UA74700C2 - An adhesive composition - Google Patents

Abstract

An adhesive composition for woodworking, building, machine-shipbuilding and other fields of industry. The adhesive composition contains organosilicon carbofunctional oligool, isocyanate component, fire retardant, pigment, solvent and initiator of opening unsaturated ties. As carbofunctional organosilicon oligool it contains individual or carbofunctional organosilicon oligool in a mixture of the general formula: , wherein : - alkyl aryl, vinyl; - remainder of oligoetherdiol with molecular mass between 206 and 1400 units and content of hydroxyl groups between 2.6 and 11.6 % by weight which contains ester groups.

Description

Description of the invention

The invention relates to woodworking, construction, machine building, shipbuilding, etc. branches of 2 industries, namely to adhesive compositions used in the production of glued materials from wood, metal, glass, plastics, etc.

A well-known filled adhesive composition (SP. Kamenetsky. In the book: Perlit!i. Properties, technology and application.

M. Gosstroystandart. 1963, p. 193) which contains, by weight: urea-formaldehyde resin (per dry residue) 100.0; hardener 0.5:1.5; loose pearlite 100.0; - water added to the composition with resin and hardener 83.8-87.8.

However, products made of such an adhesive composition are characterized by low moisture resistance and strength, which greatly limits the fields of its application.

An adhesive composition is also known (Pat. of Ukraine Mo17166 A. dated 18.03.97. OB. Mo5. 1997), which contains, wt. frequent: di or polyol 150.0:550.0; isocyanate component 172.0-309.0; flame retardant 96.6-257.0; pigment 1.0-100.0; filler 0.1-1719.22; school

Although the strength properties and moisture resistance of the adhesive joint based on such a composition are at a relatively sufficient level, compared to the previous technical solution, they are still not high.

The closest in terms of technical essence and obtainable effect to the claimed invention is the adhesive composition | Application of Ukraine Mo93007624 dated 22.11.1993. ABOUT. Mo2.1997, p.242| which contains, wt. often o (PROTOTYPE): o organosilicon carbofunctional oligool 315.0:563.0; in. polyisocyanate 240.0-619.2; ch;E flame retardant 138.75-345.65;

Zo! - pigment 1.0-100.0;

As an organosilicon carbofunctional oligool, compounds of the general formula are used: two". otonu | ch -e shi s where: x-3-0.2; n-1-9:z» K - aryl, alkyl C4-Co

K - the residue of an individual or oligomeric aliphatic diol with a simple ether bond in the chain structure, the general formula: HO-K-OH with a molecular weight from 60 to 1100 units. -1 Such organosilicon carbofunctional oligools have found use as effective surface-active substances in mixtures for ultrasonic and vibration treatment of metals (AS. USSR t» Мо1331032 and Мо13583921), as well as as polyurethane pores (AS. USSR 1078456). -1 However, even in this case, the strength of the adhesive joint or glued products based on such an adhesive composition is insufficient, especially in connection with the growing requirements put forward by modern ("in") industry, for example: for the manufacture of various structural materials , which will be done in extreme (at elevated temperatures and humidity) conditions.

The object of the claimed invention is to improve the adhesive composition in order to increase the strength characteristics of adhesive joints and products based on them, in conditions of elevated temperatures and humidity by introducing additional ester and unsaturated bonds into the carbofunctional radicals of the organosilicon oligool, which contributes to the formation of the hardened adhesive layers, with their participation, networks of additional (F) physical or chemical bonds that increase the strength and chemical resistance of the adhesive joint. d The goal is achieved by the fact that in the known adhesive composition, which contains an organosilicon carbofunctional oligool, an isocyanate component, a flame retardant and a pigment, according to the invention, as a carbofunctional organosilicon oligool, it contains individually or in a mixture carbofunctional organosilicon oligools of the general formula: two". ton 2 ve de: x 30.2; n 5 1-9 Sh

B" - C4-Co alkyl, aryl, vinyl; -D-

B" - the residue of a complex oligoetherdiol of the formula: NOV'"?OOSV sov "OH, with a molecular weight from 206 to 140 bod, with a content of hydroxyl groups from 2.6 to 11.6 b9 by mass.;

B// - the residue of an individual or oligomeric, normal or isostructural, aliphatic diol with a molecular weight from 60 to bObod;

VM - the residue of an aliphatic or aromatic, substituted or unsubstituted, saturated or unsaturated dicarboxylic acid, anhydride or dianhydride of acids, and additionally a solvent, a filler, and an initiator for the opening of unsaturated bonds at the following ratio of components by mass. parts: 70 organosilicon carbofunctional oligool 326.0-1344 0; isocyanate component 157.69-765.45; solvent, which is introduced with the isocyanate component 160.38-510.3; flame retardant 0.1-251.42; pigment 0.1-100; filler 0.1-100; the initiator of the opening of unsaturated bonds 0.1-3.4.

The claimed set of features allows, in comparison with the PROTOTYPE, to increase the strength properties of adhesive joints not only due to a number of chemical reactions between isocyanate groups and hydroxyls of the organosilicon carbofunctional oligool, as well as secondary reactions that are described in the PROTOTYPE, right before: due to the reaction of urethane formation: - -iko- -la" y, y

MSE ly luky o. o. -- C sch sh 6) - due to the interaction of an excess of isocyanate groups with moisture adsorbed both on the surface of adhesive materials, a filler, and also with moist air, when the adhesive mixture is applied to the substrate:

Ugo ZHNO - UNSO and SO (2) Fr

Shchi , , - due to the interaction of the rest of the isocyanate groups with the formed: o - amines: ich- t - MS Mu oyi sht- - Ho 5 -gmOO zhlo luk m - urethane ones: and " with -MSO those with - ureas: у / 7 th ray of office - MIO- M-S ln "y, inn y Y ry Ga y Y av) ' rda, Gl LU de "v y , ky

Gas - zl - - - with the formation of urea, allophanate and biurethane bonds; и5" - due to the realization in the grid system of physical interactions caused by the formation of polar urethane, urea, amine, allophonate and biuret bonds and other bonds and groups; - - due to the presence of a polar polyphenyl o20 (alkyl-, vinyl-) siloxane block in the structure of the organosilicon carbofunctional oligool, which increases intermolecular interactions; - and, most importantly, due to the additional strengthening of physical intermolecular interactions due to the presence in the structure of the declared series of carbofunctional organosilicon oligools of polar ester, aromatic groups or unsaturated bonds, which contributes to the increase of strength characteristics.

In addition, the use in the claimed adhesive composition of carbofunctional organosilicon oligools with 22 unsaturated bonds in the structure (a vinyl radical at the silicon atom, and a residue of maleic anhydride at

F! carbofunctional radical), allows, in comparison with the PROTOTYPE, to realize in the hardened adhesive layer not only a network of chemical cross-links caused by the flow of polyaddition reactions (see schemes 1-5), but also a network of more chemically stable ones; bonds for polymerization reactions: -с6--- bo, E b5

- plans of nota st c 7 ble; th unit 7 -hy- -e or ! ; p

Su sy --y 7 dur t Syn STU / / /2 which makes it possible not only to increase the strength of the characteristics, but at the same time, the chemical resistance (moisture resistance) of the resulting adhesive layer.

The claimed technical solution is illustrated by examples.

To confirm the positive effect, adhesive compositions (experimental and PROTOTYPE) were prepared and adhesive joints based on them were tested.

As carbo-functional organosilicon oligools with complex ether groups in the carbo-functional radical, compounds of the general formula were used: vo». ton 2 s de:x-3:02;p- 19

K - aryl, vinyl, C4--Co alkyl; and)

B" - the residue of a complex oligoetherdiol of the formula: NOV/'OSV Usoov'onNn

B" - the residue of individual (ethylene, diethylene, triethylene, tetraethylene, propylene, butylene, hexamethylene glycol) or oligomeric (polyoxaethylene, polyoxapropylene, polyoxatetramethylene glycol, 2 copolymers of ethylene oxide, propylene oxide with tetrahydrofuran), normal or isostructure, aliphatic diol with molecular weight from 60 to bObod;

BM - the residue of an aliphatic or aromatic, substituted or unsubstituted, saturated or unsaturated - dicarboxylic acid, anhydride or dianhydride of acids. "

THEY are obtained by transesterification of the corresponding silicon alkoxy derivatives of the general formula: i - vok on 2 p where: K - alkyl C4--Su; "

K - alkyl C.--Co, aryl, vinyl; From 70 x - 30.2; n - 1-9 complex oligoetherdiols of the formula: NOV'OSV UsooVv'on; c where: B// - the residue of an aliphatic diol of individual or oligomeric, normal or isostructure, :c" of the above-described series with a molecular weight from 60 to bObod.;

BM - the residue of an aliphatic or aromatic, substituted or unsubstituted, saturated or unsaturated dicarboxylic acid, anhydride or dianhydride of an acid at 160-2302C, in the presence of alkyl compounds -I titanium, with a ratio of one molecule of a complex oligoetherdiol to one alkoxy group of an alkoxy derivative of silicon. The synthesis of the initial complex oligoetherdiols is carried out in accordance with the methodology given in the article: -I "Synthesis, properties and some ways of using low molecular weight oligoetherdiols", by M.Ya. Kuzmenko, |.G. Ploshenko, V.V. Bugrym, V.V. But/, n.t.j. "Questions of chemistry and chemical technology".-1999,-Mo2,-p.34-36. o Their physicochemical constants are given in the table Mol, o The synthesis of carbofunctional organosilicon oligools with an ester bond in the carbofunctional radical is carried out in accordance with the method of synthesis of similar carbofunctional organosilicon oligools with a simple ether bond in the carbofunctional radical |that were used in the PROTOTYPE)| and which are published in the article: "Synthesis of organosilicon oligools" VV.

Bugrym, N.Ya. Kuzmenko, T. Hlushko, G.F. Vedeneeva The manuscript was deposited in NIITEKhim, Cherkassy, 1981, 10s, about Mo1019 ХП-280). ko Physico-chemical constants of the original silicon ethoxy derivatives used are given in table Мо2.

The physicochemical constants of the claimed series of carbofunctional organosilicon oligools in table MoZ, where: in - compounds 1-4 are examples of the claimed series of carbofunctional organosilicon oligools in which the nature of the acid component in the carbofunctional radical changes (adipic, sebacic, phthalic and maleic acid, respectively ); - connection 1; 5; 7 are examples of the claimed range of carbofunctional organosilicon oligools in which the nature of the diol component in the carbofunctional radical and its length change to 65 "(individual diol - diethylene glycol; oligomeric diols - polyoxypropylene glycols with a molecular weight of 200 and bObod., respectively);

- connection 1; 7; 8 characterize the examples of the claimed series of carbofunctional organosilicon-oligools in which the size of the polyorganosiloxane block changes

City O di ok hi

Y. shinyi / is / (is lu br (in IM / 906, respectively; - compounds 1; 9; 10; 11 are examples of the declared series of carbofunctional and organosilicon oligools in which the nature of the radical at the silicon atom changes (phenyl, vinyl , methyl, nonyl - respectively); - compound 12 - is an example of an oligool on the basis of which the highest strength of the adhesive layer was obtained in the prototype (recipe Mo5 table Mo3).

In" it contains a residue of polyoxypropylene glycol with a molecular weight of 400 units. (Such polyoxypropylene glycols are produced in Russia under the trade name "Laprol 402", or "Laprol 202", or "Laprol 602" for the previously mentioned polyoxypropylene glycols with a molecular weight of 200 and bObod) .

Example 1.

Synthesis of carbofunctional organosilicon oligool Mo1 Table 3.

120 grams (0.5 mol) of phenyltriethoxysilane, 483 grams (1.5 mol) of complex oligoetherdiol (compound Mo1, Table 1) and five drops of tetrabutoxytitanium are loaded into a three-necked reactor with a capacity of 1 liter, equipped with a stirrer, a direct cooler, and a thermometer in carbon dioxide air. - as a reaction catalyst.

With continuous stirring, the mixture is heated. The release of water is observed from a temperature of 16020. The end of the reaction (at a temperature of -2302С) is judged by the cessation of the release of ethyl alcohol. The reaction mixture is cooled and analyzed. 520.1 g was obtained. transparent mobile liquid, light yellow color. Its characteristics are given in table 3. Other connections are obtained by a similar method. and)

Individual or oligomeric compounds containing free isocyanate groups are used as isocyanate components.

As an isocyanate component, in the adhesive composition according to the prototype, polyisocyanate brand o zr B (according to TU 113-03-375-75) was used with the following characteristics: - appearance - mobile liquid, dark brown in color; o - index of refraction pd? - 1.6210 u- - density, g/cm - 1.2250 « - mass fraction - МСО groups, 9о - 29.6 - gram-equivalent, unit. - 137.5 -

Taking into account the fact that polyisocyanate brand B with the claimed carbofunctional organosilicon oligools with ester groups in the carbofunctional radical reacts very quickly (2-5 minutes before gelation, which contributes to difficulties in homogenizing the mixture and applying it to the substrate), as an "isocyanate component (although and the use of polyisocyanate is not excluded if the mixing of components is carried out in the nozzle of a spray nozzle), individual or oligomeric isocyanates (isocyanate - c prepolymers) are used on the basis of individual diisocyanates and aliphatic, individual or oligomeric, and normal or isostructure, low molecular weight diols, triols, tetraols. ,» Such isocyanate prepolymers are obtained by the known reaction of urethane formation, in a dry environment, solvent inert to isocyanate groups, in an inert gas atmosphere (for example: in nitrogen), at 60-702C, at a ratio of one gram/equivalent of diol (triol, tetraol) one mole of diisocyanate before reaching the estimated number of free isocyanate groups. As examples of the series of isocyanate-containing components described above, the following were used: a) an isocyanate-containing prepolymer based on trimethylolpropane and a mixture of isomers (2.4-2.6; 65/359 by weight) and toluene diisocyanate (TDI-MP adduct) of the formula: o 50 (42 )

SN- SN. - С-(СНООСМН - Her Usv, uz zv МСо о with the following characteristics: - mass fraction of free -MSO groups, bo - 19.22; co - gram/equivalent, unit - 218.8.

It is used in the form of 6095 by mass solution in cyclohexanone with the following characteristics: 60 - mass fraction of free-MSO groups, 905 -10.5 - density at 209C, g/cm - 1.12 - gram/equivalent, unit - 364.7 - appearance - light yellow liquid. b) isocyanate-containing prepolymer based on diethylene glycol and a mixture of isomers (2.4-2.6; 65/35 9romabs.) of toluene diisocyanate. It is produced on an industrial scale under the brand DUDEG-2 according to TU 6-55-33-89 and is a solution of diethylene glycol diurethane diisocyanate in an excess of a mixture of toluene diisocyanate isomers.

This isocyanate-containing prepolymer is used directly, without a solvent. Its characteristics are as follows: - appearance - light yellow liquid; - density at 209C, g/cm - 1.1870; - mass share of free - MSO groups, 90 - 29.0; - gram-equivalent, unit. - 141.8. c) individual diisocyanate - 2,4-toluenediisocyanate; produced in industry under the brand "Product 701027" according to TU 6-113-331-79

Its characteristics are as follows: - appearance - transparent, colorless liquid; - density at 209C, g/cm - 1.2206; - mass share of free - MSO groups, 90 - 39.0; - gram-equivalent, unit. - 105.13; - Tkip. "S/mm Hg. - 106-107/10;

Product 1027 is used in adhesive compositions directly, without a solvent.

To give the adhesive layer fire resistance, well-known organic compounds of phosphoric acid are introduced into the adhesive mixture, in the amount of 25-3590 mass by mass of the binder (oligool and isocyanate component).

As an example, organic compounds of phosphoric acid according to TU 6-05-1611-78 are used. Among them - tris(chloroethyloxa)phosphate of the formula: (ССНСН»)-Р-ОЙ. with

In order to give the adhesive layer a variety of colors, a variety of well-known organic and non-organic dry, finely ground (with dispersity up to 20-:4µm) pigments, which are inert to free isocyanate and) groups, are introduced into the adhesive mixture. For example: carbon black, titanium dioxide, zinc oxide, aluminum powder, etc.

In order to reduce the cost of the adhesive composition, a variety of well-known, inert to free isocyanate groups, dry, finely ground (with dispersity up to 20-40μm) dense or loose inorganic fillers are introduced into it. "with"

For example: finely ground dry river sand, microbarite, andesite, marshallite flour, etc. at

To ensure the opening of double bonds (the vinyl radical at the silicon atom, or the maleic anhydride residue in the carbofunctional radical of the oligool), well-known initiators of their radical polymerization (for example: benzoyl peroxide, dicumyl peroxide, etc.) or organometallic compounds are used (for example: butyllithium, etc.).

Rectangular parallelepipeds of size - 20x20x6bOmm from "oak" wood with a moisture content of 6--895 wt are used as samples for determining the strength of gluing.

Example 2.

The technology for the production of adhesive compositions (experimental and prototype) and the examination of adhesive joints "consisted of the following:

The components of the composition, in the ratio indicated in Table 4, are loaded into a glass, homogenized for 3-5 minutes, and the surfaces of the wooden samples to be glued are smeared with an adhesive composition (it is enough to smear only one of the surfaces to be glued). Then the samples are assembled with the smeared areas "Cross-cross", they are placed in a device in which a specific pressure of O0.1 MPa is provided and kept there at 25290 for 72 hours.

The resulting adhesive joint is examined for normal separation. - For each of the recipes of the adhesive composition, 10 parallel experiments were conducted. Of them, 5 samples of iz are examined immediately after 72 hours of exposure at 25 -292C; 5 second samples are additionally examined by the accelerated method for moisture resistance (in addition, the samples are kept for 2 hours in boiling water. Then the samples are given 4 hours in the air for 4 hours and examined for normal separation). aw! 20 For those adhesive compositions where the TDI-TMP adduct (6095 by mass solution in cyclohexane) is used as an isocyanate component, after smearing the samples, they are allowed to stand in the air for 30 minutes for maximum evaporation of the solvent from the adhesive film.

For those adhesive compositions, in the recipes of which carbofunctional organosilicon oligools with an unsaturated bond in the structure are used (recipes Mo11 and Mo16 of Tables 4 and 5), additional 10 99 parallel tests are conducted. Samples of adhesive joints based on such compositions are cured as described above 72

GF) hours at 25--220. Then they are additionally kept in a thermal cabinet at 1002C for 4 hours. 7 5 samples are then examined for a normal separation; 5 second samples are additionally kept for 2 hours in boiling water, taken out, allowed to cool in the air for 4 hours and then examined for normal separation. because the stability of adhesive joints in boiling water was determined by the coefficient of moisture resistance in parts of the unit, as the ratio of the strength of the adhesive joint at the normal separation after exposure to boiling water to the initial strength.

The obtained research results are shown in Table 5.

For the convenience of their interpretation, the experiment numbers in Tables 4 and 5 are identical.

Since the dependence of the strength of the adhesive layer on the normal separation from the ratio -МСО)/-ОН in g.eq/g.eq is of an extreme nature (experiments 1-8 of Tables 4; 5), the formulations 9-23 given in Table 4 characterize compositions and in Table М5 the strength of the adhesive layer at the optimal ratio of this or that carbofunctional organosilicon oligool with this or that isocyanate component.

As we can see from the obtained experimental results, almost all adhesive joints based on experimental adhesive compositions from 1 to 23 (tables 4 and 5) inclusively, show strength characteristics at a higher level than for the best sample according to the prototype, namely: strength on normal separation in the range from 2.8 to 4.56MPa against 2.68MPa for the best sample according to the prototype recipe (the increase is 0.12--1.88MPa or 4.5--70,290).

This difference especially increases after keeping the samples in boiling water (which modulates the behavior of the adhesive layer when operating in wet conditions). 70 Test samples of the adhesive layer, after boiling in water, show the normal tear strength at the level of 2.32 to 4.24MPa against 2.0MPa of the prototype sample (the increase is 0.32-2.24MPa or 1611296).

Even greater strength is shown by adhesive compounds in the formulation of which use carbofunctional organosilicon oligools with an unsaturated bond in the structure and at the same time substances that reveal such an unsaturated bond.

Due to the formation of an additional network of chemical bonds in such an adhesive layer, the water resistance coefficient increases from 0.87 to 0.96 (recipe 11, table. 4;5) and from 0.91 to 0.965 (recipe 16, table. 4;5) .

This invention can be used to obtain high-quality adhesive products in the woodworking, construction, machine, shipbuilding, radio engineering, etc. industries

The formula of the invention

An adhesive composition containing a carbofunctional organosilicon oligool, an isocyanate component, a flame retardant, a pigment, which differs in that as a carbofunctional organosilicon oligool it contains carbofunctional organosilicon oligool, individually or in a mixture, of the general formula: ovo syaton, 2 p dekh-3-02y -1- 95% alkyl C-Sv, aryl, vinyl; o i" - the residue of a complex oligoetherdiol of the formula: NOV/"SOSE USOOOV "OH, with a molecular weight from 206 to m 1400 units, with a content of hydroxyl groups from 2.6 to 11.6 9o wt.; c!" - the residue of an individual or oligomeric, normal or isostructure of an aliphatic diol with a molecular "

Зз5 weighing from 60 to 600 units; che vi" - the residue of an aliphatic or aromatic, substituted or unsubstituted, saturated or unsaturated dicarboxylic acid, anhydride or dianhydride of acids and additionally contains a solvent, a filler and an initiator for the opening of unsaturated bonds with the following ratio of components by weight: "silicon carbofunctional oligool and 326.0-1344.0 shsh with isocyanate component 157.69-765.45 flame retardant 0.1-251.47 "" pigment 0.1-100.0 filler 0.1-1000.0 solvent for isocyanate component 160.38-510.3 - the initiator of the opening of unsaturated bonds 0.1-3.4.

ChK" -i (in) (42) name) 60 b5