Multiblock hydrogensource polymers for adhesives

 

(57) Abstract:

Describes an adhesive composition, comprising: (a) multiblock copolymer of the formula D-A-(B-A)n-Dxand/or (D-A-B)q- Y, where A is vinylaromatic hydrocarbon polymer block (mol. m 4000 - 35000; B - gidrogenizirovannye conjugated diene polymer block (mol. m 20000 - 200000; D - gidrogenizirovannye conjugated diene polymer block (mol. m 500 - 50000, n - 1 - 5 - integer x = 0 or 1; q = 2 to 30; Y is multibody agent combination, the ratio of the molecular weight D and the molecular weight of B is varied so that the ratio of normalized molecular weight is in the range 0 - 18 10-6where the indicator is normalized molecular weight is determined by the formula (MWD/MWB)/weight. the share's total weight MW of the polymer in the composition, where MWDand MWB- the molecular weight of the blocks D and B, respectively; the weight. the proportion of S - weight fraction vinylaromatic of hydrocarbons in the polymer; total MW is the molecular weight of the polymer and the weight. the proportion of polymer in the composition; the content of vinylaromatic hydrocarbon chains in the copolymer is 9 to 35 weight. %, and when either B or D is a butadiene prior to hydrogenation, the content of vinyl units is 30 - 65 vianey, the oxidation. 3 S. and 9 C.p. f-crystals, 8 PL.

The invention relates to adhesive compositions that contain multiblock hydrogensource block copolymers of vinyl aromatic hydrocarbons and conjugated dienes. More specifically, the invention relates to such adhesive compositions which contain a polymer with at least one end block of hydrogenating conjugated diene.

The copolymers used in adhesive compositions for many years, primarily because of their high cohesive strength and their ability to sew without phase chemical vulcanization. Such copolymers, such as those described in U.S. patent N 3239478 represent either linear or radial or star-shaped styrene-butadiene or styrene-isoprene block copolymers.

When such conventional block copolymers used in adhesives, they tend to degradation during processing and/or over time, as they are not saturated in the main rubber chain. These unsaturated reactive sites are sites that are vulnerable to impact, in particular free radicals produced during oxidation, the effect of ultraviolet rays or fur is Blarney mass and deterioration of the properties, which depend on molecular weight. In other cases unsaturated sites can participate in reactions graft polymerization and formation of cross-links, resulting in higher molecular weight and undesirable rigidity of the polymer, making the polymer unsuitable for recycling or ineffective for use as an adhesive. Due to the conventional hydrogenation of unsaturated base polymers are formed nonpolar polymers, adhesion which, although they are more stable, it is difficult to increase polymer additives, which makes them behave worse than usual polymers in some applications, including use as some pressure-sensitive adhesives.

Normal saturated copolymers intended for use in adhesive compositions, are three-block copolymers, in which the end blocks are solid polymers, such as polystyrene blocks. Often in the adhesive compositions of these copolymers with solid ends, particularly block copolymers with saturated rubber blocks, no stickiness and resistance to peeling of unsaturated copolymers. The mixture of copolymers, the region is livaniou, but due to the deterioration of shear properties, in particular the holding capacity and temperature shear fracture connections (TCDC).

The present invention helps to solve some of these problems without compromising the adhesion properties of unsaturated copolymers. This is achieved by creating a polymer that has at least one less gidrogenizirovannye block of a conjugated diene at the end of the polymer chain.

The present invention offers improved adhesive compositions which include multiblock copolymer of the formula

D-A-(B-A)n-Dx,

where And denotes vinylaromatic hydrocarbon polymer block molecular weight is from 4000 to 35,000;

In denotes gidrogenizirovannye conjugated diene polymer fleas, the molecular weight of which is from 20000 to 200000, provided that if the diene monomer is butadiene, the vinyl content of the links should be from 30 to 65 wt.%;

D denotes gidrogenizirovannye conjugated diene polymer block molecular weight is from 5000 to 50,000, provided that the starting monomer is butadiene;

the ratio between the mod is running-normalized molecular weight, defined by the formula

< / BR>
is in the range from more than 0 to 18010-6preferably from more than 0 to 10010-6< / BR>
n denotes an integer from 1 to 5; and

x is 0 or 1.

MWDand MWBmean molecular weight respectively of blocks D and C. a Preferred value of the ratio of molecular masses for linear polymers is less than 0.4. Weight. the share S is the weight fraction of vinylaromatic of hydrocarbons in the polymer. The total mass MW is the full molecular weight of the polymer. Weight. the proportion of polymer in the composition means the weight fraction of the polymer used in the adhesive composition. This composition includes increasing the stickiness of the resin, which is compatible with blockcopolymers.

In another embodiment, the present invention proposes the adhesive composition, which contains a coupled block copolymers of the formula

(D-A-B)q-Y

where Y denotes a multifunctional agent combinations,

q denotes an integer from 2 to 30, and D values, a and b defined in the previous paragraph.

In the preferred embodiment, this value is the ratio of molecular masses before normalization MWDM/MWBfor such polymers varieiy of the present invention exhibit valuable properties of the compositions, containing hydrogensource conjugated block copolymers, that is, resistance to heat, oxidation, ultraviolet radiation, etc., Such compositions simultaneously also exhibit good adhesion, resistance to delamination, shear and viscometric characteristics. Such polymers retain resistance to delamination during aging for longer periods of time than other polymers. The key subject of the invention consists in the combination in the same molecule at least two structural, that is, the load-bearing solid blocks (A blocks) with one or more end hydrogensource rubber blocks (D-blocks), the stickiness which is relatively easy to improve with the use of polymer additives.

A-blocks are polymer blocks vinylaromatic hydrocarbon. Preferred vinylaromatic hydrocarbon is styrene. Other useful vinylaromatic hydrocarbons include alpha methylsterol, various alkyl substituted styrene, alkoxy-substituted styrene, vinylnaphthalene and vinyltoluene. B-and D-blocks are polymer blocks of conjugated dienes. Preferred diene include butadiene and isoprene, and the measure used butadiene, the content of vinyl units (1,2 - butadiene microstructure) should be from 30 to 65 weight. % or gidrogenizirovannye polymer contains an excessive amount of crystalline polyethylene in the diene blocks, therefore, the polymer does not have sufficient elastomeres. You can also use other dieny, including piperylene, methylpentadiene, phenylbutazon, 3,4-dimethyl-1,3-hexadiene and 4,5-diethyl-1,3 - octadiene, preferably those associated dieny that contain from 4 to 8 carbon atoms. Related diene used in B-block may differ from those in D-block. If the largest value is the simplicity of the process, it is preferable to use both blocks are the same diene. You can also apply a mixture of conjugated dienes.

Multiblock polymers of the present invention, which by nature are linear, can be obtained by the reaction of combination or sequential polymerization. Sequential polymerization mainly includes a first anionic polymerization of D-block, then the anionic polymerization of the A block on its end, after which the anionic polymerization of another A-unit at the end of this polymer and, finally, if it is desired, the polymerization of the other D-block on the end of the floor is A second-unit repeat as often as far as this is desirable. Such polymers can be twisted in a spiral.

In General, the described method is used for polymers that are associated with combined with any polymer having reactive end groups which are reactive with one or more functional groups contained in the selected agent combinations. This method is particularly suitable for receiving the associated combination of polymers of the so-called "living" polymers containing a single leaf metal ion. As is well known in the art, "living" polymers are polymers containing at least one active group, such as a metal atom that is linked directly to a carbon atom. "Living" polymers easily get anionic polymerization. Since the present invention is particularly suitable for obtaining associated with the combination of polymers with the use of "living" polymers for the formation of its branches, the invention is hereinafter set forth with respect to such polymers. However, it should be borne in mind that this invention could be equally useful when applied to polymers containing other reatio is forced into the reaction of the reactive sites, present in the polymer.

"Living" polymers containing a single terminal group in the art will, of course, well known. Methods of obtaining such polymers are described, for example, in U.S. patents NN 3150209, 3496154, 3498960, 4145298 and 4238202. Methods for obtaining block copolymers, such as those preferred for use in the implementation of the method of the present invention, are also known, e.g. from U.S. patents NN 3231635, 3265765 and 3322856. When the polymer product is a statistical or twisted in a spiral copolymer, the monomers is usually injected at the same time, although in some cases more responsive monomer can be introduced slowly, while in the case when the product is block copolymers, the monomers used to obtain the individual blocks, add at the same time.

Typically, the polymers of the present invention can be obtained by introducing the monomer or monomers in contact with the organic compound of an alkali metal in a suitable solvent at a temperature in the range from -150 to 300oC, preferably at a temperature in the range from 0 to 100oC. Particularly effective polymerization initiators are organolithium soy is alifaticheskii, aromatic or alkyl substituted aromatic hydrocarbon radical containing from 1 to 20 carbon atoms, preferably tert-butyl or sec-butyl.

Usually "living" polymers used in the branches obtained by the combination of polymer, it is necessary to enter in contact with the agent of the combination at a temperature in the range from 0 to 100oC, under a pressure in the range from 1 to 7 bar, and such contact must be maintained until, until you complete or almost complete the reaction between the branches and agent combinations, usually over a period of time ranging from 1 to 180 minutes

Usually in the process of sequential polymerization or during introduction into contact with the agent of a combination of polymers of the present invention are in solution. Suitable solvents include those that can be used during polymerization of the polymer in solution; these include aliphatic, cycloaliphatic, alkyl substituted cycloaliphatic, aromatic and alkyl substituted aromatic hydrocarbons, ethers, and mixtures thereof. The class of acceptable solvent comprises aliphatic hydrocarbons, such as butane, pentane, hexane, heptane and so on; cycloaliphatic avodarte, such as Methylcyclopentane, methylcyclohexane and methylcycloheptane; aromatic hydrocarbons such as benzene; alkyl substituted aromatic hydrocarbons such as toluene and xylene; and ethers, such as tetrahydrofuran, diethyl ether and di-n-butyl ether. Since the polymers used to obtain the associated combination of polymers of the present invention contain a single reactive end group, these polymers should be kept in solution after receipt without deactivation of the reactive (live) plots. The agents of the combination can usually be added to the polymer solution or polymer solution can be added to the agent combinations.

In the process of the present invention can use any agents of the combination, which are known in the art, as used in the production of polymer, putting them in contact with the living polymer. Suitable agents of the combination may contain two or more functional groups that react with the living polymer in place of the metal-carbon linkages. Although in theory the method of the present invention allows at least to improve the relative distribution of the different vet is characterized by a significant improvement, when the agent is the combination contains from 3 to about 12 functional groups that can react at the place of the metal-carbon connection "living" polymer. In this case, the appropriate agent combinations include dichloromethane, SiX4RSi X3, HSi X3X3Si - SiX3X3Si X3X3Si - (CH2)p-Si X3, R-C(Si X3)3, R-C(CH2Si X3)3C(CH2Si X3)4where each X independently represents fluorine atom, chlorine, bromine or iodine, alkoxy radical, carboxylate radical or a hybrid; R denotes hydrocarbonyl radical containing from 1 to about 10 carbon atoms, preferably from 1 to 6 carbon atoms; and p represents an integer from 1 to 6. Particularly useful agents in combination are tetravalent silicon, in particular tetraploid silicon, silicon tetrachloride and tetrabromide silicon.

By itself, the method of combination is described in detail in U.S. patent N 4096203. This patent describes a specific multifunctional agents combinations that can be used, but there are other agents of the combination, which can also be used for this purpose.

Star floor is melting monomer. The preferred agent is a combination palearkticheskii agent combinations, such as those described in U.S. patents NN 4391949, 4010226 and 4444953. In columns 12 and 13 of U.S. patent N 5104921 contains a full description of such polyalkanoates compounds. Preferred divinecaroline hydrocarbons containing up to 26 carbon atoms per molecule, particularly divinylbenzene, in the form of either meta-or para - isomer; acceptable technical divinylbenzene, which is a mixture of these isomers. Agent combination is preferable to add to the living polymer after virtually complete polymerization. The number of agent combinations varies within wide limits, but for every equivalent of unsaturated living polymer, which usually needs to be combined, it is preferable to use at least one equivalent. The reaction mix is usually carried out in the same solvent as the polymerization reaction. The temperature varies in a wide range, for example, from 25 to 95oC.

B - and D-diene blocks gidrogenit, as basically described in the published literature, so that vosstanovitelnij least 90%, and most preferably at least 95% of the original olefinic unsaturated groups in the polymer chains.

The hydrogenation of these diene blocks can be performed by various well-known methods, including the hydrogenation in the presence of such catalysts as Raney Nickel, noble metals such as platinum or palladium, and soluble catalysts based on transition metals. Suitable methods of hydrogenation, which can be used are those in which diesterase polymer or copolymer is dissolved in an inert hydrocarbon diluent such as cyclohexane, and hydrogenized reaction with hydrogen in the presence of a soluble hydrogenation catalysts. Such methods are described in U.S. patents NN 3113986, 4226952 and substituting the patent 27145. Polymers hydrogenized way of obtaining hydrogenating polymers, residual content of unsaturated groups in Polivanova block which is less than 20%, preferably as close to 0% as possible, from the initial content of unsaturated groups before hydrogenation. In the process of hydrogenation can also use titanium kataliza of the present invention is between 45,000 to 250,000. The molecular mass of A-blocks is equal to from 4000 to 35,000. The molecular weight of the A blocks is less than 4,000 leads to poor holding capacity, shear properties and cohesive strength. Molecular weight in excess of 35000, give a hard glue that has poor sensitivity to pressure. The molecular mass of B - blocks should be between 20000 to 200000. In the case of B-blocks with a molecular mass of less than 20,000 is formed weak polymer with poor shear properties. Polymer with a molecular weight of B - blocks more than 200,000 difficult processing. The molecular weight of D-blocks should be equal to from 5000 to 50000. D-blocks with a molecular weight less than 5000 not give the desired adhesiveness and adhesion properties. D-blocks with molecular weight more than 50,000 extremely dilute load bearing (structural) rubber fraction, causing a low holding capacity and poor cohesive strength. The ratio between the molecular weight of D-blocks and the molecular weight of B-blocks must be in the interval due to a normalizing indicator of molecular weight, which is determined in accordance with the above formula. Too high content of D-blocks leads to the dilution of the load-bearing CLASS="ptx2">

Normalizing the score is determined by several variables, namely, content polivinilatsetatnyh hydrocarbon chains, the total polymer molecular weight and the amount of polymer in the adhesive composition, which affects the adhesive properties, in particular the holding capacity. Normalizing the metric is characterized by a negative correlation of the tangent of the angle with the holding capacity. Normalizing the metric must exceed 0, but should not be more 18010-6preferably not more 10010-6because otherwise, the holding capacity of the composition is too low. In order to achieve the holding capacity to the steel at room temperature (sample 1/2 inch x 1/2 inch, 12.7 mm x 12.7 mm, a load of 2 kg) 100 min or more, normalizing the rate should not exceed 18010-6. The preferred ratio of MWD/MWB(up to normalization) for linear polymers should be less than 0.4, and for star polymers this value should be equal to from 0.1 to 2.2.

The content of the links vinylaromatic hydrocarbon, usually styrene, polymers of the present invention is in the range from 9 the haunted properties, and with their increased content are formed of rigid adhesives, which are not pressure-sensitive. The number of end rubber blocks in the polymer of the present invention ranges from 1 to 30, with higher numbers applied to the radial and the star copolymers.

The molecular weight is usually measured gel chromatography (GPC), where GPC system properly calibrated. For calibration use the polymers of known molecular weight, and they should have the same structure of molecules and chemical composition, as unknown copolymers that analyze. Anionic polymerized linear copolymers close monodisperse, so for convenience and sufficient visibility are observed "peak" molecular weight, narrow molecular mass distribution. This "peak" molecular weight very close to srednevekovoi molecular weight of blockcopolymer. In the case of copolymers, which are more polydisperse, srednevekovoy the molecular weight should be measured by scattering or count according to GPC. Measurement of the actual molecular weight of the final received combined the civil act. This is because the radial or star-like shape of the molecule are separated and suiryudan through Packed columns for GPC not as linear polymers, used for calibration, so that the time to reach the detector UV or refractive index may not be a good indicator of molecular weight. A good method is applicable for radial or star-shaped polymer is measuring srednevekovoi molecular weight by light scattering technique. The sample is dissolved in a suitable solvent at a concentration of less than 1.0 g sample in 100 ml of solvent and filtered with a syringe and a porous membrane filters with a pore size of less than 0.5 μm directly in the cell to measure light scattering. Measurement of light scattering is produced as a function of scattering angle and the concentration of the polymer using standard procedures. Differential refractive index (DPP) of the sample measured at the same wavelength and in the same solvent as in the case of determination of light scattering. To the above analytical methods include the following links:

1. Modern Size-Exclusion Liquid Chromatography, W. W. Yau, J. J. Kirkland, D. D. Bly, John Wiley & Sons, New York, N4, 1979.

2. Light Scattering ftor Polymer Solution, M. B. H978.

As indicated above, the implementation of the present invention makes it possible to combine in a single polymer properties desired for its use in the pressure-sensitive adhesives without the need of adding an additional two-block polymer to increase the stickiness and other adhesive properties. The polymers of the structure

D-A-(B-A)n-Dxor (D-A-B)q-Y

exhibit good adhesion, resistance to delamination, shear and viscometric properties. They retain the resistance to delamination during aging better than other polymers. As mentioned above, the present invention consists in the combination of at least two of the fabric, i.e. the load-bearing, solid blocks (A blocks) in the same molecule with one or more integral rubber blocks (D-blocks), the stickiness which is relatively easy to increase the use of polymer additives.

Preferred polymers for this application include S-EP-S-EP, EP-S-EP-S-EP and EP-S-EP)q-Y [respectively hydrogensource S-I-S-I, I-S-I-S-I and (I-S-I)q-Y]. Others include S-EB-S-EB (EB-S-EB)-Y and EB-S-EB-S-EB. S is styrene, " I " representing isoprene, indicates butadiene, S denotes gerla use of the present invention looks like a S-EP-S-EP, where the limit EP-a unit is significantly less than the average EP-block that you want to save a percentage of carrying a load of polymer (plot S-EP-S), which gives acceptable shear properties.

The materials of the present invention can be used in the manufacture of adhesives (including pressure sensitive adhesives, packaging adhesives, contact adhesives, adhesives for laminates, weatherproof tape and mounting glues, labels, sealants, oil gels, temporary protective coverings, coatings and films. For the composer compositions may be necessary combination of various components with the polymers of the present invention to obtain products possessing the appropriate combination of properties (such as adhesion, cohesion, reliability, low cost, and the like), for specific applications. In most of these applications are acceptable compositions could also contain various combinations of resins, plasticizers, fillers, solvents, stabilizers and other components, such as bitumen. Below are some typical examples of compositions for sealants.

The usual practice yavlyaetsya 100 parts of polymer. Normal increases the stickiness of the resin is a diene-olefin copolymer of piperylene and 2-methyl-2-butene, softening temperature which is 95oC. This resin is technically available under the trade designation WINGTACKR95; it is prepared by cationic polymerization of 60% piperylene, 10% isoprene, 5% cyclopentadiene, 15% 2-methyl-2-butene and about 10% dimer, as described in U.S. patent N 3577398. Can be used increase the adhesiveness of the resin, where the resinous copolymer comprises 20-80 weight. % piperylene and 80-20 wt.% 2-methyl-2-butene. The softening point of such resins by the ring and ball, determined according to method ASTM E28, respectively approximately 80 and 115oC.

As agents that increase stickiness, can also be used aromatic resins, provided they are compatible with the particular polymer used in the composition. Typically, the softening point of such resins for the ring and the ball must be 80 and 115oC, although it can also be used a mixture of aromatic resins with higher and lower softening points. Useful resins include coumaroneindene resin, polystyrene resin, vinyltoluene-alpha-methylstyrene copolymers and politician of the present invention, cover hydrogensource rosin, esters of rosin, polyterpenes, in primary forms, serpentinely resins, and polymerized mixed olefins, reducing the softening point of the resin and liquid resin. An example of a liquid resin is the product ADTACRLV (trade name) resin from the company "Hercules" (trademark). To achieve good resistance to thermal oxidation and discoloration as enhancing the adhesiveness of the resin, it is preferable to use a saturated resin, e.g hydrogenating Dicyclopentadiene resin, such as resin series ESCOHREZR5000 (trademark), which is produced at the company "Exxon" (trademark), hydrogenating polystyrene or poly-alpha-methylstyrene resin, in particular a resin REGALREZR(trademark) manufactured by the firm "Hercules". The softening point of the solid resins can range from 40 to 120oC. Can be used with liquid resin, that is, with softening points below room temperature, and combinations of solid and liquid resins. The number used to increase adhesion of the resin ranges from 0 to 400 weight parts per 100 parts of rubber (100 parts K.), preferably from 20 to 350 parts/100 parts to., most preferably from 50 to 250 hours is limera, used in the respective adhesive compositions.

The composition according to the present invention can contain plasticizers, as filling rubber plasticizers, compounding oil, organic or inorganic pigments and dyes. Compounding oil for rubbers are well known in the art and include both oil with a high content of saturated compounds and naphthenic oils. The preferred plasticizers are a highly saturated oils, e.g. TUFFLO oilsR6056 and 6204 (trademark), manufactured by "Arco" (trademark), and naphthenic oil for processing, such as SHELLFLEX oilR371 (trademark), manufactured by shell (trademark). The amount of oil to the rubber mixtures used in the composition according to the invention may vary from About to 150 parts/100 parts K., preferably from 0 to 100 parts per 100 parts K. , and most preferably from 0 to 60 parts /100 parts to.

Optional components of the present invention are stabilizers that inhibit or retard thermal degradation, oxidation, formation of crust and staining. Such stabilizers are usually added to technically the Deposit and storage of the composition at high temperatures.

Such a composition may include fillers and pigments of various types. This is especially true for exterior coatings and sealants, fillers which add not only to achieve a desired appearance, but also to improve the performance properties of the sealant, in particular resistance to weathering. You can use a wide variety of fillers. Suitable fillers include calcium carbonate, clay, talc, silica, zinc oxide, titanium dioxide, etc., Usually the amount of filler is in the range from 0 to 65 wt.% in terms of free of solvent portion of the composition depending on the type of filler used and the application for which the composition is intended. Particularly preferred filler is titanium dioxide.

If the composition is used in the form of a solution in a solvent, the organic part of the composition are dissolved in a solvent or mixture of solvents. For this acceptable aromatic hydrocarbon solvents such as toluene, xylene or the product SHELL CYCLO SOL 53 (SHELL CYCLO SOL are trademarks). You can also use such aliphatic hydrocarbon hydrocarbon solvent and a polar solvent. Acceptable solvents include esters, such as isopropylacetate; ketones such as methyl isobutyl ketone; and alcohols such as isopropyl alcohol. The amount of polar solvent depends on specifically selected polar solvent and the structure specifically used in the composition of the polymer. Generally, the amount used of the polar solvent contained in the solvent mixture is between 0 to 50 wt.%.

Preferred combinations of primary and secondary antioxidants. Such combinations include spatial employed phenols with phosphites or thioethers, in particular hydroxyphenylpropionic with arylphosphate or thioethers, or aminophenols with arylphosphate. Specific examples of useful antioxidant combinations include 3-(3,5-decret-butyl-4-hydroxyphenyl)-propionamide [product IRGANOXR1010 (trademark) of the firm "Ciba-Geigy"] Tris- (nonylphenyl)postitem [POLYGARDRHR (trademark) of the firm "Uniroyal"] , product IRGANOXR1010 with bis-(2,4-decret - butyl) pentaerythritol-diphosphite [product ULTRANOXR626 (trademark) of the firm "Borg-Warner"].

The composition can also enter additional stabilization of the example from oxygen, ozone and ultraviolet radiation. However, these additional stabilizers must be compatible with the basic stabilizers mentioned above, the main function for which they are intended.

All compositions based on polymers of this invention should contain some combination of the various components described herein. There are no specific rules regarding what components should be used. Any expert in the art should select the specific types of components and adjust their content in order to achieve the precise combination of properties of the composition required for any particular application of the adhesive, coating or sealant.

Specialist-compiler compositions in the art should realize the exceptional versatility of the polymers of the present invention in the preparation of adhesives having the properties that are acceptable for many different applications.

Adhesive compositions of the present invention can be prepared by mixing the components at elevated temperature, preferably from 50 to 200oC, before the formation of homog the walking is any method, which allows to prepare a homogeneous mixture. Prepared composition can be used in various applications. Alternatively, the components can be mixed in a solvent.

The preferred scope of the proposed composition is a manufacturer of adhesive tapes and labels. Adhesive tapes include a flexible sheet substrate and a layer of adhesive compositions of the present invention, which covered one main surface of the sheet substrate. This sheet, the substrate can be made of plastic film, paper or any other suitable material, and the tape may include various other layers or coatings, such as primers, lubricants, etc. that is used in the manufacture of adhesive tapes.

Examples.

Table 1A shows the structure of the polymer molecules, which are the object of the present invention, together with the structures of conventional copolymers. In table 1B in the form of data lists the parameters of molecules. The polymers according to the invention in these examples are longer versions of triple blocks S-EP-S, created by attaching a rubber block ER to one or both of the steer is thanks to them molecular weight varies from 8 to 27M. Conventional triblock S-EP-S is used as the control, as in the case of conventional triblock-S-S-S, which is mixed with debloom S-EB in the ratio of 70/30 respectively. For this comparison, the rubber block dibaca S S is called the limit of the rubber block, but it differs from the polymers according to the invention is that the end of the rubber block is not attached to the structural system.

It is important to note that the values of viscosity of the polymers according to the invention lower values of viscosity triblocal control material despite the fact that the total molecular weight of the polymers offer the same or higher. Reduced viscosity at equal or higher molecular weight is desired, because in solution it is possible to use a higher dry matter content and requires less solvent. In addition, simplified regulation of film thickness.

TCDC (temperature, shear fracture connections) was measured using the lap joints Mylar samples with dimensions of 1 inch x 1 inch, 25.4 mm x 25.4 mm under a load of 1 kg of the Test TCDC is a measure of the temperature at which collapses under shear load, the ball runs through the adhesive film with a standard initial velocity (test N6 Council sticky tape). Small values indicate a high stickiness. Holding capacity (CA) represents the time required for separating shear stress plot of the standard tape square (1/2 inch x 1/2 inch, 12.7 mm x 12.7 mm) from a standard test surface (steel, Kraft paper) under a standard load (2 kg) and angle protivostaianie 2o(method N7 Council sticky tape). Long periods of time indicate a high strength adhesive bonding. Parameter peeling angle 180owas determined by the method of N1 Council sticky tape. Larger numbers indicate a higher density and a branch of the test tape from the steel substrate. Stickiness on the Polyken probe (CRC) was determined according to ASTM D-2779. Loop stickiness (PC) was determined by means of a device for changing a loop of sticky TLMI. Large number of CRC and PC indicate high adhesiveness.

In table. II number 4-block copolymers S-EP-S-EP mapped with conventional polymer S-EB-S/S-S 70/30 in a pressure-sensitive adhesive composition. These 4-block copolymers differ from each other mainly by the length of their end of the rubber blocks (see tab. 1B). They are superior to conventional polymer his ability will inform the Yu viscosity of the melt.

In table. III illustrates the operational characteristics of the 4-block copolymer S-EP-S-EP compared to the three-block copolymer S-EP-S in the composition for labels. 4 is a Block copolymer better loop adhesiveness, holding capacity and viscosity (reduced). In table. IV presents the 5-block copolymer, EP-S - EP-S-EP songs for labels in comparison with the conventional polymer S-EB-S/S-S 70/30. In this case, the composition varies because they were prepared with the aim to achieve the same glass transition temperature (Twith): -20oC. the Main advantage of multiblock copolymer is a low viscosity.

In table. V and VI it is shown that the aging of the polymers of the present invention preserve the best resistance to delamination in the composition of the adhesive compositions than regular saturated block copolymers. In addition, the polymer according to the invention leaves a clean fracture of adhesive joints after aging, whereas conventional adhesive based on unsaturated blockcopolymer destroyed cohesion and leaves a residue on the substrate and on the backer.

To summarize, multiblock copolymers with integral rubber blocks according to the invention is superior to conventional triple and mixed triple two is awn (reduced) at the same time with the same or improved adhesion and resistance to delamination. This balance of properties is unique and increases the flexibility of the composition, allowing the authors of the compositions to achieve an improved balance of properties in a pressure-sensitive adhesives.

Table. VII illustrates the operational properties of a star (EP1-S0EP2)-DVB-blackshemalemov in adhesive compositions containing different amounts increase the adhesiveness of the resin. The results show that all the songs are from 9 to 11 containing polymers described as proposed by the present invention, showing an acceptable balance of properties, while composition 2, in which the polymer used, not covered by the scope of the present invention, showing a very low holding capacity.

In table. VIII presents the normalized indicators of molecular weight for each of polymers 1 to II. Also listed stickiness on the probe Police, loop adhesion and holding capacity to become manifest these polymers in standard compositions containing 40% polymer (polymers 1-3), 30% polymer (polymers 4-7) or 20% polymer (polymers 8-11). The remainder of each of the compositions consists of hydrogenomonas under normal pressure and at 85oC hydrocarbon resin and the the composition is approximately -15oC, and 1.5 parts/100 parts K. stabilizers (see table. II, III and VII). Also presents the logarithm of the holding capacity to the steel. If we plot the logarithm of the holding capacity to the steel index normalized molecular weight, there is a roughly linear relationship. From the study data table. VIII we can see that when the parameter of the normalized molecular weight for polymer 11 exceeds 18010-6the stickiness on the probe Police is acceptable as a loop stickiness, but retaining the ability to steel is extremely low. All other polymers characteristic of an acceptable balance of these properties.

1. The adhesive composition, comprising: (a) multiblock copolymer of the formula

D-A-(B-A)n- Dxand/or (D-A-B)q- Y

where a is vinylaromatic hydrocarbon polymer block (mol.m. 4000 - 35000,

In - gidrogenizirovannye conjugated diene polymer block (mol.m. 20000 - 200000,

D - gidrogenizirovannye conjugated diene polymer block (mol.m. 5000 - 50000,

n = 1 to 5, an integer;

x = 0 or 1;

q = 2 to 30,

Y - multibody agent combination, the ratio of the molecular weight D and the Les from more than 0 to 180 x 10-6where the indicator is normalized molecular weight is determined by the formula

< / BR>
where MWDand MWB- the molecular weight of the blocks D and B, respectively;

weight. the proportion of S - weight fraction vinylaromatic of hydrocarbons in the polymer;

total MW is the molecular weight of the polymer;

weight. the proportion of polymer in the composition is the weight fraction of the polymer used in the adhesive composition,

content vinylaromatic hydrocarbon chains in the copolymer is 9 to 35 wt.% moreover, when either or D is a butadiene hydrogenation, the content of vinyl units is 30 to 65 wt.; b) increasing the viscosity of the resin,

2. The composition according to p. 1, characterized in that the indicator is normalized molecular weight is in the range from more than 0 to 100 x 10-6.

3. The composition according to p. 1, characterized in that the ratio of molecular weight D to the molecular mass In multiblock copolymers of the formula DA-(B-A)x-Dxbefore normalization is less than 0.4.

4. The composition according to p. 1, characterized in that the ratio of molecular weight D to the molecular mass In multiblock copolymers of the formula (D-A-B)q- Y normalization is in the interval 0,1 - 2,2.

5. The composition according to al multiblock copolymer of the formula (D-A-B)q- Y, where a is vinylaromatic hydrocarbon polymer block (mol.m 4000 - 35000, gidrogenizirovannye conjugated diene polymer block (mol.m. 20000 - 200000, D - gidrogenizirovannye conjugated diene polymer block (mol.m. 5000 - 50000, and when either or D is a butadiene prior to hydrogenation, the content of vinyl units is 30 to 65 wt.%, q = 2 - 30, Y - multibody agent combination, the ratio of molecular masses of D and is in such a range that the index normalized molecular weight is in the range from more than 0 to 180 x 10-6where the indicator is normalized molecular weight is determined by the formula:

< / BR>
where MWDand MWB- the molecular weight of the blocks D and B, respectively;

weight. the proportion of S - weight fraction vinylaromatic of hydrocarbons in the polymer;

total MW is the molecular weight of the polymer;

weight. the proportion of polymer in the composition is the weight fraction of the polymer used in the adhesive composition,

content vinylaromatic hydrocarbon chains in multiblock copolymer is 9 to 35 wt.% .

7. The copolymer under item 6, where the index is normalized molecular weight is in the range of not more than 0 up to 100 x 10-6.

8. The copolymer is CLASS="ptx2">

9. Not twisted in a spiral multiblock copolymer of the formula

D-A-(B-A)n- D

where a is vinylaromatic hydrocarbon polymer block (mol.m. 4000 - 35000,

In - gidrogenizirovannye conjugated diene polymer block (mol.m. 20000 - 200000,

D - gidrogenizirovannye conjugated diene polymer block (mol.m. 5000 - 50000,

moreover, when either b or D is a butadiene prior to hydrogenation, the content of vinyl units is 30 to 65 wt.%, n = 1 to 5, an integer, the ratio of molecular masses of D and is in such a range that the index normalized molecular weight is in the range from more than 0 to 180 x 10-6where the indicator is normalized molecular weight is determined by the formula

< / BR>
where MWDand MWB- the molecular weight of the blocks D and B, respectively;

weight. the proportion of S - weight. share vinylaromatic of hydrocarbons in the polymer;

total MW is the molecular weight of the polymer;

weight. the proportion of polymer in the composition is the weight fraction of the polymer used in the adhesive composition,

and content vinylaromatic hydrocarbon chains in multiblock copolymer is 9 to 35 wt.%.

10. Multiblock copolymer on PP. 6 and 9, where D and/or B - isoprene to the ssy is in the range from more than 0 to 100 x 10-6.

12. The copolymer under item 9, where the ratio of the molecular weight D to the molecular weight of up to normalization is less than 0.4.

Priority points and features:

07.10.94 on PP. 1 - 4, 6 - 9, 11 and 12, relates to a normalized indicator of molecular weight.

03.11.93 on PP.1 - 12 - the other signs.

 

Same patents:

The invention relates to the composition of the block copolymers, method for their production and adhesive compositions and can be used in the formulation of adhesive tapes and labels

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The invention relates to the production of compositions for the production of sealing and germetezirujushie-adhesive coatings, in particular can be used for isolation joints, seams, joints, gluing roll roofing materials and waterproofing of foundations and pipelines

The invention relates to substituted functional groups of star-shaped block copolymers containing a styrene-isoprene blocks

Glue melt // 2112005
The invention relates to a hot melts and can be used in the printing industry for the production of books, brochures method of perfect binding

Glue melt // 2100397
The invention relates to the field of production of hot melt adhesives used in the production of adhesive coatings

The invention relates to adhesive compositions used in the manufacture of shoes

The invention relates to the composition of the block copolymers, method for their production and adhesive compositions and can be used in the formulation of adhesive tapes and labels

The invention relates to a method of processing a resinous block copolymers vinylaromatic compounds and conjugated dienes obtained at the initiation stage with the use of catalysts based on alkali metals

The invention relates to the production of block copolymers having the properties of thermoplastic elastomers

The invention relates to techniques for copolymerization of butadiene and styrene

The invention relates to a new process for the preparation of copolymers in the presence of the agents of the combination of polymer blocks

The invention relates to substituted functional groups of star-shaped block copolymers containing a styrene-isoprene blocks

The invention relates to the field of production of block copolymers on the basis of diene hydrocarbons and-methylstyrene

FIELD: block copolymers containing at least two rigid blocks formed by vinyl aromatic monomers.

SUBSTANCE: proposed copolymer has at least two rigid blocks formed by vinyl aromatic monomers and at least one static soft block formed by dienes and vinyl aromatic monomers; soft block containing at least 20% of 1,2-vinyl is located between rigid blocks; fraction of rigid blocks is equal to 51-74mass-% in terms of entire block copolymer. Block copolymers are obtained through anion polymerization; polymerization of soft block is performed in presence of potassium salt. Transparent glass-like polysterene thus obtained is characterized by elasticity modulus of 753 Mpa, tensile stress of 18.2 Mpa, breaking stress of 33.6 Mpa, elongation at rupture of 373%, Shore hardness of 66 and softening temperature (by Vieat) of 44.6°C. Proposed block copolymers possess good compatibility with styrene polymers and may be used for production of fibers, films and molded units.

EFFECT: enhanced efficiency.

15 cl, 9 tbl, 27 ex

FIELD: rubber industry.

SUBSTANCE: invention relates to process of manufacturing synthetic rubber, in particular solution butadiene-styrene rubber suitable in manufacture of tires with high performance characteristics, resistance to high wheel rolling and providing long lifetime, good maneuverability, adhesion to wet pavement, and low consumption of fuel. Butadiene-styrene rubber is obtained via copolymerization of butadiene with styrene in hydrocarbon solvent and in presence of organolithium catalyst and modifying additive at catalyst-to-additive molar ratio 1:(0.2-1.0). Process comprises mixing monomers with solvent, deactivation of catalyst to stabilize polymer, degassing, and drying of rubber. As modifying additive, alkali metal alcoholates originated from hydroxyalkylated secondary amines.

EFFECT: enabled manufacture of butadiene-styrene rubber with middle and predominant content of 1,2-units in butadiene portion of copolymer.

2 tbl, 22 ex

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