MXPA97002589A - Polymers of diohe monohydroxylated and derived from the same converted to epox - Google Patents

Abstract

The present invention relates to a monohydroxylated polydiene polymer, characterized in that they comprise at least two monomers of ethylenically unsaturated hydrocarbons, which can be polymerized, wherein at least one is a diene monomer which produces an unsaturation suitable for conversion to epoxide, and wherein the polymer has been hydrogenated in such a way that aliphatic double bonds remain in an amount of 0.1 to 7 milliequivalents per gram of the polymer

Description

POLYMERS OF MONOHYDROXYLED DIAMONDS AND DERIVATIVES OF THEM CONVERTED TO EPOXIDE FIELD OF THE INVENTION The present invention relates to monohydroxylated dienes, which are suitable for use in a variety of applications including adhesives, sealants, coatings and the modification of other polymers or asphalt. More specifically, the present invention relates to polydienes, monohydroxylated, epoxide-converted, particular polymers, and their derivatives converted to epoxide.

BACKGROUND OF THE INVENTION The monohydric polydienes are known. Most of these polymers are homopolymers of one or another diene. For example, monohydroxylated compounds are known in the art for use in adhesive formulations. U.S. Patent No. 4,242,468 describes coatings of REF: 24385 polyurethane, without solvents, which have an improved flexibility that results from the incorporation of monohydroxylated po bibutadi es. The epoxide-converted versions of the hydroxy-1-hydroxypropyl compounds are known as such. Also known are polydiene polymers, converted to epoxide, of low viscosity, especially for use in adhesives. These polymers are described in U.S. Patent Nos. 5,229,464 and No. 5,247,026. Although the low viscosity polymers of the prior art are useful in applications where aliphatic epoxies are generally employed, they suffer from the disadvantage that they are not reactive via a broader class of chemistry. In addition, epoxide conversion is expensive and many examples of the prior art required high levels of epoxy functionality to be useful. The incorporation of a more economical portion that provides an equal or wider chemical utility is highly desirable. The present invention provides polymers that overcome the disadvantages of limited chemical reactivity, mentioned above. In addition, in applications that require epoxy functionality, for chemical compatibility, these polymers reduce the necessary epoxy levels. The present invention relates to a monohydroxy polydiene polymer, which comprises at least two ethically unsaturated hydrocarbon monomers, which can be polymerized, wherein at least one is a diene monomer which produces a suitable unsaturation for the conversion to epoxide, and where the polymer has been hydrogenated in such a way that from 0.1 to 7 ml of 1 iquote valium (meq) per gram of polymer, of aliphatic double bonds remain. The invention also relates to partially unsaturated and / or epoxide-converted derivatives of the monohydroxylated polydiene polymers of the present invention. The hydroxylated polymers are preferably block copolymers of at least two diene monomers, preferably isoprene and butadiene, and, optionally, a lactic-acid hydrocarbon wherein a hydroxyl group is attached to one end of the polymer molecule. These polymers can be hydrogenated or non-hydrogenated but are preferably converted to epoxide. The preferred monohydroxy polydiene polymer of the present invention has the structural formula OH) X-A-Sr-B- (OH wherein A and B are polymer blocks which may be blocks of homopo-1-block-units of conjugated diolefins, blocks of copolymers of monomers of conjugated diolefins, or blocks of copolymers of monomers of diolefins and monomers of monoalkeni-1-aromatic hydrocarbons. These polymers can contain up to 60% by weight of at least one mineral hydrocarbon, preferably styrene. Preferably the A blocks have a higher concentration of more highly substituted aliphatic double bonds than the B blocks have. Thus, the A blocks have a higher concentration of unsaturated sites of subsides, tr i subsides, or tetra-substituted (double aliphatic bonds) per unit mass of the block, that which has the B blocks. This produces a polymer where the conversion to epoxide, easier, occurs in the A blocks. Conveniently, the A blocks have a molecular weight that is in the range from 100 to 6,000, preferably in the range from 500 to 4,000, and most preferably from 1,000 to 3,000, and the B blocks have a molecular weight in the range from 1,000 to 15,000, preferably in the range from 2,000 to 10,000 and in the form more preferred in the range from 3,000 to 6,000. S is a vinylaromatic hydrocarbon block that can have a molecular weight in the range of 100 to 10,000. x and y are 0 or 1. Any of x or y must be 1, but only one at a time can be 1. z is 0 or 1. Any of the blocks A or B can be crowned or terminated with a miniblock of a polymer of a composition different, having a molecular weight that is in the range from 50 to 1,000, to compensate for any initiation, tapering due to unfavorable coding speeds 1 imer ization, or difficulties in the coronation. These polymers can be converted to epoxide in such a way that they contain from 0.1 to 7.0 ml and 1 equivalents (meq) of epoxy groups per gram of polymer. Polymers containing ethylenic unsaturation can be prepared by the anionic coding 1-ionization of one or more olefins, particularly diolefins, alone or with one or more hydrocarbon monomers to which the aromatics are attached. The copolymers can, of course, be random, tapered, block or a combination thereof. Diene-containing polymers, which have a residual unsaturation, suitable for conversion to epoxide, can also be obtained by other polymerization means, such as by cationic polymerization or free-radical polymerization. By using cationic polymerization, monomers such as 1-butenes, 1-pentenes, substituted, and dienes such as isoprene and butadiene can be copolymerized. As the anionic polymerization, the cationic, latent polymerization allows the copolymers to be block copolymers having the residual diene double bond located in the polymer. The dienes can be polymerized together with acrylic monomers, by initiation with a free radical initiator, such as a peroxide or the AIBN. For applications in pressure sensitive adhesives, monomers such as n-butyl acrylate, 2-ethylhexyl acrylate, and isoprene, and other modifying monomers, such as acrylic acid or acrylate may be used. 2 -hydroxy -eti lo. Other polymerization methods can be used that include coordination / insertion mechanisms such as Ziegler-Na tta polymerizations, metallocene polymerizations and metathesis polymerizations or double chemical substitution, to make the diene-containing polymers. Polymers containing ethylenic unsaturation or unsaturation, both aromatic and ethylenic, can be prepared using anionic initiators or polymerization catalysts. These polymers can be prepared using bulk, solution or emulsion polymerization techniques. When polymerizing to a high molecular weight, the polymer containing at least the ethylenic unsaturation will be recovered, generally, as a solid such as lumps, a powder, troches or the like. When polymerized to a low molecular weight, it can be recovered as a liquid. In general, when using anionic techniques in solution, copolymers of conjugated diolefins, optionally with vinylated aromatic hydrocarbons, are prepared by contacting the monomer or monomers to be polymerized, simultaneously or sequentially, with an anionic polymerization initiator. , such as group IA metals, their alkyls, amides, silanolates, naphtalides, diphenyls or anthracenyl derivatives. It is preferred to use an organic alkali metal compound (such as sodium or potassium) in a suitable solvent, at a temperature that is in the range of -150 ° C to 300 ° C, preferably at a temperature that is in a range from 0 ° C to 100 ° C. Particularly effective anionic polymerization initiators are the organolithium compounds, which have the general formula: RLi, wherein R is an aliphatic, cyclic or aromatic or aromatic substituted alkyl aromatic hydrocarbon radical having from 1 to 20 carbon atoms and n is an integer from 1 to 4. The conjugated diolefins which are they can polymerize anioni cament and include those conjugated diolefins containing from 4 to 24 carbon atoms, such as 1,3-but-adieno, isoprene, piperylene, me ti lpent adiene, phenyl-butadiene, 3,4-dimethyl ti 1 - 1, 3 -hexadine, 4,5-diethyl-1,3-octyl adiene and the like. Isoprene and butadiene are preferred conjugated diene monomers for use in the present invention, because of their low cost and easy availability. The alqueni 1 (vini 1) aroma oils, which may be copolymerized, include the vinyl compounds such as styrene, various styrene substituted with alkyl, styrene substituted with alkoxy, vini lnaft aleño, vini lnaphthalenos, substituted with alkyl, and imides. The monohydroxylated polydienes can be synthesized by the anionic polymerization of hydrocarbons of conjugated dienes with lithium initiators. This process is well known and is described in U.S. Patent Nos. 4,039,593 and Reissued Patent No. 27,145, the descriptions of which are incorporated herein by reference. Polymerization begins with a monolithium initiator which forms a skeleton or latent polymer structure at each lithium site. Typical monolithium latent polymer structures, which contain conjugated diene hydrocarbons, are: X-A-B-Li X-A-B-A-Li wherein B represents polarized units of a conjugated diene hydrocarbon, such as butadiene, A represents polarized units of another conjugated diene such as isoprene, and any of A or B may contain one or more other vinylated compounds. laromatics such as styrene, and X is the residue of a monolithium initiator, such as s-but-i-ti-i. The hydroxyl groups can be added by the terminal coronation of the polymerization, with oxiranes such as ethylene oxide, followed by completion or termination with methanol. The monohydroxy diene polymers can also be manufactured using a monolithium initiator containing a hydroxyl group that has been blocked as the silyl ether. A suitable initiator is the hydroxypropyl ether in which the hydroxyl group is blocked as the ether ter -but i 1 -dime t i 1 s i 1 i 1 ico. This monolithium initiator can be used to polymerize isoprene or butadiene in a polar solvent or in a hydrocarbon solvent. The latent polymer is then finished with methanol. The silyl ether is then removed by acid-catalyzed decomposition, in the presence of water, to produce the desired monohydroxypolyne polymer. When one of the conjugated dienes is 1, 3-but adi eno and is the one that will be hydrogenated, the anionic polymerization of the conjugated diene hydrocarbons is typically controlled with structure modifiers such as diethyl ether or glyme (1, 2 - di ethoxyethane) to obtain the desired amount of the addition in 1.4. As described in Reissue Patent No. 27,145, which is incorporated herein by reference, the 1,2-addition level of a butadiene polymer or copolymer can greatly affect the properties after hydrogenation. Hydrogenated polymers exhibit improved thermal stability and weathering in the final adhesive, sealant or coating. The most preferred polymers are the diblock polymers that fall within the scope of formula (I) mentioned above. The overall molecular weight of these diblocks can vary from 1,500 to 20,000, preferably from 3,000 to 7,000. Any of the blocks in the diblock may contain some randomly polymerized vinylated hydrocarbon, as described above. For example, where I represents isoprene, B represents butadiene, S represents styrene, and a diagonal line (/) represents a random copolymer block, and the diblocks may have the following structures: IB-OH IB / S-OH I / SB-OH II- / B-OH or B / IB / S-OH BB / S-OH I-EB-OH I-EB / S-OH or IS / EB-OH I / S-EB-OH HO-IS / B HO-IS / EB where EB is hydrogenated butadiene, -EB / S-OH means that the hydroxyl source is attached to a block of po 1 i is pull, and -S / EB-OH means that the hydroxyl source is linked to a block of hydrogenated hydrogenated po ibuty. In the latter case, -S / EB-OH, requires the coronation or termination of the block of "random copolymer" S / EB, with a miniblock EB to compensate the tendency to taper styrene before coronation with ethylene oxide. These diblocks are advantageous because they exhibit a lower viscosity and are easier to manufacture than the corresponding triblock polymers. Preferably the hydroxyl is attached to the butadiene block because the conversion to epoxide is carried out more favorably on isoprene, and there will be a separation between the functionalities of the polymer. However, the hydroxyl may be attached to the isoprene block, if desired. This produces a molecule more similar to that of a surfactant with less capacity to bear load. The isoprene blocks can also be hydrogenated. Certain triblock copolymers can also be used suitably. These triblocks usually include a block of styrene or snowflake styrene 1 randomly imbedded to increase the glass transition temperature of the polymers, compatibility with polar materials, strength, and viscosity at room temperature. These tribloques include the following specific structures: I-EB / S-EB-OH I-B / S-B-OH I-S-EB-OH I-S-B-OH O I-I / S-I-OH I-S-I-OH B-S-B-OH B-B / S-B-OH or I-B / S-I-OH I-EB / S-I-OH or I-B-S-OH I-EB-S-OH HO-I-EB-S The last group of polymers, specified in the last line above, where the styrene block is external, is represented by the formula II) HO) x-A-B-S- (OH) and where A, B, S, x and y are as defined above. The conversion to epoxide of the base polymer can be effected by reaction with organic percents which can be preformed or formed in situ. Conveniently preformed perishes include peracetic and perbenzoic acids. The in situ formation can be carried out using hydrogen peroxide and a low molecular weight fatty acid such as formic acid. Alternatively, hydrogen peroxide in the presence of acetic acid or acetic anhydride and a cation exchange resin will form a peracid. The cation exchange resin can optionally be replaced by a strong acid such as sulfuric acid or p-toluenesulfonic acid. The conversion reaction to epoxide can be carried out directly in the polymerization cement (polymer solution in which the polymer was polymerized) or, alternatively, the polymer can be redissolved in the inert solvent. These methods are described in detail in U.S. Patent Nos. 5,229,464 and 5,247,026, which are incorporated herein by reference. In particular, it has been found that when peracetic acid is used for conversion to epoxide, the epoxide conversion rate of the residual aliphatic double bonds in polyisoprene and polybutene is as follows: 1,4-polyisoprene (double tri-substracted aliphatic bonds) > 1,4-polybutadiene (double aliphatic 1,2-di-substituted substrates) > 3,4-polyisoprene (1,1-di-substituted aliphatic double bonds) > 1,2-polybutadiene (double aliphatic monounsubstituted bonds). It has not been observed that they are converted to epoxide, 1,2-p-1-butadiene or polystyrene. The molecular weights of the linear polymers or of the non-assembled linear segments of the polymers, such as monoblocks, diblocks, triblocks, etc., star polymer arms, before coupling, are conveniently measured by Gel Permeation Chromatography ( GPC, for its acronym in English), where the GPC system has been properly calibrated. For linear anionic polymerized polymers, the polymer is essentially onodisperse (with a weight average molecular weight / number average molecular weight ratio approaching unity), and it is both convenient and adequately descriptive to report the "maximum" molecular weight of the narrow molecular weight distribution, observed. Usually, the maximum value is between the average of the molecular weights in number and weight. The maximum molecular weight is the molecular weight of the main species shown in the chroma t ógr a fo. For solid polymers, the weight average molecular weight should be calculated from the chromatograph and used as such. For the materials to be used in the GPC columns, styrene-di vini-benzene gels or silica gels are commonly used, and they are excellent materials. Tetrahydrofuran is an excellent solvent for polymers of the type described herein. A refractive index detector may be used. If desired, these block copolymers may be partially hydrogenated. The hydrogenation can be carried out selectively as described, for example, in Reissue US Patent No. 27,145 which is incorporated herein by reference. The hydrogenation of these polymers and copolymers can be carried out by a variety of well-established processes including hydrogenation in the presence of catalysts such as Raney Nickel, noble metals such as platinum and the like, transition metal catalysts, soluble , and catalysts as described in the Non-Theatrical Patent No. 5, 039,755 which is also incorporated herein by reference. The polymers can have different diene blocks and these diene blocks can be selectively hydrogenated as described in U.S. Patent No. 5,229,464 which is also incorporated herein by reference. Hydroxylated, partially unsaturated polymers are preferred for the additional functionalization such as for making the epoxide-converted polymers of this invention. They can also be chlorinated, brominated, or reacted with maleic anhydride, or used directly for vulcanization or for reaction with amine resins. Preferably, the partial unsaturation is such that from 0.1 to 0.7 meq / g of aliphatic double bonds remain for subsequent epoxide conversion. The epoxide-converted derivatives of these polymers can be used in pressure sensitive adhesives, in films, sealants, coatings, structural adhesives, adhesives for lamellar structures, pressure sensitive structural adhesives, printing plates, and in the modification of other polymers and / or asphalt (ie, mixtures with other polymers and / or asphalt, for the purpose of altering the properties of those materials). Polymers not converted to epoxides can be used in applications for which other monohydroxylated polymers have commonly been used, included as a part of a binder system for adhesives. However, their main utility is that they are functional, for example by conversion to epoxide, to form useful functional derivatives and z tones. The present invention also relates to a composition comprising any of the monohydroxylated polydiene polymers, converted to epoxides, as described hereinabove, and a resin for tack or tack. One of these compositions is useful in pressure sensitive adhesives and in sealants. Conveniently, the resin for adhesiveness is added in an amount of 20 to 400 parts per hundred parts of the polymer. A common adhesive resin is a dione-olefin copolymer of piperylene and 2-methyl t-1,2-butene, which has a softening point of about 95 ° C. This resin is commercially available under the trade name WINGTACK 95 (WINGTACK is a trademark) and is prepared by the cationic polymerization of 60% piperylene, 10 or isoprene, 5% cyclopentadiene, 15% 2 -met i 1-2 -butene and approximately 10% dimer, as described in US Pat. No. 3,577,398. Other resins can be used for the adhesiveness, wherein the resinous copolymer comprises from 20 to 80% by weight of piperylene and from 80 to 20% by weight of 2-me t i 1-2-butene. The resins usually have softening points, in ring and ball, as determined by the method E28 of the ASTM, between about 80 ° C and 115 ° C. Aromatic resins can also be used as resins for adhesiveness, provided they are compatible with the particular polymer used in the invention. Normally, these resins will also have softening points, in ring and ball, which is between 80 ° C and 115 ° C, although mixtures of aromatic resins with low and high softening points can also be used. Useful resins include coumarona-indene resins, polyoxyethylene resins, vinyl-aluminum copolymers, and polyindene resins. Other adhesion-promoting resins, which are also useful in the compositions of this invention, include hydrogenated rosins, rosin esters, pol terpenes, terpenephenol resins and mixed olefins, po 1 imides, resins with lower softening points and liquid resins. An example of a liquid resin is the ADTAC LV resin (ADTAC is a trademark) of HERCULES. In order to obtain a good color and color stability, it is preferred that the resin for the adhesiveness be a saturated resin, for example, a hydrogenated dicyclopentadiene resin, such as ESCOREZ 5000 (ESCOREZ is a trademark) series of resins manufactured by EXXON or a resin of pol i al fame ti les t ireno or of pol ies t ireno, hydrogenated, such as the resin REGALREZ manufactured by HERCULES. The softening points of the solid resins can be from 40 ° C to 120 ° C. Liquid resins can be used, that is, with softening points lower than room temperature, as well as combinations of solid and liquid resins. The amount of the adhesion promoter resin used varies from 20 to 400 parts by weight per one hundred parts of rubber (pee), preferably between 20 and 50 pee, and most preferably between 50 and 250 pee. The selection of the agent for adhesion, in particular, is largely dependent on the specific polymer employed in the adhesive and sealant compositions, respectively. The present invention further relates to a crosslinkable composition, which comprises any of the monohydroxylated polydiene polymers, converted to epoxide, as described above, and an amino resin. For the purposes of this invention, an amino resin is a resin made by the reaction of a material containing NH groups, with a carbonyl compound and an alcohol. The material containing NH groups is commonly urea, melamine, benzoguanamine, glycoluril, cyclic ureas, thioureas, guanidines, urethanes, cyanamides, etc. The most common carbonyl component is formaldehyde and other carbonyl compounds include higher aldehydes and ketones. The most commonly used alcohols are methanol, ethanol, and butanol. Others -alcohols include propanol, hexanol, etc. AMERICAN CYANAMID (renamed CYTEC) sells a variety of these amine resins, as do other manufacturers. The AMERICAN CYANAMID literature describes the following three classes or "types" of amino resins that they offer for sale.

Type 1 Type 2 Type 3 wherein Y is the material containing the NH groups, the carbonyl source is formaldehyde and R is the alkyl group of the alcohol used for the alkylation. Although this type of description presents amine resins as a monomeric material having only one pure type, commercial resins exist as mixtures of monomers, dimers, trimers, etc., and any given resin may have some character of other types. Dimers, trimers, etc., also contain methylene or ether bridges. In general, amine resins of type 1 are preferred in the present invention. The amine resins should be compatible with the monohydroxy polydiene polymer converted to epoxide. A compatible amine resin is defined as one that gives a stable mixture in its phase, with the polydiene monohydroxy polymer side, at the desired concentration and at the temperature at which the mixture will be heated and at which the composition will be mixed and applied. For example, the following amine resins of type 1 can be used to achieve the purpose of the present invention: CYMEL 1156 (CYMEL is a trademark) - a resin of the amine-formaldehyde where R is C4H9, CYMEL 1170 - a resin of gl i colur i lo-fo rma ldehí do where R is C4H9, CYMEL 1141 - a modified amino resin with carboxyl, wherein R is a mixture of CH3 and I-C4H9, and BEETLE 80 (BEETLE is a trademark) - a urea-formaldehyde resin wherein R is C4H9. All these products are manufactured by American Cynamid Company and are described in the publication 50 Years of Amino Resins for Coatings, edited and written by Albert J. Kirsch, published in 1986 together with other amino resins useful in the present invention.

CYMEL 1170 is the following gl icolur i 1- formaldehyde resin, where R is C4H9: another is BEETLE 80, a urea-formaldehyde resin, in which R is C4H9 whose ideal monomeric structure is represented by: In the crosslinkable composition of the present invention, the epoxide-converted polydiene polymer converted to epoxide conveniently comprises from 50 to 98% by weight (% p) of the composition of po 1 / res amine. Thus, the amino resin comprises from 50 to 2% by weight of the composition. In addition to the amine resin, the crosslinkable composition of the present invention may contain a reinforcing agent. Suitable reinforcing agents include ethylene glycol, 1,3-propanedio-1,4-but-anodiol, 2-methyl-1, 2-propanediol, 1,6-hexanediol, 2-me thi-1. , 3-propanediol, 2-ethyl-1- 1, 3-hexanediol 1, 2,2,4-t rime ti 1 - 1, 3 -pent anodiol, cyclohexane dimethyl, bisphenol A, neopent i 1 gl i co 1, glycerol , triamotene and trimethylolpropane. Conveniently, that composition, which can be crosslinked, comprises from 30 to 90% by weight of the monohydroxylated polydiene polymer converted to epoxide, from 8 to 60% by weight of the amine resin crosslinking agent, and from 2 to 40% by weight. weight of the reinforcing agent. The crosslinked materials, as described above, are useful in adhesives (including pressure sensitive adhesives, contact adhesives, adhesives for lamellar structures, adhesives for assemblies and structural adhesives), sealants, coatings, and films, (such as those which require resistance to heat and 1 vent is).

E g 1-6 In the examples, various tests are used for the adhesives, to demonstrate the properties of the test formulations, using the improved binders of this invention. The degree of covalent cure, obtained for each of the adhesive samples, was measured by the use of a test for the polymer gel content, developed by JR Eric for radiation curing adhesives, and first described in the article " Experimental Thermoplastic Rubbers for Radiation Reticulation, Improved, PSA Heat Melt ", TAPPI 1985 Hot Melt Sy posium Proceedings, June 1985. The method, as carried out for the following examples is essentially identical to the published method, and differs only by a few improvements and corrections The% p values indicate the percentage by weight of the binder polymers that are covally bound to the three-dimensional gel network The 180 ° detachment in polished steel is determined using Method No. 1 of the Council of Pressure Sensitive Tapes Large values indicate high strength when a test tape is detached from the substrate.Ribbon Adhesive (LT) is determined using a TLMI Loop Adhesive Analyzer. Polyken probe (PPT) is determined by ASTM D2979. High values for LT and PPT indicate aggressive stickiness or adhesion.The Power of Subjection (HP, for its acronym in English s) is the time required to pull or pull a standard area (2.54 cm x 2.54 cm) of tape, from a standard test surface (Mylar, steel) under a standard load (500 g, 2 kg), in antisense to 2 ° (Method No. 7 of the Council of Sensitive Tapes to the Pressure), to a certain temperature (23 ° C, 95 ° C). Long times indicate a high resistance to adhesion and cohesion. The Shear Adhesion Failure Test (SAFT) is similar to the HP, except that the temperature at which the failure occurs is recorded. The SAFT is carried out in an oven that increases its temperature at a rate of 4.44 ° C (44 ° F) per hour. High temperature values indicate a high resistance to cohesion and adhesion. A number of polymers are used in the binder systems of Examples 1 and 2. Many of their important characteristics are presented in the following table.

Table 1 I is polyisoprene, B is polybutyl, EB is polyethylene-butylene (fully hydrogenated polybutylene), and OH is primarily hydroxy from the coronation or termination with ethylene oxide. * * The polyisoprene was partially hydrogenated and then converted to epoxide, with peracetic acid. The polymer 13 is a polymer described by structural formula I, specifically, I-S / EB-OH, wherein a mini-block of EB is added to ensure the addition of the ethylene oxide to a latent butadiene polymer.

In these Examples a number of other formulation ingredients were also used, and these are described in the following table.

DESCRIPTION OF FORMULATION INGREDIENTS IN EXAMPLES 1-6 Example 1 Adhesive 1, as shown in Table 2, was prepared, emptied, and cured by mixing all the ingredients at room temperature with solvents using as the solvent tetrahydrofuran (THF) The adhesive solution was emptied onto a clean, 2.54 x 10 mm Mylar sheet. The final thickness of the dry film, of the adhesive, was 0.127 mm (5 x 10 in). The test film was cured directly with UV radiation, and the adhesive was oriented toward the radiation of 9.15 m / min (30 feet per minute), under a single medium pressure Hg bulb, using a Linde Photocure processor. A nitrogen atmosphere was used, only for the purpose of reducing the ozone of the bulb, since the cationic systems do not need an oxygen-free atmosphere to cure. A device for measuring the reaction dose was also passed under the lamp. A dose of 150-160 mJ / cm was recorded. Immediately after exposure to UV radiation, the test adhesive was further baked for 10 minutes at 121 ° C. Their properties were analyzed which are also presented in Table 2. The adhesive 1 is a compound wherein the diene polymer, converted to epoxide, also contains a hydroxy group. The curing of the adhesive 1 is excellent, as are its aggressive adhesion and SAFT. It presents all indications of having excellent cohesive strength, exhibited viscous splitting during the HP test at room temperature, with apparently false results.

Table 2 - Monohydroxylated diene polymer binder Formulations in 100 parts presented with the results Table 2 - Monohydric diene polymer binder (Continued) Formulations in 100 parts presented with the results "v" is the viscous splitting of the adhesive (adhesion &cohesion is the release of the adhesive from the substrate interfaces (cohesion &adhesion) Example 2 The adhesives 2, 3, and 4, which are presented in Table 3, were prepared, emptied, and cured as described in Example 1. The 180 ° peel test was not performed due to equipment malfunction. Adhesive 3 had no cohesive force at all. It remained a "sticky substance" even after curing with UV radiation and additional baking and was not sufficiently manipulated to perform even the gel test, probably because no polymer had been converted to epoxide. Adhesive 3 used Polymer 5, a polymer similar to Polymer 3 except that it was not converted to epoxide. Adhesives 3 and 4 have good PSA properties.

Table 2 Formulations in 100 parts, shown in the results Table 2 (Continued) Formulations in 100 parts, shown in the results E j emp lo 3 Formulations were prepared to analyze the concept of using mixtures of diene polymers, converted to epoxide, with diene monools and diols, as adhesives for lamellar structures. Adhesives for lamellar structures seem to work via a totally different mechanism than PSAs that are emptied into relatively thick layers. This thick layer is able to absorb a lot of energy through viscous flow during deformation and this provides the resistance of the PSA. In adhesives for lamellar structures, the layers are relatively thin and these adhesive layers must strongly bond two substrates. Due to the thinness, the viscous dissipation of energy within the adhesive layer is not a dominant resistance mechanism. On the contrary, the adhesion between the adhesive and the substrate must provide the required strength or strength. The polymers used in the formulations of adhesives for lamellar structures are described in Table 1 and Example 1. In particular, the polymer 13 is I -S / EB-EB-OH, converted to epoxide, with molecular weights of the segments of 2, 000 -2, 500/1350 - 150-OH. The S / EB block, randomized, has a strong tendency to taper, where the styrene polymerizes at the end. In order to manufacture the polymer 13 it was arbitrarily decided to join the hydroxy source to a block of hydrogenated hydrogenated po bage. Therefore, to ensure that the source of hydroxy (ethylene oxide) adhered to the block of po bibutive add, the miniblock EB of molecular weight 150 was added. Polymer 13 was manufactured by polymerization of isoprene in cyclohexane, without ether, and after all the isoprene was polymerized, diethyl ether was added to give 6% of the total solvent. Then, styrene and butadiene are added over time, until the polymerization of the polybutadiene miniblocks is completed, the ethylene oxide is added, and then the latent polymer is terminated with methanol. The polymer is partially hydrogenated to completely hydrogenate the polybutyl blocks and some of the polyisoprene blocks. The polystyrene blocks are not hydrogenated. The polymer is washed to remove the hydrogenation catalyst, and then converted to epoxide, with peracetic acid. The epoxide-converted polymer is washed, stabilized with a small amount of the antioxidant IRGANOX 1010 (IRGANOX is a trademark) and recovered by evaporation of solvents. Formulations were made in accordance with Table 3. The ingredients were dissolved in THF to prepare a 10% solids solution. Preliminary work indicated that the curing agent of the present, Leecure B1310, would have completely dissolved in THF. Partial solubility was found using toluene as the solvent. All ingredients except B1310 (a BF3 catalyst, blocked, from Leepoxi, Inc.) were dissolved in THF. Once dissolved, B1310 was added and the solution was placed on a roller for several minutes. The formulation was then emptied onto a poly- (eti lent ere phthalate) film to give a nominal thickness of the adhesive layer of 0.0076 mm (0.3 x 10 pig). The film was allowed to air dry for 1 hour. When it was dry, another film of pol i (eti lentereftalato) was laminated to the top of the adhesive layer. The laminated structure was pressurized using a 0.9 Kg (2 Ib) roller. Strips of 2.54 cm (1 pig) were cut and then treated with heat under moderate pressure at 50 ° C for 60 seconds. The laminates were then analyzed for strength, using a T-strip geometry on an Instron voltage analyzer. The detachment speed was 24.5 cm (10 pig) per minute. Table 4 shows the results for rolled products as they were manufactured and then hardened at room temperature. The total molecular weight of Polymer 13 is low and therefore must undergo substantial chemical cross-linking to form a load bearing network. With polymer 13, an improvement was found by the addition of a monol. Compare control 1 and formulations 3 and 4. the incorporation of monol alone (formulation 4) gave an increase of immeasurable low resistance, up to 124 grams by 2.54 linear centimeters (124 grams per linear inch (gpl)). The additional incorporation of a diol gave an additional increase to 211 grams by 2.54 linear centimeters (211 gli). After aging for 24 hours the curing reaction continued. It is observed, for all the samples, some increase in the value of the detachment T. The mode of the failure continues being cohesive (that is, it damages the layer of adhesive (viscous splitting) instead of the interface). The observed trend for the values of detachment T, initials, is continued after 24 hours. The incorporation of the monol or of the diol, served to increase the strength of the adhesive for lamellar structures, when the polymer, converted to epoxide, was terminated with hydroxyl. The best resistances or forces achieved are in the range of 100 to 400 gli of resistance to initial T shedding.

Table 3 Adhesive formulations for structures 1 amelar Table 4 Release results T E j us 4 Many performance properties of epoxy, modified, cured resin compositions of the present invention are important. Tension properties such as strength, elongation, and Yong modulus are measured in accordance with ASTM D-638. Flexural properties such as the modulus of bending, tension and deformation when failing are measured in accordance with ASTM D-790. Stress fracture stiffness, which is characterized by stress intensity factor (KIC) for rupture propagation, is measured in accordance with ASTM E-399-83. Using the KIC value, thus measured, the energy for the fracture (G? C) was calculated for the flat deformation conditions used. The properties of the adhesive, such as the shear stress with overlap, were measured in accordance with ASTM D-1002. The vitreous transition temperature (Tg) was measured using dynamic mechanical analysis with torsion bar. Table 5 below shows the composition of the polydiene polymers, converted to epoxide. Polydienes are compared, converted to epoxide, monohydroxylated and non-hydroxylated.

Table 5 Composition of Polymers converted to Epoxide * S = Yes, N = No In the architecture column of the base polymer of Table 5, B represents blocks of poly i (1,3-butadiene), I represents blocks of polyisoprene, and OH represents the monohydroxyl functionality. The blocks of ho opo 1 omeres are separated by a line. The cloud points, blends and exemplary polymers in the EPON 828 resin (EPON is a trademark) with a weight ratio of 1/9, are shown in Table 5. For the polymer converted to epoxide, monohydroxylated , a clear and significant advantage is shown. Very similar cloud points are achieved for the two polymers, but the polymer of the present invention achieved that cloud point only with 3.4 meq / g epoxide, 1.4 meq / g less than the non-hydroxylated, comparative polymer. They were added to 11 parts of the monohydroxylated polymer A, converted to epoxide, or 11 parts of the monohydroxylated polymer, comparative, both with the basic structure IB, to 100 parts of EPO resin 828, an ether di gl i ci di di 1 i co bisphenol-A. 33 parts of EPI-CURE 3140 (EPI-CURE is a trademark) (a curing agent based on polyamide) per 100 parts of EPON 828 resin (EPON is a trademark) were added to the mixture by manual stirring. polymer converted to epoxide. To assist in defoaming the mixture, a small amount (less than 1 part per 100 parts of EPON 828 resin plus epoxide-converted polymer) of PC-1344 / mono functional glycidyl epoxide solution was added. The mixture was degassed under vacuum and centrifuged. The mixture was emptied between glass plates to form 0.32 cm (1/8 pig) plates that were cured at room temperature for 7 days before analysis. The mechanical properties of epoxies modified with rubber, resulting, are listed in Table 6 which provides a comparison of these mixtures and the epoxy resin cured without polymer converted to epoxide, added. The incorporation of Polymer A and the comparative polymer leads to increases in energy for fracture (Gi c) of 192% and 92%, respectively, while maintaining good tensile and bending properties. These results demonstrate that these polymers, converted to epoxides, are effective in achieving a superior balance of properties in epoxy resins cured with polyamides and that the monohydroxylated epoxide-converted polymer provides superior results to those of the epoxy-converted, non-hydroxylated polymer. although the latter has a higher epoxide content.

Table 6 Mechanical properties of the modified EPON 828 E j us 5 The following examples demonstrate the utility of monohydroxylated, epoxide-converted polymers in compositions cured with amine resins. The amine resin used was CYMEL 1156 (CYMEL is a trademark), a melamine-formaldehyde resin where R is C4H9. The acid used to catalyze the reactions of the amine / hydroxyl resin and of the resin / epoxide was CYCAT 600 (CYCAT is a trademark), dodecylbenzene acid (a 70% by weight solution in alcohol is optional). co). The compositions were mixed and coated from a solution with 75% by weight (% p) solids, from the ingredients in a solvent mixture composed of 90% by weight of an aliphatic hydrocarbon solvent, VM &P naphtha, and 10% by weight n-butanol. The following formulation, given in parts by weight, was used.

Compo s i c ion PPP Po 1 number 80 CYMEL 1156 18 CYCAT 600 2 Compo s i c t ion PPP Naphtha VM &P 60 n-But ano 1 7 The following polymers were analyzed in this formulation. Polymers 3, 4, 5, and 7 were described in Example 1. Polymer 14 was a polyisoprene copolymer of PM 2,000 (I) polystyrene PM 4,000 / po 1 hydrogenated adsorbent.

(S / EB), which has only one OH at one end. The block of S / EB with PM of 4,000, in the Polymer 14, was S with PM of 2,500 and EB with MW of 1,500. Polymer 13 was an epoxide-converted version of Polymer 14 (1.5 meq epoxide / g polymer). Polymer 16 was a triblock polymer having the same block of S / EB copolymer, as Polymer 14. However, Polymer 16 had a block with 1000 PM, of polyisoprene converted to epoxide, at each end of the central block S / EB and did not have an OH group. The coatings, with a thickness of 0.05 mm (2 mils), dried, were applied on aluminum panels with a rod with wire # 52. The coatings were cured by baking 20 minutes s 175 ° C. They were qualitatively evaluated for their suitability for use as coatings. The results are the following .

Poly Type Appearance of the coating 4 EB-OH Very sticky 5 I-EB-OH Bear paste 14 IS / EB-OH Bear paste 3 I-EB-OH converted Not sticky, to epoxide and 1 asymeric 13 IS / EB-OH Not sticky, converted Epoxy to epoxide 16 IS / EB-I Non-tacky, converted to epoxies 7 H0-EB-0H Non-sticky, rich The results of Polymer 4 clearly show that a melamine-cured monohydric diene polymer with EB-OH, made from only a diene monomer, is not suitable for use as a coating because it is very tacky. The results of Polymers 5 and 14 show that a monohydric diene polymer, manufactured from at least two diene monomers and subsequently hydrogenating it, selectively, and thus placing an unsaturated block I, on the opposite end to the OH, is it behaves significantly better than the polymer 4. However, these coatings are not yet suitable because they are still sticky. The results of Polymers 3 and 13 show that the conversion to epoxide of block I on the opposite end to OH, converts the monohydroxylated polydiene polymers, manufactured from at least two diene monomers, into useful coating compositions. The results for polymers 16 and 7 confirm that a polymer with epoxy groups on both ends or an OH group on both ends is useful in coatings, as is well known.

E j us 6 The mechanical properties of the coatings manufactured in accordance with the present invention were evaluated. The appearance (gloss) of the coatings was judged visually. The pencil hardness (scratched) of the coatings was measured in accordance with the ASTM D3363 method of successively pushing softer pencil tips through the coating until the tip of the pencil no longer scratched the coating. The hardness scale (from softest to hardest) is 6B >; 5B > 4B > 3B > 2B > B > HB > F < H < 2H < 3H < 4H < 5H < 6H. Resistance of the coatings, to the metrixite (MEK, for its acronym in English) was measured in accordance with the method ASTM D4752 of rubbing a cloth moistened with MEK through the coating for 200 cycles , or until the break showing the aluminum substrate (one cycle is equal to one forward and one backward). The adhesion of the coatings was measured with the cross-hatch adhesion test, ASTM D3359, method B. In this test, a reticular pattern is drawn through the coating, pressure sensitive tape is applied and removed, and evaluates the amount of coating removed. The scale varies from 5 (no loss of adhesion) to 0 (loss of adhesion greater than 65%). The effectiveness of the monohydroxylated diene polymers, to improve the properties of the coatings, was analyzed in two acrylic urethane formulations (5 and 6) using the acrylic polyol and two different tanning agents. The compositions of these formulations are presented in the following table. The hydroxyl equivalent weight (OH) of JONCRYL 510 (JONCRYL is a trademark) (80% by weight of solids) is 500. The isocyanate equivalent weight (NCO) of DESMODUR Z-4370 (DESMODUR is a trademark) (70% by weight of solids) and DESMODUR Z-3390 (90% by weight of solids) are 365 and 216, respectively. The acrylic polyol and the curing agents based on titanium were mixed with a molar ratio of NCO to OH, from 1.1 to 1, the catalyst DABCO T-12 was added, and the coatings were applied on the steel panels. In the following experiments four different polymers were compared, all with a molecular weight of 6,000. Polymer 5 was an I-EB-OH, converted to epoxide (epoxide content of 1.5 meq / g). Polymer 13 was an I-S / EB-OH, converted to epoxide (epoxide content of 1.5 meq / g) and Polymer 14 was its precursor without converting to epoxide (content of double bonds of 1.7 meq / g). Polymer 16 was an I-S / EB-I, converted to epoxide (epoxide content of 1.2 meq / g). The polymers were dissolved so that there was a solids content of 70 or by weight, in 2-heptanone, which had been previously dried with molecular sieves. The polymer solutions were mixed with the catalyst and the catalyst for 24 hours before the acrylic polyol was added and the coatings were applied to steel panels.

The solutions were inspected to see if they were stable in their phase and those that were not separated in phases were applied on steel panels (panels D36 CRS of Q-Panel Corp.) using a rod with arroy wire # 22. The coatings were analyzed after being maintained at room temperature for two weeks. The following results were obtained . In formulation 5, the solution with Polymer 5 was separated into phases. All other polymers gave stable solutions in their phase and were applied as coatings, the properties of which are shown in the following table.

The fact that Polymer 5 separates into phases shows that the polymer must have some styrene to gain compatibility with this socially active system. Polymers 13 and 14, with and without epoxide, both influenced the properties of acrylic urethane at about the same degree - both reduced hardness and increased adhesion. The results of Polymer 16 show that, although its styrene content was sufficient to give a stable solution in its phase, it returned to the cured, sticky coating, and therefore is inadequate. Thus, the hydroxyl group is required in Polymers 15 and 14 to achieve satisfactory performance. In formulation 6, the only polymer that gave a stable mixture in its phase was Polymer 13. These results clearly show that in this case, styrene is required in the polymer, block I must be converted to epoxide, and the OH group. The coating properties for Polymer 13 in formulation 6 are shown in the following table.

These results show that Polymer 13 gives a dramatic improvement in adhesion, without apparent reduction in other properties.

E j us 7 Various tests are used on the adhesives to demonstrate the properties of the analysis formulations, using the binders comprising a viscosifying or adhesive-generating resin. The degree of covalent cure, obtained for each of the adhesive samples, was measured as described in Examples 1-6. In the binder systems, a number of polymers are used. Many of its important characteristics are presented in the following table.

DESCRIPTION OF THE POLYMERS OF EXAMPLE 7 * I is polyisoprene, DVB is di vini lbenzene, EB is polyethylene-butylene (fully hydrogenated polybutylene), n is the number of arms of the star, and OH is mainly hydroxy from the coronation or termination with ethylene oxide. ** The polyisoprene was partially hydrogenated and then converted to epoxide with peracetic acid.

In this example, a number of other formulation ingredients are also used, which are described in the following table.

DESCRIPTION OF FORMULATION INGREDIENTS FROM EXAMPLE 7 The adhesives A, B, and C, which are shown in the upper part of the following Table, were prepared by mixing all the ingredients in solvent at room temperature, using tetrahydrofuran as solvent. The adhesive solutions were applied on clean sheets or Mylar plies, 2.54 x 10-2 mm. The final thickness of the dry film, of the adhesives, was 0.127 mm (5 mils). The test films were cured directly with UV radiation using 150-160 mJ / cm of UV radiation by passing them under a medium pressure mercury bulb, at a speed of 9.15 meters per minute (30 feet per minute). Immediately after the UV radiation, the test adhesives were baked additionally for 10 minutes, at 121 ° C. Excellent pressure sensitive adhesives were prepared. These cure well to give high gel contents and have an aggressive, excellent adhesiveness, and an excellent cohesive strength.

Table - Pressure Sensitive Adhesives Formulations in 100 parts shown with the results Table (Continued) - Pressure Sensitive Adhesives Formulations in 100 parts shown with the results Foot of Table, from the previous Table: "a" is the release of the adhesive from the interfaces of the substrate (cohesion &adhesion) and "v" is the viscous splitting of the adhesive (adhesion &cohesion). * The viscous split observed during the HP test, at room temperature, seems to be a false result.

Example The following Example demonstrates the utility of the monohydroxylated polymers, converted to epoxides, in compositions cured with amine resins. The amine resin used was CYMEL 1156, a mel amine / formaldehyde resin where R is C4H9. The acid used to catalyze the reactions of amine / hydroxy resin and amino resin / epoxide resin was CYCAT 600, acid dodec and lbencensulphonic acid (a 70% by weight solution in alcohol and sodium hydroxide). co). The compositions were mixed and coated from a solution with 65% by weight (% p) solids, of the ingredients, in a solvent mixture composed of 90% by weight of an aliphatic hydrocarbon solvent, naphtha VM & P, and 10 ° 0 by weight of n-butanol. The following formulation, given in parts by weight, was used.

Composition PPP Polymer 80 CYMEL 1156 18 CYCAT 600 2 Naphtha VM &P 60 n-But ano 1 7 The following polymers were analyzed in this formulation. Polymer 20 was a hydrogen peroxide (EB) with molecular weight (MW) of 3,000, which has a single hydroxyl group (OH) at one end. Polymer 21 was a polyisoprene (I) diblock polymer with 2,000-hydrogenated polybutadiene (EP) MW with MW of 4,000, having a single OH at one end. Polymer 22 was a polyisoprene (I) with MW of 2,000 - copolymer (S / EB) of polystyrene with MW of 4,000 / poly hydrogenated ibutadiene, having a single OH at one end. The S / EB block with PM of 4,000, in Polymer 22, was S with PM of 2,500 and EB with PM of 1,500. Polymer 23 was Polymer 21, converted to epoxide, to an epoxide content of 1.5 meq / g. Polymer 24 was Polymer 22, converted to epoxide, to an epoxide content of 1.5 meq / g. Polymer 25 is a triblock polymer having the same block of S / EB copolymer, as polymer 22. However, Polymer 25 had a block with MW of 1., 000, of polyisoprene converted to epoxide, at each end of the central block S / EB and had no OH group. Polymer 26 was a hydrogenated polymer (EB) with MW of 4,000, which had a single OH group at both ends. The coatings, with a suitable thickness, in dry, of 5.8 x 10 mm, were applied on aluminum panels in a rod with wire arroyado # 52. The coatings were cured by baking for 20 minutes at 175 ° C. They were evaluated qualitatively with respect to their suitability for use as a coating. The results are the following.

Polymer Type Coating of the coating 20 EB-OH Very sticky 21 I-EB-OH Bearing paste 22 IS / EB-OH Sticky 23 I-EB-OH Non-sticky, converted to the same time gone 24 IS / EB-OH Non-tacky, converted to epoxide-rich 25 IS / EB-I Non-tacky, converted to epoxide-free 26 HO-EB-OH Non-sticky, the tartrate The results of Polymer 20 clearly show that a monohydroxylated diene polymer, ED-OH, cured with melamine, made from only a diene monomer, is not suitable for use as a coating because it is very tacky. The results of Polymers 21 and 22 show that a monohydroxylated diene polymer, manufactured from at least two diene monomers and subsequently hydrogenating it selectively, thereby placing an unsaturated block I at the opposite end of the OH, is it behaves significantly better than Polymer 20. However, these coatings are not yet suitable because they remain sticky. The results for Polymers 23 and 24 show that the conversion to epoxide, of block I, at the opposite end to OH, converts the monohydroxylated polydiene polymers, manufactured from at least two diene monomers, into useful coating compositions. . The results for Polymers 25 and 26 confirm that a polymer with epoxy groups at both ends or an OH group at both ends is useful in the coatings, as was already known. It is noted that in relation to this date, the best method known by the applicant to carry out the aforementioned invention, is the conventional one for the manufacture of the objects to which it relates. Having described the invention as an antecedent, property is claimed as contained in the following:

Claims (11)

1. A monohydroxylated polydiene polymer, characterized in that it comprises at least two ethylene-unsaturated hydrocarbon monomers, which can be polymerized, wherein at least one is a diene monomer which produces an unsaturation suitable for conversion to epoxide, and wherein the polymer it has been hydrogenated in such a way that aliphatic double bonds remain in an amount of 0.1 to 7 ml and equiv es ent per gram of the polymer.

2. The polydiene polymer, according to claim 1, characterized in that it has the formula HO) X-A-Sz-B- (OH! Or HO) XA-B-S (OH wherein A and B are polymer blocks which may be homogeneous blocks of monomers of conjugated diolefins, copolymer blocks of conjugated diolefin monomers, or copolymer blocks of diolefin monomers and monoalkeni 1-aromatic hydrocarbon monomers. S is a block of hydrocarbon vini 1 aroma ti co, x and y are 0 or 1 and any of x or should be 1, but only one at a time can be 1, and z is 0 or 1.

3. The polydiene polymer according to claim 2, characterized in that the A blocks have a molecular weight that is in the range of 100 to 6,000 and the B blocks have a molecular weight that is in the range of 1,000 to 15,000.

4. The polydiene polymer according to claim 2 or 3, characterized in that A is isoprene and B is butadiene.

5. The polymer according to any of claims 2 to 4, characterized in that it has a structure that is selected from the group consisting of IB-OH, IS / B-OH, I-EB-OH, and IS / EB- OH, wherein I is a block of isoprene, B is a block of butadiene, EB is a block of hydrogenated butadiene, S is a block of styrene, and OH is the hydroxyl group.

6. A monohydroxylated polydiene polymer, with epoxide scavenging, characterized in that it comprises a polydiene polymer according to any of claims 1 to 5, and the polymer has been converted to epoxide, such that it contains from 0.1 to 7.0 My 1 equi va 1 ent is epoxide per gram of polymer.

7. A composition, characterized in that it comprises the polymer according to claim 6 and a resin that provides adhesion.

8. A composition, characterized in that it comprises the polymer according to claim 6 and a compatible amine resin.

9. A composition according to the rei indication 8, characterized in that it also comprises a reinforcing agent.

10. An adhesive, characterized in that it comprises the polymer or composition according to any of claims 1 to 9.

11. A sealant, characterized in that it comprises the polymer or composition according to any of claims 1 to 9.