FR2482973A1 - Low temp. polyurethane adhesive - contg. aq. soln. of urea and sodium sulpho-ricinate - Google Patents

Abstract

An adhesive contains (a) 100 mols. of a prepolymer from polydiethylene glycol adipate and toluylene diisocyanate, (b) 5-30 mols. of a polyisocyanate, (c) 1-60 mols. of trichloro- ethyl phosphate, and (d) 0.1-2 mols. of a mixt. of water, urea and Na sulphoricinate in a ratio by wt. of 1:0.01-0.3:0.01-0.2. The compsn. is esp. used to bond heat-insulating blocks, e.g. onto metal substrates. The adhesive can be used at low temp. The bonding strength of the joint is improved. The compsn. has low viscosity and a low content of unconverted, reactive volatiles.

Description

 The invention relates to adhesive compositions and more specifically relates to an adhesive composition based on polyurethane.

 The invention can be used most effectively for bonding synthetic heat-insulating elements to metals in the construction of boats outside shipbuilding workshops, on open holds in the implementation of oil and gas pipelines as well as when it is necessary to stick the heat-insulating element on a metallic surface in any atmospheric condition.

Although polyurethane-based adhesive compositions have been known for a relatively long time and are widely used in industry, the problem of developing adhesive compositions exhibiting new properties still remains quite serious.
Up to now, efforts aimed at developing new polyurethane-based adhesive compositions have been directed towards the use, for the synthesis, of various hydroxyl components and isocyanates, towards the application of such or such type of bond and of their order of alternation in the macromolecular chain or towards the bringing into play of different modifying agents.

Adhesives are known based on idiol, nitroglycerophthalic and diphenylcaprolactam resins (L.YA.Popilov, Materialy dlya sudostroenia. Sudostr @ enie,
Leningrade, 1972, p.255). The adhesives also contain various fillers, for example asbestos or sodium silicate, or portland cement, etc. Its above-mentioned adhesive compositions form a monolithic sticky film characterized by low adhesion resistance and can be used at temperatures up to 0 C.

 There are also known glues based on reins of urethans marketed by the company "Farbenfabriken Bayer AG @ (REA) under the name of" Polustal "(Zarubezhnye promyshlennye polimernye materialy i ikh komponsnty. Slovarspravochnik. Izdatelstvo Akademii Nauk SSS , M @ skva, 1963, p. 187, BA Dombrow, Poliuretany.

Gosudarstvennoe nauchno-tekhnicheskoe izdatelstvo khimicheskoi literatury, Moskva, 1961, p. 107) comprising an isocyanate (Desmodur TR) and a hydroxylated polyester (Desmophen 900).

The adhesive composition in question comprises 40 parts by mass of 70% ethyl acetate solution of Desmophen 900 and 100 parts by mass of 75% ethyl acetate solution of Desmodur TH. In order to reduce the curing time of the above-mentioned adhesive composition, curing accelerators are added and heated. Once cured, the composition in question is in the form of a monolithic tacky film with low flame retardance.

The adhesives produced by the company "Monsanto" (BADombrw. Roliuretany. Gosudarstvennoe nauchno- tekhnicheskoe izdatelstvo khimicheskoi literatury, Moskva, 1961, p.112) are interaction products of isocyanates and polyalcohols under conditions such as the amount of isocyanate is twice as large as the stoichiometric amount.

The adhesive composition comprises 1 mole of polyethylene glycol 400 (molecular weight 400) and 2 moles of toluylene diisocyanate. The adhesive in question is characterized by storage stability under conditions protected from humidity.

 The glue mentioned above is used in the form of a 50% solution in benzene. Applied to the surface of parts to be assembled, the adhesive hardens at a temperature of 18 to 200C, forming a monolithic film with low flame retardance.

 When it is necessary to glue the insulation and in addition to adjust the heat-insulating blocks placed on the curvilinear surfaces, the use of these adhesives forming a monolithic film leads to a high consumption of glue.

 Taking into account the large areas to be thermally insulated during the construction of the boats, the use of adhesives whose consumption per m2 insulated is high, increases the weight of the boat thereby reducing its payload capacity. In addition, the monolithic ear of the adhesive layer alters the distribution of stresses in said layer in the case of an assembly of a metal with a plastic foam applied widely as insulation, under conditions of loads by dynamic vibrations. . Under the effect of these charges may appear local destruction of the adhesive layer, which gives rise to corrosion processes on the metal surface below the thermal insulation. In addition, the use of solvents increases the risk of explosion when carrying out work in closed rooms.

An adhesive composition is also known to have the author's certificate of URUS No. 482997) comprising (in parts by mass): - polyester and toluylene prepolymer
diisocyanate 100 - 4,4'-diphenylmethane-diisocyanate 5-30 - trichlorethyl phosphate 1-60 - 1-50% aqueous solution of tris
(dimethylaminomethyl) -2,4,6 phenol, in
as catalyst 0.02-10
Before applying the adhesive composition, the catalyst solution is applied beforehand to one of the surfaces to be bonded. The adhesive composition forms a porous glued joint which considerably reduces the consumption of glue during thermal insulation works. However, the above-mentioned adhesive composition can only be applied to bond thermal insulation to dry or wet surfaces only at temperatures up to 0 C which reduces the field of application.

In addition, the bonding formed by the adhesive composition in question is characterized by insufficient strength. In addition, the above-mentioned adhesive composition has a large amount of unreacted toxic reactive components.

 The invention relates to an adhesive composition which, by modifying its composition, both quantitatively and qualitatively, makes it possible to improve the strength of the bonding and at the same time can be used under temperature conditions below zero degrees.

The problem posed is resolved in that a adhesive composition, of the type comprising a prepolymer of polydiethylene glycoladipate and toluylene diisocyanate, a polyisocyanate and trichlorethylphosphate, is, according to the invention, added with a mixture of water, urea and sodium sulforicinate then in the following respective proportions with respect to said mixture i / (0.01 to 0.3) / (O, Q1 to 0.2), the components being taken in the following proportions (in parts by mass) :: - prepolymer of polyethylene diadipate
glycol and toluylene diisocyanate 10Q - polyisocyanate 5-30 - trichlorethyl phosphate 1-60 - mixture of water, urea and sulforicinate
sodium s 1 / (0.0l to 0.3) / (0.01 to 0.2) 0.1-2
The fact of using a mixture of water, urea and sodium sulforicinate in the adhesive composition makes it possible to increase the resistance of the bonding. In addition, the above-mentioned adhesive composition is characterized by a pot life of two hours or more, and can be used under temperature conditions below zero degrees. Another advantage of the composition in question is a reduced content of unreacted reactive volatile components. This is due to the adjustment of the polyurethane chain structure as well as the formation in the hardened adhesive layer of small pores having uniform dimensions.

it is rational to use in the adhesive composition in question a mixture of water, urea and sodium sulforicinate taken in the following respective proportions relative to said mixture of 1 / (0.1 to 0.3) j ( 0.05 to 0.2) and to use toluy lènediisocyanate as polyisocyanate, the components being taken in the following proportions (in parts by mass) - prepolymer of polyethylene glycol adipate
and toluylene diisocyanate 100 - toluylene diisocyanate 5-20 - trichlorethyl phosphate 1-60 - mixture of water, sulfur and sulforicinate
sodium: 1 / (0.1 to 0.3) / (0.05 to 0.2) 0.5-2
This embodiment of the adhesive composition is characterized by a low viscosity, which allows this composition to easily penetrate into narrow spaces separating the heat-insulating blocks.

It is reasonable to use in the adhesive composition a mixture of water, urea and sodium sulforionate then in the respective proportions -following with respect to said mixture of 1 / (0.05 to 0.3 ) / (0.03 - 0.2) and to use an adduct of toluylene diisocyanate and trimethylolpropane as polyisocyanate, the components being taken in the following proportions, in part by weight: - prepolymer of polyethylene glycol adipate
and toluylene diisocyanate 100 - adduct of toluylene diisocyanate and
trimethylolpropane 5-30 - trichlorethyl phosphate 1-60 - mixture of water, urea and sulforicinate
sodium s 1 / (0.05 to 0.3) / (0.03 to 0.2) 0.2-2
The above-mentioned embodiment of the adhesive composition is characterized by a high cohesion resistance.

The invention will be better understood and other objects, details and advantages thereof will appear more clearly in the light of the examples described below.

Example 1
To obtain the adhesive composition in accordance with the invention and comprising the following proportions by parts by mass: polyethylene diol glycol propolymer
and toluylene diisocyanate 100
4,4 '-diphenylmethanediisocyanate 5
trichlorethyl phosphate î - mixture of water, urea and sulforicinate
sodium in the respective proportions
relative to said mixture: 1 / 0.01.0.01 0.1 is introduced into the prepolymer of polyethylene glycol and toluylene diisocyanate taken at a rate of 50 g and brought to 700C, 2.5 g of 4 , 4'-diphenylmethane-diisocyanate.

The prepolymer is previously synthesized from polyethylene glycol polyadipate (molecular weight 800) and toluylene diisocyanate, the hydroxyl group / isocyanate group ratio being 1/2.

 The mixture obtained of prepolymer of polyethylene di-glycol and toluylene-diisocyanate and of 4,4 '- diphenylmethanediisocyanate being kneaded, trichlorethyl phosphate is introduced in an amount of 0.5 g.

 The composition in question is then kneaded at the same time as the temperature is reduced to 250C.

 Before using the composition obtained, this is added with a mixture of water, urea and sodium sulforicinate in the respective-following proportions relative to said mixture of 1 / 0.01 / 0.01, at a rate 0.05 g.

 My adhesive composition thus obtained is applied to the surface of a plastic foam to be bonded to 11 steel. Bonding is carried out at a temperature of plus1200C, OOC and minus 40C. Bonding at a temperature equal to minus 40C is carried out using steel plates covered with frost, the layer of which is obtained by alternating several times cooling of the metal plates to a temperature of minus 100C with a short hold at an equal temperature at over 200C.

 The bonding thus obtained is subjected to tests of resistance of the bonding to shear. In addition, the content of reactive volatile components in the adhesive is determined. The shear strength is determined as follows.

The prepared glue is applied, using a spatula, to samples of plastic foam whose dimensions are 50 x 30 x 20 mm. The samples are then superimposed symmetrically on both sides on a joint between two metal plates having dimensions of 100 x 30 x 2 mm, said plates being joined together by their short sides. To avoid deformation of the plastic foam in the clamps of the testing machine, metal plates are glued to the plastic foam. The test is carried out by applying a tensile load. The samples are placed in the testing machine so that the joint between the metal plates is located symmetrically with respect to two clamps. During the test, the tensile force is applied along the longitudinal axis of the sample. The tests are carried out at a displacement speed of the clamp under load equal to 10 mm / min. The charge is increased until the sample is destroyed, the maximum charge being recorded. The shear strength is determined according to the formula:
T = P
F (NPa), where P - breaking load - (N),
F - bonding area (m2)
The technique for determining the content of reactive volatile components in the adhesive consists in reacting an aqueous solution of diethanolamine with the isocyanate and chlorine derivative vapors present in a stream of nitrogen having passed through a sample to be examined, then identify the remains of diethanolamine and chlorides in the aqueous solution to be titrated. In order to determine the content of reactive volatile components, an aqueous diethanolamine solution (2 g per 1 1 of solution) is prepared beforehand, a 0.02 N solution of nitric acid, a 0.01 N solution of mercury nitrate and solutions of bromocresol purple (0.2 g per 0.1 l) and diphenylcarbozone (0.1 g per 0.1 l) in ethyl alcohol.

 The sample charge to be examined, in an amount of 30 + 0.2 g, is introduced into a three-necked flask, the capacity of which is 100 ml. A thermometer and a 1 ml non-graduated pipette are introduced into this flask. The balloon is placed in communication, by the internal intern of a glass tube 5 mm in diameter and 170 mm long, with a container used to absorb volatile components, provided with a porous plate and a lapping glass to which a flow meter is connected. Said container is filled with 5 ml of diethanolamine solution. The sample is brought to a temperature of 80 + 20C using a water bath, then by means of the pipette, the sample is passed through the sample slowly by a weak stream of nitrogen coming from a The nitrogen flow is controlled as indicated by the flow meter so that the average speed is 0.5 l / min.

 The stream of nitrogen passes through the samples for 10 minutes, then the valve of the bottle is closed, the container containing the diethanolamine is removed and the diethanolamine solution is transferred, in portions, into the titration flask. After adding 2 drops of bromocresol purple and 5 drops of diphenylcarbazone to the solution, add the solution with a 0.02N nitric acid solution until the cherry color turns to lemon yellow.

 Then, 0.5 ml of 0.5 N nitric acid solution is added and the solution is titrated with mercury nitrate until it turns pink.

 A control sample is further prepared by passing nitrogen through the diethanolamine for 10 minutes and the titration is carried out in an analogous manner, first with nitric acid, then with mercury nitrate, without using an adhesive composition.

The content of reactive volatile adhesive is determined according to the formulas
b1 = 1.74 (VO - V1- 0.385b2) mg
b2 = N2.130 (V2-V3) mg, where b1 = weight of volatile isocyanates calculated as toluy lènediisocyanate
VO = volume of nitric acid used to titrate
control sample;
V1 = volume of nitric acid used to titrate the
solution to consider
b2 = weight of hydrolyzable chlororganic derivatives
volatiles calculated as aniline chloride
N2 = normality of nitric acid
V @ = volume of mercury nitrate used for titration
the solution to examine
V = volume of mercury nitrate used for titration
the control sample.

 6th values obtained represent the quantity of volatile substances entrained by 5 1 of nitrogen under the conditions of determination or, which is the same thing, the quantity of volatile substances being above the glue in 5 1 of nitrogen at a temperature of 800C.

 The following results are obtained.

Bonding resistance to shear (MPa): at bonding temperature of
plus 200C 0.8
0èC 0,5
minus 40C with a thick layer of frost
0.04 - 0.07 mm 0.5
0.2 - 0.3 mm 0.3
Content of volatile components, mg 0.01.

In parallel, the resistance of the bonding obtained is determined in accordance with the USSR author's certificate N 482997. The content of volatile components in said adhesive is also determined. The results obtained are as follows o
Bonding resistance to shear (MPa): bonding temperature of
plus 20 C 0.6
0 C 0.3 content of volatile components, mg 0.9.

Example 2
To obtain an adhesive composition in accordance with the invention and comprising in parts by mass - polyethylene diadipate prepolymer
glycol and toluylene diisocyanate 100 - 4.4 '- diphenylmethanediisocyanate 30 - trichlorethyl phosphate 60 - mixture of water, urea and sulforicinate
sodium in the respective proportions
with respect to said mixture of 1 / 0.3 / 0.2 2, an amount of 0.2 kg of prepolymer of diethylene glycol polyadipate and of toluylene diisocyanate, brought to the temperature of 700C and 0.06 kg of 4.4, is introduced. '- molten diphenylmethanediisocyanate.

The prepolymer is previously synthesized from diethylene glycol polyadipate (molecular weight 800) and toluylene diisocyanate, the ratio of hydroxyl groups / isocyanic groups being 1/2.

 The mixture obtained of prepolymer of polyethylene di-glycol and toluylene diisocyanate and of 4,4 '- diphenylmethanediisocyanate being kneaded, the trichlorethyl phosphate is introduced at the rate of 0.12 kg and the said mixture is kneaded again while reducing the temperature to '' at 200 C.

 Before using the composition thus obtained, it is added with a mixture of water, urea and sodium sulforicinate relating to the following respective proportions with respect to said mixture of 1 / 0.3 / 0.2, at a rate 0.004 kg.

 The composition obtained is applied to the surface of a plastic foam to be bonded to the steel plates at a temperature of plus 20bu, OOC and minus 40c.

The bonding thus obtained is subjected to the shear strength tests. In addition, the content of reactive volatile components in the adhesive is determined.

 The tests are carried out according to the technique described in Example 1.

 The following results are obtained.

Bonding resistance to shear (MPa) bonding temperature of
plus 200C 1.3
0 C 1.0
minus 40C with a thick layer of frost
0.04 - 0.07 mm 0.8
0.2 - 0.3 mm 0.5
Content of volatile components, mg 0.02.

Simultaneously, by molding on polyethylene, a film of adhesive composition is formed for mechanical tests.

Tear resistance of the film
glue 1.0.

Example 3
To obtain an adhesive composition in accordance with the invention and comprising in parts by mass: - polyethylene diadipate prepolymer
glycol and toluylene diisocyanate 100 - 4.4 '- diphenylmethanediisocyanate 5 - trichlorethyl phosphate 1 - mixture of water, urea and sulforicinate
sodium in the respective proportions
following with respect to said mixture of
I / 0.15 / 0.1 0.1 is introduced into an amount of 50 g of prepolymer of polyethylene diadlycate glycol and toluene diisocyanate, brought to the temperature of 800C, 2.5 g of 4.4 'diphenylmethanediisocyanate molten.

 The prepolymer is previously synthesized from polyethylene glycol polyadipate (molecular weight 800) and toluylene diisocyanate, the hydroxyl group / isocyanate group ratio being 1/2.

 The mixture obtained of polydiethylene glycoladipate and toluylénediisocyanate and of 4,4 '- diphenylmethanediisocyanate being kneaded, the trichlorethyl phosphate is introduced in an amount of 0.5 g and the mixture is kneaded again while reducing the temperature of the mixture to 250C.

 Before using the composition obtained, it is added with a mixture of water, urea and sodium sulforicinate in the following respective proportions with respect to said mixture of 1 / 0.15 / 0.1, respectively, at a rate 0.05 g.

 The adhesive composition thus obtained is applied to the surface of a plastic foam to be bonded to steel plates at a temperature of 200C.

 The bonding obtained is subjected to shear strength tests.

The content of reactive volatile components in the adhesive is also determined, the determination being carried out according to the technique described in Example 1.

The following results are obtained
Bond resistance to shear (MPa)
bonding temperature of 200C 1.0
Content of volatile components, mg 0.03.

Example 4
To obtain an adhesive composition in accordance with the invention and comprising in parts by mass: - prepolymer of polyethylene diadlycate
and toluylene diisocyanate 100 - 4,4 '- diphenylmethanediisocyanate 5 - trichlorethyl phosphate 1 - mixture of water, urea and sulforicinate
sodium in the respective proportions
with respect to said mixture of 1 / 0.3 / 0.2 0.1 is introduced into an amount of 100 g of prepolymer of polyethylene diadlycate and toluylene diisocyanate, brought to the temperature of 700C, 5 g of 4, 4'diphenylmethanediisocyanate melted.

The prepolymer is previously synthesized from diethylene glycol polyadipate (molecular weight 800) and toluylene-diisocyanate, the ratio of hydroxyl groups / isocyanate groups being 1 I 2.

The mixture obtained of polyethylene dipol prepolymer and toluylene diisocyanate and 4,41-diphenylmethanediisocyanate being kneaded, trichlorethyl phosphate is introduced therein at the rate of 1 g and the mixture is kneaded again while reducing its temperature to at 250C.

 Before using the composition thus obtained, it is added with a mixture of water, urea and sodium sulforicinate in the following respective proportions relative to said mixture of 1 / 0.3 / 0.2, at a rate 0.1 g.

The adhesive composition obtained is applied to the surface of a plastic foam to be bonded to an aluminum plate at a temperature of 0 C.

The bonding thus obtained is subjected to the shear strength tests.
The content of reactive volatile components in the adhesive is also determined.
The above-mentioned content is determined according to the technique described in Example 1.

 The following results are obtained.

Bonding resistance to shear (MPa): bonding temperature of 0 C 0.9
Content of volatile components, mg 0.02.

Example 5
To obtain an adhesive composition in accordance with the invention and comprising in parts by mass: - prepolymer of polyethylene diadlycate
and toluylene diisocyanate 100 - 4.4 t - diphenylmethanediisocyanate 10 - trichlorethyl phosphate 30 - mixture of water, urea and sulforicinate
sodium in the respective proportions
following with respect to said mixture of
1 / 0.15 / 0.1 1, 10 kg of prepolymer of polyethylene glycol and toluylene diisoyanate, brought to a temperature equal to 80 ° C., are introduced into a quantity of 10 kg of molten 4,4 '-phenylmethanediisocyanate
The prepolymer is previously synthesized from diethylene glycol polyadipate (soft mass 800) and toluylene diisocyanate, the ratio of hydroxyl groups / isocyanS groups; '6-'e being 1/2.

The mixture obtained of prepolymer of polyethylene glycol and toluylene diisocyanate and of 4,4 '-diphenylmethanediisocyanete being kneaded, trichlorethyl phosphate is introduced therein at a rate of 3 kg and oP mixes said mixture again while decreasing at temperature mixture up to 250C
Before using the composition obtained, it is added with a mixture of water, urea and sodium sulforicinate in the following respective proportions with respect to said mixture of -1 / 0.15 / 0.7, at a rate 0.1 kg.

 The adhesive composition thus obtained is applied to the surface of a plastic foam to be bonded in a boat under construction, the ambient temperature being equal to plus 70C. Test samples are prepared simultaneously.

 The bonding obtained on the samples is subjected to the shear strength tests.

 The content of reactive volatile components in the adhesive is also determined, the determination being carried out according to the technique described in Example 1.

 The following results are obtained.

Shear strength (MPa) 1.2
Content of volatile components, mg 0.03.

The consumption of glue to fix the insulation in the boat is 0.3 to 0.4 kg per 1 m2 of insulation. a finely porous elastic sticky film is formed filling all the irregularities of the parts to be joined. This characteristic makes it possible not to cut the heat-insulating blocks in order to conform them to the curvilinear surfaces.

Example 6
To obtain an adhesive composition according to the invention and comprising, in parts by weight - polyethylene glycol prepolymer
and toluylene diisocyanate 100 - 4,4 '- diphenylmethanediisocyanate 10 - trichlorethyl phosphate 30 - mixture of water, urea and sulforicinate
sodium in the following respective proportions
with respect to said mixture of 1 / 0.01 / 0.01 1, 2 g of 4 are introduced into an amount of 20 g of prepolymer of diethylene glycol polyadipate and of toluylene diisocyanate, brought to a temperature equal to 700 ° C. 4'diphenylmethanediisocyanate melted.

 The prepolymer is previously synthesized from diethylene glycol polyadipate (molecular weight 800) and toluylene-diisocyanate, the hydroxyl groups / groups-isocyanate ratio being 1 d 2.

The mixture obtained of prepolymer of polyethylene di-glycol and toluylene-diisocyanate and of 4,4 '- diphenylmethanediisocyanate being kneaded, the trichlorethyl phosphate is added at a rate of 6 g and the mixture is kneaded again while decreasing the temperature mixing up to 200C,
Before using the composition obtained, this is added with a mixture of water, urea and sodium ricinate sulfo in the following respective proportions relative to said mixture of 1 to 0.01 / 0.01, respectively, in an amount of 0.2 g.

The adhesive composition thus obtained is applied to the surface of a plastic foam to be bonded to a steel plate at a temperature of 200 C.

 The bonding obtained is subjected to shear strength tests. In addition, the content of reactive volatile components in the adhesive is determined.

 The tests are carried out according to the technique described in Example 1.

The following results are obtained.

Shear strength (MPa) 1.0
Content of volatile components, mg 0.02
Example 7
To obtain an adhesive composition in accordance with the invention and comprising, in parts by mass: - polyethylene diadipate prepolymer -
glycol and toluylene diisocyanate 100 - 4,4 '- diphenylmethanediisocyanate 10 - trichlorethyl phosphate 30 - mixture of water, urea and sulforicinate
sodium in the respective proportions
following with respect to said mixture of
1 / 0.3 / 0.2 1, 2 kg of 4.4 - diphenylmethanediisocyanate are introduced into an amount of 20 kg of prepolymer of polyethylene glycol and toluylene diisocyanate, brought to the temperature of 700 ° C.

 The prepolymer is previously synthesized from diethylene glycol polyadipate (molecular weight 800) and toluylene-diisocyanate, the ratio of hydroxyl groups to isocyanate groups being 1/2.

The mixture obtained of polyethylene di-glycol and toluylene-diisocyanate and 4,4'-diphenylmethanediisocyanate being kneaded, the trichlorethyl phosphate is introduced into it in an amount of 6 kg and the mixture is kneaded again while decreasing the temperature of the mixture up to 20 C.

 Before using the composition obtained, it is added with a mixture of water, urea and sodium sulforicinate in the following respective proportions relative to said mixture of 1 / 0.3 / 0.2, 0.2 kg.

The adhesive composition thus obtained is applied to the surface of plastic foam blocks to be bonded to metallic surfaces covered with frost in a boat under construction, at an ambient temperature of minus 20C. Samples are simultaneously prepared for the adhesion tests according to the technique described in Example i.

 The samples obtained are subjected to the shear strength tests.

The following results are obtained.

Shear strength (MPa) -1.0.

 The curing of the glue takes place 12 hours after its application. it forms an elastic bonding with fine cells ensuring a solid fixing of the flat blocks of plastic foam on the curvilinear surfaces of the hull of the boat. Thanks to the foaming of the glue, the joints between the blocks are filled with hardened glue.

Example 8
- To obtain an adhesive composition in accordance with the invention and comprising in parts by weight - prepolymer of polyethylene diadlycate
and toluylene diisocyanate 100 - 4,4 '- diphenylmethanediisocyanate 30 trichlorethyl phosphate 60 - mixture of water, urea and sulforicinate
sodium in the respective proportions
following with respect to said mixture of
1 / 0.01 / 0.01 2, is introduced into an amount of 100 g of prepolymer of polyethylene diadlycate glycol and toluylene diisocyanate, brought to the temperature of 70 C, 30 g of 4,4'-diphenylmethanediisocyanate fondn.

 The prepolymer is previously synthesized from polyethylene glycol polyadipate (molecular weight 800) and toluylene-diisocyanate, the ratio of hydroxyl to j isocyanate groups being 1 d 2.

The mixture obtained of prepolymer of polyethylene di-glycol and toluylene-diisocyanate and of 4,4 '- diphenylmethanediisocyanate being kneaded, the trichlorethyl phosphate is introduced into it in an amount of 60 g and the mixture is kneaded again while reducing the temperature of the mixture up to 20 C.

 Before using the composition obtained, that bi is added with a boat mixture, urea and sodium sulforicinate in the following respective proportions relative to said mixture of 1 l 0.01 d 0.01, at a rate of 2 g.

 The adhesive composition thus obtained is applied to the surface of a plastic foam foam to be bonded to aluminum plates at temperatures of minus 4 ° C., 0 ° C., plus 25 ° C.

The bonding obtained is subjected to the shear strength tests carried out according to the technique described in Example i
The following results are obtained
Shear strength (MPa) t
temperature of
minus 4 C 0.5 oog
plus 250C 1.3
Example 9
To obtain an adhesive composition in accordance with the invention and comprising, in parts by mass - polyethylene glycol prepolymer
and toluylene diisocyanate 100 - 4,4 '- diphenylmethanediisocyanate So - trichlorethyl phosphate 60 - mixture of water, urea and sulforicinate
sodium in the respective proportions
compared to said mixture of 1 / 0.15 / 0.1 2, 200 g of prepolymer of polyethylene di-glycol and toluylene-diisocyanate, brought to the temperature of 700C, are introduced into a quantity of 200 g, 60 g of 4.4 ′ diphenylmethane dii socyanate melted.

 The prepolymer is previously synthesized from diethylene glycol polyadipate (molecular weight 800) and toluylene-diisocyanate, the hydroxyl group / isocyanate group ratio being 1/2.

The mixture obtained of polyethylene dipol prepolymer and toluylene diisocyanate and 4,4'-diphenylmethanediisocyanate being kneaded, the trichlorethyl phosphate is introduced therein in an amount equal to 120 g and the mixture is kneaded again while reducing the mixing temperature up to 200C.

 Before using the composition obtained, this is added with a mixture of water, urea and sodium sulforicinate in the following respective proportions relative to said mixture of 1 / 0.15 / 0.1, respectively , in an amount of 4 g.

 The adhesive composition thus obtained is applied to the surface of a plastic foam to be bonded to steel plates at a temperature equal to 22 μm.

Samples are prepared simultaneously for climate testing. On a steel plate whose dimensions are 300 x 300 x 5 mm, a block of plastic foam is pasted, the dimensions of which are 290 x 290 x 20 mm. The samples thus bonded are placed in a refrigeration installation where they are kept for 12 hours at a temperature equal to minus 500C, then the samples are transferred to a thermostat whose temperature is over 200C to be kept there for 6 hours. , the above-mentioned samples are installed in a thermal chamber and they are kept at a temperature of over 650 ° C. for -6 hours, finally they are quickly transferred to the refrigeration installation to be kept there for 2 hours at temperature of 00 ° and for 10 hours at a temperature equal to minus 500C.

The tests being completed, the samples are examined visually. There is no destruction of the bonded assembly.

In addition, the glue samples applied to the plastic foam are subjected to the shear strength tests according to the technique described in Example 1.

 The following results are obtained.

Shear strength (MPa) 1.4.

Example 10
To obtain an adhesive composition in accordance with the invention and comprising, in parts by mass: - prepolymer of polyethylene diadlycate and
toluylene diisocyanate 100 - 4,4'-diphenylmethanediisocyanate 5 - trichlorethyl phosphate 60 - mixture of water, urea and sulforicinate
sodium in the respective proportions
With respect to said mixture of 1 / 0.01 / 0.01 2, there is introduced into an amount of 100 g of the prepolymer of polyethylene diadlycate and toluylene diisocyanate brought to the temperature of 700 ° C., 5 g of 4.4 l molten diphenylmethane diisocyanate.

 The prepolymer is previously synthesized from diethylene glycol polyadipate (molecular weight 800) and toluylene-diisocyanate, the hydroxyl group / isocyanate group ratio being 1/2.

 The mixture obtained of prepolymer of polyethylene di-glycol and toluylene-diisocyanate and of 4,4'-diphenylmethanediisocyanate being kneaded, the trichlorethyl phosphate is introduced into it in an amount of 60 g and the mixture is kneaded again while decreasing the temperature of mixing up to 200C.

 Before using the adhesive composition, the latter is added with a mixture of water, urea and sodium sulforicinate in the following respective proportions relative to said mixture of 1 / 0.01 / 0.01, to 2 g.

 The adhesive composition thus obtained is applied to the surface of a plastic foam to be bonded to steel plates at a temperature of over 10au.

 The bonding obtained is subjected to shear strength tests.

 In addition, the content of reactive volatile components in the adhesive is determined.

The tests are carried out according to the technique described in Example 1.

 The following results are obtained.

Shear strength (MPa) 1.0
Content of volatile components, mg 0.02
Example II
To obtain an adhesive composition in accordance with the invention and comprising in parts by mass: - prepolymer of polyethylene diadlycate
and toluylene diisocyanate 100 - 4,4 '- diphenylmethanediisocyanate 30 - trichlorethyl phosphate 1 - mixture of water, urea and sulforicinate
sodium in the respective proportions
In comparison with said mixture of 1 / 0.01 / 0.01 0, 50 g of prepolymer of polyethylene glycol and toluylene diisocyanate, brought to the temperature of 700 ° C., are introduced into a quantity of 50 g, 15 g of 4.4 '-diphenylmethanediisocyanate melted.

The prepolymer is previously synthesized from polyethylene glycol polyadipate (molecular weight 800) and toluylene-diisocyanate, the hydroxyl group / isocyanate group ratio being 1/2.

 The mixture obtained of prepolymer of polyethylene glycol and toluylene diisocyanate and 4,4'-diphenylmethanediisocyanate being kneaded, the trichlorethyl phosphate is introduced into it in an amount of 0.5 g the mixture is kneaded again while decreasing, mixing temperature up to 20 C.

Before using the composition obtained, it is added with a mixture of water, urea and sodium sulforicinate in the following respective proportions relative to said mixture of 1 d 0.01 / 0.01, in an amount equal to 0.05 g.

 The adhesive composition thus obtained is applied to the surface of a plastic foam to be bonded to steel plates at a temperature equal to 30 C.

The bonding obtained is subjected to shear strength tests.

 In addition, the content of reactive volatile components in the adhesive is determined.

 The tests are carried out according to the technique described in Example 1.

 The following results are obtained.

Resistance to a temperature of 30 C
shear (MPa) 1.4
Content of volatile components, mg 0.08
Example 12
To obtain an adhesive composition in accordance with the invention and comprising in parts by mass: - prepolymer of polyethylene diadlycate
and toluylene diisocyanate 100 - 4.4 '- diphenylmethanediisocyanate 30 - trichlorethyl phosphate 60 - mixture of water, urea and sulforicinate
sodium in the respective proportions
following with respect to said mixture of
1 / 0.3 / 0.2 0.1 is introduced into an amount of 50 g of prepolymer of polyethylene diadlycate glycol and toluylene diisocyanate, brought to the temperature of 70 C, 15 g of 4,4'diphenylmethanediisocyanate molten.

 The prepolymer is previously synthesized from polyethylene glycol polyadipate (molecular weight 800) and toluylene = diisocyanate, the hydroxyl group / isocyanate group ratio being 1 d 2.

The mixture obtained of polyethylene dipol prepolymer and toluylene diisocyanate and 4,4'-diphenylmethanediisocyanate being kneaded, the trichlorethyl phosphate is introduced into an amount of 30 g and the mixture is kneaded again while reducing the temperature mixing up to 250C.

Before using the composition obtained, this is added with a mixture of water, urea and sodium sulforicinate in the following respective proportions relative to said mixture of 1 / 0.3 / 0.2, in one amount equal to 0.05 g.

 The adhesive composition thus obtained is applied to the surface of a foam to be bonded to a steel plate at a temperature equal to 250C.

The bonding obtained is subjected to shear strength tests. In addition, the content of reactive volatile components in the adhesive is determined.

 The following results are obtained.

Shear strength (MPa) 1.0
Content of volatile components, mg 0.08
Example 13
To obtain an adhesive composition in accordance with the invention, comprising in parts by mass: - polyethylene diol glycol prepolymer
and toluylene diisocyanate 100 - toluylene diisocyanate 20 - trichlorethyl phosphate 30 - mixture of water, urea and sulforicinate
of sodium in a ratio of 1 / 0.3 / 0.2 1 is introduced into an amount of 200 g of prepolymer of polyethylene di-glycol adipate and toluylene diisocyanate, brought to the temperature of 500 C, 40 g of toluylene diisocyanate.

The prepolymer is previously synthesized from diethylene glycol polyadipate (molecular weight 800) and toluylene-diisocyanate, the hydroxyl group / isocyanate group ratio being 1/2.

 The mixture obtained of polyethylene dipol prepolymer and toluylene diisocyanate being kneaded, trichlorethyl phosphate is introduced into it in an amount of 60 g and the mixture thus obtained is kneaded again while reducing the temperature of the mixture to 250C .

 Before using the composition obtained, this is added with a mixture of water, urea and sodium sulforicinate in the following respective proportions relative to said mixture of 1 / 0.3 / 0.2 in an equal amount to 2 g.

The adhesive composition thus obtained is applied to the surface of a plastic foam to be bonded to steel plates at the temperature of 0 ° C. and 250 ° C. and the joints between the blocks of plastic foam are filled with composition.

 The bonding obtained is subjected to shear strength tests. In addition, the content of reactive volatile components in the adhesive is determined, and the viscosity of the above-mentioned adhesive composition is determined.

The following results are obtained.

Shear strength (MPa)
- bonding temperature of 0 C 0.8
200C 1,2
Content of volatile components, mg 0.02
Viscosity, poise 90
The glue fills the 2 to 3 mm joints between the plastic foam blocks well.

Example 14
To obtain an adhesive composition, according to the invention, comprising in parts by mass: - prepolymer of polyethylene diadlycate
and toluylene diisocyanate 100 - toluylene diisocyanate 5 - trichlorethyl phosphate 30 - mixture of water, urea and sulforicinate
of sodium in a ratio of 1 / 0.1 / 0.05 2 is introduced into an amount of 100 g of prepolymer of polyethylene dipadolate and toluylene diisocyanate brought to the temperature of 5000 an amount of 5 g of toluylene diisocyanate.

The prepolymer is previously synthesized from polyethylene glycol polyadipate (molecular weight 800) and toluylene-diisocyanate, the hydroxyl group / isocyanate group ratio being 1/2.

The mixture obtained of prepolymer and toluylene-diisocyanate being kneaded, trichlorethyl phosphate is introduced into it in an amount of 30 g and the mixture thus obtained is kneaded again while decreasing the mixing temperature up to 200C.

Before using the composition obtained, this is added with a mixture of water, urea and sodium sulforicinate in the following respective proportions relative to said mixture of 1 / 0.1 / 0.05 in an amount of 2 g.

The adhesive composition thus obtained is applied to the surface of a plastic foam to be bonded to steel plates at a temperature equal to minus 40C, to OOC and to plus 200G,
The bonding obtained is subjected to shear strength tests. In addition, the content of reactive volatile components in the adhesive is determined.

The following results are obtained.

Shear strength (MPa)
- bonding temperature of
minus 40C 0.3
OOC 0.5
plus 200C 1.0
Content of volatile components, mg 0.01
The adhesive composition in question fills well spaces of 3 to 4 mm between the blocks of plastic foam.

Example 15
To obtain an adhesive composition in accordance with the invention, comprising in parts by weight - polyethylene glycol prepadate
and toluylene diisocyanate 100 - adduct of toluylene diisocyanate and
trimethylolpropane 30 - trichlorethyl phosphate 60 mixture of water, urea and sulforicinate
sodium in a ratio 1 to 0.3 to 0.2 2 is introduced into an amount of 200 g of prepolymer of polyethylene diadlycate glycerol and toluylene diisocyanate, brought to the temperature of 700C, 60 g of adduct of toluylene diisocyanate and molten trimethylolpropane.

The prepolymer is previously synthesized from the polyadipate of diethylene glycol and of toluylene diisocyanate, the ratio of hydroxyl groups / isocyanate groups being 1/2.

 The mixture obtained of toluene-diisocyanate and trimethylolpropane prepolymer and adduct being kneaded, trichlorethyl phosphate is introduced into it in an amount of 120 g and the mixture thus obtained is kneaded again while decreasing the mixing temperature up to at 200C.

Before using the composition obtained, this is added with a mixture of water, urea and sodium sulforicinate in the following respective proportions relative to said mixture of 1 / 0.3 to 0.2, in an amount equal to 4 g.

The adhesive composition thus obtained is applied to the surface of a plastic foam to be bonded to the steel plates at the temperature of 00C and 200C
The bonding obtained is subjected to shear strength tests. In addition, the content of reactive volatile components in the adhesive is determined.
Simultaneously, a film of adhesive composition is prepared, by applying it on polyethylene for mechanical dressing.
The following results are obtained.

Shear strength (MPa)
bonding temperature of 00e 0.6
20tC 1.4
Content of volatile components, mg 0.01
Breaking strength 1.5
Example 16 (comparative)
To obtain an adhesive composition comprising in parts by mass - polyethylene diol glycol prepolymer
and toluylene diisocyanate 100 - 4,4 '- diphenylmethanediisocyanate 30 - trichlorethyl phosphate 60 - mixture of water, urea and sulforicinate
of sodium in a ratio of 1 d 0.5 / 0.4 4 is introduced into an amount of 200 g of prepolymer of polyethylene diadlycate glycol and toluylene diisocyanate, brought to the temperature of 700C, 60 g of 4.4 ' -diphenylmethanediisocyanate melted.

 The prepolymer is previously synthesized from diethylene glycol polyadipate (molecular weight 800) and toluylene-diisocyanate, the hydroxyl group / isocyanate group ratio being 1/2.

The mixture obtained of prepolymer of polyethylene glycol and toluylene diisocyanate and 4,4'-diphenylmethanediisocyanate being kneaded, the trichlorethyl phosphate is introduced into it in an amount of 120 g and the mixture thus obtained is kneaded again while decreasing the mixing temperature up to 2500.

 Before using the composition obtained, this is added with a mixture of water, urea and sodium sulforicinate in the following respective proportions relative to said mixture of I / 0.5 / 0.4, in an amount equal to 8 g.

The adhesive composition thus obtained is applied to the surface of a plastic foam to be bonded to steel plates at the temperature of OOC and 250C.

The bonding obtained is subjected to shear strength tests. The content of reactive volatile components in the adhesive is also determined.

The following results are obtained.

Shear strength (MPa):
- OOC bonding temperature 0.3
250C 0.6
Content of volatile components, mg 0.012
it therefore appears that a water / urea / sodium sulfo ricinate ratio of 1 / 0.5 / 0.4 leads to a reduction in the bonding strength.

Example 17 (comparative)
To obtain an adhesive composition comprising in parts by mass: - prepolymer of polyethylene glycol adipate
and toluylene diisocyanate 100 - 4,4 '- diphenylmethanediisocyanate 30 - trichlorethyl phosphate 60 - mixture of water, urea and sulforicinate
sodium in a ratio of 1 / 0.005 / 0.005 0.05 is introduced into an amount of 100 g of prepolymer of polyethylene diadlycate glycol and toluylene diisocyanate, brought to the temperature of 70qu, 30 g of 4,4'-diphenylmethane di is o melted cyanate.

 The prepolymer is previously synthesized from diethylene glycol polyadipate (foam molecular weight 800) and toluylene diisocyanate, the ratio of hydroxyl groups to isocyanate groups being 1/2.

 The mixture obtained of polyethylene dipol prepolymer and toluylene diisocyanate and of 4,4'-diphenylmethanediisocyanate being mixed, trichlorethyl phosphate is introduced into it in an amount of 60 g and the mixture thus obtained is kneaded again while decreasing the temperature of the mixture up to 200G.

Before using the composition obtained, this is added with a mixture of water, urea and sodium sulforicinate in the following respective proportions relative to said mixture of 1 / 0.005 / 0.005, in an amount of 2 g.

The adhesive composition thus obtained is applied to the surface of a plastic foam to be bonded to steel plates at a temperature equal to minus 40C, to 00C and to plus 200C,
The bonding obtained is subjected to shear strength tests. The content of reactive volatile components in the adhesive is also determined.
The following results are obtained;
Shear strength (MPa)
- bonding temperature of
minus 40C does not stick
OOC 0.2
plus 200C 0.5
volatile component content, mg 0.21
So with a water / urea / sulforicinate ratio
of sodium of 1 / 0.005 / 0.005 and a reduction in the quantity of this mixture in the adhesive composition below the proposed limit, it is no longer possible to stick the plastic foam at temperatures below zero and there is a reduction in the strength of the bonding performed at temperatures above zero. In addition, the content of volatile components increases.

Example 18 (comparative)
To obtain an adhesive composition comprising, in parts by mass: - polyethylene glycol polyadipate prepolymer
and toluylene diisocyanate 100 - 4,4 '- diphenylmethanediisocyanate 10 - trichlorethyl phosphate 30 - mixture of water, urea and sulforicinate
of sodium in a ratio of 1 / 0.005 / 0.005 2 is introduced into a mass of 100 g of prepolymer of polyethylene dipadolate and toluylene diisocyanate, brought to the temperature of 700C, 10 g of 4,4'-diphenylmé thanediisocyanate.

The prepolymer is previously synthesized from diethylene glycol polyadipate (molecular weight 800) and toluylene-diisocyanate, the ratio of hydroxyl groups / isocyanate groups being 1/2.

 The mixture obtained of polyethylene dipol prepolymer and toluylene diisocyanate and 4,4'-diphenylmethanediisocyanate being kneaded, the trichlorethyl phosphate is introduced into it in an amount of 30 g and the mixture thus obtained is kneaded again while reducing the temperature of the mixture up to 200C.

Before using the composition obtained, this is added with a mixture of water, urea and sodium sulforicinate in the following respective proportions with respect to said mixture of 1 / 0.005 d 0.005, in an amount of 2 g .

The adhesive composition thus obtained is applied to the surface of a plastic foam to be bonded to the steel plates at a temperature equal to minus 4 ° C., 0 ° C. and plus 20 ° C.

 The bonding obtained is subjected to shear strength tests. In addition, the content is determined of reactive volatile components in the adhesive.

The following results are obtained.

Shear strength (MPa):
- bonding temperature of
minus 40C does not stick
0 C 0.05
plus 200th 0.20
Content of volatile components, mg 0.20
An increase in the amount of mixture of water, urea and sodium sulforicinate in the adhesive composition, the water / urea / sodium sulforicinate ratio being 1 / 0.005 / 0.005, results in the formation of a layer tacky with low shear strength and high volatile component content The above-mentioned adhesive does not allow plastic foam to stick at temperatures below zero.

Example 19 (comparative)
To obtain an adhesive composition comprising, in parts by mass t - polyethylene glycol prepadate
and toluylene diisocyanate 100 - 4,4 '- diphenylmethanediisocyanate 10 m trichlorethyl phosphate 30 - mixture of urea water and sulforicinate
sodium in a ratio of 1 / 0.5.0.4 0.1 is introduced into an amount of 50 g of prepolymer of polyethylene diadlycate glycerol and toluylene diisocyanate, brought to the temperature of 700C, 5 g of 4.4 ' -diphenylmethane-diisocyanate melted.

 The prepolymer is previously synthesized from diethylene glycol polyadipate (molecular weight 800) and toluylene-diisocyanate, the ratio of hydroxyl groups to isocyanate groups being 1/2.

 The mixture obtained of prepolymer of polyethylene di-glycol and toluylene-diisocyanate and 4,4'-diphenylmethanediisocyanate being kneaded, the trichlorethyl phosphate is introduced into it in an amount of 15 g and the mixture obtained is kneaded again while decreasing , at the same time, the temperature of the mixture up to 200C.

Before using the composition obtained, this is added with a mixture of water, urea and sodium sulforicinate in the following respective proportions relative to said mixture of 1 / 0.5 / 0.4 respectively, in quantity equal to 0.05 g.

The adhesive composition thus obtained is applied to the surface of a plastic foam to be bonded to steel plates at a temperature of minus 40C and plus 200cl
The bonding obtained is subjected to shear strength tests. In addition, the content of reactive volatile components in the adhesive is determined.

The following results are obtained.

Shear strength (MPa)
- bonding temperature of
minus 40C does not stick
plus 20QC 0.3
volatile component content, mg 0.32
Thus, a water / urea / sodium sulforicinate ratio of 1 / 0.5 / 0.4 contributes to the formation of a greater quantity of volatile components, the bonding having a low resistance which makes it impossible to fix the foam. plastic with a metal covered with frost.

Of course, the invention is in no way limited to the embodiments described and shown which have only been given by way of example. In particular, it includes all the means described, as well as their combinations, if these are carried out according to the spirit and implemented in the context of the claims which follow.

Claims (3)

REVENDI CAT IONS  1.- Adhesive composition of the type comprising a prepolymer of polyethylene diadlycate glycol and toluylene diisocyanate, a polyisocyanate and trichlorethyl phosphate, characterized in that it also comprises a mixture of water, urea and sodium sulforicinate in the following respective proportions with respect to said mixture of 1 / (0.01 to 0.3) / (0.01 to 0.2), the components being taken in the following proportions, in parts by mass: - prepolymer of diethylene glycol polyadipate and toluylene diisocyanate 100 - polyisocyanate 5-30 - trichlorethyl phosphate 1-60 - mixture of water, urea and sulforicinate  sodium in a ratio of 1 / (0.01 to 0.3) /  (0.01 to 0.2) 0.1-2  2.- adhesive composition according to claim 1, characterized in that it comprises a mixture of water, urea and sodium sulforicinate in the following ratio: 0.1 to 0.3) / (0.05 to 0.2), the polyisocyanate used being toluylene diisocyanate and the components being taken in the following proportions, in parts by mass: - prepolymer of polyethylene glycol adipate  and toluylene diisocyanate 100 - toluylene diisocyanate 5-20 - trichlorethyl phosphate 1-60 - mixture of water, urea and sulforicinate  sodium in a ratio of 1 / (0.1 to 0.3) /  (0.05 to 0.2) 0.5-2  3.- adhesive composition according to claim 1, characterized in that it comprises a mixture of water, urea and sodium sulforicinate in the following ratio 1 / (0.05 to 0.3) / (0, 03 to 0.2), the polyiso cyanate used being an adduct of toluylene diisocyanate and trimethylolpropane and the components being taken in the following proportions, in parts by mass - prepolymer of polyethylene glycol adipate and toluyene diisocyanate 100 - toluylene diisocyanate adduct and trimethylolpropane 5-30 - trichlorethyl phosphate 1-60 - mixture of water, urea and sulforicinate sodium in a ratio of: 1 / (0.05 to 0.3) / (0.03 to 0.2) 0.2-2