DE2416264A1 - TREATMENT PROCESS FOR IMPROVING THE ADHESIVE PROPERTIES OF THE SURFACES OF POLYMERIC MATERIALS - Google Patents

Description

IMPERIAL CHEMICAL INDUSTRIES LIMITED, London, Great Britain

"Treatment process to improve the adhesive properties of the surfaces of polymeric materials "

Priority: April 3, 1973, UK No. 1583V73

The present invention relates to a method of treatment to improve the adhesive properties of the surfaces of polymeric materials.

Polymeric materials, especially when they are in the form of fibers or films, are often used for purposes used where it is necessary that the surfaces adhere to other materials, for example to other polymers, treatment agents such as antistatic agents or spin finishes or dyes. Lots of these

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polymeric materials, for example rayon, polyamides such as nylon, and especially polyester such as polyethylene terephthalate, however, do not readily form strong bonds with other materials. The present invention provides now a process for the treatment of polymer surfaces, whereby the strength of such connections is improved.

According to the invention there is a method for improvement proposed the adhesive properties of the surface of polymeric materials, which consists in the fact that the polymer Material with an aqueous solution of a titanate ester treated by alkanolamine and the polymer so treated Material is then dried.

The titanate ester used in the process according to the invention is partially or completely through / one or more alkanolamines, such as mono-, di- and triethanolamine, 2- (N-ethylamino) -ethanol, 2- (N, N-dimethylamino) ethanol, 2- (N ', N-diethylamino) ethanol, 2- (2'-aminoethoxy) ethanol, 2- (3'-aminopropoxy) ethanol, N, N'-bis (2-hydroxyethyl) ethylenediamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-butyl diethanolamine, 2-aminopropane-1,3-diol, 2-amino-2-methylpropane-1,3-diol, 1-aminopropane-2,3-diol, 3- (N *, N-dimethylaminopropyl alcohol), 2-hydroxy-n-propylamine, 2-amino-n-propanol, Di- (2-hydroxy-n-propyl) -amine, tri- (2-hydroxypropyl-n-propyl) -amine, N-methyl-di- (2-hydroxy-n-propyl) -amine, N-ethyldi- (2-hydroxy-n-propyl) -amine, di- (I-hydroxyprop-2-yl) -amine, Tri- (1-hydroxyprop-2-yl) -amine and N-methyldi- (1-hydroxyprop-2-yl) -amine, esterified.

Any remaining esterifiable groups can be CU n-alkyl groups, which are optionally replaced by a or more hydroxyl groups can be substituted, such as methyl, ethyl *, isopropyl, η-butyl, n-hexyl, 2-ethyl

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hexyl, 2-hydroxyethyl, 2,3-dihydroxypropyl, ^G 2-8 ~ alkenyl, such as vinyl, allyl, but-1-enyl, 2-methylallyl, 2-amylvinyl, cycloalkyl, such as cyclohexyl groups , which are optionally substituted by one or more hydroxyl / alkyl Ke ^ th and interrupted by other ether bonds, such as can be obtained by reacting C /, o-alkanols with one or more moles of ethylene and / or propylene oxide, such as 2 -Methoxyethyl, 3- "Äthoxypropyi; 1-Äthoxyprop-2-yl, 3,6-Dioxaoctyl, 1,4,7-Trimethyl-3,6,9-trioxadecyl, 5-Hy ^< 3.roxy-3-oxapentyl, Phenyl, which are optionally substituted by one or more groups, such as hydroxy, amino, alkyl, which contain no more than 4 carbon atoms or by chlorine, such as p-chlorophenyl, 4-methyl-3-hydroxyphenyl, p-butylphenyl and 2, 3-dihydroxyphenyl.

If the esterifying groups are derived from polyols, the titanate ester can have cyclic or lower polyester structures contain.

The titanate esters can be prepared by known methods by reacting tetraalkyl titanates and alkanolamine and, if desired, for example with glycol in appropriate proportions. If, in particular, lower alkyl groups are present in the reaction product, this can be used according to be suitable for dilution with water.

The polymeric material is preferably in paser or Polienform before and can with the aqueous solution in the Treated so that it is then immersed in this for a short time, for example 30 to 60 seconds removed from solution and at any temperature at which the polymeric material does not adversely affect is dried.

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Polymeric materials, the surface of which has been treated in this way, are also an object of the Invention. Polymeric materials treated in this way can be stored for long periods of time at room temperature, without the surface properties deteriorating.

The polymeric materials treated in this way can be further treated in various ways in order to make them suitable for certain Purposes. For example, you can use the usual antistatic and anti-soiling agents, such as polyesters of terephthalic acid with polyethylene glycol or ethylene glycol and Polyethylene glycol, spin finishes, such as compositions of matter containing long-chain alkyl esters of Fatty acids, sulfated fatty acid esters, fatty alcohol / ethylene oxide condensates, mineral oil and phosphate esters of Alcohols and alcohol / ethylene oxide condensates, whitening agents such as those based on stilbene and pyrene Whitening agents, and dyes such as azo and anthraquinone dyes ^ are treated and such methods form a further feature of the invention.

A particularly important application of such polymeric Materials is in reinforced rubber, such as tires and conveyor belts. For this purpose a number of adhesive systems have been proposed. However, the more effective of these are complicated or require the use of organic solvents to treat the fibers or the use of toxic or unpleasant chemicals, such as isocyanates. The present invention now provides a simple one Process that only requires two treatments of the fibers in an aqueous solution and bonding with rubber of excellent strength.

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2A1626A

Accordingly, a method for the production of polymeric material reinforced with a laser or film is still available Rubber products proposed, which consists in that the material in an aqueous solution of a TiIjejiatester of an alkanaolamine dipped, dried and then the material into an aqueous resorcinol / 3 ormaldehyde polymer precursor is immersed, whereupon the material is heated to a temperature between 150 and 250 G. and brought into contact with a vulcanizable rubber, whereupon the material / rubber mixture is molded and is vulcanized.

The following types of rubber may be mentioned: natural rubber and also synthetic rubbers that can be vulcanized by sulfur, such as cis-polybutadiene, cis-polyisoprene, polychlorobutadiene, Mixed polymers of butadiene with isobutene, styrene, acrylonitrile and methyl methacrylate and ethylene / propylene / diolefin terpolymers.

The method is particularly useful in conjunction with Polyethylene terephthalate fibers.

The aqueous resorcinol / I-Ormaldehyde polymer precursors may be For example, aqueous solutions of resorcinol and * from 0.25 to 1.0 mol equivalents of formaldehyde and a base, called as ammonia, sodium hydroxide or potassium hydroxide, which is preferably also a rubber latex, in particular made of a mixed polymer with a vinyl pyridine, such as Butadiene / vinyl pyridine, butadiene / styrene / vinyl pyridine or Contains isoprene / S-fryrene / vinyl pyridine. The preferred Resorcinol / lformaldehyde polymer precursors are the substituted ones Phenol / iOrmaldehyde / Resorcinol condensates, like them in British Patent 1,140,528.

This additional method of the invention is preferred

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carried out in such a way that the fibers are immersed in the aqueous solution of the alkanolamine titanate ester, for example a 10 # solution of the titanate ester for 50 seconds at room temperature, then dried at a suitable temperature below the melting point of the fiber-forming polymer, then in the aqueous resorcinol / formaldehyde polymer precursor solution immersed with, for example, a solids content of 30 % at room temperature to obtain an uptake of between 2.5 and 7 »5 #» loading

to reach

pulled onto the cord material /, heating the fiber, preferably at a temperature between 200 and 235 C, by any conventional method, such as an oven or tire cord dipping system, after which the film is brought into contact with a vulcanizable compound, which is then in a Mold or otherwise shaped so as to give the final composite material in the desired shape, which is then vulcanized by heating to the usual vulcanization temperatures, ^{such as 120 to 170 0 C.} The invention also relates to composite materials made by the process which is the subject of the invention.

The methods of the invention are particularly valuable in that they can be carried out easily and effectively in aqueous media.

The invention is explained in more detail in the following examples, without, however, being restricted thereto. The parts and percentages relate to weight, unless otherwise noted.

example 1

The reaction product obtained by heating 2 mole equivalents of N-methyldiethanolamine to 1 mole equivalent Tetrabutyl titanate under reduced pressure, wherein

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4 mole equivalents of butanol are removed in water resolved to a 10 # solution. A 3 x 1100 decitex polyester cord was immersed in the solution so prepared and left to dry at room temperature for 24 hours.

The "treated cord" was then blended through

• -. directed

100 parts of a mixture of two compositions of matter ^ one of which] from 60 parts of water, 25 parts of resorcinol and 14 parts of 37 # aqueous formaldehyde and the other a.us J10 parts vinylpyridine mixed polymer latex (41 # plague content) and 591 parts of water, and 100 parts of a solution. made as in the British patent 1-140528 for solution A in Example 1.

After the second dipping treatment, the treated cord was subjected to a heat treatment at 250.degree. The cord was then molded into a rubber compound · which has been • prepared by mixing the following indicated ingredients on a two roll mill, after which the product was vulcanized by heating at 153 ⁰ C for 30 minutes.

Natural rubber smoked sheet 100 zinc oxide 5.5 Stearic acid 1.5 Usual treatment furnace soot 35 Treatment oil 5.0 Benzthiazylsulphenylcyclohexylamide 1, Q sulfur 2.5

Using a Η-type test piece, the rubber / cord bond strength was found to be 12.2 kg compared to a bond strength of 8.4 kg for a Rubber / cord compound made in a similar manner, but without treating the cord with the Titanium compounds.

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Example 2

The procedure of Example 1 was repeated using a 10 # solution of the product obtained by Reacting 1 mol equivalent of N-methyldiethanolamine with 1 equivalent of tetraisopropyltitanium was obtained. It a bond strength of 12.0 kg was found.

Example 3

The procedure of Example 1 was repeated under Use of a 10 # aqueous solution of the product which was obtained by reacting the in Example 2 product used with a further mole equivalent of 1,1,1-tris (hydroxymethyl) propane. It became a bond strength of 12.3 kg.

Examples 4 to 16

The procedure of Example 1 was repeated using alkanolamine titanate esters prepared from the tetraalkyl titanates listed in the following table, Alkanolamines and optionally glycols. It was made with a drying temperature of 100 C and a Heat treatment temperature of 200 or 235 ° C worked.

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O CD OO

ι Reaction substances and corresponding # ) Liability (*G) I. Ex. Molar ratios Werraebehand- ' treated control 0 » lung temp. I. Ti (OBu) ₄ , diethanolaminej 1.2 ⁰ O 9.4 8.1 4th Ti (OPr) ₄ , diethanolamine ·, 1.4 235 8.5 7.1 5 Ti (OPr) ₄ , diethanolamine, ethylene glycolj 1,1,1 200 17.4 9.3 6th ti Il Il 235 9.6 7.8 7th Ti (OBu) ₂ ,, N-methyldiethylanolamine, diethylene 200 8th glykoiri, 1.1 9.5 8.0 Ti (OAlIyI) ₄ , N-methyl diethanolamine; 1.1 200 11.7 9.4 ν 9 Ti (OBu) ₄ , N, N-dimethylethanolamine; 1.2 235 9.2 7.8 ro 10 ti ν π 200 15.6 9.3 11 Ti (OPr) ₄ , N- (β-hydroxyethyl) ethylenediamine; 1.4 235 6.6 5.6 12th Il Il Il • 200 8.5 7.8 13th Ti (OPr) ₄ , triethanolamine; 1.2 235 9.5 7.9 14th Ti (OBu) ₄ , N-methyl diethanolamine; 1.1 235 12.1 9.1 15th Ti (OBu) ₂ ,, N-methyldiethanolamine, ethylene glycol; 235 16 111 10.0 7.5 235

In this table, Bu means η-butyl and Pr means isopropyl.

- ίο -

Examples 17-21

The 'tetraalkyl titanates listed in the following table, Alkanolamines and optionally glycols were mixed and the exothermic reaction allowed to run out, then diluted with water to give an approximately 10 # solution of titanate ester. This solution was according to the The procedures of Examples 4 to 16 were used, with a heat treatment temperature of 235 ° C

For example, reactants and corresponding adhesion Mole ratios handles control

17 Ti (OPr) ₄ , N-methyl diethanolamine; 1.2 8.8 7.5

18 Ti (OPr) ₄ , N-methyl diethanolamine; 1.1 8.3 7.5

19 Ti (OPr) ^, Ν, Ν-dimethylethanolamine;

1.2 * 9.8 7.5

20 Ti (OEr) *, diethanolamine, ethylene

glykoiri, 1.1 9.3 7.5

21 Ti (OPr) ₄ , N-methyldiethanolamine, 1,1,1-trimethylolpropane; 1.1.1 8.4- 7.5

Example 22

The reaction product obtained by heating 2 mole equivalents of N-methyldiethanolamine with 1 mole equivalent of tetrabutyl titanate under reduced pressure to remove 4 mole equivalents of butanol was dissolved in water to make a 10% solution. A strip of a polyester film which is commercially available under the name Melinex ( ^ir Melinex "is a registered trademark) and had a thickness of Q _r 1 mm was immersed in this solution and ^{dried in an oven at 100 °} C. for 15 minutes. The treated film was then passed through a mixture of 100 parts of a mixture of two compositions, one of which was composed of 60 parts of water, 25 parts of resorcinol and 14 parts of 37% aqueous formaldehyde and the other of 310 parts of vinylpyridine

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latex (41 % solids) and 591 parts of water and 100 parts of a solution prepared according to British patent specification 1,140,528 Example 1 Solution A.

liBc) i öex second immersion treatment became the treated one Subjected film to a heat treatment at 235 ° C. The film was then incorporated into a rubber compound, which was prepared by blending the following ingredients on a two roll mill, followed by d8s Product vulcanized by heating at 153 ° C for 30 minutes became. "*

Natural rubber smoked sheet .100

Zinc oxide '3.5

Stearic acid 1.5

Usual treatment furnace soot 35

Treatment oil. 3.0

Benzthiazylsulphenylcyclohexylamide 1.0

Sulfur 2.5

When using a 25 mm wide test strip, a strength of the rubber / foil connection of 25 kg found in comparison with a very poor strength of 0.16 kg for a rubber / foil connection in a similar manner, except that the foils were not treated with the titanium compounds are.

Example 23

A χ 2 1100 Deeitex nylon cord was immersed in the Titanatesterlösung according to Example 17, and in a fen ° for only 20 minutes at 100 ⁰ C dried. The treated cord was then passed through a mixture of two compositions of matter, one of which was composed of 17 parts resorcinol, 36 parts aqueous 37% formaldehyde, 28 parts

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aqueous 10 # sodium hydroxide and 419 parts of water and the other consisted of 375 parts of vinyl pyridine latex (41 # solids) and 125 parts of water. Subsequent to 'the second immersion treatment of the treated cord to a heat treatment at 16O ⁰ C was subjected. The cord was then molded into a rubber compound using the composition and procedure of Example 1. '

When using a Η-type test piece, the strength of the rubber / cord connection was found to be 6.5 kg compared with a bond strength of 5.5 kg when using a rubber / cord composition which was produced in a similar manner, but with the cord has not been treated with the titanium compounds.

Example 24

The procedure of Example 23 was repeated using the titanate ester solution described in Example 15. A bond strength of 8.4 kg was found.

Example 25

The procedure of Example 23 was repeated using the titanate ester solution used in Example 18. A bond strength of 7.5 kg was found.

ο Example 26

The procedure of Example 1 was repeated using the Titanatesterlosung according to Example 17 and a 2 χ 1100 decitex nylon cord, but it has been subsequently subjected to the second Tauchbeh8ndlung the treated cord to a heat treatment at 160 ⁰ C. When using a Η-type test piece, a bond strength of the Keutschuk / Kord connection of 11.6 kg was determined.

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compared to a bond strength of 9.1 kg for a rubber / cord fabric composition which was made in a similar manner, but without treating the cord with the titanium compounds.

Example 27

The procedure of Example 26 was repeated using the titanate ester solution of Example Ί5. A bond strength of 12.4 kg was obtained.

Example 28

The procedure of Example 26 was repeated, and using the titanate ester solution according to Example 18. A bond strength of 12.3 kg was obtained.

Example 29

Using a standard high strength rayon / rope cord, Example 23 was made
repeatedly using the titanate ester solution of Example 17. A bond strength of 11.1 kg was obtained compared with that of 9 »3 kg for a rubber / cord composition prepared in a similar manner, but without the Treat cord with the titanium compounds.

Example 30

The procedure of Example 29 was repeated using the titanate ester solution of Example 15. It
a bond strength of 11.0 kg was obtained.

Example 31

The procedure of Example 29 was repeated using the titanate ester solution of Example 18. It
a bond strength of 12.3 kg was obtained.

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Example 32

Using a high strength having standard Kunstseidereifenkords was repeated "the procedure of Example 1, and using the Titifnatesterlösung according to Example 17 Here, however, was subjected to heat treatment at 160 ⁰ C after the second dipping treatment of the treated cord. Using an The Η-type test piece was found to have a rubber / cord bond strength of 12.5 kg compared to a bond strength of 10.1 kg for a rubber / cord composition prepared in a similar manner, except that no treatment with the Titanium compounds took place.

Example 53

The procedure of Example 32 was repeated in Use of the titanate ester solution according to Example 15 · Es a bond strength of 12.0 kg was obtained.

Example $ 4-

Bie procedure of Example 32 was repeated using the 18 Titanatesterlösung according to Example There was obtained a bonding strength of 12 ₁ 5 kg.

Claims : 409844/0684

Claims (1)

PATENT CLAIMS Λ . """* A method for improving the adhesive properties of the surface · of polymeric materials, characterized in that • the polymeric material is treated with an aqueous solution of a titanate ester of an alkane platinum and the polymeric material treated in this way is dried. 2. · The method according to claim 1, characterized in that some of the esterification groups of the titanate ester derive from an alkanolamine. 5. The method according to claim 2, characterized in that that the remaining esterification groups are C ^ o -alkyl groups are. 4- .. The method according to claim 2, characterized in that that the remaining esterification groups are C ^ o -alkyl groups which can be substituted by one or more hydroxyl groups. 5. The method according to any one of claims 1 to 4-, characterized characterized in that the aqueous solution of the titanate ester is obtained by adding water to the crude reaction product of a tetraalkyl titanate, alkenolamine and . optionally a glycol. 6. Process for the production of Keutschuk items, which are reinforced with a polymeric material in fiber or film form, characterized in that the Material first in an aqueous solution of a Titanetester of an alkanolamine dipped, dried, then in 4098 44/0684 an aqueous resorcinol / formaldehyde polymer precursor immersed to a temperature between 150 and 25O C heated, brought into contact with a vulcanizable rubber, and then the composition is molded and is vulcanized. 7. The method according to claim 6, characterized in that the material is also converted into a vinylpyridine mixed polymer latex is immersed. 409844/0684