CS239486B1 - Curing accelerator - Google Patents

Abstract

The curing accelerator belongs to the field of synthetic resins. The technical problem of accelerating the curing of air-inhibited acrylate compositions and unsaturated polyester resins is solved. The essence of the invention is an accelerator consisting of 0.001 to 99% by weight of a divalent manganese salt and 1 to 99.999% by weight of a polyamine, the use of which is based on the action of the product of their mutual reaction

Description

The invention relates to an air-curing accelerator for intumescent acrylic compositions and unsaturated polyester resins.

Nowadays, a large number of different types of air-inhibited acrylic compositions and polyester resins are produced for a variety of purposes. The essence of their use is to convert a liquid resin into a solid, which is usually done by radical polymerization or copolymerization. To start the polymerization reaction, free radicals are required, which are obtained by the decomposition of suitable initiators, most often organic peroxides. In order for the decomposition of the initiator to proceed sufficiently quickly at normal temperatures, it is necessary to add a suitable accelerator. These are usually substances with reducing properties. The most commonly used accelerators are salts of certain metals, most often cobalt (but also vanadium, possibly manganese) or tertiary aromatic amines. However, it is also possible to use, for example, quaternary ammonium salts, polyamines, dienols and a number of sulfur-containing compounds (e.g. mercaptans or thiourea derivatives). Gelation time is the time during which the resin loses fluidity during curing; when using the aforementioned accelerators, it is usually around 10 minutes (depending on the amount of accelerator and its type), which makes many applications that require gelation and sufficient polymerization of the resin in a time several times shorter impossible.

This disadvantage is eliminated by the accelerator according to the yield, which consists of:

0.001 to 99% by weight of a salt of divalent manganese with an inorganic or monobasic organic acid and up to 99.999% by weight of an amine of the general formula:

NH ₂ - (CH ₂ - CH - ΗΗ) _χ - H,

R where R - H or an aliphatic radical C, - C$, x » 1 - 10 or its salts with an organic acid C, - C _)Q or for χ 1 its adduct and an epoxy or carboxylic organic compound C, - ^ ₁₀ θ.

The accelerator is used in the form of a solution in an organic reactive or inert solvent or plasticizer, wherein the air-inhibited acrylic composition or unsaturated polyester resin contains or is added to an organic peroxide or hydroperoxide (in an amount usually of 0.5 to 5% by weight). The amount of accelerator relative to the resin is most often 0.001 to 1%, with the molar ratio of manganese to amine being most suitably 1:5 to 1:20 for curing acrylic compositions and 1:10 to 1:80 for curing unsaturated polyester resins.

Accelerators based on manganese or polyamine accelerators have already been described. The use of the accelerator according to the invention is based on the action of the product of their mutual reaction, which can be in a mixture with one of the components. This accelerator is much more effective than manganese or polyamine alone and allows a multiple reduction in the gelation time of air-inhibited acrylic compositions or unsaturated polyester resins. Its high efficiency, especially with respect to acrylic resins and compositions, is also manifested with respect to the acrylic monomers themselves (e.g. mono- or dimethacrylates), the curing or gelation of which at normal temperature using conventional peroxides and accelerators is usually difficult, while using the accelerator according to the invention it takes place in a short time. The accelerator can also be used to activate surfaces or fillers that come into contact with the cured resin or composition.

Example 1 and _f 1

Accelerator solutions were prepared by mixing 1 ml (or 1 g) of amine, 4 ml of manganese(II) octoate solution (in toluene) containing 1% Mn and 10 ml of benzene, 15 g of air-inhibited acrylate composition based on dienebisglyeidyl dimethacrylate and trimethylolpropane trimethacrylate containing 3% cumene hydroperoxide and a small amount of triethylamine (Aldurit S 100) was mixed with 0.5 ml of the accelerator solution.

Gelatinization times are given in the table:

amen wish, time (min) amen wish, time (min) isophoronediamine 50 piperidine 32 phenylenediamine 70 benzidine 57 picoline 23 xylylenediamine 63 phenylhydrazine 18 Versamide 935 5 aminoamide D 500 1 diethylenetriamine 0.3 quinoline 23 diethylamine 9 tetramethylenediamine 16 tetraethylenepenta- 0.3 min tri e tylente tramin 0.3 tetrapropylene- 0.3 pentamine ethylenediamine 0.3 pentaethylenehe- 0.4 xamíw — .........

Example 2

Accelerator solutions of diethyltriamine (DETA) and manganese octoate (5% Mn) were prepared, 20 g of the acrylate composition as in example 1 (Aldurit S 100) or 20 g of unsaturated polyester resin based on maleic anhydride, phthalic anhydride and ethylene glycol diluted with styrene (CHS Polyester 100), to which 3 » cumene hydroperoxide was added, were mixed with . ml of the accelerator solution. The gelation times and composition of the accelerators are given in the table:

number 1 2 3 4 5 6 CHILDREN (al) 2.5 1.2 0.75 0.5 0.4 0.2 Mn - 5% (ml) 0.5 0.5 0.5 0.5 0.5 0.5 benzene (ml) 3 4.3 4.75 5 5.1 5.3 isopropanol (ml) 4 4 4 4 4 4 iron d.-Poly- ester (min) 0.1 1.5 4.5 10.5 19.5 - iron d.-Aldurite (s) 14 18 17 17 15 21

Example 3

Accelerator solutions were prepared by reducing several components (as in Example 2) and adding benzene isopropanol mixtures (1:1) to 10 ml. 20 g of the acrylate composition as in Example 1 (Aldurit S 100) was mixed with 1 ml of accelerator.

The composition of accelerators and gelation time are given in the table:

number of jelly ingredients. time (sT 1 DETA 1.5 ml, Mn 5 » 1.5 ml, octoic acid 3 ml 5 2 DETA 0.5 ml, Mn 5% 0.5 ml, 2-ethylhexyl^’ acrylate 1 ml 49 3 SETA 0.5 ml, Mn 5% 0.5 ml, cumene hydro- peroxide 1 ml 14 4 DETA 1 al, Mn 5% 0.5 ml, acetic acid 0.5ml 8 5 ethylenediamine 0.5 ml, Mn 5% al, acid. acetic acid 0.5 ml that 6 DETA 0.5 al, MnClg.AHgO 0.01 g, acetone 4 ml 26

Example 4 g of methacrylic acid ester was mixed with 1 ml of cumene hydroperoxide and 1 ml of accelerator No. 1 from example 3. The gelation times are given in the table:

ester wish, time (min) ester gel, time (min) furfurylae tacrylate 5.0 cyclohexylmeth- 1,5 acrylate 1,4-butanediol dimethac. 0.3 2-hydroxyethyl- 1,0 methacrylate 3-Cl-2-OH-propylae so. 0.5

Example 5

Accelerator solutions were prepared with A: Mn 5% 1.4 ml, benzene-isopropanol (3: B: DETA 6 ml, benzene-isopropanol (3 ^: 1) and their mixtures. 20 g of acrylate composition composition:

i I 8.6 ml ml (Aldur.it S 100) was cured with 2 ml accelerator

attempt no. 1 2 3 4 5 6 7 component A (%) 100 90 50 10 99 1 component B (%) 100 10 50 90 1 99 required time (s) 530 460 3 4 6 5 7

Example 6

1.5 g of accelerator No. 1 from example 3 was dissolved in 5 g of benzene and 20 g of powdered vinyl chloride-vinyl acetate copolymer (Slovinyl KV 171) was inactivated with this solution.

After the solvent had drained, 10 g of the activated filler was mixed with 10 g of an air-inhibited acrylate composition based on dianbisglycidyl dimethacrylate and trimethylolpropane trimethacrylate, containing 3% cumene hydroperoxide and small amounts of triethylamine (Aldurit M 200), or with 10 g of polyester resin as in example 2 (CHS Polyester 100), to which 0.4 g of tert-butyl hydroperoxide was added. Gelation times: Aldurit - 2 minutes, Polyester - 7 minutes.

Example 7 ml of accelerator solution No. 1 was dissolved in 9 ml of benzene. At the same time, a solution of manganese octoate containing the same amount of manganese was prepared. Test specimens consisting of a steel cylinder with a diameter of 30 mm, a height of 10 mm, a hole with a diameter of 10 mm and a steel shaft with a diameter of 9.95 mm were inactivated with these solutions. The shaft was sealed into the hole with an acrylic composition (Aldurit S 100):

activator manipulation strength (min) shear strength after 24 h (MPa) manganese 30 21 mixed 1 23

SUBJECT OF THE INVENTION

Claims (1)

A curing accelerator of air-inhibited acrylate compositions and unsaturated polyester resins, characterized in that it consists of: 0.001 to 99% of a salt of divalent manganese with an inorganic or monobasic organic acid; and 1-99.999% of an amine of formula NH ₂ - (CH ₂ - CH - ΝΗ) _χ - H, R where R = H or an aliphatic radical 'χ = 1 to 10 or a salt thereof and an organic acid - θιο' ^{ηβ1ιθ Ρ Γθ one} of its adduct with epoxide or carboxylic organic compound C - Ο, θθ.