CS221181B1 - Emulsion of the type oil-in-water on the base of non-saturated silanes - Google Patents

Description

(54) Oil-in-water emulsion based on unsaturated silanes

The present invention provides an unsaturated silane emulsion suitable as an adhesion promoter for treating inorganic substrates to improve the adhesion of plastics, especially glass fibers. The oily phase of the emulsion consists of a mixture of 30 to 95% by weight of monoesters and / or diesters of diano-based epoxy resins based on an average molecular weight of not more than 650 with acrylic or methacrylic acid and 5 to 70% by weight of unsaturated trialkoxysilanes e.g. vinyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane. Emulsions may be prepared by emulsification using an emulsifier and / or stabilizer, optionally an organic diluent, using known emulsifying methods and devices. The use of emulsions makes it possible to improve the mechanical properties of the reinforced compositions and to increase the stability of the lubricating compositions.

The present invention relates to an unsaturated silane oil-in-water emulsion prepared by emulsification using an emulsifier and / or stabilizer or an organic diluent suitable as an adhesion promoter for treating fillers for plastic reinforcement.

In order to improve the adhesion of plastics in various inorganic substrates, whether in the form of fibers, spheres, fabrics, pulp and the like. phase interface modification is performed by various binding means, also called adhesion promoters. Industrially, the most widely used method is to apply adhesion promoters from aqueous systems, mainly because the use of organic solvents is limited, either because of their toxicity, flammability and, last but not least, for economic reasons.

Various substituted trialkoxysilanes, which are hydrolyzed to the corresponding silanols, are most commonly used as adhesion promoters. Although it is known that a number of silanols, especially silantrioles, are characterized by poor stability (Bažant V. et al .: Silicones, SNTL Prague 1954, p. 82), little attention has been given to this problem in the application of adhesion promoters. For these reasons, the most common formulations of lubricants, binders and the like. water-based compounds convert trialkoxysilanes by hydrolysis to water-soluble tilanols or alkali metal silanolates. Advancement of these known methods has been achieved by the application of adhesion promoters in the form of emulsions (CS Aut. No. 187 720 and 195 225). Using these stabilized emulsions for hydrolysis and interaction! The silantriol at birth with hydroxyl groups of the silicate occurs mainly in situ, during the heat treatment of emulsion-treated fillers. Further research in this field has revealed that it is possible to formulate emulsions whose advantage lies not only in improved adhesion by blocking polycondensation of silanols, but also in achieving a synergistic effect which is particularly pronounced when using vinyltrialkoxysilanes.

The present invention relates to an unsaturated silane oil-in-water emulsion prepared by emulsification using an emulsifier and / or stabilizer or an organic diluent suitable as an adhesion promoter for the treatment of plastic reinforcing fillers, the oil phase of which consists of a mixture of 5 to 70% % by weight of the unsaturated silane of the general formula

ri

CH 2 = C-CO (CH 2) _n Si (R 2) 3

II o

or

CH 2 = CH (CH 2) _m Si (R 2) 3 wherein R 1 is —H or —CH3, R2 is —OGH3, —OC2H5, —OC2H4OCH3, or —OC2H4OC2H5;

n is an integer of 1 to 3, m is 0.1 or 2 and 30 to 95% by weight of monoesters and / or diesters of epoxy resins based on dianes and an average molecular weight of not more than 650 with acrylic or methacrylic acid.

The unsaturated silanes used to prepare the emulsions are known. Examples of such compounds are vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (2-ethoxyethoxy) silane, vinyltri (2-methoxyethoxy) silane, allyltrimethoxysilane, allyltriethoxysilane, bulenyltrimethoxysilane, butenyltriethoxysilane, methacryloxymethyltriethylmethacryloxymethyl

2-methacryloxyethyltriethoxysilane,

3-methacryloxypropyltrimethoxysilane,

3-acryloxypropyltrimethoxysilane and the like.

The basic structural skeleton of the epoxyacrylate resins of the invention is formed from epoxy resins prepared by alkaline condensation of 2,2'-bis (4-hydroxyphenyl) propane (dianu) with epichlorohydrin, and an average molecular weight of not more than 650. Esterification of these epoxy resins with acrylic acid or methacrylic acid in a molar ratio of 1: 1 to 2 gives the corresponding monoesters, diesters or mixtures thereof.

The preparation of the emulsions can be carried out by known emulsifying methods, using mechanical energy (high speed stirrers, mixers, colloid mills), ultrasound, temperature change and the Weimarn method by solvent exchange. According to the process and equipment selected, emulsifiers and / or stabilizers can be added directly to the oil phase and / or water. The emulsions may be prepared either non-ionically, anionically or cationically, the charge of which is preferably adjusted according to the nature of the substrate. A wide variety of known nonionic surfactants can be used for this purpose. These are mainly alkyl polyglycol ethers, alkylphenyl polyglycol ethers, acyl polyglycol ethers, copolymers based on ethylene oxide and propylene oxide, sorbitol esters and their polyoxyethylated derivatives and the like. Alkyl polyglycol ether sulfates, alkyl polyglycol ether phosphates, sulfated oils and fats, soaps, whether sodium, potassium or triethanolamine of higher fatty acids, and the like can be used to prepare anionic emulsions. Cationic emulsions can be prepared using fatty acid polyamine compounds, alkylpyridine salts, quaternary imidazolinium salts, and the like. It is also possible to use their various mixtures, which are often used to adjust the hydrophilic-lipophilic balance of the emulsifying system. The emulsion can also be stabilized with water-soluble cellulose derivatives such as methylcellulose, ethylcellulose, or carboxymethylcellulose, casein and its derivatives, and the like. Selection of a suitable emulsifier, even if various auxiliary criteria exist, e.g. HLB (the ratio of hydrophobic to hydrophilic groups in the emulsifier structure) is usually to be empirically determined.

In the case of the treatment of glass and mineral fibers, which are the most widespread reinforcing foams, it is possible to add to the emulsions according to the invention various known textile preparations which enable their textile processing. The use of the emulsions according to the invention in this application makes it possible not only to improve the mechanical properties of the fiberglass, but also to make larger disposable quantities of lubricant compositions, to reduce the concentration of adhesion promoters, which is not only economical but also hygienic and ecological.

In addition to this application, the emulsions of the invention can be used to treat different powder fillers for plastic reinforcement, for example in the formulation. prepreg compositions.

The invention is further elucidated by way of examples in which the composition is given in both weight and concentrate.

Example 1

Oil phase

1 g (18.6%) vinyltrimethoxysilane g (83.4%) epoxy acrylate resin

5 g of surfactants prepared by reacting 85 moles of propylene oxide with 1 mole of trimethylolpropane were dissolved in 500 ml of water in a mixer, followed by reaction with 36 moles of ethylene oxide. To this solution was added, with stirring, an oil phase prepared by homogenizing the silane with epoxyacrylate resin A, B and C.

A - epoxy resin monoester methacrylate with an average molecular weight of 375.

B - diestermethacrylate based on epoxy resin with an average molecular weight of 375.

C - diesteracrylate based on epoxy resin with an average molecular weight of 375.

The prepared master emulsion was made up to 5000 ml with water and used to treat 15 micron thick E-glass fibers. The treated and dried fiber was used as an unsaturated polyester resin of ethylene glycol maleate type with a 33% monomer styrene content, initiated with methylcyclohexanone peroxide and accelerated with cobalt naphthenate. Evaluation of fiberglass was performed by bending strength test according to ČSN 640 607 and artificial aging for 2 hours. boiling in water. The results obtained are shown in Table 1.

Corrigendum No.

TABLE 1

3 dry bending strength (MPa) coefficient of variation (% J bending strength after boiling (MPa) coefficient of variation (%) glass content (% J

908

8.4

681

8.3

65.7

1005

7.0

830

7.5

65.6

1160 1142 1131

6.6 6.8 6.7

1120 1100 1,085

6.4 6.4 6.7

65.1 65.3 64.9

In table no. 1 shows the results obtained with untreated glass fiber no. 2 using vinyltrimethoxysilane hydrolyzate, no. 3 using epoxyacrylate resin A emulsion no. 4 using resin emulsion B and no. 5 using an emulsion based on resin C.

Example 2

Oil phase g (50%) of 3-methacryloxypropyltrimethoxysilane g (50%) more epoxyacrylate resin with an average molecular weight of 650. Preparation of emulsions as in Example 1 using resin A and D. The emulsion stock was made up to 5000 ml with water, ie composition As a comparative experiment, hydrolysis of silane in water at pH 4 with acetic acid was carried out, in which the hydrolysis was carried out in approximately 20 minutes, which resulted in a clarification of the solution. Evaluation of the laminates was carried out as described in Example 1. The results obtained are shown in Table 2.

D-diestermethacrylate based on epoxide 221181

Corrigendum No.

TABLE 2

7 8 Dry bending strength (MPa) 1269 Coefficient of variation (%) 6.7 Bending strength after boiling (MPa) 1076 Coefficient of variation (%) 6.4 Glass content (%) 65.5

In the table results no. 6 are obtained using silane hydrolyzate no. 7 using resin emulsion A and no. 8 using a D-based emulsion.

Example 3

Oil phase g (7%) silane 200 g (93%) epoxyacrylate resin, type B

Stick emulsions prepared using the following silanes:

vinyltriethoxysilane,

1326 1280

5,6 6,2

1120 1115

5.2 5.8

65.6 65.5 allyltriethoxysilane, vinyltri (2-ethoxy) silane, butenyltriethoxysilane,

3-acryloxypropyltrimethoxysilane, methacryloxymethyltriethoxysilane.

The emulsifier used was an oxyethylated sperm oil fatty acid surfactant with 16 moles of ethylene oxide. 20 g of a surfactant was dissolved in 1500 ml of water, and an oil phase prepared by homogenizing the individual silanes with an epoxyacrylate resin was added under stirring under a high speed stirrer. The prepared emulsions are white, uniform, sedimentation does not shave within 48 hours. observed with an average particle size of 0.5 to 1 micron.

Claims (1)

SUBJECT Oil-in-water emulsion based on unsaturated silanes, prepared by emulsification using an emulsifier and / or stabilizer or an organic diluent suitable as an adhesion promoter for treatment of fillers for plastic reinforcement, characterized in that the oil phase consists of a mixture of 5 to 70% the weight of the unsaturated silane of the general formula rl CH2 = C-CO (CH2) _n Si (R2) 3 ABOUT OF THE INVENTION or CHa = CH (CH 2) _m Si (R 2) 3 wherein R 1 is —H or —CH3, R2 is —OCH3, —OC2H5, —OC2H4OGH3, or —OC2H4OC2H5; n is an integer of 1 to 3, m is 0.1 or 2 and 30 to 95% by weight of monoesters and / or diesters of epoxy resins based on dianes having an average molecular weight of not more than 650 with acrylic or methacrylic acid.