Adhesive composition

 

(57) Abstract:

Usage: for connecting substrates or surfaces of various materials that can withstand high temperatures. The inventive adhesive composition contains (wt.%): product connection on the Diels-alder reaction perhalogenated cyclic diene with conjugated double bonds and refinancinga a dienophile having a vinyl content of at least 50 wt. % (35 - 75), vulcanizing agent (1 - 15), magnesium oxide or zinc (1-60), aromatic gidroksosoedinenii (1 - 15), formaldehyde donor (1 - 15), phenolic polymer (1 - 15), activated by heating unsaturated elastomer crosslinking agent is a derivative of quinone (0,1 - 15). Perhalogenated cyclic diene with conjugated bonds is selected from the group consisting of hexachlorocyclopentadiene, geksaftorpentan, hexabromocyclododecane, 5,5-deferredmediaselection and 5.5-dibromotetrachloroethane. The dienophile is a polymeric material selected from the group: polyalkalene, polyalkalene with a terminal hydroxyl group, polyalkalene with an elongated chain end with a hydroxyl group, polyalkalene with terminal carboxyl group, polyalkalene with the Yong with terminal amine group, polyalkalene with an elongated chain with a terminal amino group equivalents. Product connection on the Diels-alder reaction with halogen 26 - 35 wt.% and vinyl 88 - 98 wt.%. Phenolic resin is a condensation product of phenol and formaldehyde. Aromatic gidroksosoedinenii is selected from the group of resorcinol, phenol, p-tertbutylphenol, p-phenylphenol, p-chlorophenol, p-alkoxyphenyl, o-cresol, phenol, m-bromophenol, 2-ethylphenol, amylphenol, Nonylphenol, hydroquinone, catechin, pyragollole and gallaty. As a formaldehyde donor composition contains formaldehyde, formalin, acetaldehyde, Propionaldehyde, somerley aldehyde, 2-ethylbutyraldehyde, 2-methylbenzaldehyde, 2-ethylhexaldehyde, benzaldehyde, trioxane, furfural, hexamethylenetetramine and acetal. As the vulcanizing agent, it contains selenium, sulfur or tellurium. The composition may further contain dusty SiO2and soot in the amount of 1-3 wt.%. Adhesive compositions according to the invention can be applied as a single layer system that meets the requirements of the pairing process of injection molding. In addition, the adhesive connection is able to withstand high temperature fluids (etilogy the Xia to the compositions of materials, used for connection of substrates or surfaces of various materials. More specifically the present invention relates to environmentally adhesive composition which is capable of withstanding high temperatures and which contains the product of the merger by the Diels-alder reaction and phenolic resin.

Justification of the invention

Over the years we developed many adhesive compositions for the connection of different materials or products, such as elastomeric substrate or metal surface. As the integration technology continues to evolve, the adhesive compositions are increased requirements to the conditions of mates, when a number of ingredients used in adhesive compositions, is continuously limited environmental requirements. In order to solve this problem, for future adhesive compositions should use environmentally friendly ingredients that give the adhesive materials that can withstand the rigors of linking.

As the nearest example is invited to consider previously developed heat-resistant adhesive composition according to the U.S. patent N 4795778, 1969, which includes about the e supplements including vulcanizing agent, zinc oxide and other additives.

An example of the complexity of the binding conditions can serve as a widespread process of linking molding under pressure. The binding method of pressure die casting is an efficient, because the performance can be increased through the use of high temperature vulcanization and shorter time of vulcanization and due to the fact that the process of binding resin with metal can be automated. However, the processes of injection molding are performed at high temperatures (160 - 177oC), which can be a hindrance to the efficiency of binding adhesive composition used in the process.

Examples of previously developed adhesive compositions can be found in U.S. patents NN 3258388 and 3258389. These"rubber to metal") adhesive compositions are described as using nitrosoamine compound as a crosslinking agent, which increases the adhesion to the rubber substrate. Despite the fact that these adhesive compositions are effective for bonding rubber to metal in various conditions, it was found that aromatic nitrosoguanidine has a tendency to sublimation is the group of rubber in the reaction with aromatic nitrosoguanidine and its cure before as it will fill the cavity plastic injection moulds and interacts with the adhesive on the metal surface. Prevulcanized rubber will not mix with the rest of the rubber in the form, causing the formation of loosely coupled layers, which can lead to premature failure of the product. These adhesives, as well as many other adhesive systems have some disadvantages in that they usually require 2 layers of materials, such as the ground or floor, in order to obtain satisfactory adhesion.

The attempt to develop an adhesive composition which is free from aromatic nitroso compounds, is discussed in U.S. patent N 3640941. This adhesive composition uses the grafted polymer is polybutadiene and substituted cyclopentadiene monomer, a dibasic postit lead, resorcinol and the solvent, since this composition avoids the use of aromatic nitroso compounds, it requires the use of lead-containing compounds that can be harmful to the environment and hazardous to the health of people working with the adhesive composition.

It was necessary to single-layer adhesive composition used some environmental is fully trimmed in the process of injection molding. So the adhesive composition to provide an adhesive binding, which is resistant to aggressive environment, such as a high temperature fluid and corrosion-active agents.

Summary of the invention

The object of the present invention is a single layer of adhesive composition, which mainly uses environmentally acceptable components and which can withstand high temperature mating conditions. Adhesive binding, obtained using the present adhesive composition shows excellent resistance to surrounding high temperature liquids and corrosive conditions. The present adhesive composition comprises the product of the merger by the Diels-alder reaction of perhalogenated cyclic diene with conjugated double bonds and a dienophile with the olefinic unsaturation, having a vinyl content greater than 50%, phenolic resin, aromatic gidroksosoedinenii, formaldehyde donor, a thermally activated crosslinking agent of unsaturated elastomer, a vulcanizing agent and a metal oxide. Now, it was established that this particular composition is environmentally friendly ingredients gives the adhesive composititon Wednesday, such as conditions that occur in the process of injection molding.

The invention in its preferred embodiment avoids as aromatic nitrosoguanidine and lead compounds, which also determined the disadvantages of adhesive compositions, as described above.

The best way of carrying out the invention

The product of the merger by the reaction of Delta-alder reaction of the present invention, preferably obtained by reaction of at least one halogenated cyclic diene with conjugated double bonds and at least one polyalkalene a dienophile having a high vinyl content. The vinyl content is part of polienovykh units linked together by 1,2-type connection with the formation of lateral vinyl groups, and is quantified by the absorption of X at 110 μm using a solution of approximately 2.5 g of polymer in 100 ml of anhydrous bisulfide carbon. The addition products of Diels-alder reaction preferably have a halogen content in the range of 20 to 40 and preferably within about 26 - 35% relative to the total weight of the adduct.

Polyalkalene product connection on p is Ino at least 70% and more preferably in the range from 88 to 98% relative to the total olefin desaturation.

Halogenated cyclic diene with conjugated double bonds, which are used to obtain adducts for use in the present invention have the General formula

< / BR>
where

X is a halogen selected from the group consisting of chlorine, bromine and fluorine (where chlorine is preferred), and n is 1, 2 or 3 (preferably 1).

Halogenated cyclodiene easily get widely known methods, and at least one hexachlorocyclopentadiene is a well-known article of Commerce. Other representatives of dienes include geksaftorpentan, hexabromocyclododecane, 5-5-deferredmediaselection and 5.5-dibromotetrachloroethane, hexachlorocyclopentadiene is now preferred for use in the present invention.

Polyalkalene the dienophiles, which interact with halogenated cyclic danami with conjugated double bonds with the formation of adducts, which are used in the adhesive compositions of the present invention, as noted, are characterized by a vinyl content of not less than 50%. The dienophiles, in addition, characterized by the fact that have an elongated main carbon chain, which features isobologram carbon atoms of the main chain of polyalkalene with the formation of patterns

< / BR>
where

m indicator of the degree of polymerization and is usually an integer between 10 and 4000.

As indicated, the vinyl group is at least 50%, preferably 70-98%, especially 88-98%, residual olefinic of ninasimone of the dienophile. Polyalkalene the dienophiles further characterized by the fact that have a molecular weight in the range from 500 to 200,000, preferably 10000-120000 and more preferably 35000-120000. Thus, it is seen that polyalkalene the dienophiles, which can be used in the practice of the present invention include liquid polymers and solid polymers.

Polyalkalene materials that are suitable for use to obtain adhesive compositions described herein are polymeric materials selected from the group consisting of polyalkylene, polyalkylene with a terminal hydroxyl group, polyalkalene with an elongated chain end with a hydroxyl group, polyalkalene with terminal carboxyl group, polyalkalene with an elongated chain with a terminal carboxyl group, polyalkalene with end markatanova group, polyalkalene with an elongated chain with terminal mercaptan group, polyalkalene with the terminal amine is and the claims the term "polyalkalene" refers to polymers of at least one diene with conjugated double bonds, having from 4 to 12 carbon atoms, and includes copolymers of at least one diene and at least one other monomer, copolymerizes with him. As noted, polyalkalene can be non-modified, e.g. a random copolymer of polybutadiene, etc., or modified as having the hydroxyl - or carboxyl-end groups and containing polymeric materials with an elongated chain and hydroxy - and carboxy - terminal groups. Polyalkalene can also be block copolymers of styrene and butadiene, as described in the application N 07/657929 from 20.02.91, entitled "Adhesive compositions based on block copolymer adducts", which is reproduced here for comparison. As noted, polyalkalene can be either a liquid polymer or solid polymer. In this respect, the hydroxyl-substituted, carboxyl-substituted, amine-substituted and mercaptan-substituted polyalkylene, as received by the majority of existing serial polymerization processes are liquid polymers having a molecular weight ranging from about 500 to about 20,000; with the weight of such substituted polyalkylene having a molecular weight in the range from about 750 to about 3000. The same is usually elongated chain for in order to increase their molecular weight within the set limits, the most suitable for the present invention. Especially preferred dienophiles are 1,2-polybutadiene-homopolymers, having a vinyl content of greater than 90%, a molecular weight in the range of 35000-40000 and crystallinity 23-27%. Description obtain 1,2-polybutylmethacrylate can be found Ecyclopedia of Polymer Science and Technology, Vol, John Wiley and Sons, New York, 1985, p. 573.

The hydroxyl-substituted, carboxyl-substituted, amine-substituted and mercaptan-substituted polyalkylene the dienophiles can be easily modified to the desired range of molecular weight by conventional methods of chain elongation, such as interaction polyalkalene prepolymer with polyfunctional organic chain extender with thorough mixing, preferably followed by degassing. Reaction conditions of chain elongation are well known in science, and are not considered here in detail. As an example of such reaction conditions, the elongation of the chain dihydroxyphenylalanine prepolymer with diisocyanates by chain extension, such as 2,4-colorvision is effective at room temperature or moderately elevated temperatures.

As well sudeley conditions, qualified in science. The resulting polyalkalene with a long chain has significantly increased the spacing molecular weight and the actual manifestation may be highly viscous liquid or solid resin. A complete description of the reaction of substituted POLYHALOGENATED dienophiles with a long chain, including representatives with a long chain in the description of U.S. patent N3894982, in particular, in column 5, line 16 - column 8, line 51, the content of which is reproduced here for comparison.

The adducts used in the practice of the invention are easily obtained by traditional technology, well-known in the field of Diels-alder reaction. Basically the connection according to the Diels-alder reaction between halogenated cyclodienes and vysokonikelevye dienophiles is effective in an organic solvent, such as xylene, in a relative amount such that the stoichiometric ratio between the halogenated cyclic diene with conjugated double bonds and double bonds of the dienophile was from 0.01 to 1.0. The mixture is heated at a temperature in the range from 100 to 200oC. In this temperature range the reaction accession is exothermic and out quite often it is the Ktsia halogenated cyclic diene with conjugated double bonds and vysokobarievogo the dienophile gave adduct, having a halogen content in the range from 20 to 40, preferably about 26 to 35% relative to the total weight of the adduct. The halogen content of the adduct may be determined by known analytical methods, such as method of Saniger.

Adducts the Diels-alder reaction of the present invention are also described in detail in U.S. patent N 4795778, which is reproduced here for comparison. Adduct the Diels-alder reaction of the present invention is typically used in quantitative range of from about 35 to 75, preferably from about 45 to 65% by dry weight (excluding the solvent) of the entire adhesive composition.

Phenolic resin of the present invention can be essentially any thermosetting phenolic resin. Typical phenolic resins include soluble in an organic solvent thermosetting condensation product of an aldehyde having from 1 to 8 carbon atoms, such as formaldehyde, acetaldehyde, somerley aldehyde, ethylhexaldehyde etc., phenolic compounds such as phenol, o-cresol, m-cresol, p-cresol, mixed Cresols, such as technical cresol and m-cresol and/or p-cresol, Xylenol, diphenylolpropane, p-butylphenol, p-phenylphenol, p-chlorophenol, o-chlorophenol, m-bromophenol, 2-ethylphenol, alsomany heterogeneous mixture of phenolic resins.

Phenolic resin is preferably obtained by the traditional method of condensation of from about 0.8 to 5 moles of aldehyde per mole of phenolic compound in the presence of an alkaline, neutral or acidic catalysts to obtain soluble in an organic solvent resin having a molecular weight in the range of about 300-2000, preferably from about 3000 to about 1200. Particularly preferred phenolic resin obtained by the reaction of formaldehyde and phenol with the formation of phenol-formaldehyde resin having a methylol content within 10-60, preferably about 30-50%. Phenolic resin is usually used in an amount of about 1 to 15, preferably about 3-8% by dry weight of the adhesive composition.

Aromatic gidroksosoedinenii of the present invention can be essentially any aromatic compound having one, two or three hydroxy substituent. The aromatic compound is preferably benzene, and other digidroksimelfalana on the benzene ring or other aromatic compounds can be H, alkyl, aryl, alkylaryl, arylalkyl, carboxy, aminoxy, amide, imide, halogen, etc. Digidroksimelfalana are most preferably H and, if and amyl, nonyl. Typical monohydroxybenzene include phenol, p-tert.-the butylphenol, p-phenylphenol, p-chlorophenol, p-alkoxyphenyl, o-cresol, m-cresol, o-chlorophenol, m-bromophenol, 2-ethylphenol, aminophenol and Nonylphenol, among which preferred aromatic monohydroxybenzene is phenol, p-tert.-the butylphenol and Nonylphenol. Typical dihydroxytoluene include resorcinol, hydroquinone and catechin (pyrocatechin), and resorcinol is preferred aromatic dihydroxytoluene. Typical trihydroxystilbene include pyragollole, gallaty, such as propylgallate, robinets and astragalo, and pyrogallol is the preferred aromatic trihydroxystilbene. Now it is preferable to use resorcinol as aromatic gidroksosoedinenii invention. Aromatic gidroksosoedinenii commonly used in the invention in a quantitative range from about 1 to 15, preferably from about 7 to 11% by dry weight of the adhesive composition.

Formaldehyde donor of the invention can be essentially any type of formaldehyde or a source of formaldehyde is known to react with the aromatic hydroxidealuminum for education pheno is luchot in formaldehyde and aqueous solutions of formaldehyde, such as formaldehyde, acetaldehyde, Propionaldehyde, somerley aldehyde, 2-ethylbutyraldehyde, 2-methylbenzaldehyde, 2-ethylhexaldehyde, benzaldehyde, and compounds which decompose to formaldehyde, such as paraformaldehyde, trioxane, hexamethylenetetramine, furfural, acetamin, which release formaldehyde when heated, etc. Now it is preferable to use hexamine as a formaldehyde donor invention. Formaldehyde donor is used in the quantitative range of from about 1 to 15, preferably from about 8 to 12% by dry weight of the adhesive composition.

Thermally activated cross-linking agent for unsaturated elastomer of the present invention can be any known cross-linking agents, such as kinondoni, dibenzofuran and 1,2,4,5-tetrachlorobenzene. A crosslinking agent is usually used in quantitative range from about 0.1 to 15, preferably 1-4% by dry weight of the adhesive composition.

Vulcanizing agent of the present invention may be any known vulcanizing agent, which is able to sew the elastomer at temperatures of formation (140-200oC). The preferred vulcanizing agents and the invention in a quantity ranging from about 1 to 15, preferably from about 2 to 7 % by dry weight of the adhesive composition.

The oxide of the metal can be any metal oxide, such as zinc oxide, magnesium oxide, lead oxide, minium, the dibasic postit lead, and combinations thereof, and the oxide of zinc is the preferred metal oxide, because it is extremely effective and environmentally more acceptable than the Pb-containing alternative oxides. The metal oxide is typically used in a quantity ranging from about 1 to 60, preferably from about 10 to 20 % by dry weight adhesives composition.

The present adhesive composition may optionally contain other well-known additives including plasticizers, fillers, pigments, reinforcing fillers, etc. in quantities taken in the technology of adhesives to obtain the desired color and consistency. Typical optional additives include dusty SiO2, carbon black and titanium dioxide (TiO2). In particular, it is preferable in this invention to use Smoking SiO2or carbon black for coloring, reinforcement and control the rheology of the adhesive. Smoking SiO2typically used in a quantity ranging from about 0.5 to 5, predpochtenij the range from about 3 to 50, preferably about 8-15 % by dry weight of the entire adhesive composition.

In order to obtain the adhesive composition of the invention, the above ingredients are usually combined, dissolved and dispersed in a suitable solvent. Typical solvents used in the invention include aromatic hydrocarbons such as xylene, toluene and polar solvents such as ketones, including methyl isobutyl ketone and methyl ethyl ketone. The solvent is generally used in a quantity sufficient to obtain the formulation of the adhesive having a viscosity in the range from 25 to 5000, preferably 100 to 700 centipoise when the total solids content (TSC) in the range of about 5 to 40, preferably about 10 to 35%.

The present adhesive composition can also be obtained as an aqueous formulation by adding a typical water surface-active substances, such as arylmethylidene, the addition of water under conditions of high shear to obtain emulsion and vacuum removal of the solvent by the conventional technology.

The adhesive composition of the invention preferably is used for coupling the elastomeric material with a metal surface by heating them and so on, after which the composition is dried. Covered metal surface and the elastomeric substrate is usually subjected to pressing under a pressure of 20.7 - 172,4 MPa, preferably from about 20 MPa to 50 MPa. The obtained rubber pair simultaneously heated at a temperature of about 140 - 200oC, preferably at about 150 - 170oC. the Assembly should remain under pressure and at a temperature within a period of time from about 3 min to 6 min depending on the speed of vulcanization and the thickness of the rubber substrate. This process can be performed by applying the rubber substrate in the form of semi-molten material on a metal surface, such as during injection molding. As stated above, the adhesive compositions of the present invention are particularly suitable for use in the process of injection molding. The process may also be performed using a direct pressing, injection molding or autoclave vulcanization. After the process ends, the pairing is fully cured and ready for use in the final application.

Although the adhesives of the present invention are preferred to pair MCA or coating for any surface or substrate, you can apply the adhesive. Material that can be paired with a surface, such as a metal surface, in accordance with the present invention is preferably a polymeric material, including any elastomeric material selected from any of the natural rubbers and olefinic synthetic rubbers including polychloroprene, polybutadiene, neoprene, Buna-N, Buna-N, butyl rubber, commercially available brominated butyl rubber, nitrile rubber, etc., the Material is preferably natural rubber or the best choice rubber. The surface from which material is mated, may be any surface such as the surface of glass, plastic or fabric, which can be applied adhesive, and preferably a metal surface selected from any of the well-known structural metals such as iron, steel (including stainless steel), lead, aluminum, copper, bronze, brass, Nickel, zinc, Monel, etc.

The above description and the following examples are given to illustrate the invention and the specific amounts and combinations of ingredients contained in them, are not intended to limit the scope of the invention, which is defined toolchest interaction of 79.8 g of hexachlorocyclopentadiene, 201,5 g of 1,2-polybutadiene (vinyl content of 92%, a crystallinity of 25%, a molecular weight of 95000) and 718,7 g of xylene at 142oC for 20 h Obtained adduct containing from 27 to 29% of chlorine. The adduct is then precipitated in methanol, dried and again dissolved in a mixture of 2:1 mixture with xylene three times to remove unreacted hexachlorocyclopentadiene.

The resulting adduct is used with the ingredients and solvents to obtain adhesive compositions in accordance with the present invention, are presented in table.1, where (a) CAB-O-SILHS-5(Cat Corp.); b) phenol resin (37% methylol content, 70% S in a mixture of 3:1 ethyl ketone ethanol).

Adhesion tests.

The adhesive compositions obtained in examples 1 and 2 was applied with a layer thickness of 12.5 - of 30.5 μm on peskostrujnymi steel samples treated sand.

Coated samples were connected with the substrate E218 (profective vulcanized rubber with shore hardness 55 - 60), HC-202 (best choice rubber with a shore hardness of 60 to 65) and A060P (natural rubber with a shore hardness of 40 - 45) injection under pressure of a rubber-covered samples at 165oC subsequent vulcanization of the rubber Taniam, described below.

The definition of primary adhesion.

Related parts were subjected to destruction in accordance with the methodology D429B ASTM. The part was tested on peeling angle of exfoliation 45o.

The tests were performed at room temperature with a speed test of 500 mm/min After the pairing is destroyed, the measured maximum value of the effort of exfoliation (measured in kg) and the percentage of rubber remaining on the coated adhesive surface.

Exposure to the salt fog for 72 hours.

Related parts were polished at the ends of the grinding wheel. The rubber was then prokruchivala back on top of the metal wire of stainless steel. The connection is exposed to the environment. The destruction was initiated by applying cuts on the connection line with a razor blade. The part was then nakalyalys on stainless steel wires were placed in the camera with salt spray. The environment in the chamber had a temperature of 37.8oC, humidity 100% and 5% of the dissolved salts in the fog, which was dispergirovanija in the camera. Remained in this environment, 72 h After removal from the chamber the rubber was peeled off from the metal with pliers. Then we determined the percentage of remaining Al in the same way, as for tests in salt mist, but in this test parts were placed in chemical beaker filled with boiling water. Exposure time was 2 o'clock When the destruction of the environment, the rubber was peeled off from the metal with pliers. Then we determined the percentage of remaining rubber.

The test for 100 hours at a temperature of 150oC in a mixture of 70:30 glycol with H2O.

Related part was obtained in the same way as for tests in salt mist. In this test, the parts were placed in a Cup filled with a solution containing by weight 70% ethylene glycol and 30% water. The Cup is immersed in her mating parts and then was heated at 150oC for 100 hours At the destruction of the environment, the rubber was peeled off from the metal with pliers. Then we determined the percentage of rubber left on the part.

Test immersion for 7 days in water at room temperature.

The connecting part was obtained in the same way as for tests in salt mist. In this test, the parts were placed in chemical beaker filled with tap water to room temperature. Exposure in this environment was 7 days. When removed from the environment of the rubber was peeled off from the metal square is rougarou at 135oC.

The test is very similar to the definition of the primary adhesion. The difference of this test is that the mated parts are placed in a chamber heated to 135oC for 15 minutes After that they tested at 135oC. Angle of exfoliation and testing features are identical to those used for defining the primary adhesion. It was recorded the maximum force of exfoliation and the percentage of remaining rubber.

The results of these tests are summarized in table. 2. Data indicated the destruction on the rubber (R), destruction between the adhesive composition and rubber (RC) and failure between the adhesive composition and the metal substrate (CM). Destruction expressed in% of% and a high percentage of destruction of the rubber is desirable, as it indicates that the adhesive connection is stronger the rubber. Pre-processing refers to the period of time during which the sample is maintained at a temperature of 165oC to pair with a rubber.

As can be seen from the above data, mainly non-toxic adhesive composition - an object of the present invention can be used as a PA, thus obtained adhesive connection is able to withstand high temperature fluids (glycol/water) and corrosion-active agents (salt fog).

1. Adhesive composition, comprising the product of the merger by the Diels-alder reaction perhalogenated cyclic conjugated diene and refinancinga a dienophile having a vinyl content of at least 50 wt. %, vulcanizing agent, magnesium oxide or zinc, characterized in that it further includes aromatic gidroksosoedinenii, formaldehyde donor, phenolic resin and activated by heating unsaturated elastomer crosslinking agent is a derivative of quinone in the following ratio of the components of the composition, wt.%:

Specified product connection on the Diels-alder reaction - 35-75

Aromatic gidroksosoedinenii - 1-15

Formaldehyde donor - 1-15

Vulcanizing agent is 1.0 to 1.5

Magnesium oxide or zinc - 1-60

Phenolic polymer - 1-15

Activated by heating unsaturated elastomer crosslinking agent is a derivative of quinone - 0,1-15

2. The composition according to p. 1, characterized in that perhalogenated cyclic conjugated shall pentadien, 5,5-deferredmediaselection and 5.5-dibromotetrachloroethane

3. The composition according to p. 2, characterized in that the cyclic conjugated diene is hexachlorocyclopentadiene.

4. The composition according to PP. 1-3, characterized in that dienophile is a polymeric material selected from the group consisting of polyalkylene, polyalkylene with a terminal hydroxyl group, polyalkalene with an elongated chain end with a hydroxyl group, polyalkalene with terminal carboxyl group, polyalkalene with terminal mercaptan group, polyalkalene with an elongated chain with terminal mercaptan group, polyalkalene with the terminal amine group, polyalkalene with an elongated chain with a terminal amine group and cash equivalents.

5. The composition according to p. 4, wherein the dienophile is 1,2-polybutadiene.

6. The composition according to paragraphs 1-5, wherein the composition comprises the product of the merger by the Diels-alder reaction with halogen 26 - 35 wt.%.

7. The composition according to PP. 1 - 6, characterized in that the composition comprises the product of the interaction on the Diels-alder reaction with a vinyl content of 88 to 98 wt.%.

8. The composition according to PP. 1-7, distinguish the song on PP. 1 to 8, characterized in that the composition contains aromatic gidroksosoedinenii selected from the group consisting of resorcinol, phenol, p-tertbutylphenol, p-phenylphenol, p-chlorophenol, p-alkoxyphenyl, o-cresol, phenol, m-bromophenol, 2-ethylphenol, amylphenol, Nonylphenol, hydroquinone, catechin, pyragollole and gallaty.

10. The composition according to p. 1, characterized in that as a formaldehyde donor, it contains a compound selected from the group consisting of Formaldehyd, formaldehyde, acetaldehyde, Propionaldehyde, somerley aldehyde, 2-ethylbutyraldehyde, 2-ethylhexaldehyde, benzaldehyde, trioxane, furfural, hexamethylenetetramine and acetal.

11. The composition according to p. 1, characterized in that as the vulcanizing agent, it contains selenium, sulfur or tellurium.

12. The composition according to p. 1, characterized in that the product of the merger by the Diels-alder reaction contains 1,2-polybutadiene with a vinyl content of 90%, they say. m 35000 - 40000 and degree of crystallinity 23-27%.

13. The composition according to p. 1, characterized in that it further comprises a dusty SiO2and soot in the amount of 1 to 3 wt.%.

 

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The invention relates to the development of adhesives

FIELD: application of adhesive underlayers (adhesive primers) on base of chlorine-containing rubbers on base of natural isoprene, butadiene, butadiene nitrile, styrene-butadiene, chloroprene and butyl rubber to metal in the course of vulcanization; manufacture of rubber metal articles for automobile industry.

SUBSTANCE: proposed adhesive underlayer includes chlorinated natural rubber, fillers, stabilizer, solvent, phenol resin, resol-type phenol formaldehyde resin, wetting agent and urotropin. Used as solvent is mixture of xylol with methyl isobutyl ketone.

EFFECT: enhanced strength of attachment of rubber to metals; enhanced corrosion resistance; low cost of product; absence of toxic solvents.

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FIELD: chemistry.

SUBSTANCE: butadiene-nitrile rubber based adhesive composition contains phenol formaldehyde resin, polyvinylchloride resin which is chlorinated or chlorinated isopreprene rubber, zinc oxide, magnesium oxide, organic solvent and filler. The filler is a mixture of lignocellulose polydispersed fibre materials and ethyl cellulose. The lignocellulose polydispersed fibre materials are wastes from textile industry, wood chemical and/or cellulose and paper production.

EFFECT: composition increases adhesion strength of various substrates and improves thixotropic properties.

4 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: adhesive composition contains chlorinated natural rubber, epoxy diane resin, and an organic solvent. The organic solvent used is toluene. The adhesive composition additionally contains a modifier in form of phosphorus-boron-containing methacrylate.

EFFECT: invention increases strength when gluing together vulcanised rubber at room temperature.

1 ex, 2 tbl

FIELD: chemistry.

SUBSTANCE: method involves applying onto the glued surfaces a solution based on chlorinated natural rubber in an organic solvent, drying and bringing the surfaces into contact. The rubber used is rubber which is pre-ozonised for 0.5-2.0 hours at room temperature to obtain a product with acid number of 9.14-30.87 mgKOH/g. The solvent used is ethyl acetate. The glue is applied in two steps while drying the adhesive film at room temperature for 10 minutes after applying the first layer and for 1-2 minutes after applying the second layer.

EFFECT: high strength of the glue joint when gluing vulcanised rubber and simplification of the gluing process.

1 cl, 1 tbl, 9 ex

FIELD: chemistry.

SUBSTANCE: adhesive composition based on chlorinated natural rubber contains an organic solvent, wherein the rubber used is pre-ozonised for 0.5-2.0 hours at room temperature to obtain a product with acid number of 9.14-30.87 mg KOH/g, and the solvent is ethyl acetate, with the following ratio of components, pts.wt: chlorinated natural rubber - 20.0; organic solvent - 80.0.

EFFECT: high strength of gluing vulcanised rubber to each other.

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SUBSTANCE: vulcanised rubber is glued to each other by applying an adhesive based on isoprene rubber solution in nefras onto the surfaces to be glued. The surfaces are then dried and brought into contact. The isoprene rubber in the adhesive is SKI-3 rubber which is pre-ozonised for 0.5-1.0 hour at room temperature. The adhesive is applied in two steps while drying the adhesive film at room temperature for 10 minutes after applying the first layer and for 1-2 minutes after applying the second layer.

EFFECT: invention provides high strength of the adhesive joint when gluing vulcanised rubber to each other and simplifies the gluing technique.

2 ex, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to an adhesive sublayer based on chlorinated natural rubber used for fixing rubbers based on natural, isoprene, butadiene, butadiene-nitrile, butadiene-styrene, chloroprene, and butyl rubber to metal during vulcanization. The invention can be used in rubber industry in making heat-resistant multilayer rubber-fabric articles, particularly rubber-cord casings and pneumatic tires, as well as flexible high-pressure hoses when operating in aggressive media. The adhesive sublayer includes, ps wt: chlorinated natural rubber - 100, metal oxides - 10.0-20.0, phenol-formaldehyde resin of resole type - 1.0-5.0, phenol-formaldehyde resin of the novolac type - 20.0-50.0, the complex of resorcinol and hexamine - 2.0-15.0, stabiliser - 2.0-10.0, wetting agent - 0.01-0.1, filler - aerosil - 2.0-10.0, xylene and methyl isobutyl ketone - 345.0-400.0.

EFFECT: invention allows to increase the strength of the rubber compound attachment to metal, to reduce toxicity and to improve environmental safety for humans.

2 dwg, 2 tbl

FIELD: adhesive compositions for polyvinyl chloride-based adhesive tapes.

SUBSTANCE: claimed adhesive contains perchlorvinyl resin, plasticizer, pine-wood rosin, and filler. Mixture of dioctylphthalate and chlorinated alpha-olefins, obtained from waste of ethylene oligomerization, is used as plasticizer, and activated mixture of natural zeolite and calcium oxide is used as filler. Adhesive tapes of present invention are useful as sealing and protective coatings for gas and oil line coil.

EFFECT: polyvinyl chloride-based adhesive tapes with improved adhesive quality and reduced plasticizer migration from tape into adhesive tape.

3 ex, 1 tbl

Tape glue // 2381249

FIELD: oil-and-gas industry.

SUBSTANCE: invention related to manufacturing of gluing compositions, used for sticky polyvinylchloride (PVC) tapes, assigned for oil-gas pipelines cover as an insulating protection cover. Described tape glue, containing perchlorvinyl resin, plasticisers- diactil phthalate and chlorinated paraffin or chlorated α-olefins, received from ethylene oligomerisation waists, colophony, polyethyleneamines and chalk or zeolite fractions or granular limestone as a filling agent.

EFFECT: increase of sticky polyvinylchloride tapes adhesion to steal, cost saving.

2 cl, 1 tbl, 17 ex

FIELD: chemistry.

SUBSTANCE: invention involves applying an adhesive onto the glued surfaces and bringing the surfaces into contact. An adhesive which is based on a solution of perchlorovinyl resin in an organic solvent is applied twice onto the surfaces, followed by addition of modifiers such as polyethylene polyamine and a phosphorus-boron-chlorine-containing oligomer. The phosphorus-boron-chlorine-containing oligomer is obtained from reacting methylphosphite borate with epichlorohydrin. The solvent used is a mixture of butyl acetate and acetone. An adhesive film is applied in two layers and dried at room temperature, followed by gluing the surfaces.

EFFECT: invention simplifies the method of gluing components made from fibre glass and increases the strength of lap splicing fibre glass.

2 tbl

FIELD: chemistry.

SUBSTANCE: adhesive composition contains perchlorovinyl resin, epoxy resin ED-20, an organic solvent - mixture of butyl acetate and acetone in ratio of 1:1, a modifier in form of a phosphorus, boron and nitrogen-containing oligomer, which is obtained in advance by reacting methyl phosphite borate, epoxy resin ED-20 and aniline in weight ratio of 2.5:1:2.5. The adhesive composition contains, pts.wt: perchlorovinyl resin - 15.0, said organic solvent - 85.0, said phosphorus, boron and nitrogen-containing oligomer - 0.1-10.0.

EFFECT: high strength when gluing glass fibre to each other.

2 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to field of obtaining glue compositions, used for production of adhesive polyvinylchloride (PVC) tapes, intended for insulation and protective coating of gas and oil pipelines. Glue composition for adhesive polyvinylchloride tapes contains perchlorovinyl resin, chloroparaffin CP-470 or chlorinated α-olefins, rosin, chalk or milled marble and additionally contains plasticiser DES, basically representing modified mixture of high-boiling ethers of dioxane alcohols (4-methyl-1,3 dioxane-4ethanol) with addition of stabilisers.

EFFECT: application of invention makes it possible to increase glue stickiness, reduce area of coating detachment in cathode polarisation at temperature 20°C, cost of polymer material and extend raw material base of plasticisers.

10 ex, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to the field of obtaining glue compositions, used in the production of adhesive polyvinylchloride (PVC) tapes, intended for wrapping gas- and oil-pipelines as an insulating and protective coating, as well as for carrying out repair works. The glue composition includes a perchlorovinyl resin, a plasticiser and an adhesion-improving additive. The composition additionally contains dichlorocyclopropanated 1,2-polybutadiene or dichlorocyclopropanated syndiotactic 1,2-polybutadiene in an amount from 1 to 15 wt.p. Dichlorocyclopropanated 1,2-polybutadiene with the weight average molecular weight from 8000 to 120000 is used. A degree of dichlorocyclopropanation in dichlorocyclopropanated 1,2-polybutadiene constitutes from 2.5 to 35.9%.

EFFECT: increased adhesion of an adhesive PVC tape to a metal surface.

3 cl, 1 tbl, 12 ex

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