KR960000858B1 - Bonding of halogenated organic compounds - Google Patents

Abstract

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Description

[Name of invention]

Method of Enhancing Adhesion of Halocarbon to Substrate and Method of Bonding Halocarbon to Substrate

Detailed description of the invention

Incorporation of halocarbons into various substrates has long been required. Unfortunately, such compounds, especially fluorinated hydrocarbons such as teflon, are very difficult to bind because of their chemical inertness.

On cable insulation, self-lubricating sheathing for bearings, acid-resistant linings for tanks, non-adhesive surfaces for cookers and heat-resistant containers, permeation-resistant seals and seals on tires, eg natural rubber carcass materials In halobutyl tire liners, it is necessary to obtain a good bond between the halocarbon and the substrate.

EXAMPLES The use of zirconium compounds to enhance fluorinated hydrocarbon retention is described in US Pat. Nos. 4,423,113 and 4,317,859. Applicants of co-pending US patent application Ser. No. 651,119, filed September 14, 1984, have shown that titanium and zirconium pyrophosphates can be used to enhance the adhesion of polyester and paint primers to glass fibers. However, these materials have not proven useful for binding halogenated compounds.

In accordance with the present invention, it has been found that halocarbons can easily bind to various substrates by treating their contact zones with selected neoalkoxy zirconate compounds. The mechanism of this accidental discovery is not clear, but it is believed that the effect of the present invention is based on the ability of zirconate atoms to replace halogen with other ligands that readily bind to the substrate and to extract halogen atoms from organic materials.

The neoalkoxy zirconates of the present invention are described in detail in US Pat. No. 4,623,738, filed November 18, 1986.

Compounds used in the present invention are characterized in that halogenated organic-materials are more effectively bound to substrates, such materials can be strongly bound to substrates other than fibers or fabrics, and such materials have enhanced results in nylon bonding. It is advantageous over that described in the above United States patents.

Halocarbons, such as teflon, consist essentially of a carbon-to-carbon backbone with the accompanying halogen atoms attached thereto. Because of the stability of the carbon to carbon bonds, these compounds have been found to be very resistant to adhesion. For example, such materials are well known where they are used where resistance to adhesion is required. For example, ports and fans are often coated with such materials.

While this “adhesion-resistance” is necessary for some purposes, this is an important issue when it is necessary to bind halocarbons to other materials. Clearly, in kitchenware applications, Teflon is not supported on a suitable metal substrate. It cannot be used and a metal substrate is necessary for its structure and thermal conductivity.

According to the invention, it has been found that when the halocarbon or substrate to be bonded is treated with the selected neoalkoxy zirconate, a strong adhesive bond to the substrate is formed.

Examples of halocarbons to be bonded according to the invention include monomers and polymeric materials. Examples of polymeric materials are Teflon, Kel-F perfluorooctene, perfluorooctanoylglycine, chloronaphthalene, and chlorinated polyethylene.

Other fluorinated compounds include those containing saturated aliphatic radicals containing 3-20 carbon atoms, preferably 6-12, and having a fluorine content of 49-78% by weight, preferably 50-77% by weight, bonded to carbon; The same is used. Preferably the aliphatic radical is perfluoroalkyl, CnF2n + 1. Such fluorochemicals and their preparation are well known and react the precursor fluoroamines or alcohols with suitable anhydrides or isocyanates, for example N-ethyl perfluorooctane sulfonamidoethanol and 2,4-tolylene diisocyanate It can be prepared by providing a bis-urethane polymer containing 15-30% by weight of fluoro by reacting with a molar ratio 2: 1.

Other compounds are those formed by reacting polymethacrylate with a C4-C12 product formed by reacting tetrafluoroethylene with a chain transfer agent such as HO-CH2CH2-Cl. Usually, the chain transfer agent is sufficiently added to obtain the required chain length (eg C8) so that the product contains C4-C8 and C8-C12 compounds.

Organic-zirconates useful in the present invention can be represented by the following general formula:

In the neoalkoxy zirconate of formula (1), R, R1 and R2 are each monovalent alkyl, alkenyl, alkynyl, aralkyl, aryl or alkaryl having up to 20 carbon atoms, or halogen or ether substitution Derivatives, in addition R 2 may also be an oxy derivative of such groups. The various R, R1 and R2 may contain up to three ether oxygen or halogen substituents under the proviso that the total number of carbon atoms in each R group should not exceed 20 in total in the number of carbon atoms included in the substituent portion.

Each A group is independently diester phosphate ((R3O) (R4O) P (O) O-), diester pyrophosphate ((R3O) (R4O) P (O) OP (O)), oxyalkylamino (R5R6NR7O Or sulfonyl (ArS (O) 2 O—). Each group may contain up to 30 carbon atoms. Wherein Ar is a monovalent aryl or an alkali group and its derivative having 6-20 carbon atoms and optionally containing up to 3 ether oxygen substituents, wherein the substituents are a total of up to 3 halogens or R8 and R9 These are each an amino group group having the general formula NR8R9 which is hydrogen, an alkyl group having 1-12 carbon atoms, an alkenyl group having 2-8 carbon atoms, and an aryl group having 3-12 carbon atoms; R3 and R4 may be groups such as R, R1 and Ar, respectively. R5 and R6 may be hydrogen, aminoalkyl or alkyl having 1-15 carbon atoms and R7 may be an alkylene group having 1-6 carbon atoms or an arylene group having 6-10 carbon atoms or a combination thereof.

In the zirconium chelate of formula (II), A is as described above; B is a R'2C group or a carbonyl group; R 'is hydrogen or a hydrocarbyl group having 1-6 carbon atoms; n is 1 or 2.

Particularly preferred examples of R, R1 and R2 groups include alkyl having 1-8 carbon atoms; Aryl and aralkyl having 6-10 carbon atoms such as benzyl, phenyl, naphthyl, tolyl, xylyl; Halogen-substituted aryl such as bromophenyl; Allyloxy-substituted alkyl having 4-20 carbon atoms; Allyl oxy-substituted aryl having 9-20 carbon atoms. If R 2 is an oxy derivative, the most preferred compounds are alkoxy derivatives having 1-3 carbon atoms and a phenoxy group.

Preferred R3 and R4 groups are alkyl groups having 1-12 carbon atoms, aryl and 6-12 carbon atoms and ether-substituted alkyls having 3-12 carbon atoms.

Examples of specific R, R1, R2, R3, and R4 groups include the following: methyl, propyl, cyclohexyl, 2,4-dimethoxybenzyl, 1-methyl-4-acenaphthyl-2-ethyl-2 -Furyl and metaryl, in addition to R2 is methoxy, phenoxy, naphtheneoxy, cyclohexene-3-oxy, 4-isobutyl-3-methoxy, 1-phenanthoxy and 2,4,6-trimethylphenoxy It can be a seal.

There are likewise many examples of A ligands useful in the practice of the present invention. This includes aryl sulfonyl groups such as phenylsulfonyl, 2,4-dibutyl-1-naphthalene sulfonyl and 2-methyl-3-ethyl-4-phenanthryl sulfonyl, as well as dibutyl, methylphenyl, cyclohexyl, lauryl And diester phosphates such as bismethoxyethoxyethyl phosphate and their pyrophosphate analogs.

Treatment of the halogenated organic compounds with the organo-zirconates described herein results in the formation of novel compositions represented by the following general formulas (III) and (IV). The proposed reaction mechanism is shown below:

Wherein each A is as defined in formula (II), (RO) is as defined as R, R1, R2, CCH2O in formula (II), and D, E and G are each hydrogen, Monovalent ligands selected individually from halogen or monovalent hydrocarbyl groups each having 1-10 carbon atoms, and n represents a repeating unit in the organic chain which may be 1-10,000.

The choice of particular organic-zirconate that is preferred depends on the particular substrate to which the halocarbon is bound. For example, when bonding halocarbons to metals such as copper, aluminum and iron, pyrophosphate and phosphate species of both neoalkoxy and chelate zirconate are preferred. Phosphates exhibit the most efficient behavior, excellent results obtained with compounds such as zirconium IV, neoalkenylate, tris (dioctyl) phosphato-O.

Diester phosphates are most preferred when the polyolefin forms a substrate (ie materials such as polyethylene, polypropylene and copolymers and terpolymers of such compounds). However, aryl zirconates such as zirconium IV neoalkenylato, tris neodecanorayo-O can also be used. In addition, both neoalkoxy and chelate forms play a role. For styrene plastics (polystyrene and polyalphamethyl styrene), sulfonyl zirconates, especially alkyl benzyl sulfonyl forms such as zirconium IV neoalkenylato, tris dodecylbenzene sulfonato-O, perform best. Phosphate diesters are also effective. Bonding is best when using alkyl or aryl amino zirconates on thermoplastic polyesters such as Mylar. Examples of such compounds are zirconium IV neoalkenylato, tris (2-ethylene diamino) ethylrayto and zirconium IV neoalkenylato, tris (3-amino) phenylrayto.

Other substrates with improved adhesion of halocarbons include wool, cotton, nylon, polyester and acrylic resins. Treatment of such materials is particularly useful for improving the preservation of antifouling agents such as Scotchgard brand antifouling agents (3M) and Zeppel and Teflon (E. I. DuPont Denemouls).

Organic zirconate compounds can be applied to the surface of the halocarbons and / or substrates by various methods well known to those skilled in the art of coating. For example, roll coating, spray lamination or other thin film production techniques can be used to final coat the organic zirconate less than about 50 mm thick, preferably with a diluent. Whether halocarbons, substrates, or their surface treatments are a matter of choice is easily determined by the applicator.

In addition, it is more preferable to add-mix the organo-zirconate compound to the halocarbon during the processing treatment before applying it to the surface of the substrate. If halocarbons are bound to a substrate having processing properties consistent with the stability of the organo-zirconate compound, it is usually practical to incorporate the organo-zirconate during processing of the substrate. This method provides a bulk supply of binder.

Any combination of the above methods can be used to further enhance the binding force between this substrate and the desired halocarbon. The processing conditions required to affect the desired bonding are preferentially determined by the coating method used for the undercoating material and / or the processing needs of the substrate and halocarbon when any addition is used.

According to the present invention, it is known that halocarbons can be effectively bound to various substrates. Hydrocarbons, polycarboxylic acid derivatives such as polyesters, polyamides and polyurethanes, materials with carboxyl or derivative groups, acrylonitrile, butadiene and styrene, polyacrylates, ethylene vinyl and the like, as well as most metals The substrate can be bound.

If compression is used, the temperature may be wide, such as in the range of about 0 ° C to about 400 ° C, preferably about 50 ° C to 300 ° C.

If integral addition is used in the polymer matrix or halocarbon component, a compression temperature of about 100 ° C. to about 300 ° C. is best used. At temperatures below 100 ° C., a long contact time of 1-about 20 minutes may be required depending on the substrate to obtain optimal binding properties. If low contact pressures (i.e. below 1 gravity) are used in the bonding process, long contact times at low temperatures are particularly advantageous if they are used integrally as opposed to primer bonding.

The specific mechanisms for improved binding between halocarbons and appropriate substrates are not fully understood. In special cases, however, such bonding involves the substitution of one of the ligands attached to the organo-zirconate and the extraction of halogen atoms from the halocarbons. While other undetermined factors can regulate ligand exchange, ligands appear to be dependent on the specific compound, process conditions and stereochemical elements of the halocarbons and organo-zirconates used. The continuous binding of the partially dehalogenated halocarbons to the substrate is greatly enhanced by the interaction between the newly attached ligand and the substrate and the binding of the ligand to the organo-zirconate and / or derivative product which in turn binds to the substrate. .

Table 1 shows the organic zirconates used in the examples.

TABLE 1

The following examples illustrate the invention in more detail.

Example 1

Method of bonding teflon to copper wire.

compound

A thin film of C is coated on copper wire with a saturated sponge just prior to co-extrusion of the wire with Teflon fluoropolymer in a flat crosshead extruder system. The peel strength of the Teflon coated on the copper wire was 8-9 lbs / in as compared to the untreated coated wire of 2-5 lbs / in similarly prepared. This improvement of about twice suggests that the utility of the present invention is assured.

Example II

Process for Bonding Chlorinated Polyethylene to Nylon 6.

This example shows an embodiment of the invention in which a primer is mixed with a polymer substrate. Chlorinated polyethylene (Dow Chemical Tyrin 566) was dissolved in mixed xylene solvents and diluted to a final concentration of 10 wt%. Thereafter, 0.52 wt% of various organic zirconate compounds based on the polymer was introduced and the resulting solution was applied to nylon 6 to 2 mils thickness via a doctor blade. At ambient temperature, after evaporating, annealing and cooling the solvent and conditioning at 25 ° C. for 24 hours, the resulting CPE / nylon contact area has the following peel strength.

TABLE 2

The above data suggest that the organo-zirconate compound essentially enhances the bond between two opposing polymer species, chlorinated polyethylene and nylon.

Example III

A method of binding fluorinated polyvinylidene to polychloroprene.

Polychloroprine (Dupont-Neoprine) is combined with 50 parts of carbon black per 100 parts of resin and 0.8 parts per 100 parts of the indicated organic-zirconate additive and a combination with zinc oxide and magnesia curatives. This additive is added as a powder concentrate on the silica carrier. The compounded compound is extruded on a cross-fed polyvinylidene fluoride (PVDF) hose liner. The peel strength of the liner from the resulting hose was measured and the results were recorded as follows:

TABLE 3a

Alternatively, this PVDF liner was coated with a 1.2 wt% solution of the indicated organic-zirconate additive in 1,2-dimethoxyethane solvent. The coated PVDF liner was then crosshead extruded with the mentioned polychloroprine blend without introducing additives. Peel strength of the resulting product is shown in Table 3b.

TABLE 3b

The data in Tables 3a and 3b show the effectiveness of the organo-zirconate as a bond enhancer for PVDF / polychloroprene systems, independent of whether the additive is introduced completely or as primers in the contacting zone.

Example IV

Bonding of chlorinated, chlorosulfonated polyethylene to steel

12 wt% solution of chlorinated and chlorosulfonated polyethylene (Dupont-Hyparon 40) in a 50/50 toluene blend, 10 wt% lead monoxide dispersion, and 3 wt% well dispersed, finely divided lead monoxide curative 0.4% by weight of the indicated organic-zirconate additives in tetrahydrofuran and toluene primers were subsequently roller coated with the blasted steel. The peel strength of the resulting coating was measured and shown in the table below.

TABLE 4a

The coated steel is then exposed to 20% hydrochloric acid at ambient temperature for 30 days. The exposed panels are then washed with water, dried and the peel strength is measured again. The results are shown in the table below.

TABLE 4b

The data given in Tables 4a and 4b show that the products of the present invention maintain high bond strengths and bond strengths to a greater extent after the laminate has been exposed to the corrosion of strong acids.

Increased effluent and output reduce the porosity of the polymer film in the original steel; Direct protection by addition to the steel surface; It is believed that the formation of acid and water resistant bonds between the primer / polymer and the steel in the contacting zone accounts for the improved results.

Note the dramatic increase in peel strength during exposure of the specimen prepared with additive E to acid, which may be the result of an extended contact period between the steel and the additive containing the halogenated polymer coating during the test.

Example V

Adhesion of Polyvinyl Chloride.

The polyester adhesive comprises 10% by weight of fumed silica (Cabosil M-5), 0.2% by weight of the binder as determined in the table and 0.5% by weight of tert-butyl perbenzoate to the polyester resin (Latchhold # 30,003). It was prepared by dispersing. The resulting dispersion was degassed by standing for 24 hours at ambient temperature. This was followed by 1/16 in. Thick PVC resin (GM 103EP) 1sq. in. The pieces were applied by a doctor blade to a thickness of 1 / 1000in. The second piece with the comparative material was placed in film yarn and the resulting laminate was press vulcanized at 25 psi for 15 minutes at a temperature of 160 ° C. The specimens were equilibrated to room temperature before measuring the lap shear strength. The results are shown in the table below.

TABLE 5

This data indicates that the stickiness produced by additive "G" fails when it resists peeling. As a result, the shear strength of the laminate is limited by the shear strength of the bonded resin rather than the adhesive or its adhesive value. This demonstrates the efficacy of the sulfonate derivatives of zirconium IV as a binder for halogenated substrates.

Example IV

Cohesion of fluoroelastomer to steel.

A solution of 500 ppm of cobalt naphthenate with 12% vinyl ester resin (Dow 8044), 0.5% methyl ethyl ketone peroxide, 0.1% dimethylaminotoluene and 12% adhesive was prepared. It is applied to mild steel, each 5 / 1000in thick, in a solution containing 40% by weight of tetrahydrofuran, 0.2% of additives contained in vinyl ester resin, and a residual amount of methyl ethyl ketone, a bitron type E fluoroelastomer A 3/1000 “cloth of followed by spraying on the resulting coating. After the peel strength was measured by peeling at 90 °, the coating was aged for 72 hours at ambient temperature. The results are shown in Table 6 below.

TABLE 6

The results clearly show a marked improvement in the peel strength imparted by the additive of the present invention.

Claims (10)

The binding of the halocarbon to the substrate, consisting of treating the substrate, the halocarbon, or both the substrate and the halocarbon, with an organo-zirconate compound appended with a phosphate, pyrophosphate, amino or sulfonyl group How to promote. The binding force of halocarbon to the substrate of claim 1, comprising treating the substrate, halocarbon, or both the substrate and halocarbon with an organo-zirconate compound having any of the following general formulas: How to promote:

Wherein R, R1 and R2 are each monovalent hydrocarbon groups, or actual derivatives thereof; A group is independently selected from diester phosphate, diester pyrophosphate, oxyalkylamino, oxyalkylarylamino or sulfonyl group; B is a R'2C group or a carbonyl group; R 'is hydrogen or an alkyl group having 1-6 carbon atoms; n is 1 or 2. The substrate, which consists of contacting the substrate, halocarbon, or the surface of both the substrate and the halocarbon with an organo-zirconate compound appended with a phosphate, pyrophosphate, amino or sulfonyl group, and then contacting the halocarbon with the substrate. How to combine halocarbons. 4. The process of claim 3, comprising treating the substrate, halocarbon, or both substrate and halocarbon with an organo-zirconate compound having any of the following general formulas, followed by contacting the halocarbon with the substrate: , How to combine halocarbons with a substrate:

Wherein R, R1 and R2 are each a monovalent hydrocarbon group or an actual derivative thereof; A group is independently selected from diester phosphate, diester pyrophosphate, oxyalkylamino, oxyalkylarylamino or sulfonyl group; B is a R'2C group or a carbonyl group; R 'is hydrogen or an alkyl group having 1-6 carbon atoms; n is 1 or 2. The method of claim 1 wherein the halocarbon is a fluorinated polymer. The method of claim 5 wherein the fluorinated polymer is Teflon. The method of claim 3 wherein the substrate is a metal or polymeric material. 8. The method of claim 7, wherein the substrate material is polyolefin, polyamide, styrene or thermoplastic polyester. A laminate comprising a substrate coated with an organic-zirconate compound having one of the following general formulas and a halogenated organic compound on its contact surface:

Wherein R, R1 and R2 are each monovalent hydrocarbon groups or actual derivatives thereof; A group is independently selected from diester phosphate, diester pyrophosphate, oxyalkylamino, oxyalkylarylamino or sulfonyl group; B is a R'2C group or a carbonyl group; R 'is hydrogen or an alkyl group having 1-6 carbon atoms; n is 1 or 2. A composition comprising a reaction product of an organo-zirconate compound having any one of the following formulas with a halocarbon:

Wherein R, R1 and R2 are each monovalent hydrocarbon groups or actual derivatives thereof; A group is independently selected from diester phosphate, diester pyrophosphate, oxyalkylamino, oxyalkylarylamino or sulfonyl group; B is a R'2C group or a carbonyl group; R 'is hydrogen or an alkyl group having 1-6 carbon atoms; n is 1 or 2.