阅读说明：本技术 包含磺化的苯酚、脲和甲醛的缩聚物的用于皮革生产的鞣剂 (Tanning agent for leather production comprising a polycondensate of sulfonated phenol, urea and formaldehyde ) 是由 J·安曼 F·罗伊特 于 2018-05-16 设计创作，主要内容包括：本发明涉及磺化的苯酚、脲和甲醛的缩聚物,其中磺化的苯酚以2:1至1:5的摩尔比例含有邻苯酚磺酸和对苯酚磺酸。本发明还涉及用于制造缩聚物的方法,其包括以下步骤：a)通过使苯酚和硫酸在低于75℃的温度接触而提供磺化的苯酚,b)使磺化的苯酚与脲接触,和c)使步骤b)的反应产物与甲醛接触。本发明还涉及用于自鞣制、预鞣制和共鞣制去毛的生皮和去毛的表皮和用于后鞣制皮革和裸皮的鞣剂,其包含水以及该缩聚物；以及涉及该缩聚物用于制造皮革的用途。(The invention relates to polycondensates of sulfonated phenol, urea and formaldehyde, wherein the sulfonated phenol contains ortho-phenolsulfonic acid and para-phenolsulfonic acid in a molar ratio of 2:1 to 1: 5. The invention also relates to a method for producing a polycondensate, comprising the following steps: a) providing a sulfonated phenol by contacting phenol and sulfuric acid at a temperature below 75 ℃, b) contacting the sulfonated phenol with urea, and c) contacting the reaction product of step b) with formaldehyde. The invention also relates to a tanning agent for self-tanning, pre-tanning and co-tanning of dehaired skins and for post-tanning leather and pelts comprising water and the polycondensate; and to the use of the polycondensates for the production of leather.)

1. A condensation polymer of sulfonated phenol, urea and formaldehyde, wherein the sulfonated phenol contains ortho-phenolsulfonic acid and para-phenolsulfonic acid in a molar ratio of 2:1 to 1: 5.

2. Polycondensate according to claim 1, in which the molar ratio of ortho-phenolsulphonic acid to phenolsulphonic acid is in the range from 2:1 to 1: 3.

3. Polycondensate according to claim 1 or 2, in which the molar ratio of sulfonated phenol to urea is in the range from 2:1 to 1:2.

4. Polycondensate according to any one of claims 1 to 3, in which the molar ratio of urea to formaldehyde is in the range from 1:1 to 1: 3.

5. Polycondensate according to any one of claims 1 to 4, obtainable by a process comprising the steps of

a) Providing a sulfonated phenol by contacting phenol and sulfuric acid at a temperature of less than 75 ℃,

b) contacting the sulfonated phenol with urea,

c) contacting the reaction product of step b) with formaldehyde.

6. Polycondensate according to claim 5, in which in step a) the temperature is controlled by cooling.

7. Process for the manufacture of a polycondensate as defined in any one of claims 1 to 4, comprising the following steps

a) Providing a sulfonated phenol by contacting phenol and sulfuric acid at a temperature of less than 75 ℃,

b) contacting the sulfonated phenol with urea, and

c) contacting the reaction product of step b) with formaldehyde.

8. The method of claim 7, additionally comprising the steps of

d) Neutralizing the reaction product of step c) to a pH of 4 to 9.

9. The method according to claim 7 or 8, wherein in step a) the temperature is controlled by cooling.

10. The process of any one of claims 7 to 9, wherein the reaction product of step c) is not contacted with additional phenol or with additional formaldehyde in a subsequent step.

11. The method of any one of claims 7 to 10, wherein the molar ratio of sulfonated phenol to urea is in the range of 2:1 to 1:2.

12. The process according to any one of claims 7 to 11, wherein the molar ratio of the urea to the formaldehyde is in the range of 1:1 to 1: 3.

13. Tanning agent for self-tanning, pre-tanning and co-tanning of dehaired hides and skins and for post-tanning of leather and pelts comprising water and a polycondensate as defined in any one of claims 1 to 6 or obtainable by the process as defined in any one of claims 7 to 12.

14. Use of a polycondensate as defined in any one of claims 1 to 6 or obtainable by a process as defined in any one of claims 7 to 12 for the manufacture of leather.

15. Use according to claim 14, wherein the polycondensate is used as a tanning agent, a pre-tanning agent or a post-tanning agent.

Technical Field

The invention relates to polycondensates of sulfonated phenol, urea and formaldehyde, wherein the sulfonated phenol contains ortho-phenolsulfonic acid and para-phenolsulfonic acid in a molar ratio of 2:1 to 1: 5. The invention also relates to a method for producing the polycondensate, comprising the following steps: a) providing a sulfonated phenol by contacting phenol and sulfuric acid at a temperature below 75 ℃, b) contacting the sulfonated phenol with urea, and c) contacting the reaction product of step b) with formaldehyde. The invention also relates to a tanning agent for self-tanning (self-tanning), pre-tanning and co-tanning of dehaired skins and for post-tanning leather and pelts comprising water and the polycondensate; and to the use of the polycondensates for the preparation of leather.

Background

Tanning is the process of cross-linking collagen fibers from animal skins to resist bacterial or fungal degradation. Common tanning agents are chromium sulfate, glutaraldehyde, vegetable tanning agents or synthetic tanning agents. Since the introduction of the first syntans (syntans) over a hundred years ago, the role of syntans in the tanning process has changed significantly. By their chemical modification, increased technical requirements for leather quality can be achieved. The first syntan is made by condensation of phenolsulfonic acid and formaldehyde. Although these syntans were initially used as adjuvants and dispersants for vegetable tannins, they can be applied as tanning agents without vegetable tannins after their chemical modification. With the widespread acceptance of chrome sulfate or glutaraldehyde tanning, they are now used primarily in retanning processes where they help to structure and fill crosslinked collagen fibers.

To enhance the tanning properties of the syntan, unsulfonated phenol is introduced into the condensate. Generally, the tanning power increases with decreasing degree of sulfonation, meaning that the more unsulfonated phenol that is incorporated into the condensate, the higher the tanning power. It is clear that the focus of these field condensates is on para-substituted phenolsulfonic acids as central intermediates.

US 1841840, US 2179038, US 2242681, US 3852374 and US 5342916 describe the introduction of urea into the condensation of p-phenolsulfonic acid and formaldehyde.

In order to optimize more tanning properties and to achieve a softer leather using these syntans, a condensation with phenol and formaldehyde is subsequently carried out. By applying this second phenol formaldehyde condensation, the theory of Heidemann was applied, where the unsulfonated phenol increased the tanning properties. These heterogeneous condensates, consisting of sulfonated and unsulfonated phenols, are known as replacement syntans. They show additional softness if applied on leather and have the ability to replace vegetable tannins in leather manufacture, but unlike primary condensates of p-phenolsulfonic acid, urea and formaldehyde, lack lightfastness. The condensates of formaldehyde and urea with p-phenolsulfonic acid are described in DE1142173 in examples 8 to 10. They are not isolated but are further reacted with phenol and formaldehyde in a second condensation to increase performance.

Disclosure of Invention

However, the tanning agents have a number of disadvantages. The leathers and skins produced therewith have inadequate light and heat resistance, i.e. they tend to yellow and rapidly lose their soft hand and their fullness and become brittle. The tanning agent itself shows poor stability in terms of storage and is slightly soluble in water. For this reason, their tanning action is sometimes unsatisfactory. The aim is to overcome the disadvantages of the prior art.

This object is solved by a polycondensate of sulfonated phenol, urea and formaldehyde, wherein the sulfonated phenol contains ortho-phenolsulfonic acid and para-phenolsulfonic acid in a molar ratio of 2:1 to 1: 5.

The molar ratio of the ortho-phenolsulfonic acid to the phenolsulfonic acid is preferably in the range from 1.4:1 to 1:3, in particular from 1:1 to 1:2. In another form, the molar ratio of ortho-phenolsulfonic acid to phenolsulfonic acid is preferably in the range of from 2:1 to 1:3, especially from 2:1 to 1:2. The molar ratio of ortho-phenolsulfonic acid to phenolsulfonic acid can be determined by H-NMR.

The molar ratio of sulfonated phenol to urea is generally in the range of from 2:1 to 1:2, preferably in the range of from 1.7:1 to 1:1.7, and especially in the range of from 1.3:1 to 1: 1.3.

The molar ratio of urea to formaldehyde is generally in the range from 1:1 to 1:3, preferably in the range from 1.1:1 to 1:2.6, and especially in the range from 1.3:1 to 1: 2.2.

Formaldehyde is generally used in the form of a 10 to 50% w/w strength aqueous solution; aqueous solutions of 30 to 35% w/w strength are commercially available. Alternatively, a substance capable of eliminating formaldehyde under reaction conditions, such as paraformaldehyde, may be used, with formaldehyde being preferred.

The polycondensate of sulfonated phenol, urea and formaldehyde is generally substantially free of other monomers. Preferably, the polycondensate contains less than 15 mol%, more preferably less than 10 mol% and especially less than 5 mol% of monomers other than sulphonated phenol, urea and formaldehyde.

In another form, the condensation polymer of sulfonated phenol, urea and formaldehyde is generally substantially free of phenol. Preferably, the polycondensate contains less than 15 mol%, more preferably less than 10 mol% and especially less than 5 mol% of phenol.

In another form, the condensation polymer of sulfonated phenol, urea and formaldehyde is generally substantially free of other organic nitrogen-containing bases other than urea. Preferably, the polycondensate contains less than 10 mol%, more preferably less than 5 mol% and especially less than 1 mol% of other organic nitrogen bases than urea. The other organic nitrogen containing base other than urea may be selected from the group consisting of melamine, hydroxy- (C2-20-alkyl) -melamine, bis-hydroxy- (C2-20-alkyl) -melamine, tri-hydroxy (C2-20-alkyl) melamine, hydroxyaryl melamine and poly (alkylene oxide) -substituted melamine, melem, hydroxy (C2-20-alkyl) melem, poly (alkylene oxide) -substituted melem, guanamine, N-hydroxy (C2-20-alkyl) guanamine, poly (alkylene oxide) -substituted guanamine dicyandiamide, and mixtures thereof.

The polycondensates generally have a molecular weight in the range from 1000 to 8000 dalton, preferably from 1500 to 5000 dalton, in particular from 2500 to 3000 dalton. The molecular weight is determined by gel permeation chromatography, for example, using an internal standard (e.g., a polyacrylic acid-based internal standard).

The invention further relates to a method for producing a polycondensate, comprising the following steps

a) Providing a sulfonated phenol by contacting phenol and sulfuric acid at a temperature of less than 75 ℃,

b) contacting the sulfonated phenol with urea, and

c) contacting the reaction product of step b) with formaldehyde.

The polycondensate can be generally obtained by a production method comprising the following steps

a) Providing a sulfonated phenol by contacting phenol and sulfuric acid at a temperature of less than 75 ℃,

b) contacting the sulfonated phenol with urea, and

c) contacting the reaction product of step b) with formaldehyde.

The process for making the condensation polymer may additionally comprise a step d) of neutralizing the reaction product of step c) to a pH of 4 to 9.

In step a), phenol and sulfuric acid are preferably contacted at a temperature below 65 ℃ and especially below 60 ℃. In another preferred form of step a), phenol and sulfuric acid are contacted at a temperature of from 20 to 60 ℃, and especially from 40 to 60 ℃. In step a), phenol and sulfuric acid are preferably contacted at standard pressure.

Heat is generally generated when contacting phenol and sulfuric acid and the temperature is typically raised above 100 ℃. In step a), the temperature is generally controlled by cooling. For cooling, conventional cooling means may be used, e.g. cooling using heat exchangers, internal cooling coils, external containers.

In step a), the sulfuric acid is generally 90 to 100w/w, preferably 96 to 98w/w, strength sulfuric acid.

In step a), phenol and sulfuric acid are contacted in a molar ratio in the range of 1 to 1.5, preferably in the range of 1.05 to 1.4.

In step a), phenol and sulfuric acid are contacted for 1 to 8h, preferably 2 to 4 h.

In step a), phenol and sulfuric acid are generally contacted until at least 80 mol%, preferably 85 mol%, and in particular at least 90 mol% of the phenol is sulfonated.

The reaction product of phenol and sulfuric acid can be used in the subsequent step b) without additional purification steps.

In step b), the sulfonated phenol is contacted with urea, for example in the presence of water.

The molar ratio of sulfonated phenol to urea in step b) is generally in the range from 2:1 to 1:2, preferably in the range from 1.7:1 to 1:1.7 and especially in the range from 1.3:1 to 1: 1.3.

The contacting of the sulfonated phenol with urea is advantageously carried out in an acidic medium at a pH of from 0 to about 5, preferably from 0 to 2. The high hydrogen ion concentration is generally provided by excess sulfuric acid from the sulfonation step a) and/or by dissociation of the sulfonation product from step a) in water. The setting of the specified value within the above pH range is carried out using a usual acid and base.

The reaction product of step b) can be used in the subsequent step c) without further purification steps.

In step c), the reaction product of step b) is contacted with formaldehyde.

The molar ratio of urea to formaldehyde of step c) is generally in the range from 1:1 to 1:3, preferably in the range from 1.1:1 to 1:2.6, and especially in the range from 1.3:1 to 1: 2.2.

Contacting the reaction product of step b) with formaldehyde is advantageously carried out at a pH of from 0 to about 5, preferably from 0 to 3. The contacting of the reaction product of step b) with formaldehyde is advantageously carried out at a temperature of from 40 to 90 ℃, preferably from 50 to 80 ℃ and in particular from 60 to 70 ℃.

Typically, the reaction product of step c) is not contacted with additional phenol or with additional formaldehyde in a subsequent step.

The reaction product of step c) may be used, for example, in an optional subsequent step d) without further purification steps.

In step d), the reaction product of step c) is neutralized to a pH of 4 to 9 (preferably to a pH of 5 to 8), typically by adding a base, such as an alkali or alkaline earth metal hydroxide (e.g. NaOH).

The reaction product of step d) can be used, for example, as a tanning agent without additional purification steps.

The polycondensates can be used as aqueous solutions or in the form of spray-dried powders.

The invention also relates to a tanning agent for self-tanning, pre-tanning and co-tanning of dehaired hides and skins and for post-tanning of leather and pelts comprising water and a polycondensate as defined above or obtainable by the process as defined above.

The invention also relates to the use of the polycondensates defined above or obtainable by the process defined above for the manufacture of leather. Preferably, the polycondensate is used as a tanning agent, a pretanning agent or a post-tanning agent for the manufacture of leather.

The polycondensates of the invention can therefore be used for the self-tanning and pretanning of dehaired hides and skins in aqueous liquor. A procedure which is advantageously employed is the treatment of pickled dehaired hides, for example smooth cattle hides having a scratch thickness of 1.5 to 4mm, or of dehaired skins, for example smooth sheep skins, with an aqueous solution of the polycondensate of the invention at a pH of 2 to 7 and preferably 2.5 to 4 and at a temperature of 15 to 40 ℃ and preferably 20 to 35 ℃ over a period of 3 to 20 h. This treatment is carried out, for example, by fulling in a drum. The polycondensate of the invention is generally required in an amount of from 2 to 30% w/w and preferably from 5 to 25% w/w, based on the weight of the dehaired hide. The liquid proportion, i.e. the weight percentage ratio of liquid to material, is generally from 30 to 200% in the case of dehaired hides and from 100 to 2000% in the case of dehaired skins, in each case based on the weight of the dehaired material.

After said treatment, the leather or pelt is generally adjusted to a pH of from 2 to 8 and preferably from 3 to 5, for example by using magnesium oxide, sodium carbonate, sodium bicarbonate or organic acids such as formic acid or salts thereof, optionally treated with other tanning agents, and if desired dyed and filled immediately before or after the tanning operation.

Furthermore, the polycondensates of the invention can be used together with a main tanning agent, such as chrome or alum tanning, for co-tanning the dehaired hides and skins. In this case, the working conditions regarding pH, temperature and duration of the treatment are adjusted to meet the requirements of the main components of tanning and are equally applicable to the processing equipment and liquor ratios and also to the post-treatment. The polycondensates according to the invention are here generally required in an amount of from 0.1 to 20% w/w and preferably from 0.5 to 15% w/w, based on the weight of the dehaired hide.

Furthermore, the polycondensates of the invention can be used for the post-tanning of pretanned leather and pelts, for example chrome leather, in aqueous liquors. In this case, the procedure employed is generally to tanne pickled dehaired hides and skins, for example slick hides and skins having a skim thickness of 1.5 to 4mm, in a known manner using, for example, conventional chrome tanning agents such as chromium (III) salts (e.g. chromium (III) sulphate), to deacidify the resulting pretanned skins ("wet blue skins" in chrome tanning), and to follow treatment with an aqueous solution of the polycondensate of the invention at a pH of 2 to 7 and preferably 2.5 to 4 and a temperature of 15 to 60 ℃ and preferably 25 to 45 ℃ for a period of 1 to 12 h. This treatment is carried out, for example, by fulling in a drum. The required amount of the polycondensate of the invention is generally from 2 to 30% w/w and preferably from 5 to 25% w/w, based on the shaved weight of the leather. The liquid proportion is generally from 30 to 200% in the case of dehaired hides and from 100 to 2000% in the case of dehaired skins, in each case based on the shaved weight of the leather.

After the treatment, and possibly before the treatment if desired, the leather or pelt is usually adjusted to a pH of 3 to 5, for example by using magnesium oxide or an organic acid such as formic acid or its salts, and if desired is dyed and filled immediately before or after the treatment.

The leather or pelt thus post-tanned can additionally be treated with other tanning agents, such as other polymeric tanning agents or syntans, and then post-tanned with the polycondensates of the invention. Another possibility consists in using the polycondensate of the invention in the main tanning simultaneously with such an additional tanning agent.

Suitable tanning agents used additionally or simultaneously are all customary agents which have a tanning action on the dehaired hides or skins. In particular, types of tanning agents that can be used are mineral tanning agents, for example salts of chromium, aluminium, titanium and zirconium, synthetic tanning agents such as the aforementioned polymeric tanning agents and synthetic tanning agents, and vegetable tanning agents.

The invention has several advantages:

the leathers and skins produced with the polycondensates of the invention, in particular those tanned with prechrome, exhibit extremely high light and heat fastness and are distinguished by good fullness, high softness and firmness of the grain.

The leathers and skins produced using the polycondensates of the invention either by self-tanning or, for example, by post-tanning chrome leathers are very easy to dye and are particularly suitable for the production of light-colored leathers due to their light color.

The polycondensates of the invention have a sufficiently high tanning action per se, and they are sufficiently water-soluble and stable on storage.

One particular advantage of the polycondensates according to the invention is that they have only a very low residual content of non-sulfonated monomeric phenols which are toxic or harmful to health.

The following examples shall additionally illustrate the invention.

Examples

Analytical method

To evaluate the ratio of p-phenolsulfonic acid to o-phenolsulfonic acid, NMR analysis was applied to the sample extracted before the formaldehyde condensation at the end of the sulfonation reaction. The sample was quenched with water to terminate the reaction and neutralized with sodium hydroxide solution. The water was evaporated and the remaining solid was analyzed by proton NMR in deuterated water using tetramethylsilane as internal standard.

O-phenol sulfonic acid monobasic barium salt: 1H-NMR (400MHz, D2O): 7.02-7.06 (m,2H,4-H,6-H),7.48(t, J ═ 9Hz,1H,5-H),7.75(d, J ═ 8Hz, H, 3-H).

P-phenolsulfonic acid monosodium salt: 1H-NMR (400MHz, D2O): 6.96(d, J ═ 9Hz,2H,2-H,6-H),7.70(d, J ═ 9Hz,2H,3-H, 5-H).

To compare the ratio between ortho-phenolsulfonic acid and para-phenolsulfonic acid in the mixture, the signal at 6.96 (doublet, para-phenolsulfonic acid) was correlated with the multiplet of 7.02-7.06 (ortho-phenolsulfonic acid). The two signals represent the two protons of the corresponding phenolsulfonic acid and show separate groups of signals in the mixture.