FI62546B - FREQUENCY REARING FOR TERMINAL PHENOLARS - Google Patents

Description

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France-France (FR) 7511780 (71) Les Derives Resiniques et .Terpeniques, 30, rue Gambetta, t0102 Dax, France-France (FR) (72) Bernard Lahourcade, Vielle-St Girons, Gustave Bonneau, Vielle-St Girons, France-France (FR) (7t) Oy Roister At »(5t) Method for the production of terpene-phenolic resins - Förfarande för framställning av terpen-fenolhartser

The invention relates to a process for the preparation of improved terpene-phenolic resins which are particularly suitable as adhesives.

A number of methods for preparing terpene-phenolic resins have already been described, and in particular Indian Patent IN 126 350 discloses a method for preparing a terpene-phenolic resin by reaction with A-carene and phenol in the presence of a Friedel-Crafts type catalyst. However, previous methods, and typically the method of the Indian patent presented above, have not been able to obtain resins in the satisfactory yield required to obtain a final product with excellent color and softening point properties, mainly due to the low reactivity of the karenes.

In fact, Δ-carene, as a component used so far, has been considered a derogatory hydrocarbon due to its reactivity.

This apparent lack of reactivity is typically due to 2,62546 conventional reactions in the terpene industry, such as hydration or polycondensation reactions.

In addition, the resin obtained by reaction with phenol by known methods has very little effect on the use of the final product. This results in a really narrow macromolecular crystal structure, at least a combination of two Δ-carene molecules per phenol molecule, corresponding to a molecular weight of less than 360, thus excluding a resin for use in adhesives in the art.

However, it has now been found that by intensifying the reaction of phenol with terpene under specific conditions, it is possible to obtain a resin which is highly soluble in most organic solvents and rapidly compatible with elastomers and synthetic resins and which is particularly useful for adhesives due to its thermal and oxidation resistance. . The terpenes used in this process preferably contain Δ- and Δ-carene either alone or in combination with more reactive terpenes.

The present invention is based on a process for preparing terpene-phenol resins by reacting terpene with phenol in the presence of an acidic condensation catalyst. The process according to the invention is characterized in that a) one molar part of terpene is reacted with 1.8-2.2 molar parts of phenol having at least two reactive sites in the presence of a boron trifluoride catalyst or a complex thereof to give diphenol-terpene, b) the product obtained in step a) diphenol-terpene is reacted with terpene in the presence of said catalyst in such an amount that reactive sites remain in the substituted diphenol-terpene molecule obtained after the reaction, and c) one mole part of the substituted diphenol-terpene obtained in step b) is reacted at 90-120 ° C, With 2 to 1.5 molar parts of formaldehyde, and the reactions of steps a) to c) are carried out in an aromatic hydrocarbon solvent.

According to another embodiment of the present invention, the resin from step c) can be cooked with zinc powder.

According to the present invention, the residual catalyst, if any, 3 62546 is removed from the product obtained in step c) after treatment with zinc powder.

Other advantages of the present invention will become apparent from the following detailed descriptions.

The process for the preparation of terpene-phenolic resins comprises first reacting terpene with two molar parts of phenol in the presence of a condensation catalyst to give diphenol-terpene, then reacting the resulting diphenol-terpene to react with reacting the above-substituted diphenol terpene with a methylene bridge-forming reagent to obtain the desired resin.

The phenol used in this process should have at least two reactive sites for condensation, i.e., two free positions for the phenolic OH group. Useful phenols include phenol, cresols, typically meta-cresols, xylenones, typically meta-xylenol, thymol, naphthols, resorcinol, or mixtures thereof, the most economical and most widely used being phenol containing three reactive sites.

3 2

Suitable terpenes are A- or A-carenes, or more reactive terpenes such as cApinene, camphene, isolimoni.ini or mixtures thereof.

3 2

More typically used are pure A-carene or / _ \ -carene or carenes derived from pine resin oil or oils from papermaking plants. In the latter case, it was found that it is not absolutely necessary to subject the oil to a wider deodorization treatment, as the presence of small amounts of sulphides does not affect the production of the resins. However, it is important to use a substance from which the slightly malodorous mercaptan moiety has been removed in conjunction with heavy sesquiterpene fractions rich in sulfur compounds.

3

Pure A-carene is meant here a substance with a chromatographically determined purity of more than 95%.

Concentration distillation-karene fraction containing 55-95% karene can also be used.

4,62546

The terpene used in the process of step b) may be the same as or used in step a).

In the first condensation step, one molar part of terpene is reacted with 1.8 to 2.2 molar parts, preferably 2 molar parts of phenol, to give diphenol terpene.

This reaction is preferably carried out at a temperature of 80 to 120 ° C, especially 90 to 110 ° C in the presence of a condensation catalyst of the Lewis acid or Friedel-Crafts type. The preferred catalyst is boron trifluoride used as such or in one of its usual complexes (acetic acid, ether or phenol).

The addition of terpene can be carried out at a temperature of 20 to 100 ° C, preferably 60 to 70 ° C. The reaction itself is carried out at 80-120 ° C, preferably 90-110 ° C, and allowed to proceed for a sufficient time (usually about 1-3 hours) to obtain the desired diphenol terpene.

The reaction between phenol and terpene is generally carried out in a suitable solvent such as an aromatic hydrocarbon, typically toluene or xylene.

The reaction should take place with dry reagents free of peroxide, hydroperoxide and metal salts or oxides such as iron oxide.

To prevent the introduction of air or oxygen, the various reactions of the process are preferably carried out in an inert gas atmosphere, such as nitrogen, carbon dioxide or argon.

After the first step, a certain amount of terpene - which, as stated above may be the same as in the first step or different - is added to the reaction medium, the reaction preferably being carried out in an aromatic hydrocarbon solution in the presence of added catalyst, and the condensation is continued at 80-120 ° C, preferably 90 ° C. -110 ° C.

In this second step, the molar proportions of terpene still adhere to the reactive sites of the diphenol terpene obtained from the first step. The amount of terpene to be added in the second step should be such that the available reactive sites remain with the resulting substituted diphenol-terpene-Molecule after completion of the reaction.

For example, in the reaction between ordinary phenol and carene, one molecule of 5,62546 diphenol obtained from the first step is reacted with 2.5-3.75 molecules of carene to give a substituted diphenol carrene having 0.25-1.5 free reactive space for the subsequent reaction.

The second step of the reaction is generally carried out in the following manner:

To the appropriately diluted (if necessary with additional solvent) medium obtained from the first step is added catalyst and a stepwise amount of terpene. The addition can be carried out at 50-120 ° C, preferably at 80-110 ° C for 1-3 hours. The resulting material is then subjected to a cooking treatment at 80-120 ° C, preferably at about 100 ° C for about 1 hour.

Excessively high temperatures (e.g. above 120 ° C) can stain the substance and promote catalyst release. In contrast, too low temperatures can cause terpenes to be isomerized or dimerized to some extent at the expense of the condensation reaction.

In the third step of the process, the free reactive surfaces of the diphenol terpene obtained in the second step are used to combine the molecules of this diphenol terpene with methylene bridges. For this purpose, the substituted diphenol terpene is reacted with a reagent to form methylene bridges, and this step is preferably performed in the presence of the same catalyst. Useful reagents for this purpose include formaldehyde in its various forms (formalin, paraformaldehyde and the like) or hexamethylenetetramine.

The molecules can be obtained in long or short chains depending on the ratios between the amounts of reagent and the amounts of substituted diphenol terpene. In this reaction, 0.2 to 1.5 mole parts (calculated as formaldehyde) of the reagent forming the methylene bridges are reacted with one mole part of substituted diphenol terpene, preferably 0.3 to 1.1 moles of formaldehyde per mole of diphenol terpene.

When the 1.5 mole limit is exceeded, crosslinking can cause the reaction medium to gel.

This third step in the process can be made to happen as follows:

A calculated amount of reagents to give methylene bridges is added to the medium of the second reaction step, suitably diluted at the same time as the solvent (additional solvent may be used if necessary), at a temperature of 70-100 ° C, preferably 80-90 ° C in the case of paraffinaldehyde.

The reaction is then carried out at a temperature of 90 to 120 ° C, preferably about 100 ° C. The reaction time may be about 1 hour.

The method described above gives, in very good yield, a terpene-phenolic resin having a pure stable color and a satisfactory softening point as determined by the ring and ball test (NF.T. 66008 assays). These resins, which are soluble in most non-hydroxyl-organic solvents and also + alcohols, have excellent compatibility with many elastomers and synthetic resins. They are thermally stable, resistant to oxidation, and are particularly suitable for use as adhesives, they have also been found to be superior to conventional resins, especially of the polyterpene type. The polarity of the obtained resins is very low.

It was found that a one hour cooking treatment at 90-120 ° C in the presence of zinc powder significantly improves the color of the final product. Zinc acts as a reducing agent in relation to certain dyes, which are particularly developed during the third stage of the process.

Adding 0.3-0.8% zinc powder to the charge is sufficient to be effective.

In order to avoid discoloration or corrosion problems of the final product, after completion of the reaction, it is preferable to remove the remaining acid catalyst remaining in the resin from the third step or treated with zinc powder.

This removal can be accomplished in any suitable manner, typically at a high temperature (about 100 ° C) by the addition of lime with an absorbent metal oxide, resulting in the removal of the acidity and colorant in the resin.

The removal of the solvent is carried out by distillation under vacuum or atmospheric pressure, this distillation also making it possible to remove small fraction by-products such as diterpenes and very low molecular weight terpene phenols.

7,62546 The process of this invention is particularly significant in that the phenol is used up in conjunction with all other reagents. The solvent itself is recoverable.

This represents a substantial economic advantage in terms of cost, safety and environmental pollution.

The following non-limiting examples are provided to illustrate the invention.

Example 1 (a) The following ingredients are placed in a stainless steel reactor: ordinary phenol 100 parts toluene 50 parts boron trifluoride (vinegar complex) 1 part

O

after which Δ-carenine is added in 70 parts while maintaining the temperature at 60 ° C, and the resulting mixture is subjected to a cooking treatment at 100 ° C for 1.5 hours.

(b) The following substances are then added, in portions: boron trifluoride complex 2 parts Ζα-carene 250 parts, maintaining the temperature at 100 ° C for 1 hour.

(c) When the reaction is complete, 100 parts of toluene are added, which lowers the temperature of the medium to 80-90 ° C, followed by 12 parts of paraformaldehyde. The temperature is gradually raised to 100 ° C and the reaction mixture is refluxed at this temperature for 1 hour.

The substance obtained is then treated at this temperature with 2.5 parts of zinc powder for 1 hour and then for 10 minutes with 4 parts of lime.

It is then diluted with 100 parts of toluene and treated at 70-80 ° C: with absorbent metal oxide 15 parts of filter aid 1 part

The product is carefully filtered and distilled under vacuum or atmospheric pressure while removing solvent and small fractions of diterpenes and low molecular weight terpene phenols.

The resin obtained in 90% yield has the following characteristics: 8 62546

quality X

acidity practically O

ring-ball test 115 ° hydroxyl number about 30 average molecular weight about 650

The quality is indicated according to the French Color Scale for French natural resins.

This resulting resin is very soluble in most solvents (aliphatic and benzene hydrocarbons, higher ketones, esters, chlorinated solvents, higher alcohols and the like).

This resin is particularly good to match many elastomers and synthetic resins such as natural rubber, SBR rubbers and SBR block rubbers, neoprenes, acrylonitrile-butadiene rubbers, chlorinated rubbers, ethylene-vinyl acetate copolymers, polyethylene, polyethylene, polyamides, polyethylene, polyethylene resins, esterified resins, modified resins and their esters.

The heat resistance and resistance to oxidation of this resin is very good. Thus, at room temperature under an oxygen pressure of 20 kg, this resin absorbs less than 0.4% oxygen relative to the weight of the resin after 168 hours.

Example 2 Using exactly the same temperature, time, catalyst and solvent addition conditions as in Example 1, but using the following ingredients:

Step (a) ordinary phenol 100 parts 3 A-carene 70 parts 3 step (b) -carene 185 parts Step (c) paraformaldehyde 17 parts and zinc powder 2 parts are obtained in 90% yield WW-grade resin, which is ring-ball tested the result is 150 ° C.

Example 3

The procedure of Example 1 is repeated except that the carene is replaced either completely or only in step (b) (250 parts) of OC-pinene to give a very clear resin in 95-96% yield with a ring-ball test result of 125 ° C.

Example 4

The procedure of Example 1 is repeated except that the N-carene is replaced with camphene to give a resin with a ring-ball test result of 124 ° C in 95% yield.

Example 5

The procedure of Example 1 is repeated except that the A-carene is replaced on a weight / weight basis by isolimonene or 2,8-p-menthadiene to give a resin with a ring-ball test result of 102-103 ° C in 95% yield.

Example 6

The procedure of Example 1 is repeated except that ordinary phenol has been replaced with a molar equivalent of metacresol to give in 80% yield a clear resin with a ring-ball test result of 68-70 ° C.

Example 7

The procedure of Example 3 is repeated except that the phenol is replaced by the molar equivalent of thymol, and <* - pinene is used in steps (a) and (b). In step (b), the amount of terpene is reduced due to the isopropyl group in the o-position of the thymol molecule.

Thus, 136 parts of o (-pinene) are added instead of the 250 parts added in Example 3 to give, in 80% yield, a clear soft resin with a ring-ball test result of about 50 ° C.

Claims (10)

10 62546 A process for preparing a terpene-phenol resin by reacting terpene with phenol in the presence of an acidic condensation catalyst, characterized in that a) one molar part of terpene is reacted with 1.8-2.2 molar parts of phenol having at least two reactive sites, a boron trifluoride catalyst or in the presence of a complex to give a diphenol-terpene, b) reacting the diphenol-terpene obtained in step a) in the presence of said catalyst with an amount of terpene such that the substituted diphenol-terpene molecule obtained after the reaction has reactive sites, and c) one molar fraction obtained in step b) the substituted diphenol-terpene is reacted at 90-120 ° C with 0.2-1.5 molar parts of formaldehyde, and the reactions of steps a) -c) are carried out in an aromatic hydrocarbon solvent. Process according to Claim 1, characterized in that the resin obtained in step c) is boiled with zinc powder. Process according to Claim 1 or 2, characterized in that any remaining catalyst is removed from the product obtained in step c) or after the zinc powder treatment. Process according to one of the preceding claims, characterized in that the terpene is -carene, empinene, camphene or isolimonene. Process according to one of the preceding claims, characterized in that the phenol is hydroxybenzene, cresol or thymol. Process according to one of the preceding claims, characterized in that steps a) and b) are carried out at 80-120 ° C. Process according to Claim 1, characterized in that the aromatic hydrocarbon is toluene. Process according to one of the preceding claims, characterized in that part of the catalyst is added to step a) and the rest to step b). Process according to one of the preceding claims, characterized in that the phenol is hydroxybenzene, the terpene is -carene and the formaldehyde is in the form of paraformaldehyde. Process according to Claim 9, characterized in that in step b) one molar part of diphenol-carene is reacted with 2.5 to 3.75 molar parts -carene and in step c) one molar part of the substituted diphenol-carene is reacted with 0.2-1 , With 5 molar parts, preferably with 0.3 to 1.1 molar parts of formaldehyde. 12 o. -v 62546