RU2028334C1 - Epoxide binder for fiber glass - Google Patents

Abstract

FIELD: binder materials. SUBSTANCE: binder has the following components, mas. p. : epoxide resind КДА 19 ± 0.1; ЭТФ 19 + 0.1; УП 63IY 19 + 0.1; hardener 9 3.1 + 0.05; chloronickel complex [NiZ₂Cl₂] where L - 2-mercapto-5-trichloroacetylamino-1,3,4-thiadiazole 0.3-1.0; alcohol 24 ± 0.1, and acetone 16 + 0.1. Hardening product is nonporous monolith with improved physico-chemical properties. EFFECT: improved property of product. 4 tbl

Description

 The invention relates to the production of an epoxy binder used to obtain composite materials (KM).

 Known technological polymer binder EDT-69, which is a solution of epoxy resins KDA, ETF and hardener 9 in an alcohol-acetone mixture / 1 /, designed to impregnate glass-carbon-organo-reinforcing fillers and obtain CM based on them.

 The disadvantage of this binder is flammability.

 The closest in technological essence is the technological polymer binder EDT-69N, which is a solution of epoxy resins KDA, ETF, UP - 631U and hardener 9 in an alcohol-acetone mixture designed to impregnate glass-carbon-organo-reinforcing fillers and obtain CM based on them at the subsequent content of the components, parts by weight / 2 /.

Epoxy modified resin KDA 19 ± 0.1
Epoxy resin ETF (epoxytriphenol) 19 ± 01 Epoxy resin UP-631U 19 ± 0,1
Latent Hardener
type (-bis- (N, N-dimethylcarbamidocenylmethane) 3.1 ± 0.05
Absolute ethyl alcohol 24 ± 0.1 Acetone 16 ± 0.1 where due to the modifying additive UP-631U self-extinguishing due to ignition of the binder EDT-69N and materials based on it is provided in comparison with the binder EDT-69, which did not include epoxy resin UP-631U.

Binder EDT-69H is obtained by alternately mixing the components; first UE-631U stirred in acetone for 30-40 minutes at 40-45 ^{° C} until dissolved, then add TFE epoksitrifenolnuyu resin, previously diluted up to 50 mL at ⁰ ° C, which imparts the cured products of high heat distortion temperature, after which the epoxy compound is introduced, which increases deformability and toughness of the cured polymer grade kDa alcohol is then added and the latent curing agent of type 9 (bis (N, N-dimetilkarbamidodifenilmetan) was stirred under reflux at 60 ± 2 ^{° C} for 2.5 hours.

 The prepared binder EDT-69N is of a uniform light brown color without mechanical impurities, having self-extinguishing, viability of at least 6 months, high physicomechanical properties, which make it a high-tech binder.

 However, this composition of the binder EDT-69N does not provide a porous material during the curing of CMs based on EDT-69N at an acceptable high heating rate used for solutions of binders on an alcohol-acetone mixture, and, consequently, the improvement of the electrophysical properties of the binder during curing.

The purpose of the invention is to obtain a new epoxy brand EDT-69NU binder with porosity and improved physico-chemical characteristics after curing. This goal is achieved by the fact that the known binder containing epoxy diane resin, modified with diethylene glycol diglycidyl ether, epoxytriphenol resin, bromine-containing epoxy diane resin and hardener bis-N, N-dimethylcarbamidodiphenylmethane in alcohol-bis-acetone 2-mercapto-5-trichloroacetyl-amino-1,3,4-thiadiazole nickel (II) in the following ratio of components (parts by weight):
Epoxy Dianova Resin
modified diglyc-
diethylene glycol dilauer 19 ± 0.1 Epoxytriphenol resin 1 19 ± 0.1
Bromine-containing epoxy diane resin 19 ± 0.1 Hardener 3.1 ± 0.05 Alcohol 24 ± 0.1 Acetone 16 ± 0.1
Dichloro- (bis) -2-mercapto-5-trichloroacetylamino-1,3,4-thiadiazole nickel (II) 0.3 ± 1.0
PRI me R 1. The proposed binder EDT-69NU is prepared as follows. In the beginning, a binder of the type EDT-69N is prepared using known technology. The reactor was heated with a stirrer and reflux condenser is poured 16 ± 0,1 g of acetone was added 19 ± 0,1 g of an epoxy resin NC-631U, pre-shredded to pieces no larger than 50 mm, then at 40-45 ^{° C} stirring is within 30-40 minutes until complete dissolution of the resin UP-631U. Then poured into the reactor 19 ± 0,1 g of TFE resin, precooled ^to 5 ° C and crushed to pieces less than 50 mm. Then the apparatus is placed KDA resin in an amount of 19 ± 0,1 g, soaked at ²⁵ ° C for 15 hours, then poured into the apparatus 24 ml of alcohol and 3.1 g of a hardener introduced 9 sealingly closes the upper hatch, the agitator is activated, and device heating, the return refrigerator is checked for serviceability. When the temperature in the reactor is 60 ± 2 ^{° C} is carried out mixing the binder for 2.5 ± 0.5 h, the coolant temperature at this should be 70-75 ^C. Prepared binder EDT-69H uniform light brown color without mechanical inclusions . The resulting binder in terms of performance meets the requirements of TU 1-595-25-277-89. To select a modifier that has a set of valuable properties compared to the pure binder EDT-69N, which allows for a curing process with uniform gas evolution with a maximum release of volatiles at an acceptable high technological speed, which ensures the production of a practically non-porous material with the maximum possible reduction in the heat treatment cycle, preliminary studies of the effect of additives of complex compounds with various transition metals based on 2-mercapto-5-trichlor ligand acetylamino-1,3,4-thiadiazole in comparison with the pure binder EDT-69N by heating pure EDT-69H and binder EDT-69N, modified with additives of complex compounds in an amount of 0.5 wt. including: [CoL ₂ Cl ₂ ], [NiL ₂ Cl ₂ ], [CuL ₂ Cl ₂ ], which were studied by gravimetric analysis in a thin layer of a binder with and without additives in the bottle when the temperature rises at a speed of 2.0 ^about / min to a maximum curing temperature ^about 125 C / min and holding at 125 ± 2 ^{° C} for 1 h to constant weight. The analysis data are given in table. 1.

Based on the data table. 1 it can be concluded that in a thin layer of material when heating the EDT-69N binder pure and with the addition of various modifiers, the product with the nickel complex [NiL ₂ Cl ₂ ], where 2-mercapto-5-trichloroacetylamino-1,3, 4 thiadiazole, at a rate of temperature rise of 2.0 ° ^C / min - one of the most appropriate high skoroti heating during curing CM based binders prepared in solvents such as alcohol, acetone.

For the synthesis of the nickel-chlorine nickel complex, dichloro- (bis) -2-mercapto-5-trichloroacetylamino-1,3,4-thiadiazole nickel (II) - [NiL ₂ Cl ₂ ] take the ratio of NiCl ₂ ^. 6H ₂ O to the ligand as 1: 2, i.e. 0.47 g of NiCl ₂ ^. 6H ₂ O and 1.0 g of ligand. The ligand is dissolved in 2-3 ml of acetone, and NiCl ₂ ^. 6H ₂ O in 50 ml distilled water and then dissolved in acetone ligand was added dropwise to a solution of nickel chloride (NiCl ^_2. 6H ₂ O). The reaction product in the form of a powder is filtered from a solution on a Schott filter No. 4 and washed with distilled water, and then dried in a desiccator over KOH at room temperature. Thus, the modifier for EDT-69N has been refined, which allows to obtain a non-porous product during curing. To determine the quantitative ratio of ingredients in the analysis of limit ratios, including the boundary values of the range, various additives of the [NiL ₂ Cl ₂ ] modifier in the binder EDT-69H were studied. To do this, to 25 ml of a binder EDT-69N concentration of 62% add 0.5 wt.h. of the obtained nickel-nickel complex [NiL ₂ Cl ₂ ], the solution is thoroughly mixed for 1-2 minutes until completely dissolved, then the solution is immersed in a glass electrolytic cell with a working electrode diameter of 1 cm and heated in a thermostatic oven at a speed of 2.0 ^o C / min up to 125 ^° C with an exposure of 125 ± 2 ^° C until fully cured, characterized by the achievement of constant values of G and tanδ, continuously measured during heating on the E-7-8 meter using plane-parallel copper electrodes immersed in a binder and missing to the bottom e bone cell 1.5 cm. The amount of additives introduced into the formulation [NiL ₂ Cl _2], evaluated by referring to the final product by curing the above mode. The experimental data are given in table. 2.

As can be seen from the data table. 2 (experiment 4) with the introduction of additives complex modifier - 0.5 wt.h. [NiL ₂ Cl _2] and carrying out the optimized mode at a heating rate of 2.0 ° ^C / min to 125 ^{° C} with exposure at 125 ± 2 ^{° C} until a constant G and tgδ, obtained by visually homogeneous, without air inclusions and pores of the material.

EXAMPLE EXAMPLE 2 Analogously to Example 1, a binder EDT-69H add other quantities of the complex, and curing is carried out a series of experiments, solutions prepared based on them, while heating the modified binder various additives EDT 69H-rate of 2.0 ^C / min to 125 ° ^C and held at 125 ± 2 ^{° C} until constant values of G and tg δ.

As can be seen from the data table. 2, visually homogeneous, nonporous material not containing the air inclusions is obtained during the same single-stage heating mode at a rate ^of 2.0 C / min to ¹²⁰ ° C with exposure at 125 ± 2 ^{° C} until constant tgs and when G the introduction of the maximum additive complex [NiL ₂ Cl ₂ ] in the amount of 1 wt.h. (experiment 5) and a minimum additive in the amount of 0.3 wt.h. (experience 3). The decrease in the amount of [NiL ₂ Cl ₂ ] to 0.25 wt. hours (experiment 2) causes the formation of pores and air inclusions, and an increase in these values to 1.25 parts by weight (experiment 6) causes the formation of pores in the final product of curing. The known process EDT-69H binder without additives (experiment 1) at heating rate of 2.0 ° ^C / min bubbled, i.e. low quality curing product, highly porous.

Thus, the boundary values of the added amounts of the complex [NiL ₂ Cl ₂ ] in the binder EDT-69H were revealed. The curing product is homogeneous, non-porous, monolithic. In the case of curing the binder without additives - highly porous, highly expanded.

The identified boundary values of the added amounts of the complex [NiL ₂ Cl ₂ ] - 0.3 ± 1.0 wt.h. to the binder EDT-69N and improved visual qualities of KM obtained during the curing of the binder EDT-69N with the addition of a modifier allow us to recommend the obtained modified binder as a new binder brand EDT-69NU. Prepared binder EDT-69N, containing in its composition in an amount of 0.3-1.0 wt.h. and the known binder EDT-69N was tested for initial properties according to TU 1-595-25-277-89. Variation of the amounts of modifier in the range of 0.3-1.0 wt.h. the initial properties of the new binder were not reflected. The values of the characteristics of the concentration, gelation time and viability are identical and correspond to the norms of TU 1-595-25-277-89 indicators of the binder EDT-69N.

 The data are given in table. 3.

To study the quality of materials known (EDT-69N) and the proposed (EDT-69NU) take 25 ml of a binder EDT-69N, prepared according to the known technology and EDT-69NU with the additive [NiL ₂ Cl ₂ ], immersed in an electrophysical cell with a diameter 1 cm working electrode, is connected to the E-7-8 meter and heated in a thermostatic oven at a rate ^of 2.0 C / min to 125 ^{° C} and held at 125 ° ^C until complete curing. The data of physicochemical properties are presented in table. 4, which shows that both types of binders EDT-69H-69NU EDT and have the same temperature (minimum viscosity) 80 ^{° C,} after which the structuring process begins. In this case, the electrical conductivity of the binder EDT-69N is 2 times higher than the newly obtained binder EDT-69NU, while the lifetime is the same and is 20 minutes.

Thus, as the data in table. 4, the electrophysical properties of the known EDT-69N and the proposed EDT-69NU binders in the initial state and in the state of maximum softening are different. But if at the beginning of measurements this difference was only 15 μs, then at the point of temperature of minimum viscosity it already increased by almost two: 507.7 μs for EDT-69N and 282.7 μs for EDT-69NU, which indicates greater mobility of the molecules known binder compared with the present, which affects the layout process, which already after 20 min at 125 ^C. impossible to correctly estimate the electrical properties due to swelling material in case of EDT-69H, which can be explained by a greater mobility of molecules in the thermal exposure to known m communication. The proposed binder due to the introduction of [NiL ₂ Cl ₂ ] in its composition has the ability to reduce almost twice the mobility of the molecules, in this regard, the process of hot curing is uniform without swelling throughout the structuring area, which makes it possible to correctly assess the electrophysical properties of the material during the entire curing and at the end of curing, established upon reaching constant values of electrical conductivity (0,084μs), which makes it possible to use express analysis of the quality of the obtained material in electrophysics. Thus, the resulting unified binder has an improved quality: a non-porous homogeneous material visually, with improved electrophysical characteristics during hot curing.

The formulation and manufacturing technology of modified with a nickel complex [NiL ₂ Cl ₂ ], where L is 2-mercapto-5-trichloroacetylamino-1,3,4-thiadiazole of an epoxy binder grade EDT-69H, was developed, and its electrophysical curing parameters were established, which allows us to recommend Focusing on the improved properties of the binder during hot curing, this composition as a new binder brand EDT-69NU.

Claims (1)

EPOXY BINDER FOR FIBERGLASSES containing epoxy diane resin, modified with diethylene glycol diglycidyl ether, epoxytriphenol resin, bromine-containing epoxy diane resin and hardener - bis-N, N-dimethylmethanesulfonamide -mercapto-5-trichloroacetylamino-1,3,4-thiadiazole nickel (II) in the following ratio, wt.h .:
Epoxy Diane resin modified with diethylene glycol diglycidyl ether - 19 ± 0.1
Epoxytriphenol resin - 19 ± 0.1
Bromine-containing epoxy Dianova resin - 19 ± 0,1
Hardener - 3.1 ± 0.05
Alcohol - 24 ± 0.1
Acetone - 16 ± 0.1
Dichloro- (bis) -2-mercapto-5-trichloroacetylamino-1,3,4-thiadiazole nickel (II) - 0.3 - 1.0

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