplastic polymer contains its amount of being dispersed in wherein described compound for about 0.1%-about 5% of polymer weight, and wherein said compound has improved the repellency to low surface tension fluids.

8. the composition of claim 7, its form is long filament, supatex fabric, film or the moulded parts of extruding, the fluorine content of described composition is about 200 μ g/g-25,000 μ g/g.

9. give the method for thermoplastic polymer articles with the low surface tension fluids repellency for one kind, this method is included in and forms a kind of mixture before goods are shaped, and wherein comprises the following a kind of compound of being selected from of a kind of polymkeric substance and significant quantity:

1) compound of a kind of formula A:

In the formula

R ₁Be F (CF ₂) _x-(CH ₂) _mOr F (CF ₂) _x-SO ₂N (R ₅)-(CH ₂) _p, wherein X is that about 4-is about 20, and m is that about 2-is about 6, and P is that 1-is about 12, R ₅It is the alkyl of about 4 carbon atoms of 1-;

R ₂Be straight chain, branching or cyclic alkylidene group or poly-(oxyalkylene) alkyl that contains about 15 carbon atoms of the 2-that has an appointment;

2) compound of a kind of formula B: In the formula

R ₁Definition identical with top definition to formula A,

R ₆Be straight chain or the branched chain alkyl that contains about 20 carbon atoms of the 4-that has an appointment;

3) compound of a kind of formula C: In the formula

R ₃Be selected from F (CF ₂) _x-(CH ₂) _m, F (CF ₂) _x-(CH ₂) _m-OC (O)-(CH ₂) _nOr F (CF ₂) _x-SO ₂N (R ₅)-(CH ₂) _pOC (O)-(CH ₂) _n, wherein X is that about 4-is about 20, and m is that about 2-is about 6, and n is that about 2-is about 12, and p is that 1-is about 12, R ₅It is the alkyl of about 4 carbon atoms of 1-;

4) compound of a kind of formula D:

In the formula

R ₃Definition identical with top definition to formula C;

5) compound of a kind of formula E: In the formula

R ₃Definition identical with top definition to formula C;

R ₄Be contain the alkyl of about 20 carbon atoms of the 4-that has an appointment or alkenyl and

6) mixture of compd A-E,

And this mixture melt extruded.

10. the method for claim 17 wherein further is included in and formed goods is heated to about 25 ℃-Yue 150 ℃ temperature after adding additive.