FI62053C - SAETT ATT REDUCERA DEN MEKANISKA HAOLLFASTHETEN OCH / ELLER FOERBAETTRA MJUKHETEN HOS CELLULOSA ELLER PAPPER - Google Patents

Description

RjSCT μ rt1lKU4Ji.uTu * jiiucAi * u JNBTa ro ^ 1) UTLAOONINOtSKRIFT 62053 c Patent granted 10 11 1982

Patent aeddelat (SI) MW c 07 c 93 / 02- D 21 H 3/12 FINLAND — FINLAND (H) PmunMuhNim — PiNOiwBlimin 750175 (2¾ HsfcsnihpKt — AmMiBhipdH 23-01.75 (23) AHaipStvf — GIMfti «« 4af 23.01.75 ( 41) TMhK (vtklMkal - Mvtt effmcNg 26.07-75 fr rdd »t« rihdfftli »(44) rmtMMpm ** fr toylfrtotom py.- 30.07.82 rltsilt · OCn rsglStarityfMSSfl Ainekin utfrgd och utUkrtton pubMcsrsd (32) stseikeu · —t «tM prtartMt 25-01.7k

Sweden-Sweden (SE) 7101009-1 (71) Berol Kemi Ab, Fade, S-U1 * U 01 Stenungsund 1, Sweden-Sweden (SE) (72) Svante Ludvig W & hlln, Stenungsund, Jan Gunnar Emanuelsson,

Stenungsund, Sweden-Sweden (SE) (7 ^) Berggren Oy Ab (5 * 0 A method of reducing the mechanical strength and / or improving the softness of cellulose or paper -

The present invention relates to novel quaternary surfactants which have been found to be particularly suitable for use in the manufacture of cellulose or paper having low mechanical strength and being particularly soft.

It is previously known to treat wet cellulosic pulp with a surfactant to reduce intercellular bonding. In this case, cellulose or paper is obtained which is softer but mechanically weaker, what are the desired properties and if the cellulose has to be decomposed, e.g. into a flake, into a liquid-absorbing health care product. Surfactants useful for this purpose include e.g. quaternary nitrogen compounds containing two alkoxy (ethyleneoxy) hydroxypropylene groups in which the alkoxy groups contain 12 to 22 carbon atoms. Extensive studies have shown that if surface-active quaternary nitrogen compounds are used as text softeners and if the number of carbon atoms in the alkoxy group exceeds 13 carbon atoms, the positive effects of the compounds begin. weaken with increasing h i i1i at own, so that 22 carbon vis- 2 62053 with which the effects are largely lost. It is further known in the textile field that a plasticizer containing aliphatic groups has better softening properties than a plasticizer containing alkylaryl groups.

It has unexpectedly been shown that cellulose and. paper with improved properties, i.e. a better combination of high softness and low mechanical strength while maintaining good hydrophilic properties, by treating the pulp or paper with a new type of surfactant, quaternary nitrogen compounds characterized in that they contain a phenolic radical as a hydrophobic part , which is substituted by one or more alkyl groups, the hydrophobic moiety containing a total of 14 to 46, suitably 20 to 38 and preferably 23 to 32 carbon atoms. The Quaternary Nitrogen Surfactants of the invention have the general formula V0- <W> nf CVCHtOM-CH. ^ Rj ~ R2 ~ 0 "(C2H40> n ^ R1 | wherein R1 and R2 independently of one another denote a mono-, di- or trialkylaryl group, having 14 to 46, suitably 20 to 38, preferably 23 to 32 carbon atoms, and and R 1 independently of one another represent a methyl, ethyl or hydroxyethyl group, n 1 and n 2 independently represent the numbers 4 to 40, suitably 6 to 30, preferably 11 to 25, and Jr 'means an anion The compounds of the invention give a very satisfactory combination between good absorbency, high softness and low mechanical strength, it can generally be seen that the absorbency increases with the increase of ethylene glycol units. by increasing the number of carbon atoms in the substituents R1 and R2- By varying the number of carbon atoms in R1 and R2 and ethylene glycol the number of units is thus possible to achieve the desired combination of absorbency and fiber binding lowering properties for the particular purpose. Particularly good results have been obtained in both ratios with compounds in which R 1 and R 2 independently of one another denote an alkylaryl group having 23 to 32 carbon atoms and and R 1 (each denote a methyl group and 1 and n 2 are a number between 11 and 25).

3 62053

The compounds of the invention can be added to any of their cellulosic pulps after any bleaching. The addition usually takes place before or during the hydration of the pulp, or during or before drying, for example in the production of a web-like product on a pulp or paper machine or in flakes in a flake dryer. The cellulosic pulp can consist of all types of pulp, such as mechanical pulp, semi-chemical pulp and chemical pulp. Thus, these compounds have also been shown to have a particularly strong healing effect on mechanical or semi-chemical pulps in addition to chemical pulps, such as sulphite and sulphate pulps, which are commonly used in the manufacture of soft, highly absorbent products. The compounds are preferably used in the form of an aqueous solution having a concentration of 1 to 15% by weight of active substance. The solution may also contain viscosity reducing additives, for example ethanol or ethylene glycol, or nonionic surfactants, such as adducts between ethylene oxide or propylene oxide and aliphatic alcohols or alkylphenols, which are added if desired to further improve cellulose or paper rewetting. The addition amounts of the quaternary nitrogen compounds according to the invention vary depending on the desired effect, but normally they range from 0.02 to 3% by weight, preferably from 0.1 to 1.5% by weight, based on the weight of the dry cellulose. Cellulose or paper treated with the compounds of the invention can be used in many different fields. For example, cellulose can be broken down into a so-called floc and in this form it is used in various hygienic products. Furthermore, the compounds can be used in the manufacture of paper in which the soft feel is of great importance, such as sanitary papers, towel paper, and paper used in many Textile substitutes, such as sheets, towels, tablecloths, clothing, etc.

The compounds according to the invention can be prepared by adding 4 to 40 moles of ethylene oxide to a mole of alkyl-substituted phenol having a total of 14 to 46 carbon atoms in a manner known per se.

The phenol polyethylene glycol ether thus obtained is then reacted with epi-hydrochloride to give the corresponding chloroglyceryl ester, which is reacted with a secondary amine of formula

R3R4NH

24 62053 wherein R 1 and independently represent a methyl, ethyl or hydroxyethyl group, as a quaternary compound in the form of a chloride salt. If found suitable, chloride ions can be exchanged for other anions in a manner known per se, for example by adding a sodium salt which has a higher solubility input than sodium chloride or by ion exchange in an anion exchanger. Among the anions, in addition to the chloride ion, hydroxyl, bromide, methyl sulfate, acetate, sulfate, carbonate, citrate and tartrate ions can be mentioned, and of these, monovalent ions are more preferable. The addition of ethylene oxide to the alkyl-substituted phenol is carried out in the presence of an alkaline catalyst, preferably in the presence of sodium hydroxide, in a manner known per se. The reaction between the ethylene oxide adduct and the epichlorohydride is carried out at an elevated temperature, 30-150 ° C, in the presence of a catalyst. As catalysts, SnCl 2, BP 2 and HCl 2 in particular have proven to be excellent and give a rapid and easily controlled reaction, but other acid catalysts such as toluenesulfonic acid and sulfuric acid can also be used. In order to effect the complete reaction of the phenolic compound, an excess of epichlorohydrin is usually added. The quaternization of the secondary amine with chloroglyceryl ether is performed with sodium hydroxide at a temperature of 40-150 ° C. The reaction is usually carried out in the presence of a polar organic solvent having a boiling point above 60 ° C. Suitable organic solvents are, for example, methanol, ethanol and ethyl diglycol.

The compounds of the invention may also be prepared by variations on the above methods. Thus, chloroglyceryl ether can be reacted with ammonia or a primary amine with a methyl, ethyl or hydroxyethyl substituent and then quaternized with, for example, methyl or ethyl chloride or dimethyl or diethyl sulfate. However, this process is more complex than previously described and involves more reaction steps while giving a higher number of by-products and a lower overall yield.

Examples of phenols useful in the preparation of the compounds of the invention include octylphenol, nonylphenol, desylphenol, · dodecyl] ifenol, tetradecylphenol, hexadecylphenol, octadecylphenol, dihicosylphenol, dioctylphenol, dinonylphenol, dinonylphenol, dinonylphenol, dinonylphenol, dinonylphenol , dioctadecylphenol, tributylphenol, trihexylphenol, trioctylphenol, tridesylphenol and tridodesylphenol. Of these, octadecylphenol, dioctylphenol, dinonylphenol, dideylphenol, didodesylphenol and tritetradecylphenol should be specifically mentioned.

Among the compounds of the invention based on any of the above alkylphenols are e.g. the following were found to have good properties:

octadecylphenoxy- (C2H1O) 12-CH2CH (OH) CH2 >> ^ CH3 O

octadecylphenoxy- (C2H4O) 12-CH2CH (OH) CH2 ' dioctylphenoxy (C2H10) 12-CH2CH (OH) CH2, CH2O dioctylphenoxy (C2H10) 12-CH2CH (OH) CH2 / ditetradecylphenoxy (C2H10) 12-CH2CH (OH) CH2sCH2 and ? ci "ditetradecylphenoxy- (C2H2O) 12-CH2CH (OH) CH2 ^ CH2ditetradecylphenoxy (O2H2) (O2) (CH2) (CH2) [CH2] (CH2)

Compounds of the formula: dinonylphenoxy- (C2H10O) 12-CH2CH (OH) CH2> v ^ ^ CH ^

cP

dinonylphenoxy- (C2H10O) 12-CH2CH (OH) CH2 ^ CH2 dinoroylphenoxy- (C2Hi (O) 1g-CH2CH (OH) CH2 ^ / CH3 r \ iP ^ cr

dinonylphenoxy- (C2H18O) 1g-CH2CH (OH) CH2> / ^ CIU

6 62053 d: nonylphenoxy- (C2H40) 24-CH2CH (OH) CH2. ° H3 Θ and <n dinonylphenoxy- (C2H10O) 2j-CH2CH (OH) CH2 "/ CH2ddosylphenoxy- (C2H40) 16-CH2CH (OH) CH2 ^ ffv / CH3

and cP

dididylphenoxy- (C2H2O) ^ g-CH2CH (OH) CH2 ^ ^ CH2 - didylpheroxy- (C2H40) 2i |

iP ^ cP

diphenylphenoxy- (C2H2O) 2 ^ -CH2CH (OH) CH2y, / CH2 didodesylphenoxy (C2H10O) 1g-CH2CH (OH) CH2s> ^ CH3 /

iP cP

didodesylphenoxy (C2H2OO) 16-CH2CH (OH) CH2 '/ CH2 didodesylphenoxy (C2H2O) 21 + -CH2CH (OH) CH2SN> ^

iP cP

didodes'ylphenoxy (C2H10) 24-CH2CH (OH) CH2 / CH3

Suitable secondary amines in the process of the invention are dimethylamine and diethylamine, which are commercially available. The primary amines used are methyl, ethyl and hydroxyethylamine. The following embodiments are intended to further illustrate the invention.

Examples 1-6 2 moles of dinonylphenol are introduced into a reaction vessel equipped with heating and stirring equipment and a reflux condenser. Dinonylphenol was reacted with an alkaline catalyst using 16 moles of ethylene oxide. The resulting ethylene oxide adduct was treated and then reacted with 2.2 moles of epichlorohydride at about 100 ° C for 1.50 minutes. The catalyst used in this reaction was 6 g of SnCl 2. The residual epichlorohydride was removed under reduced pressure to give the reaction product in the form of a slightly yellowish viscous liquid. and 2 g of eLaiiolxa, a random olx ixuotcttu of 0.9 moles of methylene, 50 g of sodium hydroxide and 30 g of water.

7 62053

The mixture was kept in an autoclave at 125 ° C for 3 hours, after which the residual dimethylamine was removed by nitrogen purging. The reaction product consisted of a slightly yellowish substance and was found to consist of $ 90 quaternary amine and $ 6 tertiary amine based on the theoretical concentration of the amine. The resulting quaternary compound, which could be represented by the general idealized formula C9H19> ^ Γ j-0 (C2H40) gCH2CH (OH) CH2 CH2 ° 9H19 \ /

XP cP

C9H19XV (li-O (C2H40) 8CH2CH (OH) CH2 CH3 C9H19 is hereinafter referred to as A).

In the same manner as compound A was prepared, the following compounds B-F are prepared.

v <· B. Reaction product 2 moles of dinonylphenol, 24 moles of ethylene oxide, 2 moles of epichlorohydride and 1 mole of dimethylamine ° 9Η19χ (j -OCOjH ^ Ol ^ CHjCHtOHlCHj 'CHj

C9H19 "‘ cP

A-o (c2h4o) 12ch2ch (oh) ch2 ch3 C9H19 C. Reaction product 2 moles of dinonylphenol, 32 moles of ethylene oxide, 2 moles of epichlorohydride and 1 mole of dimethylamine.

62053 and c9Hl! Uv.

(I Λ- 0 (ϋ2Η ^ 0) ι6σΗ2ϋΗ (0Η) 0Η2 CH3 ° 9H19 \

99 V cP

C 9 H 19 N 2 O (C 2 H 1 O) 16 CH 2 CH (OH) CH 2 CH 2 C 9 H 19 D. The reaction product is 2 moles of dinonylphenol, 60 moles of ethylene oxide, 2 moles of epichlorohydride and 1 mole of dimethylamine.

° 9Η! 9Λ (Γ J-O (C2H40) 30CH2CH (OH) CH2 ch3 \ / S / \ - O (C2H40) 30CH2CH (0H) CH2 κ ch3 C9H19 E.. Reaction product 2 moles didodesylphenol, 32 moles ethylene oxide 2 moles of epichlorohydride and 1 mole of dimethylamine.

C12H25 [id-o (c2h4o) i6ch2ch (oh) ch2 ch3 C12H25v ^ \ fjTj- o (c2h4o) i6ch2ch (oh) ch2 ch3 C12H2 3 P. dimethyl amine.

C ftH 1 7 ^ ^ f [Γ j- 0 (C2H40) 12CH2CH (0H) CH2 ch C8 'lV Nq / "3 © N Cl ° 8h'- · ^. Κ \' 1 4 ---- 0 (u ti] (u) v, uh „uh (Ori) tiL Oh, V ^ 2 '1 12 2 2 3 c8h:« 7 620 5 3 K s i. me 3 -I ·: ki 7

Bleached pine »uifaatt in Iina, with a consistency of 2% 1 i.sätt j! n <> i, «some product Λ-F. D.i, - was added to the control sample.

.In <O

fatty al-coke (ethyleneoxy) - (2-hydroxypropylene) dimethylammonium chloride.

The sheets were formed into test sheets in the usual manner, which after drying were examined for mechanical strength (refractive index according to SCANJ and for water absorption according to Klemm. The results are shown in Table 1).

table 1

Increase in Refractive Index Water Absorbent

Zero test 21.1 100 A. 10.6 91 B 11.5 92 c 12.7 95 D 16.8 98 E 12.2 93. F 12.9 92

Comparative test 12.9 90

The results show that the use of the products according to the invention significantly reduces the mechanical strength (coefficient of coefficient) of the cellulose while maintaining a very high wetting property. A direct comparison with the cellulose treated with the reference product shows that only compound D gives the cellulose a higher refractive index, while all the compounds according to the invention give the cellulose better absorption properties.

Claims (9)

10 62053 A method for reducing the mechanical strength and / or improving the softness of cellulose or paper while maintaining good hydrophilic properties, characterized in that a compound of general formula R1-0- (C2H40) is added to the cellulose pulp before or during its formation into cellulose or paper. ) n -CH 2 CH (OH) CH 2 R 3 1 f / R 2 -O- (C 2 H 4 O) n -CH 2 CH (OH) CH 2 r 4 wherein R 1 and R 2 independently represent mono-, di- or trialkylphenyl groups having 14-46 carbon atoms , R 1 and R 2, independently of one another, denote methyl, ethyl or hydroxyethyl groups, n, and n 0 are, independently of one another, in the range from 4 to 40. 1 Θ ά. . numbers and X stands for Amoma. Process according to Claim 1, characterized in that R 1 and R 2 independently of one another contain from 20 to 38 carbon atoms, that R 1 and R 2 both represent methyl groups and that n 1 and n 2 are in the range from 6 to 30, preferably from 11 to 25 . Process according to Claim 2, characterized in that R 1 and R 2 independently of one another contain 23 to 32 carbon atoms. Process according to Claim 2 or 3, characterized in that R 1 and R 2 represent dialkylphenyl groups. Process according to one of Claims 1 to 4, characterized in that the compound is added in an amount of 0.02 to 3% by weight, preferably 0.1 to 1.5% by weight, based on the dry weight of the cellulose. Product for use according to Claim 1, characterized in that it contains as active component a compound of the general formula R 1 -O "(C 2 H 4 O) n -CH 2 CH (OK) CH 2 R 5 xe R 2 -O- (C 2 H 4 O) n 2" CH 2 CH 2 OH 1 CH 2 R 4 112053 wherein R 1 and R 8 independently of one another denote mono-, di- or trialkylphenyl groups having 14 to 46 carbon atoms, R 1 and R 2 independently of one another denote methyl, ethyl or hydroxyethyl groups, n 1 and n 2 are independently numbers from 4 to 40 and Χθ means an anion. Product according to Claim 6, characterized in that R 1 and R 2 independently of one another contain from 20 to 38 carbon atoms, that and R 1 both represent methyl groups, and that n 1 and N 2 are in the range from 6 to 30, preferably from 11 to 25. Product according to Claim 7, characterized in that R 1 and R 2 independently of one another contain 23 to 32 carbon atoms. Product according to Claim 7 or 8, characterized in that R 1 and R 2 denote dialkylphenyl groups.