CZ552189A3 - Epoxy resins of low viscosity - Google Patents

Description

Rajdl Josef, Usti nad Labem, CZ;

Kadlecek Frantisek, Usti nad Labem, CZ;

(54) Low Viscosity Epoxy Compositions (57) The compositions comprise epoxy resins and / or compounds with a mole percent. 80 to 1800, additives and optionally fillers, pigments or dyes. For every 100 wt. parts of epoxy resins and / or compounds contain 5 to 300 wt. parts of Ν, dig-diglycidylaniline and / or derivatives thereof, and optionally up to 100 wt. These compositions have, in particular, high thermostability in the form of hot parts, such as parts of esters of saturated and / or .alpha.,. beta.-unsaturated monocarboxylic and / or polycarboxylic acids.

The invention relates to low-viscosity epoxy compositions of higher temperature and chemical resistance, curable with basic and acid hardeners, particularly suitable for casting and pouring compositions, flooring, sealants, adhesives, paints and laminates. The compositions are characterized by good flow and good workability and are widely used in construction, electrical engineering, mechanical engineering, etc. Cured materials have good physical, mechanical and dielectric properties and low toxicity.

Appropriate mechanical or dielectric properties of the epoxy resins are achieved after curing with hardeners. For many applications, particularly at normal or reduced temperature curing, it is necessary to reduce the viscosity of the base resins and modify the properties of the cured compositions. For this purpose, various reactive and non-reactive diluents are added to the epoxy resins with plasticizers and modifiers which both reduce viscosity but also plasticize the cured compositions. The reactive diluents of the epoxy resins are mainly glycidyl ethers of phenols and alcohols, styrene or esters of [beta], [beta] -unsaturated carboxylic acids. The mono- and bisglycidyl ethers of alcohols and phenols have a pronounced viscosity-reducing effect.

xid groups, these substances incorporate basic resins and plasti115 57C, MS. U.S. Pat. 65,594). Reaction of epodo by network macromolecules.

However, their disadvantage is that they generally reduce the heat stability of cured materials and that they have an adverse toxicologist:

effects. Therefore, the use of these substances has recently been phased out and replaced by glycidyl ethers of long-chain aliphatic alcohols, which are less toxic (Japanese Pat. 56,71917). The latter substances are particularly pronounced in construction. It is a plasticizing effect and it is a disadvantage that, however, they again significantly reduce the heat-stability of cured materials. The same effect also has esters of .alpha.,. Beta.-unsaturated carboxylic acids, of which mainly esters of acrylic acid and maleic acid are used (U.S. Pat. Nos. AO 170 958 and 220 737, U.S. Pat. No. 4,588,788). In addition, acrylic esters are characterized by an unpleasant odor and relatively high volatility. Today, Μ, dig-diglycidylaniline and its substituted derivatives are used as a binder component of encapsulating materials (U.S. Pat. No. WO S5 05215) or laminating materials (Japanese Pat. Nos. 84 217721 and 85 06722). They are mostly hardenable materials at elevated temperature.

The most common non-reactive diluents are phthalic acid dibutyl ester, phthalic acid di-2-ethylhexyl ester, aromatic hydrocarbons and adipic acid derivatives. The disadvantage of these diluents is that they significantly reduce the hot shape stability of the cured materials, impair the absorbency of the products and sooner or later leak out of the cured material, which, due to their higher concentration in the resin, results mainly in adverse environmental effects. At the same time, however, volume contractions occur in cured materials and gradual changes in properties.

The foregoing drawbacks overcome the present invention to provide low-viscosity epoxy compositions with increased thermal and chemical resistance curable with both basic and acidic hardeners and consisting of epoxy resins and / or compounds with a mole. weight of 80 to 10000, additives and, optionally, fillers, pigments and dyes. The essence of the invention is that these compositions for every 100 wt. parts of epoxy resins and / or compounds contain 5 to 300 wt. parts of Ν, Ν-digly cidylaniline and / or derivatives thereof and optionally up to 100 wt. parts of esters of saturated and / or .beta.-unsaturated monocarboxylic and / or polycarboxylic acids having a carbon number of 3 to 60.

The advantage of this system over combinations with only aliphatic or aromatic glycidyl ethers, styrene, or esters of β-unsaturated mono- or polycarboxylic acids is that Μ, dig-diglycidylaniline, by virtue of its functionality, aligns to the palm types of epoxides and yet has a rigid aromatic structure. Therefore, hardened formulations with palm epoxy resins almost do not reduce the hot shape stability. Other advantages include its high boiling point, its relatively low toxicity, which is no higher than that of conventional dianium-based epoxy resins, its good resistance to chemical agents, and its virtually odor-free properties. Saturated i-unsaturated carboxylic acid esters are well soluble in admixture with epoxides and Ν, dig-diglycidylaniline, reduce the viscosity of the mixtures and have a plasticizing effect on the cured compositions. While, for example, epoxy resin blends with unsaturated and saturated low viscosity esters have a thermoforming stability of about 30 to 40 ° C upon curing, epoxy resin blends with Κ, Ν-diglycidylaniline and said esters of the same viscosity have thermoforming stability upon curing approx. 15 to 20 ° G higher at the same mechanical properties at normal temperature.

As epoxy resins and compounds, substances having a molecular weight of 80 to 1800 are used. Are, in particular, condensates of epichlorohydrin or Z? -methylepichlorohydrins with polyhydroxy compounds of the type of mono-, di-, tri- or quaternary phenols or alcohols, or with polycarboxylic acids, amines, amides and the like. Also included are substances formed by epoxidation of unsaturated compounds. They are used either singly or in mixtures.

Among the mono- or polycarboxylic acid esters of saturated or α-unsaturated acids, for example, esters of violet, adipic, maleic, fumaric, acrylic, methacrylic and the like are suitable.

By Ν, dig-diglycidylaniline is meant here the product of the alkaline condensation of aniline with epichlorohydrinine. Depending on the manufacturing process and the refining, this product contains, in addition to the main constituent Η, dig-diglycidylaniline, a greater or lesser amount of reaction by-products, in particular oligomers formed by the coupling, of two or more Ν, Ν-diglycidylaniline molecules having a resin. For special purposes this technical product can be distilled and pure Ιΐ, Ν-diglycidylaniline can be used. The epoxy group content of the distilled Ν, dig-diglycidylaniline is about 0.55 equivalents / 100 g, for technical products the epoxy group content is about 0.85 to 0.89 equivalents / 100 g. In addition to N, N-diglycidylaniline, or derivatives thereof substituted on the aromatic ring at the 2,3 or 4 position with alkyl, aryl, halogen, alkoxy or even acyl. Most preferred are methyl, ethyl, benzyl, chloro, methoxy and acetyl derivatives. A derivative of Ν, Ν-diglycidylaniline containing a glycidylether group on the nucleus, e.g. triglycidyl-p-aminophenol, or nitrogen-substituted derivatives, e.g. N-methyl-N-glycidylaniline, N-ethoxy-N-glycidylanin and the like, can also be used.

Example 1

Plastbeton

100 wt. parts of a diane-based epoxy resin having an epoxy equivalent of 0.33 / 100 g and an average mol. weight 650 is mixed with 100 wt. parts by weight of Ν, Ν-diglycidylaniline, 25 wt. parts of 2-ethylhexyl acrylate and 25 wt. parts of dibutyl maleic ester. 32 parts by weight of diethylenetriamine are added to the mixture and, after homogenization, sand is added to a consistency such that the mixture can be processed as concrete. The mass is spread on the penetrated concrete floor and the surface and layer thickness is adjusted to 0.5 to 1 cm using a trowel. The floor can be walked after 24 hours and completely hardened after 5 days.

Example 2

Self-pouring epoxy flooring material

95 wt. parts by weight of an epoxy resin based on diane having an epoxy equivalent of 0.33 / 100 g and 5 wt. 160 parts by weight of butyl glycidyl ether are mixed with 160 wt. parts of Ν, dig-diglycidylaniline and 30 wt. parts of di-2-ethylhexylphthalate. 250 wt. parts of PVC powder, 250 wt. parts of kaolin and 20 wt. parts of pigment paste. After thorough mixing, the mass is allowed to stand for 24 hours or evacuated for 5 minutes to remove air bubbles. 35 wt. parts of diethylenetriamine and mixed thoroughly. The mass thus prepared is poured onto the penetrated concrete floor. It's put

- 5 in a layer thickness of 2 to 3 m, which after 10 minutes flax to remove air bubbles. The floor is sprayed xyzy after h and fully hardened after 5 days.

Example 3

Potting epoxy composition

100 wt. parts of a low molecular weight epoxy resin based on phenolic novolak having an epoxy equivalent of 0.540 / 100 g and an average molecular weight of 540 are mixed with 50 wt. parts of 4-methyl-, Ν-diglycidylaniline. 160 parts of ground glass having a particle size of up to 20 .mu.m, then 135 wt. parts of methyltetrahydrophthalic anhydride and the resulting mixture is poured into electrical components.

The mass is cured at 155 ° C for 16 hours. The mechanical and dielectric properties are good.

Example 4

Adhesive

90 wt. of N, K, N * N-tetraglycidyl-4 _J-4 diaminodií'enylmethanu and 10 wt. parts by weight of a diane-based solid epoxy resin having an epoxy equivalent of 0.1 / 100 g and an average molecular weight of 1400 are mixed with 10 wt. 3 parts of 3-chloro-H, N-diglycidylaniline and 5 wt. parts of di-2-ethylhexyl phthalate. This mixture is cured with an adduct of a low molecular weight epoxy resin having an epoxy equivalent of 0.5 / 100 g and diethylenetriamine in mol. 1: 2 ratio. Ha 100 wt. 60 parts by weight of hardener are added to the resin component. The adhesive is suitable for bonding metals, glass, porcelain, wood, etc. It is characterized by good strengths and, after hot curing, increased hot shape stability compared to palm epoxy based adhesives.

Example 5

Solvent-free concrete coating

100 wt. parts by weight of an epoxy equivalent of 0.30 / 100 g and a molecular weight of 700 are mixed with 200 wt. parts of Ν, Η-diglycidylaniline and with 10 wt. parts of di-2-ethylhexyl ester dimerized from the rapeseed oil fatty acids.

100 wt. parts by weight of titanium dioxide, 200 wt. parts of micronized limestone, 3 wt. parts of the flow agent and 10 wt. parts of pigment paste. The resin component is cured with a polyamine amide hardener. The paint is used in the construction industry to protect concrete. It does not contain volatile solvents and can therefore be used in confined spaces.

Example 6

Resin lamination

To 100 parts by weight of diane-based epoxy resin having an epoxy equivalent of 0.50 / 100 g and a mean mol. Weight 400 adds 25 pbw of Ν, dig-diglycidylaniline, 25 wt. parts by weight of N-dodecyl-N-glycidylaniline, 20 wt. parts by weight of 2-ethylhexyl acrylate, 10 parts by weight of di-2-ethylhexyl phthalate and 5 parts by weight of di-2-ethylhexyl phthalate; xylene. To this resin was added 22 wt. parts of dipropylene triamine. The binder thus prepared can be used to impregnate fabrics based on glass, textile, carbon fibers, etc. After curing for 24 hours at room temperature, a rigid and flexible laminate is obtained which is resistant to moisture and chemicals.

Example 7

Biosolvent solvent for concrete penetration

100 wt. parts of epian resin based on diane equivalent of 0.30 / 100 g and with a mean mol. weight with 100 wt. parts of Ν, dig-diglycidylaniline, 50 wt.

parts of dibutyl tartaric acid ester are mixed with epoxy 700. To this resin and 2? wt. parts by weight of dibutyl ester 32 wt. parts of diethylenetriamine. The binder prepared in this way can be used for concrete penetration before laying casting flooring or plastic concrete.

AND

Example

ICO wt. parts by weight of epoxy resin based on diane with an epoxy equivalent of 0.30 / 100 g and an average mol. weight 700 is mixed with 100 wt. parts by weight of N, Η-diglylealaninium, 25 wt. parts by weight of di-2-ethylhenylacrylate and 12 wt. parts bensylalkohoiu. 25 wt. parts of diethylenetriamine and, after homogenization, are added to a consistency such that the mixture can be sorbed with the jacket of betene. The material is spread on the penetrated concrete floor and the surface and thickness of the layer is adjusted to 0,5 to 1 cm by means of a trowel. The floor is tricky after 24 hours and completely hardened after 5 days

- 3 PATENT CLAIMS

Claims (1)

PATENT REQUIREMENTS include low-temperature epoxy compositions with increased thermal and chemical resistance, curable with both basic and acidic hardeners and consisting of epoxy resins and / or compounds with a mol. 30 to 1800, additives and optional fillers, pigments and dyes, characterized in that for every 100 wt. parts of epoxy resins and / or compounds contain 5 to 300 wt. parts of Ν, dig-diglycidylaniline and / or derivatives thereof, and optionally up to 100 wt. parts of esters of saturated and / or?,? - unsaturated monocarboxylic and / or polycarboxylic acids having a carbon number of 3 to 60. i .J RESEARCH INSTITUTE Synthetic resin varnishes