JPH0533227B2 - - Google Patents

Description

[Detailed description of the invention]

BACKGROUND OF THE INVENTION The present invention relates to improved liquid alkenyl succinic anhydride mixtures with superior paper size properties and methods of making the same. The invention also relates to a method for improving the sizing of paper and paperboard products.
A further feature of the present invention relates to an improved method for imparting water repellency to cellulose woven or knitted fabrics. It is known in the art that long chain length alkenyl succinic anhydrides can be used as effective sizing agents for paper making. For example, US Patent No. 3102064
No. 3821069, No. 3968005, and No. 3968005.
See No. 4040900 (Reissue Patent No. 29960). These alkenyl succinic anhydrides are also used as treatment agents for woven and knitted fabrics. See US Pat. No. 2,903,382. The useful molecular weight range for the alkenyl groups of these sizing agents is 8 carbon atoms.
It is described in various documents that the number is within the range of ~35. It is also known that these prior art sizes are best applied in highly dispersed form such as aqueous emulsions. but,
Alkenyl succinic anhydrides made from linear alpha-olefins are solids at ambient temperatures and are therefore not effective in forming these emulsions. In this regard, commercial alkenyl succinic anhydride paper sizes are made from isomerized linear α-olefins (i.e., linear internal olefins) or branched chain olefins. For example, the often cited U.S. Pat.
No. 3102064 [isooctadecenyl succinic anhydride]
Please refer to The molecular weight of the alkenyl group of the more effective or preferred alkenyl succinic anhydride is 13 carbon atoms.
It is taught that this corresponds to a range of ˜22 carbons. Mixtures of several carbon numbers have also been described. For example, U.S. Pat.
(Reissue Patent No. 29960), _C15 - _C20 alkenyl succinic anhydride. SUMMARY OF THE INVENTION The present invention provides a reaction product of (A) maleic anhydride with a linear alpha-olefin in the range of _C13 to _C18 having an average molecular weight of about 182 to 238; The reaction product of maleic acid with a linear internal olefin or branched chain olefin in the range of _C14 to _C22 having an average molecular weight of about 224 to 308, provided that component (B) is at least 10 The present invention provides two-component alkenyl succinic anhydride compositions having excellent paper sizing properties having a molecular weight of at least one unit higher. Preferably, the mixture comprises about 5-40% of the components
(A), and more preferably about 10-35% of the ingredients
Contains (A). The present invention further relates to a method of sizing paper by dispersing the alkenyl succinic anhydride composition described above in wet papermaking pulp. The present invention further relates to a method for treating cellulose woven or knitted fabrics, which imparts water repellency to the woven or knitted fabrics by impregnating the woven or knitted fabrics with the novel alkenyl succinic anhydride composition of the present invention. The present invention also includes: (A) introducing an alpha-olefin into a distillation zone, vaporizing at least a portion of the lowest boiling alpha-olefin and removing it to an overhead; (B) removing residual residue from the distillation zone. liquid (bottoms)
(C) isomerizing the alpha-olefin overhead portion recovered from step (A) and the alpha-olefin overhead portion from step (B); and (D) reacting the recombined olefin from step (C) with maleic anhydride to form an alkenylsuccinic anhydride product. A preferred method of making the alkenyl succinic anhydride compositions of the present invention from maleic acid and a mixture of linear alpha-olefins in the range of _C13 to _C22 is provided. Another feature of the process of the invention is that the non-isomerized α-olefin overhead portion recovered from step (A) and the isomerized olefin bottom portion of step (B) are each independently treated with maleic anhydride. and the resulting alkenyl succinic anhydride products are then combined to form the alkenyl succinic anhydride of the present invention. Preferably, the α-olefin content in step (B) is
The total olefin bottoms content is reduced to less than 10%, and more preferably to less than 5%. Among other factors, the present invention provides that alkenyl succinic anhydrides derived from certain linear alpha-olefins, which prior to the present invention were considered ineffective, It is based on the inventor's surprising discovery that an excellent paper sizing product can be obtained that can be combined into a mixture. An additional advantage of the present invention is that when using a linear alpha-olefin as a starting feedstock for liquid alkenyl succinic anhydride production, less processing of the olefin is required prior to forming the alkenyl succinic anhydride. . DETAILED DESCRIPTION OF THE INVENTION The compositions of the present invention can be prepared by either simply combining the alkenyl succinic anhydride components described, or alternatively by combining precursor olefins and then forming the desired alkenyl succinic anhydride. It can be manufactured by the following method. For example, wax decomposition, Fischer-Tropsch
A wide range of linear α-olefin mixtures obtained from Tropsch synthesis or ethylene oligomerization can be distilled to obtain soft and light fractions. The heavy portion is then isomerized to move the double bond to an internal position and then recombined with the light portion before forming the alkenyl succinic anhydride composition of the present invention. The olefin feed for component (A) of the compositions of the invention should be predominantly linear 1-olefins. Minor amounts of branched or internal olefins, such as those present in commercial [alpha-olefins], may be present. The olefin feed of either component (A) or (B) may consist of a single carbon number, a mixture of adjacent carbon numbers, or any combination of carbon numbers within that range. The olefin feed for component (B) may be linear or branched. Branched olefins are obtained from a variety of sources, such as by oligomerization of lower olefins ranging from _C3 to _C11 . If linear, the olefin must be substantially free of α-olefin. These linear olefins are dehydrogenated and chlorinated.
Chlorination-dehydrochlorination
n- by methods well known in the art such as
Can be obtained from paraffin. Alternatively, the linear olefin can be converted to α using acidic or basic catalysts based on the preferred method of the present invention.
- They can also be produced by isomerization of olefins. In the process of the invention, the olefin feed for component (B) is a linear internal olefin obtained by isomerization of a linear α-olefin in the range of C ₁₄ to _{C 22} . This isomerization can be carried out using an acidic or basic catalyst. This isomerization is performed so that the remaining α-olefin is less than 15%, preferably 10%.
less than 5%, and more preferably less than 5%
- It must be done enough to leave the olefin behind. These olefins can also be enriched with branched or internally linear olefins obtained from other sources as mentioned above. Generally, the olefin feed for component (B) should be substantially free of linear alpha-olefins. This novel sizing agent exhibits all the characteristics and advantages cited in prior art sizing agents. Furthermore, the novel sizing agent of the present invention allows paper sized with this sizing agent to be coated with acidic liquids such as acid ink, citric acid, butyric acid, etc. as compared to paper sized with sizing agents cited in the prior art. provides particularly good resistance to In addition to the aforementioned properties, these sizing agents also contain alum
and can be used in combination with any pigments, fillers and other ingredients that can be added to paper. The sizing agents of the present invention can also be used in combination with other sizing agents to obtain additional sizing effects. As a further advantage, this sizing agent does not compromise the strength of the paper and may actually increase the strength of the finished paper when used in conjunction with certain adjuvants. Only mild drying or curing conditions are required to develop full size values. The practical use of these sizes in paper manufacture is carried out by a number of procedural variations which are further modified according to the particular requirements of the person skilled in the art. However, it is important to emphasize that in all of these methods, it is paramount to uniformly disperse this sizing agent throughout the fiber slurry in the form of microdroplets that can come into intimate contact with the surface of the paper fibers. be. Uniform dispersion is obtained by adding the size to the pulp with vigorous stirring or by adding it to the pulp in a preformed, thoroughly dispersed emulsion. Chemical dispersants may be added to the fiber slurry. Other important factors for the effective use of the sizing agents of the present invention include the combination with cationic substances or the addition of one or more cations or other positively charged components. Includes uses in conjunction with substances that can be ionized or dissociated in such a way as to produce It has been discovered that these cationic agents, as described herein below, are useful not only in helping to retain sizes in the fibers, but also as a means of promoting intimate access of these sizes to the pulp fibers. has been done. In the sizing process,
Among the substances that can be used as cationic agents, mention is made of alum, aluminum chloride, long-chain aliphatic amines, sodium aluminate, substituted polyacrylamides, chromic sulfate, animal glues, cationic thermosetting resins and polyamide polymers. be able to. Of particular interest for use as cationic agents include primary, secondary, tertiary or quaternary amine starch derivatives and other cationic nitrogen-substituted starch derivatives, also cationic sulfonium and phosphonium starch derivatives. Various cationic starch derivatives. Such derivatives can be made from all types of starch including corn, tapioca, potato, waxy corn, wheat and rice. Furthermore, they may be in their original starch form, or they may be pregelatinized,
Cold water soluble products may also be used. Any of the cationic drugs mentioned above can be added to the stock.
That is, before adding the sizing agent to the pulp slurry,
Can be added either together or later. However, for maximum distribution, it is preferred that the cationic drug be added subsequently to the sizing agent or in direct combination therewith. The actual addition of the cationic drug or size to the stock can occur at any point in the papermaking process prior to final finishing of the wet pulp into a dry web or sheet. Therefore, for example,
These sizes can be added while the pulp is in the headbox, beater, hydropulper or stock chest. To obtain good sizing, it is desirable that the sizing agent be of the smallest possible particle size and uniformly dispersed throughout the fiber. One way to achieve this is to emulsify the size before adding it to the stock using either mechanical means such as a high speed agitator, mechanical homogenizer or a suitable emulsifier. be.
If possible, it is highly desirable to use a cationic drug as an emulsifier, and this method is particularly successful when using cationic starch derivatives. Among the applicable non-cationic emulsifiers that may be used as emulsifiers in sizing agents are:
Hydrocolloids such as common starch, non-cationic starch derivatives, dextrins, carboxymethyl cellulose, gum arabic, gelatin and polyvinyl alcohol
colloids) as well as various surfactants. Examples of such surfactants include polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitol oleate-laurate. When using such non-cationic emulsifiers, it is sometimes desirable to add the cationic agent to the pulp slurry separately after adding the emulsified size to the pulp slurry. When making these emulsions using emulsifiers,
Usually the emulsifier is first dispersed in water and then the sizing agent is introduced with vigorous stirring. Alternatively, the emulsification method described in US Pat. No. 4,040,900 may be used. The water resistance of papers produced using the novel sizing agents of the present invention is further improved by curing the resulting web, sheet or molded product. The curing process involves heating the paper at a temperature of 80-150°C for a period of 1-60 minutes. However, it should be noted that post curing is not essential to the success of the method of the invention. Of course, the sizing agents of the present invention can be successfully used for sizing papers made from all types of cellulosic fibers, both cellulosic and non-cellulosic fibers. Cellulose fibers that can be used include
Included are bleached, unbleached sulfate (kraft), bleached, unbleached sulfite, bleached, unbleached soda, neutral sulfite, semi-chemical grout, groundwood fibers, and any combinations of these fibers. These names are used to refer to wood pulp fibers produced by various methods used in the pulp and paper industry. Furthermore, synthetic fibers such as viscose rayon or regenerated cellulose fibers can also be used. All types of pigments and fillers can be used in paper sized with the novel sizing agents of the present invention. Such materials include clay, talc, titanium dioxide, calcium carbonate, calcium sulfate and diatoms. Other additives can also be used with these sizes, including alum, as well as other sizes. In terms of proportions, this sizing agent accounts for approximately 0.05 of the dry weight of the pulp in the finished sheet or web.
Used in amounts ranging from ~3.0%. Amounts in excess of 3% may be used, but the benefits of increased size properties are usually not economically justified. Within the foregoing ranges, the exact amount of size to be used will be determined in large part by the type of pulp used, the specific operating conditions, and the specific end use for which the paper is intended. There will be. For example, good water resistance or ink retention (ink
Papers that will require a holdout will require the use of a higher concentration of sizing agent than papers that do not. Similar factors apply regarding the amount of cationic drug that can be used in conjunction with these sizing agents.
A skilled person will find and use any concentrations of these substances that are applicable to his particular working conditions. However, under normal circumstances, 0.5 to 2.0 parts by weight of cationic agent per part of size will usually be an appropriate range. It will be noted that the cationic drug is present in an amount of at least 0.025% of the dry pulp weight in the paper. The alkenyl succinic anhydride composition of the present invention can also be used to impart water repellency to cellulose woven or knitted fabrics. The water-repellent compositions described above can be applied to fabrics in the same aqueous emulsion used for paper sizing. The emulsion may be sprayed onto the fabric or the derivative may be distributed uniformly throughout the fabric.
The woven or knitted fabric may be impregnated with the emulsion. The impregnated fabric is then removed from the solution and air dried. After air drying, the fabric is then heated, preferably at a temperature above 100° C., to cure the impregnating agent in the fabric. about
Heating for 15-20 minutes at a temperature of 125°C has proven convenient. Lower temperatures require longer times for the curing process to be effective. For commercial practice, this curing time should be as short as possible, generally less than 1 hour. At relatively high temperatures, this heat curing can be accomplished in a relatively short time. The upper limit temperature for performing this heat curing treatment is limited to the temperature at which the woven or knitted fabric begins to brown or discolor. When using the compositions of the present invention, it is preferred to impregnate the fabric with about 0.7 to 2.5% by weight of alkenyl succinic anhydride. The following examples are provided to illustrate the invention in accordance with its principles and should not be construed as limiting the invention in any way other than as set forth in the appended claims. should not do. EXAMPLES Example 1 This example describes the preparation of standard linear alkenyl succinic anhydrides suitable for use in sizing. The feed olefins were obtained from the cracking of petroleum waxes and originally contained approximately 88% linear alpha-olefins. This is about 18% _C15 ,
It consisted of a mixture of _C15 - _C20 homologs containing 19% _C16 , 18% _C17 , 18% _C18 , 15% _C19 and 12% _C20 . . This mixture was isomerized using an acidic catalyst until its α-olefin content was reduced to 7%. The double bond moved to the 2-position and further to the internal position. The linear internal olefin mixture described above (329g, 1.35
mol) was heated with maleic anhydride (98 g, 1.0 mol) at 230° C. for 31/4 hours in an autoclave. More than 95% of the maleic anhydride reacted with the olefin to become the alkenylsuccinic anhydride product. The crude product at 25mmHg
Unreacted maleic anhydride and olefin were removed by heating to 260° C. and releasing nitrogen over a period of 40 minutes. The remaining alkenyl succinic anhydride was a brown liquid with a pour point of about 5° C., and although fluid, it formed some solids when left overnight at this temperature. This product was very similar to common commercial linear alkenyl succinic anhydride. This gave good paper size results in various tests such as those described in US Pat. No. 4,040,900 (Reissue Pat. No. 29,960). Example 2 An alkenyl succinic anhydride was prepared as described in Example 1. However, the carbon number range of the supplied olefin is 25% C ₁₅ , 30% C ₁₆ , 29% C ₁₇ and
It consisted of 15% _C18 . The residual α-olefin content after isomerization was 7%. The derived alkenyl succinic anhydride is a clear liquid at 5°C.
No solid was formed even after being left overnight. Example 3 Alkenyl succinic anhydride was prepared from the same linear α-olefin as described in Example 1, except that the olefin isomerization step was omitted. This alkenyl succinic anhydride product was a solid and completely unsuitable for sizing by conventional aqueous emulsion methods. Example 4 The alpha-olefin feed used in Example 1 was distilled to yield a relatively low boiling fraction with an average molecular weight of 212 and consisting of 88% _C15 and 9% _C16 . Alkenyl succinic anhydride was prepared using the process of Example 1. However, the isomerization step was omitted.
This alkenyl succinic anhydride was solid and unsuitable for sizing. Example 5 Examples of compositions of the invention were prepared using the alkenyl succinic anhydride of Example 4 as component A and the C _16-18 alkenyl succinic anhydride as component B. the
The C _16-18 α-olefin portion was found in the residual liquid obtained by distilling off the C ₁₅ fraction of Example 4. this
The _C16-18 portion is approximately 34% _C16 , 34% _C17 and 27
% of _C18 and had an average molecular weight of 237. This C _16-18 moiety was isomerized to reduce the α-olefin content to 7% and alkenyl succinic anhydride was prepared as in Example 1. The final alkenyl succinic anhydride mixture contains 22.5% Component A
and 77.5% component B. This composition was a clear liquid at room temperature. This is 5
It remained fluid upon standing overnight at 0.degree. C., but some solids formed. Example 6 Another example of a composition of the invention was prepared as described in Example 5, except that the C _16-18 olefin used to prepare the alkenyl succinic anhydride of component B was replaced with maleic anhydride. It was further completely isomerized before reacting with In this case, the remaining α-olefin is not 7%, but the α-olefin remaining after isomerization is
Olefin was only 2%. This C _16-18 reacts the olefin with maleic anhydride, and the resulting alkenyl succinic anhydride is combined with the alkenyl succinic anhydride of Example 4 and the alkenyl succinic anhydride of Example 5.
They were mixed at a ratio of 22.5/77.5. This composition was liquid at room temperature and did not form any solids upon standing overnight at 5°C. Example 7 Paper size experiments and size effectiveness evaluations were conducted using the method described in US Patent No. 4,040,900 (Reissue Patent No. 29960). Eight results were obtained for each alkenyl succinic anhydride tested. Alkenyl succinic anhydride was added to the paper at two levels: 0.2% and 0.4% based on dry fiber weight. In each case, twice the cationic starch was used as its alkenyl succinic anhydride level. Tests were conducted at both alkenyl succinic anhydride levels with the addition of 0.5% alum. Hercules size test on sized paper (end point, 80
% reflectance) and the potassium permanganate test described in U.S. Pat. No. 4,040,900. For each alkenyl succinic anhydride, the time to each end point was averaged and the results are shown in Table 1.

[Table] The results in Table 1 show that the alkenyl succinic anhydrides of the present invention, namely Examples 5 and 6, have superior size effects compared to the known alkenyl succinic anhydride compositions of Examples 1 and 2. It proves that. Example 8 C ₁₅ prepared by oligomerization of propylene with 20% alkenyl succinic anhydride from Example 4
Example 5 by mixing with 80% alkenyl succinic anhydride derived from a ~ _C20 branched olefin mixture
and 6 were prepared. This composition is liquid at room temperature and at 5°C
No solids were formed even after standing overnight.

Claims (1)

[Scope of Claims] 1 (A) a reaction product of maleic anhydride and a linear α-olefin within the range of C ₁₃ to _{C 18} ; and (B) a reaction product of maleic anhydride and a linear α-olefin within the range of C ₁₄ to C ₂₂ with a linear internal olefin or a branched chain olefin, and component (B) is at least 10 times more active than component (A).
An alkenyl succinic anhydride composition characterized in that it has a high molecular weight. 2. The composition of claim 1 containing from about 5 to about 40% of component (A). 3. The composition of claim 2 containing from about 10 to about 35% of component (A). 4. The average molecular weight of the olefin feed for component (A) is about 182-238, and the average molecular weight of the olefin feed for component (B) is about 224-308. Composition according to item 1. 5 (A) a reaction product of maleic anhydride and a linear alpha-olefin within the range of C ₁₃ to C ₁₈ ; and (B) a reaction product of maleic anhydride and a linear internal olefin within the range of C ₁₄ to C ₂₂ or contains a reaction product with a branched chain olefin, and component (B) is at least 100% more active than component (A).
1. A paper comprising the step of intimately dispersing an alkenyl succinic anhydride composition having a unitary high molecular weight into a wet pulp before the final conversion of the wet pulp into a dry web. Sizing method. 6. The composition contains about 5 to about 40% of component (A);
A method according to claim 5. 7. The composition contains about 10 to about 35% of component (A);
A method according to claim 6. 8. Claim No. 8, wherein the olefin feed for component (A) has an average molecular weight of about 182-238 and the olefin feed for component (B) has an average molecular weight of about 224-308. The method described in Section 5. 9. The method of claim 5, wherein the composition is in the form of an aqueous emulsion. _{or _ _ _} contains a reaction product with a branched chain olefin, and component (B) is at least 100% more active than component (A).
impregnating a cellulose knitted fabric with an alkenyl succinic anhydride composition having a high molecular weight;
A method for treating a cellulose knitted fabric for imparting water repellency to the cellulose knitted fabric, the method comprising thermally curing the impregnated knitted fabric at a temperature lower than the temperature at which the cellulose knitted fabric changes color. 11. The method of claim 10, wherein the composition contains from about 5 to about 40% component (A). 12. The method of claim 11, wherein the composition contains from about 10 to about 35% component (A). 13 The average molecular weight of the olefin feed for component (A) is about 182-238 and the average molecular weight of the olefin feed for component (B) is about 224-308. The method described in item 10. 14. A method for producing an alkenyl succinic anhydride composition from maleic anhydride and a mixture of linear α-olefins and linear internal olefins in the range of C ₁₃ to _{C 22} , comprising: (i) C ₁₃ to C 22 . A mixture of linear α-olefins in the range of C ₂₂ is introduced into the distillation zone and its lowest boiling point α
- vaporizing at least a portion of the olefin;
(ii) isomerizing the remaining bottoms from the distillation zone to reduce its α-olefin content to less than 15% of the total olefin bottoms content; and (iii) recovering from step (). recombining the α-olefin overhead portion and the isomerized olefin bottoms portion of step (), and (iv) reacting the recombined olefin from step () with maleic anhydride to form alkenyl succinic anhydride. The method, characterized in that: producing a product. 15. The method of claim 14, wherein the alpha-olefin content in step () is reduced to less than 10% of the total olefin bottoms content. 16. The method of claim 15, wherein the alpha-olefin content in step () is reduced to less than 5% of the total olefin bottoms content. 17. The method of claim 14, wherein the amount of olefin removed overhead in step () is about 5 to 40% of the total amount of olefin used. 18. The method of claim 17, wherein the amount of the olefin removed overhead in step () is about 10-35% of the total amount of olefin used. 19 In step (), the average molecular weight of the olefin taken out overhead is about 182 to 238.
and the average molecular weight of the residual olefin in step () is about 224-308. 20. A method for producing an alkenyl succinic anhydride composition from maleic anhydride and a mixture of linear α-olefins and linear internal olefins in the range of C ₁₃ to _{C 22} , comprising: (i) C ₁₃ to C 22 . A mixture of linear α-olefins in the range of C ₂₂ is introduced into the distillation zone and its lowest boiling point α
- vaporizing and removing at least a portion of the olefins overhead; (ii) isomerizing the remaining bottoms from the distillation zone to reduce its α-olefin content to less than 15% of the total olefin bottoms content; (iii) unisomerized α recovered from step ();
- reacting the olefin overhead portion and the isomerized olefin bottoms portion of step () independently with maleic anhydride, and (iv) combining the reaction products of step () to form alkenyl succinic anhydride; The method, characterized in that: producing a product. 21. The method of claim 20, wherein the alpha-olefin content in step () is reduced to less than 10% of the total olefin bottoms content. 22. The method of claim 21, wherein the alpha-olefin content in step () is reduced to less than 5% of the total olefin bottoms content. 23. Claim 2, wherein the amount of the olefin withdrawn overhead in step () is about 5-40% of the total olefin used.
The method described in item 0. 24. The process of claim 23, wherein the amount of olefin removed overhead in step () is about 10-35% of the total olefin used. 25. The average molecular weight of the olefin taken overhead in step () is about 182 to 238, and the average molecular weight of the residual olefin in step () is about 224 to 308. The method described in.