CS203382B1 - Reactive mixture with increased stability based on epoxide and polyuretane resin - Google Patents

Description

SUMMARY OF THE INVENTION The present invention provides a reactive composition with increased stability, allowing a wide modification of the properties of the resulting polymer mass.

Epoxy-based polymers are widely used in a wide variety of manufacturing industries. By suitable combination of the basic reactive components by the addition of plasticizers, many advantageous properties can be achieved, which are suitable in the treatment of cast products, coatings and coatings, in the production of simple and very complicated rigid and flexible laminates, etc.

The disadvantage of the systems used so far is mainly the limited lifetime of the mixture after mixing the reactive components, depending on the choice of the basic components, or depending on the type and amount of activator present, it is necessary to choose the deposition or casting process. Already during these technological operations it is necessary to take into account that the viscosity of the applied mixture changes due to the ongoing reaction, it is necessary to additionally regulate the thickness of the coating according to the set gap etc. Also Cleaning of the applicator is difficult if not done in time to the course of the reaction of the present epoxy and amine groups. _F

In addition, significant variations in the properties of the resulting polymer mass can be achieved within the range that allows the choice of epoxy component, a different type of polyamine extender, or the addition of plasticizers.

The above-mentioned disadvantages are overcome by the reactive stability-enhanced composition according to the invention, which comprises, as essential components, an epoxy resin modified or unmodified, or a mixture thereof with an epoxy equivalent of 0.01 to 0.65, a polyamine blocked extender, in particular an adduct. % polyamines or polyarainoamides of an aliphatic or cycloaliphatic nature, or mixtures thereof with carbon dioxide, and a prepolymer component, in an amount of 0 to 95 wt. based on the total weight of the reactive mixture, which is an addition product of a polyol, in particular a polyether or polyester with a polyisocyanate _; aromatic, aliphatic, cycloaliphatic, or mixtures thereof, wherein the chains of the addition product have a reactive isocyanate terminus having an isocyanate group content of 0.1 to 7% by weight of the prepolymer component. The reactive mixture according to the invention is distinguished by an increased stability and is particularly suitable for 2-stage deposition or casting operations, allowing a wide modification of the properties of the resulting polymer mass produced by the additional effect of heat on the reactive mixture. It contains, as a base component, an epoxy resin, modified or unmodified, or a mixture thereof, with an epoxy equivalent of 0.01 to 0.65, a polyamine blocked crosslinking agent which is a polyawine adduct, an optional polyaminoamide of aliphatic or cycloaliphatic nature, or a mixture thereof. in a quantity of 0 to 95% by weight, based on the total weight of the reactive mixture, which is the addition product, of polyols, in particular polyether or polyester with polyisocyanate, namely aromatic, aliphatic, cycloaliphatic or their mixtures, wherein the chains of this product addition have reactive isocyanate endings?

Esterified epoxy resins may be used as one of the reactants, in particular a higher fatty acid epoxy resin product having a number of carbon atoms in the chain of 6 to 18.

It is possible to increase the plastic deformation by adding 1 to 3Ό2 wt. polyvinyl chloride.

The properties of the reactive mixture can be modified by the addition of 0.1 to 20 wt. of the compounds are in particular cyclopropylglyceryl ether.

Also, the addition of 0, 20%, a plasticizer based on esters of aromatic and aliphatic dicarbonic acids or mixtures thereof, or a polymeric plasticizer based on polyesters of adipic acid significantly modifies the properties of the resulting polymer mass.

Modified and unmodified epoxy resins, low, medium and high, can be used as epoxy constituents, as is known in the art. systems with solvents in the system r such as toluene, xylene, methylcyclohexanone, ethyl acetate, butyl acetate, glycol monoethyl ether, glycol monomethyl ether and the like, and solid high molecular weight resin. The modified resins may be fatty acid esterified epoxides, modified with reactive solvents, such as butyl glycidyl ether, cresylglycidyl ether or the like, or even ammonium surfactants.

Additives of aliphatic adiamines and polyamines such as, for example, ethylenediamine, propylenediamine, butylenediamine, pentamethylenediamine, hexamethylenediamine, diethylenetriamine and triethylenetutramine, and carbon dioxide, can be used as suitable extenders. diamines, polyaminoamides, polyaminoimidazolines, aliphatic. ether diamines, modified polyamines, polyaminoimidazoines, cycloaliphatic amines and aromatic amines with carbon dioxide.

The prepolymer component is the product of the reaction of polyols such as polyether diols, polyethylene glycol, polypropylene glycol, polytetramethylene glycol by mol. % polyesters such as adipic, succinic, succinic and glutaric polyesters with ethylene glycol, di-ethylene glycol, propylene glycol, butylene glycol, hexamethylene glycol and the like with a molecular weight of 500 to 2000, polycaprolactones with a mol. weight 500 to 2 000, but also polyester and polyethertricly with mol. weight 500 to 5,000 with aromatic polyisocyanates, toluene diisocyanate, diethylmethane-4,4'-diisocyanate, naphthylene-1,5-diisocyanate, cyctaliphatic-bis- (isocyanate-cyclohexyl) -methane-diisocyanate, isophorone diisocyanate-isocyanate-isocyanate, /me. .- bexamethylandiisokyanátem, "Secret as nonvolatile isocyanate adducts of such polyisocyanates formed by reacting toluene diisocyanate and trimethylclpropanu or hexametyléndiisokyanátero, reaction of water with hexaroetyléndiisokyanátem polymeric toluene diisocyanate containing isocyanate rings, triphenylmethane-4,4 ^-, 4" triisocyanate or the like. The prepolymers are prepared isocyanate-terminated with a molar ratio of isocyanate and hydroxyl groups of - 1.1-2 / 1 or with a hydroxyl terminus with a molar ratio of isocyanate and hydroxyl groups of - 1 / 1.1-2.

The properties of the reaction mixture can be further modified by the addition of powdered polyvinyl chloride. Polyvinyl chloride has a reinforcing effect, suppressing the elastic component of polyurethanes. The foam layer has a stiffer feel and more plastic character. The effect of the polyvinyl chloride can be further modified by the addition of plasticizers in an amount of 30 to 60% in the mixture and the polyvinyl chloride. Paste-forming polyvinyl chlorides of the suspension or emulsion type with a K value of 50 to 80 and a particle size of 0.1 to 60, ura are used. The plasticizers are based on esters of aromatic and aliphatic dicarboxylic acids, or polymeric plasticizers based on polyesters. The reaction mixture containing polyvinyl chloride and polyurethane can be stabilized with hydrochloric acid acceptors which are metallized with barium, cadmium, tin compounds and modified epoxy soybean oil with, for example, 6.2 to 6.4% oxygen and epoxy groups. It should be noted that there is a synergistic effect between the organometallic stabilizers and the residual amount of unreacted epoxy resin in improving the stability of the polyvinyl chloride. The polyurethane components can be stabilized by UV-absorbers, e.g. based on benztriazole or benzoirenone, antioxidants such as alkaryl phosphides, and in polyurethane-containing polyester polyol also anti-hydrolytic stabilizers such as polycarbodiimides.

Said reactive mixtures are suitable for bonding metal formations to a cavity which is simultaneously filled with a foamed resin. Also in surface applications, especially when using solvents, these shifts, with a viscosity of 0.5 to 3 Pas / 25 ° C, produce strong, resilient and tough coatings and high weathering resistance, with excellent hydrolytic and yellowing resistance.

These blends will find use in the preparation of a wide range of rigid foams for fillings intended as thermal or acoustic insulation, and will also be used in the production of cellular laminates. They are also suitable as a base for carpets and for the preparation of synthetic leather.

The following non-limiting examples include:

Example 1

Into a duplicate 0.5 L stirred vessel was weighed 200 g of a prepolymer prepared by the addition of two moles of toluenesulfate and one mole of 2,000 molecular weight polypropylene glycol containing 3.43 g of end isocyanate groups and 10 g of epoxy resin with epoxy equivalent 0.47-0.58 and a viscosity of 1.22 Pas at 25 ° C, 11 g of adducted ethylenediamine with carbon dioxide, 20 g of precipitated calcium carbonate, 0.5 g of silicone-based surfactant and 2 g of dye. The mixture was stirred for 20 minutes with a 3000 rpm propeller stirrer. with intensive cooling. After vacuum degassing, the mixture was used to prepare coatings on a paper provided with a separating silicone layer. The mixture was spread with a 0.3 mm wiper blade and cured in an electric lab oven at 155 ° C for one minute. A foam coating with a thickness of 0.63 mm was obtained with a system of pores interconnected with a bulk density

358 kg / m < 2 >, a tensile strength of 0.637 MPa and a tear strength of 2.02 N / mm. with a relatively smooth glossy surface.

Example 2

150 g of a prepolymer of 2 moles of toluene diisocyanate and 1 mole of polypropylene glycol having a molecular weight of 2,000 containing isocyanate groups = 3.4.3 were weighed into a duplicated stirred vessel, 50 g of prepolymer also having a molar ratio of toluene diisocyanate: polyoxypropylene glycol of 2: 1; , isocyanate content in prepolymer of 6.23 2.11 g of epoxy resin with an epoxy equivalent of 0.26 to 0.32 and a viscosity

Passport at 25 ° C, 11,1 β of ethylenediamine carbon dioxide adduct, 0,5 g of surfactant, 20 g of barium sulphate and 2 g of dye. The mixture was vigorously mixed with a stirrer at 3000 rpm. with thorough cooling. The mixture was coated without separation with a 0.3 mm wiper blade onto release paper. Curing was carried out in a laboratory oven at 150 ° C for one minute. The foam layer thus prepared had a flat glossy surface. Between the upper and lower more compact layers was a set of large interconnected pores. The thickness of the foam layer 3 was 0.6 [mu] m, the tensile strength was 0.704 MPa, the density was 355 kg / m and the tear strength was 1.79 N / mm.

Example 3

62 g of prepolymer, made of polypropylene glycol mol. wt. 4000 and toluene diisocyanate with mol. weight 8,000 and 0.92% end isocyanate groups, 138 g polypropylene glycol prepolymer mol. wt. 1,000 and diphenylmethane-4,4'-diisocyanate containing 5.177% isocyanate groups, 8 g of epoxy resin with an epoxy equivalent of 0.52 to 0.57 and a viscosity of 11.0 Pas / 25 ° C, 12.4 g of hexamethylenediamine adduct with carbon dioxide 40 g precipitated calcium carbonate and 9.3 g concentrate from 1.3 g dye and 8 g silicone surfactant. The mixture was vigorously stirred with a β 3000 rpm stirrer with cooling. Immediately after mixing, the mixture was coated with a 0.3 mm wiper blade onto release paper. Curing took place in a laboratory oven at 150 ° C for one minute. The foam layer had a slightly undulating surface, a soft feel and a similar internal structure to the layers of the previous examples. The foam layer thickness was 0 73 mm, tensile strength 0.476 MPa, bulk density 233.8 kg / m, tear strength 0.638 N / mm.

Example 4

120 g of a 37.5% solution of esterified epoxy resin in toluene with an epoxy equivalent of 0.01 were poured into a duplicate stirrer flask. To this solution was. 50 g of butyl glycidyl ether, 44.2 isophorone diisocyanate prepolymers and polytetramethylene glycol with an isocyanate group content of 3.08%, 14.3 g of dicyclohexyldiaminomethane carbonate adduct and 5.8 g of ethylenediamine-carbon dioxide adduct with carbon dioxide active carbon dioxide in succession reagents. The mixture was mixed with a 1500 rpm stirrer and coated onto a release paper in a 0.3 mm thick layer. It was first dried in an oven at 60 ° C for one minute, then cured at 150 ° C for two minutes. A microporous layer with a thickness of 0.48 mm, a tensile strength of 0.937 MPa and a tear strength of 1.531 N / mm was prepared. When the mixture was coated with a 0.1 mm slot and dried at 120 ° C for two minutes, a compact film was formed. The mixture has good adhesion to metals.

Example 5

155.8 g of epoxy resin with an epoxy equivalent of 0.52 to 0.55 and a viscosity of 10.5 Pas at 25 ° C were weighed into a duplicate stirrer flask. 53 g of carbon dioxide dicyclohexyldiaminomethane adduct, 37.5 g of kaolin having a particle size of 1 to 10 µm, and 3.7 g of a surfactant silicone composition were successively mixed into this resin.

The mixture was stirred at 500 rpm for 20 minutes. and then painted onto a release paper in a 0.3 mm thick layer. Curing & foaming took place in one minute at 155 ° C in an oven,

Thus, a rigid foam layer 0.55 mm thick with fine interconnected pores was prepared, a tensile strength of 0.286 MPa, a bulk density of 293 kg / m < -1 >.

Example 6

63.1 g of polypropylene glycol of 1 mole were weighed into a duplicate vessel equipped with a stirrer. weight of 1000, and 6.6 g of triethylenetetramine. With efficient stirring and cooling to 150 ° C, the polypropylene glycol with triethylenetetramine was dried with dried carbon dioxide. The progress of the reaction was monitored by drop in pH and terminated at pH 7. The mixture was then heated to 60 ° C and 34.1 g of diphenylmethane diisocyanate was fed into it. The mixture was then kept under stirring at 60 ° C for 5 hours. In a 250 ml beaker, 50 g of diethylhexyl phthalate was heated to 90 ° C and 3.4 g of 2/2 * hydroxy-3-terebutyl-5 * methylphenyl / -5 * chlorobenzotriazole were weighed and stirred until the stabilizer had dissolved, then 2.2 g of modified soybean oil, 3.4 g of alkaryl phosphite and 1.1 g of organotin stabilizer were fed and mixed. After cooling to 20 ° C, a clear yellowish solution was formed, into which 75 g of pasty forming polyvinyl chloride having a K value of 70 was weighed and a paste was prepared with stirring, which was poured into the previously prepared mixture in a duplicate kettle. 12.5 g of epoxy resin with an epoxy equivalent of 0.52 to 0.55 and 3.7 g of silicone surfactant were also fed to this. The mixture was then vigorously homogenized with stirring for 20 minutes, 1500 rpm. After mixing, the mixture was coated onto a release paper with a 0.3 mra slit strip wiper. After curing in an oven (150 ° C / min), a foam layer of 0.57 mm thick with 0.479 MPa tensile strength, 0.929 N / mm tear strength and 322 kg / m density was formed.

Example 7

14.1 g of diethylenetriamine and 3.7 g of a silicone surfactant were fed to 62.5 g of xylene in a duplicate kettle. With stirring and cooling to 15 ° C, the content was saturated with dried carbon dioxide until the pH dropped to 7. Then, 145.6 g of polycaprolactone prepolymer and polypropylene glycol containing isocyanate groups - 3.45 Z, 75 g were mixed into the mixture. epoxy resins with an epoxy equivalent of 0.65 and 2.5 g of a paste-forming paste-forming polyvinyl chloride having a K value of 70. The mixture was homogenized by stirring for 20 minutes, 1500 rpm. Foam layers were prepared in a conventional manner by coating onto release paper and drying in an oven. A 0.3 mm thick coating resulted in a 0.52 mm thick layer with a tensile strength of 0.637 MPa and a tear strength of 1.857 N / mm, a bulk density of 383 kg / m. Coating thinner than 0.1 mm produces compact films with good mechanical properties when cured at 125 ° C *

Example

200 g of polypropylene glycol and diphenylmethane diisocyanate prepolymer containing 3.28 Z isocyanate groups were weighed into the duplicate vessel. The ethylene diamine adduct of 8.2 g and 2.4 g of 2 g silicone surfactant concentrate were then mixed into the prepolymer. 4 g dye. The resulting mixture was stirred for about 20 minutes at 500 rpm. The foam layer was prepared by coating onto a release paper at a wiper blade slot of 0.3 mm and curing in an oven at 145 ° C for 1 minute. The cured layer was 0.62 mm thick and had 0.737 MPa tensile strength, 261 kg / m bulk density and

1.818 N / mm tear strength.

Claims (6)

1. Reactive mixture with increased stability based on epoxy and polyurethane resin, reactive and non-reactive solvents and possible auxiliaries, especially suitable for application by deposition or casting, characterized in that it contains epoxy resin, modified or unmodified, or their a mixture, with an epoxy equivalent of 0.01 to 0.65, a polyamine blocked extender, in particular an adduct of a polyamine or a polyarainoaraid of an aliphatic or cycloaliphatic nature, or a mixture thereof, with carbon dioxide, and optionally a prepolymer component in an amount of up to 95% by weight %, based on the total weight of the reactive mixture, which is an addition product of a polyol, in particular a polyether or polyester with a polyisocyanate, namely aromatic, aliphatic, cycloaliphatic or mixtures thereof, the chains of this addition product having reactive isocyanates The isocyanate-terminated group contains from 0.1 to 7% by weight of the prepolymer component Reactive mixture according to Claim 1, characterized in that the basic component is an esterified epoxy resin, in particular a higher fatty acid epoxy resin addition product having a number of hydrocarbon atoms of 6 to 18. 3. A reactive mixture as claimed in claim 1, characterized in that it contains from 5 to 20% by weight. glycidyl ethers, preferably butyl glycidyl ether, cresylglycidyl ether. 4. The reactive mixture as claimed in claim 1, further comprising from 1 to 3% by weight of the composition. polyvinyl chloride. 5. The reactive mixture of claims 1 to 4, wherein:. it also contains from 0.1 to 20% by weight of a plasticizer based on aromatic or aliphatic dicarboxylic acid esters or mixtures thereof, or a polyester plasticizer and adipic acid based plasticizer. 6. A reactive mixture as claimed in any one of Claims 1 to 5, characterized in that it contains a compound or mixture of compounds which increases the resistance to light radiation, oxidative destruction or hydrolysis in the final product in an amount of 0.01 to 5% by weight. % based on polymeric components, in particular from the group of benzimidazole, benzophenone, benztriazole, aromatic amines or derivatives thereof.