DK155219B - DIFFICULT DISPERSION OF REINFORCED COLOPHONIUM RESIN USED BY LIMITING PAPER - Google Patents

Description

1 DK 155219 B

The present invention relates to an aqueous dispersion of reinforced rosin resin for use in bonding paper consisting essentially of the following by weight: (A) from 5% to 50% reinforced rosin resin, (B) from 0.5% to 10% dispersant, and 5 (C) water to 100%, the reinforced rosin resin being optionally mixed with rosin resin and extenders.

Inner bonding of rosin resin paper is discussed by Casey,

Pulp and Paper, Second Edition, Volume II: Papermaking, Chapter XIII,

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On page 1048, the author discusses reinforced rosin resin adhesives and states that reinforced rosin rosin lines are prepared by "causing maleic anhydride or other dienophiles to react with rosin resin to increase the number of carboxylic acid groups.

5 The author also states that a typical reinforced glue may contain approx. $ 1-30 maleopimaric anhydride.

On page 1047 under the heading "Free Rosin Size", the author states that the relative advantages of high content of free rosin and 10 rosin content have been a contentious issue for many years, but that it is now quite common It is recognized that high content of free rosin resin results in better bonding and uses less alum.

15 On page 1050, under the heading "Protected Rosin Size," the author states that by using a protective colloid, it is possible to produce highly stable adhesive containing as much as $ 90 free rosin resin. On page 1051, the Bewoid process for producing high content of free rosin resin is discussed, and it is stated that Bewoid glue, as it is usually manufactured, contains approx. $ 90 free rosin resin dispersed in a small amount of rosin resin soap and stabilized by the presence of approx. 2 $ casein or other protein. The casein is used as a protective colloid to prevent the growth of rosin resin particles and thereby keeps them in a finely divided state.

On pages 1051 and 1052, the author discusses the Prosize method of producing protected glue containing a high content of free rosin resin. The rosin resin particles are prevented from growing into larger aggregates by the presence of a surfactant protein such as soybean protein.

German Patent No. 1,131,348 states that glue with free rosin resin are dispersions of unsaponified resin acids with a certain percentage of rosin resin soap. It is also stated that the dispersions are prepared by a particular method that they are most commonly used with a free rosin resin content of $ 60-95 and in addition to rosin resin contains auxiliary emulsifiers and stabilizers such as stearates, triethanolamine, casein and waxes.

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German Patent No. 1,131,348 further states that heretofore, the reinforced rosin resins have not been suitable for the preparation of dispersions, because they have mostly had high melting points, tend to crystallize or, during dispersion, form fine crusts leading to for sedimentation phenomena. German Patent 5 No. 1,131,348 discloses a paper adhesive and a process for preparing a paper adhesive in the form of a high dispersion aqueous rosin resin of reinforced rosin resin which is characterized by mixing the reinforced rosin resin with fatty acids, fatty acid mixtures and / or naphthenic acids at elevated temperatures and the dispersion being carried out in a known manner.

U.S. Patent No. 3,565,755 discloses a substantially homogeneous stable aqueous suspension of rosin-based rosin material in a finely divided state. The rosin resin material may be fully reinforced rosin resin or may be a mixture of rosin resin and reinforced rosin resin. A very small amount of the rosin-based resin material is saponified and acts as a dispersant for the rosin-based resin particles. This agent, which consists essentially of the rosin-20 resin-based material, the saponified rosin resin and water, is used for bonding paper. The glue according to U.S.A. Patent No. 3,565,755 is a high content of free rosin resin, containing only a very small amount of saponified rosin resin material. Furthermore, it has good stability (good shelf life) for a long time and does not require the use of the stabilizers used so far to produce stable glue with high content of free rosin resin such as casein and soybean protein.

The prior art reinforced rosin resins have not been suitable for preparing dispersions because they have too high melting points and tendency to crystallize.

The dispersion of the present invention is characterized in that component (B) is selected from the group consisting of (1) a water-soluble polyaminopolyamide-epichlorohydrin resin, (2) a water-soluble alkylene-polyamine-epichlorohydrin resin and (3) a water-soluble poly (diallylamine) -epiklorhydrinharpiks. The aqueous dispersions of the invention have good stability and do not require presence.

* I

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see of rosin resin soap or reinforced rosin resin soap. In addition, the aqueous dispersions of the invention do not require the use of stabilizers which have heretofore been used in the production of high glue content of free rosin resin. j

If desired, the reinforced rosin resin can be stretched with known extenders therefor, such as waxes (especially paraffin wax and microcrystalline wax), hydrocarbon resins, including those derived from petroleum hydrocarbons and terpenes, and the like. This is achieved L0 by mixing the reinforced rosin resin with. from 10 to 100% by weight calculated on the weight of reinforced rosin resin of the stretching rosin rosin resin.

Mixtures of reinforced rosin resin and rosin resin L5 and mixtures of reinforced rosin resin, rosin resin and rosin resin stretching agent may also be used.

Mixtures of reinforced rosin and rosin resin will contain -, $ 25-95 reinforced rosin resin and 75-5% rosin resin. Mixtures of reinforced rosin, rosin resin and rosin resin stretching agent contain 25-45% reinforced rosin resin, 5-50% rosin resin and $ 5-50 rosin resin stretching agent.

In preparing aqueous reinforced rosin dispersions according to the invention, the reinforced rosin resin (including the extruder or rosin resin or both, if used) is first "dissolved in a water-immiscible organic solvent such as benzene, xylol, chloroform and 1,2-dichloro = 30 propane Mixtures of two or more solvents may be used if desired The selected solvent is also unreactive to the components of the aqueous dispersion to be prepared afterwards.

The organic solvent solution and reinforced rosin resin are then mixed with an aqueous solution of cationic resin dispersant to form an emulsion which is essentially

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unstable and wherein the organic solvent solution and reinforced rosin resin form the dispersed phase. The substantially unstable aqueous emulsion is subjected to very high shear forces to form a substantially stable aqueous emulsion. Very high shear forces are conveniently obtained by a homogenizer. To pass the unstable aqueous emulsion at least once through a homogenizer under a pressure of the order of approx. 70-560 Kg / cm 2, a substantially stable emulsion is obtained. Then, the organic solvent 10 is removed from the emulsion and a substantially stable aqueous dispersion of amplified rosin resin particles is obtained.

The aqueous enhanced rosin resin dispersions of the invention can be prepared by the reverse process shown in Example 16. The solution of reinforced rosin and organic solvent is mixed with an aqueous solution of cationic resin dispersant in an amount which provides a stable water content. oil emulsion which is then converted to a stable oil-in-water emulsion by the rapid addition of water with vigorous stirring. The organic solvent is then removed e.g. by distillation under reduced pressure.

The rosin resin used to prepare the reinforced rosin resin used in the invention may be any of the industrially available types of rosin resin such as wood rosin rosin, rubber rosin rosin, tall rosin rosin resin and mixtures of two or more in their crude or refined state. substantially completely hydrogenated rosin resins and polymerized rosin resins as well as rosin resins which have been treated to prevent crystallization, such as by heat treatment or reaction with formaldehyde, may be used.

The reinforced rosin resin used is the addition reaction product of rosin resin and an acidic compound containing the group 35 C = C-C = 0 and is obtained by causing rosin resin and the acidic compound to react at elevated temperatures from ca. 150 to approx. 210 ° C.

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The amount of acidic compound used is the amount which provides reinforced rosin resin containing from ca. 1 to approx. 12 weight fo adduct acidic compound based on the weight of the reinforced rosin resin. Methods for preparing reinforced cellophonium resin are described in U.S. Patents Nos. 2,628,918 and 2,684,300, which are hereby incorporated by reference.

Examples of acidic compounds containing the group} C = CC = 0 which can be used to prepare the reinforced rosin resin, 10 are α, β-unsaturated organic acids and their available anhydrides, and particular examples thereof are fumaric acid, maleic acid, acrylic acid, tartaric anhydride, itaconic acid, itaconic anhydride, citraconic acid and citric acid anhydride. Mixtures of acids can be used to prepare the reinforced rosin resin if desired. Mixtures of various reinforced rosin resins can also be used if desired. A mixture of the acrylic acid addition product of rosin resin and the fumaric acid addition product may e.g. used to prepare the novel dispersions of the invention. Also reinforced rosin resin, which has been completely hydrogenated after the addition formation, in the main a-20 gene, can be used.

If rosin resin (i.e., non-reinforced rosin resin) is used in combination with reinforced rosin resin, it may be any of the industrially available types of rosin resin, such as wood rosin rosin, rubber rosin rosin, tall oil rosin resin and mixtures of their two or more mixtures of two or more . Partially or substantially completely hydrogenated rosin resins and polymerized rosin resins as well as rosin resins which have been treated to prevent crystallization, such as by heat treatment or reaction with formaldehyde, may be used. · ·

The dispersants used to prepare the substantially stable aqueous dispersions of the invention are cationic polymeric resin-like materials which are water soluble.

J D

Particularly suitable dispersants are the cationic, thermosetting, water-soluble aminopolyamide-epichlorohydrin resins disclosed in U.S. Patents Nos. 2,926,116 and 2,926,154. Resins 7

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are water-soluble polymeric reaction products of epichlorohydrin and an aminopolyamide. The aminopolyamide is derived from the reaction of a dicarboxylic acid with a polyalkylene polyamine in a molar ratio of polyalkylene polyamine to dicarboxylic acid from ca. 0.8: 1 to approx. 1.4: 1st

Particularly suitable dicarboxylic acids are diglycolic acid and saturated aliphatic dicarboxylic acids containing from 3 to 10 carbon atoms such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, cork acid, azelaic acid and sebaceic 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 to prepare the water-soluble aminopolyamide just like 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.

Several different polyalkylene polyamines can be used, including polyethylene polyamines, polypropylene polyamines, polybutylene polyamines and the like. Polyalkylene polyamines can be represented as polyamines in which the nitrogen atoms are joined to groups of the formula where n is a small integer greater than 1, and the number of these groups in the molecule ranges from 2 up to ca. 8. The hydrogen atoms may be attached to neighboring carbon atoms in the group -CnH2; n- or to carbon atoms that are further apart but not to the same carbon atom. Polyamines such as diethylenetriamine, triethylenetetramine, tetraethylene = pentamine and dipropylenetriamine, which are available in reasonably pure form, are suitable for the preparation of water-soluble aminopolyamides. Other polyalkylene polyamines which may be used include methyl bis- (3-aminopropyl) amine, methyl bis- (2-aminoethyl) amine and 4,7-dimethyltriethylenetetramine. Mixtures of polyalkylene polyamines can be used if desired.

The distance between the amino groups of the amino polyamide can be increased if desired. This can be achieved by using a diamine such as diethylenediamine, propylenediamine, hexamethylenediamine and the like instead of 35

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for part of the polyalkylene polyamine. For this purpose, up to approx. $ 80 of the polyalkylene polyamine is replaced by a molecular equivalent amount of diamine. As a rule, compensation of approx. $ 50 or less sufficient, i

The temperatures used to carry out the reaction of the dicarboxylic acid with the polyalkylene polyamine can vary from about 1 110 ° C to approx. 250 ° C or higher at atmospheric pressure. For most purposes, temperatures between about 160 ° C and 210 ° C. The reaction time .0 will usually vary from approx. 1/2 to 2 hours. The reaction time varies inversely with the reaction temperature used.

In carrying out the reaction, it is preferred to use an amount of dicarboxylic acid sufficient to react substantially with the primary amine groups on the polyalkylene polyamine but insufficient to react with the secondary amine groups and / or tertiary amine groups to a substantial extent. As a rule, this requires a molar ratio of polyalkylene polyamine to dicarboxylic acid from ca. 0.9: 1 to approx. 1.2: 1. Mole ratio from approx. 0.8: 1 to approx. However, 1.4: 1 0 can be used. The aminopolyamide derived as described above is reacted with epichlorohydrin at a temperature of ca. 45 ° C to approx. And preferably between about 100 ° C. 45 ° C and 70 ° C until the viscosity of a solution with 20 $ solids in water at 25 ° C has reached approx. C or more on the G-ardner-Holdt scale. This reaction is preferably carried out in aqueous solution to moderate the reaction.

As a rule, pH adjustment is not necessary. However, since the pH decreases during the polymerization phase of the reaction, it may be desirable in some cases to add alkali to interact with at least some of the acid formed. Once the desired viscosity is reached 0, water can be added to adjust the solids content of the resin solution to a desired amount, usually from about 1 2 to approx. $ 50.

In the reaction between aminopolyamide and epichlorohydrin, satisfactory results can be obtained using from ca. 0.1 mole to approx.

2 moles of epichlorohydrin for each secondary or tertiary amine group in the aminopolyamide, and preferably from ca. 1 mole to approx. 1.5 moles of epichlorohydrin.

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A monofunctional alkylating agent can. is used as additional reaction participant in carrying out the above reaction, if desired. A monofunctional alkylating agent may first be reacted with the aminopolyamide followed by reaction of the formed reaction product with epichlorohydrin, or the alkylating agent may be reacted with the reaction product of aminopolyamide and epichlorohydrin. Thus, for example, epichlorohydrin can be added to an aqueous solution. solution of the aminopolyamide at a temperature of about 45 to about 55 ° C. The reaction mixture is then heated to a temperature of about 50 to 100 ° C and preferably from about 60 to 80 ° C, depending on the desired reaction rate. appropriate time at this temperature, i.e., from about 10 to 100 minutes, and preferably until the viscosity of a solution of about 25 $ solids of the reaction mixture at 25 ° C is from A to B on the Gardner-Holdt scale, of which 15 when most of the epoxy groups in the epichlorohydrin have reacted with the amino groups in the aminopolyamide, a monofunctional alkylating agent is added and the reaction mixture is preferably heated to a temperature of approx. 60 ° C to approx. 80 ° C until the viscosity of a solution of approx. $ 25 solids at 25 ° C are at least 20 A and preferably at least B to C on the G-ardner-Holdt scale. The solids to viscosity ratio 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 40 ° C and under reduced pressure to $ 25 solid-25 fer. lower alkyl esters of mineral acids such as the halides, sulfates and phosphates, substituted alkyl halides and the like are suitable monofunctional alkylating agents. Examples of the compounds which may be used are dimethyl, diethyl and dipropyl sulfate, methyl chloride, methyl iodide, ethyl iodide, methyl bromide, propyl bromide and mono-, di- or trimethyl, ethyl and propyl phosphate. Certain aromatic compounds such as benzyl chloride and methyl t-toluene sulfonate may be used. It can be used from approx. 0.1 mole to approx. 0.9 moles of monofunctional alkylating agent for each amine group.

35 In the following examples, unless otherwise indicated, all parts and percentages are by weight specified in some of the Examples, the bonding results being determined on the Hercules Sizing Tester. The sizing test determines the resistance of a glued sheet of paper to the penetration of the No. 2 sample solution (an aqueous solution of 1.0 wt.

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^ formic acid and 1.25% by weight of naphtholene green B). The time required for ink penetration to reduce the light reflectance either 80% or 85% (as indicated in the examples) of the original value of the sheet is used to represent the degree of sizing.

The following Examples AC and PJ illustrate preparation of aminopolyamide epichlorohydrin resin, alkylene polyaminoepichlorohydrin resin and poly (diallylamine) epichlorohydrin resin suitable scm cationic resin dispersant for use in the invention, Examples D and E illustrate the preparation of an amplifier resin the dispersion of the invention.

Example A

An aminopolyamide is formed by slowly adding 219.3 parts of adipic acid with stirring to 151.3 parts of diethylenetriamine in a flask equipped with a stirrer and condenser to collect distilled water.

The reaction mixture is stirred and heated to 170-180 ° C under a nitrogen blanket until amide formation is complete. After air cooling to approx. 140 ° C, hot water is added with stirring to form a solution of 50 $ solids of polyamide resin having an intrinsic viscous density of 0.140 measured using a 2 $ solution in IR RH + Cl. An epichlorohydrin derivative of the aminopolyamide is prepared by adding ca.

20.25 parts of water to approx. 50 parts of the solution with 50 $ solids and then add 14.0 parts (0.157 mol) of epichlorohydrin. The reaction mixture is heated to 70 ° C with stirring and reflux until the G-ardner-Holdt viscosity reaches a value of E to E. The reaction mixture is diluted with water to a solids content of about 25 ° C. 12.5 $.

intrinsically suitable dispersants which can be used in accordance with the invention are the water-soluble alkylene-polyamine-epichlorohydrin resins which are water-soluble polymeric reaction products of epichlorohydrin 30 and an alkylene polyamine.

Alkylene polyamines which can be reacted with epichlorohydrin have the formula where n is an integer from 2 to 8 and x is an integer of 1 or more, preferably 1-6. Examples of such alkylene polyamines are alkylenediamines such as ethylenediamine, propylenediamine-1,2, propylenediamine-1,3, tetramethylenediamine and hexamethylenediamine. The polyalkylene polyamines such as polyethylene polyamines, polypropylene polyamines, polybutylene polyamines and the like are examples of alkylene polyamines which may be used. Special examples of

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11 these are polyalkylene polyamines including diethylenetriamine, triethylene = tetramine, tetraethylene pentamine and dipropylenetriamine. Internal polyalkylene polyamines which may be used include methyl bis (3-aminopropyl) amine, methyl bis (2-aminoethyl) amine, and 4,7-dimethyltriethylethyltetramine. Mixtures of alkylene polyamines can be used if desired.

The relative amounts of alkylene polyamine and epichlorohydrin used may be varied depending on the particular alkylene polyamine used. In general, it is preferred that the mole ratio of epichlorohydrin to alkylene polyamide is above 1: 1 and less than 2: 1. For the preparation of a water-soluble resin of epichlorohydrin and tetraethylene pentamine, good results with molar ratios of approx. 1.4: 1 to 1.94: 1 · The reaction temperature is preferably in the range of approx. 40 ° C to approx. 60 ° C.

15

The following example illustrates the preparation of a dispersant of the above type.

Example B

20 µl a mixture of 29 »2 parts of triethylenetetramine and 70 parts of water, 44.4 parts of epichlorohydrin are added over approx. 12 minutes under periodic cooling. After the addition of epichlorohydrin, the reaction mixture is heated to 75 ° C and maintained at a temperature of ca. 70 ° C 25 to approx. 77 ° C for approx. 33 minutes, at which time the G-ardner-Holdt viscosity reached a value of approx. I. The resulting mass is diluted with 592 parts of water to form an aqueous solution having a solids content of approx. $ 11.7 and a pH of approx. 6.3.

2q Another suitable dispersant for use according to the invention is a poly (diallylamine) epihalohydrin resin. Resins of this type can be prepared in the manner described in IT.S.A. No. 3,700,623, which is hereby incorporated by reference.

A poly (diallylamine) epihalohydrin resin is the resinous reaction product of (A) a linear polymer having units of the formula

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.0Η? Ην / Ό

-HOC-C C- frS

d j j (i; H9C CHo \ / ir

R 1 wherein R is hydrogen or lower alkyl and R 1 is hydrogen, alkyl or a substituted alkyl group, and (B) an epihalohydrin.

In the above formula, each R may be the same or different and 5 may be hydrogen or lower alkyl as indicated. The alkyl groups contain from 1 to 6 carbon atoms and are preferably methyl, ethyl, isopropyl or n-butyl. R 'in the formula represents hydrogen, alkyl or substituted alkyl groups. R 'alkyl groups contain from 1 to 18 carbon atoms (preferably from 1 to 6 carbon atoms) such as methyl, ethyl, propyl, isopropyl, butyl, tertiary butyl, hexyl, octyl, decyl, dodecyl, tetradeyl and octadecyl. R * may also be a substituted alkyl group. Suitable substituents generally include any group which does not generate the polymerization through a vinyl double bond. Typically, the substituents may be carboxylate, cyano, ether, amino (primary, secondary or tertiary), amide, hydrazide and hydroxyl.

Polymers having units of the above formula can be prepared by polymerizing the hydrohalide salt of a diallylamine 20 CH9 ch9 U ^ It. Wherein R and R 1 are as above, either alone or as a mixture with other copolymerizable constituents in the presence of a free radical catalyst, and then neutralize the salt to form the polymer as a free base.

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13

Particular hydrohalide salts of the diallylamines which can be polymerized to form the polymeric units of the invention are diallylamine hydrochloride, N-methyldiallylamine hydrochloride, N-methyldialylylamine hydrobromide, 2,2 'dimethyl-N-methyldiallylamine hydrochloride.

C

N-ethyldiallylamine hydrobromide, N-isopyldiallylaminhydrochloride id, Nn-butyldiallylaminhydrine chloride, N-tert-butyldiallylamine hydrochloride, Nn-hexyldiallylamine hydrochloride, N-octadecyldiallylamine hydrochloride, N carboethoxymethyldiallyl = 1Π amine hydrochloride, Ν-β-methoxyethyldiallylamine hydrobromide, N₂-amino = ethyldiallylamine hydrochloride, N-hydroxyethyldiallylamine hydrobromide and N-acetohydrazide-substituted-diallylamine hydrochloride.

The diallylamines and N-alkyldiallylamines used to prepare the polymers used in the invention can be prepared by reaction of ammonia or a primary amine with an allyl halide using as catalyst for the reaction of a catalyst which promotes the ionization of the halide such as. sodium iodide, zinc iodide, ammonium iodide, cupribromide, ferric chloride, ferribromide, π n zinc chloride, mercuric iodide, mercuric nitrate, mercuric bromide, mercuric chloride and mixtures of two or more. Thus, e.g. N-Methyldi = allylamine is prepared by reaction of 2 moles of an allyl halide such as allyl chloride with 1 mole of methylamine in the presence of an ionization catalyst such as one of the above.

25

In the preparation of the homopolymers and copolymers, the reaction can be initiated by a catalytic redox system. In a redox system, the catalyst is activated by a reducing agent which produces free radicals without the use of heat. Reducing agents commonly used are sodium metabisulphite and potassium metabisulphite. Other reducing agents include water-soluble thiosulfates and bisulfites, hydrosulfites and reducing salts such as the sulfate of a metal capable of coexisting in more than one valence state such as cobalt, iron, manganese and copper. A particular example of such a sulfate is ferrous sulfate. The use of a redox initiator system has several advantages, the most important of which is efficient polymerization at lower temperatures. Usual peroxide catalysts such as tertiary butyl hydroperoxide, potassium persulfate, hydrogen peroxide and ammonium persulfate used in conjunction with the above reducing agents or

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metal activators can be used.

As mentioned above, the linear polymers of diallylamines which are reacted with an epihalohydrin may contain various units of formula I and / or contain units of one or more other copolymerizable monomers. lypically, the comonomer is another diallylamine, a monoethylene unsaturated compound containing a single vinyl group or vinylidene group or sulfur dioxide south and is present 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 repeating units have the formula I and from 0 to 95 $ of the repeating units are monomeric units derived from (1) a vinylidene monomer and / or (2) sulfur dioxide . Preferred comonomers include acrylic acid, methacrylic acid, methyl and other alkyl acrylics and methacrylates, acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl ethers such as the alkyl vinyl ethers, vinyl ethetyl ketones such as methyl vinyl ketone, the above formula II.

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Specific copolymers that can be reacted with an epihalohydrin include copolymers of B-methyldiallylamine and sulfur dioxide, copolymers of fl-methyldiallylamine and diallylamine, copolymers of diallylamine and acrylamide, copolymers of diallylamine and acrylic acid, copolymer and methyl acrylate, copolymers of di-allylamine and acrylonitrile, copolymers of M-methyldiallylamine and vinyl acetate, copolymers of diallylamine and methyl vinyl ether, copolymers of N-methyldiallylamine and vinylsulfonamide, copolymers of N-methyldiallyl amine and methyl vinylmethylamine 30 and acrylamide and terpolymers of ΪΓ-methyldiallylamine, acrylic acid and acrylamide.

The epihalohydrin which is reacted with the polymer of diallylamine can be any epihalohydrin, i.e. epichlorohydrin, epibromohydrin, epifluorohydrin or epiodohydrin, and is for stepwise epichlorohydrin. Generally, the epihalohydrin is used in an amount ranging from about 0.5 mol to approx. 1.5 mole and preferably approx. 1 mole to approx. 1.5 moles per mole of secondary plus tertiary amine found in the polymer.

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The poly (diallylamine) epihalohydrin resin can be prepared by "reacting a homopolymer or copolymer of a diallylamine as set forth above to react with an epihalohydrin at a temperature of from about 30 ° C to about 80 ° C and preferably from about 40 ° C to about 60 ° C, in-5 to the viscosity measured on a solution containing $ 20-30 $ solids at 25 ° C have ranged from 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 approx. $ 15 or less and the product is cooled to room temperature (about 25 ° C).

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The poly (diallylamine) epihalohydrin resin can be stabilized against gelling by adding to its aqueous solution sufficient water soluble acid (such as hydrochloric acid and sulfuric acid) to obtain and maintain a pH of approx. 2nd

The following example illustrates the preparation of a poly (diallylamine) epichlorohydrin resin.

Example 0 25

A solution of 69.1 parts of methyldiallylamine and 197 parts of 20 ° B hydrochloric acid in 111.7 parts of demineralized water is rinsed with nitrogen to remove air and then treated with 0.55 parts of tertiary butyl hydroperoxide and a solution of 0.0036 parts of ferrous sulfate. in 0.5 parts of water.

The resulting solution is allowed to polymerize at 60-69 ° C for 24 hours to form a polymer solution containing ca. $ 52.1 solids with a specific viscosity fraction of Q, 22. 122 parts of the above solution are adjusted to pH 8.5 by adding 95 parts of 3.8 $ sodium hydroxide and then diluted with 211 parts of water and combined with 60 parts of epichlorohydrin. The mixture is heated to 45-55 ° for 135 hours until the Gardner-Holdt viscosity of a sample cooled to 25 ° C reaches B +. The resulting solution is acidified with 25 parts of 20 DEG C. hydrochloric acid and heated to 60 DEG C. until the pH becomes constant 2.0. The resulting resin solution has a solids content of $ 20.8 and a Brookfield viscosity = 77 cp (measured using a Brookfield viscometer model ITT # 1 spindle at 60 rpm with screen , plate).

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Example I)

One example illustrates the preparation of rosin reinforced with fumaric acid. 6.5 parts of fumaric acid are added at a temperature of approx. 205 ° C to 93 "5 parts tall oil rosin resin" treated with j_Q formaldehyde. A reinforced cellophonium resin contains 6.5 $ fumaric acid, of which essentially it is all in chemical or added form.

Example 1

Eer a solution is prepared by dissolving 300 parts of a reinforced 20 rosin resin, as prepared in Example E, in 300 parts of benzene,

One solution is thoroughly mixed with 400 parts (50 parts solids) of a solution of aminopolyamide-epichlorohydrin resin prepared as in Example A, diluted with 350 parts water to give a premix which is homogenized twice at 140 kg / cm The resulting product is a stable oil-in-water emulsion. Essentially, all benzene is removed from the emulsion by distillation under reduced pressure with the container temperature of approx. 40 ° C. The solids content of the resulting dispersion is approx. $ 35. Of the solid, approx.

$ 30 reinforced rosin resin, and approx. $ 5 is epichlorohydrin aminopolylyamide epichlorohydrin resin. The egg dispersion is stable for a period of approx. 6 months.

Example 2 Example 1 is repeated using 200 parts of reinforced rosin resin prepared as in Example E, dissolved in 200 parts of benzene with 150 parts of aminopolyamide-epichlorohydrin resin (18.8 parts of solid) mixed with 550 parts of water. The solids content of the resulting aqueous dispersion is approx. $ 24. Of the solids content, approx. 22 $

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reinforced rosin resin and approx. 2 $ aminopolyamide epichlorohydrin resin. The dispersion has good stability.

Example 3 Example 1 is repeated using 750 parts of aminopolyamide epi = chlorohydrin resin (9'3.8 parts of solid) with 750 parts of water. The solids content of the resulting aqueous dispersion is approx. $ 22. Of the solids content, approx. $ 17 reinforced rosin resin, and approx. $ 5 is aminopolyamide-epichlorohydrin resin. The dispersion has good stability.

Example 4

Example 1 is repeated using 500 parts aminoamide epichloro = 15 hydrine resin (62.5 parts solid) with 250 parts water. The solids content of the resulting aqueous dispersion is approx. $ 35. Of the solids content, approx. $ 29 reinforced rosin resin, and approx. $ 6 is aminopolyamide-epichlorohydrin resin. The dispersion has good stability.

20

Example 5

Example 1 is repeated using only 150 parts of benzene to dissolve the reinforced rosin resin and only 250 parts of water to dilute the aminopolyamide-epichlorohydrin resin. The total solids content of the resulting aqueous dispersion is approx. 37.5 $.

Of the solids content, approx. $ 32 reinforced rosin resin, and approx. 5> 5 $ is aminopolyamide-epichlorohydrin resin. The dispersion has good stability.

Example 6

Example 1 is repeated using 600 parts of benzene to dissolve the reinforced rosin resin. The total solids content of the resulting aqueous dispersion is approx. $ 35. Of the 35 solids content, approx. $ 30 reinforced rosin resin, and approx. $ 5 is aminopolyamide-epichlorohydrin resin. The dispersion has good stability.

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Example E

This example illustrates the preparation of rosin reinforced with fumaric acid. 14 parts of fumaric acid are added at a temperature of approx. 205 ° C to 86 parts tall oil rosin resin treated with formaldehyde. The eumaric acid is dissolved in the molten tall oil rosin-5 resin and thus reacts to form tall oil rosin reinforced with fumaric acid. After substantially all of the fumaric acid has reacted with the tall oil rosin resin, the reinforced rosin resin is cooled to room temperature (about 23 ° C). The reinforced rosin resin contains 14 $ fumaric acid, of which generally 10 are in chemical or added form.

Example 7

A solution is prepared by dissolving 128.5 parts of reinforced cellophonium resin as prepared in Example E, 21.5 parts of tall oil rosin treated with formaldehyde and 150 parts of a copolymer of vinyltoluol and α-methylstyrene having a molecular weight of about . 1400, a softening point measured with ball and ring of approx. 120 ° C and an acid number less than 1, in 300 parts of benzene. This solution is thoroughly mixed with 400 parts (50 parts solid) of an aminopolyamide-epi-chlorohydrin solution prepared as in Example A, diluted with 350 parts of water to give a premix which is homogenized twice at 210 kg / cm 2. is a stable oil-in-water emulsion, from which substantially all benzenes) are then removed by distillation under reduced pressure with the container temperature of approx. 40 ° C. dispersions

k O

the solids content is approx. $ 33. Of the solids content, approx. $ 14.2 copolymer of vinyl toluene and α-methyl styrene, ca. $ 4.8 is aminopolyamide epichlorohydrin resin, and approx. $ 1.9 is bound fumaric acid.

Example 8

Example 7 is repeated using 134 parts tall oil rosin treated with formaldehyde and 37.5 parts copolymer of vinyl = toluene and α-methyl styrene. The solids content of the resulting dispersion is approx. $ 34. Of the solids content, approx. $ 3.6 copo-35 glue, approx. $ 4.8 is aminopolyamide epichlorohydrin resin, and approx. $ 1.9 is bound fumaric acid. The dispersion has good stability.

19 DK 155219 B

Example 9

A solution is prepared by dissolving 128.5 parts of reinforced rosin resin as prepared in Example E, 21.5 parts of tall oil-rosin lyophilized treated with formaldehyde and 150 parts of a fully refined paraffin wax (melting point about 65 ° C) in 300 parts of benzene at 5 mixing and heating to approx. 60 ° C to dissolve the paraffin wax. This solution is thoroughly mixed with 400 parts (50 parts solid) of an aminopolyamide epichlorohydrin resin solution prepared as in Example A, diluted with 350 parts water. After mixing the two solutions, the diluted aminopolyamide epichlorohydrin resin is heated to ca. 60 ° C. The hot premix is homogenized twice at 2 o 280 Rg / cnv in a homogenizer which is preheated to approx. 60 ° C. The resulting product is a stable oil-in-water emulsion from which substantially all benzene is removed by distillation under reduced pressure with the container temperature of 40-50 ° C. The total solids content of the aqueous dispersion is approx. 31 $. Of the solids content, approx. $ 13.8 wax, approx. $ 4.4 is aminopolyamide epichlorohydrin resin, and ca. $ 1.8 is bound fumaric acid. The dispersion has good stability.

Example 10

Example 9 is repeated using 14.5 parts tall oil rosin treated with formaldehyde and 30 parts fully refined paraffin wax. The total solids content of the resulting aqueous dispersion is approx. $ 36. Of the solids, approx. $ 3.1 wax, approx. $ 5.2 is aminopolyamide epichlorohydrin resin, and ca. 2 $ is bound fumaric acid. The dispersion has good stability.

Example E 30

A reaction boiler equipped with a steam jet vacuum system is filled with 704 parts of water and 476 parts of epichlorohydrin. The steam jet vacuum system is switched on to discharge vapors through a capacitor and prevent them from escaping through the open manhole. 420 parts of an amine marketed 35 by Hercules Incorporated under the term "amine 248" is added with stirring for 35 minutes while the temperature is allowed to rise to 70 ° C. Cooling water is required to limit the temperature to 70 ° C. Upon completion of amine addition, the resulting mixture has a pH of 7.8 and a viscosity of A after Gardner-Holdt.

20

DK 155219B

6 parts of 20% UaOH are added to speed the reaction. After 2 hours and 40 minutes at approx. 70 ° 0, the viscosity reached a U + value, and the resin solution was diluted with 640 parts of water, reducing the viscosity to approx. C-. A total of 44 parts of 20 $ UaOH is added in four separate portions over a period of 1/3 / hour to speed the reaction. A viscosity of S is reached after 3 hours and 35 minutes and the reaction is quenched and diluted with 26 parts of concentrated sulfuric acid in 1345 parts of water. This gives an aqueous solution with a solids content of $ 23.5, a viscosity of D and a pH of 4.4. 0 Additional HgSO4 and water are added to give a solution with a ρΞ value of 4 and a solid content of $ 22.5. The resin solution is filtered through 100 μ filter cartridges to give a total of 3336 parts of product. Amine 248 is an industrially available liquid blend of long chain aliphatic polyamines. At least $ 75 of amine 248 5 consists of bis (hexamethylene) triamine and higher homologue. The remainder consists of low molecular weight amines, nitriles and lactams.

Example 11 g A solution is prepared by dissolving 300 parts of reinforced colonium resin, as prepared in Example D, in 300 parts of benzene. This solution is thoroughly mixed with 217.4 parts (50 parts solids) of the reaction product of epichlorohydrin and polyamine prepared as in Example E and diluted with 533 parts water to form a mixture which is homogenized twice at 2000 psi. The resulting product is a stable oil-in-water emulsion, from which substantially all of the benzene is then removed by distillation under reduced pressure at ca. 40 ° 0th The solids content of the resulting dispersion is approx.

$ 35. Of the solids content, approx. $ 30 reinforced rosin-0 resin, and approx. $ 5 is the reaction product of epichlorohydrin and polyamine. The dispersion has good stability.

Example 12

A solution is prepared by dissolving 128.5 parts of reinforced cellophonium resin prepared as in Example E, 141.5 parts of tall oil rosin resin and 30 parts of fully refined paraffin wax in 300 parts of benzene by mixing and heating to 60 ° C. dissolve the paraffin wax. This solution is thoroughly mixed with 217.4 parts (50 g of solid) of the reaction product of epichlorohydrin and polyamine prepared

DK 155219B

as in Example F and diluted with 533 parts of water. Before mixing the two solutions, the diluted reaction product of epichlorohydrin and polyamine is heated to ca. 60 ° C. The hot premix is homogenized twice at 2000 psi in a homogenizer preheated to approx.

® 60 ° C. The resulting product is a stable oil-in-water emulsion, from which substantially all the benzene is then removed by distillation at atmospheric pressure, below which the temperature of the product rises from approx. 75 ° 0 to approx. 100 ° 0th The solids content of the resulting dispersion is approx. 36.0 $. Of the solids content, approx. $ 3.1 paraffin wax, approx. $ 5.2 is the reaction product of epichlorohydrin and polyamine, and ca. 2 $ is bound fumaric acid. The dispersion has good stability.

Example & To a solution of 26.2 parts of iminobis (propylamine), also called bis (3-aminopropyl) amine, in 82 parts of water, 55.6 parts of epichlorohydrin are added in one portion. The resulting mixture is kept between ca. 43 ° C and approx. 58 ° C by external cooling for approx. 0-, 7 hours until the exothermic phase of the reaction is over. The mixture is then heated to ca. 70 ° C for approx. 0.8 hours, during which the viscosity of the mixture increases to a G-ardner-Holdt value above J. The mixture is then diluted with 364 parts of water and adjusted to pH 4.5 with sulfuric acid. The resulting resin solution contains approx. $ 16.5 solids and has a Brookfield viscosity of 10 centipoise (spindle 1, 60 rpm).

25

Example 13

Example 1 is repeated using 301 parts (50 parts solid) of a reaction product of epichlorohydrin and polyamine prepared as in Example G with 300 parts water as the aqueous phase. The premix 30 2 is homogenized twice at 210 Kg / cm. The total solids content of the resulting aqueous dispersion suspension is approx. $ 39. Of the total solids content, approx. $ 5.6 reaction product of epichlorohydrin and polyamine, and ca. $ 33 is reinforced rosin resin. The dispersion has good stability.

35

Example H

74 parts of epichlorohydrin are added to a solution of 37.8 parts of tetra = ethylene pentamine in 112 parts of water over 15 minutes. The temperature

22 DK 155219 B

increases to approx. 55 ° C. The mixture is then heated from the outside and held at ca. 60 ° C for 1/2 hour, then at 70 ° C for approx. 3 hours, during which the Gardner-Holdt viscosity rises to B. The resulting resin solution is then cooled to room temperature (about 25 ° C) and aged for 11 days, 5 during which the resin solution reaches a Gardner-Holdt viscosity of Z. The resin solution is diluted then with 524 parts of water. The resulting solution contains approx. $ 15.3 non-volatile solids and has a Brookfield viscosity of 23 centipoise (Model DTE1 Viscometer, # 1 spindle, 60 rpm, 25 °).

10

Example 14

Example 13 is repeated using 327 parts (50 parts solid) reaction product of epichlorohydrin and polyamine prepared as in Example H and 327 parts water as a water phase. The total solids content of the resulting product is approx. $ 37. Of the total solids, approx. $ 5.4 reaction product of epichlorohydrin and polyamine, and ca.

$ 32 is reinforced rosin resin.

Example J

To 250 parts of methyldiallylamine, 230 parts of 37 $ hydrochloric acid are slowly added in approx. 240 parts of demineralized water. The mixture is cooled as needed to prevent volatilization of materials due to the heat of reaction. The pH of the resulting mixture is then adjusted to 3.1 by the addition of additional (19 parts) of methyldiallylamine. After the oxygen in the reaction vessel is displaced with nitrogen, 2.2 parts of t-butyl hydroperoxide are added. This is followed by 0.0014 parts of ferrous sulfate heptahydrate in 1.1 parts of demineralized water. When the reaction mixture is heated to 60 ° 0, a mild exothermic reaction occurs, 30 °

which briefly leads the reaction temperature up to approx. 66-70 ° C. IN

for the remainder of the 24 hour reaction time, the temperature is maintained at approx. 60 ° C.

After cooling to 25-30 ° C, the total solids content of the product is approx. $ 48.4, and RSV is 0.21 cp. To 220 parts of the above polymer solution, sufficient (about 160 parts) of sodium = 35 hydroxide solution (10 parts of sodium hydroxide in 376 parts of water) is added to adjust the pH to approx. 8.5. The neutralized polymer solution is diluted with 366 parts of demineralized water and then heated to ca. 40 ° C. To the hot solution are added 106 parts of epichlorohydrin, and the reaction is further heated to react the epichlorohydrin at ca.

23 DK 155219 B

50-55 ° C. The reaction is continued until the reaction mixture reaches a Gardner viscosity of approx. B + (about 1.7 hours). At this point, the reaction is cooled by rapid addition of ca. 35 parts 37 $ hydrochloric acid to give a final pH of approx. 2. 859 parts 5 of a product containing approx. $ 20.7 solid. A number of experiments are carried out approximately as described, so that a total of approx. 7395 parts product with approx. $ 20.4 solid.

Example 15 10

Example 13 is repeated using 245 parts (50 parts solid) of an epichlorohydrin modified tertiary amine polymer prepared as in Example J, diluted with 505 parts water as the aqueous phase. The total solids content of the resulting stable aqueous suspension is approx. $ 33. Of the total solids, approx. $ 4.7 tertiary amine polymer, and approx. $ 28 is reinforced rosin resin.

Example 16? A solution is prepared by dissolving 300 parts of reinforced carbon resin prepared as in Example D in 200 parts of benzene in a suitable container equipped with excellent means for stirring by means of a propeller-type air motor stirrer. To this well stirred solution are added 400 parts (50 parts solid) aminopolyamide epichloro (hydrine resin prepared as in Example A. This results in a stable water-in-oil emulsion which is reversed by the rapid addition of 350 parts cold ( After about 20 minutes after the addition of water, stirring is continued for about 23 minutes to ensure complete conversion to a stable oil-in-water emulsion, from which substantially all the benzene is then removed by distillation under reduced pressure with a container temperature of about 40 ° C. The total solids content of the resulting stable aqueous suspension is about $ 34. Of the total solids, about 4? $ 8 is aminopolyamide-epichlorohydrin resin, and about 29 $ is reinforced rosin resin.

5

Example 17

In order to determine the sizing efficiency of the aqueous dispersion of Example 1, handmade sheets are made using the dispersion as the only sizing agent. For making the handmade sheets

DK 155219 B

24, a 50:50 blend of Rayonier bleached softwood pulp and Weyerhaeuser bleached hardwood pulp will be suspended in standard hard water and turned to 500 Canadian standard liberties in a Noble and Wood Dutchman. A 2-liter portion of the Dutch slurry, diluted to 2.5 $ solids by weight, is treated with enough alum to give a pH of approx. 4.5. The slurry is then diluted to a consistency of $ 0.27 in the proportioning apparatus using acidic alumina for dilution.

• ° The dilution water is prepared by lowering the pH of water

of moderate hardness to 5.0 with sulfuric acid and then add enough alum to give 5 parts of soluble aluminum per liter. million parts. 1 liter portions of the proportioning device's pulp slurry are treated with enough of the glue of Example 1 * 5 to give $ 0.4 glue calculated on the dry weight of the pulp. They are further diluted with acidic alumina to a bucket consistency of $ 0.025 to form a handmade sheet weighing 18 kg (60 x 90 cm, 500 sheets of rice) using a Noble and Wood papermaking apparatus. A closed water system is used. The formed sheets are wet pressed to a content of 33 $ solids and then dried at 116 ° C

on a steam drum dryer. All handmade sheets are conditioned for at least 7 days at 22 ° C and $ 50 relative humidity and tested under these conditions for sizing properties using Hercules sizing test. Using an ar * .2 sample solution for 80 $ 15 reflectahs, the sample time is approx. 139 seconds.

Example 18

To determine the sizing efficiency of the aqueous dispersion of Example 1 at pH 6.5, the preparation of handmade sheets of Example 17 is repeated, using only $ 0.4 alum and adjusting the pH of the system to pH 6.5 as needed. . The results of Hercules gluing test in this case are 82 seconds.

J5 Example 19

To determine the sizing efficiency of the aqueous suspension of Examples 2, 3, 4, 5, 13, 14 and 15, surface sizing tests are performed using bleached kraft paper (18 kg per 500 sheets of 60 x 90 cm) made at pH 6.5 with $ 0.5 added alum. The sheets

DK 155219 B

25 is handled using a small horizontal laboratory sizing press by sampling the aqueous suspensions diluted to ca. $ 0.54 to the squeeze point of the sizing press and pass the sheets through the solution before being squeezed by the sizing press rollers. Under these conditions, the sheets occupy approx. 70 $ of their weight of glue press solution, so that approx. $ 0.58 glue on the sheet. The glued sheets are dried for approx. 18 seconds on a laboratory drum dryer with a surface temperature of approx. 95 ° 0th The sheets are aged for 4 days and then tested using No. 2 sample solution with Hercules bonding sample for $ 85 reflectance. The following table summarizes the results.

Hercules sizing test Glue from example Results in seconds 15 2 280 3 366 4 372 5 411 13 339 _ 14 305 20 15 245

Example 20

To determine the sizing efficiency of the aqueous suspensions of Examples 7, 8, 9, 10, 11 and 12, surface sizing is performed as in Example 19, except that the adhesive solutions are only approx. $ 0.45, so that only approx. $ 0.32 of each glue.

Hercules glue test for $ 85 reflectance

Glue from example Results in seconds 7 183 8 311 35 9 239 10 217 11 216 12 140

Claims (6)

Example 21 In another demonstration of the sizing efficiency of the aqueous suspension prepared as in Example 1 ", among other things, $ 0.4 of the solids in this suspension and about $ 0.4 of alum are applied for about 4, 5 $ Pen-ford rubber 280 (ethoxylated corn starch) on the surface of an 18 kg bleached kraft paper sheet prepared at a pH of about 7.5 In this case, No. 2 sample solution used in the Hercules glue sample gives $ 80 reflectance 252 seconds. As required) ---------- 1. Aqueous dispersion of reinforced rosin resin for use in bonding paper consisting essentially of the following by weight: (A) from 5% to 50% reinforced rosin resin, (B) from 0.5% 5 to 10% dispersant, and ( C) water to 100%, with the reinforced rosin rosin optionally mixed with rosin rosin and extender, characterized in that component (B) is selected from the group consisting of (1) a water-soluble polyaminopolyamide-epichlorohydrin resin, (2) a water-soluble alkylene polyamine -3 epichlorohydrin resin and (3) a water soluble poly (diallylamine) epichlorohydrin resin. Aqueous dispersion of reinforced rosin resin according to claim 1, characterized in that (A) is from 10% to 40% and B from 5 to 1% to 8%. Aqueous dispersion according to claims 1 and 2, characterized in that the polyaminopolyamide moiety in component (B) is derived from adipic acid and diethylenetriamine. An aqueous dispersion according to claim 2, characterized in that the reinforced rosin resin is stretched with a tensile agent in an amount of 10% to 100% by weight based on the weight of rosin rosin. Aqueous dispersion according to claim 2, characterized in that the component (A) is a mixture of reinforced rosin resin DK 155219 B and rosin resin with 25% to 95% reinforced rosin resin and 75% to 5% rosin resin. Aqueous dispersion according to claim 1, characterized in that the component (A) is a mixture of reinforced rosin resin, rosin resin and extensor comprising 25% to 45% reinforced rosin resin, 5% to 50% rosin resin and 5% to 50%. % extender. 10