DE1959550A1 - Resin-forming preparation - Google Patents

Description

k. W. Schalk dipl.-ing. P. Wirth · dipl.-inc. G. then. "

DR. V. SCHMIED-KOWARZiK DR. P. WEINHOLD DR. D. G UIV.

6 FRANKFURT AM MAIN '

OR. ESCHENHEIMER 3TRASSg 99

Case 66: 489 Wd / Rö.

KOPPERS COMPANY, Inc. λ

Pittsburgh, Pa. 15219 «USA Resin-forming preparation

U.S. Patent 3,285,938, which relates to a tetragtydidyl ether of tris (hydroxybenzyl) phenol, is described as an intermediate of such ethers as tris (hydroxybenzyl) phenol. Although the specific properties of Tr IS (hydroxybenzyl) phenol are not described, it is believed that this known compound can be used at room temperature.

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009835/1944

BATH ORIGINAL

rature is a resin-like product. The ctort described. Verbinaung is generally made by reacting 1 mole of Triii.etHylolphenol made with at least 3 moles of phenol.

gs has now been found duii a new and very useful products by aie reacting at least 3 moles of resorcinol and 1 mole of a tris-hydroxymethyl OAER Tris-methoxymethylphencls can be produced. This compound, 2,4,6-iris (dihydroxbenzyl) phenol, has been found to be an excellent resin-forming product useful in numerous resin applications in which the irls-phenolic compound, tris (hydroxybenzyl) phenol, is found to be unsuitable Has.

The present invention relates to a new preparation of the formula

OH

CH,

in which every methy learns from the respective resorcinol residue in ortho position to a hydroxyl group of ßesorcinrests is bonded, this compound by reaction of 3 moles of resorcinol and 1 mole of trimethylolphenol or oxymethylphenol can be formed.

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BATH ORIGINAL

3Pria (dih, vdroxybeni5yl) phenol is produced by conversion of t mole part tria (methoxymethyl) phenol or trimethylol phenol rait .venigatens about 3 parts by mole of resorcinol. In this formation dea tris (ciihydroxybenzyl) phenols becomes tria (methyloxymethyl) phenol or trimethylol i-henol at elevated temperature to excess resorcinol, optionally in the presence of an acidic catalyst *; given. A mole ratio of 3 moles of resorcinol per mole Trimethylolphonol or tris (methoxymethyl) phenol is for the creation of the gowunaohtun connection bonöti / jt. Eu If an excess of resorcinol is generally used,

preferably about a 10% excess.

The trimethylol phenol or tris (methoxyethyl) phenol is used added to the resorcinol. This order of addition facilitates the conversion of 1 mole of phenol with 3 moles of resorcinol for production the desired tris (dihydroxybenzyl) phenol. the the reverse order of addition, namely the addition of resorcinol to the phenolic compound, leads to various side reactions and the risk of gelatinization or crosslinking of the reaction mass.

The implementation .virα carried out at an elevated temperature. If no catalyst is used, the temperature in the range of et.va 150-210 ⁰ C, preferably from about .80-200 ⁰ C should be. Lower temperatures require longer ones

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009835/1944

Reaction times during temperatures exceeding about 210 ° C. cause decomposition of the product.

If a lower temperature is required, a acidic catalyst can be added to accelerate the reaction. Those known for condensation reactions Catalysts include hydrogen chloride, oxalic acid, and other acidic catalysts for pheriol condensations. Atmospheric pressure is preferably used during the reaction, although it can also be increased or decreased Prints could be used, but this is not seen as an advantage.

The triirethylolphenol or tris (methoxymethyl) phenol is added continuously or batchwise over a period of time sufficient for the corresponding reaction. In general, slow addition over about 1-3 hours is preferred. Lunger or shorter addition times can be used and are dependent on the temperature of the reactions. After the addition, a short reaction time should be provided, e.g. from about 1 to 1 hour. The completion of the reaction can easily be determined by the cessation of the evolution of methanol or water which occurs during the condensation. When the development stops "the condensation is over."

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After the desired reaction time, the product is removed from the reaction oil kettle and, after cooling to room temperature, is ready for use for various resin applications. The product contains the tri 3- (dihydroxybenzyl) phenol and some lower molecular weight products and condensation products. If necessary, any free resorcinol present can be removed from the product, for example by washing with water, but there is a small difference between such washed products and the direct product from the reaction vessel in terms of reactivity or usability. In general, in such manufacturing processes, about $ 5-30% free resorcinol will be present in the product.

Examples of the different uses of Tris (dihydroxybenzyl) phenol are use as an adhesive component for joining wooden parts, as an adhesive component in starch adhesives and as a component in production of adhesive dipping baths for bonding textiles with rubber. The use of tris (dihydroxybenzyl) phenol when joining textile materials with rubber, in a parallel registration from the same day. It is particularly noteworthy that the tris (monohydroxybenzyl) phenol, as described in US Pat. No. 3,285,938, for adhesive dips for joining nylon or rayon cord with rubber is unsuitable, while the inventive

009835/1944

"BAD ORIGINAL

mäjie tri j (dihydroxybenzyl) phenol for such use is excellently suited, as in the following Examples is illustrated.

The following examples serve for further explanation of the invention, unless - unless otherwise stated - all Parts are parts by weight.

example 1

14.75 kg (0.134 kg mol) of resorcinol were placed in a Patterson-Kelley kettle (56.81) flushed with nitrogen. After the resorcinol had been heated until it melted, stirring was started and the temperature was increased to 190 ° C. 9 _F 08 kg (0,398 kgmoles) tris (methoxymethyl) phenol were added at a constant rate over a period of 100 minutes while maintaining the temperature of the reaction mixture at about 186-196 ⁰ C. Methanol evolved during the reaction. A partial condenser and a total condenser were used in series to return the resorcinol to the boiler while the methanol vapor was condensed in the total condenser. After completion of the tris (methoxymethyl) phenol addition the mixture for another 10 minutes at 19o ° C was maintained and _transferred} then the contents of the vessel into containers. 20.25 kg of a product was obtained and 3.04 kg of methanol (0.095 kg mol) was recovered during the reaction. An analysis of the product

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showed that it was tris (dihydroxybenzyl) phenol and that it contained 25% free resorcinol and only a trace of free phenol. The product had a molecular weight of 315 and a Durran softening point of 116.5 ⁰ C. The viscosity of the product was aea at 25 ⁰ C 2-5 through Z-6 (Gardner-ViskosiEieter ,, 50 $ aqueous solution at a pH of 7 ). The product had a gel time of 80 minutes at a pH of 7.10 (measured with a Tecam gel timer with a solution of 10.0 parts by weight in 1.0 part by weight of ethanol, 7-3 parts by weight Water and 2.7 Gevv, parts 37 tiger Pormalin).

example 2

The procedure of Example 1 was repeated, but the product was heated for 59 minutes instead of 10 minutes after the addition of a trio (nsethoxyinethyl) phenol. There were 18 _? 75 kg of a product were obtained (3.27 kg of methanol were released). The properties of the product were measured as in Example 1:

Molecular weight 347 Resorcinol 26.5> phenol traces Verv.-VerificationpunktfDurran) 11.6 ° C viscosity Z-4 to Z-5

Gelceii (as in, Example 1) 59 minutes

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Example 3

The gelation time for · those prepared according to the invention

V.

Resin images were made with that of a conventional resorcinol-formaldehyde resin compared. Da3 conventional reaorcinol formaldehyde resin was made according to the procedure of the US patent 2,385,372 manufactured. The solutions were mixed by dissolving 100 g of resin images each in one Solvent made from 10 g of ethanol and 73 g of water.

™ The solutions were made using the conventional Resin (comparison) and the products of Example 1 and 2 manufactured. About 19 »5 g of each solution was made with either 50 point aqueous sodium hydroxide or formic acid on the set the desired pH value. After setting the pH of the solutions (the values are listed in Table I), each 18.3 g of the solutions with 2.7 g of a 37 #igen Pormalin solution mixed for 1.5 minutes, immediately afterwards passed into a 20x150 mm test tube and with a

could be fc water bath maintained at 23 + 0.2 ⁰ C, as determined by the gel by a Tecara-Gelierungsmesser (! G Model 7-1). The timer was started as soon as the mixing of the resin and the Pormalin solution began. The results can be seen from Table I:

009835/1944

BATH

Table I.

Setting times

pH value comparison Product from Example I Product from Example 2 Gel time pH value Gel time pH value Gel time

—_ 7.10 80 6.98 59 7:00 176 6.26 167 6.10 176 5.90 499 4.64 595 4.25 792 5.07 1688 4.37 598 3.88 970 3.81 5331 3.92 670 3rd-11th 709 2.65 1573 3.80 698 —— - 2.28 494 3.12 390 —_

The information given above shows the surprising response behavior of the resin former according to the invention compared to a conventional resorcinol-formaldehyde resin at pH values between about 2-7.

Example 4

Tris (hydroxybenzyl) phenol were prepared following the procedure of Example 1 part a of US Pat. No. 3,285,938 in order to compare it with the product according to the invention and to emphasize the unexpected properties of the product according to the invention over this.

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BAD ORtGINAt

-ΙΟ example 5

The product prepared according to Example 1, tris (dihydroxybenzyl) phenol, and the product prepared according to Example 4 tris. (monohydroxybenzyl) phenol, were wood-binding Properties compared. A solvent mixture was made containing 20 wt .- ^ methanol, 5 wt .- ^ EthylengIykpl and 75 wt .- $ water contained. There were ^ Adhesive mixtures made that contain 50 wt .- $ solvents and 50 wt .- ^ dea to be examined resin formers contained. Three adhesive mixtures were prepared which contained the compound from Example 1 and were adjusted to different pH values were set. Adhesive A had a pH of 8.0; Adhesive C has a pH of 8.5 and adhesive D a pH of 9.9. Her Adhesive B contained tris (monohydroxybenzyl) phenol and had a pH of 9.9.

The resins were used to bond 2.54x20.52x63 »75 cm southern pine pieces. The bonded pieces were measured for 6 days NaOH to shear pressure by AITC Test no. 107 'after two hours, and 6 days of storage at 23 ⁰ C and layer separation (delamination) of AITC Test no. 110th The results of the * tests were as follows:

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09835/19 44 ? ΠΛ BAD OBiGINAL

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009835/1944

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As the results show, tris (dihydroxybenzyl) phenol is very suitable for gluing wooden parts, while the known compound _; Tris (monohydroxybenzyl) phenol, did not even show nearly sufficient binding capacity.

Example 6

A Haftbad for use for nylon-Rei £ encörd was prepared by mixing 3.75 parts of the product of Example 2, 51 _f 2.0 parts of water, 2.85 parts of 37 tigern formalin, 35.08 parts vinylpyridine tyrolbutadien-latex (41 $> Solids, Gen.-Tac latex) and 1 , 12 parts 10 $ i like prepared aqueous sodium hydroxide. The bath had a pH of 8.8, a total solids content of $ 17.72, and a resin to rubber ratio of 1: 5.12. This immersion bath was referred to as bath A-. 5 additional immersion baths were prepared as indicated above, the pH being increased by adding more sodium hydroxide (BF). An immersion bath (bath G-) was also prepared, but using the ingredients and characteristics of bath A tris (monohydroxybenzyl) phenol (example 4) for the product of example 2. A higher pH of 9.90 was required to enable the tris (monohydroxybenzyl) phenol to dissolve and thereby obtain a stable dispersion. Four immersion baths comparable to bath G were produced (HK). Nylon cord (Du Pont type 714,840 denier, two-strand with 12/12 twist)

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009835 / 19U '· ■■' BAO ORlGiNAL

was dipped in the adhesive bath and attached to natural rubber hardened. The results of dea Η tests according to the procedures of ASTM Method D 2138-67 (average of 10 samples) are in Table III listed.

pH value of the
Bath Tabel III Detention hour 8.80 Hardening bec
Temp. C lingu
Time A. 8.80 221 40 B. 9.42 221 30th C. 9.72 221 40 D. 10.13 221 40 E. 10.58 221 40 F. 9.90 221 40 (J 10.73 221 40 H 10.81 221 30th I. 10.87 221 40 J 10.98 221 40 K 221 40

9.99 10.35

9.31 10.62

9.13 10.31

1.82 1.91 2.63 3.18 3.18

It can be seen that the adhesive baths, the tris (monohydroxybenzyl) phenyl contain, for connecting nylon cord with rubber, are unsuitable, while the tris (dihydroxybenzy1) phenol shows excellent results.

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BAD OFHGiNAt

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A rayon tire cord adhesive bath was made by mixing 2.67 parts of the product of Example. 2, 63.51 parts of water, 1.35 parts of 37 ^ igeTFormalinlösung, 0.80 parts of NaOH (10 'fix ge aqueous solution), 26.68 parts of styrene butadieniatex (40% "■ solids") and 5.0 parts of vinylpyridine Styrene-butadiene latex (.41 "/> solids, Gen-Tac latex) made. Dao finished bath had a total solids content of 15 ° / °, a resin / rubber ratio of 1: 6.36 and a pH value of 8, 8t This immersion bath was designated as bath A. 6 further immersion baths were prepared as above, but the pH was adjusted to other values by additional sodium hydroxide (BG). One bath (bath H) was made with the composition of bath A, however with tris (monohydroxybenzyl) phenol (Example 4) - prepared for the product of Example 2. The bath had to be adjusted to a higher pH value (9.8) using sodium hydroxide in order to bring about a solution of the tris (monohydroxybenzyl) phenol and thus to form a stable latex dispersion.

Four more baths were made using tris (monohydroxybenzyl) phenol produced at a higher pH value (I-L). The rayon tire cord, Tyrex type 220, 1650 denier, two strand, 12/12 Twist) was treated with the various baths and combined with natural rubber. The Η-test values were obtained by the method of ASTMD 2138-67 (average of 10 values). The results are in Table IV listed.

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Adhesive bath pH-Wurt Ilurtungobudin ^ ungen II-Test (6.35 ram.)

of the bath temp. ⁰ C time (sec .-) - kg at 100 + IC

A. 8.80 18. ' 40 8.49 B. 8.80 182 30th 4.72 C. 9.20 182 40 7.31 D. 9.42 182 40 • 9.31 E. 9.72 182 40 10.62 F. 10.13 182 40 9.13 G 10.58 182 40 10.31 H 9.80 182 40 2.63 I. 9.80 182 30th 2.63 J 10.73 182 40 3.18 K 10.87 182 40 3.27 L. 10.98 182 40 3.18

As with nylon cord, trie (monohydroxybenzyl) phenol is used Use in adhesive baths to connect flayon cord with Rubber Unsuitable, while tria (dihydroxybenzyl) phenol shows excellent results.

Example 8

Under a nitrogen atmosphere and using a

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105.1 g (0.4 mol) of trimethylphenol (commercially available, 70% aqueous solution, pH value = 7.8, viscosity = 1.65 poise at 25 ⁰ O) were added dropwise to mechanical stirrers 182.6 g (1.66 mol) of resorcinol were added at 185-195 ° C. over the course of 100 minutes. After the addition, the product was ^{stirred at 190 °} C. for a further 10 minutes. During the reaction, 40.5 g of water were collected as distillate * The experiment yielded 284 g of tria (dihydroxybenzyl) phenol, which contained 28.5% resorcinol and was analyzed by gas chromatography. The product had the following properties. (as determined in Example 1).

viscosity (Durran) 5.40 poise Molecular weight 317 Softening point 11O ⁰ O

The other physical properties and responsiveness of the product are comparable to those of the product from Example 1.

Example 9

An attempt was made to produce a resin Preparation of tris (dihydroxybenzyl) phenol-like resin by conventional methods of resin synthesis with a resorcinol / phenol / formaldehyde ratio of 75j25j75

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place. 209 g (2.0 mol) of phenol, 243 g (3.0 mol) of 37 $> sodium formaldehyde and 21 g of 50 #iges, aqueous sodium hydroxide were added with stirring to a reaction vessel and heated within 10 minutes to 7P ° C. The mixture was heated for 65 minutes back flowing, cooled to about 7O ⁰ C and 660 g (6 moles) of resorcinol were added. , Then the mixture was heated to reflux and allowed to boil for one hour under reflux (109 ⁰ C). The heat source was then removed and 122 g (1.5 mol) of 37% aqueous formaldehyde were added dropwise over a period of about 10 minutes. Then 570 g water was supplied · to the solid content to be reduced to about $ 50, and the mixture for "1.25 hours to about 100 ⁰ C. When an attempt was made the residual formaldehyde (1.5 moles, 122g) to admit the mass gelled.

Further attempts a resin product with the resorein / phenol / Forraaldehyde ratio of 75ϊ25: 75 by changing the Establish process steps and conditions, resulted also just a gelled product that is used for adhesive or Adhesive purposes was not suitable.

009835/194

Claims (1)

ig Claims Resin-forming preparation, characterized in that it contains about 70 to 95 wt. # Of a compound of the formula - OH OH OH wherein each methylene residue is bound to the respective resorcinol residue in ortho-position to a hydroxyl group of the resorcinol residue,
and comprises about 3Q to 5% by weight free resorcinol. Resin former of Pormel I « ■ 0Ό9 835/1944 · - OBlGlNAL INSPECTED