WO2000077302A1 - Use of long-chain fatty ethers - Google Patents

Abstract

The invention relates to the use of long-chain fatty ethers, selected from the group consisting of (a) the reaction products of C8-C20 olefinic epoxides with C8-C22 alcohols or their alkylene oxide adducts, (b) the reaction products of epichlorohydrine with C8-C22 alcohols or their alkylene oxide adducts and (c) C10-C22 dialkylether epoxides, as waterproofing agents for paper.

Description

Use of long chain fatty ethers

Field of the Invention

The invention is in the field of paper auxiliaries and relates to the use of special long-chain fatty ethers as water repellents.

State of the art

The generic term "paper" is understood to mean approx. 3000 different types and articles, some of which can differ considerably in their areas of application and their nature. For their preparation, highly dilute aqueous slurries of cellulose fibers and additives are applied in thin layers to tapes, felts or sieves, on which they are dewatered to a solids content of about 40% by weight at very considerable running speeds and using heat and mechanical pressure become. While the still moist raw paper is being dried in further steps, the water squeezed out returns to the cycle. So far, alkyl ketene dimers (AKD) or alkenyl succinic anhydrides (ASA) have been used to make the papers hydrophobic ("sizing"). An overview of this topic can be found, for example, in D.Eklund Paper Chemistry - An Introduction, Finland 1991, p. 203-221. A disadvantage, however, is that the AKD is produced using fatty acid chlorides, which places high demands on occupational safety. ASA dispersions, on the other hand, are not very stable and have to be produced directly in the paper machine with great effort so that they do not hydrolyze; the use of maleated fatty substances as paper water repellents has also been described [cf. CA 1069410]. Finally, resin derivatives together with aluminum salts can also be used for water repellency, and the corresponding paper production processes are running but usually in the acidic range, so that calcium carbonate is eliminated as an inexpensive filler. Representing the extensive state of the art, reference is made here to the following publications: DE 19540998 A1, EP 0437764 A1 (BASF), EP 0220941 B1 (A&W), and EP 0451842 A1 and WO 98/06898 (Hercules),

As a result, the complex task was to provide new paper water repellents that can be produced with the least possible technical effort, are largely based on ecologically compatible, ie renewable raw materials, within a wide pH range. are settable and also have at least equivalent properties to known hydrophobizing agents of the prior art.

Description of the invention

The invention relates to the use of long-chain fatty ethers selected from the group consisting of

(a) reaction products of Cβ-C22 olefin epoxides with Cβ-C22 alcohols or their alkylene oxide adducts,

(b) reaction products of epichlorohydrin with C8-C22 alcohols or their alkylene oxide adducts and

(C) Cιo-C22 dialkyl ether epoxides

as a water repellent for paper.

Surprisingly, it was found that long-chain fatty ethers of the type mentioned are particularly suitable for finishing all types of paper products (paper, cardboard, cardboard) and for hydrophobizing cellulose fibers and starch. If the long-chain fatty ethers are used in dispersions with (cationic) starch, aluminum sulfate and / or polyamidoamine-epichlorohydrin resins as well as sodium hydroxide and / or calcium carbonate, Cobb60 values comparable to those obtained with the use of established water repellents, such as e.g. Alkyl ketene dimers (AKD), alkenyl succinic anhydrides (ASA) or resin derivatives (approx. 20 to 35 gm-2). This was not to be expected, since the mechanisms of action known for AKD or ASA (chemical binding to the hydroxyl groups of the cellulose fibers, i.e. formation of ester functions) cannot be used in the case of long-chain fatty ethers. Another advantage is that the long-chain fatty ethers to be used according to the invention can be used both in the acidic and neutral range, are light-colored and practically odorless and, moreover, are based on renewable raw materials.

Reaction products of olefin epoxides with alcohols

In a first embodiment of the invention, long-chain fatty ethers of the type of the reaction products of olefin epoxides with alcohols, which preferably follow the formula (I), are suitable as paper waterproofing agents.

R1-CH (0H) -CHR2-0 (CH2CHR30) "R4 (I) in which R ^{1 represents} an alkyl radical having 6 to 20, preferably 10 to 18 carbon atoms, R ^{2 represents} hydrogen or an alkyl radical having 6 to 20 carbon atoms, R ^{3 represents} hydrogen or a methyl or ethyl group, R ^{4 represents} a linear or branched alkyl and / or alkenyl radical having 8 to 22, preferably 12 to 22 carbon atoms, n is 0 or numbers from 1 to 10, with the proviso that the sum of the carbon atoms in the two radicals R ¹ and R ^{2 is} in the range from 10 to 20. These reaction products are known vicinal hydroxy ethers which can be obtained, for example, by acid or base-catalyzed ring opening of terminal or internal olefin epoxides with fatty alcohols, oxo alcohols or their alkylene oxide adducts. Corresponding methods are described, for example, in the publications DE-OS 2318950, DE-OS 2943535, EP-A1 0130026 and in Synth.Commun. 24, 3021 (1994). Typical examples are the reaction products of α-octene epoxide, α-nonene epoxide, α-decene epoxide, α-dodecene epoxide, α-tetradecene epoxide, α-hexadecene epoxide, α-octadecene epoxide, α-eicosadecenepoxide, i-dodecene epoxide, i-tetradecenepoxide Hexadecene epoxide, i-octadecene epoxide, i-eicosadecene epoxide and mixtures thereof with octyl alcohol, nonyl alcohol, decyl alcohol, i-decyl alcohol, undecyl alcohol, i-undecyl alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, iso alcoholyl, palmyl alcohol, palmoleyl alcohol, palmoleyl alcohol, palmoleyl alcohol - Linyl alcohol, linolyl alcohol, linolenyl alcohol, elaeostearyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and their technical mixtures or their adducts with 1 to 10 mol ethylene oxide or 1 to 3 mol propylene oxide or mixtures of 1 to 10 mol ethylene oxide and 1 to 3 moles of propylene oxide (in random or block distribution).

Reaction products of epichlorohydrin with alcohols

As a second group of long-chain fatty ethers, reaction products of epichlorohydrin with alcohols, which preferably follow the formula (II), are suitable as paper hydrophobizing agents.

R5 (OCHR ⁶ CH2) nOCH2CH (OH) CH ₂ 0 (CH ₂ CHR70) mR8 (II)

in which R ⁵ and R ⁸ independently of one another represent hydrogen, a linear or branched alkyl and / or alkenyl radical having 8 to 22, preferably 12 to 18 carbon atoms, R ⁶ and R ⁷ independently of one another represent hydrogen or a methyl or ethyl group and n and m independently represent 0 or numbers from 1 to 10. Accordingly, the reaction products can be dialk (en) ylglycerol ether, dialk (en) yloxyglycerol ether or mixed alk (en) yialkenyloxyglycerin ether. In the case R ⁵ = hydrogen and n, m = 0, there are monoalk (en) ylglycerol ethers or in the case of R ⁵ = hydrogen and n = 0, m = 1 to 10 monoalk (en) yloxyglycerol ethers. These vicinal hydroxyethers are also known from the literature and are produced, for example, by base-catalyzed ring opening of epichlorohydrin with fatty alcohols, oxoalcohols or their alkylene oxide adducts and alkylation or hydrolysis of the chlorine group. Typical examples are the ring opening products of epichlorohydrin with octyl alcohol, nonyl alcohol, decyl alcohol, i-decyl alcohol, undecyl alcohol, i-undecyl alcohol, lauryl alcohol, isotridecylal- alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, alaidyl alcohol, petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, elaeostearyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol and ethylene alcohols and their mixtures, erucyl alcohol, erucyl alcohol, erucyl alcohol or 1 to 3 moles of propylene oxide or mixtures of 1 to 10 moles of ethylene oxide and 1 to 3 moles of propylene oxide (in random or block distribution).

Dialkyl ether epoxides

In a third embodiment of the invention, dialkyl ether epoxides which preferably follow the formula (III)

R9-0-R ¹⁰ (III)

in which R ⁹ and R ¹⁰ independently of one another represent epoxidized alkyl radicals having 10 to 22, preferably 16 to 18, carbon atoms. The unsaturated ethers on which the epoxides are based are known substances which can be obtained, for example, by acid-catalyzed condensation of unsaturated fatty alcohols. Typical examples are Dipalmitoleylether, Dipalmitelaidylether, Dioleylether, Dielaidyleether, Dipetroselinylether, Dipetroselaidylether, Dilinoleylether, Dilinolenylether, Digadoleylether and Derucylether, Dibrassidylether as well as their mixtures. Due to the production process, the unsaturated ethers can also contain minor amounts, ie less than 25% by weight, of saturated portions. The epoxides are prepared from the unsaturated ethers by addition of oxygen, for example by the known in-situ performic acid process. The use of dipalmitoleyl ether bise epoxide, dipalmitelaidyl ether bise epoxide, dioleyl ether bise epoxide, di alaidyl ether bise epoxide, dipetroselinyl ether bisisepoxide, dipetroselaidyl ether bise epoxide and dilinoleyl ether tetraise epoxide is particularly preferred.

The long-chain fatty ethers to be used according to the invention are preferably used in concentrations of 0.001 to 60 and in particular 0.01 to 40, based on the dispersions. A pH in the range from 3 to 9, preferably 4 to 7, has proven to be optimal for use. The water repellents can be used together with other known additives, such as, for example, alkyl ketene dimers, alkenyl succinic anhydrides or resin derivatives, the mixing ratio being in the range from 1:99 to 99: 1, preferably 20:80 to 80:20 and in particular 40:60 to 60 : 40 may be. As further constituents, the dispersions obtainable using the long-chain fatty ethers can be, for example, aluminum salts, preferably aluminum sulfate and / or polyaluminium chloride (PAC), fillers, for example kaolin, calcium carbonate (for example chalk, PCC or GCC) or titanium dioxide (for example anatase, rutile or) Brookite), polymers as flocculation or retention aids or to increase wet strength (e.g. polyamidoamine-epichlorohydrin resins (PAE), polyamidoamines (PAMAM), polyethyleneimines (PEI) or their reaction products with epichlorohydrin (PAMAM + EPI) or ethyleneimine (PAMAM + EI), carboxymethyl cellulose, plant gums or polysaccharides (guar, galacto- mannans, alginates etc.), chitosans and starches, preferably cationically derivatized starches as agents for enhancing retention and dry strength, the amount of auxiliaries used typically being in the range from 0.01 to 50, preferably 0.1 to 30 and in particular 1 to 20 wt .-% based on the dispersions. The auxiliaries are used in the dispersions according to the invention only in such amounts that the stability of the dispersions is not adversely affected thereby. When selecting the auxiliaries, care is taken that the components do not form any reaction products with one another which adversely affect the performance properties of the paper products or cellulose fibers or starch. The pulps themselves generally have a wood content in the range from 1 to 10 and preferably 2 to 5% by weight. These can be mixtures of fresh hard and softwood fibers, ie typically short and long fibers, recycled paper or mixtures of both types.

Examples

Preparation Example 1. 693.5 g (2.3 mol) of α-stearyl epoxide (5.3% by weight of epoxy) and 620.2 g (2.3 mol) of stearyl alcohol were melted at approx. 80 ° C. and Weighed in a 2 l three-necked flask with stirrer, thermometer and temperature controller. A total of 0.62 g of trifluoromethanesulfonic acid in the form of a 25% by weight aqueous solution was added as catalyst (corresponding to 0.1543 g of free acid, i.e. 1.03 mmol or 117 ppm of acid, based on the weight of epoxy + alcohol). The reaction was carried out at 80 ° to a maximum of 96 ° C. The course of the reaction was followed titrimetrically using the epoxy content (Jay method). After 3 h no epoxy was detectable. The reaction mixture was then neutralized with 2.52 g of Desmophen® PU 1952 (triethanolamine + 17 PO, Bayer AG) to pH 7. The mixture was then cooled and recrystallized from ethanol (1271, 4 g of crude product from 700 ml of ethanol). A white, powdery solid with a melting range of 52 to 64.5 ° C., a hydroxyl number of 96, an epoxy content of 0.03% by weight and a GC purity of 94.1% was obtained.

Preparation example 2: 1042 g (3.85 mol) of stearyl alcohol were weighed out in a 2 l three-necked flask with stirrer, thermometer and temperature controller and melted at about 80 ° C. 0.64 g of trifluoromethanesulfonic acid in the form of a 25% strength by weight aqueous solution (0.16 g of free acid - i.e. 1.07 mmol or 105 ppm of acid, based on the weight of alcohol + epoxide) was added as the catalyst. 488.7 g of α-palmityle epoxide (6.32% epoxide) were then added dropwise over a period of about 30 minutes at a temperature of 78 to 86 ° C. The temperature of the mixture was kept at 86 ° C. The course of the reaction was followed titrimetrically after the end of the dropping on the basis of the epoxy content. After 30 minutes, the epoxy content was still 0.09% by weight. The reaction mixture was then neutralized with 1.1 g of Lupranol® 3402 (amine-based polyetherol, BASF AG) to pH 7 to 8. The excess stearyl alcohol was distilled off in a high vacuum at 0.8 to 0.1 mm Hg to a bottom temperature of 220 ° C. (710.5 g distillate). A white solid with a hydroxyl number of 94 (theory 107.1) and an acid number of 0.1 was obtained.

Preparation example 3. 1042 g (3.85 mol) of stearyl alcohol were weighed into a 2 l three-necked flask with a stirrer, thermometer and temperature controller. 15.3 g of sodium methylate in the form of a 30% by weight methanolic solution (4.59 g of alkoxide, ie 85 mmol or 0.3% of base, based on the weight of alcohol + epoxide) were added as catalyst. The mixture was then evacuated at 80 to 100 ° C. to remove methanol. 488.7 g of α-palmityle epoxide (6.32% by weight epoxy) were then added dropwise over a period of about 30 minutes at a temperature of 140 to 165 ° C. The temperature of the mixture was kept at about 165 ° C. The course of the reaction was followed titrimetrically after the end of the dropping on the basis of the epoxy content. After 80 minutes, the epoxy content was still 0.19% by weight. The reaction mixture was then neutralized with 8.5 g of lactic acid (90% by weight). The excess stearyl alcohol was distilled off in a high vacuum to a bottom temperature of 225 ° C. (680 g distillate). The cloudy product (salt precipitation) was suctioned off at about 140 ° C. with filter aid (Primisil), which Filtrate was clear. A white solid with a hydroxyl number of 105 (theory 107.1) and an acid number of 0.1 was obtained.

Preparation Example 4. 754 g (1.6 mol) of tallow alcohol + 5EO (OHZ = 119) were mixed with 12.4 g of sodium methylate in the form of a 30% by weight methanolic solution (3.72 g of alkoxide, ie 69 mmol or 0 , 3 wt .-% base based on the weight of alcohol + epoxy) submitted. The mixture was then evacuated at 90 ° C. to remove methanoi. Thereafter, 486 g (2.0 mol) of α-palmitylepoxide were added dropwise over a period of 15 minutes at a temperature of 160 to 168 ° C. and kept in this temperature range with nitrogen transfer. The course of the reaction was followed titrimetrically after the end of the dropping on the basis of the epoxy content. After 75 minutes, the epoxy content was still 0.21% by weight. After cooling to 130 ° C., the reaction mixture was neutralized with 7.5 g of lactic acid (90% by weight). The product was dried at 120 ° C. in vacuo and a white solid with a hydroxyl number of 81 (theory 78.5) and an acid number of 0.1 was obtained.

Preparation example 5. 715 g (2 mol) of oleyl cetyl alcohol + 2PO (OHZ 157, IZ 37, SZ 2.3, M = 357.3) were mixed with 13.2 g of sodium methylate in the form of a 30% by weight methanolic solution (3rd , 96 g alkoxide, ie 73 mmol or 0.3% base based on the weight of alcohol + epoxy). The mixture was then evacuated at 90 ° C. to remove methanol. Then 607 g (2.5 mol) of α-palmitylepoxide were added dropwise over a period of 25 minutes at a temperature of 142 to 161 ° C. The mixture was then heated to 210.degree. C. in the course of the reaction while passing over nitrogen. The course of the reaction was followed titrimetrically after the end of the dropping on the basis of the epoxy content. After 4 hours, the epoxy content was still 0.33% by weight. After cooling to 130 ° C., the reaction mixture was neutralized with 7.3 g of lactic acid (90% by weight) and dried at 120 ° C. in vacuo. A light yellow, viscous liquid with a hydroxyl number of 104 (theory 93.5) and an acid number of 0.2 was obtained.

Preparation example 6. 252.2 g (0.99 mol) of cetearyl alcohol (-C ₆ : -C ₈ = 60: 40) were melted at 55 to 60 ° C., with 69.8 g (1.08 mol) of KOH in the form of an 87 % By weight aqueous solution and stirred at 60 ° C for 40 min. Then 61.4 g (0.66 mol) of epichlorohydrin were added dropwise, the mixture was stirred for a further 3 hours and then cold water was added dropwise again. After stirring for a further 2 h, the solution was left at 80 ° C. for 1 h. The upper organic phase was then removed and dried in vacuo to give a white solid.

Preparation example 7. 3775 g (13.86 mol) of technical oleyl alcohol (OHZ 206, IZ 97) were mixed with 15.1 g of trifluoromethanesulfonic acid in the form of a 25% by weight aqueous solution (3.775 g of free acid, ie 25.2 mmol or 1000 ppm acid based on the weight of alcohol) weighed in a 6 l three-necked flask with stirrer, thermocouple, control and water separator. The mixture was heated at reflux at 220 ° C. for 7 h while passing through nitrogen. 155 g of water were separated (theory 136 g). The catalyst was neutralized at 120 ° C. with 2.0 g of NaOH (50% by weight). The crude ether was then predried on a Rotavapor. Approximately 3580 g of crude ether were in an oil pump vacuum of 282 to 302 ° C. distilled. About 2059 g of dioctadecenyl ether were obtained as a colorless, viscous liquid. Key figures: OHZ = 1, SZ = 0.1, VZ = 0.1, IZ = 95, purity according to GC: approx. 98.4% (mixture of isomers). 2650 g (9.92 mol) of dioctadecenyl ether were weighed into a 4 l three-necked flask equipped with a stirrer, thermocouple, control and cooler. A mixture of 107.4 g of formic acid (85% by weight, 1.98 mol based on free acid) and 578.2 g hydrogen peroxide (70% by weight, 11.9 mol based on free peroxide) were added Dropped 51 to 65 ° C over a period of 1 h. The mixture was then stirred at 63 to 65 ° C. for 6 h. The product was washed out with water and then predried in a water jet vacuum to 80 ° C., traces of water were removed in a high vacuum. After filtration through a Perlon bag (sieve, 31 μm), 2756 g of the epoxidized ether were obtained as a white paste. Key figures: epoxy content 5.42% by weight (theory 5.65), ie degree of epoxidation 95.9%, IZ 3.2, SZ 0.2.

Application studies. A pulp with a solids content of 4.5% by weight (fiber mixture soft / hardwood 60:40) was used to test the test substances as bulk water repellents. A Panda 2300 homogenizer (Niro Soavi SpA) at a pressure of 300 kg was used to prepare the dispersions. The homogenization temperature was 20 ° C. or 5 to 10 ° C. above the melting point of the test substances. To form the sheet, the pulp was mixed with the long-chain fatty ether, cationic starch (Amylofax® 75) and optionally aluminum sulfate, cation polymers (Fibrabon® 1250) and calcium carbonate and adjusted to the desired pH. The leaves were then dried at 105 ° ^C. for 30 minutes. The glued sheets were tested in the Cobb test using the Tappi method T 441 om-98. The CobbδO values are shown in Table 1.

Table 1

Cobb60 values for sized papers (quantities based on the total mixture)

Claims

claims 1. Use of long chain fatty ethers selected from the group consisting of (a) reaction products of Cβ-C _∑ o-olefin epoxides with Cβ-C ₂ 2 alcohols or their alkylene oxide adducts, (b) reaction products of epichlorohydrin with Ce-C22 alcohols or their alkylene oxide adducts and (C) Cιo-C22 dialkyl ether epoxides as a water repellent for paper. 2. Use according to claim 1, characterized in that long-chain fatty ethers of the formula (I) are used as component (a), Ri-CH (OH) -CHR -0 (CH ₂ CHR ³ 0) _n R ⁴ (I) in which R ^{1 is} an alkyl radical having 6 to 20 carbon atoms, R ^{2 is} hydrogen or an alkyl radical having 6 to 20 carbon atoms, R ^{3 is} hydrogen or a methyl or ethyl group, R ^{4 is} a linear or branched alkyl and / or alkenyl radical with 8 to 22 carbon atoms, n is 0 or numbers from 1 to 10, with the proviso that the sum of the carbon atoms in the two radicals R and R ^{2 is} in the range from 10 to 20. 3. Use according to claim 1, characterized in that long-chain fatty ethers of the formula (II) are used as component (b), R5 (OCHR ⁶ CH ₂ ) nOCH2CH (OH) CH2θ (CH ₂ CHR70) mR ⁸ (II) in which R ⁵ and R ⁸ independently of one another for hydrogen, a linear or branched alkyl and / or alkenyl radical having 8 to 22 carbon atoms, R ⁶ and R ⁷ independently of one another for hydrogen or a methyl or ethyl group and n and m independently of one another for 0 or numbers from 1 to 10. 4. Use according to claim 1, characterized in that long-chain fatty ethers of the formula (III) are used as component (c), Rs-OR ¹⁰ (III) in which R ⁹ and R ¹⁰ independently of one another represent epoxidized hydrocarbon radicals having 10 to 22 carbon atoms. 5. Use according to at least one of claims 1 to 4, characterized in that the long-chain fatty ethers are used in amounts of 0.001 to 60% by weight, based on the paper dispersions. 6. Use according to at least one of claims 1 to 5, characterized in that the long-chain fatty ethers are used at pH values in the range from 3 to 9. 7. Use according to at least one of claims 1 to 6, characterized in that the long-chain fatty ethers are used together with alkyl ketene dimers, alkyl succinic anhydrides, greased fatty substances and / or resin derivatives. 8. Use according to at least one of claims 1 to 7, characterized in that the long-chain fatty ethers are used together with aluminum salts, fillers, polymers, polysaccharide derivatives and / or starches.