STYRENE-BUTADIENE ALKYL METHACRYLATE POLYMERS AS ADHESIVES

Abstract: Disclosed is a random copolymerization product of a monomer mixture comprising styrene, butadiene, and from 2 to 12% of an alkyl methacrylate. These products are effective pressure sensitive adhesives which, due to the level of the alkyl methacrylate, flow well under applied pressure. They give a strong but flexible bond, making them useful for textile-to-textile applications such as medical dressings, tapes and bandages.

Description: BACXGROUND OF THE INVENTION The present invention relates to styrene-butadiene polymers and particularly to styrene-butadiene polymers having improved properties for use as pressure sensitive adhesives. Styrene-butadiene polymers are essentially synthetic rubbers which are used extensively in the manufacture of industrial products, particularly tires and other products where natural rubber has previously been employed. Among the various uses of these polymers are uses 2s adhesives and binders for household, furniture, textile, medical and like applications where these polymers have been found effective due to their unique combination of properties. One major drawback of styrene-butadiene polymers for pressure sensitive adhesive applications, has been their inability to readily flow and adhere themselves to a surface upon application of pressure. This inability to readily flow also limits the flexibility of the bond formed between the two materials and thus to some extent limits the applications for which these adhesives can be employed. In particular, it was found that medical applications which require good adhesive strength and insensitivity to water, yet require the adhesive to form a flexible bond, were foreclosed due to the inherent properties of the styrene-butadiene polymers available. SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide styrene-butadiene polymers having an improved facility for flowing under applied pressure. It is a more specific object of the present invention to provide an improved styrene-butadiene polymer which has improved properties of flow under pressure while maintaining good adhesive strength, to help them function as particularly effective pressure sensitive adhesives. These and other objects are accomplished according to the present invention which provides a composition comprising the random polymerization product of a mixture of monomers comprising styrene, butadiene and from 2 to 12%, based on the combined weight of the monomers, of an alkyl methacrylate, wherein the alkyl group comprises from 1 to 18 carbon atoms. BRIEF DESCRIPTION OF THE DRAWING The invention will become better understood and its advantages more apparent from the following detailed description, especially when read in light of the attached drawing wherein: The FIGURE is a graph showing the variation of percent elongation with percent of methyl methacrylate units in a styrene-butadiene-methyl methacrylate terpolymer. DETAILED DESCRIPTION OF THE INVENTION The styrene-butadiene polymers of the present invention are endowed with superior ability to flow under pressure by virtue of the inclusion within the polymer chain of from about 2 to about 128 by weight of the polymer of an alkyl methacrylate wherein the alkyl groups comprise from 1 to 18 carbon atoms. The preparation of the styrene-butadiene copolymer itself can be effected in accordance with prior art procedures, such as the one described in Bovey et al. Emulsion Polymerization, 1955. Interscience Publishers, Inc. New York. Pg. 325. The disclosure of this reference is accordingly incorporated by reference for the disclosure of the typical processing conditions for the preparation of styrene-butadiene copolymers. The present invention differs from the teachings of this reference, primarily and importantly by the inclusion of a specific level of alkyl methacrylate monomer whicn improves the ability of the resulting polymers to flow under pressure, making them especially adaptable for use as pressure sensitive adhesives. Reference to the figure will show that for a styrene-butadiene polymer containing varying percentages of methyl methacrylate monomer in the polymerized product, the percent elongation has an unexpected peak at from between about 2 to 12% by weight of the methyl methacrylate. Because it is typical for the properties of the styrenebutadiene to vary gradually depending upon the relative monomer percentages, it is totally unexpected that the sharp increase in percent elongation would occur at this specific narrow range of alkyl methacrylate monomer inclusion. This is particularly true where it is realized that the methyl methacrylate has a relatively high glass transition temperature, Tg, as compared to the styrene-butadiene copolymer itself. Thus, it is quite surprising that a monomer capable of forming a high Tg polymer would provide an improvement in the pressure-flow properties of a styrene-butadiene polymer which it is polymerized with. The reason for this is not fully understood at the present time but it may be because the methyl methacrylate copolymerizes preferentially with the styrene during various stages of the polymerization process (based on reactivity ratios of the monomers) to yield regions that are essentially hard domains composed of a methyl methacrylate and styrene copolymer. (These hard domains have been viewed by electron photomicrography.) That way, the soft part of the resulting random copolymer will be richer in soft butadiene than the remainder of the copolymer and hence the total material will give a high elongation. This explanation is offered for the sole purpose of helping those skilled in the art understand this unexpected phenomenon to the same extent that applicants do, while applicants do not intend to be limited to any particular theory of operation. It is the composition of the terpolymer with its unique properties which is new in the art,-regardless of the theory proposed to explain the unexpected phenomenon. It is believed that the non-homogeneous nature of the terpolymer provides improved cohesive strength. This is quite unexpected in view of the improved adhesive strength of the compositions and the oridinary tendency of polymers to lose cohesive strength as their adhesive ability increases. Were one to simply form a polymer low in styrene without the use of the alkyl methacrylate monomer, the results would not be as good as those obtained according to this invention because the cohesive strength of the polymer would be unduely reduced. Moreover, the use of the alkyl methacrylate enables processing to be accomplished at reduced pressure The particular styrene-butadiene rubber composition employed in preparing the graph shown in the figure, at 08 methyl methacrylate monomer, contained 45% butadiene, 52.5% styrene and 2.5% itaconic acid. This same relative percentage of these monomers was maintained as the methyl methacrylate monomer was increased. The product of the present invention is prepared from a mixture of monomers comprising styrene, butadiene, and from 2 to 12t, based on the combined weight of the monomers, of an alkyl methacrylate having from 1 to 18 carbon atoms. The composition can also optionally include a copolymerizable carboxylic acid in an amount which perferably ranges from about 1 to about 5% based on the weight of the monomers. The excellent pressure sensitive adhesive properties of the polymers of the invention are attributed to the proper balance of the ingredients. The cohesive character of the polymer is due to the styrene-butadiene moiety. This, however, is sterically modified by the alkyl methacrylate units, so that the polymers flow under pressure. The acid groups, and probably also the methacrylate groups, assure a tight bond. There is a need in medical applications for a tetile-to-textile binder for dressings, tapes and bandages which gives a strong, flexible' bond. Such material should also be resistant to water and maintain its adhesive and other physical properties for extended periods of time. Due to the heat sensitive nature of the substrates typically employed for these applications, the adhesive binding should preferably be brought about at room temperature under pressure. Prior to the present invention, there was no single adhesive that would satisfy all of these requirements. It is now possible, however, to meet this particular set of requirements. The alkyl methacrylate is one having 1 to 18 carbon atoms. Particularly preferred among the alkyl methacrylates are those wherein the alkyl group comprises a member selected from the group consisting of methyl and stearyl. While the advantages of the invention can be obtained with levels of alkyl methacrylates within the range of about 2 to about 12% based on the weight of polymerized monomers, it is preferred to employ from about 4 to about 10% by weight on this same 'basis for a combination of good physical properties at an economical cost. The amount of styrene and butadiene monomers based on the combined weight of the monomers in the polymerized material are not critical with regard to the obtainment of of the improved properties obtained according to'- urevseent invention. However, for many pressure sensitive adhesive applications which are intended to be utilized under ambient temperature conditions, it has been found that levels of styrene of from 20 to 60%, and levels of butadiene of from 40 to 80%, are suitable. ore preferably, the styrene will be present in an amount of about 35% to about 45% and the butadiene will be present in an amount from about 55% to about 65%, based on the total weight of the monomers. Varying the percentage of styrene above this preferred range will result in a less-flowing polymer, whereas varying the percentage below this range will result in a polymer having more adhesive properties but less cohesive properties. According to the most preferred embodiment of the invention, the composition will be prepared from a monomer mixture which further comprises a copolymerizable carboxylic acid. Preferably, this carboxylic acid will be present in an amount of from about 1 to 5% based on the weight of the monomers. While any of these copolymerizable carboxylic acids known to the art for improving the cohesive strength of styrene-butadiene copolymers can be employed, it is preferred to employ a member selected from the group consisting of methacrylic acidr itaconic acid and combinations of these. One preferred procedure for preparing the copolymers of this invention is set forth in the following Examples. It is'to be understood, however, that other procedures and variations of the exemplary procedure can be employed. In addition to the presence of the monomers as previously discussed, the obtainment of the improved properties according to the invention also drepends on the use of an effective amount of a chain transferring agent such as tertiary dodecyl mercaptan, other mercaptans and alcohols and terpenes known to be effec tive. Typically, the effective range of use will be in an amount of from 0.4 to 2% based on the total weight of monomers, in case of the tertiary dodecyl mercaptan. The chain transfer agent affects the molecular weight of the polymer. Where too little is employed, the molecular weight will be too high; and where too much is employed the adhesion is good, but the material will not have the cohesive character necessary. Where the cohesive strength 'is low, the adhesive itself will lack the proper cohesive power to resist being pulled apart. To improve the stability of the resulting polymers against degradation, the additives in the art for controlling various types of degradation can be included in the final adhesive composition as desired. Also included in the final adhesive composition may be solvents or dispersants to improve initial spreadability for applying thin layers, and fillers or extenders such as talc, CaCO3, silicates and the like. Further, any of the other well known additives can also be employed. The following examples are presented for the purpose of further illustrating and explaining the present invention and are not to be taken as limiting in any regard. Unless otherwise indicated, all parts and percentages are by weight. EXAMPLE I This example describes the preparation of an improved styrene-butadiene polymer according to the present invention, prepared from styrene, butadiene, itaconic acid, methacrylic acid and stearyl methacrylate. The materials shown in Table I are sequentially charged into a one gallon high pressure kettle equipped with a mechanical stirrer, thermometer, pressure gauge and three charging inlets: TABLE I CHARGE NO. INGREDIENTS % in H2O WEIGHT A-1 Water (distilled) - 916 Hampene 100 EDTA (chelating agent) 38 2.2 Itaconic acid - 12.0 Monwet MB-45 diisobutyl sodium sulfo succinate 45 10.7 (surfactant) SBR seed latex 42 87.0 A-2 Water (distilled) - 50.0 Ammonium persulfate - 2.4 B-1 Water (distilled) - 215.0 Sodium hydroxide 20 18.0 Ammonium persulfate - 6.0 Monawet MB-45 diisobutyl sodium sulfo succinate 45 10.8 (surfactant) B-2 Styrene - 540.0 Butadiene - 612.0 Methacrylic acid - 12.0 Stearyl methacrylate - 24.0 Tertiary dodecyl mercaptan - 12.0 These materials are added and processed in the following stagewise procedure: (1) Charge A-l is added to the kettle. (2) The kettle is purged with nitrogen by first evacuating the kettle to 5" vacuum, then breaking the vacuum with nitrogen, and building pressure up to 25 psi. This sequence is repeated twice. (3) Agitation is started at 300 RPM. (4) Temperature of the contents of the kettle is raised to 1800F in 20 minutes. (5) When temperature reaches 180OF, the reaction is started by adding A-2 in one shot, and then (6) starting the Charges B-l and B-2 from two separate inlets. (7) Addition of B-1 and B-2 is completed in 4 hours, while maintaining temperature at 180 F. (8) The emulsion is then held at 1900F for 2 hours prior to cooling. EXAd-9LE II This example describes the comparison of the polymer prepared in Example I to a series of polymers (IIA IIG) prepared by the same procedure, varying only the amounts of monomers, latex seed and tertiary dodecyl mercaptan as shown in Table II below. The resulting polymers are then evaluated for peel strength and peak area. Peel strength is measured by casting a 60 mil layer of latex (50% solids) on a cotton fabric, allowing it to dry overnight at ambient conditions, and then compressing it with a second fabric on it under 10,000 psi. Specimens of 1" x 4" were peeled on the Instron by the T PEEL TEST. Peak area was obtained by measuring the area under the peak plotted in the peel test. TABLE II EMI13.1 <SEP> Components <SEP> - <SEP> % <SEP> based <SEP> on <SEP> total <SEP> monomer <SEP> weight <tb> <SEP> Peel <SEP> Peak <tb> <SEP> Itaconic <SEP> Tertiary <SEP> Strength <SEP> Area <tb> Sample <SEP> Styrene <SEP> Butadiene <SEP> Acid <SEP> Dodecyl <SEP> Seed <SEP> Stearyl <SEP> (lb/in) <SEP> (lb/inê) <tb> <SEP> Mercaptan <SEP> Methacrylate <tb> Example <tb> I <SEP> 45 <SEP> 51 <SEP> 1.0 <SEP> 1.0 <SEP> 3.0 <SEP> 2.0 <SEP> 100 <SEP> 75.0 <tb> IIA <SEP> 55 <SEP> 41 <SEP> 1.0 <SEP> 1.0 <SEP> 3.0 <SEP> 2.0 <SEP> 40 <SEP> 50.0 <tb> IIB <SEP> 45 <SEP> 49 <SEP> 1.0 <SEP> 1.0 <SEP> 3.0 <SEP> 4.0 <SEP> 135 <SEP> 97.5 <tb> IIC <SEP> 55 <SEP> 39 <SEP> 1.0 <SEP> 1.0 <SEP> 3.0 <SEP> 4.0 <SEP> 100 <SEP> 82.5 <tb> IID <SEP> 45 <SEP> 51 <SEP> 1.0 <SEP> 2.0 <SEP> 3.0 <SEP> 2.0 <SEP> 18 <SEP> 30.0 <tb> IIE <SEP> 55 <SEP> 40 <SEP> 1.0 <SEP> 2.0 <SEP> 3.0 <SEP> 4.0 <SEP> 45 <SEP> 60.0 <tb> IIF <SEP> 45 <SEP> 49 <SEP> 1.0 <SEP> 2.0 <SEP> 3.0 <SEP> 4.0 <SEP> 35 <SEP> 45.0 <tb> IIG <SEP> 55 <SEP> 39 <SEP> 1.0 <SEP> 2.0 <SEP> 3.0 <SEP> 4.0 <SEP> 55 <SEP> 77.5 <tb> EXAMPLE III This example describes the preparation of another improved styrene-butadiene polymer according to the present invention, similar to that in Example I but employing methyl methacrylate monomer instead of the stearyl methacrylate. The materials shown in Table III are sequentially charged into a one gallon high pressure reactor of the type described in Example I: TABLE III CHARGE NO. INGREDIENTS WEIGHT (g) A-1 Water (distilled) 854.4 Hampene 100 EDTA (chelating agent) 2.2 Itaconic acid 12.0 Monwet MB-45 diisobutyl sodium sulfo succinate 10.7 (surfactant) Seed latex 116.0 A-2 Water (distilled) 50.0 Ammonium persulfate 3.6 B-1 Water (distilled) 215.0 Sodium hydroxide 18.0 Ammonium persulfate 8.4 Monawet MB-45 diisobutyl sodium sulfo succinate 10.7 (surfactant) B-2 Styrene 540.0 Butadiene 554.0 Methacrylic acid 18.0 Methyl methacrylate 36.0 Tertiary dodecyl mercaptan 7.2 These materials are added and processed in the following stagewise procedure: (1) Charge A-l is added to the kettle. (2) The kettle is purged with nitrogen by first evacuating the kettle to 5" vacuum, then breaking the vacuum with nitrogen, and building pressure up to 25 psi. This sequence is repeated twice. (3) Agitation is started at 300 RPM. (4) Temperature of the contents of the kettle is raised to 180 F in 20 minutes. (5) When temperature reaches 180OF, the reaction is started by adding A-2 in one shot, and then (6) starting the Charges B-l and B-2 from two separate inlets. (7) Addition of B-l and'B-2 is completed in 4 hours. (8) The emulsion is then held at 1900F for 2 hours prior to cooling. EXAMPLE IV This example describes the comparison of the polymer prepared in Example III to a series of polymers (IVA-IVG) prepared by the same procedure, varying only the amounts of monomers, latex seed and tertiary dodecyl mercaptan as shown in Table IV below. The resulting polymers are then evaluated for peel strength and peak area as described in Example II. The results are shown in Table IV. TABLE IV EMI17.1 <SEP> Components <SEP> - <SEP> % <SEP> based <SEP> on <SEP> total <SEP> monomer <SEP> weight <tb> <SEP> Tertiary <SEP> Peel <SEP> Peak <tb> <SEP> Itaconic <SEP> Dodecyl <SEP> Methyl <SEP> Strength <SEP> Area <tb> Sample <SEP> Styrene <SEP> Butadiene <SEP> Acid. <SEP> Mercapten <SEP> Seed <SEP> Methacrylate <SEP> (1b/in) <SEP> (1n/inê) <tb> Example <tb> <SEP> III <SEP> 45 <SEP> 46.2 <SEP> 1.0 <SEP> 0.6 <SEP> 4.0 <SEP> 3.0 <SEP> 10 <SEP> 10 <tb> <SEP> IVA <SEP> 40 <SEP> 51.7 <SEP> 1.0 <SEP> 1.0 <SEP> 3.0 <SEP> 3.0 <SEP> 34 <SEP> 15 <tb> <SEP> IVB <SEP> 45 <SEP> 45.4 <SEP> 1.0 <SEP> 0.6 <SEP> 3.0 <SEP> 5.0 <SEP> 60 <SEP> 65 <tb> <SEP> IVC <SEP> 45 <SEP> 46.1 <SEP> 1.5 <SEP> 1.0 <SEP> 4.0 <SEP> 3.0 <SEP> 40 <SEP> 32.5 <tb> <SEP> IVC <SEP> 45 <SEP> 44.2 <SEP> 1.0 <SEP> 1.0 <SEP> 3.0 <SEP> 5.0 <SEP> 160 <SEP> 125 <tb> <SEP> IVE <SEP> 40 <SEP> 49.1 <SEP> 1.0 <SEP> 1.0 <SEP> 4.0 <SEP> 5.0 <SEP> 140 <SEP> 127.5 <tb> <SEP> IVF <SEP> 40 <SEP> 49.5 <SEP> 1.5 <SEP> 0.6 <SEP> 4.0 <SEP> 5.0 <SEP> 13 <SEP> 15 <tb> <SEP> IVG <SEP> 40 <SEP> 51.4 <SEP> 1.5 <SEP> 0.6 <SEP> 3.0 <SEP> 3.0 <SEP> 10 <SEP> 20 <tb> <SEP> IVH <SEP> 45 <SEP> 45.4 <SEP> 1.0 <SEP> 0.8 <SEP> 3.0 <SEP> 5.0 <SEP> 160 <SEP> 142.5 <tb> The above description is for the purpose of teaching.those skilled in the art how to practice the present invention and is not intended to recite all those obvious modifications and variations thereof which will become apparent upon reading this disclosure. It is intended, however, that all of these obvious modifications and variations be included within the scope of the present invention which is defined by the following claims.

Claims: Claims 1. A composition comprising the random polymerization product of a mixture of monomers comprising styrene, butadiene, and from 2 to 12 %, based on the combined weight of the monomers, of an alkyl methacrylate, wherein the alkyl group comprises from 1 to 18 carbon atoms. 2, A composition according to claim I where in the monomer mixture further comprises from 1 to 5 % of a copolymerizable carboxylic acid. 3. A composition according to claim 2 wherein the copolymerizable carboxylic acid comprises a member selected from the group consisting of itaconic acid, methacrylic acid and a combination of these. 4. A composition according to claim I wherein the alkyl group of the alkyl methacrylate is a member selected from the group consisting of methyl and stearyl. 5. A composition according to claim 1 wherein the styrene comprises 20 to ±0 % and the butadiene comprises 40 to 80 % of the combined weight of monomers. 6. A composition according to claim I wherein the alkyl methacrylate comprises from 4 to 10 % based on the combined weight of the monomers. 7. A composition according to claim 1 which is polymerized in the presence of from 0.4 to 2 %, based on the total weight of the monomers, of chain transfer agent. 8. A composition according to claim 7 wherein the chain transfer agent comprises tertiary dodecyl mercaptan. 9. A composition according to claim 7 wherein the monomer mixture comprises from I to 5 weight % of a copolymerizable carboxylic acid, 20 to 60 weight % styrene, and from 40 to 80 weight % butadiene, and the alkyl group of the alkyl methacrylate is a member selected from the group consisting of methyl and stearyl. 10. A pressure sensitive adhesive comprising a composition according to claim 1. 11. The composition of claim 1, wherein said monomer mixture comprises from 35 to 45 weight percent styrene, and from 55 to 65 weight percent butadiene. 12. The composition of claim II, wherein monomer mixture comprises from 4 to 10 weight percent alkyl methacrylate. 13. The pressure-sensitive adhesive of claim 10, wherein said monomer mixture comprises from 20 to 60 % styrene and from 40 to 80 % butadiene based on the combined weight of monomers. 14. The pressure-sensitive adhesive of claim 13, wherein said monomer mixture comprises from 1 to 5 % carboxylic acid. 15. The pressure-sensitive adhesive of claim 13, wherein said monomer mixture comprises 4 to 10 % alkyl methacrylate

Inventors: BARABAS, EUGENE S., OZARI, YEHUDA, WOTIER, EDWARD J.
Applicants: POLYSAR INTERNATIONAL S.A.
Application year: 1980
Main classification: C08F236
IPC codes: C09J7, C08F236, C08F212