CA1092738A - Aqueous dispersions of wax blends and a water-soluble cationic resin and paper sized therewith - Google Patents
Aqueous dispersions of wax blends and a water-soluble cationic resin and paper sized therewithInfo
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- CA1092738A CA1092738A CA270,987A CA270987A CA1092738A CA 1092738 A CA1092738 A CA 1092738A CA 270987 A CA270987 A CA 270987A CA 1092738 A CA1092738 A CA 1092738A
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Abstract
Disclosed are essentially stable aqueous dispersions of wax--fatty acid blends, wax-ketene dimer blends, or mixtures thereof; a water-soluble cationic resin dispersing agent; and water. The dispersions are useful in the sizing of paper.
Description
10'.3Z738 Aldrich Case 25-31 This invention relates to novel aqueous suspensions or dispersions which contain finely divided particles of a blend of wax and a fatty acid or a blend of wax and an alkyl ketene dimer.
The novel aqueous suspensions are useful in the sizing of paper.
Aqueous dispersions of wax and their use in sizing paper are known in the art. Such aqueous suspensions consist essenti-ally of water, finely divided wax particles, and a dispersing agent for the finely divided wax particles.
According to the invention there is provided an aqueous dispersion of finely divided solid particles consisting essenti-ally of, by weight, i (A) from about 5% to about 50% of finely divided solid ., : particles, said solid particles being selected from the group consisting of (1) a blend consisting essentially of, by weight, from about 99% to about 93% of a wax selected from the group con- ~ -sisting of petroleum waxes, synthetic hydrocarbon waxes, and mix-tures thereof and from about 1% to about 7% of a C18 to C24 sat-urated fatty acid, (2) a blend consisting essentially of, by weight, from about 99.5% to about 75% of a wax selected from the group consisting of petroleum waxes, synthetic hydrocarbon waxes, and mixtures thereof and from about 0.5% to about 25% of at least one alkyl ketene dimer having the formula ~RCH=C=O]2 where R is an alkyl radical having 10 to about 20 carbon atoms, and (3) mix-tures of (1) and (2), (B) from about 0.5% to about 20% of water-soluble cation-ic resin dispersing agent selected from the group consisting of (i) a water-soluble polyaminopolyamide--epichlorohydrin resin, - ?
(ii) a water-soluble alkylenepolyamine--epichlorohydrin resin, (iii) a water-soluble poly(diallylamine)--epichlorohydrin resin, and - (iv) mixtures of any two or more of (i), (ii), and (iii), and
The novel aqueous suspensions are useful in the sizing of paper.
Aqueous dispersions of wax and their use in sizing paper are known in the art. Such aqueous suspensions consist essenti-ally of water, finely divided wax particles, and a dispersing agent for the finely divided wax particles.
According to the invention there is provided an aqueous dispersion of finely divided solid particles consisting essenti-ally of, by weight, i (A) from about 5% to about 50% of finely divided solid ., : particles, said solid particles being selected from the group consisting of (1) a blend consisting essentially of, by weight, from about 99% to about 93% of a wax selected from the group con- ~ -sisting of petroleum waxes, synthetic hydrocarbon waxes, and mix-tures thereof and from about 1% to about 7% of a C18 to C24 sat-urated fatty acid, (2) a blend consisting essentially of, by weight, from about 99.5% to about 75% of a wax selected from the group consisting of petroleum waxes, synthetic hydrocarbon waxes, and mixtures thereof and from about 0.5% to about 25% of at least one alkyl ketene dimer having the formula ~RCH=C=O]2 where R is an alkyl radical having 10 to about 20 carbon atoms, and (3) mix-tures of (1) and (2), (B) from about 0.5% to about 20% of water-soluble cation-ic resin dispersing agent selected from the group consisting of (i) a water-soluble polyaminopolyamide--epichlorohydrin resin, - ?
(ii) a water-soluble alkylenepolyamine--epichlorohydrin resin, (iii) a water-soluble poly(diallylamine)--epichlorohydrin resin, and - (iv) mixtures of any two or more of (i), (ii), and (iii), and
- 2 -... . , .;, . , . ' - ! , 10~3~73~
(C) water to 100%.
A preferred blend (1) is a blend consisting essentially of, by weight, from about 99% to about 95% of a wax selected from the group consisting of petroleum waxes, synthetic hydrocarbon waxes, and mixtures thereof and from about 1% to about 5% of a C18 to C24 saturated fatty acid. A preferred blend (2) is a blend consisting essentially of, by weight, from about 99% to about 90%
of a wax selected from the group consisting of petroleum waxes, synthetic hydrocarbon waxes, and mixtures thereof, and from about 1% to about 10% of at least one alkyl ketene dimer.
A suitable polyethylene wax for use in the dispersion ac-cording to the invention will have a molecular weight of from about 1500 to about 10,000 and a density of from about 0.91 to about 0.94.
i The C18-C24 saturated fatty acid component of the disper-; sion according to the invention may be, for example, stearic acid, nonadecanoic acid, arachidic acid, heneicosanoic acid, behenic acid, tricosanoic acid, and tetracosanoic acid. The fatty acid ~ component can consist of mixtures of two or more of the saturated ,; 20 acids. Up to about 50% of the C18-C24 saturated acid can be sub-`d~ stituted with saturated C14-C16 fatty acids such as myristic acid, pentadecanoic acid and palmitic acid.
The alkyl ketene dimers which are used as components of the blend are dimers having the formula [RCH=C=O]2 where R is an alkyl radical (saturated or unsaturated) having 10 to about 20 ~j carbon atoms. In naming ketene dimers, the radical "R" is named j followed by "ketene dimer". The decyl ketene dimer is [CloH21~CH=C=O]2. Examples of ketene dimers include decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, docosyl, and tetracosyl, as well as the ketene dimers prepared from palmit--~ oleic acid, oleic acid, ricinoleic acid, linoleic acid, linolenic acid, myristoleic acid, and eleostearic acid. Mixtures of any of the above-named fatty acids with each other may also be used. A
fatty acid fractiGn obtained from the fractional distillation of .
10~738 call oil, whlch is predominantly oleic acid and linoleic acid, is -~ an example of a fatty acid mixture.
The dispersing agents used to prepare the substantially stable aqueous dispersions or suspensions of this invention are cationic polymeric resinous materials that are water-soluble.
Particularly suitable dispersing agents are the cationic thermosettable water-soluble aminopolyamide--epichlorohydrin res-ins disclosed and described in U.S. patents 2,926,116 and 2,926,154. These resins are water-soluble polymeric reaction ..,~
products of epichlorohydrin and an aminopolyamide. The amino-polyamide is derived by reaction of a dicarboxylic acid and a polyalkylenepolyamine in a mole ratio of polyalkylenepolyamine to dicarboxylic acid of from about 0.8:1 to about 1.4:1.
Particularly suitable dicarboxylic acids are diglycolic ~1 acid and saturated aliphatic dicarboxylic acids, containing from
(C) water to 100%.
A preferred blend (1) is a blend consisting essentially of, by weight, from about 99% to about 95% of a wax selected from the group consisting of petroleum waxes, synthetic hydrocarbon waxes, and mixtures thereof and from about 1% to about 5% of a C18 to C24 saturated fatty acid. A preferred blend (2) is a blend consisting essentially of, by weight, from about 99% to about 90%
of a wax selected from the group consisting of petroleum waxes, synthetic hydrocarbon waxes, and mixtures thereof, and from about 1% to about 10% of at least one alkyl ketene dimer.
A suitable polyethylene wax for use in the dispersion ac-cording to the invention will have a molecular weight of from about 1500 to about 10,000 and a density of from about 0.91 to about 0.94.
i The C18-C24 saturated fatty acid component of the disper-; sion according to the invention may be, for example, stearic acid, nonadecanoic acid, arachidic acid, heneicosanoic acid, behenic acid, tricosanoic acid, and tetracosanoic acid. The fatty acid ~ component can consist of mixtures of two or more of the saturated ,; 20 acids. Up to about 50% of the C18-C24 saturated acid can be sub-`d~ stituted with saturated C14-C16 fatty acids such as myristic acid, pentadecanoic acid and palmitic acid.
The alkyl ketene dimers which are used as components of the blend are dimers having the formula [RCH=C=O]2 where R is an alkyl radical (saturated or unsaturated) having 10 to about 20 ~j carbon atoms. In naming ketene dimers, the radical "R" is named j followed by "ketene dimer". The decyl ketene dimer is [CloH21~CH=C=O]2. Examples of ketene dimers include decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, docosyl, and tetracosyl, as well as the ketene dimers prepared from palmit--~ oleic acid, oleic acid, ricinoleic acid, linoleic acid, linolenic acid, myristoleic acid, and eleostearic acid. Mixtures of any of the above-named fatty acids with each other may also be used. A
fatty acid fractiGn obtained from the fractional distillation of .
10~738 call oil, whlch is predominantly oleic acid and linoleic acid, is -~ an example of a fatty acid mixture.
The dispersing agents used to prepare the substantially stable aqueous dispersions or suspensions of this invention are cationic polymeric resinous materials that are water-soluble.
Particularly suitable dispersing agents are the cationic thermosettable water-soluble aminopolyamide--epichlorohydrin res-ins disclosed and described in U.S. patents 2,926,116 and 2,926,154. These resins are water-soluble polymeric reaction ..,~
products of epichlorohydrin and an aminopolyamide. The amino-polyamide is derived by reaction of a dicarboxylic acid and a polyalkylenepolyamine in a mole ratio of polyalkylenepolyamine to dicarboxylic acid of from about 0.8:1 to about 1.4:1.
Particularly suitable dicarboxylic acids are diglycolic ~1 acid and saturated aliphatic dicarboxylic acids, containing from
3 through 10 carbon atoms such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid.
Other suitable dicarboxylic acids include terephthalic acid, isophthalic acid, phthalic acid, maleic acid, fumaric acid, itaconic acid, glutaconic acid, citraconic acid, and mesaconic acid. ~-The available anhydrides of the above acids can be used ~ s in preparing the water-soluble aminopolyamide as well as the esters of the acids. Mixtures of two or more dicarboxylic acids, their anhydrides, and their esters can be used to prepare the water-soluble aminopolyamides, if desired.
A number of polyalkylene polyamines, including poly-ethylene polyamines, polypropylene polyamines, polybutylene poly- ~ ~-amines and the like can be employed. Polyalkylene polyamines are polyamines in which the nitrogen atoms are linked together by groups of the formula ~CnH2n- where n is a small integer greater than unity and the number of such groups in the molecule ranges from two up to about eight. The nitrogen atoms can be attached ., ~ - 4 -~ .
lOg,4~738 co adjacent carbon atoms in the group -Cn~2 - or to carbon atom~
farther apart, but not to the same carbon atom. Polyamines such as diethyle~etriamine, triethylenetetramine, tetraethylene-pentamine, arld dipropylenetriamine, which can be obtained in reasonably pure form are suitable for preparing water-soluble aminopolyamides. Other polyalkylene polyamines that can be used include methyl bis-(3-aminopropyl)amine; methyl bis-(2-aminoethyl)-amine; and 4,7-dimethyltriethylenetetramine. Mixtures of poly-alkylene polyamines can be used, if desired.
The spacing of an amino group on the aminopolyamide can be increased if desired. This can be accomplished by substitut-ing a diamine such as ethylenediamine, propylenediamine, hexa-methylenediamine and the like for a portion of the polyalkylene polyamine. For this purpose, up to about 80% of the polyalkylene polyamine can be replaced by a molecularly equivalent amount of :;~
diamine. Usually, a replacement of about 50% or less will be adequate.
Temperatures employed for carrying out reaction between the dicarboxylic acid and the polyalkylene polyamine can vary from about 110C. to about 250C. or higher at atmospheric pres-sure. For most purposes temperatures between about 160C. and 210C. are preferred. The time of reaction will usually vary from about 1/2 hour to 2 hours. Reaction time varies inversely with reaction temperatures employed.
In carrying out the reaction, it is preferred to use an amount of dicarboxylic acid sufficient to react substantially completely with the primary amine groups of the polyalkylene poly-amine but insufficient to react with the secondary amine groups and/or tertiary amine groups to any substantial extent. This will usually require a mole ratio of polyalkylene polyamine to dicar-boxylic acid of from about 0.9:1 to about 1.2:1. However, mole ratios of from about 0.8:1 to about 1.4:1 can be used. The aminopolyamide, derived as above described, is reacted with epi-chlorohydrin at a temperature of from about 45C. to about 100C., .
`
- 10.'~:73~
and preferably between about 45C. and 70C., until the viscosity of a 20% solids solution in water at 25C. has reached about C or higher on the Gardner-Holdt scale. This reaction is preferably carried out in aqueous solution to moderate the reaction. pH ad-justment is usually not necessary. However, since the pH de-creases during the polymerization phase of the reaction, it may be desirable, in some cases, to add alkali to combine with at least some of the acid formed. When the desired viscosity is reached, water can be added to adjust the solids content of the resin solution to a desired amount, usually from about 2~ to about 50%.
In the aminopolyamide--epichlorohydrin reaction, satis-factory results can be obtained utilizing from about 0.1 mole to about 2 moles of epichlorohydrin for each secondary or tertiary amine group of the aminopolyamide, and preferably from about 1 mole to about 1.5 moles of epichlorohydrin.
A monofunctional alkylating agent can be employed as an additional reactant in carrying out the above reaction, if desired.
A monofunctional alkylating agent can be first reacted with the aminopolyamide followed by reaction of the aminopolyamide--alkylating agent reaction product with epichlorohydrin, or the alkylating agent can be reacted with the aminopolyamide--epi-chlorohydrin reaction product. Thus, for example, epichlorohydrin can be added to an aqueous solution of the aminopolyamide at a temperature from about 45C. to 55C. The reaction mixture is then heated at a temperature from about 50C. to 100C., and preferably from about 60C. to 80C., depending upon the rate of reaction desired. After a suitable time at this temperature, i.e., from about 10-100 minutes, and preferably until the viscos-ity of an approximately 25% solids solution of the reaction mix-ture at 25C. is from A to B on the Gardner-Holdt scale, at which time most of the epoxy groups of the epichlorohydrin have reacted with the amine groups of the aminopolyamide, a monofunctional alkylating agent is added and the reaction mixture heated, 1C~'3Z73~
preferably at a t~mperature from about 60C. to about 80C., until the viscosity of an approximately 25% solids solution at 25C. is at least A and preferably at least B to C on the Gardner-Holdt scale. The solids-viscosity relationship can be obtained by direct reaction at the 25~ level followed by dilution to 25%
solids, or reaction at a lower level followed by concentration at less than 40C. and under reduced pressure to 25% solids. Lower alkyl esters of mineral acids such as the halides, sulfates and phosphates, substituted alkyl halides, and the like are suitable monofunctional alkylating agents. Illustrative of the compounds ` which can be used are dimethyl, diethyl and dipropyl sulfate;
` methyl chloride; methyl iodide; ethyl iodide; methyl bromide;
~ propyl bromide; and the mono-, di- or tri-methyl, ethyl and propyl `~'t phosphates. Certain aromatic compounds such as benzyl chloride and methyl p-toluene sulfonate can be used. From about 0.1 mole to about 0.9 mole of monofunctional alkylating agent for each , . .
amine group can be used.
In the examples that follow, all parts and percentages are by weight unless otherwise specified. Sizing results are set forth in some of the examples. Sizing results are determined on the Hercules Sizing Tester. The sizing test determines the re-sistance of a sized sheet of paper to penetration by No. 2 Test Solution, (an aqueous solution of, by weight, 1.0% formic acid and .~
~; 1.25% naphthol Green B). The time necessary for ink penetration to reduce light reflectance to 80% of the sheet's initial value is used to represent the degree of sizing.
The following example is illustrative of the preparation of an aminopolyamide-~epichlorohydrin resin that is particularly useful as a cationic resin dispersing agent for use in this invention.
Example 1 An aminopolyamide is formed by adding 219.3 parts of adipic acid slowly, with stirring, to 151.3 parts of diethylene-triamine in a flask fitted with a stirrer and a condenser for ,~ - . . . . .
1()9Z738 collecting water distillate. The reaction mixture is stirred and heated at 170-180C. under a nitrogen blanket until amide forma-tion is complete. After air cooling to approximately 140C., hot water is added with stirring to provide a 50% solids solution of polyamide resin with an intrinsic viscosity of 0.140 measured by using a 2% solution in 1 N NH4Cl. An epichlorohydrin derivative of the aminopolyamide is prepared by adding about 110.25 parts of water to about 50 parts of the 50% solids solution and then adding 14.4 parts (0.157 mole) of epichlorohydrin. The reaction mixture is heated at 70C. with stirring under a reflux condenser until the Gardner-Holdt viscosity attains a value of E to F. The reac-;/` tion mixture is diluted with water to a solids content of about 12.5~.
Other suitable dispersing agents that can be used in thisinvention are the water-soluble alkylene polyamine--epichlorohydrin resins which are water-soluble polymeric reaction products of epi-chlorohydrin and an alkylene polyamine.
Alkylene polyamines which can be reacted with epichloro-hydrin have the formula H2N(CnH2nNH)XH wherein n is an integer 2 ;
through 8 and x is an integer 1 or more, preferably 1 through 6.
~' Examples of such alkylene polyamines are the alkylene diamines - -. ~ - . .
such as ethylenediamine; propylene diamine-1,2; propylene diamine- -1,3; tetramethylenediamine; and hexamethylenediamine. The poly-, alkylene polyamines such as the polyethylene polyamines, polypro-pylene polyamines, polybutylene polyamines and the like are ex-amples of alkylene polyamines that can be used. Specific examples of these polyalkylene polyamines include diethylenetriamine, tri-ethylenetetramine, tetraethylenepentamine, and dipropylenetriamine.
Other polyalkylene polyamines that can be used include methyl bis-(3-aminopropyl)amine; methyl bis(2-aminoethyl)amine; and 4,7-dimethyltriethylenetetramine. Mixtures of alkylene polyamines j can be used if desired.
The relative proportions of alkylene polyamine and epi-~ chlorohydrin employed can be varied depending upon the particular .
.;~.. . .
~.... . . .
10'~73~
alkylene polyamin~ used. In general, it is preferred that the molar ratlo of epiclhlorohydrin to alkylene polyamine be in excess of 1:1 and less thdn 2:1. In the preparation of a water-soluble resin from epichk~rohydrirl and tetraethylenepentamine, good re-sults are obtained at molar ratios of from about 1.4:1 to 1.94:1.
Reaction temperature is preferably in the range of from about 40C. to about 60C.
The followln~ example illustrates the preparation of a ; dispersing agent of the above type.
Example A
To a mixture of 29.2 parts triethylenetetramine and 70 parts water is added 44.4 parts epichlorohydrin over a period of i3 about 12 minutes with periodic cooling. After the epichlorohydrin addition is complete, the reaction mixture is heated to 75C. and maintained at a temperature of from about 70C. to about 77C.
for about 33 minutes, at which point the Gardner-Holdt viscosity reached about I. The resulting reaction mass is diluted with t 592 parts water to provide an aqueous solution that has a solids content of about 11.7% and a pH of about 6.3.
Another suitable dispersing agent for use in this inven-tion is a poly(diallylamine)--epihalohydrin resin. Resins of this type can be prepared in accordance with the teachings of U.S.
patent 3,700,623, reference to which is hereby made.
A poly(diallylamine)--epihalohydrin resin is the resin-ous reaction product of (A) a linear polymer having units of the formula (I) R\CH~ R
-s . H2C / CH2 s \N
R' where R is hydrogen or lower alkyl and R' is hydrogen, alkyl or a substituted alkyl group and (B) an epihalohydrin.
s 30 In the above formula, each R can be the same or different and, as stated, can be hydrogen or lower alkyl. The alkyl groups g _ ,., . :
~10'~'~73~
contain frorn 1 to 6 carbons an~ are preferably methyl, ethyl, isopropyl or n-butyl. R' of the formula represents hydrogen, alkyl or substituted alkyl groups. The R' alkyl groups will con-tain from 1 to 18 carbon ato~s (preferably from 1 to 6 carbon i atoms) such as methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, hexyl, octyl, decyl, dodecyl, tetradecyl and octadecyl.
R' can also be a substituted alkyl group. Suitable substituents include, in general, any group which will not interfere with polymerization through a vinyl double bond. Typically, the sub-stituents can be carboxylate, cyano, ether, amino (primary, sec-ondary or tertiary), amide, hydrazide and hydroxyl.
Polymers having units of the above formula can be pro-duced by polymerizing the hydrohalide salt of a diallylamine ~ ~ ( II ) jIH2 CH2 R-C -R
I H2 1H2 ~ -N /
R' where R and R' are as indicated above, either alone or as a mix-ture with other copolymerizable ingredients, in the presence of ~ .
a free radical catalyst and then neutralizing the salt to give , , the polymer free base.
Specific hydrohalide salts of the diallylamines which can be polymerized to provide the polymer units of the invention .~
include diallylamine hydrcchloride; N-methyldiallylamine hydro-chloride; N-methyldiallylamine hydrobromide; 2,2'-dimethyl-N-methyldiallylamine hydrochloride; N-ethyldiallylamine hydrobromide;
N-isopropyldiallylamine hydrochloride; N-n-butyldiallylamine hydro-bromide; N-tert-butyldiallylamine hydrochloride; N-n-hexyldiallyl-amine hydrochloride; N-octadecyldiallylamine hydrochloride; N-acetamidodiallylamine hydrochloride; N-cyanomethyldiallylamine :
hydrochloride; N-~-propiGnamidodiallylamine hydrobromide; N-carboethoxymethyldiallylamine hydrochloride; N-~-methoxyethyl-diallylamine hydrobromide; N-~-aminoethyldiallylamine :`
:.................................... .. . . .
-: -. .- -. - ., . , . :. . , ::
IO~Z73~
nydrochloride; N-hydroxyethyldiallylamine hydrobromide; and N-acetohydrazide substituted diallylamine hydrochloride.
Diallylamines and N-alkyldiallylamines, used to prepare the polymers employed in this invention, can be prepared by the ; reaction of ammonia or a primary amine with an allyl halide em-ploying as a catalyst for the reaction a catalyst that promotes the ionization of the halide such~ for example, as sodium iodide, zinc iodide, ammonium iodide, cupric bromide, ferric chloride, ferric bromide, zinc chloride, mercuric iodide, mercuric nitrate, mercuric bromide, mercuric chloride, and mixtures of two or more.
Thus, for example, N-methyldiallylamine can be prepared by reac-tion of two moles of an allyl halide, such as allyl chloride, with one mole of methylamine in the presence of an ionization catalyst such as one of those enumerated above.
In preparing the homopolymers and copolymers, reaction can be initiated by redox catalytic system. In a redox system, the catalyst is activated by means of a reducing agent which pro-duces free radicals without the use of heat. Reducing agents commonly used are sodium metabisulfite and potassium metabisul-fite. Other reducing agents include water-soluble thiosulfates and bisulfites, hydrosulfites and reducing salts such as the sul-fate of a metal which is capable of existing in more than one valence state such as cobalt, iron, manganese and copper. A
specific example of such a sulfate is ferrous sulfate. The use of a redox initiator system has several advantages, the most im-portant of which is efficient polymerization at lower temperature.
Conventional peroxide catalysts such as tertiary-butyl hydroper-oxide, potassium persulfate, hydrogen peroxide and ammonium per-sulfate used in conjunction with the above reducing agents or metal activators, can be employed.
As stated above, the linear polymers of diallylamines ~ which are reacted with an epihalohydrin can contain different i units of formula (I) and/or contain units of one or more other co-~ polymerizable monomers. Typically, the comonomer is a different -r 109Z'~3t~
diallylamine, a monoethylenically unsaturated compound containing a single vinyl or vinylidene group or sulfur dioxide, and is pres-ent in an amount ranging from 0 to 95 mole % of the polymer. Thus the polymers of diallylamine are linear polymers wherein from 5~
to 100~ of the recurring units have the formula (I) and from 0 to 95% of the recurring units are monomer units derived from (1) a vinylidene monomer and/or (2) sulfur dioxide. Preferred comono-p mers include acrylic acid, methacrylic acid, methyl and other alkyl acrylates and methacrylates, acrylamide, methacrylamide, 10 acrylonitrile, methacrylonitrile, vinyl acetate, vinyl ethers such i as the alkyl vinyl ethers, vinyl ketones such as methyl vinyl ke-; tone and ethyl vinyl ketone, vinyl sulfonamide, sulfur dioxide or ;
a different diallylamine embraced by the above formula ~II).
! Specific copolymers which can be reacted with an epihalo-hydrin include copolymers of N-methyldiallylamine and sulfur di-oxide; copolymers of N-methyldiallylamine and diallylamine; co-polymers of diallylamine and acrylamide; copolymers of diallylamine and acrylic acid; copolymers of N-methyldiallylamine and methyl acrylate, copolymers of diallylamine and acrylonitrile; copolymers 20 of N-methyldiallylamine and vinyl acetate; copolymers of diallyl-amine and methyl vinyl ether; copolymers of N-methyldiallylamine and vinylsulfonamide; copolymers of N-methyldiallylamine and methyl vinyl ketone; terpolymers of diallylamine, sulfur dioxide and acrylamide; and terpolymers of N-methyldiallylamine, acrylic acid and acrylamide.
The epihalohydrin which is reacted with the polymer of a diallylamine can be any epihalohydrin, i.e., epichlorohydrin, epi-bromohydrin, epifluorohydrin or epiiodohydrin and is preferably ~ epichlorohydrin. In general, the epihalohydrin is used in an amount .
30 ranging from about 0.5 mole to about 1.5 moles and preferably about 1 mole to about 1.5 moles per mole of secondary plus tertiary amine ;~ present in the polymer.
The poly(diallylamine)--epihalohydrin resin can be prepared by reacting a homopolymer or copolymer of a diallylamine as set , .
'': , ~ : :: , - lO~Z73~
forth above with an epihalohydrin at a temperature of from about ! 30C. to about 80C. and preferably from about 40C. to about 60C.,~
until the viscosity measured on a solution containing 20% to 30~
solids at 25C. has reached a range of A to E and preferably about , C to D on the Gardner-Holdt scale. The reaction is preferably carried out in aqueous solution to moderate the reaction, and at a pH of from about 7 to about 9.5.
When the desired viscosity is reached, sufficient water is added to adjust the solids content of the resin solution to about ,.~
10 15% or less and the product cooled to room temperature (about 25C.) The poly(diallylamine)--epihalohydrin resin can be stabi-.
lized against gelation by adding to the aqueous solution thereof sufficient water-soluble acid (such as hydrochloric acid and sul-furic acid) to obtain and maintain the pH at about 2.
The following example illustrates the preparation of a poly-~ .
(diallylamine)--epichlorohydrin resin.
Example B .
A solution of 69.1 parts of methyldiallylamine and 197 parts of 20 Be hydrochloric acid in 111.7 parts of demineralized w~ter .
20 i9 sparged with nitrogen to remove air, then treated with 0.55 part of tertiary butyl hydroperoxide and a solution of 0.0036 part of ferrous sulfate in 0.5 part of water. The resulting solution is allowed to polymerize at 60-69C. for 24 hours to give a polymer solution containing about 52,1% solids with an RSV of 0.22. 122 ;~ parts of the above solution is adjusted to pH 8.5 by the addition of 95 parts of 3.8% sodium hydroxide and then diluted with 211 ~i, parts of water and combined with 60 parts of epichlorohydrin. The ; ~
- , mixture is heated at 45-55C. for 1.35 hours until the Gardner-;~ Holdt viscosity of a sample cooled to 25C. reaches B+. The rer ~`~ 30 sulting solution is acidified with 25 parts of 20 Be hydrochloric acid and heated at 60C. until the pH becomes constant at 2Ø The ~` resulting resin solution has a solids content of 20.8% and a Brook-field viscosity = 77 cp. ~measured using a Brookfield Model LVF
Viscometer, No. 1 spindle at 60 r,p.m, with guard).
10~738 Examples 2, 3 and 4 below are illustrative of suspensions of unblended wax particles.
Example 2 , Three hundred twenty parts of a 12.5% solids solution of an aminopolyamide--epichlorohydrin resin prepared in accordance with Example 1 and 440 parts water are mixed and heated quickly to 90C.
and added to the supply tank of a Manton-Gaulin laboratory (15 gal.
per hour) homogenizer. Two hundred forty parts of fused refined paraffin wax ~m.p. 140-145F.) is added to the hot solution in the - ~
' 10 supply tank with mixing by means of a propeller type stirrer. Be- ~ -fore addition of the aqueous resin solution to the supply tank, the homogenizer is preheated by circulating water at about 85C. through the body of the homogenizer and back to the supply tank where the water is heated by flowing steam through a stainless steel coil brazed onto the outside of the tank. The mixture is homogenized ~! with two passes through the homogenizer at 3000 psi. The homoge-nized product is collected in a glass bottle and cooled to room temperature by placing the bottle in a cold water bath with stir-ring of the product during cooling. The product is a blue-white 20 aqueous dispersion with 28% total solids (24% wax and 4% amino-polyamide--epichlorohydrin resin). After standing 24 hours, a small amount of undispersed wax present in the dispersion is sepa-rated by filtration through a 100 mesh screen. This is collected, dried and weighed to measure the percentage of the added wax which separates under these conditions. Longer term stability is meas-ured by allowing about 235 parts of the filtered dispersion to stand about four weeks when it is filtered a second time through a 100 mesh screen. The separated wax is dried and weighed. Wax separation results are set forth in Table I below.
Example 3 Example 2 is repeated. Wax separation results are set forth in Table I below.
i Example 4 ) ~ Example 2 is repeated. Wax separation results are set forth .
.... . .
~: ' n Table I below.
Table I
Parts Wax From 235 Parts of wax Separated Filtered Dispersion After 4 . Example (24 Hours) Weeks Standing '` 2 3.9 .13 ~ 3 2.8 .05 f, 4 1.0 .01 Examples 5-7 below are illustrative of the suspensions of 10 this invention.
s Examples 5-7 Examples 2, 3 and 4 are repeated using the same starting materials with the exception that, instead of the 240 parts of fused wax, there is added to the hot solution in the supply tank, in the fused state, a blend of 9.6 parts hydrogenated tallow fatty -~; acids and 230.4 parts refined paraffin wax prepared by melting the two components together. Solids (blend of the wax and fatty acid) separation results are set forth in Table II below.
Table II
Parts Solids From 235 Parts of Solids Separated Filtered Dispersion After 4 Example ~24 Hours) _ Weeks Standing 0.2 None 6 0.1 None 7 0.1 None Example 8 shows sizing properties of the dispersions of Ex-amples 2-7-Example 8 The dispersions of Examples 2-7 are applied to 40 lb./3000 `~ 30 ft.2 bleached kraft waterleaf paper in a size press in an amount sufficient to provide 0.38% ~dispersion solids) based on the :~
weight of the paper and the thus treated paper drum dried. Sizing - test results are as follows;
` Hercules Sizing Test, Example Seconds
Other suitable dicarboxylic acids include terephthalic acid, isophthalic acid, phthalic acid, maleic acid, fumaric acid, itaconic acid, glutaconic acid, citraconic acid, and mesaconic acid. ~-The available anhydrides of the above acids can be used ~ s in preparing the water-soluble aminopolyamide as well as the esters of the acids. Mixtures of two or more dicarboxylic acids, their anhydrides, and their esters can be used to prepare the water-soluble aminopolyamides, if desired.
A number of polyalkylene polyamines, including poly-ethylene polyamines, polypropylene polyamines, polybutylene poly- ~ ~-amines and the like can be employed. Polyalkylene polyamines are polyamines in which the nitrogen atoms are linked together by groups of the formula ~CnH2n- where n is a small integer greater than unity and the number of such groups in the molecule ranges from two up to about eight. The nitrogen atoms can be attached ., ~ - 4 -~ .
lOg,4~738 co adjacent carbon atoms in the group -Cn~2 - or to carbon atom~
farther apart, but not to the same carbon atom. Polyamines such as diethyle~etriamine, triethylenetetramine, tetraethylene-pentamine, arld dipropylenetriamine, which can be obtained in reasonably pure form are suitable for preparing water-soluble aminopolyamides. Other polyalkylene polyamines that can be used include methyl bis-(3-aminopropyl)amine; methyl bis-(2-aminoethyl)-amine; and 4,7-dimethyltriethylenetetramine. Mixtures of poly-alkylene polyamines can be used, if desired.
The spacing of an amino group on the aminopolyamide can be increased if desired. This can be accomplished by substitut-ing a diamine such as ethylenediamine, propylenediamine, hexa-methylenediamine and the like for a portion of the polyalkylene polyamine. For this purpose, up to about 80% of the polyalkylene polyamine can be replaced by a molecularly equivalent amount of :;~
diamine. Usually, a replacement of about 50% or less will be adequate.
Temperatures employed for carrying out reaction between the dicarboxylic acid and the polyalkylene polyamine can vary from about 110C. to about 250C. or higher at atmospheric pres-sure. For most purposes temperatures between about 160C. and 210C. are preferred. The time of reaction will usually vary from about 1/2 hour to 2 hours. Reaction time varies inversely with reaction temperatures employed.
In carrying out the reaction, it is preferred to use an amount of dicarboxylic acid sufficient to react substantially completely with the primary amine groups of the polyalkylene poly-amine but insufficient to react with the secondary amine groups and/or tertiary amine groups to any substantial extent. This will usually require a mole ratio of polyalkylene polyamine to dicar-boxylic acid of from about 0.9:1 to about 1.2:1. However, mole ratios of from about 0.8:1 to about 1.4:1 can be used. The aminopolyamide, derived as above described, is reacted with epi-chlorohydrin at a temperature of from about 45C. to about 100C., .
`
- 10.'~:73~
and preferably between about 45C. and 70C., until the viscosity of a 20% solids solution in water at 25C. has reached about C or higher on the Gardner-Holdt scale. This reaction is preferably carried out in aqueous solution to moderate the reaction. pH ad-justment is usually not necessary. However, since the pH de-creases during the polymerization phase of the reaction, it may be desirable, in some cases, to add alkali to combine with at least some of the acid formed. When the desired viscosity is reached, water can be added to adjust the solids content of the resin solution to a desired amount, usually from about 2~ to about 50%.
In the aminopolyamide--epichlorohydrin reaction, satis-factory results can be obtained utilizing from about 0.1 mole to about 2 moles of epichlorohydrin for each secondary or tertiary amine group of the aminopolyamide, and preferably from about 1 mole to about 1.5 moles of epichlorohydrin.
A monofunctional alkylating agent can be employed as an additional reactant in carrying out the above reaction, if desired.
A monofunctional alkylating agent can be first reacted with the aminopolyamide followed by reaction of the aminopolyamide--alkylating agent reaction product with epichlorohydrin, or the alkylating agent can be reacted with the aminopolyamide--epi-chlorohydrin reaction product. Thus, for example, epichlorohydrin can be added to an aqueous solution of the aminopolyamide at a temperature from about 45C. to 55C. The reaction mixture is then heated at a temperature from about 50C. to 100C., and preferably from about 60C. to 80C., depending upon the rate of reaction desired. After a suitable time at this temperature, i.e., from about 10-100 minutes, and preferably until the viscos-ity of an approximately 25% solids solution of the reaction mix-ture at 25C. is from A to B on the Gardner-Holdt scale, at which time most of the epoxy groups of the epichlorohydrin have reacted with the amine groups of the aminopolyamide, a monofunctional alkylating agent is added and the reaction mixture heated, 1C~'3Z73~
preferably at a t~mperature from about 60C. to about 80C., until the viscosity of an approximately 25% solids solution at 25C. is at least A and preferably at least B to C on the Gardner-Holdt scale. The solids-viscosity relationship can be obtained by direct reaction at the 25~ level followed by dilution to 25%
solids, or reaction at a lower level followed by concentration at less than 40C. and under reduced pressure to 25% solids. Lower alkyl esters of mineral acids such as the halides, sulfates and phosphates, substituted alkyl halides, and the like are suitable monofunctional alkylating agents. Illustrative of the compounds ` which can be used are dimethyl, diethyl and dipropyl sulfate;
` methyl chloride; methyl iodide; ethyl iodide; methyl bromide;
~ propyl bromide; and the mono-, di- or tri-methyl, ethyl and propyl `~'t phosphates. Certain aromatic compounds such as benzyl chloride and methyl p-toluene sulfonate can be used. From about 0.1 mole to about 0.9 mole of monofunctional alkylating agent for each , . .
amine group can be used.
In the examples that follow, all parts and percentages are by weight unless otherwise specified. Sizing results are set forth in some of the examples. Sizing results are determined on the Hercules Sizing Tester. The sizing test determines the re-sistance of a sized sheet of paper to penetration by No. 2 Test Solution, (an aqueous solution of, by weight, 1.0% formic acid and .~
~; 1.25% naphthol Green B). The time necessary for ink penetration to reduce light reflectance to 80% of the sheet's initial value is used to represent the degree of sizing.
The following example is illustrative of the preparation of an aminopolyamide-~epichlorohydrin resin that is particularly useful as a cationic resin dispersing agent for use in this invention.
Example 1 An aminopolyamide is formed by adding 219.3 parts of adipic acid slowly, with stirring, to 151.3 parts of diethylene-triamine in a flask fitted with a stirrer and a condenser for ,~ - . . . . .
1()9Z738 collecting water distillate. The reaction mixture is stirred and heated at 170-180C. under a nitrogen blanket until amide forma-tion is complete. After air cooling to approximately 140C., hot water is added with stirring to provide a 50% solids solution of polyamide resin with an intrinsic viscosity of 0.140 measured by using a 2% solution in 1 N NH4Cl. An epichlorohydrin derivative of the aminopolyamide is prepared by adding about 110.25 parts of water to about 50 parts of the 50% solids solution and then adding 14.4 parts (0.157 mole) of epichlorohydrin. The reaction mixture is heated at 70C. with stirring under a reflux condenser until the Gardner-Holdt viscosity attains a value of E to F. The reac-;/` tion mixture is diluted with water to a solids content of about 12.5~.
Other suitable dispersing agents that can be used in thisinvention are the water-soluble alkylene polyamine--epichlorohydrin resins which are water-soluble polymeric reaction products of epi-chlorohydrin and an alkylene polyamine.
Alkylene polyamines which can be reacted with epichloro-hydrin have the formula H2N(CnH2nNH)XH wherein n is an integer 2 ;
through 8 and x is an integer 1 or more, preferably 1 through 6.
~' Examples of such alkylene polyamines are the alkylene diamines - -. ~ - . .
such as ethylenediamine; propylene diamine-1,2; propylene diamine- -1,3; tetramethylenediamine; and hexamethylenediamine. The poly-, alkylene polyamines such as the polyethylene polyamines, polypro-pylene polyamines, polybutylene polyamines and the like are ex-amples of alkylene polyamines that can be used. Specific examples of these polyalkylene polyamines include diethylenetriamine, tri-ethylenetetramine, tetraethylenepentamine, and dipropylenetriamine.
Other polyalkylene polyamines that can be used include methyl bis-(3-aminopropyl)amine; methyl bis(2-aminoethyl)amine; and 4,7-dimethyltriethylenetetramine. Mixtures of alkylene polyamines j can be used if desired.
The relative proportions of alkylene polyamine and epi-~ chlorohydrin employed can be varied depending upon the particular .
.;~.. . .
~.... . . .
10'~73~
alkylene polyamin~ used. In general, it is preferred that the molar ratlo of epiclhlorohydrin to alkylene polyamine be in excess of 1:1 and less thdn 2:1. In the preparation of a water-soluble resin from epichk~rohydrirl and tetraethylenepentamine, good re-sults are obtained at molar ratios of from about 1.4:1 to 1.94:1.
Reaction temperature is preferably in the range of from about 40C. to about 60C.
The followln~ example illustrates the preparation of a ; dispersing agent of the above type.
Example A
To a mixture of 29.2 parts triethylenetetramine and 70 parts water is added 44.4 parts epichlorohydrin over a period of i3 about 12 minutes with periodic cooling. After the epichlorohydrin addition is complete, the reaction mixture is heated to 75C. and maintained at a temperature of from about 70C. to about 77C.
for about 33 minutes, at which point the Gardner-Holdt viscosity reached about I. The resulting reaction mass is diluted with t 592 parts water to provide an aqueous solution that has a solids content of about 11.7% and a pH of about 6.3.
Another suitable dispersing agent for use in this inven-tion is a poly(diallylamine)--epihalohydrin resin. Resins of this type can be prepared in accordance with the teachings of U.S.
patent 3,700,623, reference to which is hereby made.
A poly(diallylamine)--epihalohydrin resin is the resin-ous reaction product of (A) a linear polymer having units of the formula (I) R\CH~ R
-s . H2C / CH2 s \N
R' where R is hydrogen or lower alkyl and R' is hydrogen, alkyl or a substituted alkyl group and (B) an epihalohydrin.
s 30 In the above formula, each R can be the same or different and, as stated, can be hydrogen or lower alkyl. The alkyl groups g _ ,., . :
~10'~'~73~
contain frorn 1 to 6 carbons an~ are preferably methyl, ethyl, isopropyl or n-butyl. R' of the formula represents hydrogen, alkyl or substituted alkyl groups. The R' alkyl groups will con-tain from 1 to 18 carbon ato~s (preferably from 1 to 6 carbon i atoms) such as methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, hexyl, octyl, decyl, dodecyl, tetradecyl and octadecyl.
R' can also be a substituted alkyl group. Suitable substituents include, in general, any group which will not interfere with polymerization through a vinyl double bond. Typically, the sub-stituents can be carboxylate, cyano, ether, amino (primary, sec-ondary or tertiary), amide, hydrazide and hydroxyl.
Polymers having units of the above formula can be pro-duced by polymerizing the hydrohalide salt of a diallylamine ~ ~ ( II ) jIH2 CH2 R-C -R
I H2 1H2 ~ -N /
R' where R and R' are as indicated above, either alone or as a mix-ture with other copolymerizable ingredients, in the presence of ~ .
a free radical catalyst and then neutralizing the salt to give , , the polymer free base.
Specific hydrohalide salts of the diallylamines which can be polymerized to provide the polymer units of the invention .~
include diallylamine hydrcchloride; N-methyldiallylamine hydro-chloride; N-methyldiallylamine hydrobromide; 2,2'-dimethyl-N-methyldiallylamine hydrochloride; N-ethyldiallylamine hydrobromide;
N-isopropyldiallylamine hydrochloride; N-n-butyldiallylamine hydro-bromide; N-tert-butyldiallylamine hydrochloride; N-n-hexyldiallyl-amine hydrochloride; N-octadecyldiallylamine hydrochloride; N-acetamidodiallylamine hydrochloride; N-cyanomethyldiallylamine :
hydrochloride; N-~-propiGnamidodiallylamine hydrobromide; N-carboethoxymethyldiallylamine hydrochloride; N-~-methoxyethyl-diallylamine hydrobromide; N-~-aminoethyldiallylamine :`
:.................................... .. . . .
-: -. .- -. - ., . , . :. . , ::
IO~Z73~
nydrochloride; N-hydroxyethyldiallylamine hydrobromide; and N-acetohydrazide substituted diallylamine hydrochloride.
Diallylamines and N-alkyldiallylamines, used to prepare the polymers employed in this invention, can be prepared by the ; reaction of ammonia or a primary amine with an allyl halide em-ploying as a catalyst for the reaction a catalyst that promotes the ionization of the halide such~ for example, as sodium iodide, zinc iodide, ammonium iodide, cupric bromide, ferric chloride, ferric bromide, zinc chloride, mercuric iodide, mercuric nitrate, mercuric bromide, mercuric chloride, and mixtures of two or more.
Thus, for example, N-methyldiallylamine can be prepared by reac-tion of two moles of an allyl halide, such as allyl chloride, with one mole of methylamine in the presence of an ionization catalyst such as one of those enumerated above.
In preparing the homopolymers and copolymers, reaction can be initiated by redox catalytic system. In a redox system, the catalyst is activated by means of a reducing agent which pro-duces free radicals without the use of heat. Reducing agents commonly used are sodium metabisulfite and potassium metabisul-fite. Other reducing agents include water-soluble thiosulfates and bisulfites, hydrosulfites and reducing salts such as the sul-fate of a metal which is capable of existing in more than one valence state such as cobalt, iron, manganese and copper. A
specific example of such a sulfate is ferrous sulfate. The use of a redox initiator system has several advantages, the most im-portant of which is efficient polymerization at lower temperature.
Conventional peroxide catalysts such as tertiary-butyl hydroper-oxide, potassium persulfate, hydrogen peroxide and ammonium per-sulfate used in conjunction with the above reducing agents or metal activators, can be employed.
As stated above, the linear polymers of diallylamines ~ which are reacted with an epihalohydrin can contain different i units of formula (I) and/or contain units of one or more other co-~ polymerizable monomers. Typically, the comonomer is a different -r 109Z'~3t~
diallylamine, a monoethylenically unsaturated compound containing a single vinyl or vinylidene group or sulfur dioxide, and is pres-ent in an amount ranging from 0 to 95 mole % of the polymer. Thus the polymers of diallylamine are linear polymers wherein from 5~
to 100~ of the recurring units have the formula (I) and from 0 to 95% of the recurring units are monomer units derived from (1) a vinylidene monomer and/or (2) sulfur dioxide. Preferred comono-p mers include acrylic acid, methacrylic acid, methyl and other alkyl acrylates and methacrylates, acrylamide, methacrylamide, 10 acrylonitrile, methacrylonitrile, vinyl acetate, vinyl ethers such i as the alkyl vinyl ethers, vinyl ketones such as methyl vinyl ke-; tone and ethyl vinyl ketone, vinyl sulfonamide, sulfur dioxide or ;
a different diallylamine embraced by the above formula ~II).
! Specific copolymers which can be reacted with an epihalo-hydrin include copolymers of N-methyldiallylamine and sulfur di-oxide; copolymers of N-methyldiallylamine and diallylamine; co-polymers of diallylamine and acrylamide; copolymers of diallylamine and acrylic acid; copolymers of N-methyldiallylamine and methyl acrylate, copolymers of diallylamine and acrylonitrile; copolymers 20 of N-methyldiallylamine and vinyl acetate; copolymers of diallyl-amine and methyl vinyl ether; copolymers of N-methyldiallylamine and vinylsulfonamide; copolymers of N-methyldiallylamine and methyl vinyl ketone; terpolymers of diallylamine, sulfur dioxide and acrylamide; and terpolymers of N-methyldiallylamine, acrylic acid and acrylamide.
The epihalohydrin which is reacted with the polymer of a diallylamine can be any epihalohydrin, i.e., epichlorohydrin, epi-bromohydrin, epifluorohydrin or epiiodohydrin and is preferably ~ epichlorohydrin. In general, the epihalohydrin is used in an amount .
30 ranging from about 0.5 mole to about 1.5 moles and preferably about 1 mole to about 1.5 moles per mole of secondary plus tertiary amine ;~ present in the polymer.
The poly(diallylamine)--epihalohydrin resin can be prepared by reacting a homopolymer or copolymer of a diallylamine as set , .
'': , ~ : :: , - lO~Z73~
forth above with an epihalohydrin at a temperature of from about ! 30C. to about 80C. and preferably from about 40C. to about 60C.,~
until the viscosity measured on a solution containing 20% to 30~
solids at 25C. has reached a range of A to E and preferably about , C to D on the Gardner-Holdt scale. The reaction is preferably carried out in aqueous solution to moderate the reaction, and at a pH of from about 7 to about 9.5.
When the desired viscosity is reached, sufficient water is added to adjust the solids content of the resin solution to about ,.~
10 15% or less and the product cooled to room temperature (about 25C.) The poly(diallylamine)--epihalohydrin resin can be stabi-.
lized against gelation by adding to the aqueous solution thereof sufficient water-soluble acid (such as hydrochloric acid and sul-furic acid) to obtain and maintain the pH at about 2.
The following example illustrates the preparation of a poly-~ .
(diallylamine)--epichlorohydrin resin.
Example B .
A solution of 69.1 parts of methyldiallylamine and 197 parts of 20 Be hydrochloric acid in 111.7 parts of demineralized w~ter .
20 i9 sparged with nitrogen to remove air, then treated with 0.55 part of tertiary butyl hydroperoxide and a solution of 0.0036 part of ferrous sulfate in 0.5 part of water. The resulting solution is allowed to polymerize at 60-69C. for 24 hours to give a polymer solution containing about 52,1% solids with an RSV of 0.22. 122 ;~ parts of the above solution is adjusted to pH 8.5 by the addition of 95 parts of 3.8% sodium hydroxide and then diluted with 211 ~i, parts of water and combined with 60 parts of epichlorohydrin. The ; ~
- , mixture is heated at 45-55C. for 1.35 hours until the Gardner-;~ Holdt viscosity of a sample cooled to 25C. reaches B+. The rer ~`~ 30 sulting solution is acidified with 25 parts of 20 Be hydrochloric acid and heated at 60C. until the pH becomes constant at 2Ø The ~` resulting resin solution has a solids content of 20.8% and a Brook-field viscosity = 77 cp. ~measured using a Brookfield Model LVF
Viscometer, No. 1 spindle at 60 r,p.m, with guard).
10~738 Examples 2, 3 and 4 below are illustrative of suspensions of unblended wax particles.
Example 2 , Three hundred twenty parts of a 12.5% solids solution of an aminopolyamide--epichlorohydrin resin prepared in accordance with Example 1 and 440 parts water are mixed and heated quickly to 90C.
and added to the supply tank of a Manton-Gaulin laboratory (15 gal.
per hour) homogenizer. Two hundred forty parts of fused refined paraffin wax ~m.p. 140-145F.) is added to the hot solution in the - ~
' 10 supply tank with mixing by means of a propeller type stirrer. Be- ~ -fore addition of the aqueous resin solution to the supply tank, the homogenizer is preheated by circulating water at about 85C. through the body of the homogenizer and back to the supply tank where the water is heated by flowing steam through a stainless steel coil brazed onto the outside of the tank. The mixture is homogenized ~! with two passes through the homogenizer at 3000 psi. The homoge-nized product is collected in a glass bottle and cooled to room temperature by placing the bottle in a cold water bath with stir-ring of the product during cooling. The product is a blue-white 20 aqueous dispersion with 28% total solids (24% wax and 4% amino-polyamide--epichlorohydrin resin). After standing 24 hours, a small amount of undispersed wax present in the dispersion is sepa-rated by filtration through a 100 mesh screen. This is collected, dried and weighed to measure the percentage of the added wax which separates under these conditions. Longer term stability is meas-ured by allowing about 235 parts of the filtered dispersion to stand about four weeks when it is filtered a second time through a 100 mesh screen. The separated wax is dried and weighed. Wax separation results are set forth in Table I below.
Example 3 Example 2 is repeated. Wax separation results are set forth in Table I below.
i Example 4 ) ~ Example 2 is repeated. Wax separation results are set forth .
.... . .
~: ' n Table I below.
Table I
Parts Wax From 235 Parts of wax Separated Filtered Dispersion After 4 . Example (24 Hours) Weeks Standing '` 2 3.9 .13 ~ 3 2.8 .05 f, 4 1.0 .01 Examples 5-7 below are illustrative of the suspensions of 10 this invention.
s Examples 5-7 Examples 2, 3 and 4 are repeated using the same starting materials with the exception that, instead of the 240 parts of fused wax, there is added to the hot solution in the supply tank, in the fused state, a blend of 9.6 parts hydrogenated tallow fatty -~; acids and 230.4 parts refined paraffin wax prepared by melting the two components together. Solids (blend of the wax and fatty acid) separation results are set forth in Table II below.
Table II
Parts Solids From 235 Parts of Solids Separated Filtered Dispersion After 4 Example ~24 Hours) _ Weeks Standing 0.2 None 6 0.1 None 7 0.1 None Example 8 shows sizing properties of the dispersions of Ex-amples 2-7-Example 8 The dispersions of Examples 2-7 are applied to 40 lb./3000 `~ 30 ft.2 bleached kraft waterleaf paper in a size press in an amount sufficient to provide 0.38% ~dispersion solids) based on the :~
weight of the paper and the thus treated paper drum dried. Sizing - test results are as follows;
` Hercules Sizing Test, Example Seconds
4 259 ., :
: ., - ~09Z73H
Example 9 Example 2 is repe~ted. Solids (wax) separation results are set forth in Table III below.
Examples 10-15 Example 2 is repeated using varying amounts of commercial docosanoic acid (a mixture of saturated fatt~ acids containing about 27% stearic acid, 12% eicosanoic acid, 56% docosanoic acid and small amounts of other fatty acids) in place of part of the ~,~ wax. Prior to addition to the hot solution in the supply tank the 10 wax and acid are blended together by melting the two together. The blend is added in the fused state. In these examples, the second filtrations are made five weeks after the first. Solids (wax--fatty acids blend) separation results are set forth in Table III
below.
..
Table III
Parts Solids From 235 Parts of Parts% Solids Filtered Dispersion Docosanoic Parts Separated After 5 Weeks 20 Example_ Acid Wax(24 Hours) Standing 9(Control) 0 240 .33 .63 1.2 238.8.05 .00 11 2.4 237.6.08 .00 12 4.8 235,2.04 .00 13 9.6 230.4.00 .00 ~ 14 16.9 223.1.06 .01 `~ 15 24.0 216.0100 Example 16 shows sizing properties of the dispersions of Examples 9-14.
Example 16 3 ~` 30 The dispersions of Examples 9 through 14 are applied to 40 lb./3000 ft.2 bleached kraft waterleaf in a size press in an amount : .
su~ficient to provide 0.38% (dispersion solids) based on the weight ~ of paper and the thus treated paper drum dried. Sizing tests re-`~ sults are as follows:
Hercules Sizing Test, ~ Example Second l ~ 174 : - 16 -.~ ~
'.~
.~............. . . . .
Example 17 Example 9 is repeated. Solids (wax) separation results are set forth in Table IV below.
Examples 18-23 Examples 10-15 are repeated using an alkyl ketene dimer ;1 made from tall oil fatty acids in place of commercial docosanoic acid. In these examples, the second filtrations are made two weeks after the first. Solids (wax--ketene dimer blends) separa-tion results are set forth in Table IV below:
TABLE IV
Parts % Solids Parts Solids From 235 Parts Ketene Parts Separated of Filtered Dispersion Example Dimer Wax 24 Hours After 2 Weeks Standing 17(Control) 0 240 .98 .05 18 1.2 238.8 .14 .02 19 2.4 237.6 .14 .06 4.8 235.2 .08 .00 21 9.6 230.4 .03 .00 22 16.9 223.1 .02 .00 23 24.0 216.0 .02 .00 Example 24 shows slzing properties of the dispersions of Examples 17-23.
~ 20 Example 24 -~ . The dispersions of Examples 17-23 are applied to 40 lb./
3 3000 ft.2 bleached kraft waterleaf in a size press in an amount sufficient to provide 0.38% (dispersion solids) based on the weight of paper and the thu~-treated paper drum dried. Sizing re-ult- are as fol low~
Hercule~ 81~1ng Te~t xalr~le ~0ao~d~
17 ~ lC2 1~ 15 ~ 19 139 i51 22 ~8 ~ 23 473 ¦ Example 2$ i~ a ~ont~ol to be compared with Example 26 which 18 an example o~ applicant'~ invention~
'5_ . ; . . ;. ' . 1 ,"'' '' ~ "' ; Example 25 Three hundred parts polyethyl~ne wax having a mol. wt.
2200, a ring and ball softening point 108C., and a density 0.921 (Epolene 11) is dissolved in 300 parts xylene by heating to about 95C. To this solution is added a hot (about 90C.) mixture of 400 parts of aminopolyamide--epichlorohydrin resin prepared as in ~ Example 1 with 1060 parts water. The hot premix i8 homogenized $ twice at 3000 psi in a homogenizer preheated to about 95C. The resulting product is a stable oil-in-water emulsion from which 10 sub~tantially all of the xylene is removed by distillation at at-mospheric pressure during which the product temperature increa~es from about 94C. to about 100C. The solids content of the resulting stable aqueous suspension is about 25%. After cooling to room temperature, the mixture is filtered through a 100 mesh screen to separate the undispersed wax. The dried undispe~sed ~ax represents about 2.6~ of the wax in the dispersion.
Example 26 -Example 25 is repeated using 3 parts stearic acid to re-.
place 3 parts of the polyethylene wax in the xylene solution. In 20 this case, less than 0.1% of the dispersed wax is collected when the final product is filtered through a 100 mesh screen.
~ ~, Example 27 illustrates the preparation of a dispersing agent for u8e in this invention, the dispersing agent being a water-soluble poly(diallylamine)--epichlorohydrin resin.
Example ~7 .-To 250 parts of methyldiallylamine is added slowly 230 :
paxts 37% hydrochloria acid in about 240 parts demineralized water. The mixtuxe is cooled as needed to prevent volatilization of materlal~ due to the heat of reaction. The pH of the resulting ~ ~ 30 mixture is then adjusted to 3.1 by additional (19 part~) methyl-'r, `~:'`. ` diallylamine. After the oxygen in the reaction ves~el i8 dis-placed with nitrogen, 2.2 parts t-butyl hydroperoxide is added.
.
This is followed by .0014 part ferrous sulfate hepta hydrate in , ~ .
1.1 parts demineralized water. When the reaction miXture is t '}
. , ,, , , , . ~
,~: '- ; . -~ . ' ` ... . .
iO92738 warmed to 60C., there is a mild exothermic reaction which carries the reaction temperature briefly to about 66-70C. For the remainder of the 24-hour reaction time, the temperature i8 - held at about 60C. After cooling to 25-30C., the total solids of the product is about 48.4% and the RSV is .21 cp. To 220 parts of the above polymer solution is added sufficient (about 160 parts) sodium hydroxide solution (10 parts sodium hydroxide in 376 part~
water) to adjust the pH to about 8.5. The neutralized polymer solution is diluted with 366 parts demineralized water and then 10 heated to about 40C. To the warm solution is added 106 parts epichlorohydrin and the reaction warmed further to react the epi-chlorohydrin at about 50-55C. Reaction is continued until the reaction mixture reaches a Gardner viscosity of about B+ (about 1.7 hours)~ At this time the reaction is quenched by the rapid addition of about 35 parts 37% hydrochloric acid to give a final pH of about 2. There is obtained 859 parts of a product con-taining about 20.7% total solids. A series of runs are made sub-stantially as described above to give a total of about 7395 parts r:
of product with about 20.4% total solids.
, 20 Example 28 uses as a dispersing agent the resin of Example ;j 27 and is a control for comparison with Examples 29-33.
Example 28 Two hundred and seven (207) parts of a 20.4~ solids solu-~ tion of an epichlorohydrin modified tertiary amino polymer prepared ¦ in accordance with Example 27 and 473 parts water are mixed and heated quickly to 90C. and added to the supply tank of a Manton-Gaulin laboratory (15 gal. per hour) homogenizer. Two hundred forty part8 of fused refined paraffin wax (m.p. 140-145F.) is added to the hot solution in the supply tank with mixing by means ~ 30 of a propeller type stirrer. Before addition of the aqueous resin j solution to the supply tank, the homogenizer is preheated by cir-' culating water at about 85C. through the body of the homogenizer and back to the supply tank where the water is heated by blowing steam through a stainless steel coil brazed onto the outside of :; - . - - - . . .
~09Z~738 the tank. The mixture is homogenized with two pas~es th~ough the homogenizer at 3000 psi. The homogenized product i8 collected in a glass bottle and cooled to room temperature by placing the bottle in a cold water bath with stirring of the product during cooling. The product is a blue-white aqueous dispersion with 28%
total solids, 24% wax and 4~ poly(diallylamine)--epichlorohydrin resin. After standing 24 hours, a small amount of undispersed wax present in the dispersion is separated by filtration through a 100 mesh screen. This is collected, dried, and weighed to 10 measure the percentage of the added wax which separates under these conditions. Longer term stability is measured by allowing about 235 parts of the filtered dispersion to stand for about 4 weeks when it is filtered a second time through a 100 mesh screen.
The separated wax is dried and weighed. Results are given in Table V below.
Examples 29-33 !
Example 28 is duplicated with the exception that varying amounts of wax are replaced by an alkyl ketene dimer made from commercial stearic acid. The wax and the alkyl ketene dimer are 20 fir9t fused together to provide a homogeneous blend which is added, in the fused form, to the hot solution in the supply tank.
ll Solids (wax--ketene dimer blend) separation results are set forth in Table V below.
TABLE V
Parts Solid From 235 Parts of Parts ~ Solids Filtered Dispersion Ketene Parts Separated After 4 Weeks Example Dimer Wax (24 Hours) Standing . 28 (Control) 0 240 16.4 .58 i 29 2.4 237.66.6 .15 `~ 30 4.8 235.26.7 .18 `' 31 9.6 230.43.5 .03 32 16.9 223.14.0 1.82 33 24.0 216.00.25 2.19 Example 34 The dispersions of Examples 28-33 are applied to 40 lb./
3000 ft.2 bleached kraft waterleaf in a size press in an amount .
.
....
~092738 sufficient to provide 0.38% (dispersion solids) based on theweight of paper and the thus-treated paper drum dried. Sizing results are as follows:
Hercules Sizing Test Example Seconds ~ 32 676 j 33 842 ,Example 35 illustrates the preparation of a diqpercing 10 agent for use in this invention, the dispersing agent being a water-soluble alkylenepolyamine--epichlorohydrin resin.
Example 35 A reaction vessel i~ charged with 704 parts water and 476 parts epichlorohydrin. A steam jet vacuum system is turned on to exhaust vapors through a condenser and to prevent them from es-caping through the open manhole. Four hundred twenty parts of Amine 248 is added with agitation in 35 minutes while the tempera-ture is allowed to rise to 70C. Cooling water is required to ~limit the temperature rise to 70C. After amine addition is ;320 complete, the reactor charge has a pH of 7.8 and an A viscosity by Gardner Holdt. Six parts of 20% NaOH is added to speed reac-tion. After 2 hours and 40 minutes at about 70C., the viscosity reaches a U+ viscosity and the resin solution is diluted with 640 i~parts water which reduces the viscosity to about C-. A total of 44 part~ of 20% NaOH i8 added in four separate additions during 1-3/4 hour period to speea reaotion. An S viscosity i9 reached after 3 hours and 35 minut~s, and the rea¢tion i~ killed and diluted with 26 parts concentsated sul~uxic acid in 1345 parts water. This glves an aqueous solutio~ of 23.3% total solids, a P visco~ity, 30 and a pH of 4.4. Further addition of H2S04 and wa~er give~ 22.5%
total solids, (113 cp, vi~c.) and 4.0 pH. The resin solution is filtered through 10~ filtex cartridges to give a total of 3336 parts of product. Amine 248 i~ a dark, viscous liquid or pa~te with a slight ammoniacal odor. At least 75% of Amine 248 consists .
of bis(hexamethylene)-triamine and higher homologues:
H2N- (CH2) 6-N- (CH2) 6-NH2 bis-(hexamethylene)-triamine and H2N [ ( CH2 ) 6NH ] ( 2 +N ) H
~ higher homologues ,^ The remainder consists of lower molecular weight amines, nitriles and lactams. ~ -Example 36 uses as a dispersing agent the resin of Example 35 and is a control for comparison with Examples 37-42.
Example 36 ;~
One hundred seventy four (174) parts of a 22.5% solids solution of an alkylenepolyamine--epichlorohydrin reaction product prepared in accordance with Example 35 and 506 parts water are mixed and heated quickly to 90C. and added to the supply tank of a Manton-Gaulin laboratory (15 gal. per hour) homogenizer. Two hundred forty parts of fu~ed refined paraffin wax (m.p~ 140-145F.) ~
`~ is added to the hot solution in the ~upply tank with mixing by - ;-`"
; ~ means of a propeller type stirrer. Before addition of the aqueous resin solution to the supply tank, the homogenizer is preheated by circulating water at about 85C. through the body of the homo- ~;
genizer and back to the supply tank where the water i~ heated by blowing steam through a stainle~s steel coil brazed onto the out- `
; side of the tank. Thç mixtu~e i~ homogenized with two p~88e8 ~ ~
through the h~mog~nizex at 3000 psi, Th~ h~moge~lzed pX~duct i8 ." :`
collectod in a gla~ bQ~tle and coQled to room te~peratuxe by : :~
placing the bottle in a ~old wateX ~a~h with ~tlrrin~ of the product durin~ ~oli~. The pFodu~ i8 a blue-white a~ueou~ di~-persion with 28~ total ~olids, 24~ wax ~nd ~ alkylenepolyamine epichloxohydrin re~i~. A~ter s~a~ding ~ hou~, a ~mal~ amount ~ .
of undispersed wax pre~ent in the di~per~lon i~ ~qpaxated by ~
- tration throu~h a 100 me~h ~axeen. Thig i~ ~olIe~ted, dxied and . :
~,: ~: . ., .... , . - .. .
weighed to measure the percentage of the added wax which separate~
under these conditions. Longer term stability i~ mea~ured by allowing about 235 parts of the filtered dispersion to stand for about two weeks when it is filtered a second time through a 100 mesh screen. The separated wax is dried and weighed. Results are shown in Table VI below.
s Examples 37-42 Example 36 is repeated using varying amounts of fatty acids y (as indicated in Table VI below) to replace part of the paraffin 10 wax. The wax and fatty acids are first fused together to provide a homogeneous blend thereof which blend is added, in the fused state, to the hot solution in the supply tank. The fatty acids are the same as used in Examples 5-7. Solids separation results are set forth in Table VI below.
~` TAB~E VI
Parts Solids From ~3 Parts % Solids 235 Parts Filtered ;~ Fatty Parts Separated Dispersion After ~' Example Acids Wax (24 Hours) 2 Weeks Standing 36 (Control) 0 240 .36 .00 37 1.2 238.8 .63 .00 38 2.4 237.6 .57 .00 20 3g 4.8 235.2 .47 .00 9.6 231.4 .10 .00 ' 41 16.9 223.1 .13 .00 42 24.0 216.0 .15 .00 The dispersions of Examples 37-42 can be satisfactorily employed in the manufacture of sized paper.
~¦ Commercially available 8aturated ~atty aciA~ will often contain 8mall amoUnts of u~saturated fatty acids. These fatty ¦ acids ¢an be empl~yeA in pxepa~ing the blends used in thi~ i~ven-tion provided the un~aturated cQntent Aoes not exceed about 10%
by weight.
It i8 to be under~to~d that ~e above aesaription and j 30 , working examples a~e illustrative of this inVention and not in '~ limitation thereQf.
".. .. . .. . ...
: ., - ~09Z73H
Example 9 Example 2 is repe~ted. Solids (wax) separation results are set forth in Table III below.
Examples 10-15 Example 2 is repeated using varying amounts of commercial docosanoic acid (a mixture of saturated fatt~ acids containing about 27% stearic acid, 12% eicosanoic acid, 56% docosanoic acid and small amounts of other fatty acids) in place of part of the ~,~ wax. Prior to addition to the hot solution in the supply tank the 10 wax and acid are blended together by melting the two together. The blend is added in the fused state. In these examples, the second filtrations are made five weeks after the first. Solids (wax--fatty acids blend) separation results are set forth in Table III
below.
..
Table III
Parts Solids From 235 Parts of Parts% Solids Filtered Dispersion Docosanoic Parts Separated After 5 Weeks 20 Example_ Acid Wax(24 Hours) Standing 9(Control) 0 240 .33 .63 1.2 238.8.05 .00 11 2.4 237.6.08 .00 12 4.8 235,2.04 .00 13 9.6 230.4.00 .00 ~ 14 16.9 223.1.06 .01 `~ 15 24.0 216.0100 Example 16 shows sizing properties of the dispersions of Examples 9-14.
Example 16 3 ~` 30 The dispersions of Examples 9 through 14 are applied to 40 lb./3000 ft.2 bleached kraft waterleaf in a size press in an amount : .
su~ficient to provide 0.38% (dispersion solids) based on the weight ~ of paper and the thus treated paper drum dried. Sizing tests re-`~ sults are as follows:
Hercules Sizing Test, ~ Example Second l ~ 174 : - 16 -.~ ~
'.~
.~............. . . . .
Example 17 Example 9 is repeated. Solids (wax) separation results are set forth in Table IV below.
Examples 18-23 Examples 10-15 are repeated using an alkyl ketene dimer ;1 made from tall oil fatty acids in place of commercial docosanoic acid. In these examples, the second filtrations are made two weeks after the first. Solids (wax--ketene dimer blends) separa-tion results are set forth in Table IV below:
TABLE IV
Parts % Solids Parts Solids From 235 Parts Ketene Parts Separated of Filtered Dispersion Example Dimer Wax 24 Hours After 2 Weeks Standing 17(Control) 0 240 .98 .05 18 1.2 238.8 .14 .02 19 2.4 237.6 .14 .06 4.8 235.2 .08 .00 21 9.6 230.4 .03 .00 22 16.9 223.1 .02 .00 23 24.0 216.0 .02 .00 Example 24 shows slzing properties of the dispersions of Examples 17-23.
~ 20 Example 24 -~ . The dispersions of Examples 17-23 are applied to 40 lb./
3 3000 ft.2 bleached kraft waterleaf in a size press in an amount sufficient to provide 0.38% (dispersion solids) based on the weight of paper and the thu~-treated paper drum dried. Sizing re-ult- are as fol low~
Hercule~ 81~1ng Te~t xalr~le ~0ao~d~
17 ~ lC2 1~ 15 ~ 19 139 i51 22 ~8 ~ 23 473 ¦ Example 2$ i~ a ~ont~ol to be compared with Example 26 which 18 an example o~ applicant'~ invention~
'5_ . ; . . ;. ' . 1 ,"'' '' ~ "' ; Example 25 Three hundred parts polyethyl~ne wax having a mol. wt.
2200, a ring and ball softening point 108C., and a density 0.921 (Epolene 11) is dissolved in 300 parts xylene by heating to about 95C. To this solution is added a hot (about 90C.) mixture of 400 parts of aminopolyamide--epichlorohydrin resin prepared as in ~ Example 1 with 1060 parts water. The hot premix i8 homogenized $ twice at 3000 psi in a homogenizer preheated to about 95C. The resulting product is a stable oil-in-water emulsion from which 10 sub~tantially all of the xylene is removed by distillation at at-mospheric pressure during which the product temperature increa~es from about 94C. to about 100C. The solids content of the resulting stable aqueous suspension is about 25%. After cooling to room temperature, the mixture is filtered through a 100 mesh screen to separate the undispersed wax. The dried undispe~sed ~ax represents about 2.6~ of the wax in the dispersion.
Example 26 -Example 25 is repeated using 3 parts stearic acid to re-.
place 3 parts of the polyethylene wax in the xylene solution. In 20 this case, less than 0.1% of the dispersed wax is collected when the final product is filtered through a 100 mesh screen.
~ ~, Example 27 illustrates the preparation of a dispersing agent for u8e in this invention, the dispersing agent being a water-soluble poly(diallylamine)--epichlorohydrin resin.
Example ~7 .-To 250 parts of methyldiallylamine is added slowly 230 :
paxts 37% hydrochloria acid in about 240 parts demineralized water. The mixtuxe is cooled as needed to prevent volatilization of materlal~ due to the heat of reaction. The pH of the resulting ~ ~ 30 mixture is then adjusted to 3.1 by additional (19 part~) methyl-'r, `~:'`. ` diallylamine. After the oxygen in the reaction ves~el i8 dis-placed with nitrogen, 2.2 parts t-butyl hydroperoxide is added.
.
This is followed by .0014 part ferrous sulfate hepta hydrate in , ~ .
1.1 parts demineralized water. When the reaction miXture is t '}
. , ,, , , , . ~
,~: '- ; . -~ . ' ` ... . .
iO92738 warmed to 60C., there is a mild exothermic reaction which carries the reaction temperature briefly to about 66-70C. For the remainder of the 24-hour reaction time, the temperature i8 - held at about 60C. After cooling to 25-30C., the total solids of the product is about 48.4% and the RSV is .21 cp. To 220 parts of the above polymer solution is added sufficient (about 160 parts) sodium hydroxide solution (10 parts sodium hydroxide in 376 part~
water) to adjust the pH to about 8.5. The neutralized polymer solution is diluted with 366 parts demineralized water and then 10 heated to about 40C. To the warm solution is added 106 parts epichlorohydrin and the reaction warmed further to react the epi-chlorohydrin at about 50-55C. Reaction is continued until the reaction mixture reaches a Gardner viscosity of about B+ (about 1.7 hours)~ At this time the reaction is quenched by the rapid addition of about 35 parts 37% hydrochloric acid to give a final pH of about 2. There is obtained 859 parts of a product con-taining about 20.7% total solids. A series of runs are made sub-stantially as described above to give a total of about 7395 parts r:
of product with about 20.4% total solids.
, 20 Example 28 uses as a dispersing agent the resin of Example ;j 27 and is a control for comparison with Examples 29-33.
Example 28 Two hundred and seven (207) parts of a 20.4~ solids solu-~ tion of an epichlorohydrin modified tertiary amino polymer prepared ¦ in accordance with Example 27 and 473 parts water are mixed and heated quickly to 90C. and added to the supply tank of a Manton-Gaulin laboratory (15 gal. per hour) homogenizer. Two hundred forty part8 of fused refined paraffin wax (m.p. 140-145F.) is added to the hot solution in the supply tank with mixing by means ~ 30 of a propeller type stirrer. Before addition of the aqueous resin j solution to the supply tank, the homogenizer is preheated by cir-' culating water at about 85C. through the body of the homogenizer and back to the supply tank where the water is heated by blowing steam through a stainless steel coil brazed onto the outside of :; - . - - - . . .
~09Z~738 the tank. The mixture is homogenized with two pas~es th~ough the homogenizer at 3000 psi. The homogenized product i8 collected in a glass bottle and cooled to room temperature by placing the bottle in a cold water bath with stirring of the product during cooling. The product is a blue-white aqueous dispersion with 28%
total solids, 24% wax and 4~ poly(diallylamine)--epichlorohydrin resin. After standing 24 hours, a small amount of undispersed wax present in the dispersion is separated by filtration through a 100 mesh screen. This is collected, dried, and weighed to 10 measure the percentage of the added wax which separates under these conditions. Longer term stability is measured by allowing about 235 parts of the filtered dispersion to stand for about 4 weeks when it is filtered a second time through a 100 mesh screen.
The separated wax is dried and weighed. Results are given in Table V below.
Examples 29-33 !
Example 28 is duplicated with the exception that varying amounts of wax are replaced by an alkyl ketene dimer made from commercial stearic acid. The wax and the alkyl ketene dimer are 20 fir9t fused together to provide a homogeneous blend which is added, in the fused form, to the hot solution in the supply tank.
ll Solids (wax--ketene dimer blend) separation results are set forth in Table V below.
TABLE V
Parts Solid From 235 Parts of Parts ~ Solids Filtered Dispersion Ketene Parts Separated After 4 Weeks Example Dimer Wax (24 Hours) Standing . 28 (Control) 0 240 16.4 .58 i 29 2.4 237.66.6 .15 `~ 30 4.8 235.26.7 .18 `' 31 9.6 230.43.5 .03 32 16.9 223.14.0 1.82 33 24.0 216.00.25 2.19 Example 34 The dispersions of Examples 28-33 are applied to 40 lb./
3000 ft.2 bleached kraft waterleaf in a size press in an amount .
.
....
~092738 sufficient to provide 0.38% (dispersion solids) based on theweight of paper and the thus-treated paper drum dried. Sizing results are as follows:
Hercules Sizing Test Example Seconds ~ 32 676 j 33 842 ,Example 35 illustrates the preparation of a diqpercing 10 agent for use in this invention, the dispersing agent being a water-soluble alkylenepolyamine--epichlorohydrin resin.
Example 35 A reaction vessel i~ charged with 704 parts water and 476 parts epichlorohydrin. A steam jet vacuum system is turned on to exhaust vapors through a condenser and to prevent them from es-caping through the open manhole. Four hundred twenty parts of Amine 248 is added with agitation in 35 minutes while the tempera-ture is allowed to rise to 70C. Cooling water is required to ~limit the temperature rise to 70C. After amine addition is ;320 complete, the reactor charge has a pH of 7.8 and an A viscosity by Gardner Holdt. Six parts of 20% NaOH is added to speed reac-tion. After 2 hours and 40 minutes at about 70C., the viscosity reaches a U+ viscosity and the resin solution is diluted with 640 i~parts water which reduces the viscosity to about C-. A total of 44 part~ of 20% NaOH i8 added in four separate additions during 1-3/4 hour period to speea reaotion. An S viscosity i9 reached after 3 hours and 35 minut~s, and the rea¢tion i~ killed and diluted with 26 parts concentsated sul~uxic acid in 1345 parts water. This glves an aqueous solutio~ of 23.3% total solids, a P visco~ity, 30 and a pH of 4.4. Further addition of H2S04 and wa~er give~ 22.5%
total solids, (113 cp, vi~c.) and 4.0 pH. The resin solution is filtered through 10~ filtex cartridges to give a total of 3336 parts of product. Amine 248 i~ a dark, viscous liquid or pa~te with a slight ammoniacal odor. At least 75% of Amine 248 consists .
of bis(hexamethylene)-triamine and higher homologues:
H2N- (CH2) 6-N- (CH2) 6-NH2 bis-(hexamethylene)-triamine and H2N [ ( CH2 ) 6NH ] ( 2 +N ) H
~ higher homologues ,^ The remainder consists of lower molecular weight amines, nitriles and lactams. ~ -Example 36 uses as a dispersing agent the resin of Example 35 and is a control for comparison with Examples 37-42.
Example 36 ;~
One hundred seventy four (174) parts of a 22.5% solids solution of an alkylenepolyamine--epichlorohydrin reaction product prepared in accordance with Example 35 and 506 parts water are mixed and heated quickly to 90C. and added to the supply tank of a Manton-Gaulin laboratory (15 gal. per hour) homogenizer. Two hundred forty parts of fu~ed refined paraffin wax (m.p~ 140-145F.) ~
`~ is added to the hot solution in the ~upply tank with mixing by - ;-`"
; ~ means of a propeller type stirrer. Before addition of the aqueous resin solution to the supply tank, the homogenizer is preheated by circulating water at about 85C. through the body of the homo- ~;
genizer and back to the supply tank where the water i~ heated by blowing steam through a stainle~s steel coil brazed onto the out- `
; side of the tank. Thç mixtu~e i~ homogenized with two p~88e8 ~ ~
through the h~mog~nizex at 3000 psi, Th~ h~moge~lzed pX~duct i8 ." :`
collectod in a gla~ bQ~tle and coQled to room te~peratuxe by : :~
placing the bottle in a ~old wateX ~a~h with ~tlrrin~ of the product durin~ ~oli~. The pFodu~ i8 a blue-white a~ueou~ di~-persion with 28~ total ~olids, 24~ wax ~nd ~ alkylenepolyamine epichloxohydrin re~i~. A~ter s~a~ding ~ hou~, a ~mal~ amount ~ .
of undispersed wax pre~ent in the di~per~lon i~ ~qpaxated by ~
- tration throu~h a 100 me~h ~axeen. Thig i~ ~olIe~ted, dxied and . :
~,: ~: . ., .... , . - .. .
weighed to measure the percentage of the added wax which separate~
under these conditions. Longer term stability i~ mea~ured by allowing about 235 parts of the filtered dispersion to stand for about two weeks when it is filtered a second time through a 100 mesh screen. The separated wax is dried and weighed. Results are shown in Table VI below.
s Examples 37-42 Example 36 is repeated using varying amounts of fatty acids y (as indicated in Table VI below) to replace part of the paraffin 10 wax. The wax and fatty acids are first fused together to provide a homogeneous blend thereof which blend is added, in the fused state, to the hot solution in the supply tank. The fatty acids are the same as used in Examples 5-7. Solids separation results are set forth in Table VI below.
~` TAB~E VI
Parts Solids From ~3 Parts % Solids 235 Parts Filtered ;~ Fatty Parts Separated Dispersion After ~' Example Acids Wax (24 Hours) 2 Weeks Standing 36 (Control) 0 240 .36 .00 37 1.2 238.8 .63 .00 38 2.4 237.6 .57 .00 20 3g 4.8 235.2 .47 .00 9.6 231.4 .10 .00 ' 41 16.9 223.1 .13 .00 42 24.0 216.0 .15 .00 The dispersions of Examples 37-42 can be satisfactorily employed in the manufacture of sized paper.
~¦ Commercially available 8aturated ~atty aciA~ will often contain 8mall amoUnts of u~saturated fatty acids. These fatty ¦ acids ¢an be empl~yeA in pxepa~ing the blends used in thi~ i~ven-tion provided the un~aturated cQntent Aoes not exceed about 10%
by weight.
It i8 to be under~to~d that ~e above aesaription and j 30 , working examples a~e illustrative of this inVention and not in '~ limitation thereQf.
".. .. . .. . ...
Claims (20)
1. An essentially stable aqueous dispersion of finely divided solid particles consisting essentially of, by weight (A) from about 5% to about 50% of finely divided solid particles, said solid particles being selected from the group consisting of (1) a blend consisting essentially of, by weight, from about 99% to about 93% of a wax selected from the group consisting of petroleum waxes, synthetic hydrocarbon waxes, and mixtures thereof and from about 1% to about 7% of a C18 to C24 saturated fatty acid, (2) a blend consisting essentially, by weight, from about 99.5% to about 75%
of a wax selected from the group consisting of petroleum waxes, synthetic hydrocarbon waxes, and mixtures thereof and from about 0.5% to about 25% of at least one alkyl ketene dimer having the formula [RCH=C=O]2 where R is an alkyl radical having 10 to about 20 carbon atoms, and (3) mixtures of (1) and (2), (B) from about 0.5% to about 20% of water-soluble cationic resin dispersing agent selected from the group consisting of (i) a water-soluble poly-aminopolyamide--epichlorohydrin resin, (ii) a water-soluble alkyl-enepolyamine--epichlorohydrin resin, (iii) a water-soluble poly-(diallylamine)--epichlorohydrin resin, and (iv) mixtures of any two or more of (i), (ii), and (iii), and (C) water to 100%.
of a wax selected from the group consisting of petroleum waxes, synthetic hydrocarbon waxes, and mixtures thereof and from about 0.5% to about 25% of at least one alkyl ketene dimer having the formula [RCH=C=O]2 where R is an alkyl radical having 10 to about 20 carbon atoms, and (3) mixtures of (1) and (2), (B) from about 0.5% to about 20% of water-soluble cationic resin dispersing agent selected from the group consisting of (i) a water-soluble poly-aminopolyamide--epichlorohydrin resin, (ii) a water-soluble alkyl-enepolyamine--epichlorohydrin resin, (iii) a water-soluble poly-(diallylamine)--epichlorohydrin resin, and (iv) mixtures of any two or more of (i), (ii), and (iii), and (C) water to 100%.
2. An essentially stable aqueous dispersion of finely divided solid particles consisting essentially of, by weight, (A) from about 5% to about 45% of finely divided solid particles, said solid particles being selected from the group consisting of (1) a blend consisting essentially of, by weight, from about 99% to about 95% of a wax selected from the group consisting of petroleum waxes, synthetic hydrocarbon waxes, and mixtures thereof and from about 1%
to about 5% of a C18 to C24 saturated fatty acid, (2) a blend con-sisting essentially of, by weight, from about 99% to about 90% of a wax selected from the group consisting of petroleum waxes, syn-thetic hydrocarbon waxes, and mixtures thereof and from about 1%
o about 10% of at least one alkyl ketene dimer having the formula [RCH=C=O]2 where R is an alkyl radical having 10 to about 20 car-bon atoms, and (3) mixtures of (1) and (2), (B) from about 0.5% to about 10% of water-soluble cationic resin dispersing agent selected from the group consisting of (i) a water-soluble polyaminopoly-amide--epichlorohydrin resin, (ii) a water-soluble alkylenepoly-amine--epichlorohydrin resin, (iii) a water-soluble poly(diallyl-amine)--epichlorohydrin resin, and (iv) mixtures of any two or more of (i), (ii) and (iii), and (C) water to 100%.
to about 5% of a C18 to C24 saturated fatty acid, (2) a blend con-sisting essentially of, by weight, from about 99% to about 90% of a wax selected from the group consisting of petroleum waxes, syn-thetic hydrocarbon waxes, and mixtures thereof and from about 1%
o about 10% of at least one alkyl ketene dimer having the formula [RCH=C=O]2 where R is an alkyl radical having 10 to about 20 car-bon atoms, and (3) mixtures of (1) and (2), (B) from about 0.5% to about 10% of water-soluble cationic resin dispersing agent selected from the group consisting of (i) a water-soluble polyaminopoly-amide--epichlorohydrin resin, (ii) a water-soluble alkylenepoly-amine--epichlorohydrin resin, (iii) a water-soluble poly(diallyl-amine)--epichlorohydrin resin, and (iv) mixtures of any two or more of (i), (ii) and (iii), and (C) water to 100%.
3. The dispersion of claim 2 wherein (A) is blend (1).
4. The dispersion of claim 2 wherein (A) is blend (2).
5. The dispersion of claim 3 wherein (B) is (i).
6. The dispersion of claim 3 wherein (B) is (ii).
7. The dispersion of claim 3 wherein (B) is (iii).
8. The dispersion of claim 4 wherein (B) is (i).
9. The dispersion of claim 4 wherein (B) is (ii).
10, The dispersion of claim 4 wherein (B) is (iii).
11. Paper sized by use of the dispersion of claim 1.
12. Paper sized by use of the dispersion of claim 2,
13. Paper sized by use of the dispersion of claim 3.
14. Paper sized by use of the dispersion of claim 4.
15. Paper sized by use of the dispersion of claim 5.
16. Paper sized by use of the dispersion of claim 6.
17. Paper sized by use of the dispersioin of claim 7.
18. Paper sized by use of the dispersion of claim 8.
19. Paper sized by use of the dispersion of claim 9.
20. Paper sized by use of the dispersion of claim 10.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/697,008 US4017431A (en) | 1973-11-28 | 1976-06-17 | Aqueous dispersions of wax blends and a water-soluble cationic resin and paper sized therewith |
| US697,008 | 1985-01-31 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1092738A true CA1092738A (en) | 1980-12-30 |
Family
ID=24799408
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA270,987A Expired CA1092738A (en) | 1976-06-17 | 1977-02-03 | Aqueous dispersions of wax blends and a water-soluble cationic resin and paper sized therewith |
Country Status (2)
| Country | Link |
|---|---|
| AU (1) | AU504678B2 (en) |
| CA (1) | CA1092738A (en) |
-
1977
- 1977-01-26 AU AU21674/77A patent/AU504678B2/en not_active Expired
- 1977-02-03 CA CA270,987A patent/CA1092738A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| AU2167477A (en) | 1978-08-03 |
| AU504678B2 (en) | 1979-10-25 |
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| Date | Code | Title | Description |
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| MKEX | Expiry |