COMPOSITION CONTAINING A NOVOLAC

Abstract

The invention relates to a composition containing a novolak and water.

In order to provide novolaks in a liquid preparation, which owing to their viscosity allow uncomplicated processing at temperatures of <100° C., a composition containing novolak and water is proposed, wherein a) the percentage of ortho linkages of the phenol rings of the novolak is greater than that of the para linkages and b) the novolak has been produced from a phenolic compound and an aldehyde in a molar ratio of from 1:0.2 to 1:0.45 and c) the composition contains from 2 to 20% by weight of water based on the weight of the sum of novolak and water.

Claims

1. Composition containing a novolak and water, wherein a) the percentage of ortho linkages of the phenol rings of the novolak is greater than that of the para linkages and b) the novolak has been produced from a phenolic compound and an aldehyde in a molar ratio of from 1:0.2 to 1:0.45 and c) the composition contains from 2 to 20% by weight of water based on the weight of the sum of novolak and water.

2. Composition according to claim 1, characterized in that the composition contains from 2 to 15% by weight of water based on the weight of the sum of novolak and water.

3. Composition according to claim 2, characterized in that the composition contains from 2 to 9% by weight of water based on the weight of the sum of novolak and water.

4. Composition according to at least one of the preceding claims, characterized in that the molar ratio of the phenolic compound to the aldehyde is from 1:0.25 to 1:0.4.

5. Composition according to at least one of the preceding claims, characterized in that the composition contains one or more solvents as further component.

6. Composition according to claim 5, characterized in that the solvent is selected from among triethyl phosphate, tris(2-chloroisopropyl)phosphate, benzyl alcohol, dibasic esters, diethylene glycol and ethylene glycol and also further diols or glycols ethers and/or mixtures thereof.

7. Composition according to claim 7, characterized in that the solvent is diethylene glycol.

8. Composition according to claim 7, characterized in that the solvent is present in a concentration of from 1 to 10% by weight based on all components of the composition.

9. Composition according to at least one of the preceding claims, characterized in that the composition does not contain any protective colloid.

10. Process for producing a composition containing a novolak and water, which contains the following steps: a) production of a novolak in which the percentage of the ortho linkages of the phenol rings is greater than that of the para linkages by condensation of a phenolic compound and an aldehyde in a ratio of from 1:0.2 to 1:0.45, b) mixing of the condensate produced under a) with from 2 to 20% by weight of water based on the weight of the sum of novolak and water at temperatures in the range from 80 to 100° C. to produce the composition.

11. Use of the composition according to at least one of claims 1 to 9 for producing novolak polyols.

12. Use of the composition according to claim 11 for producing novolak polyols by reacting the composition with alkylene oxides, e.g. ethylene oxide, propylene oxide, butylene oxide, and/or alkylene carbonates, e.g. ethylene carbonate, propylene carbonate, butylene carbonate, and/or mixtures thereof.

13. Use of the composition according to at least one of claims 1 to 9 for producing polyurethane materials.

14. Use of the composition according to claim 13 for producing polyurethane foams.

15. Use of the composition according to at least one of claims 1 to 9 for producing coatings, paints and varnishes, adhesives, insulation materials, binders, laminates, abrasives, shaped products and/or refractory materials.

Description

[0042] The invention will now be illustrated with the aid of a working example: [0043] a) Production of the o-novolak (ratio of phenol:formaldehyde=1:0.36) [0044] 1. 179.72 kg of phenol are introduced as solid into a reactor and melted at temperatures of 55-65° C. [0045] 2. 0.27 kg of zinc acetate dihydrate is dissolved in 1.03 kg of water and subsequently added while stirring. The reaction mixture is heated to 100° C.-110° C. [0046] 3. 45.9 kg of formalin 45% are then added over 1 hour at 100° C.-110° C., followed by an after-reaction under reflux for 3 hours. [0047] 4. A distillation under atmospheric pressure up to 130° C. follows. [0048] 5. A halt phase of 2 hours at 130° C. can subsequently be carried out. [0049] 6. The phenol distillate is recovered in further distillation steps. [0050] 7. To reduce the free phenol content (<0.1%) and water content (max. 0.1%), the product is subjected again to a distillation in the presence of steam and under reduced pressure at temperatures in the range from 170° C. to 180° C. [0051] Materials data for the o-novolak: [0052] Cone-and-plate viscosity at 75° C.: 25 600 mPa*s [0053] Cone-and-plate viscosity at 100° C.: 1040 mPa*s [0054] Water content determined by the Karl-Fischer method: 0.13% [0055] Molar mass (M.sub.n) by means of GPC: 298 g/mol [0056] Molar mass (M.sub.w) by means of GPC: 432 g/mol [0057] b) Production of the composition according to the invention (o-novolak/water mixture containing 5.3% by weight of water) [0058] 7. At 90° C., 5.3 kg of water are added to 94.7 kg of the o-novolak produced under a) over a period of 1 hour. [0059] 8. The product is cooled to 60° C. and drained through a filter. [0060] Materials data for the o-novolak/water mixture: [0061] Cone-and-plate viscosity at 50° C.: 20 160 mPa*s [0062] Cone-and-plate viscosity at 60° C.: 4960 mPa*s [0063] Cone-and-plate viscosity at 75° C.: 920 mPa*s [0064] Water content determined by the Karl-Fischer method: 5.47% [0065] Molar mass (M.sub.n) by means of GPC: 298 g/mol [0066] Molar mass (M.sub.w) by means of GPC: 432 g/mol

[0067] In Tables 1 and 2, the influence of different amounts of water on the properties of the composition of the invention were examined; in Table 1 the o-novolak was produced according to method a) (ratio of phenol:formaldehyde=1:0.36) and in Table 2 the ratio of phenol:formaldehyde was 1:0.3. The o-novolak/water mixtures were provided according to method b) using the amounts of water indicated in Tables 1 and 2.

[0068] The viscosities were measured by the cone-and-plate method (ISO 2884-1).

[0069] The molar mass was determined by means of gel permeation chromatography (GPC—commercial, separation column set: 6 columns in series, column packing: crosslinked polystyrene, eluent: THF, detector: UV 280 nm, calibration substance: phenol novolak).

TABLE-US-00001 TABLE 1 o-Novolak o-Novolak o-Novolak (1:0.36) + (1:0.36) + (1:0.36) + 5.3% by weight 7% by weight 10% by weight of water (I) of water (II) of water (III) Viscosity at 50° C. 20160 7200 2960 [mPa*s] Viscosity at 60° C. 4960 2000 1100 [mPa*s] Viscosity at 75° C. 920 570 320 [mPa*s] Viscosity at 100° C. 170 230 50 [mPa*s] Water content [%] 5.47 7.07 10.08 Phenol content [%] 0.21 0.19 0.07 pH in acetone/water 5.87 6.14 6.16 Molar mass M.sub.n 298 307 x [g/mol] (GPC) Molar mass M.sub.w 432 442 x [g/mol] (GPC)

TABLE-US-00002 TABLE 2 o-Novolak o-Novolak o-Novolak (1:0.3) + (1:0.3) + (1:0.3) + 3.5% by weight 7% by weight 10% by weight of water (IV) of water (V) of water (VI) Viscosity at 50° C. 19200 3200 1160 [mPa*s] Viscosity at 60° C. 4720 1320 400 [mPa*s] Viscosity at 75° C. 920 320 170 [mPa*s] Viscosity at 100° C. 160 80 45 [mPa*s] Water content [%] 3.48 6.41/6.55 10.19/10.25 Phenol content [%] 0.01 0.03 0.03 pH in acetone/water 6.52 6.28 6.34 Molar mass M.sub.n 267 274 267 [g/mol] (GPC) Molar mass M.sub.w 354 364 356 [g/mol] (GPC)

[0070] When, for example, the viscosities at 60° C. of the inventive compositions (I) to (VI) in Tables 1 and 2 are compared with the pure o-novolak produced in a), it can be seen that even a few percent by weight of water decrease the viscosity of the compositions of the invention to a great extent.

[0071] In addition, it was found that at 20° C. all compositions (I) to (VI) are stable in respect of their crystallization behaviour for at least 6 months. Likewise, separation of water occurred to only a slight extent, which did not impair the usability and handling of the compositions.

[0072] In Table 3, the o-novolak was produced as indicated under a) and admixed with 10% by weight of water and the indicated amount (% by weight) of the appropriate solvent based on the weight of the sum of novolak, water and solvent (all components).

TABLE-US-00003 TABLE 3 Mixture of o-novolak/water (10% by weight)/solvent mixture Stor- Stor- age age Concen- stabil- stabil- tration ity ity of Viscos- Viscos- Viscos- for 4 for 4 solvent ity at ity at ity at months months [% by 60° C. 35° C. 25° C. at at Solvent weight] [mPa*s] [mPa*s] [mPa*s] 20° C. 60° C. VII Triethyl 10 560 + / − phosphate VIII Triethyl 5 640 − phosphate IX DBE- 10 390 13 120 − − dibasic ester X DBE- 5 580 16 980 − − − dibasic ester XI Benzyl 10 290 3920 − − − alcohol XII Benzyl 5 490 10 720 58 880 − − alcohol XIII Diethylene 10 390 4400 16 000 + + + + glycol XIV Diethylene 5 540 9920 51 200 + + + glycol Unsatisfactory storage stability: − (minus) Good, satisfactory storage stability: + (plus)

[0073] It can be seen from Table 3 that the viscosity of the inventive compositions admixed with appropriate solvents (VII-XIV) is at the desired level, but at the same time the compositions may have, depending on the type and concentration of the solvent and the storage temperature, a surprisingly attractive storage stability. Diethylene glycol appears to be the best solvent here, as shown in Table 3. Owing to the consistency of the samples, quantitative analysis of separated fractions was not possible, so that determination of the degree of crystallization (measure of storage stability) was carried out by visual comparison of the samples with one another.