FI81860C - NOW FOERFARANDE FOER LIMNING AV PAPPER. - Google Patents

Description

1 81860

The present invention relates to alkenyl succinic anhydrides (ASA) and processes for their preparation which are used for gluing cellulosic materials such as paper products, and more particularly to water-soluble vinyl addition polymers for better emulsification of ASA adhesives.

Alkenyl succinic anhydrides useful in bonding cellulosic materials have achieved considerable commercial success. These materials are first disclosed in U.S. Patent 3,102,064, which describes a particular class of chemicals having the general formula

Wherein o represents a dimethylene or trimethylene radical, and R 1 represents a hydrophobic group containing more than 5 carbon atoms, which may be selected from the group consisting of •; · 'Alkyl, alkenyl, aralkyl or aralkenyl groups.

According to this patent, for the effective use of ASA adhesives, sizing agents must be used in conjunction with an agent that is either cationic in nature or capable of ionizing or dissociating to produce one or more cations or other positively charged groups. Cationic agents, as defined in this reference, include "alum, aluminum chloride, long chain fatty acid amines, sodium aluminate, polyacrylamide, chromium sulfate, animal glue, cationic thermosetting resins, and polyamide polymers." Particularly preferred are cationic. various cationic starch derivatives have been identified as such, including primary, secondary, 2,881,860 tertiary or quaternary amine starch derivatives, amine starch derivatives and other cationic nitrogen-substituted starch derivatives, as well as cationic sulfonium starch and sulfonium sulfonium derivatives. Such derivatives, as disclosed in the patent, can be prepared from all types of starches, including corn, tapioca, potato, etc.

As the commercial use of adhesives of the type described above increases, serious problems remain in adding adhesives to the pulp 10 prior to forming into sheets or other useful forms. Part of the problem has been that ASA adhesives are not water soluble and must accordingly be suspended homogeneously in the pulp so that the adhesive can have sufficient contact with the pulp fibers and thus give the desired effect to the final product.

Although the Katonic substances disclosed in U.S. Patent 3,103,061 have been successful, there has been a need in the paper industry to find a more effective "cationic agent" for 20 ASA adhesives. In addition, such a cationic agent would advantageously aid in the retention of the adhesive with the fiber and, if desired, increase the wet and / or dry strength of the final sheet material.

•; It is an object of the present invention to provide additives which emulsify the ASA adhesive into the pulp and improve the retention of the adhesive on the fibers.

The invention relates to a process for the preparation of an emulsified alkenyl succinic anhydride adhesive which is useful in the preparation of glued paper products, wherein the emulsion contains water, alkenyl succinic anhydride and a cationic agent.

: The invention is characterized in that a water-soluble cationic vinyl addition is used as the cationic substance. a polymer having a molecular weight of 10,000 to 1,000,000.

U.S. Pat. No. 3,102,069 describes additives for emulsifying ASA adhesives and states that cationic water-soluble polymers can be used which do not dry.

II

3,81860 However, there is no embodiment. The presence of corn starch in the known composition does not contribute to the formation of a stable emulsion obtained by the present invention. Said U.S. patent lists 5 different cationic polymers, including polyacrylamide. However, one skilled in the art will recognize that polyacrylamide is not cationic in nature. Column 12, lines 1-24, shows the only factual information on the use of polyacrylamide. This material has been used in conjunction with a corn starch acid-10 ester emulsifier. There is no mention of cathionically modified or substituted polyacrylamides or the degree of cationization. Molecular weight is also not given. Since polyacrylamide has been used in an amount of 0.1% by dry weight, this suggests that the molecular weight of the polyacrylamide used is high.

U.S. Patent 4,040,900 relates to the use of certain nonionic surfactant emulsifiers in an amount of 3 to 20, preferably 5 to 20 parts by weight in compositions containing 80 to 97, preferably 90 to 95 parts by weight of cyclic dicarboxylic acid hydride adhesive. According to the examples, ASA-type adhesives containing 10% of a specific: nonionic surfactant emulsifier are preferred. The particle size of the emulsifier should be small.

: According to the present invention, surprising results have been obtained by combining an ASA adhesive with a water-soluble low molecular weight vinyl addition polymer to improve the emulsification of the adhesive. The advantage is that the driving characteristics of the paper machine are improved: no clumping or tarry deposits occur.

In a particularly useful embodiment of the present invention, 81860 4

A surfactant has also been used in the preparation of the ASA adhesives of this invention. This surfactant may be anionic, nonionic or cationic in nature. The surfactants used have generally been water soluble and have HLB values in the range of about 8 to about 30 or greater, and preferably about 8 to 15. The surfactant is generally used to make an ASA adhesive simply by mixing it with the crude ASA. The ASA used in accordance with the present invention and its preferred embodiment

the adhesive generally contains 75 to 99.5 parts by weight of ASA and preferably 90 to 99 parts by weight of ASA together with 0.5 to 25 parts by weight, preferably 0.75 to 10 parts by weight and most preferably 1.0 to 5 parts by weight with a surfactant.

Surfactants are preferably added to the ASA prior to emulsification in the aqueous medium. The surfactant may also be added to the aqueous medium prior to the addition of ASA.

Surfactants useful in this invention are further described in U.S. Patent 4,040,900, which is incorporated herein by reference. The relevant parts of U.S. Patent 4,040,900 begin in column 4, line 34 and continue in column 5, line 46. Other parts of this patent are also relevant.

Suitable classes for use as surfactants in this invention include: ethoxylated alkyl phenols such as nonylphenoxypolyethoxyethanols and octylphenoxypolyethoxyethanols; polyethylene glycols such as PEG 400 monooleate and PEG 600 dilaurate and saunas than other substances including certain ethoxylated phosphate esters.

;;; Preferred surfactants for use in our invention are GAFAC RM510 and GAFAC RE610, both; :: free acids of complex phosphate esters, prepared by GAF Corporation.

Il 5 81 860

Water-Soluble Polymers Water-soluble polymers useful as cationic agents in this invention include water-soluble vinyl addition homopolymers and copolymers having molecular weights greater than 10,000 and less than 1,000,000, with at least 10% by weight and up to 100% by weight of the polymeric monomer or cationic monomer. Preferably, at least 15% and at most 95% by weight of the meric units in the polymer 10 may be cationic or cationically adapted monomers. Most preferably, 20-75% by weight of the meric units in the polymer or copolymer are cationic or cationically modified.

The polymers selected for use in this invention generally have a molecular weight greater than 10,000 and less than 1,000 Q00. Polymers of this type should preferably be water soluble, and the preferred molecular weight has been found to be between 20,000 and 750,000. Most preferably, the polymers used have molecular weights in the range of 50,000 to 150,000.

The polymers which can be used in the practice of this invention, but are not limited to the example and homopolymers include: acrylamide-dimethylaminoethyl acrylate, quaternary 25-blooded acrylamide-dimethylaminoethyl acrylate, acrylamide, diethylaminoethyl, quaternary akryyliamididietyyliaminoetyyliakrylaatit, acrylamide, dimethylaminoethyl methacrylate, acrylamide-quaternary dimetyyliaminoetyylimetakry-30 plates, acrylamide diallyldimethylammonium chloride, polydiallyl dimethyl ammonium chloride, polydimethylaminoethyl methacrylate and quaternary polydimethylaminoethyl methacrylates, polymethacrylamidopropyl •; : trimethylammonium chloride and acrylamide methacrylamine-; 35 dopropyltrimethylammonium chloride.

6 81860

Also useful are polymers and copolymers of acrylamide which have been subjected to a Mannich reaction with formaldehyde and a secondary lower alkylamine, which polymers may or may not be quaternized.

As can be seen, all polymers useful in this invention are cationically charged or water soluble. Many are made from vinyl addition monomers, although condensation polymers also work.

10 Since the number of possible cationically charged monomers that produce a water-soluble polymer is virtually unlimited, and it is assumed that all water-soluble, cationically charged vinyl addition polymers having a molecular weight of 10,000 or more but less than 1,000,000 work, we do not want to limit to the list above.

The polymers used, as described above, can be copolymers and even terpolymers of various vinyl addition monomers. Although acrylamide is a preferred nonionic monomer for use in the preparation of. Copolymers useful in this invention, other nonionic monomers such as methacrylamide and even certain anionically charged monomers such as acrylic acid, methacrylic acid, various sulfonated water-soluble vinyl addition monomers, etc. may be used.

The polymers used in this invention may be in the form of water-in-oil emulsions (such as those described in U.S. Re 28,474 and 28,576, both of which are incorporated herein by reference), dry powders, or dilute aqueous solutions. To use the polymers of the subject invention ASA

in the emulsification of adhesives, the polymer must first be prepared; aqueous solution. In the case of water-in-oil emulsions of vinyl addition polymers, we have found that the water-soluble surfactants used to invert emulsions in water-in-oil are not harmful.

II

7 81860 effect on the activity of the polymer used to emulsify the ASA adhesive. In preparing a polymer solution in water-in-oil from an emulsion polymer, a useful method or apparatus for forming a solution is disclosed as an example in U.S. Patent 4,057,223, which discloses a blending group.

Depending on the molecular weight and cationic charge of the polymer, 0.01 to 25% and preferably 0.1 to 10% by weight of the final adhesive emulsion to be added to the pulp feedstock may be polymer.

The ASA emulsions fed to the pulp slurry according to the present invention generally contain: 50-99.9% by weight of water, 0.1-50% by weight of ASA, 0.001-25.0% by weight of water-soluble polymer.

Preferably, these emulsions contain: 50-99.9% water, 0.01-40% ASA, 0.010-10% polymer.

Most preferably, the ASA emulsion contains 0.01 to 7.5 and generally 0.01 to 5.0 parts of polymer.

The polymers are thus used in the preparation of dispersions or emulsions of the ASA sizing material.

The polymers of this invention can be used to emulsify ASA or can be added to previously formed ASA emulsions. In either case, the polymer promotes the behavior of the emulsion compared to emulsions that do not contain polymer. When the polymer is added to an ASA emulsion that has already been formed, conventional 3Q emulsifiers should be used in addition to the polymer.

When adding or using ASA during emulsion preparation, no additional emulsifier needs to be used.

To test the subject invention, the following experiments were performed. The polymers listed below were obtained commercially or prepared as shown.

8 81860

Example 1

Acrylamide solution copolymers of the types DMAEM-MeCl quat., MAPTAC and polyDADMAC, molecular weights ranging from 10,000 to 400,000, were evaluated as ASA emulsifiers and retention aids. These new sizing compositions were compared in their ASA particle size, physical emulsion stability, and sizing behavior to conventional ASA emulsions in water or cationic starch. A description of these polymers is given in Table I.

1Q ASA emulsions in water were prepared by combining 95 parts of distilled water and 5 parts of ASA in an Eberbach semi-microemulsion cup. The mixture was dispersed for 3 minutes at high speed. The resulting emulsion was diluted to 0.50% with distilled water based on ASA dry matter and used in Example 1. ASA emulsions in cationic starch were first prepared by hydrating 5 parts of pregelatinized cationic potato starch in 95 parts of water and stirring for 30 minutes. Adhesive emulsions were then prepared by combining 75 parts of starch slurry in 25 parts of ASA in an emulsion cup and dispersing for 25 seconds. This emulsion was diluted to 0.50% siAA based on dry matter and used in Example 2. Finally, ASA emulsions in vinyl addition polymers were prepared by dispersing ASA in polymer solutions in a ratio of 5: 1 based on dry matter. These emulsions were diluted to 0.50% ASA based on dry matter by the method described above. Examples 3-8 illustrate a new use of these addition polymers.

ASA emulsions were tested separately in paper slurry 30 with a composition of 50 percent recycled corrugated board, 50 percent recycled newsprint. Other sludge parameters were a consistency of 0.5%, 400 Canadian Standard Free, pH 7.5, and 25 ° C, to which 12.5 ppm hydrated aluminum sulfate was added. Hand sheets with a basis weight of 22.5 kg per 2,35,297 m were prepared according to TAPPI T-205 methods.

Il 9 81860

The sizing compositions listed above were added to the paper slurry just prior to forming the wet paper roll in portions of 0/10 and 0/15 percent of the paper dry matter. The hand sheets were immediately dried on a rotary-5 drum to 98% dry matter. The results are shown in Table I.

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n 81860

Example 2

Vinyl addition polymers such as acrylamide copolymers DMAEM-MeCl quat. or MAPTAC and polyDADMAC, were further evaluated as ASA emulsifiers and retention aids. These new sizing compositions were compared in terms of their ASA emulsion particle size, their physical emulsion stability as they aged, and their sizing behavior compared to conventional ASA emulsions in water or cationic starch. The molecular weight of these polymers ranged from 10,000 to 400,000. The description of these polymers is shown in Table II.

ASA emulsions in water were prepared by combining 95 parts of distilled water and 5 parts of ASA in a laboratory in a 0.22 kg Osterizer cup. The mixture was dispersed at high speed for 15 minutes. The resulting emulsion was diluted with distilled water to 0.50% based on ASA dry matter and used in Example 9. ASA emulsions in cationic starch solution were first prepared by hydrating 5 parts of pregelatinized cationic potato starch in 95 parts of water and stirring for 30 minutes. The adhesive emulsions were then prepared by combining 95 parts of the starch solution with 5 parts in an ASA Osterizer cup and dispersing the adhesive for 25 seconds. This emulsion was diluted to 0.50% based on ASA solids 25 and used in Example 10. ASA emulsions in vinyl addition polymers were prepared by dispersing ASA in polymer solutions in a 1: 1 ratio of ASA polymer solids in an Osterizer cup for 5-30 seconds. These emulsions are then diluted to 0.50% based on ASA dry matter as described above. Examples 11-16 illustrate a new use of these vinyl addition polymers.

Each ASA emulsion was tested separately in a paper slurry having a composition of 50 percent bleached softwood sulfate cellulose and 50 percent bleached hardwood sulfate cellulose. Other sludge parameters were 81,860 12 with a consistency of 0.5 percent, 330 Canadian Standard Freeness, pH 7.3, and 27 ° C. Hand sheets with a basis weight of 22.5 kg per 2,297 m were prepared according to TAPPI T-205 methods. The sizing compositions listed above were added to the paper-5 slurry just prior to wet paper roll formation in portions of 0.20% ASA dry matter based on paper dry matter. The hand sheets were immediately pressed to a residual moisture content of approximately 50% and dried in a tumble dryer to 98% based on the dry matter of the paper. The results are shown in Table II below.

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Example 3

The following examples further illustrate the new use of DMAEM-MeSQ, DMAEA-MeSQ, DEAEA-MeSQ and DADMAC type acrylamide copolymers having an molecular weight of more than 1,000,000 as emulsifying and retention aids for alkenyl succinic anhydride sizing compositions. The ASA emulsions thus formed were compared in terms of their particle size and sizing behavior compared to ASA aqueous emulsions and conventional emulsions made from cationic starch. For comparison, ASA emulsions in water were prepared by combining 95 parts of distilled water and 5 parts of ASA in an Eber-Bach semi-microemulsion cup and dispersing the adhesive for 60 seconds. The resulting emulsion was diluted to 0.50% based on ASA solids with water and used in Example 17. ASA emulsions in cationic starch were first prepared by hydrating three parts of pregelatinized cationic potato starch in 97 parts of stirred cold water for 30 minutes. Emulsions were then prepared with two ASA-starch dry matter ratios of 1: 1 and 3: 1 dis-20 by percolating 30 parts of ASA to 70 parts of 3% cationic starch or 9 parts of ASA to 91 parts of 3% cationic starch using a semi-microemulsion cup, respectively. The resulting emulsions were diluted to 0.5% based on ASA solids with water and used in Examples 25 19 and 20, respectively.

Polymer solutions were prepared by hydrating 0.6 parts (as polymer solids) of the acrylamide copolymers listed below to 99.4 parts of water, respectively, providing sufficient time and mixing for complete hydration. Emulsions were then prepared with two ASA-polymer dry matter ratios of 10: 1 and 3: 1 by dispersing 6 parts of ASA in 94 parts of 0.6% polymer dry solution or 1.8 parts of ASA in 98.2 parts of 0.6% polymer dry matter. correspondingly by means of a semi-microemulsion cup 35.

16 81 860

An additional dilution to 0.5% ASA dry matter was then performed. The following example illustrates the advantages provided by this invention: The ability of these cationic, water-soluble acrylamide copolymers to initiate ASA emulsion 5 and make ASA emulsion particles cellulose resistant.

Each ASA emulsion listed below was added separately to the pulp slurry with a consistency of 0.5%, a composition of 40% bleached softwood sulphate pulp, 40% bleached hardwood sulphate pulp and 20 1Q calcium carbonate, 300 Canadian Standard 2

Freeness (pH 8.2). Hand sheets with a basis weight of 22.5 kg per 297 m were prepared according to TAPPI T-205 methods. ASA emulsions were added to the pulp slurry just prior to the formation of the wet paper roll at doses of 0.250 and 2.00% of the pulp dry matter. The hand sheets were immediately dried in a tumble dryer to 98% dry matter (2% residual moisture). The results are shown in Table III.

This example clearly illustrates the new use of cationic vinyl-2Q addition copolymers as ASA emulsifying aids and emulsion retention aids. Water resistance is found to be.. · Improved over conventional ASA in water or cationic starch emulsions. Second, the improved water resistance provided by this invention cannot be counted in favor of improved paper machine retention alone, as shown by the separate additions of these same cationic polymers to the paper.

However, the use of polymers in this molecular weight range resulted in the formation of sticky precipitates and unstable emulsions. Further study by examples herein has shown that polymers having a molecular weight greater than 10,000 but less than 1,000,000, and preferably between 20,000 and 750,000, behaved substantially equivalent to polymers having a higher molecular weight. In addition, the use of 35 polymers with preferred molecular weights in our range of 50,000 to 150 ° C resulted in the elimination of the above precipitate formation and increased, we believe, the stability of the ASA emulsions thus prepared.

5

Table III

Brand Quaternary Acrylic Molecular Form Amide Copolymers Weight! calculated intrinsic viscosity 1Q --- tista_ I DMAEA, methyl 1 chloride, quat. 5,700,000 dry powder J 12% by weight DEAEA, monomethyl 9,200,000 dry powder sulphate salt K 12.5% by weight EMAEM, dimethyl- dry powder sulphate, quat.

^ L 35% by weight No MM, monomethyl 8,900,000 emulsion sulphate, quat.

M 28.6 wt% DADMAC 4,300,000 emulsion (continued) 18 81 860

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Claims (12)

81 860 A process for preparing glued paper products using an effective amount of an emulsified alkenyl succinic anhydride glue containing water, alkenyl succinic anhydride, surfactants and a cationic polymer, characterized in that the cationic polymer used is a water-soluble cation. about 10,000,000, that a phosphatized ethoxylate or a sulfonated emulsifier is used as the surfactant in an amount of 0 to 2% by weight, that the adhesive is mixed before gluing so that the particle diameter of the alkenyl succinic anhydride is not more than 5. and the weight ratio of active cationic vinyl polymer is in the range of about 1: 1 to 15: 1. Process according to Claim 1, characterized in that the cationic vinyl addition polymer 20 is a water-soluble vinyl addition polymer having a molecular weight of more than 10,000 but less than 1,000,000 and having a sea content of 10 to 100% by weight made from a cationic or cationically modified vinyl addition monomer. Process according to Claim 2, characterized in that the cationic or cationically modified vinyl addition monomer is a) diallyldimethylammonium chloride; b) methacrylamidopropyltrimethylammonium chloride; c) dimethylaminoethyl methacrylate; D) a quaternary dimethylaminoethyl methacrylate; e) dimethylaminoethyl acrylate; f) a quaternary dimethylaminoethyl acrylate; 35 g) diethylaminoethyl acrylate; h) a quaternary diethylaminoethyl acrylate; 20 81 860 i) a reaction product obtained by reacting acrylamide, formaldehyde and a lower secondary amine according to the Mannich reaction; or j) a quaternary acrylamide which has undergone a Mannich reaction. Process according to Claim 1, characterized in that the weight ratio of alkenyl succinic anhydride adhesive to polymer is 2: 1 to 15: 1. 5. A method of gluing paper using an alkenyl succinic anhydride glue by adding an alkenyl succinic anhydride emulsion to a stock, characterized in that a water-soluble cationic vinyl additive polymer is used as the emulsifier of , wherein the weight ratio of cationic polymer to anionic surfactant is about 100: 1 to 1: 0. Process according to Claim 5, characterized in that the cationic water-soluble vinyl addition polymer is a homopolymer or copolymer of one or more of the following monomers: a) diallyldimethylammonium chloride; b) methacrylamidopropyltrimethylammonium chloride; c) dimethylaminoethyl methacrylate; D) a quaternary dimethylaminoethyl methacrylate; e) dimethylaminoethyl acrylate; f) a quaternary dimethylaminoethyl acrylate; G) diethylaminoethyl acrylate; h) a quaternary diethylaminoethyl acrylate; i) a reaction product obtained by reacting acrylamide, formaldehyde and a lower secondary amine according to the Mannich reaction; and 35 j) a Mannich reaction quaternary acrylamide. Il 21 81860 Process according to Claim 5, characterized in that an emulsion containing a water-soluble polymer is added to the stock. An alkenyl succinic anhydride emulsion, characterized in that it contains: a) 50 to 99.9% by weight of water b) 0.01 to 40% by weight of alkenyl succinic anhydride; c) 0.001-10.0% by weight, based on the dry matter of the polymer, of a water-soluble cationic vinyl addition polymer having a molecular weight of more than 10,000. Emulsion according to Claim 8, characterized in that the water-soluble cationic vinyl addition polymer is a homo- and copolymer of one of the following monomers: a) diallyldimethylammonium chloride; b) methacrylamidopropyltrimethylammonium chloride; c) dimethylaminoethyl methacrylate; d) a quaternary dimethylaminoethyl methacrylate; E) dimethylaminoethyl acrylate; f) a quaternary dimethylaminoethyl acrylate; g) diethylaminoethyl acrylate; h) a quaternary diethylaminoethyl acrylate; I) a reaction product obtained by reacting acrylamide, formaldehyde and a lower secondary amine with each other according to the Mannich reaction; or j) a Mannich reaction quaternary acrylamide. Paper sizing emulsion, characterized in that it contains a) 50-99.9% by weight of water; b) 0.01-10% by weight of alkenyl succinic anhydride; c) 0.01-10.0% by weight, based on the dry matter of the polymer, of a water-soluble cationic vinyl addition polymer having a molecular weight of more than 10,000 but less than 1,000,000, 22 81 860 d) 0-2% by weight of an anionic surface an active substance with an HLB value of 8-30. Sizing emulsion according to Claim 10, characterized in that the cationic condensation polymer is a copolymer of epichlorohydrin and dimethylamine. Sizing emulsion according to Claim 10, characterized in that it contains a phosphated ethoxylate as an anionic surfactant. 23 81 860