CA1042466A - Quaternary surface active compounds and process of treating cellulose fibers therewith - Google Patents
Quaternary surface active compounds and process of treating cellulose fibers therewithInfo
- Publication number
- CA1042466A CA1042466A CA218,551A CA218551A CA1042466A CA 1042466 A CA1042466 A CA 1042466A CA 218551 A CA218551 A CA 218551A CA 1042466 A CA1042466 A CA 1042466A
- Authority
- CA
- Canada
- Prior art keywords
- quaternary ammonium
- process according
- range
- group
- carbon atoms
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/62—Quaternary ammonium compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/16—Amines or polyamines
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
- D21H17/07—Nitrogen-containing compounds
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Paper (AREA)
- Detergent Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Quaternary surface active compounds provided, useful for preparing cellulose fibers such as paper of low mechanical strength and good softness, having the structure:
wherein:
R1 and R3 are selected from the group consisting of mono-, di-, and tri- alkyl phenyl groups having from about fourteen to about forty-six, suitably about twenty to about thirty-eight, preferably about twenty-three to about thirty-two carbon atoms, of the form wherein R is alkyl having from one to about twenty-two carbon atoms, and n, is 1, 2 or 3; R can be in any position on the ring, ortho, para, or meta to the phenolic hydroxyl.
R3 and R4 are selected from the group consisting of methyl, ethyl, and hydroxyethyl groups;
n1 and n2 are numbers within the range from about 4 to about 40, suitably from about 6 to about 30, preferably from about 11 to about 25, representing the average number of oxyethylene units present; and X is an anion.
Quaternary surface active compounds provided, useful for preparing cellulose fibers such as paper of low mechanical strength and good softness, having the structure:
wherein:
R1 and R3 are selected from the group consisting of mono-, di-, and tri- alkyl phenyl groups having from about fourteen to about forty-six, suitably about twenty to about thirty-eight, preferably about twenty-three to about thirty-two carbon atoms, of the form wherein R is alkyl having from one to about twenty-two carbon atoms, and n, is 1, 2 or 3; R can be in any position on the ring, ortho, para, or meta to the phenolic hydroxyl.
R3 and R4 are selected from the group consisting of methyl, ethyl, and hydroxyethyl groups;
n1 and n2 are numbers within the range from about 4 to about 40, suitably from about 6 to about 30, preferably from about 11 to about 25, representing the average number of oxyethylene units present; and X is an anion.
Description
SPECIFICATION
Treatment of wet cellul~se pulp with a surface active agent reduces the interfibre bonds oE the c.ellulose. Thus, cellulose pulp or paper with improved softness ancl low mechanical strength is ob-tained, which are desirable properties for example if the cellulose fibers are to be disintegrated int~ fluff, for liquid-absorbing sani-tary products. Surface-active agents useful for this purpose and as textile softeners include the qlaternary ammonium compounfls hav-ing tw~ R-O-(CH2CH20)n -CH2CH-CH2- groups, where n is rom 1 to lo bH :~
10 and :R is an ~lkoxy group having from twelve to twenty-two carbon atoms.
; , . .
Extensive investigations have shown that when the number of ~.
carbon atoms in the alkoxy group exceeds eighteen in such surface 15 active quaterna.ry ammonium compounds, the effectiveness of the compounds as cellulose fiber softeners is re~uced, and.has mainly disappeared when the num~er of carbon atoms reaches twenty-twoO It is also known that softening agents which contain aliphatic groups have better softening properties than softenin~ agents containing alkyl ~0 aryl groups..
- Unexpectedly,. it ha~ now been found that to cellulose fibers such as pulp or paper, surface-active quate.rnary ammonium com- -~
pounds of this class having in place of the Pc al~oxy group an a~yl~
substituted phenolic .group having from about Pourteen to about 25 forty-six, preferably from about twen~ to about thirty-eight, and still ~lore prefer~ly from about twenty-three t~ about thirty-tw~, , ;~,,,, , , . . . : , .
~ 0~ 6~
carbon atoms,are capable of imparting an improved c~mbinatioll o s~ftness ancl lo~v mech~nical streng~h, in acldition to good hydrophilic properties. The surEace-active quaternary ammonium compounds according to the inv~3ntion have the general formula:
CATION ANION
.. , I _ lRl O-(C2E~O)n-C~I2-C~r-CH2 E~`2~~(C2Hg~)n -CH2-.~H-C~I2 \
C)H
wherein:
Rl and ~?2 are selected from the group consisting of mon~-, di-~ a~ld tri- a~kyl phenyl gr~ups having from about four~een t~ ab~ut :~
- forty-six, suitably about twenty to about thirty-eight, preEerably a~out twenty-three to about thir~two,carbon~ a~oms,o~ the fvrm ~ ~:
Rn 0 where Pc is alkyl having from ~ne to ab~ut twenty-two carb~n a~oms, and n3 is l~ 2 or 3;
R3 and R~L are selected from the group consisting o~ methyl, ethyl, and hydroxyethyl gr~ups; - . :
nl and n2 are numbers within the range from about 4 to ab~ut 40, suitably îrom about 6 ~ about 307 preferably from 11 to about 25, representing the average mlmber of o~Tethylene units present; and X i~ an anion.
Treatment of wet cellul~se pulp with a surface active agent reduces the interfibre bonds oE the c.ellulose. Thus, cellulose pulp or paper with improved softness ancl low mechanical strength is ob-tained, which are desirable properties for example if the cellulose fibers are to be disintegrated int~ fluff, for liquid-absorbing sani-tary products. Surface-active agents useful for this purpose and as textile softeners include the qlaternary ammonium compounfls hav-ing tw~ R-O-(CH2CH20)n -CH2CH-CH2- groups, where n is rom 1 to lo bH :~
10 and :R is an ~lkoxy group having from twelve to twenty-two carbon atoms.
; , . .
Extensive investigations have shown that when the number of ~.
carbon atoms in the alkoxy group exceeds eighteen in such surface 15 active quaterna.ry ammonium compounds, the effectiveness of the compounds as cellulose fiber softeners is re~uced, and.has mainly disappeared when the num~er of carbon atoms reaches twenty-twoO It is also known that softening agents which contain aliphatic groups have better softening properties than softenin~ agents containing alkyl ~0 aryl groups..
- Unexpectedly,. it ha~ now been found that to cellulose fibers such as pulp or paper, surface-active quate.rnary ammonium com- -~
pounds of this class having in place of the Pc al~oxy group an a~yl~
substituted phenolic .group having from about Pourteen to about 25 forty-six, preferably from about twen~ to about thirty-eight, and still ~lore prefer~ly from about twenty-three t~ about thirty-tw~, , ;~,,,, , , . . . : , .
~ 0~ 6~
carbon atoms,are capable of imparting an improved c~mbinatioll o s~ftness ancl lo~v mech~nical streng~h, in acldition to good hydrophilic properties. The surEace-active quaternary ammonium compounds according to the inv~3ntion have the general formula:
CATION ANION
.. , I _ lRl O-(C2E~O)n-C~I2-C~r-CH2 E~`2~~(C2Hg~)n -CH2-.~H-C~I2 \
C)H
wherein:
Rl and ~?2 are selected from the group consisting of mon~-, di-~ a~ld tri- a~kyl phenyl gr~ups having from about four~een t~ ab~ut :~
- forty-six, suitably about twenty to about thirty-eight, preEerably a~out twenty-three to about thir~two,carbon~ a~oms,o~ the fvrm ~ ~:
Rn 0 where Pc is alkyl having from ~ne to ab~ut twenty-two carb~n a~oms, and n3 is l~ 2 or 3;
R3 and R~L are selected from the group consisting o~ methyl, ethyl, and hydroxyethyl gr~ups; - . :
nl and n2 are numbers within the range from about 4 to ab~ut 40, suitably îrom about 6 ~ about 307 preferably from 11 to about 25, representing the average mlmber of o~Tethylene units present; and X i~ an anion.
- 2 . . .. . . . , .. .. . ~ .
~)4Z4~i~
The compounds of the invention give a very sati~factory com-bination of wettabilit~, good sof~ness and low mechanical strength.
Generally, the wettability impro~es as the number of o}~ëthylene units increases. The reduction in strength increases and the wetta-bility diminishes as the number of carbon atoms in the alkyl phenyl substituents Rl and R2 increases. Thus, by varying the numher of carbon atoms in Rl and R2 and the number o~ oxyethylene units it is passible to obtain the combination of wettability and interfibre bond-reducing properties desired for each special purpose. Particularly good properties from both these points of view are found in com- ~`
pounds where Rl and R2 are a~yl phenyl groups having from twenty-three to thirty-two carbon atoms, and nl and n2 are within the range ~;
from 11 to 25.
- The alk~rl groups R of Rl and R2 either have7 or are ~aken irl ~
; su~icient number to aggregate, the number ~f carbon atvms includ- ~ -ing the six carbon atoms of the phenyl ring within the above-stal:ed .
ranges. - -The a~71 groups can for e2~Lmple be methyl, ethyl, pr~pyl, isopropyl, butyl, isobutyl7 ter~-butyl, amyl, isoamyl, tert-amyl, hexyl, 2-ethyl hexyl, heptyl, octyl, isooctyl, nonyl, isononyl~ decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, palmit~rl, stearyl7 behenyl, eicosyl, heptadecyl, myricyl, lacceryl, and heptacosyl.
The compounds according to the in~rention can be added to the cellulos~ fibers at any stage after screening and/or bleach~g of the - ~5 pulp. (~enerally the addition is done before or during dehydratian or drying of the cellulose pulp, for example, during processing int~
c~ntinuous webs on a cellulose drying machine, or on a paper .
- .
. .. . . . : .. . . ~ ' .. . : ' machine, or into flakes in a fla~e dryer.
~ ny kind of cellulose pulp can be tr~ated, such as mech~nical pulp, s~mi-chemical pulp and chemical pulp, bleacln-ed or unbleached. Thus, the compounds in qucstion have been found useful for .reating mechanical or semi-cllemical pul~s as well as che~ical pulps, such as sulphite or sulpnate pulps, commonly used in manufacturing of soft products with good water-a~sorption properties.
The compounds of the invention will improve softness of substratPs o~ all kinds including both woven and non~oven sheet materials, especially substrates made of cellulose fibers, either entirely or in admixtures with other natural or synthetic fi~ers. Examples of such substrates are regenerated callulose or rayon, acetate rayon, cellulose acetate-propionate, cellulose acetate-butyrate, polyvinyl chloride, polyamide, polypropylene, polyethylene, polyacrylonitrile, polyesters sucn as ethylene glyco`l-terepht~alic acid polymers, cotton, linen, jute, ramie, .
sisal, wool, mohair, alginate fi~ers, zein fibPrs, glass, potassium titanate, bast, ~agasse, polyvinylidene chloride, and fur fibers of various kinds such as beaver, rabbit, seal, mus'-rat, otter, mink, caracul, lamb and squirrel.
The substrate materials can ta~e any form, including non~woven materials such as felts, bats, ~nd mats; wovan mater ials such as fabrics, cloth, carpets, rugs and upholstery;
synthetic fur materials; curtains, and covering materials of all kinds.
The co~pounds are preferably added as aqueous solutions in a concentration of from 1 to 15~ by weiglit o~ active substance.
Viscosity reducing additives may be included in the solution, for example t~e monoetilyl ether of diethylene glycol~ r7onionic cb/
. .
~1~4~
surfactants such as a~lclucts of ethylene oxicle or propylene oxide to aliphatic alcohols or alkyl phenols may be aclded for an additional improvemerlt of the rewettability of the cellulose fibers in pulp s~r paper.
While the usual solvent is water, if rapid volatilizati~n of the solvent is desirad, the quaternary amm~nium compounds of the invention can be applied frs)m a sohltivn in a rapidly volatllizable organic solvent, such as acetnne~ methanol, ethanol, isopropanol, or mixtures thereoI. In this case, the concentrations are the s~me as aque~us solutions.
The solutis)ns of the quaternary ammonium compounds ~E the inventi~n call be applied by dlpping, spraying3 or coating, using c~n-ventional techniques.
The amount s~f the quaternary ammonium comp~urlds accord-15 - ing to the invention va~ies accorcling to the desired effect but is normally within the range from about 0. 02.~to abou~ 3~ by weight, preferably from 0.1 to l. 5% by weight, calculated on the dry weight of the cellulose fibers.
The cellulose fibers, pulp or pape~ treated with compounds according to the i~vention can be used for many differen~ purposes.
Cellulose pulp ~ibers can be disintegrated into so-called fluff fibers used for differen~ sanitary products, The compounds can also b~
used in manufacturin~ pa.per when softness îs of grea~ importance, such as sanitary paper, tissue paper,and paper included in different te}:tile substitutes for bed linen, towels, table-cloths, clothes, etc.
.- .. :
6~
The SyntileSiS of the alkyl pheno~cy ethyleneoxy-2-hydroxy-propylene quatern~l~y ~mmoni~lm cc)mpounds in accordance with the ~-invention includes the following reaction steps:
1) Rl(C2~I4)n OH + CH2-- /C:EICHzCl > Rl(C2H~.)n OCH2CHCHaCl OH
R~ R3 2) 2Rl(C2H40)n OCH2CHC~2Cl ~ NH~R1(C2H~O)n OC~2CHCHZ~ N\ C
OH R~ OH R~
In the above reaction formulae7 R~ 3, R4, and nl have the meaning earlier mentioned.
The aLkylphenoxyethylene oxy-(2-hydroxy)propylene quaternary ammonium ~ompounds in accordance with the invention can be pre-pared by reaction of from about four to about forty mols of ethylene oxide with one mol of an aLkyl phenol having from about fourteen to 1~ about forty-six carbon atoms. The reaction of ethylene oxide with ~ -the phenol is carried out in the presence of an a~ali catalyst, preferably po~assium hydroxide~ at an elevated temperature within the range from about 30 to about 150Co The resulting alkyl phenoxyethylene glycol ether is reacted with epichlorhydrin, producing the corresponding chloroglyceryl or chlorohydroxypropylene ether, which is then preferably reacted with a secondary amine having the formular :R3R~NH, where R3 and P~ are methyl, ethyl, or hydroxyethyl.
Suitable secondary amines for the process according to the invention are dimethyl amine and diethyl amine, which are commer-cially available O
. ~:
1 . ' ' '' " ' : ' ' i6 The procluct i9 a quaternary amm~nium compo~md of the invention, in the form of its chloride salt. The chlnride ion can then be exchanged by another anion, using known techniques, for example, by a~dltion of a sodium salt with a higher solubility constant than s~dium chloride, or ~T ion exchange in an anion ex-changer. Amon~ anions ~her than chloride ion which can serve as X in the quaternary ammonium compounds of the inventi~ are hydroxyl, nitrate, carbonate, hydro~rl, phosphate, iodide, bromide, methyl sulfate, acetate, carbonate, farmate, citrate, propionate, and tartrate. The mono~ralent anions are preferred.
The reaction between the all{ylphenoxyethyleneoxide adduct and the epichlorhydrin proceeds at an elevated temperature within the range from about 30 to about 159C in the presence of a catalyst, such as stannic chloride, boron trifluoride, and perchloric acid, HCl~. These give a rapid easily controllable reactis)n, but ~her acid catalysts such as toluene sulfonic acid and sulfuric acid can also be used.
In order to ensure complete reaction of the ethylene oxide adduct~ an excess nf epichlorhydrin is generally added.
The quaterni2a$ion of the secondary amine with the chloro~ly-- ceryl ether is carried out in the presence of alkali, generally sodium hydroxide, at an elevated temperature within the range from abo~lt 40 to about 150C, in the presence of water or a water-miscible organic solvent.
- It is not necessary that the organic solvent be miscible wi~h wat@r in all proportions, but it should be miscible with water in the proportions use~ so as to form a h~mogeneous solvent mixture, if wate.r is also present.
- -- - - - -- - - .
.' . ~ .
a6~
Any ~ater-lni,sci~Te organic solvent wllicll is inert under the re~ction conditions c~n be used. The organic salvent accordi~Lg;ly can be select~cl from the clas~es consisting of lower aliphatic alcohols having from one to about six carbon atoms, lower aliphatic polyhydric alcohols having from two to about si:c carbon a~oms and ~rvm two to six hydrs:~xyl groups, and monoa~kyl ethers of such lower aliphatic polyhydric alcohols having~ from two to about six carbon atoms in the aLkyl group; polyoxyalkylene glycols and polyoxyalkylene glycol monoethers ha~ing at least one oxyether linkage anA two alkylene groups, the alkylene gr~ups having from two to four carbon atoms i~
a straight or branched chain, and having not more than one hydroxyl group etherified with a lower alkyl group having from one t~ about six carbon at~ms; and heterocyclic ethers having ilp to six ring atoms oE
which one or two may be ether o}ygen, and four or five carbo~} atoms.
16 Exemplary lower aliphatic alcohol9 include methànol, ethanol~
propanol, isopropanol, butanol~ isobutan~l, tertiarybutanol9 secondary ~ :
butanol, pentan~l, isopentanol~ hexanol, isohex~nol~ and tertiaryhex-anol.
Exemplary polyoxya~kylene glycols and glycol ethers include the monoethyl ethers of diethylene glycol, diethylene glycDI~ tri-ethylene glycol~ tetraethylene glycoI, the monomethyl ether of triethylene glycol, dipropylene glycol, dibutylene glycol, tributylene glycol, tetrabut~lene glycol, tetrapropylene glycol~ the monomethyl : .
ether of dipropylene glycol, and the monomethyl ether of dibu~Tlene 2~ glycs~l.
Exemplary polyhydric alcohols include ethylene glycol, propylene glycal, butylene glycol, the monomethyl ethers ~f ethylene glycol, propylene glycol and butylene glycol, and the m~no-ethyl ethers of ethylene glyco~ propylene glycol and butylene glycol~
~)4Z4~i~
The compounds of the invention give a very sati~factory com-bination of wettabilit~, good sof~ness and low mechanical strength.
Generally, the wettability impro~es as the number of o}~ëthylene units increases. The reduction in strength increases and the wetta-bility diminishes as the number of carbon atoms in the alkyl phenyl substituents Rl and R2 increases. Thus, by varying the numher of carbon atoms in Rl and R2 and the number o~ oxyethylene units it is passible to obtain the combination of wettability and interfibre bond-reducing properties desired for each special purpose. Particularly good properties from both these points of view are found in com- ~`
pounds where Rl and R2 are a~yl phenyl groups having from twenty-three to thirty-two carbon atoms, and nl and n2 are within the range ~;
from 11 to 25.
- The alk~rl groups R of Rl and R2 either have7 or are ~aken irl ~
; su~icient number to aggregate, the number ~f carbon atvms includ- ~ -ing the six carbon atoms of the phenyl ring within the above-stal:ed .
ranges. - -The a~71 groups can for e2~Lmple be methyl, ethyl, pr~pyl, isopropyl, butyl, isobutyl7 ter~-butyl, amyl, isoamyl, tert-amyl, hexyl, 2-ethyl hexyl, heptyl, octyl, isooctyl, nonyl, isononyl~ decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, palmit~rl, stearyl7 behenyl, eicosyl, heptadecyl, myricyl, lacceryl, and heptacosyl.
The compounds according to the in~rention can be added to the cellulos~ fibers at any stage after screening and/or bleach~g of the - ~5 pulp. (~enerally the addition is done before or during dehydratian or drying of the cellulose pulp, for example, during processing int~
c~ntinuous webs on a cellulose drying machine, or on a paper .
- .
. .. . . . : .. . . ~ ' .. . : ' machine, or into flakes in a fla~e dryer.
~ ny kind of cellulose pulp can be tr~ated, such as mech~nical pulp, s~mi-chemical pulp and chemical pulp, bleacln-ed or unbleached. Thus, the compounds in qucstion have been found useful for .reating mechanical or semi-cllemical pul~s as well as che~ical pulps, such as sulphite or sulpnate pulps, commonly used in manufacturing of soft products with good water-a~sorption properties.
The compounds of the invention will improve softness of substratPs o~ all kinds including both woven and non~oven sheet materials, especially substrates made of cellulose fibers, either entirely or in admixtures with other natural or synthetic fi~ers. Examples of such substrates are regenerated callulose or rayon, acetate rayon, cellulose acetate-propionate, cellulose acetate-butyrate, polyvinyl chloride, polyamide, polypropylene, polyethylene, polyacrylonitrile, polyesters sucn as ethylene glyco`l-terepht~alic acid polymers, cotton, linen, jute, ramie, .
sisal, wool, mohair, alginate fi~ers, zein fibPrs, glass, potassium titanate, bast, ~agasse, polyvinylidene chloride, and fur fibers of various kinds such as beaver, rabbit, seal, mus'-rat, otter, mink, caracul, lamb and squirrel.
The substrate materials can ta~e any form, including non~woven materials such as felts, bats, ~nd mats; wovan mater ials such as fabrics, cloth, carpets, rugs and upholstery;
synthetic fur materials; curtains, and covering materials of all kinds.
The co~pounds are preferably added as aqueous solutions in a concentration of from 1 to 15~ by weiglit o~ active substance.
Viscosity reducing additives may be included in the solution, for example t~e monoetilyl ether of diethylene glycol~ r7onionic cb/
. .
~1~4~
surfactants such as a~lclucts of ethylene oxicle or propylene oxide to aliphatic alcohols or alkyl phenols may be aclded for an additional improvemerlt of the rewettability of the cellulose fibers in pulp s~r paper.
While the usual solvent is water, if rapid volatilizati~n of the solvent is desirad, the quaternary amm~nium compounds of the invention can be applied frs)m a sohltivn in a rapidly volatllizable organic solvent, such as acetnne~ methanol, ethanol, isopropanol, or mixtures thereoI. In this case, the concentrations are the s~me as aque~us solutions.
The solutis)ns of the quaternary ammonium compounds ~E the inventi~n call be applied by dlpping, spraying3 or coating, using c~n-ventional techniques.
The amount s~f the quaternary ammonium comp~urlds accord-15 - ing to the invention va~ies accorcling to the desired effect but is normally within the range from about 0. 02.~to abou~ 3~ by weight, preferably from 0.1 to l. 5% by weight, calculated on the dry weight of the cellulose fibers.
The cellulose fibers, pulp or pape~ treated with compounds according to the i~vention can be used for many differen~ purposes.
Cellulose pulp ~ibers can be disintegrated into so-called fluff fibers used for differen~ sanitary products, The compounds can also b~
used in manufacturin~ pa.per when softness îs of grea~ importance, such as sanitary paper, tissue paper,and paper included in different te}:tile substitutes for bed linen, towels, table-cloths, clothes, etc.
.- .. :
6~
The SyntileSiS of the alkyl pheno~cy ethyleneoxy-2-hydroxy-propylene quatern~l~y ~mmoni~lm cc)mpounds in accordance with the ~-invention includes the following reaction steps:
1) Rl(C2~I4)n OH + CH2-- /C:EICHzCl > Rl(C2H~.)n OCH2CHCHaCl OH
R~ R3 2) 2Rl(C2H40)n OCH2CHC~2Cl ~ NH~R1(C2H~O)n OC~2CHCHZ~ N\ C
OH R~ OH R~
In the above reaction formulae7 R~ 3, R4, and nl have the meaning earlier mentioned.
The aLkylphenoxyethylene oxy-(2-hydroxy)propylene quaternary ammonium ~ompounds in accordance with the invention can be pre-pared by reaction of from about four to about forty mols of ethylene oxide with one mol of an aLkyl phenol having from about fourteen to 1~ about forty-six carbon atoms. The reaction of ethylene oxide with ~ -the phenol is carried out in the presence of an a~ali catalyst, preferably po~assium hydroxide~ at an elevated temperature within the range from about 30 to about 150Co The resulting alkyl phenoxyethylene glycol ether is reacted with epichlorhydrin, producing the corresponding chloroglyceryl or chlorohydroxypropylene ether, which is then preferably reacted with a secondary amine having the formular :R3R~NH, where R3 and P~ are methyl, ethyl, or hydroxyethyl.
Suitable secondary amines for the process according to the invention are dimethyl amine and diethyl amine, which are commer-cially available O
. ~:
1 . ' ' '' " ' : ' ' i6 The procluct i9 a quaternary amm~nium compo~md of the invention, in the form of its chloride salt. The chlnride ion can then be exchanged by another anion, using known techniques, for example, by a~dltion of a sodium salt with a higher solubility constant than s~dium chloride, or ~T ion exchange in an anion ex-changer. Amon~ anions ~her than chloride ion which can serve as X in the quaternary ammonium compounds of the inventi~ are hydroxyl, nitrate, carbonate, hydro~rl, phosphate, iodide, bromide, methyl sulfate, acetate, carbonate, farmate, citrate, propionate, and tartrate. The mono~ralent anions are preferred.
The reaction between the all{ylphenoxyethyleneoxide adduct and the epichlorhydrin proceeds at an elevated temperature within the range from about 30 to about 159C in the presence of a catalyst, such as stannic chloride, boron trifluoride, and perchloric acid, HCl~. These give a rapid easily controllable reactis)n, but ~her acid catalysts such as toluene sulfonic acid and sulfuric acid can also be used.
In order to ensure complete reaction of the ethylene oxide adduct~ an excess nf epichlorhydrin is generally added.
The quaterni2a$ion of the secondary amine with the chloro~ly-- ceryl ether is carried out in the presence of alkali, generally sodium hydroxide, at an elevated temperature within the range from abo~lt 40 to about 150C, in the presence of water or a water-miscible organic solvent.
- It is not necessary that the organic solvent be miscible wi~h wat@r in all proportions, but it should be miscible with water in the proportions use~ so as to form a h~mogeneous solvent mixture, if wate.r is also present.
- -- - - - -- - - .
.' . ~ .
a6~
Any ~ater-lni,sci~Te organic solvent wllicll is inert under the re~ction conditions c~n be used. The organic salvent accordi~Lg;ly can be select~cl from the clas~es consisting of lower aliphatic alcohols having from one to about six carbon atoms, lower aliphatic polyhydric alcohols having from two to about si:c carbon a~oms and ~rvm two to six hydrs:~xyl groups, and monoa~kyl ethers of such lower aliphatic polyhydric alcohols having~ from two to about six carbon atoms in the aLkyl group; polyoxyalkylene glycols and polyoxyalkylene glycol monoethers ha~ing at least one oxyether linkage anA two alkylene groups, the alkylene gr~ups having from two to four carbon atoms i~
a straight or branched chain, and having not more than one hydroxyl group etherified with a lower alkyl group having from one t~ about six carbon at~ms; and heterocyclic ethers having ilp to six ring atoms oE
which one or two may be ether o}ygen, and four or five carbo~} atoms.
16 Exemplary lower aliphatic alcohol9 include methànol, ethanol~
propanol, isopropanol, butanol~ isobutan~l, tertiarybutanol9 secondary ~ :
butanol, pentan~l, isopentanol~ hexanol, isohex~nol~ and tertiaryhex-anol.
Exemplary polyoxya~kylene glycols and glycol ethers include the monoethyl ethers of diethylene glycol, diethylene glycDI~ tri-ethylene glycol~ tetraethylene glycoI, the monomethyl ether of triethylene glycol, dipropylene glycol, dibutylene glycol, tributylene glycol, tetrabut~lene glycol, tetrapropylene glycol~ the monomethyl : .
ether of dipropylene glycol, and the monomethyl ether of dibu~Tlene 2~ glycs~l.
Exemplary polyhydric alcohols include ethylene glycol, propylene glycal, butylene glycol, the monomethyl ethers ~f ethylene glycol, propylene glycol and butylene glycol, and the m~no-ethyl ethers of ethylene glyco~ propylene glycol and butylene glycol~
3~ glycer~l, sorbitol, pentaerythritol~ and neopentyl glycol.
. ~, . .
.; . . . . . . . .
., .. , . ~ : .
.. , , ~ . .
61~
It i~ also possible to react the chl~roglyceryl ether wil:h arnmonia or with a primary ~mine having a methyl, ethyl, or hydroxy- ~ :
ethyl group, ancl the resulting product may then be q.uaternized with :~
methyl or ethyl chloride or dimethyl or diethyl suLfate. However, this procedure is more complicated than the previously described - procedure, and it involves more reaction steps, and results in larger amounts of byproducts and lower total yields of the desired quatern-ary amm~nium compounds.
Phenols which can be used as the source of Rl and R2 in the compounds according to the inventl~n are for example octyl phenol, nonyl phenol, decyl phenol, dodecyl phenol, tetradecyl phenol, hexadecyl phenol~ octadecyl phenol, eicosyl phenol, dioctyl phenol, dinonyl phenol, didecyl phenol, didodecyl phen~l, ditetradecyl phen~l, dihexadecyl phen~l, dioctadecyl phenol, tributyl phenol, trihe~yl phenol, trioctyl phenol, tridecyl phenol~ and tridodecyl phen~l.
- Among these octadecyl phen~lg dioctyl phenol, dinonyl phenolg didecyl phenol, didodecyl phen31 and ditetradecyl phenol should be ~mphasized.
The dialkyl phenols preferably have the alkyl groups in the ~9 4- p~sition but 2, 3-; ~, 6- and 2, 6-dialkyl phenols can be used. The - triaLkyl phenols have th~ a~yl groups preferably in the 29 4, 6- posi- : ;
tions, but 2, 3, 6-; 2, 3, 5- and 2, 3, 4- can also be used. `~
Among the compounds according to the invention based on the above-mentioned alkyl phenols~ the f~llowing have been found to have go~d properties:
' "
' .. . ..
~ 42~
C~I37--O~O (c2H4o)~2-c~lcHcET2 ~ C~I3 C ~1~,O_O--(C2H~O),Z.-c~I2c~Ic~-I2 \ C~I3 - OH
C8Erl7 ~O_(C2~I40)~ H2lCHC~2 /CH3 C8 H 17 ~ ~N~ . C 1 C 8E~17--O--o~CzH40) 8-CH~ 2 CE3~3 .C8 H l7 OH
C8 ~17--O--O--~C2H40) l2~CEI2CHCH2 CE3 `C8 E lq lH N/ Cl C8~l7--O--O--(C2EI~O)~-~H2l ~ICF2/ \C~I3 C8 H 17 ~ -C~4Hz9--l--~ 2~ 8~ ~2\ ~jC~I3 89 0~ N Cl 15C~4 Ea~,{>~ (C2H~0)~2-C~ICEI2 \C~I3 ~;
C ~H29 H
C~4 H~'29--~ (C2:EI40)22-CH~2l HCII2 (~I3 -29 . OH N . C l C4~12f~OI--~)~C2~0)22-CH2j~ECH2 \C1~13 . iC 14 H;!~ O~I ~ `::
: , ' , ' ~, '' The ollowing coxnpoun(ls sllow particularly go~d properties:
C9Hl9 `^~S>~o (c2~I~,o),~-cH2lcHcH~ /C~I3 C 9 ~ 9 O~E N C l Cg Hl9--q--O--(C2H40),2-CH2lC~:C~I2 Cl:I3 Cg Hlg OH
Mlg~ (C2H,I0)l6-C~2lcHc~I2 /CH3 Cg Hl9 OH N Cl Cg Hlg - - O O~C2H,~O)l,J-C~12~HCF~ CH3 Cg Hlg OH
Cg Hlg I----(C2H4O~z4-CEI2l~CH2 /CH3 CgHlg N Cl Cg Hlg--O--~--(C2H~O)2g-CH2l HCH2/ \ CH3 C9 Hlg OH ~ .
CloH2~ - I----(C2H4(3)l6-~2l HCH2 /~H3 Q ~ :
CloH2l OH N Cl :
clo~)--(C2H4O),~-CH2lHC~I2 \CH3 C~ lo H2 l H ~ ~;
C1O E2~OI~--(C2H4O)24-CH2l HCH2\ 0~CH3 CloH2l OH N Cl Cl0E2~ --~c2EI4o)2~l-cH2~c~2 - \CH3 cloH2l . ~ .
'.''' ~'' Cl2~I2~ 0--O----(C2H~0)l6-C~I2l ~IC~2 /CH3 C l2H2s OH /N C 1 C,?H2s-- I :)~C2H,EO)l~,-CH2l HCH~ I3 C l2H25 OH
C~H2s~ (C2F[~O)2~-CHzl HCH2 /CH3 C 12~25 OE N C 1 Cl2H25--<~>~O~C2EI40)2~-CH2CHCH2 \CH
C ,2H25 IOH
The in~enti~n is further illustrated by the following Examples, 10 whîch in the opini~n of the inventor represent pra~erred e~nb~diments of the invention.
E~AMPL 1 In a r~action vessel pr~vided with devices for heating,s~irring, and a reflux condenser, 2 m~les of 2, 4- dinonyl phenol were intro~
15 duc~d. The dinonyl phenol was reacted with 16 moles ethylene o~ide together with 0.1% ~odium hydroxid~ catalyst.
The ethylene 1~xide adduct ~hus obtained was wor~ed up, and reacted with 2~2 moles epichlorhydrin at a temperature of about 100C
during 100 miIlutes. As catalyst during this reaction 6 g SnCl~ wa~
20 - used. ~esidues of epichl~rhydrin were rem~ved by vacuum treatment ~ .
.
-- .
.
. ~, . .
.; . . . . . . . .
., .. , . ~ : .
.. , , ~ . .
61~
It i~ also possible to react the chl~roglyceryl ether wil:h arnmonia or with a primary ~mine having a methyl, ethyl, or hydroxy- ~ :
ethyl group, ancl the resulting product may then be q.uaternized with :~
methyl or ethyl chloride or dimethyl or diethyl suLfate. However, this procedure is more complicated than the previously described - procedure, and it involves more reaction steps, and results in larger amounts of byproducts and lower total yields of the desired quatern-ary amm~nium compounds.
Phenols which can be used as the source of Rl and R2 in the compounds according to the inventl~n are for example octyl phenol, nonyl phenol, decyl phenol, dodecyl phenol, tetradecyl phenol, hexadecyl phenol~ octadecyl phenol, eicosyl phenol, dioctyl phenol, dinonyl phenol, didecyl phenol, didodecyl phen~l, ditetradecyl phen~l, dihexadecyl phen~l, dioctadecyl phenol, tributyl phenol, trihe~yl phenol, trioctyl phenol, tridecyl phenol~ and tridodecyl phen~l.
- Among these octadecyl phen~lg dioctyl phenol, dinonyl phenolg didecyl phenol, didodecyl phen31 and ditetradecyl phenol should be ~mphasized.
The dialkyl phenols preferably have the alkyl groups in the ~9 4- p~sition but 2, 3-; ~, 6- and 2, 6-dialkyl phenols can be used. The - triaLkyl phenols have th~ a~yl groups preferably in the 29 4, 6- posi- : ;
tions, but 2, 3, 6-; 2, 3, 5- and 2, 3, 4- can also be used. `~
Among the compounds according to the invention based on the above-mentioned alkyl phenols~ the f~llowing have been found to have go~d properties:
' "
' .. . ..
~ 42~
C~I37--O~O (c2H4o)~2-c~lcHcET2 ~ C~I3 C ~1~,O_O--(C2H~O),Z.-c~I2c~Ic~-I2 \ C~I3 - OH
C8Erl7 ~O_(C2~I40)~ H2lCHC~2 /CH3 C8 H 17 ~ ~N~ . C 1 C 8E~17--O--o~CzH40) 8-CH~ 2 CE3~3 .C8 H l7 OH
C8 ~17--O--O--~C2H40) l2~CEI2CHCH2 CE3 `C8 E lq lH N/ Cl C8~l7--O--O--(C2EI~O)~-~H2l ~ICF2/ \C~I3 C8 H 17 ~ -C~4Hz9--l--~ 2~ 8~ ~2\ ~jC~I3 89 0~ N Cl 15C~4 Ea~,{>~ (C2H~0)~2-C~ICEI2 \C~I3 ~;
C ~H29 H
C~4 H~'29--~ (C2:EI40)22-CH~2l HCII2 (~I3 -29 . OH N . C l C4~12f~OI--~)~C2~0)22-CH2j~ECH2 \C1~13 . iC 14 H;!~ O~I ~ `::
: , ' , ' ~, '' The ollowing coxnpoun(ls sllow particularly go~d properties:
C9Hl9 `^~S>~o (c2~I~,o),~-cH2lcHcH~ /C~I3 C 9 ~ 9 O~E N C l Cg Hl9--q--O--(C2H40),2-CH2lC~:C~I2 Cl:I3 Cg Hlg OH
Mlg~ (C2H,I0)l6-C~2lcHc~I2 /CH3 Cg Hl9 OH N Cl Cg Hlg - - O O~C2H,~O)l,J-C~12~HCF~ CH3 Cg Hlg OH
Cg Hlg I----(C2H4O~z4-CEI2l~CH2 /CH3 CgHlg N Cl Cg Hlg--O--~--(C2H~O)2g-CH2l HCH2/ \ CH3 C9 Hlg OH ~ .
CloH2~ - I----(C2H4(3)l6-~2l HCH2 /~H3 Q ~ :
CloH2l OH N Cl :
clo~)--(C2H4O),~-CH2lHC~I2 \CH3 C~ lo H2 l H ~ ~;
C1O E2~OI~--(C2H4O)24-CH2l HCH2\ 0~CH3 CloH2l OH N Cl Cl0E2~ --~c2EI4o)2~l-cH2~c~2 - \CH3 cloH2l . ~ .
'.''' ~'' Cl2~I2~ 0--O----(C2H~0)l6-C~I2l ~IC~2 /CH3 C l2H2s OH /N C 1 C,?H2s-- I :)~C2H,EO)l~,-CH2l HCH~ I3 C l2H25 OH
C~H2s~ (C2F[~O)2~-CHzl HCH2 /CH3 C 12~25 OE N C 1 Cl2H25--<~>~O~C2EI40)2~-CH2CHCH2 \CH
C ,2H25 IOH
The in~enti~n is further illustrated by the following Examples, 10 whîch in the opini~n of the inventor represent pra~erred e~nb~diments of the invention.
E~AMPL 1 In a r~action vessel pr~vided with devices for heating,s~irring, and a reflux condenser, 2 m~les of 2, 4- dinonyl phenol were intro~
15 duc~d. The dinonyl phenol was reacted with 16 moles ethylene o~ide together with 0.1% ~odium hydroxid~ catalyst.
The ethylene 1~xide adduct ~hus obtained was wor~ed up, and reacted with 2~2 moles epichlorhydrin at a temperature of about 100C
during 100 miIlutes. As catalyst during this reaction 6 g SnCl~ wa~
20 - used. ~esidues of epichl~rhydrin were rem~ved by vacuum treatment ~ .
.
-- .
.
4~i6 and a reaction product in the state oP a yellowish viscous liquid was obtainecl.
~ n ~ autoclave with a stirrer and a heating device 1.8 mol~s of this reaction product was introduced together with ~50 grams
~ n ~ autoclave with a stirrer and a heating device 1.8 mol~s of this reaction product was introduced together with ~50 grams
5 ethanol in which were ~issolved 0. 9 mole dimethyl amine, 50 grams sodium hydrox~de, and 30 grams of water. The mixture was kept in the autoclave for three hours at 125C. Traces of residual dimethyl amine were removed by bubbling nitrogen gas through the reaction mixture.
10The reaction product was a yellowish substance, 90% quater~
nar~r amine and 6q~o tertiary amine, calculated on the the~re~ical yield of amine. The quaternary amm~nitlm compound thus ~btained had the --fs~rmula:
, Cg H~ ~ (C8H~0)8 -CH2fHCH8 ~CEI3 .
1~ CgH~ O~I N Cl `
CH
Cg Hlg--q--O-(C2H~0)8 -CH2CHGH~
CglIlg OH
EXAMPLES 2 to 6 .
- In the same way as the compound ~, of Ex~mple 1, the fol~
. ~
aDlowing comp~unds were synthesized: ;
,.~ .
Example 2. Reaction product of 2 moles dinonyl phenol, 24 moles ethylene oxide, 2 m~les epichl~rhydrin and 1 mole of dimethyi-amine:
`
.. . . .
.. ,.~.,. .. , . ; ... . - . . .
" ; ! ~ ,.. . ..
C~ Hl9--0~ (c2EI~o),2c}I2c~lc~2 CEI9 / \C~I3 C9Hl9--C~o--(C2H,I0)12CI-IaC~ HCH2 ~9 Hl9 OH
Example 3. Reaction product aE. 2 moles dinonyl phenol7 32 moles ethylene oxide, 2 moles epichlorhydrin and 1 m~le dimethyl amine:
Cg H~> O-(C2H4Q~1~CH2,~C~ 9/CH
0 C9H~l9 ~ O--(C2HgO)16!: H2CEICE~
9 ~19 ~)H ;
~: Example 4. Reaction product of 2 moles dinonyl phen~l,., 60 moles ethylene oxide, ~ m~les epi~hlorhydrin and 1 mole dimethyl amine~
CgHl~o--(C2H40)3~CH2CHcE~ ~,CH
Cg Hlg--0--0--(C2HgO)30CH2CHClI2/ CH3 Cg H39 ~H ~ .
Example 5. ~eacti~ product o~ 2 moles didodecyl phenol7 20 ~2 moles ethylene oxid~,2 moles epichlorhydrin alld 1 m~le dimethyl amine: .
C~2HZ5 0--O--~C2H~LO)l.6 ~H2CbHcH2\ ~)~CE~3 ~3 .
C~ZH25 ~ ~ H~
C~[2D--O--O--(C2H0~ 16 C H2~E3CH2 ~;L3 bl2H25 bH
., . ,. ~ . . . -- . . . .
~04~66 ~ . Rcaction product of 2 mol~s dioctyl phenol, 2~ mol~s etl~ylen~ oxide, 2 moles eplchlorhydrin and 1 mole dim~thyl amine.
C8ll17 - I ( 2 4 )12 21 2 \ ~? / C~
C8H17 N Cl C8E~17 C~- (C2~l }) 1~C~ CHCH2 C8~17 ~ ' 0.5~ each of the products of Examples 1 to 6 were added to samples of an aqueous ~leached pine sulphate cellulose pulp slurry of 2% consistency.
In a control, for comparison, 0.5% of di(C16-C20-fatty-alkoxy (ethyleneoxy)6-2-hydroxy propylene) dimetnyl ammonium chloride was added.
-- ~and sheets were form~d ~rom the pulp slurries in tha usual way, and tes,ed after dr~ing for mec~anical strength ~burs~ factor according to SC~I) and water absorption according to Klemm. The results are shown in Table I:
,;
TABLE I
20Additive; __ Burst Factor Water Absorption, mm No additive 21.1 100 Example 1 10.6 91 Example 2 11.5 92 Exa~lple 3 12.7 95 Example 4 16.8 98 Example 5 12.2 93 Example 6 12.9 92 Control 12.9 90 ' ' ' ~' , ':
cb/ ~ 15 _ ,~.. ... . ..
4L6~
From the results it is evident that a~dition of the compounds oE Examples 1 to 6 according to the inventi~n in a very noticeable way reduces the mechanical strength (burst factor) of the cellulose pulp fibers, while preserving a high wettability. Comparison of the re-sults with those of the cellulose treated with the control makes evident that only the Example 4 gives cellulose pulp fibers with a higher burst factor, while on the other hand all the compounds according to the in-vention give cellulose pulp fibers with better wettability.
.
' ` -.
.. ,~ . .
. .~
10The reaction product was a yellowish substance, 90% quater~
nar~r amine and 6q~o tertiary amine, calculated on the the~re~ical yield of amine. The quaternary amm~nitlm compound thus ~btained had the --fs~rmula:
, Cg H~ ~ (C8H~0)8 -CH2fHCH8 ~CEI3 .
1~ CgH~ O~I N Cl `
CH
Cg Hlg--q--O-(C2H~0)8 -CH2CHGH~
CglIlg OH
EXAMPLES 2 to 6 .
- In the same way as the compound ~, of Ex~mple 1, the fol~
. ~
aDlowing comp~unds were synthesized: ;
,.~ .
Example 2. Reaction product of 2 moles dinonyl phenol, 24 moles ethylene oxide, 2 m~les epichl~rhydrin and 1 mole of dimethyi-amine:
`
.. . . .
.. ,.~.,. .. , . ; ... . - . . .
" ; ! ~ ,.. . ..
C~ Hl9--0~ (c2EI~o),2c}I2c~lc~2 CEI9 / \C~I3 C9Hl9--C~o--(C2H,I0)12CI-IaC~ HCH2 ~9 Hl9 OH
Example 3. Reaction product aE. 2 moles dinonyl phenol7 32 moles ethylene oxide, 2 moles epichlorhydrin and 1 m~le dimethyl amine:
Cg H~> O-(C2H4Q~1~CH2,~C~ 9/CH
0 C9H~l9 ~ O--(C2HgO)16!: H2CEICE~
9 ~19 ~)H ;
~: Example 4. Reaction product of 2 moles dinonyl phen~l,., 60 moles ethylene oxide, ~ m~les epi~hlorhydrin and 1 mole dimethyl amine~
CgHl~o--(C2H40)3~CH2CHcE~ ~,CH
Cg Hlg--0--0--(C2HgO)30CH2CHClI2/ CH3 Cg H39 ~H ~ .
Example 5. ~eacti~ product o~ 2 moles didodecyl phenol7 20 ~2 moles ethylene oxid~,2 moles epichlorhydrin alld 1 m~le dimethyl amine: .
C~2HZ5 0--O--~C2H~LO)l.6 ~H2CbHcH2\ ~)~CE~3 ~3 .
C~ZH25 ~ ~ H~
C~[2D--O--O--(C2H0~ 16 C H2~E3CH2 ~;L3 bl2H25 bH
., . ,. ~ . . . -- . . . .
~04~66 ~ . Rcaction product of 2 mol~s dioctyl phenol, 2~ mol~s etl~ylen~ oxide, 2 moles eplchlorhydrin and 1 mole dim~thyl amine.
C8ll17 - I ( 2 4 )12 21 2 \ ~? / C~
C8H17 N Cl C8E~17 C~- (C2~l }) 1~C~ CHCH2 C8~17 ~ ' 0.5~ each of the products of Examples 1 to 6 were added to samples of an aqueous ~leached pine sulphate cellulose pulp slurry of 2% consistency.
In a control, for comparison, 0.5% of di(C16-C20-fatty-alkoxy (ethyleneoxy)6-2-hydroxy propylene) dimetnyl ammonium chloride was added.
-- ~and sheets were form~d ~rom the pulp slurries in tha usual way, and tes,ed after dr~ing for mec~anical strength ~burs~ factor according to SC~I) and water absorption according to Klemm. The results are shown in Table I:
,;
TABLE I
20Additive; __ Burst Factor Water Absorption, mm No additive 21.1 100 Example 1 10.6 91 Example 2 11.5 92 Exa~lple 3 12.7 95 Example 4 16.8 98 Example 5 12.2 93 Example 6 12.9 92 Control 12.9 90 ' ' ' ~' , ':
cb/ ~ 15 _ ,~.. ... . ..
4L6~
From the results it is evident that a~dition of the compounds oE Examples 1 to 6 according to the inventi~n in a very noticeable way reduces the mechanical strength (burst factor) of the cellulose pulp fibers, while preserving a high wettability. Comparison of the re-sults with those of the cellulose treated with the control makes evident that only the Example 4 gives cellulose pulp fibers with a higher burst factor, while on the other hand all the compounds according to the in-vention give cellulose pulp fibers with better wettability.
.
' ` -.
.. ,~ . .
. .~
Claims (22)
1. A process for treating a substrate comprising cellulose fibers to impart improved wettability, softness and low mechanical strength thereto, which comprises applying to the substrate a quaternary ammonium compound having the general formula:
wherein:
R1 and R2 are alkyl phenyl groups totalling from about fourteen to about forty-six carbon atoms in from one to three alkyl groups and the phenyl group;
R3 and R4 are selected from the group consisting of methyl, ethyl and hydroxyethyl;
n1 and n2 are numbers within the range from about 4 to about 40, representing the average number of oxyethylene groups present in each substituent; and X is an anion.
wherein:
R1 and R2 are alkyl phenyl groups totalling from about fourteen to about forty-six carbon atoms in from one to three alkyl groups and the phenyl group;
R3 and R4 are selected from the group consisting of methyl, ethyl and hydroxyethyl;
n1 and n2 are numbers within the range from about 4 to about 40, representing the average number of oxyethylene groups present in each substituent; and X is an anion.
2. A process according to claim 1, in which n1 and n2 are numbers within the range from about 6 to about 30.
3. A process according to claim 1, in which R1 and R2 have from about twenty to about thirty-eight carbon atoms.
4. A process according to claim 1, in which the quaternary ammonium compound is in aqueous solution in a concentration within the range from about 1% to about 15% by weight.
5. A process according to claim 1, in which the amount of quaternary ammonium compound applied to the substrate is within the range from about 0. 02% to about 3% by weight of the substrate.
6. A process according to claim 1, in which the quaternary ammonium compound is applied to cellulose pulp after screening the pulp.
7. A process according to claim 1, in which the quaternary ammonium compound is applied to cellulose pulp after bleaching the pulp.
8. A process according to claim 1, in which the quaternary ammonium is applied to cellulose pulp prior to drying the pulp.
9. A process according to claim 1, in which the substrate to which the quaternary ammonium compound is applied is cellulose pulp.
10. A process according to claim 1, in which the substrate to which the quaternary ammonium compound is applied is paper.
11. A process according to claim 1, in which the substrate to which the quaternary ammonium compound is applied is a sheet material including cellulose fiber s in admixture with other fibers of natural or synthetic fibrous material.
12. Quaternary ammonium compounds capable of imparting improved wettability, softness and low mechanical strength to a substrate comprising cellulose fibers, and having the general formula:
wherein:
R1 and R2 are alkyl phenyl groups totalling from about fourteen to about forty-six carbon atoms in from one to three alkyl groups and the phenyl group;
R3 and R4 are selected from the group consisting of methyl, ethyl and hydroxyethyl;
n1 and n2 are numbers within the range from about 4 to about 40, representing the average number of oxyethylene groups present in each substituent; and X is an anion.
wherein:
R1 and R2 are alkyl phenyl groups totalling from about fourteen to about forty-six carbon atoms in from one to three alkyl groups and the phenyl group;
R3 and R4 are selected from the group consisting of methyl, ethyl and hydroxyethyl;
n1 and n2 are numbers within the range from about 4 to about 40, representing the average number of oxyethylene groups present in each substituent; and X is an anion.
13. Quaternary ammonium compounds in accordance with claim 12, in which n1 and n2 are numbers within the range from 6 to 30.
14. Quaternary ammonium compounds in accordance with claim 12, in which R1 and R2 have from about twenty to about thirty-eight carbon atoms.
15. A stable aqueous solution comprising a quaternary ammonium compound in accordance with claim 12, in a concentration from about 1% to about 15% by weight.
16. Quaternary ammonium compounds in accordance with claim 12, in which R3 and R4 are methyl groups.
17. Quaternary ammonium compounds in accordance with claim 12, in which R1 and R2 are nonyl.
18. Quaternary ammonium compounds in accordance with claim 12, in which R1 and R2 are dodecyl.
19. A process for the preparation of alkyl phenoxy ethylene oxy (2-hydroxy) propylene quaternary ammonium compounds having the formula:
wherein:
R1 and R2 are alkyl phenyl groups, totalling from about fourteen to about forty-six carbon atoms in from one to three alkyl groups and the phenyl group;
R3 and R4 are selected from the group consisting of methyl, ethyl and hydroxyethyl;
n1 and n2 are numbers within the range from about 4 to about 40, representing the average number of oxyethylene groups present in each substituent; and X is an anion;
which comprises reacting from four to about forty mols of ethylene oxide with one mol of an alkyl phenol having from about fourteen to about forty-six carbon atoms, in the presence of an alkaline catalyst at an elevated temperature within the range from about 30° to about 150°C;
reacting the resulting alkyl phenoxy ethylene glycol ether with epichlorohydrin, producing the corresponding chloroglyceryl or chlorohydroxypropylene ether, and then reacting this ether with a secondary amine having the formula R3R4NH, where R3 and R4, are selected from the group consisting of methyl, ethyl and hydroxy-ethyl in the presence of alkali and in the presence of an organic solvent with a boiling point of at least 60°C at an elevated temperature within the range from about 30° to about 150°C, to obtain the quaternary ammonium compound of the above formula in the form of its chloride salt.
wherein:
R1 and R2 are alkyl phenyl groups, totalling from about fourteen to about forty-six carbon atoms in from one to three alkyl groups and the phenyl group;
R3 and R4 are selected from the group consisting of methyl, ethyl and hydroxyethyl;
n1 and n2 are numbers within the range from about 4 to about 40, representing the average number of oxyethylene groups present in each substituent; and X is an anion;
which comprises reacting from four to about forty mols of ethylene oxide with one mol of an alkyl phenol having from about fourteen to about forty-six carbon atoms, in the presence of an alkaline catalyst at an elevated temperature within the range from about 30° to about 150°C;
reacting the resulting alkyl phenoxy ethylene glycol ether with epichlorohydrin, producing the corresponding chloroglyceryl or chlorohydroxypropylene ether, and then reacting this ether with a secondary amine having the formula R3R4NH, where R3 and R4, are selected from the group consisting of methyl, ethyl and hydroxy-ethyl in the presence of alkali and in the presence of an organic solvent with a boiling point of at least 60°C at an elevated temperature within the range from about 30° to about 150°C, to obtain the quaternary ammonium compound of the above formula in the form of its chloride salt.
20. A process according to claim 19, which comprises exchanging the chloride anion by another anion.
21. A process according to claim 19, in which the re-action between the ethylene oxide adduct and the epichlorhydrin is carried out in the presence of a catalyst selected from the group consisting of stannic chloride, boron trifluoride, perchloric acid HClO4, toluene sulfonic acid and sulfuric acid.
22. A process according to claim 19, in which the solvent during quaternization is selected from the group consisting of methanol, ethanol, and the monoethylether of diethylene glycol.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SE7401009A SE388222C (en) | 1974-01-25 | 1974-01-25 | SETS AND MEANS TO REDUCE THE MECHANICAL BALANCE SHEETS AND / OR IMPROVE THE SOFTNESS OF CELLULOSA OR PAPER |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1042466A true CA1042466A (en) | 1978-11-14 |
Family
ID=20320016
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA218,551A Expired CA1042466A (en) | 1974-01-25 | 1975-01-24 | Quaternary surface active compounds and process of treating cellulose fibers therewith |
Country Status (10)
| Country | Link |
|---|---|
| JP (1) | JPS5310038B2 (en) |
| BR (1) | BR7500423A (en) |
| CA (1) | CA1042466A (en) |
| DE (1) | DE2502357C3 (en) |
| FI (1) | FI62053C (en) |
| FR (1) | FR2258892A1 (en) |
| IT (1) | IT1027365B (en) |
| NO (1) | NO141049C (en) |
| SE (1) | SE388222C (en) |
| ZA (1) | ZA75125B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SE443138B (en) * | 1979-12-10 | 1986-02-17 | Berol Kemi Ab | SURFACTIVE QUARTER AMMONIUM ASSOCIATION AND USE OF THIS IN THE TREATMENT OF TEXTILE AND CELLULO MATERIAL |
| CH671314B (en) * | 1982-10-04 | 1990-02-28 | Sandoz Ag | AQUEOUS WAX DISPERSIONS, THEIR PRODUCTION AND USE. |
| DE3237574A1 (en) * | 1982-10-09 | 1984-04-12 | Hoechst Ag, 6230 Frankfurt | Use of amine oxides in the pulp and paper manufacture |
| US4659802A (en) * | 1982-12-23 | 1987-04-21 | The Procter & Gamble Company | Cationic compounds having clay soil removal/anti-redeposition properties useful in detergent compositions |
| US4597898A (en) * | 1982-12-23 | 1986-07-01 | The Proctor & Gamble Company | Detergent compositions containing ethoxylated amines having clay soil removal/anti-redeposition properties |
| US4664848A (en) | 1982-12-23 | 1987-05-12 | The Procter & Gamble Company | Detergent compositions containing cationic compounds having clay soil removal/anti-redeposition properties |
| US4551506A (en) * | 1982-12-23 | 1985-11-05 | The Procter & Gamble Company | Cationic polymers having clay soil removal/anti-redeposition properties useful in detergent compositions |
| US4661288A (en) | 1982-12-23 | 1987-04-28 | The Procter & Gamble Company | Zwitterionic compounds having clay soil removal/anti/redeposition properties useful in detergent compositions |
| US4676921A (en) * | 1982-12-23 | 1987-06-30 | The Procter & Gamble Company | Detergent compositions containing ethoxylated amine polymers having clay soil removal/anti-redeposition properties |
| US4548744A (en) * | 1983-07-22 | 1985-10-22 | Connor Daniel S | Ethoxylated amine oxides having clay soil removal/anti-redeposition properties useful in detergent compositions |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3326927A (en) * | 1964-05-18 | 1967-06-20 | Dow Chemical Co | Certain pyridinium and quaternary ammonium derivatives of phenolic-polyoxy alkylene compounds and a method for their preparation |
| DE1619058A1 (en) * | 1967-12-01 | 1971-01-28 | Hoechst Ag | Preparations for treating textiles |
| US3554862A (en) * | 1968-06-25 | 1971-01-12 | Riegel Textile Corp | Method for producing a fiber pulp sheet by impregnation with a long chain cationic debonding agent |
| SE377349C (en) * | 1971-11-19 | 1983-09-12 | Berol Kemi Ab | WANT TO REDUCE THE MECHANICAL HALF STRENGTH AND / OR IMPROVE THE SOFTWARE OF CELLULOSA OR PAPER |
-
1974
- 1974-01-25 SE SE7401009A patent/SE388222C/en not_active IP Right Cessation
-
1975
- 1975-01-07 ZA ZA00750125A patent/ZA75125B/en unknown
- 1975-01-21 NO NO750178A patent/NO141049C/en unknown
- 1975-01-22 BR BR423/75A patent/BR7500423A/en unknown
- 1975-01-22 DE DE2502357A patent/DE2502357C3/en not_active Expired
- 1975-01-23 JP JP1013075A patent/JPS5310038B2/ja not_active Expired
- 1975-01-23 FI FI750175A patent/FI62053C/en not_active IP Right Cessation
- 1975-01-24 FR FR7502295A patent/FR2258892A1/en active Granted
- 1975-01-24 IT IT67165/75A patent/IT1027365B/en active
- 1975-01-24 CA CA218,551A patent/CA1042466A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| FI62053C (en) | 1982-11-10 |
| ZA75125B (en) | 1976-01-28 |
| FR2258892B1 (en) | 1978-02-24 |
| FI750175A (en) | 1975-07-26 |
| FI62053B (en) | 1982-07-30 |
| NO141049C (en) | 1980-01-02 |
| AU7748575A (en) | 1976-07-22 |
| NO141049B (en) | 1979-09-24 |
| SE388222C (en) | 1985-09-09 |
| FR2258892A1 (en) | 1975-08-22 |
| JPS5310038B2 (en) | 1978-04-11 |
| NO750178L (en) | 1975-08-18 |
| DE2502357C3 (en) | 1985-10-24 |
| IT1027365B (en) | 1978-11-20 |
| SE7401009L (en) | 1975-07-28 |
| DE2502357A1 (en) | 1975-08-07 |
| DE2502357B2 (en) | 1977-06-23 |
| JPS50126585A (en) | 1975-10-04 |
| SE388222B (en) | 1976-09-27 |
| BR7500423A (en) | 1975-11-04 |
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