Epoxy binder for reinforced plastics


The invention relates to the field of production of epoxy resins for impregnation of reinforced materials press materials, glass and plastics, recyclable methods, direct compression, dry winding, etc. Binder comprises, by weight. hours : apositively resin 100, anilinopiperidine resin (hardener) 35-60, low molecular weight butadiene-Acrylonitrile rubber with terminal carboxyl groups (modifier) 10-50, bis-[3-(3,5-di-tert.butyl-4 oksifenil)propyl]sulfide (curing accelerator and amendment) 1-5, spiroatsetaley mixture (mass ratio of alcohol and acetone 1:1) 90-200. The invention allows to obtain pre-impregnated binder non-sticky materials with high viability. A large-sized product, obtained by impregnation of the binder according to the invention, have low porosity, high strength properties and low water absorption. 3 table.

The invention relates to the field of production of epoxy compositions (binder), pre-impregnated materials (prepregs), epoxypropanol and composites with high deformation resistance and water resistance, high electrical insulation, fenolformaldegidnoj resin.

They can be used as a binder for press materials (volokita) and structural composite materials (glass-fiber-reinforced plastics and their combined variants), which are processed by methods of direct compression, dry winding and so on and so forth; it is Known binder for reinforced plastics (Ed. mon. 226146, 08 L 63/00. 1968), including apositively resin and hardener - anilinopiperidine resin.

The disadvantages of this binder are obtained by impregnation of data binding prepregs are hard (dry) and have limited viability (no more than 7 days at a storage temperature2oC), which hinders their processing by the method of "dry" winding and requires high pressure forming; low resistance to shock loads and insufficient interlayer strength plastics, which causes them to crack (delamination) in the machining process or operation; - low level of durability at high (150-200oC) temperatures.

Known epoxy binder for glass-reinforced plastics (U.S. Pat. RF 2028334, 1995) containing epoxy resin, a modified diglycidyl ether diethylenglycol and dichloro-(bis)-2-mercapto-5-trichloroacetamido-1,3,4-thiadiazole Nickel in spectaculorum solvent.

However, the gelling time of the specified binder at (12220)oWith is10 C. Hence it cannot be used for industrial production of pre-impregnated materials (prepregs) on the basis of different reinforcing fibers, as in the mine impregnating machines for solvent removal, the required temperature is from 100 to 120oAnd stay soaked tissue in the mine is 15-20 minutes it is Quite clear that during this time connecting sailfinsims the prepreg will be unsuitable for further processing by winding, pressing, etc.

The closest technical solution set of core essential features and achieved technical result is binding for reinforced plastics (Ed. mon. 726137, 08 L 63/04, 1980) prototype, including apositively resin - 60-70 wt.h., hardener - anilinopiperidine resin - 10-20 wt.h., modifier-Novolac phenol-formaldehyde resin - 10-20 wt. including the curing accelerator - Tris-(dimethylaminomethyl)phenol - 0,05-0,1 wt.h.

It should be noted that neither in the description nor in the claims, there is no mention of the solvent of the binder. Homesouth into pieces of appropriate (required) size, collect the package and pressed at 100-200oWith, the specific pressure - 10-6O kgf/cm2within 20 min/mm thickness of the package.

All of the resin in the specified spanning - ETF (amoxicilina), rezol anilinopiperidine and phenol-formaldehyde Novolac are solid. Their melting point (dropping) is in the range from 90 to 110oC. Only the curing accelerator pack-606/2-Tris-(dimethylaminomethyl)-phenol is a liquid, but its content is very little.

Hence, to obtain high-quality pre-impregnated materials (prepregs) for the existing impregnating machines shaft type required (for fabrics at the level of 25 to 33 wt.%) sediment binding is only possible to use 50-70% green solutions binder.

As solvents typically use a mixture of alcohols (ethyl, isopropyl and other) with acetone or toluene in the ratio of 1:1 or 2:1 (by weight). The main requirement for the solvent - all components of the binder should quickly dissolve and give stable solutions within permissible for a binding period of storage in a production environment at a temperature of (202)oC.

In addition, the solvent in the process is>C). The residence time of the prepreg in the mine (depending on the speed of impregnation) - 20-30 minutes At the same time with heating is forced air flow in the mine (1700-2000 m3/h).

Middleware ed. mon. 726137 according to the description, allows to ensure the viability of the prepreg during storage up to 100 days at a storage temperature (02)oWith against 6-7 days for middleware ed.mon. 226146.

However, in this case the notion of "viability" of the prepreg is very relative. As mentioned binder prepregs immediately after impregnation work hard (brittle). And viability of paepegem based on epoxy, epoxy-novolak and other binder is characterized, first of all, the time when the prepreg remains elastic (flexible), no flaking, bending does not delaminations binder.

Hence, the prepregs based middleware ed. mon. 226146 and 726137 can be recycled, mainly by extrusion method, mainly for insulating materials assignments that do not meet strict requirements for strength characteristics.

When "dry" winding large which leads to delamination, cracks and makes it impossible to provide high values of interlaminar strength plastic (strength under shearing of not less than 3 kgf/mm2).

The basis for the claimed invention was based on the task of creating such epoxy resins for reinforced plastics, on the basis of which the pre-impregnated materials were elastic, non-sticky, had a viability of at least 100 days (at a temperature of storage (02)oC). it was possible to prepare by the method of "dry" winding oversized fiberglass products with minimal porosity, high mechanical strength, especially at elevated temperatures (200oAnd higher) and low water absorption.

The task is ensured by the fact that the epoxy binder for reinforced plastics, including apositively resin, hardener - anilinopiperidine resin modifier, a curing accelerator and a solvent, contains as a modifier of low molecular weight butadiene-Acrylonitrile rubber with terminal carboxyl groups, as a curing accelerator and simultaneously amendment - bis-[3-(3,5-di-tert-butyl-4 oksifenil)propyl] sulfide and in which the ratio of the binder components, wt.h.: Amoxicilina smola - 100 Anilinopiperidine resin - 5-60 low Molecular weight butadiene - Acrylonitrile rubber with terminal carboxyl groups - 0-50 Bis-[3-(3,5-di-tert-butyl-4 oksifenil)propyl]sulfide 1 -5 Spiroatsetaley mix - 90-200
Distinctive features of the proposed epoxy resins for reinforced plastics are the following features:
- introduction hardener - anilinopiperidine resin other quantitative limits than in the analogue and the prototype;
- the content in quality modifier is a low molecular weight butadiene-Acrylonitrile rubber with terminal carboxyl groups;
content as a curing accelerator and simultaneously amendment bis-[3-(3,5-di-tert-butyl-4 oksifenil)propyl]sulfide;
- the content of the solvent alcohol-acetone mixture at a mass ratio of alcohol and acetone 1:1.

Amoxicilina resin (ETF) - THE 2225-316-09201208-94 is the product of the condensation of epichlorohydrin with triphenols (in the presence of alkali). The content of epoxy groups is not less than 19.5 per cent. Is a solid melt with a melting temperature of 65-75oC.

Rezol anilinopiperidine Smalley pieces of uncertain shape. Dropping temperature is 90-110oC.

Low molecular weight butadiene-Acrylonitrile rubber with terminal carboxyl groups brands SKN-TR (TU 38.103474-86) or SKN-TR (TU 003-124-86).

Bis-[3-(3,5-di-tert-butyl-4 oksifenil)propyl] sulfide is produced by interaction of 2,6-di-tert-butyl-4(-chloropropyl)phenol with sulfur in sodium. Is a white crystalline powder.

Empirical formula: C34H54About2S
The structural formula is:

Molecular weight: 526,86.

Melting point: 71-75oC.

The product is produced in pilot scale under the brand "3" (THE 88-15326-01-90).

These distinctive essential features are new, because their use in the proposed population, quantitative and qualitative relationships in the prior art, analogs and prototype not found, which allows to characterize the proposed epoxy binder for reinforced plastics by the criterion of "novelty."

One set of new essential features with commonly known essential features that allow one to solve the problem and achieve new technical riehecky, analogs and prototypes.

New epoxy binder is the result of scientific and experimental research and creative contribution, obtained without the use of any standard developments, guidelines or recommendations in the art of plastics processing, based on the use of a new concept of its receipt, it is not obvious to experts, is characterized by the criterion of "inventive step".

The quantitative limits of ingredients of epoxy resin were established on the basis of conditions:
- elastic, non-sticky prepregs with long-term viability;
- ensure maximum strength characteristics, including 200oC and above;
- minimum water absorption.

Bis-[3-(3.5-di-tert-butyl-4 oksifenil)propyl] sulfide (the product of CO-3) in the inventive binder performs the function not only of the accelerator curing process of the resin ETF hardener - anilinopiperidine resin, but at the same time plays the role of the amendment, creating (due to chemical interaction with the resin and rubber) more streamlined and less defective structure of the reticulated polymer, which, in turn, provides improved physico-meenie groups butadiene-Acrylonitrile rubber when heated interact with the epoxy groups of the resin ETF. This allows in combination with the accelerator (amendment) - product-WITH-3 - to provide a high deformation resistance of epoxy and significantly reduced (in comparison with analogue and prototype) water absorption of plastics.

The solvent selected is cheap, available and easily volatile solvent - spiroatsetaley the mixture at a mass ratio of alcohol and acetone 1: 1. On the basis of the good solubility of all components of epoxy resin, from alcohols selected the most affordable and environmentally safe - ethyl and isopropyl.

A method of obtaining a patent and epoxy prepregs and plastics based on it is as follows:
A. Preparation of epoxy resin
Binder in large (50-400 kg) quantities is prepared in the mixer with a stirrer, a sunroof to boot and the bottom drain valve. A small amount of a binder is prepared in any suitable vessel with stirring manually. In order to accelerate the dissolution process anilinopiperidine resin its pre-ground in a crusher, mill or roll mill until the particle size is not more than 2 mm

In the mixer pour calculated (according to recipe) live in digidna resin and powdered bis-[3-(3,5-di-tert-butyl-4 oksifenil)propyl] sulfide and stirred the mixture (at room temperature) to obtain a homogeneous solution (approximately 1-1 .5 hours). Then in the mixer while the mixer load estimated number of alcohol (ethyl, isopropyl or another brand, which is well to dissolve all the components of the binder) and heated to a fluid state apositively resin and a low molecular weight butadiene - Acrylonitrile rubber stamps SKN-TR or SKN-TR, after which the mixture is still stirred for 1-1,5 hours Ready to use epoxy binder is poured into appropriate containers.

Depending on the requirements of specific impregnated material in the impregnation process adjusts the density of the binder due to the dilution directly into the bath of impregnating machine (manual mixing). For dilution using the same solvent.

B. obtaining a pre-impregnated materials (prepregs)
To evaluate the strength characteristics of reinforced plastics industrial impregnating machine (shaft type) were drenched with structural fiberglass brand TSU 8/3 - VM -78 (TU 6-11-292-84).

Parameters impregnation:
The rate of impregnation, m/min - 1-1,5
The temperature in the mine,oWith 110-120
The impregnated glass cloth was elastic, non-sticky and had the following characteristic 9,6
The content (mass fraction) binder, % - 302
C. research Methods
The viability of binder impregnated glass fabric (prepreg) at a storage temperature (00,2)oWith evaluated:
1) time during which preserves the elasticity (flexibility) of the prepreg;
2) time during which no change of mass fraction of soluble;
3) change the strength characteristics of fiberglass, made from a prepreg with a different retention period.

The mode of winding rings diameter 592 x 606 mm (plastic thickness of 7 mm, the width of the fabric 900 mm):
Speed, rpm - 4,5
Tension, kg/canvas - 250
The temperature of the supporting shafts,oWith:
a) 1 shaft - 120-130
b) 2nd shaft 90
Heat treatment:
- speed temperature rise with exposure 120oC - 2 h, 160oC - 2 h, 180oC - 2 h, (2005)oWith 6 hours;
- cooling for 6-8 h to 60-80oC.

Gelling time of the binder was determined using the curing plate, as described in GOST 901-78.

The glass transition temperature (Tarticle) hardened binder, depending on their formulation was evaluated by dynamic method using the device - the torso is atory 250oWith a constant heating rate of 1oC/min:

where0the period of oscillation (time unwinding disk rigidly mounted on the lower end of microplastic at room temperature,oC);
tthe period of oscillation at a temperature toC.

All microplastic were prepared by hand-impregnated glass yarn Navy-80 (58 Tex) binder 60% concentration with subsequent removal of the solvent in a heating Cabinet and curing in an optimal way for each recipe binder mode, providing maximum TST. The content of the binder in the micro-plastic was (302) wt.%.

Physical-mechanical testing of GFRP specimens were prepared according OST 3-4791-81, OST 3-4792-81 etc.

Data on strength in static bending (20 and 200oC), PL.1, to preserve strength after thermal aging (200oWith -700 h) and water absorption at boiling for 100 h, PL.2, obtained on fiberglass samples (fiberglass brand TSU 8/3 - VM - 78), produced by the method of direct compression at specific pressure of 10 kgf/cm2and stepwise heating from 20 to 200oWith exposure at 20 is atii and chipping, table.3, obtained on samples cut from the filament winding fiberglass (see above). The samples were cut in the warp and weft.

The content of pores (voids) in the samples of the laminate were determined using microstructural analysis. Water absorption of glass fiber in boiling water was estimated by the change in mass of the samples according to GOST 4650-82.

Example 1 (similar)
In the capacity of the mixer pour calculated (according to the recipe) quantity of acetone, then when running the mixer estimated number shredded anilinopiperidine resin SF-340A or SF-A (abbreviation AFF). The mixture is stirred (at room temperature) until a homogeneous solution (approximately 1-1 .5 hours). Then when running the mixer load calculation quantity of ethyl alcohol and heated to a fluid state apositively resin (abbreviation ETF), after which the mixture continued to stir for 0.5-1 hours

Example 2 (prototype)
In the tank (mixer) pour calculated (according to the recipe) quantity of acetone, then when running the mixer estimated number shredded AFF resin. The mixture is stirred (at room temperature) until a homogeneous solution (approximately 1-1 .5 hours). Then, when p is 1:1) and powdered phenol-formaldehyde Novolac resin (abbreviated PF), then the mixture is stirred until a homogeneous solution (approximately 1-1 .5 hours). After that, when operating the mixer load according to the recipe preheated fluid status ETF and pour a little accelerator - Tris-(dimethylaminomethyl)phenol (yn-606/2), after which the mixture continued to stir for 0.5-1 hours

Examples 3 -11
The procedure for their preparation are described above (see section a).

Examples 3-5
The content of AFF, rubber SKN-TR and accelerator (amendment) - product CO-3 is in the claimed range.

Examples of 6.7
The content of AFF, rubber SKN-TR and accelerator (amendment) - product CO-3 respectively below and above the stated limits.

Example 8
Analogous to example 5, but instead of rubber SKN-CAR taken rubber SKN-TR.

Examples 9-11
The content of AFF, rubber SKN-TR (example 9,11 - SKN-TR, example 10 - SKN-TR) and accelerator (amendment) - product CO-3 is in the claimed range, but is, according to the properties of the optimal. In example 11 instead of ethyl alcohol taken isopropyl alcohol.

The content of solvent - spermazetovoe mixture at a mass ratio of ethanol and acetone 1:1 (examples 1 to 10) and isopropyi the above parameters impregnation mass fraction of resin in the impregnated fiberglass trailer hitch 8/3 - VM-78-(302) wt.%.

In the impregnation process (as mentioned above) the solvent is removed completely, and impregnated materials (fabrics), and especially in Presolana (winding) the fiberglass is missing. For this reason, apparently, in the claims the author. mon. 726137 in the composition of the binder solvent is not specified.

In recipes binder (examples 3-11) more hardener AFF matches and more modifier (rubber), and accelerator (amendment) - product WITH 3 less.

Optimization of the number entered in the inventive epoxy binder curing agent, modifier and accelerator (amendment) was carried out on the basis of the following requirements:
- time gelatinization, which should be no more than 5 minutes at 160o;
- providing a high deformation resistance (Tarticledetermined by the dynamic method in contact with the glass - not less than 120oC) and the level of durability of FRP Flexural 200oWith not less than 45%;
- high resistance to heat ageing;
- minimum water absorption, especially at elevated temperatures.

When the content in the binder is now within, unable to meet these requirements, i.e., the fiberglass has the properties of a-level and analog prototype.

On the optimal formulation of the claimed binder (examples 9-11) fiberglass significantly surpasses the similar material to the binder of example 1 (analog) and example 2(prototype):
- to preserve the strength in bending (200oC) 1.5-3 times;
water absorption (100oWith -100 h) more than 2 times lower than that of analog and prototype;
- to preserve the strength in bending (200o(C) after 700 hours of thermal aging at 200oWith - in 1.5-3 times.

At the stated binders after impregnation of the fiberglass work non-sticky, flexible prepregs with greater viability (when 02oC).

Strength properties (Flexural, compressive and shearing) winding of fiberglass on the claimed binder (optimal formulations for examples 9-11) is also higher than that of analogue and prototype. This is because the prepregs on the binders of examples 1 and 2 rigid, and the porosity of fiberglass above 2-3 times.

Thus, a new technical solution in the aggregate, the proposed essential features when implemented in an epoxy binder for Amirova applicability", i.e., the level of invention.

Can be different versions of the epoxy binder composition and the quantitative ratio of the components, if it is not beyond the scope of the technical solution described in the claims.


Epoxy binder for reinforced plastics, including apositively resin, hardener, anilinophenol-formaldehyde resin, a modifier, a curing accelerator and a solvent, characterized in that it contains as a modifier of low molecular weight butadiene-Acrylonitrile rubber with terminal carboxyl groups, as a curing accelerator and simultaneously amendment - bis-[3-(3,5-di-tert-butyl-4 oksifenil)propyl] sulfide and the solvent - spiroatsetaley the mixture at a mass ratio of alcohol and acetone 1: 1, in the following ratio of the binder components, wt. including :
Amoxicilina resin - 100
Anilinopiperidine resin - 35-60
Low molecular weight butadiene-acrylic-nitrile rubber with terminal carboxyl groups of 10-50
Bis-[3-(3,5-di-tert-butyl-4 oksifenil)- propyl] sulfide 1-5
Spiroatsetaley mix - 90-200


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