Composition containing a novolac

Abstract

The invention relates to a composition containing a novolak and water. In one embodiment, a composition is provided comprising novolak and water with the percentage of ortho linkages of the phenol rings of the novolak is greater than that of para linkages, the novolak having a phenolic compound and an aldehyde molar ratio of from 1:0.2 to 1:0.45 and the composition having from 2% to 20% by weight of water based on the weight of the sum of the novolak and the water.

Claims

1. A homogenous novolak composition comprising: a novolak and 3.48 wt % to about 10 wt % water based on the total weight of the novolac and water, wherein: a percentage of ortho linkages of phenol rings of the novolak is greater than that of para linkages of the phenol rings of the novolak, the novolak has a phenolic compound to aldehyde molar ratio of from 1:0.25 to 1:0.4; and the composition has a viscosity of from 1,000 mPa*s to 5,000 mPa*s at 60 C., as determined by ISO 2884 1, and wherein the composition is a homogeneous liquid phase solution at a temperature of from 20 C. to 80 C.

2. The composition according to claim 1, wherein the composition contains about 10 wt % of water based on the total weight of the novolak and the water.

3. The composition according to claim 1, wherein the composition contains from 7 wt % to about 10 wt % of water based on the total weight of the novolak and the water.

4. The composition according to claim 2, wherein the molar ratio of the phenolic compound to the aldehyde is from 1:0.3 to 1:0.4.

5. The composition according to claim 1, comprising one or more solvents.

6. The composition according to claim 5, wherein the solvent is selected from the group consisting of triethyl phosphate, tris(chloropropyl)phosphate, benzyl alcohol, dibasic esters, diethylene glycol and ethylene glycol and combinations thereof.

7. The composition according to claim 6, wherein the solvent is diethylene glycol.

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

9. The composition according to claim 1, wherein the composition does not contain a protective colloid.

10. A process for producing a composition comprising a novolak and water, comprising: a) producing a novolak comprising a 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 1:0.25 to 1:0.4, b) mixing of the condensate produced under a) with from 3.48 wt % to about 10 wt % of water based on the total weight of the novolak and the water at temperatures in the range from 80 to 100 C. to produce a composition comprising the novolak and water, wherein the composition has a viscosity of from 1,000 mPa*s to 5,000 mPa*s at 60 C., as determined by ISO 2884 1, and the composition is a homogeneous liquid phase solution at a temperature of from 20 C. to 80 C.

11. A novolak polyol comprising the composition of claim 1.

12. The process according to claim 10, further comprising reacting the composition with one or more alkylene oxides, alkylene carbonates, or combinations thereof.

13. The composition according to claim 5, wherein the solvent is selected from the group consisting of diols, glycols ethers and combinations thereof.

14. The process according to claim 12, wherein the one or more alkylene oxides are selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, and combinations thereof, and wherein the alkylene carbonates are selected from the group consisting of ethylene carbonate, propylene carbonate, butylene carbonates, and combinations thereof.

15. A homogenous novolak composition comprising: a novolak having a molar ratio of phenolic compound to aldehyde of from 1:0.25 to 1:0.4, wherein a percentage of ortho linkages of the phenol rings is greater than that of para linkages; 1 to 10% by weight of a solvent selected from the group consisting of triethyl phosphate, tris(chloropropyl)phosphate, benzyl alcohol, dibasic esters, diethylene glycol and ethylene glycol and combinations thereof, based on total weight of the composition; and 3.48 wt % to about 10 wt % water based on the total weight of the novolac and water, wherein the composition does not contain a protective colloid, and wherein the composition has a viscosity of from 1,000 mPa*s to 5,000 mPa*s at 60 C., as determined by ISO 2884 1, and the composition is a homogeneous liquid phase solution at a temperature of from 20 C. to 80 C.

16. The composition according to claim 15, wherein the solvent is diethylene glycol.

17. The composition according to claim 1, wherein the composition is a homogeneous liquid phase solution at a temperature of from 20 C. to 60 C.

18. The composition according to claim 15, wherein the composition is a homogeneous liquid phase solution at a temperature of from 20 C. to 60 C.

19. The composition according to claim 1, wherein the composition has a number average molecular weight (Mn) of 210-400 g/mol.

Description

EXAMPLES

(1) The invention will now be illustrated with the aid of a working example: a) Production of the o-novolak (ratio of phenol:formaldehyde=1:0.36) 1. 179.72 kg of phenol are introduced as solid into a reactor and melted at temperatures of 55-65 C. 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. 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. 4. A distillation under atmospheric pressure up to 130 C. follows. 5. A halt phase of 2 hours at 130 C. can subsequently be carried out. 6. The phenol distillate is recovered in further distillation steps. 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. Materials data for the o-novolak: Cone-and-plate viscosity at 75 C.: 25 600 mPa*s Cone-and-plate viscosity at 100 C.: 1040 mPa*s Water content determined by the Karl-Fischer method: 0.13% Molar mass (M.sub.n) by means of GPC: 298 g/mol Molar mass (M.sub.w) by means of GPC: 432 g/mol b) Production of the composition according to the invention (o-novolak/water mixture containing 5.3% by weight of water) 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. 8. The product is cooled to 60 C. and drained through a filter. Materials data for the o-novolak/water mixture: Cone-and-plate viscosity at 50 C.: 20 160 mPa*s Cone-and-plate viscosity at 60 C.: 4960 mPa*s Cone-and-plate viscosity at 75 C.: 920 mPa*s Water content determined by the Karl-Fischer method: 5.47% Molar mass (M.sub.n) by means of GPC: 298 g/mol Molar mass (M.sub.w) by means of GPC: 432 g/mol

(2) 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.

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

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

(5) TABLE-US-00001 TABLE 1 o-Novolak o-Novolak o-Novolak (1:0.36) + (1:0.36) + (1:0.36) + 5.3% by 7% by 10% by weight of weight of weight of water (I) water (II) water (III) Viscosity at 50 C. 20 160 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 5.87 6.14 6.16 acetone/water Molar mass M.sub.n 298 307 X [g/mol] (GPC) Molar mass M.sub.w 432 442 X [g/mol] (GPC)

(6) TABLE-US-00002 TABLE 2 o-Novolak o-Novolak o-Novolak (1:0.3) + (1:0.3) + (1:0.3) + 3.5% by 7% by weight 10% by weight weight of of water of water water (IV) (V) (VI) Viscosity at 50 C. 19 200 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)

(7) 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.

(8) 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.

(9) 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).

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

(11) 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 depending on the type and concentration of the solvent and the storage temperature, may also have 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.