RU2087510C1 - Adhesive composition for adhesion of materials being optically transparent - Google Patents

Abstract

FIELD: radically polymerized adhesives which are intended for using as intermediate polymer layer at manufacturing of multilayer impact constructions in which optically transparent materials (silicate glass, organic glass, polyethylene terephthalate, polycarbonate and other) are used. SUBSTANCE: adhesive composition comprises (met)acrylic derivative of oligoether, radically polymerized monomer, initiator and allyl derivative of oligoether being additionally added. Said allyl derivative of oligoether has common formula I:

where R¹ is (met)allyl; 3-allyloxy-2-hydroxypropyl(phthaloyl)allyloxycarbamoyl; R² is H; alkyl(C₁-C₆); (met)allyl; 3-allyloxy-2-hydroxylpropyl(phthaloyl); A is

Description

 The invention relates to radically polymerizable adhesives intended for use as an intermediate polymer layer in the manufacture of multilayer shock-resistant structures using optically transparent materials (silicate glass, plexiglass, polyethylene terephthalate, polycarbonate, etc.).

 Known adhesive composition for gluing glass [1] including: oligoester (meth) acrylate based on oligoesters; (meth) acrylic monomer containing a glycidyl group and a photoinitiator.

 The disadvantage of this composition is the deterioration of the color of the products during operation and the relatively low strength of the adhesive joint.

 Radical polymerizable compositions are also known, containing along with (meth) acrylate monomers diallyl, allyl carbonate or allyl acrylic monomers [2-4] These compositions, having satisfactory properties, have low physical and mechanical properties, especially at subzero temperatures, since the allyl component is present in as a hard monomer segment.

Closest to the proposed is an adhesive composition [5] comprising: 1) 2-hydroxy-3-methacryloylpropyl ethers of polyether carboxylic acids with a molar mass of 3900 12000 and functionality for methacrylate groups 1.6 2.9; 2) (meth) acrylate monomer; 3) photoinitiator in the following ratio of components (parts by weight):
1) (meth) acrylate oligoester 20 80
2) (meth) acrylate monomer 80 20
3) photoinitiator 0.1 2.0
The specified composition is characterized by good mechanical strength of the adhesive layer at room temperature, however, it has relatively low values of specific fracture work (a _p ) and impact resistance at minus 20 ^o C. In addition, it is characterized by relatively low adhesive properties.

The aim of this invention is to increase the specific work of fracture (a _p ), shear strength (τ)) of the adhesive layer, impact resistance of glued products, improvement of adhesive properties, while maintaining high optical characteristics.

с мольной массой 300 9000,
где R¹=(мет)аллил; 3-аллилокси-2 гидроксипропил(фталоил)аллилоксикарбамоил;
R²=H; алкил(C₁-c₆;(мет)аллил; 3-аллиокси-2-гидроксил-пропил(фталоил)
A=O(CH₂)_2-4O; C₆H₂[C(O)OH]₂ [C(O)O]₂; CH₃C₆H₃[NHC(O)O]₂; (CH₂)₆[NHC(O)O] ₂; OCH₂CH(CH₃)O;
k=0-30; l=1-0; m=0-20; x=1-3; y=1-3
при следующем соотношении компонентов в мас.ч. (мет)акрилатное производное простого олигоэфира 100; радикально полимеризующийся мономер 40-120; аллильное производное формулы I 5-60; инициатор 0,05-10.This goal is achieved in that the adhesive composition for bonding optically transparent materials, consisting of a (meth) acrylate derivative of a simple oligoester, a radically polymerizable monomer and an initiator, additionally contains an allyl derivative of a simple oligoester of the general formula I:

with a molar mass of 300 9000,
where R ¹ = (meth) allyl; 3-allyloxy-2 hydroxypropyl (phthaloyl) allyloxycarbamoyl;
R ² = H; alkyl (C ₁ -c ₆ ; (meth) allyl; 3-allyoxy-2-hydroxyl-propyl (phthaloyl)
A = O (CH ₂ ) _2-4 O; C ₆ H ₂ [C (O) OH] ₂ [C (O) O] ₂ ; CH ₃ C ₆ H ₃ [NHC (O) O] ₂ ; (CH ₂ ) ₆ [NHC (O) O] ₂ ; OCH ₂ CH (CH ₃ ) O;
k = 0-30; l is 1-0; m is 0-20; x is 1-3; y = 1-3
in the following ratio of components in parts by weight (meth) acrylate derivative of the simple oligoester 100; radically polymerizable monomer 40-120; an allyl derivative of the formula I 5-60; initiator 0.05-10.

Copolymers of allyl monomers with other unsaturated compounds are often used in the production of translucent polymeric materials with high mechanical strength, thermal and chemical resistance, good insulating and adhesive properties [6,7]
The free radical initiation of homopolymerization of allyl compounds is difficult, but they are able to easily copolymerize with other monomers, forming alternating structures, due to which valuable physical, mechanical and optical properties are realized. It should be noted that the introduction of precisely oligomeric allyl compounds with various molecular characteristics (molar mass and functionality) makes it possible to obtain specific comb-like low-shrinkable polymeric materials whose high mechanical and adhesive properties are preserved over a wide temperature range while maintaining good optical characteristics.

 To achieve the inventive task, we specially synthesized oligomeric allyl compounds corresponding to formula I, many of which have not been previously described. The following are examples of the synthesis of these compounds.

=1600. Иодное число (по ГОСТ 25240-82) 15,3 г I₂/100 г; гидроксильное число (по ГОСТ 25261-82) 1,4 мгКОН/г.Example 1
To the starting material obtained by dissolving 1.2 g of potassium metal in 0.5 mol of aliphatic alcohol (methanol, n-butanol, n-hexanol, etc.), 377 g (6.5 mol) of propylene oxide and 374 g (8 , 5 moles) of ethylene oxide at a temperature of 90 ^o C and pressure not higher than 300 kPa. After the reaction, 99 g of KOH • 1 / 2H ₂ O and 77 g (1 mol) of allyl chloride are added to the polymerizate and stirred for 12 15 hours at 80 ^o C. The excess alkali and the resulting salt are washed with 300 ml of water, the remaining product is neutralized with 20% - solution of phosphoric acid, dried in a stream of nitrogen and filtered. When using n-butanol, the resulting product has R ¹ = allyl, R ² = n-C ₄ H ₉ ; A = OCH ₂ CH (CH ₃ ) O; k is 17; l is 12; m is 0; x = y = 1;

= 1600. Iodine number (GOST 25240-82) 15.3 g I _2/100 g; hydroxyl number (according to GOST 25261-82) 1.4 mgKOH / g.

350. Иодное число (по ГОСТ 25240-82) 73 г I₂/100 г; гидроксильное число (по ГОСТ 25261-82) 163 мгКОН/г.Example 2
A mixture of 58 g (1 mol) of propylene oxide and 220 g (5 mol) of ethylene oxide is added to 72 g (1 mol) of metal alcohol and 0.3 g of sodium hydroxide at a temperature of 80 ^° C and a pressure of not higher than 400 kPa. At the end of the reaction, the polymerizate is neutralized with a 5% hydrochloric acid solution, dried in a stream of nitrogen and filtered. Get the product of formula I, where: R ¹ = metall; A = O (CH ₂ ) ₂ O; R ² = H, k = 2; l is 1; m is 0; x = y = 1,

350. The iodine number (GOST 25240-82) 73 g I _2/100 g; hydroxyl number (according to GOST 25261-82) 163 mgKOH / g.

1600. Иодное число (по ГОСТ 25240-82) 15,9 г I₂/100 г; гидроксильное число (по ГОСТ 25261-82) 35 мгКОН/г.Example 3
To the starting material obtained by dissolving 1.5 g of metallic Na in 29 g (0.5 mol) of dry allyl alcohol, 232 g (4 mol) of propylene oxide and 550 g (12.5 mol) of ethylene oxide were added at a temperature of 80 ^o C and pressure not higher than 300 kPa. After the reaction, the polymerizate is neutralized with a 6% phosphoric acid solution, dried in vacuo in a stream of nitrogen and filtered. The resulting product according to formula I has the composition: R ¹ = allyl; R ² = H, A = O (CH ₂ ) ₂ O; k is 24; l is 8; m = 0, x = y = 1,

Iodine number 1600 (GOST 25240-82) 15.9 g I _2/100 g; hydroxyl number (according to GOST 25261-82) 35 mgKOH / g.

1000. Иодное число (по ГОСТ 25240-82) 25,8 г I₂/100 г; гидроксильное число (по ГОСТ 25261-82) 55,4 мгКОН/г.Example 4
To a suspension containing 29.5 g (0.5 mol) of allyl alcohol, 29.5 g (0.4 mol) of tetrahydrofuran and 25 g of a bentonite catalyst (bentonite with a concentration of strongly acidic centers of 0.13 mmol / g) is added a solution containing 362 g (5 moles) of tetrahydrofuran and 117 g (2 moles) of propylene oxide at a temperature of 40 ^o C and atmospheric pressure for 4 hours. After completion of the reaction, the catalyst was separated by filtration and the volatiles were removed in a stream of nitrogen at a temperature of 70 120 ^o C. The resulting product formula I has: R ¹ = allyl; R ² = H, A = O (CH ₂ ) ₂ O; k is 0; l is 4; m is 10; x = y = 1;

Iodine number 1000 (GOST 25240-82) 25.8 g I _2/100 g; hydroxyl number (according to GOST 25261-82) 55.4 mgKOH / g.

1600. Иодное число (по ГОСТ 25240-82) 30,5 г I₂/100 г; гидроксильное число (по ГОСТ 25261-82) 3,0 мгКОН/г.Example 5
To the starting material obtained by dissolving 1.5 g of sodium metal in 29 g (0.5 mol) of dry allyl alcohol, 232 g (4 mol) of propylene oxide and 550 g (12.5 mol) of ethylene oxide are added at a temperature of 80 ^o C and pressure not higher than 300 kPa. After the reaction, 40 g of NaOH (1 mol) and 44 g (0.6 mol) of allyl chloride are added to the polymerizate and stirred for 13 16 hours at 80 ^o C. The excess alkali and the resulting salt are washed with 300 ml of water, the remaining product is neutralized with 20% - solution of phosphoric acid, dried in a stream of nitrogen and filtered. The resulting product of formula I has R ¹ = R ² = allyl, A = O (CH ₂ ) ₂ O; k is 24; l is 8; m = 0, x = y = 1,

Iodine number 1600 (GOST 25240-82) 30.5 g I _2/100 g; hydroxyl number (according to GOST 25261-82) 3.0 mgKOH / g.

1700. Пример 7
В колбу загружают 350 г (0,1 моля) олигооксипропиленоксиэтилендиола с содержанием этиленоксида 20% мас. и гидроксильным числом 32,0 мгКОН/г (Лапрол 3502-2Б-20), 0,8 г ацетата калия, 30,6 г (0,2 моля) фталевого ангидрида, 0,4 г ионола и перемешивают реакционную массу при температуре (115±5)^oC в течение 3 ч. Затем загружают 24,4 г (0,21 моля) аллилглицидилового эфира и перемешивают реакционную массу в течение 5 ч при температуре (115±5)^oC. Получают продукт формулы I, где R¹=R²=аллилокси-2-гидроксипропилфталоил; A=O(CH₂)₂O; k=16; l=48; m=0, x=y=1,

4000.Example 6
From the monoallyl oligooxypropyleneoxyethylene glycol obtained as described in Example 3 and the methacrylic acid chloride, a product of formula I was synthesized, where R ¹ = allyl; R ² = methacryl, A = O (CH ₂ ) ₂ O; k is 24; l is 8; m = 0, x = y = 1,

1700. Example 7
350 g (0.1 mol) of oligooxypropyleneoxyethylenediol with an ethylene oxide content of 20% by weight are charged into the flask. and a hydroxyl number of 32.0 mgKOH / g (Laprol 3502-2B-20), 0.8 g of potassium acetate, 30.6 g (0.2 mol) of phthalic anhydride, 0.4 g of ionol and the reaction mixture is stirred at a temperature ( 115 ± 5) ^o C for 3 hours. Then 24.4 g (0.21 mol) of allyl glycidyl ether are charged and the reaction mixture is stirred for 5 hours at a temperature of (115 ± 5) ^o C. The product of formula I is obtained, where R ¹ = R ² = allyloxy-2-hydroxypropylphthaloyl; A = O (CH ₂ ) ₂ O; k = 16; l = 48; m = 0, x = y = 1,

4000.

Example 8
324 g (0.2 mol) of the oligoester obtained in accordance with the synthesis description in Example 3, 0.1 g of BF ₃ • tetrahydrofuran are charged into a flask and 19 g (0.2 mol) of epichlorohydrin are added dropwise with stirring at a rate such that the temperature the reaction mixture remained at a level of (60 ± 2) ^o C. Subsequent dehydrochlorination of this product was carried out with a 20% aqueous NaOH solution at 40 ^o C for 4 5 hours. Residual alkalinity was neutralized with CO ₂ and after drying at (110 115) ^o C and a pressure of N _{2 of} 0.005 MPa by filtration emit oligoester with the content of epoxy groups of 2.3% of the mass.

1700.1.4 potassium methacrylate, 0.3 ionol are charged into 255 g (0.15 mol) of this oligomer, and 12.8 g (0.15 mol) of methacrylic acid are added at a temperature of (100 ± 5) ^o C within 4 hours. A product of formula I is obtained with the following characteristics: R ¹ = allyl; R ² = 3-methacryloxy-2-hydroxypropyl-; A = O (CH ₂ ) ₂ O; k is 24; l is 8; m = 0, x = y = 1,

1700.

3400.Example 9
324 g (0.2 mol) of the oligoester obtained in accordance with the synthesis description in Example 3, 21.8 (0.1 mol) of pyromellitic dianhydride, 0.7 g of potassium acetate, 0.35 g of ionol, are charged into the flask. The reaction mixture was stirred for 2 hours at (115-120) ^° C and the product was obtained according to the formula I, wherein R ¹ = R ² = allyl; A = residue of pyromellitic acid, k = 25, l = 8, m = 0, x = 2, y = 1,

3400.

5300.Example 10
165 g (0.1 mol) of oligooxypropyleneoxyethylenediol with an ethylene oxide content of 70% by weight are charged into the flask. and a hydroxyl number of 70 mgKOH / g of 26.1 g (0.15 mol) of 2,4 (2,6) -toluylene diisicyanate, 0.25 g of tin dibutyl dilaurate and the reaction mixture is stirred at a temperature of (70 75) ^o C for 3 hours 2.9 (0.05 mol) of allyl alcohol and 81.0 g (0.05 mol) of oligooxypropyleneoxyethylene glycol monoallyl ether obtained according to the procedure of Example 3 are then charged, stirring is continued at (75-80) ^o C for another 3 hours and the product is obtained formula I, where R ¹ = allyloxycarbamoyl; R ² = allyl; A residue of toluene diisocyanate; k is 25; l is 8; m is 0; x = 3; y = 3;

5300.

4600.Example 11
324 g (0.2 mol) of oligooxypropyleneoxyethylene glycol monoallyl ether obtained according to the procedure of Example 3, 32.8 g (0.2 mol) of hexamethylene diisocyanate, 0.36 g of tin octoate are charged into a flask and the reaction mixture is stirred at a temperature of (70 75) ^o C for 3 hours. Then 118 g (0.1 mol) of a copolymer of tetrahydrofuran with propylene oxide with a tetrahydrofuran content of 80% by weight are charged. and with a hydroxyl number of 95 mgKOH / g (Laprol 1102-4-80), stirring is continued at a temperature of (75 80) ^o C for another 4 hours and a product of formula I is obtained, where R ¹ = R ² = allyl; A = hexamethylene diisocyanate residue; k = 16; l is 7; m is 4; x = 3; y = 2;

4600.

1600. Иодное число 15,0, гидроксильное число 1,7 мгКОН/г.Example 12
324 g (0.2 mol) of the oligoester obtained in accordance with the synthesis description in Example 3, 0.8 sodium acetate, 22.5 g of acetic anhydride are charged into a flask and stirred for 3 hours at a temperature of 110 115 ^o C. Then, by treating the reaction mixture with an aqueous solution of phosphoric acid, sodium acetate is converted into phosphate, and after drying at (110 115) ^° C and a pressure of N ₂ 0.005 MPa, an oligoester of the formula I is isolated by filtration, where R ₁ = allyl; R ₂ = acetyl; A = O (CH ₂ ) ₂ O; k is 24; l is 8; m is 0; x = y = 1;

1600. Iodine number 15.0, hydroxyl number 1.7 mgKOH / g.

The molar mass of the allyl derivative of the simple oligoester of the general formula I is 300 9000. A decrease in the molar mass leads to a decrease in the a _p and τ of the adhesive layer (Examples 1 to 4, Table 1). An increase in molar mass complicates the synthesis and increases the viscosity of the allyl derivative, which leads to an increase in the viscosity of the adhesive composition itself.

 Widely used monomers such as styrene, vinyl pyridine, as well as (meth) acrylic monomers such as acrylic and methacrylic acids, their esters (e.g. methyl methacrylate, butyl (meth) acrylate, hexyl acrylate, octyl methacrylate, can be used as a radically polymerizable monomer, glycidyl (meth) acrylate, ethylene glycol monomethacrylic ester, as well as mixtures of these (meth) acrylic monomers.

 The type of radical polymerization initiator is not critical to the practice of this invention. Depending on the chosen method of bonding the optically transparent material, both thermal initiators (e.g. azobisisobutyronitrile, benzoyl peroxide, bicyclohexyl peroxydicarbonate) and photoinitiators (e.g. 2,2-dimethoxy-2-phenylacetophenone, diisopropoxyacetophenone, di-benzyl ether butyr anthiraone can be used) ) The amount of initiator in the composition depends on the particular initiator and is selected based on the condition of curing the composition in a technically acceptable time. Commonly used are 0.05 to 10 parts by weight.

 The adhesive composition is prepared by mixing the (meth) acrylate derivative of the simple oligoester, the radical polymerizable monomer, the allyl derivative of formula I and the initiator at room temperature until the components are completely dissolved.

The ratio of the main components in the composition is:
1) 100 parts by weight (meth) acrylate derivative of the simple oligoester.

 2) 40 120 parts by weight radically polymerizable monomer.

 3) 5 to 60 parts by weight allyl derivative of the formula 1.

The monomer content of less than 40 parts by weight does not provide a technologically acceptable viscosity of the composition and reduces a _p , t and adhesion (A _p ) of the cured adhesive layer (for example, 5.6 table. 1). On the other hand, when the monomer content is more than 120 parts by weight the composition does not completely cure (during photo curing), the product loses its impact resistance at minus 20 ^o C, and optical distortions appear (cured) (Examples 7-8, Table 1).

The content of the allyl derivative of the formula I is less than 5 parts by weight does not give advantages compared with the known adhesive composition (example 9 of table. 1). On the other hand, an increase in its content in the composition of more than 60 parts by weight leads to a decrease in the work of destruction (a _p ) of the adhesive layer and loss of impact resistance of the product (example 10 of table. 1).

k=0-30; l=1-80; m=0-20; y=1-4; z=1-3; x=1-3
2-гидрокси-3-(мет)акрилоилпропиловые эфиры полиэфиркарбоновых кислот по формуле II, где: D=CH₂-CH(OH)CH₂; Q остаток двухосновной карбоновой кислоты, представляют собой продукты взаимодействия гидроксилсодержащих олигоэфиров с циклическими ангидридами двухосновных карбоновых кислот с последующей этерификацией глицидил(мет)акрилатом в присутствии катализатора.As the (meth) acrylate derivative of the simple oligoester, the adhesive composition contains compounds of the general formula II:
II. (R ³ D) _x Q _y {(CH ₂ CH ₂ O) _k [CH ₂ CH (CH ₃ ) O] _l [(CH ₂ ) ₄ O] _m L} _z with a molar mass of 1600-13000, where R ³ = (meth) acryloxy; D = CH ₂ CH (OH) CH ₂ ; CH ₂ CH ₂ ; CH ₂ CH (CH ₃ ); CH ₂ CH (CH ₂ C) Q = o-C ₆ H ₄ [C (O) O] ₂ ; C ₆ H ₂ [C (O) OH] ₂ [C (O) O] ₂ ; C ₂ H ₄ [C (O) O] ₂ ; C ₃ H ₆ [C (O) O] ₂ ; C ₂ H ₂ [C (O) O] CH ₃ C ₆ H ₃ [NHC (O) O] ₂ ; (CH ₂ ) ₆ [NHC (O) O] ₂ ; OCH ₂ CH ₂ O; OCH ₂ CH (CH ₃ ) O; O (CH ₂ ) ₄ O;

k = 0-30; l is 1-80; m is 0-20; y is 1-4; z is 1-3; x = 1-3
2-hydroxy-3- (meth) acryloylpropyl esters of polyether carboxylic acids according to formula II, where: D = CH ₂ —CH (OH) CH ₂ ; Q residue of a dibasic carboxylic acid, are the products of the interaction of hydroxyl-containing oligoesters with cyclic anhydrides of dibasic carboxylic acids, followed by esterification of glycidyl (meth) acrylate in the presence of a catalyst.

 Examples of the use of these compounds and the properties of the corresponding adhesive layers are given in table. 1 (examples 11-13, 24, 27-29).

(Meth) acrylate derivatives of oligoesters according to the formula II (where: D = CH ₂ CH ₂ ; CH ₂ CH (CH ₃ ); CH ₂ CH (CH ₂ Cl); Q residue of diisocyanate) are the reaction product
a) simple oligoesters,
b) diisocyanates and
c) (meth) acrylic monomers containing active hydrogen.

 The ratio of a), b) and c) is (1-2) / (2-3) / 2 (mol.). Examples of oligourethane acrylates used and the properties of the corresponding adhesive layers are given in table 1 (examples 14-16).

(Meth) acrylate derivatives of oligoesters according to formula II, where D = CH ₂ CH ₂ ; CH ₂ CH (CH ₃ ); CH ₂ CH (CH ₂ Cl); Q residue of pyromellitic acid, are the products of the interaction of hydroxyl-containing simple oligoesters with pyromellitic dianhydride followed by the addition of a (meth) acrylic monomer containing a hydroxyl group. These oligomers, their properties and the method of preparation are not described in the literature. The following are examples of the synthesis of oligooxyalkylene glycol pyromellitate (meth) acrylates.

8200.Example 13
In a three-necked flask equipped with a stirrer, a nitrogen supply and a device for maintaining a predetermined temperature, (0.1 mol) 360 g of oligooxypropyleneoxyethylenediol with an ethylene oxide content of 20% wt. and a hydroxyl number of 31.2 mgKOH / g (Laprol 3502-2B-20), 32.7 g (0.15 mol) of pyromellitic dianhydride, 2.0 g of dimethylbenzylamine and 0.4 g of ionol. The reaction mixture was stirred for 2 hours at 120 ^° C. 13.0 g (0.1 mol) of ethylene glycol monomethacrylic ester were added, stirred for another 2 hours to give the product according to formula II, where D = CH ₂ CH ₂ ; Q is the remainder of pyromellitic acid; R ³ = methacryl; L = CH ₂ CH (CH ₃ ); k is 18; l = 54; m is 0; x = 2; y = 3; z is 2;

8200.

13000.Example 14
According to the method of example 13 of 360 g (0.1 mol) of oligooxypropyleneoxyethylenediol with an ethylene oxide content of 40% wt. and a hydroxyl number of 34 mgKOH / g, 29.2 g (0.133 mol) of pyromellitic dianhydride, 0.8 g of potassium acetate, 0.4 g of ionol and 8.7 g (0.067 mol) of propylene glycol monoacrylic ester receive the oligomer according to formula II, where D = CH ₂ CH (CH ₃ ); Q = pyromellitic acid residue; R ³ = acrylic; L = CH ₂ CH ₂ ; k = 29; l = 34; m is 0; x = 2; y = 4; z is 3;

13000.

 Example 15

300.According to the method of example 13 of 190 g (0.2 mol) of a copolymer of propylene oxide with tetrahydrofuran with a tetrahydrofuran content of 80% by weight. and a hydroxyl number of 118 mgKOH / g (Laprol 1102-4-80), 65 g (0.3 mol) of pyrometillite dianhydride, 0.5 g of potassium acetate, 0.25 g of ionol and 35.6 g (0.2 mol) hydroxychloropropyl methacrylate receive the oligomer according to the formula II, where D = CH ₂ CH (CH ₂ Cl); Q = pyromellitic acid residue; R ³ = methacryl; L = CH ₂ CH (CH ₃ ); k is 0; l is 2; m is 10; x = 2; y = 3; z is 2;

300.

 Example 16

2600. Примеры используемых олигогликольпиромеллитат (мет) акрилатов и свойства соответствующих клеевых слоев приведены в табл. 1 (примеры 17-20).According to the method of example 13 of 183 g (0.1 mol) of a copolymer of propylene oxide, ethylene oxide and tetrahydrofuran with a content of propylene oxide of 3% wt. ethylene oxide 57% wt. tetrahydrofuran 40% wt. and a hydroxyl number of 61.3 mgKOH / g, 43.6 (0.2 mol) of pyrometillite dianhydride, 0.45 g of potassium acetate, 0.22 g of ionol and 26 g (0.2 mol) of ethylene glycol monomethacrylate give the product according to the formula II, where D = CH ₂ CH ₂ ; Q = pyromellitic acid residue; R ³ = methacryl; L = CH ₂ CH ₂ ; k is 23; l is 1; m is 10; x = 2; y = 2; z is 1;

2600. Examples of used oligoglycol pyromellitate (meth) acrylates and the properties of the corresponding adhesive layers are given in table. 1 (examples 17-20).

Hydroxy (meth) acrylate derivatives of oligoesters according to the formula II (where D = CH ₂ CH (OH) CH ₂ ; Q = OCH ₂ CH ₂ O; OCH ₂ CH (CH ₃ ) O; O (CH _{2 4} O) are products of the interaction of diepoxides of simple oligoesters with (meth) acrylic acid in the presence of a catalyst.

 Examples of the use of hydroxy (meth) acrylic production simple oligoesters and properties of adhesive layers based on them are given in table. 1 (examples 21-23).

 The range of molar masses indicated for (meth) acrylic derivatives of oligoesters (according to Formula II) is selected on the basis of the following data.

When using oligoester (meth) acrylates with a molar mass of less than 1600, a deterioration of the shock-resistant glued product is observed both at room temperature and at minus 20 ^o C (examples 25-26 table 1). On the other hand, the use of these products with a molar mass of more than 13000 is impractical due to the complexity of the synthesis of high molecular weight oligomers. To improve the consumer properties of the product during operation, the adhesive composition may further comprise a light stabilizer. The type of light stabilizer is selected depending on the type of (meth) acrylate derivative of the simple oligoester. For oligomers of the formula II, where the Q-residue is polycarboxylic acid, organophosphorus stabilizers are preferred, such as Forstab K-201 (diphenyl-2-ethylhexylphosphite), Phosphite NF (Trinonylphenylphosphite), Phosphite DE ^* , Phosphite A ^* (Table 2) .

 For oligomers of the formula II, where the Q-residue of the aromatic diisocyanate, benzotriazole and its derivatives are usually used, for example, products from Siba-Geigy, Switzerland: 2 (2-hydroxy-3,5-ditretbutyl-phenyl) -5-chloro-benzoitriazole ( Tinuvin 327), 2 (2-hydroxy-3-dodecyl-5-methylphenyl) benzotriazole (Tinuvin 571), 2 (2-hydroxy-5-methylphenyl) benzotriazole (Tinuvin 171), 2 (2-hydroxy-3,5- ditretamylphenyl) benzotriazole (Tinuvin 328).

 The amount of light stabilizer applied depends on the structure and its compatibility with other components of the composition and is usually 0.1-5 wt. h

 Examples of the use of light-stabilizing additives and a change in the properties of the cured adhesive layer for the "Glass-glue-glass" triplex under conditions of accelerated photoaging are given in table. 2.

 To regulate the viscosity of the properties of the adhesive composition, it may additionally contain a plasticizer in an amount of 5-15 wt. including ester plasticizers (for example, dibutyl phthalate, dioctyl sebacinate, dihexyl adipate) and oligooxyalkylene glycols (for example, Laprol 1052, Laprol 2102). The test results of the images of trilex "glass-glue-glass" are given in table. 3.

 The glue can be used for bonding not only silicate glass, but also other transparent optical materials, for example, polymer films and sheets of polymethyl (meth) acrylic (PM (M) A), polystyrene, polycarbonate, polyethylene terephthalate, etc., as well as for gluing wood, paper, metal. In the table. Figure 4 shows the values of static shear strength (τ) of adhesive joints for various materials.

From the data table. 1-3 it follows that the complex of properties of the proposed composition significantly exceeds the known:
1) the value of the specific work of the destruction of the polymer layer (a _p ) increases by 10-50%
2) the value of static shear strength (τ) increases by 10-105%
3) the adhesion of the adhesive layer to various materials increases by 10-115%
4) improved impact-mechanical properties of products, especially at subzero temperatures, while maintaining high optical properties.

In general, the proposed adhesive composition is characterized by the following set of advantages:
ease of preparation;
availability of raw materials;
simplicity of technology for glued products;
high adhesive and physico-mechanical properties of glued products in a wide temperature range.

 In accordance with the purpose of the adhesive layer, suitable additives, for example pigments, dyes, fillers, can be added to the composition.

These adhesive compositions can be used for the manufacture of multilayer laminated optically transparent sheet structures for a wide range of purposes:
triplex for ground transport windshields or for furniture, construction purposes (doors, tables, stained-glass windows, shop windows, pavilions, glass structures, etc.);
multilayer (where there are more than two glass or polymer sheets) for armored products of various levels of protection (depending on the number and composition of glued sheets in the bag).

 Adhesion of optically transparent materials using these compositions is carried out in the presence of radical type initiators thermally or under the influence of ultraviolet radiation.

When gluing, for example, two glasses (or more), they are pretreated on one side with an adhesive apparatus, a bag is collected with the sides processed to each other, a sealant made of elastic polymer material (for example, tubes of polyvinyl chloride, polyethylene, sovilen, silicone is laid along the perimeter between the glasses etc.), clamp the glass with clamps or calibrated clamps so that a gap of 0.5-0.3 mm thick is formed. The estimated amount of the composition is poured into the assembled double-glazed unit, which is determined based on the surface area of the glass and the thickness of the polymer layer. At the end of pouring the glass unit, the air bubbles are sealed and removed. The filled-in double-glazed window is placed in a horizontal position in the thermostat and cured for 6-10 hours at a temperature of 60-100 ^o C (in the case of thermosetting). In the case of photocuring, the process is carried out using a polychromatic UV radiation source (DRT lamp, LUV, etc.) or monochromatic (LGI generator, DRUFZ lamp, etc.) at a distance that provides uniform energy illumination of the glass unit surface in the region of 10- 55 W / m ² in the wavelength range of 320-400 nm and irradiated for 20-50 minutes

 The impact resistance of glued products was determined on samples of triplex glasses with a size of 300x300 mm (the thickness of each glass is 2.5 ± 0.2 mm, the thickness of the adhesive layer is 1.5 ± 0.1 mm). The double-glazed window was assembled according to the method described above, having previously treated the glass with an adhesive apparatus with a 20% solution of K-2 or K-3 methacrylate in ethanol or isopropanol. A PVC tube with an outer diameter of 3.0-5.0 mm and a wall thickness of 0.3-0.6 mm was used as a sealant.

 A fully assembled and filled with the composition double-glazed window was placed horizontally under the LUF-80 lamp panel and irradiated for 20-50 minutes.

The mechanical strength of the obtained triplex upon impact with a steel ball weighing (227 ± 2) g at a temperature of minus (20 ± 2) ^o C was determined according to GOST 5727-88 by dropping the ball from a height of 9.5 m. For each adhesive composition, tests were carried out on ten samples triplex glasses separately. The adhesive composition is considered to have passed the test, if out of ten glass samples based on it, at least eight are not broken into separate parts and no less than eight balls should not pass through the samples.

The mechanical strength of triplex upon impact by a ball weighing (2260 ± 20) g at a temperature of (22 ± 5) ^o C was determined according to GOST 5727-88 on six samples by dropping the ball from a height of 4 m. On all samples, the ball should not pass through the hole formed in within 5s from the moment of impact.

To determine the specific work of the destruction of the polymer layer (a _p ) under impact tension at 20 ^o C used the installation for determining the impact strength by Izod. The latter was modified in such a way that it allowed to carry out shock tension of the samples in the form of strips 15 mm long, 3 mm wide and 1-2 mm thick. The value of a _{p was} determined as the arithmetic mean value of five parallel tests.

The shear strength of adhesive joints (τ) was determined according to GOST 14759-69 on standard samples of glass, polymethyl (meth) acrylate, etc. 5 ± 0.2 mm thick, 25 ± 0.25 mm wide and 100 ± 0.25 mm long glued overlap. An adhesive composition in an amount of 10 g / m ^{2 was} applied to the glued sample, applied on top of another of an optically transparent material and irradiated for 5 min from a distance of 10 cm with a DRT-400 mercury-quartz lamp. Shear strength was determined on an Instron 11.22 test machine.

The adhesive strength of the cured adhesive composition to glass was determined according to GOST 6768-75 also on an Instron 11.22 testing machine. On silicate polished glass treated with an adhesive sizing (for example, a 2% solution of K-2 or K-3 methacrylate in ethanol), polymer strips with a thickness of 1.5 ± 0.2 mm and a width of 25 ± 1.0 mm were obtained by polymerization of the test composition and a length of 150 ± 5 mm. The value of adhesive strength A _p (table. 1) was determined as the arithmetic mean of five parallel tests.

 The light fastness of adhesive compositions during accelerated photoaging was determined according to GOST 27904-88 on triplex glass samples of size 76x300 mm when they were irradiated for 100 hours at a distance of 230 mm from a radiation source with a power of 800 W and the light transmission of these samples was measured according to GOST 27902-88 after irradiation. Symbols of radicals are given in table. 5.

All monomers used, oligoesters, plasticizers, stabilizers are available substances:
methyl methacrylate GOST 20370-74
methacrylic acid TU 6-02-59-89
octyl methacrylate TU 6-09-15-274-76
hexyl acrylate TU 6-09-08-123-75
2,2-dimethoxy-2-phenylacetophenone oligoesters TU 6-09-14-2142-83 according to the Oligoesters catalog. Isocyanates. Systems, Cherkasy, NIITEKHIM, 1987
pyromellitic dianhydride TU 6-14-526-79
ethylene glycol monomethacrylic ester TU 6-01-1240-90
potassium acetate GOST 5820-78
4-methyl-2,6-ditretbutylphenol ("ionol") OST 3801420-87
sodium acetate TU 6-09-246-84
ester plasticizers GOST 8728-88
diphenyl-2-ethylhexylphosphite (Forstab K-201) TU 6-09-4328-77
Trinonylphenylphosphite (Phosphite NF) TU 6-02-680-83 amended. N1
propylene oxide GOST 23001-88
ethylene oxide GOST 7568-73
tetrahydrofuran TU 6-02-621-81
GOST 2222-78 methanol
butyl alcohol (butanol-1) GOST 6006-78
allyl alcohol TU 601-1033-75
allyl chloride TU 6-01-753-77
acetic anhydride GOST 21039-75
epichlorohydrin GOST 12844-74
glycidyl methacrylate TU 6-02-1338-86
toluene diisocyanate TU 113-03-1716-84 as amended. 1 N2
phthalic anhydride GOST 5869-77о

Claims (2)

1. An adhesive composition for gluing optically transparent materials containing a (meth) acrylate derivative of a simple oligoester, a radically polymerizable monomer and an initiator, characterized in that it contains (meth) acrylate derivative of a simple oligoester, oligooxyalkylene glycol pyromellite (meth) acrylene oligomethane, acrylate or 2-hydroxy-3-methacryloylpropyl esters of polyester carboxylic acids and optionally oligooxyalkylene glycol mono (meth) allylate of the general formula

with a mol.m. 300 9000,
where R ¹ (meth) allyl; 3-allyloxy-2-hydroxypropyl (phthaloyl); allyloxycarbamoyl;
R ^{2 is} hydrogen; C ₁ -C ₆ alkyl, (meth) acryl, (meth) allyl, 3-allyloxy-2 hydroxypropyl (phthaloyl), allyloxycarbamoyl, acetyl;
AO (CH _{2) 2 - 4} O; C ₆ H ₂ [C (O) OH] ₂ [C (O) O] ₂ , CH ₃ C ₆ H ₃ [NHC (O) O] ₂ ; (CH ₂ ) ₆ [NHC (O) O] ₂ ; OCH ₂ CH (CH ₃ ) O;
k 0 30;
l 1 50;
m 0 20;
x 1 3;
y 1 3,
in the following ratio of components, parts by weight (Meth) acrylate derivative of the simple oligoester 100
Radically polymerizable monomer 40 120
Mono (meth) allylate oligooxyalkylene glycol 5 60
Initiator 0.05 10.0
2. The composition according to claim 1, characterized in that it further comprises a light stabilizer in an amount of 0.1 to 5.0 wt.h.  3. The composition according to claim 1, characterized in that it further comprises a plasticizer in an amount of 5 to 15 wt.h.

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