SE461668B - ALKENYLBARSTYLIC ACID ANHYDRIDE COMPOSITION, PROCEDURES FOR PREPARING THEREOF AND ITS APPLICATION - Google Patents

Description

461 668 (B) the reaction product of maleic anhydride and straight chain internal olefins or branched chain olefins within the C14 to C22 range and having an average molecular weight of from about 224 to 308, wherein component (B) has a molecular weight of at least 10 units higher than component (A).

Suitably the above mixture contains about S to 40% of component (A) and, more suitably, about 10 to 35% of component (A).

The present invention also relates to a method of gluing paper by dispersing within the wet pulp an alkenyl succinic anhydride composition, as described above.

The present invention further relates to a method of treating cellulosic tissue to make it water-repellent by impregnating the tissue with the novel alkenyl succinic anhydride compositions of the present invention.

The present invention also provides a suitable process for preparing the present alkenyl succinic acid anhydride composition from maleic anhydride and a blend of straight chain alpha-olefins in the C13 to C22 range, which process comprises: (A) introducing alpha-olefins into a distillation zone, in which at least a portion of the lowest boiling alpha-olefin is evaporated and taken as a peak fraction; (B) isomerizing what remains at the bottom of the distillation zone to reduce the alpha-olefin content to less than 15% of the total olefin content of the fraction down; (C) recombining the alpha-olefin from the top fraction, which is recovered from step (A) with the fraction down with isomerized olefin in step (B); and (D) reacting the reconstituted olefins from step (C) with maleic anhydride to provide the alkenyl succinic anhydride product.

In another aspect of the process of the present invention, the unisomerized alpha-olefin in the peak fraction recovered from step (A) and the isomerized olefin in the fraction down in step (B) are each independently brought to 35 ° 461. reacting with maleic anhydride and resulting alkenyl succinic anhydride products are then combined to provide the alkenyl succinic anhydride of the present invention.

Suitably the alpha-olefin content in step (B) is reduced to less than 10% the content of the lower fraction.

Among other factors, the present invention is based on the surprising discovery that certain alkenyl succinic anhydrides derived from straight chain alpha-olefins which have hitherto been considered not useful can be combined in specific mixtures or with other alkenyl succinic anhydrides to provide a superior paper adhesive. means.

A further advantage of the present invention is the fact that when straight chain alpha-olefins are used as starting materials to make liquid alkenyl succinic anhydrides, less olefin processing is required before the alkenyl succinic anhydride is formed.

The composition of the present invention can be prepared by simply combining the described alkenyl succinic anhydride components or alternatively by combining the intermediate olefins and then preparing the desired alkenyl succinic anhydride. For example, a straight chain and wide range alpha-olefin mixture, which mixture can be obtained from wax cracking, Fischer-Tropsch synthesis or ethylene oligomerization, could be distilled to yield light and heavy fractions. The heavy fraction is then isomerized to move the double bond to internal positions and reunited with the light fraction before preparing the alkenyl succinic anhydride of the present invention.

The olefin feed for component (A) of the present invention should be predominantly straight chain 1-olefin. and more suitably less than 5% of the total olefin. Minor amounts of chain branching or internal olefin, as found in commercial "alpha-olefins", may also be present.

The olefin feed for either component (A) or (B) may consist of a single carbon number, a mixture of adjacent carbon numbers or may consist of any combination of carbon numbers within this range. 5 10 15 20 25 30 35 461 668 The olefin feed for component (B) may be straight chain or branched. Branched chain olefin can be obtained from various sources, such as by oligomerization of lower olefins in the C3 to C11 range. If it has a straight chain, the olefin must be substantially free of alpha-olefin. These straight chain olefins can be obtained from n-paraffins by methods well known in the art, such as dehydration and chlorination-dehydrochlorination.

Alternatively, straight chain olefins can be prepared by isomerizing alpha-olefins using acidic and basic catalysts in accordance with the appropriate process of the present invention. According to the process of the present invention, the olefin feed for component (B) is a straight chain internal olefin obtained by isomerizing straight chain alpha-olefins within the C14 to C22 range. This isomerization can be completed Isomeric alpha-olefin remaining, preferably less than 10%, and more suitably by using acidic or basic catalysts. should be sufficient to leave no more than about 15% less than 5 a alpha-olefin. These olefins can be increased by enclosing branched chain olefins or straight chain internal olefins obtained from other sources, as described above. In general, the olefin feed for component (B) should be substantially free of straight chain alpha-olefin.

The new sizing agents develop all the characteristics and advantages of the sizing agents according to the state of the art. In addition, the novel sizing agents of the present invention impart to the paper glued therewith a particularly good resistance to acidic liquids, such as acidic inks, citric acid, lactic acid, etc., as compared to paper glued with the sizing agents according to the prior art. In addition to the properties already mentioned, these sizing agents can also be used in combination with alum as well as with any of the pigments, fillers and other constituents which can be added to paper. The sizing agents of the present invention can also be used in conjunction with other sizing agents to obtain additive sizing effects.

A further advantage is that they do not reduce the strength of the paper and when used with certain aids they will in fact increase the strength of the finished sheets. 10 15 20 25 30 35 461 668 Only mild drying or curing conditions are required to develop full sizing value.

The actual use of these sizing agents in the manufacture of paper is subject to a number of variations in technology, any of which may be further specified in light of the specific requirements of the practitioner. However, it is important to point out that with all these methods, it is most essential to achieve a uniform distribution of the sizing agent through the fiber slurry, in the form of extremely small droplets, which can come into intimate contact with the fiber surface. Uniform spreading can be obtained by adding the sizing agent to the pulp by vigorous stirring or by adding a previously formed, completely dispersed emulsion. Chemical dispersants can also be added to the fiber slurry.

Another important factor in the efficient use of the sizing agents of the present invention comprises their use together with a material which is either cationic in nature or on the other hand is capable of being ionized or dissociated in such a way that one or more cations or other positively charged parts are formed. These cationic agents, as they will be referred to hereinafter, have been found to be useful as a means of assisting in the retention of the sizing agents herein as well as of bringing the latter into intimate proximity with the pulp fibers. Materials which can be used as cationic agents in bonding processes include alum, aluminum chloride, long chain fatty amines, sodium aluminate, substituted polyacrylamide, chromium sulfate, animal glue, cationic curable resins and polyamide polymers. Of particular interest for use as cationic agents are various cationic starch derivatives including primary, secondary, tertiary or quaternary amine starch derivatives or other cationic nitrogen-substituted starch derivatives, as well as cationic sulfonium and phosphonium starch derivatives. Such derivatives can be prepared from all types of starch, including corn, tapioca, potatoes, wax corn, wheat and rice. In addition, they may be in their original grain form or they may be converted to pregelatinized products soluble in cold water. 461 ess 6 10 15 20 25 30 35 Any of the above cationic agents can be added to the stock, i.e. the pulp slurry, either before, together with, or after the addition of the sizing agent.

However, in order to achieve maximum distribution, it is convenient that the cationic agent is added either after or in direct combination with the sizing agent. The actual addition to the stock of either the cationic agent or the sizing agent can take place at any point in the papermaking process prior to the final conversion of the wet pulp into a dry web or sheet. "Thus, for example, these sizing agents can be added to seagulls. while the latter is in the headbox, the grinding Dutchman, the hydropulper or the milk vessel.

In order to obtain good gluing, it is desirable that the gluing agents are uniformly dispersed through the fiber slurry in as small a particle size as is possible to obtain.

One method of accomplishing this is to emulsify the sizing agent prior to its addition to the stock using either mechanical means, such as high speed stirrers, mechanical homogenizers or by adding a suitable emulsifier. Whenever possible, it is highly desirable to use the cationic agent as an emulsifier, and this process is particularly successful when cationic starch derivatives are used. Among useful non-cationic emulsifiers which can be used as emulsifiers for the sizing agents, such are listed as hydrocolloids such as common starches, non-cationic starch derivatives, dextrins, carboxymethylcellulose, gum arabic, gelatin and polyvinyl alcohols as well as various surfactants. Examples of such surfactants include polyoxyethylene sorbitan triolate, polyoxyethylene sorbitol hexaoleate, polyoxyethylene sorbitol laurate and polyoxyethylene sorbitol laurate. When such non-cationic emulsifiers are used, it is often desirable to separately add a cationic agent to the pulp slurry after the addition to the latter of the emulsified sizing agent. In the preparation of these emulsions with the use of an emulsifier, the latter is usually first dispersed in water and the sizing agent is then introduced together with vigorous stirring. Alternatively, the emulsifying methods described in U.S. Pat. No. 4,040,900 may be used.

Further improvements in the water resistance of the paper made with these new sizing agents can be obtained by curing obtained webs, sheets or shaped products.

This curing process involves heating the paper to temperatures in the range of 800 to 100 ° C for times from 1 to 60 minutes. However, it should again be noted that post-curing is not essential for successful surgery in the present invention.

The sizing agents of the present invention can, of course, be successfully used for sizing paper made from all types of both cellulosic fibers and combinations of cellulosic fibers with non-cellulosic fibers. The cellulosic fibers that can be used include bleached and unbleached sulfate (kraft), bleached and unbleached sulfite, bleached and unbleached soda, neutral sulfite, semi-chemical chemical abrasive, abrasive and any combination of these fibers. The terms refer to wood pulp fibers, which have been produced by a variety of methods used in the pulp and paper industry. In addition, synthetic fibers of viscose rayon or generated cellulose type can also be used.

All types of pigments and fillers can be added to the paper to be glued with the new gluing agents of the present invention. Such materials include clay, talc, titanium dioxide, calcium carbonate, calcium sulfate and diatomaceous earth. Other additives, including alum, as well as other sizing agents, can also be used in these sizing agents.

With respect to the proportions, the sizing agents can be used in amounts ranging from about 0.05 to about 3% of the dry weight of the pulp in the finished sheet or web.

While amounts in excess of 3% can be used, the benefits of increased gluing properties are usually not economically justifiable. Within the specified range, the precise amount of glue to be used will largely depend on the type of pulp used, the specific operating conditions as well as the particular end use for which the paper is intended. Thus, for example, paper, which requires good water resistance or ink resistance, will necessitate the use of a higher concentration of sizing agent, than paper, which does not require this. The same factors are also applied in relation to the amount of cationic agent, which can be used together with these sizing agents. The practitioner will be able to use these materials in any concentration that proves to be useful for his specific operating conditions. However, in ordinary circumstances, a range from 0.5 to 2.0 parts by weight of cationic agent per 1.0 part of sizing agent is usually suitable. It can be noted that the cationic agent is present in a quantity of at least 0.025% of the dry weight of the pulp in the paper.

The alkenyl succinic anhydride compositions of the present invention can also be used to provide water repellency to cellulosic tissues. The water-repellent compositions described above can be applied to the fabric in aqueous emulsions similar to those used for paper gluing. The emulsion can be sprayed on the tissue or the tissue can be dipped into the emulsion to distribute the derivative evenly throughout the tissue. The impregnated tissue is then removed from the solution and air dried. After air drying, the tissue is then heated, preferably to a temperature above 100 ° C, to effect a curing of the impregnated agent within the tissue. It has been found that a temperature of about 125 ° C can be suitably used for a period of 15 to 20 minutes. At lower temperatures, longer periods of time are required to perform the curing process. To be commercially practical, the curing time should be as short as possible and usually less than an hour. At higher temperatures, heat curing can be completed in shorter time periods. The upper temperature limit at which the thermosetting process can be performed is limited to temperatures at which the tissues begin to turn brown or become discolored. Using the composition of the present invention, it is convenient to impregnate the fabric with from about 0.7 to 2.5 weight percent of the fabric of the alkenyl succinic anhydride.

The following examples are provided to illustrate the present invention in accordance with the principles of the present invention but are not to be construed as limiting the invention in any way except as indicated by the appended claims. EXAMPLE 1 This example describes the preparation of a standard straight chain alkenyl succinic anhydride suitable for bonding applications.

The olefin feed originated from cracking of petroleum wax and originally contained about 88% straight chain alpha-olefin.

It consisted of a mixture of homologues from C15 to C20 containing 18% QS, 19% Q6.18% Q7.18% Q8.15% Q9 and 12% C20. This mixture was isomerized using an acid catalyst until the alpha-olefin content was reduced to 7%. The double binding had been moved to the 2-position and further internal positions.

The above straight chain internal olefin mixture (329 g, 1.35 mol) was heated with maleic anhydride (98 g, 1.0 mol) in an autoclave for 3 1/4 hours at 230 ° C. Over 95% of the maleic anhydride was reacted with the olefin to give an alkenyl succinic anhydride product. Unreacted maleic anhydride and olefin were evaporated from this crude product by heating to 260 ° C at 25 mm Hg with a nitrogen purge over a 40 minute period. The remaining alkenyl succinic anhydride was a straw colored liquid with a pour point of about 5 ° C, which remained liquid but formed some solids on standing overnight at this temperature.

This product is very similar to normal commercial straight chain alkenyl succinic anhydride. It gives good paper sizing results in a variety of tests, such as those described in U.S. Patent 4,040,900 (Re. 29,960).

Example 2 An alkenyl succinic anhydride was prepared as described in Example 1, except that the carbon number range of the olefin feed consisted of ZS% C15, 30% C16, 29% C17 and 15% C18.

The alpha-olefin content remaining after the isomerization was 7%. The resulting alkenyl succinic anhydride was a clear liquid which did not produce solids when standing overnight at 5 ° C.

Example 3 An alkenyl succinic anhydride was made from the same straight chain alpha-olefins described in Example 1, except that the olefin isomerization step was omitted. The alkenyl succinic anhydride product was a solid, completely unsuitable for gluing by the normal aqueous emulsion methods.

Example 4 The alpha-olefin title feed used in Example 1 was distilled to give a low boiling fraction, which was 88% C15 and 9% C16, with an average molecular weight of 212. An alkenyl succinic anhydride was made from this olefin using the steps in Example 1, except that the isomerization step was omitted. This alkenyl succinic anhydride was a solid, unsuitable for bonding.

Example S An example of the composition of the present invention was prepared using the alkenyl succinic anhydride of Example 4 as component A and a C16-18 alkenyl succinic anhydride as component B. The C16-18 alpha-olefin fraction was in the lower fraction from the distillation of Example C15. 4. This C16-18 fraction contained about 34% C16, 34% C17 and 27% C18, with an average molecular weight of 237. The C16-18 fraction was isomerized to reduce the alpha-olefin content to 7% and an alkenyl succinic anhydride was prepared as in Example 1. The final alkenyl succinic anhydride mixture contained 22.5% of component A and 77.5% of component B. This composition was a clear liquid at room temperature. It remained liquid but formed some solids when standing overnight at SOC.

Example 6 Another example of the composition of the present invention was prepared as described in Example 5, except that the C16-18 olefin used to make the alkenyl succinic anhydride in component B was more completely isomerized before the reaction with neleic acid idndride. In this case, instead of 7% alpha-olefin, only 2% alpha-olefin remained after isomerization. This C16-18 olefin was reacted with maleic anhydride and the resulting alkenyl succinic anhydride was mixed with the alkenyl succinic anhydride of Example 4 in a 22, S / 77, S ratio as in Example 5. This composition was a liquid at room temperature and did not form any solids. when standing overnight at 5 ° C.

U. 10 15 20 25 461 668 Example 7 Paper gluing experiments and evaluation of the adhesive efficiency were performed using methods described in U.S. Patent Nos. 4,040,900 (Re. 29,960). For each alkenyl succinic anhydride tested, eight results were obtained.

The alkenyl succinic anhydride was added to paper at two different levels: 0.2% and 0.4%, based on dry fiber weight.

A cationic starch aid was used in each case at twice the content of alkenyl succinic anhydride. At both alkenyl succinic anhydride levels, experiments were also performed with 0.5% added alum. The glued papers were evaluated using both the Hercules glue test (80% reflector end point) and the potassium permanganate test, which is described in U.S. Pat. No. 4,040,900.

For each alkenyl succinic anhydride, the average of the times for obtaining each end point was taken to give the results shown in Table 1.

Table 1 Time, in seconds to end point Alkenyl succinic anhydride Example no. Carbon range (average of 8 tests) 1 15-20 I 104 2 15-18 110 5 15-18 121 6 15-18 165 The results in Table 1 show that the alkenyl succinic anhydride of the present invention invention, namely Examples 5 and 6, gives superior sizing efficiency over the known alkenyl succinic anhydride compositions of Examples 1 and 2.

Example 8 A composition similar to those of 6 was prepared by mixing 20% of the alkenyl succinic anhydride of Example 4 with 80% of an alkenyl succinic anhydride obtained from a branched olefin mixture within the G1 S-C20 range prepared by oligomerizing propylene. This composition was a liquid at room temperature and did not form as described in Example 5 any solids on standing overnight at 5 ° C.

Claims (2)

1. 461 ess 1 * PATENT REQUIREMENTS g: o. 1. Alkenyl carboxylic acid anhydride composition, k ä n n e- i? t a c k a a d of: (A) from about 5 to about 40 X, preferably from about 10 X to about 35 Z, of the reaction product of maleic anhydride and straight chain alpha-olefins in the C13 to C18 range; and (B) the reaction product of maleic anhydride and straight chain or branched chain olefins within the C14 to C22 range, wherein component (B) has a molecular weight of at least 10 molecular weight units higher than component (A), the average molecular weight of the olefin feed for component (A) is from about 182 to 238 and the average molecular weight of the olefin feed for component (B) is from 224 to 308. Process for the preparation of alkenyl succinic anhydride composition from maleic anhydride and a mixture of straight-chain alpha-olefins in the C13 to C22 range, characterized in that (A) the alpha-olefins are introduced into a distillation zone, wherein at least one part of a lowest boiling alpha-olefin is evaporated and taken as a top fraction; (B) isomerizing what remains at the bottom of the distillation zone to reduce the alpha-olefin content to less than 15 Z of the total content of the lower fraction; (C) reuniting the alpha-olefin from the top fraction recovered from (A) with the isomerized olefin from the lower fraction in step (B); and (D) reacting the reconstituted olefins of step (C) with maleic anhydride to provide the alkenyl succinic anhydride composition. A process for the preparation of alkenyl succinic anhydride composition from maleic anhydride and a mixture of straight chain alpha-olefins in the C13 to C22 range, characterized in that (A) the alpha-olefins are introduced into a distillation zone, wherein at least a portion of the lowest boiling alpha-olefin is evaporated and taken as the top fraction; 461 668 (B) isomerizes what remains at the bottom of the distillation zone to reduce the alpha-olefin content to less than 15 Z of the total olefin content in the lower fraction; . (C) independently reacting unisomerized alpha-olefin from the top fraction recovered from step (A) and isomerized clefin from the lower fraction in step (B) with maleic anhydride and (D) combining the reaction products in step (C) to provide the alkenyl succinic anhydride composition. Process according to Claim 2 or 3, characterized in that the alpha-olefin content in step (B) is reduced to less than 10 X of the total olefin content in the lower fraction, suitably less than 1.5. Process according to claim 2 or 3, characterized in that the amount of olefin taken as peak fraction in step (A) is about 5 to 40% of the total olefin used, i.e. about 10: 6. A process according to claim 2 or 3, characterized in that the average molecular weight of the olefin taken as the peak fraction in step (A) is from about 182 to 238 and the average molecular weight of the olefin in the lower fraction in step (B) is from about 224 to 308. Use of the composition according to claim 1 for (a) gluing paper, the composition being intimately dispersed within the wet pulp, before the final conversion of the pulp to a dry web, or (b) treating cellulosic tissue to make it water-repellent, the tissue being impregnated with the composition and the impregnated fabric is heat hard at temperatures lower than the temperatures at which the cellulosic fabric is discolored. Use according to claim 7 (a), wherein the sizing agent is in the form of an aqueous emulsion.