RU2717836C1 - Pigmented epoxy-phenol binder for polymer composites with fibrous fillers - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to chemical industry, specifically to a pigmented epoxy-phenol binder, which is used to produce colored high-filled polymer composites containing fibrous fillers, comprising glass fiber, carbon fiber, basalt fiber, Kevlar fiber. Pigmented epoxy-phenol binder contains low-molecular epoxy and phenol-formaldehyde oligomers as a dispersion medium, hardener – isomethyl tetrahydrophthalic anhydride, filler, as a disperse phase – an inorganic pigment and an organic pigment dye. Phenol-formaldehyde oligomer used is novolac combined with urotropin, which is a phenolic powder binder (PPB). Inorganic pigment used is an achromatic white pigment selected from a group comprising rutile modification titanium dioxide, zinc oxide. Organic pigment dye used is a pigment selected from a group comprising phthalocyanine blue, phthalocyanine green, technical carbon. Base ratio of the low-molecular epoxide oligomer to isomethyl tetrahydrophthalic anhydride is 10/8 pts.wt. Filler used is talc or omicarb. Binding phenolic powder is basis for charge. Proposed method consists in adding PPB, inorganic achromatic white pigment and filler to said organic pigment in batches with grinding. Charge is a curing accelerator-modifier for epoxy binder containing said low-molecular epoxy oligomer and isomethyl tetrahydrophthalic anhydride. Quantitative content of PPB in the charge composition ranges from 1 to 3 wt%. Charge has corresponding color due to presence of organic pigment dye. Epoxy-phenol binder contains components in the following ratio, wt%: 41.67–47.60 of low-molecular epoxy oligomer, 33.75–38.08 of isomethyl tetrahydrophthalic anhydride, 11.61–24.01 of said inorganic achromatic white pigments and fillers, 0.12-0.24 of said organic pigment dyes, 0.75–2.57 of said phenolic powder binder.

EFFECT: invention increases degree of hardening of epoxy-phenol binder, as well as increases mechanical strength and weather resistance of high-filled polymer composites.

1 cl, 5 tbl, 4 ex

Description

The invention relates to the chemical industry, and in particular, to a technology for producing highly colored non-ferrous epoxy composites in which the dispersed phase is fibrous materials (glass, carbon, basalt, Kevlar fiber), as well as pigments, fillers and functional additives.

Known pigmented epoxy binders used in the technology of paints intended for polymer coatings. The main components of cold cured epoxy binders are thermosetting systems: pigmented epoxy oligomer (component A) - hardener (component B). As hardeners, polyfunctional chemical compounds are used — aliphatic and aromatic polyamines, ketimines, phosphoric acid, etc. [1. Bodo Muller, Ulrich Pot Paints and varnishes and coatings. The principles of formulation. - M .: Paint-Media LLC, 2007. - 237 pp .: 85 tablets, 140 ill.].

Curing with crosslinking hardeners - polyamines having primary and secondary amino groups in the structure of molecules proceeds according to the polyaddition mechanism, as a result of which a polymer network structure is formed. Catalytic hardeners - tertiary amines - cure epoxy oligomers by anionic polymerization. [Sorokin M.F., Kochnova Z.A., Shode L.G. Chemistry and technology of film-forming substances: textbook. for universities with a degree in Chemical Technology of High-Molecular Compounds. - 2nd ed., Revised. and add. - M.: Chemistry, 1989. - 477 p.].

The role of hardener in epoxy binders can be performed by a co-oligomer, in which novolac or rezol phenol-formaldehyde oligomers are most often used. In this case, curing catalysts may be used. Tertiary amines are most commonly used as catalysts for curing epoxy phenol binders. The most common catalyst for curing epoxy binders is the aminophenol catalyst-2,4,6-tris- (dimethylaminomethyl) phenol (UP-606/2 or K-54). Most often it is used to catalyze the curing of dicarboxylic acid anhydrides [A.S. 1761903 USSR MKI E04C 5/07. A rod for concrete reinforcement and a method for its manufacture / S.Kh. Avramenko, L.G. Aslanova, I.E. Evgeniev, B.E. Karpanova, I.I. Kokanov, A.L. Levchenko, L.G. Nedobor, V.A. Semchenko, C.F. Tkachuk (USSR). - No. 4765786/33; declared 12/07/89; publ. 09/15/92, Bull. No. 34].

The closest technical solution to the proposed invention is a pigmented epoxy phenolic binder containing low molecular weight epoxy and resol phenol formaldehyde oligomers, chromatic inorganic pigment - chromium oxide and organic pigment dye of bright orange color - a derivative of naphthalene tetracarboxylic acid [A.s. 1024479 USSR, MKI C08L 63/02, C08G 59/68, B32B 17/04, 27/38. Binder for fiberglass / A.S. Lipatov, E.P. Kanina, V.V. Yenyutin, V.G. Volkov and G.V. Arkhipov (USSR). - No. 3344986 / 23-05; declared 09/28/81; publ. 06/23/83, Bull. No. 23].

The disadvantage of the binder - prototype is the low degree of curing in the product (76-77%) and the resulting reduced mechanical strength of the cured product, as well as low weather resistance of composite products, for example, fiberglass reinforcement or mesh.

The technical result of the invention is to increase the degree of curing of the epoxy binder and the resulting mechanical strength of the fiber plastic product, as well as increasing its weather resistance, variety of colors and applications of epoxy composites.

This result is achieved in that the pigmented epoxy phenolic binder for polymer composites with fibrous fillers containing low molecular weight epoxy and phenol formaldehyde oligomers as a dispersion medium, the inorganic pigment and the organic pigment dye, according to the invention, contain phenol formaldehyde oligome as oligomer as a dispersed phase with urotropine, which is a phenolic powder binder (TFP), as an inorganic o the pigment contains an achromatic white pigment selected from the group comprising rutile titanium dioxide, zinc oxide as an organic pigment dye - a pigment selected from the group including phthalocyanine blue, phthalocyanine green, technical carbon and additionally contains isomethyltetrahydrophthalic anhydride hardener low molecular weight epoxy oligomer: anhydride 10/8 parts by weight, a filler selected from the group consisting of talc, omiacarb; at the same time, TFP is the basis for the charge, which is prepared as follows: TFP, inorganic achromatic white pigment and filler are added portionwise with milling to the weighed portion of the organic pigment, and the charge has a corresponding color due to the presence of organic pigment and acts as a curing accelerator - a modifier for epoxy a binder containing a low molecular weight epoxy oligomer and isomethyl tetrahydrophthalic anhydride, the amount of TFP - a catalytic and modifying base is administered , the charge modifier curing accelerator is from 1 to 3 wt. % by weight of the epoxy binder, while the components of the epoxy phenol binder are taken in the following ratio in wt. %;

Low molecular weight epoxy oligomer 41.67-47.60 Isomethyltetrahydrophthalic anhydride 33.75-38.08 The above inorganic achromatic white pigments and fillers 11.61-24.01 The above organic pigment dyes 0.12-0.24 The above phenolic binder powder 0.75-2.57

Component Feature

1. An epoxy binder is prepared by mixing low molecular weight epoxy oligomers of the CYD-128, YD-128, KER-828, CHS Epoxy 520, ED-22, ED-20, ED-16 brands with isomethyl tetrahydrophyte with the left anhydride TU 2418-399-05842324-2004 in the ratio of parts by weight 10: 8;

2. Curing accelerator - a modifier of epoxy binders is a mixture, which includes:

2.1. Achromatic white pigments: GOST 9808-84. Pigmented titanium dioxide. Technical conditions; GOST 202-84 Interstate Standard. Zinc white; Inorganic chromatic pigments, for example, iron oxide TU 20.30.21-021-88737636;

2.2. Carbonate fillers: GOST R 56775-2015 Microcalcite, omiakarb; silicate fillers: microtalc GOST 19 284-79, talcon T-20, talcon MM-20 GOST, TU 21-25-159-90;

2.3. Technical carbon P 803 according to GOST 7885-86 amended. 1-4 (black carbon black, P 803 carbon black, carbon black, PM-15 carbon black) imported technical carbon, for example Black pigment / black pigment Parivashchemical;

2.4. Organic dyes. The pigment is blue phthalocyanine. Specifications GOST 6220-76 or imported analogues according to CAS No. 1309-37-1, No. 1332-37-2;

2.5. Organic dyes. Green phthalocyanine pigment. Technical conditions GOST 4579-79 or imported analogues according to CAS No. 1328-53-6;

2.6. Binding phenolic powder SFP 012 A2-U12 TU 2257-074-05015227-2002 and other brands according to OST 6-05-441-78, TU 6-07-5751766-26-90, etc.

The invention is as follows:

A preliminary calculation is made for 100 g of pigmented epoxy phenol binder. The formulation of the charge of the curing accelerator is chosen - an epoxy binder modifier, which provides the initial degree of pigmentation (the ratio of the masses of the dispersed phase and the dispersion medium). Having determined the quantitative ratio: dispersed phase / dispersion medium, calculate the specified amount of the curing accelerator - phenolic powder binder - the basis of the accelerator-modifier. The ratio of the inorganic and organic components of the dispersed phase is calculated.

Then get the curing accelerator - modifier.

A calculated amount of organic pigment dye is loaded into a porcelain mortar or mixer for bulk materials, and a phenolic powder binder (TFP), a mixture of urotropine and novolak, is introduced portionwise with milling, and the system is dispersed to a segregationally stable state, an inorganic filler and pigment are introduced portionwise and continue to disperse the system until state of homogeneity. Download is carried out in accordance with the selected recipe.

Then a pigmented epoxy phenolic binder is obtained: the obtained dispersed phase-charge is introduced into an epoxy binder with a stoichiometric ratio epoxy oligomer: isomethyl tetrahydrophthalic anhydride and a liquid viable compound is obtained - a pigmented epoxy phenolic binder with a viscosity that is directly proportional to , on the line for producing fiberglass reinforcement (SPA).

Examples of the practical implementation of the invention

Example 1

Initial data for loading formulations: a) epoxy binder for black fiberglass; b) the degree of pigmentation 1/6; c) the amount of the base of the curing accelerator - modifier - phenolic powder binder - 3% of the mass. to an epoxy binder.

47.62 g of a liquid epoxy oligomer and 38.08 g of isomethyltetrahydrophthalic anhydride are loaded into a mixer with a high-speed mixer - mixer. Mix the contents until smooth. 14.30 g of the charge of the accelerator-modifier containing 11.61 g of talc, 0.12 g of carbon black and 2.57 g of TFP are portioned into the resulting base. Monitoring the completeness of wetting is carried out in bulk on glass and the degree of dispersion - according to the Grindometer - the device "Wedge", which should not exceed a value of 50 microns.

The formulation of the epoxy-phenolic binder obtained in example 1, are given in table. 1.

As a result of using an epoxy binder and a curing accelerator - a modifier in the amounts given above, we obtain an epoxy-phenolic binder for black polymer composites.

The initial degree of pigmentation is 14.3 / 85.7 = 1/6. The content of the base of the curing accelerator - a modifier to the mass of the epoxy binder: (2.57⋅100) / 85.7 = 3.0% wt.

Example 2

Initial data for loading formulations: a) an epoxy binder for a light blue polymer composite; b) the degree of pigmentation 1/3; c) the amount of the basis of the curing accelerator - modifier - phenolic powder binder - 3% wt. to an epoxy binder.

41.67 g of a liquid epoxy oligomer and 33.33 g of isomethyltetrahydrophthalic anhydride are loaded into a mixer with a high-speed mixer - mixer. Mix the contents until smooth. In 75 g of the obtained epoxy binder, 25.00 g of the mixture of the curing accelerator, a modifier containing, are dosed portionwise with stirring, containing: 18.02 g of titanium dioxide; 4.51 g of talc; 0.22 g phthalocyanine blue and 2.25 g TFP. Monitoring the completeness of wetting is carried out in bulk on glass and the degree of dispersion - according to the Grindometer - the device "Wedge", which should not exceed a value of 50 microns.

The formulation of the epoxy phenolic binder obtained in example 2, are given in table. 2.

The initial degree of pigmentation according to the recipe given in table. 2, is (22.53 + 0.22 + 2.25) / (41.67 + 33.33) = 1/3; the content of the base of the curing accelerator - modifier to the mass of the epoxy binder: (2.25⋅100) / 75 = 3.0% wt.

As a result of using an epoxy binder and a curing accelerator - a modifier in the amounts given above, we obtain an epoxy phenolic binder for a light blue colored polymer composite.

Example 3

Initial data for loading formulations: a) epoxy binder for fiberglass light green; b) the degree of pigmentation 1/6; c) the amount of the base of the curing accelerator - modifier - phenolic powder binder - 1% wt. to an epoxy binder.

85.70 g of epoxy binder are obtained in a mixer with a high-speed mixer - mixer, for which 47.62 g of liquid epoxy oligomer and 38.08 g of isomethyl tetrahydrophthalic anhydride are loaded into the mixer. Mix the contents until smooth. In 85.70 g of the obtained epoxy binder, 14.30 g of a mixture of a curing accelerator-modifier are metered in with batch with stirring, containing: 10.64 g of omiakarb; 2.66 g of zinc white; 0.14 g phthalocyanine green and 0.86 g TFP. Monitoring the completeness of wetting is carried out in bulk on glass and the degree of dispersion - according to the Grindometer - the device "Wedge", which should not exceed a value of 50 microns.

The formulation of the epoxy-phenolic binder obtained in example 3 are shown in table. 3

The initial degree of pigmentation is 14.30 / 85.70 = 1/6. The content of the base of the accelerator-modifier to the mass of the epoxy binder: (0.86⋅100) / 85.7 = 1% wt.

As a result of using an epoxy binder and an accelerator-modifier in the amounts given above, we obtain an epoxy phenolic binder for a light green colored polymer composite.

Example 4

Initial data for the calculation of loading formulations: a) an epoxy binder for fiberglass black, blue, light green; b) the degree of pigmentation 1/3; c) the amount of the base of the curing accelerator - modifier - phenolic powder binder - 1% wt. to an epoxy binder.

41.67 g of a liquid epoxy oligomer and 33.33 g of isomethyl tetrahydrophthalic anhydride are loaded into a mixer with a high-speed mixer - mixer. Mix the contents until smooth. In 75 g of the obtained epoxy binder, 25.00 g of the mixture of the curing accelerator — a modifier containing batch, are dosed in doses: 19.21 g of talc; 4.80 g of titanium dioxide; 0.24 g of organic pigment (phthalocyanine blue or green, soot) and 0.75 g of TFP. Monitoring the completeness of wetting is carried out in bulk on glass. The degree of dispersion is determined by the Grindometer - the device "Wedge", which should not exceed the value of 50 microns.

The formulation of the epoxy-phenolic binder obtained in example 4 are shown in table. 4.

The initial degree of pigmentation according to the recipe given in table. 4, is (24.01 + 0.24 + 0.75) / (41.67 + 33.33) = 1/3; the content of the base of the curing accelerator - modifier to the mass of the epoxy binder: (0.75⋅100) / 75 = 1.0% wt.

As a result of using an epoxy binder and a curing accelerator - a modifier in the amounts given in table. 4, we obtain an epoxy-phenolic binder for the polymer composite in black, light blue and light green.

The use of a binder according to the proposed formulations and technology allows to obtain technological impregnating compounds and colored fiberglass reinforcement with improved physical, mechanical and decorative properties. In this case, it is possible to reduce the curing temperature or increase the speed of the glass roving at the selected curing temperature.

Comparative data on the properties of binders and fiberglass reinforcement based on them, obtained according to the recipe of the prototype and examples 1-4 are shown in table. 5.

It can be seen from the table that the use of an epoxy phenolic binder with a curing accelerator - a modifier of the properties of the compound and SPA based on it in the form of a previously obtained mixture allows to increase the strength of fiberglass reinforcement by 20-30%. In comparison with the requirements of GOST 31938, the compressive strength increases by 1.7-1.5 times.

The use of a new curing accelerator - a modifier of the properties of the compound and fiberglass reinforcement can also reduce the curing temperature by 80-50 ° C or increase the speed of glass roving at a given temperature. This leads to a decrease in the energy intensity of the process and an increase in the productivity of the fiber-filled composites production line - composite polymer reinforcement obtained in accordance with GOST 31938-2012. The tactile properties of the surface of fiberglass reinforcement are improved.

Tests of the epoxy phenolic binders of the prototype and with the use of a mixture of an accelerator-modifier were carried out on the line SPA-1 for the production of fiberglass reinforcement in LLC NPO Zvezda in Ivanovo. As a fibrous filler used direct roving ECR17-2400 D-601 of glass type "E".

The samples of staple fiberglass reinforcement (SPA), tested for strength, were obtained in compliance with the requirements set forth in the monograph [Tarnopolsky, Yu.M. Methods of static testing of reinforced plastics / Yu.M. Tarnopolsky, T.Ya. Kinzis. 3rd ed., Revised. and add. - M .: Chemistry, - 1981. - 272 p.] And in [GOST 4651-2014 (ISO 604-2012) Plastics. Compression Test Method - Introduction. 2015-03-01.M.: Standartinform, 2014, 16 pp.].

The diameter of the SPA staple was 10 mm, the height was 10-15 mm, the maximum load was 50 kN, and the loading rate was 250 mm / min. The compression test results were processed using the software of the tensile testing machine 2099 Р-5.

Claims (2)

A pigmented epoxy phenol binder for fiber-reinforced polymer composites containing low molecular weight epoxy and phenol formaldehyde oligomers as a dispersion medium, an inorganic pigment and an organic pigment dye, characterized in that the phenol formaldehyde oligomer contains novol as the dispersed phase powder phenolic binder (TFP), as an inorganic pigment contains achromatic white a pigment selected from the group comprising rutile-modified titanium dioxide, zinc oxide as an organic pigment dye — a pigment selected from the group including phthalocyanine blue, phthalocyanine green, technical carbon and additionally contains hardener isomethyltetrahydrophthalic anhydride with a base ratio of low molecular weight epoxy molecule: 10/8 parts by weight, an excipient selected from the group consisting of talc, omiakarb; in this case, TFP is the basis for the mixture, which is prepared as follows: TFP, inorganic achromatic white pigment and filler are added to the organic pigment in portions with grinding, the mixture has a corresponding color due to the presence of an organic pigment dye, the mixture is a curing accelerator - a modifier for epoxy a binder containing a low molecular weight epoxy oligomer and isomethyltetrahydrophthalic anhydride, the amount of TFP - a catalytic base introduced into the rest of the mixture of the curing accelerator-modifier, is from 1 to 3 wt.% by weight of the epoxy binder, while the components of the epoxy phenol binder are taken in the following ratio, in wt.%: Low molecular weight epoxy oligomer 41.67-47.60 Isomethyltetrahydrophthalic anhydride 33.75-38.08 The above inorganic achromatic white pigments and fillers 11.61-24.01 The above organic pigment dyes 0.12-0.24 The above phenolic binder powder 0.75-2.57